TWI570511B - Coloring the photosensitive resin composition - Google Patents

Description

Colored photosensitive resin composition

The present invention relates to a colored photosensitive resin composition.

The colored photosensitive resin composition is used for the production of a color filter. Japanese Laid-Open Patent Publication No. 2004-83857 discloses a coloring photosensitive resin composition containing a resin composed of a benzyl methacrylate/methacrylic acid copolymer and 2-benzyl-2. -Dimethylamino-(4-morpholinylphenyl)-butan-1-one, 4,4'-bis(diethylamino)-benzophenone, pentaerythritol oxime (3-sulfonate) Propionate), photopolymerizable compound, solvent, pigment, and pigment dispersant.

In the conventional coloring photosensitive resin composition, the resolution and durability of the resulting pattern may not be satisfactory.

The present invention provides the following [1] to [9].

[1] A colored photosensitive resin composition comprising (A), (B), (C), (D), (E) and (F): (A) a colorant; (B) a copolymer obtained by copolymerizing the following (a) and (b) with (c) a resin obtained by reacting; (a): a group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride selected At least one kind of (b): a monomer having an unsaturated bond copolymerizable with (a) and different from (a): a cyclic ether skeleton having a carbon number of 2 to 4 and an ethylenicity a saturated bond monomer (C) a polymerizable compound; (D) a polymerization initiator; (E) a polyfunctional thiol compound; (F) a solvent.

[2] The colored photosensitive resin composition according to [1], wherein (D) is an oxime compound.

[3] The colored photosensitive resin composition according to [1] or [2], which further contains a thioxanthone compound.

[4] The colored photosensitive resin composition according to any one of [1] to [3] wherein (D) contains an acyl phosphine oxide compound or an alkylphenone. Compound.

[5] The colored photosensitive resin composition according to any one of [1], wherein (b) contains at least one of a tricyclodecane skeleton and three a skeleton selected from the group consisting of a tricyclodecene skeleton, and a compound having an ethylenically unsaturated bond.

[6] The colored photosensitive resin group as described in any one of [1] to [5] A compound wherein (c) is a monomer having an oxiranyl group and an ethylenically unsaturated bond.

[7] A pattern (patern) formed by using the colored photosensitive resin composition according to any one of [1] to [6].

[8] A color filter comprising the pattern as described in [7].

[9] A method of manufacturing a color filter, comprising the steps (1) to (3) below: (1) A step of applying a colored photosensitive resin composition according to any one of [1] to [6] to a substrate to obtain a coating film; (2) exposing on the coating film via a mask to obtain a film after exposure; (3) A step of developing a post-exposure coating film by an alkali developing solution to obtain a pattern.

According to the colored photosensitive resin composition of the present invention, a pattern excellent in resolution and durability can be obtained.

The colored photosensitive resin composition of the present invention contains a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), a polyfunctional thiol compound (E), and a solvent ( F), the resin (B) is a resin obtained by reacting the copolymer obtained by copolymerizing the following (a) and (b) with (c).

(a): at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides

(b): having an unsaturated bond copolymerizable with (a), and (a) Different monomers

(c): a monomer having a cyclic ether skeleton of 2 to 4 carbon atoms and an ethylenically unsaturated bond.

The colored photosensitive resin composition of the present invention contains a coloring agent (A). Although the coloring agent (A) is a pigment and a dye, it is preferable to contain a pigment from a viewpoint of heat resistance and light resistance.

Examples of the pigments include organic pigments and inorganic pigments, and examples thereof include compounds classified into pigments by using a color index (published by The Society of Dyers and Colourists).

The organic pigment, specifically, for example, CI pigment yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110 Yellow pigments of 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214, and the like.

CI pigment orange, orange pigments of 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73; CI pigment red 9, 97, 105, 122, 123, Red pigments of 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, etc.; CI pigment blue 15, 15, 3, 15: 4, 15:6, 60, etc. blue pigment; CI pigment purple 1,19,23,29,32,36,38, etc. purple pigment; CI pigment green 7,36,58, etc. green pigment; CI pigment brown Brown pigment of 23, 25, etc.; C.I. Black pigments such as pigment black 1, 7, etc.

Among them, C.I. pigment yellow 138, 150; C.I. pigment red 177, 254, C.I. pigment red purple 23; C.I. pigment blue 15:6 and C.I. pigment green 36, 58 are preferred. These pigments may be used singly or in combination of two or more kinds.

The pigment may be subjected to a rosin treatment, a surface treatment such as a pigment derivative or a pigment dispersant introduced with an acidic group or a basic group, or a graft treatment of a pigment surface formed of a polymer compound or the like, as needed. The micronization treatment by the sulfuric acid microparticle method or the like, the cleaning treatment by an organic solvent or water for removing impurities, the removal treatment by ion exchange method using ionic sub-impurities, or the like. Further, it is preferred that the pigment be uniform in particle size. By allowing the pigment to contain a pigment dispersant and performing a dispersion treatment, a pigment dispersion liquid in which the pigment is uniformly dispersed in the solution can be obtained.

As the pigment dispersant, a commercially available surfactant can be used, and examples thereof include polyoxymethylene, fluorine, ester, cationic, anionic, nonionic, amphoteric, polyester, and polyamine. A surfactant such as acrylic or the like. The above surfactants may, for example, be polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, grade 3 In addition to amine-modified polyurethanes and polyethyleneimine, KP (Shin-Etsu Chemical Co., Ltd.), FLOWLEN (Kyoeisha Chemical Co., Ltd.), and Solsperse (Zeneca) are listed. ()), EFKA (manufactured by CIBA), AJISPER (manufactured by Ajinomoto Fine-Techno Co., Inc.), Disperbyk (made by BYK), etc. These may be used alone or in combination of two or more.

