KR101795815B1 - Colored photosensitive composition - Google Patents

Abstract

assignment
Provided is a colored photosensitive composition capable of obtaining a green color filter excellent in color separation ability from a red filter.
Solution
A colorant, a polymerizable compound, a polymerization initiator and a solvent, wherein the colorant contains a halogenated copper phthalocyanine pigment, a halogenated zinc phthalocyanine pigment, and a quinophthalone pigment.

Description

COLORED PHOTOSENSITIVE COMPOSITION [0002]

The present invention relates to a colored photosensitive composition suitable for forming a colored image constituting a color filter used for a liquid crystal display element or a solid-state image pickup element.

Color filters used in display devices such as liquid crystal display panels, electroluminescence panels, and plasma display panels are manufactured using colored photosensitive compositions. Such a colored photosensitive composition includes a colorant, a resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, wherein the colorant is CI Pigment Green 36 and CI Pigment Yellow 150 (Patent Document 1).

Japanese Laid-Open Patent Publication No. 2005-157311

The green color filter formed using the above-mentioned colored photosensitive composition is not necessarily satisfactory enough for the color separation performance with the red filter.

The present invention provides the following [1] to [8].

[1] A colored photosensitive composition comprising a colorant, a polymerizable compound, a polymerization initiator, and a solvent, wherein the colorant is a colorant containing a halogenated copper phthalocyanine pigment, a halogenated zinc phthalocyanine pigment, and a quinophthalone pigment.

[2] The colored photosensitive composition according to the above [1], wherein the content of the copper halide phthalocyanine pigment is 20 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the zinc halphthalocyanine pigment.

[3] The colored photosensitive composition according to the above [1], wherein the content of the quinophthalone pigment is 50 parts by mass or more and 200 parts by mass or less based on 100 parts by mass of the zinc phthalocyanine pigment.

[4] The image forming method according to any one of [1] to [4], wherein the content of the copper halide phthalocyanine pigment is 20 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the zinc phthalocyanine pigment, and the content of the quinophthalone pigment is 100 parts by mass Is not less than 50 parts by mass and not more than 200 parts by mass based on 100 parts by mass of the colorant.

[5] The colored photosensitive composition according to any one of [1] to [4], wherein the halogenated copper phthalocyanine pigment is CI Pigment Green 7.

[6] The colored photosensitive resin composition according to any one of [1] to [3], wherein the quinophthalone pigment is CI Pigment Yellow 138.

[7] The colored photosensitive composition according to any one of [1] to [6], which contains a colorant, a polymerizable compound, a polymerization initiator, a solvent and a resin.

[8] A color filter formed from the colored photosensitive composition according to any one of [1] to [7].

According to the colored photosensitive composition of the present invention, it is possible to obtain a green color filter excellent in color separation ability from a red filter.

The colored photosensitive composition of the present invention comprises a colorant (A), a polymerizable compound (C), a polymerization initiator (D) and a solvent (E), wherein the colorant is a halogenated copper phthalocyanine pigment, a halogenated zinc phthalocyanine pigment, Is a colored photosensitive composition containing a pigment. The colored photosensitive composition of the present invention preferably contains the resin (B).

In the present specification, the compounds exemplified as respective components can be used alone or in combination, unless otherwise specified.

The colorant (A) used in the colored photosensitive composition of the present invention contains a halogenated copper phthalocyanine pigment, a zinc halide phthalocyanine pigment, and a quinophthalone pigment.

As copper halide copper phthalocyanine pigments, chlorinated copper phthalocyanine pigments are preferable, and C. I. Pigment Green 7 is more preferable. If the halogenated copper phthalocyanine pigment is the above-mentioned pigment, the transmittance in the vicinity of 600 nm can be lowered, so that the color separating ability with the red filter is excellent.

CI Pigment Green 58 is preferable as the zinc halide phthalocyanine pigment.

The content of the halogenated copper phthalocyanine pigment is preferably 20 parts by mass or more and 150 parts by mass or less, more preferably 80 parts by mass or more and 120 parts by mass or less, based on 100 parts by mass of the zinc halphthalocyanine pigment. When the content of the copper phthalocyanine halide pigment is within the above range, the transmittance in the vicinity of 600 nm can be lowered while the transmittance at 520 nm is maintained at a high level. Therefore, the color separating ability with respect to the red filter is excellent, A filter can be obtained. When such a green filter is used as a color filter formed in a green pixel of a display device such as a liquid crystal display device, the color reproducibility of the display device can be improved.

The colorant (A) further contains a quinophthalone pigment. The content of the quinophthalone pigment is preferably 50 parts by mass or more and 200 parts by mass or less, more preferably 120 parts by mass or more and 200 parts by mass or less, based on 100 parts by mass of the zinc halphthalocyanine pigment. As the quinophthalone pigment, CI Pigment Yellow 138 is preferable. The inclusion of the quinophthalone pigment as described above tends to provide an excellent color separation capability with the blue filter.

The pigment may be subjected to a surface treatment using a pigment derivative or a pigment dispersant into which a rosin treatment, an acidic group or a basic group is introduced, a graft treatment on the surface of the pigment with a polymer compound or the like, an atomization treatment such as a sulfuric acid atomization method, A cleaning treatment with an organic solvent or water for removal, a removal treatment with an ion exchange method of ionic impurities, or the like may be performed. It is preferable that the pigment has a uniform particle size. By containing the pigment dispersant and carrying out the dispersion treatment, a pigment dispersion in which the pigment is uniformly dispersed in the solution can be obtained.

As the pigment dispersing agent, commercially available surfactants can be used. Examples of the surfactant include silicon surfactants, fluorine surfactants, ester surfactants, cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, polyester surfactants, polyamines surfactants, acrylic surfactants and urethane surfactants. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine modified polyurethanes, polyethyleneimines (Manufactured by Shin-Etsu Chemical Co., Ltd.), Fluren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Zeneca), EFKA (manufactured by CIBA) (Manufactured by Fine Techno Co., Ltd.), and Disperbyk (manufactured by Big Chemical). These may be used alone or in combination of two or more.

When a pigment dispersant is used, its amount to be used is preferably 100% by mass or less, more preferably 5 to 50% by mass, based on the total mass of the pigment. When the amount of the pigment dispersant is in the above range, a pigment dispersion in a uniformly dispersed state tends to 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 composition. Within the above range, desired spectral or color density can be obtained. Here, the solid content refers to the sum of the amounts excluding the solvent from the colored photosensitive composition.

The colored photosensitive composition of the present invention preferably contains the resin (B).

The resin (B) used in the colored photosensitive composition of the present invention is preferably a resin exhibiting alkali solubility. Here, the alkali solubility refers to a property of dissolving in a developer which is an aqueous solution of an alkaline compound.

As the resin exhibiting alkali solubility,

At least one kind (a) (hereinafter sometimes referred to as "(a)") selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride and a cyclic (B) (hereinafter also referred to as " b) "

Resin (B-2): Monomer (c) copolymerizable with (a) and (b) (provided that there is no cyclic ether having 2 to 4 carbon atoms) (hereinafter occasionally referred to as "(c) And (a) and (b)

Resin (B-3): a copolymer obtained by polymerizing (a) and (c)

Resin (B-4): A resin obtained by reacting (b) a copolymer obtained by polymerizing (a) and (c)

Resin (B-5): Resin obtained by reacting the copolymer (b) and (c) with (a).

(a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid 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, 1,2,3,6-tetrahydrophthalic acid, Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid;

Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hepto-2- 5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hepto- Cyclo [2.2.1] hept-2-ene, and 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride , Unsaturated dicarboxylic acid anhydrides such as dimethyl tetrahydrophthalic anhydride and 5,6-dicarboxybicyclo [2.2.1] hept-2-eno anhydride (hymic acid anhydride);

(Meth) acryloyloxyalkyl (meth) acrylate of a divalent or higher polyvalent carboxylic acid such as succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- Esters;

and unsaturated acrylates containing a hydroxyl group and a carboxyl group in the same molecule, such as? - (hydroxymethyl) acrylic acid.

Of these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferably used in terms of copolymerization-reactive surface and alkali solubility.

In the present specification, the term "(meth) acrylic acid" means at least one kind selected from the group consisting of acrylic acid and methacrylic acid. Quot ;, " (meth) acryloyl ", and " (meth) acrylate "

(b) is a polymerizable compound having a cyclic ether having 2 to 4 carbon atoms (for example, at least one member selected from the group consisting of oxiran ring, oxetane ring and tetrahydrofuran ring (oxolane ring)) to be. (b) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and an ethylenic unsaturated bond, more preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group.

