JP4604976B2 - Photocurable resin composition, and liquid crystal display element or solid imaging element member using the same - Google Patents

Description

  The present invention relates to a photocurable resin composition containing a fumarate ester copolymer and forming a color filter protective film, RGB pixel, black matrix or spacer, and a color filter using the same.

  In recent years, color liquid crystal display devices have rapidly spread as flat displays for personal computers and televisions. Generally, a color liquid crystal display device has a structure in which a color filter and an electrode substrate such as a TFT substrate are opposed to each other, a gap of about 1 to 10 μm is provided, a liquid crystal compound is filled in the gap, and the periphery is sealed with a sealing material. I'm taking it. The color filter includes a black matrix layer formed in a predetermined pattern to shield a boundary portion between pixels, an arrayed pixel portion or a pixel portion recently using a hologram, a protective film, and a transparent electrode. It has a structure in which layers are stacked in this order from the side close to the transparent substrate. An alignment film is provided on the inner surface side of the color filter and the electrode substrate facing the color filter. Furthermore, a spacer is provided in the gap portion in order to maintain a constant and uniform cell gap between the color filter and the electrode substrate. A color image is obtained by controlling the light transmittance of each of the pixels colored in each color or the liquid crystal layer behind the color filter.

The RGB pixels formed in the color filter generally have a plurality of colors (usually, three primary colors of red (R), green (G), and blue (B)), and a predetermined color such as carbon black in the black matrix. One or two or more pigments selected so as to be capable of developing a color are blended in a photocurable resin composition, applied onto a transparent substrate, dried, and a predetermined region of the obtained coating film. Can be selectively exposed and cured, and developed with an organic solvent or an alkaline solution.
The protective film formed on the color filter plays a role of protecting the pixel portion and flattening the color filter. In a color liquid crystal display device, gaps in the transparent substrate surface of the color filter, gap unevenness between the R, G, and B pixels, or gap unevenness in each pixel are caused by the presence of the transparent electrode film. There is a problem that flatness is impaired, color unevenness or contrast unevenness is caused, and as a result, image quality is deteriorated. Accordingly, the protective film is required to have high flatness.

As the spacer, when the particulate pearl is randomly dispersed in the display region, that is, the pixel portion, and when the columnar spacer having a height corresponding to the cell gap is formed in the region overlapping the position where the black matrix layer is formed. There is.
The spacer described above is required not to be broken by an impact such as when a color filter is manufactured or when a liquid crystal display element is transported, and to keep the liquid crystal cell gap constant. For this reason, it is necessary for the cured resin forming the spacer to have sufficient hardness and elastic recovery rate.
In addition, the elution of organic substances and the leaching of ionic impurities into the liquid crystal layer may cause contamination of the liquid crystal layer, and as a result, may cause a significant deterioration in image quality. For this reason, members (such as a colored layer, a black matrix, a protective film, and a spacer) used in a liquid crystal image element are required to have an ability to prevent contamination by ionic impurities (ion barrier property).

The colored layer such as the pixel portion and the black matrix layer, the protective film, and the columnar spacer can be formed using a resin. The colored layer needs to be formed in a predetermined pattern for each color pixel or black matrix line. The protective film is preferably one that can cover only the region where the pixel portion is formed on the transparent substrate in consideration of the adhesiveness and sealing property of the seal portion. In addition, the columnar spacer needs to be accurately provided in the black matrix layer forming region, that is, in the non-display region. For this reason, it has been proposed to form a colored layer, a protective film and a columnar spacer using a photocurable resin that can be subjected to alkali development after selectively exposing a region to be cured.
The color filter is exposed to a high temperature during the assembly of the liquid crystal panel. For example, in the case where an ITO (Indium Tin Oxide) transparent electrode layer is formed by an alignment film forming process or vapor deposition (sputtering), the color filter is about 250 ° C. Heat for about 1 hour. In such a case, the color may change during the high-temperature heating process, which may cause problems such as yellowing and a decrease in transparency. For this reason, the photocurable resin composition used for a color filter needs to have sufficient heat-resistant discoloration property.

  Thus, various performance is calculated | required by the photocurable resin composition used for the color filter for liquid crystal display elements. Many studies have been made so far in order to satisfy the above required performance. For example, in Patent Document 1, an epoxy group-containing (meth) acrylate copolymer represented by (meth) acrylic acid and glycidyl (meth) acrylate is an essential component, and the copolymer side chain epoxy group is further added. A photocurable copolymer to which (meth) acrylic acid is added is disclosed. Furthermore, in Patent Document 2, a copolymer obtained by adding a (meth) acryloylalkyl isocyanate compound via a carboxyl group or a hydroxyl group of a copolymer of (meth) acrylic acid and a hydroxyl group-containing (meth) acrylate is an essential component. A photocurable resin composition is disclosed.

  Furthermore, in order to obtain heat discoloration and strength, for example, in Patent Document 3, an aliphatic cyclic hydrocarbon group that contributes to heat resistance and strength, such as a dicyclopentanyl group and a dicyclopentenyl group, is a structural unit. As a photocurable resin containing a copolymer as an essential component, Patent Document 4 discloses a photocurable resin composition containing an N-substituted maleimide-containing copolymer as an essential component. However, in these disclosed technologies, it is difficult to satisfy both the characteristics of alkali developability and heat discoloration / strength.

  In patent document 5, it has a structural unit derived from a fumaric acid ester compound and (meth) acrylic acid or itaconic acid, and a part of the carboxyl group of the structural unit is esterified with an epoxy group-containing (meth) acrylate compound. A photocurable resin composition containing a copolymer having a reactive ethylenically unsaturated bond introduced by chemical modification is disclosed. In this disclosed technique, the heat discoloration and strength of the cured product of the photocurable resin composition can be increased by having a structural unit derived from a fumaric acid ester compound, but it is desired to further improve these characteristics. It was.

JP 2000-034319 A JP 2000-105456 A Japanese Patent Laid-Open No. 2002-293737 JP 2003-215322 A JP 2003-344636 A

  The first object of the present invention is to provide a photocurable resin composition having good ion barrier properties and chemical resistance, and color filter protection, which is compatible with developability after curing, heat discoloration, and high hardness. The object is to provide a photocurable resin composition for forming a film, a pixel for RGB, a black matrix or a spacer.

  The second object of the present invention is to cure the above-mentioned photo-curable resin composition, and can be suitably used as a member for a liquid crystal display element or a solid-state image sensor, an RGB pixel, a black matrix, a spacer. And providing a color filter.

  As a result of intensive studies to solve the above problems, the present inventors have found that a structural unit derived from a fumaric acid ester compound (hereinafter referred to as fumarate), a structural unit derived from (meth) acrylic acid or itaconic acid, and A photocurable resin comprising a copolymer in which a part of the carboxyl group is esterified by an epoxy group-containing (meth) acrylate compound and a reactive ethylenically unsaturated bond is introduced. In the resin composition, a photocurable resin composition that solves the problems of the present invention can be obtained by further containing 3-45% by weight of a structural unit having an aromatic carbocyclic ring in the copolymer. Obtaining knowledge, the present invention has been completed.

That is, the present invention includes the following [1] to [8].
[1] The following components (A), (B), and (C) include (A) 2 to 80% by weight, (B) 5 to 90% by weight, and (C) 1 to 10% by weight, (B) The photocurable resin composition characterized in that the total of both components is 45% by weight or more and 99% by weight or less.
(A) The fumarate structural unit (a1) represented by the following formula (1) is 1.5 to 35% by weight, and the structural unit (a2) having an acidic functional group represented by the following formula (2) is 10 To 50% by weight, 3 to 45% by weight of the structural unit (a3) having an aromatic carbocycle represented by the following formula (3), and ethylenic unsaturation represented by the following formula (4a) or (4b) Fumarate copolymer having 20 to 65% by weight of structural unit (a4) having a bond

(Wherein R ¹ and R ² each independently represents a branched alkyl group or substituted branched alkyl group having 3 to 8 carbon atoms, or a cycloalkyl group or substituted branched cycloalkyl group having 4 to 8 carbon atoms). )

(In the formula, R ³ is a hydrogen atom, a methyl group or a carboxymethyl group.)

(In the formula, R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ represents an aromatic hydrocarbon group having 6 to 12 carbon atoms.)

(In the formula, R ⁶ and R ⁷ are a hydrogen atom or a methyl group.)

(Wherein R ⁸ and R ¹¹ are a hydrogen atom or a methyl group, R ⁹ is an alkylene group having 2 to 4 carbon atoms, R ¹⁰ is an alkylene group, and h is a number of 0 or 1) is there.)
(B) Photopolymerizable polyfunctional (meth) acrylate compound (C) Photopolymerization initiator [2] The concentration of ethylenically unsaturated bonds in the fumarate copolymer (A) is 2.1 to 4.1 mmol / The photocurable resin composition according to the above [1], which is g.

[3] Further, in (1) or [2] above, (D) the epoxy resin is contained in an amount of 5 to 45% by weight, and the total of both components (A) and (B) is 45% by weight to 94% by weight The photocurable resin composition as described.
[4] The photocurable resin composition according to any one of [1] to [3], which is used for producing a color filter.
[5] An RGB pixel or black matrix having a resin cured product obtained by curing the photocurable resin composition according to any one of [1] to [3].

[6] A protection in which the protective film covering the colored layer formed on the transparent substrate is formed by curing the photocurable resin composition according to any one of [1] to [3]. film.
[7] The photocurable resin composition according to any one of the above [1] to [3], wherein a spacer provided between the colored layer formed on the transparent substrate and the electrode substrate to be opposed is A spacer that is formed by curing.
[8] A color filter using, as a member, a resin cured product obtained by curing the photocurable resin composition according to any one of [1] to [3].

Since the photocurable resin composition of the present invention is cured to obtain a uniform cross-linked structure, it is excellent in alkali developability, excellent in heat discoloration and hardness, and has an ion barrier property, chemical resistance, and remaining film ratio. Is good.
By curing and using the photocurable resin composition of the present invention, a protective film, RGB pixel, black matrix, spacer, and color filter that can be suitably used as a member for a liquid crystal display element or a solid-state imaging element are obtained. be able to.

