JP2003105207A - Resin composition and display device using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition, especially a photosensitive resin composition, giving a film with good in-plane uniformity of thickness, and to provide a display device such as a liquid crystal device with uniform thickness of layer using the composition. SOLUTION: The photosensitive resin composition comprises (1) a copolymer having an unsaturated carboxylic acid monomer and a vinylic monomer whose homopolymer is insoluble in alkali as structural units (hereinafter referred to as an alkali-soluble resin), (2) an alkali-insoluble epoxy group-containing polymer, (3) an ethylenically unsaturated bond-containing compound and (4) a photopolymerization initiator and a photosensitizer, and further added with a fluorine-containing glyceral derivative expressed by the formula and a solvent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for a display device, which is particularly excellent in film thickness uniformity during coating, particularly a photosensitive resin composition, and a display device using the same.

[0002]

2. Description of the Related Art In liquid crystal elements used in microcomputers, word processors, televisions, watches and calculators, nematic liquid crystal molecules are aligned at 90 degrees between a pair of upper and lower transparent electrode substrates. A twisted nematic (TN) mode with a twisted structure is adopted. In addition, a super twisted nematic (hereinafter abbreviated as STN) mode having a large twist angle of 180 to 300 degrees has been developed, and a liquid crystal element having a good display quality even on a large screen can be obtained. Furthermore, in recent years, since matrix display and color display have come to be performed, a large number of pixel electrodes and an MIM adopting an active TN mode capable of performing ON / OFF of these pixel electrodes are employed.
The development of (metal-insulating phase-metal) elements and TFT (field effect thin film transistor) elements has become active. Also,
A device using a ferroelectric liquid crystal capable of high-speed response or an antiferroelectric liquid crystal capable of high-definition display has also been developed. Furthermore, IPS (In-Plane Switchin) using a lateral electric field
g) method, OCB (Optically Compensated Bend) method that combines a bend mode of liquid crystal and a compensation film, and VA (Vertically Aligned Nematic) method that uses homeotropic alignment (alignment perpendicular to the substrate, vertical alignment) Being developed.

As a gap control technique for a liquid crystal element common to all of these modes, spacer particles such as glass beads and plastic beads are dispersed in the middle of two substrates, and the thickness of the liquid crystal layer is controlled by their size. The method of doing has been used. However, this method has the following problems. 1) When spacer particles are arranged in the effective pixel area,
Pixels in the area where the spacer particles are present do not contribute to the display, so that the contrast and aperture ratio are lowered, and the display quality is lowered. 2) Display defects are caused by damage to the alignment film due to the movement of the spacer particles, aggregation of the spacer particles, or abnormal alignment around the spacer particles. 3) The panel strength decreases as the spacer particle size decreases. Further, these problems become more remarkable as the LCD has a larger screen and higher definition (narrower gap, higher resolution).

In order to solve these problems, a method of forming a spacer by photolithography has been proposed. According to this method, it is possible to form a dot-shaped or stripe-shaped spacer by applying a photosensitive resin to a substrate, irradiating ultraviolet rays through a predetermined mask, and then developing. According to this, the spacer can be formed in a place other than the effective pixel portion. Further, according to this method, the cell gap can be controlled by the coating film thickness of the photosensitive resin, so that the control of the gap thickness is easy and the accuracy is high. Further, it is possible to use spacer particles mixed with a photosensitive resin. However, there is variation in the coating thickness of the photosensitive resin within the substrate surface, which results in variation in the thickness of the obtained spacers,
There is a problem that the uniformity of the cell gap becomes low.

In the process of manufacturing a liquid crystal device, the following three methods can be used as a method of providing a spacer and a rubbed alignment film. a. Before applying the alignment film, a spacer is formed and rubbing is performed. b. After applying the alignment film, a spacer is formed and rubbing is performed. c. A spacer is formed on the rubbed alignment film. The spacer formed of the photosensitive resin is
In order to be usable in all methods of c, the following properties are required.

1) In the photolithography process for forming spacers, in order to improve the yield, the thickness of the coating film is uniform within the surface, the sensitivity is high, and there is no development residue (scum) after development. It is necessary to be able to control the shape. 2) In addition, the formed spacer has a uniform height in the plane, has alkali resistance and water resistance in the washing step before applying the alignment film, and is used for the alignment film. Solvent resistance to the solvent used, heat resistance that does not cause thermal deformation in the baking process of the alignment film, high rubbing resistance to prevent display defects due to rubbing, and liquid crystal alignment It is necessary not to cause a defect and to reduce the voltage holding ratio and the residual DC.

Further, conventionally, a sealant has been used as an adhesive for bonding liquid crystal elements and for sealing a liquid crystal compound (liquid crystal composition). Generally, an epoxy thermosetting resin is used as this sealing agent, but the problem of the occurrence of misalignment in the peripheral area of this sealing agent is caused by the epoxy curing accelerator and the resin itself. Is believed to be dissolved in the liquid crystal. Therefore, by forming the seal portion with the photosensitive resin, it is possible to prevent the defective orientation around the seal portion.

Conventionally, as a diffuse reflection surface of a reflection type or semi-transmission type liquid crystal element, there is a metal surface having aluminum or the like deposited on a random uneven surface. A photoresist is used to form the uneven shape. However, the conventional photoresist has a problem that the in-plane uniformity of the film thickness is insufficient and it is difficult to control the distribution of reflected light.

Conventionally, a photoresist has been used as a projection material for improving the viewing angle by dividing a pixel of a liquid crystal element using the VA method, but the conventional photoresist has insufficient in-plane uniformity of the film thickness. Therefore, there is a problem that the viewing angle becomes uneven.

[0010]

SUMMARY OF THE INVENTION The main object of the present invention is to improve the in-plane uniformity of the above-mentioned problems, namely, the thickness of the coating film. In addition to the above-mentioned physical and chemical characteristics. A resin composition and a photosensitive resin composition having the above are provided. More specifically, the liquid crystal has good liquid crystal orientation, has no deterioration in electrical characteristics such as afterimage phenomenon and voltage holding ratio, has excellent aperture ratio and contrast, has high mechanical strength, and has a uniform liquid crystal layer thickness. An element and a display element such as a flat panel display.

[0011]

DISCLOSURE OF THE INVENTION The present inventors have found that a resin composition containing an organic polymer compound and an organic solvent, particularly a photosensitive resin composition, has a general formula (I).

[Chemical 2] (In the formula, A₁O is an oxyethylene group, A₂O is oxypro
Represents a pyrene group, an oxyethylene group and an oxypropyl group.
The array of len groups can be random, block or multi-block.
You can use lock, R₁~ R₃And each R_FourIs independently C₆F
₁₁-, C₉F₁₇-, C₉F₁₇OC₆H_Four-CO-, young
Represents a hydrogen atom, at least one of which is
Any of fluorinated groups, m₁₁, M₁₂, M_{twenty one}, M_{twenty two},
m₃₁, M₃₂, M ₄₁, And m₄₂Are independently integers from 0 to 30
Yes, (m₁₁+ M₁₂), (M_{twenty one}+ M_{twenty two}), (M₃₁+
m₃₂) And (m₄₁+ M₄₂) Is 0 to 30, and n is 0
Specifically, it represents an integer of 1 to 9. ) Surfactant
And to use the resulting resin composition
The present invention was found to be able to solve the above problems, and
It came to completion.

The present invention has the following configuration. A first invention of the present invention is a resin composition for display devices, which contains a surfactant represented by the general formula (I) and contains an organic polymer compound and an organic solvent as essential components.

Furthermore, preferred embodiments are the compounds of formula (I), R ₁ ~R ₃ and at least 2 Tsuga含fluorine group C ₆ F ₁₁ of the _{R 4 -, C 9 F 17} - or C ₉ F ₁₇ O -C ₆ H
_4- CO- is represented, and the rest is the above resin composition containing a surfactant which is a hydrogen atom. Furthermore, a preferred embodiment is that in the general formula (I), m ₁₂ , m ₂₂ , m ₃₂ and m ₄₂
Is the case where all are 0, which is any of the above resin compositions containing such a surfactant.

In another preferred embodiment, the above organic polymer compound is a polymer shown in the following (1) and (2), and by further adding the following (3) and (4) as an essential component to it, it is exposed to light. A photosensitive resin composition is formed.
The resin composition according to any one of 1 to 3. (1) a copolymer having an unsaturated carboxylic acid monomer and a vinyl monomer whose homopolymer is alkali-insoluble as a structural unit (hereinafter abbreviated as alkali-soluble resin), (2) alkali-insoluble epoxy group-containing weight Coalescing,
(3) Ethylenically unsaturated bond-containing compound, (4) Photopolymerization initiator, Photosensitizer. In a further preferred embodiment, the organic solvent is
Propylene glycol-1-monomethyl ether-2-
The photosensitive resin composition is a solvent containing acetate.

