KR20120035868A - Colored photosensitive resin composition - Google Patents

Abstract

PURPOSE: A colored photo-sensitive resin composition, a pattern based on the composition, a color filter based on the composition, and a method for manufacturing the composition are provided to improve the solvent resistance characteristic of the composition although a high temperature-based baking process is omitted. CONSTITUTION: A colored photo-sensitive resin composition includes a coloring agent, copolymer, resin, polymeric compound, polymerization initiator, and a solvent. Ethylenically unsaturated bond is arranged at the side chain of the resin. The copolymer includes structural units derived from at least one selected from unsaturated carboxylic acid and unsaturated carboxylic anhydride and derived from C2 to C4 cyclic ether and monomer with ethylenically unsaturated bond.

Description

Colored photosensitive resin composition {COLORED PHOTOSENSITIVE RESIN COMPOSITION}

This invention relates to the coloring photosensitive resin composition suitable for formation of the colored image which comprises the color filter used for a liquid crystal display element or a solid-state image sensor.

The color filter used for display apparatuses, such as a liquid crystal display panel, an electroluminescent panel, and a plasma display panel, is manufactured using colored photosensitive resin composition. As such colored photosensitive resin composition, the composition containing a pigment, resin, a photopolymerizable compound, a photoinitiator, and a solvent, and resin is a copolymer of the unsaturated compound which has methacrylic acid and an oxylanyl group is known (patent document 1). .

Japanese Unexamined Patent Publication No. 2007-333847

When forming a pattern using the said colored photosensitive resin composition, it was not necessarily able to fully be satisfied about the resolution of the pattern.

The present invention is the following [1]? [8] to provide.

[1] Colored photosensitive resin composition containing (A), (B1), (B2), (C), (D) and (E):

(A) coloring agent;

(B1) The structural unit derived from at least 1 sort (s) chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride, and C2-C? Copolymers containing a structural unit derived from a cyclic ether of 4 and a monomer having an ethylenically unsaturated bond (but do not have an ethylenically unsaturated bond in the side chain);

(B2) Resin which has ethylenically unsaturated bond in a side chain;

(C) polymeric compound;

(D) polymerization initiator;

(E) Solvent.

[2] The colored photosensitive resin composition according to the above [1], wherein (B2) is a resin obtained by reacting (b) with a copolymer obtained by copolymerizing the following (a) and (c):

(a): at least 1 sort (s) chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride;

(b): 2 carbon atoms? Monomers having a cyclic ether of 4 and an ethylenically unsaturated bond;

(c): Monomer which has an unsaturated bond copolymerizable with (a) and (b).

[2-2] The colored photosensitive resin composition according to the above [1], wherein (B2) is a resin obtained by reacting (b) with a copolymer obtained by copolymerizing the following (a) and (c):

(a): at least 1 sort (s) chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride;

(b): monomer which has an oxylanyl group and ethylenically unsaturated bond;

(c): Monomer which has an unsaturated bond copolymerizable with (a) and (b).

[3] The colored photosensitive resin composition according to the above [1] or [2], wherein the content of (B1) is 10% by mass to 95% by mass with respect to the total amount of (B1) and (B2).

[4] above [1]? The pattern formed from the coloring photosensitive resin composition in any one of [3].

[5] A color filter comprising the pattern of [4].

[6] the following (1)? The manufacturing method of the color filter containing the process shown by (4):

(1) above [1]? Process of obtaining a coating film by apply | coating the coloring photosensitive resin composition in any one of [3] to a board | substrate;

(2) obtaining a post-exposure coating film by exposing through a mask to a coating film;

(3) Process of obtaining pattern by developing after-exposure coating film with alkaline developing solution;

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

[7] The method for producing a color filter according to the above [6], wherein the step (4) is a step of baking at a temperature of 25 ° C or more and 120 ° C or less.

[8] The method for producing a color filter according to [6] or [7], wherein the substrate in the step (1) is a plastic substrate.

According to the coloring photosensitive resin composition of this invention, the pattern excellent in resolution can be obtained.

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

(B1) The structural unit derived from at least 1 sort (s) chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride, and C2-C? Copolymer containing the structural unit derived from the cyclic ether of 4 and the monomer which has an ethylenically unsaturated bond (However, it does not have ethylenically unsaturated bond in a side chain) (Hereinafter, it may be called "resin (B1).") ) And

(B2) It is resin containing resin which has an ethylenically unsaturated bond in a side chain (henceforth "resin (B2)").

The coloring photosensitive resin composition of this invention contains a coloring agent (A). Although a pigment and dye are mentioned as a coloring agent (A), It is preferable to contain a pigment from the point of heat resistance and light resistance.

Examples of the pigment include organic pigments and inorganic pigments, and the compounds classified as pigments in the color index (The Society of Dyers and Colourists).

As an organic pigment, specifically, CI pigment yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110 Yellow pigments such as 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, and 214;

C. I. Orange pigments, such as pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;

CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, etc. Pigments;

C. I. Blue pigments, such as Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60;

C. I. Violet pigments, such as pigment violet 1, 19, 23, 29, 32, 36, 38;

C. I. Green pigment, such as Pigment Green 7, 36, 58;

C. I. Brown pigments, such as Pigment Brown 23 and 25; And

C. I. Black pigments, such as Pigment Black 1 and 7, are mentioned.

Among them, CI Pigment Yellow 138, 139, 150, CI Pigment Red 177, 242, 254, CI Pigment Red Violet 23, CI Pigment Blue 15: 3, 15: 6 and CI Pigment Green 7, 36, 58 is preferred. You may use these pigments individually or in mixture of 2 or more types.

The pigment may be rosin-treated, surface-treated with a pigment derivative or a pigment dispersant having an acid group or a basic group introduced therein, graft treatment on the surface of the pigment with a high molecular compound, atomization by sulfuric acid atomization, or the like, or removing impurities as necessary. For example, the washing treatment with an organic solvent, water, or the like, the removal treatment by an ion exchange method of ionic impurities, or the like may be performed. Moreover, it is preferable that a pigment is uniform in particle size. By containing a pigment dispersant and performing a dispersion process, the pigment dispersion liquid of the state in which the pigment was disperse | distributed uniformly in the solution can be obtained.

As the pigment dispersant, a commercially available surfactant can be used. As surfactant, surfactant of silicone type, fluorine type, ester type, cation type, anion type, nonionic type, amphoteric, polyester type, polyamine type, and acryl type is mentioned, for example. As said surfactant, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol diester, sorbitan fatty acid ester, fatty acid modified polyester, tertiary amine modified polyurethane, polyethyleneimine In addition to KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperth (manufactured by Geneca Co., Ltd.), EFKA (manufactured by CIBA), Ajisper (Ajinomoto Fine) And Techno Co., Ltd., Disperbyk (manufactured by Vicchemy). These can be used individually or in combination of 2 types or more, respectively.

When using a pigment dispersant, the usage-amount is preferably 100 mass% or less with respect to the weight of a pigment, More preferably, it is 5? 50 mass%. When the usage-amount of a pigment dispersant exists in the said range, there exists a tendency for the pigment dispersion liquid of a uniform dispersion state to be obtained.

Content of a coloring agent (A) becomes like this with respect to the quantity of solid content of a coloring photosensitive resin composition, Preferably it is 5? 60 mass%, More preferably, it is 5? 45 mass%. If content of a coloring agent (A) is the said range, desired spectroscopy and color concentration can be obtained. Here, solid content in this specification means the total amount of the component remove | excluding the solvent from the coloring photosensitive resin composition.

The coloring photosensitive resin composition of this invention contains resin (B) containing resin (B1). The resin (B1) is a structural unit derived from at least one kind selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic anhydride (hereinafter may be referred to as "(a)"), and carbon number 2? Copolymer containing a structural unit derived from the cyclic ether of 4 and the monomer which has an ethylenically unsaturated bond (Hereinafter, it may be called "(b).") However, it does not have an ethylenically unsaturated bond in a side chain. to be.

When colored photosensitive resin composition contains resin (B1), there exists a tendency for reliability, such as heat resistance of a pattern obtained, chemical-resistance, etc. to become more favorable.

As the resin (B1), for example,

Resin (B1-1): A copolymer obtained by superposing | polymerizing (a) and (b), and

Resin (B1-2): polymerizes monomer (c) (hereinafter may be referred to as "(c)") having an unsaturated bond copolymerizable with (a) and (b) and (a) and (b) The copolymer which consists of is mentioned. As resin (B1), (B1-1) is preferable.

Specific examples of (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, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexenedicarboxylic acid;

Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hepto-2-ene, 5,6-dicarboxybicyclo [2.2.1] hepto-2- N, 5-carboxy-5-methylbicyclo [2.2.1] hepto-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hepto-2-ene, 5-carboxy-6-methyl ratio Bicyclo unsaturated compounds containing carboxyl groups, such as cyclo [2.2.1] hepto-2-ene and 5-carboxy-6-ethylbicyclo [2.2.1] hepto-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 anhydrides such as dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo [2.2.1] hepto-2-ene anhydride (hymic acid anhydride);

Unsaturated mono [(meth) acryloyloxyalkyl of bivalent or more polyvalent carboxylic acids, such as monosuccinate mono [2- (meth) acryloyloxyethyl] and phthalate mono [2- (meth) acryloyloxyethyl] Esters;

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

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

Here, in this specification, "(meth) acrylic acid" represents at least 1 sort (s) chosen from the group which consists of acrylic acid and methacrylic acid. Notation, such as "(meth) acryloyl" and "(meth) acrylate", has the same meaning.

As (b), it has a monomer (b-1) (Hereinafter, it may be called "(b-1)"), an oxetanyl group, and ethylenically unsaturated bond which have an oxylanyl group and ethylenically unsaturated bond, for example. Monomer (b-2) (hereinafter may be referred to as "(b-2)") and monomer (b-3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter referred to as "(b-3)" It may be a case).

As (b-1), the monomer (b-11) (Hereinafter, it may be called "(b-11)") and cycloalkene which have a structure which epoxidized chain olefin, and ethylenically unsaturated bond are mentioned, for example. The monomer (b-12) (Hereinafter, it may be called "(b-12)") which has an epoxidized structure and ethylenically unsaturated bond is mentioned.

As (b-1), the monomer which has an oxylanyl group and a (meth) acryloyloxy group is preferable, and (b-12) which has a (meth) acryloyloxy group is more preferable.

Specific examples of (b-11) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, and glycidyl vinyl ether. -Vinylbenzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, α-methyl-o-vinyl benzyl glycidyl ether, α-methyl-m-vinyl benzyl glycidyl Ether, α-methyl-p-vinylbenzylglycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (gly Cydyloxymethyl) 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-tris (glycidyloxymethyl) styrene And the compound described in JP-A-7-248625.