(b2) having an oxyanyl group (hereinafter referred to as " b2) " (hereinafter referred to as " b2) " , And a monomer (b3) having a tetrahydrofuryl group (hereinafter sometimes referred to as "(b3)").

The monomer (b1) having an oxiranyl group means a polymerizable compound having an oxiranyl group. (b1-1) having an ethylenically unsaturated bond (hereinafter may be referred to as " (b1-1) ")) and a cycloalkene having a structure obtained by epoxidizing a chain olefin (B1-2) having an epoxidized structure and an ethylenic unsaturated bond (hereinafter sometimes referred to as " (b1-2) ").

(b1) is preferably a monomer having an oxiranyl group and an ethylenic unsaturated bond, more preferably a monomer having an oxiranyl group and a (meth) acryloyloxy group, and a monomer having a (meth) acryloyloxy group, 2) is more preferable.

(meth) acrylate,? -ethylglycidyl (meth) acrylate, glycidylvinylether, o (meth) acrylate, -Vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether,? -Methyl-o-vinylbenzyl glycidyl ether,? -Methyl-m-vinylbenzyl glycidyl (Glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, Styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5-tris (glycidyloxymethyl) ) Styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6- , Compounds described in JP-A 7-248625, and the like.

(b1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (for example, Verticalizer 2000 manufactured by Daicel Chemical Industries, Ltd.), 3,4- (For example, Cychroma A400, manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (for example, Cychroma M100, manufactured by Daicel Chemical Industries, , Compounds represented by the formula (I) and compounds represented by the formula (II).

[Chemical Formula 1]

[In the formulas (I) and (II), R ¹ and R ² independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is substituted with a hydroxy group do.

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

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

* Represents the number of bonds with O.]

Specific 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 and tert-butyl group.

Examples of the hydroxyalkyl group include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, Hydroxyethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group and the like.

As R ¹ and R ² , a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group are preferable, and a hydrogen atom and a methyl group are more preferable.

Examples of the alkanediyl group include a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane- And a 1,6-diyl group.

X ¹ and X ² are preferably a single bond, a methylene group, an ethylene group, * -CH ₂ -O- (* represents the number of bonds with O) group, * -CH ₂ CH ₂ -O- group More preferably a single bond, * -CH ₂ CH ₂ -O- group.

Examples of the compound represented by formula (I) include compounds represented by formulas (I-1) to (I-15). (I-1), (I-3), (I-5), (I-7) ). (I-1), (I-7), (I-9) and (I-15) are more preferable.

(2)

Examples of the compound represented by the formula (II) include compounds represented by the formulas (II-1) to (II-15). (II-1), Formula (II-3), Formula (II-5), Formula (II-7), Formula ). (II-1), (II-7), (II-9) and (II-15).

(3)

The compound represented by formula (I) and the compound represented by formula (II) may be used alone. In addition, they can be mixed at an arbitrary ratio. In the case of mixing, the mixing ratio thereof is preferably from 5:95 to 95: 5, more preferably from 10:90 to 90:10, particularly preferably from 20:90 to 90:10 in the formula (I): formula (II) : 80 to 80:20.

The monomer (b2) having an oxetanyl group means a polymerizable compound having an oxetanyl group. (b2) is preferably a monomer having an oxetanyl group and an ethylenically unsaturated bond, more preferably a monomer having an oxetanyl group and a (meth) acryloyloxy group. (meth) acryloyloxymethyloxetane, 3-methyl-3- ((meth) acryloyloxymethyloxetane, (Meth) acryloyloxyethyl oxetane and 3-ethyl-3- (meth) acryloyloxyethyl oxetane.

The monomer (b3) having a tetrahydrofuryl group means a polymerizable compound having a tetrahydrofuryl group. (b3) is preferably a monomer having a tetrahydrofuryl group and an ethylenically unsaturated double bond, more preferably a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group.

 Specific examples of the compound (b3) include tetrahydrofurfuryl acrylate (for example, Viscot V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

(meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (Meth) acrylic acid alkyl esters;

Cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (in the art, dicyclopentanil (Meth) acrylate), (meth) acrylic acid cyclic alkyl esters such as dicyclopentanyloxyethyl (meth) acrylate and isobornyl (meth) acrylate;

Aryl (meth) acrylates or aralkyl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate;

Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconate;

Hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

2,2-hept-2-ene, 5-methylbicyclo [2.2.1] hepto-2-ene, 5-ethylbicyclo [2.2.1] 2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] 2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2.1] 2,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2'- hydroxyethyl) bicyclo [2.2.1] 2-ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept- 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbo 2,6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, ] Hept-2-ene, and 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N- Dicarbonylimide derivatives such as N-succinimidyl-3-maleimidepropionate and N- (9-acridinyl) maleimide;

And examples thereof include styrene,? -Methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, Vinyl, 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene.

Of these, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and bicyclo [2.2.1] hept-2-ene are preferred from the viewpoint of copolymerization reactivity and alkali solubility.

In the resin (B-1), the ratio of the structural units derived from each monomer is preferably in the following range with respect to the total number of moles of the structural units constituting the resin (B-1).

(5 to 60 mol% (more preferably 10 to 50 mol%) of a structural unit derived from the structural unit (a)

(more preferably 50 to 90 mol%) derived from the structural unit (b)

When the ratio of the structural unit of the resin (B-1) is within the above range, storage stability, developability, solvent resistance, heat resistance and mechanical strength tend to be improved.

As the resin (B-1), the resin (b) is preferably the resin (b1), and the resin (b) is the resin (b1-2).

The resin (B-1) can be produced by, for example, a method described in "Experimental Method of Polymer Synthesis" (published by Otsu Takayuki Co., Ltd., 1st Edition, First Edition, March 1, 1972) Can be produced by referring to the cited document.

Specifically, there is exemplified a method of stirring, heating, and keeping the oxygen in the deoxygenation by injecting a predetermined amount of (a) and (b), a polymerization initiator and a solvent into the reaction vessel and replacing oxygen by nitrogen. The polymerization initiator, solvent and the like used herein are not particularly limited, and any of those conventionally used in the art can be used. Examples of the polymerization initiator include azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), and organic peroxides such as benzoyl peroxide The solvent may be any one that dissolves the respective monomers, and a solvent, which will be described later, may be used as a solvent for the colored photosensitive composition.

The solution obtained after the reaction may be used as it is, or a concentrated or diluted solution may be used. Alternatively, a solution obtained as a solid (powder) by re-precipitation or the like may be used. In particular, by using the same solvent as the solvent (E) described below as a solvent in the polymerization, the solution after the reaction can be used as it is, and the production process can be simplified.

In the resin (B-2), the proportion of the structural units derived from each monomer is preferably in the following range with respect to the total number of moles of the total structural units constituting the resin (B-2).

2 to 40 mol% (more preferably 5 to 35 mol%) of a structural unit derived from the structural unit (a)

2 to 95 mol% (more preferably 5 to 80 mol%) of a structural unit derived from the structural unit (b)

1 to 65 mol% (more preferably 1 to 60 mol%) of a structural unit derived from the structural unit (c)

When the ratio of the structural unit of the resin (B-2) is within the above range, storage stability, developability, solvent resistance, heat resistance and mechanical strength tend to be improved.

As the resin (B-2), the resin (b) is preferably the resin (b1), and the resin (b) is the resin (b1-2).

The resin (B-2) can be produced by the same method as the resin (B-1).

In the resin (B-3), the proportion of the structural units derived from each monomer is preferably in the following range with respect to the total number of moles of the total structural units constituting the resin (B-3).

2 to 40 mol% (more preferably 5 to 35 mol%) of a structural unit derived from the structural unit (a)

60 to 98 mol% (more preferably 65 to 95 mol%) of a structural unit derived from the structural unit (c)

When the proportion of the structural unit of the resin (B-3) is in the above range, storage stability, developability and solvent resistance tends to be good.

The resin (B-3) can be produced by the same method as the resin (B-1).

The resin (B-4) and the resin (B-5) can be produced, for example, by a two-step process. Also in this case, the method described in the aforementioned " Experimental Method of Polymer Synthesis " (published by Otsu Takayuki Co., Ltd., 1st Edition, 1st Edition, March 1, 1972), Japanese Patent Laid- 89533, and the like.

