CN103376654A - Colored photosensitive resin composition - Google Patents

Abstract

A colored photosensitive resin composition, which contains a colorant, a resin, a polymerizable compound, and a polymerization initiator, wherein the colorant contains C.I. Pigment Green 36, a yellow pigment, and a color selected from blue pigments, red pigments, purple pigments and At least one of the group consisting of orange pigments, the resin being a copolymer containing: a structural unit derived from at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and, A structural unit with an alicyclic hydrocarbon structure.

Description

Colored photosensitive resin composition

technical field

The present invention relates to a colored photosensitive resin composition.

Background technique

The colored photosensitive resin composition is used for production of color filters used in display devices such as liquid crystal display devices, electroluminescent display devices, and plasma displays. As such a colored photosensitive resin composition, a composition containing a copolymer of methacrylic acid, methyl methacrylate, n-butyl methacrylate and 2-hydroxyethyl methacrylate as a resin is known (JP2004- 309537-A).

In the conventionally known colored photosensitive resin composition, when a colored pattern is formed by photolithography, unexposed portions cannot be sufficiently removed by development, and residues and film residues may be generated.

Contents of the invention

The present invention includes the following technical solutions.

[1] A colored photosensitive resin composition containing a colorant, a resin, a polymerizable compound, and a polymerization initiator, wherein,

The coloring agent contains C.I. Pigment Green 36, a yellow pigment, and at least one selected from the group consisting of a blue pigment, a red pigment, a purple pigment, and an orange pigment,

The resin is a copolymer containing: a structural unit derived from at least one selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic anhydride; and a structural unit having an alicyclic hydrocarbon structure.

[2] The colored photosensitive resin composition described in [1], wherein the structural unit having an alicyclic hydrocarbon structure is a structural unit derived from a monomer having a substituent with carbon atoms of 3-18 alicyclic hydrocarbon groups.

[3] The colored photosensitive resin composition according to [1] or [2], wherein the polymerization initiator contains an O-acyl oxime compound.

[4] The colored photosensitive resin composition described in any one of [1] to [3], wherein at least one selected from the group consisting of blue pigments, red pigments, purple pigments and orange pigments is C.I. Pigment Red 177.

[5] A color filter formed from the colored photosensitive resin composition according to any one of [1] to [4].

[6] A display device comprising the color filter described in [5].

When the colored photosensitive resin composition of the present invention is used, it is excellent in developability when forming a colored pattern by photolithography.

Detailed ways

The colored photosensitive resin composition of this invention contains a coloring agent (A), resin (B), a polymeric compound (C), and a polymerization initiator (D).

The colored photosensitive resin composition of the present invention preferably further contains at least one selected from the group consisting of a solvent (E), a thiol compound (T), a leveling agent (F) and an adhesion promoter (G).

The colored photosensitive resin composition of this invention can further contain a polymerization start adjuvant (D1).

<Colorant (A)>

The colorant (A) contains C.I. Pigment Green 36, a yellow pigment, and at least one selected from the group consisting of a blue pigment, a red pigment, a purple pigment, and an orange pigment.

Examples of yellow pigments include C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125 , 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214, etc., preferably C.I. Pigment Yellow 138, 150.

As a blue pigment, C.I. pigment blue 15, 15:3, 15:4, 15:6, 60, 80 etc. are mentioned, for example.

Examples of red pigments include C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 175, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254 , 255, 264, 265, etc., preferably C.I. Pigment Red 177.

As a purple pigment, C.I. Pigment Violet 1, 19, 23, 29, 32, 36, 38 etc. are mentioned, for example, C.I. Pigment Violet 23 is preferable.

Examples of orange pigments include C.I. Pigment Violet 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, and 73. C.I. Pigment Violet 38 is preferred.

Among at least one selected from the group consisting of blue pigments, red pigments, violet pigments, and orange pigments, C.I. Pigment Red 177 is preferable in terms of contrast enhancement of the resulting color filter.

The pigment used in the colored photosensitive resin composition of the present invention may be subjected to rosin treatment, surface treatment using a pigment derivative having an acidic group or a basic group introduced therein, or surface treatment using a polymer compound or the like to the pigment surface as necessary. Branch treatment, micronization treatment using sulfuric acid micronization method, etc., washing treatment using organic solvent or water for removing impurities, removal treatment of ionic impurities using ion exchange method, etc., etc. The particle diameters of the pigments are preferably each uniform.

These pigments can be prepared as a pigment dispersion in a uniformly dispersed state in a pigment dispersant solution by dispersing them by adding a pigment dispersant. The pigments can be dispersed individually or in combination of multiple types.

Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, acrylic and other pigment dispersants. These pigment dispersants may be used alone or in combination of two or more. Examples of pigment dispersants include trade names KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by ZENECA Co., Ltd.), EFKA (manufactured by BASF), Ajisper (manufactured by Ajinomoto Fine-Techno Co., Inc.), Disperbyk (manufactured by BYK), etc.

When a pigment dispersant is used, the amount used is preferably 100 parts by mass or less, more preferably 5 parts by mass or more and 50 parts by mass or less, based on 100 parts by mass of the pigment. When the usage-amount of a pigment dispersant is in the said range, the pigment dispersion liquid of a uniform dispersion state tends to be obtained.

The content of C.I. Pigment Green 36 is preferably 20 to 99% by mass, more preferably 30 to 95% by mass based on the total amount of the colorant (A).

The content of the yellow pigment is preferably 0.1 to 79.9% by mass, more preferably 4.9 to 60% by mass based on the total amount of the colorant (A).

The content of at least one selected from the group consisting of blue pigments, red pigments, purple pigments and orange pigments is preferably 0.1 to 5% by mass, more preferably 0.1 to 3% by mass relative to the total amount of the colorant (A). .

The content of the coloring agent (A) is preferably 20% by mass or more and 50% by mass or less, more preferably 28 to 45% by mass based on the total solid content. In this specification, "the total amount of solid content" means the total amount of the component which removed the solvent (E) from the colored photosensitive resin composition of this invention.

<Resin (B)>

The resin (B) is a copolymer containing: a structural unit derived from at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter sometimes referred to as "(a)"), and, a structural unit having an alicyclic hydrocarbon structure.

A structural unit having an alicyclic hydrocarbon structure is obtained from a monomer (hereinafter, sometimes referred to as "(x)") having an alicyclic hydrocarbon structure.

As resin (B), the following copolymer [K1]-[K5] is mentioned, for example.

Copolymer [K1]: a copolymer of (a) and (x);

Copolymer [K2]: (a), (x), and monomer (c) copolymerizable with (a) (wherein, (a) and (x) are different.) (hereinafter sometimes referred to as "(c) ") copolymers;

Copolymer [K3]: Copolymer [K1] or copolymer [K2] and a monomer (b) having a cyclic ether structure with 2 to 4 carbon atoms and an ethylenically unsaturated bond (hereinafter sometimes referred to as "( b) ") the resin obtained by the reaction;

Copolymer [K4]: the resin obtained by reacting the copolymer of (b) and (x) with (a);

Copolymer [K5]: a resin obtained by reacting a copolymer of (b) and (x) with (a), and further reacting with a carboxylic anhydride.

As (a), specifically, for example, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, ortho-, meta-, and p-vinylbenzoic acid;

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid Dicarboxylic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexene dicarboxylic acid and other unsaturated dicarboxylic acids;

Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[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-ene, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene and other carboxyl-containing bicyclic unsaturated compounds;

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1, 2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride and other unsaturated dicarboxylic acids anhydride;

Unsaturated mono [ (meth)acryloyloxyalkyl] esters;

α-(Hydroxymethyl)acrylic acid and the like are unsaturated acrylic esters containing a hydroxyl group and a carboxyl group in the same molecule.