Examples of (b-12) include vinylcyclohexene monooxide and 1,2-epoxy-4-vinylcyclohexane (for example, ceoxide 2000; manufactured by Daicel Chemical Industry Co., Ltd.), 3,4-epoxycyclohexyl Methyl acrylate (for example, cyclomer A400; manufactured by Daicel Chemical Industry Co., Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (for example, cyclomer M100; manufactured by Daicel Chemical Industry Co., Ltd.) ), A compound represented by formula (I), a compound represented by formula (II), and the like.

[In formula (I) and formula (II), R <^1> and R <^2> Are independently of each other a hydrogen atom, or 1? The alkyl group of 4 is represented, and the hydrogen atom contained in this alkyl group may be substituted by the hydroxy group.

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

R ³ Is carbon number 1? The alkanediyl group of 6 is shown.

* Represents the number of bonds with O]

Carbon number 1? As an alkyl group of 4, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert- butyl group etc. are mentioned specifically ,.

As a hydroxyalkyl group, a hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy-1- Methyl ethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, etc. are mentioned.

As R <^1> and R <^2> , Preferably, a hydrogen atom, a methyl group, a hydroxymethyl group, 1-hydroxyethyl group, and 2-hydroxyethyl group are mentioned, More preferably, a hydrogen atom and a methyl group are mentioned.

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

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), and a * -CH ₂ CH ₂ -O- group. and, more preferably, there may be mentioned a single bond, * -CH ₂ CH ₂ -O- group.

As a compound represented by Formula (I), it is Formula (I-1)? The compound etc. which are represented by Formula (I-15) are mentioned. Preferably, formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9) and formula (I-11)? Formula (I-15) is mentioned. More preferably, Formula (I-1), Formula (I-7), Formula (I-9), and Formula (I-15) are mentioned.

As a compound represented by Formula (II), it is a formula (II-1)? The compound etc. which are represented by Formula (II-15) are mentioned. Preferably formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9), or formula (II-11)? Formula (II-15) is mentioned. More preferably, Formula (II-1), Formula (II-7), Formula (II-9), and Formula (II-15) are mentioned.

The compound represented by Formula (I) and the compound represented by Formula (II) can be used independently, respectively. Moreover, they can be mixed in arbitrary ratios. When mixing, the mixing ratio is in molar ratio, Preferably it is Formula (I): Formula (II), and it is 5:95? 95: 5, more preferably 10: 90? 90: 10, particularly preferably 20: 80? 80: 20.

As (b-2), it is preferable that it is a monomer which has an oxetanyl group and a (meth) acryloyloxy group. As (b-2), it is 3-methyl-3- (meth) acryloyloxy methyl oxetane, 3-ethyl-3- (meth) acryloyloxy methyl oxetane, 3-methyl-3-, for example. (Meth) acryloyloxyethyl oxetane and 3-ethyl-3- (meth) acryloyloxyethyl oxetane are mentioned.

As (b-3), the monomer which has a tetrahydrofuryl group and a (meth) acryloyloxy group is more preferable. Specific examples of (b-3) include tetrahydrofurfuryl acrylate (for example, biscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like. .

As (c), For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert- butyl (meth) acrylate, etc. Alkyl (meth) acrylates;

Cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate (in the art, dicyclopentanyl as conventional name) (Meth) acrylic-acid cyclic alkylesters, such as (meth) acrylate), 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;

Bicyclo [2.2.1] hepto-2-ene, 5-methylbicyclo [2.2.1] hepto-2-ene, 5-ethylbicyclo [2.2.1] hepto-2-ene, 5-hydroxybi Cyclo [2.2.1] hepto-2-ene, 5-hydroxymethylbicyclo [2.2.1] hepto-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] hepto-2 -Ene, 5-methoxybicyclo [2.2.1] hepto-2-ene, 5-ethoxybicyclo [2.2.1] hepto-2-ene, 5,6-dihydroxybicyclo [2.2.1] hepto 2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hepto-2-ene, 5,6-di (2'-hydroxyethyl) bicyclo [2.2.1] hepto- 2-ene, 5,6-dimethoxybicyclo [2.2.1] hepto-2-ene, 5,6-diethoxybicyclo [2.2.1] hepto-2-ene, 5-hydroxy-5-methyl Bicyclo [2.2.1] hepto-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hepto-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] Hepto-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hepto-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hepto-2-ene, 5-phenoxy Cycarbonyl Bicyclo [ 2.2.1] hepto-2-ene, 5,6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hepto-2-ene, 5,6-bis (cyclohexyloxycarbonyl) ratio Bicyclo unsaturated compounds, such as cyclo [2.2.1] hepto-2-ene;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl Dicarbonylimide derivatives such as -6-maleimide caproate, N-succinimidyl-3-maleimide propionate and N- (9-acridinyl) maleimide;

Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, acetic acid Vinyl, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like.

Among them, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hepto-2-ene and the like are preferable in terms of copolymerization reactivity and alkali solubility.

It is preferable that the ratio of the structural unit derived from each monomer in resin (B1-1) exists in the following ranges with respect to the total number of moles of the structural unit which comprises resin (B1-1).

structural unit derived from (a); 5? 60 mol% (more preferably 10-50 mol%)

structural unit derived from (b); 40? 95 mol% (more preferably 50-90 mol%)

When the ratio of the structural unit of resin (B1-1) exists in the said range, there exists a tendency for storage stability, developability, solvent resistance, heat resistance, and mechanical strength to become favorable.

As resin (B1-1), resin in which (b) is (b-1) is preferable, and resin in which (b-1) is (b-12) is more preferable.

The resin (B1-1) is, for example, the method described in the document "Experimental Method of Polymer Synthesis" (Otsu Takayuki Kogyo KK Chemical Co., Ltd. First Edition First Edition March 1, 1972) and the citations described in this document. It can be manufactured with reference to the literature.

Specifically, the method of stirring, heating, and keeping warm in deoxygenation is illustrated by inject | pouring predetermined amount of (a) and (b), a polymerization initiator, a solvent, etc. in a reaction container, and replacing oxygen with nitrogen. In addition, the polymerization initiator, the solvent, etc. which are used here are not specifically limited, What is normally used in the said field | area can be used. As a polymerization initiator, For example, an azo compound (2,2'- azobisisobutyronitrile, 2,2'- azobis (2, 4- dimethylvaleronitrile), etc.), an organic peroxide (benzoyl peroxide, etc.) ), And any solvent may be used as long as it dissolves each monomer, and a solvent or the like described later can be used as the solvent of the colored photosensitive resin composition.

In addition, the obtained copolymer may use the solution after reaction as it is, the solution concentrated or diluted may be used, and what was taken out as solid (powder) by methods, such as reprecipitation, may be used. In particular, by using the same solvent as the solvent (E) described later as the solvent during this polymerization, the solution after the reaction can be used as it is, and the manufacturing process can be simplified.

In resin (B1-2), it is preferable that the ratio of the structural unit derived from each monomer exists in the following ranges with respect to the total number of moles of all the structural units which comprise resin (B1-2).

structural unit derived from (a); 2 ? 40 mol% (more preferably 5-35 mol%)

structural unit derived from (b); 2 ? 95 mol% (more preferably 5-80 mol%)

structural unit derived from (c); One ? 65 mol% (more preferably 1-60 mol%)

When the ratio of the structural unit of resin (B1-2) exists in the said range, storage stability, developability, solvent resistance, heat resistance, and mechanical strength tend to become favorable.

As resin (B1-2), resin whose (b) is (b-1) is preferable, and resin whose (b) is (b-12) is more preferable.

Resin (B1-2) can be manufactured by the method similar to resin (B1-1).

Preferably the weight average molecular weight (Mw) of polystyrene conversion of resin (B1) is 3,000? 100,000, more preferably 5,000? 50,000. When the weight average molecular weight of resin (B1) exists in the said range, applicability | paintability tends to become favorable, and film | membrane decrease does not generate | occur | produce well at the time of image development, and there exists a tendency for the detachability of a non-pixel part at the time of image development to be favorable. .

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of resin (B1) becomes like this. 6.0, more preferably 1.8? 4.0. When the molecular weight distribution of the resin (B1) is in the above range, it tends to be excellent in developability.

The acid value of the resin (B1) is 20? 150 mg-KOH / g, preferably 30? 135 mg-KOH / g, more preferably 40? 125 mg-KOH / g. The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B1), and can be obtained by titration using an aqueous potassium hydroxide solution.

The content of the resin (B1) is preferably 10? To the total amount of the resin (B1) and the resin (B2). 95 mass%, More preferably, it is 10? 85 mass%, Especially preferably, it is 10? 80 mass%. When content of resin (B1) exists in the said range, there exists a tendency for developability, adhesiveness, solvent resistance, and a mechanical characteristic to become favorable.

Resin (B) contained in the coloring photosensitive resin composition of this invention contains resin (B2) further. Resin (B2) is resin which has an ethylenically unsaturated bond in a side chain, Resin (B2-1) and (b) obtained by making (b) react with the copolymer obtained by copolymerizing (a) and (c) again Resin (B2-2) etc. which are obtained by making (a) react with the copolymer obtained by copolymerizing (c) again are mentioned. Especially, as resin (B2), resin (B2-1) is preferable.

As (a), (b) and (c) which comprise resin (B2), although the thing similar to resin (B1) mentioned above is mentioned, Especially as (c) group which consists of a tricyclodecane skeleton and a tricyclodecene skeleton It is preferable that it is a compound (c1) (Hereinafter, it may be called "(c1)") which has at least 1 sort (s) of skeleton chosen from and ethylenically unsaturated bond. When (c) is (c1), the film | membrane reduction of the pattern by image development can be suppressed.

Here, the "tricyclodecane skeleton" and "tricyclodecene skeleton" in this specification mean the following structures (each carbon atom has a coupling | bonding number each), respectively.

Specific examples of (c1) include dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate. Can be mentioned. These can be used individually or in combination of 2 types or more, respectively.

Resin (B2-1) and resin (B2-2) can be manufactured through a two-step process, for example. Also in this case, the method described in the above-mentioned document "Experimental method of polymer synthesis" (Otsu Takayuki Co., Ltd. Chemical Co., Ltd. First Edition First Printing March 1, 1972), Japanese Unexamined Patent Publication No. 2001-89533 It can manufacture with reference to the method etc. which were described in.

Resin (B2-1) first obtains the copolymer of (a) and (c) similarly to the manufacturing method of resin (B1-1) mentioned above as a 1st step.

In this case, the obtained copolymer may use the solution after reaction as it is, the concentrated or diluted solution may be used, and the thing taken out as solid (powder) by methods, such as reprecipitation, may be used for the obtained copolymer.

It is preferable that the ratio of the structural unit derived from (a) and (c) exists in the following ranges with respect to the total mole number of all the structural units which comprise the said copolymer.

structural unit derived from (a); 5? 50 mol% (more preferably 10-45 mol%)

structural unit derived from (c); 50? 95 mol% (more preferably 55-90 mol%)

Next, as a 2nd step, some of the carboxylic acid and carboxylic anhydride of (a) derived from the obtained copolymer are made to react with the cyclic ether of (b). (B-1) is preferable and (b-11) is preferable as (b) from the point that reactivity of a cyclic ether is high, and unreacted (b) is hard to remain.

