JP2014056975A - Method for manufacturing resin layer having pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method capable of keeping excellent pattern forming properties when a pattern is repeatedly formed even if a mold release property is not imparted to a mold when a resin layer having a pattern is formed by an imprint method.SOLUTION: A method for manufacturing a resin layer having a pattern comprises the steps of: irradiating a resin layer 10a composed of a resin composition with light; pressing a mold 5 having an uneven pattern against the resin layer 10a irradiated with light to form a pattern inverted to the uneven pattern on the resin layer 10a; and removing the mold 5 from a resin layer 10b in which a pattern is formed.

Description

  The present invention relates to a method for producing a resin layer having a pattern by an imprint method.

  In recent years, an imprint method has attracted attention as a method for producing an article having a fine pattern, such as an optical element or a semiconductor (for example, see Non-Patent Document 1). In addition, with the development of microfabrication technology, there is a need for a technology that uniformly forms a release film on the surface of a substrate having a fine pattern and imparts releasability to the substrate.

As the imprint method, a thermal imprint method and an optical imprint method have been proposed. In the thermal imprint method, an imprint mold having a fine pattern on the surface is pressed against a thermoplastic resin that has been heated and softened above the glass transition temperature, and the resin is removed from the mold after cooling and solidifying the resin. Then, the fine pattern is transferred to the resin on the substrate (for example, Patent Document 1). On the other hand, in the photoimprint method, after a photocurable resin composition is filled into a transparent mold for imprinting having a fine pattern on the surface, light such as UV is irradiated through the mold, and the photocurable resin composition is then applied. The fine pattern is transferred onto the substrate by curing and removing the resin from the mold (for example, Patent Document 2). In any of the methods, the releasability between the imprint mold and the resin is usually insufficient, and when the resin is removed from the mold, the fine pattern on the resin surface may be deformed or missing, resulting in patterning. Accuracy tends to decrease. Therefore, generally, means such as applying mold release properties to the mold by a method such as applying a release agent in advance is used. Conventionally, fluorine-containing compounds having a small surface energy have been widely used as these release agents. As the fluorine-containing compound, a fluorine-containing silane coupling agent is used from the viewpoints of adhesion to a substrate, wiping of contaminants, and durability. For example, a method of forming a chemical adsorption film having a covalent bond on the substrate surface by applying a coating solution containing a chlorosilane-based chemical adsorbent having a —CF ₂ — group as a component by spraying (see, for example, Patent Document 3) Etc. are known.

JP 2000-232095 JP-T-2006-521682 JP-A-6-327971

S. Y. Chou et. al. , Science, vol. 272, p. 85-87, April, 1996.

  However, when a fluorine-containing silane coupling agent is applied to a mold for imprinting as a mold release agent, the adhesion between the mold at the time of mold release and the resin for imprinting is large, and the mold releasability may not be sufficient. there were.

  On the other hand, when an inorganic film is used as the release layer, the thickness of the release layer is large, and the pattern dimensions are likely to change greatly due to the influence of the release layer. Therefore, this method is difficult to apply in order to form a fine pattern. In addition, there is a problem that it takes a lot of cost to peel off a film that has deteriorated after imprinting and to apply the film again.

  In practical use of imprinting, it is extremely important that not only the mold releasability for each transfer but also a good pattern can be formed repeatedly and stably. Particularly in mass production, it is required to maintain a high yield even when pattern formation is continuously performed. That is, it is required to maintain good pattern formability (repeated patterning resistance) even when repeated pattern transfer is performed.

  Therefore, the main object of the present invention is to provide a good pattern formability when a pattern is repeatedly formed without imparting mold release properties to the mold when a resin layer having a pattern is formed by an imprint method. It is to provide a method that can be maintained.

  The present invention includes a step of irradiating a resin layer made of a resin composition with light, a mold having a concavo-convex pattern pressed against the resin layer irradiated with light, and a pattern inverted with respect to the concavo-convex pattern applied to the resin layer. The present invention relates to a method for producing a resin layer having a pattern, comprising a step of forming and a step of removing a mold from the resin layer on which the pattern is formed.

  According to the method of the present invention, the resin layer is irradiated with light before the mold is pressed against the resin layer, so that the release property of the resin layer is improved while maintaining fluidity suitable for imprinting. It is done. Therefore, even if the mold release property is not imparted to the mold by a method such as providing a mold release layer, a defect is hardly generated in the pattern when the mold is removed from the resin layer. Since the resin layer itself is given releasability, processing such as re-applying a release agent to the mold is essential even when pattern transfer is repeated as in the case of giving releasability to the mold. And not. That is, good pattern formability can be maintained when a pattern is repeatedly formed without imparting mold release properties to the mold. Further, when a resin that is too soft is applied to the resin layer, the resin layer may adhere to a mold to which a release agent is applied if it is left unexposed. However, according to the method of the present invention, even when a soft resin is applied to the resin layer, the release property of the resin layer can be improved while maintaining fluidity suitable for imprinting.

  You may further provide the process of hardening the resin layer in which the pattern was formed after the process of removing a type | mold from a resin layer. In this case, preferably, the step of curing the resin layer on which the pattern is formed includes irradiating the resin layer on which the pattern is formed with light.

  By curing the resin layer by light irradiation, the pattern shape can be satisfactorily maintained when the resin layer is heated for thermosetting or the like.

  The resin composition may contain a photopolymerizable compound and a photopolymerization initiator. Thereby, effects, such as a mold release improvement by light irradiation, are acquired notably.

  The resin composition may further contain a compound different from the photopolymerizable compound selected from a polymer compound and a thermosetting resin. The polymer compound and the thermosetting resin can impart high heat resistance to the cured resin layer.

  The present invention relates to a resin layer having a pattern, which can be obtained by the above method. The resin layer may be a permanent film. The present invention also relates to an electronic component including the resin layer as a permanent film.

  According to the method of the present invention, when a resin layer having a pattern is formed by an imprint method, good pattern formability is maintained when the pattern is repeatedly formed without imparting release properties to the mold. it can. A good pattern can be repeatedly and stably formed without requiring treatment such as re-applying the release agent to the mold. Since it is not necessary to provide mold release properties by a method such as applying a mold release agent such as a fluororesin to the mold in advance, a significant cost reduction is expected.

It is process drawing which shows one Embodiment of the method of manufacturing the resin layer which has a pattern. It is process drawing which shows one Embodiment of the method of manufacturing the resin layer which has a pattern. It is sectional drawing which shows one Embodiment of a semiconductor device provided with the resin layer which has a pattern as a permanent film. It is an electron micrograph after thermosetting of the resin layer which has a pattern of Example 1. 4 is an electron micrograph of a resin layer having a pattern of Comparative Example 1 after thermosetting.

  Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

<Method for producing resin layer having pattern>
FIG.1 and FIG.2 is process drawing which shows one Embodiment of the method of manufacturing the resin layer which has a pattern. The method shown in FIGS. 1 and 2 mainly includes a step of providing a resin layer 10a made of an imprinting resin composition on a substrate 1 (FIG. 1A) and a resin layer 10a on the substrate 1. And irradiating light (FIG. 1 (b)) and pressing the mold 5 having the concavo-convex pattern against the resin layer 10a irradiated with the light, the pattern reversed with respect to the pattern of the mold 5 is applied to the resin layer 10a. Steps of forming (FIGS. 1C and 1D), removing the mold 5 from the resin layer 10b on which the pattern is formed (FIG. 2E), and the resin layer 10b on which the pattern is formed It comprises a step of irradiating light ((f) in FIG. 2) and a step of thermally curing the resin layer 10b on which the pattern is formed ((g) in FIG. 2).

  As shown to (a) of FIG. 1, it is preferable that the resin layer 10a is formed by the method in which the film thickness becomes uniform. The preferred thickness of the resin layer 10a is about 1/3 to 2 times the height of the convex portion of the concave / convex pattern of the mold 5. When the resin layer 10a has an appropriate thickness, the resin composition is particularly easily filled in the uneven pattern, and the resin can be more effectively suppressed from remaining on the mold when the mold is removed from the resin layer. The thickness of the resin layer 10a is usually 1 to 100 μm, preferably 1 to 50 μm, more preferably 1 to 25 μm. When the thickness of the resin layer 10a is particularly 15 μm or less, the remaining film thickness after imprinting (imprint) can be reduced while maintaining a good pattern shape.

