TWI600970B - Resin composition, color filter, production method of color filter, and image display element - Google Patents

Description

Resin composition, color filter, manufacturing method thereof and image display element

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

The color filter is generally a transparent substrate such as a glass substrate; red (R), green (G), and blue (B) pixels formed on the transparent substrate; and a black matrix formed at the boundary of the pixels (BM) ); and a protective film formed on the pixels and the 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. As a method of forming a pixel and a black matrix (hereinafter referred to as a "coloring pattern" for a pixel and a black matrix), various methods have been proposed, and a photosensitive resin composition is used as a photoresist to be repeatedly coated. The pigment/dye dispersion method made by the light lithography method of cloth, exposure, development and baking is currently the mainstream.

In general, photosensitive resin used in photolithography The composition contains an alkali-soluble resin, a reactive diluent, a photopolymerization initiator, a colorant, and a solvent. The pigment/dye dispersion method is advantageous in that it has excellent durability such as light resistance and heat resistance, and a coloring pattern having few defects such as pinholes, but conversely, a black matrix, R, and G are repeatedly formed. The pattern of B, or the protective film, therefore requires high solvent resistance for the hard coat film.

Here, there has been proposed a method of improving solvent resistance by using a copolymer having an epoxy group or an oxetanyl group and a carboxyl group or a phenolic hydroxyl group (Patent Documents 1 and 2); or As a polymerization initiator, a method of improving solvent resistance by using a polymerization initiator having a oxadiazole structure or a triazine structure containing a trihalomethyl group in a molecule is used (Patent Document 3).

Further, in order to enhance the color reproduction characteristics of the color filter, it is necessary to prepare a coloring agent having a large amount of the coloring agent, or to increase the thickness of the film, and the like, and these tend to cause problems such as lowering the sensitivity and lowering the developability. Further improvement in performance is required (Patent Document 4).

[Previous Technical Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2012-22048

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2013-25203

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2003-330184

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2014-164021

However, the conventional photosensitive resin composition has a case where the sensitivity or developability is insufficient, or a cured coating film having excellent solvent resistance cannot be obtained.

In view of the above, it is an object of the present invention to provide a resin composition which can provide a cured coating film which is excellent in sensitivity and developability and which is excellent in solvent resistance. Moreover, the present invention has an object of providing a color filter having a color pattern formed of a cured coating film excellent in solvent resistance.

That is, the present invention is as shown in the following [1] to [14].

[1] A resin composition comprising: an epoxy group and an acid group-containing resin (A); a hydroxyl group-containing polyfunctional (meth) acrylate polybasic acid monoester (B); and a solvent (C) It is characterized in that the epoxy group is 0.5 to 3.0 mole with respect to the acid group 1 mol in the epoxy group- and acid group-containing resin (A).

[2] The resin composition of the above-mentioned [1], wherein the constituent monomer unit of the epoxy group and the acid group-containing resin (A) contains an ethylenic carbon-carbon double bond derived from one molecule. A monomer unit of the monomer (a-1) with an epoxy group.

[3] The resin composition according to the above [1] or [2], wherein the constituent monomer unit containing the epoxy group and the acid group-containing resin (A) is contained A monomer unit derived from an unsaturated carboxylic acid (a-2).

[4] The resin composition according to the above [3], wherein the epoxy group-containing acid group-containing resin (A) contains a part of a carboxyl group derived from the unsaturated carboxylic acid (a-2). a constituent monomer unit having an ethylenic carbon-carbon double bond which is added to the monomer (a-3), and the monomer (a-3) has a functional group capable of reacting with a carboxyl group and ethylene in one molecule. Carbon-carbon double bond.

[5] The resin composition according to the above [2], wherein the monomer (a-1) having an ethylenic carbon-carbon double bond and an epoxy group in the above molecule contains an epoxy group (meth) Acrylate.

[6] The resin composition according to the above [4], wherein the monomer (a-3) having a functional group capable of reacting with a carboxyl group and an ethylenic carbon-carbon double bond in the above molecule is selected from the group consisting of an epoxy group. One or two or more kinds of the (meth) acrylate and the (meth) acrylate containing an isocyanate group.

The resin composition of any one of the above-mentioned [1] to [6], wherein the polyfunctional (meth) acrylate polybasic acid monoester (B) containing a hydroxyl group is selected from dipentaerythritol or One or more selected from the group consisting of polybasic monoesters of tris(meth)acrylate and polybasic monoesters of di, tri, tetra or penta(meth)acrylate of dipentaerythritol.

[8] The resin composition according to any one of the above [1] to [7] wherein the epoxy group and the acid group-containing resin (A) have an acid value of 10 to 350 mgKOH/g.

[9] The resin composition according to any one of the above [1] to [8], further comprising a photopolymerization initiator (D).

[10] The resin composition according to any one of the above [1] to [9] wherein Further, a coloring agent (E) is contained.

[11] The resin composition according to the above [10], wherein the coloring agent (E) is at least one selected from the group consisting of a dye and a pigment.

[12] A color filter comprising a coloring pattern formed of a cured coating film of the resin composition of the above [10] or [11].

[13] An image display element comprising the color filter of the above [12].

[14] A method of producing a color filter, comprising: coating, exposing, and developing a resin composition of the above [10] or [11] on a substrate; Baking at a temperature of 215 ° C or less to form a color pattern.

According to the present invention, it is possible to provide a resin composition capable of forming a cured coating film which is excellent in sensitivity or developability and excellent in solvent resistance. Further, since the cured coating film formed in the state after exposure and before baking by the resin composition of the present invention has developability, it is highly valuable in various photoresist fields, and particularly in a state after baking. Since the hardened coating film is excellent in solvent resistance, it is advantageous in forming a color pattern of a color filter.

[Simple description of the diagram]

Fig. 1 is a cross-sectional view showing a color filter according to an embodiment of the present invention.

[Best Practice for Carrying Out the Invention]

The resin composition of the present invention contains: an epoxy group and an acid group-containing resin (A); a hydroxyl group-containing polyfunctional (meth) acrylate polybasic acid monoester (B); and a solvent (C), which are characterized The epoxy group is 0.5 to 3.0 mols with respect to the acid group 1 mol in the epoxy group- and acid group-containing resin (A).