Specifically, following the above, the atmosphere in the flask is replaced with nitrogen by air, and the molar number of (a) is 5? 80 mol% (b) and the reaction catalyst (for example, tris (dimethylaminomethyl) phenol) of a carboxyl group and a cyclic ether are 0.001? With respect to the total amount of (a), (b) and (c). 5 mass% and a polymerization inhibitor (for example, hydroquinone) are 0.001-about the total amount of (a), (b) and (c). 5 mass% was put in a flask, and 60? 1 at 130 ℃? Reaction (B2-1) can be obtained by making it react for 10 hours. In addition, similarly to the polymerization conditions, the injection method and the reaction temperature can be appropriately adjusted in consideration of the amount of heat generated by the production equipment, the polymerization and the like.

In this case, the number of moles of (b) is 10? To the number of moles of (a). It is preferable to set it as 75 mol%, More preferably, it is 15? 70 mol%. There exists a tendency for the balance of storage stability, solvent resistance, and heat resistance to become favorable by making the number-of-moles of (b) into this range.

As a specific example of resin (B2-1), resin which made glycidyl (meth) acrylate react with the copolymer of (meth) acrylic acid / dicyclopentanyl (meth) acrylate, and (meth) acrylic acid / benzyl (meth Resin which the glycidyl (meth) acrylate was made to react with the copolymer of an acrylate, resin which made glycidyl (meth) acrylate react with the copolymer of (meth) acrylic acid / cyclohexyl (meth) acrylate, ( Resin which glycidyl (meth) acrylate was made to react with the copolymer of meth) acrylic acid / styrene, resin which glycidyl (meth) acrylate was made to react with the copolymer of (meth) acrylic acid / methyl (meth) acrylate, ( Glycidyl (meth) acrylate to the copolymer of the resin of which glycidyl (meth) acrylate was made to react the copolymer of (meth) acrylic acid / N-cyclohexyl maleimide, and a crotonic acid / dicyclopentanyl (meth) acrylate Resin which reacted;

Glycidyl (meth) acrylate is reacted with a resin obtained by reacting glycidyl (meth) acrylate with a copolymer of crotonic acid / benzyl (meth) acrylate and a copolymer of crotonic acid / cyclohexyl (meth) acrylate. Resin obtained by reacting glycidyl (meth) acrylate with a copolymer of crotonic acid / styrene and resin obtained by reacting glycidyl (meth) acrylate with a copolymer of methyl crotonic acid / crotonate, crotonic acid / Resin which made glycidyl (meth) acrylate react with the copolymer of N-cyclohexyl maleimide;

Glycidyl (meth) acrylate is added to a copolymer of maleic acid / dicyclopentanyl (meth) acrylate with glycidyl (meth) acrylate and a copolymer of maleic acid / benzyl (meth) acrylate. Glycidyl (meth) acrylate is made to react with resin and maleic acid / styrene copolymer which made glycidyl (meth) acrylate react with the copolymer of maleic acid / cyclohexyl (meth) acrylate. Resin, Glycidyl (meth) acrylate reacted with a copolymer of maleic acid / methyl maleate, Glycidyl (meth) acrylate reacted with a copolymer of maleic acid / N-cyclohexyl maleimide ;

Resin obtained by reacting glycidyl (meth) acrylate with a copolymer of (meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate, and of (meth) acrylic acid / maleic anhydride / benzyl (meth) acrylate Resin obtained by reacting glycidyl (meth) acrylate with a copolymer, resin obtained by reacting glycidyl (meth) acrylate with a copolymer of (meth) acrylic acid / maleic anhydride / cyclohexyl (meth) acrylate, ( Glycidyl (meth) to a copolymer of (meth) acrylic acid / maleic anhydride / methyl (meth) acrylate by reacting glycidyl (meth) acrylate with a copolymer of (meth) acrylic acid / maleic anhydride / styrene Resin which glycidyl (meth) acrylate was made to react the resin which made acrylate react, and the copolymer of (meth) acrylic acid / maleic anhydride / N-cyclohexyl maleimide;

Resin obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of (meth) acrylic acid / dicyclopentanyl (meth) acrylate, 3, to a copolymer of (meth) acrylic acid / benzyl (meth) acrylate Resin to which 4-epoxycyclohexyl methyl methacrylate was reacted, resin to which 3, 4- epoxycyclohexyl methyl methacrylate was reacted with the copolymer of (meth) acrylic acid / cyclohexyl (meth) acrylate, (meth) acrylic acid 3,4-epoxycyclohexylmethyl methacrylate reacted with a resin of 3,4-epoxycyclohexylmethyl methacrylate reacted with a copolymer of / styrene and a copolymer of (meth) acrylic acid / methyl (meth) acrylate Resin and 3, 4- epoxycyclohexyl methyl methacrylate made to react the copolymer of (meth) acrylic acid / N-cyclohexyl maleimide;

Resin obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of crotonic acid / dicyclopentanyl (meth) acrylate, and 3,4-epoxycyclo to a copolymer of crotonic acid / benzyl (meth) acrylate 3, to a copolymer of crotonic acid / styrene, a resin obtained by reacting a hexyl methyl methacrylate, a copolymer of crotonic acid / cyclohexyl (meth) acrylate, and 3,4-epoxycyclohexyl methyl methacrylate Of a resin in which 4-epoxycyclohexylmethyl methacrylate is reacted, a resin in which 3,4-epoxycyclohexylmethyl methacrylate is reacted with a copolymer of crotonic acid / methyl crotonate, and crotonic acid / N-cyclohexyl maleimide Resin which made 3, 4- epoxycyclohexyl methyl methacrylate react with the copolymer;

Resin obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of maleic acid / dicyclopentanyl (meth) acrylate, and 3,4-epoxycyclo to a copolymer of maleic acid / benzyl (meth) acrylate 3, to a copolymer of maleic acid / styrene and a copolymer of maleic acid / cyclohexyl (meth) acrylate, to which a hexyl methyl methacrylate was reacted, a resin of 3,4-epoxycyclohexyl methyl methacrylate, Of resin in which 4-epoxycyclohexylmethyl methacrylate is reacted, resin in which 3,4-epoxycyclohexylmethyl methacrylate is reacted with a copolymer of maleic acid / methyl maleate, and maleic acid / N-cyclohexyl maleimide Resin which made 3, 4- epoxycyclohexyl methyl methacrylate react with the copolymer;

Resin obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of (meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate, (meth) acrylic acid / maleic anhydride / benzyl (meth) 3,4-epoxycyclohexylmethyl to the copolymer of (meth) acrylic acid / maleic anhydride / cyclohexyl (meth) acrylate which made 3, 4- epoxycyclohexyl methyl methacrylate react with the copolymer of acrylate Resin to which methacrylate was reacted, resin to which 3,4-epoxycyclohexylmethyl methacrylate was reacted with the copolymer of (meth) acrylic acid / maleic anhydride / styrene, (meth) acrylic acid / maleic anhydride / (meth) 3,4-epoxycyclohexyl methyl methacrylate to a copolymer of (meth) acrylic acid / maleic anhydride / N-cyclohexyl maleimide by reacting 3,4-epoxycyclohexyl methyl methacrylate with a copolymer of methyl acrylate Krill There may be mentioned resins such as by reacting the site.

Moreover, as resin (B2-1), it is more preferable that it is resin obtained by making (b) react with the copolymer obtained by copolymerizing (c) other than (a), (c1), and (c1). The pattern obtained by resin (B2-1) having the said structure tends to be excellent in adhesiveness and solvent resistance with a board | substrate.

When the copolymer of (a) and (c) consists of (c) other than (a) and (c1) and (c1), the ratio of the structural unit derived from (c) other than (c1) and (c1) This 10: 90? 60:40 is preferable and 10:90? 40:60 is more preferable, and 10:90? 30:70 is more preferable.

As resin obtained by making (b) react with the copolymer obtained by copolymerizing (c) other than (a) and (c1) and (c1), specifically (meth) acrylic acid / dicyclopentanyl (meth) acrylate / Glyci to the copolymer of resin (meth) acrylic acid / dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate which made glycidyl (meth) acrylate react with the copolymer of benzyl (meth) acrylate Resin by which di (meth) acrylate was reacted, resin by which glycidyl (meth) acrylate was reacted with a copolymer of (meth) acrylic acid / dicyclopentanyl (meth) acrylate / styrene, (meth) acrylic acid / dicyclo Of resin (meth) acrylic acid / dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide which has reacted glycidyl (meth) acrylate to a copolymer of fentanyl (meth) acrylate / methyl (meth) acrylate Glycidyl (in the copolymer Resin by reacting the agent) acrylate;

Resin obtained by reacting glycidyl (meth) acrylate with a copolymer of crotonic acid / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate; crotonic acid / dicyclopentanyl (meth) acrylate / cyclohexyl ( Resin which glycidyl (meth) acrylate was made to react with the copolymer of meth) acrylate, and glycidyl (meth) acrylate was made to react with the copolymer of crotonic acid / dicyclopentanyl (meth) acrylate / styrene Resin obtained by reacting glycidyl (meth) acrylate with a copolymer of crotonic acid / dicyclopentanyl (meth) acrylate / methyl crotonate; crotonic acid / dicyclopentanyl (meth) acrylate / N-cyclohexylmalee Resin which made glycidyl (meth) acrylate react with the copolymer of mead;

Resin obtained by reacting glycidyl (meth) acrylate with a copolymer of maleic acid / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate, maleic acid / dicyclopentanyl (meth) acrylate / cyclohexyl ( Resin which glycidyl (meth) acrylate was made to react with the copolymer of meth) acrylate, and glycidyl (meth) acrylate was made to react with the copolymer of maleic acid / dicyclopentanyl (meth) acrylate / styrene Resin obtained by reacting glycidyl (meth) acrylate with a copolymer of maleic acid / dicyclopentanyl (meth) acrylate / methyl maleate; maleic acid / dicyclopentanyl (meth) acrylate / N-cyclohexylmalee Resin which made glycidyl (meth) acrylate react with the copolymer of mead;

Resin, (meth) acrylic acid / maleic anhydride /, in which a glycidyl (meth) acrylate is reacted with a copolymer of (meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate Resin which glycidyl (meth) acrylate was made to react the copolymer of dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate, (meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate Glycidyl (to the copolymer of the resin of glycidyl (meth) acrylate to the copolymer of / styrene, copolymer of (meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate / methyl (meth) acrylate Resin in which glycidyl (meth) acrylate was reacted with a copolymer of (meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide reacted with meth) acrylate;

Resin obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of (meth) acrylic acid / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate, (meth) acrylic acid / dicyclopentanyl (meth To the copolymer of (meth) acrylic acid / dicyclopentanyl (meth) acrylate / styrene which made 3, 4- epoxycyclohexyl methyl methacrylate react with the copolymer of acrylate / cyclohexyl (meth) acrylate 3,4-epoxycyclohexylmethyl methacrylate to a copolymer of (meth) acrylic acid / dicyclopentanyl (meth) acrylate / methyl (meth) acrylate reacted with 3,4-epoxycyclohexylmethyl methacrylate Resin which 3, 4- epoxycyclohexyl methyl methacrylate was made to react with resin and (meth) acrylic acid / dicyclopentanyl (meth) acrylate / N-cyclohexyl maleimide which made it react;