The resin (B-4) is first obtained in the same manner as in the above-mentioned production method of the resin (B-1) described above to obtain a copolymer of (a) and (c).

In this case, similarly to the above, the solution obtained after the reaction may be used as it is, or a solution obtained by concentration or dilution may be used, or it may be taken out as a solid (powder) by a method such as re-precipitation .

it is preferable that the ratio of the structural units derived from (a) and (c) is in the following range with respect to the total number of moles of the total structural units constituting the copolymer.

(5 to 50 mol% (more preferably 10 to 45 mol%) derived from the structural unit (a)

(50 to 95 mol% (more preferably 55 to 90 mol%) derived from the structural unit (c)

Next, as a second step, a part of the carboxylic acid (a) and the carboxylic acid anhydride derived from the obtained copolymer are reacted with the cyclic ether of (b). (B1) is more preferable, and (b1-1) is more preferable in respect of (b) from the viewpoint that the reactivity of the cyclic ether is high and the unreacted phosphorus (b)

Specifically, the atmosphere in the flask is replaced with air in the flask, and 5 to 80 mol% (b) of the reaction catalyst of a carboxyl group and a cyclic ether (for example, tris (A), (b) and (c) in an amount of 0.001 to 5% by mass relative to the total amount of (a), (b) and (c), and a polymerization inhibitor (such as hydroquinone) ) Is added to the flask in an amount of 0.001 to 5 mass% with respect to the total amount of the resin (A-4). The resin (A-4) can be obtained by reacting at 60 to 130 ° C for 1 to 10 hours. In addition, the injection method and the reaction temperature can be appropriately adjusted in consideration of the production facility or the amount of heat generated by polymerization, as in the case of the polymerization conditions.

In this case, the number of moles of (b) is preferably 10 to 75 mol%, and more preferably 15 to 70 mol% with respect to the number of moles of (a). When the number of moles of (b) is within this range, balance between storage stability, solvent resistance and heat resistance tends to be improved.

Specific examples of the resin (B-4) include resins obtained by reacting glycidyl (meth) acrylate with a copolymer of (meth) acrylic acid / dicyclopentanyl (meth) acrylate, resins obtained by reacting (meth) acrylic acid / benzyl (Meth) acrylate, a resin obtained by reacting glycidyl (meth) acrylate with a copolymer of (meth) acrylic acid / cyclohexyl (meth) acrylate, A resin obtained by reacting glycidyl (meth) acrylate with a copolymer of (meth) acrylic acid / methyl (meth) acrylate and a resin obtained by reacting a copolymer of (meth) acrylic acid / (Meth) acrylic acid / N-cyclohexylmaleimide, a copolymer of (meth) acrylic acid / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate Aglycidyl (meth) acrylate (Meth) acrylic acid / dicyclopentyl (meth) acrylate / cyclohexyl (meth) acrylate, a resin obtained by reacting a (meth) acrylic acid / dicyclopentyl (Meth) acrylic acid / dicyclopentanyl (meth) acrylate / methyl (meth) acrylate, a resin obtained by reacting glycidyl (meth) acrylate with a copolymer of cyclopentanyl (Meth) acrylate, a resin obtained by reacting a copolymer of (meth) acrylic acid / dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide with glycidyl (meth) A resin obtained by reacting a copolymer of an acid / dicyclopentanyl (meth) acrylate with glycidyl (meth) acrylate;

(Meth) acrylate is reacted with a copolymer of crotonic acid / cyclohexyl (meth) acrylate and a resin obtained by reacting a copolymer of crotonic acid / benzyl (meth) acrylate with glycidyl (Meth) acrylate on a copolymer of crotonic acid / styrene, a resin obtained by reacting a copolymer of crotonic acid / methyl crotonate with glycidyl (meth) acrylate, a crotonic acid / (Meth) acrylate in a copolymer of crotonic acid / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate, a resin obtained by reacting a copolymer of N-cyclohexylmaleimide with glycidyl ), A resin obtained by reacting a copolymer of crotonic acid / dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate with glycidyl (meth) acrylate, a crotonic acid / dicyclo (Meth) acrylate on a copolymer of crotonic acid / dicyclopentanyl (meth) acrylate / methyl crotonate and a resin obtained by reacting glycidyl (meth) acrylate with a copolymer of tannyl (meth) Acrylate, a resin obtained by reacting a copolymer of crotonic acid / dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide with glycidyl (meth) acrylate;

(Meth) acrylate is added to a copolymer of maleic acid / dicyclopentanyl (meth) acrylate and a copolymer of maleic acid / benzyl (meth) acrylate with glycidyl (Meth) acrylate is reacted with a copolymer of maleic acid / cyclohexyl (meth) acrylate, glycidyl (meth) acrylate is allowed to react with a copolymer of maleic acid / styrene A resin obtained by reacting a copolymer of maleic acid / methyl maleic acid with glycidyl (meth) acrylate, or a resin obtained by reacting glycidyl (meth) acrylate with a copolymer of maleic acid / N-cyclohexylmaleimide , A resin obtained by reacting a copolymer of maleic acid / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate with glycidyl (meth) acrylate, maleic acid / dicyclopentanyl (meth) acrylate / cyclohexyl (Meth) acrylate A resin obtained by reacting glycidyl (meth) acrylate with a copolymer of maleic acid / dicyclopentanyl (meth) acrylate / styrene, a resin obtained by reacting glycidyl (meth) (Meth) acrylate / dicyclopentanyl (meth) acrylate / maleic acid methyl ester is reacted with glycidyl (meth) acrylate, a copolymer of maleic acid / dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide A resin obtained by reacting a glycidyl (meth) acrylate with a co-monomer;

(Meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate, a resin obtained by reacting glycidyl (meth) acrylate with a copolymer of (meth) acrylic acid / maleic anhydride / dicyclopentanyl A resin obtained by reacting a copolymer of glycidyl (meth) acrylate with a copolymer of (meth) acrylic acid / maleic anhydride / cyclohexyl (meth) acrylate, (Meth) acrylic acid / maleic anhydride / methyl (meth) acrylate is copolymerized with a copolymer of a (meth) acrylic acid / maleic anhydride / styrene copolymer and a glycidyl (meth) Acrylate, (meth) acrylic acid / maleic anhydride / dicyclohexyl (meth) acrylate, a resin obtained by reacting a copolymer of (meth) acrylic acid / maleic anhydride / N-cyclohexylmaleimide with glycidyl Fentanyl (Meth) acrylate / maleic anhydride / dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate / benzyl (meth) acrylate, (Meth) acrylate on a copolymer of (meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate / styrene, a resin obtained by reacting glycidyl (Meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate / methyl (meth) acrylate, a resin obtained by reacting a (meth) acrylic acid / A resin obtained by reacting glycidyl (meth) acrylate with a copolymer of maleic anhydride / dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide;

(Meth) acrylic acid / dicyclopentanyl (meth) acrylate, a resin obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of (meth) acrylic acid / Epoxy cyclohexylmethyl methacrylate, a resin obtained by reacting a copolymer of (meth) acrylic acid / cyclohexyl (meth) acrylate with 3,4-epoxycyclohexylmethyl methacrylate, a resin obtained by reacting (meth) acrylic acid / Styrene is reacted with 3,4-epoxycyclohexylmethyl methacrylate, and a copolymer of (meth) acrylic acid / methyl (meth) acrylate is reacted with 3,4-epoxycyclohexylmethyl methacrylate Resin, a resin obtained by reacting a copolymer of (meth) acrylic acid / N-cyclohexylmaleimide with 3,4-epoxycyclohexylmethyl methacrylate, a resin obtained by reacting (meth) acrylic acid / dicyclopentanyl (meth) acrylate / benzyl )Ah (Meth) acrylic acid / dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate was added to the copolymer of (meth) acrylic acid / dicyclopentanyl (Meth) acrylate / dicyclopentanyl (meth) acrylate / styrene, a resin obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of (meth) acrylic acid / (Meth) acrylic acid / dicyclopentanyl (meth) acrylate / methyl (meth) acrylate, a resin obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of / N-cyclohexylmaleimide copolymer is reacted with 3,4-epoxycyclohexylmethyl methacrylate;

