JP5358907B2 - Resin composition for color filter protective film and color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition for a color filter protective film having excellent barrier property, liquid crystal staining property and chemical resistance, and a color filter having excellent protective film properties. <P>SOLUTION: The resin composition for the color filter protective film comprises (A) a hemiacetal ester compound represented by formula (1) (wherein R<SP>1</SP>is a 3-30C alkyl group, a cycloalkyl group, an aryl group or an isocyanuric trialkyl group; n is an integer of 2-8; m is an integer of 1-4; R<SP>2</SP>is a 1-4C alkylene group; and R<SP>3</SP>is a hydrogen atom or a methyl group) and (B) a compound having two or more epoxy groups or oxetanyl groups per molecule, wherein the mol equivalent ratio of hemiacetal ester groups which the component (A) has to the epoxy groups or oxetanyl groups which the component (B) has, [(A)/(B)] is 2/10 to 50/10. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a curable resin composition for a color filter protective film used for a liquid crystal display (LCD) or the like, and a color filter protective film obtained by curing the curable resin composition.

In recent years, color liquid crystal display devices have been rapidly spread for personal computer monitors and televisions. The color filter used in the color liquid crystal display device is an important member that affects the display performance of the liquid crystal display device. The color filter has a layer called a protective film. The protective film of the color filter includes an RGB resist as a base material for forming the protective film, and a transparent electrode deposited (sputtered) on the protective film. Good adhesion, excellent ability to smooth the unevenness of the RGB resist layer, good visible light transmittance, and no change in appearance such as coloring under high temperature and high humidity, etc. Various performances are required.
The RGB resist used for the color filter is rich in ionic impurities derived from photopolymerization initiator decomposition products, surfactants, pigments and dyes. When these decomposition products and ionic impurities migrate to the liquid crystal layer, there is a problem that the reliability of the liquid crystal display device is lowered.
For this reason, among the required performance of the color filter protective film, it is strongly required to have high barrier performance that suppresses the migration of decomposition products and ionic impurities to the liquid crystal layer.
Furthermore, with the advancement of the technology of the liquid crystal display device, the required performance for the protective film has also been advanced. In particular, when a liquid crystal display device is used as a television, there is a demand for reliability, that is, display image quality that does not deteriorate even when used for a long time. For this reason, the above-mentioned ion barrier properties are often evaluated in a harsh test for a long period of time.
When an unreacted substance is contained in the protective film itself, when the unreacted substance moves to the liquid crystal layer, the liquid crystal layer may be contaminated to deteriorate the liquid crystal display performance. In addition, when the transparent electrode formed on the protective film is etched with an acid or alkali solution to form a pattern, if the protective film is deteriorated or damaged by these etching process conditions, it is reliable. It can cause a decrease in sex.

On the other hand, various resin compositions for color filter protective films have been conventionally proposed. For example, Patent Document 1 discloses a thermosetting resin composition containing a glycidyl (meth) acrylate polymer and a polyvalent carboxylic acid or polyvalent carboxylic acid anhydride as essential components. Since the compounding ratio of each component is limited due to the lack of a sufficient amount, a sufficient crosslinking density cannot be obtained, resulting in poor ion barrier properties and chemical resistance.
Further, Patent Document 2 discloses a photosensitive resin composition containing a compound in which a carboxyl group contained in a polymer is blocked with a (meth) acryloyloxy group-containing vinyl ether as an essential component, but (meth) acryloyloxy is disclosed. In addition, it is difficult to obtain a sufficient crosslink density only by polymerization of groups, and since it contains a large amount of highly polar functional groups such as carboxyl groups, it is actually inferior in ion barrier properties, liquid crystal contamination, and chemical resistance. there were.

In contrast, Patent Documents 3 and 4 disclose thermosetting resin compositions containing, as essential components, a carboxylic acid derivative obtained by reacting an alkyl vinyl ether and a carboxylic acid and an epoxy resin. By using this technique, since the compatibility between the carboxylic acid derivative and the epoxy resin is excellent, an appropriate amount of a curing agent can be blended, and a cured product having a high crosslinking density can be obtained. Furthermore, if these disclosed technologies are used, the vinyl ether released from the carboxylic acid derivative during the crosslinking reaction reacts with the hydroxyl group produced by the reaction between the carboxylic acid compound and the epoxy compound, so that the polar group contained in the cured product The ratio is reduced, and a cured product having a relatively high ion barrier property, liquid crystal contamination property and chemical resistance can be obtained.
However, in recent years, liquid crystal display devices have been used for television applications, and there has been a strong demand for longer life of liquid crystal display devices, and higher ion barrier properties have been required for color filter protective films. . According to the disclosed techniques in Patent Documents 3 and 4, a cured product having a high ion barrier property as described above can be obtained. In order to further increase the crosslinking density, a carboxyl group in a carboxylic acid derivative, an epoxy group in an epoxy resin When the ratio of the compound is increased, the reaction rate decreases, and many unreacted functional groups remain in the cured product. As a result, the ion barrier property and the liquid crystal contamination property are lowered. It has been difficult to obtain such excellent reliability.

JP 61-292604 A JP-A-2005-202134 JP 2001-091732 A JP 2001-350010 A

The present invention has been accomplished in view of the above circumstances, and a first object thereof is to provide a resin composition for a color filter protective film having excellent barrier properties, liquid crystal contamination properties, and chemical resistance. .
The second object of the present invention is to provide a color filter having the above excellent protective film characteristics.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have obtained a polyvalent carboxylic acid obtained by reacting a carboxyl group of a polyvalent carboxylic acid compound with a specific (meth) acryloyloxy group-containing vinyl ether compound. A resin composition for a color filter protective film in which a specific hemiacetal ester compound (A) and a compound (B) having two or more epoxy groups or oxetanyl groups in one molecule are blended in a specific amount ratio solves the above problems. As a result, the present invention was completed.

That is, the present invention includes the following [1] to [3].
[1] The following (A) and (B) components are contained, and the molar equivalent ratio of the hemiacetal ester group (A) component and the epoxy group or oxetanyl group (B) component [(A) / (B )] Is 2/10 to 50/10. A resin composition for a color filter protective film.
(A) A hemiacetal ester compound represented by the following formula (1).

(R ¹ is an alkyl group having 3 to 30 carbon atoms, a cycloalkyl group, an aryl group, or an isocyanuric trialkyl group, n is an integer of 2 to 8, m is an integer of 1 to 4, and R ² is carbon. The number is an alkylene group having 1 to 4, and R ³ is a hydrogen atom or a methyl group.)
(B) A compound having two or more epoxy groups or oxetanyl groups in one molecule.
[2] (C) 0.1 to 10 parts by weight of the compound that generates radicals by heat or light with respect to a total of 100 parts by weight of components (A) and (B) [1] The resin composition for color filter protective films as described in 2.
[3] A color filter having a cured product layer obtained by curing the resin composition for a color filter protective film according to [1] or [2].

  When the resin composition for a color filter protective film of the present invention is applied, cured, and used, a color filter protective film that is remarkably excellent in ion barrier property, liquid crystal contamination property, and chemical resistance can be obtained.