Resin, crotonic acid / dicyclopentanyl (meth) acrylate / made by reacting 3,4-epoxycyclohexyl methyl methacrylate with a copolymer of crotonic acid / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate 3,4-epoxycyclo to the copolymer of the resin of crosonic acid / dicyclopentanyl (meth) acrylate / styrene which made 3, 4- epoxycyclohexyl methyl methacrylate react with the copolymer of cyclohexyl (meth) acrylate Resin which the hexyl methyl methacrylate was made to react, the resin which made 3, 4- epoxycyclohexyl methyl methacrylate react with the copolymer of crotonic acid / dicyclopentanyl (meth) acrylate / methyl crotonate, and crotonic acid / dicyclo Resin in which 3,4-epoxycyclohexyl methyl methacrylate is reacted with a copolymer of fentanyl (meth) acrylate / N-cyclohexyl maleimide;

Resin, maleic acid / dicyclopentanyl (meth) acrylate, in which 3,4-epoxycyclohexylmethyl methacrylate was reacted with a copolymer of maleic acid / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate 3,4-epoxycyclo to the copolymer of maleic acid / dicyclopentanyl (meth) acrylate / styrene which made 3, 4- epoxycyclohexyl methyl methacrylate react with the copolymer of cyclohexyl (meth) acrylate Resin to which hexyl methyl methacrylate was reacted, a copolymer of maleic acid / dicyclopentanyl (meth) acrylate / methyl maleate, to which 3,4-epoxycyclohexyl methyl methacrylate was reacted, maleic acid / dicyclo Resin in which 3,4-epoxycyclohexyl methyl methacrylate is reacted with a copolymer of fentanyl (meth) acrylate / N-cyclohexyl maleimide;

Resin obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of (meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate, (meth) acrylic acid / male Resin obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of acid anhydride / dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate, (meth) acrylic acid / maleic anhydride / dicyclo Resin obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of fentanyl (meth) acrylate / styrene, (meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate / (meth) acrylic acid Copolymerization of (meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate / N-cyclohexyl maleimide by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of methyl A resin or the like can be given by reacting a 3,4-epoxycyclohexylmethyl methacrylate.

Resin (B2-2) is obtained similarly to the manufacturing method of resin (B1-1) mentioned above as a 1st step, and obtains the copolymer of (b) and (c).

In this case, the copolymer obtained as mentioned above may use the solution after reaction as it is, the solution concentrated or diluted may be used, and what was taken out as solid (powder) by methods, such as reprecipitation, may be used.

It is preferable that the ratio of the structural unit derived from (b) and (c) exists in the following ranges with respect to the total number-of-moles of all the structural units which comprise the said copolymer.

structural unit derived from (b); 5? 95 mol% (more preferably 10-90 mol%)

structural unit derived from (c); 5? 95 mol% (more preferably 10-90 mol%)

Moreover, the carboxylic acid or carboxylic anhydride which (a) has in the cyclic ether derived from (b) in the copolymer of (b) and (c) similarly to the manufacturing method of resin (B2-1). It can be obtained by reacting. The carboxylic acid anhydride may be reacted again with the hydroxy group generated by the reaction of the cyclic ether with the carboxylic acid or the carboxylic anhydride.

The usage-amount of (a) made to react with the said copolymer is 5? With respect to the number-of-moles of (b). It is preferable that it is 80 mol%. (B-1) is preferable and (b-11) is preferable as (b) from the point that reactivity of a cyclic ether is high and unreacted (b) is hard to remain.

As a specific example of resin (B2-2), resin which made (meth) acrylic acid react with the copolymer of dicyclopentanyl (meth) acrylate / glycidyl (meth) acrylate, and benzyl (meth) acrylate / gly Resin which (meth) acrylic acid was made to react with the copolymer of cylyl (meth) acrylate, resin which (meth) acrylic acid was made to react with the copolymer of cyclohexyl (meth) acrylate / glycidyl (meth) acrylate, and styrene Resin which (meth) acrylic acid was made to react with the copolymer of / glycidyl (meth) acrylate, resin which made (meth) acrylic acid react with the copolymer of methyl (meth) acrylate / glycidyl (meth) acrylate, N Resin which (meth) acrylic acid was made to react the copolymer of cyclohexyl maleimide / glycidyl (meth) acrylate, and dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate / glycidyl (meth) acryl (Meth) arc to the copolymer of the rate Resin and dicyclopentanyl (meth) which made (meth) acrylic acid react with the copolymer of resin which made acid react, and the copolymer of dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate / glycidyl (meth) acrylate Of a resin obtained by reacting (meth) acrylic acid to a copolymer of acrylate / styrene / glycidyl (meth) acrylate and dicyclopentanyl (meth) acrylate / methyl (meth) acrylate / glycidyl (meth) acrylate Resin which (meth) acrylic acid was made to react with the copolymer of (meth) acrylic acid, and the copolymer of dicyclopentanyl (meth) acrylate / N-cyclohexyl maleimide / glycidyl (meth) acrylate;

Crotonic acid was added to a resin obtained by reacting crotonic acid with a copolymer of dicyclopentanyl (meth) acrylate / glycidyl (meth) acrylate and a copolymer of benzyl (meth) acrylate / glycidyl (meth) acrylate. Crotonic acid was made to react with the resin which made the reacted resin and the copolymer of cyclohexyl (meth) acrylate / glycidyl (meth) acrylate, and the copolymer of styrene / glycidyl (meth) acrylate reacted. Resin, the resin which made crotonic acid react with the copolymer of methyl crotonate / glycidyl (meth) acrylate, and the resin which made crotonic acid react with the copolymer of N-cyclohexyl maleimide / glycidyl (meth) acrylate Resin which made crotonic acid react with the copolymer of dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate / glycidyl (meth) acrylate, and dicyclopentanyl (meth) acrylate / cyclohexyl (meth Crotonic acid is reacted with the resin which made crotonic acid react with the copolymer of acrylate / glycidyl (meth) acrylate, and the copolymer of dicyclopentanyl (meth) acrylate / styrene / glycidyl (meth) acrylate. Resin, dicyclopentanyl (meth) acrylate / N-cyclohexyl maleimide, in which crotonic acid was reacted with a copolymer of a resin, a dicyclopentanyl (meth) acrylate / methyl crotonic acid / glycidyl (meth) acrylate Resin which made crotonic acid react with the copolymer of / glycidyl (meth) acrylate;

Maleic acid is added to a copolymer of dicyclopentanyl (meth) acrylate / glycidyl (meth) acrylate in which maleic acid is reacted and a copolymer of benzyl (meth) acrylate / glycidyl (meth) acrylate. The maleic acid was made to react with the copolymer of resin and styrene / glycidyl (meth) acrylate which made maleic acid react with the copolymer of resin and cyclohexyl (meth) acrylate / glycidyl (meth) acrylate which were made to react. Resin, maleic acid to a copolymer of methyl maleate / glycidyl (meth) acrylate, and maleic acid to a copolymer of N-cyclohexyl maleimide / glycidyl (meth) acrylate. Resin obtained by reacting maleic acid with a copolymer of dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate / glycidyl (meth) acrylate; dicyclopentanyl (meth) acrylate / cyclohexyl (meth) Acrylate / Written Resin which maleic acid was made to react with the copolymer of lycidyl (meth) acrylate, resin which maleic acid was made to react with the copolymer of dicyclopentanyl (meth) acrylate / styrene / glycidyl (meth) acrylate, and dicyclo Resin, dicyclopentanyl (meth) acrylate / N-cyclohexyl maleimide / glycidyl, in which maleic acid was reacted with a copolymer of fentanyl (meth) acrylate / methyl maleate / glycidyl (meth) acrylate Resin in which maleic acid is reacted with a copolymer of meth) acrylate;

Of resin and benzyl (meth) acrylate / glycidyl (meth) acrylate in which (meth) acrylic acid and maleic anhydride are reacted with a copolymer of dicyclopentanyl (meth) acrylate / glycidyl (meth) acrylate. Resin and (styrene) which made (meth) acrylic acid and maleic anhydride react with the copolymer of (meth) acrylic acid and maleic anhydride, and the copolymer of cyclohexyl (meth) acrylate / glycidyl (meth) acrylate, and styrene Resin obtained by reacting (meth) acrylic acid and maleic anhydride with a copolymer of / glycidyl (meth) acrylate, (meth) acrylic acid and male to a copolymer of methyl (meth) acrylate / glycidyl (meth) acrylate Resin obtained by reacting (meth) acrylic acid and maleic anhydride with a copolymer of N-cyclohexylmaleimide / glycidyl (meth) acrylate in which an acid anhydride is reacted, dicyclopentanyl (meth) acrylate Resin, dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate, in which (meth) acrylic acid and maleic anhydride are reacted with a copolymer of / benzyl (meth) acrylate / glycidyl (meth) acrylate. Resin obtained by reacting (meth) acrylic acid and maleic anhydride with a copolymer of glycidyl (meth) acrylate, and a copolymer of dicyclopentanyl (meth) acrylate / styrene / glycidyl (meth) acrylate (meth Resin which (meth) acrylic acid and maleic anhydride were made to react copolymer of dicyclopentanyl (meth) acrylate / methyl (meth) acrylate / glycidyl (meth) acrylate which made acrylic acid and maleic anhydride react Resin obtained by reacting (meth) acrylic acid and maleic anhydride with a copolymer of dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide / glycidyl (meth) acrylate;

Resin by which (meth) acrylic acid was reacted with the copolymer of dicyclopentanyl (meth) acrylate / 3,4-epoxycyclohexylmethylmethacrylate, benzyl (meth) acrylate / 3,4-epoxycyclohexylmethylmethacryl Resin in which (meth) acrylic acid was made to react with the copolymer of the rate, resin in which (meth) acrylic acid was made to react with the copolymer of cyclohexyl (meth) acrylate / 3,4-epoxycyclohexylmethylmethacrylate, styrene / 3, Resin which (meth) acrylic acid was made to react with the copolymer of 4-epoxycyclohexyl methyl methacrylate, and (meth) acrylic acid which was made to react with the copolymer of methyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate Resin and dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate / 3 which made (meth) acrylic acid react with the copolymer of resin and N-cyclohexyl maleimide / 3,4-epoxycyclohexylmethyl methacrylate ,4- Resin which (meth) acrylic acid was made to react with the copolymer of the epoxy cyclohexyl methyl methacrylate, and the air of dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate / 3,4-epoxycyclohexyl methyl methacrylate Resin which (meth) acrylic acid was made to react with copolymer, and copolymer of dicyclopentanyl (meth) acrylate / styrene / 3, 4- epoxycyclohexyl methyl methacrylate (meth) acrylic acid reacted, dicyclopentanyl ( Resin and dicyclopentanyl (meth) acrylate / N-cyclohexyl maleimide which (meth) acrylic acid was made to react the copolymer of meth) acrylate / methyl (meth) acrylate / 3,4-epoxycyclohexylmethylmethacrylate Resin which (meth) acrylic acid was made to react the copolymer of / 3, 4- epoxycyclohexyl methyl methacrylate;