The present invention is described in detail below. In the present invention, (meth) acryl means either an acryl group or a methacryl group, and (meth) acryloyl means either an acryloyl group or a methacryloyl group.
Moreover, in this invention, the mixture ratio of each component of the photocurable resin composition of this invention shall represent with the ratio with respect to solid content. Solid content means the sum total of all the mixing components except a solvent, and a liquid component is also contained in solid content among epoxy resins (D).
In the photocurable resin composition of the present invention, the following components (A), (B), and (C) are respectively (A) 2 to 80 wt%, (B) 5 to 90 wt%, and (C) 1. 10% by weight, and the total of both components (A) and (B) is 45% by weight to 99% by weight.
(A) Fumarate copolymer (B) Photopolymerizable polyfunctional (meth) acrylate compound (C) Photopolymerization initiator

<Fumarate copolymer (A)>
The fumarate-based copolymer (A) used in the photocurable resin composition of the present invention has a fumarate structural unit (a1) represented by the following formula (1) in an amount of 1.5 to 35% by weight, the following formula ( 2) The structural unit (a2) having an acidic functional group represented by 10) to 50% by weight, the structural unit (a3) having an aromatic carbocycle represented by the following formula (3) to 3 to 45% by weight, And 20 to 65% by weight of a structural unit (a4) having an ethylenically unsaturated bond represented by the following formula (4a) or (4b).

(Wherein R ¹ and R ² each independently represents a branched alkyl group or substituted branched alkyl group having 3 to 8 carbon atoms, or a cycloalkyl group or substituted branched cycloalkyl group having 4 to 8 carbon atoms). )

(In the formula, R ³ is a hydrogen atom, a methyl group or a carboxymethyl group.)

(In the formula, R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ represents an aromatic hydrocarbon group having 6 to 12 carbon atoms.)

(In the formula, R ⁶ and R ⁷ are a hydrogen atom or a methyl group.)

(Wherein R ⁸ and R ¹¹ are a hydrogen atom or a methyl group, R ⁹ is an alkylene group having 2 to 4 carbon atoms, R ¹⁰ is an alkylene group, and h is a number of 0 or 1) is there.)
<Fumarate unit (a1)>
The fumarate structural unit (a1) represented by the formula (1) is a component mainly contributing to the heat discoloration and transparency of the cured resin. As the monomer used for introducing the fumarate structural unit (a1) into the fumarate copolymer (A), a fumarate represented by the following formula (5) can be used.

(In the formula, R ¹ and R ² are the same as those in the formula (1).)
Specific examples of the functional group in which R ¹ and R ² in Formulas (1) and (5) are a branched alkyl group having 3 to 8 carbon atoms or a substituted branched alkyl include an isopropyl group, a sec-butyl group, tert-butyl group, sec-amyl group, 3-pentyl group, 2,3-dimethyl-3-pentyl group, tert-amyl group, neopentyl group, isopentyl group, 4-methyl-2-pentyl group, 2-ethyl- A hexyl group etc. are mentioned.

  Specific examples of the fumarate having such a branched alkyl group or substituted branched alkyl group include diisopropyl fumarate, di-sec-butyl fumarate, di-tert-butyl fumarate, diisobutyl fumarate, di-sec- Amyl fumarate, di-tert-amyl fumarate, di-4-methyl-2-pentyl fumarate, di-sec-amyl fumarate, di-3-pentyl fumarate, bis (2,4-dimethyl-3-pentyl) fumarate, isopropyl-sec -Butyl fumarate, tert-butyl-4-methyl-2-pentyl fumarate, isopropyl-tert-butyl fumarate, sec-butyl-tert-butyl fumarate, sec-butyl-tert-amyl fumarate, di-4-methyl -Pentyle fumarate, te t- butyl - isoamyl fumarate, and the like.

Specific examples of the functional group in which R ¹ and R ^{2 in the} above formulas (1) and (6) are cycloalkyl groups or substituted cycloalkyl groups having 4 to 8 carbon atoms include a cyclobutyl group, a cyclopentyl group, and cyclohexyl. Group, cycloheptyl group, 4-tert-butyl-cyclohexyl group, isobornyl group, bornyl group, norbornyl group and the like.

  Specific examples of the fumarate having such a cycloalkyl group and / or a substituted cycloalkyl group include dicyclobutyl fumarate, dicyclopentyl fumarate, dicyclohexyl fumarate, dicycloheptyl fumarate, dicyclooctyl fumarate, bis (4-Chloro-cyclohexyl) fumarate, bis (4-tert-butyl-cyclohexyl) fumarate, diisobornyl fumarate, dibornyl fumarate, dinorbornyl fumarate and the like can be mentioned.

Specific examples of the fumarate in which R ¹ in the formula (1) is an alkyl group and R ² is a cycloalkyl group include isopropyl-cyclobutyl fumarate, 1-chloro-2-propyl-cyclopentyl fumarate, 1 , 3-dichloro-2-propyl-cyclohexyl fumarate, sec-butyl-cyclohexyl fumarate, tert-butyl-cyclopentyl fumarate, tert-butylcyclohexyl fumarate, sec-amyl-cyclohexyl fumarate, 3-pentyl-bornyl Fumarate, 2,3-dimethyl-3-pentyl-adamantyl fumarate, tert-amyl-cyclohexyl fumarate, neopentyl-cyclopentyl fumarate, 4-methyl-2-pentyl-cyclohexyl fumarate, 2-ethyl-hexyl-cycl Hexyl fumarate, and the like.
Among the fumarate, diisopropyl fumarate, di-sec-butyl fumarate, di-tert-butyl fumarate, dicyclohexyl fumarate, and di-tert-amyl fumarate are preferable from the viewpoint of availability.

  The content of the fumarate structural unit (a1) in the fumarate copolymer (A) is 1.5 to 35% by weight, preferably 5 to 25% by weight. When the fumarate-containing structural unit (a1) contained in the fumarate copolymer (A) is less than 1.5% by weight, sufficient heat discoloration and transparency of the cured resin cannot be obtained. When the amount is more than% by weight, the copolymerizability deteriorates and the alkali developability deteriorates.

<Structural Unit (a2) Having Acidic Functional Group>
The structural unit (a2) having an acidic functional group represented by the formula (2) is a component that contributes to alkali developability, and the content ratio thereof is adjusted depending on the degree of alkali solubility required for the resin. . As a monomer used for introducing the structural unit (a2) having an acidic functional group into the fumarate copolymer (A), it is possible to use a compound having an ethylenically unsaturated bond and an acidic functional group. it can.
As the monomer used for introducing the structural unit (a2) having an acidic functional group, acrylic acid, methacrylic acid or itaconic acid can be used, and among these, copolymerization with fumarate is good. For the reason, R ³ in formula (2) is preferably a methyl group or a carboxymethyl group.
Content of the structural unit (a2) which has an acidic functional group in a fumarate-type copolymer (A) is 10 to 50 weight%, Preferably it is 20 to 40 weight%. When the structural unit (a2) having an acidic functional group contained in the fumarate-based copolymer (A) is less than 10% by weight, developability deteriorates and problems such as a residue occur. When the amount is more than 50% by weight, problems such as poor developability and difficulty in controlling the pattern shape during pattern exposure occur.

  The amount of the acidic functional group in the fumarate copolymer (A) used in the photocurable resin composition of the present invention is preferably 120 to 750 mgKOH / g, more preferably 200 to 400 mgKOH / g as the acid value. The charge ratio of the monomer used for copolymerization is adjusted. By making the amount of the acidic functional group within the above range, alkali developability, heat resistance discoloration and high hardness of the cured resin can be obtained, and the cured resin can be used as a member for a liquid crystal display element or a solid-state imaging element. In addition, basic performances such as ion barrier properties and chemical resistance can be satisfactorily satisfied.

<Structural Unit (a3) Having Aromatic Carbocycle>
The photocurable resin composition of the present invention contains the structural unit (a3) having an aromatic carbocycle represented by the above formula (3) in the fumarate copolymer (A) used in the present invention. By doing so, it is possible to simultaneously impart alkali developability after pattern photocuring and heat stability under the subsequent color filter manufacturing process conditions. This cannot be explained only by the effect of increasing the glass transition point of the fumarate copolymer (A) based on the amount of the compound having an aromatic carbocycle. Although the mechanism of action has not been proved, the fumarate is probably used by using a specific amount of a compound having an aromatic carbocyclic ring that has good copolymerizability with respect to both fumarate and acrylate, which are originally not sufficiently copolymerizable. Segmental distribution of the structural unit (a1) and the structural unit (a2) having an acidic functional group is eliminated, a uniform crosslinked structure is formed, and the entire molecular chain of the fumarate copolymer (A) is alkalinized. This is presumably because a synergistic effect that significantly improves the solubility in the solution is obtained.
Specific examples of the monomer used to introduce the structural unit (a3) having an aromatic carbocycle include, for example, styrene, vinyltoluene, t-butylstyrene, α-methylstyrene. , And α-ethylstyrene.
In the above formula (3), R ⁴ is preferably a hydrogen group, and R ⁵ is preferably a phenyl group. As the corresponding monomer, specifically, styrene is preferable from the viewpoint of copolymerization with other monomers used in the fumarate copolymer (A) and availability.

  Content of the structural unit (a3) which has an aromatic carbocyclic ring in a fumarate-type copolymer (A) is 3-45 weight%, Preferably it is 5-30 weight%. When the constituent unit (a3) having an aromatic carbocyclic ring contained in the fumarate-based copolymer (A) is less than 3% by weight, the intended effect of the present application cannot be obtained, and it is more than 45% by weight. In this case, the cured resin becomes brittle and unsuitable for use.

<Structural unit (a4) having an ethylenically unsaturated bond>
The structural unit (a4) having an ethylenically unsaturated bond represented by the above formula (4a) or (4b) is a component that contributes to the reaction curability of the photo-curable resin composition, and the required curability. The content ratio may be increased depending on the height. Since ethylenically unsaturated bonds that contribute to curability co-polymerize together under the polymerization conditions when coexisting with the monomer component, after the formation of the copolymer, it may be modified by a modification process using a known reaction. Introduce into the copolymer.
In order to introduce the structural unit (a4) having an ethylenically unsaturated bond into a copolymer, first, fumarate and (meth) acrylic acid or itaconic acid are copolymerized, and then the (meth) acrylic acid or itaconic acid is copolymerized. What is necessary is just to make ester group modification by making epoxy group containing (meth) acrylate react with the carboxyl group derived from. When the alkali developability is insufficient, the concentration of the unmodified carboxyl group may be increased.