The present invention is described in detail below.
1. Color Filter Protective Film Resin Composition The color filter protective film resin composition of the present invention comprises the following components (A) and (B) and, if necessary, component (C).
(A) A hemiacetal ester compound represented by the following formula (1).

(R ¹ is an alkyl group having 3 to 30 carbon atoms, a cycloalkyl group, an aryl group, or an isocyanuric trialkyl group, n is an integer of 2 to 8, m is an integer of 1 to 4, and R ² is carbon. The number is an alkylene group having 1 to 4, and R ³ is a hydrogen atom or a methyl group.)
(B) A compound having two or more epoxy groups or oxetanyl groups in one molecule.
(C) Compound that generates radicals by heat or light

  In the present invention, the color filter protective film is a color filter used in a liquid crystal display device (LCD) or the like between an RGB pixel and a liquid crystal alignment film, a transparent electrode layer, a light emitter, or a light receiver. It means the organic layer that is formed.

<Hemiacetal ester compound (A)>
The hemiacetal ester compound (A) in the resin composition for a color filter protective film of the present invention has a hemiacetal ester bond of a carboxylic acid represented by the following formula (2).

R ² is an alkylene group having 1 to 4 carbon atoms, m is an integer of 1 to 4, and R ³ is a hydrogen atom or a methyl group.
The hemiacetal ester compound (A) represented by the above formula (1) is represented by the following formula (3) by cleaving the hemiacetal ester bond of the carboxylic acid represented by the above formula (2) by heating. A polyvalent carboxylic acid compound (a1) and a vinyl ether compound (a2) represented by the following formula (4) are produced.

(R ¹ and n are the same as those in formula (1).)

(M, R ² and R ³ are the same as those in formula (1).)
The polyvalent carboxylic acid compound represented by the formula (3) forms a crosslinked structure by an esterification reaction with a compound having two or more epoxy groups or oxetanyl groups in one molecule.
Further, the vinyl ether compound represented by the formula (4) generates an addition reactant by an addition reaction to a hydroxyl group generated by the esterification reaction.

  The vinyl ether compound represented by the formula (4) further contains a radically polymerizable (meth) acryloyloxy group. Thus, the addition reactant further produces a polymer by applying heat or light energy.

The cured product obtained by curing the resin composition for a color filter protective film of the present invention has a crosslinked structure obtained by using these series of reactions.
The crosslinked structure formed by the cured product obtained by curing the resin composition for a color filter protective film of the present invention includes (meth) acryloyloxy in addition to the crosslinked structure formed by the epoxy reaction with the polyvalent carboxylic acid. It forms a structure that coexists with the polymer of the group. Furthermore, the hydroxyl group produced | generated by reaction of polyhydric carboxylic acid and epoxy forms the structure which the (meth) acryloyloxy group polymer couple | bonded.

  The hemiacetal bond-containing compound (A) used in the present invention is soluble in various organic solvents, so that an appropriate amount of a curing agent can be blended. A cross-linked structure generated by the reaction and a (meth) acryloyloxy group polymer coexist, and a hydroxyl group generated by a carboxylic acid / epoxy reaction and a (meth) acryloyloxy group polymer are combined. By forming such a structure, a cured product having a high crosslinking density and a small number of polar functional groups can be obtained. That is, a cured product having excellent barrier properties, liquid crystal contamination properties, and chemical resistance can be obtained.

In the above formula (1), R ¹ is an alkyl group having 3 to 30 carbon atoms, a cycloalkyl group, an aryl group, or an isocyanuric trialkyl group. R ¹ in the formula (1) is a functional group that contributes to the curability of the resin composition for a color filter protective film of the present invention and the mechanical properties, heat resistance, and transparency of the resulting cured product. For this reason, in order to obtain sufficient curability, sufficient mechanical properties as a cured product, heat resistance and transparency, among the above-mentioned alkyl group, cycloalkyl group, aryl group, or isocyanuric trialkyl group, the number of carbon atoms is particularly large. A 6-8 aryl group, a C3-C6 cycloalkyl group, and an isocyanuric group are preferable. Furthermore, in said Formula (1), n is an integer of 2-8. The number of n is a part that contributes to the mechanical properties, heat resistance, and adhesion between the cured product and the substrate of the cured product. When n is less than 2, the function as a curing agent is impaired, and sufficient machine Physical properties and heat resistance cannot be obtained. Moreover, when n is larger than 8, sufficient adhesion cannot be obtained between the obtained cured product and the base.

^{R 2} in the formula (1) of the is an alkylene group having 1 to 4 carbon atoms. R ² is a site that contributes to the barrier property, liquid crystal contamination, and chemical resistance of the cured product. When the carbon number of R ² is more than 4, the distance between the crosslinking points of the cured product is increased. The crosslinking density is lowered and sufficient performance cannot be obtained. Furthermore, in said Formula (1), m is an integer of 1-4. The number of m is a part that contributes to the barrier property, liquid crystal contamination, and chemical resistance of the cured product. When the number of m is more than 4, the distance between the cross-linking points of the cured product becomes longer. The density decreases and sufficient performance cannot be obtained.
The hemiacetal ester compound (A) in the resin composition for a color filter protective film of the present invention is represented by, for example, a polyvalent carboxylic acid compound (a1) represented by the following formula (3) and the following formula (4). It can be obtained by reacting with a vinyl ether compound (a2) containing an ethylenically unsaturated group.

(R ¹ and n are the same as those in formula (1).)

(M, R ² and R ³ are the same as those in formula (1).)
Examples of the polyvalent carboxylic acid compound (a1) include an aliphatic polyvalent carboxylic acid such as adipic acid, in which R ¹ in the formula (1) is an alkyl group having 3 to 30 carbon atoms. Further, as ^{R 1} in Formula (1) is a cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexane alicyclic dicarboxylic acids such as dicarboxylic acid; 1,2,4-cyclohexane tricarboxylic acid (hereinafter, CHTA And alicyclic tricarboxylic acids such as cyclohexanetetracarboxylic acid. As R ¹ in formula (1) is an aryl group having 3 to 30 carbon atoms, aromatic dicarboxylic acid such as phthalic acid; aromatic such as 1,2,4-benzenetricarboxylic acid (hereinafter trimellitic acid) Tricarboxylic acid; aromatic tetracarboxylic acid such as 1,2,4,5-benzenetetracarboxylic acid (pyromellitic acid) can be used, and R ¹ in formula (1) is an isocyanuric trialkyl group having 3 to 30 carbon atoms. Some include heterocyclic tricarboxylic acids such as tris (2-carboxyethyl) isocyanurate (CIC acid). Among the above carboxylic acids, since they have excellent curability and mechanical properties and heat resistance including a glass transition temperature (Tg) sufficient as a color filter protective film, pyromellitic acid, A tri- or tetravalent carboxylic acid compound having a carbon 6-membered ring structure such as merit acid or CHTA, or a heterocyclic tricarboxylic acid such as CIC acid is preferred.
When the carbon number of R ¹ is less than 3, the heat resistance of the cured product is not sufficient, and when the carbon number of R ¹ is more than 30, it is sufficient when preparing the resin composition for a color filter protective film of the present invention. Miscibility cannot be obtained and the object of the present invention cannot be achieved.

