JP2018009043A - Resin composition, method for producing the same, color filter, and image display element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition which has good sensitivity and developability and gives a colored pattern having excellent solvent resistance.SOLUTION: The resin composition contains: a copolymer (A) which contains a polymerizable monomer (a-1) having an acid group and a polymerizable monomer (a-2) having an epoxy group, as constituent monomers; and a glycol ether-based solvent (B) represented by chemical formula (1). Moisture contained in the resin composition is 3.5 mass% or less based on the amount of the copolymer (A). (In the formula (1), Rrepresents a 1 to 8C alkyl group, an allyl group, a phenyl group, or a benzyl group; Rrepresents a hydrogen atom or a methyl group; Rrepresents a hydrogen atom, a 1 to 4C alkyl group, or an acetoxy group; and n is an integer of 1 to 10).SELECTED DRAWING: None

Description

  The present invention relates to a resin composition, a method for producing the same, a color filter obtained using the resin composition, and an image display element.

  The color filter generally includes a transparent substrate such as a glass substrate, red (R), green (G) and blue (B) pixels formed on the transparent substrate, a black matrix formed at the pixel boundary, It is comprised from the protective film formed on a pixel and a black matrix. A color filter having such a configuration is usually manufactured by sequentially forming a black matrix, a pixel, and a protective film on a transparent substrate. Various methods have been proposed as a method for forming a pixel and a black matrix (hereinafter, the pixel and the black matrix are referred to as a “colored pattern”). However, application of a photosensitive resin composition as a resist, exposure, A pigment / dye dispersion method using photolithography in which development and baking are repeated is the current mainstream.

  Generally, the photosensitive resin composition used for photolithography contains an alkali-soluble resin, a reactive diluent, a photopolymerization initiator, a colorant, and a solvent. The pigment / dye dispersion method has the advantage of being able to form a colored pattern that is excellent in durability such as light resistance and heat resistance and has few defects such as pinholes, but the pattern of black matrix, R, G, B Therefore, the alkali-soluble resin serving as the binder for the coating film is required to have high solvent resistance.

Therefore, for example, methods for improving solvent resistance using a copolymer having an epoxy group or oxetanyl group and a carboxyl group or a phenolic hydroxyl group (Patent Documents 1 and 2) and an oxadi having a trihalomethyl group as a polymerization initiator A method (Patent Document 3) for improving the solvent resistance using a molecule containing a molecule having an azole structure or a triazine structure has been proposed, but these have insufficient solvent resistance.
In addition, in order to improve the color reproduction characteristics of the color filter, it is necessary to increase the content of the colorant to be blended or to increase the film thickness. However, these simultaneously reduce sensitivity, developability, etc. Therefore, further performance improvement is required (Patent Document 4).

JP 2012-22048 A JP 2013-25203 A JP 2003-330184 A JP 2014-164021 A

As described above, the conventional photosensitive resin composition may not have sufficient sensitivity and developability, or a colored pattern having excellent solvent resistance may not be obtained.
Accordingly, the present invention has been made to solve the above-described problems, and provides a resin composition that provides a colored pattern with excellent sensitivity and developability and excellent solvent resistance. Objective. Moreover, it aims at providing the color filter which has a coloring pattern excellent in solvent resistance.

That is, this invention is shown by the following [1]-[11].
[1] a copolymer (A) containing a polymerizable monomer (a-1) having an acid group and a polymerizable monomer (a-2) having an epoxy group as constituent monomers;
A resin composition containing a glycol ether solvent (B) represented by the following chemical formula (1), wherein the water content in the resin composition is 3.5 based on the amount of the copolymer (A). A resin composition characterized by being not more than mass%.

(In Formula (1), R ¹ represents an alkyl group having 1 to 8 carbon atoms, an allyl group, a phenyl group, or a benzyl group, R ² represents a hydrogen atom or a methyl group, R ³ represents a hydrogen atom, and 1 carbon atom. Represents an alkyl group or an acetoxy group of -4, and n is an integer of 1-10.)

[2] The resin composition according to [1], wherein the polymerizable monomer (a-1) is a carboxyl group-containing ethylenically unsaturated compound.
[3] The resin composition according to [1] or [2], wherein the polymerizable monomer (a-2) is an epoxy group-containing (meth) acrylate.
[4] In the formula (1), any one of [1] to [3], wherein R ¹ is an alkyl group having 1 to 8 carbon atoms, and R ³ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The resin composition described in 1.
[5] The resin composition according to any one of [1] to [4], wherein the copolymer (A) has a weight average molecular weight of 1,000 to 50,000 and an acid value of 20 to 300 KOHmg / g.
[6] The copolymer (A) contains 10 to 50 mol% of the polymerizable monomer (a-1) and 30 to 90 mol% of the polymerizable monomer (a-2) as constituent monomers [1]. -The resin composition in any one of [5].
[7] The resin composition according to any one of [1] to [6], further containing a reactive diluent (C), a photopolymerization initiator (D), and a colorant (E).
[8] The resin composition according to [7], wherein the colorant (E) is at least one selected from the group consisting of a dye and a pigment.
[9] A color filter having a colored pattern formed from the resin composition according to [7] or [8].
[10] An image display device comprising the color filter according to [9].
[11] A polymerizable monomer containing a polymerizable monomer (a-1) having an acid group and a polymerizable monomer (a-2) having an epoxy group is converted into a glycol ether solvent (B) represented by the chemical formula (1). In the method for producing a resin composition comprising a step of obtaining a copolymer (A) containing a polymerizable monomer (a-1) and a polymerizable monomer (a-2) as constituent monomers by copolymerization in the presence of There,
Based on the water content of the glycol ether solvent (B), the glycol ether solvent so that the water content in the resin composition is 3.5% by mass or less based on the amount of the copolymer (A). The manufacturing method of the resin composition characterized by determining the usage-amount of (B).

  According to the present invention, it is possible to provide a resin composition capable of forming a cured coating film having excellent sensitivity and developability and excellent solvent resistance. In addition, the cured coating film formed from the resin composition of the present invention has developability, so it has a very high utility value in various resist fields, and among them, provides a color filter having a colored pattern with excellent solvent resistance. can do.

It is sectional drawing of the color filter which is one Embodiment of this invention.