In the present invention, "(meth) acrylate" means at least one selected from the group consisting of methacrylate and acrylate. The same is true for "(meth)acrylic acid".

The epoxy group-containing acid group-containing resin (A) used in the present invention has an epoxy group and an acid group in the resin, and has an epoxy group of 0.5 to the acid group 1 in the resin. 3.0 Moore can be, not particularly limited. The acid group is not particularly limited, and a carboxyl group (-COOH), a phosphate group (-PO(OH) ₂ ), a sulfonic acid group (-SO ₃ H) or the like can be generally exemplified. From the viewpoint of the curability of the resin composition of the present invention, a carboxyl group is preferred. The ease of obtaining the raw material, the ease of production of the epoxy group-containing and acid group-containing resin (A), and the improvement of the solvent resistance when the resin composition of the present invention is cured are contained as a constituent monomer unit. A resin derived from a monomer unit of a monomer (a-1) having an ethylenic carbon-carbon double bond and an epoxy group in one molecule is preferable; as a constituent monomer unit, from the viewpoint of developability A resin containing a monomer unit derived from the unsaturated carboxylic acid (a-2) is further preferred. Further, when the number of constituent monomers of the epoxy group and the acid group-containing resin (A) is 1 mole of the epoxy group, it can be known that the type of the monomer is a molar ratio. More than to calculate. When the number of moles of the epoxy group based on the acid group 1 mol is calculated from the synthesized epoxy group- and acid group-containing resin (A), the epoxy equivalent weight measured according to JIS K 7236 and Calculated based on the value of the acid value measured by JIS K 0070.

The monomer (a-1) is preferably an epoxy group-containing (meth) acrylate from the viewpoint of easiness of production of the epoxy group and the acid group-containing resin (A). Specific examples of the monomer (a-1) include glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate having an alicyclic epoxy group, and a lactone thereof. Adducts (for example, Cyclomer (registered trademark) A200, M100 manufactured by DAICEL, 3,4-epoxycyclohexylmethyl-3', 4'-epoxycyclohexanecarboxylate (methyl) An epoxide such as an acrylate, a dicyclopentenyl (meth)acrylate, or an epoxide of dicyclopentenyloxyethyl (meth)acrylate. Among these, in particular, glycidyl (meth)acrylate is preferred from the viewpoint of ease of availability and reactivity.

Specific examples of the unsaturated carboxylic acid (a-2) include (meth)acrylic acid, crotonic acid, cinnamic acid, itaconic acid, maleic acid, fumaric acid, vinylsulfonic acid, and 2-(methyl group). Propylene methoxyethyl succinic acid, 2-propenyl methoxyethyl phthalic acid, 2-(methyl) propylene methoxyethyl hexahydrophthalic acid, and the like. From the viewpoint of obtaining raw materials, (meth)acrylic acid and crotonic acid are preferred, and (meth)acrylic acid is further preferred.

The epoxy group-containing acid group-containing resin (A) used in the present invention may contain, as a constituent monomer unit, free of monomers other than the monomer (a-1) and the unsaturated carboxylic acid (a-2). The monomer unit of the monomer polymerized. Specific examples of the radically polymerizable monomer other than the monomer (a-1) and the unsaturated carboxylic acid (a-2) include 2-(meth)acryloxyethyl acid phosphate and butyl. a diene such as a diene; methyl (meth)acrylate, isopropyl (meth)acrylate, amyl (meth)acrylate, benzyl (meth)acrylate, isoamyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, cyclohexyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, ( Methyl) rosin ester, decyl (meth) acrylate, allyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 1,1,1-trifluoroethyl (meth) acrylate , (fluoro)ethyl (meth)acrylate, triphenylmethyl (meth)acrylate, isophenylpropyl (meth)acrylate, 3-(N,N-dimethylamino)(methyl) Propyl acrylate, glycerol mono(meth) acrylate, glutol mono(meth) acrylate, dicyclopentanyl (meth) acrylate, isodecyl (meth) acrylate, gold (meth) acrylate Alkyl ester, naphthalene (meth) acrylate, etc. (meth) acrylates; decene (double Ring [2.2.1]hept-2-ene), 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[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 ]癸-8-ene, tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 .0 ^1,6 ]dodec-3-ene, pentacyclic [6.5.1.1 ^3,6 .0 ^2,7 .0 ^9,13 ] fifteen-4-ene, 5-northene-2 -carboxylic acid, 5-northene-2,3-dicarboxylic anhydride, decyl (meth) acrylate, N,N-diethyl decyl (meth) acrylate, decyl decyl (meth) acrylate And (meth)acrylic acid morpholine, diacetone (meth) acrylamide, etc. (meth)acrylic acid decylamine, (meth) acrylamide benzene, (meth) acrylonitrile, acrolein, Vinyl compounds such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinyl pyrrolidone, vinyl pyridine, vinyl acetate, vinyl toluene, etc. α-, o of styrene and styrene -, m-, p-alkyl, nitro, cyano, decylamine derivatives; unsaturated dicarboxylic acid diesters such as diethyl citrate, diethyl maleate; N-phenyl Malay Single horse, such as quinone imine, N-cyclohexylmaleimide, etc. Imines; maleic anhydride, itaconic anhydride and the like unsaturated polybasic acid anhydride. These may be used alone or in combination of two or more. Further, in the viewpoints of heat resistance or transparency, benzyl (meth)acrylate, dicyclopentanyl (meth)acrylate, styrene, vinyltoluene, isodecyl (meth)acrylate Ester, adamantyl (meth) acrylate, norbornene, N-isopropyl (meth) acrylamide, (meth) propylene morpholine, and diacetone (meth) acrylamide Preferably, benzyl (meth) acrylate, dicyclopentanyl (meth) acrylate, styrene, vinyl toluene, isodecyl (meth) acrylate, adamantyl (meth) acrylate, and Terpenes are also preferred.

The proportion of the monomer (a-1) is not particularly limited as long as it is 0.5 to 3.0 moles per 1 mole of the acid group in the resin (A) containing the epoxy group and the acid group. The total of the constituent monomers of the resin (A) containing an epoxy group and an acid group is preferably 40 to 90 mol%, more preferably 50 to 90 mol%, still more preferably 60 to 80 mol. ear%. When the compounding ratio of the monomer (a-1) is 40 to 90 mol%, the developability is good, and sufficient solvent resistance can be obtained.