Among these, acrylic acid, methacrylic acid, maleic anhydride, and the like are preferable from the viewpoint of copolymerization reactivity and the solubility of the resulting resin in an aqueous alkali solution.

(x) is, for example, a monomer having an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent.

Examples of alicyclic hydrocarbon groups having 3 to 18 carbon atoms include cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl; tricyclodecanyl, decahydronaphthyl, and adamantyl; , norbornyl and other polycyclic alicyclic hydrocarbon groups, etc., preferably polycyclic alicyclic hydrocarbon groups, more preferably tricyclodecanyl.

Examples of substituents these groups may have include aliphatic hydrocarbon groups having 1 to 18 carbon atoms, aromatic hydrocarbon groups having 6 to 18 carbon atoms, hydroxyl groups, halogen atoms, epoxy groups, and the like.

Examples of the aliphatic hydrocarbon group having 1 to 18 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl and hexyl.

Examples of the aromatic hydrocarbon group having 6 to 18 carbon atoms include phenyl, naphthyl, anthracenyl, toluoyl, xylyl, cumyl, m-methylphenyl, biphenyl, phenanthrenyl, etc. .

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The monomer having an alicyclic hydrocarbon structure is, for example, a monomer having an alicyclic hydrocarbon structure and an ethylenically unsaturated bond, preferably a monomer having an alicyclic hydrocarbon structure and a (meth)acryloyloxy group.

In addition, in this specification, a "(meth)acryloyl group" means at least 1 sort(s) chosen from the group which consists of an acryloyl group and a methacryloyl group. Expressions such as "(meth)acrylic acid" and "(meth)acrylate" have the same meaning.

Examples of (x) include cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ] Decane-8-yl (meth)acrylate (in this technical field, known as the customary name "(meth)acrylate dicyclopentyl (pentanyl) ester". Also sometimes called "(meth)acrylic acid Tricyclodecanyl ester".), tricyclo[5.2.1.0 ^2,6 ]decen-8-yl (meth)acrylate (in the technical field, known as the customary name "(meth)acrylate dicyclopentanyl Alkenyl (pentenyl) ester".), dicyclopentyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, etc. base) acrylates;

Bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 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-ethoxybicyclo[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-ene, 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]hept-2-ene, 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene Bicyclic unsaturated compounds such as N-cyclohexylmaleimide and other N-substituted maleimides with alicyclic hydrocarbon structure; etc.

In addition, (x) may be a monomer having a structure in which, as an alicyclic hydrocarbon structure, two hydrogen atoms bonded to two adjacent carbon atoms of the alicyclic hydrocarbon are replaced by epoxy groups (hereinafter Sometimes referred to as "(x')").

Examples of such (x) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide 2000; manufactured by Daicel Corporation), acrylic acid 3, 4-epoxycyclohexylmethyl ester (for example, Cyclomer A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl methacrylate (for example, Cyclomer M100; manufactured by Daicel Corporation), formula Compounds represented by (I), compounds represented by formula (II), and the like.

[In formula (I) and formula (II), R ^a and R ^b represent a hydrogen atom or an alkyl group with 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted by a hydroxyl group.

X ^a and X ^b represent a single bond, -R ^c -, *-R ^c -O-, *-R ^c -S-, or *-R ^c -NH-.

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

＊Indicates the connection key with O. ]

Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group and the like.

Examples of the alkyl group in which a hydrogen atom is substituted by a hydroxyl group include hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxy- 1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, etc.

As R ^a and R ^b , preferably a hydrogen atom, a methyl group, a hydroxymethyl group, 1-hydroxyethyl group, and 2-hydroxyethyl group, more preferably a hydrogen atom and a methyl group.

Examples of the alkanediyl group include methylene, ethylene, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5 -diyl, hexane-1,6-diyl, etc.

Examples of X ^a and X ^b preferably include a single bond, methylene, ethylene, *-CH ₂ -O- and *-CH ₂ CH ₂ -O-, more preferably a single bond, *-CH ₂ CH ₂ - O-(* indicates the bond with O).

Examples of the compound represented by the formula (I) include compounds represented by any one of the formulas (I-1) to (I-15), and the like. Among them, preferred formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9) or formula (I-11) ~ formula (I-15 ), more preferably a compound represented by formula (I-1), formula (I-7), formula (I-9) or formula (I-15).

Examples of the compound represented by the formula (II) include compounds represented by any one of the formulas (II-1) to (II-15), and the like. Among them, preferred formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) or formula (II-11) ~ formula (II-15 ), more preferably a compound represented by formula (II-1), formula (II-7), formula (II-9) or formula (II-15).

The compound represented by formula (I) and the compound represented by formula (II) may be used alone, respectively, or the compound represented by formula (I) and the compound represented by formula (II) may be used in combination. When these compounds are used together, the content ratio of the compound represented by the formula (I) to the compound represented by the formula (II) is preferably 5:95 to 95:5, more preferably 10:90 to 90:10 on a molar basis, and further Preferably 20:80 to 80:20.

(c) is not particularly limited as long as it is a monomer that is copolymerizable with (a) and is different from (a) and (x).

Examples of (c) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate ester, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, allyl (meth)acrylate , (meth)acrylates such as propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, benzyl (meth)acrylate, etc.;

Hydroxyl-containing (meth)acrylates such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate;

Diethyl maleate, diethyl fumarate, diethyl itaconate and other dicarboxylic acid diesters;

N-phenylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4- Maleimide butyrate, N-succinimidyl-6-maleimide hexanoate, N-succinimidyl-3-maleimide propionate, N-( 9-acridyl) maleimide and other dicarbonyl imide derivatives;

Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide , methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc.

Among these, styrene, vinyltoluene, benzyl (meth)acrylate, N-phenylmaleimide, N-benzylmaleimide are preferable in terms of copolymerization reactivity and heat resistance. Amines etc.

In addition, in (c), as having a cyclic ether structure with 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring ) monomer (hereinafter sometimes referred to as "(c')"), for example, glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, (meth)acrylic acid β-Ethyl glycidyl ester, 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(glycidyl Oxymethyl) styrene, 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl) base) styrene, 2,3,4-tris(glycidyloxymethyl)styrene, 2,3,5-tris(glycidyloxymethyl)styrene, 2,3,6-tris(glycidyloxymethyl)styrene, Glyceryloxymethyl)styrene, 3,4,5-tris(glycidyloxymethyl)styrene, 2,4,6-tris(glycidyloxymethyl)styrene, etc. have ethylene oxide monomers with radicals and ethylenically unsaturated bonds;

3-Methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxy Methyloxetane, 3-ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl -3-Acryloyloxyethyloxetane, 3-Ethyl-3-methacryloyloxyethyloxetane, 3-Ethyl-3-acryloyloxyethyloxetane Alkanes and other monomers with oxetanyl groups and ethylenically unsaturated bonds;

Monomers having a tetrahydrofuryl group and an ethylenically unsaturated bond such as tetrahydrofurfuryl acrylate (for example, VISCOAT V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, etc.

In the copolymer [K1], in the total structural units constituting the copolymer [K1], the ratio of the structural unit derived from each monomer is,

Preferred:

Structural unit derived from (a): 2 to 60 mol%

Structural unit derived from (x): 40 to 98 mol%

More preferably:

Structural unit derived from (a): 10 to 50 mol%

Structural unit derived from (x): 50 to 90 mol%.