On the other hand, in the vinyl ether compound (a2) containing the ethylenically unsaturated group as a raw material of the hemiacetal ester compound (A) used in the present invention, m is an integer of 1 to 4. The number of m is a part that contributes to the barrier property, liquid crystal contamination, and chemical resistance of the cured product. When the number of m is more than 4, the distance between the cross-linking points of the cured product becomes longer. The density decreases and sufficient performance cannot be obtained. R ² is an alkylene group having 1 to 4 carbon atoms. If the number of carbon atoms in R ² is greater than 4, the crosslinking density decreases by the distance between crosslinking points of the cured product becomes longer, sufficient barrier properties and liquid crystal contamination property, no chemical resistance can be obtained.

  In the vinyl ether compound (a2) containing the ethylenically unsaturated group, suitable examples include 2-vinyloxyethyl (meth) acrylate and 2- (2-vinyloxyethoxy) ethyl (meth) acrylate. It can be used alone or in combination of two or more.

  The hemiacetal ester compound (A) used in the present invention reacts the polyvalent carboxylic acid (a1) with the ethylenically unsaturated group-containing vinyl ether compound (a2) at a temperature ranging from room temperature to 150 ° C. It can be obtained by (blocking reaction). Since the blocking reaction is an equilibrium reaction, if the ethylenically unsaturated group-containing vinyl ether compound (a2) is used slightly more than the polyvalent carboxylic acid (a1), the reaction is promoted and the yield can be improved. Specifically, the molar equivalent ratio [the molar equivalent ratio of (vinyl group / carboxyl group)] of the vinyl group of the ethylenically unsaturated group-containing vinyl ether compound (a2) to the carboxyl group of the polyvalent carboxylic acid (a1) is 1 / 1 to 2/1 is desirable. When this molar equivalent ratio exceeds 2/1, the reaction temperature cannot be increased, and the reaction rate may be extremely low.

  When the blocking reaction is performed, an acid catalyst can be used for the purpose of accelerating the reaction. Examples of such a catalyst include an acidic phosphate compound represented by the following formula (5).

(In the formula, R ⁴ is an alkyl group having 3 to 10 carbon atoms, a cycloalkyl group or an aryl group, and k is 1 or 2.)
Moreover, when performing blocking reaction, you may use an organic solvent for the purpose of making a reaction system uniform and making reaction easy. Examples of organic solvents used here include aromatic hydrocarbons, ethers, esters and ether esters, ketones, phosphate esters, nitriles, aprotic polar solvents, propylene glycol alkyl ether acetates, and the like. Is mentioned. More preferred are cyclohexanone and propylene glycol monomethyl ether acetate. The organic solvent is preferably an organic solvent excluding alcohol or ionic solvent. It is known that the deblocking reaction may proceed with respect to the alcohol or the ionic solvent, and the storage stability of the color filter protective film resin composition is remarkably lowered, and it becomes difficult to obtain the effects of the present invention. Because there are cases.
Furthermore, a radical polymerization inhibitor can be added for the purpose of preventing polymerization of ethylenically unsaturated groups during the blocking reaction using the ethylenically unsaturated group-containing vinyl ether compound (a2) used in the present invention. As the radical polymerization inhibitor, polymerization inhibitors such as p-methoxyphenol and hydroquinone are used.

<Compound (B) having two or more epoxy groups or oxetanyl groups in one molecule>
More specifically, as the compound (B) having two or more epoxy groups or oxetanyl groups in one molecule, a polyvalent epoxy resin (B1), a polyvalent oxetanyl compound (B2), or an epoxy group or oxetanyl group-containing ( Examples thereof include compounds having two or more epoxy groups or oxetanyl groups in one molecule such as (meth) acrylic resin (B3).
<Polyvalent epoxy resin (B1)>
Examples of the polyvalent epoxy resin (B1) include bisphenol A type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, and cresol. Novolac type epoxy resin, biphenol type or bixylenol type epoxy resin or a mixture thereof, naphthalene group-containing epoxy resin, stilbene type epoxy resin, hydroquinone type epoxy resin, epoxy resin having a fluorene skeleton, tetraphenylolethane type epoxy resin, DPP (di-n-pentylphthalate) type epoxy resin, trishydroxyphenylmethane type epoxy resin, dicyclopentadienephenol type epoxy resin, di Black pentadiene skeleton-containing epoxy resins, aromatic polyglycidyl ethers of brominated epoxy resin, trisphenolmethane type epoxy resin, resorcinol diglycidyl ether;
Aliphatic polydiglycidyl esters such as phthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, adipic acid diglycidyl ester, succinic acid diglycidyl ester, sebacic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester;
Aromatic amine-based polyvalent epoxy resins such as N, N-diglycidyl-4-glycidyloxyaniline, tetraglycidyldiaminophenylmethane;

Hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, hydrogenated or semi-hydrogenated polyvalent epoxy resin of various aromatic glycidyl ethers;
Aliphatic polyglycidyl ethers such as ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether;
1,2: 8,9 diepoxy limonene, 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate, ε-caprolactone modified 3,4-epoxycyclohexenylmethyl-3 ′, 4′- Epoxycyclohexenecarboxylate, 3,1-bis (3,4-epoxycyclohexylmethyl) adipate, 2- (7-oxabicyclo [4.1.0] heptyl 3-)-spiro [1,3-dione-5, Alicyclic polyvalent epoxy compounds such as 3 ′-[7] oxabicyclo [4.1.0] heptane, dicyclopentadiene dioxide;
N, N-diglycidyl-4-glycidyloxyaniline, tetraglycidyldiaminophenylmethane, aniline diglycidyl ether, N- (2-methylphenyl) -N- (oxiranylmethyl) oxiranemethanamine, N-glycidylphthalimide, etc. Examples include glycidylamines and polyvalent heterocyclic epoxy compounds such as tris (2,3-epoxypropyl) isocyanurate.
Among the polyvalent epoxy resins (B1), in order to obtain the mechanical properties of the cured product, high heat resistance, and good adhesion to the substrate, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, bisphenol A novolak type epoxy resin, phenol novolak type epoxy resin, and cresol novolak type epoxy resin are preferable, and a cured product having higher ion barrier properties can be obtained. A novolac type epoxy resin and a phenol novolac type epoxy resin are more preferable.

