KR101516613B1 - Material for pattern formation, apparatus for pattern formation, and method for pattern formation - Google Patents

Abstract

The present invention is characterized in that the I / O value and the glass transition temperature of the binder contained in the photosensitive layer are all within a constant numerical range, thereby providing a pattern forming process which is excellent in resolution and tent property, A pattern forming apparatus having the pattern forming material, and a pattern forming method using the pattern forming material. To this end, it is preferable that a photosensitive layer is provided on a support and the photosensitive layer contains a binder, a polymerizable compound and a photopolymerization initiator, the binder has an I / O value of 0.300 to 0.650 and an acid value of 130 to 250 / g). < / RTI > It is preferable that the binder contains a copolymer and the copolymer contains 30 mass% or more of a monomer constituting a homopolymer having an I / O value of 0.35 or less. A pattern forming apparatus having the pattern forming material and a pattern forming method using the pattern forming material are provided.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pattern forming material,

The present invention relates to a pattern forming material preferable for a dry film resist (DFR) or the like, a pattern forming apparatus having the pattern forming material, and a pattern forming method using the pattern forming material.

Conventionally, in forming a permanent pattern such as a wiring pattern, a pattern forming material in which a photosensitive layer is formed by applying and drying a photosensitive resin composition on a support is used. The permanent pattern can be produced, for example, by laminating the pattern forming material on a substrate such as a copper-clad laminate on which the permanent pattern is formed to form a laminate, and exposing the photosensitive layer in the laminate to exposure And after the exposure, the photosensitive layer is developed to form a pattern, and thereafter etching treatment or the like is performed, and the cured pattern is peeled off to form the permanent pattern.

The photosensitive layer in the pattern forming material generally contains a binder. However, attention is focused on the combination of the I / O value (inorganic / organic ratio of the organic conceptual diagram, see Non-Patent Documents 1 to 5) , It is not known that when both the I / O value and the acid value are within a certain numerical value range, the resolution and the tent property are excellent, the developing property is excellent, and the peelability of the cured pattern after etching is improved.

Therefore, the I / O value and the glass transition temperature of the binder contained in the photosensitive layer are all within a constant numerical range, thereby providing excellent resolution and tentability and also excellent developing property, A pattern forming apparatus having the pattern forming material having excellent properties and a pattern forming method using the pattern forming material have not yet been provided and it is the present condition that a further improved development is required.

Non-Patent Document 1: Organic concept diagram [Yoshio Koda, Sankyo Publishing (1984)] Non-Patent Document 2: KUMAMOTO PHARMACEUTICAL BULLETIN, No. 1, pages 1 to 16 (1954) Non-Patent Document 3: Area of Chemistry, Vol. 11, No. 10, pp. 719-725 (1957) Non-Patent Document 4: Pregrance Journal, No. 34, pp. 97-111 (1979) Non-Patent Document 5: Pregrance Journal, No. 50, pages 79 to 82 (1981)

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances, and it is an object of the present invention to solve all of the above problems and to achieve the following objects. That is, according to the present invention, since the I / O value and the glass transition temperature of the binder contained in the photosensitive layer are all within a constant numerical range, the binder resin has excellent resolution and tentability, A pattern forming material provided with the pattern forming material, and a pattern forming method using the pattern forming material.

Means for solving the above problems are as follows. In other words,

<1> A photosensitive composition comprising at least a photosensitive layer on a support, wherein the photosensitive layer contains a binder, a polymerizable compound and a photopolymerization initiator, wherein the binder has an I / O value of 0.300 to 0.650 and an acid value of 130 to 250 As a pattern forming material. The pattern forming material according to < 1 >, wherein the photosensitive layer contains the binder, the polymerizable compound and the photopolymerization initiator, the binder has an I / O value of 0.300 to 0.650, 250 (mgKOH / g), the resolution and tentability are improved together, and the resolution, tentability and developability are both high, and the peelability of the cured pattern after etching is improved.

&Lt; 2 > The pattern forming material according to < 1 >, wherein an I / O value of the binder is 0.350 to 0.630.

<3> The pattern forming material according to <1> or <2>, wherein the acid value of the binder is 150 to 230 (mgKOH / g).

&Lt; 4 > a pattern forming method according to any one of < 1 > to < 3 >, wherein the binder contains a copolymer and the copolymer contains 30 mass% or more of a monomer constituting a homopolymer having an I / O value of 0.350 or less Material. In the pattern forming material described in the item < 4 >, the copolymer of the binder contains a monomer constituting the homopolymer having an I / O value of 0.350 or less in an amount of 30 mass% or more so that a low I / O value and a high acid value are compatible .

<5> The pattern forming material according to any one of <1> to <4>, wherein the binder contains a copolymer and the copolymer has a structural unit derived from at least one of styrene and a styrene derivative.

<6> The pattern forming material according to any one of <1> to <5>, wherein the binder has an acidic group.

<7> The pattern forming material according to any one of <1> to <6>, wherein the binder contains a vinyl copolymer.

<8> The pattern forming material according to any one of <1> to <7>, wherein the binder has a glass transition temperature of 80 ° C. or higher.

<9> The pattern forming material according to any one of <1> to <8>, wherein the polymerizable compound contains a monomer having at least one of a urethane group and an aryl group.

<10> The composition according to any one of <1> to <10>, wherein the photopolymerization initiator comprises at least one selected from halogenated hydrocarbon derivatives, hexaarylbimidazoles, oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, and metallocenes. Is a pattern forming material according to any one of &lt; 1 &gt;

<11> The pattern forming material according to any one of <1> to <10>, wherein the thickness of the photosensitive layer is 1 to 100 μm.

<12> The photosensitive resin composition according to any one of <1> to <11>, wherein the photosensitive layer contains 30 to 90% by mass of a binder, 5 to 60% by mass of a polymerizable compound, and 0.1 to 30% by mass of a photopolymerization initiator Forming material described above.

<13> The pattern forming material according to any one of <1> to <12>, wherein the support contains a synthetic resin and is transparent.

<14> The pattern forming material according to any one of <1> to <13>, wherein the support is a long length.

<15> The pattern forming material according to any one of <1> to <14>, wherein the pattern forming material is an elongated phase and wound in a roll form.

<16> The pattern forming material according to any one of <1> to <15>, which has a protective film on the photosensitive layer in the pattern forming material.

<17> A pattern forming material according to any one of <1> to <16>

And a light modulating means for modulating light from the light irradiating means and performing exposure to the photosensitive layer of the pattern forming material . In the pattern forming apparatus described in (17), the light irradiating means irradiates light toward the light modulating means. And the light modulation means modulates light received from the light irradiation means. And the light modulated by the light modulating means is exposed to the photosensitive layer. For example, when the photosensitive layer is then developed, a high-definition pattern is formed.

And a pattern signal generating means for generating a control signal based on the pattern information formed by the optical modulation means, wherein the pattern signal generating means includes means for modulating the light emitted from the light irradiation means in accordance with the control signal generated by the pattern signal generating means Is a pattern forming apparatus according to < 17 >. In the pattern forming apparatus described in (18), the light modulating means has the pattern signal generating means, whereby the light irradiated from the light irradiating means is modulated in accordance with the control signal generated by the pattern signal generating means .

The light modulation means may have n number of grave portions and may be controlled in accordance with the pattern information forming the graveyard portions of less than n successively arranged among the n grave portions. Is a pattern forming apparatus. In the pattern forming apparatus described in (19), by controlling arbitrary n or less grave portions successively arranged among n grave portions in the light modulating means according to the pattern information, light from the light irradiating means Is modulated at high speed.

<20> The pattern forming apparatus according to any one of <17> to <19>, wherein the light modulating means is a spatial light modulating element.

<21> The pattern forming apparatus according to <20>, wherein the spatial light modulation element is a digital micromirror device (DMD).

<22> The pattern forming apparatus according to any one of <19> to <21>, wherein the grave portion is a micromirror.

<23> The pattern forming apparatus according to any one of <17> to <22>, wherein the light irradiation means can synthesize and irradiate two or more lights. In the pattern forming apparatus described in (23), the light irradiating means can synthesize and irradiate two or more lights, whereby the exposure is performed by exposure light having a deep focal depth. As a result, exposure to the pattern forming material is performed very finely. For example, when the photosensitive layer is then developed, a very fine pattern is formed.

<24> In the above-mentioned <17> to <23>, wherein the light irradiating means has a plurality of lasers, a multimode optical fiber, and an aggregating optical system for collecting the laser beams respectively irradiated from the plurality of lasers, Which is the pattern forming apparatus described in any one of the above. In the pattern forming apparatus described in (24), since the laser beam irradiated from each of the plurality of lasers is condensed by the collective optical system and can be coupled to the multimode optical fiber, And is performed in exposure light. As a result, exposure to the pattern forming material is performed very finely. For example, when the photosensitive layer is then developed, a very fine pattern is formed.

<25> A pattern forming method, comprising at least the step of exposing the photosensitive layer in the pattern forming material according to any one of <1> to <16>. In the pattern forming method according to the present invention, exposure is performed on the pattern forming material. For example, when the photosensitive layer is then developed, a high-definition pattern is formed.

After modulating the light from the light irradiation means by means of light modulation means having n number of grave portions for receiving and emitting light from the light irradiation means with respect to the photosensitive layer, The exposure method according to the above-mentioned < 25 >, wherein exposure is performed with light passed through a microlens array having microlenses having aspheric surfaces capable of correcting aberration caused by deformation. In the pattern forming method described in the above, the light from the light irradiation means is modulated by the light modulation means having n number of grave portions for receiving and emitting light from the light irradiation means with respect to the photosensitive layer The micro lens array having the aspheric surface capable of correcting the aberration caused by the deformation of the exit surface of the graveyard portion is exposed to light passing through the microlens array, The aberration caused by the deformation of the surface is corrected, and the exposure is performed with the light whose deformation of the image formed on the pattern forming material is suppressed. As a result, since the pattern forming material is exposed to high detail, a highly detailed pattern is formed by developing the photosensitive layer thereafter.

The pattern forming method according to the above-mentioned <25> or <26>, wherein the pattern forming material is laminated on a substrate and exposed.

The pattern forming method according to the above-mentioned < 27 >, wherein the substrate is a printed wiring forming substrate.

<29> A pattern forming method according to <27> or <28>, wherein the pattern forming material is laminated on at least one of heating and pressurizing the pattern forming material.

<30> A pattern forming method according to any one of <25> to <29>, wherein the pattern is formed in a phase shape based on pattern information formed by exposure.

<31> A pattern forming method according to any one of <25> to <30>, wherein a control signal is generated based on pattern information formed by exposure and modulated according to the control signal. In the pattern formation method described in (31), a control signal is generated based on pattern formation information to be formed, and light is modulated in accordance with the control signal.

<32> The liquid crystal display device according to any one of <25> to <31>, wherein light is irradiated with light and light modulating means for modulating light irradiated from the light irradiating means based on the pattern information to be formed Is a pattern formation method described in one.

After the exposure modulates the light by the light modulating means, the microlens array having microlenses having aspherical surfaces capable of correcting aberration caused by deformation of the exit surface of the graveyard portion in the light modulating means is passed Is carried out by the above-mentioned method. In the pattern forming method described in this aspect, since the light modulated by the light modulating means passes through the aspherical surface of the microlens array, the aberration caused by the deformation of the exit surface in the graveyard portion is corrected do. As a result, deformation of the image formed on the pattern forming material is suppressed, and exposure to the pattern forming material is performed very finely. For example, when the photosensitive layer is then developed, a very fine pattern is formed.

<34> The pattern forming method according to <33>, wherein the aspherical surface is a toric surface. In the pattern forming method described above, since the aspherical surface is a toric surface, the aberration caused by the deformation of the radiation surface in the graveyard portion is efficiently corrected, and the deformation of the image formed on the pattern- . As a result, exposure to the pattern forming material is performed very finely. For example, when the photosensitive layer is then developed, a very fine pattern is formed.

<35> A pattern forming method according to any one of <25> to <34>, wherein the exposure is performed through the aperture array. In the pattern forming method described above, the extinction ratio is improved by performing the exposure through the aperture array. As a result, the exposure is performed very finely. For example, when the photosensitive layer is then developed, a very fine pattern is formed.

<36> The pattern forming method according to any one of <25> to <35>, wherein the exposure is performed while relatively moving the exposure light and the photosensitive layer. In the pattern forming method described above, exposure is performed at high speed by exposing the modulated light while moving the photosensitive layer relatively. For example, after that, when the photosensitive layer is developed, a fine pattern is formed.

<37> The pattern forming method according to any one of <25> to <36>, wherein the exposure is performed on a part of the photosensitive layer.

<38> The pattern forming method according to any one of <25> to <37>, wherein the development of the photosensitive layer is performed after the exposure. In the pattern forming method described in this embodiment, after the exposure is performed, the photosensitive layer is developed to form a high-definition pattern.

The pattern forming method according to any one of <25> to <38>, wherein the permanent pattern is formed after development.

<40> The pattern forming method according to <39>, wherein the permanent pattern is a wiring pattern, and the permanent pattern is formed by at least one of an etching treatment and a plating treatment.

According to the present invention, it is possible to solve the problems in the prior art, and the I / O value and the glass transition temperature of the binder contained in the photosensitive layer are all within a constant numerical range, whereby the resolution and the tent property are excellent, A pattern forming material excellent in peelability of a cured pattern after etching, a pattern forming apparatus provided with the pattern forming material, and a pattern forming method using the pattern forming material can be provided.

1 is an example of a partial enlarged view showing a configuration of a digital micromirror device (DMD).
2A is an example of an explanatory diagram for explaining the operation of the DMD.
FIG. 2B is an example of an explanatory diagram for explaining the operation of the DMD which is the same as FIG. 2A.
3A is an example of a plan view in which the DMD is not obliquely disposed and obliquely disposed, and the arrangement of exposure beams and the scanning lines are compared.
FIG. 3B is an example of a plan view in which the same DMD as in FIG. 3A is arranged obliquely and in a case of obliquely arranged, and in which arrangement of exposure beams and scanning lines are compared.
Fig. 4A is an example of a drawing showing an example of a use area of the DMD. Fig.
FIG. 4B is an example of a diagram showing an example of the use area of the DMD similar to FIG. 4A.
5 is an example of a plan view for explaining an exposure method for exposing a pattern forming material by a single scan by a scanner.
6A is an example of a plan view for explaining an exposure method for exposing a pattern forming material by a plurality of scans by a scanner.
FIG. 6B is an example of a plan view for explaining an exposure method for exposing a pattern forming material by a plurality of scans by the same scanner as FIG. 6A.
7 is an example of a schematic perspective view showing the appearance of an example of the pattern forming apparatus.
8 is an example of a schematic perspective view showing the configuration of the scanner of the pattern forming apparatus.
FIG. 9A is an example of a plan view showing an exposed area formed in the pattern forming material. FIG.
9B is an example of a diagram showing the arrangement of exposure areas by each exposure head.
10 is an example of a perspective view showing a schematic structure of an exposure head including light modulation means.
11 is an example of a cross-sectional view in the sub-scan direction along the optical axis showing the structure of the exposure head shown in Fig.
12 is an example of a controller for controlling the DMD based on the pattern information.
13A is an example of a cross-sectional view along the optical axis showing a configuration of another exposure head in which the coupling optical system is different.
13B is an example of a plan view showing an optical image projected on a surface to be exposed when a microlens array or the like is not used.
13C is an example of a plan view showing an optical image projected on a surface to be exposed when a microlens array or the like is used.
14 is an example of a diagram showing the deformation of the reflecting surface of the micromirror constituting the DMD by contour lines.
15A is an example of a graph showing the deformation of the reflecting surface of the micro mirror with respect to two diagonal directions of the mirror.
Fig. 15B is an example of a graph showing the deformation of the reflecting surface of the micro mirror as in Fig. 15A with respect to two diagonal directions of the mirror. Fig.
16A is an example of a front view of a microlens array used in a pattern forming apparatus.
16B is an example of a side view of the microlens array used in the pattern forming apparatus.
17A is an example of a front view of a microlens constituting a microlens array.
17B is an example of a side view of a microlens constituting a microlens array.
18A is an example of a schematic diagram showing the condensed state of the microlenses in one cross section.
FIG. 18B is an example of a schematic diagram showing the condensed state of the microlenses in one section and in a section different from FIG. 18A. FIG.
19A is an example of a diagram showing the result of simulating the beam diameter in the vicinity of the condensing position of the microlens of the present invention.
FIG. 19B is an example of a diagram showing the simulation results similar to FIG. 19A with respect to other positions. FIG.
FIG. 19C is an example of a diagram showing simulation results similar to FIG. 19A and FIG. 19B for different positions. FIG.
FIG. 19D is an example of a diagram showing simulation results similar to FIG. 19A to FIG. 19C at different positions.
20A is an example of a diagram showing a result of simulating the beam diameter in the vicinity of the light collecting position of the microlens in the conventional pattern forming method.
FIG. 20B is an example of a diagram showing the same simulation results as in FIG. 20A at different positions.
20C is an example of a diagram showing simulation results similar to those of FIGS. 20A and 20B at different positions.
Fig. 20D is an example of a diagram showing simulation results similar to Figs. 20A to 20C at different positions. Fig.
21 is an example of a plan view showing another configuration of the multiplexed laser light source.
22A is an example of a front view of a microlens constituting a microlens array.
22B is an example of a side view of a microlens constituting the microlens array.
23A is an example of a schematic diagram showing an example of the condensed state of the microlenses shown in Figs. 22A and 22B in one cross-section.
FIG. 23B is an example of a schematic diagram showing the condensed state of the condensed light by the microlenses of FIGS. 22A and 22B in one section and in a section different from the example of FIG. 23A.
24A is an example of an explanatory diagram of the concept of correction by the light amount distribution correcting optical system.
Fig. 24B is an example of an explanatory diagram of the concept of correction by the light amount distribution correcting optical system as in Fig. 24A.
Fig. 24C is an explanatory diagram of the concept of correction by the light amount distribution correcting optical system, which is the same as Figs. 24A and 24B.
25 is an example of a graph showing the light amount distribution when the light irradiating means is Gaussian distribution and the correction of the light amount distribution is not performed.
26 is an example of a graph showing the light amount distribution after correction by the light amount distribution correcting optical system.
FIG. 27A is a perspective view showing a configuration of a fiber array light source. FIG.
Fig. 27B is an example of a front view showing the arrangement of light-emitting points in the laser emitting portion of the fiber array light source. Fig.
28 is an example of a diagram showing a configuration of a multimode optical fiber.
29 is an example of a plan view showing a configuration of a multiplexing laser light source.
30 is an example of a plan view showing a configuration of the laser module.
31 is an example of a side view showing the configuration of the laser module shown in Fig.
32 is a partial side view showing the configuration of the laser module shown in Fig.
33 is an example of a perspective view showing a configuration of a laser array.
34A is an example of a perspective view showing a configuration of a multicavity laser.
Fig. 34B shows a case where the multi-cavity lasers shown in Fig. 34A are arrayed
Is an example of a perspective view of a multi-cavity laser array.
35 is an example of a plan view showing another configuration of the multiplexing laser light source.
36A is an example of a plan view showing another configuration of the multiplexing laser light source.
FIG. 36B is an example of a cross-sectional view along the optical axis of FIG. 36A.
FIG. 37A is an example of a cross-sectional view along the optical axis showing the difference between the depth of focus in the conventional exposure apparatus and the depth of focus by the pattern forming method (pattern forming apparatus) of the present invention.
FIG. 37B is an example of a cross-sectional view along the optical axis showing the difference between the depth of focus in the conventional exposure apparatus as in FIG. 37A and the depth of focus by the pattern forming method (pattern forming apparatus) of the present invention.

(Pattern forming material)

The pattern forming material of the present invention may have at least a photosensitive layer on a support and another layer appropriately selected.

<Photosensitive Layer>

The photosensitive layer is not particularly limited as long as it contains a binder, a polymerizable compound, and a photopolymerization initiator, and may contain other components appropriately selected according to the purpose. The number of layers of the photosensitive layer may be one, or two or more layers.

-bookbinder-

The binder is not particularly limited as long as the I / O value is from 0.300 to 0.650 and the acid value is from 130 to 250, and the binder can be appropriately selected according to the purpose.

It is also preferable that the binder contains a copolymer and the copolymer has a structural unit derived from at least one of styrene and a styrene derivative.

As the upper limit value of the I / O value, for example, from the viewpoint of further improving at least one of the resolution and the tent property, 0.630 is more preferable, and 0.600 is particularly preferable.

The lower limit value of the I / O value is more preferably 0.350, and particularly preferably 0.40, from the viewpoint of improving developability, for example.

The I / O value is a value obtained by treating the polarity of various organic compounds, which is also referred to as (inorganic value) / (organic value), in an organic conceptual manner, and is one of the functional group contributing methods for setting parameters in each functional group. Specifically, the I / O value is an organic concept diagram [Yoshio Koda, Sankyo Publishers (1984)]; KUMAMOTO PHARMACEUTICAL BULLETIN, No. 1, pp. 1-16 (1954); Area of Chemistry, Vol. 11, No. 10, pp. 719-725 (1957); Pregens Journal, No. 34, pp. 97-111 (1979); Pregens Journal, No. 50, pp. 79-82 (1981); And the like.

The concept of the I / O value is made by dividing the property of a compound into an organic group having covalent bonding property and an inorganic group having ionic bonding property, Position is indicated.

The inorganic value is obtained by quantifying the influence of various substituents or bonds of the organic compound on the boiling point with reference to the hydroxyl group. Concretely, when the distance between the boiling curve of the straight chain alcohol and the boiling curve of the straight chain paraffin is taken to be about 100 ° C, the influence of one hydroxyl group is set to 100 as a numerical value. Based on this numerical value, The value obtained by quantifying the influence on the boiling point of various bonds and the like is the inorganic value of the substituent of the organic compound. For example, the inorganic value of the -COOH group is 150, and the inorganic value of the double bond is 2. Therefore, the inorganic value of a certain kind of organic compound means the sum of inorganic values such as various substituents and bonds possessed by the compound.

The organic value is determined based on the influence of the carbon atom representing the methylene group on the boiling point, with the methylene group in the molecule as a unit. That is, since the average value of the boiling point increase due to the addition of one carbon at about 5 to 10 carbon atoms in the linear saturated hydrocarbon compound is 20 ° C, the organic value of one carbon atom is set to 20 based on this, The value obtained by quantifying the influence of substituents or bonds on the boiling point is an organic value. For example, the organic value of the nitro group (-NO 2) is 70.

The closer to 0 the I / O value, the more nonpolar (hydrophobic and organic) the organic compound, the larger the polarity (hydrophilic and inorganic).

Hereinafter, an example of a method of calculating the I / O value will be described.

The I / O value of the methacrylic acid / methyl methacrylate / styrene copolymer [copolymer composition (molar ratio): 2/5/3] was calculated by the following method in terms of the inorganic value and the organic value of the copolymer , The following equation, (inorganic value of the copolymer) / (organic value of the copolymer).

The inorganic value of the copolymer is a value (the inorganic value of the methacrylic acid) x (the molar ratio of the methacrylic acid) and (the inorganic value of the methyl methacrylate) x (the molar ratio of the methyl methacrylate) And the (inorganic value of the styrene) x (the molar ratio of the styrene).

Wherein the methacrylic acid has one carboxyl group, the methyl methacrylate has one ester group, and the styrene has one aromatic ring,

The inorganic value of the methacrylic acid is 150 (inorganic value of carboxyl group) x 1 (the number of carboxyl groups) = 150,

The inorganic value of the methyl methacrylate is 60 (inorganic value of ester group) x 1 (number of ester groups) = 60,

The inorganic value of the styrene is 15 (inorganic value of aromatic ring) x 1 (number of aromatic rings) = 15.

Accordingly, the inorganic value of the copolymer was calculated to be 645 (maleic anhydride) by calculating the following formula: 150 x 2 (molar ratio of methacrylic acid) + 60 x 5 (molar ratio of methyl methacrylate) + 15 x 3 Is calculated.

The organic value of the copolymer was calculated from the following formula: (organic value of methacrylic acid) × (molar ratio of methacrylic acid) (organic value of methyl methacrylate) × (molar ratio of methyl methacrylate) The organic value of the styrene) x (the molar ratio of the styrene).

The methacrylic acid has 4 carbon atoms, the methyl methacrylate has 5 carbon atoms, and the styrene has 8 carbon atoms,

The organic value of the methacrylic acid is 20 (organic value of carbon atoms) x 4 (number of carbon atoms) = 80,

The organic value of the methyl methacrylate is 20 (organic value of carbon atom) x 5 (number of carbon atoms) = 100,

The organic value of the styrene is 20 (organic value of carbon atom) x 8 (number of carbon atoms) = 160.

Accordingly, the organic value of the copolymer was 1140 (molar ratio) by calculating the following formula: 80 x 2 (the molar ratio of the methacrylic acid) + 100 5 (the molar ratio of the methyl methacrylate) + 160 3 Is calculated.

Therefore, it can be seen that the I / O value of the copolymer is 645 (inorganic value of the copolymer) / 1140 (organic value of the copolymer), 0.566.

There is no particular limitation on the acid value (content of the acidic group) of the binder in the range of 130 to 250 (mgKOH / g), and 150-230 (mgKOH / g) To 220 (mgKOH / g) are particularly preferable.