The proportion of the unsaturated carboxylic acid (a-2), as long as it is relative The acid group 1 mole in the epoxy group- and acid group-containing resin (A) is not particularly limited as long as it has an epoxy group of 0.5 to 3.0 mol, and is equivalent to a resin containing an epoxy group and an acid group (A). The total of the constituent monomers is preferably from 10 to 60 mol%, more preferably from 10 to 50 mol%, still more preferably from 20 to 40 mol%. The blending ratio of the unsaturated carboxylic acid (a-2) is from 10 to 60 mol%, and the developability is good, and sufficient solvent resistance can be obtained.

When a radically polymerizable monomer other than the monomer (a-1) and the unsaturated carboxylic acid (a-2) is used, the ratio of the compounding is not particularly limited with respect to the resin containing an epoxy group and an acid group. The total of the constituent monomers of (A) is preferably 0 mol% or more and 50 mol% or less, and more preferably 0 mol% or more and more than 40 mol%.

The total of the constituent monomer units of the epoxy (A) group containing the epoxy group and the acid group is 40 to 90 mol%, and the unsaturated carboxyl group is derived from the monomer unit derived from the monomer (a-1). The monomer unit of the acid (a-2) preferably contains 10 to 60 mol%; the monomer unit derived from the monomer (a-1) contains 60 to 80 mol%, and is derived from the unsaturated carboxyl group. The monomer unit of the acid (a-2) is preferably 20 to 40 mol%.

The copolymerization reaction for producing the epoxy group- and acid group-containing resin (A) can be carried out in accordance with a radical polymerization method well known in the art. For example, a monomer (a-1), an unsaturated carboxylic acid (a-2), and a radically polymerizable monomer other than the monomer (a-1) and the unsaturated carboxylic acid (a-2) (optional) After the component is dissolved in a solvent, a polymerization initiator is added to the solution, and the reaction is carried out at 50 to 130 ° C for 1 to 20 hours. By this copolymerization reaction, a ratio of the blending ratio with the monomer can be obtained. A random copolymer of equivalent monomer unit ratio.

Examples of the solvent which can be used in the copolymerization reaction include ethylene glycol monomethyl ether, triethylene glycol monomethyl ether, polyethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and diethyl ether. Glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene 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, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether acetate, ethylene glycol dimethyl ether , diethylene glycol methyl ethyl ether, and dipropylene glycol dimethyl ether. These may be used alone or in combination of two or more.

The water content of the solvent is not particularly limited, and is preferably 1% by mass or less. When the water content is 1% by mass or less, an epoxy group-containing acid group-containing resin (A) having more excellent solvent resistance can be obtained. Further, the moisture content of the solvent is measured by the Karl-Fisher method under the following conditions.

Device: Kyoto Electronics Industry Co., Ltd., KF moisture meter MKA-520

Injection amount: 1mL

Titration solution: AQUAMICRON (registered trademark) titrant SS3mg (manufactured by API Corporation)

Electrode solution: AQUAMICRON (registered trademark) dehydration solvent PP (manufactured by API Corporation)

The amount of the solvent to be used in the production of the epoxy group and the acid group-containing resin (A) is not particularly limited, and when the total of the constituent monomers of the epoxy group and the acid group-containing resin (A) is 100 parts by mass. , preferably 30 to 1000 parts by mass, preferably 50 to 800 parts by mass. In particular, by setting the amount of the solvent to be 1000 parts by mass or less, it is possible to suppress not only the molecular weight of the epoxy group-containing acid group-containing resin (A) due to chain transfer but also the epoxy group and The viscosity of the acid-based resin (A) is controlled within an appropriate range. In addition, by setting the amount of the solvent to 30 parts by mass or more, the polymerization reaction can be stabilized without preventing an abnormal polymerization reaction, and the coloring of the epoxy group- or acid group-containing resin (A) can be prevented or Gelatinized.

The polymerization initiator which can be used for the production of the epoxy group and the acid group-containing resin (A) is not particularly limited, and examples thereof include azobisisobutyronitrile, azobisisovaleronitrile, and benzoyl peroxide. , t-butylperoxy-2-ethylhexanoate, and the like. These may be used alone or in combination of two or more.

When the total amount of the constituent monomers of the epoxy group and the acid group-containing resin (A) is 100 parts by mass, it is preferably 0.5 to 20 parts by mass, and more preferably 1.0%. 10 parts by mass.

In addition, a monomer (a-1), an unsaturated carboxylic acid (a-2), and an optional component other than the monomer (a-1) and the unsaturated carboxylic acid (a-2) are used without using an organic solvent. The radical polymerization monomer and the polymerization initiator may be used for the bulk polymerization.

An epoxy carbon-carbon double bond can be further introduced to the epoxy group-containing acid group-containing resin (A) obtained by the above copolymerization reaction. Thereby, the sensitivity or developability of the resin composition will be improved.

For example, a part of the carboxyl group derived from the unsaturated carboxylic acid (a-2) constituting the epoxy group and the acid group-containing resin (A) and the monomer (a-3) are added. The ethylene carbon-carbon double bond may be introduced, and the monomer (a-3) has a functional group reactive with a carboxyl group in one molecule, and an ethylenic carbon-carbon double bond. Thus, the epoxy group and the acid group-containing resin (A) have a portion obtained by adding a part of a carboxyl group derived from the unsaturated carboxylic acid (a-2) to the monomer (a-3). The monomer unit of the ethylenic carbon-carbon double bond, which has a functional group capable of reacting with a carboxyl group and an ethylenic carbon-carbon double bond in one molecule. Examples of the functional group reactive with a carboxyl group include an isocyanate group, an epoxy group, a vinyl ether group and the like. Among them, an isocyanate group is preferred from the viewpoint of reactivity in the addition reaction. The monomer (a-3) having an epoxy group can be used in the same manner as the monomer (a-1). Further, the monomer (a-3) having an isocyanate group is not particularly limited, and a (meth) acrylate having an isocyanate group is preferable. Specifically, 2-(meth)acryloxyloxy group is exemplified. Ethyl isocyanate, 1,1-(bis(meth)acryloxymethyl)ethyl isocyanate, 2-(isocyanateethyloxy)ethyl (meth)acrylate, and the like. Among these, a monomer having an isocyanate and an ethylenic carbon-carbon double bond in one molecule is preferred, and 2-(meth)acryloxyethyl isocyanate is more preferred. The monomer (a-3) having a vinyl ether group is not particularly limited, and a vinyl ether (meth) acrylate is preferable. Specifically, 2-(2-ethylene) (meth) acrylate can be exemplified. Gethoxyethoxy)ethyl ester and the like.