When the pigment dispersant is used, the amount thereof is preferably 100% by mass or less, and more preferably 5 to 50% by mass based on the pigment. When the amount of the pigment dispersant used is within the above range, there is a tendency that a pigment dispersion liquid in a uniformly dispersed state can be obtained.

The content of the colorant (A) is preferably 5 to 60% by mass, and more preferably 5 to 45% by mass based on the solid content of the colored photosensitive resin composition. If the content of the colorant (A) is within the above range, the resulting color filter can obtain a desired spectral or color density.

Here, in the present specification, the solid content refers to the total amount of components after the solvent is removed from the colored photosensitive resin composition.

The colored photosensitive resin composition of the present invention contains a resin (B). The resin (B) is a resin obtained by reacting the copolymer obtained by copolymerizing the following (a) and (b) with (c);

(a): at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides

(b): a monomer having an unsaturated bond copolymerizable with (a) and different from (a)

(c): a monomer having a cyclic ether skeleton of 2 to 4 carbon atoms and an ethylenically unsaturated bond.

(a) Specifically, an unsaturated monocarboxylic acid such as acrylic acid, methacrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid or p-vinylbenzoic acid; Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1, 4-cyclohexene dicarboxylic acid, etc., unsaturated dicarboxylic acid; containing methyl-5-formylene -2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methyl Bicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2- a bicyclic unsaturated compound of a carboxyl group such as a olefin or a 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene; maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic acid Anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride , 5,6-dicarboxylic acid bicyclo[2.2.1]hept-2-ene anhydride (nadic anhydride), etc., unsaturated dicarboxylic anhydrides; succinic acid mono[2-(methyl)propenyloxyethyl ], or a polycarboxylic acid of 2 or more yuan such as [2-(methyl)acryloyloxyethyl] Saturated mono[(meth)acryloyloxyalkyl]esters; such as α-(hydroxymethyl)acrylic acid, unsaturated acrylates containing a hydroxyl group and a carboxyl group in the same molecule.

Among these, acrylic acid, methacrylic acid, maleic anhydride, and the like are preferably used from the viewpoint of copolymerization reactivity or alkali solubility.

(b) Examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert- (meth)acrylic acid alkyl esters such as butyl (meth) acrylate; cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^{2, 6} ] decane-8-yl (meth) acrylate (also known in the art as dicyclopentanyl (meth) acrylate), dicyclopentadialkyl a (meth)acrylic cyclic alkyl ester such as oxyethyl (meth) acrylate or isodecyl (meth) acrylate; phenyl (meth) acrylate, benzyl (meth) acrylate Or an aryl or aralkyl ester of (meth)acrylic acid; a dicarboxylic acid diester of diethyl maleate, diethyl fumarate or diethyl itaconate; 2-hydroxyethyl ( a hydroxyalkyl ester such as methyl acrylate or 2-hydroxypropyl (meth) acrylate; bicyclo [2.2.1] hept-2-ene, 5-methyl bicyclo [2.2.1] g-2 - alkene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1] Hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxyl Bicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-bis(hydroxymethyl)bicyclo[2.2.1]hept-2- Alkene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6 -diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1 Hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5 -cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo [2.2.1] Hetero-2-ene, 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene and the like; a bicyclic unsaturated compound; N-phenyl malayan Amine, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimide-3-maleimide benzoate, N-succinimide-4- Malayanimine butyrate, N-succinimide-6-maleimine caproate (caproate), N-succinimide-3-marine a dicarbonyl quinone imine derivative such as imidium propionate or N-(9-acridinyl)maleimide; styrene, α-methylstyrene, m-methylstyrene, P-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, dichloroethylene glycol, decylamine amide, decylamine methacrylate, vinyl acetate, 1, 3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like.

In addition, (b) is a compound (b1) which has a skeleton selected from a group consisting of a tricyclodecane skeleton and a tricyclodecene skeleton, and an ethylenically unsaturated bond (hereinafter sometimes) Called "(b1)").

When (b) is (b1), film reduction of the pattern due to development can be suppressed.

Here, the "tricyclodecane skeleton" and the "tricyclic terpene skeleton" in the present specification mean the following structures (each of the bonding bonds is an arbitrary carbon atom).

(b1), specifically, dicyclopentadienyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, dicyclopentadienyl oxyethyl (methyl) Acrylate, dicyclopentadienyloxyethyl (meth) acrylate.

(b) Each of them may be used alone or in combination of two or more.

When two or more types of (b) are used in combination, at least one of them is preferably the above b1, and the other is an aralkyl ester such as phenyl (meth) acrylate or benzyl (meth) acrylate. Classes (hereinafter sometimes referred to as "(b2)") are preferred.

In the copolymer obtained by copolymerizing (a), (b1), and (b2), the ratio of the copolymer obtained by copolymerizing (a), (b1), and (b2) is produced by each monomer. The proportion of the structural unit is preferably in the range described below.

(a) The structural unit produced: 5~80 mol% (more preferably 15~60 mol%)

(b1) The structural unit produced: 5~80 mol% (more preferably 5-20 mol%)

(b2) The structural unit produced: 0~90% by mole (more preferably 10) ~70 mole%)

The total of (a), (b1), and (b2) is set to 100 mol% or less. When the composition ratio is within the above range, the curability tends to be good.

(c), for example, a monomer (c-1) having an oxirane group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(c-1)"), and having an oxypropylene group (Oxetanyl) Groups) and monomers (c-2) having an ethylenically unsaturated bond (hereinafter sometimes referred to as "(c-2)"), a monomer having a tetrahydrofuranyl group and an ethylenically unsaturated bond (c-3) (below) Sometimes called "(c-3)").

(c-1), for example, a monomer (c-11) having a structure in which a linear olefin is epoxidized and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(c-11)")) The monomer (c-12) having an epoxidized structure and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(c-12)").

(c-1) is preferably a monomer having an oxiranyl group and a (meth) propylene fluorenyloxy group, and more preferably a (meth) propylene fluorenyloxy group (c-12).

