TW201520691A - Photosensitive resin composition - Google Patents

Abstract

This invention provides a photosensitive resin composition, containing a binder resin (A), a polymerizable compound (B), a polymerization initiator (C), an extender pigment (D) and a solvent (E), wherein the solvent (E) contains 70 to 99 mass% of a solvent (E1) with respect to the solvent (E), which has a solubility parameter of 8.0 to 9.1(cal /cm3)<SP>1/2</SP>, and contains 1 to 30 mass% of a solvent (E2) with respect to the solvent (E), which has a solubility parameter of 9.2 to 11.0(cal/cm3)<SP>1/2</SP>.

Description

Photosensitive resin composition

The present invention relates to a photosensitive resin composition.

A pattern such as a color filter used in a display device such as a liquid crystal display panel, a light-emitting panel, a plasma display panel, or an electronic paper is manufactured using a photosensitive resin composition. Specifically, the photosensitive resin composition is applied onto a substrate, dried, and the obtained dried film is selectively exposed, and then developed to form a pattern.

For example, Japanese Laid-Open Patent Publication No. 2011-221310 discloses a photosensitive resin composition containing a binder resin, a polymerizable compound, a polymerization initiator, an extender pigment, and a solvent. And propylene glycol monomethyl ether acetate was used as an example of the aforementioned solvent.

The dry film obtained from the conventional photosensitive resin composition described above may not necessarily have a low tack, and the pattern obtained by the conventional photosensitive resin composition may have a hardness. A situation that cannot be satisfied.

In order to solve the aforementioned problems, the present invention provides the following [1].

[1] A photosensitive resin composition comprising a binder resin (A), a polymerizable compound (B), a polymerization initiator (C), an extender pigment (D), and a solvent (E), wherein the solvent (E) And a solvent (E1) having a solubility parameter of from 8.0 to 9.1 (cal/cm ³ ) ^1/2 with respect to the solvent (E) of 70 to 99% by mass, and containing 1 relative to the aforementioned solvent (E) The solubility parameter to 30% by mass is 9.2 to 11.0 (cal/cm ³ ) ^1/2 of the solvent (E2).

Further, the present invention provides the following [2] to [10].

[2] The photosensitive resin composition according to the above [1], wherein the polymerization initiator (C) is a ruthenium compound.

[3] The photosensitive resin composition according to the above [1], wherein the acid value of the binder resin (A) is from 50 to 180 mg-KOH/g.

[4] The photosensitive resin composition according to any one of the above [1], wherein the content of the binder resin (A) is relative to the binder resin (A) and the polymerizability. The total amount of the compound (B) is 100 parts by mass, and is 30 to 80 parts by mass.

[5] The photosensitive resin composition according to any one of [1] to [4] wherein the extender pigment (D) is cerium oxide.

[6] The photosensitive resin composition according to any one of [1] to [5] further comprising a coloring agent.

[7] The photosensitive resin composition according to the above [6], wherein the colorant is a pigment-containing coloring agent.

[8] The photosensitive resin composition according to the above [6], wherein the colorant is a dye-containing coloring agent.

[9] A pattern according to any one of the above [1] to [8] A person formed by a photosensitive resin composition.

[10] A display device comprising the pattern as described in [9] above.

According to the present invention, it is possible to provide a photosensitive resin composition which is imparted with a dry film which can satisfy a low viscosity and which is provided with a pattern having a hardness which can be satisfied.

The photosensitive resin composition of the present invention contains a binder resin (A), a polymerizable compound (B), a polymerization initiator (C), an extender pigment (D), and a solvent (E).

The binder resin (A) preferably contains: In the addition polymer (a) of the structural unit of a carboxylic acid (hereinafter referred to as "(a)"), an epoxy group-containing unsaturated compound (b) (hereinafter, referred to as "( In the case of b), the adhesive resin (Aa) is reacted.

As (a), for example, an unsaturated carboxylic acid can be exemplified Acid (a1) (hereinafter, referred to as "(a1)"), and monomer (a2) having an unsaturated bond which can be polymerized and polymerized with (a1) (hereinafter, referred to as "(a2)" In the case of an addition polymer obtained by addition polymerization.

As (a1), for example, (meth)acrylic acid, An unsaturated monocarboxylic acid such as crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid or p-vinylbenzoic acid;

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-ethylene Phthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrogen Unsaturated dicarboxylic acids such as phthalic acid and 1,4-cyclohexene dicarboxylic acid; methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]heptane- 2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethyl Bicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2- a bicyclic unsaturated compound containing a carboxyl group such as a olefin; a mono[2-(methyl)propenyloxyethyl] succinate; a mono[2-(methyl)propenyloxyethyl phthalate; a polyvalent carboxylic acid unsaturated mono[(methyl) propylene fluorenyloxyalkyl] ester having two or more esters such as an ester; an unsaturated compound containing a hydroxyl group and a carboxyl group in the same molecule such as α-(hydroxymethyl)acrylic acid; Classes, etc.

Among them, (meth)acrylic acid is suitably used from the viewpoint of copolymerization reactivity or alkali solubility.

Therefore, in the present specification, "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. The descriptions of "(meth)acrylonitrile" and "(meth)acrylate" have the same meaning.

Examples of (a2) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, n-butyl (meth)acrylate, and (meth)acrylic acid. Intermediate (meth)acrylic acid alkyl ester such as butyl acrylate; cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo(methyl) acrylate [5.2.1.0 ^2.6 ]癸-8-ester (in the technical field, dicyclopentyl (meth)acrylate is used as a customary name), dicyclopentyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, etc. (meth)acrylic acid cyclic alkyl esters; (meth)acrylic acid phenyl esters, (meth)acrylic acid benzyl esters and the like (meth)acrylic acid aryl esters or arylalkyl esters; diethyl maleate, Fumar Dicarboxylic acid diesters such as diethyl acid and diethyl isonate; hydroxyalkyl esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; bicyclo [2.2.1 Hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]heptane- 2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[ 2. 2.1] Hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxyl Methyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[ 2.2.1] hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-tertiarybutoxycarbonyl Bicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5 , 6-bis(tris-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene, etc. Saturated compounds; N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, 3-maleimide benzoate N-succinimide Ester, 4-maleimide butyric acid N-succinimide, 6-maleimide caproic acid N-succinimide, 3-maleimide propionic acid N-amber Dicarbonyl ruthenium imide derived from amine ester, N-(9-acridinyl) maleimide Class; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, Vinylene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like.