If the acid value is less than 130 (mgKOH / g), the developability may be insufficient or the resolution may be inferior, so that a permanent pattern such as a wiring pattern may not be obtained finely. When the acid value is more than 250 (mgKOH / g) Any one or more of the resistance to development and adhesion of the pattern is deteriorated and the resolution and the tent property are inferior, so that a permanent pattern such as a wiring pattern can not be obtained with high precision.

In order to adjust the I / O value and the acid value of the binder together so as to satisfy the constant numerical value range, either of the kinds of the monomers constituting the copolymer contained in the binder and the polymerization ratio (content) when the monomers are polymerized It can be adjusted by appropriately selecting one or more.

For example, when the ratio of the monomer having an acidic group to the monomer constituting the copolymer contained in the binder is a% by mass, the ratio of monomers constituting the homopolymer having an I / O value of 0.35 or less is represented by b% When the value of a is increased for the purpose of improving the peelability of the cured pattern after etching, when the ratio of the monomer is c% by mass (where a + b + c = 100 and c may be 0) Since the I / O value of the binder tends to increase, a, b, and c preferably satisfy the relationship a <(b + c).

Specifically, the copolymer contained in the binder preferably contains 25 mass% or more of the monomer constituting the homopolymer having an I / O value of 0.35 or less, more preferably 30 mass% or more.

Examples of the monomer constituting the homopolymer having the I / O value of 0.35 or less include styrene, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate and the like.

The acidic group is not particularly limited and may be appropriately selected according to the purpose. Examples thereof include a carboxyl group, a sulfonic acid group, and a phosphoric acid group, and among these, a carboxyl group is preferable.

Examples of the binder having a carboxyl group include a vinyl copolymer having a carboxyl group, a polyurethane resin, a polyamide acid resin, a modified epoxy resin and the like. Among them, solubility in a coating solvent, solubility in an alkali developer, A vinyl copolymer having a carboxyl group is preferable from the viewpoints of suitability, ease of adjustment of film properties, and the like.

The carboxyl group-containing vinyl copolymer can be obtained by copolymerizing at least (1) a vinyl monomer having a carboxyl group, and (2) a monomer copolymerizable therewith.

Examples of the vinyl monomer having a carboxyl group include monomers having (meth) acrylic acid, vinylbenzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimer, (Meth) acrylate) and an addition reaction product of a cyclic anhydride (e.g. maleic anhydride or phthalic anhydride, cyclohexanedicarboxylic acid anhydride), ω-carboxy-polycaprolactone mono (meth) acrylate And the like. Of these, (meth) acrylic acid is particularly preferable from the viewpoint of copolymerization, cost, solubility and the like.

Monomers having anhydrides such as maleic anhydride, itaconic anhydride, and citraconic anhydride may be used as precursors of carboxyl groups.

The other copolymerizable monomer is not particularly limited and may be appropriately selected depending on the purpose. Examples of the other copolymerizable monomer include (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, (Meth) acrylonitrile, a vinyl ether-substituted heterocyclic group (for example, a methyl group, an ethyl group, an n-propyl group, (E.g., vinylpyridine, vinylpyrrolidone, vinylcarbazole, etc.), N-vinylformamide, N-vinylacetamide, N-vinylimidazole, vinylcaprolactone, 2- (1-methyl-2-acryloyloxyethyl ester), a functional group (e.g., urethane group, urea group, sulfonamide group, phenol The And a vinyl monomer having a carboxyl group and a hydroxyl group. Of these, the styrene and styrene derivatives are preferable in that the I / O value of the binder can be lowered, permanent patterns such as wiring patterns can be formed with high precision, and the tent property can be improved .

Examples of the (meth) acrylic esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, Butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl Acrylate, hexyl (meth) acrylate, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, (Meth) acrylate, 2-methoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl Phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, diethylene (Meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol monophenyl ether (Meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, polyethylene glycol monomethyl ether , Dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, trifluoroethyl (meth) acrylate, octafluoropentyl (Meth) acrylate, perfluorooctylethyl (meth) acrylate, tribromophenyl (meth) acrylate, tribromophenyloxy Butyl (meth) acrylate.

Examples of the crotonic acid esters include butyl crotonate, hexyl crotonate, and the like.

Examples of the vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxy acetate, and vinyl benzoate.

Examples of the maleic acid diesters include dimethyl maleate, diethyl maleate, dibutyl maleate, and the like.

Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate and dibutyl fumarate.

Examples of the itaconic acid diesters include dimethyl itaconate, diethyl itaconate, dibutyl itaconate, and the like.

Examples of the (meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N- (Meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-butyl (Meth) acrylamide, N, N-diethyl (meth) acrylamide, N-phenyl Acrylamide, and the like.

Examples of the styrenes include styrenes, styrenic derivatives such as methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, hydroxystyrene, methoxystyrene, butoxystyrene, Hydroxystyrene protected with a group capable of being deprotected by an acidic substance (e.g., t-Boc, etc.), methyl vinyl benzoate, [alpha] -methyl methyl styrene, Styrene, etc.) and the like.

Examples of the vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.

Examples of a method for synthesizing a vinyl monomer having a urethane group or a urea group as the functional group include an addition reaction between an isocyanato group and a hydroxyl group or an amino group. More specifically, a monomer having an isocyanato group and a Addition reaction of a compound containing one or a primary or secondary amino group, addition reaction of a monomer having a hydroxyl group or a monomer having a primary or secondary amino group with a monoisocyanate.

Examples of the monomer having an isocyanate group include compounds represented by the following structural formulas (1) to (3).

In the structural formulas (1) to (3), R 'represents a hydrogen atom or a methyl group.

Examples of the monoisocyanate include cyclohexyl isocyanate, n-butyl isocyanate, tolyl isocyanate, benzyl isocyanate, phenyl isocyanate and the like.

Examples of the monomer having a hydroxyl group include compounds represented by the following structural formulas (4) to (12).

In the structural formulas (4) to (12), R 'represents a hydrogen atom or a methyl group, and n ₁ , n ₂ and n ₃ each represent an integer of 1 or more.

Examples of the compound containing one hydroxyl group include alcohols such as methanol, ethanol, n-propanol, i-propanol, n-butanol, sec-butanol, t-butanol, n- (For example, phenol, cresol, naphthol, etc.) such as ethyl alcohol, n-octanol, Examples of the organic solvent further containing a substituent include fluoroethanol, trifluoroethanol, methoxyethanol, phenoxyethanol, chlorophenol, dichlorophenol, methoxyphenol and acetoxyphenol.

Examples of the monomer having a primary or secondary amino group include vinylbenzylamine and the like.

Examples of the compound containing one of the primary or secondary amino groups include alkylamines such as methylamine, ethylamine, n-propylamine, i-propylamine, n-butylamine, sec-butylamine, And examples thereof include cyclic alkylamines such as cyclopentylamine, cyclopentylamine, cyclohexylamine, cyclohexylamine, cyclohexylamine, and the like; ), Aralkylamine (benzylamine, phenethylamine and the like), arylamine (aniline, toluylamine, xylylamine, naphthylamine and the like) (Trifluoroethylamine, hexafluoroisopropylamine, methoxyaniline, methoxypropylamine, etc.), which further contain a substituent, and the like.

As the other copolymerizable monomer, it is preferable to use a monomer constituting a homopolymer having an I / O value of 0.35 or less. Examples thereof include styrene, styrene derivatives, 2-ethylhexyl (meth) acrylate, Acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, cyclohexyl (meth) acrylate, t-octyl (Meth) acrylate, benzyl methacrylate, isobornyl (meth) acrylate, and adamantyl (meth) acrylate. Of these, styrene and styrene derivatives are more preferable.

These other copolymerizable monomers may be used singly or in combination of two or more kinds.

These vinyl copolymers can be prepared by copolymerizing corresponding monomers according to a conventional method by a known method. For example, it can be prepared by dissolving the monomer in an appropriate solvent, adding a radical polymerization initiator thereto, and polymerizing in a solution (solution polymerization method). Further, it can be prepared by using polymerization in the state of dispersing the above-mentioned monomers in an aqueous medium by so-called emulsion polymerization.

Suitable solvents to be used in the solution polymerization method are not particularly limited and may be appropriately selected depending on the solubility of the monomers to be used and the resulting copolymer. Examples thereof include methanol, ethanol, propanol, isopropanol, 1-methoxy- 2-propanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl acetate, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran, dimethylformamide, chloroform and toluene. These solvents may be used singly or in combination of two or more kinds.

The radical polymerization initiator is not particularly limited and includes, for example, 2,2'-azobis (isobutyronitrile) (AIBN), 2,2'-azobis- (2,4'-dimethylvaleronitrile) And peroxides such as benzoyl peroxide; persulfates such as potassium persulfate and ammonium persulfate; and the like.

The content of the polymerizable compound having a carboxyl group in the vinyl copolymer is not particularly limited as long as the I / O value and the acid value fall within the above-described numerical ranges, and can be appropriately selected according to the purpose. For example, By mass, more preferably from 15 to 65% by mass, and particularly preferably from 20 to 60% by mass.

If the content is less than 10% by mass, developability to alkaline water may be insufficient, and if it exceeds 70% by mass, the developer resistance of the cured portion (image portion) may be insufficient.

The molecular weight of the binder having a carboxyl group is not particularly limited and may be appropriately selected depending on the purpose. For example, the weight average molecular weight is preferably 2,000 to 300,000, more preferably 4,000 to 150,000.

If the weight average molecular weight is less than 2,000, the strength of the film tends to be insufficient and stable production may become difficult. When the weight average molecular weight is more than 300,000, the developability may be deteriorated.

The above-mentioned binder having a carboxyl group may be used singly or in combination of two or more kinds. Examples of the case where two or more kinds of binders are used in combination include two or more kinds of binders composed of different copolymerizing components, two or more kinds of binders having different mass average molecular weights, and two or more kinds of binders having different degrees of dispersion.

In the binder having a carboxyl group, a part or all of the carboxyl groups may be neutralized with a basic substance. The binder may further comprise a resin having a different structure such as a polyester resin, a polyamide resin, a polyurethane resin, an epoxy resin, a polyvinyl alcohol, or a gelatin.

A resin soluble in an alkaline solution described in Japanese Patent No. 2873889 or the like may also be used in combination. When these resins are used in combination, the content of the binder described above relative to the total amount of the binder contained in the photosensitive layer may be appropriately selected in accordance with the purpose. For example, 50 mass% or more is preferable, and 70 mass% And particularly preferably 90% by mass or more.

As the binder having an I / O value of 0.300 to 0.650 and an acid value of 130 to 250 (mgKOH / g), methacrylic acid / methyl methacrylate / styrene / benzyl methacrylate copolymer [copolymer composition ): 25/8/30/37], methacrylic acid / methyl methacrylate / styrene / benzyl methacrylate copolymer [copolymer composition (mass ratio): 23/8/15/54] methacrylic acid / methyl methacrylate Methacrylic acid / methyl methacrylate / styrene / ethyl acrylate copolymer [copolymer composition (mass ratio): methacrylic acid / methyl methacrylate / styrene / ethyl acrylate copolymer] [copolymer composition (mass ratio): 21/47/23/9] ): 23/30/30/17], methacrylic acid / methyl methacrylate / styrene / ethyl acrylate copolymer [copolymer composition (mass ratio): 25/25/45/5], methacrylic acid / methyl methacrylate Acrylate copolymer [copolymer composition (mass ratio): 25/34/33/8], methacrylic acid / cyclohexyl methacrylate / 2-ethylhexyl methacrylate (Copolymer composition (mass ratio): 25/70/5), methacrylic acid / cyclohexyl methacrylate / 2-ethylhexyl methacrylate copolymer [copolymer composition (mass ratio): 23/70/7 Methacrylic acid / styrene / methyl acrylate copolymer [copolymer composition (mass ratio): 25/38], methacrylic acid / styrene / methyl acrylate copolymer [copolymer composition (mass ratio): 22/58/20] / 37], methacrylic acid / styrene / methyl acrylate copolymer [copolymer composition (mass ratio): 29/61/10], methacrylic acid / styrene / ethyl acrylate copolymer [copolymer composition (mass ratio): 23 Styrene / ethyl acrylate copolymer [copolymer composition (mass ratio): 29/61/10], methacrylic acid / styrene / ethyl acrylate copolymer [copolymer composition (mass ratio) : Methacrylic acid / styrene copolymer [copolymer composition ratio (mass ratio): 29/71], methacrylic acid / styrene copolymer [copolymer composition ratio (mass ratio): 21/79] Methacrylic acid / styrene / 2-ethylhexyl methacrylate copolymer [copolymer composition ratio (mass ratio): 23/50/27], and methacrylic acid / methacrylic acid / styrene copolymer [copolymer composition ratio (mass ratio): 36/64] / Styrene / 2-ethylhexyl methacrylate copolymer [copolymer composition ratio (mass ratio): 29/60/11], methacrylic acid / styrene / 2-ethylhexyl methacrylate copolymer [ 33/31], methacrylic acid / methyl methacrylate / styrene / 2-ethylhexyl methacrylate copolymer [copolymer composition ratio (mass ratio): 25/25/37/13], methacrylic acid / methyl methacrylate / Styrene / 2-ethylhexyl methacrylate copolymer [copolymer composition ratio (mass ratio): 29/15/47/9], methacrylic acid / methyl methacrylate / styrene / 2-ethylhexyl methacrylate copolymer (Mass ratio): 29/18/50/3], methacrylic acid / methyl methacrylate / styrene / 2-ethylhexyl methacrylate copolymer [copolymer composition ratio (mass ratio) : Methacrylic acid / methyl methacrylate / styrene / 2-ethylhexyl methacrylate copolymer [copolymer composition ratio (mass ratio): 36/5/45/14], methacrylic acid / Styrene / cyclohexylmethacrylate copolymer [copolymer composition ratio (mass ratio): 25/15/60], and a styrene / cyclohexyl methacrylate copolymer [copolymer composition ratio (mass ratio): 31/64/5] Methacrylic acid / methyl methacrylate / styrene / butyl methacrylate copolymer [copolymer composition ratio (mass ratio): 23/37/30/10], methacrylic acid / methyl methacrylate / styrene / butyl methacrylate copolymer Methacrylic acid / methyl methacrylate / styrene / butyl methacrylate copolymer [copolymer composition ratio (mass ratio): 25/27/36/12], meta Methacrylic acid / methyl methacrylate / styrene / butyl methacrylate copolymer [copolymer composition ratio (mass ratio): 29/13/38/20], methacrylic acid / methyl methacrylate / Styrene / butyl methacrylate copolymer [copolymer composition ratio (mass ratio): 24/10/29/37], methacrylic acid / methyl methacrylate / styrene copolymer [copolymer composition ratio (mass ratio): 25/29/46] Methacrylic acid / methyl methacrylate / styrene copolymer [copolymer composition ratio (mass ratio): 29/19/27], methacrylic acid / methyl methacrylate / styrene copolymer [copolymer composition ratio (mass ratio) Methacrylic acid / methyl methacrylate / styrene copolymer [copolymer composition ratio (mass ratio): 31/57], methacrylic acid / methyl methacrylate / styrene copolymer [copolymer composition ratio (mass ratio): 30/13/57] Methacrylic acid / methyl methacrylate / styrene copolymer [copolymer composition ratio (mass ratio): methacrylic acid / methyl methacrylate / styrene copolymer [copolymer composition ratio (mass ratio): 36/15/49] 29/31/40], methacrylic acid / methyl methacrylate / styrene copolymer [copolymer composition ratio (mass ratio): 25/41/34], methacrylic acid / methyl methacrylate Methacrylic acid / methyl methacrylate / styrene copolymer [copolymer composition ratio (mass ratio): 24/46/30], and the like can be given as examples of the methacrylic acid / methacrylic acid / styrene copolymer ,

Of these, methacrylic acid / methyl methacrylate / styrene / benzyl methacrylate copolymer [copolymer composition (mass ratio): 25/8/30/37], methacrylic acid / methyl methacrylate / styrene / benzyl methacrylate Methacrylic acid / methyl methacrylate / styrene / ethyl acrylate copolymer [copolymer composition (mass ratio): 25/25/45 / 5], methacrylic acid / methyl methacrylate / styrene / ethyl acrylate copolymer [copolymer composition (mass ratio): 25/34/33/8], methacrylic acid / cyclohexyl methacrylate / 2-ethylhexyl Methacrylic acid / styrene / methyl acrylate copolymer [copolymer composition (mass ratio): 22/58/20], methacrylic acid / methacrylic acid copolymer [copolymer composition (mass ratio): 25/70/5] Styrene / methyl acrylate copolymer [copolymer composition (mass ratio): 25/38/37], methacrylic acid / styrene / methyl acrylate copolymer [copolymer Methacrylic acid / styrene / ethyl acrylate copolymer [copolymer composition (mass ratio): 23/60/17), methacrylic acid / styrene / ethyl acrylate copolymer [weight ratio: 29/61/10] Methacrylic acid / styrene copolymer [copolymer composition ratio (mass ratio): 29/71], methacrylic acid / styrene copolymer [copolymer composition ratio (mass ratio): 36/64 , Methacrylic acid / styrene / 2-ethylhexyl methacrylate copolymer [copolymer composition ratio (mass ratio): 23/40/27], methacrylic acid / styrene / 2-ethylhexyl methacrylate copolymer [ Methacrylic acid / methyl methacrylate / styrene / 2-ethylhexyl methacrylate copolymer [copolymer composition ratio (mass ratio): 25/25/37/13], methacrylic acid / Methyl methacrylate / styrene / 2-ethylhexyl methacrylate copolymer [copolymer composition ratio (mass ratio): 29/15/47/9], methacrylic acid / methyl methacrylate / styrene / Methacrylic acid / methyl methacrylate / styrene / 2-ethylhexyl methacrylate copolymer [copolymer composition ratio (mass ratio): 25/15 (mass ratio): copolymer composition ratio (mass ratio): 29/18/50/3] / 40/20], methacrylic acid / methyl methacrylate / styrene / 2-ethylhexyl methacrylate copolymer [copolymer composition ratio (mass ratio): 36/5/45/14], methacrylic acid / styrene / cyclohexyl Methacrylic acid / styrene / cyclohexyl methacrylate copolymer [copolymer composition ratio (mass ratio): 25/15/60], methacrylic acid / cyclohexyl methacrylate copolymer [copolymer composition ratio (mass ratio): 31/64/5] Methyl methacrylate / styrene / butyl methacrylate copolymer [copolymer composition ratio (mass ratio): 23/37/30/10], methacrylic acid / methyl methacrylate / styrene / butyl methacrylate copolymer [copolymer composition ratio Mass ratio): 25/27/36/12], methacrylic acid / methyl methacrylate / styrene / butyl methacrylate copolymer [copolymer composition ratio Methacrylic acid / methyl methacrylate / styrene / butyl methacrylate copolymer [copolymer composition ratio (mass ratio): 24/10/29/37], methacrylic acid / methyl Methacrylic acid / methyl methacrylate / styrene copolymer [copolymer composition ratio (mass ratio): 29/19/52], methacrylic acid / styrene copolymer [copolymer composition ratio (mass ratio): 25/29/46] / Methacrylate / styrene copolymer [copolymer composition ratio (mass ratio): 31/5/64], methacrylic acid / methyl methacrylate / styrene copolymer [copolymer composition ratio (mass ratio): 30/13/57] Methacrylic acid / methyl methacrylate / styrene copolymer [copolymerization composition ratio (mass ratio): 25/41/34], acrylic acid / methyl methacrylate / styrene copolymer [copolymer composition ratio (mass ratio): 29/31/40] , And methacrylic acid / methyl methacrylate / styrene copolymer [copolymer composition ratio (mass ratio): 36/5/59] are preferable,

Methacrylic acid / methyl methacrylate / styrene / benzyl methacrylate copolymer [copolymer composition (mass ratio): 25/8/30/37], methacrylic acid / methyl methacrylate / styrene / ethyl acrylate copolymer [Copolymer composition (mass ratio): 29/61/10], methacrylic acid / styrene / methyl acrylate copolymer [copolymer composition (mass ratio): 29/61/10] Acrylate copolymer [copolymer composition (mass ratio): 29/61/10], methacrylic acid / styrene copolymer [copolymer composition ratio (mass ratio): 29/71], methacrylic acid / styrene / 2-ethylhexyl methacryl Methacrylic acid / methyl methacrylate / styrene / 2-ethylhexyl methacrylate copolymer [copolymer composition ratio (mass ratio): 25/25/37 / 13), methacrylic acid / methyl methacrylate / styrene / 2-ethylhexyl methacrylate copolymer [copolymer composition ratio (mass ratio): 29/18/50/3], methacrylic acid / methyl Methacrylic acid / styrene / cyclohexyl methacrylate copolymer [copolymer composition ratio (mass ratio): copolymerization ratio (mass ratio): 25/15/40/20], methacrylic acid / styrene / cyclohexyl methacrylate copolymer [ : 31/64/5], methacrylic acid / methyl methacrylate / styrene / butyl methacrylate copolymer [copolymer composition ratio (mass ratio): 25/27/36/12], methacrylic acid / methyl methacrylate / Methacrylic acid / methyl methacrylate / styrene copolymer [copolymer composition ratio (mass ratio): 25/29/46], styrene / butyl methacrylate copolymer [copolymer composition ratio (mass ratio): 29/13/38/20] Methacrylic acid / methyl methacrylate / styrene copolymer [copolymer composition ratio (mass ratio): 30/13/57 (methacrylic acid / methyl methacrylate / styrene copolymer [copolymer composition ratio (mass ratio): 29/19/52] ], Methacrylic acid / methyl methacrylate / styrene copolymer [copolymer composition ratio (mass ratio): 31/5/64], methacrylic acid / methyl methacrylate / Styrene copolymer [copolymer composition ratio (mass ratio): 29/31/40] and methacrylic acid / methyl methacrylate / styrene copolymer [copolymer composition ratio (mass ratio): 25/41/34] are particularly preferable.

When the binder is a material having a glass transition temperature, the glass transition temperature is not particularly limited and may be appropriately selected according to the purpose. For example, the viscosity of the pattern forming material, the edge fusion, and the peelability From at least one viewpoint, 80 DEG C or more is preferable, 100 DEG C or more is more preferable, and 115 DEG C or more is particularly preferable.

When the glass transition temperature is lower than 80 占 폚, the viscosity of the pattern forming material may increase or the releasability of the support may deteriorate.

The content of the binder in the photosensitive layer is not particularly limited and may be appropriately selected according to the purpose. For example, the content is preferably from 10 to 90% by mass, more preferably from 20 to 80% by mass, % By mass is particularly preferable.

If the content is less than 10% by mass, alkali developability or adhesion to a substrate for forming a printed wiring board (for example, a copper-clad laminate) may deteriorate. When the content exceeds 90% by mass, The strength of the cured film (tent film) may be lowered. The content may be the total content of the binder and the polymer binder used in combination as needed.

- polymerizable compounds -

The polymerizable compound is not particularly limited and may be appropriately selected according to the purpose. For example, monomers or oligomers having at least one of a urethane group and an aryl group are preferably used. In addition, they preferably have two or more kinds of polymerizable groups.

Examples of the polymerizable group include a vinyl group such as an ethylenic unsaturated bond (e.g., (meth) acryloyl group, (meth) acrylamide group, styryl group, vinyl ester or vinyl ether, allyl ether or allyl ester (E.g., an epoxy group, an oxetane group, etc.), and among these, an ethylenically unsaturated bond is preferable.

- Monomers having urethane groups -

The monomer having a urethane group is not particularly limited as long as it has a urethane group and can be appropriately selected in accordance with the purpose. For example, Japanese Patent Publication No. 48-41708, Japanese Patent Application Laid-Open No. 51-37193, Compounds described in JP-A-50737, JP 7-7208, JP-A-2001-154346, JP-A-2001-356476 and the like, and examples thereof include polyisocyanates having two or more isocyanate groups in the molecule Adducts of compounds and vinyl monomers having a hydroxyl group in the molecule, and the like.

Examples of the polyisocyanate compound having two or more isocyanate groups in the molecule include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, xylene diisocyanate, toluene diisocyanate, phenylene diisocyanate, norbornene diisocyanate, Diisocyanates such as diphenyl diisocyanate, diphenylmethane diisocyanate and 3,3'-dimethyl-4,4'-diphenyl diisocyanate; The diisocyanate is further reacted with a bifunctional alcohol with a bifunctional alcohol (in this case both ends are isocyanate groups); Trimer such as bidentate isocyanurate of the above diisocyanate; Adducts of the diisocyanates or diisocyanates with polyfunctional alcohols such as trimethylol propane, pentaerythritol, glycerin, etc., or ethylene oxide adducts thereof, and the like.

Examples of the vinyl monomer having a hydroxyl group in the molecule include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, diethylene glycol mono (Meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, octaethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, dipropylene glycol mono (Meth) acrylate, dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, tetrapropylene glycol mono (meth) acrylate, octapropylene glycol mono (Meth) acrylate, tributylene glycol mono (meth) acrylate, tetrabutyleneglycol mono (meth) acrylate, Other butylene may include glycol mono (meth) acrylate, polybutylene glycol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate and the like. (Meth) acrylate of a diol compound having a different alkylene oxide moiety such as a copolymer (random, block, etc.) of ethylene oxide and propylene oxide.