Here, in the present specification, "(meth)acryloxyloxy group" means at least one selected from the group consisting of an acryloxy group and a methacryloxy group. The expressions "(meth)acrylonitrile" and "(meth)acrylate" have the same meaning.

(c-11) Specifically, glycidyl (meth) acrylate, β-methyl glycidyl (meth) acrylate, β-ethyl glycidyl (meth) acrylate , glycidyl vinyl ether, O-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α -Methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidyloxymethyl)styrene, 2,4 - bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl)styrene, 2,3,4 - Ginseng (glycidyloxymethyl) styrene, 2,3,5-glycol (glycidyloxymethyl)styrene, 2,3,6-glycol (glycidyloxymethyl)styrene, 3 4,5-glycol (glycidyloxymethyl)styrene, 2,4,6-glycol (glycidyloxymethyl)styrene, a compound described in JP-A-H07-248625, and the like.

(c-12): vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, CELLOXIDE 2000; manufactured by Daicel Corporation, Daicel Corporation), 3 , 4-epoxycyclohexyl methacrylate (for example, CYCLOMER A400; manufactured by Daicel Corporation, Daicel Corporation), 3,4-epoxycyclohexylmethyl methacrylate (for example, CYCLOMER M100; DAICEL Co., Ltd. (made by Daicel Corporation), a compound represented by the formula (I), a compound represented by the formula (II), and the like.

[In the formulae (I) and (II), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be represented by a hydroxyl group. Replace.

X ¹ and X ² each independently represent a single bond, -R ³ -, *-R ³ -O-, *-R ³ -S-, *-R ³ -NH-.

R ³ represents an alkanediyl group having 1 to 6 carbon atoms.

* indicates the bond with O].

Specific examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group.

The alkyl group which may be substituted by a hydroxyl group may, for example, be a methylol group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group or a 1-hydroxy group. 1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, and the like.

R ¹ and R ² are preferably a hydrogen atom, a methyl group, a methylol group, a 1-hydroxyethyl group or a 2-hydroxyethyl group, and more preferably a hydrogen atom or a methyl group.

Alkanediyl groups, for example, methyl, ethyl, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane -1,5-diyl, hexane-1,6-diyl and the like.

X ¹ and X ² are preferably a single bond, a methyl group, a methyl group, a methyl group, a —CH ₂ —O— (* is a bond to an O group), and a —CH ₂ CH ₂ group. More preferably, the -O- group is a single bond or a *-CH ₂ CH ₂ -O- group.

The compound represented by the formula (I) is a compound represented by the formula (I-1) to the formula (I-15). Preferably, it is a formula (I-1) and a formula (I- 3) A compound represented by any one of the formula (I-5), the formula (I-7), the formula (I-9), and the formula (I-11) to the formula (I-15). More preferably, it is a compound represented by any one of Formula (I-1), Formula (I-7), Formula (I-9), and Formula (I-15).

The compound represented by the formula (II) is a compound represented by the formula (II-1) to the formula (II-15). Preferably, it is a formula (II-1), a formula (II-3), a formula (II-5), a formula (II-7), a formula (II-9), and a formula (II-11) to a formula (II). -15) A compound represented by any one of them. More preferably, it is a compound represented by any one of Formula (II-1), Formula (II-7), Formula (II-9), and Formula (II-15).

The compound represented by the formula (I) and the compound represented by the formula (II) can be used singly. In addition, these can be mixed in any ratio. When mixing, the mixing ratio is in molar ratio, and formula (I): formula (II) is preferably 5:95 to 95:5, more preferably 10:90 to 90:10, and particularly preferably 20 :80~80:20.

(c-2) is preferably a monomer having an oxyalkylene group and a (meth)acryloxy group. (c-2) is exemplified by 3-methyl-3-(methyl)propenyl methoxymethyl propylene oxide, 3-ethyl-3-(methyl) propylene fluorenyl oxymethyl epoxide Propane, 3-methyl-3-(meth)acryloyloxyethyl propylene oxide, 3-ethyl-3-(methyl) propylene sulfhydryl Ethyl propylene oxide and the like.

(c-3) is more preferably a monomer having a tetrahydrofuranyl group and a (meth)acryloxy group. (c-3), specifically, tetrahydrofurfuryl acrylate (for example, VISCOAT V #150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, or the like.

The amount of (c) added is converted from the added value, and is preferably 10 to 60% by mass, and 15 to 40% by mass based on the copolymer obtained by copolymerizing (a), (b1), and (b2). Better.

The content of the resin (B) is usually 0.5 to 30 parts by mass, preferably 1 to 20 parts by mass, more preferably 2 to 15 parts by mass, per 100 parts by mass of the colored photosensitive resin composition of the present invention.

The colored photosensitive resin composition of the present invention contains a polymerizable compound (C).

The polymerizable compound (C) is a compound which can be polymerized by an active radical generated by a polymerization initiator (D), an acid or the like, and examples thereof include a compound having a polymerizable ethylenically unsaturated bond. Preferred examples thereof include a (meth) acrylate compound.

The polymerizable compound (C) having one ethylenically unsaturated bond may be the same as those exemplified in the above (a), (b) and (c), wherein the (meth) acrylate is good.

The polymerizable compound (C) having two ethylenically unsaturated bonds may, for example, be 1,3-butanediol di(meth)acrylate or 1,3-butanediol (meth)acrylate. 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)propene Acid ester, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol diacrylate, bisphenol A double (acryloyloxyethyl) ether, ethoxylated bisphenol A di(meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, ethoxylated neopentyl Diol (meth) acrylate, 3-methylpentane diol di (meth) acrylate, and the like.