  Examples of the epoxy group-containing (meth) acrylate include glycidyl or methyl glycidyl (meth) acrylate represented by the following formula (6), and alicyclic epoxy compounds represented by the following formula (7). . As the glycidyl methacrylate of the formula (6), Blemmer GH (trade name, manufactured by NOF Corporation) and Cyclomer M-GMA (trade name, manufactured by Daicel Chemical Industries, Ltd.) are commercially available as methyl glycidyl methacrylate. Cyclomers M100 and A200 (trade name, manufactured by Daicel Chemical Industries, Ltd.) are commercially available as the alicyclic epoxy compound of the formula (7).

(Wherein R ¹² and R ¹³ are each independently a hydrogen atom or a methyl group.)

(In the formula, R ¹⁴ is a hydrogen atom or a methyl group.)
Moreover, as an ethylenically unsaturated bond containing unit, the structural unit represented by following formula (4b) is also one of preferable things.

(Wherein R ⁸ and R ¹¹ are a hydrogen atom or a methyl group, R ⁹ is an alkylene group having 2 to 4 carbon atoms, R ¹⁰ is an alkylene group, and h is a number of 0 or 1) is there.)
R ⁹ included in Formula (5) is an alkylene group having 2 to 4 carbon atoms, and examples thereof include an ethylene group, a propylene group, and a butylene group. R ¹⁰ is preferably an alkylene group having 2 to 6 carbon atoms.

  In order to introduce the structural unit of the formula (5) into the fumarate copolymer (A), first, hydroxyalkyl (meth) represented by the following formula (8) together with fumarate and (meth) acrylic acid or itaconic acid. Acrylate is copolymerized.

(Wherein R ⁸ and R ⁹ are the same as in formula (5).)
Examples of the hydroxyalkyl (meth) acrylate of the formula (8) include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, and the like. Is exemplified.
By copolymerizing this hydroxyalkyl (meth) acrylate, a structural unit having a hydroxyl group represented by the following formula (9) is introduced into the fumarate copolymer (A).

(Wherein R ⁸ and R ⁹ are the same as those in formula (5).) Thereafter, the hydroxyl group derived from the hydroxyalkyl (meth) acrylate may be reacted with an isocyanate compound represented by the following formula (10). .

(In the formula, R ¹⁵ is an alkylene group, R ¹⁶ is a hydrogen atom or a methyl group, and h is a number of 0 or 1.)
Examples of the (meth) acryloyloxyalkyl isocyanate of the formula (10) include methacryloyl isocyanate, 2-acryloyloxyethyl isocyanate, 2-methacryloylethyl isocyanate and the like. Among these, those in which a (meth) acryloyl group is bonded to an isocyanate group (—NCO) via an alkylene group having 2 to 6 carbon atoms, such as 2-acryloyloxyethyl isocyanate, 2-methacryloylethyl isocyanate, etc. are used. It is preferable to do this. Among these, methacryloyl isocyanate is represented by the following formula (14), and is commercially available, for example, under a trade name such as “MAI” manufactured by Nippon Paint Co., Ltd. Moreover, 2-methacryloyl ethyl isocyanate is marketed with brand names, such as "Karenz MOI" by Showa Denko KK, for example.

In the above example, the site where the structural unit having an ethylenically unsaturated bond is introduced into the fumarate copolymer (A) is a structural unit derived from a monomer having a hydroxyl group or a carboxyl group. A structural unit derived from a monomer having a group or an epoxy group can also be used as the introduction site.
For example, methacryloyl isocyanate represented by the above formula (11), glycidyl (meth) acrylate represented by the above formula (6), alicyclic epoxy compound represented by the above formula (7), and the like can be used. These are easy to control and produce, as with the monomers exemplified above. After forming a copolymer using these monomers, by reacting a compound having an ethylenically unsaturated bond with a functional group (hydroxyl group or carboxyl group) that reacts with the introduced isocyanate group or epoxy group And a structural unit having an ethylenically unsaturated bond can be introduced.

Content of the structural unit (a4) which has an ethylenically unsaturated bond in a fumarate-type copolymer (A) is 20 to 65 weight%, Preferably it is 30 to 60 weight%. When the constituent unit (a4) having an ethylenically unsaturated bond contained in the fumarate copolymer (A) is less than 20% by weight, the hardness of the resin cured product is not sufficient because the crosslinking points are insufficient. If it is more than 65% by weight, the alkali developability is insufficient and it is not suitable for use.
The amount of ethylenically unsaturated bonds in the fumarate copolymer (A) used in the photocurable resin composition of the present invention is preferably 2.1 to 4.1 mmol / g, more preferably 2. The charging ratio and modification rate of the monomer used for copolymerization are adjusted so as to be 1 to 3.5 mmol / g. When the amount of the ethylenically unsaturated bond is within the above range, the heat-resistant discoloration and high hardness of the cured resin can be obtained, and further when the cured resin is used as a member for a liquid crystal display element or a solid-state imaging element. The basic performance, ie, ion barrier properties, chemical resistance, etc. can be satisfactorily satisfied.

<Other structural units>
The fumarate copolymer (A) used in the present invention may have other structural units in addition to the structural units (a1) to (a4). Other structural units have good copolymerizability with the respective monomers for introducing the structural units (a1) to (a4) of the fumarate copolymer (A), and the fumarate copolymer (A ) Is introduced using a monomer that does not significantly change the physical properties. Specifically, a structural unit having an ester group represented by the following formula (12) is preferably exemplified.

(In the formula, R ¹⁷ represents a hydrogen atom or a methyl group, and R ¹⁸ represents an alkyl group or an aralkyl group.)
R ¹⁸ contained in the above formula is an alkyl group or an aralkyl group, and examples thereof include aralkyl groups such as an alkyl group having 1 to 12 carbon atoms, a benzyl group, and a phenylethyl group. Examples of the monomer used to introduce the structural unit include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ( (Meth) acrylic acid phenyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid dicyclopentanyl, (meth) acrylic acid dicyclopentanyloxyethyl, (meth) acrylic acid isobonyl, (meth) acrylic acid benzyl, ( Examples include esters of (meth) acrylic acid such as phenylethyl methacrylate.
The content of other structural units in the fumarate copolymer (A) used in the present invention is 32% by weight or less, preferably 20% by weight or less. If the content of other structural units exceeds 32% by weight, the physical properties of the fumarate copolymer (A) change, and the intended effect of the present application cannot be obtained.
The monomers used for introducing each of the above structural units into the fumarate copolymer (A) may be used alone or in admixture of two or more.

  In order to produce the fumarate-based copolymer (A) used in the present invention, first, it comprises an fumarate structural unit (a1) and a structural unit (a2) having an acidic functional group, and has an ethylenically unsaturated bond. Manufactures a polymer (hereinafter referred to as a raw material polymer) containing a structural unit having a functional group into which the structural unit (a4) can be introduced later, a structural unit (a3) having an aromatic carbocyclic ring, or other structural units. Then, the ethylenically unsaturated bond may be introduced by reacting the raw material polymer with a compound having another functional group together with the ethylenically unsaturated bond.

  As a polymerization solvent used for producing the raw material polymer, a generally known solvent can be used. For example, aliphatic alcohols having 1 to 3 carbon atoms such as methanol, ethanol and glycol; cellosolvs such as cellosolve and butylcellosolve; carbitols such as carbitol and butylcarbitol; propylene glycol monomethyl ether, diethylene glycol monomethyl ether and the like Glycol ethers; polar solvents such as dimethylacetamide and dimethylformamide; ethers such as tetrahydrofuran; glycol ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol methyl ethyl ether; cellosolv esters such as methyl cellosolve acetate and propylene glycol Monomethyl ether acetate, 3-methoxybutyl acetate, etc. Hydrocarbons, ketones, can also be used esters.

  As the polymerization initiator used for producing the raw material polymer, those generally known as radical polymerization initiators can be used. Specific examples thereof include 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobis- (4-methoxy-2,4). -Nitrile azo compounds such as dimethylvaleronitrile); Non-nitrile azo such as dimethyl 2,2'-azobis (2-methylpropionate), 2,2'-azobis (2,4,4-trimethylpentane) Compound: t-hexylperoxypivalate, tert-butylperoxypivalate, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, 1,1,3,3-tetramethylbutylperoxy 2 Ethylhexanoate, succinic peroxide, 2,5-dimethyl-2,5-di ( -Ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethylperoxy 2-ethylhexanoate, t-hexylperoxy 2-ethylhexanoate, 4-methylbenzoyl peroxide, benzoyl peroxide, 1,1'-bis Organic peroxides such as-(tert-butylperoxy) cyclohexane; and hydrogen peroxide. When a peroxide is used as the radical polymerization initiator, it may be used as a redox polymerization initiator in combination with a reducing agent.

In the production of the raw material polymer, a molecular weight modifier can be used to adjust the weight average molecular weight, such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, thioglycol. Examples include mercaptans such as acids; xanthogens such as dimethylxanthogen disulfide and diisopropylxanthogen disulfide; terpinolene and α-methylstyrene dimer.
The raw material polymer may be either a random copolymer or a block copolymer. In the case of producing a random copolymer, a blending composition containing each monomer, catalyst, etc. for deriving each structural unit is placed in a polymerization tank containing a solvent under a temperature condition of 80 to 110 ° C. It can be polymerized by dripping over -5 hours and aging.

  The raw material polymer preferably has a polystyrene-equivalent weight average molecular weight (hereinafter simply referred to as “weight average molecular weight” or “Mw”) in the range of 5,000 to 100,000, and the acid value is preferably 120 to 750 mgKOH / g. More preferably, those having 200 to 400 mgKOH / g and hydroxyl values of 5 mgKOH / g to 400 mgKOH / g are more preferable.

The reaction for introducing an ethylenically unsaturated bond into the raw material polymer uses a known functional group modification reaction depending on the combination of the molecular structure of the raw material polymer and the molecular structure of the unit into which the ethylenically unsaturated bond is introduced. be able to.
In order to introduce an ethylenically unsaturated bond into a raw material polymer containing a fumarate structural unit (a1), a structural unit (a2) having an acidic functional group, and a structural unit (a3) having an aromatic carbocyclic ring In the case of reacting glycidyl (meth) acrylate, the glycidyl (meth) acrylate is added to the raw polymer solution all at once in the presence of a small amount of catalyst, and then the reaction is continued for a certain time, or By adding dropwise little by little, the copolymer represented by the formula (14) is obtained.