A second aspect of the present invention is a step of applying the above-mentioned photosensitive resin composition onto a substrate, a step of prebaking the obtained coating film, a step of exposing through a photomask, and an exposing part using a developing solution. Alternatively, it is a liquid crystal element containing a patterned resin film, which comprises a patterning step including a step of removing an unexposed portion and a step of post-baking.

A more preferred embodiment is a liquid crystal element in which the patterned resin film is a spacer of the liquid crystal element.
Another preferred embodiment is a liquid crystal device in which the patterned resin film is a spacer containing beads. Another preferred embodiment is a liquid crystal element in which the patterned resin film is a sealant for the liquid crystal element. Another preferred embodiment is a liquid crystal element in which the patterned resin film is a projection for light reflection and scattering of the liquid crystal element. Another preferred embodiment is a liquid crystal element in which the patterned resin film is a protrusion for the vertical alignment mode of the liquid crystal element.

The third invention of the present invention is a liquid crystal device containing a color filter protective film obtained from the above resin composition. A fourth invention in the present invention is a plasma display panel containing a resin film obtained from the above resin composition. A fifth aspect of the present invention is a light emitting diode element containing a resin film obtained from the above resin composition. A sixth invention in the present invention is an organic electroluminescence device containing a resin film obtained from the above resin composition.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The surfactant used in the present invention is a fluorinated glycerin derivative represented by the general formula (I). Such a compound can be synthesized by the method described in JP-A-4-140441. In the general formula (I), C ₆ F _11- , C ₉ F ₁₇ -or C ₉ F
_{17 O-C 6 H 4 C} 6 in _{-CO- F 11 -, C 9 F} 17 -
Is a dimer or trimer residue of hexafluoropropene. One kind or several kinds of such compounds can be mixed and used. The surfactant is used to improve the wettability to the base substrate, the leveling property and the coating property, and is 0.005 to 1 part by weight, more preferably 0.01 part by weight with respect to 100 parts by weight of the resin composition. ~ 0.5
It is used in the addition amount of parts by weight.

[0019] Formula Preferred compounds among the compounds represented by (I) is, R ₁ to R ₃ and at least 2 Tsuga含fluorine group C ₆ F ₁₁ of the _{R 4 -, C 9 F 17} - or C ₉ F ₁₇ O
-C ₆ H ₄ is -CO-, is the remainder are hydrogen atoms. Further, in the formula (I), (A ₁ O) and (A
_{In the} segment consisting of ₂ O), these sequences may be random, block or multi-block, but most preferably all are oxyethylene groups (A ₁ O).

The following compounds may be mentioned as specific examples of the surfactant, but the surfactant is not necessarily limited to these. Surfactant A:

[Chemical 3] (However, 5 of the oxyethylene group represents an average value.)

Surfactant B:

[Chemical 4] (However, 10 of the oxyethylene group represents an average value.)

Surfactant C:

[Chemical 5] (However, 15 of the oxyethylene group represents an average value.)

Surfactant D:

[Chemical 6] (However, 8 of the oxyethylene group represents an average value.)

Surfactant E:

[Chemical 7] (However, 10 of the oxyethylene group represents an average value.)

Examples of commercially available surfactants include FT-250, FT-251, FTX-218 and DFX-18 manufactured by Neos Co., Ltd. Further, as other surfactants, silicon-based surfactants, acrylic-based surfactants, other fluorine-based surfactants, etc. can be mixed and used.

The organic polymer compound used in the resin composition of the present invention may be selected from known compounds according to its use. For example, in the case of a transparent resin such as a color filter protective film, an acrylic resin, an epoxy resin, or a polyimide resin is used. The acrylic resin and epoxy resin are homopolymers or copolymers of (meth) acrylic acid esters such as glycidyl (meth) acrylate and methyl (meth) acrylate. A resin composition in which an epoxy resin is mixed with these (meth) acrylic resins, and a resin composition in which an epoxy curing agent such as trimellitic anhydride or phthalic acid is further added thereto. Further, a composition obtained by removing a photopolymerization initiator or a photosensitizer which is a photosensitive component from a photosensitive resin composition described below, or a composition obtained by removing a photosensitive component and a monomer component can also be used. As the solvent for these acrylic resins and epoxy resins, the solvent used in the photosensitive resin composition described later can be used. Further, when patterning is required, the photosensitive resin composition can be used as it is.

Further, since the polyimide resin is usually inferior in solubility in a solvent, its precursor polyamic acid is used. Polyamic acid is obtained by the reaction of tetracarboxylic dianhydride and diamine. Examples of the tetracarboxylic dianhydride include 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, bis- (3,4-dicarboxyphenyl) sulfone dianhydride and bis- (3,4-dianhydride. Carboxyphenyl) ether dianhydride, 2,2-bis-
(3,4-dicarboxyphenyl) hexafluoropropane dianhydride and the like. As a diamine, 3,3'-
Diaminodiphenyl sulfone, 2,2-bis (4- (4
-Aminophenoxy) phenyl) hexafluoropropane and the like. These are combined appropriately and N-methyl-
2-pyrrolidone, N, N-dimethylacetamide, N, N
-Polyamic acid can be obtained by reacting in dimethylacetamide or an organic solvent described later. A system obtained by adding an epoxy resin and a curing agent such as trimellitic anhydride or phthalic acid to such a solution can also be used.

However, the preferred embodiment of the resin composition of the present invention is a photosensitive resin composition. The photosensitive resin composition described in detail below is particularly preferable. That is, a copolymer having a vinyl monomer in which an unsaturated carboxylic acid monomer and its homopolymer are alkali-insoluble as a structural unit (hereinafter referred to as an alkali-soluble resin), an epoxy group-containing polymer, an ethylenically unsaturated bond-containing polymer It is a solution obtained by using a compound, a photopolymerization initiator and a photosensitizer as essential components, further adding a surfactant represented by the general formula (I), and dissolving these in an organic solvent.

The alkali-soluble resin which is the first component of the photosensitive resin composition used in the present invention is obtained by polymerizing at least one unsaturated carboxylic acid monomer and at least one other radically polymerizable monomer. Is obtained by As the unsaturated carboxylic acid monomer, (meth)
Examples thereof include acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid and mesaconic acid. These are used alone or in combination.
(Note that the above (meta) indicates that the compound includes both compounds with and without the prefix "meta", and the same shall apply hereinafter.)

The alkali-soluble resin used in the present invention has an appropriate solubility in an alkaline aqueous solution,
It is obtained by copolymerizing an unsaturated carboxylic acid monomer and a radically polymerizable monomer other than that. The content of the polymerization component derived from the unsaturated carboxylic acid monomer in the alkali-soluble resin is 5 to 40% by weight, preferably 10 to 20% by weight. If the amount of the polymerization component derived from the unsaturated carboxylic acid monomer is less than 5% by weight in the alkali-soluble resin, it becomes difficult to dissolve it in the alkaline aqueous solution, and if it exceeds 40% by weight, the solubility in the alkaline aqueous solution becomes too large, and after development. Roughness of the film tends to occur. That is, the radical-polymerizable monomer other than the unsaturated carboxylic acid monomer must be a radical-polymerizable monomer whose homopolymer is alkali-insoluble or contain a radical-polymerizable monomer which is alkali-insoluble.

As the radical-polymerizable monomer whose homopolymer is insoluble in alkali, aromatic vinyl compounds such as styrene, methylstyrene and vinyltoluene, methyl (meth) acrylate, ethyl (meth) acrylate,
Unsaturated carboxylic acid alkyl esters such as butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, ethyl crotonate, diethyl maleate, (meth) acrylamide, dimethylaminopropyl (meth) acrylamide , N, N
-(Meth) acrylamides such as dimethyl (meth) acrylamide, glycidyl (meth) acrylate, 3,
(Meth) acrylic acid ester having an epoxy group such as 4-epoxybutyl (meth) acrylate, 2-methyl-3,4-epoxycyclohexyl (meth) acrylate, 3-cyclohexenylmethyl (meth) acrylate, dicyclopentenyl ( (Meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decanyl (meth) acrylate, 2,2,6,6-tetramethylpiperidinyl (meth)
(Meth) acryl having an alicyclic group or a heterocyclic group such as acrylate, N-methyl-2,2,6,6-tetramethylpiperidinyl (meth) acrylate, 5-tetrahydrofurfuryloxycarbonylpentyl acrylate Examples thereof include acid esters, but are not necessarily limited thereto. And these can obtain a single item or a mixed item as a commercial item.