Examples of the polymerizable compound (C) having three or more ethylenically unsaturated bonds include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and bis(2-hydroxyethyl). Tris(meth)acrylate isocyanurate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol tetra ( Methyl) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa Methyl) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, pentaerythritol tri(meth) acrylate and anhydride reactant, dipentaerythritol penta (meth) acrylate and Anhydride reactant, trimellitic acid hepta (meth) acrylate and anhydride caprolactone modified trimethylolpropane tri(meth) acrylate, caprolactone modified pentaerythritol tri(meth) acrylate, Ester modified ginseng (2-hydroxyethyl) isocyanuric acid tris(meth)acrylic acid , caprolactone modified pentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, caprolactone modification Tripentaerythritol tetra(meth)acrylate, caprolactone Modified tripentaerythritol penta (meth) acrylate, caprolactone modified trimellititol hexa(meth) acrylate, caprolactone modified tripellitate pentoxide (meth) acrylate, caprolactone modified trimellititol VIII (Meth) acrylate, caprolactone modified pentaerythritol tri(meth) acrylate and anhydride reaction, caprolactone modified dipentaerythritol penta (meth) acrylate and anhydride reaction, caprolactone modification Trispentaerythritol hepta (meth) acrylate and anhydride.

Among them, a trifunctional or higher monomer is preferred, and dipentaerythritol hexa(meth)acrylate is more preferred.

The content of the polymerizable compound (C) is preferably from 5 to 50% by mass, more preferably from 10 to 45% by mass, based on the solid content of the colored photosensitive resin composition. Further, the total amount of the resin (B) and the polymerizable compound (C) is preferably 20 to 80% by mass, and more preferably 40 to 60% by mass. When the content of the polymerizable compound (C) is within the above range, the sensitivity, the smoothness of the pattern, the smoothness, and the reliability tend to be good.

The colored photosensitive resin composition of the present invention contains a polymerization initiator (D).

The polymerization initiator (D) is not particularly limited as long as it generates a living radical, an acid or the like by the action of light, and starts polymerization of the polymerizable compound (C), and a well-known polymerization reaction can be used. Starting agent.

The polymerization initiator (D) is a diimidazole compound, an alkylphenone compound, a triazabenzene compound, a mercaptophosphine oxide compound, and a deuteration. The composition is preferred. Further, a photocationic polymerization initiator (for example, an anion produced by a phosphonium cation and a Lewis acid) described in JP-A-2008-181087 can also be used. Among them, from the viewpoint of sensitivity, a ruthenium compound is preferred.

The above biimidazole compound may, for example, be 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis (2,3) -Dichlorophenyl)-4,4',5,5'-tetraphenylbisimidazole (for example, see JP-A-6-75372, JP-A-6-75373, etc.), 2, 2 '-Bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5, 5'-tetrakis(alkoxyphenyl)bisimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)bisimidazole 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)bisimidazole (for example, refer to Japanese Patent Publication No. Sho 48-38403, Japanese Patent Publication No. Sho 62-174204, etc., and an imidazole compound in which a phenyl group at the 4,4', 5, 5'-position is substituted with a carbamoyloxy group (for example, see JP-A-7-10913, etc.) Wait. Preferred examples are: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis(2,3-dichloro Phenyl)-4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetra Phenyl diimidazole.

The alkylphenone compound refers to a compound having a partial structure represented by the formula (d2) or a partial structure represented by the formula (d3). The benzene ring in some of these structures may also have a substituent.

The compound having a partial structure represented by the formula (d2) may, for example, be 2-methyl-2-morpholinyl-1-(4-methylsulfonylphenyl)propan-1-one, 2 -Dimethylamino-1-(4-morpholinylphenyl)-2-benzylbutan-1-one, and 2-(dimethylamino)-2-[(4-methylbenzene) Methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one. Commercial products such as Irgacure (registered trademark) 369, 907, and 379 (above, manufactured by BASF Corporation) can also be used.

The compound having a partial structure represented by the formula (d3) may, for example, be 2-hydroxy-2-methyl-1-phenylpropan-1-one or 2-hydroxy-2-methyl-1-[ 4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane - 1-ketone oligomer, and α,α-diethoxyacetophenone, Benzyl dimethyl ketal.

The above-mentioned triazabenzene compound may, for example, be 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazabenzene, 2, 4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazabenzene, 2,4-bis(trichloromethyl)-6-sunflower Base-1,3,5-triazabenzene, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazabenzene, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-triazabenzene, 2,4-bis ( Trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-triazabenzene, 2,4-bis(trichloromethyl)-6- [2-(4-Diethylamino-2-methylphenyl)vinyl]-1,3,5-triazabenzene, 2,4-bis(trichloromethyl)-6-[ 2-(3,4-Dimethoxyphenyl)vinyl]1,3,5-triazabenzene and the like.

The above-mentioned mercaptophosphine oxide initiator may, for example, be 2,4,6-trimethylbenzimidyldiphenylphosphine oxide or the like. Commercial products such as Irgacure 819 (made by Ciba. Japan) can also be used.

The above-mentioned hydrazine compound may, for example, be N-benzylideneoxy-1-(4-phenylsulfonylphenyl)butan-1-one-2-imine, N-benzhydryloxy 1-(4-phenylsulfonylphenyl)octane-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzene Mercapto)-9H-indazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3, 3-Dimethyl-2,4-dioxalanyloxy)benzimidyl}-9H-indazol-3-yl]ethane-1-imine and the like. Commercial products such as Irgacure OXE-01, OXE-02 (above, BASF Japan), N-1919 (made by Adeka) can also be used.

Further, a polymerization initiator which can cause chain transfer can also be used as a photopolymerization initiator as described in JP-A-2002-544205.

The above-mentioned polymerization initiator which can cause chain transfer can be, for example, a compound of the following formula (D-1) to (D-6).

The above-mentioned polymerization initiator which can cause chain transfer can also be used as the component (c) constituting the resin (A).