(a2) is a compound (a2-1) having at least one skeleton selected from the group consisting of a tricyclodecane skeleton and a tricyclodecene skeleton, and an ethylenically unsaturated bond (hereinafter referred to as (a2) -1) The situation is better. (a2) is the case of (a2-1), and it is possible to suppress the film reduction of the pattern due to development.

Here, the "tricyclodecane skeleton" and the "tricyclic terpene skeleton" in the present specification mean the following structures (each bonding key is at any point).

Examples of (a2-1) include dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentyloxyethyl (meth)acrylate, and (methyl). Dicyclopentenyloxyethyl acrylate. These may be used alone or in combination of two or more.

As (b), for example, there may be mentioned chain olefins The epoxidized structure and the ethylenically unsaturated bond monomer (b-1) (hereinafter referred to as "(b-1)"), the cyclic olefin epoxidized structure and the ethylenically unsaturated bond Monomer (b-2) (hereinafter referred to as "(b-2)"). As (b), (b-1) is preferable from the viewpoint of reactivity.

As (b-1), it can be cited that: (meth)acrylic acid shrinks Glyceride, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m- Vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, α-methyl-o-vinyl benzyl glycidyl ether, α-methyl-m-vinyl benzoyl Glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidyloxymethyl)styrene, 2,4-bis(glycidyloxy) Methyl)styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl)styrene, 2,3,4-parameter (shrinkage) Glyceryloxymethyl)styrene, 2,3,5-gin (glycidyloxymethyl)styrene, 2,3,6-gin (glycidyloxymethyl)styrene, 3, 4,5-glycol (glycidyloxymethyl)styrene, 2,4,6-glycol (glycidyloxymethyl)styrene, a compound described in JP-A-H07-248625, etc. .

As (b-2), one can cite: vinyl cyclohexene Oxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide 2000; manufactured by Daicel Co., Ltd.), 3,4-epoxycyclohexylmethyl acrylate (for example, Cyclomer-A400; Daicel (manufactured by Daicel Co., Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (for example, Cyclomer-M100; manufactured by Daicel Co., Ltd.), a compound represented by the formula (I), and a formula (II) Show compounds and the like.

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

X ¹ and X ² each independently represents a single ^{bond, -R 3 -, * - R} 3 -O -, * - R 3 -S -, * - R 3 -NH-.

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

* indicates the bond key with O].

The binder resin (Aa) can be produced through a two-stage process. In this case, for example, reference may be made to the method described in the "Experimental Method for Polymer Synthesis" (Otsuka Ryokan, Ltd.; Chemical Co., Ltd., 1st Edition, 1st Brush, March 1, 1972), and It is produced by the method and the like described in JP-A-2001-89533.

In the production of the binder resin (Aa), first, as the first stage, the addition polymer (a) of (a1) and (a2) is obtained. Specifically, for example, a predetermined amount of (a1) and (a2), a polymerization initiator, a solvent, and the like are placed in a reaction vessel, and oxygen is substituted for oxygen, and the mixture is stirred, heated, and kept warm in a deoxidizing environment. . The polymerization initiator, the solvent and the like used herein are not particularly limited, and any of the usual users of the art can be used. As a polymerization initiator, for example, an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) or An organic peroxide (such as benzamidine peroxide) may be used as a solvent, and any solvent may be dissolved as a solvent. The solvent of the substance.

Moreover, the addition polymer obtained can be directly used as a counter As the solution to be used, a solution which is concentrated or diluted may be used, or a solid (powder) may be used by a method such as reprecipitation to take it out.

The ratio of structural units derived from (a1) and (a2), as opposed to The total number of moles of the entire structural unit constituting the addition polymer (a) is preferably in the following range.

The structural unit derived from (a1): 5 to 50 mol%, more preferably 10 to 45 mol%

Structural unit derived from (a2): 50 to 95% by mole, more preferably 55 to 90% by mole

Next, as a second stage, a part of the carboxyl group derived from the structural unit of (a1) which the obtained addition polymer has is obtained is reacted with (b). Since the reactivity is high and the unreacted (b) is not easily left, it is preferable that (b) is (b-1).

Specifically, continuing the above, the ambient gas in the flask The nitrogen gas is replaced by air, and (b) is set to be 5 to 80 mol% with respect to the molar number of (a1), and a reaction catalyst (for example, dimethylaminomethylphenol) is set. The total amount of (a1), (b), and (a2) is 0.001 to 5% by mass, and a polymerization inhibitor (for example, hydroquinone or the like) is set to be relative to (a1), (b), and (a2). The total amount is 0.001 to 5% by mass, and it is placed in a flask. Usually, at 60 to 130 ° C for 1 to 10 hours, a binder resin (Aa) can be obtained. Further, similarly to the polymerization conditions, the production method, the calorific value generated by the polymerization, and the like can be considered, and the introduction method and the reaction temperature can be appropriately adjusted.

Further, at this time, the number of moles of (b) is preferably 10 to 75 mol%, more preferably 15 to 70 mol%, with respect to the number of moles of (a1). When the number of moles of (b) is within this range, the balance of storage stability, solvent resistance, and heat resistance tends to be good.