  The resin layer 10a can be formed, for example, by applying an imprinting resin composition to the substrate 1 and removing the solvent from the coating film as necessary. If necessary, the resin composition may be dissolved or dispersed in a solvent to prepare a coating solution, and the coating solution may be applied to the substrate 1. The method of application is not particularly limited, and for example, a method such as spin coating or dip coating can be used. Details of the resin composition for imprint will be described later.

  Alternatively, the resin layer 10a is formed in advance on the support film, and the imprint resin film having the support film and the resin layer 10a provided on the support film is prepared. The resin layer 10a can be provided on the substrate. Apply a resin composition for imprinting or a solution or dispersion thereof to a support film, and use a hot plate, oven, etc., for example, at 60 to 120 ° C. to dry the coating film by heating for 1 minute to 1 hour, The resin layer 10a can be formed on the support film. As the support film, for example, an organic film such as a polyethylene terephthalate film can be used. A protective film selected from a polyethylene terephthalate film, a polyethylene film, a polypropylene film, and the like may be laminated on the resin layer 10a. If the resin layer 10a has self-supporting properties, the support film can be peeled off and the resin layer 10a can be used alone as an imprinting resin film.

  In this case, the thickness of the resin layer 10a of the imprint resin film is usually 1 to 100 μm, preferably 1 to 50 μm, more preferably 1 to 25 μm. The thickness of the resin layer 10a may be 15 μm or less. When the mold having a concavo-convex pattern with a depth (or height) of 10 μm is used when the thickness of the resin layer 10a is particularly 15 μm or less, the embossing (imprinting) is performed while maintaining a good pattern shape. ) The remaining film thickness afterwards can be reduced.

  After forming the resin layer 10 a on the substrate 1, as shown in FIG. 1B, the resin layer 10 a is irradiated with light (active light) from the side opposite to the substrate 1. This light irradiation can improve the mold release property on the surface of the resin layer 10a while maintaining the fluidity of the resin layer suitable for imprinting. As a result, after the mold 5 is pressed against the resin layer 10a to form a pattern on the resin layer 10a, the adhesion of the resin layer to the mold 5 is suppressed.

The type of light to be irradiated is not particularly limited. For example, at least one actinic ray selected from the group consisting of ultraviolet rays, visible rays, electron beams and X-rays is irradiated using a light source usually used in the field. The Among these, ultraviolet rays and visible rays are particularly preferable. The exposure amount is, for example, 1 to 4000 mJ / cm ² , preferably 1 to 2000 mJ / cm ² , more preferably 1 to 100 mJ / cm ² , particularly preferably 5 to 50 mJ / cm ² , and release of the resin layer. Can be appropriately adjusted in consideration of a suitable balance between the property and fluidity. When the exposure amount is increased, the releasability of the resin layer is improved, and the fluidity of the resin layer tends to be lowered. In particular, when the resin layer 10a contains a photopolymerizable compound, the resin layer 10a is irradiated with light at an exposure amount such that the photopolymerization of the photopolymerizable compound partially proceeds. A good balance can be easily achieved.

  Next, as shown in FIGS. 1C and 1D, a mold 5 having a concavo-convex pattern inverted with respect to the pattern of the finally formed resin layer 10 is prepared, and this is pressed onto the resin layer 10a. Hit it. The method of pressing the mold is not particularly limited, and for example, a method of pressing the mold by hand, a method of pressing the mold at a high pressure using a press device, or the like can be used. As the mold 5, for example, a silicon mold can be used. The mold 5 does not necessarily need to be subjected to a release treatment, but may be subjected to a release treatment.

  When the mold 5 is pressed against the resin layer 10 a, the resin layer 10 a flows and fills the uneven pattern of the mold 5. Thereby, the resin layer 10b having a pattern inverted with respect to the concave / convex pattern of the mold 5 is formed. That is, the resin layer is patterned by imprinting using the mold 5. In the step of pressing the mold 5 against the resin layer 10a, it is preferable that the mold 5 is heated, particularly when the viscosity of the resin layer is high, in order to ensure good filling properties of the resin. The temperature of the mold 5 is preferably 40 ° C. or higher. Further, the temperature of the mold 5 is preferably 300 ° C. or lower for reasons such as preventing decomposition of the resin.

  The atmosphere when pressing the mold 5 against the resin layer is not particularly limited, but it is preferable to perform the step under reduced pressure in order to prevent bubbles from remaining in the resin layer. In particular, when the resin layer contains a polymerizable unsaturated compound (photopolymerizable compound) having a carbon-carbon double bond such as a (meth) acryloyl group, an allyl group, or a vinyl group, the pressure is reduced to prevent polymerization inhibition by oxygen. It is preferred to carry out the process below.

  After the resin layer 10b having a pattern is formed, the mold 5 is removed from the resin layer 10b as shown in FIG.

  After the mold 5 is removed, the heat resistance, physical strength, and the like of the resin layer 10b can be increased by further curing the resin layer 10b. The resin layer 10b is heated by heating the resin layer 10b ((g) in FIG. 2, thermosetting), irradiating the resin layer 10b with light ((f) in FIG. 2, photocuring), or a combination thereof. It can be cured.

  The heating method for thermosetting is not particularly limited. For example, the formed pattern can be particularly easily held by gradually raising the temperature while maintaining the temperature below the glass transition point of the resin layer 10a. Moreover, the thermal decomposition of resin can be prevented by making the temperature of heating into 300 degrees C or less.

Photocuring can be performed by irradiating the resin layer 10b with active rays such as ultraviolet rays and visible rays in the same manner as the light irradiation before imprinting ((b) in FIG. 1). As light curing sufficiently proceeds, the exposure amount, for example 1~4000mJ / cm ^2, preferably adjusted within a range of 1000~4000mJ / cm ^2. This photocuring makes it difficult to soften the resin layer during thermosetting, and can more effectively prevent the pattern shape from collapsing. Therefore, the resin layer 10b is preferably photocured before thermosetting. The effect of pattern holding by photocuring is particularly prominent when the resin layer 10a contains a photopolymerization initiator. The fact that the shape of the pattern is easily maintained is particularly advantageous when, for example, a fine pattern is formed.

<Resin composition for imprint>
The resin composition that can be suitably used for forming the resin layer in the method according to this embodiment will be described in detail.

  The resin composition according to this embodiment preferably contains (A) a photopolymerizable compound and (B) a photopolymerization initiator.

  The resin composition which concerns on this embodiment can contain the compound which has a photopolymerizable functional group 1 type, or 2 or more types as a photopolymerizable compound of (A) component. The number of photopolymerizable functional groups is not particularly limited, but two or more photopolymerizable groups in the molecule can be used from the viewpoints of curing speed during pattern formation and physical and chemical durability of the coating after curing. A compound having a functional group of The proportion of the compound having two or more photopolymerizable functional groups in the component (A) is preferably 30% by mass to 100% by mass, more preferably 50% by mass to 100% by mass.

  The photopolymerizable functional group may be, for example, at least one selected from the group consisting of a (meth) acryloyl group, a vinyl group, an allyl group, an epoxy group, and an oxetanyl group. Among these functional groups, a (meth) acryloyl group is preferable in order to shorten the curing time and realize high throughput. (A) The ratio of the compound which has a (meth) acryloyl group in the whole component becomes like this. Preferably they are 30 mass% or more and 100 mass% or less.

  Examples of the compound having one (meth) acryloyl group include methyl (meth) acrylate, ethyl (meth) acrylate, (n-propyl) (meth) acrylate, isopropyl (meth) acrylate, and (meth) acrylic acid. -N-butyl, isobutyl (meth) acrylate, (sec) -butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acryl Decyl acid, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid-2- Hydroxypropyl, (meth) acrylic acid-3-hydroxypropyl, (meth) acrylic acid-2- Mono (meth) acrylates such as droxybutyl, (meth) acrylic acid-2-hydroxyphenylethyl, and N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-acryloylmorpholine, etc. It may be at least one selected from the group consisting of (meth) acrylamide.