Further, it contains a fumarate structural unit (a1), a structural unit (a2) having an acidic functional group, a structural unit (a3) having an aromatic carbocycle, and a hydroxyl group-containing unit represented by the above formula (9) When the isocyanate compound represented by the formula (10) is reacted in order to introduce an ethylenically unsaturated bond into the raw material polymer, the raw material polymer is reacted in the presence of a small amount of catalyst. The copolymer represented by the above formula (15) can be obtained by adding the whole amount to the solution at once and continuing the reaction for a certain period of time or by adding dropwise little by little. In this case, dibutyltin laurate is used as a catalyst, and a polymerization inhibitor such as p-methoxyphenol, hydroquinone, naphthylamine, tert-butylcatechol, 2,3-di-tert-butyl p-cresol is required. Used depending on.
The isocyanate compound having an ethylenically unsaturated bond causes an addition reaction to the alcoholic hydroxyl group of the raw material polymer via the isocyanate group to form a urethane bond. As a result, an ethylenically unsaturated bond is introduced into the portion of the hydroxyl group-containing unit represented by the formula (9) in the raw material polymer, and the constituent unit of the formula (5) is formed.

Moreover, the isocyanate compound which has an ethylenically unsaturated bond raise | generates the condensation reaction accompanying elimination | elimination of a carbon dioxide gas with respect to the carboxyl group of a raw material polymer via an isocyanate group, and forms an amide bond. As a result, an ethylenically unsaturated bond is also introduced into the portion of the carboxyl group-containing unit represented by the above formula (2) in the raw material polymer. However, since the reactivity of the isocyanate compound with respect to the carboxyl group is very small compared with the reactivity of the isocyanate compound with respect to the alcoholic hydroxyl group, the ethylenically unsaturated bond is mainly introduced into the portion of the alcoholic hydroxyl group-containing unit. The amount of ethylenically unsaturated bonds introduced into the containing unit is generally very small. Therefore, most of the carboxyl groups remain and the alkali developability is not lost.
When the fumarate copolymer (A) thus obtained is used to form a colored layer of a color filter, a protective film covering the colored layer, or a columnar spacer for maintaining the cell gap of a liquid crystal panel The weight average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography) is preferably adjusted in the range of 2,000 to 100,000, preferably 8,000 to 70,000. If the weight average molecular weight is less than 5,000, developability is too good to control the pattern shape during pattern exposure, and even if a pattern can be produced, the final film thickness is reduced (film reduction). is there. On the other hand, when the weight average molecular weight is larger than 100,000, there are problems that the viscosity at the time of resist formation becomes too high and the coating suitability is deteriorated, the developing property is deteriorated and the pattern is hardly removed.

The fumarate copolymer (A) used in the present invention comprises a fumarate structural unit (a1) that contributes to heat discoloration, a structural unit (a2) that has an acidic functional group that contributes to acidity and alkali solubility, The structural unit (a3) having an aromatic carbocyclic ring that contributes to the improvement of copolymerizability is linked to form a structural unit (a4) having an ethylenically unsaturated bond that contributes to reaction curability, and, if necessary, an alkali. The ester group-containing unit that suppresses solubility with respect to is formed, and not only has excellent heat discoloration, but also by changing the content ratio of each of these structural units, reaction curability, alkali solubility, The coatability can be adjusted appropriately.
Therefore, using the fumarate copolymer (A), an alkali developable photocurable resin composition for forming a color filter protective film, RGB pixel, black matrix or spacer can be prepared, It can be suitably used to form details of a color filter. The photocurable resin composition using the fumarate copolymer (A) is particularly suitable for forming a columnar spacer for maintaining the color gap of the color filter, the protective film, or the cell gap of the liquid crystal panel. However, since it has excellent heat discoloration resistance and hardly yellows, it is very suitable for forming a portion requiring high transparency such as a pixel portion or a protective film.

Hereinafter, a photocurable resin composition for forming a color filter protective film, RGB pixel, black matrix, or spacer formed by blending the fumarate copolymer (A) will be described in detail.
The photocurable resin composition of the present invention contains 2 to 80% by weight, preferably 10 to 50% by weight of the fumarate copolymer (A). When the content of the fumarate copolymer (A) is more than 80% by weight, the viscosity becomes too high, and as a result, the fluidity may be lowered and the coating property may be deteriorated. Further, when the content of the fumarate copolymer (A) is less than 2% by weight, the viscosity becomes too low. As a result, the coating film stability after coating and drying is insufficient, and exposure and development suitability are improved. May cause problems such as damage.

<Photopolymerizable polyfunctional (meth) acrylate compound (B)>
The photocurable resin composition of the present invention contains a photopolymerizable polyfunctional (meth) acrylate compound (B). The photopolymerizable polyfunctional (meth) acrylate compound (B) is a polyfunctional polymerizable compound having two or more ethylenically unsaturated bonds having an action of curing the photocurable resin composition. Specifically, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,4 -Polyhydric alcohol di (meth) acrylate having two ethylenically unsaturated bonds such as butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) acrylate; polyethylene glycol di Polyol di (meth) acrylate having two ethylenically unsaturated bonds having a molecular weight of 10,000 or less, such as (meth) acrylate and polypropylene glycol di (meth) acrylate; glycerin tri (meth) acrylate, trimer Polyhydric alcohol di (meth) acrylate having 3 ethylenically unsaturated bonds such as roll propane tri (meth) acrylate; ethylenically unsaturated bond such as pentaerythritol tetra (meth) acrylate and dipentaerythritol hexa (meth) acrylate Examples thereof include polyhydric alcohol di (meth) acrylate having 4 or more.
The number of ethylenically unsaturated bonds in one molecule is preferably 3 or more, and more preferably 5 or more in order to improve reactivity and crosslink density.
The photopolymerizable polyfunctional (meth) acrylate compound (B) may be used in combination of two or more.

  The photopolymerizable polyfunctional (meth) acrylate compound (B) is contained in the photocurable resin composition in an amount of 5 to 90% by weight, preferably 10 to 75% by weight. When the photopolymerizable polyfunctional (meth) acrylate compound (B) is less than 5% by weight, there is a disadvantage that various physical strengths such as adhesive strength and heat resistance of the formed film are insufficient, and 80% by weight. If it exceeds 1, the stability of the photocurable resin composition is lowered, and there is a disadvantage that the flexibility of the formed film becomes insufficient. Furthermore, in order to improve the dissolution characteristics in the developer, the above range of the content is necessary. If the content is outside this range, the pattern is resolved but the curing speed is increased, and the scum and the surroundings of the pattern are increased. Causes a beard. Further, outside of the above range, in a severe case, resist redeposition may occur due to partial swelling / peeling, which may hinder accurate pattern formation.

<Photopolymerization initiator (C)>
In the present invention, the photopolymerization initiator (C) refers to a radical polymerization initiator that can be activated by ultraviolet rays, ionizing radiation, visible light, or other various wavelengths, particularly energy rays of 365 nm or less. Specific examples include, for example, benzophenone derivatives such as benzoin and benzophenone, or derivatives thereof; xanthone and thioxanthone derivatives; chlorosulfonyl, chloromethyl polynuclear aromatic compounds, chloromethyl heterocyclic compounds, chloromethyl benzophenones, and the like. Examples include halogen compounds; triazines; fluorenones; haloalkanes; acridines; redox couples of a photoreducing dye and a reducing agent; organic sulfur compounds; peroxides.
Among these, 1-hydroxy-cyclohexyl-phenyl-ketone (Ciba Specialty Chemicals, trade name “Irgacure 184”), 2,2-dimethoxy-2-phenylacetophenone (“Irgacure 651”), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (same as “Darocur 1173”), 2-benzyl-2- (dimethylamino) -4-morpholinobutylphenone (same as “Irgacure 369”), 2-methyl-4 ′-(methylthio) -2-morpholino-propiophenone (“Irgacure 907”), 1,7- (9-acridinyl) heptane (trade name “Adekaoptomer N”, Asahi Denka Kogyo Co., Ltd.) -1717 "), and 2,2'-bis (o-chlorophenyl) -4,5,4 ', 5'-tetra Mention may be made of phenyl-1,2'-biimidazole (trade name “bimidazole”, Kurogane Kasei Co., Ltd.).
The photoinitiator (C) used for this invention can be used individually by 1 type or in combination of 2 or more types. When two or more kinds are used in combination, it is preferable not to inhibit the absorption spectral characteristics.

The radical polymerization initiator is usually contained in the photocurable resin composition in an amount of 0.1 to 18% by weight, preferably 0.5 to 10% by weight. When the addition amount of the radical polymerization initiator is less than 0.05% by weight, the photocuring reaction does not proceed, and the remaining film ratio, heat resistance, chemical resistance and the like tend to decrease. Further, when this addition amount exceeds 18% by weight, the solubility in the base resin reaches saturation, and crystals of the initiator are precipitated during spin coating or coating leveling, so that the uniformity of the film surface cannot be maintained. There arises a problem of film roughness.
In preparing the photocurable resin composition, the photopolymerization initiator (C) may be added from the beginning to the photocurable resin composition containing the fumarate copolymer (A). However, when storing for a relatively long period of time, it is preferable to disperse or dissolve in the photocurable resin composition immediately before use.

<Epoxy resin (D)>
Furthermore, in the photocurable resin composition of this invention, an epoxy resin (D) can be mix | blended in order to aim at the improvement of heat resistance, adhesiveness, and chemical resistance (especially alkali resistance). In the present invention, the epoxy resin refers to a compound having two or more epoxy groups in the molecule. Specifically, for example, Epicoat 1001, 1002, 1003, 1004, 1007, 1009, 1010 (trade name, manufactured by Japan Epoxy Resins Co., Ltd.) as bisphenol A type epoxy resin, and Epicoat 807 (product) as bisphenol F type epoxy resin Name, manufactured by Japan Epoxy Resin Co., Ltd.), EPPN201, 202 (trade name, manufactured by Nippon Kayaku Co., Ltd.), Epicoat 154 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), etc. Examples of the cresol novolac type epoxy resin include EOCN102, 103S, 104S, 1020, 1025, 1027 (trade name, manufactured by Nippon Kayaku Co., Ltd.), Epicoat 180S (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), and the like. Furthermore, cycloaliphatic epoxy resin and aliphatic polyglycidyl ether can also be illustrated.