<Polyvalent Oxetanyl Compound (B2)>
Examples of the polyvalent oxetanyl compound (B2) include aliphatic alkyl groups which may have 1 to 4 carbon atoms such as 3-methyl-3-methoxymethyloxetane and 3-ethyl-3-methoxymethyloxetane. I) an etherified product of a hydroxyl compound and a 3-alkyl-3-hydroxymethyloxetane derived from 3-alkyl-3-hydroxymethyloxetanes having the following: or ii) a carboxyl compound and 3-alkyl-3-hydroxy Examples include esterified products with methyl oxetanes.
i) Etherified products of hydroxyl compounds and 3-alkyl-3-hydroxymethyloxetanes, for example, aliphatic glycols composed of alkylene groups having 2 to 8 carbon atoms, aromatic alcohols having 2 to 18 carbon atoms, phenol novolac resins And a compound obtained by ether condensation of a hydroxyl compound such as a polysiloxane having a quaternary structure with a polymerization degree of 2 to 8 and an oxetane such as 3-ethyl-3-methoxymethyloxetane. More specifically, for example, bis ((3-ethyl-3-oxetanyl) methyl) ether, 1,4-bis (((3-ethyl-3-oxetanyl) methoxy) methyl) benzene, 1,4-bis ( ((3-Ethyl-3-oxetanyl) methoxy) methyl) benzene, 4,4′-bis (((3-ethyl-3-oxetanyl) methoxy) methyl) biphenyl, 3,3 ′, 5,5′-methyl -4,4'-bis (((3-ethyl-3-oxetanyl) methoxy) methyl) biphenyl, 1,4-bis ((3-ethyl-3-oxetanyl) methoxy) benzene, 4,4'-bis ( (3-ethyl-3-oxetanyl) methoxy) biphenyl, 3,3 ′, 5,5′-methyl-4,4′-bis ((3-ethyl-3-oxetanyl) methyl) biphenyl and the like.

  ii) As an esterified product of a carboxyl compound and 3-alkyl-3-hydroxymethyloxetane, for example, a carboxyl compound such as adipic acid, terephthalic acid, cyclohexanedicarboxylic acid, and an oxetane such as 3-ethyl-3-methoxymethyloxetane More specifically, for example, bis ((3-ethyl-3-oxetanyl) methyl) carbonate, bis ((3-ethyl-3-oxetanyl) methyl) adipate, bis ( (3-ethyl-3-oxetanyl) methyl) benzene-1,4-dicarboxylate, bis ((3-ethyl-3-oxetanyl) methyl) cyclohexane-1,4-dicarboxylate and the like.

<Epoxy group or oxetanyl group-containing (meth) acrylic resin (B3)>
The epoxy group or oxetanyl group-containing (meth) acrylic resin (B3) has a structural unit having an epoxy group or oxetanyl group in the molecular skeleton. The structural unit having an epoxy group is specifically represented by any of the following formulas (6) to (8), and the structural unit having an oxetanyl group is specifically represented by the following formula (9). .

(In the formula, R ⁵ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, p is an integer of 1 to 5. R ⁶ is a hydrogen atom or a methyl group.)

(Wherein R ⁷ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ⁸ is a —CH ₂ O— group or —CH ₂ — group, R ⁹ is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, q represents an integer of 0 to 7.)

(In the formula, R ¹⁰ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and r represents an integer of 1 to 8)

^(Wherein, R ^{11, R 12,} and ^{R 13} is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, s is an integer of 1-5.)
The structural units represented by the formulas (6) to (9) are each derived from an epoxy group or oxetanyl group-containing monomer represented by the following formulas (10) to (13).

(In the formula, R ⁵ and p are the same as those in formula (6).)

(Wherein R ^{7 to} R ⁹ and q are the same as those in formula (7).)

(Wherein R ¹⁰ and r are the same as those in formula (8).)

(Wherein R ^{11 to} R ¹³ and s are the same as those in formula (9).)
In the above formulas (6) and (10), R ⁵ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a methyl group. If the number of carbon atoms exceeds 5, it becomes inconvenient in terms of polymerizability. Moreover, p is an integer of 1-5, and p = 1 is more preferable. If p exceeds 5, sufficient mechanical properties such as Tg of the cured product cannot be obtained after curing.
In the above formulas (7) and (11), R ⁷ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a methyl group. If the number of carbon atoms exceeds 5, it becomes inconvenient in terms of polymerizability. R ⁸ is a —CH ₂ O— group or a —CH ₂ — group, and R ⁹ is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, preferably a —CH ₂ — group. Q is an integer of 1 to 7, preferably q = 1. If q exceeds 7, sufficient mechanical properties such as Tg of the cured product cannot be obtained after curing.

In the above formulas (8) and (12), R ¹⁰ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a methyl group. If the number of carbon atoms exceeds 5, it becomes inconvenient in terms of polymerizability. R is an integer of 1 to 8, preferably r = 1. If r exceeds 8, sufficient mechanical properties such as Tg of the cured product cannot be obtained after curing.
In the above formulas (9) and (13), R ¹¹ and R ¹² are a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a methyl group. If the number of carbon atoms exceeds 5, it becomes inconvenient in terms of polymerizability and reactivity. R ¹³ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom. If the number of carbon atoms exceeds 5, it becomes inconvenient in terms of polymerizability. Further, s is an integer of 1 to 5, preferably s = 1. When s exceeds 5, sufficient mechanical properties such as Tg of the cured product cannot be obtained after curing.
Of these epoxy group or oxetanyl group-containing monomers, glycidyl methacrylate is preferred from the standpoint of availability.

  When using an acrylic copolymer containing glycidyl (meth) acrylate, oxetane (meth) acrylate, alicyclic epoxy (meth) acrylate, etc. in the molecular skeleton as the compound (B) having an epoxy group or an oxetanyl group, The polymer can be polymerized by a conventional polymerization method. That is, the polymerization method is not particularly limited, and a polymerization method such as radical polymerization or ionic polymerization can be employed. More specifically, in the presence of a polymerization initiator, a bulk polymerization method, a solution polymerization method, a suspension polymerization method, A polymerization method such as an emulsion polymerization method can be employed.

In the present invention, when the epoxy group or oxetanyl group-containing (meth) acrylic resin (B3) is used as the compound (B) having two or more epoxy groups or oxetanyl groups in one molecule, the glass transition temperature (Tg) Improvements in mechanical properties such as hardness and heat-resistant transparency can be achieved.
The molecular weight of the epoxy group or oxetanyl group-containing (meth) acrylic resin (B3) is usually 3,000 or more, preferably 5,000 or more, and if the molecular weight is too low, the significance of introducing the (meth) acryl skeleton is reduced, In some cases, the hardness of the protective film decreases and the flatness after coating and curing decreases.

In the present invention, the molecular weight of the compound (B) having two or more epoxy groups or oxetanyl groups in one molecule is usually 180 to 300,000, preferably 185 to 100,000, more preferably 250 to 20,000. is there. When the molecular weight of the compound (B) having two or more epoxy groups or oxetanyl groups in one molecule is less than 180, the crosslink density of the cured product is lowered, so that the mechanical properties of the protective film, the barrier properties, the liquid crystal contamination properties, Chemical resistance may be reduced, and if it exceeds 300,000, compatibility with other compounding components may be reduced.
The epoxy equivalent of the compound (B) having two or more epoxy groups or oxetanyl groups in one molecule is preferably 60 to 4,000 g / eq, more preferably 90 to 3,500 g / eq. is there. When the epoxy equivalent of the compound (B) having two or more epoxy groups or oxetanyl groups in one molecule is less than 60 g / eq, the crosslinking density becomes too high, resulting in a large shrinkage at the time of curing, resulting in protection. Defects such as cracks may occur in the film, and if it exceeds 4,000 g / eq, the crosslink density of the protective film will decrease, and the protective film's barrier properties, liquid crystal contamination, and chemical resistance may be significantly reduced. There is.