  Examples of the compound having two or more (meth) acryloyl groups include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and diethylene glycol di (meth) acrylate. Polyfunctional (meth) acrylates such as triethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol penta (meth) acrylate, and epoxy resin ( It may be at least one selected from the group consisting of so-called epoxy (meth) acrylates obtained by adding meth) acrylic acid. Epoxy (meth) acrylates include, for example, bisphenol A type epoxy resins, hydrogenated bisphenol A type epoxy resins, brominated bisphenol A type epoxy resins, bisphenol F type epoxy resins, novolac type epoxy resins, phenol novolac type epoxy resins, cresol novolacs. Type epoxy resin, cycloaliphatic epoxy resin, N-glycidyl type epoxy resin, bisphenol A novolac type epoxy resin, chelate type epoxy resin, glyoxal type epoxy resin, amino group-containing epoxy resin, rubber-modified epoxy resin, dicyclopentadiene phenolic Derived from type epoxy resin, silicone modified epoxy resin or ε-caprolactone modified epoxy resin.

  Examples of the compound having one vinyl group include n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, octadecyl vinyl ether, monovinyl ether such as cyclohexyl vinyl ether, vinyl acetate, vinyl propionate, butyric acid. Monovinyl esters such as vinyl and vinyl benzoate; divinyl esters such as divinyl adipate; N-vinylamides such as N-vinylpyrrolidone and N-methyl-N-vinylacetamide; and styrene and 2,4-dimethyl-α-methyl Styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 2,6-dimethylstyrene, 3, -Dimethylstyrene, 3,5-dimethylstyrene, 2,4,6-trimethylstyrene, 2,4,5-trimethylstyrene, pentamethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, o- Chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-bromostyrene, m-bromostyrene, p-bromostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-hydroxystyrene, m- Hydroxystyrene, p-hydroxystyrene, 2-vinylbiphenyl, 3-vinylbiphenyl, 4-vinylbiphenyl, 1-vinylnaphthalene, 2-vinylnaphthalene, 4-vinyl-p-terphenyl, 1-vinylanthracene, α-methyl Styrene, o-isopropenyltoluene, m- Sopropenyl toluene, p-isopropenyl toluene, 2,4-dimethyl-α-methylstyrene, 2,3-dimethyl-α-methylstyrene, 3,5-dimethyl-α-methylstyrene, p-isopropyl-α-methyl It may be at least one selected from the group consisting of styrene derivatives such as styrene, α-ethylstyrene and α-chlorostyrene.

  Examples of the compound having two or more vinyl groups include ethylene glycol divinyl ether, 1,4-butanediol divinyl ether, 1,6-hexanediol divinyl ether, 1,9-nonanediol divinyl ether, and cyclohexanedimethanol divinyl ether. , Diethylene glycol divinyl ether, triethylene glycol divinyl ether, trimethylolpropane trivinyl ether, polyfunctional vinyl ethers such as pentaerythritol tetravinyl ether, divinylbenzene, and at least one selected from the group consisting of divinylbiphenyl.

  The compound having one allyl group may be at least one selected from allyl esters such as allyl alcohol, ethylene glycol monoallyl ether, allylamine, allyl glycidyl ether, allyl acetate, and allyl benzoate. The compound having two or more allyl groups may be, for example, at least one selected from the group consisting of diallylamine, diallyl 1,4-cyclohexanedicarboxylate, diallyl phthalate, diallyl terephthalate, and diallyl isophthalate.

  The compound having one epoxy group is selected from, for example, glycidol and cyclohexene oxide. Examples of the compound having two or more epoxy groups include bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, and phenol novolac type epoxy. Resin, cresol novolac type epoxy resin, alicyclic epoxy resin, N-glycidyl type epoxy resin, bisphenol A novolac type epoxy resin, chelate type epoxy resin, glyoxal type epoxy resin, amino group-containing epoxy resin, rubber-modified epoxy resin, It may be at least one selected from the group consisting of a dicyclopentadiene phenolic epoxy resin, a silicone-modified epoxy resin, and an ε-caprolactone-modified epoxy resin.

  The compound having one oxetanyl group is selected from, for example, 3-ethyl-3-hydroxymethyloxetane and 3-ethyl-3-methacryloxymethyloxetane. Compounds having two or more oxetanyl groups include, for example, Aron Oxetane OXT-121 (trade name) manufactured by Toagosei Co., Ltd., OXTP (trade name) manufactured by Nippon Steel Chemical Co., Ltd., and OXBP (trade name) ).

  It is preferable that the resin composition which concerns on this embodiment contains the (meth) acrylate compound which has a urethane bond as a photopolymerizable compound. By including the (meth) acrylate compound which has a urethane bond in a resin composition, the heat resistance of the resin layer after hardening can be improved. More specifically, the high-temperature rigidity of the cured product of the resin layer is increased, the resin layer is further prevented from becoming brittle, and the resin layer can maintain good adhesion to the substrate and the like.

  Examples of the (meth) acrylate compound having a urethane bond include urethane (meth) acrylate and ethylene oxide (EO) -modified urethane di (meth) which are addition reaction products of a (meth) acrylic monomer having a hydroxyl group at the β-position and the like and a diisocyanate compound. Acrylate, ethylene oxide (EO) or propylene oxide (PO) modified urethane di (meth) acrylate, urethane (meth) acrylate having carboxyl group, diol compound, and bifunctional epoxy having two hydroxyl groups and two ethylenically unsaturated groups It may be at least one selected from the group consisting of a reaction product of (meth) acrylate and polyisocyanate.

  The (meth) acrylic monomer having a hydroxyl group at the β-position is at least selected from the group consisting of 2-hydroxyethyl (meth) acrylate, dipentaerythritol penta (meth) acrylate, and pentaerythritol tri (meth) acrylate, for example. One kind may be sufficient. The isocyanate compound may be, for example, at least one selected from the group consisting of isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, and 1,6-hexamethylene diisocyanate.

  Optimize the number of functional groups (number of (meth) acryloyloxy groups) and weight average molecular weight of (meth) acrylate compounds with urethane bonds to achieve both higher levels of heat resistance, rigidity and high adhesion. Is preferred. Thereby, since the range of the material which can be selected without increasing a viscosity excessively becomes wide, the viscosity of the resin composition for imprint apply | coated on a board | substrate can be adjusted easily. The viscosity of the resin composition for imprinting can be lowered by using a solvent, but by using a (meth) acrylate compound having a urethane bond with an appropriate number of functional groups and weight average molecular weight, the amount of the solvent Can be reduced. By reducing the amount of the solvent, it is easy to maintain good characteristics and reliability of the cured resin layer.

  The number of functional groups (number of (meth) acryloyloxy groups) of the (meth) acrylate compound having a urethane bond is preferably 2 to 15 from the viewpoints of heat resistance, adhesion, coatability, and pattern formability. The number of functional groups is more preferably 2 to 12, and still more preferably 2 to 10 from the viewpoint of the physical properties of the resin layer after curing and the stability of characteristics.

  When the number of functional groups is 2 or more, the heat resistance of the cured resin layer and the rigidity of the resin layer at high temperatures can be further increased. When the number of the functional groups is 15 or less, the cured resin layer can be prevented from becoming brittle and good adhesion can be obtained. Moreover, since the weight average molecular weight of a (meth) acrylate compound will not become large too much when the said functional group number is small, it is easy to adjust the viscosity of a resin composition to an appropriate range. Therefore, good coatability is easily obtained. Furthermore, after photo-curing and / or heat-curing, a large amount of unreacted (meth) acryloyl groups remain, and as a result, variations in physical properties and characteristics of the resin film can be more effectively avoided. .

  The weight average molecular weight (Mw) of the (meth) acrylate compound having a urethane bond is preferably 950 to 25000. The weight average molecular weight is more preferably 950 to 15000 from the viewpoint of improving coatability, and further preferably 950 to 11,000 from the viewpoint of compatibility. In the present specification, the value of the weight average molecular weight (Mw) means a value converted to standard polystyrene, which is measured using an eluent such as tetrahydrofuran or toluene by a gel permeation chromatography craft (GPC) method. .

  When the weight average molecular weight is 950 or more, the viscosity of the resin composition does not become too low, and it is possible to prevent the resin composition applied on the substrate from dripping. Moreover, it is preferable that a weight average molecular weight is 950 or more also from the point that formation of a thick film is easy and the reliability fall resulting from hardening shrinkage does not occur easily. When the weight average molecular weight is 25000 or less, the viscosity of the resin composition does not become too high, and particularly good coatability is obtained. Moreover, thick film formation is also easy.