Epoxycyclohexylmethyl methacrylate on a copolymer of crotonic acid / dicyclopentanyl (meth) acrylate and a copolymer of crotonic acid / benzyl (meth) acrylate with 3,4-epoxycyclohexylmethyl methacrylate, Cyclohexylmethyl methacrylate, a resin obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of crotonic acid / cyclohexyl (meth) acrylate, and a copolymer of crotonic acid / styrene with 3, 4-epoxycyclohexylmethyl methacrylate, a resin obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of crotonic acid / methyl crotonate and a resin obtained by reacting crotonic acid / N-cyclohexylmaleimide A copolymer obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer and a copolymer of crotonic acid / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate with 3,4-epoxycyclohexyl A resin obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of crotonic acid / dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate, crotonic acid / Dicyclopentanyl (meth) acrylate / styrene, a resin obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of crotonic acid / dicyclopentanyl (meth) acrylate / Epoxycyclohexylmethyl methacrylate, and a resin obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of crotonic acid / dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide Reacted resin;

A resin obtained by reacting a copolymer of maleic acid / dicyclopentanyl (meth) acrylate with 3,4-epoxycyclohexylmethyl methacrylate, and a copolymer of maleic acid / benzyl (meth) acrylate with 3,4-epoxycyclo Maleic acid / cyclohexyl (meth) acrylate is reacted with 3,4-epoxycyclohexylmethyl methacrylate, a copolymer obtained by reacting maleic acid / cyclohexyl (meth) acrylate with 3,4- 4-epoxycyclohexylmethyl methacrylate, a resin obtained by reacting a copolymer of maleic acid / methyl maleic acid with 3,4-epoxycyclohexylmethyl methacrylate, a resin obtained by reacting maleic acid / N-cyclohexylmaleimide Epoxycyclohexylmethyl methacrylate was added to a copolymer of maleic acid / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate and 3,4-epoxycyclohexylmethyl methacrylate Creel , A resin obtained by reacting a copolymer of maleic acid / dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate with 3,4-epoxycyclohexylmethyl methacrylate, a resin obtained by reacting maleic acid / dicyclopentanyl (Meth) acrylate / styrene is reacted with a copolymer of 3,4-epoxycyclohexylmethyl methacrylate and a copolymer of maleic acid / dicyclopentanyl (meth) acrylate / maleic acid methyl ester with 3,4- Epoxycyclohexylmethyl methacrylate; a resin obtained by reacting a copolymer of maleic acid / dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide with 3,4-epoxycyclohexylmethyl methacrylate;

(Meth) acrylic acid / maleic anhydride / benzyl (meth) acrylate, a resin obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of (meth) acrylic acid / maleic anhydride / dicyclopentanyl (Meth) acrylic acid / maleic anhydride / cyclohexyl (meth) acrylate was added to a copolymer of 3,4-epoxycyclohexylmethyl methacrylate and 3,4-epoxycyclohexylmethyl methacrylate (Meth) acrylic acid / maleic anhydride / (meth) acrylic acid / maleic anhydride / styrene, a resin obtained by reacting a (meth) acrylic acid / maleic anhydride / (Meth) acrylic acid / maleic anhydride / N-cyclohexylmaleimide was added to a copolymer of 3,4-epoxycyclohexylmethyl methacrylate and 3,4-epoxycyclohexylmethyl methacrylate Krill Resin reacted with 3,4-epoxycyclohexylmethyl methacrylate on a copolymer of (meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate, (Meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate, a resin obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate with a (Meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate / styrene copolymer obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of maleic anhydride / dicyclopentanyl (Meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate / N-cyclohexyl (meth) acrylate / A resin obtained by reacting a copolymer of maleimide with 3,4-epoxycyclohexylmethyl methacrylate, and the like.

In the first step of the resin (B-5), the copolymer of (b) and (c) is obtained in the same manner as the resin (B-1) described above.

In this case, in the same manner as described above, the solution obtained after the reaction may be used as it is, or a concentrated or diluted solution may be used, or a solid (powder) obtained by re-precipitation or the like may be used.

it is preferable that the ratio of the structural units derived from (b) and (c) is in the following range with respect to the total number of moles of the total structural units constituting the copolymer.

(5 to 95 mol% (more preferably 10 to 90 mol%) derived from the structural unit (b)

(more preferably 10 to 90 mol%) derived from the structural unit (c)

In the same manner as in the production of the resin (B-4), the cyclic ether derived from the copolymer (b) in the copolymer (b) and the copolymer (c) And then reacting the resulting mixture with an anhydride. A carboxylic acid anhydride may be further reacted with a hydroxyl group generated by the reaction of a cyclic ether and a carboxylic acid or carboxylic acid anhydride.

The amount of (a) to be reacted with the copolymer is preferably 5 to 80 mol% with respect to the number of moles of (b). (B1) is preferable and (b1-1) is more preferable in (b) because the reactivity of the cyclic ether is high and unreacted phosphorus (b) is difficult to remain.

Specific examples of the resin (B-5) include resins obtained by reacting a copolymer of dicyclopentanyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid, benzyl (meth) (Meth) acrylic acid to a copolymer of cyclohexyl (meth) acrylate and glycidyl (meth) acrylate, a resin obtained by reacting a copolymer of cyclohexyl (meth) acrylate / glycidyl (Meth) acrylic acid to a copolymer of (meth) acrylic acid methyl / glycidyl (meth) acrylate, a resin obtained by reacting a copolymer of (meth) acrylic acid / glycidyl (Meth) acrylate / glycidyl (meth) acrylate, dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate / glycidyl Lt; RTI ID = 0.0 > (meth) < (Meth) acrylate, a resin obtained by reacting a copolymer of dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid, dicyclopentanyl (Meth) acrylate / (meth) acrylate / glycidyl (meth) acrylate, a resin obtained by reacting a copolymer of dicyclopentanyl (meth) acrylate / A resin obtained by reacting a (meth) acrylic acid with a copolymer of dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide / glycidyl (meth) acrylate;

A resin obtained by reacting a copolymer of dicyclopentanyl (meth) acrylate / glycidyl (meth) acrylate with a crotonic acid, and a copolymer of benzyl (meth) acrylate / glycidyl (meth) A resin obtained by reacting a copolymer of styrene / glycidyl (meth) acrylate with a resin obtained by reacting a resin reacted with crotonic acid to a copolymer of cyclohexyl (meth) acrylate / glycidyl (meth) acrylate and crotonic acid A resin obtained by reacting a copolymer of crotonic acid methyl / glycidyl (meth) acrylate with a crotonic acid, a resin obtained by reacting a copolymer of N-cyclohexylmaleimide / glycidyl (meth) acrylate with crotonic acid (Meth) acrylate / cyclohexyl (meth) acrylate / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate / glycidyl (Meth) acrylate / glycidyl (meth) acrylate is reacted with a copolymer of dicyclopentanyl (meth) acrylate / styrene / glycidyl (Meth) acrylate / N-cyclohexylmaleimide (meth) acrylate / dicyclopentanyl (meth) acrylate / methyl crotonate / glycidyl (meth) / Glycidyl (meth) acrylate with crotonic acid;

A resin obtained by reacting maleic acid with a copolymer of dicyclopentanyl (meth) acrylate / glycidyl (meth) acrylate and maleic acid with a copolymer of benzyl (meth) acrylate / glycidyl (meth) (Meth) acrylate / glycidyl (meth) acrylate, a resin obtained by reacting maleic acid with a copolymer of styrene / glycidyl (meth) acrylate, a resin obtained by reacting maleic acid with a copolymer of cyclohexyl A resin obtained by reacting a copolymer of maleic acid methyl / glycidyl (meth) acrylate with maleic acid, a resin obtained by reacting maleic acid with a copolymer of N-cyclohexylmaleimide / glycidyl (meth) (Meth) acrylate / cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate / glycidyl Acrylate / Writing A resin obtained by reacting maleic acid with a copolymer of dicyclopentanyl (meth) acrylate / styrene / glycidyl (meth) acrylate, a resin obtained by reacting maleic acid with a copolymer of glycidyl (meth) A resin obtained by reacting a copolymer of fentanyl (meth) acrylate / maleic acid methyl / glycidyl (meth) acrylate with maleic acid, dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide / glycidyl Methacrylate; maleic acid;