Examples of the monomer having a urethane group include tri (meth) acryloyloxyethyl isocyanurate such as tri (meth) acryloyloxyethyl isocyanurate, di (meth) acryl isocyanurate, and ethylene oxide modified isocyanuric acid And compounds having an isocyanurate ring. Among them, a compound represented by the following structural formula (13) or a structural formula (14) is preferable, and from the viewpoint of tent property, it is particularly preferable to contain at least a compound represented by the above structural formula (14). These compounds may be used singly or in combination of two or more.

In the structural formulas (13) and (14), R ^'1 to R ^{' 3} each represent a hydrogen atom or a methyl group. X ₁ to X _{3 each} represent an alkylene oxide, which may be used singly or in combination of two or more.

Examples of the alkylene oxide group include an ethylene oxide group, a propylene oxide group, a butylene oxide group, a pentylene oxide group, a hexylene oxide group, and a group (may be combined with any one of random or block) Of these, an ethylene oxide group, a propylene oxide group, a butylene oxide group, or a combination thereof is preferable, and an ethylene oxide group and a propylene oxide group are more preferable.

In the structural formulas (13) and (14), m ₁ to m ₃ represent an integer of 1 to 60, preferably 2 to 30, and more preferably 4 to 15.

In the structural formulas (13) and (14), Y ¹ and Y ² are each a divalent organic group having 2 to 30 carbon atoms, and examples thereof include an alkylene group, an arylene group, an alkenylene group, an alkynylene group, -CO-), oxygen atom (-O-), sulfur atom (-S-), an imino group (-NH-), already substituted imino group substituted with a hydrocarbon group hydrogen atom of a monovalent group, a sulfonyl group (-SO ₂ -), or a combination thereof, among which an alkylene group, an arylene group, or a group formed by combining these groups is preferable.

The alkylene group may have a branched structure or a cyclic structure, and examples thereof include a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group, a pentylene group, a neopentylene group, A hexylene group, a cyclohexylene group, a heptylene group, an octylene group, a 2-ethylhexylene group, a nonylene group, a decylene group, a dodecylene group, an octadecylene group, .

The arylene group may be substituted with a hydrocarbon group, and examples thereof include a phenylene group, a tolylene group, a diphenylene group, a naphthylene group, and groups shown below.

Examples of the group combining these groups include xylylene group and the like.

Examples of the substituent include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), an aryl group, an arylene group, An alkoxy group (e.g., methoxy group, ethoxy group, 2-ethoxyethoxy group), an aryloxy group (e.g., phenoxy group), an acyl group (e.g., acetyl group, propionyl group) An alkoxycarbonyl group (for example, a methoxycarbonyl group or an ethoxycarbonyl group), an aryloxycarbonyl group (for example, a phenoxycarbonyl group), and the like can be given.

In the structural formulas (13) and (14), n ₄ represents an integer of 3 to 6, preferably 3, 4, or 6 from the viewpoint of raw material feedability for synthesizing a polymerizable monomer.

In the structural formulas (13) and (14), Z ₁ represents a linking group of n ₄ (3 to 6), for example, any of the following groups.

Provided that X ₄ represents an alkylene oxide. m ₄ represents an integer of 1 to 20; and n ₅ represents an integer of 3 to 6. A ₂ represents an organic group of n ₅ (3 to 6).

Wherein A ₂ includes, for example, n ₅ is (3 to 6 a) an aliphatic group, n aromatic group of ₅ (3 to 6 a), or mixtures thereof with an alkylene group, an aryl group, an alkenylene group, an alkynyl of A substituted imino group in which the hydrogen atom of the imino group is substituted with a monovalent hydrocarbon group or a group in which a sulfonyl group is combined are preferable, and n ₅ is (3 to 6) an aliphatic group of an aliphatic group, n ₅ is an aromatic group, or mixtures thereof with an alkylene group, an arylene group, more preferred groups are a combination of the oxygen atoms, n ₅ is (3 to 6 a) of (3 - 6 a), Particularly preferred are groups in which n ₅ (3 to 6) aliphatic groups, alkylene groups and oxygen atoms are combined.

The number of carbon atoms in A ₂ is preferably an integer of 1 to 100, more preferably an integer of 1 to 50, and particularly preferably an integer of 3 to 30.

The aliphatic group represented by the above n ₅ (3 to 6) may have a branched structure or a cyclic structure.

The number of carbon atoms of the aliphatic group is preferably an integer of 1 to 30, more preferably an integer of 1 to 20, and particularly preferably an integer of 3 to 10.

The number of carbon atoms in the aromatic group is preferably an integer of 6 to 100, more preferably an integer of 6 to 50, and an integer of 6 to 30 is particularly preferable.

Wherein n ₅ is an aliphatic group of (3-VI), or an aromatic group may optionally further have a substituent, Examples of the substituent, a hydroxyl group, a halogen atom (e.g., fluorine, chlorine, bromine An alkoxy group (for example, methoxy group, ethoxy group, 2-ethoxyethoxy group), an aryloxy group (for example, phenoxy group), an acyl group (for example, An alkoxycarbonyl group (e.g., a methoxycarbonyl group, an ethoxycarbonyl group), an aryloxycarbonyl group (e.g., a phenoxyl group such as a phenoxyl group), an acyl group A cyclic carbonyl group).

The alkylene group may have a branched structure or a cyclic structure.

The number of carbon atoms of the alkylene group is preferably an integer of 1 to 18, more preferably an integer of 1 to 10, for example.

The arylene group may be further substituted with a hydrocarbon group.

The number of carbon atoms of the arylene group is preferably an integer of 6 to 18, more preferably an integer of 6 to 10.

The number of carbon atoms of the monovalent hydrocarbon group of the substituted imino group is preferably an integer of 1 to 18, more preferably an integer of 1 to 10.

Preferable examples of A ₂ are as follows.

Examples of the compound represented by the above structural formulas (13) and (14) include compounds represented by the following structural formulas (15) to (34).

In the structural formulas (15) to (34), n ₆ , n ₇ , n ₈ and m ₅ represent 1 to 60, 1 represents 16 to 20, R 'represents a hydrogen atom or a methyl group .

- a monomer having an aryl group -

The monomer having an aryl group is not particularly limited as long as it has an aryl group, and may be appropriately selected in accordance with the purpose. For example, it is possible to use any one or more of an aryl group-containing polyhydric alcohol compound, a polyvalent amine compound and a polyvalent amino alcohol compound, Esters or amides of a carboxylic acid, and the like.

Examples of the polyvalent alcohol compound, polyvalent amine compound or polyvalent amino alcohol compound having an aryl group include polystyrene oxide, xylylene diol, di- (beta -hydroxyethoxy) benzene, 1,5-dihydroxy- , 2,3,4-tetrahydronaphthalene, 2,2-diphenyl-1,3-propanediol, hydroxybenzyl alcohol, hydroxyethyl resorcinol, 1-phenyl- Tetramethyl-p-xylene -?,? '- diol, 1,1,4,4-tetraphenyl-1,4-butanediol, 1,1,4,4- Dihydroxynaphthalene, 1,1'-methylene-di-2-naphthol, 1,2,4-benzene triol, biphenol, (4-hydroxyphenyl) cyclohexane, bis (hydroxyphenyl) methane, catechol, 4-chlororesorcinol, hydroquinone , Hydroxybenzyl alcohol, methylhydroquinone, methylene-2,4,6-trihydroxybenzoate, fluoroglycinol, pyrogallol , Resorcinol,? - (1-aminoethyl) -p-hydroxybenzyl alcohol,? - (1-aminoethyl) -p-hydroxybenzyl alcohol, 3-amino- . In addition to these, compounds obtained by adding an?,? - unsaturated carboxylic acid to glycidyl compounds such as xylylene bis (meth) acrylamide, novolak type epoxy resin and bisphenol A diglycidyl ether, , Trimellitic acid triallyl, benzenedisulfonic acid diallyl, cationic polymerizable divinyl ethers (e.g., trimethylolpropane triallyl dimethacrylate, trimethylolpropane triallyl dimethacrylate, etc.) and polymerizable monomers (for example, (E.g., bisphenol A divinyl ether), an epoxy compound (e.g., novolak type epoxy resin, bisphenol A diglycidyl ether, etc.), vinyl esters (e.g., divinyl phthalate, divinyl terephthalate, -1,3-disulfonate, etc.), styrene compounds (for example, divinylbenzene, p-allylstyrene, p-isopropenestyrene and the like). Among them, the compound represented by the following structural formula (35) is preferable.

In the above structural formula (35), R ^'4 and R ^{' 5} represent a hydrogen atom or an alkyl group.

In the above structural formula (35), X ₅ and X ₆ represent alkylene oxide groups, and may be used singly or in combination of two or more. Examples of the alkylene oxide group include an ethylene oxide group, a propylene oxide group, a butylene oxide group, a pentylene oxide group, a hexylene oxide group, and a group (may be combined with any one of random or block) Of these, an ethylene oxide group, a propylene oxide group, a butylene oxide group, or a combination thereof is preferable, and an ethylene oxide group and a propylene oxide group are more preferable.

In the structural formula (35), m ₆ and m ₇ are preferably an integer of 1 to 60, more preferably an integer of 2 to 30, and particularly preferably an integer of 4 to 15.

In the structural formula (35), T represents a divalent linking group, and examples thereof include methylene, ethylene, MeCMe, CF ₃ CCF ₃ , CO, SO ₂ and the like.

In the above structural formula (35), Ar ¹ and Ar ² represent an aryl group which may have a substituent, and examples thereof include phenylene and naphthylene. Examples of the substituent include an alkyl group, an aryl group, an aralkyl group, a halogen group, an alkoxy group, and combinations thereof.

Specific examples of the monomer having an aryl group include 2,2-bis [4- (3- (meth) acryloxy-2-hydroxypropoxy) phenyl] propane, 2,2- Bis (4 - ((meth) acryloyloxypolyethoxy) phenyl) propane having 2 to 20 ethoxy groups substituted with one phenolic OH group (for example, , 2, 2-bis (4 - ((meth) acryloyloxydiethoxy) phenyl) propane, Bis (4 - ((meth) acryloyloxypentaethoxy) phenyl) propane, 2,2-bis Bis (4 - ((meth) acryloyloxypentadecaethoxy) phenyl) propane, etc.), 2,2-bis Bis (4 - ((meth) acryloyloxypolypropoxy) phenyl) propane in which the number of substituted ethoxy groups is 2 to 20 (Meth) acryloyloxydipropoxy) phenyl) propane, 2,2-bis (4 - ((meth) acryloyloxydipropoxy) Bis (4 - ((meth) acryloyloxydecaproxy) phenyl) propane, 2, 2-bis 2-bis (4 - ((meth) acryloyloxypentadecapropoxy) phenyl) propane), or polyether moieties of these compounds, both of polyethylene oxide skeleton and polypropylene oxide skeleton BPE-200, BPE-500, and BPE-1000), a compound having a bisphenol skeleton and a urethane group (for example, a compound described in WO01 / 98832 or commercially available from Shin Nakamura Kagakuko Co., Compounds and the like. These may be compounds obtained by changing the portion derived from the bisphenol A skeleton to bisphenol F or bisphenol S or the like.

Examples of the polymerizable compound having a bisphenol skeleton and a urethane group include adducts such as bisphenol and ethylene oxide or propylene oxide, compounds having an isocyanate group and a polymerizable group in a compound having a hydroxyl group at the terminal, (2-isocyanatoethyl (meth) acrylate,?,? -Dimethyl-vinylbenzyl isocyanate and the like).

- Other polymerizable monomers -

As the pattern forming material of the present invention, a monomer having a urethane group and a polymerizable monomer other than the monomer having an aryl group may be used.

Examples of the polymerizable monomer other than the urethane group-containing monomer and the monomer containing the aromatic ring include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, Maleic acid, etc.) with aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and polyvalent amine compounds, and the like.

Examples of the monomer of the ester of the unsaturated carboxylic acid and the aliphatic polyhydric alcohol compound include ethylene glycol di (meth) acrylate as the (meth) acrylic acid ester, polyethylene glycol di (meth) acrylate having the number of the ethylene groups of 2 to 18 (Meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, dodecaethylene glycol di Propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate having 2 to 18 propylene groups (for example, di (meth) acrylate, Propylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, Propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide modified neopentyl glycol di (meth) acrylate, propylene oxide modified neopentyl glycol di Trimethylol propane tri (meth) acrylate, trimethylol propane di (meth) acrylate, trimethylol propane tri (meth) acryloyloxypropyl ether, trimethylol ethane tri (meth) Butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, (Meth) acrylates such as methylene glycol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, 1,2,4- , Pentaerythritol di (meth) acrylate, pentaerythritol (Meth) acrylate, sorbitol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (Meth) acrylate, neopentyl glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, sorbitol penta (meth) acrylate, sorbitol hexa Di (meth) acrylates of alkylene glycol chains each having one or more ethylene glycol chain / propylene glycol chain (for example, those disclosed in WO01 / 98832 Tri (meth) acrylic acid ester of trimethylolpropane having at least one of ethylene oxide and propylene oxide added, poly (Meth) acrylate, glycerin di (meth) acrylate, glycerin tri (meth) acrylate, xylenol di (meth) acrylate and the like.

Among these (meth) acrylate esters, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di Acrylate, trimethylol propane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and diethylene glycol di (meth) acrylate having at least one ethylene glycol chain / propylene glycol chain, (Meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin tri 1,3-propanediol di (meth) acrylate, 1,2,4-butanetriol tri (meth) acrylate, 1,4-cyclohexane The oldi (meth) acrylate, 1,5-pentanediol (meth) acrylate, neopentyl glycol di (meth) acrylate, tri (meth) of adding ethylene oxide trimethylolpropane acrylic acid ester and the like.

Examples of the esters (itaconic acid esters) of itaconic acid and the aliphatic polyhydric alcohol compound include ethylene glycol diacetonate, propylene glycol diacetonate, 1,3-butanediol diacetonate, 1,4-butanediol diacetonate , Tetramethylene glycol diaconate, pentaerythritol diacetonate, and sorbitol tetra taconate.

Examples of the ester of the crotonic acid and the aliphatic polyhydric alcohol compound (crotonic ester) include ethylene glycol dichlorotetranate, tetramethylene glycol dichlonate, pentaerythritol dichlortonate, and sorbitol tetradichlorotinate.

Examples of esters (isocrotonic acid esters) of the isocrotonic acid and the aliphatic polyhydric alcohol compound include, for example, ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.

Examples of the ester (maleic acid ester) of the maleic acid and the aliphatic polyhydric alcohol compound include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, sorbitol tetramale and the like.

Examples of the amide derived from the polyvalent amine compound and the unsaturated carboxylic acids include methylene bis (meth) acrylamide, ethylene bis (meth) acrylamide, 1,6-hexamethylene bis (meth) acrylamide, Bis (meth) acrylamide, diethylenetriamintris (meth) acrylamide, diethylenetriamine bis (meth) acrylamide and the like.

In addition to the above, as the polymerizable monomer, for example, butanediol-1,4-diglycidyl ether, cyclohexanedimethanol glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl A glycidyl group-containing compound such as an ether, dipropylene glycol diglycidyl ether, hexanediol diglycidyl ether, trimethylol propane triglycidyl ether, pentaerythritol tetraglycidyl ether, or glycerin triglycidyl ether, , compounds obtainable by adding? -unsaturated carboxylic acids, Japanese Patent Application Laid-Open No. 48-64183, Japanese Patent Publication No. 49-43191, Japanese Patent Publication No. 52-30490, (Meth) acrylate oligomers, epoxy compounds (for example, butanediol-1,4-diglycidyl ether, cyclohexanedimethanol glycidyl ether, Ethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, hexanediol diglycidyl ether, trimethylol propane triglycidyl ether, pentaerythritol tetraglycidyl ether, glycerin triglycidyl ether, etc.) and Acrylate or methacrylate such as epoxy acrylates obtained by reacting (meth) acrylic acid, photocurable monomers and oligomers described in Japan Adhesion Society vol.20, No. 7, pages 300 to 308 (1984) Allyl esters (e.g., diallyl phthalate, diallyl adipate, diallyl malonate, diallyl amide (e.g., diallylacetamide), cationically polymerizable divinyl ethers (e.g., butanediol- 1,4-divinyl ether, cyclohexanedimethanol divinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether, dipropylene glycol divinyl ether, hexanediol divinyl ether , Trimethylol propane trivinyl ether, pentaerythritol tetravinyl ether, glycerin trivinyl ether, etc.), epoxy compounds (for example, butanediol-1,4-diglycidyl ether, cyclohexanedimethanol glycidyl ether, Ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, hexanediol diglycidyl ether, trimethylol propane triglycidyl ether, pentaerythritol tetraglycidyl ether , Glycerin triglycidyl ether and the like), oxetanes (for example, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene), epoxy compounds, oxetanes (Compounds described in WO 01/22165), N-β-hydroxyethyl- β- (methacrylamide) ethyl acrylate, N, N-bis (β-methacryloxyethyl) acrylamide, allyl methacryl Other ethylenically unsaturated double bonds such as &lt; RTI ID = 0.0 &gt; , And the like.

Examples of the vinyl esters include divinyl succinate and divinyl adipate.

These polyfunctional monomers or oligomers may be used singly or in combination of two or more.

The polymerizable monomer may be used in combination with a polymerizable compound (monofunctional monomer) containing one polymerizable group in the molecule, if necessary.

Examples of the monofunctional monomer include a compound exemplified as a raw material of the binder, a monobutyl (mono (meth) acryloyloxyalkyl ester) mono (halohydrophthalate) compound described in Japanese Patent Application Laid-open No. 6-236031 (E.g.,? -Chloro-? -Hydroxypropyl-? '- methacryloyloxyethyl-o-phthalate and the like) such as a hydroxyalkyl ester And Japanese Patent No. 2548016, and the like.

The content of the polymerizable compound in the photosensitive layer is, for example, preferably 5 to 90% by mass, more preferably 15 to 60% by mass, and particularly preferably 20 to 50% by mass.

When the content is 5% by mass, the strength of the tent film may be lowered. When the content is more than 90% by mass, the edge fusion upon storage (exudation failure from the roll end) may be deteriorated.

The content of the polyfunctional monomer having two or more polymerizable groups in the polymerizable compound is preferably 5 to 100% by mass, more preferably 20 to 100% by mass, and particularly preferably 40 to 100% by mass.

- Photopolymerization initiator -

The photopolymerization initiator is not particularly limited as long as the photopolymerization initiator has the ability to initiate polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, it is preferable that the photopolymerization initiator has photosensitivity to visible light from the ultraviolet region , An activator capable of generating an action with a photoexcited sensitizer and generating an active radical, or an initiator that initiates cationic polymerization depending on the type of the monomer.

The photopolymerization initiator preferably contains at least one component having a molecular extinction coefficient of about 50 or more within a range of about 300 to 800 nm (more preferably, 330 to 500 nm).

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton and oxadiazole skeleton), hexaarylbimidazoles, oxime derivatives, organic peroxides, thio compounds, ketone compounds , Aromatic onium salts, and metallocenes. Of these, halogenated hydrocarbons, oxime derivatives, ketone compounds, and hexaarylbimidazole-based compounds having a triazine skeleton are preferable from the viewpoints of the sensitivity of the photosensitive layer, storage stability, and adhesiveness of the photosensitive layer and the substrate for forming a printed wiring board.

Examples of the hexaarylbiimidazole include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'- 4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-bromophenyl) -4,4' (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5 , 5'-tetra (3-methoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- Bis (4-methoxyphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,4-dichlorophenyl) , 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-nitrophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis Methylphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-trifluoromethylphenyl) -4,4', 5,5'- And compounds described in WO00 / 52529.

The non-imidazoles are described, for example, in Bull. Chem. Soc. Japan, 33, 565 (1960), and J. Org. Chem., 36 (16) 2262 (1971).

As the halogenated hydrocarbon compound having a triazine skeleton, for example, see Wakabayashi et al., Bull. Chem. Soc. Compounds described in Japanese Patent Publication No. 1388492, compounds described in JP 53-133428, compounds described in German Patent No. 3337024, compounds described in FC Schaefer et al., J. 0rg . Chem .; 29, 1527 (1964), compounds described in JP 62-58241 A, compounds described in JP 5-281728 A, compounds described in JP 05-34920 A, Compounds described in the specification of Japanese Patent No. 4212976, and the like.

Wakabayashi et al., Bull. Chem. Soc. Examples of the compound described in Japan, 42, 2924 (1969) include 2-phenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (Trichloromethyl) -1,3,5-triazine, 2- (4-tolyl) -4,6-bis Bis (trichloromethyl) -1,3,5-triazine, 2- (2,4-dichlorophenyl) -4,6-bis Triazine, 2,4,6-tris (trichloromethyl) -1,3,5-triazine, 2-methyl-4,6-bis (trichloromethyl) Triazine, 2-n-nonyl-4,6-bis (trichloromethyl) -1,3,5-triazine, and 2- (?,? Bis (trichloromethyl) -1,3,5-triazine, and the like.

Examples of the compound described in the specification of British Patent No. 1388492 include 2-styryl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methylstyryl) -4 , Bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxystyryl) -4,6-bis 2- (4-methoxystyryl) -4-amino-6-trichloromethyl-1,3,5-triazine and the like.

Examples of the compound described in Japanese Patent Application Laid-Open No. 53-133428 include 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -Triazine, 2- (4-ethoxy-naphth-1-yl) -4,6-bis (trichloromethyl) Yl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4,7-dimethoxy-naphth- (Trichloromethyl) -1,3,5-triazine, and 2- (acenaphtho-5-yl) -4,6-bis Azine, and the like.

Examples of the compound described in the specification of German Patent 3337024 include 2- (4-styrylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (Trichloromethyl) -1,3,5-triazine, 2- (1-naphthylvinylphenyl) -4,6-bis (trichloro Methyl) -1,3,5-triazine, 2-chlorostyrylphenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (Trichloromethyl) -1,3,5-triazine, 2- (4-thiophene-3-vinylene phenyl) -4,6-bis (Trichloromethyl) -1,3,5-triazine, and 2- (4-benzoylphenyl) -4,6-bis Furan-2-vinylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine.

F. C. Schaefer et al., J. Org. Chem .; 29, 1527 (1964), there can be mentioned, for example, 2-methyl-4,6-bis (tribromomethyl) -1,3,5-triazine, 2,4,6- Methyl) -1,3,5-triazine, 2,4,6-tris (dibromomethyl) -1,3,5-triazine, 2-amino- ) -1,3,5-triazine, and 2-methoxy-4-methyl-6-trichloromethyl-1,3,5-triazine.

Examples of the compound described in Japanese Patent Application Laid-Open No. 62-58241 include 2- (4-phenylethynylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2 - (4-naphthyl-1-ethynylphenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- Bis (trichloromethyl) -1,3,5-triazine, 2- (4- (4-methoxyphenyl) ethynylphenyl) (Trichloromethyl) -1,3,5-triazine, 2- (4- (4-tert-butylphenyl) Ethylphenylethynyl) phenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine.

Examples of the compound described in Japanese Unexamined Patent Application Publication No. 5-281728 include 2- (4-trifluoromethylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2 - (2,6-difluorophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (2,6-dibromophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, and the like can be given .

Examples of the compound described in Japanese Unexamined Patent Application Publication No. 5-34920 include 2,4-bis (trichloromethyl) -6- [4- (N, N-diethoxycarbonylmethylamino) M-phenyl] -1,3,5-triazine, trihalomethyl-s-triazine compounds described in US Patent No. 4239850, and 2,4,6-tris (trichloromethyl) -s- Triazine, and 2- (4-chlorophenyl) -4,6-bis (tribromomethyl) -s-triazine.

Examples of the compound described in the specification of US 4212976 include compounds having an oxadiazole skeleton (for example, 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2 - trichloromethyl-5- (4-chlorophenyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1,3,4-oxadiazole, 2 - trichloromethyl-5- (2-naphthyl) -1,3,4-oxadiazole, 2-tribromomethyl-5-phenyl-1,3,4-oxadiazole, Methyl-5- (2-naphthyl) -1,3,4-oxadiazole, 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, (4-chlorostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (4-methoxystyryl) -1,3,4-oxadiazole, 2-trichloromethyl Oxadiazole, 2-trichloromethyl-5- (4-n-butoxystyryl) -1,3,4-oxadiazole, 2 -Trichloromethyl-5-styryl-1,3,4-oxadiazole), and the like.

Examples of the oxime derivative preferably used in the present invention include compounds represented by the following structural formulas (36) to (69).

Examples of the ketone compound include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4- 2-ethoxycarbonylbenzophenone, benzophenone tetracarboxylic acid or its tetramethyl ester, 4,4'-bis (dialkylamino) benzophenones [for example, , 4,4'-bis (dimethylamino) benzophenone, 4,4'-bisdicyclohexylamino] benzophenone, 4,4'-bis 4-dimethylamino benzophenone, 4-dimethylamino benzophenone, 4-dimethylamino acetophenone, benzyl, anthraquinone, 2-chlorobenzoic acid, 2-t-butyl anthraquinone, 2-methyl anthraquinone, phenanthraquinone, xanthone, thioxanthone, Dimethylamino Methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-hydroxy- Benzoin ethers (e.g., benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin ethyl ether, Benzoin phenyl ether, benzyl dimethyl ketal), acridone, chloroacridone, N-methylacridone, N-butylacridone, N-butyl-chloroacridone and the like.