Further, the polymerization initiator (D) may, for example, be in the rest Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc.; benzophenone, methyl o-benzoyl benzoate, 4-phenyl diphenyl Methyl ketone, 4-benzylidene-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4, a benzophenone compound such as 6-trimethylbenzophenone; an anthraquinone compound such as 9,10-phenanthrenequinone, 2-ethylhydrazine, camphorin or the like; 10-butyl-2-chloropyridinium A ketone, a benzyl group, a methyl phenylglyoxylate, a titanocene compound, and the like. These are preferably used in combination with a polymerization starting aid (D1) (particularly an amine) to be described later.

Further, a polymerization initiation aid (D1) may be further contained. The polymerization initiation aid (D1), which is used in combination with the polymerization initiator (D), is a compound used to promote polymerization of a polymerizable compound which starts polymerization by a polymerization initiator, or Sensitizer.

The polymerization initiation aid (D1) may, for example, be an amine compound, a thiazoline compound, an alkoxyfluorene compound, a thioxanthone compound or a carboxylic acid compound. Among them, a thioxanthone compound is preferred.

The amine compound may, for example, be triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate or 4-dimethyl group. Isoamyl benzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4 '-Bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 4,4'-double (Ethylmethylamino)benzophenone or the like, of which 4,4'-bis(diethylamino)benzophenone is preferred. Can also use EAB-F (preservation Commercial products such as the Valley Chemical Industry Co., Ltd.).

The thiazoline compound may, for example, be a compound represented by the formula (III-1) to the formula (III-3).

The alkoxy oxime compound may, for example, be 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene or 2-ethyl- 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, and the like.

The thioxanthone compound is exemplified by 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1 -Chloro-4-propoxythioxanthone and the like.

Examples of the carboxylic acid compound include phenylsulfonyl acetic acid, methylphenylsulfonyl acetic acid, ethylphenylsulfonyl acetic acid, methyl ethylphenylsulfonyl acetic acid, and dimethylphenylsulfonate. Thioglycolic acid, methoxyphenylsulfonyl acetic acid, dimethoxyphenylsulfonyl acetic acid, chlorophenylsulfonyl acetic acid, dichlorophenylsulfonyl acetic acid, N-phenylglycine Acid, phenoxyacetic acid, naphthylthio Acid, N-naphthylglycine, naphthyloxyacetic acid, and the like.

The content of the polymerization initiator (D) is preferably from 0.1 to 40 parts by mass, more preferably from 1 to 30 parts by mass, per 100 parts by mass of the total of the resin (B) and the polymerizable compound (C). When the total amount of the polymerization initiator (D) is within this range, the pattern can be formed with high sensitivity, and the chemical resistance, mechanical strength, and surface smoothness of the pattern tend to be good.

In the case of using the polymerization initiation aid (D1), the amount thereof is preferably from 0.01 to 50 parts by mass, more preferably from 0.1 to 100 parts by mass based on 100 parts by mass of the total of the resin (B) and the polymerizable compound (C). 40 parts by mass. Further, it is preferably 0.01 to 10 moles, more preferably 0.01 to 5 moles per 1 mole of the polymerization initiator (D). When the amount of the polymerization starting aid (D1) is within this range, the pattern can be formed with high sensitivity, and the productivity of the pattern tends to increase.

Further, the colored photosensitive resin composition of the present invention contains a polyfunctional thiol compound (E). The polyfunctional thiol compound (E) is a compound having two or more sulfonyl groups in the molecule. Among them, when a compound having two or more -CH ₃ SH in the molecule is used, it is preferable because the pattern can be formed with high sensitivity.

The polyfunctional thiol compound (E) may, for example, be hexanedithiol, decanedithiol, 1,4-bis(methylsulfonyl)benzene or butanediol bis(3-sulfonyl). Propionate), butanediol bis(3-sulfonyl acetate), ethylene glycol bis(3-sulfonyl acetate), trimethylolpropane ginseng (3-sulfonyl acetic acid) Ester), butanediol bis(3-sulfonylpropionate), trimethylolpropane ginseng (3-sulfonylpropionate), trimethylolpropane ginseng (3-sulfonylacetate) Ester), pentaerythritol bismuth (3-sulfonylpropionate), pentaerythritol bismuth (3-sulfonyl acetate), hydroxyethyl ginseng (3-sulfonylpropionate), pentaerythritol bismuth (3- Sulfohydrylbutyrate), 1,4-bis(3-sulfonylbutyloxy)butane, etc., of which pentaerythritol lanthanum (3-sulfonylpropionate) is preferred.

The content of the polyfunctional thiol compound (E) is preferably from 10 to 150 parts by mass, more preferably from 30 to 80 parts by mass, per 100 parts by mass of the polymerization initiator (D). When the content of the polyfunctional thiol compound (E) is within this range, the sensitivity is improved and the developability tends to be good.

The solvent (F) is not particularly limited, and a solvent which is usually used in the field can be used. For example, an ester solvent (a solvent containing a -COO-structure in a molecule), an ether solvent other than an ester solvent (a solvent containing a -O-structure in a molecule), an ether ester solvent (a -COO-structure and -O in a molecule) - a solvent of the structure), a ketone solvent other than an ester solvent (a solvent containing a -CO-structure in the molecule), an alcohol solvent, an aromatic hydrocarbon solvent, a guanamine solvent, dimethyl hydrazine, or the like. These solvents may be used alone or in combination of two or more.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl acetate, and isoamyl acetate. Ester, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl valerate, ethyl valerate, propyl valerate, methyl acetate, ethyl acetate Cyclohexanol acetate, γ-butyrolactone, and the like.

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, and diethylene glycol monomethyl. Ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy- 1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether , diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenethyl ether, methyl anisole and the like.

The ether ester solvent may, for example, be methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate or 3-methoxypropionic acid. Methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, 2-methoxypropionic acid Ethyl ester, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2- Ethyl ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol Monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate , diethylene glycol monobutyl ether acetate, and the like.

The ketone solvent may, for example, be 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone or 4-methyl-2- Pentanone, cyclopentanone, cyclohexanone, isophorone, and the like.