Further, when the resin (A) containing an epoxy group and an acid group contains an acid anhydride group, a monomer having a functional group capable of reacting with an acid anhydride group and an ethylenic carbon-carbon double bond in one molecule is added and then introduced into ethylene. Carbon-carbon double bonds are also available. As the functional group reactive with the acid anhydride group, a hydroxyl group can be exemplified.

A reaction in which a carboxyl group, an epoxy group or an acid anhydride group in a resin (A) containing an epoxy group and an acid group, and a monomer having a reactive functional group are added to introduce a carbon-carbon double bond, and is added and contained. The epoxy group and the acid group-containing resin (A)-added monomer, polymerization inhibitor, and catalyst are preferably reacted at 50 to 150 ° C, preferably 80 to 130 ° C. Further, in the addition reaction, even if the solvent used in the above copolymerization reaction is not particularly problematic, the addition reaction can be carried out without removing the solvent after completion of the copolymerization reaction.

Here, a polymerization inhibitor may be added in order to prevent gelation by polymerization of the epoxy group and the acid group-containing resin (A). The polymerization inhibitor is not particularly limited, and examples thereof include hydroquinone, methylhydroquinone, and hydroquinone monomethyl ether. Further, the catalyst is not particularly limited, and examples thereof include a third-order amine such as triethylamine, a fourth-order ammonium salt such as triethylbenzylammonium chloride, and a phosphorus such as triphenylphosphine. a compound, a chelating compound of chromium, and the like.

The acid value (JIS K6901: 2008 5.3.2) of the epoxy group-containing acid group-containing resin (A) used in the present invention is not limited, and when used in a color filter, it is preferably 10 to 350 mgKOH/ g is preferably from 30 to 200 mgKOH/g, more preferably from 50 to 180 mgKOH/g, and particularly preferably from 70 to 150 mgKOH/g. When the acid value is 10 mgKOH/g or more, sufficient developability can be obtained. On the other hand, when the acid value is 350 mgKOH/g or less, the exposed portion (photohardenable portion) will not dissolve in the alkali developing solution, and sufficient developability can be obtained.

Further, the molecular weight of the resin (A) containing an epoxy group and an acid group (in terms of polystyrene measured by gel permeation chromatography (GPC) described later) The weight average molecular weight) is preferably from 1,000 to 50,000, and more preferably from 3,000 to 40,000. When the molecular weight is 1,000 or more, no defect of the coloring pattern occurs after development, and good sensitivity can be obtained. On the other hand, when the molecular weight is 50,000 or less, the development time is extremely short and practical.

Further, when the epoxy group and the acid group-containing resin (A) have an unsaturated group, the unsaturated group equivalent is not particularly limited, and is preferably from 100 to 4,000 g/mol, more preferably from 200 to 3,000 g/mol. When the unsaturated group equivalent is 100 g/mol or more, it is effective in further improving thermal decomposition resistance and heat yellowing resistance. On the other hand, when the unsaturated group equivalent is 4000 g/mol or less, it is effective in further improving the sensitivity.

The resin composition of the present invention contains a polyhydric acid monoester (B) having a polyfunctional (meth) acrylate having a hydroxyl group. Examples of the polybasic acid monoester (B) containing a hydroxyl group-containing polyfunctional (meth) acrylate include a polybasic acid monoester of di- or tri(meth)acrylate of pentaerythritol, and two, three, or four of dipentaerythritol. A polybasic acid monoester of penta (meth) acrylate, specifically, for dipentaerythritol pentaacrylate succinic acid modification, pentaerythritol triacrylate succinic acid modification, dipentaerythritol pentaacrylate phthalic acid A polybasic acid modified product obtained by modifying a hydroxy group-forming anhydride of a hydroxyl group-containing polyfunctional (meth) acrylate such as a dicarboxylic acid modified product or a pentaerythritol triacrylate phthalic acid modified product. These may be used alone or in combination of two or more. Among these, from the viewpoint of solvent resistance, succinic acid modification with a polyfunctional (meth) acrylate containing a hydroxyl group The object is preferred.

The compounding amount of the polyfunctional (meth) acrylate polybasic acid monoester (B) having a hydroxyl group is preferably from 10 to 90% by mass, more preferably from 10 to 90% by mass based on the total of the components (A) and (B). 20 to 80% by mass, more preferably 25 to 70% by mass. As long as it is a compounding amount in this range, it will become a resin composition which has a suitable viscosity, and it has suitable photocurability by mixing the photopolymerization initiator (D) mentioned later.

The resin composition of the present invention contains a solvent (C). The solvent (C) is a polybasic acid monoester (B) which can dissolve the "epoxy group and acid group-containing resin (A)" and the "hydroxy group-containing polyfunctional (meth) acrylate", and does not The inert solvent of the reaction is not particularly limited.

The solvent (C) can be used in the same manner as the solvent used for the copolymerization reaction for producing the epoxy group and the acid group-containing resin (A), and can be used as it is in the solvent after the copolymerization reaction. Further, a solvent may be added in the preparation of the resin composition of the present invention. Alternatively, when adding other components described later, a solvent which coexists with the components may be used as it is. Specific examples of the solvent (C) include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, isopropyl acetate, and Propylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethylene glycol Monoethyl ether acetate, diethylene glycol monoethyl ether acetate, and the like. These may be used alone or in combination of two or more. Moreover, among these, a resin containing an epoxy group and an acid group is produced. A glycol ether solvent such as propylene glycol monomethyl ether or propylene glycol monomethyl ether acetate used in the copolymerization reaction at the time of (A) is preferred.