When the ratio of the structural unit of copolymer [K1] is the said range, it exists in the tendency for the developability at the time of forming a colored pattern, and the solvent resistance of the obtained color filter to be excellent.

Copolymer [K1] can be referred to, for example, the method described in the document "Experimental Method for Polymer Synthesis" (Otsu Takayuki Publishing Co., Ltd. Chemical Doujin First Edition, First Edition, March 1, 1972) and the method described in this document. Recorded citations are produced.

Specifically, the following method can be cited: put (a) and (x) predetermined amount, polymerization initiator, solvent, etc. into a reaction vessel, for example, replace oxygen with nitrogen to make a deoxidizing atmosphere, stir, heat and The method of heat preservation. In addition, the polymerization initiator, solvent, and the like used here are not particularly limited, and those commonly used in this field can be used. For example, examples of the polymerization initiator include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.), organic peroxide The solvent (benzoyl peroxide, etc.) may be any solvent as long as it dissolves each monomer, and the solvent (E) of the colored photosensitive resin composition of the present invention includes the solvents described later.

In addition, the obtained copolymer may be used as it is after the reaction, may be used as a concentrated or diluted solution, or may be taken out as a solid (powder) by reprecipitation or the like. In particular, by using the solvent contained in the colored photosensitive resin composition of the present invention as a solvent at the time of this polymerization, the solution after the reaction can be used as it is in the preparation of the colored photosensitive resin composition of the present invention, so that The manufacturing process of the colored photosensitive resin composition of this invention is simplified.

In the copolymer [K2], in the total structural units constituting the copolymer [K2], the ratio of the structural unit derived from each monomer is,

Preferred:

Structural unit derived from (a): 2 to 45 mol%

Structural unit derived from (x): 2 to 95 mol%

Structural unit derived from (c): 1 to 65 mol%

More preferably:

Structural unit derived from (a): 5 to 40 mol%

Structural unit derived from (x): 5 to 80 mol%

Structural unit derived from (c): 5 to 60 mol%.

When the ratio of the structural unit of copolymer [K2] is the said range, it exists in the tendency for the developability at the time of forming a colored pattern, and the solvent resistance, heat resistance, and mechanical strength of the obtained color filter to be excellent.

Copolymer [K3] can be produced by adding (b) to copolymer [K1] or copolymer [K2]. Examples of (b) include the aforementioned (c') and (x'). Copolymer [K1] and copolymer [K2] used for the production of copolymer [K3] are preferably copolymers that do not have a structural unit derived from (x') and a structural unit derived from (c').

The copolymer [K1] or the copolymer [K2] produced as described above is made such that a part of the carboxylic acid and/or carboxylic acid anhydride derived from (a) and (b) in the copolymer have 2 carbon atoms ~4 cyclic ether reactions.

After the manufacture of copolymer [K1] or copolymer [K2], the atmosphere in the flask is replaced by nitrogen to air, and the reaction catalyst (such as tris(dimethyl (aminomethyl)phenol, etc.) and a polymerization inhibitor (such as hydroquinone, etc.) are put into a flask, and the copolymer [K3] is produced by, for example, reacting at 60 to 130° C. for 1 to 10 hours.

The usage-amount of (b) is preferably 5-80 mol with respect to 100 mol of (a), More preferably, it is 10-75 mol. By being within this range, the balance between the storage stability of the colored photosensitive resin composition, the developability at the time of pattern formation, and the solvent resistance, heat resistance, mechanical strength, and sensitivity of the obtained pattern tends to be improved. From the viewpoint of high reactivity of cyclic ethers and difficulty in remaining unreacted (b), as (b) used in the production of copolymer [K3], those having an oxiranyl group and an ethylenically unsaturated bond are preferable. monomer.

It is preferable that the usage-amount of the said reaction catalyst is 0.001-5 mass parts with respect to 100 mass parts of total amounts of the whole monomer used for manufacture of copolymer [K1] or copolymer [K2], and (b). It is preferable that the usage-amount of the said polymerization inhibitor is 0.001-5 mass parts with respect to 100 mass parts of total amounts of the whole monomer used for manufacture of copolymer [K1] or copolymer [K2], and (b).

Reaction conditions, such as a feeding method, reaction temperature, and time, can be appropriately adjusted in consideration of production facilities, heat generation due to polymerization, and the like. In addition, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production equipment, the heat generated by the polymerization, and the like in the same manner as the polymerization conditions.

Regarding the copolymer [K4], the copolymer of (b) and (x) was obtained in the same manner as the production method of the above-mentioned copolymer [K1] as the first step. Similar to the above, the obtained copolymer may be used as it is after the reaction, may be used as a concentrated or diluted solution, or may be taken out as a solid (powder) by reprecipitation or the like. As (b) used for manufacture of copolymer [K4], the monomer which has an oxirane group and an ethylenic unsaturated bond is preferable.

The ratios of the structural units derived from (b) and (x) relative to the total number of moles of all structural units constituting the aforementioned copolymer are, respectively,

Preferred:

Structural unit derived from (b): 5 to 95 mol%

Structural unit derived from (x): 5 to 95 mol%

More preferably:

Structural unit derived from (b): 10 to 90 mol%

Structural unit derived from (x): 10 to 90 mol%.

Furthermore, the cyclic ether derived from (b) contained in the copolymer of (b) and (x) and the cyclic ether contained in (a) can be obtained under the same conditions as the production method of the copolymer [K4]. Carboxylic acid or carboxylic acid anhydride is reacted to obtain a copolymer [K4].

The usage-amount of (a) reacted with the said copolymer is preferably 5-80 mol with respect to 100 mol of (b).

The copolymer [K5] is a resin obtained by further reacting the copolymer [K4] with carboxylic anhydride. A hydroxyl group produced by reacting a cyclic ether with a carboxylic acid or carboxylic anhydride is reacted with a carboxylic anhydride.

Examples of carboxylic anhydrides include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, Diformic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride, etc. . The usage-amount of carboxylic anhydride is preferably 0.5 to 1 mole relative to the usage-amount of 1 mole of (a).

As the resin (B), specifically, 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2. 1.0 ^2.6 ]decyl (meth)acrylate/(meth)acrylic acid copolymer, tricyclic [5.2.1.0 ^2.6 ]decyl (meth)acrylate/(meth)acrylic acid copolymer, etc. [K1] ;

3,4-epoxy tricyclo[5.2.1.0 ^2.6 ]decyl (meth)acrylate/(meth)acrylic acid/N-cyclohexylmaleimide copolymer, 3,4-epoxytricyclo Cyclo[5.2.1.0 ^2.6 ]decyl (meth)acrylate/(meth)acrylic acid/vinyl toluene copolymer, Tricyclo[5.2.1.0 ^2.6 ]decyl (meth)acrylate/(meth)acrylic acid Copolymers/copolymers such as benzyl (meth)acrylate [K2];

Resin obtained by adding tricyclodecanyl (meth)acrylate/styrene/(meth)acrylic acid copolymer to glycidyl (meth)acrylate, tricyclodecanyl (meth)acrylate/(meth)acrylic acid Copolymers such as resins obtained by addition of benzyl ester/(meth)acrylic acid copolymer and glycidyl (meth)acrylate [K3];

Resin obtained by reacting tricyclodecanyl (meth)acrylate/glycidyl (meth)acrylate copolymer with (meth)acrylic acid, tricyclodecanyl (meth)acrylate/styrene/(meth)acrylic acid Copolymers such as resins obtained by reacting glycidyl ester copolymers with (meth)acrylic acid [K4];

Copolymers such as resins obtained by reacting tricyclodecanyl (meth)acrylate/glycidyl (meth)acrylate copolymers with (meth)acrylic acid and then reacted with tetrahydrophthalic anhydride [K5] wait.