The second component of the photosensitive resin composition used in the present invention is an alkali-insoluble epoxy group-containing polymer, which is a homopolymer of a radical polymerizable monomer having an epoxy group or a radical polymerizable monomer having an epoxy group. Two
Obtained by copolymerization of one or more species or by copolymerization of at least one radical polymerizable monomer having an epoxy group with at least one radical polymerizable monomer which is not an unsaturated carboxylic acid and does not have an epoxy group. . As the radical polymerizable monomer having an epoxy group, glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 2-methyl-3,4-
Examples thereof include epoxycyclohexyl (meth) acrylate. These may be used alone or in combination of two or more. As a compound which is a radical-polymerizable monomer which is not an unsaturated carboxylic acid and which does not have an epoxy group, a homopolymer thereof has an epoxy group of the radical-polymerizable monomer which is insoluble in alkali (meth)
A compound other than an acrylic ester can be mentioned as an example. And these can also be used individually or in combination of 2 or more types.

It is also possible to use an alkali-insoluble epoxy resin as the alkali-insoluble epoxy group-containing polymer which is the second component of the photosensitive resin composition used in the present invention. Examples of the alkali-insoluble epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, glycidyl ester type epoxy resin, and alicyclic epoxy resin. As a specific example, Epicoat 801, Epicoat 802, Epicoat 807, Epicoat 815, Epicoat 825, Epicoat 827, Epicoat 828, Epicoat 152,
Epicoat 152, Epicoat 190P, Epicoat 1
91P (trade name, manufactured by Yuka Shell Epoxy Co., Ltd.), Araldite CY177, Araldite CY184 (trade name, manufactured by Nippon Ciba Geigy Co., Ltd.), Celoxide 20
21, EHPE-3150 (above trade name, manufactured by Daicel Chemical Industries, Ltd.) and the like.

The content of the polymerization component derived from the radical-polymerizable monomer having an epoxy group in the alkali-insoluble epoxy group-containing polymer is usually 20 to 100% by weight, preferably 50 to 100% by weight. The content of the polymerization component derived from the radically polymerizable monomer having an epoxy group is 2
This is because if it is less than 0% by weight, the alkali resistance of the coating film obtained by thermosetting after patterning tends to decrease.

The alkali-soluble resin and the alkali-insoluble epoxy group-containing polymer can be obtained by a conventionally known polymerization method. The polymerization solvent may be any compound that is inert to the polymerization reaction and stable under the polymerization reaction conditions. Specifically, methanol, ethanol, 2-propanol, ethyl acetate, butyl acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethyl carbitol, propylene glycol monomethyl ether, propylene glycol-1-monomethyl ether-2-acetate. , Ethylene glycol monobutyl ether acetate, methyl ethyl ketone, cyclohexanone, diethylene glycol dimethyl ether,
Diethylene glycol diethyl ether, toluene, xylene, γ-butyrolactone, N, N-dimethylacetamide, tetrahydrofuran and the like are preferable, and among these, methanol, ethyl acetate, cyclohexanone, methyl ethyl ketone, propylene glycol monomethyl ether and the like are particularly preferable. Of course, a mixed solvent of two or more kinds may be used.

In the polymerization reaction, the monomer concentration in the reaction solution is usually 5 to 50% by weight, and the polymerization initiator concentration is 0.01%.
-5% by weight, reaction temperature 50-160 ° C, reaction time 3
~ 12 hours. Chain transfer agents such as thioglycolic acid may be added to control the molecular weight. After the completion of the polymerization reaction, the reaction solution can be used as it is in the next step, or the reaction solution is poured into a large amount of a non-solvent to precipitate the polymer, and oligomers and unreacted monomers are removed to precipitate the polymer. Can also be used after drying. When the reaction solution is poured into a large amount of a non-solvent for purification, it is preferable to use a mixed solution of methanol and ethyl acetate as a reaction solvent and cyclohexane or an ethyl acetate / cyclohexane mixed solution as a non-solvent because the drying property is good.

Both the alkali-soluble resin and the polymer containing an alkali-insoluble epoxy group have a weight average molecular weight (Mw) of 1,000 to 10 in terms of polyethylene oxide in GPC analysis using N, N-dimethylformamide as a solvent.
It is desirable that it is 2,000, and it is 2,000 to 30,000.
It is more preferably 00. This average molecular weight (M
When w) is less than 1,000, the strength of the film is weak and the film is rough during development, and pattern peeling easily occurs. On the other hand, 200,0
If it exceeds 00, the developability and sensitivity may be deteriorated, or a residue may remain after development.

The ethylenically unsaturated bond-containing compound which is the third component of the photosensitive resin composition used in the present invention is preferably a (meth) acrylic acid ester, and specific examples thereof include methyl (meth) acrylate and ethyl (meth). ) Acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy Butyl (meta)
Acrylate, 3-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 2-methyl-3,
4-epoxycyclohexyl (meth) acrylate, ω
-Carboxypolycaprolactone mono (meth) acrylate, monohydroxyethyl phthalate (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate , Tricyclo [5.2.1 · 0 ^2,6 ] decanyl (meth) acrylate, 2,2,6,6-tetramethylpiperidinyl (meth) acrylate, N-methyl-2,2,6,
6-tetramethylpiperidinyl (meth) acrylate,
5-tetrahydrofurfuryloxycarbonylpentyl acrylate,

1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, diethylene glycol di (meth) acrylate , Triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, Ditrimethylolpropane tetra (meth) acrylate, pentaerythritol di (meth) acrylate,
Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dicyclopentanyl di (meth) acrylate, ethoxylated hydrogenated bisphenol A Di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, ethoxylated bisphenol F di (meth) acrylate, ethoxylated bisphenol S di (meth) acrylate, hydroxypropyl di (meth) acrylate, diethylene glycol bishydroxypropyl (meth ) Acrylate and monohydroxypentaerythritol tri (meth) acrylate. These compounds may be used alone or in combination, but are not necessarily limited thereto.

The ethylenically unsaturated bond-containing compound is preferably a compound containing three or more ethylenically unsaturated bonds, and if a part of the examples is selected from the above compounds, trimethylolpropane tri ( Examples thereof include (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate.

The photopolymerization initiator and the photosensitizer which are the fourth component of the photosensitive resin composition used in the present invention may be known compounds, but one kind or a mixture of several kinds thereof is used. be able to. As a specific example of the photopolymerization initiator,
The following compounds may be included, but are not necessarily limited to these. That is, benzophenone,
Xanthone, thioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-
Methyl propiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2
-Diethoxyacetophenone, 2,2-dimethoxy-2
-Phenylacetophenone, benzyl, 2-methyl-1
-{4- (Methylthio) phenyl} -2-morpholinopropan-1-one, 2-benzyl-2-dimethyl-1
-(4-morpholinophenyl) -butanone-1,3,
3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, N-phenylglycine, p-hydroxy-N-phenylglycine, tetramethylthiuram monosulfide, tetramethylthiuram disulfide,
p-Tolyl disulfide, 2,6-bis (p-azidobenzylidene) cyclohexanone, 2,6-bis (p-azidobenzylidene) -4-t-butylcyclohexanone, bis (2,4,6-trimethylbenzoyl) -phenyl Phosphine oxide, 2- (4-methoxy-1-)
Naphthyl) -4,6-bis (trichloromethyl) -s-
Examples thereof include triazine.

The following compounds may be mentioned as specific examples of the photosensitizer, but they are not necessarily limited to these. That is, Michler's ketone, 4,4'-diethylaminobenzophenone, camphorquinone, benzanthrone, ethyl 4-dimethylaminobenzoate, 4
-Isoamyl dimethylaminobenzoate, 3,3'-carbonyl-bis (7-diethylamino) coumarin, ethyl-p- (N, N-dimethylamino) benzoate and the like can be mentioned.

The photosensitive resin composition used in the present invention is
Alkali-soluble resin as the first component, alkali-insoluble epoxy group-containing polymer as the second component, ethylenically unsaturated bond-containing compound as the third component, photopolymerization initiator and light as the fourth component Although it comprises a sensitizer and a surfactant which is the fifth component, it can be used as a resin composition without using either the third component or the fourth component or both of them. The resin film obtained from these resin compositions can be used for a color filter protective film which does not require photosensitivity, a plasma display panel, a light emitting diode element, and an organic electroluminescence element.