Examples of the binder resin (Aa) include a resin obtained by reacting a copolymer of (meth)acrylic acid/dicyclopentanyl (meth)acrylate with glycidyl (meth)acrylate, and (meth)acrylic acid/ A copolymer of a copolymer of benzyl (meth)acrylate and a glycidyl (meth)acrylate, a copolymer of (meth)acrylic acid/cyclohexyl (meth)acrylate and a (meth)acrylic acid shrinkage a resin reacted with a glyceride, a copolymer of (meth)acrylic acid/styrene, a resin reacted with glycidyl (meth)acrylate, a copolymer of (meth)acrylic acid/methyl (meth)acrylate and Resin of methyl glycidyl methacrylate reaction, copolymer of (meth)acrylic acid/N-cyclohexylmaleimide and resin of glycidyl (meth)acrylate, crotonic acid/(methyl) a resin obtained by reacting a copolymer of dicyclopentanyl acrylate with glycidyl (meth)acrylate, a copolymer of crotonic acid/benzyl methacrylate, and a resin reacted with glycidyl (meth)acrylate, Crotonic acid/cyclohexyl (meth)acrylate copolymer and glycidyl (meth)acrylate Resin, a resin of crotonic acid/styrene, a resin reacted with glycidyl (meth)acrylate, a copolymer of crotonic acid/methyl crotonate, and a resin reacted with glycidyl (meth)acrylate, croton Resin of acid/N-cyclohexylmaleimide copolymer reacted with glycidyl (meth)acrylate; maleic acid/dicyclopentyl (meth)acrylate copolymer and (meth) propyl Resin of methacrylate reaction, resin of maleic acid / benzyl (meth) acrylate copolymerized with glycidyl (meth) acrylate, maleic acid / cyclohexyl (meth) acrylate Copolymerization of a resin reacted with glycidyl (meth)acrylate, a copolymer of maleic acid/styrene and a resin reacted with glycidyl (meth)acrylate, maleic acid/methyl maleate a resin reacted with glycidyl (meth)acrylate, a copolymer of maleic acid/N-cyclohexylmaleimide and a resin reacted with glycidyl (meth)acrylate; (meth)acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate copolymer reacted with glycidyl (meth) acrylate resin, (meth) acrylic acid / maleic anhydride / (methyl) Resin copolymerized with benzyl acrylate and glycidyl (meth)acrylate, (meth)acrylic acid/maleic anhydride/cyclohexyl (meth)acrylate copolymer and glycidol (meth)acrylate Ester-reactive resin, (meth)acrylic acid/maleic anhydride/styrene copolymer and (meth)acrylic acid glycidyl ester-reactive resin, (meth)acrylic acid/maleic anhydride/(meth)acrylic acid A copolymer of an ester copolymer and a glycidyl (meth)acrylate, a copolymer of (meth)acrylic acid/maleic anhydride/N-cyclohexylmaleimide and glycidyl (meth)acrylate Reactive resin; Resin (meth)acrylic acid/(meth)acrylic acid benzene reacted with a copolymer of (meth)acrylic acid/dicyclopentanyl (meth)acrylate and 3,4-epoxycyclohexylmethyl methacrylate Resin of methyl ester copolymer reacted with 3,4-epoxycyclohexylmethyl methacrylate, copolymer of (meth)acrylic acid/cyclohexyl (meth)acrylate and methacrylic acid 3,4 -Epoxycyclohexylmethyl ester Reaction resin, resin of (meth)acrylic acid/styrene copolymer with 3,4-epoxycyclohexylmethyl methacrylate, and (meth)acrylic acid/methyl (meth)acrylate Resin reacting polymer with 3,4-epoxycyclohexylmethyl methacrylate, copolymer of (meth)acrylic acid/N-cyclohexylmaleimide and 3,4-epoxy methacrylate a resin reacted with a cyclohexylmethyl ester; Copolymer of crotonic acid/dicyclopentanyl (meth) acrylate copolymer with 3,4-epoxycyclohexyl methacrylate, co-polymer of crotonic acid/benzyl methacrylate Resin reacted with 3,4-epoxycyclohexylmethyl methacrylate, reacted with crotonic acid/cyclohexyl (meth)acrylate copolymer and 3,4-epoxycyclohexylmethyl methacrylate Copolymer of resin, crotonic acid/styrene copolymer reacted with 3,4-epoxycyclohexylmethyl methacrylate, co-polymer of crotonic acid/methylcrotonate and 3,4-cyclomethacrylate a resin reacted with oxycyclohexylmethyl ester, a copolymer of crotonic acid/N-cyclohexylmaleimide and a resin reacted with 3,4-epoxycyclohexylmethyl methacrylate; Copolymer of maleic acid/dicyclopentanyl (meth)acrylate and 3,4-epoxycyclohexylmethyl methacrylate reacted with maleic acid/benzyl methacrylate Resin reacting polymer with 3,4-epoxycyclohexylmethyl methacrylate, maleic acid/cyclohexyl (meth) acrylate copolymer and 3,4-epoxycyclohexyl methacrylate Resin for ester reaction, copolymer of maleic acid/styrene with 3,4-epoxycyclohexylmethyl methacrylate, copolymer of maleic acid/methyl maleate and methyl group Resin for the reaction of 3,4-epoxycyclohexylmethyl acrylate, maleic acid/N-cyclohexyl a resin in which a copolymer of maleimide and 3,4-epoxycyclohexylmethyl methacrylate is reacted; Resin (meth)acrylic acid/Malay reacted with a copolymer of (meth)acrylic acid/maleic anhydride/dicyclopentanyl (meth)acrylate and 3,4-epoxycyclohexylmethyl methacrylate Resin of anhydride/benzyl methacrylate acrylate and 3,4-epoxycyclohexylmethyl methacrylate, (meth)acrylic acid/maleic anhydride/(meth)acrylic acid cyclohexane Resin copolymerized with 3,4-epoxycyclohexylmethyl methacrylate, copolymer of (meth)acrylic acid/maleic anhydride/styrene and 3,4-epoxy methacrylate a resin reacted with a cyclohexylmethyl ester, a copolymer of (meth)acrylic acid/maleic anhydride/methyl (meth)acrylate and a resin reacted with 3,4-epoxycyclohexylmethyl methacrylate, (a) a resin which reacts with a copolymer of acrylic acid/maleic anhydride/N-cyclohexylmaleimine and 3,4-epoxycyclohexylmethyl methacrylate; Further, as the binder resin (Aa), an addition polymer obtained by copolymerization with (a2) and (a2-1) and (a2) other than (a2), and (b) The resin obtained by the reaction is more preferable. The adhesive resin (Aa) has a structure in which the obtained pattern tends to have excellent adhesion to a substrate and solvent resistance.