The resin (B) is preferably one selected from the group consisting of copolymer [K1] and copolymer [K2]. These resins are excellent in the developability of the colored photosensitive resin composition. The copolymer [K2] is more preferable from the viewpoint of the adhesiveness of a colored pattern and a board|substrate.

The polystyrene conversion weight average molecular weight of resin (B) becomes like this. Preferably it is 3,000-100,000, More preferably, it is 5,000-50,000, More preferably, it is 5,000-30,000. When the molecular weight is within the aforementioned range, the hardness of the coating film increases, the remaining film rate is also high, the solubility of the unexposed portion to the developing solution becomes favorable, and the resolution of the colored pattern tends to improve.

The molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the resin (B) is preferably 1.1-6, more preferably 1.2-4.

The acid value of the resin (B) is preferably 50 to 170 mg-KOH/g, more preferably 60 to 150 mg-KOH/g, and still more preferably 70 to 135 mg-KOH/g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the resin (B), and can be obtained by titration using, for example, an aqueous potassium hydroxide solution.

The content of the resin (B) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and still more preferably 17 to 55% by mass based on the total solid content. When the content of the resin (B) is within the above range, the resolution of the colored pattern and the residual film ratio tend to be improved.

<Polymerizable compound (C)>

The polymerizable compound (C) is a compound that can be polymerized under the action of active radicals and/or acids generated by the polymerization initiator (D), for example, compounds having polymerizable ethylenically unsaturated bonds, etc., (Meth)acrylate compounds are preferred.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate Dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, tetrapentaerythritol nona(meth)acrylate Ester, Tris(2-(meth)acryloyloxyethyl)isocyanurate, Ethylene glycol-modified pentaerythritol tetra(meth)acrylate, Ethylene glycol-modified dipentaerythritol hexa(meth)acrylate , propylene glycol modified pentaerythritol tetra(meth)acrylate, propylene glycol modified dipentaerythritol hexa(meth)acrylate, caprolactone modified pentaerythritol tetra(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth)acrylate base) acrylate, etc.

Among them, dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate are preferable.

The weight average molecular weight of the polymerizable compound (C) is preferably 150 to 2,900, more preferably 250 to 1,500.

The content of the polymerizable compound (C) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and still more preferably 17 to 55% by mass based on the total solid content.

In addition, the content ratio of the resin (B) to the polymerizable compound (C) [resin (B):polymerizable compound (C)] is preferably 20:80 to 80:20, more preferably 35:65 to 80 on a mass basis :20, more preferably 50:50 to 75:25, especially preferably 55:50 to 70:30.

When content of a polymeric compound (C) exists in the said range, the residual film rate at the time of color pattern formation and the chemical resistance of a color filter tend to improve.

<Polymerization Initiator (D)>

The polymerization initiator (D) is not particularly limited as long as it is a compound that generates active radicals, acids, etc. under the action of light or heat to initiate polymerization, and known polymerization initiators can be used.

Examples of the polymerization initiator (D) include alkylphenone compounds, triazine compounds, acyl phosphine oxide compounds, O-acyl oxime compounds, and bisimidazole compounds.

The aforementioned O-acyl oxime compound is a compound having a partial structure represented by formula (d1). Hereinafter, * represents a connection key.

As the aforementioned O-acyl oxime compound, for example, N-benzoyloxy-1-(4-phenylmercapto (sulfanil) phenyl) butane-1-one-2-imine, N-benzyl Acyloxy-1-(4-phenylmercaptophenyl)octane-1-one-2-imine, N-benzoyloxy-1-(4-phenylmercaptophenyl)-3-cyclo Amylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane -1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxolylmethyl Oxy)benzoyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl) -9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl) -9H-carbazol-3-yl]-3-cyclopentylpropan-1-one-2-imine, etc. Commercially available products such as Irgacure OXE01 and OXE02 (above, manufactured by BASF), and N-1919 (manufactured by ADEKA) can be used. Among them, the O-acyl oxime compound is preferably selected from N-benzoyloxy-1-(4-phenylmercaptophenyl)butan-1-one-2-imine, N-benzoyloxy-1 -(4-phenylmercaptophenyl)octane-1-one-2-imine and N-benzoyloxy-1-(4-phenylmercaptophenyl)-3-cyclopentylpropane-1 -at least one species from the group consisting of keto-2-imine, more preferably N-benzoyloxy-1-(4-phenylmercaptophenyl)octan-1-one-2-imine.

The aforementioned alkylphenone compound is a compound having a partial structure represented by formula (d2) or a partial structure represented by formula (d3). In these partial structures, the benzene ring may have a substituent.

As a compound having a partial structure represented by the formula (d2), for example, 2-methyl-2-morpholine-1-(4-methylmercaptophenyl)propan-1-one, 2-dimethyl Amino-1-(4-morpholinephenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1- [4-(4-morpholine)phenyl]butan-1-one, etc. Commercial items such as Irgacure 369, 907, and 379 (above, manufactured by BASF Corporation) can be used.

As a compound having a partial structure represented by formula (d3), for example, 2-hydroxyl-2-methyl-1-phenylpropane-1-one, 2-hydroxyl-2-methyl-1-[4 -(2-Hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane-1 -Oligomers of ketones, α,α-diethoxyacetophenone, benzyl dimethyl ketal, and the like.

In terms of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by the formula (d2).

The aforementioned bis-imidazole compound is, for example, a compound represented by formula (d5).

[In the formula (d5), R ³ to R ⁸ represent an optionally substituted aryl group having 6 to 10 carbon atoms. ]

Examples of the aryl group having 6 to 10 carbon atoms include phenyl, toluoyl, xylyl, ethylphenyl and naphthyl, among which phenyl is preferred.

As a substituent, a halogen atom, an alkoxy group with 1-4 carbon atoms, etc. are mentioned, for example. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, among which a chlorine atom is preferred. Examples of the alkoxy group having 1 to 4 carbon atoms include methoxy, ethoxy, propoxy, butoxy and the like, preferably methoxy.

As the bisimidazole compound, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis(2,3- Dichlorophenyl)-4,4',5,5'-tetraphenylbisimidazole (for example, refer to JPH06-75372-A, JPH06-75373-A, etc.), 2,2'-bis(2-chloro Phenyl)-4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxybenzene base) bisimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)bisimidazole, 2,2'-bis(2- Chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (for example, refer to JPS48-38403-B, JPS62-174204-A, etc.), 4,4'5 , an imidazole compound in which a phenyl group at the 5'-position is substituted with a carboalkoxy group (for example, refer to JPH07-10913-A, etc.), and the like. Among them, compounds represented by the following formulas and mixtures thereof are preferred.

As the aforementioned triazine compound, there are, for example, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl) Methyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine , 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[ 2-(5-methylfuran-2-yl)ethenyl (ethenyl)]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2 -yl) vinyl (ethenyl)]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl ) vinyl (ethenyl)]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl) vinyl (ethenyl )]-1,3,5-triazine, etc.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and the like. Commercial items such as Lucirin (registered trademark) TPO (manufactured by BASF Corporation) and Irgacure (registered trademark) 819 (manufactured by BASF Corporation) can also be used.