  The (meth) acrylate compound having a urethane bond is preferably a compound represented by the following general formula from the viewpoint of heat resistance and adhesion.

R ₁ and R ₂ each independently represent a divalent organic group, for example, a linear or branched alkylene group having 1 to 15 carbon atoms, or an alicyclic group that may have a substituent, having 1 to 1 carbon atoms. There are 20 groups. n is an integer greater than or equal to 1, for example, 1-5. In particular, from the viewpoint of improving heat resistance, R ₂ is preferably a divalent group represented by the following structure.

  As a commercial item of the compound represented by the said general formula, UN-952 (the number of functional groups: 10, Mw: 6500-11000) etc. are mentioned, for example. Moreover, as a commercial item of the acrylate compound (compound which has acryloyloxy group) which has a urethane bond, UN-904 (functional group number: 10) which is an acrylate compound (compound which has acryloyloxy group) which has a urethane bond, for example. Mw: 4900), UN-952 (functional group number: 10, Mw: 6500 to 11000), UN-333 (functional group number: 2, Mw: 5000), UN-1255 (functional group number: 2, Mw: 8000), UN -2600 (functional group number: 2, Mw: 2500), UN-6200 (functional group number: 2, Mw: 6500), UN-3320HA (functional group number: 6, Mw: 1500), UN-3320HC (functional group number: 6, Mw: 1500), UN-9000 PEP (functional group number: 2, Mw: 5000), UN-9200A ( Number of functional groups: 2, Mw: 15000), UN-3320HS (functional group number: 15, Mw: 4900), UN-6301 (functional group number: 2, Mw: 33000) (all are trade names, manufactured by Negami Kogyo Co., Ltd.) ), TMCH-5R (trade name, manufactured by Hitachi Chemical Co., Ltd.), KRM8452 (number of functional groups = 10, Mw = 1200), EBECRYL8405 (urethane acrylate / 1,6-hexanediol diacrylate = 80/20 addition reaction product, (The number of functional groups: 4, Mw: 2700) (all are trade names, manufactured by Daicel-Cytec Co., Ltd.).

  Examples of the methacrylate compound having a urethane bond (compound having a methacryloyloxy group) include UN-6060PTM (functional group number: 2, Mw: 6000, trade name, manufactured by Negami Kogyo Co., Ltd.), JTX-0309 (trade name, Hitachi). Kasei Kogyo Co., Ltd.) and UA-21 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.).

  From the viewpoint of improving heat resistance, the content of the (meth) acrylate compound having a urethane bond is preferably 10% by mass or more, more preferably 30% by mass, based on the total amount of the photopolymerizable compound as the component (A). As mentioned above, More preferably, it is 50 mass% or more. When the content is 10% by mass or more, various physical properties and characteristics required for coating properties and a cured product of the resin composition can be maintained at a higher level.

  In view of the coating properties of the resin composition and the physical properties and properties required for the cured product of the resin composition, in order to selectively blend other (meth) acrylate compounds described later, a urethane bond ( The content of (meth) acrylate is preferably 95% by mass or less, more preferably 85% by mass or less, and still more preferably 75% by mass or less.

  The resin composition according to this embodiment includes a (meth) acrylate compound having an amide bond, a compound obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid, a bisphenol A-based (meth) acrylate compound, and glycidyl. At least one light selected from the group consisting of a compound obtained by reacting a group-containing compound with an α, β-unsaturated carboxylic acid and a (meth) acrylic acid alkyl ester copolymer having an ethylenically unsaturated group It may contain a polymerizable compound. Among them, a (meth) acrylate compound having an amide bond can be preferably used in terms of increasing the tolerance of the imprint process in addition to improving resolution and adhesion.

  Among these, a (meth) acrylate compound having an amide bond is preferable in terms of increasing the tolerance of the imprint process in addition to improving heat resistance, resolution, and adhesion. The (meth) acrylate compound having an amide bond is preferably a compound represented by the following general formula (1) from the viewpoint of resolution and adhesion.

In formula (1), R ³¹ , R ³² and R ³³ each independently represent a divalent organic group, R ³⁴ represents a hydrogen atom or a methyl group, and R ³⁵ and R ³⁶ each independently represent hydrogen. An atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group is shown.

The divalent organic group as R ³¹ , R ³² or R ³³ is, for example, a phenylene group which may have a substituent, a pyridylene group which may have a substituent, a linear chain having 1 to 10 carbon atoms, or A branched alkylene group, a group having 1 to 10 carbon atoms including an alicyclic group which may have a substituent, or a hydroxyl group from bisphenol (such as 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane) Is a group formed by removing

  The compound represented by the general formula (1) can be obtained, for example, by reacting a compound having two oxazoline groups with a compound having two carboxy groups and / or a compound having two phenolic hydroxyl groups. . Thereby, a high elastic modulus and high heat resistant resin cured product is particularly easily formed.

Examples of the compound containing an oxazoline group used for synthesizing the compound represented by the formula (1) include a bisoxazoline represented by the following general formula (2). In the formula ^(2), R ^{33, R 35} and ^{R 36} have the same meanings as ^{R 33, R 35} and ^{R 36} in the formula (1).

  Examples of the bisoxazoline represented by the formula (2) include 2,2 ′-(1,3-phenylene) bis-2-oxazoline and 2,6-bis (4-isopropyl-2-oxazolin-2-yl). At least one selected from the group consisting of pyridine, 2-2'-isopropylidenebis (4-phenyl-2-oxazoline), and 2-2'-isopropylidenebis (4-tertiarybutyl-2-oxazoline) is there.

Examples of the compound having two phenolic hydroxyl groups (bisphenol) include biphenol, tetramethylbiphenol, dihydroxynaphthalene, dihydroxymethylnaphthalene, dihydroxydimethylnaphthalene, bis (4-hydroxyphenyl) ketone, and bis (4-hydroxy-3,5). -Dimethylphenyl) ketone, bis (4-hydroxy-3,5-dichlorophenyl) ketone, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3,5-dimethylphenyl) sulfone, bis (4-hydroxy- 3,5-dichlorophenyl) sulfone, bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dimethylphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dichlorophenyl) Nyl) hexafluoropropane, bis (4-hydroxyphenyl) dimethylsilane, bis (4-hydroxy-3,5-dimethylphenyl) dimethylsilane, bis (4-hydroxy-3,5-dichlorophenyl) dimethylsilane, bis (4 -Hydroxyphenyl) methane, bis (4-hydroxy-3,5-dichlorophenyl) methane, bis (4-hydroxy-3,5-dibromophenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 2, 2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) Propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, bis (4- Droxyphenyl) ether, bis (4-hydroxy-3,5-dimethylphenyl) ether, bis (4-hydroxy-3,5-dichlorophenyl) ether, 9,9-bis (4-hydroxyphenyl) fluorene, 9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxy-3-chlorophenyl) fluorene, 9,9-bis (4-hydroxy-3-bromophenyl) fluorene, 9, 9-bis (4-hydroxy-3-fluorophenyl) fluorene, 9,9-bis (4-hydroxy-3-methoxyphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene 9,9-bis (4-hydroxy-3,5-dichlorophenyl) fluorene, and 9,9-bis (4- It may be at least one selected from the group consisting of (hydroxy-3,5-dibromophenyl) fluorene. Among these, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane is preferable. R ³¹ in the formula (1) is usually a residue obtained by removing a hydroxyl group from a compound having these two phenolic hydroxyl groups.

  The reaction between the compound having an oxazoline group and the compound having a carboxy group and / or the compound having a phenolic hydroxyl group is preferably performed at 50 to 200 ° C. If reaction temperature is 50 degreeC or more, reaction can be advanced efficiently, and if it is 200 degrees C or less, a side reaction can fully be suppressed. If necessary, the reaction may be carried out in a polar organic solvent such as dimethylformamide, dimethylacetamide, dimethylsulfoxide.

  Examples of the compound obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid include, for example, polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 14 propylene groups. Polypropylene glycol di (meth) acrylate, polyethylene polypropylene glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 14 propylene groups, trimethylolpropane di (meth) acrylate, trimethylol Propane tri (meth) acrylate, ethylene oxide (EO) modified trimethylolpropane tri (meth) acrylate, propylene oxide (PO) modified trimethylolpropane tri (meth) acrylate, EO and PO modified trimethylolpropane tri (meth) acrylate Or at least one selected from the group consisting of tetramethylolmethane tri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate Good.