The addition polymer (a) is composed of (a1) and (a2-1) and (a2-1) In the case of (a2), the structural unit ratio derived from (a2) and (a2-1) (a2) is derived from (a2-1) structural unit: derived from (a2-1) The structural unit other than (a2) is preferably 10:90 to 60:40, more preferably 10:90 to 40:60, and even more preferably 10:90 to 30:70.

In the addition polymer obtained by copolymerizing (a1) and (a2-1) and (a2) other than (a2-1), the resin obtained by the reaction with (b) may be exemplified by (methyl) a resin obtained by reacting a copolymer of acrylic acid/dicyclopentyl (meth)acrylate/benzyl methacrylate with glycidyl (meth)acrylate, (meth)acrylic acid/(meth)acrylic acid Copolymerization of a copolymer of cyclopentyl ester/cyclohexyl (meth)acrylate with glycidyl (meth)acrylate, copolymerization of (meth)acrylic acid/dicyclopentanyl (meth)acrylate/styrene Resin reacting with glycidyl (meth)acrylate, copolymer of (meth)acrylic acid/dicyclopentyl (meth)acrylate/methyl (meth)acrylate and glycidyl (meth)acrylate Reaction resin, resin of (meth)acrylic acid/dicyclopentyl (meth)acrylate/N-cyclohexylmaleimide and resin reacted with glycidyl (meth)acrylate; crotonic acid/( Resin of (meth)acrylic acid dicyclopentyl acrylate / benzyl (meth) acrylate copolymer with glycidyl (meth) acrylate, crotonic acid / dicyclopentyl (meth) acrylate / ( Resin of a copolymer of cyclohexyl acrylate and glycidyl (meth)acrylate, a copolymer of crotonic acid/dicyclopentyl (meth)acrylate/styrene and glycidol (meth)acrylate Ester-reactive resin, co-polymer of crotonic acid/dicyclopentyl (meth)acrylate/methyl crotonate and resin reacted with glycidyl (meth)acrylate, crotonic acid/dicyclopentyl (meth)acrylate a resin in which a copolymer of ester/N-cyclohexylmaleimide is reacted with glycidyl (meth)acrylate; maleic acid/dicyclopentyl (meth)acrylate/benzoic acid (meth)acrylate Resin of ester copolymer reacted with glycidyl (meth)acrylate, copolymer of maleic acid/dicyclopentyl (meth)acrylate/cyclohexyl (meth)acrylate and (meth)acrylic acid a resin of a glycidyl ester reaction, a copolymer of maleic acid/dicyclopentyl (meth)acrylate/styrene, a resin reacted with glycidyl (meth)acrylate, maleic acid/(meth)acrylic acid Resin of cyclopentyl ester/methyl maleate copolymer reacted with glycidyl (meth)acrylate, maleic acid/dicyclopentanyl (meth)acrylate/N-cyclohexylmaleimide a resin in which a copolymer is reacted with glycidyl (meth)acrylate; Resin (meth)acrylic acid (meth)acrylic acid/maleic anhydride/dicyclopentyl (meth)acrylate/benzyl methacrylate acrylate and glycidyl (meth)acrylate /Reagents of maleic anhydride/dicyclopentyl (meth)acrylate/cyclohexyl (meth)acrylate reacted with glycidyl (meth)acrylate, (meth)acrylic acid/maleic anhydride/ Resin (meth)acrylic acid/maleic anhydride/dicyclopentanyl (meth)acrylate/(co)polymer of dicyclopentyl (meth)acrylate/styrene reacted with glycidyl (meth)acrylate Resin copolymerized with methyl methacrylate and glycidyl (meth)acrylate, (meth)acrylic acid/maleic anhydride/dicyclopentanyl (meth)acrylate/N-cyclohexylmalanium a resin in which a copolymer of an imine is reacted with glycidyl (meth)acrylate; Resin (meth)acrylic acid/dicyclopentyl (meth)acrylate/benzyl methacrylate acrylate and 3,4-epoxycyclohexylmethyl methacrylate a copolymer of acrylic acid/dicyclopentyl (meth)acrylate/cyclohexyl (meth)acrylate and a 3,4-epoxy ring of methacrylic acid a resin reacted with hexylmethyl ester, a copolymer of (meth)acrylic acid/dicyclopentyl (meth)acrylate/styrene, and a resin reacted with 3,4-epoxycyclohexylmethyl methacrylate, (a) (meth)acrylic acid / (meth)acrylic acid / methacrylic acid / (meth) acrylate / methacrylic acid methacrylate / methacrylic acid 3, 4- epoxy cyclohexyl methyl ester a resin obtained by reacting a copolymer of dicyclopentanyl (meth)acrylate/N-cyclohexylmaleimide with 3,4-epoxycyclohexylmethyl methacrylate; Resin for the reaction of crotonic acid/dicyclopentyl (meth)acrylate/benzyl methacrylate with 3,4-epoxycyclohexylmethyl methacrylate, crotonic acid/(methyl a resin obtained by reacting a copolymer of dicyclopentyl acrylate/cyclohexyl (meth) acrylate with 3,4-epoxycyclohexylmethyl methacrylate, crotonic acid / dicyclopentanyl (meth) acrylate /Resin copolymer of styrene and 3,4-epoxycyclohexylmethyl methacrylate, co-polymer of m-crotonic acid / dicyclopentyl (meth) acrylate / methyl crotonate and methyl 3,4-Epoxycyclohexylmethyl acrylate-reactive resin, co-polymer of crotonic acid/dicyclopentanyl (meth)acrylate/N-cyclohexylmaleimide and methacrylic acid 3,4- a resin reactive with epoxycyclohexylmethyl ester; Resin of maleic acid/dicyclopentyl (meth)acrylate/benzyl (meth)acrylate reacted with 3,4-epoxycyclohexylmethyl methacrylate, maleic acid/( Resin of methylene)dicyclopentyl acrylate/cyclohexyl (meth) acrylate copolymer with 3,4-epoxycyclohexyl methacrylate, maleic acid/(meth)acrylic acid Resin of cyclopentyl ester/styrene copolymer reacted with 3,4-epoxycyclohexylmethyl methacrylate, maleic acid/dicyclopentyl (meth)acrylate/methyl maleate Polymer and nail a copolymer of 3,4-epoxycyclohexylmethyl acrylate, a copolymer of maleic acid/dicyclopentanyl (meth)acrylate/N-cyclohexylmaleimide and methacrylic acid 3, a resin reacted with 4-epoxycyclohexylmethyl ester; Resin reacting a copolymer of (meth)acrylic acid/maleic anhydride/dicyclopentyl (meth)acrylate/benzyl methacrylate with 3,4-epoxycyclohexylmethyl methacrylate a (meth)acrylic acid/maleic anhydride/dicyclopentyl (meth)acrylate/cyclohexyl (meth)acrylate copolymer with 3,4-epoxycyclohexylmethyl methacrylate Resin, (meth)acrylic acid/maleic anhydride/dicyclopentyl (meth)acrylate/styrene copolymer and 3,4-epoxycyclohexylmethyl methacrylate resin, (methyl a resin which reacts acrylic acid/maleic anhydride/dicyclopentyl (meth)acrylate/methyl (meth)acrylate with 3,4-epoxycyclohexylmethyl methacrylate, (methyl) a resin in which a copolymer of acrylic acid/maleic anhydride/dicyclopentanyl (meth)acrylate/N-cyclohexylmaleimide is reacted with 3,4-epoxycyclohexylmethyl methacrylate; These binder resins (A) may be used alone or in combination of two or more.