  The resin composition of the present invention comprises a copolymer (A) containing a copolymerizable monomer (a-1) having an acid group and a polymerizable monomer (a-2) having an epoxy group as constituent monomers, and the following chemical formula: It contains the glycol ether solvent (B) represented by (1), and the water content in the resin composition is 3.5% by mass or less based on the amount of the copolymer (A). And

(In Formula (1), R ¹ represents an alkyl group having 1 to 8 carbon atoms, an allyl group, a phenyl group, or a benzyl group, R ² represents a hydrogen atom or a methyl group, R ³ represents a hydrogen atom, and 1 carbon atom. Represents an alkyl group or an acetoxy group of -4, and n is an integer of 1-10.)

  In the present invention, (meth) acrylate means at least one selected from methacrylate and acrylate.

The amount of water can be measured by the Karl Fischer method under the following conditions.
Apparatus: Kyoto Electronics Industry Co., Ltd., KF moisture meter MKA-520
Injection volume: 1 mL
Titration solution: Aquamicron titrant SS3mg (manufactured by API Corporation)
Electrode solution: Aquamicron (registered trademark) dehydrated solvent PP (manufactured by API Corporation)

  The resin composition of the present invention has a good sensitivity when used for color filters by setting the moisture measured under the above conditions to 3.5% by mass or less based on the amount of the copolymer (A). And solvent resistance can be achieved. The water content can be adjusted by using a solvent having a low water content when producing the copolymer (A), adjusting the amount of the solvent used, or avoiding the mixing of water during the production process. In the present invention, the water content is preferably 3% by mass or less, more preferably 2% by mass or less based on the amount of the copolymer (A), more preferably 2% by mass or less based on the copolymer (A). When the water content exceeds 4% by mass, the curing performance of the resin composition is lowered, which adversely affects the sensitivity and solvent resistance when used in color filter applications. Although it is preferable that the amount of water is small, it is not necessary to make it 0.01% by mass or less.

"Copolymer (A)"
First, the copolymer (A) used for this invention is demonstrated.
The copolymer (A) contains at least a polymerizable monomer (a-1) having an acid group and a polymerizable monomer (a-2) having an epoxy group as constituent monomers.

The acid group of the polymerizable monomer (a-1) having an acid group constituting the copolymer (A) is not particularly limited, but is usually a carboxyl group (—COOH), a phospho group (—PO (OH) _2. ), A sulfo group (—SO ₃ H), and the like. From the viewpoint of easy availability of raw materials and solvent resistance when used for color filter production, a carboxyl group is particularly preferred, and a carboxyl group-containing ethylenically unsaturated compound is more preferred as the polymerizable monomer (a-1). . Specific examples of the polymerizable monomer (a-1) include (meth) acrylic acid, crotonic acid, cinnamic acid, vinyl sulfonic acid, 2- (meth) acryloyloxyethyl succinic acid, and 2- (meth) acryloyloxyethyl phthalate. An acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl acid phosphate, etc. are mentioned. Among these, (meth) acrylic acid is preferable from the viewpoint of easy availability and reactivity.

  The polymerizable monomer (a-2) having an epoxy group and constituting the copolymer (A) is not particularly limited as long as it is a monomer having an epoxy group and an ethylenically unsaturated double bond group. Preferably, an epoxy group-containing (meth) acrylate is used, and specific examples include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate having an alicyclic epoxy group, and a lactone adduct thereof (for example, , Daicel Cyclomer (registered trademark) A200, M100), 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate mono (meth) acrylate, dicyclopentenyl (meth) acrylate And an epoxidized product of dicyclopentenyloxyethyl (meth) acrylate. Among these, glycidyl (meth) acrylate is particularly preferred from the viewpoint of availability and reactivity.

Moreover, it is also possible to use the polymerizable monomer (a-3) other than the polymerizable monomer (a-1) and the polymerizable monomer (a-2) as a constituent monomer of the copolymer (A). is there. The polymerizable monomer (a-3) is generally a radically polymerizable compound having an ethylenically unsaturated group. Examples thereof include dienes such as butadiene; methyl (meth) acrylate, ethyl (meth) acrylate, n- Propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, benzyl (meth) acrylate, isoamyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) ) Acrylate, cyclohexyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, rosin (meth) acrylate, norbornyl (meth) acrylate, allyl (meth) acrylate, tetrahydrofurfuryl (meth) Acrylate, 1,1,1-trifluoroethyl (meth) acrylate, perfluoroethyl (meth) acrylate, triphenylmethyl (meth) acrylate, cumyl (meth) acrylate, 3- (N, N-dimethylamino) propyl ( (Meth) acrylate, glyceryl mono (meth) acrylate, butanetriol mono (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, naphthalene (meth) acrylate, anthracene (meta) ) (Meth) acrylic acid esters such as acrylate; norbornene (bicyclo [2.2.1] hept-2-ene), 5-methylbicyclo [2.2.1] hept-2-ene, tetracyclo [4 4.0.1, ^{2, 5} . 1 ^7,10 ] dodec-3-ene, dicyclopentadiene, tricyclo [5.2.1.0 ^2,6 ] dec-8-ene, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 . 0 ^1,6 ] dodec-3-ene, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13] pentadeca-4-ene, 5-norbornene-2,3-dicarboxylic acid, 5-norbornene-2,3-dicarboxylic acid anhydride, (meth) acrylic acid amide, (meth) acrylic acid N, N -(Meth) acrylic acid amides such as dimethylamide, (meth) acrylic acid anthracenylamide, N-isopropyl (meth) acrylamide, (meth) acryl morpholine, diacetone (meth) acrylamide; Vinyl compounds such as anilide, (meth) acryloylnitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate, vinyltoluene; styrene, α-, o-, m- of styrene , P-alkyl, nitro, cyano, amide derivatives; diethyl citraconic acid Unsaturated dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate; monomaleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, N- (4-hydroxyphenyl) maleimide; Examples thereof include unsaturated polybasic acid anhydrides such as maleic anhydride and itaconic anhydride. These can be used alone or in combination of two or more. Of these, from the viewpoint of heat resistance and transparency, benzyl (meth) acrylate, dicyclopentanyl (meth) acrylate, styrene, vinyltoluene, isobornyl (meth) acrylate, adamantyl (meth) acrylate, norbornene, N- Isopropyl (meth) acrylamide, (meth) acryl morpholine, diacetone (meth) acrylamide are preferred, benzyl (meth) acrylate, dicyclopentanyl (meth) acrylate, styrene, vinyltoluene, isobornyl (meth) acrylate, adamantyl ( More preferred are (meth) acrylates and norbornene.