A resin obtained by reacting a copolymer of dicyclopentanyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid and maleic anhydride, a resin obtained by reacting benzyl (meth) acrylate / glycidyl (meth) A resin obtained by reacting a copolymer of (meth) acrylic acid with maleic anhydride, a resin obtained by reacting a copolymer of cyclohexyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid and maleic anhydride, (Meth) acrylic acid and maleic anhydride are added to a copolymer of a copolymer of (meth) acrylic acid / glycidyl (meth) acrylate with a copolymer of (meth) acrylic acid and glycidyl (Meth) acrylic acid and maleic anhydride to a copolymer of N-cyclohexylmaleimide / glycidyl (meth) acrylate, dicyclopentanyl (meth) acrylate (Meth) acrylate / cyclohexyl (meth) acrylate / benzyl (meth) acrylate / glycidyl (meth) acrylate reacted with (meth) acrylic acid and maleic anhydride, dicyclopentanyl (Meth) acrylate / styrene / glycidyl (meth) acrylate, a resin obtained by reacting a copolymer of glycidyl (meth) acrylate with (meth) acrylic acid and maleic anhydride, a copolymer of dicyclopentanyl (Meth) acrylic acid and maleic anhydride to a copolymer of a dicyclopentanyl (meth) acrylate / methyl (meth) acrylate / glycidyl (meth) acrylate resin reacted with acrylic acid and maleic anhydride , A resin obtained by reacting a copolymer of dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide / glycidyl (meth) acrylate with (meth) acrylic acid and maleic anhydride;

A resin obtained by reacting a copolymer of dicyclopentanyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate with (meth) acrylic acid, a resin obtained by reacting benzyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate (Meth) acrylic acid to a copolymer of cyclohexyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate, a resin obtained by reacting a copolymer of styrene / 3, (Meth) acrylic acid is reacted with a copolymer of a (meth) acrylic acid methyl / 3,4-epoxycyclohexylmethyl methacrylate and a resin obtained by reacting a copolymer of (meth) acrylic acid and 4-epoxycyclohexylmethyl methacrylate with a (Meth) acrylate / benzyl (meth) acrylate / 3, a resin obtained by reacting a copolymer of N-cyclohexylmaleimide / 3,4-epoxycyclohexylmethyl methacrylate with (meth) acrylic acid, dicyclopentanyl ,4- (Meth) acrylate / cyclohexyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate in the copolymer of dicyclopentanyl (meth) acrylate and cyclohexylmethyl methacrylate A resin obtained by reacting (meth) acrylic acid with a copolymer of dicyclopentanyl (meth) acrylate / styrene / 3,4-epoxycyclohexylmethyl methacrylate, dicyclopentanyl (Meth) acrylate / N-cyclohexylmaleimide (meth) acrylate / (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate copolymer obtained by reacting (meth) acrylic acid with a copolymer of dicyclopentanyl / 3,4-epoxycyclohexylmethyl methacrylate is reacted with (meth) acrylic acid;

A resin obtained by reacting a copolymer of dicyclopentanyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate with crotonic acid, a resin obtained by reacting benzyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate A resin obtained by reacting a copolymer of crotonic acid with a copolymer, a resin obtained by reacting a copolymer of cyclohexyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate with crotonic acid, a resin obtained by reacting styrene / 3,4-epoxycyclohexylmethyl A resin obtained by reacting a copolymer of methacrylate with crotonic acid, a resin obtained by reacting a copolymer of crotonic acid methyl / 3,4-epoxycyclohexylmethyl methacrylate with crotonic acid, N-cyclohexylmaleimide / 3,4 -Epoxy cyclohexylmethyl methacrylate, a resin obtained by reacting a copolymer of dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate A resin obtained by reacting a polymer with crotonic acid, a resin obtained by reacting a copolymer of dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate with crotonic acid, A resin obtained by reacting a copolymer of fentanyl (meth) acrylate / styrene / 3,4-epoxycyclohexylmethyl methacrylate with crotonic acid, dicyclopentanyl (meth) acrylate / methyl crotonate / 3,4- Crotonic acid was added to a copolymer of dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide / 3,4-epoxycyclohexylmethyl methacrylate, a resin obtained by reacting a copolymer of hexylmethyl methacrylate with crotonic acid Reacted resin;

A resin obtained by reacting a copolymer of dicyclopentanyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate with maleic acid, a resin obtained by reacting benzyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate A resin obtained by reacting a copolymer of maleic acid with a copolymer of cyclohexyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate, a resin obtained by reacting styrene / 3,4-epoxycyclohexylmethyl A resin obtained by reacting a copolymer of methacrylate with maleic acid, a resin obtained by reacting a copolymer of maleic acid methyl / 3,4-epoxycyclohexylmethyl methacrylate with maleic acid, N-cyclohexylmaleimide / 3,4 (Meth) acrylate / benzyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate in a copolymer of dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate Male A resin obtained by reacting a copolymer of dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate with maleic acid, dicyclopentanyl (meth) Acrylate / styrene / 3,4-epoxycyclohexylmethyl methacrylate, a resin obtained by reacting maleic acid with a copolymer of dicyclopentanyl (meth) acrylate / maleic acid methyl / 3,4-epoxycyclohexylmethyl methacrylate A resin obtained by reacting a copolymer of dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide / 3,4-epoxycyclohexylmethyl methacrylate with maleic acid;

(Meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate, a resin obtained by reacting a copolymer of (meth) acrylic acid and maleic anhydride with a copolymer of dicyclopentanyl (meth) acrylate and 3,4- (Meth) acrylic acid and maleic anhydride are reacted with a copolymer of cyclohexylmethyl methacrylate and cyclohexyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate, and (meth) acrylic acid and (Meth) acrylic acid / maleic anhydride, a resin obtained by reacting a copolymer of styrene / 3,4-epoxycyclohexylmethyl methacrylate with (meth) acrylic acid and maleic anhydride, a resin obtained by reacting a (Meth) acrylic acid and maleic anhydride reacted with a copolymer of (meth) acrylic acid and hexylmethyl methacrylate, and a resin obtained by reacting a copolymer of N-cyclohexylmaleimide / 3,4-epoxycyclohexylmethyl methacrylate with (meth) (Meth) acrylic acid and maleic anhydride to a copolymer of dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate, (Meth) acrylic acid and maleic anhydride to a copolymer of dicyclopentyl (meth) acrylate / cyclohexyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate, (Meth) acrylate / (meth) acrylate / dicyclopentanyl (meth) acrylate / styrene / 3,4-epoxycyclohexylmethyl methacrylate, a resin obtained by reacting a copolymer of (meth) acrylic acid and maleic anhydride with a copolymer of (Meth) acrylate / N-cyclohexyl (meth) acrylate and a resin obtained by reacting a copolymer of methyl acrylate / 3,4-epoxycyclohexylmethyl methacrylate with (meth) acrylic acid and maleic anhydride, Maleimide can be given a mid / 3,4-epoxycyclohexylmethyl methacrylate to a copolymer of acrylate (meth) acrylic resin is reacted with maleic anhydride and the like.

The weight average molecular weight of the resin (B) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000. When the weight average molecular weight of the resin (B) is within the above range, the coating property tends to be good, the film is hardly reduced at the time of development, and the unexposed portion of the non-exposed portion tends to be good at the time of development.

The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the resin (B) is preferably 1.1 to 6.0, and more preferably 1.2 to 4.0. When the molecular weight distribution is in the above range, the developability tends to be excellent.

The acid value of the resin (B) is preferably 20 to 150 mg / g-KOH, more preferably 50 to 135 mg / g-KOH, particularly preferably 70 to 135 mg / g-KOH. The acid value is a value measured as the amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the resin (B), and can be obtained by titration using an aqueous solution of potassium hydroxide.

When the colored photosensitive composition of the present invention contains the resin (B), the content of the resin (B) is usually 5 to 95 mass%, preferably 5 to 95 mass%, relative to the total amount of the resin (B) Is 20 to 80% by mass, and more preferably 40 to 60% by mass. When the content of the resin (B) is in the above range, developability, adhesiveness, solvent resistance of the cured pattern, and mechanical characteristics tend to be good.

The colored photosensitive 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 or an acid generated from the polymerization initiator (D), and includes, for example, a compound having a polymerizable ethylenically unsaturated bond, ) Acrylic acid ester compound.