Of a resin obtained by reacting crotonic acid to a copolymer of dicyclopentanyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate and benzyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate Resin which made crotonic acid react with the copolymer, the resin which made crotonic acid react with the copolymer of cyclohexyl (meth) acrylate / 3,4-epoxycyclohexylmethylmethacrylate, and styrene / 3,4-epoxycyclohexylmethyl Resin which made crotonic acid react with the copolymer of methacrylate, resin which made crotonic acid react with the copolymer of methyl crotonate / 3,4-epoxycyclohexylmethylmethacrylate, and N-cyclohexyl maleimide / 3,4 -A resin of dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate in which a crotonic acid is reacted with a copolymer of epoxycyclohexyl methyl methacrylate. Dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate resin which made crotonic acid react with the polymer, and the cyclocyclone Resin which made crotonic acid react with the copolymer of fentanyl (meth) acrylate / styrene / 3, 4- epoxycyclohexyl methyl methacrylate, dicyclopentanyl (meth) acrylate / methyl crotonate / 3, 4- epoxycyclo Crotonic acid was added to a resin obtained by reacting crotonic acid with a copolymer of hexylmethyl methacrylate and a copolymer of dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide / 3,4-epoxycyclohexylmethyl methacrylate. Reacted resin;

Of a resin obtained by reacting maleic acid with a copolymer of dicyclopentanyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate and benzyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate Resin which maleic acid was made to react with copolymer, resin which maleic acid was made to react with copolymer of cyclohexyl (meth) acrylate / 3,4-epoxycyclohexylmethylmethacrylate, and styrene / 3,4-epoxycyclohexylmethyl Resin obtained by reacting maleic acid with a copolymer of methacrylate, Resin obtained by reacting maleic acid with a copolymer of methyl maleate / 3,4-epoxycyclohexylmethylmethacrylate, N, cyclohexylmaleimide / 3,4 To a copolymer of dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate in which a maleic acid is reacted with a copolymer of epoxycyclohexyl methyl methacrylate. Male Resin and dicyclopentanyl (meth) which made maleic acid react with the copolymer of resin which made this reaction, the copolymer of dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate / 3, 4- epoxycyclohexyl methyl methacrylate Resin obtained by reacting maleic acid with a copolymer of acrylate / styrene / 3,4-epoxycyclohexylmethylmethacrylate, dicyclopentanyl (meth) acrylate / methyl maleate / 3,4-epoxycyclohexylmethylmethacryl Resin which maleic acid was made to react the copolymer of maleic acid with the copolymer of a rate, and the copolymer of dicyclopentanyl (meth) acrylate / N-cyclohexyl maleimide / 3,4-epoxycyclohexyl methyl methacrylate;

Resin, benzyl (meth) acrylate / 3,4-epoxycyclo, in which (meth) acrylic acid and maleic anhydride are reacted with a copolymer of dicyclopentanyl (meth) acrylate / 3,4-epoxycyclohexylmethylmethacrylate (Meth) acrylic acid and a copolymer of cyclohexyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate in which a (meth) acrylic acid and maleic anhydride were reacted with a copolymer of hexylmethyl methacrylate. Resin obtained by reacting maleic anhydride, a copolymer of styrene / 3,4-epoxycyclohexylmethyl methacrylate, a resin (meth) acrylic acid and maleic anhydride reacted, methyl (meth) acrylate / 3,4-epoxycyclo (Meth) acryl to a copolymer of N-cyclohexyl maleimide / 3,4-epoxycyclohexylmethyl methacrylate in which a (meth) acrylic acid and maleic anhydride are reacted with a copolymer of hexyl methyl methacrylate. (Meth) acrylic acid and maleic anhydride were added to a copolymer of resin and dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate reacted with lylic acid and maleic anhydride. Resin which reacted (meth) acrylic acid and maleic anhydride to the copolymer of resin which was made to react, dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate / 3, 4- epoxycyclohexyl methyl methacrylate, and dish A resin obtained by reacting (meth) acrylic acid and maleic anhydride with a copolymer of clofentanyl (meth) acrylate / styrene / 3,4-epoxycyclohexylmethylmethacrylate, dicyclopentanyl (meth) acrylate / (meth) Resin, dicyclopentanyl (meth) acrylate / N-cyclohex, in which (meth) acrylic acid and maleic anhydride were reacted with a copolymer of methyl acrylate / 3,4-epoxycyclohexylmethyl methacrylate 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.

Preferably the weight average molecular weight (Mw) of polystyrene conversion of resin (B2) is 3,000? 100,000, more preferably 5,000? 50,000. When the weight average molecular weight of resin (B2) exists in the said range, applicability | paintability tends to become favorable, and film | membrane decrease does not generate | occur | produce well at the time of image development, and there exists a tendency for the detachment | absorption property of a non-pixel part at the time of image development to be favorable. .

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B2) is preferably 1.5? 6.0, more preferably 1.8? 4.0. When the molecular weight distribution of resin (B2) exists in the said range, it exists in the tendency which is excellent in developability.

The acid value of the resin (B2) is 20? 150 mg-KOH / g, Preferably it is 50? 135 mg-KOH / g, more preferably 65? 135 mg-KOH / g. An acid value is a value measured as the amount (mg) of potassium hydroxide required in order to neutralize 1 g of resin (B2), and can be calculated | required by titration using aqueous potassium hydroxide solution.

The content of the resin (B2) is preferably 5? To the total amount of the resin (B1) and the resin (B2). 90 mass%, More preferably, it is 15? 90 mass%, Especially preferably, it is 20? 90 mass%. When content of resin (B2) exists in the said range, there exists a tendency for developability, adhesiveness, solvent resistance, and a mechanical characteristic to become favorable.

The colored photosensitive resin composition of this invention may contain resin (BX) different from resin (B1) and resin (B2) as resin (B). As resin (BX), the copolymer of (a) and (c) is mentioned, for example. Content of resin (BX) is 0? With respect to the gross mass of resin (B). It is preferable that it is 50 mass%, and 0? It is more preferable that it is 30 mass%.

The total mass of the resin (B) contained in the colored photosensitive resin composition of the present invention is 20? To the amount of solid content of the colored photosensitive resin composition. 70 mass% is preferable, and 25? 50 mass% is more preferable.

In addition, the total amount of resin (B) is 20? With respect to the total amount of resin (B) and the polymerizable compound (C). 80 mass% is preferable, and 40? 60 mass% is more preferable.

The coloring photosensitive resin composition of this invention contains a polymeric compound (C).

The polymerizable compound (C) is a compound which can be polymerized by an active radical and an acid generated from the polymerization initiator (D), and examples thereof include a compound having an ethylenically unsaturated bond, and preferably (meth) acrylic acid ester The compound can be mentioned.

As a polymeric compound (C) which has one ethylenically unsaturated bond, the thing similar to the compound illustrated as said (a), (b) and (c) is mentioned, Especially, (meth) acrylic acid ester is preferable. .

As a polymeric compound (C) which has two ethylenically unsaturated bonds, 1, 3- butanediol di (meth) acrylate, 1, 3- butanediol (meth) acrylate, 1, 6- hexanediol di (meth) acryl Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) 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, 3-methylpentanediol di (meth) acrylate, etc. are mentioned.

Examples of the polymerizable compound (C) having three or more ethylenically unsaturated bonds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and tris (2-hydroxyethyl) isocyanurate tree. (Meth) acrylate, ethoxylated trimethylol propane tri (meth) acrylate, propoxylated trimethylol propane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylic Elate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol Hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, pentaerythritol tri (meth) acrylate and a reactant of an acid anhydride, Reactant of pentaerythritol penta (meth) acrylate and acid anhydride, reactant of tripentaerythritolhepta (meth) acrylate and acid anhydride, caprolactone modified trimethylolpropane tri (meth) acrylate, caprolactone modified pentaerythritol Tri (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 Reactant of other (meth) acrylate, caprolactone modified tripentaerythritol octa (meth) acrylate, caprolactone modified pentaerythritol tri (meth) acrylate, and acid anhydride, caprolactone modified dipentaerythritol penta (meth) The reactant of an acrylate and an acid anhydride, the reactant of a caprolactone modified tripentaerythritol hepta (meth) acrylate, and an acid anhydride, etc. are mentioned. Especially, a trifunctional or more than trifunctional monomer is preferable and dipentaerythritol hexa (meth) acrylate is more preferable.

Content of a polymeric compound (C) is 5? With respect to the quantity of solid content of a coloring photosensitive resin composition. 50 mass% is preferable and 10? 45 mass% is more preferable. Moreover, Preferably it is 20? With respect to the total amount of resin (B) and a polymeric compound (C). 80 mass%, More preferably, it is 40? 60 mass%. When content of a polymeric compound (C) exists in the said range, there exists a tendency for the sensitivity, the intensity | strength of a pattern, smoothness, and reliability to become favorable.

The coloring photosensitive resin composition of this invention contains a polymerization initiator (D).

As a polymerization initiator (D), if it is a compound which generate | occur | produces an active radical, an acid, etc. by the effect of light, and starts superposition | polymerization of a polymeric compound (C), it will not specifically limit, A well-known polymerization initiator can be used.

As a polymerization initiator (D), a biimidazole compound, an alkylphenone compound, a triazine compound, an acyl phosphine oxide compound, and an oxime compound are preferable. Moreover, you may use the photocationic polymerization initiator (for example, what consists of onium cation and an anion derived from Lewis acid) of Unexamined-Japanese-Patent No. 2008-181087. Especially, an oxime compound is preferable at a sensitivity.

Examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,3-dichlorophenyl ) -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) -4,4', 5,5'-tetra (alkoxyphenyl ) Biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole (see, for example, Japanese Patent Laid-Open No. 48-38403 and Japanese Patent Laid-Open No. 62-174204), 4,4' And imidazole compounds in which the phenyl group at the 5,5'-position is substituted with a carboalkoxy group (see, for example, JP-A-7-10913). Preferably 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole.

Examples of the alkylphenone compound include diethoxy acetophenone, 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propane-1-one, and 2-dimethylamino-1- (4-morpholin). Nophenyl) -2-benzylbutan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2- (4-methylphenylmethyl) butan-1-one, 2-hydroxy-2- Methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclo An oligomer of hexylphenyl ketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propane-1-one, and the like, and preferably 2-methyl-2-morpholino-1. -(4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one, etc. are mentioned. You may use commercial items, such as Irgacure 369 and 907 (above, BASF Japan company make).

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -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] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine, etc. are mentioned.