The polystyrene-equivalent weight average molecular weight (Mw) of the binder resin (A) is preferably from 8 × 10 ³ to 100 × 10 ³ , more preferably from 10 × 10 ³ to 50 × 10 ³ . When the weight average molecular weight (Mw) of the binder resin (A) is within the above range, the coating property of the photosensitive resin composition and the low viscosity of the dried film tend to be improved, and the film is less likely to occur during development. Reduction, in addition, there is a tendency for the removal of the non-pixel portion to be good at the time of development.

The acid value of the binder resin (A) is preferably 30 to 200 mg-KOH/g, more preferably 40 to 190 mg-KOH/g, still more preferably 50 to 180 mg-KOH/g. The acid value is a value obtained by measuring the amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the binder resin (A), and can be determined by titration using an aqueous potassium hydroxide solution.

Adhesive resin (A), although only by the aforementioned adhesive The resin (Aa) is preferably formed, but may contain other resins. As such a resin, an epoxy resin, an acrylic resin, an urethane resin, a polyester resin, a polyimide resin, a polyolefin resin, a novolak resin, a polyamine resin, etc. are mentioned.

In addition to the binder resin (A), the binder resin (A) In the case of the resin, the content of the binder resin (Aa) is preferably from 20 to 99% by mass, more preferably from 50 to 99% by mass, based on the binder resin (A).

Polymerizable compound (B), as long as it can be light or The compound which starts to polymerize by the active radical, the acid, etc. which are produced by the polymerization initiator (C) by the action of heat is not particularly limited. The polymerizable compound (B) may, for example, be a compound having a polymerizable carbon-carbon unsaturated bond, and a monofunctional monomer, a bifunctional monomer or a trifunctional or higher polyfunctional monomer is preferably used. Further, as the polymerizable compound (B), it is preferred to use a compound having no acidic group.

As a monofunctional monomer, a mercaptophenyl group can be mentioned. Carbitol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, 2-hydroxyl (meth) acrylate Ethyl ester, N-vinylpyrrolidone, and the like.

As the bifunctional monomer, there may be mentioned 1,6-hexane two Alcohol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, bisphenol A double ( Propylene methoxyethyl ether, 3-methylpentane diol di(meth) acrylate, tricyclodecane dimethanol di(meth) acrylate, and the like.

As a trifunctional or higher polyfunctional monomer, it can be listed For example: trimethylolpropane tri (meth) acrylate, neopentyl alcohol tri (meth) acrylate, neopentyl alcohol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate a reaction product of an ester, dipentaerythritol hexa(meth) acrylate, neopentyl alcohol tri(meth) acrylate and an acid anhydride, dipentaerythritol penta (meth) acrylate and an acid anhydride, V#1000, V#802, STAR-501, manufactured by Osaka Organic Chemical Industry Co., Ltd., and UA-306H, UA-306T, UA-306I, manufactured by Kyoeisha Chemical Co., Ltd., First Industrial Pharmaceutical Co., Ltd. Amino acrylate such as New Frontier R-1150. Among them, a bifunctional monomer or a trifunctional or higher polyfunctional monomer is preferably used.

Further, as the polymerizable compound (B), it is also possible to use The following polymerizable compound.

These polymerizable compounds (B) can be individually used It is also possible to use two or more types in combination.

The content of the polymerizable compound (B) relative to the photosensitive tree The solid content of the lipid composition is preferably from 1 to 50% by mass, more preferably from 5 to 30% by mass. In addition, the content of the binder resin (A) is preferably 30 to 80 parts by mass based on 100 parts by mass of the total of the binder resin (A) and the polymerizable compound (B).

Here, the solid component means that the composition is removed in the photosensitive resin. The total composition of the solvent contained in the product.

When the content of the binder resin (A) is within the aforementioned range, The viscosity of the dried film is more suppressed, and it is preferable to obtain a color filter having no color unevenness.

Polymerization initiator (C) for starting polymerization polymerization The compound (B) produces a compound such as an active radical or an acid, and may be a photopolymerization initiator which generates an active radical, an acid or the like by the action of light, or may be active by the action of heat. A thermal polymerization initiator such as a radical or an acid, but a photopolymerization initiator is preferred, and a photoradical polymerization initiator which generates an active radical by the action of light is more preferable.

The polymerization initiator (C) is preferably a ruthenium compound. By By using such a polymerization initiator, the photosensitive resin composition becomes highly sensitive, and The film formed by such a film is excellent in a pattern excellent in resolution and solvent resistance. In addition, it is preferable to change the high sensitivity of the photosensitive resin composition obtained by using the polymerization initiation auxiliary (C-1) in combination, and to improve the productivity when forming a color filter.