  Although there is no restriction | limiting in particular in content of a polymerizable monomer (a-1), Preferably it is 10-70 mol% with respect to the sum total of the structural monomer of a copolymer (A), More preferably, 15-50 mol%, More preferably, it is 20-40 mol%. The developability of a resin composition improves by making content of a polymerizable monomer (a-1) into 10-70 mol%.

  Although there is no restriction | limiting in particular in content of a polymerizable monomer (a-2), Preferably it is 30-90 mol% with respect to the sum total of the structural monomer of a copolymer (A), More preferably, it is 35-85 mol%, More preferably, it is 40-80 mol%. By setting the content of the polymerizable monomer (a-2) to 30 to 90 mol%, the solvent resistance of the color filter formed using the resin composition is improved.

  When the polymerizable monomer (a-3) is used, the content thereof is not particularly limited, but is preferably 10 to 50 mol%, more preferably 10 to 10%, based on the total of the constituent monomers of the copolymer (A). It is 40 mol%, More preferably, it is 10-30 mol%. By setting the content of the polymerizable monomer (a-3) to 10 to 50 mol%, the contents of the polymerizable monomer (a-1) and the polymerizable monomer (a-2) are sufficiently secured, and accordingly Desired developability and solvent resistance.

  The copolymerization reaction for producing the copolymer (A) can be performed according to a radical polymerization method known in the art. For example, after dissolving a polymerizable monomer (a-1), a polymerizable monomer (a-2), and an arbitrary polymerizable monomer (a-3) in a solvent, a polymerization initiator is added to the solution, What is necessary is just to make it react at 130 degreeC for 1 to 20 hours.

  The solvent used in this copolymerization reaction is not particularly limited. However, when a glycol ether solvent (B) represented by the following chemical formula (1) is used, the solvent of the present invention is used without removing the solvent after the copolymerization reaction is completed. Since it can be used as a component of a resin composition, it is preferable. Moreover, you may use solvents other than a glycol ether type solvent (B) as a solvent used for a copolymerization reaction.

In the formula, R ¹ represents an alkyl group, an allyl group, a phenyl group or a benzyl group having 1 to 8 carbon atoms, is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms . Specific examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, a hexyl group, an octyl group, and the like, and a methyl group or an ethyl group is more preferable from the viewpoint of availability of raw materials.
In the formula, R ² represents a hydrogen atom or a methyl group.
In the formula, R ³ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an acetoxy group, preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. . Specific examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-butyl group, and a t-butyl group, and a methyl group or an ethyl group is more preferable from the viewpoint of availability of raw materials.
In formula, n is an integer of 1-10, Preferably it is 1-6, More preferably, it is 1-4.
From the viewpoint of solvent resistance of the colored pattern formed from the resin composition of the present invention as the glycol ether solvent (B), R ¹ is an alkyl group having 1 to 8 carbon atoms, and R ² is a hydrogen atom or a methyl group. , R ³ is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, n is an integer of 1 to 6, R ¹ is an alkyl group having 1 to 4 carbon atoms, R ² is a hydrogen atom or a methyl group, More preferably, R ³ is a hydrogen atom and n is an integer of 1 to 4.

  Specific examples of the glycol ether solvent (B) include ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, polyethylene glycol monomethyl ether, ethylene glycol monoethyl ether, triethylene glycol monoethyl ether, ethylene glycol monoisopropyl. Ether, ethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, ethylene glycol monohexyl ether, ethylene glycol mono 2-ethylhexyl ether, ethylene glycol monoallyl ether, ethylene glycol monophenyl ether, diethylene glycol monobenzyl ether, ethylene glycol monoethyl ether acetate Over DOO, propylene glycol monomethyl ether, dipropylene glycol monobutyl ether, ethylene glycol dimethyl ether and diethylene glycol diethyl ether and dipropylene glycol dimethyl ether. These can be used alone or in combination of two or more.

  The water content of the glycol ether solvent (B) is not particularly limited, but is preferably 0.7% by mass or less. By using the glycol ether solvent (B) having a water content of 0.7% by mass or less, the glycol ether solvent (B) is blended as it is without removing it from the copolymer (A) obtained. The water content contained in the resin composition of the present invention can be suppressed to 3.5% by mass or less based on the amount of the copolymer (A), which is economical. The water content of the glycol ether solvent (B) can be measured by the Karl Fischer method in the same manner as the measurement of the water content described above.

  The blending amount of the glycol ether solvent (B) when producing the copolymer (A) is such that the water content contained in the obtained resin composition is 3.5 mass based on the amount of the copolymer (A). % May be appropriately determined based on the water content of the glycol ether solvent (B), preferably when the total of the constituent monomers of the copolymer (A) is 100 parts by mass. It is 30-1000 mass parts, More preferably, it is 50-800 mass parts. In particular, by setting the blending amount of the glycol ether solvent (B) to 1000 parts by mass or less, a decrease in the molecular weight of the copolymer (A) due to chain transfer action is suppressed, and the viscosity of the copolymer (A) is appropriately set. Can be controlled within a wide range. Moreover, by setting the blending amount of the glycol ether solvent (B) to 30 parts by mass or more, an abnormal polymerization reaction can be prevented and the polymerization reaction can be performed stably, and the copolymer (A) can be colored. And gelation can also be prevented.

Although it does not specifically limit as a polymerization initiator which can be used for manufacture of a copolymer (A), For example, azobisisobutyronitrile, azobisisovaleronitrile, benzoyl peroxide, t-butylperoxy- Examples include 2-ethylhexanoate. These can be used alone or in combination of two or more.
The blending amount of the polymerization initiator is preferably 0.5 to 20 parts by mass, more preferably 1.0 to 10 parts by mass, when the total of the constituent monomers of the copolymer (A) is 100 parts by mass. .
In addition, bulk polymerization is performed using a polymerizable monomer (a-1), a polymerizable monomer (a-2), a polymerizable monomer (a-3) (optional) and a polymerization initiator without using an organic solvent. You may go.