Examples of senryu to the metal, bis (η ⁵ -2,4- cyclopentadiene-1-yl) -bis (2,6-difluoro -3- (1H- pyrrol-1-yl) -phenyl ) titanium, η ⁵ - cyclopentadienyl -η ^{6-cumenyl-iron} (1 +) - hexafluorophosphate (1-), Japanese Laid-Open Patent Publication No. 53-133428 cattle, Japanese Patent Publication No. 57-1819 cattle And the compounds described in the specification of U.S. Pat. No. 3,615,455, and the like.

As other photopolymerization initiators than the above, acridine derivatives (e.g., 9-phenylacridine, 1,7-bis (9,9'-acridinyl) heptane and the like), N-phenylglycine, A halogenated compound (for example, carbon tetrabromide, phenyltribromomethylsulfone, phenyltrichloromethylketone and the like), coumarins (for example, 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3 (2-benzofuroyl) Diethylaminocoumarin, 3,3'-carbonylbis (5,7-di-n-propoxyquimarin), 3,3'-carbonylbis (7-di Ethylamino coumarin), 3-benzoyl-7-methoxy coumarin, 3- (2-furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) Methoxy-3- (3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, 7-benzotriazol- Lin, Japanese Patent Application Laid-Open Nos. 5-19475, 7-271028, 2002-363206, 2002-363207, 2002-363208, 2002 -363209 and the like), amines (for example, ethyl 4-dimethylaminobenzoate, n-butyl 4-dimethylaminobenzoate, phenethyl 4-dimethylaminobenzoate, 2- Dimethylaminobenzoate, 3-dimethylaminobenzoate, phenethyl, pentamethylene ester, 4-dimethylaminobenzaldehyde, 2- (4-dimethylaminobenzaldehyde) Dimethylaminobenzoyl acetate, 4-piperidino acetophenone, 4-dimethylaminobenzoin, N, N-dimethyl-4-toluidine, N, N-diethyl-3-phene N, N-dimethylaniline, tridodecylamine, aminofluororanes (ODB, ODBII, etc.), crystal violet (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4-dihydroxybenzoate, 4-trimethyl-pentylphenylphosphine oxide, Lucirin TPO, etc.].

Further, the bisphenol polyketal dopyl compound described in U.S. Patent No. 2367660, the acyloin ether compound described in U.S. Patent No. 2448828, the α-hydrocarbon described in U.S. Patent No. 2722512 Substituted aromatic acyloin compounds, polynuclear quinone compounds described in U.S. Patent Nos. 3046127 and 2951758, organic boron compounds described in JP-A-2002-229194, radical generators, triarylsulfonium salts (examples (For example, a salt with hexafluoroantimony or hexafluorophosphate), a phosphonium salt compound (e.g., (phenylthiophenyl) diphenylsulfonium salt, etc.) (effective as a cationic polymerization initiator), WO01 / 71428 And the like.

The photopolymerization initiator may be used singly or in combination of two or more. As a combination of two or more kinds, there may be mentioned, for example, a combination of hexaarylbimidazole and 4-aminoketones described in U.S. Patent No. 3549367, a combination of a benzothiazole compound described in Japanese Patent Publication No. 51-48516, a combination of an aromatic ketone compound (e.g., thioxanthone) with a hydrogen donor (e.g., a dialkylamino-containing compound, a phenol compound, etc.), a combination of hexaarylbiimidazole And titanocene, a combination of coumarins, titanocenes, and phenylglycines.

The content of the photopolymerization initiator in the photosensitive layer is preferably from 0.1 to 30% by mass, more preferably from 0.5 to 20% by mass, and particularly preferably from 0.5 to 15% by mass.

- Other ingredients -

Examples of the other components include a sensitizer, a thermal polymerization inhibitor, a plasticizer, a coloring agent, a colorant, and the like. In addition, adhesion promoters and other additives (for example, pigments, conductive particles, Anti-foaming agent, flame retardant, leveling agent, peeling accelerator, antioxidant, fragrance, heat crosslinking agent, surface tension adjusting agent, chain transfer agent, etc.) may be used in combination. By suitably containing these components, properties such as stability, photographic properties, flammability, and film properties of a target pattern forming material can be adjusted.

 - Increase -

The sensitizer may be appropriately selected by visible light, ultraviolet light, visible light laser or the like as the light irradiation means described later.

The sensitizer is brought into an excited state by an active energy ray and is capable of interacting with other substances (for example, a radical generator and an acid generator) (for example, energy transfer, electron transfer, And the like.

The sensitizer is not particularly limited and may be appropriately selected from among known sensitizers. Examples of the sensitizer include well-known polynuclear aromatic compounds (e.g., pyrene, perylene, triphenylene), xanthrene (for example, Erythrosine, rhodamine B, rose bengal), cyanines (e.g., indocarbocyanine, thiacarbocyanine, oxacarbocyanine), merocyanines (e. G. Cyanine, carbomerocyanine), thiazines (e.g. thionine, methylene blue, toluidine blue), acridines (e.g., acridine orange, chloroflavin, acriflavine) But are not limited to, quinones (e.g., anthraquinone), squaryliums (e.g., squarylium), acridides (e.g., acridone, chloroacridone, N-methylacridone, Acridone, N-butyl-chloroacridone, etc.), coumarins (for example, 3- (2-benzofuroyl) 7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- (1-pyrrolidinyl) coumarin, 3-benzoyl- , 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3'-carbonylbis (5,7-di-n-propoxyquimarin), 3,3'-carbonylbis -Diethylaminocoumarin), 3-benzoyl-7-methoxy coumarin, 3- (2-furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) (3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin and the like can be mentioned. In addition, JP-A 5-19475, Coumarin compounds described in respective publications such as JP-A 7-271028, JP-A 2002-363206, JP-A 2002-363207, JP-A 2002-363208 and JP-A 2002-363209) have.

Examples of the combination of the photopolymerization initiator and the sensitizer include the electron transportable electronic timepiece described in JP 2001-305734 A [(1) an electron donating type initiator and a sensitizing dye, (2) an electron accepting type initiator and a sensitizing dye , (3) an electron donating type initiator, a sensitizing dye, and an electron accepting type initiator (three-way clock)].

The content of the sensitizer is preferably from 0.05 to 30 mass%, more preferably from 0.1 to 20 mass%, and particularly preferably from 0.2 to 10 mass%, based on the total components of the photosensitive resin composition.

When the content is less than 0.05% by mass, the sensitivity to the active energy ray is lowered and the exposure process takes time, resulting in a decrease in productivity. When the content exceeds 30% by mass, There is work.

- Thermal polymerization inhibitor -

 The heat polymerization inhibitor may be added in order to prevent thermal polymerization or polymerization over time of the polymerizable compound in the photosensitive layer.

Examples of the thermal polymerization inhibitor include 4-methoxyphenol, hydroquinone, alkyl or aryl substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy- Dihydroxybenzophenone, phenoxybenzene, phenoxybenzene, phenoxybenzene, phenoxybenzene, phenoxybenzene, phenoxybenzene, phenoxybenzene, phenoxybenzene, 6-t-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, methylene blue, reactants with organic chelating agents, methyl salicylate, phenothiazine, nitroso compounds, And the like.

The content of the thermal polymerization inhibitor is preferably 0.001 to 5 mass%, more preferably 0.005 to 2 mass%, and particularly preferably 0.01 to 1 mass% with respect to the polymerizable compound of the photosensitive layer.

When the content is less than 0.001% by mass, stability at the time of storage may be deteriorated. When the content is more than 5% by mass, sensitivity to an active energy ray may be lowered.

- Plasticizer -

The plasticizer may be added to control physical properties (flexibility) of the photosensitive layer.

Examples of the plasticizer include dimethyl phthalate, dibutyl phthalate, diisobutyl phthalate, diheptyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, ditridecyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, Phthalic acid esters such as diallyl phthalate and octylcarbyl phthalate; Glycol esters such as triethylene glycol diacetate, tetraethylene glycol diacetate, dimethylglycosophthalate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate and triethylene glycol dicaprylic acid ester ; Phosphoric acid esters such as tricresyl phosphate and triphenyl phosphate; Amides such as 4-toluenesulfonamide, benzenesulfonamide, N-n-butylbenzenesulfonamide and N-n-butylacetamide; Aliphatic dibasic acid esters such as diisobutyl adipate, dioctyl adipate, dimethyl sebacate, dibutyl sebacate, dioctyl sebacate, dioctyl azelate and dibutyl malate; Glycols such as triethyl citrate, tributyl citrate, glycerin triacetyl ester, butyl laurate, dioctyl 4,5-diepoxycyclohexane-1,2-dicarboxylate and the like, glycols such as polyethylene glycol and polypropylene glycol .

The content of the plasticizer is preferably 0.1 to 50 mass%, more preferably 0.5 to 40 mass%, and particularly preferably 1 to 30 mass% with respect to the total components of the photosensitive layer.

- Coloring agent -

 The coloring agent may be added to impart a visible image to the photosensitive layer after exposure (a printing function).

Examples of the coloring agent include tris (4-dimethylaminophenyl) methane (leuco crystal violet), tris (4-diethylaminophenyl) methane, tris (4-dimethylamino- Diethylamino-2-methylphenyl) methane, bis (4-dibutylaminophenyl) - [4- (2-cyanoethyl) methylaminophenyl] methane, bis , And tris (4-dipropylaminophenyl) methane; Aminocarboxylic acids such as 3,6-bis (dimethylamino) -9-phenylxanthine and 3-amino-6-dimethylamino-2-methyl-9- (2-chlorophenyl) xanthine; Aminothioxanthenes such as 3,6-bis (diethylamino) -9- (2-ethoxycarbonylphenyl) thioxanthene and 3,6-bis (dimethylamino) thioxanthene; (Diethylamino) -9,10-dihydro-9-phenylacridine and 3,6-bis (benzylamino) -9,10-dihydro-9-methylacridine. Amino-9,10-dihydraacridines; Aminophenoxazines such as 3,7-bis (diethylamino) phenoxazine; Aminophenothiazines such as 3,7-bis (ethylamino) phenothiazine; Amino dihydrophenazines such as 3,7-bis (diethylamino) -5-hexyl-5,10-dihydrophenazine; Aminophenylmethanes such as bis (4-dimethylaminophenyl) anilinomethane; Amino-hydrocinnamic acids such as 4-amino-4'-dimethylaminodiphenylamine and 4-amino-α, β-dicyanohydrosinic acid methyl ester; Hydrazines such as 1- (2-naphthyl) -2-phenylhydrazine; Amino-2,3-dihydroanthraquinones of 1,4-bis (ethylamino) -2,3-dihydroanthraquinones; Phenethyl anilines such as N, N-diethyl-4-phenethylaniline; Acyl derivatives of leuco dye containing basic NH such as 10-acetyl-3,7-bis (dimethylamino) phenothiazine; Leuco form compounds which do not have oxidizable hydrogen such as tris (4-diethylamino-2-tolyl) ethoxycarbonyl menthane but can be oxidized to a coloring compound; Leuco indigo dye; 4,4'-ethylenediamine, diphenylamine, N, N-dimethylaniline, 4, 4'-ethylenediamine, 4,4'-ethylenediamine, 4'-methylene diamine triphenylamine, N-vinylcarbazole). Of these, triarylmethane compounds such as leuco crystal violet are preferable.

In addition, it is generally known that the above-mentioned coloring agent is combined with a halogen compound for the purpose of coloring the leukocyte.

Examples of the halogen compound include halogenated hydrocarbons such as carbon tetrabromide, iodoform, ethylene bromide, methylene bromide, amyl bromide, isoamyl bromide, amyl iodide, isobutyl bromide, butyl iodide, diphenylmethyl bromide , Hexachloroethane, 1,2-dibromoethane, 1,1,2,2-tetrabromoethane, 1,2-dibromo-1,1,2-trichloroethane, 1,2,3 -Tribromopropane, 1-bromo-4-chlorobutane, 1,2,3,4-tetrabromobutane, tetrachlorocyclopropene, hexachlorocyclopentadiene, dibromosucciohexane, 1,1 , 1-trichloro-2,2-bis (4-chlorophenyl) ethane, etc.); Halogenated alcohol compounds such as 2,2,2-trichloroethanol, tribromoethanol, 1,3-dichloro-2-propanol, 1,1,1-trichloro-2-propanol, di (iodohexa Methylene) amino isopropanol, tribromo-t-butyl alcohol, 2,2,3-trichlorobutane-1,4-diol, etc.); Halogenated carbonyl compounds such as 1,1-dichloroacetone, 1,3-dichloroacetone, hexachloroacetone, hexabromoacetone, 1,1,3,3-tetrachloroacetone, 1,1,1-trichloro Acetone, 3,4-dibromo-2-butanone, 1,4-dichloro-2-butanone-dibromo cyclohexanone, etc.); Halogenated ether compounds (for example, 2-bromoethyl methyl ether, 2-bromoethyl ethyl ether, di (2-bromoethyl) ether, 1,2-dichloroethyl ethyl ether and the like); Halogenated ester compounds (for example, bromoethyl acetate, ethyl trichloroacetate, trichloro trichloroethyl acetate, homopolymers and copolymers of 2,3-dibromopropyl acrylate, trichloroethyl dibromopropionate, alpha, beta -dichloroacrylic acid ethyl and the like); Halogenated amide compounds (for example, chloroacetamide, bromoacetamide, dichloroacetamide, trichloroacetamide, tribromoacetamide, trichloroethyltrichloroacetamide, 2-bromoisopropionamide, 2,2-trichloropropionamide, N-chlorosuccinimide, N-bromosuccinimide, etc.); Compounds having sulfur or phosphorus (e.g., tribromomethylphenylsulfone, 4-nitrophenyltribromomethylsulfone, 4-chlorophenyltribromomethylsulfone, tris (2,3-dibromopropyl) phosphate, etc. ), 2,4-bis (trichloromethyl) 6-phenyltriazole, and the like. In the organohalogen compound, a halogen compound having two or more halogen atoms bonded to the same carbon atom is preferable, and a halogen compound having three halogen atoms in one carbon atom is more preferable. The organohalogen compounds may be used singly or in combination of two or more. Among them, tribromomethylphenylsulfone and 2,4-bis (trichloromethyl) -6-phenyltriazole are preferable.

The content of the color developer is preferably 0.01 to 20% by mass, more preferably 0.05 to 10% by mass, and particularly preferably 0.1 to 5% by mass with respect to the total components of the photosensitive layer. The content of the halogen compound is preferably from 0.001 to 5 mass%, more preferably from 0.005 to 1 mass%, based on the total components of the photosensitive layer.

--coloring agent--

The colorant is not particularly limited and may be appropriately selected in accordance with the purpose. Examples thereof include known pigments or dyes such as red, green, blue, yellow, purple, magenta, cyan and black, (CI Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), Pigment Blue HB (CI Pigment Yellow 12), Pigment Yellow HB Permanent Yellow HR (CI Pigment Yellow 83), Permanent Carmine FBB (CI Pigment Red 146), Hoster Bam Red ESB (CI Pigment Violet 19), Permanent Ruby FBH (CI Pigment Red 11) (CI Pigment Red 81), Monostarial First Blue (CI Pigment Blue 15), Monolight First Black B (CI Pigment Black 1), and carbon black.

Examples of the coloring agent suitable for the production of the color filter include CI Pigment Red 97, CI Pigment Red 122, CI Pigment Red 149, CI Pigment Red 168, CI Pigment Red 177, CI Pigment Red 180 CI Pigment Blue 15: 4, CI Pigment Blue 15: 6, CI Pigment Blue 36, CI Pigment Blue 15: 1, CI Pigment Blue 15: 4, CI Pigment Blue 15: Pigment Blue 22, CI Pigment Blue 60, CI Pigment Blue 64, CI Pigment Yellow 139, CI Pigment Yellow 83, CI Pigment Violet 23, and JP-A No. 2002-162752 (0138) to ), And the like. The average particle diameter of the colorant is not particularly limited and may be appropriately selected according to the purpose. For example, it is preferably 5 탆 or less, and more preferably 1 탆 or less. When a color filter is produced, the average particle diameter is preferably 0.5 占 퐉 or less.

--dyes--

The photosensitive layer may be colored with a dye for the purpose of coloring the photosensitive resin composition or imparting storage stability in order to improve handling properties.

Examples of the dyes include brilliant green (e.g., a sulfate thereof), eosin, ethyl violet, erythrosine B, methyl green, crystal violet, basic fuchsin, phenolphthalein, 1,3-diphenyltriazine, alizarin red S, , Methyl violet 2B, quinaldine red, rose bengal, methanyl-yellow, thymol sulfopthalene, xylenol blue, methyl orange, orange IV, diphenylthiocarbazone, 2,7-dichlorofluorescein, para Methyl blue, malachite green, parafluxine, oil blue # 603 (manufactured by Orient Kagaku Co., Ltd.), rhodamine B, methylprednisolone, methylprednisolone, methyl red, congo red, benzofurfurin 4B, alpha -naphthyl red, Rhodamine 6G, and Victoria Pure Blue BOH. Of these, cationic dyes (for example, malachite green oxalate, malachite green sulfate and the like) are preferable. The counter anion of the cationic dye may be an organic acid or a residue of an inorganic acid. Examples of the counter anion include residues (anions) such as bromic acid, iodic acid, sulfuric acid, phosphoric acid, oxalic acid, methanesulfonic acid and toluenesulfonic acid.

The content of the dye is preferably 0.01 to 10 mass%, more preferably 0.01 to 5 mass%, and particularly preferably 0.1 to 2 mass% with respect to the total components of the photosensitive layer.

- Adhesion promoter -

In order to improve the adhesion between the respective layers or the adhesion between the pattern forming material and the substrate, known adhesion promoters known in the art may be used.

As the adhesion promoter, for example, the adhesion promoter described in JP-A-5-11439, JP-A-5-341532, and JP-A-6-43638 can be preferably used. Specific examples include benzimidazole, benzoxazole, benzthiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 3-morpholinomethyl-1-phenyl 3-morpholinomethyl-5-phenyl-oxadiazole-2-thione, 5-amino-3-morpholinomethyl-thiadiazole-2-thione, 5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole, amino group-containing benzotriazole, and silane coupling agent.

The content of the adhesion promoter is preferably from 0.001% by mass to 20% by mass, more preferably from 0.01% by mass to 10% by mass, and particularly preferably from 0.1% by mass to 5% by mass, with respect to the total components of the photosensitive layer.

The photosensitive layer may be, for example, an organic sulfur compound, a peroxide, a redox compound, an azo or diazo compound, a photo-reducible dye, an organic halogen compound And the like.

Examples of the organic sulfur compound include di-n-butyldisulfide, dibenzyldisulfide, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, thiophenol, ethyltrichloromethane sulfate, 2- Benzimidazole and the like.

Examples of the peroxide include di-t-butyl peroxide, benzoyl peroxide, and methyl ethyl ketone peroxide.

The redox compound is a combination of a peroxide and a reducing agent, and includes ferrous ions, persulfate ions, ferric ions, and peroxides.

The azo and diazo compounds include, for example, α, α'-azobisisobutyronitrile, 2-azobis-2-methylbutyronitrile and 4-aminodiphenylamine diazonium.

Examples of the above-mentioned photoreducible dye include rose bengal, erythrosine, eosin, acriflavine, lipoflavin and thionine.

--Surfactants--

A known surfactant may be used in combination to improve the surface deviation that occurs when the pattern forming material of the present invention is produced.

Examples of the surfactant include anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, and fluorine-containing surfactants.

The content of the surfactant is preferably 0.001 to 10% by mass based on the solid content of the photosensitive resin composition.

If the content is less than 0.001% by mass, the effect of improving the surface area may not be obtained. If the content is more than 10% by mass, the adhesion may be deteriorated.

The thickness of the photosensitive layer is not particularly limited and may be appropriately selected according to the purpose. For example, it is preferably 1 to 100 占 퐉, more preferably 2 to 50 占 퐉, and particularly preferably 4 to 30 占 퐉.

<Support and Protective Film>

The support is not particularly limited and may be appropriately selected according to the purpose. It is preferable that the photosensitive layer can be peeled off, the light transmittance is favorable, and the surface smoothness is more preferable.

The support is made of a synthetic resin and is preferably transparent. Examples of the support include polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, alkyl (meth) ) Acrylic acid ester copolymer, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinyl chloride-vinyl acetate copolymer, polytetrafluoroethylene, And various plastic films such as fluoroethylene, cellulose-based film and nylon film. Of these, polyethylene terephthalate is particularly preferable. These may be used singly or in combination of two or more kinds.

The thickness of the support is not particularly limited and may be appropriately selected according to the purpose. For example, the thickness is preferably 2 to 150 占 퐉, more preferably 5 to 100 占 퐉, and particularly preferably 8 to 50 占 퐉.

The shape of the support is not particularly limited and may be suitably selected in accordance with the purpose, but it is preferably a long length. The length of the long-axis-shaped support is not particularly limited and may be, for example, 10 m to 20,000 m in length.

The pattern forming material may form a protective film on the photosensitive layer.

Examples of the protective film include those used for the support, paper, polyethylene, polypropylene-laminated paper, and the like. Among them, a polyethylene film and a polypropylene film are preferable.

The thickness of the protective film is not particularly limited and may be appropriately selected according to the purpose. For example, it is preferably 5 to 100 占 퐉, more preferably 8 to 50 占 퐉, and particularly preferably 10 to 30 占 퐉.

Examples of the combination of the support and the protective film (support / protective film) include polyethylene terephthalate / polypropylene, polyethylene terephthalate / polyethylene, polyvinyl chloride / cellophane, polyimide / polypropylene, polyethylene terephthalate / polyethylene terephthalate And the like. Further, by subjecting at least one of the support and the protective film to a surface treatment, the above-described adhesion force relationship can be satisfied. The surface treatment of the support may be performed in order to increase the adhesion with the photosensitive layer. For example, application of a primer layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency irradiation treatment, glow discharge irradiation treatment, Irradiation treatment, laser beam irradiation treatment, and the like.

The static friction coefficient of the support and the protective film is preferably 0.3 to 1.4, more preferably 0.5 to 1.2.

When the static friction coefficient is less than 0.3, it is too slippery, and therefore, in the case of rolling, the winding may be shifted. If the static friction coefficient is more than 1.4, it may become difficult to roll the roll in a good roll state.

Preferably, the pattern forming material is wound on a cylindrical core, for example, rolled up into a long form and stored. The length of the pattern forming material in the longitudinal direction is not particularly limited and may be suitably selected within a range of, for example, 10 m to 20,000 m. In addition, the slits may be slit-processed so as to be easy for the user to use, and the elongated body in the range of 100 m to 1,000 m may be rolled. In this case, it is preferable that the support is rolled so as to be the outermost side. Further, the pattern-forming material on the roll may be slit into a sheet form. It is desirable to provide a separator (particularly one having moisture-proof property and a desiccant material) on its end face in view of protection of the cross-section at the time of storage and prevention of edge diffusion, and it is also preferable to use a material having low moisture permeability.

The protective film may be surface-treated to adjust adhesion between the protective film and the photosensitive layer. In the surface treatment, for example, a primer layer composed of a polymer such as a polyorganosiloxane, a fluorinated polyolefin, a polyfluoroethylene, or a polyvinyl alcohol is formed on the surface of the protective film. The primer layer can be formed by applying a coating liquid of the polymer onto the surface of the protective film and then drying the coated film at 30 to 150 ° C (particularly 50 to 120 ° C) for 1 to 30 minutes.

<Other Floor>

The other layer is not particularly limited and can be appropriately selected in accordance with the purpose. Examples thereof include layers such as a cushion layer, a barrier layer, a peeling layer, an adhesive layer, a light absorbing layer, and a surface protective layer. The pattern forming material may have a single kind of these layers, two or more kinds of these layers, or two or more layers of the same type.

The photosensitive layer in the pattern forming material of the present invention modulates the light from the light irradiation means by means of light modulation means having n number of grave portions for receiving and emitting the light from the light irradiation means, It is preferable that the light is passed through the microlens array in which microlenses having aspheric surfaces capable of correcting aberration caused by deformation of the exit surface in the optical system are arranged. Details of the light irradiation means, the graveyard portion, the light modulation means, the aspherical surface, the microlens, and the microlens array will be described later.

[Method for producing pattern forming material]

The pattern forming material can be produced, for example, in the following manner.

First, the coating liquid is prepared by dissolving, emulsifying or dispersing the material contained in the photosensitive layer and the other layers in water or a solvent.

The solvent of the coating liquid is not particularly limited and may be appropriately selected in accordance with the purpose. Examples of the solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol and n-hexanol; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and diisobutyl ketone; Esters such as ethyl acetate, butyl acetate, n-amyl acetate, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, and methoxypropyl acetate; Aromatic hydrocarbons such as toluene, xylene, benzene and ethylbenzene; Halogenated hydrocarbons such as carbon tetrachloride, trichlorethylene, chloroform, 1,1,1-trichloroethane, methylene chloride, and monochlorobenzene; Ethers such as tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and 1-methoxy-2-propanol; Dimethylformamide, dimethylacetamide, dimethylsulfoxide, sulfolane and the like. These may be used singly or in combination of two or more kinds. In addition, a known surfactant may be added.