  Among these, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, and cresol novolac type epoxy resin are preferable. Many of these epoxy resins (D) are high molecular weight substances, but glycidyl ethers of bisphenol A and bisphenol F are low molecular weight substances, and such low molecular weight substances are more preferable. In addition, acrylic copolymers containing glycidyl (meth) acrylate, oxetane (meth) acrylate, alicyclic epoxy (meth) acrylate and the like in the molecular skeleton are also effective.

When mix | blending an epoxy resin (D) in a photocurable resin composition, it is 60 weight% or less normally, Preferably it contains 5 to 45 weight%, More preferably, it contains in the ratio of 10 to 35 weight%. When content of an epoxy resin (D) exceeds 60 weight%, an epoxy group density | concentration will become high too much, and the storage stability and developability of a photocurable resin composition may fall. In addition, the epoxy resin is effective for removing the tack of the dry coating film of the photocurable resin composition, and a sufficient effect is exhibited when the addition amount is about 5% by weight. The epoxy resin reacts with the acidic group remaining in the coating film without reacting even after exposure and alkali development, and imparts excellent alkali resistance to the coating film.
In the photocurable resin composition of the present invention, when the epoxy resin (D) is blended, the total of both the components (A) and (B) is preferably 94% by weight or less.

  A sensitizer may be added to the photocurable resin composition of the present invention when it is desired to improve the photosensitivity. The sensitizer used is preferably a styryl compound or a coumarin compound. Specifically, 2- (p-dimethylaminostyryl) quinoline, 2- (p-diethylaminostyryl) quinoline, 4- (p-dimethylaminostyryl) quinoline, 4- (p-diethylaminostyryl) quinoline, 2- ( p-dimethylaminostyryl) -3,3-3H-indole, 2- (p-diethylaminostyryl) -3,3-3H-indole, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-diethylamino) Styryl) -benzoxazole, 2- (p-dimethylaminostyryl) benzimidazole, 2- (p-diethylaminostyryl) -benzimidazole and the like.

  Examples of the coumarin compound include 7-diethylamino-4-methylcoumarin, 7-ethylamino-4-trifluoromethylcoumarin, 4,6-diethylamino-7-ethylaminocoumarin, and 3- (2-benzimidazolyl)-. 7-N, N-diethylaminocoumarin, 7-diethylaminocyclopenta (c) coumarin, 7-amino-4-trifluoromethylcoumarin, 1,2,3,4,5,3H, 6H, 10H-tetrahydro-8- Trifluoromethyl (1) benzopyrano- (9,9a, 1-gh) -quinolizin-10-one, 7-ethylamino-6-methyl-4-trifluoromethylcoumarin, 1,2,3,4,5, 3H, 6H, 10H-tetrahydro-9-carbethoxy (1) benzopyrano- (9,9a, 1-gh) -quinolidine-10 On and the like.

When the photocurable resin composition of the present invention is expected to be cured by heat treatment after exposure and alkali development, a nitrile azo polymerization initiator or a non-nitrile azo polymerization initiator is used as a thermal polymerization initiator. And organic oxides can be blended. By blending these thermal polymerization initiators, the reaction by the heat treatment of the ethylenically unsaturated bonds remaining in the coating film is promoted without reacting even after exposure and alkali development, and the crosslinking density is improved. be able to.
In the photocurable resin composition of the present invention, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, and ethylhexyl (meth) are used as reaction diluents. Monofunctional monomers such as acrylate, styrene, methylstyrene, N-vinyl pyrrolidone can be added.
Various additives, such as surfactant and a silane coupling agent, can be mix | blended with the photocurable resin composition of this invention.

Furthermore, when forming the colored layer of a color filter using the said photocurable resin composition, coloring materials, such as a pigment and dye, are mix | blended in this curable resin composition. The color material has heat resistance that can withstand the heating process of the color filter from among organic and inorganic colorants according to the desired color of R, G, B, etc. of the pixel portion, and is well dispersed. The fine particles obtained can be selected and used.
Examples of organic pigments include compounds classified as pigments in the color index (CI; issued by The Society of Dyersand Colorists). Specific examples of the inorganic pigment or extender pigment include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red rose (red iron oxide (III)), cadmium red, ultramarine blue, Examples include bitumen, chromium oxide green, cobalt green, amber, titanium black, synthetic iron black, and carbon black. In the present invention, the color materials can be used alone or in admixture of two or more.

When mix | blending a coloring material, it mix | blends in the ratio of 40 to 75 weight% normally in a photocurable resin composition, Preferably it is 45 to 70 weight%. When the blending ratio of the color material is less than 40% by weight, the coloring power of each pixel portion is insufficient, and it is difficult to display a clear image. On the other hand, when it exceeds 75% by weight, light transmission in each pixel portion is performed. Inconvenience such as insufficient rate occurs.
When blending a color material in the photocurable resin composition, a dispersant may be blended in the photocurable resin composition in order to disperse the color material uniformly and stably. Examples of the dispersant that can be used include cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants. Among the surfactants, polymer surfactants (polymer dispersants) as exemplified below are preferable.

  That is, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkyl phenyl ethers such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether Polymeric surfactants such as polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; sorbitan fatty acid esters; fatty acid-modified polyesters; tertiary amine-modified polyurethanes are preferably used.

  The photocurable resin composition of the present invention usually contains a solvent having good solubility in a fumarate copolymer (A), a photocurable compound, a photopolymerization initiator, etc. in consideration of coating and application suitability. Contained. Examples of usable solvents include alcohol solvents such as methyl alcohol, ethyl alcohol, n-propyl alcohol and isopropyl alcohol; cellosolv solvents such as methoxyethanol and ethoxyethanol; carbitols such as methoxyethoxyethanol and ethoxyethoxyethanol. Solvents; Ester solvents such as ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, and ethyl lactate; Ketone solvents such as acetone, methyl isobutyl ketone, cyclohexanone; methoxyethyl acetate, ethoxyethyl acetate, ethyl cellosolve acetate Cellosolve acetate solvents such as carbitol acetate such as methoxyethoxyethyl acetate and ethoxyethoxyethyl acetate Solvents; ether solvents such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and tetrahydrofuran; aprotic amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone; and γ-butyrolactone Examples include lactone solvents; unsaturated hydrocarbon solvents such as benzene, toluene, xylene, and naphthalene; and organic solvents such as saturated hydrocarbon solvents such as N-heptane, N-hexane, and N-octane. Among these solvents, cellosolve acetate solvents such as methoxyethyl acetate, ethoxyethyl acetate, and ethyl cellosolve acetate; carbitol acetate solvents such as methoxyethoxyethyl acetate and ethoxyethoxyethyl acetate; ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene Ether solvents such as glycol diethyl ether; ester solvents such as methyl methoxypropionate, ethyl ethoxypropionate and ethyl lactate are more preferably used. More preferably, 3-methoxybutyl acetate (3-MBA), propylene glycol monomethyl ether acetate (PGMEA), diethylene glycol dimethyl ether (DMDG), or a mixture thereof can be used. The solid content concentration is adjusted to 5 to 50% by weight using these solvents.

  To produce the photocurable resin composition, the fumarate copolymer (A), the photopolymerizable polyfunctional (meth) acrylate compound (B), the photopolymerization initiator (C), and others Is added to a suitable solvent and dissolved and dispersed by a general method such as a paint shaker, bead mill, sand grind mill, ball mill, attritor mill, two roll mill, or three roll mill. As the fumarate copolymer (A), a product obtained by isolating and purifying the fumarate copolymer (A) which is an active ingredient after the synthesis reaction, a reaction solution obtained by the synthesis reaction, and a dried product thereof are used. Etc. may be used as they are.

When the photocurable resin composition thus obtained is applied to some support to form a coating film, and the coating film is irradiated with an activation energy ray such as ultraviolet ray or ionizing radiation, the photocurable compound is crosslinked. A bond is formed to wrap the fumarate copolymer (A), or the ethylenically unsaturated bond of the fumarate copolymer (A) itself forms a crosslink and is cured.
The cured film has excellent heat discoloration resistance, and hardly discolors such as yellowing and transparency. In addition, since a cross-linked bond is formed between the fumarate copolymer (A) and the photopolymerizable polyfunctional (meth) acrylate compound (B), the cross-linking reaction point density increases, exposure sensitivity, and film Strength and hardness are improved.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. In the following, “part” means part by weight unless otherwise specified.
The measurement method and test method used for preparing the materials are shown below.
<Acid value>
The acid value is determined according to JIS K0070: 1992 “Testing method for acid value, saponification value, ester value, iodine value, hydroxyl value and unsaponified product of chemical products”. Was dissolved and titrated with a KOH / ethanol solution using phenolphthalein as an indicator for measurement.
<Weight average molecular weight>
The weight average molecular weight (Mw) was measured by using a gel permeation chromatography device HLC-8220GPC manufactured by Tosoh Corporation, using SHODEX K-801 manufactured by Showa Denko KK as a column, THF as an eluent, and using an RI detector. Measured and calculated by polystyrene conversion.

The test method of the cured film is as follows.
<380 nm light transmittance>
The light transmittance (380 nm) of the cured film on the obtained glass substrate was measured using an absorption meter (manufactured by Shimadzu Corporation, UV-3100PC) using the glass substrate as a reference.
<Pencil hardness>
JIS K5600-5-4: 1999 “Paint General Test Method-Part 5: Mechanical Properties of Coating Film—Section 4: Scratch Hardness (Pencil Method)” shows a pencil hardness of 3H or higher by the hand-scratching method. Sometimes judged good.
<Heat resistance test (250 ° C. × 1 h.)>
The glass substrate with the cured film was heated in a clean oven at 250 ° C. for 1 hour to obtain a heat test cured film. The visible light (380 to 780 nm) transmittance of the heat test cured film on the glass substrate thus obtained was measured using an absorption meter (UV-3100PC, manufactured by Shimadzu Corporation) with the glass substrate as a reference. It was measured.