A double bond can be further introduced into the copolymer (A) obtained by the above copolymerization reaction. Thereby, the sensitivity and developability of the resin composition are improved.
The reaction of adding a double bond to the acid group or epoxy group in the copolymer (A) is carried out by adding an epoxy group-containing unsaturated ethylenic monomer, carboxyl group-containing unsaturated ethylenic monomer or hydroxyl group to the copolymer (A). An unsaturated ethylenic monomer, a polymerization inhibitor and a catalyst are added, and the reaction may be carried out at 50 to 150 ° C., preferably 80 to 130 ° C. In this addition reaction, there is no particular problem even if the glycol ether solvent (B) used in the copolymerization reaction for obtaining the copolymer (A) is included. The addition reaction can be carried out without removing.
Specific examples of the epoxy group-containing unsaturated ethylenic monomer include glycidyl (meth) acrylate. Specific examples of the carboxyl group-containing unsaturated ethylenic monomer include (meth) acrylic acid. Specific examples of the hydroxyl group-containing unsaturated ethylenic monomer include 2-hydroxyethyl (meth) acrylate.
Here, a polymerization inhibitor may be added in order to prevent gelation due to polymerization of the copolymer (A). Although it does not specifically limit as a polymerization inhibitor, For example, hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, etc. are mentioned. The catalyst is not particularly limited, and examples thereof include tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzylammonium chloride, phosphorus compounds such as triphenylphosphine, and chelate compounds of chromium. Can be mentioned.

The acid value (JIS K6901 5.3.2) of the copolymer (A) obtained as described above is not limited, but is preferably 20 to 300 KOHmg / g, more preferably 30 to 200 KOHmg / g. . If the acid value is 20 KOHmg / g or more, the developability when producing a colored pattern is improved. Further, when the acid value is 300 KOHmg / g or less, sufficient developability can be obtained without dissolving the exposed portion (photocured portion) in the alkaline developer.
The molecular weight (polystyrene equivalent weight average molecular weight) of the copolymer (A) is preferably 1000 to 50000, more preferably 3000 to 40000, and still more preferably 5000 to 25000. When the weight average molecular weight is 1000 or more, sufficient performance can be obtained without occurrence of color pattern chipping after development. Further, when the weight average molecular weight is 50000 or less, the development time can be suppressed to a practical range.
Moreover, when a copolymer (A) has an unsaturated group, there is no restriction | limiting of the unsaturated group equivalent, However, 100-4000 g / mol is preferable, More preferably, it is 200-3000 g / mol. When the unsaturated group equivalent is 100 g / mol or more, it is effective from the viewpoint of further improving the heat decomposition resistance and heat yellowing. On the other hand, when the unsaturated group equivalent is 4000 g / mol or less, it is effective to further increase the sensitivity.

"Glycol ether solvent (B)"
The resin composition of the present invention contains a glycol ether solvent (B) represented by the chemical formula (1). As the glycol ether solvent (B), the same solvent as used in the production of the copolymer (A) (copolymerization reaction) can be used, and the solvent contained after the copolymerization reaction can be used. It can also be used as it is, and can also be added when preparing the resin composition of the present invention. Alternatively, when other components described later are added, the glycol ether solvent (B) coexisting with these components may be used as it is.

  The blending amount of the glycol ether solvent (B) is preferably 30 to 1000 parts by mass, more preferably 50 to 800, when the total of the components excluding the solvent (B) in the resin composition of the present invention is 100 parts by mass. It is 100 mass parts, More preferably, it is 100-700 mass parts. By setting the blending amount of the glycol ether solvent (B) to 30 to 1000 parts by mass, a resin composition having an appropriate viscosity can be obtained.

  When using the resin composition of this invention for formation of the coloring pattern of a color filter, each of a reactive diluent (C), a photoinitiator (D), and a coloring agent (E) is further mix | blended and used.

“Reactive Diluent (C)”
Although it does not specifically limit as a reactive diluent (C), For example, aromatic vinyl-type monomers, such as styrene, alpha-methyl styrene, alpha-chloromethyl styrene, vinyl toluene, divinyl benzene, diallyl phthalate, diallyl benzene phosphonate; Polycarboxylic acid monomers such as vinyl acetate and vinyl adipate; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, β-hydroxyethyl (meth) acrylate, hydroxypropyl ( (Meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, trimethylol group (Meth) such as pandi (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tris (hydroxyethyl) isocyanurate tri (meth) acrylate Acrylic monomers; triallyl cyanurate and the like. These can be used alone or in combination of two or more.

  The content of the reactive diluent (C) is preferably 10 to 90% by mass, more preferably 20 to 80%, based on the sum of the components excluding the glycol ether solvent (B) in the resin composition of the present invention. It is 25 mass%, More preferably, it is 25-70 mass%. By setting the content of the reactive diluent (C) to 10 to 90% by mass, a resin composition having an appropriate viscosity is obtained, and sufficient photocurability is exhibited.

"Photopolymerization initiator (D)"
Although it does not specifically limit as a photoinitiator (D), For example, benzoin, such as benzoin, benzoin methyl ether, benzoin ethyl ether, and its alkyl ethers; acetophenone, 2,2-dimethoxy-2-phenyl acetophenone, 1, Acetophenones such as 1-dichloroacetophenone and 4- (1-t-butyldioxy-1-methylethyl) acetophenone; 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one and the like Alkylphenones; anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone; 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthate Thioxanthones such as 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone, 4- (1-t-butyldioxy-1-methylethyl) benzophenone, 3,3 ′, 4,4′- Benzophenones such as tetrakis (t-butyldioxycarbonyl) benzophenone; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl Oxime esters such as -6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime); 2-methyl-1- [4- (methylthio) phenyl] -2 -Morpholino-propan-1-one; 2-benzyl-2-dimethylamino-1- (4-morpholino Phenyl) butanone-1; acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide; and xanthones. These can be used alone or in combination of two or more.

  The content of the photopolymerization initiator (D) is preferably 0.1 to 15 when the total of the copolymer (A) and the reactive diluent (C) in the resin composition of the present invention is 100 parts by mass. It is a mass part, More preferably, it is 0.5-10 mass part, More preferably, it is 1-5 mass part. By setting the content of the photopolymerization initiator (D) to 0.1 to 15 parts by mass, a resin composition having appropriate photocurability is obtained.