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and 1,3,5-trimethylbenzene.

The guanamine solvent may, for example, be N,N-dimethylformamide, N,N-dimethylacetamide or N-methylpyrrolidone.

Among the above-mentioned solvents, from the viewpoint of coatability and drying property, an organic solvent having a boiling point of 1 atm of 120 ° C to 180 ° C is preferred. Among them, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and the like are preferred.

The content of the solvent (F) is preferably 60 to 95% by mass, and more preferably 70 to 90% by mass based on the coloring photosensitive resin composition. In other words, the solid content of the colored photosensitive resin composition is preferably from 5 to 40% by mass, more preferably from 10 to 30% by mass. When the content of the solvent (F) is within the above range, the flatness at the time of coating tends to be good.

The colored photosensitive resin composition of the present invention is preferably one containing a surfactant (G). Examples of the surfactant include a polyfluorene-based surfactant, a fluorine-based surfactant, and a polyfluorene-based surfactant having a fluorine atom. When the surfactant is contained, the flatness at the time of coating tends to be good.

The polyoxo-based surfactant may be a surfactant having a decane bond.

Specifically, it can be exemplified by Toray polyoxane DC3PA, same SH7PA, same DC11PA, same SH21PA, same SH28PA, same SH29PA, same SH30PA, polyether modified polyketone oil SH8400 (trade name: Dow Corning Toray Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (manufactured by Momentive Performance Materials Japan Co., Ltd.), and the like.

The fluorine-based surfactant may be a surfactant having a fluorocarbon chain.

Specifically, FLUORINERT (registered trademark) FC430, FC431 (Sumitomo 3M (share) system), MEGAFACE (registered trademark) F142D, F171, F172, F173, F177, F183, and R30 (DIC (share) system), F-Top (registered trademark) EF301, EF303, EF351, EF352 (Mitsubishi Metal Electronics Co., Ltd.), SURFLON (registered trademark) S381, same as S382, same as SC101, same SC105 (Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Institute of Precision Chemistry, etc.).

The polyoxo-based surfactant having a fluorine atom may be a surfactant having a siloxane chain and a fluorocarbon chain. Specific examples include MEGAFACE (registered trademark) R08, BL30, F475, F477, and F443 (DIC). Preferably, MEGAFACE (registered trademark) F475 is mentioned.

The surfactant (G) is 0.001% by mass or more and 0.2% by mass or less, preferably 0.002% by mass or more and 0.1% by mass or less, more preferably 0.01% by mass or more and 0.05% by mass or less, based on the coloring photosensitive resin composition. The flatness of the coating film can be improved by including the surfactant in this range.

The colored photosensitive resin composition of the present invention may also be included as needed There are various additives such as a filler, other polymer compound, adhesion promoter, antioxidant, ultraviolet absorber, light stabilizer, and chain transfer agent.

The colored photosensitive resin composition of the present invention can be prepared, for example, in the following manner.

First, the pigment of the colorant (A) is mixed with the solvent (E) in advance, and the average particle diameter of the pigment is dispersed to a level of 0.2 μm or less using a bead mill. At this time, a part or all of the pigment dispersant and the resin (B) may be blended as needed. In the obtained pigment dispersion liquid, a component other than the resin (B), the polymerizable compound (C), and the polymerization initiator (D) may be used as needed, and an additional solvent may be further added depending on the necessity. The desired coloring photosensitive resin composition is obtained at a specific concentration.

Examples of the method for obtaining the pattern include a photolithography method, an inkjet method, a printing method, and the like. Among them, photolithography is preferred. The photolithography method is a method in which the coloring photosensitive resin composition is applied onto a substrate, dried, and exposed and developed through a light mask to obtain a pattern.

Examples of the substrate include glass, metal, plastic, and the like, and may be in the form of a plate or a film.

Examples of the plastics include polyolefins such as polyethylene, polypropylene, and borneol-based polymers, polyvinyl alcohol, polyethylene terephthalate, polyethylene naphthalate, and poly(methyl). Acrylate, cellulose ester, polycarbonate, polyfluorene, polyether oxime, polyether ketone, polyphenylene sulfide, polyphenylene ether and the like. Here, (meth)acrylic acid means at least one kind derived from acrylic acid and methacrylic acid. The selected one of the group of acids. A structure such as a color filter, various insulating or conductive films, and a driving circuit may be formed on the substrate.

According to the colored photosensitive resin composition of the present invention, since the pattern can be formed to be cured at a lower temperature, it is particularly useful when the pattern is formed on a plastic substrate.

Examples of the method of applying the substrate include an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, a CAP coating method, a die coating method, and the like. . In addition, an impregnation coater, a roll coater, a bar coater, a spin coater, a slit & spin coater, a slit coater (also referred to as a die coater, a shower curtain) may also be used. A coating device such as a coater or a slit precision coater or an inkjet is applied. Among them, it is preferred to apply it by using a slit coater, a spin coater, a roll coater or the like.

The drying method of the film applied to the substrate includes, for example, heat drying, natural drying, air drying, and vacuum drying. A plurality of methods can also be combined.

The drying temperature is preferably from 10 to 120 ° C, more preferably from 25 to 100 ° C. In addition, the heating time is preferably from 10 seconds to 60 minutes, and more preferably from 30 seconds to 30 minutes.

Drying under reduced pressure is preferably carried out at a temperature of 50 to 150 ° C and a temperature range of 20 to 25 ° C.

The thickness of the coating film after drying is not particularly limited, and may be appropriately adjusted depending on the material to be used, the use, and the like, and is, for example, 0.1 to 20 μm, preferably 1 to 6 μm.

The coated film after drying is exposed through a light mask for forming a pattern of interest. The shape of the pattern on the light mask at this time is not particularly limited, and a pattern shape that is intended for the purpose can be used.