Examples of the polymerizable compound (C) having one polymerizable ethylenically unsaturated bond include the same compounds as those exemplified as the above-mentioned (a), (b) and (c), among which (meth) .

Examples of the polymerizable compound (C) having two polymerizable ethylenically unsaturated bonds include 1,3-butanediol di (meth) acrylate, 1,3-butanediol (meth) acrylate, 1,6-hexanediol di Acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di Acrylate, polyethylene glycol diacrylate, bis (acryloyloxyethyl) ether of bisphenol A, ethoxylated bisphenol A di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, ethoxylated neopentyl Glycol di (meth) acrylate, and 3-methylpentanediol di (meth) acrylate.

Examples of the polymerizable compound (C) having three or more polymerizable ethylenically unsaturated bonds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tri (meth) acrylate, ethoxylated trimethylol propane tri Acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) (Meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tri A reaction product of dipentaerythritol penta (meth) acrylate and an acid anhydride, tripentaerythritol (meth) acrylate and acid anhydride caprolactone-modified trimethylolpropane tri (meth) acrylate, caprolactone-modified pentaerythritol (Meth) acrylate, caprolactone modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol penta (Meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, caprolactone modified tripentaerythritol tetra (meth) acrylate, caprolactone-modified tripentaerythritol penta (meth) acrylate, caprolactone Modified tripentaerythritol hexa (meth) acrylate, caprolactone-modified tripentaerythritol Acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate and acid anhydride, caprolactone-modified dipentaerythritol penta (meth) A reaction product of an acrylate and an acid anhydride, caprolactone-modified tripentaerythritol hepta (meth) acrylate, and an acid anhydride.

Of these, monomers having three or more functionalities are preferable, and dipentaerythritol hexa (meth) acrylate is more preferable.

The content of the polymerizable compound (C) is preferably 5 to 95% by mass, more preferably 20 to 80% by mass, based on the total amount of the resin (B) and the polymerizable compound (C). When the content of the polymerizable compound (C) is in the above range, the sensitivity and the smoothness, reliability and mechanical strength of the resulting pattern tends to be good.

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

The polymerization initiator (D) is not particularly limited as long as it is a compound which generates an active radical, an acid or the like by the action of light and initiates polymerization, and a known polymerization initiator can be used.

As the polymerization initiator (D), a nonimidazole compound, an alkylphenone compound, a triazine compound, an acylphosphine oxide compound or an oxime compound is preferable. The photocathione polymerization initiator described in JP-A No. 2008-181087 (for example, one composed of onium cation and anion derived from Lewis acid) may be used.

Examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- ) -4,4 ', 5,5'-tetraphenylbiimidazole (see, for example, JP-A 6-75372 and JP-A 6-75373), 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) ) Diimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) 4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole (see, for example, Japanese Patent Publication No. 48-38403 and Japanese Patent Application Laid-Open No. 62-174204) Imidazole compounds in which the phenyl group at the 5,5'-position is substituted by a carboalkoxy group (see, for example, JP-A-7-10913). Preferred are 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole.

Examples of the alkylphenone compounds include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan- 2- (4-methylphenylmethyl) butan-1-one, 2-hydroxy-2- Methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) Oligomers of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propane-1-one and the like, preferably 2-methyl- (4-methylsulfanylphenyl) propan-1-one, and 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one. IRGACURE 369, 907 (manufactured by BASF Japan), and the like may be used.

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (Trichloromethyl) -6- [2- (5-methylfuran-2-yl) -1,3,5-triazine, ) Ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] Bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like. A commercially available product such as Irgacure 819 (manufactured by BASF Japan) may be used.

Examples of the oxime compounds include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy- Yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) Benzoyl} -9H-carbazol-3-yl] ethan-1-imine or the like is used instead of 9-ethyl-6- {2- methyl- 4- (3,3- . Commercially available products such as Irgacure OXE-01, OXE-02 (manufactured by BASF Japan) and N-1919 (manufactured by ADEKA) may be used.

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- Benzoyl-4'-methyldiphenyl sulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, etc. Benzophenone compounds such as 9,10-phenanthrene quinone, 2-ethyl anthraquinone, camphorquinone, etc., 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, . These are preferably used in combination with a polymerization initiating auxiliary (D1) described later (particularly an amine compound described below).

The colored photosensitive composition of the present invention may contain a polymerization initiator (D1). The polymerization initiation assistant (D1) is used in combination with the polymerization initiator (D), and is a compound or a sensitizer used for promoting the polymerization of the polymerizable compound initiated by the polymerization initiator.

Examples of the polymerization initiator (D1) include an amine compound, a thiazoline compound, an alkoxyanthracene compound, a thioxanthone compound, and a carboxylic acid compound.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, (Dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (ethyl Methylamino) benzophenone, among which 4,4'-bis (diethylamino) benzophenone is preferable. And commercially available products such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) may be used.

Examples of the thiazoline compound include compounds represented by the formulas (III-1) to (III-3).

[Chemical Formula 4]

Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, Dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene and the like.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1- City Oak Mountain, and the like.

Examples of the carboxylic acid compound include phenylsulfanyl acetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, Chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like.

The content of the polymerization initiator (D) is preferably 0.1 to 40 mass%, more preferably 1 to 30 mass%, based on the total amount of the resin (B) and the polymerizable compound (C).

When the total amount of the polymerization initiator (D) is within this range, the colored photosensitive composition becomes highly sensitive, and the chemical resistance, mechanical strength and surface smoothness of the resulting pattern tends to be good.

The amount of the polymerization initiator (D1) to be used is preferably 0.01 to 50% by mass, more preferably 0.1 to 40% by mass, based on the total amount of the resin (B) and the polymerizable compound (C) . 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 initiator (D1) is within this range, the sensitivity of the resulting colored photosensitive composition is further increased, and the productivity of the obtained pattern tends to be improved.

The colored photosensitive composition of the present invention may further contain a polyfunctional thiol compound (T). The polyfunctional thiol compound (T) is a compound having two or more sulfanyl groups in the molecule. Among them, the use of a compound having two or more sulfanyl groups adjacent to the aliphatic hydrocarbon group is preferable because sensitivity of the colored photosensitive composition of the present invention is increased.

Examples of the polyfunctional thiol compound (T) include hexane dithiol, decanediol, 1,4-bis (methylsulfanyl) benzene, butanediol bis (3-sulfanylpropionate), butanediol bis (3-sulfanyl acetate) , Trimethylolpropane tris (3-sulfanyl acetate), butanediol bis (3-sulfanyl propionate), trimethylolpropane tris (3-sulfanyl propionate), ethylene glycol bis Pentaerythritol tetrakis (3-sulfanyl acetate), pentaerythritol tetrakis (3-sulfanyl propionate), pentaerythritol tetrakis (3-sulfanyl acetate), tris hydroxyethyl tris Propionate), pentaerythritol tetrakis (3-sulfanylbutylate), and 1,4-bis (3-sulfanylbutyloxy) butane.

The content of the polyfunctional thiol compound (T) is preferably 0.5 to 20% by mass, more preferably 1 to 15% by mass, based on the polymerization initiator (D). When the content of the polyfunctional thiol compound (T) is within this range, the sensitivity tends to be high and the developability tends to be good.

The colored photosensitive composition of the present invention contains a solvent (E). The solvent (E) is not particularly limited, and a solvent commonly used in the art can be used. For example, an ester solvent (a solvent containing -COO- in the molecule and not containing -O-), an ether solvent other than an ester solvent (a solvent containing -O- in the molecule and not containing -COO- ), Ether ester solvents (solvents containing -COO- and -O- in the molecule), ketone solvents other than ester solvents (solvents containing -CO- in the molecule and containing -COO-), alcohol solvents, An aromatic hydrocarbon solvent, an amide solvent, and dimethylsulfoxide.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate , Butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone.

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, Propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydrofuran , 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, A brush, and the like.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, Ethoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, ethyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-methoxypropionate, Methyl propionate, methyl propionate, methyl 2-ethoxy-2-methyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate , Di, and the like ethylene glycol monobutyl ether acetate.

Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4- Cyclopentanone, cyclohexanone, isophorone, and the like.

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, and mesitylene.

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

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

Among these solvents, an organic solvent having a boiling point of 120 ° C or more and 180 ° C or less at 1 atm is preferable from the viewpoint of coatability and dryness. Among them, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol methyl ethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol and the like are preferable.