2,4,6-trimethylbenzoyldiphenylphosphine oxide etc. are mentioned as said acylphosphine oxide initiator. You may use commercial items, such as Irgacure 819 (made by Chiba Japan Corporation).

Examples of the oxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1- On-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-dioxacyclopentanylmethyloxy) benzoyl'-9H-carbazol-3-yl] ethane-1-imine Can be mentioned. You may use commercial items, such as Irgacure OXE-01, OXE-02 (above BASF Japan make), and N-1919 (ADEKA make).

Moreover, as a polymerization initiator (D), 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'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, Benzophenone compounds such as 2,4,6-trimethylbenzophenone; Quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone and camphor quinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compound, etc. are mentioned. It is preferable to use these in combination with the polymerization start adjuvant (D1) (especially amines) mentioned later.

Moreover, the polymerization start adjuvant (D1) may contain. A polymerization start adjuvant (D1) is used in combination with a polymerization initiator (D), and is a compound or sensitizer used in order to accelerate superposition | polymerization of the polymeric compound in which superposition | polymerization was started with a polymerization initiator.

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

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid isoamyl, benzoic acid 2-dimethylaminoethyl, and 4-dimethyl Aminobenzoic acid 2-ethylhexyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (ethyl Methylamino) benzophenone etc. are mentioned, Especially, 4,4'-bis (diethylamino) benzophenone is preferable. You may use commercial items, such as EAB-F (made by Hodogaya Chemical Industry Co., Ltd.).

As a thiazolin compound, it is a formula (III-1)? The compound etc. which are represented by Formula (III-3) are mentioned.

Examples of the alkoxy anthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10- Dibutoxy anthracene, 2-ethyl-9, 10- dibutoxy anthracene, etc. are mentioned.

As a thioxanthone compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-4- propoxide Citioxanthone etc. are mentioned.

Examples of the carboxylic acid compound include phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, Chlorophenylsulfanyl acetic acid, dichlorophenylsulfanyl acetic acid, N-phenylglycine, phenoxy acetic acid, naphthylthioacetic acid, N-naphthyl glycine, naphthoxy acetic acid, and the like.

The content of the polymerization initiator (D) is preferably 0.1? To 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). 40 parts by mass, more preferably 1? 30 parts by mass. When content of a polymerization initiator (D) exists in this range, a pattern can be formed with high sensitivity, and there exists a tendency for the chemical-resistance, mechanical strength, and surface smoothness of a pattern to become favorable.

When using a polymerization start adjuvant (D1), the usage-amount becomes like this. Preferably it is 0.01? 50 parts by mass, more preferably 0.1? 40 parts by mass. Moreover, Preferably it is 0.01-per mole of polymerization initiator (D). 10 mol, more preferably 0.01? 5 moles. When the amount of the polymerization initiation assistant (D1) is within this range, the pattern can be formed with higher sensitivity, and the productivity of the pattern tends to be improved.

Moreover, the coloring photosensitive resin composition of this invention may contain the polyfunctional thiol compound (T) further. This polyfunctional thiol compound (T) is a compound which has 2 or more sulfanyl group in a molecule | numerator. Especially, since the compound which has two or more sulfanyl groups adjacent to an aliphatic hydrocarbon group can form a pattern with high sensitivity, it is preferable.

Examples of the polyfunctional thiol compound (T) include hexanedithiol, decandithiol, 1,4-bis (methylsulfanyl) benzene, butanediolbis (3-sulfanylpropionate) and butanediolbis (3-sulfanyl acetate). , Ethylene glycol bis (3-sulfanyl acetate), trimethylol propane tris (3-sulfanyl acetate), butanediol bis (3-sulfanyl propionate), trimethylol propane tris (3-sulfanyl propionate), Trimethylolpropane tris (3-sulfanyl acetate), pentaerythritol tetrakis (3-sulfanyl propionate), pentaerythritol tetrakis (3-sulfanyl acetate), tris hydroxyethyl tris (3-sulfanyl Propionate), pentaerythritol tetrakis (3-sulfanylbutylate), 1,4-bis (3-sulfanylbutyloxy) butane and the like.

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

Solvent (E) is not specifically limited, The solvent normally used in the said field | area can be used. For example, an ester solvent (a solvent which contains -COO- in a molecule and does not contain -O-) and an ether solvent other than the ester solvent (a solvent which contains -O- in a molecule and does not contain -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 not containing -COO-), alcohol solvents, It can select from an aromatic hydrocarbon solvent, an amide solvent, and dimethyl sulfoxide. These solvents may be used independently and may be used in combination of 2 or more type.

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

As an ether solvent, 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 monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran , 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phentol, methyl an Or a brush.

As an ether ester solvent, methyl methoxy acetate, ethyl methoxy acetate, methoxy acetate, methyl ethoxy acetate, ethyl ethoxy acetate, 3-methoxy propionate, ethyl 3-methoxy propionate, 3-ethoxy propionic acid Methyl, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-methoxy-2 -Methyl methyl propionate, 2-ethoxy-2-methyl ethyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol Monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate , Di, and the like ethylene glycol monobutyl ether acetate.

As a ketone solvent, 4-hydroxy-4-methyl- 2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2- pentanone, Cyclopentanone, cyclohexanone, isophorone, etc. are mentioned.

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

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

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

The organic solvent whose boiling point in 1 atm is 120 degreeC or more and 180 degrees C or less among the said solvents is preferable. Especially, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc. are preferable.

The content of the solvent (E) is preferably 60? To the amount of the colored photosensitive resin composition. 95 mass%, More preferably, it is 70? 90 mass%. In other words, solid content of a coloring photosensitive resin composition becomes like this. 40 mass%, More preferably, it is 10? 30 mass%. When content of a solvent (E) exists in the said range, there exists a tendency for the flatness at the time of application | coating to become favorable.

It is preferable that the coloring photosensitive resin composition of this invention contains surfactant (F). As surfactant, silicone type surfactant which has silicone type surfactant, a fluorine type surfactant, and a fluorine atom is mentioned, for example. By containing surfactant, the flatness at the time of application | coating tends to become favorable.

As silicone type surfactant, surfactant which has a siloxane bond is mentioned. Specifically, Toray silicone 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, KP322 , KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (Momental Performance Materials Japan) Joint company manufacture) etc. are mentioned.

As a fluorine type surfactant, surfactant which has a fluorocarbon chain | strand is mentioned. Specifically, Floriner ™ FC430, Copper FC431 (manufactured by Sumitomo 3M Co., Ltd.), Mega Pack (trademark) F142D, Copper F171, Copper F172, Copper F173, Copper F177, Copper F183, Copper R30 (DIC) Co., Ltd.), F-top (registered trademark) EF301, copper EF303, copper EF351, copper EF352 (manufactured by Mitsubishi Material Electrochemical Co., Ltd.), Sufron (registered trademark) S381, copper S382, copper SC101, copper SC105 (Asahi Glass Co., Ltd. product), E5844 (made by Daikin Fine Chemical Research Institute), etc. are mentioned.

As silicone type surfactant which has a fluorine atom, surfactant which has a siloxane bond and a fluorocarbon chain | strand is mentioned. Specifically, Mega Pack (registered trademark) R08, Copper BL20, Copper F475, Copper F477, Copper F443 (manufactured by DIC Corporation), etc. may be mentioned. Preferably Megapack (trademark) F475 is mentioned.

Surfactant (F) is 0.001 mass% or more and 0.2 mass% or less with respect to the coloring photosensitive resin composition whole quantity of this invention, Preferably it is 0.002 mass% or more and 0.1 mass% or less, More preferably, it is 0.01 mass% or more and 0.05 mass% It is as follows. By containing surfactant in this range, flatness of a coating film can be made favorable.

The colored photosensitive resin composition of this invention may contain various additives, such as a filler, another high molecular compound, an adhesion promoter, antioxidant, a ultraviolet absorber, a light stabilizer, a chain transfer agent, as needed.

The coloring photosensitive resin composition of this invention can be prepared as follows, for example.

First, the pigment of a coloring agent (A) is mixed with a solvent (E), and it disperse | distributes using a beads mill etc. until the average particle diameter of a pigment becomes about 0.2 micrometer or less. Under the present circumstances, you may mix | blend a part or all of pigment dispersant and resin (B) as needed. To the obtained pigment dispersion liquid, the remainder of the resin (B), the polymerizable compound (C) and the polymerization initiator (D), other components used as necessary, and further additional solvents are added to a predetermined concentration, if necessary, Colored photosensitive resin composition can be obtained.

The colored photosensitive resin composition of this invention is following (1), for example. It processes into a color filter through the process shown to (4).

(1) Process of obtaining coating film by apply | coating coloring photosensitive resin composition of this invention to board | substrate

(2) Process of obtaining a post-exposure coating film by exposing through a mask to a coating film

(3) Process of obtaining pattern by developing after-exposure coating film with alkaline developing solution

(4) Process of obtaining hardened pattern by baking pattern

As a method of obtaining a pattern, the photolithography method, the inkjet method, the printing method, etc. are mentioned. Especially, the photolithographic method is preferable. The photolithography method is a method of obtaining a pattern by applying the colored photosensitive resin composition to a substrate, drying the film, exposing through a photomask, and developing the same.

As said board | substrate, glass, a metal, and a plastics are mentioned, for example, A plate shape may be sufficient and a film shape may be sufficient.

As plastic, For example, polyolefin, such as polyethylene, a polypropylene, norbornene-type polymer, polyvinyl alcohol, polyethylene terephthalate, polyethylene naphthalate, poly (meth) acrylic acid ester, a cellulose ester, polycarbonate, polysulfone, polyether Sulfone, polyether ketone, polyphenylene sulfide and polyphenylene oxide. Here, (meth) acrylic acid means at least 1 sort (s) chosen from the group which consists of acrylic acid and methacrylic acid. These substrates may be formed with structures such as color filters, various insulating or conductive films, and drive circuits.

According to the coloring photosensitive resin composition of this invention, since the pattern hardened | cured at low temperature can be formed, it is especially useful when forming a pattern in a plastic substrate.

As a coating method to a board | substrate, the extrusion coating method, the direct gravure coating method, the reverse gravure coating method, the CAP coating method, and the die coating method are mentioned, for example. Moreover, you may apply | coat using a coating apparatus, such as a dip coater, a roll coater, a bar coater, a spin coater, a slit & spin coater, a slit coater (it may also be called a die coater, a curtain flow coater, a spinless coater), and an inkjet. . Especially, it is preferable to apply | coat using a slit coater, a spin coater, a roll coater, etc.

As a drying method of the film | membrane apply | coated to the board | substrate, the method of heat drying, natural drying, ventilation drying, and reduced pressure drying is mentioned, for example. You may implement combining several methods.

The drying temperature is 10? 120 degreeC is preferable and 25? 100 degreeC is more preferable. Also, the heating time is 10 seconds? It is preferable that it is 60 minutes, and for 30 seconds. It is more preferable that it is 30 minutes.

50 degree drying under reduced pressure Under pressure of 150 kPa, 20? It is preferable to carry out in the temperature range of 25 degreeC.