The content ratio of each component of the photosensitive resin composition used in the present invention is a mixture of an alkali-soluble resin and an alkali-insoluble epoxy group-containing polymer (hereinafter, this mixture is referred to as "polymer component"). 10 to 200 parts by weight of the compound containing an ethylenically unsaturated bond with respect to 100 parts by weight,
Preferably 20 to 150 parts by weight, 0.1 photopolymerization initiator
To 50 parts by weight, preferably 0.5 to 30 parts by weight, and 0.1 to 30 parts by weight of the photosensitizer, preferably 0.5 to 20 parts by weight.
The amount of the surfactant is 0.005 to 1 part by weight, preferably 0.01 to 0.5 part by weight, based on the photosensitive resin composition solution.

When the amount of the ethylenically unsaturated bond-containing compound is less than 10 parts by weight with respect to the polymer component, the curing of the photosensitive resin by light becomes insufficient, and the solubility in the developing solution increases, and after development, Roughness may occur on the coating film surface. Even when the ratio of the ethylenically unsaturated bond-containing compound to the polymer component exceeds 200 parts by weight, the tack on the surface of the coating film becomes too large, and the film obtained after curing has film roughness or remains after development. May remain. If the ratio of the photopolymerization initiator to the polymer component is less than 0.1 part by weight, the crosslinking (curing) reaction of the ethylenically unsaturated bond-containing compound may not proceed sufficiently. If the ratio of the photopolymerization initiator to the polymer component exceeds 50 parts by weight, the developability may decrease. When the ratio of the photosensitizer to the polymer component is less than 0.1 part by weight, the sensitizing effect on the photopolymerization initiator is insufficient, the sensitivity is lowered, and the film may be roughened after development. . When the ratio of the photosensitizer to the polymer component exceeds 30 parts by weight, the residual film rate of the obtained film may be too low.

When the ratio of the surfactant to the photosensitive resin composition solution is less than 0.005 part by weight, the in-plane uniformity of the film thickness of the coating film is deteriorated and striation occurs. There is. If the ratio of the surfactant to the photosensitive resin composition solution exceeds 1 part by weight, the photosensitive resin may become brittle or the heat resistance may be lowered.

The polymer component is a mixture of the alkali-soluble resin and the alkali-insoluble epoxy group-containing polymer as described above. The content of the alkali-insoluble epoxy group-containing polymer in the polymer component is 1 to 60% by weight, preferably 10 to 40% by weight. The alkali-insoluble epoxy group-containing polymer is used for imparting alkali resistance and heat resistance to the film after thermosetting, and the above ratio is 5% by weight.
If it is less than 100%, these physical properties may deteriorate,
When using a radical polymerizable monomer having an epoxy group as a copolymerization monomer when producing an alkali-soluble resin, or when using a compound having an epoxy group as the ethylenically unsaturated bond-containing compound, an alkali-insoluble The epoxy group-containing polymer may be 1% by weight in some cases.

The resin composition used in the present invention may contain components other than the above components, if necessary, within a range not impairing the object of the present invention. Examples of such other components include a coupling agent (surface treatment agent). The coupling agent is used to improve the adhesiveness to the substrate, and the resin composition, the remaining components of the photosensitive resin composition excluding the solvent (hereinafter abbreviated as "solid content") It is used in an amount of 10 parts by weight or less.

As the coupling agent, silane-based, aluminum-based and titanate-based compounds are used.
Specifically, 3-glycidoxypropyldimethylethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-acryloxypropyldimethylethoxysilane, 3-acryloxypropyl Methyldiethoxysilane, 3-acryloxypropyltriethoxysilane, 3
-Methacryloxypropyldimethylethoxysilane, 3
-Methacryloxypropylmethyldiethoxysilane, 3
-Silane-based compounds such as methacryloxypropyltriethoxysilane, 3-methacryloxypropyldimethylmethoxysilane, 3-methacryloxypropylmethyldimethoxysilane and 3-methacryloxypropyltrimethoxysilane, aluminum-based compounds such as acetoalkoxyaluminum diisopropylate, A titanate compound such as tetraisopropyl bis (dioctyl phosphite) titanate can be mentioned.

The photosensitive resin composition used in the present invention is
Usually, it is dissolved in an appropriate solvent and used in a solution state.
This solution is prepared by adding a polymer component to a solvent and completely dissolving it, and then adding an ethylenically unsaturated bond-containing compound, a photopolymerization initiator, a photosensitizer, a surfactant and, if necessary, to the solution. A coupling agent or the like is mixed at a predetermined ratio to prepare a solid content concentration of 10 to 60% by weight, and then the mixture is stirred to completely dissolve it.

This solid content concentration is a setting necessary for smooth coating on the surface of the substrate or as means for adjusting the thickness of the coating film, and when the molecular weight of the polymer component is large, or The solid content concentration may be adjusted to be low when the thickness of the film is to be reduced, and the solid content concentration may be adjusted to be high when the molecular weight of the polymer component is small or when the thickness of the coating film is to be increased.

The solvent used at this time is methoxydiethanol, ethoxyethanol, 1-methoxy-
2-propanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl lactate, Ethyl pyruvate,
Methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 2-heptanone, butyl acetate, N-methyl-2-pyrrolidone, N, N-dimethylacetamide and the like can be mentioned, and particularly preferably propylene glycol-1- It is monomethyl ether-2-acetate. These solvents may be used alone or in admixture of two or more.

A coating film can be formed by applying the resin composition solution or the photosensitive resin composition solution prepared as described above on the surface of a substrate and removing the solvent by heating. The photosensitive resin composition solution can be applied to the surface of the substrate by a conventionally known method such as a spin coating method, a roll coating method, or a dipping method. Next, this coating film is heated and dried (hereinafter abbreviated as "prebaking") on a hot plate, an oven, or the like. The pre-baking condition varies depending on the type and blending ratio of each component, but is usually 70 to 110 ° C., 1 to 5 minutes for a hot plate, and 5 to 15 minutes for an oven.

As the substrate, for example, a transparent glass substrate such as white plate glass, blue plate glass, silica-coated blue plate glass, polycarbonate, polyester, acrylic resin,
Sheets of synthetic resin such as vinyl chloride resin, aromatic polyamide resin, polyamideimide, and polyimide, film or substrate, metal substrate such as aluminum plate, copper plate, nickel plate, and stainless plate, other ceramic plate, semiconductor substrate having photoelectric conversion element And so on.
If desired, these substrates may be treated with a chemical such as a silane coupling agent, plasma treatment, ion plating,
A pretreatment such as sputtering, a vapor phase reaction method, or vacuum deposition can be performed.

The resin film obtained from the photosensitive resin composition used in the present invention is formed by forming a coating film on an electrode substrate for a liquid crystal element, and then applying ultraviolet rays through a photomask on which a predetermined pattern is formed. It is obtained by irradiating radiation such as, and then developing with a developing solution to remove unnecessary portions. Examples of the radiation used when forming the resin film include visible rays, ultraviolet rays, far ultraviolet rays, electron beams, and X-rays. Particularly preferably, the wavelength is 190n
Radiation in the range of m to 450 nm. The irradiation energy of radiation is preferably 1 to 1000 mJ / cm ² .

As the developing solution, an aqueous solution of an inorganic alkali such as sodium carbonate, sodium hydroxide or potassium hydroxide, or an organic alkali such as tetramethylammonium hydroxide or tetraethylammonium hydroxide can be used. In addition, it is also possible to add an appropriate amount of methanol, ethanol, a surfactant or the like to the above alkaline aqueous solution and use it. The developing method may be any of a dipping method, a shower method, a spray method, etc., and the developing time is usually 30 to 240 seconds.
A pattern can be formed by rinsing with running water and drying.

After that, this pattern was applied to a hot plate,
By heating in an oven or the like (hereinafter abbreviated as "post-baking"), the unreacted portion of the ethylenically unsaturated bond-containing compound is further crosslinked, and at the same time the solvent is completely removed to obtain a predetermined resin film pattern. be able to. The post-baking conditions vary depending on the type of compound constituting each component and the compounding ratio, but usually 180 to 250 ° C.
Then 5-30 minutes for hot plate, 3 for oven
0 to 90 minutes.