<Adhesion after heat-resistant pure water test>
After immersing the glass substrate provided with the protective film in pure water at 80 ° C. for 1 hour, JIS K5600-5-6: 1999 “Paint General Test Method—Part 5: Mechanical Properties of Coating Film—Section 6: Adhesiveness ( When the film remaining ratio as a result of performing the “cross-cut method” was 95% to 100%, it was determined to be good.
<Water vapor permeability>
The evaluation of the ion barrier property was performed using the measurement of water vapor permeability. In accordance with method B of JIS K7129: 1992 “Water vapor permeability test method for plastic film and sheet (instrument measurement method)”, the cured film was measured at 40 ° C. and 90% R.D. using PERMATRAN manufactured by MOCON. H. When the result performed on condition was 5.0 g / m < ² > / day or less, it determined with it being favorable.
<ITO sputtering resistance>
An ITO film was formed on a glass substrate provided with a protective film by sputtering at 230 ° C. so that a resistance value of 10 to 15 Ω / cm ² was obtained. The haze value (Hz) value of this substrate was determined to be good when the result of evaluation using DIRECT READING HAZE METER (manufactured by Toyo Seiki Seisakusho Co., Ltd.) was 1.0 or less.

<Color difference after heat test>
The substrate on which the R pixel pattern was formed was heated in a clean oven at 250 ° C. for 1 hour, and the color difference ΔEab before and after the heating test of the obtained cured film was measured using a microspectrophotometer DSP-SP100 (Olympus Optical Co., Ltd.). ) And calculated based on the CIE 1976 standard. The evaluation criteria were ◯ when ΔEab before and after heating for 1 hour at 250 ° C. was less than 1, and Δ when ΔEab was 1 or more and less than 3, and × when 3 or more.
<Alkali developability>
On a 10-cm glass substrate, it was applied and dried by a spin coater to form a coating film having a dry film thickness of 2.2 μm. A negative photomask having a dot pattern with a diameter of 10 μm is arranged at a distance of 100 μm from the coating film, and an intensity of 100 mJ / cm ² (405 nm illuminance conversion) using a 2.0 kW ultrahigh pressure mercury lamp by a proximity aligner. Irradiated with ultraviolet rays. Subsequently, it was immersed in 0.05 wt% potassium hydroxide aqueous solution (liquid temperature 23 degreeC) for 1 minute, and alkali image development was carried out, and only the uncured part of the coating film of a photocurable resin composition was removed. Thereafter, when the dimensional error of the diameter of the resin pattern formed after the heat treatment is performed by leaving the substrate in an atmosphere of 200 ° C. for 30 minutes with respect to the dot pattern of the photomask is 0 to 2%. , When it was 2 to 5%, Δ when it was 5 to 10%, × when it was 10 to 20%, and xx when it was 20% or more. ○ If it has the above performance, it can be put to practical use.

Synthesis example 1
<Synthesis of Precursor of Fumarate Copolymer A-1>
The following amount of monomer dicyclohexyl fumarate (DCHF): 174.4 g
・ Itaconic acid: 279.5 g (2.1 mol)
・ Styrene (St): 546.1 g
And a solution prepared by dissolving 10 g of perbutyl O (trade name, organic peroxide manufactured by NOF Corporation) in 500 g of 3-methoxybutyl acetate (3-MBA) at a temperature of 80 ° C., 2500 g Of 3-MBA was added dropwise to a polymerization tank in a nitrogen atmosphere over 6 hours, and then aged and polymerized at the same temperature for 4 hours to obtain a raw polymer solution (precursor of fumarate copolymer A-1). Body).
<Synthesis of Fumarate Copolymer A-1>
Glycidyl methacrylate (GMA) (491.5 g, 3.5 mol), pyridine (35.0 g), and hydroquinone (1.1 g) were charged into the raw polymer solution obtained by the above synthesis and dissolved uniformly. Next, it heated up to 80 degreeC, bubbling air in the reaction liquid under stirring, and reacted at 80 degreeC for 5 hours, and obtained the solution of the fumarate-type copolymer A-1.
The weight average molecular weight of the fumarate copolymer A-1 was 15,000. Further, when the acid value per solid content of the copolymer resin solution was measured, the acid value was 30 mgKOH / g, and the amount of unmodified carboxyl group calculated from this was 0.53 mmol / g, which was modified by GMA. The conversion rate of the reaction was 100%, and it was confirmed that a fumarate copolymer A-1 having an ethylenically unsaturated bond content of 2.2 mmol / g was produced according to the formulation design.

Synthesis example 2
<Synthesis of Precursor of Fumarate Copolymer A-2>
The amount of the following monomer: Dicyclohexyl fumarate (DCHF): 230.0 g
Acrylic acid (AA): 701.1 g (9.7 mol)
・ Styrene (St): 68.9 g
A raw material polymer solution (precursor of fumarate copolymer A-2) was obtained by performing the same operation as in Synthesis Example 1 except that the above was changed.
<Synthesis of Fumarate Copolymer A-2>
The same operation as in Synthesis Example 1 was performed except that the amount of glycidyl methacrylate (GMA) charged to the raw polymer solution obtained in the above synthesis was changed to 118.4 g (8.4 mol) and 85.3 g of pyridine. By performing, the solution of the fumarate-type copolymer A-2 was obtained.
The weight average molecular weight of the fumarate copolymer A-2 was 34,000. Further, when the acid value per solid content of the copolymer resin solution was measured, the acid value was 32 mgKOH / g, and the amount of unmodified carboxyl group calculated from this was 0.57 mmol / g, which was modified by GMA. The conversion rate of the reaction was 100%, and it was confirmed that a fumarate copolymer A-2 having an ethylenically unsaturated bond content of 3.7 mmol / g was produced according to the formulation design.

Synthesis example 3
<Synthesis of Precursor of Fumarate Copolymer A-3>
The amount of the following monomer: Dicyclohexyl fumarate (DCHF): 453.8 g
Methacrylic acid (MAA): 515.1 g (5.98 mol)
・ Styrene (St): 31.2 g
A raw material polymer solution (precursor of fumarate copolymer A-3) was obtained by performing the same operation as in Synthesis Example 1 except that the above was changed.
<Synthesis of Fumarate Copolymer A-3>
A fumarate-based co-polymer is obtained by performing the same operation as in Synthesis Example 1 except that the amount of cyclomer M100 charged to the raw polymer solution obtained in the above synthesis is changed to 3486.7 g and 248.2 g of pyridine. A solution of polymer A-3 was obtained.
The weight average molecular weight of the fumarate copolymer A-3 was 4,000. Further, when the acid value per solid content of the copolymer resin solution was measured, the acid value was 30 mgKOH / g, and the amount of unmodified carboxyl group calculated from this was 0.53 mmol / g, which was modified by GMA. The conversion rate of the reaction was 100%, and it was confirmed that the fumarate copolymer A-3 having an ethylenically unsaturated bond content of 2.8 mmol / g was produced according to the formulation design.

Synthesis example 4
<Synthesis of Precursor of Fumarate Copolymer A-4>
The following amount of monomer dicyclohexyl fumarate (DCHF): 14.6 g
2-hydroxyethyl acrylate (HEA): 773.5 g (6.8 mol)
・ Styrene (St): 211.8 g
And a solution prepared by dissolving 10 g of perbutyl O (trade name, organic peroxide manufactured by NOF Corporation) in 500 g of 3-methoxybutyl acetate (3-MBA) at a temperature of 80 ° C., 2500 g Was added dropwise to a polymerization tank in a nitrogen atmosphere containing 3-MBA over 6 hours, and then aged and polymerized at the same temperature for 4 hours to obtain a solution of a raw material polymer (precursor of fumarate copolymer A-4). Body).
<Synthesis of Fumarate Copolymer A-4>
To the raw material polymer solution obtained by the above synthesis, 1053.6 g of 2-acryloylethyl isocyanate (AOI), 1.1 g of dibutyltin laurate and 1.1 g of hydroquinone were charged and dissolved uniformly. Next, it heated up to 80 degreeC, bubbling air in the reaction liquid under stirring, and reacted at 80 degreeC for 5 hours, and the solution of the fumarate-type copolymer A-4 was obtained.
The weight average molecular weight of the fumarate copolymer A-4 was 78,000. Further, when the acid value per solid content of the copolymer resin solution was measured, the acid value was 30 mgKOH / g, and the amount of unmodified carboxyl group calculated from this was 0.53 mmol / g, which was modified by AOI. The conversion rate of the reaction was 100%, and it was confirmed that a fumarate copolymer A-4 having an ethylenically unsaturated bond content of 3.0 mmol / g was produced according to the formulation design.

<Synthesis of Precursor of Copolymer Resin Solution (a-1)>
Monomer methyl methacrylate (MMA) in the following amount: 639.4 g
Methacrylic acid (MAA): 360.6 g
And a solution prepared by dissolving 10.0 g of Perbutyl O (trade name, organic peroxide manufactured by NOF Corporation) in 500 g of 3-methoxybutyl acetate (3-MBA) at a temperature of 80 ° C., 2500 g Was added dropwise to a polymerization tank in a nitrogen atmosphere containing 3-MBA over 6 hours, and then aged and polymerized at the same temperature for 4 hours to prepare a polymer solution (precursor of copolymer resin solution (a-1)). Body).
<Synthesis of copolymer resin solution (a-1)>
Glycidyl methacrylate (GMA) 327.1 g, pyridine 23.3 g, and hydroquinone 1.0 g were charged into 4010 g of the raw material polymer solution obtained by the above synthesis and dissolved uniformly. Next, it heated up to 80 degreeC, bubbling air in the reaction liquid under stirring, and reacted at 80 degreeC for 5 hours, and obtained the copolymer resin solution (a-1).

Comparative Synthesis Example 2
<Synthesis of Precursor of Copolymer Resin Solution (a-2)>
The amount of monomers in Comparative Synthesis Example 1 is methyl methacrylate (MMA): 33.9 g
-Methacrylic acid (MAA): 966.1 g
A raw material polymer solution (precursor of copolymer resin solution (a-2)) was obtained by carrying out the same operations as in Comparative Synthesis Example 1 except that the above was changed.
<Synthesis of copolymer resin solution (a-2)>
Except that the amount of glycidyl methacrylate (GMA) in Comparative Synthesis Example 1 was changed to 1552.4 g and the amount of pyridine was changed to 110.5 g to 4010 g of the raw material polymer solution obtained by the above synthesis, By performing the same operations as in Comparative Synthesis Example 1, a copolymer resin solution (a-2) was obtained.