Next, the coating liquid is coated on the support and dried to form each layer, thereby producing a pattern forming material. For example, a pattern forming material can be produced by applying a photosensitive resin composition solution in which the components of the photosensitive layer are dissolved, emulsified or dispersed on a support and drying to form a photosensitive layer and forming a protective film thereon .

The coating method of the coating liquid is not particularly limited and may be appropriately selected according to the purpose. Examples of the coating method include a spray method, a roll coating method, a spin coating method, a slit coat method, an extrusion coating method, a curtain coating method, Various coating methods such as a coating method, a gravure coating method, a wire bar coating method, and a knife coating method.

The drying conditions are usually from 60 to 110 DEG C for about 30 seconds to about 15 minutes although they vary depending on the components, the kind of solvent, the use ratio and the like.

The pattern forming material of the present invention is excellent in resolution and tent property and also excellent in developing property and also excellent in peeling property at the time of etching. Therefore, the pattern forming material can be used for forming various patterns, for forming permanent patterns such as wiring patterns, It can be suitably used for the production of liquid crystal structural members such as filters, columns, ribs, spacers and barrier ribs, and for pattern formation of holograms, micromachines, prophes and the like. . Further, it can be preferably used for the pattern forming method and the pattern forming apparatus of the present invention.

(Pattern forming apparatus and pattern forming method)

The pattern forming apparatus of the present invention comprises the pattern forming material of the present invention, and has at least a light irradiation means and an optical modulation means.

The pattern forming method of the present invention includes at least an exposure process and other processes suitably selected.

Further, the pattern forming apparatus of the present invention is clarified through the description of the pattern forming method of the present invention.

[Exposure step]

The exposure process is a process for exposing the photosensitive layer in the pattern forming material of the present invention. The pattern forming material of the present invention is as described above.

The object to be exposed is not particularly limited as long as it is a photosensitive layer in the pattern forming material and can be appropriately selected in accordance with the purpose. For example, for a laminate formed by forming the pattern forming material on a substrate .

The substrate is not particularly limited and may be appropriately selected from known materials having a high surface smoothness and a surface having unevenness, but a substrate (substrate) in a plate form is preferable. Specifically, a known printed wiring board is formed (For example, soda glass plate), synthetic resin-based film, paper, metal plate, and the like. Among them, adhesion to copper-containing materials is excellent The above-mentioned copper-clad laminate is preferable.

The method of forming the laminate is not particularly limited and may be suitably selected in accordance with the purpose. Preferably, the pattern forming material is laminated on the substrate while heating or pressurizing the pattern forming material.

The heating temperature is not particularly limited and may be appropriately selected according to the purpose. For example, the heating temperature is preferably 15 to 180 占 폚, more preferably 60 to 140 占 폚.

The pressurizing pressure is not particularly limited and may be appropriately selected according to the purpose. For example, the pressure is preferably 0.1 to 1.0 MPa, and more preferably 0.2 to 0.8 MPa.

The apparatus for performing at least one of the above heating and pressurization is not particularly limited and can be appropriately selected in accordance with the purpose. For example, a laminator, a vacuum laminator and the like are preferably used.

The apparatus for carrying out at least one of the above heating and pressurization is not particularly limited and can be appropriately selected in accordance with the purpose. For example, a laminator (for example, VP-II manufactured by Taihei Laminator Co., Ltd.) have.

The exposure is not particularly limited and may be appropriately selected in accordance with the purpose. Examples of the exposure include digital exposure and analog exposure. Among them, digital exposure is preferable.

The digital exposure is not particularly limited and may be appropriately selected in accordance with the purpose. For example, it is preferable that control signals are generated based on the pattern formation information to be formed, and the light is modulated in accordance with the control signal .

The means for digital exposure is not particularly limited and may be appropriately selected in accordance with the purpose. For example, light irradiation means for irradiating light, light for modulating light irradiated from the light irradiation means on the basis of pattern information to be formed A modulation means and the like.

&Lt; Light modulation means >

The light modulating means is not particularly limited as long as it can modulate light, and can be appropriately selected in accordance with the purpose. For example, it is preferable to have n graveyard portions.

The light modulating means having the n grave portions is not particularly limited and may be appropriately selected in accordance with the purpose. For example, a spatial light modulating element is preferable.

Examples of the spatial light modulation element include a digital micromirror device (DMD), a special light modulator (SLM) type of a micro electro mechanical system (MEMS) type, an optical element for modulating transmitted light by the optical effect (PLZT element), liquid crystal optical shutter (FLC), and the like. Of these, DMD is preferably used.

It is preferable that the light modulating means has pattern signal generating means for generating a control signal based on the pattern information to be formed. In this case, the light modulating means modulates the light according to the control signal generated by the pattern signal generating means.

The control signal is not particularly limited and can be appropriately selected in accordance with the purpose. For example, a digital signal is preferably used.

Hereinafter, an example of the optical modulation means will be described with reference to the drawings.

1, the DMD 50 includes a plurality of (for example, 1024 x 768) micromirrors (micromirrors) constituting a graveyard (pixel) on SRAM cells (memory cells) 60, (62) are arranged in a lattice pattern. In each pixel, a micro mirror 62 supported by a support is provided at the uppermost portion, and a material having a high reflectivity such as aluminum is deposited on the surface of the micro mirror 62. In addition, the reflectance of the micromirror 62 is 90% or more, and the arrangement pitch is 13.7 占 퐉 as an example in both the longitudinal direction and the lateral direction. A silicon gate CMOS SRAM cell 60, which is fabricated in a manufacturing line of a conventional semiconductor memory, is disposed directly below the micro mirror 62 via a column including a hinge and a yoke, .

When a digital signal is inputted to the SRAM cell 60 of the DMD 50, the micro mirror 62 supported by the support is rotated about ± (for example, ± 12 degrees). 2A shows a state in which the micromirror 62 is in an ON state and a state in which the micromirror 62 is inclined + alpha, and FIG. 2B shows a state in which the micromirror 62 is in an OFF state and inclined to -α. Therefore, by controlling the inclination of the micromirror 62 in each pixel of the DMD 50 in accordance with the pattern information as shown in Fig. 1, the laser beam B incident on the DMD 50 is reflected by each micro- And is reflected in the oblique direction of the mirror 62.

1 shows an example of a state in which a part of the DMD 50 is enlarged and the micro mirror 62 is controlled to + alpha degree or-alpha degree. The ON / OFF control of each micromirror 62 is performed by the controller 302 (see Fig. 12) connected to the DMD 50. Fig. A light absorber (not shown) is disposed in the direction in which the laser beam B reflected by the micromirror 62 in the OFF state advances.

It is also preferable that the DMD 50 is slightly inclined so that the short side thereof forms a predetermined angle? (For example, 0.1 to 5 degrees) from the sub-scan direction. 3A shows the scan locus of the reflected light image (exposure beam) 53 by each micromirror when the DMD 50 is not inclined. FIG. 3B shows the scan locus of the exposure beam 53 when the DMD 50 is inclined. As shown in Fig.

A plurality of micromirror columns arranged in the longitudinal direction of the DMD 50 are arranged in the width direction (for example, 756 sets). However, as shown in FIG. 3B, The pitch P ₂ of the scan locus (scan line) of the exposure beam 53 by each micromirror is smaller than the pitch P ₁ of the scan line when the DMD 50 is not inclined by inclining the DMD 50 And the resolution can be greatly improved. On the other hand, since the inclination angle of the DMD 50 is small, the scan width W ₂ when the DMD 50 is inclined and the scan width W ₁ when the DMD 50 is not inclined are approximately the same.

Next, a method of increasing the modulation speed in the optical modulation means (hereinafter referred to as &quot; high-speed modulation &quot;) will be described.

It is preferable that the light modulating means is capable of controlling any of the n grabbing portions successively arranged among the n graveyards according to the pattern information. The data processing speed of the optical modulating means is limited and the modulation speed per one line is determined in proportion to the number of mounds to be used. Therefore, by using only fewer than n successively arranged mound portions, It accelerates.

Hereinafter, the fast modulation will be further described with reference to the drawings.

When the DMD 50 is irradiated with the laser beam B from the fiber array light source 66 and the micromirror of the DMD 50 is in the ON state, the reflected laser light is guided by the lens system 54, 150). In this way, the laser beam emitted from the fiber array light source 66 is turned on and off for each grave, and the pattern forming material 150 is exposed with a grave unit (exposure area 168) approximately equal to the number of gravestones of the DMD 50 do. The pattern forming material 150 is moved at a constant speed together with the stage 152 so that the pattern forming material 150 is sub-scanned by the scanner 162 in the direction opposite to the stage moving direction, An exposed region 170 is formed in every stripe.

In this example, as shown in Figs. 4A and 4B, in the DMD 50, 768 sets of micromirrors in which 1024 micro mirrors are arranged in the main scanning direction are arranged in the sub-scanning direction. In this example, however, ) (See Fig. 12), only some of the micro mirror columns (for example, 1024 x 256 columns) are driven.

In this case, as shown in FIG. 4A, a micromirror array disposed at the center of the DMD 50 may be used, or a micromirror array disposed at the end of the DMD 50 as shown in FIG. 4B may be used. When a defect occurs in some of the micro mirrors, the micro mirror column to be used may be appropriately changed depending on the situation, such as using a micro mirror column in which no defect occurs.

The data processing speed of the DMD 50 is limited, and the modulation speed per line is determined in proportion to the number of graveyards to be used. Therefore, by using only some micro mirror columns, the modulation speed per line is increased. On the other hand, in the case of the exposure system in which the exposure head is moved relative to the exposure surface continuously, it is not necessary to use all the gravestones in the sub-scan direction.

When the rear end of the pattern forming material 150 is detected by the sensor 164 and the stage 162 is stopped by the stage driving device 304, Returning to the origin at the most upstream side of the gate 160 along the guide 158 and again moving along the guide 158 from the upstream side of the gate 160 to the downstream side at a constant speed.

For example, when only 384 sets of 768 sets of micromirror columns are used, modulation can be performed twice faster per line as compared with the case where all 768 sets are used. When only 256 sets of 768 sets of micromirror columns are used, modulation can be performed three times faster per line as compared with the case where all 768 sets are used.

As described above, according to the pattern forming method of the present invention, DMDs in which 768 sets of micro mirror columns in which 1,024 micro mirrors are arranged in the main scanning direction are arranged in the sub-scanning direction are provided, but only some micro mirror columns So that the modulation speed per line is faster than in the case where all the micromirror columns are driven.

Although an example of partially driving the micromirrors of the DMD has been described, it is also possible to arrange such that on the substrate longer than the length in the direction corresponding to the predetermined direction the length in the direction intersecting the predetermined direction, The number of micromirrors for controlling the angle of the reflection surface is reduced even if an elongated DMD having a plurality of changeable micromirrors arranged in two dimensions is used, so that the modulation speed can be similarly increased.

As the exposure method, it is preferable that the exposure light and the photosensitive layer are moved while relatively moving. In this case, it is preferable to use the exposure light in combination with the high-speed modulation. Thus, high-speed exposure can be performed in a short time.

5A and 5B, the entire surface of the pattern forming material 150 may be exposed by one scanning in the X direction by the scanner 162. As shown in FIGS. 6A and 6B, The pattern formation material 150 is scanned in the X direction by the scanner 162 and the scanner 162 is moved by one step in the Y direction to perform scanning in the X direction, The entire surface of the pattern forming material 150 may be exposed. Further, in this example, the scanner 162 has 18 exposure heads 166. Further, the exposure head has at least the light irradiating means and the light modulating means.

The exposure is performed with respect to a part of the photosensitive layer so that a part of the area is cured. In the developing step described later, the uncured areas other than the cured area are removed to form a pattern.

Next, an example of a pattern forming apparatus including the light modulating means will be described with reference to the drawings.

As shown in Fig. 7, the pattern forming apparatus including the light modulating means includes a flat stage 152 for holding a sheet-like pattern forming material (laminate) 150 on the surface and holding the same.

On the upper surface of the thick plate-like mounting table 156 supported by the four leg portions 154, two guides 158 extending along the stage moving direction are provided. The stage 152 is arranged so that its longitudinal direction faces the stage moving direction, and is supported so as to be reciprocatable by a guide 158. Further, the pattern forming apparatus has a driving device (not shown) for driving the stage 152 along the guide 158.

In the center of the mounting table 156, a gate 160 in the shape of a chisel is provided so as to extend over the movement path of the stage 152. Each end of the gate 160 in the U-shape is fixed to both sides of the mounting base 156. A scanner 162 is provided on one side of the gate 160 and a plurality of (e.g., two) detecting sensors (not shown) for detecting the leading and trailing edges of the pattern forming material 150 164 are installed. The scanner 162 and the detection sensor 164 are respectively attached to the gate 160 and fixedly disposed above the movement path of the stage 152. [ The scanner 162 and the detection sensor 164 are connected to a controller (not shown) for controlling them.

8 and 9B, the scanner 162 includes a plurality of (for example, fourteen) exposure heads 166 arranged in an approximately matrix of m rows and n columns (for example, three rows and five columns) . In this example, in relation to the width of the pattern forming material 150, four exposure heads 166 are arranged in the third row. When each of the exposure heads arranged in the n-th column of the m-th row is indicated, the exposure head 166 _mn is used.

The exposure area 168 by the exposure head 166 is rectangular in shape with the short side in the sub scanning direction. Accordingly, in accordance with the movement of the stage 152, the patterned material 150 is provided with a striped exposed area 170 for each of the exposure heads 166. In the case of representing the exposure area by the respective exposure heads arranged in the n-th column on the m-th row, the exposure area is denoted by 168 _mn .

As shown in Figs. 9A and 9B, each of the exposure heads of each row arranged in a line is arranged in a predetermined direction in the arrangement direction so that the striped exposure area 170 is arranged in a direction orthogonal to the sub- (A natural multiple of the long side of the exposure area, in this example, two times). Therefore, the exposure is not part can be between the first row of the exposure area (168 ₁₁₎ and the exposed area (168 ₁₂₎ is to be exposed by an exposure area (168 ₂₁₎ and _the exposed area (168 ₃₁₎ of the third row of the second row .

As shown in Figs. 10 and 11, each of the exposure heads 166 ₁₁ to 166 _mn is a spatial light modulator that modulates the incident light beam according to the pattern information by the light modulating means (each spatial light modulating element) And a digital micromirror device (DMD) 50 made by Mentz. The DMD 50 is connected to the controller 302 (see Fig. 12) having a data processing section and a mirror drive control section. The data processing section of the controller 302 generates a control signal for driving and controlling each micromirror in the area to be controlled by the DMD 50 for each exposure head 166 based on the inputted pattern information. The area to be controlled will be described later. The mirror drive control unit controls the angle of the reflecting surface of each micromirror of the DMD 50 for each of the exposure heads 166 based on the control signal generated by the pattern information processing unit. The control of the angle of the reflecting surface will be described later.

A fiber array light source 66 having a laser emitting portion in which the emitting end of the optical fiber is arranged in a line along a direction corresponding to the long side direction of the exposure area 168 is provided on the light incident side of the DMD 50, A lens system 67 for correcting the laser light emitted from the laser light source 66 onto the DMD and a mirror 69 for reflecting the laser light transmitted through the lens system 67 toward the DMD 50 are arranged in this order . In Fig. 10, the lens system 67 is schematically shown.

11, the lens system 67 includes a condenser lens 71 for condensing the laser light B as the illumination light emitted from the fiber array light source 66, a condenser lens 71 for condensing the laser light B as the optical path of the light passing through the condenser lens 71 (Hereinafter referred to as a rod integrator) 72 and an imaging lens 74 disposed on the front side of the rod integrator 72, that is, on the mirror 69 side . The condenser lens 71, the rod integrator 72 and the image forming lens 74 are arranged so that the laser light emitted from the fiber array light source 66 is irradiated to the DMD 50 as a light beam close to the parallel light, . The shape and operation of the rod integrator 72 will be described later in detail.

The laser beam B emitted from the lens system 67 is reflected by the mirror 69 and irradiated to the DMD 50 through the TIR (total reflection) prism 70. In Fig. 10, this TIR prism 70 is omitted.

An imaging optical system 51 for imaging the laser beam B reflected by the DMD 50 onto the pattern forming material 150 is disposed on the light reflecting side of the DMD 50. [ Although this imaging optical system 51 is schematically shown in Fig. 10, as shown in detail in Fig. 11, the imaging optical system 51 includes a first imaging optical system made up of lens systems 52 and 54 and a second imaging optical system made up of lens systems 57 and 58 A microlens array 55 sandwiched between these imaging optical systems, and an aperture array 59.

The microlens array 55 is formed by arranging a plurality of microlenses 55a corresponding to each graveyard of the DMD 50 two-dimensionally. In this example, as described later, only 1024 x 256 columns out of the 1024 x 768 columns of the DMD 50 are driven, so that the micro lenses 55a are arranged in 1024 x 256 columns. The arrangement pitch of the microlenses 55a is 41 mu m in both the longitudinal direction and the lateral direction. The microlens 55a has, for example, a focal length of 0.19 mm and an NA (numerical aperture) of 0.11, and is formed of an optical glass BK7. The shape of the microlens 55a will be described later in detail. The beam diameter of the laser beam B at the position of each microlens 55a is 41 占 퐉.

The aperture array 59 is formed with a plurality of apertures 59a corresponding to the microlenses 55a of the microlens array 55. The diameter of the aperture 59a is, for example, 10 占 퐉.

The first imaging optical system expands the image by the DMD 50 three times and forms an image on the microlens array 55. Then, the second imaging optical system magnifies an image obtained through the microlens array 55 by a factor of 1.6 to form an image on the pattern forming material 150 and project it. Therefore, as a whole, the image formed by the DMD 50 is magnified by 4.8 times and is projected on the pattern forming material 150.

A prism pair 73 is disposed between the second imaging optical system and the pattern forming material 150 and the prism pair 73 is vertically moved in Fig. So that the focus of the image can be adjusted. In the same figure, the pattern forming material 150 is sub-scan fed in the direction of arrow F.

The grave portion is not particularly limited as long as it can receive and emit light from the light irradiating means and can be appropriately selected in accordance with the purpose. For example, the pattern formed by the pattern forming method of the present invention is an image In the case of a pattern, it is a pixel, and when the light modulating means includes a DMD, it is a micromirror.

The number (n) of graveyard portions of the optical modulation element is not particularly limited and may be appropriately selected in accordance with the purpose.

The arrangement of the graveyard in the optical modulation element is not particularly limited and can be appropriately selected in accordance with the purpose. For example, it is preferable that the grains are arranged in two-dimensional form, and more preferably arranged in a lattice pattern.

<Light irradiation means>

The light irradiating means is not particularly limited and may be appropriately selected according to the purpose. Examples of the light irradiating means include a fluorescent tube such as a (second) high pressure mercury lamp, xenon, etc., a carbon arc lamp, a halogen lamp or a radiator, Or a means capable of irradiating two or more lights, and among these, a means capable of irradiating two or more light beams is preferable.

Examples of the light irradiated from the light irradiation means include an electromagnetic wave that transmits the support and activates a photopolymerization initiator or a sensitizer to be used when visible light is irradiated through a support, A laser beam, and the like. Of these, a laser beam is preferable, and a laser (hereinafter sometimes referred to as a "multiplexed laser") in which two or more lights are synthesized is more preferable. Even when the support is peeled and light irradiation is performed, the same light can be used.

As the wavelength of the visible light from the outside, for example, 300 to 1500 nm is preferable, 320 to 800 nm is more preferable, and 330 nm to 650 nm is particularly preferable.

The wavelength of the laser beam is preferably, for example, 200 to 1500 nm, more preferably 300 to 800 nm, further preferably 330 nm to 500 nm, and particularly preferably 400 nm to 450 nm.

Means capable of irradiating the multiplexing laser include, for example, a plurality of lasers, a multimode optical fiber, and a means having an aggregating optical system for condensing the laser beams respectively irradiated from the plurality of lasers and coupling them to the multimode optical fiber desirable.

Hereinafter, the means (fiber array light source) capable of irradiating the multiplexing laser will be described with reference to the drawings.

27A, the fiber array light source 66 includes a plurality of (for example, 14) laser modules 64, and one end of the multimode optical fiber 30 is connected to each laser module 64 Lt; / RTI &gt; The optical fiber 31 having the same core diameter as that of the multimode optical fiber 30 and having a clad diameter smaller than that of the multimode optical fiber 30 is coupled to the other end of the multimode optical fiber 30. 27B, seven ends of the multimode optical fiber 31 on the opposite side to the optical fiber 30 are arranged along the main scanning direction orthogonal to the sub-scanning direction, and are arranged in two rows to form laser output portions 68 ).

27B, the laser output portion 68 composed of the end portion of the multimode optical fiber 31 is fitted and fixed to two support plates 65 whose surfaces are flat. It is preferable that a transparent shielding plate such as glass is disposed on the light emission end face of the multimode optical fiber 31 for protection thereof. The optical emission face of the multimode optical fiber 31 is easy to collect due to its high optical density and is liable to deteriorate. However, by disposing the above-described protection plate, it is possible to prevent dust from adhering to the end face and delay deterioration.

In this example, since the outgoing ends of the optical fibers 31 having a small clad diameter are arranged in one line without a gap, the multimode optical fiber 30 is stacked between the adjacent two multimode optical fibers 30 in the portion having a large clad diameter , The output end of the optical fiber 31 coupled to the stacked multimode optical fiber 30 is positioned between the two output ends of the optical fiber 31 coupled to the adjacent two multimode optical fibers 30 in the portion where the clad diameter is large Respectively.

28, for example, an optical fiber 31 having a small clad diameter of 1 to 30 cm in length is attached to the tip end of the multimode optical fiber 30 having a large clad diameter on the laser beam output side, . &Lt; / RTI &gt; The two optical fibers are fused such that the incident end face of the optical fiber 31 is fused so that the central axes of both optical fibers coincide with the outgoing end face of the multimode optical fiber 30. As described above, the diameter of the core 31a of the optical fiber 31 is the same as the diameter of the core 30a of the multimode optical fiber 30.

Alternatively, a short optical fiber in which an optical fiber having a small clad diameter is fused to an optical fiber having a short length and a large clad diameter may be coupled to the output end of the multimode optical fiber 30 through a ferrule or an optical connector. By using a connector or the like to be detachably coupled, it becomes easy to replace the tip portion, for example, when the optical fiber having a small clad diameter is broken, and the cost required for maintenance and repair of the exposure head can be reduced. Hereinafter, the optical fiber 31 may be referred to as an emission end of the multimode optical fiber 30 in some cases.

The multimode optical fiber 30 and the optical fiber 31 may be either a step index type optical fiber, a grained index type optical fiber, or a composite type optical fiber. For example, a step index type optical fiber manufactured by Mitsubishi Denki Kogyo Co., Ltd. can be used. In the present embodiment, the multimode optical fiber 30 and the optical fiber 31 are step index-type optical fibers, and the multimode optical fiber 30 has a clad diameter of 125 m, a core diameter of 50 m, NA of 0.2, = 99.5% or more, and the optical fiber 31 has a clad diameter = 60 占 퐉, a core diameter = 50 占 퐉, and NA = 0.2.

Generally, in the laser light of the infrared region, if the clad diameter of the optical fiber is made small, the propagation loss increases. Therefore, a preferable clad diameter is determined according to the wavelength band of the laser beam. However, the shorter the wavelength, the smaller the propagation loss. In the case of the laser light having a wavelength of 405 nm emitted from the GaN semiconductor laser, the thickness of the clad {(clad diameter - core diameter) / 2} The propagation loss does not substantially increase even when the propagation time is about one-half of that in the case of propagating infrared light having a wavelength band of 1.5 mu m for communication. Therefore, the clad diameter can be reduced to 60 占 퐉.

However, the clad diameter of the optical fiber 31 is not limited to 60 mu m. The cladding diameter of the optical fiber used in the conventional fiber array light source is 125 탆. However, since the depth of focus becomes deeper as the clad diameter becomes smaller, the clad diameter of the multimode optical fiber is preferably 80 탆 or less, more preferably 60 탆 or less And more preferably 40 m or less. On the other hand, the clad diameter of the optical fiber 31 is preferably 10 占 퐉 or more because the core diameter is required to be 3 to 4 占 퐉 or more.

The laser module 64 is composed of a multiplexed laser light source (fiber array light source) shown in Fig. This multiplexed laser light source is composed of a plurality of (for example, seven) chip-on-chip multimode or single mode GaN semiconductor lasers LD1, LD2, LD3, LD4, LD5, LD6 13, 14, 15, 16 and 17 provided corresponding to the respective GaN semiconductor lasers LD1 to LD7, one condenser lens 20, one condenser lens 20, Mode multi-mode optical fiber 30. The number of semiconductor lasers is not limited to seven. For example, 20 semiconductor laser beams can be incident on a multimode optical fiber having a clad diameter of 60 占 퐉, a core diameter of 50 占 퐉, and NA = 0.2, thereby realizing the required light quantity of the exposure head, .