The light source used for the exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, a light that is not up to 350 nm can be cut using a filter for cutting out the wavelength region, or a light band filter for extracting the wavelength regions can be used for light near 436 nm, near 408 nm, and near 365 nm. take out. Specifically, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, etc. are mentioned.

In order to uniformly irradiate the parallel light to the entire exposed surface, or to perform the correct alignment of the mask and the substrate, it is preferable to use a mask to align the exposure machine, the stepper, or the like.

A pattern can be obtained by causing a coating film after exposure to contact a developing liquid to dissolve and develop a specific portion, for example, an unexposed portion. In the developing solution, an organic solvent may be used. However, the developing portion of the coating film is hardly dissolved or swollen by the developing solution, and in order to obtain a pattern having a good shape, it is preferable to use an aqueous solution of a basic compound. .

The developing method may be any one of a liquid filling method, a dipping method, a spraying method, and the like. Furthermore, the substrate can be tilted at any angle during development.

After the development, it is better to wash the water.

Examples of the basic compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium citrate, potassium citrate, and the like. An inorganic basic compound of sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium borate, potassium borate, ammonia, or the like; Tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, single An organic basic compound such as isopropylamine, diisopropylamine or ethanolamine. Among them, potassium hydroxide, sodium carbonate and tetramethylammonium hydroxide are preferred.

The concentration in the aqueous solution of the inorganic and organic basic compounds is preferably from 0.01 to 10% by mass, more preferably from 0.03 to 5% by mass.

The aqueous solution of the above basic compound may also contain a surfactant.

Examples of the surfactants include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers, other polyoxyethylene derivatives, oxyethylene/oxypropylene block polymers, and sorbents. Nonionic interface of alcohol fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, glycerol fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, etc. An active surfactant; an anionic surfactant such as sodium lauryl sulfate, sodium oleyl sulfate, sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate or sodium dodecyl naphthalenesulfonate; A cationic surfactant such as stearylamine hydrochloride or lauryl trimethylammonium chloride.

The concentration of the surfactant in the aqueous solution of the basic compound is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, particularly preferably 0.1 to 5% by mass.

The hardened pattern can be obtained by further baking the pattern obtained above. The baking temperature is 25 ° C or more and 230 ° C or less, preferably 25 ° C or more and 200 ° C or less, more preferably 25 ° C or more and 160 ° C or less, and even more preferably 25 ° C or more and 120 ° C or less. The baking time is 1 to 300 minutes, preferably 1 to 180 minutes, more preferably 1 to 60 minutes.

A pattern and a color filter can be obtained from the colored photosensitive composition of the present invention. These patterns or color filters are well-known aspects, and display devices having a pattern or a color filter as a part of a component, such as a well-known liquid crystal display device, an organic EL device, and a solid. It is used in a machine in which various color images of an imaging element, electronic paper, and the like are associated.

Example

Hereinafter, the present invention will be described in more detail by way of examples. In the example, "%" and "parts" are % by mass and parts by mass unless otherwise stated.

<Synthesis of Resin Solution B1> Synthesis Example 1

In a flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel, and a nitrogen introduction tube, 133 g of propylene glycol monomethyl ether acetate was introduced, and after the atmosphere in the flask was replaced with nitrogen by air, the temperature was raised to 100 ° C. Thereafter, it will consist in 96.0 g (0.55 mol) of benzyl methacrylate, 17.6 g (0.21 mol) of methacrylic acid, 22.0 g (0.10 mol) of dicyclopentadienyl methacrylate. 3.6 g of azobisisobutyronitrile was added to a mixture of 133 g of propylene glycol monomethyl ether acetate (Hitachi Chemical Co., Ltd.) and 133 g of propylene glycol monomethyl ether acetate. It took 2 hours to drip from the dropping funnel. The flask was further stirred at 100 ° C for 5 hours. Next, the atmosphere in the flask was replaced with nitrogen from air, and 21.3 g [0.15 mol] of glycidyl methacrylate, 0.9 g of dimethylglycolamino cresol, and 0.145 g of hydroquinone were placed in the flask. The reaction was continued at 110 ° C for 6 hours to obtain a resin solution B1 having a solid content of 37.6% and an acid value of 67.7 mgKOH/g (in terms of solid content). The polystyrene-equivalent weight average molecular weight measured by GPC was 9,500.

<Synthesis of Resin Solution B2> Synthesis Example 2

In a flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel, and a nitrogen introduction tube, 161 g of propylene glycol monomethyl ether acetate was introduced, and the atmosphere in the flask was replaced with nitrogen from air, and then the temperature was raised to 100 ° C. Thereafter, it will be in 66.1 g (0.38 mol) of benzyl methacrylate, 45.2 g (0.23 mol) of methacrylic acid, 22.0 g (0.10 mol) of dicyclopentadienyl methacrylate. 3.6 g of azobisisobutyronitrile was added to a mixture of propylene glycol monomethyl ether acetate (Hitachi Chemical Co., Ltd.) and 133 g of propylene glycol monomethyl ether acetate. It took 2 hours to drip into the flask from the dropping funnel. Further, stirring was further continued at 100 ° C for 5 hours. Next, the atmosphere in the flask was replaced with nitrogen from air, and 42.6 g of [0.30 mol] glycidyl methacrylate, 0.9 g of dimethylglycine cresol, and 0.145 g of hydroquinone were placed in the flask. The reaction was continued at 110 ° C for 6 hours to obtain a resin solution B2 having a solid content of 37.4% and an acid value of 71.8 mgKOH/g (in terms of solid content). Polystyrene-converted weight measured by GPC The amount average molecular weight was 8,500.

Example 1~5

Among the components described in Table 1, the total amount of the pigment and the pigment dispersant was previously mixed with propylene glycol monomethyl ether acetate as a solvent. In this case, propylene glycol monomethyl ether acetate was mixed so that the total amount of the pigment and the pigment dispersant was 20% by mass based on the mixture. The pigment in the mixture was sufficiently dispersed using a ball mill, and the residual component containing the residual amount of propylene glycol monomethyl ether acetate was added thereto, and the above mixture was further mixed to obtain a photosensitive resin composition.