  Examples of bisphenol A-based (meth) acrylate compounds include 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane and 2,2-bis (4-((meth) acryloxypolypropoxy). Phenyl) propane, 2,2-bis (4-((meth) acryloxypolybutoxy) phenyl) propane, and 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane It may be at least one selected from the group.

  The compound obtained by reacting a glycidyl group-containing compound with an α, β-unsaturated carboxylic acid is, for example, at least one epoxy selected from the group consisting of a novolac type epoxy resin, a bisphenol type epoxy resin and a salicylaldehyde type epoxy resin The epoxy (meth) acrylate compound obtained by making resin and (meth) acrylic acid react may be sufficient.

  An acid-modified epoxy acrylate compound obtained by reacting an acid anhydride such as tetrahydrophthalic anhydride with the hydroxyl group of the epoxy (meth) acrylate compound can also be used as a photopolymerizable compound. As such an acid-modified epoxy acrylate compound, for example, EA-6340 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.) represented by the following general formula (3) is commercially available. In formula (3), m and n represent 0 or an integer of 1 or more, and the ratio of m to n is 100/0 to 0/100.

  Examples of (meth) acrylic acid alkyl ester copolymers having an ethylenically unsaturated group include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, and (meth) acrylic. It contains at least one (meth) alkyl acid ester selected from the group consisting of acid 2-ethylhexyl ester as a monomer unit.

  The (meth) acrylate compound used as the photopolymerizable compound of the component (A) preferably has a carbon-nitrogen bond and has an amide bond and / or a urethane bond from the viewpoint of improving heat resistance and adhesion ( More preferred are meth) acrylate compounds.

  The resin composition has a (meth) acrylate compound having an amide bond and a urethane bond from the viewpoint of improving the adhesion density by increasing the crosslink density, increasing the tolerance of the imprint process, and balancing heat resistance. It is preferable to contain a (meth) acrylate compound. In this case, the ratio of the (meth) acrylate compound having a urethane bond and the (meth) acrylate compound having an amide bond ((meth) acrylate compound having a urethane bond / (meth) acrylate compound having an amide bond) is preferably It is 40 / 60-90 / 10, More preferably, it is 50 / 50-85 / 15, More preferably, it is 60 / 40-80 / 20.

(B) Photopolymerization initiator The resin composition for imprints according to this embodiment may contain a photopolymerization initiator. Thereby, a photopolymerizable compound can be bridge | crosslinked efficiently by light irradiation and the viscoelasticity of a resin layer can be easily adjusted to the range suitable for an imprint process. When the resin layer is thermoset after the imprint process, depending on the heating conditions, the resin may melt and the pattern may sag and deform, but the resin composition contains a photoinitiator, and after patterning Since the photopolymerizable compound can be efficiently cured by the light irradiation, pattern shape deterioration (sag of the pattern) associated with thermosetting can be more effectively suppressed.

  The photopolymerization initiator is not particularly limited as long as it is a compound that generates a free radical by actinic rays. For example, acylphosphine oxide, oxime ester, aromatic ketone, quinones, benzoin ether compound, benzyl derivative, 2, 4 , 5-triarylimidazole dimer, acridine derivative, coumarin compound, N-phenylglycine, and at least one selected from the group consisting of N-phenylglycine derivatives. Among these, acylphosphine oxide and oxime ester are preferable from the viewpoint of improvement of photocurability and high sensitivity, and transparency of the cured film.

  Examples of the acylphosphine oxide include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (commercial product: “IRGACURE-819”, manufactured by BASF), 2,4,6-trimethylbenzoyl-diphenyl. -Phosphine oxide (commercial product, "LUCIRIN TPO", manufactured by BASF).

  Examples of the oxime ester include 1,2-octanedione-1- [4- (phenylthio) phenyl-2- (O-benzoyloxime) represented by the following formula (4) (commercially available product: “IRGACURE-OXE01”, Manufactured by BASF), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone-1- (O-acetyloxime) (commercially available product: “IRGACURE-OXE02”, BASF And at least selected from the group consisting of 1-phenyl-1,2-propanedione-2- [o- (ethoxycarbonyl) oxime] (commercially available product: “Quantacure-PDO”, manufactured by Nippon Kayaku Co., Ltd.) One kind may be sufficient.

  Aromatic ketones include, for example, benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (ie Michler ketone), N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4. '-Dimethylaminobenzophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one (commercial product: “IRGACURE-651”, manufactured by BASF), 2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) -butan-1-one (commercial product: "IRGACURE-369", manufactured by BASF) and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1- It may be at least one selected from the group consisting of ON (commercial product: “IRGACURE-907”, manufactured by BASF).

  The quinones are, for example, 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, and at least selected from the group consisting of 2,3-dimethylanthraquinone One kind may be sufficient.

  The benzoin ether compound may be at least one selected from the group consisting of benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether, for example.

  The benzyl derivative may be, for example, at least one selected from the group consisting of benzoin compounds such as benzoin, methylbenzoin, and ethylbenzoin, and benzyldimethyl ketal.

  2,4,5-Triarylimidazole dimer is, for example, 2- (2-chlorophenyl) -1- [2- (2-chlorophenyl) -4,5-diphenyl-1,3-diazol-2-yl ] 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, such as 4,5-diphenylimidazole, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, and 2- (p-methoxyphenyl) -4, It may be at least one selected from the group consisting of 5-diphenylimidazole dimers.

  The acridine derivative may be at least one selected from the group consisting of 9-phenylacridine and 1,7-bis (9,9′-acridinyl) heptane, for example.

  Coumarin compounds include, for example, 7-amino-4-methylcoumarin, 7-dimethylamino-4-methylcoumarin, 7-diethylamino-4-methylcoumarin, 7-methylamino-4-methylcoumarin, 7-ethylamino- 4-methylcoumarin, 7-dimethylaminocyclopenta [c] coumarin, 7-aminocyclopenta [c] coumarin, 7-diethylaminocyclopenta [c] coumarin, 4,6-dimethyl-7-ethylaminocoumarin, 4, 6-diethyl-7-ethylaminocoumarin, 4,6-dimethyl-7-diethylaminocoumarin, 4,6-dimethyl-7-dimethylaminocoumarin, 4,6-diethyl-7-ethylaminocoumarin, 4,6-diethyl -7-dimethylaminocoumarin, 2,3,6,7,10,11-hexanehydro-1H, H-cyclopenta [3,4] [1] benzopyrano- [6,7,8-ij] quinolizine 12 (9H) -one, 7-diethylamino-5 ′, 7′-dimethoxy-3,3′-carbonylbiscoumarin 3,3′-carbonylbis [7- (diethylamino) coumarin] and 7-diethylamino-3-thienoxysilkine may be at least one selected from the group consisting of

  The content of the photopolymerization initiator is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, and still more preferably 0 with respect to 100 parts by mass of the photopolymerizable compound (A). .75 to 5 parts by mass. When the content is within these ranges, the sensitivity and photocurability of the imprint resin composition are particularly enhanced, and the adjustment of the viscoelasticity of the resin layer and the maintenance of the pattern shape during thermosetting are further facilitated. Become.

(C) Polymer compound, thermosetting resin The resin composition according to the present embodiment is selected from a polymer compound and a thermosetting resin, and is different from the above-mentioned photopolymerizable compound (hereinafter referred to as “heat resistance in some cases”). Resin ")). Thereby, regarding the resin layer after curing, the effects of high heat resistance, thermal conductivity, heat cycle resistance, and high mounting reliability with respect to lead-free high-temperature solder can be obtained.

  Examples of the heat resistant resin include phenol resin, novolac resin, epoxy resin, unsaturated polyester resin, alkyd resin, furan resin, urea resin, melamine resin, polyurethane resin, aniline resin, thermosetting modified polyphenylene ether resin, thermosetting It may be at least one selected from the group consisting of polyimide resins, allyl resins, bismaleimide triazine resins, silicon resins, and benzoxazine resins. Among these, epoxy resins, phenol resins, urea resins, unsaturated polyester resins, allyl resins, thermosetting polyimide resins, bismaleimide triazine resins, thermosetting modified polyphenylene ether resins, silicon resins, and benzoxazine resins are suitable. The epoxy resin is an organic compound (thermosetting resin) having at least one oxirane ring (epoxy group).