The GaN-based semiconductor lasers LD1 to LD7 have a common oscillation wavelength (for example, 405 nm) and a maximum output power is substantially common (for example, 100 mW for a multimode laser and 30 mW for a single mode laser). As the GaN semiconductor lasers (LD1 to LD7), a laser having an oscillation wavelength other than 405 nm in the wavelength range of 350 to 450 nm may be used.

As shown in Figs. 30 and 31, the above-mentioned multiplexing laser light source is housed in a package 40 on a box with its upper part opened together with other optical elements. The package 40 is provided with a package cover 41 that is designed to close the opening and a sealing gas is introduced after the degassing process to close the opening of the package 40 with the package cover 41, And the package cover 41, the hermetic laser light source is hermetically sealed.

A base plate 42 is fixed to the bottom surface of the package 40. A condenser lens holder 45 for holding the heat block 10 and the condenser lens 20 is provided on the upper surface of the base plate 42, A fiber holder 46 for holding an incident end of the multimode optical fiber 30 is attached. The outgoing end of the multimode optical fiber 30 is drawn out of the package from the opening formed in the wall surface of the package 40.

A collimator lens holder 44 is attached to the side surface of the heat block 10, and the collimator lenses 11 to 17 are held. An opening is formed in the lateral wall surface of the package 40, and a wiring 47 for supplying a driving current to the GaN-based semiconductor laser LD1 to LD7 through the opening is drawn out of the package.

31, only the GaN-based semiconductor laser LD7 among the plurality of GaN-based semiconductor lasers is numbered so as to avoid the burden of the drawing, and only the collimator lens 17 among the plurality of collimator lenses is numbered.

Fig. 32 shows the frontal shape of the attachment portion of the collimator lenses 11 to 17. Fig. Each of the collimator lenses 11 to 17 is formed in such a shape that a region including an optical axis of a circular lens having an aspherical surface is slit in a plane parallel to the plane. The elongated collimator lens can be formed, for example, by molding a resin or an optical glass. The collimator lenses 11 to 17 are closely arranged in the arrangement direction of the light emitting points so that the longitudinal direction thereof is orthogonal to the arrangement direction of the light emitting points of the GaN semiconductor lasers LD1 to LD7 (the right and left direction in Fig. 32).

On the other hand, as the GaN semiconductor lasers (LD1 to LD7), an active layer having an emission width of 2 mu m is provided, and diffusion angles in a direction parallel to the active layer and in a direction perpendicular to the active layer are respectively 10 DEG and 30 DEG, A laser for generating the lights B1 to B7 is used. These GaN semiconductor lasers (LD1 to LD7) are arranged so that light emitting points are arranged in one line in a direction parallel to the active layer.

Therefore, the laser beams B1 to B7 generated from the respective light emitting points are aligned in the longitudinal direction with respect to the respective collimator lenses 11 to 17 having the elongated shape as described above, and the direction in which the diffusion angle is small (The direction orthogonal to the longitudinal direction). That is, the widths of the collimator lenses 11 to 17 are 1.1 mm and the length is 4.6 mm, and the beam diameters in the horizontal direction and the vertical direction of the laser beams B1 to B7 incident on the collimator lenses 11 to 17 are 0.9 mm and 2.6 mm, respectively . Further, the respective collimator lenses (11-17) has a focal length _{f 1 = 3㎜, NA = 0.6} , a lens arrangement pitch = 1.25㎜.

The condensing lens 20 has a configuration in which an area including an optical axis of a circular lens having an aspherical surface is slit in a plane parallel to the longitudinal direction of the collimator lenses 11 to 17, And is formed in a short shape. This condensing lens 20 has a focal length f ₂ = 23 mm and NA = 0.2. The condenser lens 20 is also formed by, for example, molding resin or optical glass.

Further, since a high-intensity fiber array light source in which the emitting end of the optical fiber of the multiplexed laser light source is arranged in an array over the array is used in the light irradiating means for illuminating the DMD, a pattern forming apparatus with high output and deep focal depth can be realized . In addition, since the output of each fiber array light source is increased, the number of fiber array light sources required for obtaining a desired output is reduced, and the cost of the pattern forming apparatus is reduced.

Further, since the clad diameter of the emitting end of the optical fiber is made smaller than the clad diameter of the incident end, the diameter of the light emitting portion becomes smaller, and the fiber array light source has a higher brightness. Thus, a pattern forming apparatus having a deeper depth of focus can be realized. For example, even in the case of an ultra-high-resolution exposure with a beam diameter of 1 탆 or less and a resolution of 0.1 탆 or less, a deep focal depth can be obtained, and high-speed and high-definition exposure becomes possible. Therefore, it is preferable for an exposure process of a thin film transistor (TFT) in which a high resolution is required.

The light irradiating means is not limited to a fiber array light source having a plurality of the multiplexing laser light sources. For example, the light irradiating means may include one optical fiber for emitting laser light incident from a single semiconductor laser having one light emitting point A fiber array light source in which one fiber light source is arrayed can be used.

33, a plurality of (for example, seven) semiconductor lasers LD1 to LD7 on a chip are arranged on the heat block 100, May be used. Further, a chip-based multicavity laser 110 shown in Fig. 34A, in which a plurality of (for example, five) emission points 110a are arranged in a predetermined direction, is known. The multi-cavity laser 110 can easily arrange the light emitting points with high positional accuracy as compared with the case of arranging the semiconductor lasers on the chip, so that it is easy to combine the laser light emitted from each light emitting point. However, if the number of light emitting points is increased, warping of the multicavity laser 110 is liable to occur at the time of manufacturing the laser, so that the number of the light emitting points 110a is preferably 5 or less.

34B, a plurality of multicavity lasers 110 are arranged on the heat block 100 in the same direction as the arrangement direction of the light emitting points 110a of the respective chips, as shown in Fig. 34B, Direction can be used as a laser light source.

Further, the multiplexing laser light source is not limited to the combination of the laser light emitted from the semiconductor lasers on a plurality of chips. For example, as shown in Fig. 21, a multiplexed laser light source including a multicavity laser 110 on a chip having a plurality of (for example, three) emission points 110a can be used. This multiplexed laser light source is composed of a multi-cavity laser 110, a multimode optical fiber 130, and a condenser lens 120. The multi-cavity laser 110 can be constituted by, for example, a GaN-based laser diode having an oscillation wavelength of 405 nm.

Each of the laser beams B emitted from each of the plurality of emission points 110a of the multi-cavity laser 110 is condensed by the condenser lens 120 and is incident on the core 130a of the multimode optical fiber 130 . The laser light incident on the core 130a is propagated in the optical fiber, and the laser light is multiplexed and emitted.

A plurality of light emission points 110a of the multi-cavity laser 110 are arranged in a substantially same width as the core diameter of the multimode optical fiber 130, By using a rod lens that collimates only a convex lens having a focal distance substantially equal to the diameter or an exit beam from the multicavity laser 110 only in a plane perpendicular to the active layer of the multimode optical fiber 130 ) Can be increased.

35, a plurality (for example, nine) of laser beams are emitted on the heat block 111 by using the multicavity laser 110 having a plurality of (for example, three) It is possible to use a multiplex laser light source having a laser array 140 in which the multi-cavity lasers 110 are arranged at equal intervals from each other. The plurality of multicavity lasers 110 are arranged and fixed in the same direction as the arrangement direction of the emission points 110a of the respective chips.

This multiplexed laser light source includes a laser array 140, a plurality of lens arrays 114 arranged in correspondence with the respective multicavity lasers 110, and a plurality of laser arrays 114 arranged between the laser arrays 140 and the plurality of lens arrays 114 A single rod lens 113, a single multimode optical fiber 130, and a condenser lens 120. The lens array 114 has a plurality of microlenses corresponding to the emission points of the multicavity lasers 110.

The laser beams B emitted from each of the plurality of light emission points 10a of the plurality of multicavity lasers 110 are condensed in a predetermined direction by the rod lenses 113, Are collimated by the respective microlenses of the second lens group. The collimated laser light L is condensed by the condenser lens 120 and is incident on the core 130a of the multimode optical fiber 130. [ The laser light incident on the core 130a is propagated in the optical fiber, and the laser light is multiplexed and emitted.

An example of another multiplexed laser light source is also shown. As shown in Figs. 36A and 36B, this multiplexing laser light source is provided with a heat block 182 having an L-shaped cross section in the direction of the optical axis mounted on a substantially rectangular heat block 180, Respectively. A plurality of (for example, two) multicavity lasers 110 in which a plurality of light emitting points (for example, five) are arranged in an array are arranged on the upper surface of the L-shaped heat block 182, Are arranged at equal intervals in the same direction as the arrangement direction of the points 110a.

A concave portion is formed in a substantially rectangular heat block 180. A plurality of light emitting points (for example, five light emitting points) arranged in an array on the space side of the heat block 180 Cavity laser 110 is arranged so that its light emitting point is located on the same vertical plane as the light emitting point of the laser chip disposed on the upper surface of the heat block 182. [

A collimator lens array 184 in which a collimator lens is arranged corresponding to the light emission point 110a of each chip is disposed on the laser light emission side of the multicavity laser 110. [ The collimator lens array 184 is arranged so that the longitudinal direction of each collimator lens and the direction in which the diffusing angle of laser light is large (fast axis direction) coincide and the width direction of each collimator lens coincides with the direction Respectively. As described above, by integrating the collimator lenses into an array, the efficiency of space utilization of the laser light is improved, the power of the multiplexed laser light source is increased, and the number of parts is reduced and the cost can be reduced.

A single multimode optical fiber 130 and a condenser lens 120 for focusing and coupling the laser beam to the incident end of the multimode optical fiber 130 are arranged on the laser beam output side of the collimator lens array 184 .

The laser beams B emitted from each of the plurality of emission points 10a of the plurality of multicavity lasers 110 arranged on the laser blocks 180 and 182 are collimated by the collimator lens array 184 Is condensed by the condenser lens 120, and is incident on the core 130a of the multimode optical fiber 130. [ The laser light incident on the core 130a is propagated in the optical fiber, and the laser light is multiplexed and emitted.

As described above, the multiplexed laser light source can achieve high output by means of multi-stage arrangement of the multicavity laser and arraying of the collimator lens. The use of this multiplexed laser light source makes it possible to construct a fiber array light source or a bundled fiber light source of higher luminance, and thus is particularly preferable as a fiber light source constituting the laser light source of the pattern forming apparatus of the present invention.

In addition, it is possible to construct the laser module in which the respective multiplexed laser light sources are accommodated in the casing and the emitting end of the multimode optical fiber 130 is drawn out from the casing.

Further, although an example has been described in which the fiber array light source is increased in brightness by combining another optical fiber whose core diameter is the same as that of the multimode optical fiber and whose clad diameter is smaller than that of the multimode optical fiber at the output end of the multimode optical fiber of the multiplexed laser light source, For example, multimode optical fibers having cladding diameters of 125 mu m, 80 mu m, 60 mu m, and the like may be used without coupling other optical fibers to the emitting end.

Hereinafter, the pattern forming method of the present invention will be further described.

The laser beams B1 and B2 emitted from the respective GaN semiconductor lasers LD1 to LD7 constituting the multiplexing laser light source of the fiber array light source 66 in the divergent light state in the exposure head 166 of the scanner 162, , B3, B4, B5, B6, and B7 are collimated by the corresponding collimator lenses 11 to 17, respectively. The collimated laser beams B1 to B7 are condensed by the condenser lens 20 and converged on the incidence end face of the core 30a of the multimode optical fiber 30. [

In this example, the condensing optical system is constituted by the collimator lenses 11 to 17 and the condensing lens 20, and the multiplexing optical system and the multimode optical fiber 30 constitute a multiplexing optical system. That is, the laser beams B1 to B7 condensed by the condenser lens 20 as described above are incident on the core 30a of the multimode optical fiber 30 and are propagated in the optical fiber, And is output from the optical fiber 31 coupled to the emitting end of the multimode optical fiber 30.

In each laser module, when the coupling efficiency of the laser beams B1 to B7 to the multimode optical fiber 30 is 0.85 and the respective outputs of the GaN semiconductor lasers LD1 to LD7 are 30 mW, The multiplexed laser beam B having an output of 180 mW (= 30 mW x 0.85 x 7) can be obtained for each of the optical fibers 31. Therefore, the output from the laser outputting unit 68 in which the six optical fibers 31 are arranged in an array is about 1 W (= 180 mW x 6).

In the laser emitting portion 68 of the fiber array light source 66, the light emitting points having such high luminance are arranged in a line along the main scanning direction. Since the conventional fiber light source that couples the laser light from a single semiconductor laser to one optical fiber has a low output power, a desired output can not be obtained without arranging a plurality of rows. However, since the multiplexing laser light source has high output, The desired output can be obtained even in one column.

For example, in a conventional fiber light source in which a semiconductor laser and an optical fiber are combined one-to-one, a laser having an output of about 30 mW (milliwatts) is usually used as a semiconductor laser. As the optical fiber, a core diameter of 50 탆, a clad diameter of 125 탆, Mode optical fiber is used, it is necessary to bundle 48 (8x6) multimode optical fibers in order to obtain an output of about 1W (watt), and the area of the light emitting region is 0.62mm 2 (0.675mm x since 0.925㎜), the luminance at laser emitting portion 68 is ^{1.6 × 10 6 (W / ㎡} ), the optical fiber per brightness is ^{3.2 × 10 6 (W / ㎡} ).

On the other hand, when the light irradiating means is a means capable of irradiating a multiplexing laser, an output of about 1 W can be obtained with six multimode optical fibers, and the area of the light emitting region in the laser emitting portion 68 is 0.0081 mm & 0.325 mm x 0.025 mm), the brightness at the laser outputting section 68 is 123 x 10 ⁶ (W / m 2), and the brightness can be increased by about 80 times as compared with the conventional technique. Further, the luminance per one optical fiber is 90 × 10 ⁶ (W / m 2), and the brightness can be increased by about 28 times as compared with the conventional one.

Here, with reference to Figs. 37A and 37B, the difference in depth of focus between the conventional exposure head and the exposure head of this embodiment will be described. The diameter of the light emitting region of the bundled fiber light source of the conventional exposure head in the sub scanning direction is 0.675 mm and the diameter of the light emitting region of the fiber array light source of the exposure head in the sub scanning direction is 0.025 mm. 37A, in the conventional exposure head, since the light emitting area of the light irradiating means (bundled fiber light source) 1 is large, the angle of the light beam incident on the DMD 3 becomes large, and as a result, The larger the angle of the light beam is. Therefore, the beam diameter tends to become larger with respect to the light converging direction (deviation in the focus direction).

37B, since the diameter of the light emitting region of the fiber array light source 66 in the sub-scan direction is small in the exposure head in the pattern forming apparatus of the present invention, the light passes through the lens system 67 and passes through the DMD 50 The angle of the light beam incident on the scanning surface 56 becomes small. That is, the depth of focus is deepened. In this example, the diameter of the light emitting region in the sub-scan direction is about 30 times larger than the conventional one, and the depth of focus corresponding to the diffraction limit can be obtained. Therefore, it is preferable for exposure of a minute spot. The effect on the depth of focus is remarkably effective as the required light quantity of the exposure head is large. In this example, the size of one grave projected on the exposure surface is 10 占 퐉 占 10 占 퐉. The DMD is a reflection type spatial light modulation element, but FIGS. 37A and 37B are developed views for explaining the optical relationship.

Pattern information corresponding to the exposure pattern is input to a controller (not shown) connected to the DMD 50, and is temporarily stored in the frame memory in the controller. This pattern information is data indicating the density of each grave constituting the image by binary (presence or absence of dot recording).

The stage 152 on which the pattern forming material 150 is adhered to the surface is moved at a constant speed from the upstream side to the downstream side of the gate 160 along the guide 158 by a driving device not shown. When the tip of the pattern forming material 150 is detected by the detection sensor 164 attached to the gate 160 when the stage 152 passes under the gate 160, Line, and a control signal is generated for each exposure head 166 based on the pattern information read by the data processing unit. Then, the micromirrors of the DMD 50 are controlled on and off for each of the exposure heads 166 based on the generated control signal by the mirror drive control unit.

When the DMD 50 is irradiated with the laser light from the fiber array light source 66 and the micromirror of the DMD 50 is in the ON state, the reflected laser light is reflected by the lens system 54, And forms an image on the light-exiting surface 56. In this way, the laser beam emitted from the fiber array light source 66 is turned on and off for each grave, and the pattern forming material 150 is transferred to a grave unit (exposure area 168) which is approximately the same as the number of graves used for the DMD 50 Is exposed. The pattern forming material 150 is moved at a constant speed together with the stage 152 so that the pattern forming material 150 is sub-scanned by the scanner 162 in the direction opposite to the stage moving direction, An exposed region 170 is formed in every stripe.

<Micro Lens Array>

The exposure is preferably performed by passing the modulated light through a microlens array, or may be performed through an aperture array, an imaging optical system, or the like.

The microlens array is not particularly limited and may be appropriately selected in accordance with the purpose. For example, microlenses having aspherical surfaces capable of correcting aberration caused by deformation of the exit surface of the graveyard are preferably arranged .

The aspherical surface is not particularly limited and can be appropriately selected according to the purpose. For example, a toric surface is preferable.

Hereinafter, the microlens array, the aperture array, and the imaging optical system will be described with reference to the drawings.

13A shows a DMD 50, light irradiating means 144 for irradiating the DMD 50 with laser light, lens systems (imaging optical systems) 454 and 458 for magnifying and forming the laser light reflected by the DMD 50, A microlens array 472 in which a plurality of microlenses 474 are arranged corresponding to the respective grave portions of the DMD 50 and a plurality of apertures 478 corresponding to microlenses of the microlens array 472 are installed An aperture array 476, and a lens system (imaging optical system) 480, 482 for forming a laser beam that has passed through an aperture on an object surface 56.

Here, FIG. 14 shows the result of measurement of a planar view of the reflecting surface of the micromirror 62 constituting the DMD 50. As shown in FIG. In the figure, the same height positions of the reflection surfaces are connected by contour lines, and the pitch of the contour lines is 5 nm. The x and y directions shown in the figure are two diagonal directions of the micromirror 62, and the micromirror 62 rotates about the rotation axis extending in the y direction as described above. Figs. 15A and 15B show height position displacements of the reflecting surfaces of the micromirrors 62 along the x-direction and y-direction, respectively.

As shown in Figs. 14, 15A and 15B, there is a deformation on the reflecting surface of the micromirror 62, and particularly when attention is paid to the center of the mirror, a deformation in one diagonal direction (y direction) (x direction). For this reason, there may arise a problem that the shape of the laser beam B condensed at the microlens 55a of the microlens array 55 at the converging position is deformed.

In the pattern forming method of the present invention, the microlenses 55a of the microlens array 55 have a special shape different from the conventional one in order to prevent the above problem. Hereinafter, this point will be described in detail.

16A and 16B show the front and side shapes of the entire microlens array 55 in detail. In these drawings, the dimensions of the respective portions of the microlens array 55 are also written, and these units are mm. In the pattern forming method of the present invention, as described with reference to FIG. 4, the micro-mirror 62 of 1024 x 256 columns of the DMD 50 is driven, and the micro-lens array 55 corresponds to 1024 256 columns of the microlenses 55a arrayed in the longitudinal direction are arranged in parallel. In Fig. 16A, the arrangement order of the microlens arrays 55 is represented by j in the horizontal direction and k in the vertical direction.

17A and 17B show the front shape and side shape of one microlens 55a in the microlens array 55, respectively. In Fig. 17A, contour lines of the microlenses 55a are also shown. The end face of each microlens 55a on the light exit side has an aspherical shape for correcting aberration caused by deformation of the reflecting surface of the micromirror 62. [ More specifically, the microlens 55a is a toric lens, and has a curvature radius Rx = -0.125 mm in the optically corresponding direction in the x direction, a curvature radius Ry = -0.1 mm in the direction corresponding to the y direction to be.

Therefore, the condensed state of the laser beam B in the cross section parallel to the x direction and the y direction is schematically shown in Figs. 18A and 18B. That is, when the cross section in the x-direction and the cross section in the y-direction are compared, the radius of curvature of the microlens 55a is smaller and the focal length is shorter in the latter cross section.

Figs. 19A to 19D show the results of simulating the beam diameter in the vicinity of the condensing position (focus position) of the microlens 55a when the microlens 55a has the above-described shape. For comparison, FIGS. 20A to 20D show the results of simulation in which the microlens 55a has a spherical shape with a radius of curvature Rx = Ry = -0.1 mm. In the drawings, the value of z indicates the evaluation position of the microlens 55a in the focus direction as a distance from the beam emergence surface of the microlens 55a.

The surface shape of the microlens 55a used in the simulation is calculated by the following equation.

In the above formula, Cx denotes curvature in the x direction (= 1 / Rx), Cy denotes the curvature in the y direction (= 1 / Ry), X denotes the lens optical axis O in the x direction, And Y denotes the distance from the lens optical axis O with respect to the y direction.

19A to 19D and Figs. 20A to 20D, in the pattern forming method of the present invention, the focal length of the microlens 55a in the cross section parallel to the y direction is smaller than the focal distance in the cross section parallel to the x direction By using a toric lens, the deformation of the beam shape in the vicinity of the light condensing position is suppressed. Then, a more detailed image without deformation can be exposed to the pattern forming material 150. It can also be seen that the area of the beam diameter smaller in the present embodiment shown in Figs. 19A to 19D is wider, i.e., the depth of focus is larger.

When the magnitude of the deformation of the central portion in the x and y directions of the micromirror 62 is opposite to the above, the focal length in the section parallel to the x direction is smaller than the focal distance in the section parallel to the y direction When the microlens is constituted by a small toric lens, it is possible to expose the pattern forming material 150 to a finer image without deformation.

The aperture array 59 disposed in the vicinity of the condensing position of the microlens array 55 is arranged such that only the light passing through the microlens 55a corresponding thereto is incident on each of the apertures 59a. That is, since the aperture array 59 is provided, the light from the adjacent microlens 55a, which does not correspond to each aperture 59a, is prevented from being incident on each of the apertures 59a, and the extinction ratio is increased.

Originally, by reducing the diameter of the aperture 59a of the aperture array 59 provided for the above purpose to some extent, the effect of suppressing the deformation of the beam shape at the condensing position of the microlens 55a is also obtained. However, in such a case, the amount of light blocked by the aperture array 59 is further increased, and the light utilization efficiency is lowered. On the other hand, when the microlenses 55a are formed into an aspherical shape, the light is not blocked, and the light utilization efficiency is also kept high.

Further, in the pattern forming method of the present invention, the microlenses 55a may be a secondary aspherical shape or a higher order (quadratic, sixth order, ...) aspherical shape. By adopting the higher order aspherical shape, the beam shape can be further refined.

In the above-described embodiment, the microlens 55a has an aspheric surface (toric surface) on the light exit side. However, the microlens 55a has a spherical surface on one side and a microlens surface on the other side It is possible to obtain the same effect as that of the above-described embodiment.

In the embodiment described above, the micro lens 55a of the microlens array 55 is an aspherical surface for correcting aberration caused by the deformation of the reflecting surface of the micromirror 62. However, instead of adopting such an aspherical shape The same effect can be obtained even if each microlens constituting the microlens array has a refractive index distribution for correcting aberration caused by deformation of the reflecting surface of the micromirror 62. [

An example of such a microlens 155a is shown in Figs. 22A and 22B. 22A and 22B show the front and side surfaces of the microlens 155a. As shown in the figure, the outer shape of the microlens 155a is a parallel flat plate. The x and y directions in the figure are as described above.

23A and 23B schematically show the condensed state of the laser beam B in the cross section parallel to the x direction and the y direction by the microlens 155a. The microlenses 155a have a refractive index profile that gradually increases from the optical axis O toward the outside. In the figure, the broken lines in the microlenses 155a indicate that the refractive index of the microlenses 155a is shifted from the optical axis O to a predetermined value Indicating the changed position. As shown in the figure, in the section in the cross section parallel to the x direction and the section in the cross section parallel to the y direction, the ratio of change in the refractive index of the microlens 155a is larger in the latter section, have. It is possible to obtain the same effect as in the case of using the microlens array 55 by using a microlens array composed of such a refractive index distribution type lens.

17 and 18, a refractive index distribution as described above is imparted to the microlens having a surface shape of an aspherical surface, and by the surface shape and the refractive index distribution, The aberration caused by the deformation of the reflecting surface of the mirror 62 may be corrected.

In the embodiment described above, the aberration due to the deformation of the reflecting surface of the micromirror 62 constituting the DMD 50 is corrected. However, in the pattern forming method of the present invention using the spatial light modulation element other than the DMD , And when deformation exists on the surface of the graveyard portion of the spatial light modulation element, the present invention is applied to correct aberration caused by the deformation, and it is possible to prevent deformation from occurring in the beam shape.

Next, the imaging optical system will be further described.

In the exposure head, when the laser beam is irradiated from the light irradiating means 144, the cross sectional area of the beam line reflected by the DMD 50 in the ON direction is multiplied by the lens system 454 or 458 a plurality of times (for example, twice) . The enlarged laser light is condensed by each microlens of the microlens array 472 corresponding to each grave portion of the DMD 50 and passes through the corresponding aperture of the aperture array 476. [ The laser light having passed through the aperture is imaged on the surface 56 to be exposed by the lens system 480 or 482.