Comparative Synthesis Example 3
<Synthesis of copolymer resin solution (a-3) precursor>
The following amount of monomer: Dicyclohexyl fumarate (DCHF): 639.4 g
-Methacrylic acid (MAA): 360.6 g
And a solution prepared by dissolving 10.0 g of Perbutyl O (trade name, organic peroxide manufactured by NOF Corporation) in 500 g of 3-methoxybutyl acetate (3-MBA) at a temperature of 80 ° C., 2500 g Was added dropwise over 6 hours into a polymerization tank in a nitrogen atmosphere containing 3-MBA, and then aged and polymerized at the same temperature for 4 hours to prepare a polymer solution (precursor of copolymer resin solution (a-3)). Body).
<Synthesis of copolymer resin solution (a-3)>
Glycidyl methacrylate (GMA) 327.1 g, pyridine 23.3 g, and hydroquinone 1.0 g were charged into the raw polymer solution 4010 g obtained by the above synthesis and dissolved uniformly. Next, the temperature is raised to 80 ° C. while bubbling air into the stirred reaction solution, and the reaction is performed at 80 ° C. for 5 hours to obtain a copolymer resin solution (a-3).
Got.

Comparative Synthesis Example 4
<Synthesis of copolymer resin solution (a-4) precursor>
Monomer dicyclohexyl fumarate (DCHF): 436.4g
-Methacrylic acid (MAA): 553.6 g
・ Styrene (St): 10.0 g
And a solution prepared by dissolving 10.0 g of Perbutyl O (trade name, organic peroxide manufactured by NOF Corporation) in 500 g of 3-methoxybutyl acetate (3-MBA) at a temperature of 80 ° C., 2500 g Was added dropwise over 6 hours into a polymerization tank in a nitrogen atmosphere containing 3-MBA, and then aged and polymerized at the same temperature for 4 hours to prepare a polymer solution (precursor of copolymer resin solution (a-3)). Body).
<Synthesis of copolymer resin solution (a-4)>
To 4010 g of the raw material polymer solution obtained by the above synthesis, 612.6 g of glycidyl methacrylate (GMA), 43.6 g of pyridine, and 1.0 g of hydroquinone were charged and dissolved uniformly. Next, it heated up to 80 degreeC, bubbling air in the reaction liquid under stirring, and reacted at 80 degreeC for 5 hours, and obtained the copolymer resin solution (a-4).

Comparative Synthesis Example 5
<Synthesis of copolymer resin solution (a-5) precursor>
The following amount of monomer dicyclohexyl fumarate (DCHF): 457.9 g
-Methacrylic acid (MAA): 397.8 g
・ Styrene (St): 144.4 g
And a solution prepared by dissolving 10.0 g of Perbutyl O (trade name, organic peroxide manufactured by NOF Corporation) in 500 g of 3-methoxybutyl acetate (3-MBA) at a temperature of 80 ° C., 2500 g Was added dropwise to a polymerization tank in a nitrogen atmosphere containing 3-MBA over 6 hours, and then aged and polymerized at the same temperature for 4 hours to obtain a polymer solution (copolymer resin solution ((a-3))) Precursor).
<Synthesis of copolymer resin solution (a-5)>
To 4010 g of the raw material polymer solution obtained by the above synthesis, 382.1 g of glycidyl methacrylate (GMA), 27.2 g of pyridine, and 1.0 g of hydroquinone were charged and dissolved uniformly. Next, it heated up to 80 degreeC, bubbling air in the reaction liquid under stirring, and reacted at 80 degreeC for 5 hours, and obtained the copolymer resin solution (a-5).

Comparative Synthesis Example 6
<Synthesis of copolymer resin solution (a-6) precursor>
The following amount of monomer dicyclohexyl fumarate (DCHF): 12.2 g
・ Itaconic acid: 244.4 g
・ Styrene (St): 743.5 g
And a solution prepared by dissolving 10.0 g of Perbutyl O (trade name, organic peroxide manufactured by NOF Corporation) in 500 g of 3-methoxybutyl acetate (3-MBA) at a temperature of 80 ° C., 2500 g Was added dropwise to a polymerization tank in a nitrogen atmosphere containing 3-MBA over 6 hours, and then aged and polymerized at the same temperature for 4 hours to prepare a polymer solution (precursor of copolymer resin solution (a-6)). Body).
<Synthesis of copolymer resin solution (a-6)>
To 4010 g of the raw material polymer solution obtained by the above synthesis, 505.6 g of glycidyl methacrylate (GMA), 36.0 g of pyridine, and 1.0 g of hydroquinone were charged and dissolved uniformly. Next, it heated up to 80 degreeC, bubbling air in the reaction liquid under stirring, and reacted at 80 degreeC for 5 hours, and obtained the copolymer resin solution (a-6).

Comparative Synthesis Example 7
<Synthesis of copolymer resin solution (a-7) precursor>
The following amount of monomer dicyclohexyl fumarate (DCHF): 15.3 g
・ Itaconic acid: 885.5g
・ Styrene (St): 99.3 g
And a solution prepared by dissolving 10.0 g of Perbutyl O (trade name, organic peroxide manufactured by NOF Corporation) in 500 g of 3-methoxybutyl acetate (3-MBA) at a temperature of 80 ° C., 2500 g Was added dropwise to a polymerization tank in a nitrogen atmosphere containing 3-MBA over 6 hours, and then aged and polymerized at the same temperature for 4 hours to prepare a polymer solution (precursor of copolymer resin solution (a-7)). Body).
<Synthesis of copolymer resin solution (a-7)>
To 4010 g of the raw material polymer solution obtained by the above synthesis, 1972.7 g of glycidyl methacrylate (GMA), 140.4 g of pyridine, and 1.0 g of hydroquinone were charged and dissolved uniformly. Next, it heated up to 80 degreeC, bubbling air in the reaction liquid under stirring, and reacted at 80 degreeC for 5 hours, and obtained the copolymer resin solution (a-7).

Examples 1-10
A solution of a photocurable resin composition for a color filter dissolved and mixed in 3-methoxybutyl acetate (3-MBA) at the blending ratio shown in Table 1 was filtered through a membrane filter having a pore size of 0.2 μm, On the glass substrate, it apply | coated and dried with the spin coater (Type 1H-DX2, Mikasa Co., Ltd. product), and formed the coating film with a dry film thickness of 2.2 micrometers. This coating film was heated on a hot plate at 90 ° C. for 3 minutes. After heating, the coating film was irradiated with ultraviolet rays at an intensity of 100 mJ / cm ² (converted to 405 nm illuminance) by a UV aligner (model MA1200, manufactured by Dainippon Screen Mfg. Co., Ltd.) equipped with a 2.0 kW ultrahigh pressure mercury lamp. .
After the ultraviolet irradiation, the coating film was dried at 200 ° C. for 30 minutes in a clean oven to obtain a cured film having a thickness of 2.0 μm. About the obtained cured film, 380 nm light transmittance, pencil hardness, heat resistance test (230 ° C. × 1 h.), Heat resistance test (250 ° C. × 1 h.), Adhesion after heat-resistant pure water test, water vapor transmission rate, ITO sputtering Each test of the resistance test was performed. The results are also shown in Table 1.

Examples 11-20
Next, a red (R) photocurable ink composition prepared by mixing in 3-methoxybutyl acetate (3-MBA) at a blending ratio shown in Table 2 and sufficiently dispersing with a sand mill On a glass substrate, a spin coater (type 1H-DX2, manufactured by Mikasa Co., Ltd.) was applied and dried to form a coating film having a dry film thickness of 2.2 μm. This coating film was heated on a hot plate at 90 ° C. for 3 minutes. After heating, the coating film was irradiated with ultraviolet rays at an intensity of 100 mJ / cm ² (converted to 405 nm illuminance) by a UV aligner (model MA1200, manufactured by Dainippon Screen Mfg. Co., Ltd.) equipped with a 2.0 kW ultrahigh pressure mercury lamp. .
After the ultraviolet irradiation, the coating film was dried at 200 ° C. for 30 minutes in a clean oven to obtain a cured film having a thickness of 2.0 μm. The obtained cured film was subjected to each test of pencil hardness, color difference after heat resistance test (250 ° C. × 1 h.), Adhesion after temperature-resistant pure water test, water vapor permeability, and ITO sputtering resistance test. The results are also shown in Table 1.

The abbreviations and names in Tables 1 and 2 indicate the following.
A-1: Copolymer resin obtained in Synthesis Example 1. Solid content 33.7%, acid value 30 mgKOH / g
A-2: Copolymer resin obtained in Synthesis Example 2. Solid content 40.4%, acid value 32mgKOH / g
A-3: Copolymer resin obtained in Synthesis Example 3. Solid content 54.4%, acid value 30mgKOH / g
A-4: Copolymer resin obtained in Synthesis Example 4. Solid content 39.4%, acid value 30mgKOH / g
DPE-6A (dipentaerythritol hexaacrylate): manufactured by Kyoeisha Chemical Co., Ltd., trade name “light acrylate DPE-6A”.
PE-4A (pentaerythritol tetraacrylate): manufactured by Kyoeisha Chemical Co., Ltd., trade name “light acrylate PE-4A”.

Irgacure 184: 1-hydroxy-cyclohexyl-phenyl ketone, manufactured by Ciba Specialty Chemicals.
Irgacure 369: Ciba Specialty Chemicals, Inc., 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1.
EP-828: manufactured by Japan Epoxy Resin Co., Ltd., bisphenol A type epoxy resin EP-1001: manufactured by Japan Epoxy Resin Co., Ltd., bisphenol A type epoxy resin Park Mill D: manufactured by Nippon Oil & Fats Co., Ltd., organic peroxide heat Polymerization initiator, dicumyl peroxide.
Perbutyl P: manufactured by NOF Corporation, an organic peroxide thermal polymerization initiator, α, α′-bis (tert-butylperoxy) diisopropylbenzene.

* 1: Comparative Examples 1 to 8 which are solid parts by weight of each component
Using a solution of a photocurable resin composition for a color filter dissolved and mixed in 3-methoxybutyl acetate (3-MBA) at a blending ratio shown in Table 3, a cured film was formed in the same manner as in Examples 1-10. Each of the 380 nm light transmittance, pencil hardness, heat resistance test (230 ° C. × 1 h.), Heat resistance test (250 ° C. × 1 h.), Adhesion after heat-resistant pure water test, water vapor transmission rate, ITO sputtering resistance test A test was conducted. The results are also shown in Table 3.