As described above, a step of applying the photosensitive resin composition of the present invention on the substrate from the photosensitive resin composition containing the surfactant as an essential component, a step of prebaking the obtained coating film, It consists of a patterning process consisting of exposing the coating film through a photomask, removing the unexposed part using a developing solution, and post-baking. It is possible to obtain a patterned film having excellent in-plane uniformity of. When the amount of the surfactant added to the photosensitive resin composition solution is less than 0.005 part by weight, the in-plane uniformity of the film thickness of the obtained patterned resin film is low, and conversely, the amount added is 1 part by weight. If it exceeds the amount, the patterned resin film becomes brittle and the heat resistance is lowered, which is not preferable. Only when the amount of the surfactant added is 0.005 to 1 part by weight with respect to the resin composition or the photosensitive resin composition solution, a coating film or pattern having excellent in-plane uniformity of film thickness Can be formed, and the patterned film also has liquid crystal resistance and has good physical and chemical properties.

The liquid crystal element of the present invention is characterized in that it has a resin film formed of the above-mentioned photosensitive resin composition used in the present invention. A method for manufacturing the liquid crystal element will be described. The spacer controls the thickness of the liquid crystal layer, and can be produced by the following method. That is, inside the upper and lower substrates, transparent conductive electrodes (for example, indium-tin oxide (ITO), tin oxide (SnO _X ), etc.) and an alignment film subjected to alignment treatment are sequentially laminated. The resin film is applied to the surface of the alignment film or the surface of the electrode on which the alignment film is not laminated, the photosensitive resin composition is applied so as to have a desired thickness, and light irradiation is performed through a photomask, and then development and baking are performed. Then, columnar spacers are formed in places other than the openings (for example, between pixels).
The resin film may be formed on either or both of the upper and lower substrates. Here, the spacer may have a dot shape or a linear shape, but the latter is preferable from the viewpoint of preventing light leakage between pixels. Further, conventionally used beads can be dispersed and fixed in the resin film for use.

Further, the photosensitive resin composition was applied onto a glass substrate and patterned in the same manner, leaving the composition only in the peripheral portion of the substrate, and assembling a liquid crystal cell so that another substrate was opposed to the composition. The sealing material can be incorporated into the liquid crystal element by pressure bonding and firing. Further, as a diffuse reflection surface of a reflection type or semi-transmission type liquid crystal element, there is a metal surface having aluminum or the like deposited on a random uneven surface. Since the surface which retains the shape of the unevenness is formed as it is, it is possible to form a resin film on the photosensitive resin composition and form a liquid crystal element in which the distribution of reflected light is controlled.

Further, it is possible to manufacture a liquid crystal element in which a projection portion for improving the viewing angle by dividing the pixel of the liquid crystal element using the VA method is formed with the resin film. Further, the resin composition, the resin film obtained from the photosensitive resin composition can be used also as an alignment treatment agent, and can be used as a resin film in which a pigment is dispersed in a photosensitive resin composition for a color filter. Is also possible. It can also be used as various protective films and insulating films.

The shape of the patterned resin film of the present invention is not particularly limited, but when viewed from directly above, it is preferably square, rectangular, circular or elliptical, and in the case of rectangular or elliptical, The major axis direction is preferably horizontal or perpendicular to the rubbing direction. Also, when viewed from the side,
It is preferably square, rectangular, trapezoidal or semicircular.
The trapezoidal shape is effective when applying an alignment film to the resin film and rubbing it, when uniformly applying the alignment film, or when uniformly rubbing it.

The resin film thus formed may be dot-shaped or linear. Further, conventionally used beads can be dispersed and fixed in the resin film for use. Further, the photosensitive resin composition is applied onto a glass substrate, and the patterning is performed in the same manner to leave the composition only in the peripheral portion of the substrate, and a liquid crystal cell is assembled so as to face another substrate thereon, and pressure-bonded, The composition can be incorporated into a liquid crystal element as a sealant by firing.
Further, a film to be oriented may be formed on the resin film.

The liquid crystal element is manufactured by aligning the positions of the upper and lower element substrates formed as described above, pressure-bonding, heat-treating and combining, then injecting liquid crystal and sealing the injection port. . Alternatively, the liquid crystal device may be manufactured by spraying the liquid crystal on the liquid crystal device substrate, stacking the substrates, and sealing the liquid crystal device so as not to leak. In this way, the resin film having liquid crystal resistance excellent in the in-plane film thickness uniformity of the present invention can be present in the liquid crystal element.

The liquid crystal used in the liquid crystal device of the present invention, that is, the liquid crystal compound and the liquid crystal composition are not particularly limited, and are disclosed in JP-A-9-281506, JP-A-10-168134, and JP-A-11-15154. Any of the liquid crystal compounds and liquid crystal compositions described in each of the publications can be used.

The alignment film used in the liquid crystal device of the present invention is not particularly limited as long as it controls the alignment of liquid crystal molecules, and may be an inorganic substance or an organic substance. Generally, polyimide-based and polyamide-based resins are often used, but specifically, resins having a structural unit represented by the following formula (1) or formula (2) are preferable.

[0067]

[Chemical 8] (In the formula, G is a residue of a diamine compound, which is an organic group or an aliphatic group containing an aromatic group, and Y is a residue of a tetracarboxylic acid compound, which is an aliphatic group or an aromatic group. ,
It is an alicyclic group, a condensed cyclic group, a bridged cyclic group, or an organic group containing two or more of these groups. )

Specific examples of the divalent organic group G include groups represented by the following formulas (G1) to (G10).

[0069]

[Chemical 9] (In the formula, R ₁ represents H or alkyl having 1 to 10 carbons, R ₂ represents alkyl having 1 to 10 carbons, and n is 1 to 1).
3 is an integer, and m is 1 or 2. )

Specific examples of the tetravalent organic group Y are represented by the formula (Y
Examples thereof include groups represented by 1) to (Y11).

[0071]

[Chemical 10]

(In the formula, R ₁ is H or alkyl having 1 to 10 carbon atoms, q is an integer of 0 to 4, and r is 0 or 1.)

[0073]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples. (Synthesis of Alkali-Soluble Resin [A]) Alkali-soluble resins [A-1] to [A-4] used in Examples and Comparative Examples were synthesized as follows.

<Synthesis of [A-1]> In a separable flask equipped with a stirrer, a cooling tube, a nitrogen introduction tube and a thermometer, 20 g of methacrylic acid, 130 g of benzyl methacrylate, 20 g of 2-hydroxyethyl methacrylate as resin raw materials and 30 g of 5-tetrahydrofurfuryloxycarbonylpentyl acrylate, 1 g of 2,2'-azobisisobutyronitrile as a polymerization initiator, 3 g of thioglycolic acid as a chain transfer agent, 167 g of methanol as a solvent and 333 g of ethyl acetate were charged. Then, the air in the flask was removed by nitrogen for 30 minutes, and the internal temperature of the flask was kept at 65 ° C. in an oil bath to carry out a polymerization reaction for 6 hours. Then, 3,000 g of cyclohexane was added to the polymerization solution to precipitate a polymer, and the supernatant was removed by decantation, followed by vacuum drying at 40 ° C. for 20 hours to obtain an alkali-soluble resin [A-1]. The polyethylene oxide-equivalent weight average molecular weight of the obtained [A-1] was 7,000.

<Synthesis of [A-2]> Using the same equipment as in [A-1], 30 g of methacrylic acid, 130 g of benzyl methacrylate, 20 g of 2-hydroxyethyl methacrylate and 5-tetrahydrofurfuryloxycarbonyl were used as resin raw materials. 20 g of pentyl acrylate, 2,2'-azobisisobutyronitrile as a polymerization initiator 1
g, thioglycolic acid 3 g as a chain transfer agent, methanol 167 g and ethyl acetate 333 g as a solvent were charged. Then, the air in the flask was removed by nitrogen for 30 minutes, and the internal temperature of the flask was kept at 65 ° C. in an oil bath to carry out a polymerization reaction for 6 hours. Then, cyclohexane 3,0 was added to the polymerization solution.
00 g was added to precipitate a polymer, and the supernatant was removed by decantation, followed by vacuum drying at 40 ° C. for 20 hours to obtain an alkali-soluble resin [A-2]. Obtained [A-
2] has a polyethylene oxide equivalent weight average molecular weight of 7,
It was 200.

<Synthesis of [A-3]> Using the same apparatus as in [A-1], 20 g of methacrylic acid, 90 g of benzyl methacrylate and 8 g of methyl methacrylate were used as resin raw materials.
0 g and 2-hydroxyethyl methacrylate 10
g, 2,2′-azobisisobutyronitrile 1 g as a polymerization initiator, thioglycolic acid 3 g as a chain transfer agent,
As a solvent, 167 g of methanol and ethyl 333
I charged g. Then, the air in the flask was removed with nitrogen for 30 minutes, and the internal temperature of the flask was kept at 65 ° C. in an oil bath for 6 minutes.
The polymerization reaction was carried out for a time. Then, 3,000 g of cyclohexane was added to the polymerization solution to precipitate a polymer, and the supernatant was removed by decantation, followed by vacuum drying at 40 ° C. for 20 hours to obtain an alkali-soluble resin [A-3]. The weight average molecular weight of the obtained [A-3] in terms of polyethylene oxide was 8,300.