"Colorant (E)"
The colorant (E) is not particularly limited as long as it dissolves or disperses in the glycol ether solvent (B), and examples thereof include dyes and pigments.

  As the dye, from the viewpoints of solubility in glycol ether solvent (B) and alkali developer, interaction with other components in the resin composition, heat resistance, etc., an acidic dye having an acidic group such as carboxylic acid, It is preferable to use a salt of an acidic dye with a nitrogen compound, a sulfonamide of an acidic dye, or the like. Examples of such dyes include acid alizarin violet N; acid black 1, 2, 24, 48; acid blue 1, 7, 9, 25, 29, 40, 45, 62, 70, 74, 80, 83, 90, 92, 112, 113, 120, 129, 147; acid chroma violet K; acid Fuchsin; acid green 1, 3, 5, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95; acid red1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 69, 73 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 38, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257, 260, 266, 274; acid violet 6B, 7, 9, 17, 19; acid yellow1, 3, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116; food yellow3 and these Derivatives and the like. Among these, azo, xanthene, anthraquinone, or phthalocyanine acid dyes are preferable. These can be used alone or in combination of two or more depending on the color of the target pixel.

Examples of pigments include C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 194, 214; I. CI orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73; I. Red pigments such as CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265; C. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60; I. Violet color pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38; I. Green pigments such as C.I. Pigment Green 7, 36, 58; I. Brown pigments such as C.I. Pigment Brown 23 and 25; I. And black pigments such as CI pigment blacks 1 and 7, carbon black, titanium black, and iron oxide. These can be used alone or in combination of two or more depending on the color of the target pixel.
Note that the above dyes and pigments may be used in combination depending on the target pixel color.

  The content of the colorant (E) is preferably 5 to 60% by mass, more preferably 5 to 55% by mass, based on the sum of the components excluding the glycol ether solvent (B) in the resin composition of the present invention. More preferably, it is 10-50 mass%.

When a pigment is used as the colorant (E), a known dispersant may be blended in the resin composition from the viewpoint of improving the dispersibility of the pigment. As the dispersant, it is preferable to use a polymer dispersant excellent in dispersion stability over time. Examples of polymer dispersants include urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene glycol diester dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified esters. System dispersants and the like. As such a polymer dispersant, commercially available under trade names such as EFKA (manufactured by EFKA Chemicals Beebuy (EFKA)), Disperbyk (manufactured by BYK Chemie), Disparon (manufactured by Enomoto Kasei Co., Ltd.), SOLPERSE (manufactured by GENEKA). You may use what is done.
What is necessary is just to set suitably the compounding quantity of the dispersing agent in the resin composition of this Embodiment according to kinds, such as a pigment to be used.

  When the resin composition of this Embodiment contains a coloring agent (E), the compounding quantity of (A)-(E) component, Preferably, with respect to the sum total of the component except the solvent (B) in a resin composition. The copolymer (A) is 10 to 70% by mass, the reactive diluent (C) is 10 to 70% by mass, the colorant (E) is 5 to 60% by mass, and the solvent (B) in the resin composition. When the total of the components excluding the component is 100 parts by mass, the glycol ether solvent (B) is 30 to 1000 parts by mass, and when the total of the components (A) and (C) is 100 parts by mass, the photopolymerization initiator (D) is It is 0.1-15 mass parts, More preferably, 15-65 mass% of copolymers (A) are reactive diluents with respect to the sum total of the components except the solvent (B) in a resin composition ( C) is 15 to 65% by mass, the colorant (E) is 5 to 55% by mass, and the sum of the components excluding the solvent (B) in the resin composition is When it is 00 parts by mass, the glycol ether solvent (B) is 50 to 800 parts by mass, and when the total of the components (A) and (C) is 100 parts by mass, the photopolymerization initiator (D) is 0.5 to 10 parts by mass. More preferably, the copolymer (A) is 20 to 60% by mass and the reactive diluent (C) is 20 to 60% with respect to the sum of the components excluding the solvent (B) in the resin composition. When the total amount of components excluding the solvent (B) in the resin composition is 100 parts by mass, the glycol ether solvent (B) is 100-700 parts by mass, When the sum total of A) component and (C) component shall be 100 mass parts, a photoinitiator (D) will be 1-5 mass parts.

Even when the resin composition of the present embodiment does not contain the colorant (E), the above numerical values can be applied to the blending amounts of the components (A) to (D).
When the resin composition of the present embodiment does not contain the components (D) to (E), the blending amount of the copolymer (A), the glycol ether solvent (B) and the reactive diluent (C) The copolymer (A) is 10 to 90% by mass, the reactive diluent (C) is 10 to 90% by mass, and the solvent in the resin composition with respect to the sum of the components excluding the solvent (B) in the composition. When the total sum of the components excluding (B) is 100 parts by mass, the glycol ether solvent (B) is 30 to 1000 parts by mass, preferably with respect to the total of the components excluding the solvent (B) in the resin composition. When the total of the components excluding the solvent (B) in the resin composition is 100 parts by mass, the copolymer (A) is 20 to 80% by mass, the reactive diluent (C) is 20 to 80% by mass. The solvent (B) is 50 to 800 parts by mass, more preferably in the resin composition The copolymer (A) is 30 to 75% by mass, the reactive diluent (C) is 25 to 70% by mass, and the solvent (B) in the resin composition is based on the sum of the components excluding the solvent (B). When the total sum of the components to be removed is 100 parts by mass, the glycol ether solvent (B) is 100 to 700 parts by mass.

  In addition to the above components, the resin composition of the present embodiment may be blended with known additives such as known coupling agents, leveling agents, and thermal polymerization inhibitors in order to impart predetermined characteristics. Good. The amount of these additives is not particularly limited as long as it does not impair the effects of the present invention.

The resin composition of this Embodiment can be manufactured by mixing said component using a well-known mixing apparatus.
In addition, the resin composition of this Embodiment prepared the reactive diluent (C) and the photoinitiator (D) after preparing the resin composition containing a copolymer (A) and a solvent (B) previously. It is also possible to manufacture by mixing any colorant (E).