In this imaging optical system, the laser light reflected by the DMD 50 is magnified several times by the enlarged lenses 454 and 458 to be projected onto the surface 56, so that the entire image area is widened. At this time, if the microlens array 472 and the aperture array 476 are not disposed, as shown in Fig. 13B, the size of one grayscale (beam spot size) of each beam spot BS projected onto the surface 56 Becomes larger in accordance with the size of the exposure area 468, and the MTF (Modulation Transfer Function) characteristic of the sharpness of the exposure area 468 is lowered.

On the other hand, when the microlens array 472 and the aperture array 476 are disposed, the laser light reflected by the DMD 50 is reflected by the microlenses of the microlens array 472 And is condensed corresponding to the mausoleum portion. 13C, even when the exposure area is enlarged, the spot size of each beam spot BS can be reduced to a desired size (for example, 10 mu m x 10 mu m), and the MTF characteristic It is possible to prevent the deterioration of the photoresist layer and to perform high-definition exposure. The reason why the exposure area 468 is inclined is that the DMD 50 is inclined to eliminate the distance between graves.

Further, even if the beam is enlarged due to the aberration of the microlens, it is possible to form the beam so that the spot size on the surface 56 is constant by the aperture array, By passing through the array, it is possible to prevent crosstalk between adjacent graveyards.

Further, by using the high-intensity light source described later in the light irradiating means 144, the angle of the light beam incident on each microlens of the microlens array 472 from the lens 458 becomes small, so that a part of the light flux of the adjacent mausoleum It is possible to prevent incidence. That is, a high extinction ratio can be realized.

<Other optical systems>

The pattern formation method of the present invention may be used in combination with other optical systems suitably selected from known optical systems, and examples thereof include a light amount distribution correction optical system comprising a pair of combination lenses.

The light amount distribution correcting optical system changes the light beam width at each exit position so that the ratio of the light beam width at the central portion close to the optical axis to the light beam width at the peripheral portion is smaller than that at the incident side, When the DMD is irradiated, the light amount distribution on the surface to be irradiated is corrected so as to be substantially uniform. Hereinafter, the light amount distribution correcting optical system will be described with reference to the drawings.

First, as shown in FIG. 24A, the case where the total luminous flux width (total luminous flux width) (H0, H1) of the incident luminous flux and the luminous flux of emitted luminous flux is the same will be described. In Fig. 24A, the portions denoted by reference numerals 51 and 52 virtually represent the incident surface and the exit surface of the light amount distribution correcting optical system.

In the light amount distribution correcting optical system, it is assumed that the light fluxes h0 and h1 of the light flux incident on the central portion close to the optical axis Z1 and the light fluxes incident on the peripheral portion are the same (h0 = h1). The light amount distribution correcting optical system enlarges the light beam width h0 for the incident light flux at the central portion with respect to light having the same light beam width h0 and h1 at the incident side and conversely increases the light flux width h0 for the incident light flux at the peripheral portion, (h1). That is, h11 < h10 is set for the width h10 of the outgoing light flux in the central portion and the width h11 of the outgoing light flux in the peripheral portion. Quot; h11 / h10 &quot; of the light flux width at the peripheral portion with respect to the light flux width at the central portion at the light output side is smaller than the ratio (h1 / h0 = 1) at the incident side h11 / h10) &lt; 1 &gt;

By changing the luminous flux width in this way, the luminous flux in the central portion, which is usually increased in the luminous intensity distribution, can be utilized as a peripheral portion lacking in the amount of light, so that the light quantity distribution on the illuminated surface is made substantially uniform without lowering the utilization efficiency of the light. For example, the degree of uniformization is such that the light quantity variation within the effective area is within 30%, preferably within 20%.

The action and effect of the light amount distribution correcting optical system are the same in the case of changing the total luminous flux width on the incident side and the emission side (Figs. 24B and 24C).

Fig. 24B shows a case (H0 > H2) in which the entire light flux width H0 on the incidence side is reduced and output to the width H2. Even in such a case, the light amount distribution correcting optical system is configured such that the light beam width h10 at the central portion becomes larger than the peripheral portion at the incident side on the incident side and the light beam width (h0, h1) (h11) is smaller than the central portion. When the reduction rate of the light flux is considered, the reduction ratio with respect to the incident light flux at the central portion is made smaller than that at the peripheral portion, and the reduction ratio with respect to the incident light flux at the peripheral portion is made larger than that at the central portion. In this case as well, the ratio of the luminous flux width at the peripheral portion to the luminous flux width at the center portion becomes smaller than the ratio (h1 / h0 = 1) at the incidence side [(h11 / h10) <1].

Fig. 24C shows a case (H0 < H3) in which the entire luminous flux width H0 on the incident side is "enlarged" and outputted with a width H3. Even in such a case, the light amount distribution correcting optical system is configured such that the light beam width h10 at the central portion becomes larger than the peripheral portion at the incident side on the incident side and the light beam width (h0, h1) (h11) is smaller than the central portion. Considering the enlargement ratio of the luminous flux, the enlargement ratio with respect to the incident luminous flux at the central portion is made larger than that at the peripheral portion, and the enlargement ratio with respect to the incident luminous flux at the peripheral portion is made smaller than that at the central portion. In this case as well, the ratio h11 / h10 of the light flux width at the peripheral portion to the light flux width at the central portion becomes smaller than the ratio h1 / h0 = 1 at the incident side ((h11 / h10) <1).

In this way, the light amount distribution correcting optical system changes the light beam width at each exit position so that the ratio of the light beam width at the peripheral portion to the light beam width at the central portion close to the optical axis Z1 is made smaller on the exit side as compared with the incident side , The light flux having the same light flux width at the incidence side becomes larger at the exit side than at the peripheral portion and the light flux width at the peripheral portion becomes smaller than the central portion. As a result, the light flux in the central portion can be utilized as a peripheral portion, and a light flux cross-section in which the light amount distribution is substantially uniform can be formed without reducing the utilization efficiency of the optical system as a whole.

Next, an example of specific lens data of a pair of combination lenses used as the light amount distribution correcting optical system is shown. In this example, the lens data in the case where the light amount distribution on the cross section of the emitted light flux is Gaussian distribution, as in the case where the light irradiation means is a laser array light source. On the other hand, when one semiconductor laser is connected to the incident end of the single mode optical fiber, the light amount distribution of the outgoing light flux from the optical fiber becomes a Gaussian distribution. The pattern forming method of the present invention can also be applied to such a case. The present invention is also applicable to a case in which the core diameter of the multimode optical fiber is reduced to approach the configuration of the single mode optical fiber, or the like, so that the light amount at the central portion closer to the optical axis is larger than the light amount at the peripheral portion.

The basic lens data are shown in Table 1 below.

As can be seen from Table 1, the pair of combination lenses is composed of two aspheric lenses of rotational symmetry. When the first incident surface side of the first lens disposed on the light incidence side and the second incident surface side are defined as the first surface and the second surface, the first surface is aspherical. When the light incident side of the second lens disposed on the light emitting side is referred to as the third surface and the light emitting side surface is defined as the fourth surface, the fourth surface is aspherical.

In Table 1, the surface number Si represents the number of the i-th surface (i = 1 to 4), the curvature radius ri represents the curvature radius of the i-th surface, the surface interval di is the i- Represents the surface interval on the optical axis of the first surface. The unit of plane interval di value is millimeter (mm). The refractive index Ni represents the value of the refractive index with respect to the wavelength of 405 nm of the optical element having the i-th surface.

Aspheric data of the first and fourth surfaces are shown in Table 2 below.

The above-mentioned aspherical surface data is represented by a coefficient in the following formula (A) representing an aspherical shape.

The respective coefficients in the above formula (A) are defined as follows.

Z is the length (mm) of the waterline falling from the point on the aspheric surface at the position of the height rho from the optical axis to the tangential plane of the vertex of the aspheric surface (plane perpendicular to the optical axis)

ρ: distance from the optical axis (mm)

K: cone coefficient

C: paraxial curvature (1 / r, r: paraxial radius of curvature)

ai: Aspherical surface coefficient of the i-th order (i = 3 to 10)

In the numerical values shown in Table 2, the symbol &quot; E &quot; indicates that the numerical value subsequent to the symbol &quot; E &quot; is &quot; Multiplied by the numerical value. For example, "1.0E-02" indicates "1.0 × 10 ^-2 ".

26 shows the light amount distribution of the illumination light obtained by the pair of combination lenses shown in Tables 1 and 2 above. The horizontal axis represents coordinates from the optical axis, and the vertical axis represents the light amount ratio (%). For comparison, FIG. 25 shows the light amount distribution (Gaussian distribution) of the illumination light in the case where correction is not performed. As can be seen from Figs. 25 and 26, by performing correction with the light amount distribution correcting optical system, a substantially uniformized light amount distribution is obtained as compared with the case where correction is not performed. This makes it possible to perform exposure without deviation with uniform laser light without deteriorating the utilization efficiency of light.

[Other Process]

The other processes are not particularly limited and may be appropriately selected from the processes in the known pattern formation, and examples thereof include a development process, an etching process, a plating process, and the like. These may be used singly or in combination of two or more kinds.

The developing step is a step of exposing the photosensitive layer in the pattern forming material by the exposure step, curing the exposed area of the photosensitive layer, and then removing the uncured area to develop and form a pattern.

The above developing step can be preferably carried out, for example, by a developing means.

The developing means is not particularly limited as long as it can be developed using a developing solution, and can be appropriately selected in accordance with the purpose. For example, means for spraying the developing solution, means for applying the developing solution, means for soaking in the developing solution And the like. These may be used singly or in combination of two or more kinds.

Further, the developing means may have a developer exchanging means for exchanging the developer, a developer supplying means for supplying the developer, and the like.

The developing solution is not particularly limited and may be appropriately selected according to the purpose. Examples thereof include an alkaline solution, an aqueous developer, and an organic solvent. Of these, a weakly alkaline aqueous solution is preferable. Examples of the basic component of the weakly alkaline solution include lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium phosphate, potassium phosphate, sodium pyrophosphate , Potassium pyrophosphate, borax and the like.

The pH of the slightly alkaline aqueous solution is, for example, preferably about 8 to 12, more preferably about 9 to 11. Examples of the slightly alkaline aqueous solution include an aqueous solution of sodium carbonate or potassium carbonate in an amount of 0.1 to 5% by mass.

The temperature of the developing solution may be appropriately selected in accordance with the developability of the photosensitive layer, and is preferably about 25 占 폚 to 40 占 폚, for example.

The developing solution may contain a surfactant, a defoaming agent, an organic base (e.g., ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, triethylenepentamine, morpholine, triethanolamine, (For example, alcohols, ketones, esters, ethers, amides, lactones, etc.) may be used in combination. The developer may be a water-based developer obtained by mixing water or an aqueous alkali solution with an organic solvent, or may be an organic solvent alone.

The etching process may be performed by a method selected appropriately from known etching processing methods.

The etching solution used in the etching treatment is not particularly limited and may be appropriately selected according to the purpose. For example, when the metal layer is formed of copper, a solution of cupric chloride, a solution of ferric chloride, Solution, a hydrogen peroxide-based etching solution, and the like. Among them, a ferric chloride solution is preferable in terms of the etching factor.

By removing the pattern after the etching process by the etching process, a permanent pattern can be formed on the surface of the base.

The permanent pattern is not particularly limited and can be appropriately selected in accordance with the purpose. For example, a wiring pattern and the like are preferably used.

The plating process may be carried out by a well-selected plating process.

Examples of the plating treatment include solder plating such as copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high-speed solder plating, nickel plating such as nickel sulfate plating (nickel sulfate-nickel chloride plating), nickel sulfamate plating, And gold plating such as gold plating.

A permanent pattern can be formed on the surface of the substrate by removing the pattern after the plating process by the plating process and further removing unnecessary portions by an etching process or the like as necessary.

[Method for Producing Printed Circuit Board and Color Filter]

The pattern forming method of the present invention can be suitably used for the production of a printed wiring board, particularly for the production of a printed wiring board having a hole portion such as a through hole or a via hole, and a color filter. Hereinafter, a method of manufacturing a printed wiring board and a method of manufacturing a color filter using the pattern forming method of the present invention will be described

- Manufacturing method of printed wiring board -

Particularly, as a manufacturing method of a printed wiring board having a hole portion such as a through hole or a via hole, (1) a method for manufacturing a printed wiring board having a hole portion as a base, (2) curing the photosensitive layer by irradiating a desired area of the laminate opposite to the substrate with light, and (3) curing the photosensitive layer from the laminate to form a support The cushion layer and the barrier layer are removed, (4) the photosensitive layer in the laminate is developed, and the uncured portions in the laminate are removed to form a pattern.

The removal of the support in (3) may be carried out between (1) and (2) above instead of between (2) and (4) above.

Thereafter, in order to obtain a printed wiring board, a method of etching or plating the printed wiring board using the above-described pattern (for example, a known subtractive method or an additive method (for example, Semi-additive method, full additive method)]. Among them, the subtractive method is preferable in order to form a printed wiring board with an industrially advantageous tent. The cured resin remaining on the printed wiring board formation substrate after the above treatment is peeled off. In the case of the semi-additive method, a desired printed wiring board can be produced by etching the copper film portion again after peeling off. The multilayer printed wiring board can also be manufactured in the same manner as the above-mentioned method for producing the printed wiring board.

Next, a method of manufacturing a printed wiring board having a through hole using the above pattern forming material will be described.

First, a board for forming a printed wiring board having a through hole and whose surface is covered with a metal plating layer is prepared. Examples of the substrate for forming a printed wiring board include a substrate on which a copper plating layer is formed on an insulating substrate such as a copper-clad laminated substrate and a glass-epoxy or a substrate (laminated substrate) on which an interlayer insulating film is laminated and copper- Can be used.

Next, in the case of having a protective film on the pattern forming material, the protective film is peeled off, and the protective film is peeled off by using a pressure roller so that the photosensitive layer in the pattern forming material is in contact with the surface of the substrate for forming a printed wiring board (Lamination step). As a result, a laminate having the printed wiring board-forming substrate and the laminate in this order can be obtained.

The lamination temperature of the pattern forming material is not particularly limited and may be, for example, room temperature (15 to 30 ° C) or heating (30 to 180 ° C) desirable.

The roll pressure of the press roll is not particularly limited, and is preferably 0.1 to 1 MPa, for example.

The speed of the compression bonding is not particularly limited and is preferably 1 to 3 m / min.

The printed wiring board forming substrate may be preliminarily heated or may be laminated under pressure.

The laminate may be formed by laminating the pattern forming material on the substrate for forming a printed wiring board or by directly applying a photosensitive resin composition solution for forming the pattern forming material on the surface of the substrate for forming a printed wiring board, The barrier layer, the cushion layer, and the support may be laminated on the substrate for forming a printed wiring board by drying.

Next, the photosensitive layer is cured by irradiating light from the surface of the laminate opposite to the substrate. Further, at this time, the support, the cushion layer and the barrier layer may be peeled off and then exposed, if necessary (for example, when the light transmittance of the support is insufficient).

At this time, if the support, the cushion layer and the barrier layer have not yet been peeled off, the support, the cushion layer and the barrier layer are peeled from the laminate (peeling step).

Next, a non-cured region of the photosensitive layer on the printed wiring board formation substrate is dissolved and removed with a suitable developer to form a pattern of a cured layer for forming a wiring pattern and a metal layer for protecting a metal layer of a through hole, (A developing step).

After the development, a treatment for further accelerating the curing reaction of the cured portion may be performed by a post-heating treatment or a post-exposure treatment, if necessary. The development may be a wet developing method as described above or a dry developing method.

Subsequently, the metal layer exposed on the surface of the substrate for forming a printed wiring board is dissolved and removed by an etching solution (etching step). Since the opening portion of the through hole is covered with the hardened resin composition (tent film), the metal plating in the through hole remains in a predetermined shape without causing the etching solution to enter the through hole and corrode the metal plating in the through hole. Thus, a wiring pattern is formed on the printed wiring board formation board.

The etchant is not particularly limited and may be appropriately selected according to the purpose. For example, when the metal layer is formed of copper, a solution of cupric chloride, a ferric chloride solution, an alkali etching solution, a hydrogen peroxide- Among them, a ferric chloride solution is preferable in terms of the etching factor.

Next, the hardened layer is removed from the substrate for forming a printed wiring board using a strong alkaline aqueous solution or the like (a cured product removing step).

The base component in the strong alkaline aqueous solution is not particularly limited, and examples thereof include sodium hydroxide, potassium hydroxide and the like.

The pH of the aqueous strong alkaline solution is, for example, preferably about 12 to 14, more preferably about 13 to 14.

The strong alkali aqueous solution is not particularly limited, and for example, an aqueous solution of sodium hydroxide or potassium hydroxide in an amount of 1 to 10 mass% can be used.

The printed wiring board may be a printed wiring board having a multilayer structure.

The pattern forming material may be used not only in the etching process but also in the plating process. Examples of the plating method include solder plating such as copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high-speed solder plating, nickel plating such as nickel sulfate plating (nickel sulfate-nickel chloride plating), nickel sulfamide plating, hard gold plating, And gold plating such as gold plating.

- Manufacturing method of color filter -

In the case of attaching the photosensitive layer of the pattern forming material of the present invention to a substrate such as a glass substrate and peeling the support, the cushion layer and the barrier layer from the pattern forming material, the charged support (film) There is a problem that an unpleasant electric shock may be received or dust adheres to the charged support. For this reason, it is preferable to form a conductive layer on the support or perform treatment to impart conductivity to the support itself. When the conductive layer is formed on the support on the side opposite to the cushion layer, it is preferable to form the hydrophobic polymer layer in order to improve the damage resistance.

Next, a pattern forming material having a red photosensitive layer colored with red, green, blue and black as the photosensitive layer, a pattern forming material having a green photosensitive layer, a pattern forming material having a blue photosensitive layer, To form a pattern forming material having a layer. A red photosensitive layer is laminated on the surface of the substrate using the pattern forming material having the red photosensitive layer for a red color to form a laminate and then exposed and developed in the form of a phase to form red pixels. After forming red pixels, the laminate is heated to cure the uncured portions. This is similarly performed for green and blue pixels to form respective pixels.

The formation of the laminate may be performed by laminating the pattern forming material on the glass substrate or by directly applying a photosensitive resin composition solution or the like for producing the pattern forming material on the surface of the glass substrate, The barrier layer, the cushion layer, and the support may be laminated on the photosensitive layer. When three kinds of pixels of red, green, and blue are arranged, any arrangement such as a mosaic type, a triangle type, and a 4-pixel arrangement type may be used.

A pattern forming material having the black photosensitive layer is laminated on the surface on which the pixels are formed, and the back surface is exposed from the side where pixels are not formed and developed to form a black matrix. By heating the laminate on which the black matrix is formed, the uncured portions can be cured to produce a color filter.

Since the pattern forming method of the present invention uses the pattern forming material of the present invention, it is possible to form various patterns, to form a permanent pattern such as a wiring pattern, to form a liquid crystal structure such as a color filter, a columnar material, a rib material, a spacer, It can be suitably used for the production of members, holograms, micromachines, prophes and the like, and can be suitably used particularly for formation of high-precision wiring patterns. Since the pattern forming apparatus of the present invention is provided with the pattern forming material of the present invention, it is possible to form various patterns, to form a permanent pattern such as a wiring pattern, a liquid crystal structure such as a color filter, a columnar material, a rib material, a spacer, It can be suitably used for the production of members, holograms, micromachines, prophes and the like, and can be suitably used particularly for formation of high-precision wiring patterns.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

(Example 1)

A photosensitive resin composition solution having the following composition was applied to a polyethylene terephthalate film having a thickness of 20 占 퐉 as a support and dried to form a photosensitive layer having a thickness of 15 占 퐉 and then a protective film having a thickness of 20 占 퐉 Of a polyethylene film was laminated with a laminate to prepare the pattern forming material.

[Composition of photosensitive resin composition solution]

· Methacrylic acid / methyl methacrylate / styrene copolymer

[Copolymer composition ratio (mass ratio): 24/46/30, mass average molecular weight: 77,000,

 Acid value: 156 (mgKOH / g)] 15 parts by mass

7.0 parts by mass of a polymerizable monomer represented by the following structural formula (70)

7.0 parts by mass of adduct of hexamethylene diisocyanate and ½ mole ratio of tetraethylene oxide monomethacrylate

N-Methylacridone 0.11 parts by mass

2,2-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole 2.17 parts by mass

· 2-mercaptobenzimidazole 0.23 parts by mass

0.02 part by mass of malachite green oxalate

0.26 parts by mass of Ryuko crystal violet

Methyl ethyl ketone 40 parts by mass

· 20 parts by mass of 1-methoxy-2-propanol

The I / O value of the methacrylic acid / methyl methacrylate / styrene copolymer (copolymer composition (mass ratio): 24/46/30) as the binder was 0.645 as calculated above.

However, in the structural formula (70), m + n represents 10. The structural formula (70) is an example of the compound represented by the structural formula (35).

The protective film of the pattern forming material was peeled off from the surface of the copper clad laminate (without through hole, thickness: 12 mu m) having its surface polished, washed and dried as the substrate, (MODEL 8B-720-PH, manufactured by TAISEI LAMINATOR CO., LTD.) To prepare a laminate in which the above-mentioned copper-clad laminate, the photosensitive layer and the support were laminated in this order.

The compression conditions were a compression roll temperature of 105 DEG C, a compression roll pressure of 0.3 MPa, and a laminating speed of 1 m / min.

The laminate thus prepared was evaluated for developability, resolution, etchability, peelability of the cured pattern after etching, tent property, and exposure speed. The results are shown in Table 3.

<Developability>

The support was peeled from the laminate, and a 1 mass% sodium carbonate aqueous solution at 30 캜 was sprayed on the entire surface of the photosensitive layer on the copper clad laminate at a pressure of 0.15 MPa. After the spraying of the sodium carbonate aqueous solution started, The time required was measured, and this was regarded as the shortest developing time. The shorter the shortest developing time, the more excellent the developing property.

As a result, the shortest development time was 10 seconds.

<Resolution>

(1) Measurement of sensitivity

Using a pattern forming apparatus having a laser light source of 405 nm as the light irradiating means, the photosensitive layer of the pattern forming material in the laminate was irradiated with light from the support at a rate of 2 ^1/2 times at 0.1 mJ / A light energy amount of up to 100 mJ / cm &lt; 2 &gt; was irradiated with another light to expose a part of the photosensitive layer. The support was peeled off from the laminate, and an aqueous solution of sodium carbonate (30 DEG C, 1 mass%) was applied to the entire surface of the photosensitive layer on the copper clad laminate at a spray pressure of 0.15 MPa to evaluate the developability And the thickness of the remaining cured region was measured by dissolving and removing the uncured region. Then, the relationship between the amount of light irradiation and the thickness of the cured layer is plotted to obtain a sensitivity curve. The amount of light energy when the thickness of the cured region became 15 mu m from the thus obtained sensitivity curve was regarded as the amount of light energy necessary for curing the photosensitive layer. As a result, the amount of light energy required for curing the photosensitive layer was 3 mJ / cm 2. Further, the pattern forming apparatus has the light modulating means made of the DMD and includes the pattern forming material.

(2) Measurement of resolution

The laminate was prepared by the same method and under the same conditions as those for the evaluation of developability, and the laminate was allowed to stand at room temperature (23 DEG C, 55% RH) for 10 minutes. On the support of the obtained laminate, each line width was exposed at a line width of 5 占 퐉 to 20 占 퐉 every 1 占 퐉 in line / space = 1/1 using the pattern forming apparatus, And each line width was exposed every 탆. The amount of exposure at this time is the amount of light energy required for curing the photosensitive layer of the pattern forming material measured in the above-mentioned sensitivity measurement (1). After standing at room temperature for 10 minutes, the support was peeled from the laminate. An aqueous solution of sodium carbonate (30 占 폚, 1 mass%) was sprayed over the entire surface of the photosensitive layer on the copper-clad laminate for a time of twice the shortest developing time determined by the above (1) with spray pressure of 0.15 MPa, did. The surface of the thus obtained copper-clad laminate with the cured resin pattern was observed with an optical microscope, and the minimum line width without any abnormality such as clogging or twist in the line of the cured resin pattern was measured and used as the resolution. The smaller the resolution, the better.

<Etching Properties>

(Ferric chloride-containing etching solution, 40 ° Boome, solution temperature: 40 ° C) was applied to the surface of the exposed copper-clad laminate in the laminate using the laminate having the pattern formed in the measurement of the resolution, Was sprayed at 0.25 MPa for 36 seconds to dissolve and remove the copper layer of the exposed area not covered with the cured layer to perform the etching treatment. Subsequently, the formed pattern was removed by spraying an aqueous solution of 2% by mass of sodium hydroxide to prepare a printed wiring board having a wiring pattern of a copper layer as the permanent pattern on the surface. The wiring pattern on the printed wiring board was observed with an optical microscope, and the minimum line width of the wiring pattern was measured. The smaller the minimum line width, the higher the fine wiring pattern is, and the better the etching property.

<Peelability of Cured Pattern>

The photosensitive layer of the pattern forming material in the laminate was irradiated with light having a light energy amount of 10 mJ / cm 2 from the support side using a pattern forming apparatus having a 405 nm laser light source as the light irradiating means The entire surface of the photosensitive layer was cured by exposure. After standing at room temperature for 10 minutes, the support was peeled off from the laminate, and an aqueous solution of sodium carbonate was sprayed on the entire surface of the photosensitive layer of the laminate under the same conditions as the evaluation method for the resolution to develop the cured pattern, And dried. The copper clad laminate having the cured pattern thus obtained was immersed so as to lean against an aqueous solution of 3% by mass of sodium hydroxide.