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

The colored photosensitive composition of the present invention preferably contains a surfactant (F). Examples of the surfactant include a silicone surfactant, a fluorinated surfactant, and a silicon surfactant having a fluorine atom. The inclusion of the surfactant tends to make the flatness at the time of coating good.

As the silicone surfactant, a surfactant having a siloxane bond can be mentioned. Concretely, it is possible to use a silicone resin such as Tororensilicon DC3PA, Copper SH7PA, Copper DC11PA, Copper SH21PA, Copper SH28PA, Copper SH29PA, Copper SH30PA, Polyether Modified Silicone Oil SH8400 (trade name: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP323, KP324, KP340, KP341 (manufactured by 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.

Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain. Specifically, the following materials were used: Florinato (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Ltd.), Megapack (registered trademark) F142D, copper F171, copper F172, copper F173, copper F177, copper F183, copper R30 (Registered trademark) S381, S382, SC101, SC105 (manufactured by Mitsubishi Materials Corporation), EF301, EF351, EF351 and EF352 (Manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Research Co., Ltd.).

Examples of the silicone surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain. Specific examples thereof include Megapac (registered trademark) R08, Copper BL20, Copper F475, Copper F477, Copper F443 (manufactured by DIC Corporation). And preferably Megapak (registered trademark) F475.

The surfactant (F) is 0.001 mass% or more and 0.2 mass% or less, preferably 0.002 mass% or more and 0.1 mass% or less, and more preferably 0.01 mass% or more and 0.05 mass% or less, with respect to the color photosensitive composition. When the surfactant is contained in this range, the flatness of the coating film can be improved.

The colored photosensitive composition of the present invention may contain various additives such as fillers, other polymer compounds, adhesion promoters, antioxidants, ultraviolet absorbers, light stabilizers, and chain transfer agents, if necessary.

The colored photosensitive composition of the present invention can be prepared, for example, as follows.

First, the pigment of the colorant (A) is mixed with the solvent (E) and dispersed using a bead mill or the like until the average particle diameter of the pigment becomes about 0.2 탆 or less. At this time, if necessary, a part or all of the pigment dispersant and the resin (B) may be blended. To the pigment dispersion thus obtained, the polymerizable compound (C) and the polymerization initiator (D), the residue of the resin (B) optionally contained, other components and, if necessary, further solvent (E) So that the intended colored photosensitive composition can be obtained.

The colored photosensitive composition of the present invention is processed into a color filter, for example, through the steps shown in the following (1) to (4).

(1) A step of obtaining a coating film by applying the colored photosensitive composition of the present invention to a substrate

(2) A step of obtaining a coated film after exposure by exposing the coated film through a mask

(3) a step of obtaining a pattern by developing the coated film after exposure with an alkali developer

(4) A step of obtaining a cured pattern by baking a pattern

Examples of the method for obtaining the pattern include a photolithography method, an inkjet method, a printing method, and the like. Among them, a photolithography method is preferable.

In the photolithography method, the above-mentioned colored photosensitive composition is applied to a substrate, dried, exposed through a photomask, and developed to obtain a pattern.

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

Examples of the plastic include polyolefins such as polyethylene, polypropylene and norbornene polymer, polyvinyl alcohol, polyethylene terephthalate, polyethylene naphthalate, poly (meth) acrylate, cellulose ester, polycarbonate, polysulfone, poly Ether sulfone, polyether ketone, polyphenylene sulfide, and polyphenylene oxide. Here, (meth) acrylic acid means at least one kind selected from the group consisting of acrylic acid and methacrylic acid.

On these substrates, a structure such as a color filter, various insulating or conductive films, and a drive circuit may be formed.

The colored photosensitive composition of the present invention is particularly useful when a pattern is formed on a plastic substrate in that it can form a cured pattern at a lower temperature.

Examples of the application method for the substrate include extrusion coating, direct gravure coating, reverse gravure coating, CAP coating and die coating. It may also be applied by using a coating device such as a dip 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 curtain flow coater or a spinless coater) . Among them, it is preferable to apply by using a slit coater, a spin coater, a roll coater or the like.

Examples of the drying method of the film coated on the substrate include heat drying, natural drying, air drying, and vacuum drying. A plurality of methods may be combined.

The drying temperature is preferably 10 to 120 占 폚, more preferably 25 to 100 占 폚. The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes.

The vacuum drying is preferably carried out at a temperature of 20 to 25 캜 under a pressure of 50 to 150 Pa.

The film thickness of the coated film after drying is not particularly limited and can be appropriately adjusted depending on the material to be used and the application, and is usually 0.1 to 20 탆, preferably 1 to 6 탆.

The coated film after drying is exposed through a photomask for forming a desired pattern. The pattern shape on the photomask at this time is not particularly limited, and a pattern shape according to the intended use is used.

As a light source used for exposure, a light source that generates light having a wavelength of 250 to 450 nm is preferable. For example, light having a wavelength of less than 350 nm is cut using a filter for cutting the wavelength band, or a band-pass filter for extracting light in the vicinity of 436 nm, around 408 nm, and around 365 nm is used Or may be selectively taken out. Specific examples thereof include mercury lamps, light emitting diodes, metal halide lamps, and halogen lamps.

It is preferable to use a device such as a mask aligner or a stepper because it is possible to uniformly irradiate the entire exposure surface with parallel rays or accurately align the mask and the substrate.

After exposure, a pattern can be obtained by contacting a predetermined portion, for example, an unexposed portion with a developing solution to develop the resist. As the developing solution, an organic solvent may be used, but an aqueous solution of a basic compound is preferable because dissolution or swelling hardly occurs in the exposed portion of the coating film and a pattern of a good shape can be obtained.

The developing method may be paddle method, dipping method, spray method, or the like. Further, the substrate may be inclined at an arbitrary angle at the time of development.

After development, it is preferable to wash with water.

Examples of the basic compound include sodium hydroxide, potassium hydroxide, disodium hydrogenphosphate, sodium dihydrogenphosphate, ammonium dihydrogenphosphate, ammonium dihydrogenphosphate, potassium dihydrogenphosphate, sodium silicate, potassium silicate, potassium carbonate, Inorganic basic compounds such as sodium carbonate, potassium hydrogen carbonate, sodium borate, potassium borate and ammonia; organic basic compounds such as tetramethyl ammonium hydroxide, 2-hydroxyethyl trimethyl ammonium hydroxide, , Organic basic compounds such as diethylamine, triethylamine, monoisopropylamine, diisopropylamine, and ethanolamine. Among them, potassium hydroxide, sodium hydrogencarbonate and tetramethylammonium hydroxide are preferable.

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

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

Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan Nonionic surfactants such as fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters and polyoxyethylene alkylamines;

Anionic surfactants such as sodium lauryl alcohol sulfate, sodium oleyl alcohol sulfate, sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate and sodium dodecylnaphthalenesulfonate;

And cationic surfactants such as stearylamine hydrochloride and lauryltrimethylammonium 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, and particularly preferably 0.1 to 5% by mass.

Further post-baking may be carried out if necessary. The post-baking is preferably carried out at a temperature in the range of, for example, 50 to 230 DEG C for 2 to 240 minutes.

The colored photosensitive composition of the present invention can obtain a good pattern such as color density, brightness, contrast, sensitivity, resolution, heat resistance, and color filter. It is also possible to use a display device having such a color filter or pattern as a part of its constituent parts, for example, a device related to a colored image such as a known liquid crystal display device, an organic EL device, a solid- Gt; < / RTI >

Example

Hereinafter, the present invention will be described in more detail with reference to Examples. In the examples, "% " and " part " are by mass% and part by mass unless otherwise specified.

Synthesis Example 1

182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube, the atmosphere in the flask was changed to nitrogen in air, 22.0 g (0.10 mole) of mono methacrylate (FA-513M, manufactured by Hitachi Chemical Co., Ltd.) and 43.0 g (0.5 mole) of methacrylic acid were mixed with 70.5 g (0.40 mole) of benzyl methacrylate, And 136 g of monomethyl ether acetate, to which 3.6 g of azobisisobutyronitrile had been added, was added dropwise to the flask over 2 hours from the dropping funnel, and further stirred at 100 DEG C for 5 hours. Next, 35.5 g (0.25 mol) of glycidyl methacrylate (50 mol% with respect to the carboxyl group of the methacrylic acid used in the present reaction) of 0.9 g of trisdimethylaminomethylphenol, And hydroquinone (0.145 g) were charged into a flask, and the reaction was continued at 110 DEG C for 6 hours to obtain a resin solution B1 having a solid acid value of 79 mgKOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 13,000 and the molecular weight distribution (Mw / Mn) was 2.1.