When the total amount of the solvent (C) in the resin composition of the present invention is 100 parts by mass, it is preferably 30 to 1000 parts by mass, and more preferably 50 to 800. The mass fraction is more preferably 100 to 700 parts by mass. As long as it is a blending amount in this range, it will become a resin composition having an appropriate viscosity.

When the resin composition of the present invention is used in the formation of a color pattern of a color filter, the photopolymerization initiator (D) and the color former (E) are further used.

The photopolymerization initiator (D) is not particularly limited, and examples thereof include benzoin such as benzoin and benzoin methyl ether, and the alkyl ethers; acetophenone and 2,2-dimethoxy-2-phenyl group; Acetophenones such as acetophenone, 1,1-dichloroacetophenone, 4-(1-t-butyldioxy-1-methylethyl)acetophenone; 1-hydroxycyclohexylbenzene Phenyl ketones such as ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one; 2-methylindole, 2-pentylindole, 2-t-butylindole Anthraquinones such as hydrazine and 1-chloroindole; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone and 2-chlorothioxanthone; benzene a ketal such as ethyl ketone dimethyl ketal or benzyl dimethyl ketal; diphenyl ketone, 4-(1-t-butyldioxy-1-methylethyl) diphenyl ketone Diphenyl ketones such as 3,3',4,4'-fluorene (t-butyldioxycarbonyl)diphenyl ketone; 1,2-octanedione, 1-[4-(phenylsulfonate) Base, -, 2-(O-benzhydrazide), ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]- , an oxime ester such as 1-(0-acetamidine); 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-propane-1- Ketone; 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butanone-1; 2,4,6-trimethylbenzimidyldiphenylphosphine oxide And mercaptophosphine oxides such as bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide; and xanthone. These may be used alone or in combination of two or more.

When the total amount of the component (A) and the component (B) is 100 parts by mass, the amount of the photopolymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass. More preferably, it is 1 to 15 parts by mass. As long as it is a blending amount in this range, it can be a resin composition having appropriate photocurability.

The coloring agent (E) is not particularly limited as long as it is soluble or dispersible in the resin composition of the present invention, and examples thereof include a dye and a pigment.

In particular, the resin composition of the present invention is baked at a relatively low temperature (215 ° C or lower) as described later, and since sufficient solvent resistance can be obtained, there is an advantage that the dye is less likely to be deteriorated by heat. Therefore, the resin composition of the present invention can use a plurality of types of dyes more freely to obtain a colored pattern.

The dye is an acid dye having an acidic group having a carboxyl group or the like from the viewpoints of solubility or dispersibility of the resin composition of the present invention, interaction with other components in the resin composition, heat resistance, and the like. A salt of a nitrogen compound of an acid dye, a sulfonamide of an acid dye, or the like is preferred. As an example of such a dye, 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 chrome 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, 138, 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; VALIFAST Blue 2620 and such derivatives. Among these, an acid dye of an azo type, a xanthene type, an anthraquinone type or an anthraquinone type is preferable. These may be used alone or in combination of two or more depending on the color of the pixel.

As examples of the pigment, CIPigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128 can be exemplified. Yellow pigments of 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214, etc.; CIPigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59 Orange pigments of 61, 64, 65, 71, 73, etc.; CIPigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, Red pigments of 224, 242, 254, 255, 264, 265, etc.; CIPigment Blue15, 15:3, 15:4, 15:6, 60, etc. blue pigment; CIPigment Violet1, 19, 23, 29, 32, 36, 38, etc. purple pigment; CIpigment green 7, 36, A green pigment such as 58; a brown pigment such as CIPigment Brown 23 or 25; a black pigment such as CIPigment Black 1, 7, carbon black, titanium black, or iron oxide. These may be used alone or in combination of two or more depending on the color of the pixel.

In addition, the dyes and pigments described above may be used in combination with the color of the target.

When the coloring agent (E) is blended, the blending amount is preferably from 5 to 80 parts by mass, more preferably from 5 to 80 parts by mass, per 100 parts by mass of the total of the components of the solvent (C) in the resin composition of the present invention. 70 parts by mass, more preferably 10 to 60 parts by mass.

When a pigment is used as the coloring agent (E), a known dispersing agent may be blended in the resin composition from the viewpoint of improving the dispersibility of the pigment. As the dispersant, a polymer dispersant excellent in dispersion stability over time is preferably used. Examples of the polymer dispersant include a urethane dispersant, a polyethyleneimine dispersant, a polyoxyethylene alkyl ether dispersant, a polyoxyethylene glycol diester dispersant, and dewatering. A sorbitol aliphatic ester dispersant, an aliphatic modified ester dispersant, or the like. As such a polymer dispersant, EFKA (registered trademark, FK chemicals BV (BASF) company), Disperbyk (registered trademark, BYK Chemie. Japan), Disparlon (registered trademark, Nanben Chemical Co., Ltd.) can be used. Stock system), SOLSPERSE (registered trademark, A trade name of a product such as Lubrizo Co., Ltd.).

The blending amount of the dispersing agent may be appropriately set depending on the type of the pigment or the like to be used.

When the resin composition of the present invention is used in the formation of a color pattern of a color filter, a resin (A) containing an epoxy group and an acid group, and a polybasic acid group containing a polyfunctional (meth) acrylate having a hydroxyl group. The compounding amount of the ester (B), the solvent (C), the photopolymerization initiator (D), and the coloring agent (E) is preferably a ratio of the components (A) and (B) to the epoxy group. The acid-based resin (A) is 90 to 10% by mass, and the hydroxyl group-containing polyfunctional (meth) acrylate polybasic acid monoester (B) is 10 to 90% by mass; if the solvent in the resin composition is removed When the total of the components (C) is 100 parts by mass, the solvent (C) is 30 to 1000 parts by mass, and when the total of the components (A) and (B) is 100 parts by mass, photopolymerization is used. The starting agent (D) is 0.1 to 30 parts by mass, and when the total of the components of the solvent (C) in the resin composition is removed to 100 parts by mass, the coloring agent (E) is used in an amount of 5 to 80 parts by mass. Further, it is preferably a polyfunctional (meth) acrylate having a hydroxyl group of 80 to 20% by mass based on the total of the components (A) and (B), and the resin (A) containing an epoxy group and an acid group. The polybasic acid monoester (B) is 20 to 80% by mass; and when the total of the components of the solvent (C) in the resin composition is removed to 100 parts by mass, the solvent (C) is 50 to 800 parts by mass; When the total of the component (A) and the component (B) is 100 parts by mass, the photopolymerization initiator (D) is used in an amount of 0.5 to 20 parts by mass; if the component of the solvent (C) in the resin composition is removed, When the sum is set to 100 parts by mass, the coloring agent (E) It is 5 to 70 parts by mass. More preferably, it is a polyfunctional (meth) acrylate having a hydroxyl group-containing resin (A) in an amount of 75 to 30% by mass based on the total of the (A) component and the (B) component. The acid monoester (B) is 25 to 70% by mass; and when the total of the components of the solvent (C) in the resin composition is removed to 100 parts by mass, the solvent (C) is 100 to 700 parts by mass; When the total of the components (A) and (B) is 100 parts by mass, the photopolymerization initiator (D) is 1 to 15 parts by mass; and the sum of the components of the solvent (C) in the resin composition is removed. When it is 100 parts by mass, the coloring agent (E) is used in an amount of 10 to 60 parts by mass.