The required time (peeling time) from the initiation of immersion of the copper-clad laminate having the cured pattern until the cured resin pattern on the copper-clad laminate was completely removed was measured and evaluated according to the following criteria. The shorter the peeling time, the better the peeling property.

-Evaluation standard-

○ ... Peel time within 60 seconds

△ ... Peeling time 60 ~ 300 sec

× ... Peel time is over 300 seconds

<Tent castle>

A laminate for tentability evaluation was prepared in the same manner as in the case of the above laminate except that the copper-clad laminate in the above-mentioned laminate was replaced with a copper-clad laminate having 200 through-holes each having a diameter of 2 mm. %) For 10 minutes. Next, the entire surface of the photosensitive layer of the laminate was exposed using the pattern forming apparatus on the support of the prepared laminate. The amount of exposure at this time is the amount of light energy required for curing the photosensitive layer of the pattern forming material measured in (2) in the evaluation of the resolution. After standing at room temperature for 10 minutes, the support was peeled from the laminate. (30 占 폚, 1 mass%) as the developing solution was sprayed onto the entire surface of the photosensitive layer on the copper-clad laminate with a spraying time of 0.15 MPa at a spraying time of twice the shortest developing time obtained in the above- did. The presence or absence of defects such as peeling and tearing of the cured layer (tent film) formed on the through-hole opening in the thus obtained copper-clad laminate was observed with a microscope to count the incidence of defects.

<Exposure speed>

The speed at which the exposure light and the photosensitive layer were moved relative to each other was changed using the pattern forming apparatus to obtain the speed at which a general wiring pattern was formed. The exposure was performed from the support side for the photosensitive layer of the pattern forming material in the prepared laminate. In addition, the faster the setting speed, the more efficient pattern formation becomes possible.

(Example 2)

In the same manner as in Example 1 except that the methacrylic acid / methyl methacrylate / styrene copolymer (copolymer composition ratio (mass ratio) 24/46/30) in the photosensitive resin composition solution was changed to methacrylic acid / styrene copolymer A pattern forming material and a laminate were produced in the same manner as in Example 1 except that the weight ratio of the copolymer (copolymer composition ratio (mass ratio): 29/71, mass average molecular weight: 63,100, acid value: 189 (mgKOH / g)

Resolution, etchability, peelability of the cured pattern, tent property, and exposure speed were evaluated using the produced pattern forming material and the laminate. The results are shown in Table 3.

The I / O value of the methacrylic acid / styrene copolymer [copolymer composition ratio (mass ratio): 29/71] as the binder was 0.447 as described above, the shortest developing time was 12 seconds, Was 3 mJ / cm &lt; 2 &gt;.

(Reference Example 3)

In the same manner as in Example 1 except that the methacrylic acid / methyl methacrylate / styrene copolymer (copolymer composition ratio (mass ratio) 24/46/30) in the photosensitive resin composition solution was changed to methacrylic acid / styrene copolymer , A pattern forming material and a laminate were prepared in the same manner as in Example 1 except that the weight ratio of the copolymer (copolymer composition ratio (mass ratio): 21/79, mass average molecular weight: 30,000, acid value: 137 (mgKOH / g)

Resolution, etchability, peelability of the cured pattern, tent property, and exposure speed were evaluated using the produced pattern forming material and the laminate. The results are shown in Table 3.

The I / O value of the methacrylic acid / styrene copolymer (copolymer composition ratio (mass ratio): 21/79) as the binder was 0.340 as calculated above, the shortest development time was 15 seconds, Was 3 mJ / cm &lt; 2 &gt;.

(Example 4)

In the same manner as in Example 1 except that the methacrylic acid / methyl methacrylate / styrene copolymer (copolymer composition ratio (mass ratio) 24/46/30) in the photosensitive resin composition solution was changed to methacrylic acid / methyl methacrylate Except that the copolymer was changed to acrylate / styrene / 2-ethylhexyl methacrylate copolymer [copolymer composition ratio (mass ratio): 36/5/45/14, mass average molecular weight: 82,000, acid value: 235 (mgKOH / g)] A pattern forming material and a laminate were produced in the same manner as in Example 1. [

Resolution, etchability, peelability of the cured pattern, tent property, and exposure speed were evaluated using the produced pattern forming material and the laminate. The results are shown in Table 3.

Further, the I / O value of the methacrylic acid / methyl methacrylate / styrene / 2-ethylhexyl methacrylate copolymer [copolymer composition ratio (mass ratio): 36/5/45/14] The shortest developing time was 10 seconds, and the amount of light energy required for curing the photosensitive layer was 3 mJ / cm 2.

(Reference Example 5)

In the same manner as in Example 1 except that the methacrylic acid / methyl methacrylate / styrene copolymer (copolymer composition ratio (mass ratio): 24/46/30) in the photosensitive resin composition solution was changed to methacrylic acid / styrene Except that the amount of the pattern forming material and the amount of the pattern forming material were changed in the same manner as in Example 1, except that the weight ratio of the copolymer To prepare a laminate.

Resolution, etchability, peelability of the cured pattern, tent property, and exposure speed were evaluated using the produced pattern forming material and the laminate. The results are shown in Table 3.

The I / O value of the methacrylic acid / styrene / methyl acrylate copolymer [copolymer composition ratio (mass ratio): 22/58/20] as the binder was 0.473 as described above, and the shortest developing time 11 seconds, and the amount of light energy required for curing the photosensitive layer was 3 mJ / cm 2.

(Example 6)

In the same manner as in Example 1 except that the methacrylic acid / methyl methacrylate / styrene copolymer (copolymer composition ratio (mass ratio) 24/46/30) in the photosensitive resin composition solution was changed to methacrylic acid / methyl methacrylate Except that the copolymer was changed to acrylate / styrene / 2-ethylhexyl methacrylate copolymer [copolymer composition ratio (mass ratio): 25/25/37/13, mass average molecular weight: 54,500, acid value: 163 (mgKOH / g) A pattern forming material and a laminate were produced in the same manner as in Example 1.

Resolution, etchability, peelability of the cured pattern, tent property, and exposure speed were evaluated using the produced pattern forming material and the laminate. The results are shown in Table 3.

The I / O value of the methacrylic acid / methyl methacrylate / styrene / 2-ethylhexyl methacrylate copolymer [copolymer composition ratio (mass ratio): 25/25/37] as the binder was calculated as described above The shortest development time was 10 seconds, and the amount of light energy required for curing the photosensitive layer was 3 mJ / cm 2.

(Example 7)

In the same manner as in Example 1 except that the methacrylic acid / methyl methacrylate / styrene copolymer (copolymer composition ratio (mass ratio) 24/46/30) in the photosensitive resin composition solution was changed to methacrylic acid / methyl methacrylate Except that the amount of the pattern forming material and the amount of the pattern forming material were changed in the same manner as in Example 1, except that the amount of the pattern forming material and the amount of the pattern forming material were changed to 20 parts by weight Sieve.

Resolution, etchability, peelability of the cured pattern, tent property, and exposure speed were evaluated using the produced pattern forming material and the laminate. The results are shown in Table 3.

The I / O value of the methacrylic acid / methyl methacrylate / styrene copolymer [copolymer composition ratio (mass ratio): 29/19/52] as the binder was 0.552 as described above, and the shortest developing time 10 seconds, and the amount of light energy required for curing the photosensitive layer was 3 mJ / cm &lt; 2 &gt;.

(Example 8)

In the same manner as in Example 1 except that the methacrylic acid / methyl methacrylate / styrene copolymer (copolymer composition ratio (mass ratio) 24/46/30) in the photosensitive resin composition solution was changed to methacrylic acid / methyl methacrylate Except that the amount of the pattern forming material and the number of layers of the laminated layer were changed in the same manner as in Example 1, except that the amount of the pattern forming material and the amount of the pattern forming material were changed to 20 parts by weight of the acrylate / styrene copolymer (copolymer composition ratio (mass ratio): 31/5/64, mass average molecular weight: 46,400, acid value: Sieve.

Resolution, etchability, peelability of the cured pattern, tent property, and exposure speed were evaluated using the produced pattern forming material and the laminate. The results are shown in Table 3.

The I / O value of the methacrylic acid / methyl methacrylate / styrene copolymer (copolymer composition ratio (mass ratio): 31/5/64) as the binder was 0.501 as described above, and the shortest developing time 10 seconds, and the amount of light energy required for curing the photosensitive layer was 3 mJ / cm &lt; 2 &gt;.

(Example 9)

In the same manner as in Example 1 except that the methacrylic acid / methyl methacrylate / styrene copolymer (copolymer composition ratio (mass ratio) 24/46/30) in the photosensitive resin composition solution was changed to methacrylic acid / methyl methacrylate Except that the amount of the pattern forming material and the amount of the pattern forming material were changed in the same manner as in Example 1, except that the amount of the pattern forming material and the layer thickness of the pattern forming material were changed to 100 parts by weight of the acrylate / styrene copolymer (copolymer composition ratio (mass ratio): 29/31/40, mass average molecular weight: 58,900, acid value: Sieve.

Resolution, etchability, peelability of the cured pattern, tent property, and exposure speed were evaluated using the produced pattern forming material and the laminate. The results are shown in Table 3.

The I / O value of the methacrylic acid / methyl methacrylate / styrene copolymer (copolymer composition ratio (mass ratio): 29/31/40) as the binder was 0.627 as described above, and the shortest developing time 9 seconds, and the amount of light energy required for curing the photosensitive layer was 3 mJ / cm &lt; 2 &gt;.

(Example 10)

In the same manner as in Example 1 except that the methacrylic acid / methyl methacrylate / styrene copolymer (copolymer composition ratio (mass ratio) 24/46/30) in the photosensitive resin composition solution was changed to methacrylic acid / methyl methacrylate Except that the amount of the pattern forming material and the amount of the pattern forming material were changed in the same manner as in Example 1 except that the amount of the pattern forming material and the amount of the pattern forming material were changed to 20 parts by weight of the acrylate / styrene copolymer (copolymer composition ratio (mass ratio): 25/41/34, mass average molecular weight: 55,300, acid value: Sieve.

Resolution, etchability, peelability of the cured pattern, tent property, and exposure speed were evaluated using the produced pattern forming material and the laminate. The results are shown in Table 3.

The I / O value of the methacrylic acid / methyl methacrylate / styrene copolymer [copolymer composition ratio (mass ratio): 25/41/34] as the binder was 0.627 as described above, and the shortest developing time 14 seconds, and the amount of light energy required for curing the photosensitive layer was 3 mJ / cm &lt; 2 &gt;.

(Example 11)

Resistivity, resolution, etchability, and curability were measured using the pattern forming material and the laminate prepared in the same manner as in Example 7, except that the pattern forming apparatus was changed to the pattern forming apparatus described below in Example 7 Peelability, tent property, and exposure speed were evaluated. The results are shown in Table 3.

The I / O value of the methacrylic acid / methyl methacrylate / styrene copolymer (copolymer composition ratio (mass ratio): 29/19/52) as the binder was 0.552 as shown in Example 7, and the shortest developing time Was 10 seconds, and the amount of light energy required for curing the photosensitive layer was 3 mJ / cm &lt; 2 &gt;.

<< Pattern forming device >>

278 to 32 as the light irradiation means and 768 sets of micromirror columns in which 1024 micro mirrors are arranged in the main scanning direction shown in Figs. 4A and 4B as the light modulation means are arranged in the sub scanning direction A DMD 50 controlled to drive only 1024 x 256 columns and a microlens array 472 in which a microlens 474 having a toric surface as shown in Fig. Optical systems (480, 482) for forming light on the pattern forming material through the lens array, and a pattern forming apparatus having the pantone forming material. The DMD 50 is connected to a controller 302 having a data processing unit and a mirror drive control unit shown in Fig. The data processing section of the controller 302 can generate a control signal for driving and controlling each micromirror in the area to be controlled by the DMD 50 for each of the exposure heads 166 based on the inputted pattern information, The mirror drive control section can control the angle of the reflecting surface of each micromirror of the DMD 50 for each exposure head 166 based on the control signal generated by the pattern information processing section.

The exposure in the pattern forming apparatus was performed while relatively moving the exposure light and the photosensitive layer in the pattern forming material.

The toric surface of the microlens described below was used.

First, the deformation of the exit surface was measured in order to correct the deformation of the exit surface of the microlens 474 as the grave portion of the DMD 50. [ The results are shown in Fig. In Fig. 14, the same height positions of the reflection surfaces are connected by contour lines, and the pitch of the contour lines is 5 nm. The x and y directions shown in the figure are two diagonal directions of the micromirror 62, and the micromirror 62 rotates about the rotation axis extending in the y direction. 15A and 15B show the height positional displacements of the reflecting surfaces of the micromirrors 62 along the x and y directions, respectively.

As shown in Figs. 14, 15A, and 15B, there is a deformation on the reflecting surface of the micromirror 62, and particularly when attention is paid to the center of the mirror, the deformation in one diagonal direction (y direction) Direction (x-direction). Therefore, it can be seen that the shape at the converging position of the laser beam B condensed by the microlens 55a of the microlens array 55 is deformed in this state.

16A and 16B show the front and side shapes of the entire microlens array 55 in detail, respectively. In these drawings, the dimensions of the respective portions of the microlens array 55 are also written, and these units are mm. As described above with reference to Figs. 4A and 4B, the micro mirrors 62 of 1024 x 256 columns of the DMD 50 are driven, and the micro lens arrays 55 corresponding to the micro mirrors 62 are arranged in a matrix of 1024 micro- And the rows of lenses 55a are arranged in 256 columns in the longitudinal direction. In Fig. 4A, the arrangement order of the microlens arrays 55 is indicated by j in the horizontal direction and k in the vertical direction.

17A and 17B show the front and side shapes of one microlens 55a in the microlens array 55, respectively. In Fig. 17A, contour lines of the microlenses 55a are also shown. The end face of each microlens 55a on the light exit side has an aspherical shape for correcting aberration caused by deformation of the reflecting surface of the micromirror 62. [ More specifically, the microlens 55a is a toric lens, and has a curvature radius Rx = -0.125 mm in the optically corresponding direction in the x direction, a curvature radius Ry = -0.1 mm in the corresponding direction in the y direction to be.

Therefore, the condensed state of the laser beam B in the cross section parallel to the x direction and the y direction is schematically shown in Figs. 18A and 18B. That is, when the inside of the cross section parallel to the x direction and the cross section of the cross section parallel to the y direction are compared, it can be seen that the radius of curvature of the microlens 55a is smaller in the latter section, have.

19A to 19D show the results of simulating the beam diameter in the vicinity of the condensing position (focal position) of the microlens 55a when the microlens 55a has the above shape. For comparison, FIGS. 20A to 20D show the results of simulations in which the microlens 55a has a spherical shape with a radius of curvature Rx = Ry = -0.1 mm. In the drawings, the value of z indicates the evaluation position of the microlens 55a in the focus direction as a distance from the beam emergence surface of the microlens 55a.

The surface shape of the microlens 55a used in the simulation is calculated by the following equation.

In the above formula, Cx denotes curvature in the x direction (= 1 / Rx), Cy denotes the curvature in the y direction (= 1 / Ry), X denotes the lens optical axis O in the x direction, And Y denotes the distance from the lens optical axis O with respect to the y direction.

As apparent from a comparison between Figs. 19A to 19D and Figs. 20A to 20D, the microlens 55a is formed of a toric lens having a focal length in a section parallel to the y direction smaller than a focal length in a section parallel to the x direction, Deformation of the beam shape in the vicinity of the condensing position is suppressed. As a result, it becomes possible to expose the pattern forming material 150 to a more detailed pattern without deformation. It can also be seen that the area of the beam diameter of the present embodiment shown in Figs. 19A to 19D is smaller, that is, the depth of focus is larger.

The aperture array 59 disposed in the vicinity of the condensing position of the microlens array 55 is arranged such that only the light passing through the microlens 55a corresponding thereto is incident on each of the apertures 59a. That is, since the aperture array 59 is provided, the light from the adjacent microlens 55a, which does not correspond to the apertures 59a, is prevented from being incident on each aperture 59a, and the extinction ratio can be increased.

(Example 12)

Resistivity, resolution, etchability, and curing pattern were measured using the pattern forming material and the laminate produced in the same manner as in Example 9, except that the pattern forming apparatus in Example 9 was replaced with the pattern forming apparatus in Example 11. [ The tent property, and the exposure speed were evaluated. The results are shown in Table 3.

The I / O value of the methacrylic acid / methyl methacrylate / styrene copolymer (copolymer composition ratio (mass ratio): 29/31/40) as the binder was 0.627 as shown in Example 9, and the shortest developing time Was 9 seconds, and the amount of light energy required for curing the photosensitive layer was 3 mJ / cm &lt; 2 &gt;.

(Example 13)

Resistivity, resolution, etchability, and curing pattern were measured using the pattern forming material and the laminate produced in the same manner as in Example 10, except that the pattern forming apparatus of Example 10 was replaced with the pattern forming apparatus of Example 11 The tent property, and the exposure speed were evaluated. The results are shown in Table 3.

The I / O value of the methacrylic acid / methyl methacrylate / styrene copolymer (copolymer composition ratio (mass ratio): 25/41/34) as the binder was 0.627 as shown in Example 10, and the shortest developing time Was 10 seconds, and the amount of light energy required for curing the photosensitive layer was 3 mJ / cm &lt; 2 &gt;.

(Comparative Example 1)

The same procedure as in Example 1 was carried out except that the methacrylic acid / styrene copolymer (copolymer composition ratio (mass ratio): 29/71) in the photosensitive resin composition solution was changed to methacrylic acid / methyl methacrylate / styrene copolymer (Mass ratio): 18/50/32, mass average molecular weight: 47,300, acid value: 117 (mgKOH / g)].

Resolution, etchability, peelability of the cured pattern, tent property, and exposure speed were evaluated using the produced pattern forming material and the laminate. The results are shown in Table 3.

The I / O value of the methacrylic acid / methyl methacrylate / styrene copolymer (copolymer composition ratio (mass ratio): 18/50/32) as the binder was 0.569 as described above, and the shortest developing time was 25 seconds, and the amount of light energy required for curing the photosensitive layer was 3 mJ / cm &lt; 2 &gt;.

(Comparative Example 2)

The same procedure as in Example 1 was carried out except that the methacrylic acid / styrene copolymer (copolymer composition ratio (mass ratio): 29/71) in the photosensitive resin composition solution was changed to methacrylic acid / methyl methacrylate / styrene copolymer (Mass ratio): 25/45/30, mass average molecular weight: 35,000, acid value: 163 (mgKOH / g)], a pattern forming material and a laminate were prepared in the same manner as in Example 1.

Resolution, etchability, peelability of the cured resin pattern, tent property, and exposure speed were evaluated using the produced pattern forming material and the laminate. The results are shown in Table 3.

The I / O value of the methacrylic acid / methyl methacrylate / styrene copolymer [copolymer composition ratio (mass ratio): 25/45/30] as the binder was 0.655 as described above, and the shortest developing time 10 seconds, and the amount of light energy required for curing the photosensitive layer was 3 mJ / cm &lt; 2 &gt;.

(Comparative Example 3)

(Meth) acrylic acid / methyl methacrylate / styrene / 2-ethylhexyl methacrylate / styrene copolymer [copolymer composition ratio (mass ratio): 29/71] in the photosensitive resin composition solution as the binder in Example 1, Except that the weight average molecular weight (Mw / Mn) of the copolymer was changed to the weight average molecular weight (Mw / Mn) of the ethylhexyl methacrylate copolymer [copolymer composition ratio (mass ratio): 40/30/15/15, mass average molecular weight: 50,200, acid value: 261 Material and a laminate.

Resolution, etchability, peelability of the cured pattern, tent property, and exposure speed were evaluated using the produced pattern forming material and the laminate. The results are shown in Table 3.

The I / O value of the methacrylic acid / methyl methacrylate / styrene / 2-ethylhexyl methacrylate copolymer [copolymer composition ratio (mass ratio): 40/30/15/15] The calculated value was 0.871, the shortest developing time was 5 seconds, and the amount of light energy required for curing the photosensitive layer was 3 mJ / cm 2.

(Comparative Example 4)

In the same manner as in Example 1 except that the methacrylic acid / styrene copolymer (copolymer composition ratio (mass ratio): 29/71) in the photosensitive resin composition solution was changed to methacrylic acid / methyl methacrylate / 2- Except that the copolymer was changed to acrylate / butyl acrylate copolymer [copolymer composition ratio (mass ratio): 19/61/10/10, mass average molecular weight: 60,700, acid value: 124 (mgKOH / g) Forming material and a laminate.

Resolution, etchability, peelability of the cured pattern, tent property, and exposure speed were evaluated using the produced pattern forming material and the laminate. The results are shown in Table 3.

The I / O value of the methacrylic acid / methyl methacrylate / 2-ethylhexyl acrylate / butyl acrylate copolymer [copolymer composition ratio (mass ratio): 19/61/10/10] The shortest developing time was 15 seconds, and the amount of light energy required for curing the photosensitive layer was 3 mJ / cm 2.

From the results of Table 3, it is understood that the pattern forming materials of Examples 1 to 13 have an I / O value in the range of 0.300 to 0.650 and an acid value in the range of 130 to 250 (mgKOH / g) , The resolution, the etching property and the tent property, the shortest developing time is short, the developing property is excellent, and the peelability of the cured pattern is excellent. It was also found that Examples 11 to 13 using a pattern forming apparatus having a toric surface had better resolution and higher exposure speed than Examples 1 to 10.

The pattern forming material of the present invention is excellent in resolution and tent property and also in developing property because the I / O value and the glass transition temperature of the binder contained in the photosensitive layer are all within a constant numerical range, The formation of various patterns, the formation of permanent patterns such as wiring patterns, the production of liquid crystal structural members such as color filters, columns, ribs, spacers and partitions, and the manufacture of holograms, micromachines, Can be preferably used, and can be suitably used particularly for forming a fine wiring pattern. Since the pattern forming apparatus of the present invention is provided with the pattern forming material of the present invention, it is possible to form various patterns, to form a permanent pattern such as a wiring pattern, a liquid crystal structure such as a color filter, a columnar material, a rib material, a spacer, Can be preferably used for the production of members, holograms, micromachines, and prophes, and can be suitably used for forming particularly fine wiring patterns. Since the pattern forming method of the present invention uses the pattern forming material of the present invention, it is possible to form various patterns, to form a permanent pattern such as a wiring pattern, to form a liquid crystal structural member such as a color filter, a columnar material, a rib material, a spacer, A hologram, a micromachine, and a prophes, and can be preferably used for forming a fine wiring pattern.

Claims (15)

A photosensitive resin composition comprising at least a photosensitive layer on a support, wherein the photosensitive layer contains a binder, a polymerizable compound and a photopolymerization initiator, wherein the binder has an I / O value (inorganic / organic ratio of organic conceptual diagram) of 0.300 to 0.650, An acid value of 156 to 250 (mgKOH / g)
Wherein the binder contains a copolymer and the copolymer has a structural unit derived from at least one of styrene and a styrene derivative and has an I / O value (inorganic / organic ratio of organic conceptual diagram) of 0.35 or less Characterized in that it contains 30 mass% or more of the constituent monomers. The pattern forming material according to claim 1, wherein the I / O value (inorganic / organic ratio of the organic conceptual diagram) of the binder is 0.350 to 0.630. The pattern forming material according to claim 1, wherein the acid value of the binder is 156 to 230 (mgKOH / g). delete delete The pattern forming material according to claim 1, wherein the polymerizable compound contains a monomer having at least one of a urethane group and an aryl group. The photopolymerization initiator according to claim 1, wherein the photopolymerization initiator comprises at least one member selected from halogenated hydrocarbon derivatives, hexaarylbimidazoles, oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts and metallocenes Forming material. Comprising a pattern forming material according to claim 1;
And a light modulating means for modulating light from the light irradiating means and exposing the photosensitive layer of the pattern forming material to light. A pattern forming method, comprising at least the step of exposing the photosensitive layer in the pattern forming material according to claim 1. 10. The image forming apparatus according to claim 9, wherein after modulating the light from the light irradiating means by optical modulating means having n graveyard portions for receiving and emitting light from the light irradiating means with respect to the photosensitive layer, Wherein exposure is performed with light passed through a microlens array in which microlenses having aspheric surfaces capable of correcting aberrations caused by deformation of the surface are arranged. 10. The pattern forming method according to claim 9, wherein the exposure is performed using light that is generated based on pattern information to be formed and modulated in accordance with the control signal. 10. The exposure apparatus according to claim 9, wherein the exposure is performed by modulating light by an optical modulating means, and then modulating the aberration caused by the deformation of the exit surface of the grave portion in the light modulating means, Wherein the pattern is formed by passing through an array. 13. The pattern forming method according to claim 12, wherein the aspherical surface is a toric surface. The pattern forming method according to claim 9, wherein the development of the photosensitive layer is performed after the exposure. 15. The pattern forming method according to claim 14, wherein the permanent pattern is formed after development.

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