The film thickness of the coating film after drying is not specifically limited, It can adjust suitably according to the material to be used, a use, etc., and is normally 0.1? 20 µm, preferably 1? 6 μm.

The coating film after drying is exposed through the photomask for forming the target pattern. The pattern shape on the photomask at this time is not specifically limited, The pattern shape according to the intended use is used.

As a light source used for exposure, 250? Preference is given to light sources which generate light of 450 nm wavelength. For example, light of less than 350 nm may be cut using a filter that cuts this wavelength range, or light around 436 nm, 408 nm, or 365 nm may be selectively selected using a band pass filter that extracts these wavelength ranges. May be taken out. Specifically, a mercury lamp, a light emitting diode, a metal halide lamp, and a halogen lamp are mentioned.

In order to irradiate a parallel light beam uniformly to the whole exposure surface, or to accurately position a mask and a base material, it is preferable to use apparatuses, such as a mask aligner and a stepper, at the time of exposure.

After exposure, a pattern can be obtained by making a coating film contact a developing solution, dissolving and developing a predetermined part, for example, an unexposed part. Although an organic solvent can also be used as a developing solution, since the exposed part of a coating film is hard to melt | dissolve and swell by a developing solution, and a pattern of a favorable shape can be obtained, it is preferable to use the aqueous solution of an alkaline compound.

The developing method may be any of a paddle method, a dipping method, a spray method, and the like. In addition, you may incline a board | substrate at arbitrary angles at the time of image development.

It is preferable to wash with water after image development.

Examples of the alkaline compound include sodium hydroxide, potassium hydroxide, sodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate, hydrogen carbonate Inorganic alkaline compounds such as sodium, potassium hydrogencarbonate, sodium borate, potassium borate and ammonia; And tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine And organic alkaline compounds such as ethanolamine. As said alkaline compound, potassium hydroxide, sodium hydrogencarbonate, and tetramethylammonium hydroxide are preferable.

The concentration in the aqueous solution of these alkaline compounds is preferably 0.01? 10 mass%, More preferably, it is 0.03? 5 mass%.

The aqueous solution of the said alkaline compound may contain surfactant.

As surfactant, polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivative, oxyethylene / oxypropylene block copolymer, sorbitan fatty acid ester, 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 dodecylbenzene sulfonate and sodium dodecyl naphthalene sulfonate; And cationic surfactants such as stearylamine hydrochloride and lauryltrimethylammonium chloride.

The concentration of the surfactant in the aqueous solution of the alkaline compound is preferably 0.01? 10 mass%, More preferably, it is 0.05? 8 mass%, Especially preferably, it is 0.1? 5 mass%.

The pattern hardened | cured can be obtained by baking again the pattern obtained as mentioned above. As baking temperature, 25 degreeC or more and 230 degrees C or less, Preferably they are 25 degreeC or more and 200 degrees C or less, More preferably, they are 25 degreeC or more and 160 degrees C or less, More preferably, they are 25 degreeC or more and 120 degrees C or less. 1 as the baking time? 300 minutes, preferably 1? 180 minutes, more preferably 1? 60 minutes.

From the coloring photosensitive resin composition of this invention, a color filter can be produced by appropriately repeating the pattern preparation by the above-mentioned method. The obtained color filter can be used by a method known to a display device including the color filter as a part of a component, for example, a liquid crystal display device, an organic EL device, a solid-state imaging device, an electronic paper, or a device associated with a colored image. .

Example

Hereinafter, an Example demonstrates this invention in more detail. "%" And "part" in an example are the mass% and a mass part, unless there is particular notice.

Synthesis Example 1

An appropriate amount of nitrogen was flowed into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to make a nitrogen atmosphere, and 100 parts of propylene glycol monomethyl ether acetate was added and heated to 85 ° C while stirring. Subsequently, 19 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (compound represented by formula (I-1) and compound represented by formula (II-1)) were added to the flask in a molar ratio. 50:50) 171 parts of a solution dissolved in 40 parts of propylene glycol monomethyl ether acetate were added dropwise over about 5 hours using a dropping pump. On the other hand, the solution which melt | dissolved 26 parts of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 120 parts of propylene glycol monomethyl ether acetates was dripped in the flask over about 5 hours using another dropping pump. . After completion of the dropwise addition of the polymerization initiator, the mixture was maintained at the same temperature for about 3 hours, and then cooled to room temperature to obtain a resin solution Ba having a solid content of 43.5% and an acid value of 53 mgKOH / g (solid content conversion). The weight average molecular weight Mw of obtained resin Ba was 8000, and molecular weight distribution (Mw / Mn) was 1.98.

Synthesis Example 2

123 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, and the atmosphere in the flask was nitrogen in air, and then heated to 100 ° C., and then benzyl meta 72.6 g (0.41 mol) of methacrylate, 42.0 g (0.49 mol) of methacrylic acid, monomethacrylate of tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) 23.0 g (0.10 mol) and propylene glycol monomethyl The solution which added 3.6 g of azobisisobutyronitrile to the mixture which consists of 137 g of ether acetate was dripped at the flask over 2 hours from the dropping funnel, and stirring was continued at 100 degreeC for 5 hours. Next, the atmosphere in the flask was changed from nitrogen to air, 21.3 g of glycidyl methacrylate [0.15 mol, (31 mol% of the carboxyl groups of methacrylic acid used in this reaction)], and 0.9 g of trisdimethylaminomethylphenol. And 0.145 g of hydroquinone were charged into a flask, and the reaction was continued at 110 ° C for 6 hours to obtain a resin solution Bb having a solid content of 38.3% and an acid value of 120.1 mgKOH / g (solid content conversion). The weight average molecular weight of polystyrene conversion measured by GPC was 10,500, and molecular weight distribution (Mw / Mn) was 2.1.

Synthesis Example 3

125.1 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, and the atmosphere in the flask was changed from nitrogen to air. 96.0 g (0.55 mol) of methacrylate, 30.6 g (0.36 mol) of methacrylic acid, monomethacrylate of tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) 22.0 g (0.10 mol) and propylene glycol monomethyl The solution which added 3.6 g of azobisisobutyronitrile to the mixture which consists of 149 g of ether acetates was dripped at the flask over 2 hours from the dropping funnel, and stirring was continued at 100 degreeC for 5 hours. Next, the atmosphere in the flask was changed from nitrogen to air, 21.3 g of glycidyl methacrylate [0.15 mol, (42 mol% of the carboxyl groups of methacrylic acid used in this reaction)], and 0.9 g of trisdimethylaminomethylphenol. And 0.145 g of hydroquinone were charged into a flask, and the reaction was continued at 110 ° C. for 6 hours to obtain a resin solution Bc having a solid content of 37.8% and an acid value of 67.7 mgKOH / g (solid content conversion). The weight average molecular weight of polystyrene conversion measured by GPC was 9,400, and molecular weight distribution (Mw / Mn) was 2.0.

Synthesis Example 4

Into a flask equipped with a reflux cooler, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 l / min to a nitrogen atmosphere, and 200 parts of 3-methoxy-1-butanol and 100 parts of 3-methoxybutyl acetate were added to 70 ° C while stirring. Heated. Subsequently, 54 parts of methacrylic acid and 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (compound represented by formula (I-1) and compound represented by formula (II-1) are molar ratios of 50:50. 180 parts and 67 parts of N-cyclohexylmaleimide were dissolved in 140 parts of 3-methoxy-1-butanol to prepare a solution, and the solution was insulated at 70 ° C. over 4 hours using a dropping pump. It was dripped in the flask. On the other hand, the solution which melt | dissolved 20 parts of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 240 parts of 3-methoxybutyl acetates was dripped in the flask over 4 hours using another dropping pump. After completion of the dropwise addition of the solution of the polymerization initiator, the mixture was kept at 70 ° C for 4 hours, and then cooled to room temperature to obtain a solution of resin solution Bd having a solid content of 32.6% and a solution acid value of 34.3 mg-KOH / g. The weight average molecular weight Mw of obtained resin Bd was 9000, and molecular weight distribution (Mw / Mn) was 1.9.

Synthesis Example 5

250 parts of propylene glycol monomethyl ether acetate were introduced into a flask equipped with a stirrer, a thermometer, a reflux cooler, a dropping funnel and a gas introduction tube. Thereafter, nitrogen gas was introduced into the flask using a gas introduction tube, and the atmosphere in the flask was replaced with nitrogen gas. Then, after heating up the solution in a flask at 100 degreeC, the mixture consisting 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 acetates was dripped. It was dripped at the flask over 2 hours, and after completion | finish of dripping, stirring was continued again at 100 degreeC for 2.5 hours, and the resin solution Be whose weight average molecular weight Mw is 2.3 * 10 <^4> , solid content 34%, and the solution acid value 47 mg-KOH / g. Got.

The measurement of the weight average molecular weight (Mw) and number average molecular weight (Mn) of resin obtained by the synthesis example was performed on condition of the following using GPC method.

Device ; K2479 (manufactured by Shimadzu Corporation)

column ; SHIMADZU Shim-pack GPC-80M

Column temperature; 40 ℃

Solvent; THF (tetrahydrofuran)

Flow rate; 1.0 ml / min

Detector; RI

The ratio (Mw / Mn) of the weight average molecular weight and number average molecular weight of polystyrene conversion obtained above was made into molecular weight distribution.

Example 1

[Preparation of Colored Photosensitive Resin Composition 1]

Pigment: C. I. Pigment Red 177 49 parts

16 parts of polyester pigment dispersant

Resin solution Be 29 parts

Propylene Glycol Monomethyl Ether Acetate 280 parts

Pigment Dispersion A, in which the pigments were mixed and the pigment was sufficiently dispersed using a beads mill,

Pigment: C. I. Pigment Red 254 5.9 parts

2.2 parts of acrylic pigment dispersant

Resin solution Be 4.9 parts

Propylene glycol monomethyl ether acetate 29 parts

Pigment dispersion B which mixed the pigment, and fully disperse | distributed the pigment using the bead mill,

Resin (B1): 126 parts of resin solution Ba,

Resin (B2): 72 parts of resin solution Bb,

Polymerizable compound: 63 parts of dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Gunpowder Co., Ltd.),

Polymerization initiator: 9.4 parts of N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (irgacure OXE-01; made by BASF Japan),

Solvent: 313 parts of propylene glycol monomethyl ether acetate, and

Surfactant: Polyether modified silicone oil (Toray Silicone SH8400; Toray Dow Corning Co., Ltd.) 0.02 parts

Was mixed and the coloring photosensitive resin composition 1 was obtained.