Even when the resin composition of the present invention does not contain the colorant (E), the epoxy group and the acid group-containing resin (A), the hydroxyl group-containing polyfunctional (meth) acrylate polybasic acid monoester (B), and the solvent The above values can still be applied to the blending amount of (C) and photopolymerization initiator (D).

Similarly, even if the resin composition of the present invention does not contain the photopolymerization initiator (D) and the color former (E), the epoxy group and the acid group-containing resin (A) and the hydroxyl group-containing polyfunctional (meth) group The above-mentioned values can still be applied to the compounding amount of the acrylate polybasic acid monoester (B) and the solvent (C).

In addition to the above components, the resin composition of the present invention may be formulated with a well-known additive such as a known coupling agent, a homogenizer, or a thermal polymerization inhibitor in order to impart a specified characteristic. The amount of the additives to be added is not particularly limited as long as it does not impair the effects of the present invention.

The resin composition of the present invention can be produced by mixing the above components using a well-known mixing device.

Further, the resin composition of the present invention is first prepared to contain an epoxy group and an acid group. After the resin (A), the polyfunctional acid monoester (B) of the hydroxyl group-containing poly (meth) acrylate, and the resin composition of the solvent (C), the photopolymerization initiator (D) and any color former are used. (E) It is also possible to mix and manufacture later. Further, the resin composition of the present invention can be used for other purposes in addition to the formation of a color pattern for a color filter.

Since the resin composition of the present invention obtained as described above has alkali developability, development can be carried out by using an aqueous alkali solution. In particular, the resin composition of the present invention can provide a cured coating film which is excellent in sensitivity or developability and excellent in solvent resistance. Therefore, the resin composition of the present invention is suitably used as a photoresist used as a color pattern of various photoresists, particularly for forming a color filter built in an organic EL display, a liquid crystal display device, or a solid-state imaging device. Moreover, since the resin composition of the present invention is a cured coating film which is excellent in properties such as solvent resistance, it can be used in various coatings, adhesives, and binders for printing inks.

Next, a description will be given of a color filter manufactured using the resin composition of the present invention. The color filter of the present invention has a coloring pattern obtained from the above resin composition.

Hereinafter, a color filter according to an embodiment of the present invention will be described using a drawing.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a cross-sectional view showing a color filter according to an embodiment of the present invention. In FIG. 1, the color filter is composed of: a substrate 1; RGB pixels 2 formed on the substrate 1 and a black matrix 3 forming a boundary of the pixel 2; protection formed on the pixel 2 and the black matrix 3. The film 4 is composed of. In this configuration, at least one of the pixel 2 and the black matrix 3 (coloring pattern) is used. Other than the formation of the above resin composition, other configurations can be employed. Further, the color filter shown in Fig. 1 is an example and is not limited by this configuration.

Next, a method of manufacturing a color filter according to an embodiment of the present invention will be described.

First, a color pattern is formed on the substrate 1. Specifically, the black matrix 3 and the pixel 2 are sequentially formed on the substrate 1. Here, the substrate 1 is not particularly limited, and a glass substrate, a tantalum substrate, a polycarbonate substrate, a polyester substrate, a polyamide substrate, a polyimide substrate, a polyimide substrate, an aluminum substrate, or the like can be used. Printed circuit board, array substrate, and the like.

The coloring pattern can be formed by using a photolithography method. Specifically, after the resin composition is applied onto the substrate 1 to form a coating film, the coating film is exposed through a mask of a predetermined pattern, and the exposed portion is photocured. Further, after the unexposed portion is developed with an aqueous alkali solution, a prescribed pattern can be formed by baking.

The coating method of the resin composition is not particularly limited, and a screen printing method, a roll coating method, a curtain coating method, a spray coating method, a spin coating method, or the like can be used. In addition, after the application of the resin composition, the volatile component such as the solvent (C) may be volatilized by heating by a heating method such as a circulating oven, an infrared heater, or a hot plate. The heating conditions are not particularly limited, and may be appropriately set depending on the type of the resin composition to be used. In general, it can be heated at a temperature of 50 ° C to 120 ° C for 30 seconds to 30 minutes.

The light source used for the exposure is not particularly limited, and Use low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, xenon lamps, metal halide lamps, etc. Further, the amount of exposure is not particularly limited, and may be appropriately adjusted depending on the type of the resin composition to be used.

The aqueous alkali solution used for development is not particularly limited, and an aqueous solution of sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide or potassium hydroxide; an amine such as ethylamine, diethylamine or dimethylethanolamine can be used. An aqueous solution of a compound; 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3- Methyl-4-amino-N-ethyl-N-β-methanesulfonamide ethyl aniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline And an aqueous solution of a p-phenylenediamine compound such as a sulfate, a hydrochloride or a p-toluenesulfonate. Among these, an aqueous solution using a p-phenylenediamine compound is preferred. Further, in such aqueous solutions, an antifoaming agent or a surfactant may be added as needed. Further, it is preferred to carry out water washing and drying after the development by the aqueous alkali solution.