Comparative example 1

Except that the resin B1 in Example 1 was changed to the resin B3 (benzyl methacrylate/methacrylic acid copolymer (mass composition ratio 80/20, polystyrene equivalent weight average molecular weight 35,000)), and Example 1 Do the same.

A1: C.I. Pigment Green 36

A2: C.I. Pigment yellow 150

A3: C.I. Pigment Green 58

A4: C.I. Pigment yellow 138

A5: C.I. Pigment Red 177

A6: C.I. Pigment Red 254

A7: C.I. Pigment Blue 15:6

A8: C.I. Pigment purple 23

B3: benzyl methacrylate/methacrylic acid copolymer (mass composition ratio 80/20, polystyrene-equivalent weight average molecular weight 35,000)

C1: dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)

D1: 2-benzyl-2-dimethylamino-(4-morpholinylphenyl)-butan-1-one (IRGACURE 369; manufactured by BASF Japan)

D2: 4,4'-bis(diethylamino)-benzophenone (EAB-F; manufactured by Hodogaya Chemical Co., Ltd.)

D3: N-benzylideneoxy-1-(4-phenylsulfonylphenyl)octane-1-one-2-imine (OXE-01; manufactured by BASF Japan)

D4: bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide (Irgacure 819; manufactured by BASF. Japan)

D5: 2-methyl-2-morpholinyl (4-methyldecylphenyl)-propan-1-one (Irgacure 907; manufactured by BASF. Japan)

D6: diethyl thioxanthone (KAYACURE DETX; manufactured by Nippon Kayaku Co., Ltd.)

E1: pentaerythritol bismuth (3-sulfonyl propionate) (PEMP; SC organic chemistry (stock) system)

F1: propylene glycol monomethyl ether acetate

F2: ethyl 3-ethoxypropionate

G1: pigment dispersant (polyester)

G2: pigment dispersant (acrylic)

G3: SUMI-EPOXY ESCN-195XL

G4: surfactant: polyether modified polyketone oil

(Toray SILICONESH8400; manufactured by Dow Corning Toray Co., Ltd.)

<Solvent resistance evaluation>

The colored photosensitive compositions 1 to 6 were applied onto a substrate of a PET film (LUMILER 75-T60 manufactured by Toray) on a glass plate of 2 inches square by a spin coating method, and on a hot plate. Prebaking at 80 ° C for 2 minutes.

After the cooling, the exposure was carried out using an exposure machine (TME-150RSK; TOPCON) to expose the light to an exposure amount of 150 mJ/cm ² (365 nm basis) in an air atmosphere. After light irradiation, it was immersed in an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23 ° C for 50 seconds, and after washing with whiteness, Heating at 60 ° C for 5 minutes to form a color pattern. The film thickness of the obtained pattern was measured to be 2 μm using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.).

The chromaticity is a value measured using a microscopic spectrophotometer (manufactured by OSP-SP200 OLYMPUS). In addition, the source of color measurement A C light source is used.

1 ml of propylene glycol monomethyl ether acetate was dropped onto the measured coating film, and after standing for 30 s in a paddle stirrer, it was shaken for 10 s at a rotation number of 1000 rpm.

Then, the film thickness and the chromaticity were measured in the same manner as described above. The film thickness change rate before and after the contact measurement of propylene glycol monomethyl ether acetate was calculated by the following formula.

Film thickness retention ratio (%) = film thickness after contact / film thickness before contact × 100

Further, the excellent difference was calculated based on the chromaticity before and after the measurement of JIS Z 8730 and propylene glycol monomethyl ether acetate.

When the film thickness retention ratio is higher and the chromatic aberration is smaller, the solvent resistance is better, and when a color filter is formed, color mixing can be prevented.

<Resolution Evaluation>

The previously formed pattern was observed with a laser microscope (manufactured by Axio Imager MAT Carl Zeiss Co., Ltd.), and the minimum size of the solution was set as the resolution. The resolution is such that a finer pattern can be formed, and the workability is more excellent.

Industrial availability

According to the colored photosensitive resin composition of the present invention, a pattern having excellent resolution and durability can be obtained.

Claims (6)

A colored photosensitive resin composition comprising (A), (B), (C), (D), (E) and (F) with a thioxanthone compound, a mercaptophosphine oxide compound or an alkyl group a benzophenone compound: (A) a colorant; (B) a copolymer obtained by copolymerizing the following (a) and (b) with (c) a resin obtained by reacting; (a): an unsaturated carboxylic acid and At least one selected from the group consisting of unsaturated carboxylic anhydrides (b): a monomer having an unsaturated bond copolymerizable with (a) and different from (a): having a carbon number of 2~ a cyclic ether skeleton and an ethylenically unsaturated bond monomer (C) polymerizable compound; (D) a ruthenium compound polymerization initiator; (E) a polyfunctional thiol compound; (F) a solvent. The colored photosensitive resin composition according to the first aspect of the invention, wherein (b) comprises a skeleton selected from the group consisting of at least one tricyclodecane skeleton and a tricyclodecene skeleton, and A compound of ethylenically unsaturated bonds. The colored photosensitive resin composition according to the first aspect of the invention, wherein (c) is a monomer having an oxirane group and an ethylenically unsaturated bond. A pattern formed by using the colored photosensitive resin composition described in the first aspect of the patent application. A color filter comprising the pattern as recited in claim 4 of the patent application. A method for producing a color filter, comprising the steps of (1) to (3): (1) coating a colored photosensitive resin composition as described in claim 1 of the patent application; a step of obtaining a coating film on the substrate; (2) exposing on the coating film through a mask to obtain a film after exposure; (3) coating the film after exposure by an alkali developing solution Visualize the steps to get the pattern.