<Synthesis of [A-4]> Using a device similar to that of [A-1], 40 g of methacrylic acid, 110 g of dicyclopentanyl methacrylate, 30 g of 2-hexahydrophthaloyloxyethyl methacrylate as a resin raw material, and 20 g of isoprene, 1 g of 2,2'-azobisisobutyronitrile as a polymerization initiator, 3 g of thioglycolic acid as a chain transfer agent, and 500 g of ethyl 2-hydroxypropionate as a solvent were charged. Thereafter, the air in the flask was removed with nitrogen for 30 minutes, and the internal temperature of the flask was kept at 90 ° C. in an oil bath to carry out a polymerization reaction for 6 hours. After that, 3,000 g of methanol was added to the polymerization solution to precipitate the polymer, and the supernatant was removed by decantation, followed by 2 ° C. at 40 ° C.
It was vacuum dried for 0 hour to obtain an alkali-soluble resin [A-4]. The weight average molecular weight of the obtained [A-4] in terms of polyethylene oxide was 7,100.

(Synthesis of alkali-insoluble epoxy group-containing polymer [B]) The alkali-insoluble epoxy group-containing polymers [B-1] to [B-4] used in Examples and Comparative Examples were synthesized as follows.

<Synthesis of [B-1]> 160 g of glycidyl methacrylate as a resin raw material was placed in a separable flask equipped with a stirrer, a cooling tube, a nitrogen introducing tube and a thermometer.
Then, 40 g of methyl methacrylate, 2,2′-azobisisobutyronitrile as a polymerization initiator, 8 g of methyl ethyl ketone as a solvent were charged, and after removing air in the flask with nitrogen for 30 minutes, the flask was heated to an internal temperature in an oil bath. Was kept at 80 ° C. for 6 hours to carry out a polymerization reaction. Then, 3,000 g of cyclohexane was added to the polymerization solution to precipitate a polymer, and the supernatant was removed by decantation, followed by vacuum drying at 40 ° C. for 20 hours to obtain [B-1].
The polyethylene oxide equivalent weight average molecular weight of [B-1] was 6,100.

<Synthesis of [B-2]> Using the same apparatus as in [B-1], 160 g of glycidyl methacrylate and 40 g of 2-hydroxyethyl methacrylate as resin raw materials and 2,2'-azobis as a polymerization initiator. Isobutyronitrile 8g, solvent methyl ethyl ketone 800
After charging g, the air in the flask was removed with nitrogen for 30 minutes, and then the polymerization reaction was carried out for 6 hours while maintaining the internal temperature of the flask at 80 ° C. in an oil bath. Then, 3,000 g of cyclohexane was added to the polymerization solution to precipitate a polymer, the supernatant was removed by decantation, and vacuum drying was performed at 40 ° C. for 20 hours to obtain [B-2]. The polyethylene oxide equivalent weight average molecular weight of [B-2] was 6,100.

[0081] <[B-3] Synthesis of> [B-1] using the same apparatus as glycidyl methacrylate 160g and tricyclo as resin raw material {5-2, 1, 0 ^2.6} decanyl (meth) acrylate 40 g, 2, as a polymerization initiator
8 g of 2'-azobisisobutyronitrile and 800 g of methyl ethyl ketone as a solvent were charged, the air in the flask was removed by nitrogen for 30 minutes, and then the internal temperature of the flask was kept at 80 ° C in an oil bath to carry out a polymerization reaction for 6 hours. went. Then, 3,000 g of cyclohexane was added to the polymerization solution to precipitate a polymer, and the supernatant was removed by decantation.
It vacuum-dried at 20 degreeC for 20 hours, and obtained [B-3]. [B-
3] has a weight average molecular weight in terms of polyethylene oxide of 7,
It was 000.

<Synthesis of [B-4]> Using the same apparatus as in [B-1], 200 g of glycidyl methacrylate as a resin raw material, 8 g of 2,2'-azobisisobutyronitrile as a polymerization initiator, and a solvent. As methyl ethyl ketone 8
Charge 00 g, remove the air in the flask with nitrogen for 30 minutes, and then keep the internal temperature of the flask at 80 ° C. in an oil bath for 6 minutes.
The polymerization reaction was carried out for a time. Then, 3,000 g of cyclohexane was added to the polymerization solution to precipitate a polymer, and the supernatant was removed by decantation, followed by vacuum drying at 40 ° C. for 20 hours to obtain [B-4]. The polyethylene oxide equivalent weight average molecular weight of [B-4] was 6,200.

In the following, the resin film of the present invention having excellent in-plane uniformity of film thickness was prepared, its performance was evaluated, a liquid crystal device using the same was prepared, and the results of those evaluations are shown in the following Examples. Will be explained.

(Preparation of Photosensitive Resin Composition) Example 1 100 g of alkali-soluble resin [A-1], 15 g of alkali-insoluble epoxy group-containing polymer [B-1], and propylene glycol-1-monomethyl-2-acetate. Two
After mixing and dissolving 50 g, a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate as an ethylenically unsaturated bond-containing compound (“Aronix M4 manufactured by Toagosei Chemical Industry Co., Ltd.”)
00 ") 60 g and 3,3 ', 4, as a photopolymerization initiator
40 g of 25% by weight toluene solution of 4'-tetra (t-butylperoxycarbonyl) benzophenone, 4,4'-dimethylaminobenzophenone 1 as a photosensitizer
g, and propylene glycol-1-monomethyl-2-acetate was added so that the solid content concentration was 30% by weight. Furthermore, surfactant G-1 (surfactant A)
062 g was mixed, then stirred until a uniform solution was obtained, and filtered with a membrane filter having a pore size of 0.2 μm to obtain a solution of a photosensitive resin composition.

Examples 2 to 24 The same procedure as in Example 1 was carried out except that the respective components shown in Tables 1 to 4 were added in predetermined amounts, to obtain respective photosensitive resin compositions.

Comparative Examples 1 to 6 A photosensitive resin composition solution was prepared in the same manner as in Example 1 except that the amount and type of surfactant added were changed and each component was added as shown in Table 5. .

The meanings of the abbreviations shown in Tables 1 to 5 are as follows. <1> Alkali-insoluble epoxy resin C-1: Epicoat 815 (Yukaka Shell Epoxy Co., Ltd.)
C-2: Epicoat 828 (Okaka Shell Epoxy Co., Ltd.)
C-3: Araldite CY184 (Japan Ciba Gaige
<2> Ethylenically unsaturated bond-containing compound D-1: Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (Aronix M-40 manufactured by Toagosei Chemical Industry Co., Ltd.)
0 ") D-2: trimethylolpropane triacrylate D-3: pentaerythritol triacrylate D-4: polyester acrylate (Toagosei Chemical Industry Co., Ltd.
(Aronix M-8060 manufactured by Co., Ltd.))

<3> Photopolymerization initiator E-1: 25% by weight toluene solution of 3,3'-4,4'-tetra (t-butylperoxycarbonyl) benzophenone E-2: 2,4-diethylthioxanthone E -3: 2,2-dimethoxy-1,2-diphenylethan-1-one <4> photosensitizer F-1: 4,4'-dimethylaminobenzophenone F-2: 3-benzoyl-7-diethylaminocoumarin

<5> Surfactant G-1: Surfactant A represented by the formula (II) G-2: Surfactant B represented by the formula (III) B G-3: Formula (IV) Surfactant represented by CG-4: Surfactant represented by formula (V) DG-5: Surfactant represented by formula (VI) E G-6: Surfactant (Co., Ltd.) Neos "Fugent F
T-250 ") G-7: Surfactant (" Fogent F "manufactured by Neos Co., Ltd.)
T-251 ") G-8: Surfactant (" Fogent F, manufactured by Neos Co., Ltd. "
TX-218 ") G-9: Surfactant (" Fogent D "manufactured by Neos Co., Ltd.)
FX-18 ") H-1: Surfactant (" Megafuck F-475 "manufactured by Dainippon Ink and Chemicals, Inc.) H-2: Surfactant (" Florard FC-431 "manufactured by Sumitomo 3M Limited) ) H-3: Surfactant ("Surflon KH-40" manufactured by Seimi Chemical Co., Ltd.)