  The resin composition of the present embodiment containing the components (A) to (E) obtained as described above volatilizes the component (B) after coating, and after irradiating the predetermined pattern with light, By using it, development can be performed. In particular, the resin composition of the present embodiment is excellent in sensitivity and developability, and can give a colored pattern excellent in solvent resistance. Therefore, it is suitable for use as various resists, particularly resists used for manufacturing color filters incorporated in organic EL displays, liquid crystal display devices, solid-state imaging devices and the like. Moreover, since the resin composition of this Embodiment gives the cured film excellent in characteristics, such as solvent resistance, it can also be used for a various coating, an adhesive agent, a binder for printing inks, etc.

Next, a color filter prepared using the resin composition of the present invention will be described. The color filter of this invention has a coloring pattern obtained from the resin composition containing said (A)-(E) component.
Hereinafter, a color filter according to an embodiment of the present invention will be described with reference to the drawings.
FIG. 1 is a cross-sectional view of the color filter of the present embodiment. In FIG. 1, the color filter includes a substrate 1, a black matrix 3 formed on the boundary between the RGB pixels 2 and the pixels 2 formed on the substrate 1, and a protection formed on the pixels 2 and the black matrix 3. And the membrane 4. In this configuration, other configurations can be used except that at least one of the pixel 2 and the black matrix 3 (colored pattern) is formed using the above resin composition. The color filter shown in FIG. 1 is an example, and the present invention is not limited to this configuration.

Next, the manufacturing method of the color filter of one Embodiment of this invention is demonstrated.
First, a colored pattern is formed on the substrate 1. Specifically, the black matrix 3 and the pixels 2 are sequentially formed on the substrate 1. Here, the substrate 1 is not particularly limited, but a glass substrate, a silicon substrate, a polycarbonate substrate, a polyester substrate, a polyamide substrate, a polyamideimide substrate, a polyimide substrate, an aluminum substrate, a printed wiring substrate, an array substrate, or the like may be used. it can.

The coloring pattern can be formed by using photolithography. Specifically, after applying the above resin composition on the substrate 1 to form a coating film, the coating film is exposed through a photomask having a predetermined pattern, and the exposed portion is photocured. And a predetermined pattern can be formed by developing after baking an unexposed part with aqueous alkali solution, and baking.
A method for applying the resin composition is not particularly limited, and screen printing, roll coating, curtain coating, spray coating, spin coating, and the like can be used. Moreover, after application | coating of a resin composition, you may volatilize volatile components, such as a glycol ether solvent (B), by heating using heating means, such as a circulation oven, an infrared heater, and a hotplate, as needed. Good. The heating conditions are not particularly limited, and may be set as appropriate according to the type of resin composition to be used. In general, heating may be performed at a temperature of 50 ° C. to 120 ° C. for 30 seconds to 30 minutes.

The light source used for exposure is not particularly limited, and a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like can be used. Further, the exposure amount is not particularly limited, and may be appropriately adjusted according to the type of the resin composition to be used.
The aqueous alkali solution used for development is not particularly limited, but an aqueous solution of sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide, etc .; an aqueous solution of an amine compound such as ethylamine, diethylamine, dimethylethanolamine; 3 -Methyl-4-amino-N, N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β- Aqueous solutions of methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and p-phenylenediamine compounds such as sulfate, hydrochloride or p-toluenesulfonate Etc. can be used. Among these, it is preferable to use an aqueous solution of a p-phenylenediamine compound. In addition, you may add an antifoamer and surfactant to these aqueous solutions as needed. Moreover, it is preferable to wash and dry after development with the above-mentioned alkaline aqueous solution.
The baking conditions are not particularly limited, and heat treatment may be performed according to the type of resin composition to be used. In general, it may be heated at 130 to 250 ° C. for 10 to 60 minutes.

A desired coloring pattern can be formed by sequentially repeating the coating, exposure, development and baking as described above using the resin composition for the black matrix 3 and the resin composition for the pixel 2.
In addition, although the formation method of the coloring pattern by photocuring was demonstrated above, if the resin composition which mix | blended the hardening accelerator and the well-known epoxy resin was used instead of the photoinitiator (D), it will be by inkjet method. A desired coloring pattern can also be formed by heating after application.
Next, the protective film 4 is formed on the colored pattern (pixel 2 and black matrix 3). The protective film 4 is not particularly limited, and may be formed using a known film.

  The color filter manufactured in this way is manufactured using a resin composition that gives a colored pattern with excellent sensitivity and developability and excellent solvent resistance, so that a colored pattern with excellent solvent resistance can be obtained. Have.

EXAMPLES Hereinafter, although this invention is demonstrated in detail with reference to an Example, this invention is not limited by these Examples. In this example, all parts and percentages are based on mass unless otherwise specified. The acid value is the acid value of the copolymer (A) measured according to JIS K6901 5.3.2, and is used to neutralize the acidic component contained in 1 g of the copolymer (A). It means the number of mg of potassium hydroxide required. Moreover, a volatile matter is measured according to JISK6901 5.11, and means the ratio of the volatile component contained in the reaction solution at the time of a copolymer (A) synthesis | combination. Moreover, molecular weight (Mw) means the standard polystyrene conversion weight average molecular weight measured on condition of the following using gel permeation chromatography (GPC).
Column: Shodex (registered trademark) LF-804 + LF-804 (manufactured by Showa Denko KK)
Column temperature: 40 ° C
Sample: 0.2% tetrahydrofuran solution of copolymer Development solvent: Tetrahydrofuran Detector: Differential refractometer (Showex RI-71S) (manufactured by Showa Denko KK)
Flow rate: 1 mL / min

In Examples, the water content of the glycol ether solvent used in the synthesis and the reaction solution obtained by the procedure described later was measured by the Karl Fischer method under the following conditions.
Apparatus: Kyoto Electronics Industry Co., Ltd., KF moisture meter MKA-520
Injection volume: 1 mL
Titration solution: Aquamicron titrant SS3mg (manufactured by API Corporation)
Electrode solution: Aquamicron dehydrated solvent PP (manufactured by API Corporation)

  A synthesis example of the copolymer (A) of the present invention is shown below. Propylene glycol monomethyl ether is manufactured by Kyowa Hakko Chemical Co., Ltd., methacrylic acid is manufactured by Kuraray Co., Ltd., glycidyl methacrylate and t-butylperoxy-2-ethylhexanoate are manufactured by Nippon Oil & Fats Co., Ltd., diethylene glycol diethyl ether and triethylene Glycol dimethyl ether was manufactured by Nippon Emulsifier Co., Ltd., n-butanol was manufactured by Nacalai Tesque Co., Ltd., ethylene glycol was manufactured by Wako Pure Chemical Industries, Ltd., and propylene glycol was manufactured by Asahi Glass Co., Ltd.