Comparative Examples 9-16
Next, using a red (R) photocurable ink composition prepared by mixing with 3-methoxybutyl acetate (3-MBA) at a blending ratio shown in Table 4 and thoroughly dispersing with a sand mill. About the cured film produced by the method similar to Examples 11-20, each test of pencil hardness, a color difference after a heat test (250 degreeC x 1 h.), Adhesiveness after a heat-resistant pure water test, water vapor permeability, and ITO sputter resistance test is carried out. went. The results are also shown in Table 4.

From the results of Table 1, in the case of Examples 1 to 10 using the resin composition of the present invention, the obtained resin cured product has sufficient general performance such as transparency, pencil hardness, heat resistance, and adhesion. While satisfying, the water vapor permeability and the performance of high temperature ITO treatment resistance are remarkably excellent, and it can be seen that the effects of the object of the present invention are obtained satisfactorily. Furthermore, from the results in Table 2, even when a color pigment is dispersed in the resin composition of the present invention and used as an ink for a colored layer, the obtained cured film is excellent in color difference after a heat test and has good adhesion. The water vapor permeability is not impaired.
On the other hand, in each of the comparative examples in Tables 3 and 4, when the copolymer used in the present invention is not used, the heat-resistant transmittance is inferior or the ethylenic defect contained in the copolymer as the binder component. When the content of the saturated bond is insufficient, there are problems in the transmittance after the heat resistance test, pencil hardness, water vapor permeability, high temperature ITO treatment resistance performance, and the effect of the present invention cannot be obtained. I understand.

Example 21
(1) Formation of black matrix The following components were mixed and sufficiently dispersed in a sand mill to prepare a black pigment dispersion.
<Composition of black pigment dispersion>
-Black pigment: 20 parts by weight-Polymer dispersant (trade name Disperbyk 111, manufactured by Big Chemie Japan Co., Ltd.): 5 parts by weight-Solvent (3-MBA): 75 parts by weight The mixture was sufficiently mixed to obtain a photocurable black matrix resin composition.
<Composition of the resin composition for photocurable black matrix>
-Black pigment dispersion liquid: 55 parts by weight-Photocurable resin composition of Example 1: 20 parts by weight-Solvent (3-MBA): 35 parts by weight And a glass substrate having a thickness of 1.1 mm (Asahi Glass Co., Ltd.) The above-mentioned resin composition for photocurable black matrix was applied on a) AL material with a spin coater and dried at 100 ° C. for 3 minutes to form a photocurable black matrix layer having a thickness of about 1 μm. The photocurable black matrix layer is exposed to a light-shielding pattern with an ultra-high pressure mercury lamp, developed with a 0.05% aqueous potassium hydroxide solution, and then heated by leaving the substrate in an atmosphere at 180 ° C. for 30 minutes. The black matrix was formed in the area | region which should process and should form a light-shielding part.

(2) Formation of colored layer On the substrate on which the black matrix was formed as described above, a red (R) photocurable resin ink having the following composition was applied by spin coating (coating thickness: 1.5 μm), and then Dry in an oven at 70 ° C. for 30 minutes.
Next, only a region corresponding to a colored layer formation region is disposed by using a 2.0 kW super high pressure mercury lamp by a proximity aligner by arranging a photomask at a distance of 100 μm from the red (R) photocurable ink coating film. Were irradiated with ultraviolet rays for 10 seconds. Subsequently, it was immersed in a 0.05 wt% potassium hydroxide aqueous solution (liquid temperature 23.0 ° C.) for 1 minute for alkali development to remove only the uncured portion of the red (R) photocurable resin ink coating film. Thereafter, the substrate was left in an atmosphere of 180 ° C. for 30 minutes to perform heat treatment, thereby forming a relief pattern in a region where a red pixel was to be formed.

Next, using a green (G) photocurable resin ink having the following composition, a green relief pattern was formed in a region where a green pixel was to be formed, in the same process as that for forming a red relief pattern.
Further, using a blue (B) photocurable resin ink having the following composition, a green relief pattern is formed in a region where a green pixel is to be formed in the same process as that for forming a red relief pattern, and red (R) A colored layer composed of three colors, green (G) and blue (B) was formed.

<Composition of red (for R) photocurable resin ink>
・ C. I. Pigment Red 177: 9 parts by weight-Polysulfonic acid type polymer dispersant: 3 parts by weight- Photocurable resin composition of Example 1: 1:12 parts by weight- 3-methoxybutyl acetate: 76 parts by weight <green (for G ) Composition of photocurable resin ink>
・ C. I. Pigment Green 36: 9 parts by weight-Polysulfonic acid type polymer dispersant: 3 parts by weight- Photocurable resin composition of Example 1 1: 12 parts by weight- 3-methoxybutyl acetate: 76 parts by weight <blue (for B ) Composition of photocurable resin ink>
・ C. I. Pigment Blue 15: 9 parts by weight-Polysulfonic acid type polymer dispersant: 3 parts by weight- Photocurable resin composition of Example 1: 1:12 parts by weight- 3-methoxybutyl acetate: 76 parts by weight

Formation of Protective Film On the glass substrate on which the colored layer was formed, the photocurable resin composition 1 of Example 1 was applied by a spin coating method and dried to form a coating film having a dry film thickness of 2 μm.
A photomask is placed at a distance of 100 μm from the coating film of the photocurable resin composition 1, and an ultraviolet ray is applied to only the region corresponding to the colored layer formation region using a 2.0 kW ultrahigh pressure mercury lamp by a proximity aligner. Irradiated for 2 seconds. Subsequently, it was immersed in 0.05 wt% potassium hydroxide aqueous solution (liquid temperature 23 degreeC) for 1 minute, and alkali image development was carried out, and only the uncured part of the coating film of a photocurable resin composition was removed. Thereafter, the substrate was left to stand in an atmosphere of 200 ° C. for 30 minutes to perform a heat treatment to form a protective film, thereby obtaining the color filter of the present invention.
A transparent electrode film was formed on the surface of the obtained color filter using a DC magnetron sputtering method with argon and oxygen as discharge gases at a substrate temperature of 230 ° C. and using ITO as a target. Thereafter, an alignment film made of polyimide was further formed on the transparent electrode film.
The resistance value of the transparent electrode film formed on the obtained color filter was 13.9 Ω / cm ² while the resistance value of the transparent electrode film formed on the glass substrate was 13.4 Ω / cm ² . The color filter protective film prepared from the photocurable resin composition of the present invention has sufficient ITO suitability.

Formation of Spacer On the glass substrate on which the colored layer was formed, the photocurable resin composition obtained in Example 1 was applied by a spin coating method and dried to form a coating film having a dry film thickness of 5 μm.
A photomask is placed at a distance of 100 μm from the coating film of the photocurable resin composition 1, and an ultra-high pressure mercury lamp of 2.0 kW is used by a proximity aligner, and ultraviolet rays are applied only to the spacer formation region on the black matrix. Irradiated for 2 seconds. Subsequently, it was immersed in 0.05 wt% potassium hydroxide aqueous solution (liquid temperature 23 degreeC) for 1 minute, and alkali image development was carried out, and only the uncured part of the coating film of a photocurable resin composition was removed. Thereafter, the substrate was left to stand in an atmosphere of 200 ° C. for 30 minutes to perform heat treatment to form a fixed spacer, thereby obtaining the color filter of the present invention.

Next, the color filter and the glass substrate on which the TFT is formed are bonded to each other by using 29 kPa (0.3 kgf / cm ² ) pressure at 150 ° C. using epoxy resin as a sealing material, and assembled into a cell. Was sealed to prepare a liquid crystal display device.
As described above, when the photocurable resin composition of the present invention is used as an RGB pixel, a black matrix, a protective film, or a spacer of a color filter, a color filter can be produced without problems.

Claims (8)

Each of the following components (A), (B), and (C) contains (A) 2 to 80% by weight, (B) 5 to 90% by weight, and (C) 1 to 10% by weight. ) A photocurable resin composition characterized in that the total of both components is 45% by weight or more and 99% by weight or less.
(A) The fumarate structural unit (a1) represented by the following formula (1) is 1.5 to 35% by weight, and the structural unit (a2) having an acidic functional group represented by the following formula (2) is 10 To 50% by weight, 3 to 45% by weight of the structural unit (a3) having an aromatic carbocycle represented by the following formula (3), and ethylenic unsaturation represented by the following formula (4a) or (4b) Fumarate copolymer having 20 to 65% by weight of structural unit (a4) having a bond

(Wherein R ¹ and R ² each independently represents a branched alkyl group or substituted branched alkyl group having 3 to 8 carbon atoms, or a cycloalkyl group or substituted branched cycloalkyl group having 4 to 8 carbon atoms). )

(In the formula, R ³ is a hydrogen atom, a methyl group or a carboxymethyl group.)

(In the formula, R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ represents an aromatic hydrocarbon group having 6 to 12 carbon atoms.)

(In the formula, R ⁶ and R ⁷ are a hydrogen atom or a methyl group.)

(Wherein R ⁸ and R ¹¹ are a hydrogen atom or a methyl group, R ⁹ is an alkylene group having 2 to 4 carbon atoms, R ¹⁰ is an alkylene group, and h is a number of 0 or 1) is there.)
(B) Photopolymerizable polyfunctional (meth) acrylate compound (C) Photopolymerization initiator   The photocurable resin composition according to claim 1, wherein the content concentration of the ethylenically unsaturated bond in the fumarate copolymer (A) is 2.1 to 4.1 mmol / g.   The photocurable resin composition according to claim 1, further comprising (D) an epoxy resin in an amount of 5 to 45% by weight, and the total of both components (A) and (B) being 45% by weight to 94% by weight. object.   The photocurable resin composition of any one of Claims 1-3 used for manufacture of a color filter.   A pixel for RGB or a black matrix having a resin cured product obtained by curing the photocurable resin composition according to claim 1.   The protective film which forms the protective film which coat | covers the colored layer formed on the transparent substrate by hardening the photocurable resin composition of any one of Claims 1-3.   The spacer provided between the colored layer formed on the transparent substrate and the electrode substrate to be opposed is formed by curing the photocurable resin composition according to any one of claims 1 to 3. A spacer that is a thing.   The color filter which used the resin cured material formed by hardening | curing the photocurable resin composition of any one of Claims 1-3 as a member.