Furthermore, examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; Benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'- Benzophenone compounds such as tetrakis(tert-butylperoxycarbonyl)benzophenone and 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, 2-ethylanthraquinone, camphor Benzoquinone compounds such as quinones; 10-butyl-2-chloroacridone, benzil, methyl phenylglyoxylate, titanocene compounds, etc. These are preferably used in combination with a polymerization initiation adjuvant (D1) (especially amines) described later.

The content of the polymerization initiator (D) is preferably 1 to 30% by mass, more preferably 5 to 20% by mass based on the total solid content.

In addition, the content of the polymerization initiator (D) is preferably 1 to 50 parts by mass, more preferably 10 to 45 parts by mass, and still more preferably 20 to 40 parts by mass relative to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). parts by mass.

<Polymerization Initiation Auxiliary (D1)>

The polymerization initiation adjuvant (D1) is a compound or a sensitizer used to accelerate the polymerization of a polymerizable compound whose polymerization is initiated by a polymerization initiator. When a polymerization initiation adjuvant (D1) is contained, it is usually used in combination with a polymerization initiator (D).

As a polymerization start adjuvant (D1), an amine compound, an alkoxy anthracene compound, a thioxanthone compound, a carboxylic acid compound, etc. are mentioned.

Examples of the aforementioned amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzene Isoamyl formate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(di Methylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, etc. , among which, 4,4'-bis(diethylamino)benzophenone is preferred. Commercial items such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can be used.

Examples of the aforementioned alkoxyanthracene compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl- 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, etc.

Examples of the aforementioned thioxanthone compounds include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1- Chloro-4-propoxythioxanthone, etc.

Examples of the aforementioned carboxylic acid compound include phenylmercapto (sulfanil) acetic acid, methylphenyl mercaptoacetic acid, ethylphenyl mercaptoacetic acid, methylethylphenyl mercaptoacetic acid, dimethylphenyl mercaptoacetic acid, methoxy Phenylthioglycolic acid, dimethoxyphenylthioglycolic acid, chlorophenylthioglycolic acid, dichlorophenylthioglycolic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, Naphthyloxyacetic acid, etc.

When using these polymerization initiation adjuvant (D1), its content is preferably 0.1-30 mass parts with respect to 100 mass parts of total amounts of resin (B) and a polymeric compound (C), More preferably, it is 1-20 mass parts. When the quantity of a polymerization initiation adjuvant (D1) exists in this range, it exists in the tendency which can form a colored pattern with higher sensitivity, and improves the productivity of a color filter.

<Thiol compound (T)>

The thiol compound (T) is a compound having -SH in the molecule.

As a compound having one -SH in the molecule, for example, 2-mercapto (sulfanil) oxazole, 2-mercaptothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole , 2-mercaptonicotinic acid, 2-mercaptopyridine, 2-mercaptopyridine-3-ol, 2-mercaptopyridine-N-oxide, 4-amino-6-hydroxy-2-mercaptopyrimidine, 4-amino-6- Hydroxy-2-mercaptopyrimidine, 4-amino-2-mercaptopyrimidine, 6-amino-5-nitroso-2-thiouracil, 4,5-diamino-6-hydroxy-2-mercaptopyrimidine, 4, 6-diamino-2-mercaptopyrimidine, 2,4-diamino-6-mercaptopyrimidine, 4,6-dihydroxy-2-mercaptopyrimidine, 4,6-dimethyl-2-mercaptopyrimidine, 4-hydroxy -2-mercapto-6-methylpyrimidine, 4-hydroxy-2-mercapto-6-propylpyrimidine, 2-mercapto-4-methylpyrimidine, 2-mercaptopyrimidine, 2-thiouracil, 3,4, 5,6-tetrahydropyrimidine-2-thiol, 4,5-diphenylimidazole-2-thiol, 2-mercaptoimidazole, 2-mercapto-1-methylimidazole, 4-amino-3-hydrazino -5-mercapto-1,2,4-triazole, 3-amino-5-mercapto-1,2,4-triazole, 2-methyl-4H-1,2,4-triazole-3-sulfur Alcohol, 4-methyl-4H-1,2,4-triazole-3-thiol, 3-mercapto 1H-1,2,4-triazole-3-thiol, 2-amino-5-mercapto- 1,3,4-thiadiazole, 5-amino-1,3,4-thiadiazole-2-thiol, 2,5-dimercapto-1,3,4-thiadiazole, (furan-2 -yl) methylmercaptan, 2-mercapto-5-thiazolidinone, 2-mercaptothiazoline, 2-mercapto-4(3H)-quinazolinone (kinazolinon), 1-phenyl-1H-tetrazole- 5-thiol, 2-quinolinethiol, 2-mercapto-5-methylbenzimidazole, 2-mercapto-5-nitrobenzimidazole, 6-amino-2-mercaptobenzothiazole, 5-chloro -2-Mercaptobenzothiazole, 6-ethoxy-2-mercaptobenzothiazole, 6-nitro-2-mercaptobenzothiazole, 2-mercaptonaphthazole, 2-mercaptonaphthoxazole, 3-mercapto- 1,2,4-triazole, 4-amino-6-mercaptopyrazolo[2,4-d]pyridine, 2-amino-6-purinethiol, 6-mercaptopurine, 4-mercapto-1H-pyridine Azolo[2,4-d]pyrimidine, etc.

Examples of compounds having two or more -SH in the molecule include hexanedithiol, decanedithiol, 1,4-bis(methylmercapto)benzene, butanediol bis(3-mercaptopropionate) , butanediol bis(3-mercaptoacetate), ethylene glycol bis(3-mercaptoacetate), trimethylolpropane tris(3-mercaptoacetate), butanediol bis(3-mercaptoacetate) propionate), trimethylolpropane tris(3-mercaptopropionate), trimethylolpropane tris(3-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate) -mercaptoacetate), trihydroxyethyltris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyloxy)butane and the like.

As the thiol compound (T), a compound having one -SH in the molecule is preferable.

The content of the thiol compound (T) is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass, based on 100 parts by mass of the polymerization initiator (D). When content of a thiol compound (T) exists in this range, there exists a tendency for sensitivity to become high and developability to become favorable.

<Solvent (E)>

The solvent (E) is not particularly limited, and solvents generally used in this field can be used. For example, ester solvents (solvents containing -COO- in the molecule and not containing -O-), ether solvents (solvents containing -O- in the molecule and not containing -COO-), ether ester solvents (solvents containing - COO- and -O- solvents), ketone solvents (solvents containing -CO- in the molecule, not containing -COO-), alcohol solvents (containing OH in the molecule, not containing -O-, -CO- and -COO- solvents), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, etc.

Examples of ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, Butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, γ-butyrolactone, etc.

Examples of ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, and diethylene glycol monomethyl ether. Ethyl 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 Oxy-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, phenetole, methyl anisole, etc.

Examples of ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and methyl 3-methoxypropionate. ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate ester, 2-methoxypropyl propionate, 2-ethoxymethyl propionate, 2-ethoxy ethyl propionate, 2-methoxy-2-methylpropionate methyl, 2-ethyl Oxy-2-methylpropanoic acid ethyl ester, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol mono Ethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, Glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, etc.

Examples of ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, and 4-methyl-2-pentanone Ketone, cyclopentanone, cyclohexanone, isophorone, etc.

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

Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, mesitylene and the like.

Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and the like.

These solvents may be used alone or in combination of two or more.

Among the above-mentioned solvents, organic solvents having a boiling point at 1 atm of 120° C. to 180° C. are preferable from the viewpoint of coating properties and drying properties. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diglycol Alcohol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N, N-dimethylformamide, more preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3- Methoxybutyl acetate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate.