  The thermosetting resin as the heat resistant resin is preferably used in combination with a curing agent. Curing agents include, for example, polyphenolic curing agents, polyamine curing agents, carboxylic acid hydrazides, diaminomaleonitrile, dicyandiamide and derivatives thereof, imidazoles, polyamine nylon salts and phosphates, and Lewis acids and amine complexes thereof. It may be at least one selected from more.

  The polymer compound used as the heat resistant resin may be a polyamic acid or a polyamic acid ester. The polyamic acid or polyamic acid ester is represented, for example, by the following general formula (5).

In Formula (5), R ¹ represents a tetravalent organic group, R ² represents a divalent organic group, R ³ represents a hydrogen atom or a monovalent organic group, and a plurality of R ³ in the same molecule May be the same or different.

R ¹ is not particularly limited, but is a group formed by removing four hydrogen atoms from, for example, benzene, biphenyl, naphthalene, benzophenone, cyclobutane, cyclohexane, xanthene, or thioxanthene from the viewpoint of excellent low thermal expansion. Also good. R ² may be, for example, a group formed by removing two hydrogen atoms from benzene, biphenyl, benzophenone, or cyclohexane. These skeletons may be substituted with one or more substituents selected from a methyl group, a trifluoromethyl group, a fluorine atom and a hydroxyl group.

The monovalent organic group as R ³ is, for example, an aliphatic or aromatic hydrocarbon group having 1 to 10 carbon atoms such as methyl group, ethyl group, isopropyl group, t-butyl group, phenyl group, benzyl group, It may be at least one selected from the group consisting of an alkoxyalkyl group having 2 to 10 carbon atoms such as a methoxyethyl group and a group formed by substituting a fluorine atom for them. Of these, a hydrogen atom, an ethyl group, a 2,2,2-trifluoroethyl group, an isopropyl group, a t-butyl group, and a benzyl group are preferable.

As the heat-resistant resin, polyhydroxyamide, which is a polybenzoxazole precursor that forms polybenzoxazole by ring closure by heating, is preferable because of its excellent heat resistance, mechanical properties, and electrical properties. This polyhydroxyamide has, for example, a structural unit represented by the following general formula (6). The amide unit containing a hydroxy group is finally converted into an oxazole having excellent heat resistance, mechanical properties, and electrical properties by dehydration and ring closure during curing. In formula (6), R ¹¹ represents a tetravalent organic group, and R ¹² represents a divalent organic group.

  The polyhydroxyamide having a repeating unit represented by the formula (6) can be synthesized from, for example, a dicarboxylic acid compound and a diamine compound having a hydroxy group. Specifically, after converting a dicarboxylic acid compound into a dihalide compound, a polyhydroxyamide having a repeating unit represented by the formula (6) can be synthesized by reacting the dihalide compound with the diamine compound. As the dihalide compound, a dichloride compound is preferable.

  The dichloride compound can be synthesized by reacting a dicarboxylic acid compound with a halogenating agent. As the halogenating agent, those used in usual acid chlorideation reaction of carboxylic acid, for example, thionyl chloride, phosphoryl chloride, phosphorus oxychloride, phosphorus pentachloride and the like can be used.

  The synthesis of the dichloride compound should be carried out by reacting the dicarboxylic acid compound and the halogenating agent in a reaction solvent, or by reacting in an excess halogenating agent and then distilling off the excess halogenating agent. Can do. As a reaction solvent, N-methyl-2-pyrrolidone, N-methyl-2-pyridone, N, N-dimethylacetamide, N, N-dimethylformamide, toluene, benzene and the like can be used. When the reaction is carried out in a solvent, the amount of the halogenating agent is preferably 1.5 to 3.0 mol, more preferably 1.7 to 2.5 mol, relative to 1.0 mol of the dicarboxylic acid compound. When the reaction is carried out in a halogenating agent, the amount of the halogenating agent is preferably 4.0 to 50 mol, more preferably 5.0 to 20 mol, relative to 1.0 mol of the carboxylic acid compound. The reaction temperature is preferably -10 to 70 ° C, more preferably 0 to 20 ° C.

  The reaction between the dichloride compound and the diamine is preferably performed in an organic solvent in the presence of a dehydrohalogenating agent. As the dehydrohalogenating agent, organic bases such as pyridine and triethylamine are usually used. As the organic solvent, N-methyl-2-pyrrolidone, N-methyl-2-pyridone, N, N-dimethylacetamide, N, N-dimethylformamide and the like can be used. The reaction temperature is preferably −10 to 30 ° C., more preferably 0 to 20 ° C.

In formula (6), the tetravalent organic group represented by R ¹¹ is generally a residue of a diamine compound having two amino groups and two hydroxy groups. The hydroxy group may be located at the ortho position of the amino group. R ¹¹ is preferably a group containing an aromatic ring. The number of carbon atoms in R ¹¹ is preferably 6 to 40. R ¹¹ is preferably a tetravalent group having 6 to 40 carbon atoms and containing an aromatic ring. In the diamine compound, it is preferable that both the amino group and the hydroxyl group are directly bonded to the aromatic ring in R ¹¹ .

  Examples of the diamine compound include 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, bis (3-amino-4-hydroxyphenyl) propane, Bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, 2,2-bis (3-amino-4) -Hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane and 2,2-bis (4-amino-3-hydroxyphenyl) -1,1,1,3,3,3-hexa It may be at least one selected from the group consisting of fluoropropane.

  In addition to the structural unit of the formula (6), the polyhydroxyamide may further include a structural unit having no hydroxyl group. That is, the polyhydroxyamide may be a polymer represented by the following general formula (7), for example.

In the formula (7), R ¹³ represents a tetravalent organic group, and R ¹² represents a divalent organic group. j and k represent mole fractions, and the sum of j and k is 100 mol%, preferably j is 60 to 100 mol% and k is 40 to 0 mol%. More preferably, j is 80 to 100 mol% and k is 20 to 0 mol%.

In formula (7), the divalent organic group represented by R ¹³ is generally a residue of a diamine compound having no hydroxyl group, which reacts with a dicarboxylic acid compound to form a polyamide structure. R ¹³ is preferably a divalent aromatic group or an aliphatic group. The number of carbon atoms is preferably 4 to 40, and more preferably a divalent aromatic group having 4 to 40 carbon atoms.

  Examples of the diamine compound having no hydroxyl group include 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenyl sulfide, benzidine, m- Phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl And at least one aromatic diamine compound selected from the group consisting of bis [4- (4-aminophenoxy) phenyl] ether and 1,4-bis (4-aminophenoxy) benzene. The diamine compound may be a diamine having a silicone group. Examples of the diamine having a silicone group include LP-7100, X-22-161AS, X-22-161A, X-22-161B, X-22-161C, and X-22-161E (all manufactured by Shin-Etsu Chemical Co., Ltd.). However, it is not limited to these. These compounds can be used alone or in combination of two or more.

In formulas (6) and (7), the divalent organic group represented by R ¹² is generally a residue of a dicarboxylic acid compound used to synthesize polyhydroxyamide. R ¹² is preferably a divalent group containing an aromatic ring. R ¹² preferably has 6 to 40 carbon atoms. R ¹² is more preferably a divalent group having 6 to 40 carbon atoms including an aromatic ring. It is preferred that none of the two carboxyl groups are bonded directly to the aromatic ring in R ^12.

  Examples of the dicarboxylic acid compound include isophthalic acid, terephthalic acid, 2,2-bis (4-carboxyphenyl) -1,1,1,3,3,3-hexafluoropropane, and 4,4′-dicarboxybiphenyl. 4,4′-dicarboxydiphenyl ether, 4,4′-dicarboxytetraphenylsilane, bis (4-carboxyphenyl) sulfone, 2,2-bis (p-carboxyphenyl) propane, 5-tert-butylisophthalic acid , Aromatic dicarboxylic acids such as 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2,6-naphthalenedicarboxylic acid, and 1,2-cyclobutanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid , 1,3-cyclopentanedicarboxylic acid, oxalic acid, malonic acid, succinic acid, etc. It may be at least one selected from the group consisting of carboxylic acid.