  In the present invention, the epoxy equivalent is the number of grams (g / eq; theoretical value) of a compound containing 1 gram equivalent of an epoxy group, and the molar equivalent of active oxygen not directly related to the formula weight of the epoxy group. Therefore, a compound containing an oxetanyl group can be applied mutatis mutandis with an epoxy equivalent. When the structure and molecular weight of the compound (B) having two or more epoxy groups or oxetanyl groups in one molecule are known, it is obtained by calculation. When the structure is unknown, JIS K7236: 2001 “Determining the epoxy equivalent of epoxy resin It is obtained from the hydrochloric acid-dioxane titration defined in “Method”.

In the resin composition for a color filter protective film of the present invention, the compound (B) having an epoxy group or an oxetanyl group is not only a barrier property, liquid crystal contamination property and chemical resistance of the resulting cured product, but also the heat resistance of the cured product. It is an important component that contributes to performance such as transparency, mechanical properties, and adhesion to the substrate.
The layer of the resin cured product of the present invention thus obtained is a cross-linked structure made of a compound containing a polyvalent carboxylic acid compound and an epoxy group, so that it has transparency, chemical resistance, and heat resistance (film reduction by heating). And the degree of discoloration). Furthermore, a crosslinked structure formed by the reaction of polyvalent carboxylic acid and epoxy and a polymer of (meth) acryloyloxy group coexist to form a highly crosslinked density structure. By forming a structure in which the hydroxyl group produced by the reaction and the (meth) acryloyloxy group polymer are combined, a protective film with high crosslink density, few polar functional groups, and excellent barrier properties, liquid crystal contamination, and chemical resistance can be obtained. Therefore, a color filter having excellent reliability can be obtained.

<Compound that generates radicals by heat or light (C)>
In the resin composition for a color filter protective film of the present invention, the compound (C) that generates a radical by heat or light is a (meth) acryloyloxy group that is a radical polymerizable group of the hemiacetal ester compound (A). It is added for the purpose of accelerating the polymerization reaction of (meth) acryloyloxy groups, and has a function of further increasing the crosslinking density.
As the compound (C) for generating radicals by heat used in the resin composition for a color filter protective film of the present invention, 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 (nitrile azo polymerization initiators) such as -dimethylvaleronitrile); dimethyl 2,2'-azobis (2-methylpropionate), 2,2'-azobis (2,4,4- Non-nitrile azo compounds (non-nitrile azo polymerization initiators) such as trimethylpentane); t-hexyl peroxypivalate, tert-butyl peroxypivalate, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, Lauroyl peroxide, stearoyl peroxide, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, Xenic peroxide, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethylperoxy 2-ethylhexanoate, t-hexylperoxy 2-ethylhexanoate And organic peroxides (peroxide polymerization initiators) such as 4-methylbenzoyl peroxide, benzoyl peroxide, and 1,1′-bis- (tert-butylperoxy) cyclohexane.

  Moreover, as a compound which generates radicals by light, radical polymerization initiators that can be activated by ultraviolet rays, ionizing radiation, visible light, or other wavelengths, particularly energy rays of 365 nm or less, can be preferably used. Radical polymerization initiators are compounds that generate free radicals by, for example, the energy of ultraviolet light, and are derivatives such as benzophenone derivatives such as benzoin and benzophenone or their esters; xanthone and thioxanthone derivatives; chlorosulfonyl, chloromethyl polynuclear aromatic compounds , Chloromethyl heterocyclic compounds, halogen-containing compounds such as chloromethylbenzophenones; triazines; fluorenones; haloalkanes; redox couples of photoreducing dyes and reducing agents; organic sulfur compounds; peroxides . Preferably, 1-hydroxy-cyclohexyl-phenyl ketone, 2-methyl-1 [4-methylthio] phenyl] -2-morpholinopropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1- ON, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1,2-hydroxy-2-methyl-1-phenyl-propane-1,2,2′-bis (o-chlorophenyl)- Examples thereof include ketone-based and biimidazole-based compounds such as 4,5,4′-tetraphenyl-1,2′-biimidazole. These initiators can be used alone or in combination of two or more. When two or more kinds are used in combination, it is preferable not to inhibit the absorption spectral characteristics.

  When the compound (C) that generates radicals by heat or light is used, ultraviolet rays, ionizing radiation, visible light, or other wavelengths, particularly 365 nm or less, depending on the heat applied when the cured product is fired or as necessary. By irradiating the energy beam of the above, by promoting the polymerization reaction by heat of the (meth) acryloyloxy group of the polyvalent carboxylic acid derivative, it is possible to reduce unreacted functional groups present in the cured product, A cured product having a higher crosslink density, that is, a higher barrier property can be obtained.

<(A), (B), (C) Mixing ratio of each component>
In the resin composition for a color filter protective film of the present invention, the molar equivalent ratio of the latent polyvalent carboxylic acid group (A) component and the epoxy group or oxetanyl group (B) component [(A) / (B) ] Is 2/10 to 50/10.
The molar equivalent ratio [(A) / (B)] of the latent polyvalent carboxylic acid group of component (A) and the epoxy group or oxetanyl group of component (B) is preferably 4/10 to 30/10. Yes, more preferably 5/10 to 20/10. When the molar equivalent ratio [(A) / (B)] of the latent polyvalent carboxylic acid group of the component (A) and the epoxy group or oxetanyl group of the component (B) is less than 2/10, it is obtained. Since the crosslink density of the cured product is low, sufficient barrier properties, liquid crystal contamination properties, and chemical resistance, which are intended by the present application, cannot be obtained. When the molar equivalent ratio [(A) / (B)] of the latent polyvalent carboxylic acid group of the component (A) and the epoxy group or oxetanyl group of the component (B) is greater than 50/10, the polarity is high. Since excessive carboxyl groups remain, the chemical resistance of the cured product decreases.
In the resin composition for a color filter protective film of the present invention, the total amount of the component (A) and the component (B) is preferably 70% by weight or more, more preferably 80% by weight or more, and further preferably 90% by weight or more. is there. If the total amount is too small, the excellent effects of the present application may not be exhibited.

  Furthermore, in the resin composition for a color filter protective film of the present invention, when the compound (C) that generates radicals by heat or light is blended, the blending ratio of the component (C) is the sum of the components (A) and (B). It is 0.1-10 weight part with respect to 100 weight part, More preferably, it is 1.0-6.0 weight part. When the blending ratio of the component (C) is less than 0.1 parts by weight, a sufficient catalytic effect cannot be obtained, and when the blending ratio is more than 10 parts by weight, unreacted low molecules are cured. It will remain in, and the heat-resistant yellowing and chemical resistance of the cured product will decrease.