The content of the solvent (E) is preferably 70 to 95% by mass, more preferably 75 to 92% by mass based on the total amount of the colored photosensitive resin composition. In other words, the solid content of the colored photosensitive resin composition is preferably 5 to 30% by mass, more preferably 8 to 25% by mass.

When the content of the solvent (E) is within the above range, the flatness at the time of coating becomes favorable and the display characteristics tend to be favorable because the color density does not become insufficient when forming a color filter.

<Leveling agent (F)>

Examples of the leveling agent (F) include silicone-based surfactants, fluorine-based surfactants, silicone-based surfactants having a fluorine atom, and the like. These may have a polymerizable group in a side chain.

Examples of the silicone-based surfactant include surfactants having a siloxane bond in the molecule, and the like. Specifically, TORAY SILICONE DC3PA, TORAY SILICONE SH7PA, TORAY SILICONE DC11PA, TORAY SILICONE SH21PA, TORAY SILICONE SH28PA, TORAY SILICONE SH29PA, TORAY SILICONE SH30PA, TORAY SILICONE SH8400 (trade name: Dow P32, manufactured by KLi32 Toray1, KLi32 Toray1) KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials (Japan) Inc.), etc. .

As said fluorine-type surfactant, the surfactant etc. which have a fluorocarbon chain in a molecule|numerator are mentioned. Specifically, Fluorad (registered trademark) FC430, Fluorad FC431 (manufactured by Sumitomo3M Limited), MEGAFAC (registered trademark) F142D, MEGAFAC F171, MEGAFAC F172, MEGAFAC F173, MEGAFAC F177, MEGAFAC F183, MEGAFAC F554, MEGAFAC R30, MEGAFAC S-718-K (manufactured by DIC), EFTOP (registered trademark) EF301, EFTOP EF303, EFTOP EF351, EFTOPEF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (manufactured by Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Institute of Fine Chemicals), etc.

Examples of the aforementioned silicone-based surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule, and the like. Specifically, MEGAFAC (registered trademark) R08, MEGAFAC BL20, MEGAFAC F475, MEGAFAC F477, MEGAFAC F443 (manufactured by DIC Co., Ltd.) etc. are mentioned.

The content of the leveling agent (F) is preferably not less than 0.001% by mass and not more than 0.2% by mass, preferably not less than 0.002% by mass and not more than 0.1% by mass, more preferably not less than 0.005% by mass and not more than 0.05% by mass, based on the total amount of the colored photosensitive resin composition . When content of a leveling agent (F) exists in the said range, the flatness of a color filter can be made favorable.

<Adhesion accelerator (G)>

Examples of the adhesion promoter (G) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, 3-glycidyloxy Glycidoxypropyltrimethoxysilane, 3-Glycidoxypropylmethyldimethoxysilane, 3-Glycidoxypropylmethyldimethoxysilane, 3-Glycidoxypropyl Diethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxy Silane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, N-2 -(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxysilane, N-2-(aminoethyl base)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyl Triethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, etc.

The content of the adhesion promoter (G) is preferably not less than 0.1% by mass and not more than 5% by mass, preferably not less than 0.2% by mass and not more than 2% by mass relative to the total amount of the solid content. When content of an adhesion promoter (G) exists in the said range, the adhesion with a board|substrate can be made favorable.

<other ingredients>

The colored photosensitive resin composition of the present invention may contain fillers, other polymer compounds, adhesion promoters, antioxidants, photostabilizers, chain transfer agents, and other known additives in the technical field as needed.

<Manufacturing method of colored photosensitive resin composition>

The colored photosensitive resin composition of the present invention can be obtained by, for example, mixing a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and, if necessary, a solvent (E), a thiol Compound (T), leveling agent (F), polymerization initiation assistant (D1), adhesion promoter (G) and other components are prepared.

The pigment is preferably mixed with part or all of the solvent (E) in advance, and dispersed using a bead mill or the like so that the average particle diameter of the pigment is about 0.2 μm or less. At this time, part or all of the above-mentioned pigment dispersant and resin (B) may be blended as needed. The desired colored photosensitive resin composition can be prepared by mixing the remaining components at a predetermined concentration in the pigment dispersion obtained in this way.

The mixed colored photosensitive resin composition is preferably filtered through a filter having a pore diameter of about 0.1 to 10 μm.

<Manufacturing method of color filter>

As a method of manufacturing a colored patterned coating film from the colored photosensitive resin composition of this invention, a photolithography method, an inkjet method, a printing method, etc. are mentioned. Among them, photolithography is preferable. The photolithography method is a method of applying and drying the colored photosensitive resin composition on a substrate to form a colored composition layer, exposing and developing the colored composition layer through a photomask. In the photolithography method, by not using a photomask and/or not developing at the time of exposure, a colored coating film that is a cured product of the above-mentioned colored composition layer can be formed. The colored patterned coating film or colored coating film formed in this way is the color filter of this invention.

The film thickness of the produced color filter is not particularly limited, and can be appropriately adjusted depending on the purpose or use, for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, more preferably 0.5 to 6 μm.

As the substrate, glass plates such as quartz glass, borosilicate glass, alumina silicate glass, soda lime glass coated with silica, polycarbonate, polymethylmethacrylate, polyterephthalate, etc. can be used. Resin plates such as ethylene glycol formate, silicon, and substrates on which aluminum, silver, silver/copper/palladium alloy thin films, etc. are formed. Other color filter layers, resin layers, transistors, circuits, and the like can be formed on these substrates.

Formation of pixels of each color using photolithography can be performed using known or commonly used equipment and conditions. For example, it can be produced as follows.

First, a colored photosensitive resin composition is coated on a substrate, and dried by removing volatile components such as solvents by heat drying (prebaking) and/or reduced pressure drying to obtain a smooth colored composition layer.

As a coating method, a spin coating method, a slit coating method, a slit and spin coating method, etc. are mentioned.

The temperature at the time of heat drying is preferably 30 to 120°C, more preferably 50 to 110°C. In addition, the heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes.

When performing reduced-pressure drying, it is preferable to carry out in the temperature range of 20-25 degreeC under the pressure of 50-150 Pa.

The film thickness of the coloring composition layer is not particularly limited, and may be appropriately selected according to the film thickness of the intended color filter.

Next, in order to form a target colored patterned coating film, the colored composition layer is exposed through a photomask. The pattern on this photomask is not particularly limited, and a pattern corresponding to the intended use can be used.

As a light source used for exposure, the light source which generate|occur|produces the light of the wavelength of 250-450 nm is preferable. For example, light below 350 nm can be cut with a filter that cuts this wavelength region, or light near 436 nm, 408 nm, and 365 nm can be selectively extracted using a bandpass filter that can extract these wavelength regions. Specifically, mercury lamps, light emitting diodes, metal halide lamps, halogen lamps, etc. are mentioned.

It is preferable to use a mask aligner and a photolithography machine (stepper) because parallel rays of light can be uniformly irradiated on the entire exposure surface or accurate alignment between the photomask and the substrate on which the colored composition layer is formed can be performed. and other exposure devices.

By bringing the exposed colored composition layer into contact with a developing solution for development, a colored patterned coating film is formed on the substrate. By image development, the unexposed part of a coloring composition layer dissolves in a developing solution, and is removed.

As a developer, for example, an aqueous solution of a basic compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, tetramethylammonium hydroxide, or the like is preferable. The concentration in the aqueous solution of these basic compounds is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Furthermore, the developer may contain a surfactant.

The developing method may be any of paddle method, dip method, spray method and the like. Furthermore, the substrate can be inclined at any angle during image development.