The baking conditions are not particularly limited, and heat treatment may be carried out depending on the type of the resin composition to be used. However, by using the resin composition of the present invention, it is possible to use a lower temperature than conventional baking, preferably It is preferably 215 ° C or less, and preferably heated at 130 to 215 ° C for 10 to 60 minutes. Since sufficient solvent resistance can be obtained even at a baking temperature lower than that of the prior art, it is possible to use a wider variety of dyes for dyes which have not been conventionally used due to deterioration due to heat.

By using the resin composition for the black matrix 3 and the resin composition for the pixel 2, the coating, exposure, development, and baking as described above are sequentially repeated, and a desired color pattern can be formed. .

Further, in the above, a method of forming a coloring pattern by photohardening has been described, but instead of using the photopolymerization initiator (D), a resin composition containing a curing accelerator and a well-known epoxy resin is used. The desired color pattern can also be formed by heating after coating by an inkjet method.

Next, a protective film 4 is formed on the coloring pattern (pixel 2 and black matrix 3). The protective film 4 is not particularly limited and may be formed by using a known person.

The color filter manufactured in such a manner is produced by using a resin composition which is excellent in sensitivity and developability and has excellent solvent resistance and is excellent in solvent resistance, so that it has excellent solvent resistance. Graphic type.

[Examples]

The invention is described in detail below with reference to the embodiments, and the invention is not limited by the embodiments. In addition, in the present embodiment, unless otherwise specified, the parts and percentages are based on mass. In addition, the acid value means the acid value of the epoxy group and the acid group-containing resin (A) measured in accordance with JIS K6901:2008 5.3.2, in order to neutralize the epoxy group and the acid group-containing resin (A). The number of mg of potassium hydroxide required for the acidic component contained in 1 g is intended. In addition, the weight average molecular weight means the weight average molecular weight converted by the standard polystyrene measured by the following conditions using the gel permeation chromatography (GPC).

Pipe column: Shodex (registered trademark) LF-804+LF-804 (Showa Denko (share) system)

Column temperature: 40 ° C

Sample: 0.2% tetrahydrofuran solution of resin

Developer: tetrahydrofuran

Detector: Shodex (registered trademark) RI-71S (Showa Electric Co., Ltd.)

Flow rate: 1mL/min

<Synthesis Example 1>

In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 324 parts by mass of propylene glycol monomethyl ether acetate was added, and the mixture was stirred while stirring with nitrogen gas, and the temperature was raised to 80 °C. Next, 17 parts by mass of 2,2-azobis (yield) was added to a monomer mixture of 86 parts by mass of methacrylic acid (1 mol) and 71 parts by mass of glycidyl methacrylate (0.5 mol). 2,4-Dimethylvaleronitrile) (Polymerization Initiator, V-65, manufactured by Wako Pure Chemical Industries, Ltd.), and the obtained product was dropped into the flask from the dropping funnel over 2 hours. After the completion of the dropwise addition, the mixture was further stirred at 80 ° C for 2 hours to carry out a copolymerization reaction to obtain a resin-containing liquid of No. 1 (solid content acid value: 320 mgKOH/g, weight average molecular weight: 10,000). Further, the number of moles of the epoxy group of the acid group 1 mol of the resin in the obtained resin-containing resin was 0.5.

<Synthesis Example 2~5>

As shown in Table 1, in addition to propylene glycol monomethyl ether acetate (PGMEA), methacrylic acid (MAa) and dimethyl methacrylate A resin-containing liquid of Nos. 2 to 5 can be obtained in the same manner as in Synthesis Example 1 except that the amount of use of the oil ester (GMA) is changed.

<Synthesis Example 6>

470 parts by mass of propylene glycol monomethyl ether acetate was placed in a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, and the mixture was stirred and heated to 80 ° C while being replaced with nitrogen. Next, 25 parts by mass of 2,2-azobis (25 parts by mass) was added to a monomer mixture of 86 parts by mass of methacrylic acid (1 mol) and 142 parts by mass of glycidyl methacrylate (1 mol). 2,4-Dimethylvaleronitrile) (Polymerization Initiator, V-65, manufactured by Wako Pure Chemical Industries, Ltd.), and the obtained product was dropped into a flask through a dropping funnel over 2 hours. After completion of the dropwise addition, the copolymerization reaction was carried out by further stirring at 80 ° C for 2 hours.

After that, 0.1 parts by mass of dibutyltin laurate (manufactured by Wako Pure Chemical Industries, Ltd.) and 2-isocyanate ethyl methacrylate (manufactured by Showa Denko Co., Ltd.) were added in an amount of 78 parts by mass (0.5 mol) at 60 °C. Ear) to burn The mixture was stirred for 1 hour, and then 160 parts by mass of propylene glycol monomethyl ether acetate was added to obtain a resin-containing liquid of No. 6 (solid content acid value: 85 mgKOH/g, weight average molecular weight: 13,000). Further, the number of moles of the epoxy group having 1 mol of the acid group of the resin in the obtained resin-containing resin was 2.

<Synthesis Example 7>

In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 977 parts by mass of propylene glycol monomethyl ether acetate was added, and the mixture was stirred while stirring with nitrogen, and the temperature was raised to 80 °C. Next, 52 parts were added to a monomer mixture of 86 parts by mass of methacrylic acid (1 mol), 104 parts by mass of styrene (1 mol), and 284 parts by mass of glycidyl methacrylate (2 mol). 2 parts by mass of 2,2-azobis(2,4-dimethylvaleronitrile) (polymerization initiator, V-65 manufactured by Wako Pure Chemical Industries, Ltd.), and the obtained product was dropped by 2 hours. The funnel was dropped into the flask. After completion of the dropwise addition, the mixture was further stirred at 80 ° C for 2 hours to carry out a copolymerization reaction to obtain a resin-containing liquid of No. 7 (solid content acid value: 120 mgKOH/g, weight average molecular weight: 8,000). Further, the number of moles of the epoxy group having 1 mol of the acid group of the resin in the obtained resin-containing resin was 2.

<Modulation of Resin Composition>

The formulation shown in Table 2 was used as a basic formulation, and the types of the resin-containing liquid and the polymerizable monomer were changed as shown in Tables 3 and 4, and the examples were prepared. The resin compositions of 1 to 10 and Comparative Examples 1 to 7.