<Other ingredients>
The resin composition for a color filter protective film of the present invention may be used with an organic solvent added for the purpose of adjusting viscosity and the like. Examples of organic solvents used here include aromatic hydrocarbons, ethers, esters and ether esters, ketones, phosphate esters, nitriles, aprotic polar solvents, propylene glycol alkyl ether acetates, and the like. It is done.
These organic solvents can be used alone or in combination of two or more.
Moreover, there is no restriction | limiting in particular about the addition amount of these organic solvents, According to the predetermined film thickness, the smoothness of expression, a film-forming method, etc., arbitrary amounts can be added and the applicability | paintability can be provided. Usually, 5 to 2000 parts by weight is added to 100 parts by weight of the resin composition for a color filter protective film of the present invention.

A silane coupling agent can also be added to the resin composition for a color filter protective film of the present invention as an auxiliary agent for improving the adhesion between the obtained protective film and the substrate. Examples of the silane coupling agent that can be added include a silane coupling agent having an epoxy group, a silane coupling agent having an amino group, a silane coupling agent having a (meth) acryloyl group, or a polymer thereof. Can be mentioned. These silane coupling agents can be added singly or in appropriate combination of two or more.
When using the said silane coupling agent, it is 1-30 weight% normally with respect to 100 weight part of resin compositions for color filter protective films of this invention, Preferably it is 2-25 weight%, More preferably, it is 3-3 weight%. 20% by weight. If the amount of the silane coupling agent is less than 1% by weight, the effect of improving the adhesion of the resulting protective film to the substrate is insufficient. On the other hand, when the silane coupling agent exceeds 30% by weight, the performance such as the hardness of the protective film is lowered.

A surface conditioner may be added to the resin composition for a color filter protective film of the present invention for the purpose of improving the appearance of the protective film obtained. A surface conditioning agent can be used individually by 1 type or in combination of 2 or more types as appropriate. Further, the surface conditioner may be added for the purpose of improving the compatibility of each component including the essential components (A) to (C) of the present invention.
When using the above surface conditioner, it is usually preferable to add 0.001 to 3% by weight with respect to 100 parts by weight of the resin composition for a color filter protective film of the present invention.
To the resin composition for a color filter protective film of the present invention, a viscosity adjusting agent such as a thickener or a thixotropic agent may be further added for the purpose of adjusting the viscosity. Further, infrared rays or ultraviolet absorbers may be added.
In addition, for the purposes of adjusting the linear expansion coefficient, improving flatness, improving surface hardness, adjusting viscosity, adjusting refractive index, absorbing light of a predetermined wavelength, improving adhesiveness, etc., the resin composition for color filter protective film of the present invention An arbitrary amount of filler can be added to the product. The filler used in this case is not particularly limited as long as it does not hinder transparency, and examples thereof include silica sol, silica gel, titanium oxide, aluminum oxide, cerium oxide, tin oxide, zinc oxide, and zirconium oxide. These fillers can be used individually by 1 type or in combination of 2 or more types as appropriate.
In addition, the resin composition for a color filter protective film of the present invention includes a carbon dioxide gas generation inhibitor, a flexibility-imparting agent, an antioxidant, and a plasticizer, as necessary, within a range that does not impair the effects of the present invention. , Lubricants, surface treatment agents, flame retardants, antistatic agents, coloring agents, leveling agents, ion trapping agents, slidability improving agents, various rubbers, organic polymer beads, glass beads, thixotropic agents, surface tension reducing agents, Additives such as an antifoaming agent, a light diffusing agent, an antioxidant, and a fluorescent agent can be blended.

<Method for producing resin composition for color filter protective film>
Hereinafter, the blending, stirring and dispersing methods of the resin composition for a color filter protective film of the present invention will be described.
In the resin composition for a color filter protective film of the present invention, the respective components including the essential components (A) to (C) may be blended at once, or may be blended sequentially after each component is dissolved in a solvent. May be. In addition, there are no particular restrictions on the charging order and working conditions when blending. For example, all the components may be prepared by dissolving in a solvent at the same time. If necessary, each component may be appropriately made into two or more solutions, and these solutions may be mixed at the time of use (at the time of application). It may be prepared.
In the resin composition for a color filter protective film of the present invention, for stirring after mixing each component including the essential components (A) to (C), a blade-type stirrer, a desolver, a kneader, a ball mill blender, Stirring may be performed using a roll disperser or the like, and each component may be blended in a container such as a gallon bottle and then the container may be rotated by a mix rotor and stirred. Although the temperature of mixing and stirring is based also on a mixing | blending component, in order to avoid condensation and volatilization of a solvent, 10-60 degreeC is preferable normally.

  When a viscosity modifier or filler is added to the resin composition for a color filter protective film of the present invention, dispersion using a high shear disperser such as a motor mill or a shaker may be performed. In this case, it is also possible to prepare a master batch in which each component including the essential components (A) to (C) in the present invention is used as a binder and mix it at the time of use. . However, since the deblocking reaction proceeds with heat in the hemiacetal ester compound (A) of the present invention, when dispersing the composition containing the hemiacetal ester compound (A), care should be taken not to heat to 80 ° C. or higher. Necessary.

2. Color Filter The resin composition for a color filter protective film of the present invention can be cured to form a cured product layer and used as a protective film. In this method, a solvent is added to the resin composition for a color filter protective film of the present invention to appropriately adjust the viscosity to obtain a coating solution, which is first applied to, for example, the surface of the color filter on which the colored layer is formed. The coating method is not particularly limited. Examples of commonly used coating methods include spin coater coating method, dip coating method, spray coater coating method, roll coater coating method, screen printing coating method, and offset printing coating. It can be applied to the substrate by a single method or a combination of a coating method, a slit coater coating method, a die coater coating method and the like.
Next, after drying the obtained coating film and performing preheating (hereinafter referred to as pre-baking) as necessary, a cured resin layer is formed through main curing heating (hereinafter referred to as post-baking). In this case, 40 to 140 ° C. and 0 to 1 hour are preferable as prebaking conditions, and 150 to 280 ° C. and 0.2 to 2 hours are preferable as post baking conditions. In addition, the heating method in this case is not particularly limited, and for example, a curing apparatus such as a closed curing furnace or a tunnel furnace capable of continuous curing can be employed. The heating source is not particularly limited, and can be performed by a method such as hot air circulation, infrared heating, high frequency heating or the like.

  In addition, the layer of the resin cured material of this invention is 5-20 micrometers normally as a film thickness after application | coating, Preferably it is 0.2-5 micrometers, More preferably, it is 0.5-4 micrometers. When the film thickness after coating is too small, it is difficult to obtain performances required for a protective film such as barrier properties and flatness, and when it is too large, performance such as transparency and ITO forming processability is deteriorated.