As the bismuth compound, it can be mentioned that N-benzhydryloxy 1-(4-phenylthiophenyl)butan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoate) Mercapto)-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3 -Dimethyl-2,4-dioxolylmethyloxy)benzimidyl}-9H-indazol-3-yl]ethane-1-imine and the like. Commercial products such as Irgacure (registered trademark) OXE-01, OXE-02 (above, Japanese BASF Co., Ltd.), and N-1919 (made by ADEKA Co., Ltd.) can also be used. Among them, N-benzylideneoxy-1-(4-phenylthiophenyl)octane-1-one-2-imine (the following formula) is preferred.

Further, examples of the polymerization initiator other than the ruthenium compound include a biimidazole compound, an alkylphenone compound, and three. a compound, a mercaptophosphine oxide, or the like.

As the biimidazole compound, there can be mentioned 2, 2'-bis (2- Chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenyl The benzyl imidazole (for example, refer to JP-A-6-75372, JP-A-6-75373, etc.), 2,2'-bis(2-chlorophenyl)- 4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(alkoxyphenyl)biimidazole , 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl) -4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (for example, refer to Japanese Patent Publication No. Sho 48-38403, JP-A-62-174204, etc.), 4, 4 The phenyl group at the '5,5'-position is an imidazole compound substituted with an alkoxycarbonyl group (for example, refer to JP-A-7-10913, etc.). Preferably, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl) -4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole .

As a phenylalkyl ketone compound, it can be cited as: Oxyacetophenone, 2-methyl-2-(N-morpholinyl)-1-(4-methylthiophenyl)propan-1-one, 2-dimethylamino-1- 4-(N-morpholinyl)phenyl)-2-benzylidenebutan-1-one, 2-dimethylamino-1-(4-(N-morpholinyl)phenyl)-2 -(4-methylphenylmethyl)butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylacetal, 2-hydroxy- 2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-(4- An oligomer or the like of isopropenylphenyl)propan-1-one, preferably 2-methyl-2-(N-morpholinyl)-1-(4-methylthiophenyl)propane-1 a ketone, 2-dimethylamino-1-(4-(N-morpholinyl)phenyl)-2-benzylbutane-1-one or the like. Commercial products such as Irgacure (registered trademark) 369, 907 (above, Japanese BASF Co., Ltd.) can also be used.

As three As the compound, there may be mentioned: 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-three , 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-three , 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-three , 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-three Wait.

As a mercaptophosphine oxide compound, it can be enumerated 2,4,6-trimethylbenzimidyldiphenylphosphine oxide or the like. Commercial products such as Irgacure (registered trademark) 819 (manufactured by BASF Co., Ltd.) can also be used.

Further, as a ruthenium compound, a biimidazole compound, a phenylalkyl ketone compound, and three Examples of the polymerization initiator (C) other than the compound and the mercaptophosphine oxide include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin. Benzoin compounds such as isobutyl ether; benzophenone, methyl o-benzhydrylbenzoate, 4-phenylbenzophenone, 4-benzylidene-4'-methyldiphenyl a benzophenone compound such as sulfide, 3,3',4,4'-tetrakis(tertiary butylperoxycarbonyl)benzophenone or 2,4,6-trimethylbenzophenone; An anthraquinone compound such as 10-phenanthrenequinone, 2-ethylhydrazine, camphorquinone; 10-butyl-2-chloroacridone, benzhydrin, methyl phenylglyoxylate, a titanocene compound, and the like.

These polymerization initiators (C) can be used separately, It is also possible to use two or more types in combination.

The content of the polymerization initiator (C) relative to the resin (A) and the polymerization The total amount of the compound (B) is 100 parts by mass, preferably 0.1 to 80 parts by mass, more preferably 1 to 60 parts by mass. When the total amount of the polymerization initiator is within this range, the pattern can be formed with high sensitivity, and the chemical resistance and mechanical strength of the pattern are strong. The degree of surface smoothness tends to be good.

The polymerization initiator (C) is a polymerization initiator (C-1) It is preferred to use (in particular, an amine) in combination. The polymerization initiation aid (C-1) is a compound used to promote polymerization of a polymerizable compound which starts polymerization by polymerization initiator (C), or a sensitizer.

As the polymerization initiation aid (C-1), an amine can be exemplified a compound, a thiazoline compound, an alkoxyquinone compound, a thioxanthone compound, a carboxylic acid compound, a thiol compound, or the like.

As an amine compound, a triethanolamine, Methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, benzoic acid 2-Dimethylaminoethyl ester, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamine) Benzophenone (commonly known as michelone), 4,4'-bis(diethylamine)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, etc. 4,4'-bis(diethylamine)benzophenone is preferred. Commercial products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can also be used.

As the thiazoline compound, the formula (III-1) can be enumerated A compound represented by the formula (III-3) and the like.

As the alkoxy oxime compound, it can be mentioned that: 9,10- Dimethoxy hydrazine, 2-ethyl-9,10-dimethoxy hydrazine, 9,10-diethoxy hydrazine, 2-ethyl-9,10-diethoxy hydrazine, 9,10- Dibutoxy fluorene, 2-ethyl-9,10-dibutoxy fluorene, and the like.

As the thioxanthone compound, a 2-isopropyl group can be cited. Thioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.

As the carboxylic acid compound, a phenylthio group can be cited. Acetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxy Phenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthyloxy Acetic acid, etc.