<Evaluation of solvent resistance>

Solvent resistance was evaluated for the solvent N-methyl-2-pyrrolidone (NMP) generally used in the protective film forming step of the color filter.

The prepared resin composition was spin-coated on a 5 cm square glass substrate (alkali-free glass substrate), and the thickness after baking at 210 ° C was 2.5 μm, and then heated at 90 ° C for 3 minutes to volatilize the solvent. Next, the coating film was exposed to light having an exposure wavelength of 365 nm (exposure amount: 300 mJ/cm ² ), and the exposed portion was photocured, and then placed in a desiccator at a baking temperature of 210 ° C for 20 minutes to prepare a cured coating film. The transmittance of the test piece with the cured coating film at a wavelength of 675 nm was measured using a spectrophotometer UV-1650PC (manufactured by Shimadzu Corporation). Next, 55 parts by mass of N-methyl-2-pyrrolidone (NMP) was placed in a petri dish with a lid, and a test piece with a hardened coating film was immersed therein, and then measured at 60 ° C for 30 minutes. Transmittance. The results are shown in Table 5. The increase in transmittance is indicative of the fact that the colorant is being dissolved to N-methyl-2-pyrrolidone (NMP), and the initial transmittance is intrinsic to N-methyl-2-pyrrolidone (NMP) after impregnation. If the difference is small, it can be said that the solvent resistance is high.

<Evaluation of alkali developability>

The prepared resin composition was spin-coated on a 5 cm square glass substrate (alkali-free glass substrate) so that the thickness after the exposure became 2.5 μm, and then heated at 90 ° C for 3 minutes to volatilize the solvent. Next, a mask of a predetermined pattern was placed at a distance of 100 μm from the coating film, and the coating film was exposed through the mask (exposure amount: 150 mJ/cm ² ), and the exposed portion was photo-cured. Next, an aqueous solution containing 0.1% by mass of sodium carbonate was sprayed at a temperature of 23 ° C and a pressure of 0.3 MPa to dissolve the unexposed portion and developed, and then baked at 210 ° C for 30 minutes. The specified pattern was formed, and the residue after alkali development was confirmed. The residue after alkali development was confirmed by observation using an electron microscope S-3400 manufactured by Hitachi High-Technologies Corporation. The basis of this evaluation is as follows. The results are shown in Table 5.

○: no residue

×: There is residue

<Evaluation of sensitivity>

The development of the alkali of the spray was carried out for 30 seconds, and the amount of reduction in the thickness of the pattern before and after the alkali development was measured by a stylus type height difference meter ET4000M (manufactured by Otaru Laboratory) to determine the sensitivity. The thickness of this pattern is because the sensitivity is reduced as the amount of reduction is less, so the basis of the evaluation is as follows. The results are shown in Table 5.

○: less than 0.20 μm

×: 0.20 μm or more

As is clear from the results of Table 5, when the resin compositions of Examples 1 to 10 were used, the developability and sensitivity were good, and a cured coating film having excellent solvent resistance was provided. The solvent resistance of the resin composition of 1 to 7 will be insufficient.

[Industry Utilization]

As is apparent from the above results, according to the present invention, it is possible to provide a resin composition which is excellent in sensitivity or developability and which can form a cured coating film having sufficient solvent resistance. Therefore, the resin composition of the present invention is suitable as a photoresist for a color filter. Further, by using the resin composition of the present invention, a color filter having a coloring pattern excellent in solvent resistance and having high reliability can be obtained.

1‧‧‧Substrate

2‧‧‧ pixels

3‧‧‧Black matrix

4‧‧‧Protective film

Claims (13)

A resin composition comprising: an epoxy group and an acid group-containing resin (A); a hydroxyl group-containing polyfunctional (meth) acrylate polybasic acid monoester (B); a solvent (C); and photopolymerization The initiator (D) is characterized in that the epoxy group is 0.5 to 3.0 mols based on 1 mol of the acid group in the epoxy group- and acid group-containing resin (A). The resin composition of claim 1, wherein the constituent monomer unit of the epoxy group and the acid group-containing resin (A) contains an ethylenic carbon-carbon double bond and an epoxy group in one molecule. Monomer unit of monomer (a-1). The resin composition of claim 1 or 2, wherein the constituent monomer unit of the epoxy group and the acid group-containing resin (A) contains a monomer unit derived from the unsaturated carboxylic acid (a-2). The resin composition of claim 3, wherein the epoxy group-containing acid group-containing resin (A) contains a part of a carboxyl group derived from the unsaturated carboxylic acid (a-2) and a monomer ( A-3) an exemplified monomer unit having an ethylenic carbon-carbon double bond which has a functional group capable of reacting with a carboxyl group and an ethylene carbon-carbon double in one molecule key. The resin composition of claim 2, wherein the monomer (a-1) having an ethylenic carbon-carbon double bond and an epoxy group in the above molecule is an epoxy group-containing (meth) acrylate. The resin composition of claim 4, wherein the one molecule having a functional group capable of reacting with a carboxyl group and an ethylenic carbon-carbon double bond (a- 3) One or two or more selected from the group consisting of an epoxy group-containing (meth) acrylate and an isocyanate group-containing (meth) acrylate. The resin composition of claim 1 or 2, wherein the polyhydric (meth) acrylate-containing polybasic acid monoester (B) containing the hydroxy group is selected from the group consisting of di- or tri-(meth) acrylate polybasic acid of pentaerythritol. One or more selected from the group consisting of monoesters and dipentaerythritol di-, tri-, tetra- or penta-(meth) acrylate polybasic monoesters. The resin composition of claim 1 or 2, wherein the epoxy group and the acid group-containing resin (A) have an acid value of 10 to 350 mgKOH/g. The resin composition of claim 1 or 2, further comprising a colorant (E). The resin composition of claim 9, wherein the coloring agent (E) is at least one selected from the group consisting of a dye and a pigment. A color filter having a color pattern formed by a hard coat film of the resin composition of claim 9 or 10. An image display element having the color filter of claim 11. A method of manufacturing a color filter, comprising: coating, exposing, and developing a resin composition of claim 9 or 10 on a substrate; and drying at a temperature of 215 ° C or lower Bake, to form the step of coloring the pattern.