Next, the present invention will be described more specifically with reference to examples and comparative examples.
The measurement methods and evaluation methods used in the examples and comparative examples are shown below.
<Total acid equivalent>
The total acid equivalent was measured by hydrolysis acid value measurement according to JIS K 0070: 1992 “Testing method for acid value, saponification value, ester value, iodine value, hydroxyl value and unsaponified product of chemical products”.
<Average molecular weight>
The weight average molecular weight (Mw), number average molecular weight (Mn), and polydispersity (Mw / Mn) were measured by using a gel permeation chromatography device HLC-8220GPC manufactured by Tosoh Corporation and using SHODEX manufactured by Showa Denko KK as a column. Using K-801, THF was used as an eluent, measured by an RI detector, and determined in terms of polystyrene.
<Epoxy equivalent>
The epoxy equivalent was measured by a method defined by JIS K 7236: 2001 “How to Determine Epoxy Equivalent of Epoxy Resin”.

<Barrier properties>
The barrier property was evaluated using measurement of water vapor permeability.
In accordance with method B of JIS K7129: 1992 “Water vapor permeability test method for plastics and sheets (instrument measurement method)”, the cured product was subjected to 90% R.D. using PERMATRAN manufactured by MOCON. H. I went there.
Judgment criteria are as follows.
The result X (g / m2 / day) obtained by measuring the water vapor transmission rate is
A: X ≦ 4.0
○: 4.0 <X ≦ 5.0
Δ: 5.0 <X ≦ 7.0
X: X> 7.0
For practical use, Δ or more is necessary, and in order to obtain high reliability required in recent years, ○ or more is necessary.

<Liquid crystal contamination>
An evaluation sample of liquid crystal contamination was produced as follows.
The cured product produced on the glass substrate was peeled off and pulverized to obtain a powder of each cured product. Next, 0.1 g of the obtained powder was mixed with 1.0 g of a liquid crystal material ZLI-4792 manufactured by Merk in a test tube, and the sealed one was subjected to an acceleration test at 150 ° C. for 60 minutes.
The supernatant of the liquid crystal material after the acceleration test was injected into a small evaluation cell imitating an actual liquid crystal panel, and used as a measurement sample.
The liquid crystal contamination property was measured by measuring the voltage holding ratio.
The voltage holding ratio was measured at 80 ° C. and a frame period of 166.7 milliseconds using a liquid crystal property measuring system 6254 type manufactured by Toyo Corporation.
The judgment criteria are as follows.
The result Y (%) obtained by the voltage holding ratio measurement is
A: Y ≧ 95
○: 95> Y ≧ 90
Δ: 90> Y ≧ 85
X: Y <85
○ or more is necessary for practical use, and ◎ or more is necessary to obtain the high reliability required in recent years.

<Chemical resistance>
The chemical resistance was evaluated by measuring the film thickness before and after the immersion test of the cured product in an acid / alkali solution.
The glass substrate on which the cured product was produced was subjected to acid treatment (H ₂ O / HCl / HNO ₃ = 1/1 / 0.04 <weight ratio>, 50 ° C. × 8 minutes), and alkali treatment (5% NaOHaq, 60 ° C. The change rate of the sample film thickness when measured for 5 minutes or 10 minutes) was measured.
The film thickness change rate was calculated by the following equation: [film thickness change rate (%)] = {[film thickness after immersion (μm) −film thickness before immersion (μm)] / [film thickness before immersion (μm )]} × 100
Judgment criteria are as follows.
The absolute value | Z | of the calculation result Z of the film thickness change rate is ◎: | Z | ≦ 1.0
○: 1.0 <| Z | ≦ 2.0
Δ: 2.0 <| Z | ≦ 3.0
×: | Z |> 3.0
For practical use, ○ or more is required.

Synthesis example 1
<Synthesis of hemiacetal ester compound A-1>
In a four-necked flask equipped with a thermometer, reflux condenser, stirrer, and dropping funnel, 31.8 g of PMA, 13.7 g of trimellitic acid (hereinafter, TMA) manufactured by Mitsubishi Gas Chemical Co., Ltd., 2- (2-vinyloxy) Ethoxy) ethyl (meth) acrylate (hereinafter referred to as VEEA) 54.5 g and p-methoxyphenol 0.05 g were charged and heated with stirring to 70 ° C. Next, stirring was continued while maintaining the temperature, and the reaction was terminated when the acid value of the mixture became 2.0 mgKOH / g or less, and two or more blocked carboxyl groups having an acid value of 0.64 mgKOH / g in the solution were obtained. A solution of the hemiacetal ester compound (A-1) was obtained.

Synthesis Examples 2-5
<Synthesis of hemiacetal ester compound A-2 to 5>
In the same manner as in Synthesis Example 1, hemiacetal ester compounds (A-2 to 5) were obtained. Table 1 shows the charging ratio, reaction temperature, acid value, and total acid equivalent of each raw material.

The meanings of the abbreviations used in the table are as follows.
TMA: trimellitic anhydride ADA: adipic acid CHTA: 1,2,4-cyclohexanetricarboxylic acid CIC: tris (2-carboxyethyl) isocyanurate VEEA: 2- (2-vinyloxyethoxy) ethyl acrylate
VEEM: 2- (2-vinyloxyethoxy) ethyl methacrylate pMP: p-methoxyphenol PMA: propylene glycol monomethyl ether acetate

Polymerization example 1
<Polymerization of polymer (B-1)>
152 g of propylene glycol monomethyl ether acetate (hereinafter referred to as PMA) was charged into a 500 mL four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel, and heated to 80 ° C. while stirring. Next, “Blemmer GH” (; trade name) 113.7 g of glycidyl methacrylate (hereinafter referred to as GMA), 86.3 g of cyclohexyl methacrylate (hereinafter referred to as CHMA), Nippon Oil & Fats Co., Ltd. at a temperature of 80 ° C. ) Peroxide polymerization initiator “Perhexyl O (hereinafter PHO) (; trade name, purity 93%)” 16 g and PMA 32 g previously mixed uniformly (dropping component) was added to the dropping funnel over 2 hours. It was dripped more uniformly. After completion of dropping, the temperature was maintained at 80 ° C. for 7 hours, and then the reaction was terminated. Polymer solution (polymer epoxy with weight average molecular weight (Mw) 14,000, number average molecular weight (Mn) 6,700 and polydispersity (Mw / Mn) 2.1, epoxy equivalent of solution 1.000 g / eq Equivalent 500 g / eq) was obtained.

Polymerization example 2
<Polymer (polymerization of B-2)>
The same operation as in Polymerization Example 1 was performed to obtain a polymer (B-2). Table 2 shows the charging ratio, weight average molecular weight, number average molecular weight, polydispersity, and epoxy equivalent of each raw material.

The meanings of the abbreviations used in the table are as follows.
GMA: glycidyl methacrylate OXMA: 3-methyl-3-oxetane-ylmethyl ester methacrylate PHO: peroxide-based polymerization initiator “Perhexyl O”
PMA: Propylene glycol monomethyl ether acetate

Comparative Synthesis Example 1
<Synthesis of hemiacetal ester compound (a-1)>
In a four-necked flask equipped with a thermometer, reflux condenser, stirrer, and dropping funnel, 36 g of PMA, 22.5 g of trimellitic acid (hereinafter, TMA) manufactured by Mitsubishi Gas Chemical Co., Ltd., n-propyl vinyl ether (hereinafter, nPr- VE) 41.5 g was charged, heated with stirring, and heated to 70 ° C. Next, stirring was continued while maintaining the temperature, and the reaction was terminated when the acid value of the mixture became 2.0 mgKOH / g or less, and two or more blocked carboxyl groups having an acid value of 0.64 mgKOH / g in the solution were obtained. A solution of the hemiacetal ester compound (a-1) was obtained.