As the thiol compound, a 2-thio group can be cited. Oxazole, 2-thiothiazole, 2-thiobenzimidazole, 2-thiobenzothiazole, 2-thiobenzophenone Oxazole, 2-thionicotinic acid, 2-thiopyridine, 2-thiopyridin-3-ol, 2-thiopyridine, 2-thiopyridin-3-ol, 2-thiopyridine-N- Oxide, 4-amino-6-hydroxy-2-thiopyrimidine, 4-amino-6-hydroxy-2-thiopyrimidine, 4-amino-2-thiopyrimidine, 6-amino-5 - nitroso-2-thiouracil, 4,5-diamino-6-hydroxy-2-thiopyrimidine, 4,6-diamino-2-thiopyrimidine, 2,4-diamino -6-thiopyrimidine, 4,6-dihydroxy-2-thiopyrimidine, 4,6-dimethyl-2-thiopyrimidine, 4-hydroxy-2-thio-6-methylpyrimidine, 4 -hydroxy-2-thio-6-propylpyrimidine, 2-thio-4-methylpyrimidine, 2-thiopyrimidine, 2-thiouracil, 3,4,5,6-tetrahydropyrimidine-2 -thiol, 4,5-diphenylimidazole-2-thiol, 2-thioimidazole, 2-thiol-1-methylimidazole, 4-amino-3-linked amino-5-thio -1,2,4-triazole, 3-amino-5-thio-1,2,4-triazole, 2-methyl-4H-1,2,4-triazole-3-thiol, 4-methyl-4H-1,2,4-triazole-3-thiol, 3-thio-1H-1,2,4-triazole-3-thiol, 2-amino-5-sulfur Base-1,3,4-thiadiazole, 5-amino-1,3,4-thiadiazole-2-thiol, 2,5-dithio-1,3,4-thiadiazole, (furan-2-yl)methanethiol, 2-thio-5- Thiazolone, 2-thiothiazoline, 2-thio-4(3H)-quinazolinone, 1-phenyl-1H-tetrazole-5-thiol, 2-quinoline thiol, 2-sulfur 5-methylbenzimidazole, 2-thio-5-nitrobenzimidazole, 6-amino-2-thiobenzothiazole, 5-chloro-2-thiobenzothiazole, 6- Ethoxy-2-thiobenzothiazole, 6-nitro-2-thiobenzothiazole, 2-thionaphthazolyl, 2-thionaphthyl Oxazole, 3-thio-1,2,4-triazole, 4-amino-6-thiopyrazolo[2,4-d]pyridine, 2-amino-6-anthracenethiol, 6- Thioquinone, 4-thio-1H-pyrazolo[2,4-d]pyrimidine, hexanedithiol, decanedithiol, 1,4-bis(methylthio)benzene, dibutyl Alcohol bis(3-thiopropionate), butanediol bis(3-thioacetate), ethylene glycol bis(3-thioacetate), trimethylolpropane ginseng (3-sulfuric acid) Acetate), butanediol bis(3-thiopropionate), trimethylolpropane ginseng (3-thiopropionate), trimethylolpropane ginseng (3-thioacetate) ), neopentyl alcohol oxime (3-thiopropionate), neopentyl sterol oxime (3-thioacetate), hydroxyethyl ginseng (3-thiopropionate), neopentyl Alcohol oxime (3-thiobutyrate), 1,4-bis(3-thiobutyloxy)butane, and the like.

In the case of using a polymerization starting aid (C-1), it contains The amount is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 40 parts by mass, per 100 parts by mass of the total of the resin (A) and the polymerizable compound (B). Further, it is preferably 0.01 to 10 moles, more preferably 0.01 to 5 moles per 1 mole of the polymerization initiator (C). When the content of the polymerization initiation aid (C-1) is within this range, the pattern can be formed with higher sensitivity, and the productivity of the pattern tends to be improved.

The body pigment (D) is not particularly limited, but can be used. At least one selected from the group consisting of cerium oxide, cerium sulfate, titanium oxide, zinc oxide, aluminum oxide, magnesium oxide, and calcium carbonate. Further, from the viewpoint of transparency, the average particle diameter of the extender pigment is preferably 500 nm or less. Among them, cerium oxide is preferred from the viewpoint of reliability and low viscosity of the dried film.

The content of the extender pigment (D) relative to the resin (A) and polymerization The total amount of the compound (B) is 100 parts by mass, preferably 0.1 to 80 parts by mass, more preferably 1 to 30 parts by mass. When the content of the extender pigment is within this range, the low viscosity of the dried film and the solvent resistance tend to be good.

The photosensitive resin composition of the present invention is a solvent (E1) having a solubility parameter of 8.0 to 9.1 (cal/cm ³ ) ^{1/2 and} a solvent having a solubility parameter of 9.2 to 11.0 (cal/cm ³ ) ^1/2 . (E2). By using a photosensitive composition containing such a predetermined solvent, a dried film having a low viscosity which can be satisfied can be obtained, and a pattern having a hardness which can be satisfied can be obtained.

When the solvent (E1) having a solubility parameter of 8.0 to 9.1 (cal/cm ³ ) ^1/2 is described in parentheses and the solubility parameter ((cal/cm ³ ) ^1/2 ) is attached, it is exemplified: Ethylene glycol monoisobutyl ether (8.9), diethylene glycol mono-2-ethylhexyl ether (8.4), dipropylene glycol mono-n-propyl ether (8.8), dipropylene glycol mono-n-butyl ether (8.5), three Propylene glycol mono-n-propyl ether (8.5), tripropylene glycol mono-n-butyl ether (8.2), ethylene glycol dimethyl ether (8.6), diethylene glycol dimethyl ether (8.6), diethylene glycol diethyl Ethyl ether (8.6), diethylene glycol di-n-butyl ether (8.3), triethylene glycol dimethyl ether (8.4), diethylene glycol ethyl methyl ether (8.6), diethylene glycol single positive Butyl ether acetate (9.0), propylene glycol monomethyl ether acetate (9.0), dipropylene glycol monomethyl ether acetate (8.1), ethyl-3-ethoxypropionate (9.1), N-propyl acetate (8.6), n-propyl propionate (8.6), n-butyl propionate (8.3), n-amyl propionate (8.4), ethyl acetate (9.1), butyl acetate (8.3), and the like. Among them, from the viewpoint of solubility, it is preferred to use an acylate of a diol monoether such as propylene glycol monomethyl ether acetate, such as an alkylene glycol, a dialkylene glycol or a tri-alkylene. The alkanoate of the monoalkyl ether of the diol is more preferred.