Washing with water is preferable after development.

Furthermore, it is preferable to perform postbaking on the obtained colored patterned coating film. The post-baking temperature is preferably 150 to 250°C, more preferably 160 to 235°C. The post-baking time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes.

According to the colored photosensitive resin composition of this invention, since generation|occurrence|production of especially a residue and film residue is small, the color filter with few defects can be manufactured. This color filter is useful as a color filter used in display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging elements.

Example

Next, an Example is given and this invention is demonstrated concretely. "%" and "part" in an example are mass % and a mass part, unless there is special mention.

Synthesis Example 1

In a flask equipped with a stirrer, a thermometer, a reflux cooler and a dropping funnel, nitrogen gas is flowed at a rate of 0.02 L/min to form a nitrogen atmosphere, and 257 parts by mass of propylene glycol monomethyl ether acetate is added, and heated to 70°C. Next, 8 parts of acrylic acid, 70 parts of N-cyclohexylmaleimide, 3,4-epoxy tricyclo[5.2.1.0 ^2.6 ]decane-8-yl acrylate and 3,4-epoxy A solution was prepared by dissolving 32 parts by mass of a mixture of tricyclic [5.2.1.0 ^2.6 ]decane-9-yl acrylate (50:50 by molar ratio) in 140 parts by mass of propylene glycol monomethyl ether acetate , using a dropping funnel, dropwise added the solution to a flask kept at 70° C. over 4 hours.

On the other hand, 15 parts by mass of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in 225 parts by mass of propylene glycol monomethyl ether acetate to obtain a solution, and another drop The solution was added dropwise to the flask from the funnel over 4 hours. After completion|finish of dripping the solution of a polymerization initiator, it maintained at 70 degreeC for 4 hours, and cooled to room temperature after that, and obtained the resin B1 solution whose solid content was 26.7 mass %. Resin B1 had a weight average molecular weight of 6.8×10 ³ , a molecular weight distribution of 2.23, and an acid value in terms of solid content of 114 mg-KOH/g. Resin B1 has the following structural units.

Synthesis example 2

An appropriate amount of nitrogen gas was flowed into a flask equipped with a reflux cooler, a dropping funnel, and a stirrer to replace it with a nitrogen atmosphere, 371 parts of propylene glycol monomethyl ether acetate were added, and the mixture was heated to 85° C. while stirring. Next, 54 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decane-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decane-9 225 parts, 81 parts of vinyl toluene (mixture of isomers) of the mixture (containing ratio is 50: 50 in molar ratio) of methacrylic acid ester are dissolved in 80 parts of propylene glycol monomethyl ether acetate, make mixed solution, This mixed solution was dropped into the flask over 4 hours.

On the other hand, 30 parts of the polymerization initiator 2,2-azobis(2,4-dimethylvaleronitrile) was dissolved in 160 parts of propylene glycol monomethyl ether acetate to obtain a solution, and the solution was added dropwise over 5 hours. . After the dropwise addition of the initiator solution was completed, it was kept at 85° C. for 4 hours, and then cooled to room temperature to obtain a copolymer solution. This copolymer was referred to as resin B2. The solid content of the resin B2 solution was 37.5%, and the viscosity measured with a B-type viscometer (23° C.) was 246 mPa·s. Resin B2 had a weight average molecular weight of 1.06×10 ⁴ , a molecular weight distribution of 2.01, and an acid value in terms of solid content of 115 mg-KOH/g. Resin B2 has the following structural units.

Synthesis example 3

200 parts of propylene glycol monomethyl ether acetate were introduced into a flask equipped with a stirrer, a thermometer, a reflux cooling pipe, a dropping funnel, and a gas introduction pipe. Thereafter, nitrogen gas was introduced into the flask through a gas introduction tube to replace the atmosphere in the flask with nitrogen gas. After the solution in the flask was heated to 70°C, 144 parts of benzyl methacrylate, 30 parts of tricyclic [5.2.1.0 ^2.6 ] decyl methacrylate, A mixture consisting of 35 parts of methacrylic acid, 5.2 parts of azobisisobutyronitrile, and 213 parts of propylene glycol monomethyl ether acetate was further stirred at 100° C. for 5 hours after completion of the dropwise addition. After the dropwise addition of the polymerization initiator solution was completed, it was kept at 70° C. for 4 hours, and then cooled to room temperature to obtain a resin B3 solution having a solid content of 33.6%. Resin B3 had a weight average molecular weight of 1.03×10 ⁴ , a molecular weight distribution of 2.16, and an acid value in terms of solid content of 110.4 mg-KOH/g. Resin B3 has the following structural units.

Synthesis Example 4

200 parts of propylene glycol monomethyl ether acetate were introduced into a flask equipped with a stirrer, a thermometer, a reflux cooling pipe, a dropping funnel, and a gas introduction pipe. Thereafter, nitrogen gas was introduced into the flask through a gas introduction tube to replace the atmosphere in the flask with nitrogen gas. After the solution in the flask was heated to 70°C, 144 parts of benzyl methacrylate, 30 parts of tricyclic [5.2.1.0 ^2.6 ] decyl methacrylate, A mixture consisting of 42 parts of acrylic acid, 5.2 parts of azobisisobutyronitrile, and 213 parts of propylene glycol monomethyl ether acetate was further stirred at 100° C. for 5 hours after completion of the dropwise addition. After the dropwise addition of the polymerization initiator solution was completed, it was kept at 70° C. for 4 hours, and then cooled to room temperature to obtain a resin B4 solution with a solid content of 34.1%. Resin B4 had a weight average molecular weight of 1.13×10 ⁴ , a molecular weight distribution of 2.18, and an acid value in terms of solid content of 108.5 mg-KOH/g. Resin B4 has the following structural units.

The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polystyrene conversion of resin was performed on the following conditions by the GPC method.

Device: HLC-8120GPC (manufactured by TOSOH CORPORATION)

Column: TSK-GELG2000HXL

Column temperature: 40°C

Solvent: THF

Flow rate: 1.0mL/min

Solid content concentration of the liquid to be tested: 0.001 to 0.01% by mass

Injection volume: 50μL

Detector: RI

Standard material for calibration: TSK STANDARD POLYSTYRENE

F-40, F-4, F-288, A-2500, A-500

(manufactured by TOSOH CORPORATION)

The ratio (Mw/Mn) of the polystyrene-equivalent weight average molecular weight obtained above to the number average molecular weight was made molecular weight distribution.

[Preparation of Pigment Dispersion A1]

C.I. Pigment Green 36 15.0 parts

Acrylic pigment dispersant 3.0 parts

78.0 parts of propylene glycol monomethyl ether acetate

Mix and fully disperse the pigment using a bead mill to obtain pigment dispersion liquid A1.

[Preparation of Pigment Dispersion A2]

C.I. Pigment Yellow 150 11.9 parts

Acrylic pigment dispersant 5.4 parts

77.3 parts of propylene glycol monomethyl ether acetate

The mixture was mixed, and the pigment was sufficiently dispersed using a bead mill to obtain a pigment dispersion liquid A2.

[Preparation of Pigment Dispersion A3]

C.I. Pigment Yellow 139 15.0 parts

Acrylic pigment dispersant 4.5 parts

80.6 parts of propylene glycol monomethyl ether acetate

The mixture was mixed, and the pigment was sufficiently dispersed using a bead mill to obtain a pigment dispersion liquid A3.