<6> Other Components (Coupling Agent) I-1: 3-methacryloxypropyltrimethoxysilane The amount of each component in Tables 1 to 5 is the amount of the alkali-soluble resin [A] used. It is represented by the weight ratio of each component when the amount is 100 parts by weight.

[0091]

[Table 1]

[0092]

[Table 2]

[0093]

[Table 3]

[0094]

[Table 4]

[0095]

[Table 5]

The photosensitive resin compositions obtained in the above Examples and Comparative Examples were used for coating on glass substrates and the coating properties were evaluated. Furthermore, a patterned resin film was formed and its performance was evaluated. The method and results are described below.

<Coatability> The photosensitive resin composition solutions obtained in Examples and Comparative Examples were placed on a glass substrate having a size of 300 mm × 400 mm in a predetermined amount, spin-coated at 900 rpm for 15 seconds, and then coated on a hot plate. Prebaking was performed at 90 ° C. for 3 minutes to form a coating film. After that, the obtained coating film was applied to a proximity exposure device TME-400PRC.
(Manufactured by Topcon Co., Ltd.) was used for exposure without a photomask. While measuring the exposure dose with an integrating photometer,
It was irradiated with ultraviolet rays of 100 mJ / cm ^{2 in} line conversion. The integrated light meter UIT-102 (USHIO INC.)
Manufactured by the manufacturer, and the light receiver has a sensitivity wavelength range of 330 to 390 nm.
The light receiver UVD-365PD (manufactured by USHIO INC.) Was used. The resulting coating film was observed with a 400 × optical microscope to evaluate the presence or absence of striation. In addition, the film thickness on two diagonal lines of the glass substrate was evaluated. The film thickness measurement position is
The positions are 10 mm apart from the center of the glass substrate (49 points including the center point on one diagonal line).

<Method for Forming Patterned Resin Film> Similarly, a photosensitive resin composition solution was applied to 100 mm × 100 mm.
After spin-coating on a glass substrate having a transparent electrode made of the above size and / or an ITO film at 900 rpm for 15 seconds, it was prebaked on a hot plate at 90 ° C. for 3 minutes to form a coating film. Then, the obtained coating film was exposed using a proximity exposure device TME-400PRC (manufactured by Topcon Corp.) through a photomask which forms a grid pattern pattern with a light-transmitting portion of 10 μm × 10 μm. The exposure amount is 100 mJ / cm ² in terms of i-line. Then, using a 0.05 wt% potassium hydroxide aqueous solution at 23 ° C. for a predetermined time (30 sec to 120 sec).
c) After development (shower development, shower pressure 0.1 MPa), shower rinse with pure water for 15 seconds and drying. Further, it was heated and baked at 230 ° C. for 30 minutes in an oven to form a resin film having a thickness of 5 μm, which was patterned in a lattice pattern by a cured film of a photosensitive resin composition having a columnar shape of 10 μm × 10 μm on the substrate. .

The following physical properties of the patterned resin film obtained as described above were examined. <Residual film ratio> In the patterned resin film obtained as described above, the residual film ratio (film thickness after post-baking / film thickness after pre-baking × 100) was measured. <Pattern size (shape)> In the patterned resin film obtained as described above, the pattern size is 10 μm × 1
It was measured whether it was 0 μm.

<Alkali resistance> A glass substrate with a transparent electrode having a resin film, which was obtained by exposure without using a photomask, was immersed in a 5% by weight sodium hydroxide aqueous solution at 60 ° C. for 10 days.
After dipping for a minute, the cross-cut tape method (JIS K5
400, 8.5.2, cross-cut guide 1mm square x 1
Adhesion test with 100 pieces was performed, and the change rate of the film thickness before and after the dipping treatment and the change of the coating film surface with an optical microscope of 400 times were observed and judged according to the following criteria. ◯: No peeling by the cross-cut tape method, the rate of change in film thickness is 5%
Less than, and when there is no change in the coating surface before and after treatment. ×: In cases other than the above

<Water resistance> A glass substrate with a transparent electrode having a resin film, which was obtained by exposing without using a photomask,
Immerse in ultrapure water at 80 ° C for 1 hour, further immerse in ultrapure water and ultrasonically wash at 60 ° C for 1 hour, and then use the cross-cut tape method (JIS K5400, Section 8.5.2, cross-cut). Adhesion test with 1mm square x 100 guides) was performed, and the rate of change in film thickness before and after processing, and 400
The change of the coating film surface was observed with a double optical microscope and judged according to the following criteria. ◯: In any of the treatments, there is no peeling by the cross-cut tape method, the rate of change in film thickness is less than 5%, and there is no change in the coating film surface before and after the treatment. ×: In other cases

<Heat Resistance> After the patterned resin film formed on the substrate was reheated at 240 ° C. for 1 hour, the residual film rate after reheating ((film thickness after reheating / film after post bake Thickness) × 100) was measured and judged according to the following criteria. ◯: Remaining film rate after reheating is 95% or more ×: Remaining film rate after reheating is less than 95%

<Solvent resistance> A patterned resin film formed on a substrate was coated with N-methyl-2-pyrrolidone 25
After the immersion treatment was performed at 0 ° C. for 1 hour, the change rate of the film thickness before and after the treatment and the change of the coating film surface were observed with an optical microscope of 400 times, and the judgment was made according to the following criteria. ◯: When the change rate of the film thickness is less than 5% and the coating film surface is not changed before and after the treatment. X: When the change rate of the film thickness is 5% or more.

Table 6 shows the evaluation results of the coating properties of the coating films formed using the photosensitive resin compositions obtained in Examples, Tables 7 to 9 the evaluation results of the patterned resin films, and comparisons. Table 6 shows the evaluation results of the coating properties of coating films formed using the photosensitive resin compositions obtained in Examples, and Table 10 shows the evaluation results of patterned resin films.

[0105]

[Table 6]

[0106]

[Table 7]

[0107]

[Table 8]

[0108]

[Table 9]

[0109]

[Table 10]

Next, a spacer for a liquid crystal element, which is composed of a resin film patterned by using the photosensitive resin composition used in the present invention, was produced, and further a liquid crystal element provided with this spacer was produced. An example will be described below.

Example 25 A glass substrate with a transparent electrode made of an ITO film was subjected to spin coating, pre-baking, exposure, development and post-baking steps in accordance with the above-mentioned method (a) for forming a patterned resin film, and the thickness was 10 μm. Spacer patterns having a size of 10 μm were formed in a grid pattern at intervals of 100 μm in length and 50 μm in width. Next, a liquid crystal aligning agent (“LIX” manufactured by Chisso Corporation)
ON aligner PIA-5004 ") is applied to the spacer-forming substrate, dried on a hot plate at 70 ° C for 10 minutes, and then heat-treated in an oven at 200 ° C for 60 minutes to obtain an alignment film having a thickness of 0.06 µm. Was formed on a substrate with a spacer. Using a rubbing device having a roll in which a nylon cloth is wound around this alignment film, the rotation speed of the roll is 1000 rpm and the feed speed of the stage is 59 mm
The rubbing process was performed at a speed of 1 second. The epoxy-based sealant containing 2% of glass fiber spacers is applied to the outer edge of the substrate with a spacer having the alignment film surface subjected to the alignment treatment, and the pair of substrates are rubbed so that the liquid crystal alignment film surfaces face each other. The pieces were overlapped with each other so that the directions thereof were orthogonal to each other, pressure-bonded, and cured by heat. Then, the liquid crystal composition for TFT was sealed between the pair of substrates through the liquid crystal injection port, and then the injection port was sealed with a photocurable resin. After that, at 110 ℃ 3
An isotropic treatment was performed for 0 minutes, and the liquid crystal element was obtained by gradually cooling to room temperature.

The liquid crystal element thus obtained was evaluated for rubbing resistance, liquid crystal orientation, voltage holding ratio, and residual DC by the following methods. <Rubbing resistance> An alignment film was formed on the spacer, and the state when the alignment film surface was rubbed was evaluated according to the following criteria. ◯: When the spacer was not scraped or peeled off ×: In other cases <Liquid crystal alignment property> The alignment property was confirmed using a polarizing plate, and the judgment was made according to the following criteria. ◯: In case of good orientation X: In case of poor orientation

<Voltage holding ratio> The gate pulse width is 6
A rectangular wave of 9 μs, a frequency of 60 Hz and a wave height of ± 4.5 V was applied to the source, and the changing drain was read by an oscilloscope. This was repeated 4 times to calculate the average value, and when the voltage did not decrease at all, the relative value was defined as the voltage holding ratio, which was defined as 100%. The measurement was performed at 60 ° C. <Residual DC> measurement is a commonly used method C
It was performed by the -V curve method. That is, 25m for the liquid crystal element
V, 1KHz AC is applied, and frequency is 0.003
A DC bias voltage of 6 Hz was swept within a range of ± 10 V, a DC triangular wave was applied, and the changing capacitance C was measured. The measurement was performed at 60 ° C. Table 11 shows the measurement and determination results of each characteristic.