(Other ingredients)
The imprinting resin composition may contain an adhesion aid in order to improve the adhesiveness between the imprinting resin composition and the substrate, if necessary. Examples of the adhesion assistant include silane coupling agents such as γ-glycidoxysilane, aminosilane, and γ-ureidosilane. The content of the adhesion assistant is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass, and still more preferably 0.1 to 100 parts by mass of the photopolymerizable compound (A). 5 to 2 parts by mass.

  From the viewpoint of workability when applied to a substrate, a support film or the like, a solution or dispersion of the resin composition may be prepared as a coating liquid by adding a solvent to the imprint resin composition. The solvent to be used is not particularly limited, but includes, for example, polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, propylene glycol monomethyl ether acetate, and γ-butyrolactone. It may be at least one selected from the group. The concentration of the resin composition for imprint in the coating solution is preferably 20 to 85% by mass, more preferably 30 to 80% by mass, based on the mass of the coating solution.

<Electronic parts>
The electronic component according to the present embodiment includes a resin layer (cured film) having a pattern formed by the above-described method as a permanent film. The electronic component may be, for example, a semiconductor device, a multilayer wiring board, various electronic devices, or the like.

  The “permanent film” is a film constituting an electronic component or the like as a finished product without being removed in the process of manufacturing the electronic component or the like. Specific examples of the permanent film include a surface protective film and an interlayer insulating film of an electronic component, and an interlayer insulating film of a multilayer wiring board. The electronic component according to the present embodiment is not particularly limited as long as it has a permanent film formed by the method according to the present embodiment.

  FIG. 3 is a cross-sectional view showing an embodiment of a semiconductor device provided with a resin layer having a pattern as a permanent film. A semiconductor device 100 shown in FIG. 3 includes a silicon chip 23, an interlayer insulating film 11 provided on one side of the silicon chip 23, and an Al having a pattern including a pad portion 15 formed on the interlayer insulating film 11. A wiring layer 12, an insulating layer 13 (for example, a P-SiN layer) and a surface protective layer 14, which are sequentially stacked on the interlayer insulating film 11 and the Al wiring layer 12 while forming an opening on the pad portion 15, and a surface protective layer 14 is in contact with the pad portion 15 in the openings of the insulating layer 13 and the surface protective layer 14 and is opposite to the surface protective layer 14 of the core 18 for the rewiring layer. And a rewiring layer 16 extending on the surface protective layer 14 so as to be in contact with the surface. Further, the semiconductor device 100 includes a cover coat layer 19 that covers the surface protective layer 14, the rewiring core 18, and the rewiring layer 16, and forms an opening in the portion of the rewiring layer 16 on the core 18. The conductive ball 17 connected to the rewiring layer 16 with the barrier metal 20 interposed therebetween in the opening of the layer 19, the collar 21 that holds the conductive ball, and the cover coat layer 19 around the conductive ball 17 are provided. The underfill 22 is provided. The conductive ball 17 is used as an external connection terminal and is formed of solder, gold or the like. The underfill 22 is provided to relieve stress when the semiconductor device 100 is mounted.

  In the semiconductor device 100, at least one permanent film selected from the group consisting of an interlayer insulating layer, a surface protective layer, a cover coat layer, a rewiring core, a collar, and an underfill can be formed with the above-described resin composition. It is a membrane. The cured film formed with the resin composition for imprints according to the present embodiment is excellent in adhesiveness with a metal layer and a sealant, and has a high stress relaxation effect. Therefore, the semiconductor element 100 has extremely excellent reliability. The semiconductor device according to the present invention is not limited to the one having the structure shown in FIG.

  In order to make the interlayer insulating layer, surface protective layer, cover coat, core for rewiring, ball collar such as solder, underfill, etc. more reliable, 50 after the resin composition for imprinting is cured The coefficient of thermal expansion at -100 ° C is preferably 50 ppm / K or less, more preferably 30 ppm / K or less. By including an appropriate amount of inorganic filler in the imprinting resin composition used to form the permanent film, the thermal expansion coefficient can be significantly reduced.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

<Synthesis of (C) Component Polymer>
Hereinafter, the synthesis method will be shown. The weight average molecular weight was determined by GPC method using a mixed solution of tetrahydrofuran and N, N-dimethylacetamide as an eluent. Details of the GPC method are as follows.
Device name: HLC-8320GPC (product name, manufactured by Tosoh Corporation)
Column: TSKgel SuperAWM-H, TSKgelguardcolumn SuperAW-H, TSKgel SuperH2500, TSKgel SuperH3000, TSKgel SuperH4000, TSKgelguardcolumn Super-L
Detector: UV, RI detector Column temperature: 40 ° C
Eluent: Mixed solution of tetrahydrofuran and N, N-dimethylacetamide
(Mixing ratio 1: 1)
Additives: lithium bromide monohydrate (0.03 mol / L), phosphoric acid (0.06 mol / L)
Flow rate: 0.35 ml / min Standard material: Polystyrene

(Synthesis Example 1) Polyamide acid 5.4 g (50 mmol) of p-phenylenediamine and 16.0 g (50 mmol) of 2,2′-bis (trifluoromethyl) benzidine are dissolved in 150 ml of N-methyl-2-pyrrolidone. I let you. Thereafter, 39.4 g (100 mmol) of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride was added to proceed the polymerization, and a solution of the produced polyamic acid (Polymer I) was obtained. The weight average molecular weight of the polyamic acid determined by standard polystyrene conversion was 41400.

(Synthesis Example 2) Polyamide acid The synthesis was performed under the same conditions as in Synthesis Example 1 except that 2,2′-bis (trifluoromethyl) benzidine was replaced with an equimolar amount of 2,2′-dimethylbenzidine. A solution of (Polymer II) was obtained. The weight average molecular weight of the polyamic acid determined by standard polystyrene conversion was 51500.

Synthesis Example 3 Polyhydroxyamide (Polybenzoxazole Precursor)
In a 0.5 liter flask equipped with a stirrer and a thermometer, 15.48 g (60 mmol) of 4,4′-diphenyl ether dicarboxylic acid and 90 g of N-methylpyrrolidone were charged. While the flask was cooled to 5 ° C., 23.9 g (120 mmol) of thionyl chloride was added dropwise and reacted for 30 minutes to obtain a solution of 4,4′-diphenyl ether dicarboxylic acid chloride. Next, 87.5 g of N-methylpyrrolidone was placed in a 0.5 liter flask equipped with a stirrer and a thermometer, and 18.30 g of bis (3-amino-4-hydroxyphenyl) hexafluoropropane (6FAP) was added thereto. (50 mmol) was dissolved. Further, 9.48 g (120 mmol) of pyridine was added, and while maintaining the temperature at 0 to 5 ° C., a solution of 4,4′-diphenyl ether dicarboxylic acid chloride was added dropwise over 30 minutes, followed by stirring for 30 minutes. The reaction solution was poured into 3 liters of water, and the precipitate was collected. The precipitate was washed three times with pure water and then dried under reduced pressure to obtain polyhydroxyamide (Polymer III) having a carboxyl group at the terminal. The weight average molecular weight of the polymer III calculated | required by standard polystyrene conversion of GPC method was 17600, and dispersion degree was 1.6.

Synthesis Example 4 Polyhydroxyamide (Polybenzoxazole Precursor)
In a 0.5 liter flask equipped with a stirrer and a thermometer, 12.90 g (50 mmol) of 4,4′-diphenyl ether dicarboxylic acid and 75 g of N-methylpyrrolidone were charged. While cooling the flask to 5 ° C., 19.9 g (100 mmol) of thionyl chloride was added dropwise and reacted for 30 minutes to obtain a solution of 4,4′-diphenyl ether dicarboxylic acid chloride. Next, 105 g of N-methylpyrrolidone was placed in a 0.5 liter flask equipped with a stirrer and a thermometer, and 22.0 g (60 mmol) of bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 5 g were added thereto. -Norbornene-2,3-dicarboxylic anhydride 3.28 g (20 mmol) was dissolved. Further, 7.9 g (100 mmol) of pyridine was added, and while maintaining the temperature at 0 to 5 ° C., a solution of 4,4′-diphenyl ether dicarboxylic acid chloride was added dropwise over 30 minutes, and then stirring was continued for 30 minutes. The reaction solution was poured into 3 liters of water, and the precipitate was collected. The precipitate was washed three times with pure water and then dried under reduced pressure to obtain polyhydroxyamide (Polymer IV) having a double bond at the end. The weight average molecular weight of the polymer IV calculated | required by GPC method standard polystyrene conversion was 22800, and dispersion degree was 1.8.