[Preparation of Pigment Dispersion A4]

C.I. Pigment Red 177 14.2 parts

Acrylic pigment dispersant 2.8 parts

77.3 parts of propylene glycol monomethyl ether acetate

The mixture was mixed, and the pigment was sufficiently dispersed using a bead mill to obtain a pigment dispersion liquid A4.

[Preparation of Pigment Dispersion A5]

C.I. Pigment Red 254 11.1 parts

Acrylic pigment dispersant 6.4 parts

80.0 parts of propylene glycol monomethyl ether acetate

The mixture was mixed, and the pigment was sufficiently dispersed using a bead mill to obtain a pigment dispersion liquid A5.

Examples 1-7 and Comparative Example 1

[Preparation of colored photosensitive resin composition]

The components described in Table 1 were mixed to obtain a colored photosensitive resin composition.

[Table 1]

In Table 1, the column of "resin (B)" shows content (part) in terms of solid content.

Colorant (A) Pigment dispersion liquids A1 to A5 were prepared in advance and used for mixing. The column of "colorant (A)" in Table 1 shows the content (parts) of the colorant contained in the pigment dispersion used.

The column of "acrylic dispersant" shows the total amount (part) of the acrylic dispersant contained in the pigment dispersion liquid used.

The column of "solvent (E)" shows the total amount (part) of each solvent contained in a colored photosensitive resin composition.

In Table 1, each component is as follows.

Colorant (A): A1: C.I. Pigment Green 36 (pigment dispersion A1)

Colorant (A): A2: C.I. Pigment Yellow 150 (pigment dispersion A2)

Colorant (A): A3: C.I. Pigment Yellow 139 (pigment dispersion A3)

Colorant (A): A4: C.I. Pigment Red 177 (pigment dispersion A4)

Colorant (A): A5: C.I. Pigment Red 254 (pigment dispersion A5)

Resin (B): B1: Resin B1

Resin (B): B2: Resin B2

Resin (B): B3: Resin B3

Resin (B): B4: Resin B4

Resin (B): B5: methacrylic acid/methyl methacrylate/n-butyl methacrylate/2-hydroxymethacrylate copolymer [copolymerization ratio is 20/10/55/15, weight Average molecular weight: about 40000, synthesized according to the examples in JP-A-2004-309537]

Polymerizable compound (C): C1: dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)

Polymer compound (C): C2: trimethylolpropane acrylate (NK ester ATMPT: manufactured by Shin-Nakamura Chemical Co., Ltd.)

Polymerization initiator (D): D1: N-benzoyloxy-1-(4-phenylmercaptophenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE01: manufactured by BASF : O-acyl oxime compound)

Polymerization initiator (D): D2: 2-methyl-2-morpholine-1-(4-methylmercaptophenyl) propan-1-one (Irgacure (registered trademark) 907; manufactured by BASF Corporation; alkylbenzene Ketones)

Polymerization initiator (D): D3: a mixture of compounds represented by the following formula (CHEMCURE-TCDM: manufactured by Cambrige, Ltd.: bis-imidazole compound)

Polymerization initiation aid (D1): 4,4'-bis(diethylamino)benzophenone (EAB-F; manufactured by Hodogaya Chemical Industry Co., Ltd.)

Thiol compound (T): D1a: 2-Mercaptobenzothiazole (Sokusinol (registered trademark) M; manufactured by Sumitomo Chemical Co., Ltd.: a compound represented by the following formula)

Adhesion promoter (G): D1b: 3-methacryloyloxypropyltrimethoxysilane (KBM-503; manufactured by Shin-Etsu Chemical Co., Ltd.)

Solvent (E): E1: Propylene Glycol Monomethyl Ether Acetate

Solvent (E): E2: ethyl lactate

Solvent (E): E3: Cyclohexanone

Surfactant (F): polyether-modified silicone oil (manufactured by Dow Corning Toray Company, Limited; SH8400)

〔Formation of patterned coating film〕

On a 2-inch-square glass substrate (EAGLE XG; manufactured by Corning Incorporated), the colored photosensitive resin composition was applied by spin coating, and then prebaked at 100° C. for 3 minutes to form a colored composition layer. After natural cooling, the distance between the substrate on which the coloring composition layer was formed and the photomask made of quartz glass was set to 100 μm, and an exposure machine (TME-150RSK; manufactured by TOPCON CORPORATION) was used in the air atmosphere at a temperature of 30 mJ/cm ² . Light irradiation was performed at an exposure amount (365 nm basis). As the photomask, a photomask formed with a 50 μm line and space pattern was used. After light irradiation, the above-mentioned coating film was developed by immersing the above-mentioned coating film in an aqueous developer solution containing 0.12% of nonionic surfactant and 2% of sodium carbonate at 24°C for 60 seconds, and after washing with water, it was developed in an oven at 230°C for 30 seconds. After 10 minutes, it is baked to obtain a colored and patterned coating film.

〔Development evaluation〕

When the glass substrate on which the colored patterned coating film was formed was observed with an optical microscope, if residue or film residue was not confirmed in the unexposed portion, it was rated as ◯, and if residue or film residue was confirmed, it was rated as x. The results are shown in Table 2.

〔Adhesion evaluation〕

When the colored patterned coating film was observed with an optical microscope, if no peeling was confirmed, it was ○, if a part of the colored patterned coating film was peeled off, it was Δ, and if the colored patterned coating film was completely peeled off, then it was ×. The results are shown in Table 2.

〔Film thickness measurement〕

The film thickness of the obtained colored patterned coating film was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.). The results are shown in Table 2.

〔Chroma evaluation〕

For the obtained colored patterned coating film, the spectrum was measured using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation), and the xy chromaticity coordinates in the XYZ chromaticity system of CIE (x , y) and three stimulus values Y (tristimulusvalues). The larger the value of Y, the higher the brightness. The results are shown in Table 2.

[Contrast evaluation]

Except not using a photomask at the time of exposure, the same operation as for the production of the colored patterned coating film was carried out to prepare a colored patterned coating film. For the obtained colored patterned coating film, using a contrast meter (CT-1; manufactured by Tsubosaka Electric Co., Ltd., color difference meter BM-5A; manufactured by TOP CONCORPORATION, light source; F-10, polarizing film; manufactured by Tsubosaka Electric Co., Ltd.), Contrast was measured using 30000 as a blank value.

The results are shown in Table 2. When coloring agent A1 and coloring agent A4 are used together, the contrast of a colored patterned coating film tends to become high.

[Table 2]

When the colored photosensitive resin composition of the present invention is used, it is excellent in developability when forming a colored patterned coating film.

Claims (6)

1. photosensitive composition, it contains colorant, resin, polymerizable compound and polymerization initiator, wherein,

Colorant contains C.I. pigment green 36, yellow uitramarine and is selected from least a in the group that is comprised of blue pigment, red pigment, violet pigment and orange pigment,

Resin is multipolymer, and this multipolymer contains: be derived from the structural unit that is selected from least a structural unit in the group that is comprised of unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides and has the ester ring type hydrocarbon structure.

2. photosensitive composition according to claim 1, wherein, the structural unit with ester ring type hydrocarbon structure is the structural unit that is derived from following monomer, this monomer has, and can to have substituent carbon number be 3～18 ester ring type alkyl.

3. photosensitive composition according to claim 1 and 2, wherein, polymerization initiator comprises O-acyl group oxime compound.

4. each described photosensitive composition according to claim 1～3 wherein, is selected from least a for C.I. paratonere 177 in the group that is comprised of blue pigment, red pigment, violet pigment and orange pigment.

5. color filter, it is formed by each described photosensitive composition in the claim 1～4.

6. display device, it comprises color filter claimed in claim 5.