Synthesis Example 2

250 parts of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a gas introduction tube. Thereafter, nitrogen gas was introduced into the flask by using a gas introduction tube, and the atmosphere in the flask was replaced with nitrogen gas. Thereafter, the solution in the flask was heated to 100 DEG C, and then a mixture of 152.6 parts of benzyl methacrylate, 41.7 parts of methacrylic acid, 1.5 parts of azobisisobutyronitrile and 150 parts of propylene glycol monomethyl ether acetate was added to a dropping funnel And the mixture was further stirred at 100 ° C for 2.5 hours. The weight average molecular weight Mw was 2.3 × 10 ⁴ , the solid content was 34% by mass, the solution acid value was 47 mg-KOH / lt; 2 > / g.

The weight-average molecular weight (Mw) and the number-average molecular weight (Mn) of the resin obtained in Synthesis Example were measured by the GPC method under the following conditions.

Apparatus: K2479 (manufactured by Shimadzu Corporation)

Column: SHIMADZU Shim-pack GPC-80M

Column temperature: 40 占 폚

Solvent: THF (tetrahydrofuran)

Flow rate: 1.0 ml / min

Detector; RI

The ratio (Mw / Mn) of the weight average molecular weight and the number average molecular weight in terms of polystyrene obtained as described above was defined as a molecular weight distribution.

Example 1

[Preparation of colored photosensitive composition]

Pigment: CI Pigment Green 58 51 parts

Acrylic pigment dispersant 10 parts

Resin solution B2 (in terms of solid content) 20 parts

Propylene glycol monomethyl ether acetate 267 parts

, And the pigment dispersion A in which the pigment was sufficiently dispersed by using a bead mill,

Pigment: CI Pigment Yellow 138 81 parts

Acrylic pigment dispersant 12 parts

Resin solution B2 (in terms of solid content) 28 parts

Propylene glycol monomethyl ether acetate 402 parts

A pigment dispersion B in which pigments were sufficiently dispersed using a bead mill,

Pigment: C.I. Pigment Green 7 29 parts

Acrylic pigment dispersant 5.7 parts

Resin solution B2 (in terms of solid content) 11 parts

Propylene glycol monomethyl ether acetate 173 parts

And a pigment dispersion C in which pigments were fully dispersed using a bead mill,

Resin: Resin solution B1 (in terms of solid content) 66 parts

Polymerizable compound: 57 parts of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.)

Polymerization initiator: 15 parts of 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one (Irgacure 369; BASF Japan)

Polymerization initiator: 4.9 parts of 4,4'-bis (diethylamino) benzophenone (EAB-F manufactured by Hodogaya Chemical Co., Ltd.)

Solvent: 450 parts of propylene glycol monomethyl ether acetate, and

Additive: Sumi-epoxy ESCN-195XL (manufactured by Sumitomo Chemical Co., Ltd.) 6.1 parts

To obtain a colored photosensitive composition.

Comparative Example

[Preparation of colored photosensitive composition]

Pigment: C.I. Pigment Green 36 5.5 parts

Pigment: 2.4 parts of C. I. Pigment Yellow 150

Polyester-based pigment dispersant 1.2 parts

Propylene glycol monomethyl ether acetate 38 parts

Were mixed, and the pigment dispersion in which the pigment was sufficiently dispersed by using a bead mill,

Resin: Resin solution B1 (in terms of solid content) 6.6 parts

Polymerizable compound: 5.7 parts of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.)

Polymerization initiator: 1.5 parts of 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one (Irgacure 369; BASF Japan)

Polymerization initiator: 4,4'-bis (diethylamino) benzophenone (EAB-F manufactured by Hodogaya Chemical Co., Ltd.) 0.49 parts

Additive: Sumi-epoxy ESCN-195XL (Sumitomo Chemical Co., Ltd.) 0.61 part

Solvent: Propylene glycol monomethyl ether acetate 38 parts

To obtain a colored photosensitive composition.

<Fabrication of pattern>

A PET film (Toore Lumira 75-T60) was stuck on a 2-inch-wide glass plate to prepare a substrate. On the PET film side of the substrate, the colored photosensitive composition was applied by a spin coat method and prebaked on a hot plate at 80 DEG C for 2 minutes. After cooling down, the space between the substrate coated with the colored photosensitive composition and the quartz glass photomask was adjusted to 200 mJ / cm &lt; 2 &gt; (365 nm) using an exposure machine (TME-150RSK; Standard) exposure dose. The irradiation of the colored photosensitive composition at this time was carried out by passing the radiation from the ultra-high pressure mercury lamp through an optical filter (UV-35; manufactured by Asahi Spectroscopy). As the photomask, a line and space pattern of 10 to 100 mu m was formed. After irradiation with light, it was immersed in a 0.1% aqueous solution of tetramethylammonium at 23 DEG C for 80 seconds, developed and cleaned with pure water to form a pattern. The film thickness of the obtained pattern was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.), and found to be 2 占 퐉.

The pattern formed in the same manner as described above was further heated (post-baking) at 50 캜 for 5 minutes to obtain a cured pattern. Further, the pattern formed in the same manner as above was further heated (post-baking) at 100 DEG C for 5 minutes to obtain a cured pattern. The film thickness of the obtained cured pattern was measured in the same manner as described above, and found to be 2 탆 in all cases.

&Lt; Evaluation of color performance &

The transmittance (T1) at 600 nm and the transmittance (T2) at 520 nm were measured using a spectroscopic spectrophotometer (OSP-SP200 OLYMPUS CO., LTD. The smaller the ratio of T1 to T2 (T1 / T2) is, the better the color separation performance from the red filter is. The results are shown in Table 1.

The ratio of T1 to T2 (T1 / T2) No post bake Post bake ℃ 50 Post bake ℃ 100 Example 0.23 0.23 0.23 Comparative Example 0.49 0.49 0.49

<Evaluation of solvent resistance>

One milliliter of propylene glycol monomethyl ether acetate was added dropwise to the pattern formed on the substrate, and the mixture was stopped for 30 seconds and then rotated at a rotation number of 1000 rpm for 10 seconds using a spin coater to swell the patterned propylene glycol monomethyl ether acetate Removed.

The film thickness retention was calculated from the film thickness values measured before and after contact with propylene glycol monomethyl ether acetate by the following formula. The higher the film thickness retention ratio is, the better the curability is, and when the colored photosensitive composition other than green is overlaid, the elution to the solvent contained in the colored photosensitive composition is suppressed. Therefore, . The results are shown in Table 2.

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

<Evaluation of resolution>

The obtained pattern was observed with a laser microscope (Axio Imager MAT manufactured by Carl Zeiss), and the minimum resolution was determined as the resolution. The higher the resolution, the more precise the color filter can be produced. The results are shown in Table 2.

Resolution (탆) Film thickness retention (%) No post bake Post bake ℃ 50 Post bake ℃ 100 No post bake Post bake ℃ 50 Post bake ℃ 100 Example 20 20 20 90 92 92 Comparative Example 40 40 40 88 91 90

According to the colored photosensitive composition of the present invention, a green color filter excellent in color separation ability from a red filter can be obtained.

Claims (8)

Wherein the colorant is a coloring agent containing a halogenated copper phthalocyanine pigment, a halogenated zinc phthalocyanine pigment and a quinophthalone pigment, the halogenated copper phthalocyanine pigment is CI Pigment Green 7, Wherein the content of the copper halide phthalocyanine pigment is 20 parts by mass or more and 150 parts by mass or less based on 100 parts by mass of the zinc phthalocyanine pigment. delete The method according to claim 1,
Wherein the content of the quinophthalone pigment is 50 parts by mass or more and 200 parts by mass or less based on 100 parts by mass of the zinc phthalocyanine pigment. delete delete The method according to claim 1,
Wherein the quinophthalone pigment is &lt; RTI ID = 0.0 &gt; CI Pigment Yellow 138. &lt; / RTI &gt; The method according to claim 1,
A colored photosensitive composition comprising a colorant, a polymerizable compound, a polymerization initiator, a solvent and a resin. A color filter formed from the colored photosensitive composition according to claim 1.