Synthesis Example 5 Polyhydroxyamide (Polybenzoxazole Precursor)
In a 0.5 liter flask equipped with a stirrer and a thermometer, 12.90 g (50 mmol) of 4,4′-diphenyl ether dicarboxylic acid and 75 g of N-methylpyrrolidone were charged. While the flask was cooled to 5 ° C., 19.9 g (100 mmol) of thionyl chloride was added dropwise and reacted for 30 minutes to obtain a solution of 4,4′-diphenyl ether dicarboxylic acid chloride. Next, 105 g of N-methylpyrrolidone was charged into a 0.5 liter flask equipped with a stirrer and a thermometer, and 14.7 g (40 mmol) of bis (3-amino-4-hydroxyphenyl) hexafluoropropane and m -2.16 g (20 mmol) of aminophenol was dissolved. Further, 7.9 g (100 mmol) of pyridine was added, and while maintaining the temperature at 0 to 5 ° C., a solution of 4,4′-diphenyl ether dicarboxylic acid chloride was added dropwise over 30 minutes, and then stirring was continued for 30 minutes. The reaction solution was poured into 3 liters of water, and the precipitate was collected. The precipitate was washed three times with pure water and then dried under reduced pressure to obtain a polyhydroxyamide (Polymer V) having a phenol terminal. The weight average molecular weight of the polymer V determined by GPC standard polystyrene conversion was 15600, and the degree of dispersion was 1.7.

(Preparation of resin composition for imprint)
(A) The photopolymerizable compound as the component, the photopolymerization initiator as the component (B), and the polymer as the component (C) are mixed in the ratio shown in Table 1 in N-methylpyrrolidone as a solvent, The solution of the resin composition for imprint of each Example and a comparative example was obtained. The numbers in the table indicate the mass parts of the solid content of each component. The detail of each component in a table | surface is shown below.
(A) Component: Photopolymerizable compound / UN-904, UN-952 (trade name, urethane acrylate, manufactured by Negami Kogyo Co., Ltd.)
FA-7220M (trade name, amide bond-containing methacrylate, manufactured by Hitachi Chemical Co., Ltd.)
Component (B): Photopolymerization initiator / I-819 (trade name, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, manufactured by Ciba Specialty Chemicals Co., Ltd.)

Table 1 shows the number of functional groups (acryloyloxy groups) and weight average molecular weight of urethane acrylate. The weight average molecular weight (Mw) is determined by GPC method using tetrahydrofuran and N, N-dimethylacetamide as an eluent. Details of the GPC method are as follows.
Device name: HLC-8320GPC (product name, manufactured by Tosoh Corporation)
Column: TSKgel Super AWM-H, TSK gel guard column Super A W-H, TSK gel Super H 2500, TSK gel Super H 3000, TSK gel Super H 4000, TSK gel guard column, Super H-L
Detector: UV, RI detector Column temperature: 40 ° C
Eluent: Mixed solution of tetrahydrofuran and N, N-dimethylacetamide
(Mixing ratio 1: 1)
Additives: lithium bromide monohydrate (0.03 mol / L), phosphoric acid (0.06 mol / L)
Flow rate: 0.35 ml / min Standard material: Polystyrene

<Preparation of resin film for imprint>
The solution of the resin composition for imprint of an Example and a comparative example was apply | coated uniformly using the applicator on the polyethylene terephthalate as a support film. The applied solution is heated in a 120 ° C. dryer for 30 minutes to remove the solvent, thereby forming an imprint resin layer, and a two-layer imprint having a support film and a resin layer on the support film A resin film was obtained.

<Evaluation of pattern formability>
On the test substrate, the imprinting resin film was laminated in such a direction that the support film was positioned on the side opposite to the test substrate. Lamination was performed using a laminator. The resin film for imprint laminated on the test substrate was exposed at an exposure amount of 10 mJ / cm ² using a high-precision parallel exposure machine (Oak Seisakusho) (light irradiation before imprinting). The presence or absence of light irradiation before imprinting is shown in Table 2.

Next, after peeling off the support film, the resin layer is placed on the silicon mold together with the test substrate, and these are set in a crimping machine and pressurized while heating at 60-200 ° C. for 2 minutes at 8 MPa. did. The mold was removed and the film of the patterned resin layer was observed using a scanning electron microscope, and the pattern forming property was evaluated based on the following criteria.
A: The resin pattern remained in the mold, and a good pattern was formed.
B: Resin remains partially in the mold, and the chipping can be confirmed.
C: Most of the resin remains in the mold, and pattern formation is difficult.
D: The mold does not peel from the resin layer.

<Evaluation of pattern retention>
Similar to the evaluation of pattern formation, an imprinting resin film was laminated on the test substrate. Next, after peeling off the support film, the resin layer was placed on a silicon mold together with the test substrate, and these were set in a crimping machine and pressurized while heating at 60-200 ° C. for 2 minutes at 8 MPa. . After pressurization, the mold was removed from the resin layer, and then the resin layer on which the pattern was formed was irradiated with light at an exposure amount of 4000 mJ / cm ² using a high-precision parallel exposure machine (Oak Seisakusho). After the exposure, the temperature was raised from room temperature to 200 ° C. at 2.8 ° C./min in an oven, and then the resin layer was thermally cured by heating at 200 ° C. for 1 hour.

The cured resin layer (cured film) was observed using a scanning electron microscope, and pattern retention was evaluated based on the following criteria.
A: The resin layer is not melted.
B: Shape change due to melting is observed.

  Table 2 shows the evaluation results. It was confirmed that the light irradiation before imprinting reduced the adhesion between the resin layer and the mold, and resulted in excellent pattern formability. It was also confirmed that a good pattern was maintained even after thermosetting by proceeding with a crosslinking reaction in the resin layer by light irradiation before thermosetting. FIG. 4 is an electron micrograph of the resin layer having the pattern formed in Example 1 after thermosetting.

  On the other hand, as in the comparative example, when the light irradiation before imprinting was not performed, the adhesiveness between the resin layer and the mold was excessively large, and thus the mold was not peeled off from the resin layer after the mold was pressed. It became. In addition, it was confirmed that, after imprinting, when thermosetting was performed without light irradiation, heat softening occurred and it was difficult to maintain the shape. FIG. 5 is an electron micrograph of the resin layer having the pattern formed in Comparative Example 1 after thermosetting.

DESCRIPTION OF SYMBOLS 1 ... Substrate, 5 ... Mold, 10 ... Resin layer (cured film) having a pattern, 10a ... Resin layer, 10b ... Resin layer having a pattern, 11 ... Interlayer insulating film, 12 ... Al wiring layer, 13 ... Insulating layer, DESCRIPTION OF SYMBOLS 14 ... Surface protective layer, 15 ... Pad part, 16 ... Redistribution layer, 17 ... Conductive ball, 18 ... Core, 19 ... Cover coat layer, 20 ... Barrier metal, 21 ... Collar, 22 ... Underfill, 23 ... Silicon Chip, 100... Semiconductor device (electronic component).

Claims (8)

Irradiating the resin layer made of the resin composition with light;
A step of pressing a mold having a concavo-convex pattern on the resin layer irradiated with light to form a pattern reversed on the concavo-convex pattern on the resin layer;
Removing the mold from the resin layer on which a pattern is formed;
A method for producing a resin layer having a pattern.   The method according to claim 1, further comprising a step of curing the resin layer on which the pattern is formed after the step of removing the mold from the resin layer.   The method according to claim 2, wherein the step of curing the resin layer on which the pattern is formed includes irradiating light to the resin layer on which the pattern is formed.   The method according to any one of claims 1 to 3, wherein the resin composition contains a photopolymerizable compound and a photopolymerization initiator.   The method according to claim 4, wherein the resin composition further contains a compound different from the photopolymerizable compound selected from a polymer compound and a thermosetting resin.   The resin layer which has a pattern which can be obtained by the method as described in any one of Claims 1-5.   The resin layer having a pattern according to claim 6, which is a permanent film.   An electronic component comprising a resin layer having the pattern according to claim 6.