<Example 1>
Into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 157.7 parts by mass of propylene glycol monomethyl ether was added, stirred while purging with nitrogen, and heated to 108 ° C. Next, 15 parts by mass of a monomer mixture composed of 20.6 parts by mass (0.24 mol) of methacrylic acid (a-1) and 79.5 parts by mass (0.56 mol) of glycidyl methacrylate (a-2) What added t-butylperoxy-2-ethylhexanoate (polymerization initiator) was dripped in the said flask from the dropping funnel. After completion of dropping, the mixture was stirred at 130 ° C. for 2 hours to conduct a copolymerization reaction. 1 (solid content acid value 120 mgKOH / g, weight average molecular weight 8000) was obtained. In addition, the mass part number of a polymerization initiator is a value when the sum total of a monomer is 100 mass parts.

As shown in Table 1, sample No. 1 was changed in the same manner as in Example 1 except that the type of solvent and the monomer ratio were changed. 2 to 7 reaction solutions were obtained. The solvent used in Comparative Example 1 was prepared by adding water to PGME and adjusting the water content to 1.24% by mass. Moreover, the water content based on the quantity of the copolymer (A) was calculated | required from the following formula on the assumption that the non volatile matter in a reaction solution consists of a copolymer (A). The results are shown in Table 1.
Water content (mass%) = a ÷ (100−b) × 100 based on the amount of copolymer (A)
a: Moisture content (% by mass) of the reaction solution
b: Volatile content of reaction solution (mass%)

  The obtained sample No. Using the reaction solutions 1 to 7, a resin composition (pigment type) and a resin composition (dye type) were prepared according to the following method.

<Preparation of resin composition (pigment type)>
In a stainless steel container filled with 180 parts by mass of zirconia beads having a diameter of 0.5 mm, as a coloring agent (E), C.I. 10 parts by weight of I Pigment Green 36, 33.75 parts by weight of propylene glycol monomethyl ether acetate, and 6.25 parts by weight of a dispersant (Disperbyk-161 manufactured by Big Chemie Japan Co., Ltd.) are charged and mixed for 3 hours in a paint shaker. And a green pigment dispersion was prepared.
Using this green pigment dispersion, the other ingredients shown in Table 2 (that is, copolymer (A), glycol ether solvent (B), reactive diluent (C) and photopolymerization initiator (D)). And a resin composition was prepared. The blending ratio of each component is as shown in Table 2. In addition, the amount of the copolymer (A) in Table 2 does not include a solvent, and the amount of the glycol ether solvent (B) in Table 2 is propylene glycol monomethyl ether additionally blended with the solvent contained in the reaction solution. And the sum. Here, the water content of propylene glycol monomethyl ether, which is an additionally blended glycol ether solvent (B), is 0.08% by mass, and the water content of trimethylolpropane acrylate, which is a reactive diluent (C), is 0.38. It was mass%.

<Evaluation of color resist>
The performance when using the resin composition (pigment type) in Table 2 as a color resist was evaluated as follows.
(1) Pattern formation by color resist After spin coating the prepared resin composition (pigment type) on a 5 cm square glass substrate (non-alkali glass substrate) so that the thickness after exposure is 2.5 μm. The solvent was volatilized by heating at 90 ° C. for 3 minutes. Next, a photomask having a predetermined pattern was disposed at a distance of 100 μm from the coating film, and the coating film was exposed (exposure amount 150 mJ / cm ² ) through this photomask, and the exposed portion was photocured. Next, an unexposed part was dissolved and developed by spraying an aqueous solution containing 0.1% by mass of sodium carbonate at a temperature of 23 ° C. and a pressure of 0.3 MPa, and then baked at 230 ° C. for 30 minutes. A predetermined pattern was formed.

(2) Evaluation of pattern formed from color resist About the pattern formed as mentioned above, alkali developability and sensitivity were evaluated as follows.
(2-1) Alkali developability Alkali developability was confirmed by the residue after alkali development and the development form. The residue after alkali development was confirmed by observing the pattern after alkali development using an electron microscope S-3400 manufactured by Hitachi High-Technologies Corporation. The criteria for this evaluation are as follows.
○: No residue ×: Residue (2-2) Sensitivity Alkali development using the above-mentioned spray is performed for 30 seconds. The quality of the sensitivity was determined by measuring at. It can be said that the smaller the reduction amount of the pattern thickness is, the more specifically, the sensitivity is better when the reduction amount is less than 0.20 μm.

(2-3) Evaluation of solvent resistance The solvent resistance of N-methyl-2-pyrrolidone generally used in the color filter protective film forming step was evaluated.
The prepared resin composition was spin-coated on a 5 cm square glass substrate (non-alkali glass substrate) so that the thickness after baking was 2.5 μm, and then heated at 90 ° C. for 3 minutes to volatilize the solvent. I let you. Next, the coating film was exposed to light having a wavelength of 365 nm, the exposed portion was photocured, and then left in a drier at a baking temperature of 230 ° C. for 30 minutes to prepare a cured coating film. 200 mL of N-methyl-2-pyrrolidone was placed in a glass bottle with a cap having a capacity of 500 mL, the test piece with the cured coating film was immersed therein, and then allowed to stand for 30 minutes while being maintained at 23 ° C. The color change (ΔE ^* ab) of the test piece before and after immersion in N-methyl-2-pyrrolidone was measured with a spectrophotometer UV-1650PC (manufactured by Shimadzu Corporation). When the value of ΔE ^* ab before and after immersion is 3.0 or less, it can be said that the cured film has good solvent resistance. The results are shown in Table 3. Further, the water content based on the amount of the copolymer (A) was determined from the following formula. Here, it was assumed that no water was contained in the photopolymerization initiator (D) and the colorant (E).
Water content (mass%) = (c + d + e) ÷ f × 100 based on the amount of copolymer (A)
c: Water content (parts by mass) contained in the reaction solution
d: Water content (parts by mass) contained in propylene glycol monomethyl ether added additionally
e: Water content (parts by mass) contained in the reactive diluent (C)
f: Amount of copolymer (A) (parts by mass)

Furthermore, considering the blending ratios in Table 2, cf are expressed as follows.
c = (2.8 ÷ (1-b ÷ 100)) × (a ÷ 100)
d = (45.8-2.8 × b ÷ (100−b)) × 0.0008
e = 5.7 × 0.0038 = 0.02166
f = 2.8

  As can be seen from the results in Table 3, the color resists (Examples 7 to 12) using the reaction solutions (resin compositions) obtained in Examples 1 to 6 have good alkali developability and sensitivity, Whereas a pattern having excellent solvent properties was given, the color resist using the reaction solution obtained in Comparative Example 1 (Comparative Example 2) was not sufficient in solvent resistance and sensitivity was not sufficient.