Examples 26 to 48 As shown in Table 11 below, the photosensitive resin compositions obtained in Examples 2 to 24 were combined with the liquid crystal compositions described below, and each was prepared in the same manner as in Example 25. A liquid crystal element was produced. Table 11 shows the characteristic data of the obtained liquid crystal element.

[0115]

[Table 11]

The composition of the liquid crystal composition used in the liquid crystal element of the above example is shown below. In addition, those physical property values are shown in Table 12.

[0117]

[Table 12]

<Liquid Crystal Composition LA>

[Chemical 11]

<Liquid Crystal Composition LB>

[Chemical 12]

<Liquid Crystal Composition LC>

[Chemical 13]

<Liquid Crystal Composition LD>

[Chemical 14]

<Liquid Crystal Composition LE>

[Chemical 15]

Tables 1 to 4 show the content of each photosensitive resin composition of the present invention as Examples 1 to 24, and Table 5 shows Comparative Examples 1 to 4.
6 shows each photosensitive resin composition using a surfactant other than that used in the present invention. Furthermore, the measurement results of the flatness of the film obtained by using each photosensitive resin composition are shown in Table 6, the physical properties of the film are shown in Tables 7 to 10, and the resin film obtained from the resin composition of the present invention is incorporated. The characteristics of the liquid crystal element are shown in Table 11.

According to this result, the characteristics of the resin film such as the residual film rate, the pattern size, the alkali resistance, the water resistance, the heat resistance and the solvent resistance were all good results. However, regarding the flatness of the film, in the case of the comparative example, the difference between the maximum value and the minimum value of the in-plane film thickness is 0.18 to 0.30 μm, and the standard deviation value is 0.075 to 0.156 μm (average film Thickness is 7.33-7.
71 μm). On the other hand, in the case of the example, the difference between the maximum value and the minimum value of the in-plane film thickness is 0.03 to 0.11 μm,
Standard deviation value is 0.005-0.015 (average film thickness is 7.1)
4 to 8.93 μm). Thus, the in-plane uniformity of the film obtained from the resin composition of the present invention was very excellent, and there was no striation. Furthermore, the characteristics of the rubbing resistance, liquid crystal orientation, voltage holding ratio, residual DC, etc. of the liquid crystal device incorporating the film obtained from the resin composition of the present invention were all good.

[0125]

As is clear from the above results, the resin composition of the present invention is characterized by containing a specific surfactant, so that the film thickness of the obtained resin film is in-plane uniform. Is excellent. Furthermore, the resin film obtained from the specific resin composition of the present invention has excellent chemical and physical properties such as alkali resistance, water resistance, alkali resistance, solvent resistance, heat resistance, and mechanical strength. When it is used as a liquid crystal element, it is possible to provide a liquid crystal element of the present invention which is excellent in rubbing resistance, has good electrical characteristics such as liquid crystal afterimage phenomenon and voltage holding ratio, and has a uniform liquid crystal layer thickness. In particular, it is suitable for a liquid crystal device such as a TN system, an STN system, a ferroelectric system, an antiferroelectric system, an IPS system, an OCB system, and a VA system, and a display device for a flat panel display. Furthermore, the film obtained from the resin composition of the present invention can be used for display devices such as plasma display panels, light emitting diode devices, and organic electroluminescence devices.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G02B 1/04 G02B 1/04 4J011 G02F 1/1333 505 G02F 1/1333 505 4J026 1/1335 520 1/1335 520 5C040 1/1337 520 1/1337 520 5C094 1/1339 500 1/1339 500 505 505 G03F 7/004 504 G03F 7/004 504 G09F 9/30 320 G09F 9/30 320 349 349Z 9/313 9/313 Z 9/35 9/35 H01J 11/02 H01J 11/02 ZF Term (Reference) 2H025 AA18 AB14 AB17 AC01 AD01 BC31 CA00 CB08 CB30 CB41 CB43 CC03 CC08 DA01 DA31 2H089 LA06 LA41 MA03X MA03Y NA05 NA14 2H090 HA16 HB07X HB07Y HB07Y HB07Y HB07Y HB07Y HB07Y HB07Y HB07Y HD01 HD11 LA02 LA03 LA10 MA01 2H091 FA16Y FB02 FB12 FC26 GA06 GA07 GA08 GA0 9 LA30 4J002 BG021 CD001 CH012 CH052 CM041 ED046 FD312 FD316 GP03 4J011 PA69 PA86 PA87 PC02 4J026 AA45 AB05 AC18 BA27 DB06 DB36 FA05 GA07 5C040 GH10 JA02 KA14 5C094 AA03 AA42 AA43 BA15A23 BA15 ABA23 AA23 AA47 AA27 AA23 AA47 AA23 AA47 AA27 AA27 AA23 AA23 AA23 AA47 AA23 AA23 AA23 AA23 AA27

Claims (15)

[Claims] 1. The general formula (I) [Chemical 1] (In the formula, A₁O is an oxyethylene group, A₂O is oxypro
Represents a pyrene group, an oxyethylene group and an oxypropyl group.
The array of len groups can be random, block or multi-block.
You can use lock, R₁~ R₃And each R_FourIs independently C₆F
₁₁-, C₉F₁₇-, C₉F₁₇OC₆H_Four-CO-, young
Represents a hydrogen atom, at least one of which is
Any of fluorinated groups, m₁₁, M₁₂, M_{twenty one}, M_{twenty two},
m₃₁, M₃₂, M ₄₁, And m₄₂Are independently integers from 0 to 30
Yes, (m₁₁+ M₁₂), (M_{twenty one}+ M_{twenty two}), (M₃₁+
m₃₂) And (m₄₁+ M₄₂) Is 0 to 30, and n is 0
Specifically, it represents an integer of 1 to 9. ) Surfactant
Containing an organic polymer compound and an organic solvent as essential components
A resin composition for a display element. 2. In the general formula (I), at least two of R _{1 to} R ₃ and each R ₄ are fluorine-containing groups C ₆ F ₁₁ —, C ₉
F ₁₇ - or represents a _{C 9 F 17 O-C 6} H 4 -CO-,
The resin composition according to claim 1, wherein the rest are hydrogen atoms. 3. In the general formula (I), m ₁₂ , m ₂₂ , m
The resin composition according to claim 1 or 2, wherein ₃₂ and m ₄₂ are all 0. 4. An organic polymer compound is a polymer shown in the following (1) and (2), and a photosensitive resin composition is obtained by adding the following (3) and (4) as essential components to the polymer. The resin composition according to claim 1, which is formed. (1) Copolymer having unsaturated carboxylic acid monomer and vinyl monomer whose homopolymer is alkali-insoluble as a structural unit (hereinafter abbreviated as alkali-soluble resin) (2) Alkali-insoluble epoxy group-containing polymer (3) Ethylenically unsaturated bond-containing compound (4) Photopolymerization initiator, photosensitizer 5. The organic solvent is propylene glycol-1.
-The resin composition according to claim 4, which is a solvent containing monomethyl ether-2-acetate. 6. A step of applying the photosensitive resin composition according to claim 4 or 5 onto a substrate, a step of prebaking the obtained coating film, a step of exposing through a photomask, and an exposure using a developing solution. A liquid crystal element containing a patterned resin film, which comprises a patterning step including a step of removing a portion or an unexposed portion and a step of post-baking. 7. A liquid crystal device, wherein the patterned resin film according to claim 6 is a spacer of the liquid crystal device. 8. A liquid crystal device in which the patterned resin film according to claim 6 is a spacer containing beads. 9. A liquid crystal device, wherein the patterned resin film according to claim 6 is a sealant for a liquid crystal device. 10. A liquid crystal device, wherein the patterned resin film according to claim 6 is a projection for light reflection and scattering of the liquid crystal device. 11. A liquid crystal device, wherein the patterned resin film according to claim 6 is a protrusion for a vertical alignment mode of the liquid crystal device. 12. A liquid crystal device containing a color filter protective film obtained from the resin composition according to claim 1. 13. A plasma display panel containing a resin film obtained from the resin composition according to claim 1. 14. A light emitting diode element containing a resin film obtained from the resin composition according to claim 1. 15. An organic electroluminescence device containing a resin film obtained from the resin composition according to claim 1.