Example 2

[Preparation of Colored Photosensitive Resin Composition 2]

Pigment: C. I. Pigment Yellow 139 18 parts

Polyester pigment dispersant 7.2 parts

Resin solution Be 13 parts

Propylene glycol monomethyl ether acetate 116 parts

Pigment Dispersion A, in which the pigments were mixed and the pigment was sufficiently dispersed using a beads mill,

Pigment: C. I. Pigment Red 177 72 parts

20 parts of polyester pigment dispersant

Resin solution Be 61 parts

Propylene Glycol Monomethyl Ether Acetate 310 Parts

Pigment dispersion B which mixed the pigment and fully disperse | distributed the pigment using the bead mill,

Resin (B1): 90 parts of resin solution Ba,

Resin (B2): 78 parts of resin solution Bc,

Polymerizable compound: 40 parts of dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Gunpowder Co., Ltd.),

Polymerization initiator: 8.1 parts of N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (irgacure OXE-01; manufactured by BASF Japan)

Solvent: 165 parts of propylene glycol monomethyl ether acetate, and

Surfactant: Polyether modified silicone oil (Toray Silicone SH8400; Toray Dow Corning Co., Ltd.) 0.02 parts

Was mixed and the coloring photosensitive resin composition 2 was obtained.

Example 3

[Preparation of Colored Photosensitive Resin Composition 3]

Pigment: C. I. Pigment Red 254 51 parts

15 parts of polyester pigment dispersant

Propylene glycol monomethyl ether acetate 287 parts

To the pigment dispersion, in which the pigment was sufficiently dispersed using a beads mill,

Resin (B1): 184 parts of resin solution Ba

Resin (B2): 50 parts of resin solution Bb

Polymerizable compound: 64 parts of dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Gunpowder Co., Ltd.)

Polymerization initiator: 13 parts of N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (irgacure OXE-01; manufactured by BASF Japan)

Solvent: Propylene glycol monomethyl ether acetate 336 parts

Surfactant: Polyether modified silicone oil (Toray Silicone SH8400; Toray Dow Corning Co., Ltd.) 0.02 parts

Was mixed and the coloring photosensitive resin composition 3 was obtained.

Example 4

[Preparation of Colored Photosensitive Resin Composition 4]

Pigments: C. I. Pigment Green 36 Part 14

Polyester pigment dispersant 2.7 parts

Resin solution Be 4.0 parts

Propylene glycol monomethyl ether acetate 56 parts

Pigment Dispersion A, in which the pigments were mixed and the pigment was sufficiently dispersed using a beads mill,

Pigment: C. I. Pigment Yellow 138 12 parts

Polyester pigment dispersant 2.5 parts

Resin solution Be 1.9 parts

Propylene glycol monomethyl ether acetate 66 parts

Pigment dispersion B which mixed the pigment, and fully disperse | distributed the pigment using the bead mill,

Resin (B1): 142 parts of resin solution Ba,

Resin (B2): 41 parts of resin solution Bc,

Polymerizable compound: 80 parts of dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Gunpowder Co., Ltd.),

Polymerization initiator: 9.6 parts of N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (irgacure OXE-01; manufactured by BASF Japan);

Solvent: 570 parts of propylene glycol monomethyl ether acetate, and

Surfactant: Polyether modified silicone oil (Toray Silicone SH8400; Toray Dow Corning Co., Ltd.) 0.02 parts

Was mixed and the coloring photosensitive resin composition 4 was obtained.

Example 5

[Preparation of Colored Photosensitive Resin Composition 5]

Pigments: C. I. Pigment Green 58 53 parts

Acrylic pigment dispersant 11 parts

Resin solution Be 62 parts

Propylene glycol monomethyl ether acetate 251 parts

Pigment Dispersion A, in which the pigments were mixed and the pigment was sufficiently dispersed using a beads mill,

Pigment: C. I. Pigment Yellow 138 30 parts

4.4 parts of polyester pigment dispersant

Resin solution Be 31 parts

Propylene Glycol Monomethyl Ether Acetate-136 Parts

Pigment dispersion B which mixed the pigment and fully disperse | distributed the pigment using the bead mill,

Resin (B1): 18 parts of resin solution Ba,

Resin (B2): 147 parts of resin solution Bb,

Polymerizable compound: 64 parts of dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Gunpowder Co., Ltd.),

Polymerization initiator: 13 parts of N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure OXE-01; made by BASF Japan),

Solvent: 181 parts of propylene glycol monomethyl ether acetate, and

Surfactant: Polyether modified silicone oil (Toray Silicone SH8400; Toray Dow Corning Co., Ltd.) 0.02 parts

Was mixed and the coloring photosensitive resin composition 5 was obtained.

Example 6

[Preparation of Colored Photosensitive Resin Composition 6]

Pigment: C. I. Pigment Red 177 28 parts

Pigment: C. I. Pigment Red 254 86 parts

10 parts of polyester pigment dispersant

Resin solution Be 27 parts

Propylene glycol monomethyl ether acetate 403 parts

To the pigment dispersion, in which the pigment was sufficiently dispersed using a beads mill,

Resin (B1): resin solution Bd 87 parts

Resin (B2): 99 parts of resin solution Bb

Polymerizable compound: dipentaerythritol hexaacrylate (manufactured by Nippon Gunpowder Co., Ltd.) 33 parts

Polymerization initiator: 13 parts of 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one (irgacure 907; manufactured by BASF Japan)

Polymerization Initiation Aid: 4,4'-bis (diethylamino) benzophenone (EAB-F; manufactured by Hodogaya Chemical Industry Co., Ltd.) 7.6 parts

Solvent: Propylene glycol monomethyl ether acetate 294 parts

Was mixed and the coloring photosensitive resin composition 6 was obtained.

Comparative Example 1

[Preparation of Colored Photosensitive Resin Composition 7]

Pigment: C. I. Pigment Red 177 28 parts

Pigment: C. I. Pigment Red 254 86 parts

10 parts of polyester pigment dispersant

Resin solution Be 27 parts

Propylene glycol monomethyl ether acetate 404 parts

To the pigment dispersion, in which the pigment was sufficiently dispersed using a beads mill,

Resin: Resin Solution Bd 169 parts

Polymerizable compound: dipentaerythritol hexaacrylate (manufactured by Nippon Gunpowder Co., Ltd.) 32 parts

Polymerization initiator: 12 parts of 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one (irgacure 907; manufactured by BASF Japan)

Polymerization Initiation Aid: 4,4'-bis (diethylamino) benzophenone (EAB-F; manufactured by Hodogaya Chemical Industry Co., Ltd.) 7.4 parts

Solvent: Propylene Glycol Monomethyl Ether Acetate 92 parts

3-methoxy-1-butanol 67 parts

3-methoxybutyl acetate 67 parts

Was mixed and the coloring photosensitive resin composition 7 was obtained.

<Production of pattern>

The PET film (Toray Lumirror 75-T60) was bonded together on the glass plate of 2 inches in width and length, and the board | substrate was produced. The coloring photosensitive resin composition was apply | coated to the PET film side of the board | substrate by the spin coat method, and it prebaked for 2 minutes at 60 degreeC on the hotplate. After cooling, the exposure amount of 150 mJ / cm <2> in air | atmosphere using an exposure machine (TME-150RSK; Topcon Co., Ltd.) at 150 micrometers with the space | interval of the board | substrate which apply | coated this coloring photosensitive resin composition, and the quartz glass photomask. The light was irradiated at (365 nm standard). In addition, as a photo mask, 10? The thing in which the line-and-space pattern of 100 micrometers was formed was used. After light irradiation, it developed by dipping for 40 second at 23 degreeC in aqueous developing solution containing 0.12% of nonionic surfactant and 0.04% of potassium hydroxide, and wash | cleaned with pure water, and the pattern was formed. It was 2 micrometers when the film thickness of the obtained pattern was measured using the film thickness measuring apparatus (DEKTAK3; Nippon Vacuum Technology Co., Ltd. product).

The pattern formed in the same manner as above was heated (postbaked) again at 50 degreeC for 5 minutes, and the hardened pattern was obtained. Moreover, the pattern formed in the same manner to the above was heated (post-baked) again at 100 degreeC for 5 minutes, and the hardened pattern was obtained. As a result of measuring the film thickness of the obtained hardened pattern similarly to the above, it was all 2 micrometers.

<Solvent resistance evaluation>

1 ml of propylene glycol monomethyl ether acetate was added dropwise to the pattern formed on the substrate, and stopped for 30 seconds, and then rotated at a rotational speed of 1000 rpm for 10 seconds using a spin coater to produce propylene glycol monomethyl ether acetate on the pattern. Robbed.

The film thickness retention rate was calculated from the film thickness value measured before and after contact with propylene glycol monomethyl ether acetate. The higher the film thickness retention rate, the better the curability and the more the mixture can be prevented when the color filter is produced. The results are shown in Table 1.

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

<Resolution evaluation>

The obtained pattern was observed with a laser microscope (manufactured by Axio Imager MAT Cartiers Co., Ltd.), and the minimum resolution resolved was taken as the resolution. The higher the resolution, the more accurate color filters can be produced. The results are shown in Table 1.

It was confirmed that the pattern formed using the colored photosensitive resin composition of the Example was excellent in resolution. Moreover, even when the baking process at high temperature exceeding 200 degreeC is not performed, it was confirmed that it was excellent in solvent resistance. In this respect, it is understood that a high-precision and high-quality color filter can be obtained even with a substrate having low heat resistance.

According to the coloring photosensitive resin composition of this invention, a pattern with high resolution and a high quality color filter can be obtained.

Claims (8)

Colored photosensitive resin composition containing (A), (B1), (B2), (C), (D), and (E):
(A) coloring agent;
(B1) The structural unit derived from at least 1 sort (s) chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride, and C2-C? Copolymers containing a structural unit derived from a cyclic ether of 4 and a monomer having an ethylenically unsaturated bond (but do not have an ethylenically unsaturated bond in the side chain);
(B2) Resin which has ethylenically unsaturated bond in a side chain;
(C) polymeric compound;
(D) polymerization initiator;
(E) Solvent. The method of claim 1,
Colored photosensitive resin composition whose resin (B2) is resin obtained by making (b) react with the copolymer obtained by copolymerizing following (a) and (c) again:
(a): at least 1 sort (s) chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride;
(b): 2 carbon atoms? Monomers having a cyclic ether of 4 and an ethylenically unsaturated bond;
(c): Monomer which has an unsaturated bond copolymerizable with (a) and (b). The method according to claim 1 or 2,
Colored photosensitive resin composition whose content of (B1) is 10 mass% or more and 95 mass% or less with respect to the total amount of (B1) and (B2). The pattern formed from the coloring photosensitive resin composition of Claim 1. The color filter containing the pattern of Claim 4. (1)? The manufacturing method of the color filter containing the process shown by (4):
(1) Process of obtaining a coating film by apply | coating the coloring photosensitive resin composition of any one of Claims 1-3 to a board | substrate;
(2) obtaining a post-exposure coating film by exposing through a mask to a coating film;
(3) Process of obtaining pattern by developing after-exposure coating film with alkaline developing solution;
(4) A step of obtaining a cured pattern by baking the pattern. The method according to claim 6,
The manufacturing method of the color filter which is a process of baking at the temperature of 25 degreeC or more and 120 degrees C or less of process (4). The method according to claim 6 or 7,
The manufacturing method of the color filter whose board | substrate in a process (1) is a plastic substrate.