<Preparation of resin composition (dye type)>
According to the blending components and blending ratios shown in Table 4, a resin composition (dye type) containing a dye (VALIFAST BLUE 2620) as a colorant (E) was prepared. In addition, the amount of the copolymer (A) in Table 4 does not include a solvent, and the amount of the glycol ether solvent (B) in Table 4 is propylene glycol monomethyl ether additionally blended with the solvent contained in the reaction solution. And the sum. Here, the water content of propylene glycol monomethyl ether, which is an additionally blended glycol ether solvent (B), is 0.08% by mass, and the water content of trimethylolpropane acrylate, which is a reactive diluent (C), is 0.38. It was mass%.

<Evaluation of color resist>
The performance when using the obtained resin composition (dye type) as a color resist was evaluated by the same method as that for the resin composition (pigment type). However, in the case of a dye type, when the value of ΔE ^* ab before and after immersion is 4.5 or less, it can be said that the cured film has good solvent resistance. The results are shown in Table 5. Further, the water content based on the amount of the copolymer (A) was determined from the following formula. Here, it was assumed that no water was contained in the photopolymerization initiator (D) and the colorant (E).
Water content based on the amount of the copolymer (A) (% by mass) = (c ′ + d ′ + e ′) ÷ f ′ × 100
c ′: Water content (part by mass) contained in the reaction solution
d ': Water content (parts by mass) contained in propylene glycol monomethyl ether added additionally
e ′: Water content (parts by mass) contained in the reactive diluent (C)
f ′: amount of copolymer (A) (parts by mass)

Furthermore, considering the blending ratios in Table 4, c ′ to f ′ are expressed as follows.
c ′ = (16.0 ÷ (1−b ÷ 100)) × (a ÷ 100)
d ′ = (55.8-16.0 × b ÷ (100−b)) × 0.0008
e ′ = 19.2 × 0.0038 = 0.07296
f ′ = 16.0

  As can be seen from the results in Table 5, the color resists (Examples 13 to 18) using the reaction solutions (resin compositions) obtained in Examples 1 to 6 have good alkali developability and sensitivity, Whereas a pattern having excellent solvent properties was provided, the color resist (Comparative Example 3) using the reaction solution obtained in Comparative Example 1 was not sufficient in solvent resistance and sensitivity was not sufficient.

  As can be seen from the above results, according to the present invention, it is possible to provide a resin composition capable of forming a cured coating film having good sensitivity and developability and sufficient solvent resistance. Therefore, the resin composition of the present invention is suitable as a color filter resist. Furthermore, by using the resin composition of the present invention, a highly reliable color filter having a colored pattern excellent in solvent resistance can be obtained.

  1 substrate, 2 pixels, 3 black matrix, 4 protective film.

Claims (11)

A copolymer (A) containing a polymerizable monomer (a-1) having an acid group and a polymerizable monomer (a-2) having an epoxy group as constituent monomers;
A resin composition containing a glycol ether solvent (B) represented by the following chemical formula (1):
The resin composition characterized in that the moisture contained in the resin composition is 3.5% by mass or less based on the amount of the copolymer (A).

(In Formula (1), R ¹ represents an alkyl group having 1 to 8 carbon atoms, an allyl group, a phenyl group, or a benzyl group, R ² represents a hydrogen atom or a methyl group, R ³ represents a hydrogen atom, and 1 carbon atom. Represents an alkyl group or an acetoxy group of -4, and n is an integer of 1-10.)   The resin composition according to claim 1, wherein the polymerizable monomer (a-1) is a carboxyl group-containing ethylenically unsaturated compound.   The resin composition according to claim 1, wherein the polymerizable monomer (a-2) is an epoxy group-containing (meth) acrylate. Formula (1), R ¹ is an alkyl group having 1 to 8 carbon atoms, resin composition according to any one of claims 1 to 3 R ³ is an alkyl group having 1 to 4 hydrogen atoms or carbon atoms object.   The resin composition according to any one of claims 1 to 4, wherein the copolymer (A) has a weight average molecular weight of 1,000 to 50,000 and an acid value of 20 to 300 KOHmg / g.   The copolymer (A) contains 10 to 50 mol% of the polymerizable monomer (a-1) and 30 to 90 mol% of the polymerizable monomer (a-2) as constituent monomers. The resin composition in any one.   The resin composition according to any one of claims 1 to 6, further comprising a reactive diluent (C), a photopolymerization initiator (D), and a colorant (E).   The resin composition according to claim 7, wherein the colorant (E) is at least one selected from the group consisting of a dye and a pigment.   A color filter having a colored pattern formed from the resin composition according to claim 7 or 8.   An image display device comprising the color filter according to claim 9. The presence of a glycol ether solvent (B) represented by the following chemical formula (1), a polymerizable monomer containing a polymerizable monomer (a-1) having an acid group and a polymerizable monomer (a-2) having an epoxy group A process for producing a resin composition comprising a step of obtaining a copolymer (A) containing a polymerizable monomer (a-1) and a polymerizable monomer (a-2) as constituent monomers by copolymerization under the following conditions:
Based on the water content of the glycol ether solvent (B), the glycol ether solvent so that the water content in the resin composition is 3.5% by mass or less based on the amount of the copolymer (A). The manufacturing method of the resin composition characterized by determining the usage-amount of (B).

(In Formula (1), R ¹ represents an alkyl group having 1 to 8 carbon atoms, an allyl group, a phenyl group, or a benzyl group, R ² represents a hydrogen atom or a methyl group, R ³ represents a hydrogen atom, and 1 carbon atom. Represents an alkyl group or an acetoxy group of -4, and n is an integer of 1-10.)

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