Comparative Synthesis Examples 2-4
In the same manner as in Synthesis Example 1, hemiacetal ester compounds (a-2 to 4) were obtained. Table 3 shows the charging ratio, reaction temperature, acid value, and total acid equivalent of each raw material.

The meanings of the abbreviations used in the table are as follows.
TMA: trimellitic anhydride ADA: adipic acid CHTA: 1,2,4-cyclohexanetricarboxylic acid nPr-VE: n-propyl vinyl ether PMA: propylene glycol monomethyl ether acetate

<Examples 1 to 10>
The color filter protective film resin compositions of Examples 1 to 10 dissolved and mixed at the blending ratios shown in Table 4 were filtered through a membrane filter having a pore size of 0.2 μm, and then spin coater (model 1H) on a 10 cm square glass substrate. -DX-2, manufactured by Mikasa Co., Ltd.). The coating film was dried at 90 ° C. for 2 minutes on a hot plate, and then heated at 220 ° C. for 30 minutes in a clean oven to obtain a cured product having a thickness of 1.5 μm.
About the obtained hardened | cured material, barrier property, liquid-crystal stain | contamination property, and chemical resistance were evaluated. The results are shown in Table 4 together with the blending ratio.

<Examples 11 and 12>
The resin compositions for color filter protective films of Examples 11 and 12 dissolved and mixed at the blending ratios shown in Table 4 were filtered through a membrane filter having a pore size of 0.2 μm, and then spin coater (model 1H on a 10 cm square glass substrate). -DX-2, manufactured by Mikasa Co., Ltd.). This coating film was dried at 90 ° C. for 2 minutes on a hot plate, and then 100 mJ / mm using a UV aligner (model MA1200, manufactured by Dainippon Screen Co., Ltd.) equipped with a 2.0 kW super high pressure mercury lamp. Ultraviolet rays were irradiated at an intensity of cm ² (converted to 405 nm illuminance).
After ultraviolet irradiation, a cured product having a thickness of 1.5 μm was obtained by heating at 220 ° C. for 30 minutes in a clean oven.
About the obtained hardened | cured material, barrier property, liquid-crystal stain | contamination property, and chemical resistance were evaluated. The results are shown in Table 4 together with the blending ratio.

<Comparative Examples 1-9>
A cured product having a film thickness of 1.5 μm is obtained by performing the same procedure as in Examples 1 to 10 for the resin compositions for color filter protective films of Comparative Examples 1 to 9 which are dissolved and mixed at the blending ratio shown in Table 5. It was.
About the obtained hardened | cured material, barrier property, liquid-crystal stain | contamination property, and chemical resistance were evaluated. The results are shown in Table 5 together with the blending ratio.

<Comparative Example 10>
The resin composition for color filter protective film of Comparative Example 10 dissolved and mixed at the blending ratio shown in Table 5 was subjected to the same procedures as in Examples 11 and 12 to obtain a cured product having a film thickness of 1.5 μm.
In all cases of Examples and Comparative Examples, the surface of the obtained coating film was extremely smooth, and no pinholes were observed.

The meanings of the abbreviations used in the table are as follows.
Ep-157: Bisphenol A novolac type epoxy resin, trade name “Epicoat 157” manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent 210 g / eq.
PBP: peroxide-based polymerization initiator, di (2-t-butylperoxyisopropyl) benzene, manufactured by NOF Corporation, trade name “Perbutyl P”
PHI: peroxide-based polymerization initiator, t-hexyl peroxyisopropyl monocarbonate, manufactured by NOF Corporation, trade name “Perhexyl I”
Irg184: photosensitive polymerization initiator, 1-hydroxy-cyclohexyl-phenylketone, manufactured by Ciba Specialty Chemicals Co., Ltd., trade name “Irgacure 184”
Irg907: 2-methyl-1 [4-methylthio] phenyl] -2-morpholinopropan-1-one, photosensitive polymerization initiator, manufactured by Ciba Specialty Chemicals Co., Ltd., trade name “Irgacure 907”
LCAT-1: Reaction product of zinc octylate and N-methylmorpholine (described in JP-A-2001-350010)
BYK-355: Leveling agent (manufactured by Big Chemie Japan Co., Ltd.)
GPS: 3-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBM-403”

From the results of the table, Examples 1 to 12 are excellent in barrier property, liquid crystal contamination property, and chemical resistance by using the resin composition for a color filter protective film of the present invention. It turns out that it is obtained perfectly.
On the other hand, in Comparative Examples 1 and 2, since the hemiacetal ester compound used in the present invention is not used, it is understood that sufficient ion barrier property, liquid crystal contamination property, and chemical resistance are not obtained.
Moreover, in Comparative Examples 3-6, although the favorable performance was acquired compared with Comparative Example 1 and 2 by using the conventional hemiacetal ester compound, the hemiacetal ester compound used for this invention is obtained. Since it does not contain, sufficient performance which this application aimed at cannot be obtained.
Furthermore, in Comparative Examples 7 and 8, the molar equivalent ratio [(A) / (B)] of the latent carboxyl group of the component (A) and the epoxy group or oxetanyl group of the component (B) is Since it deviated from the range in the resin composition for a color filter protective film, the effect of the present invention was not obtained.
In Comparative Examples 9 and 10, the content of the component (C) was out of the range in the resin composition for a color filter protective film of the present invention, so that the liquid crystal contamination was poor.
From the above results, it is apparent that the object of the present application can be achieved only when the color filter protective film resin composition of the present invention is used.

Claims (3)

The following (A) and (B) components are contained, and the molar equivalent ratio [(A) / (B)] of the hemiacetal ester group that (A) component has and the epoxy group or oxetanyl group that (B) component has: A resin composition for a color filter protective film, wherein the resin composition is 2/10 to 50/10.
(A) A hemiacetal ester compound represented by the following formula (1).

(R ¹ is an alkyl group having 3 to 30 carbon atoms, a cycloalkyl group, an aryl group, or an isocyanuric trialkyl group, n is an integer of 2 to 8, m is an integer of 1 to 4, and R ² is carbon. The number is an alkylene group having 1 to 4, and R ³ is a hydrogen atom or a methyl group.)
(B) A compound having two or more epoxy groups or oxetanyl groups in one molecule.   Furthermore, (C) 0.1-10 weight part of compounds which produce a radical by heat or light are contained with respect to a total of 100 weight part of (A) and (B) component, It is characterized by the above-mentioned. Resin composition for color filter protective film.   A color filter having a layer of a cured product obtained by curing the resin composition for a color filter protective film according to claim 1 or 2.