When the solvent (E2) having a solubility parameter of 9.2 to 11.0 (cal/cm ³ ) ^1/2 is described in parentheses and the solubility parameter ((cal/cm ³ ) ^1/2 ) is attached, it is exemplified: Ethylene glycol monopropyl ether (10.6), ethylene glycol monoisopropyl ether (9.2), ethylene glycol mono-n-butyl ether (10.2), ethylene glycol monohexyl ether (9.4), ethylene glycol monobenzene Ether (10.9), ethylene glycol monomethyl ether (10.8), ethylene glycol monoallyl ether (9.8), diethylene glycol monomethyl ether (10.7), diethylene glycol mono-n-butyl Ether (10.0), diethylene glycol monohexyl ether (9.7), diethylene glycol mono 2-ethylhexyl ether (9.2), diethylene glycol monobenzyl ether (9.6), triethylene glycol monomethyl Ether (10.2), triethylene glycol monoethyl ether (9.9), triethylene glycol mono-n-butyl ether (9.3), polyethylene glycol monomethyl ether (9.2), propylene glycol monomethyl ether (10.7 ), propylene glycol mono-n-propyl ether (9.7), propylene glycol mono-n-butyl ether (9.3), propylene glycol mono-tert-butyl ether (9.7), propylene glycol monophenyl ether (11.0), dipropylene glycol monomethyl ether (9.6) ), tripropylene glycol monomethyl ether (9.4), ethylene glycol mono-n-butyl ether acetate (10.3), propylene glycol diacetate (9.6), methyl 3-methoxypropionic acid (9.5), methyl lactate (10.7), butyl lactate (9.8), cyclohexanone (9.9), 4-hydroxy-4-methyl-2-pentanone (alias diacetone alcohol) (10.2), 1- Butanol (11.4), two Alkane (10.0), chloroform (9.3), acetone (9.9), 1,1,2,2-tetrachloroethane (9.7), and the like. Among them, from the viewpoint of solubility, a hydroxy compound is preferred, and a diol monoether such as propylene glycol monomethyl ether or a hydroxy ketone such as 4-hydroxy-4-methyl-2-pentanone is more preferred. More preferably, it is a monoalkyl ether or a hydroxyalkanone of an alkylene glycol, a dialkylene glycol or a trialkylene glycol.

The solvent (E1) content of the solubility parameter of 8.0 to 9.1 (cal/cm ³ ) ^1/2 is 70 to 99% by mass, preferably 70 to 97% by mass, based on the solvent (E), and the solubility parameter is 9.2 to The solvent (E2) content of 11.0 (cal/cm ³ ) ^1/2 is 1 to 30% by mass, preferably 3 to 30% by mass based on the solvent (E). When the ratio of the mass % of the solvent is within the above range, the solubility and flatness at the time of coating tend to be improved. In addition, the solvent (E) may contain a solvent other than the solvent (E1) and the solvent (E2), but the content thereof is usually 20% by mass or less, preferably 10% by mass or less based on the solvent (E). .

Further, the solubility parameter was obtained by the following formula.

Solubility parameter = (ΔE/V) ^1/2

△E: agglutination energy (enthalpy), V: molar volume

The solvent (E) can be used in the synthesis of the binder resin (A).

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

The photosensitive resin composition of the present invention preferably contains a coloring agent (F). Examples of such a coloring agent (F) include a pigment and a dye. From the viewpoint of heat resistance and light resistance of the pattern, it is preferable to contain a pigment, and from the viewpoint of light transmittance of the pattern, a dye is contained. It is preferred to contain pigments and dyes as better.

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

As an organic pigment, the series: CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125 Yellow pigments such as 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214; CI pigments orange 13, 13, 36, 38, 40, 42, 43, 51, 55 , 59, 61, 64, 65, 71, 73 and other orange pigments; 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 and other red pigments; CI pigment blue 15, 15:3, 15:4, 15:6, 60 and other blue pigments; CI pigment purple 1, 19, 23, 29, 32, 36, 38 and other purple Pigment; CI pigment green 7, 36, 58 and other green pigments; CI pigment brown 23, 25 and other brown pigments; CI pigment black 1, 7 and other black pigments.

Among them, C.I. Pigment Yellow 138, 139, 150, C.I. Pigment Red 177, 242, 254, C.I. Pigment Violet 23, C.I. Pigment Blue 15:3, 15:6, C.I. Pigment Green 7, 36, 58 are preferred.

These pigments may be used singly or in combination of two or more.

The pigment may be subjected to the following treatments as needed: rosin treatment, surface treatment using a pigment derivative or a pigment dispersant introduced with an acidic group or a basic group, grafting of a pigment surface by a polymer compound or the like. The treatment is performed by a micronization treatment such as a sulfuric acid micronization method, a cleaning treatment by an organic solvent or water to remove impurities, a removal treatment by an ion exchange method using an ionic impurity, or the like. Further, the pigment is preferably a uniform particle size. By dispersing the pigment dispersant, a pigment dispersion in a state in which the pigment is uniformly dispersed in the solution can be obtained.

As the pigment dispersant, commercially available surfactants can be used, and examples thereof include an anthracene oxygen system, a fluorine system, an ester system, a cationic system, an anionic system, a nonionic system, an amphoteric acid, a polyester system, a polyamine system, and an acrylic acid. Such as surfactants and the like. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, and polyethylene glycol diesters. In addition to the class, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine modified polyurethanes, polyethyleneimine, etc., the trade name can be listed as KP (Shin-Etsu Chemical Industry ( Stocks), Flowlen (Kyoeisha Chemical Co., Ltd.), Solsperse (Zeneca), EFKA (Japan BASF), Ajisper (registered trademark) (Ajinomoto Exquisite Technology) System), Disperbyk (BYK company), etc. These may be used alone or in combination of two or more.

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

As the coloring agent (F), a known dye can be used, and examples of the dye include oil-soluble dyes and acid dyes.

These dyes are appropriately selected in accordance with the solubility in a solvent and the light fading resistance or the spectral spectrum when a color filter composition containing the dye is used to form a pattern of a color filter.

The dye is not particularly limited, and a known dye can be used. For example, a solvent dye, an acid dye, a direct dye, a mordant dye, or the like can be given. As the dye, for example, a compound classified as a colored phase other than a pigment in a color index (published by The Society of Dyers and Colourists) or a conventional dye described in a dyeing note (color dyeing company) can be cited. Further, depending on the chemical structure, there may be mentioned azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinone imine dyes. Hypomethyl dye Materials, azo methine dyes, squarylium dyes (Squarylium Dyes), acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, and nitro dyes. Among them, organic solvent-soluble dyes are preferred.

Specifically, CI solvent yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 117, 162, 163, 167, 189; CI solvent red 45, 49, 111, 125, 130, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247; CI solvent orange 2, 7 , 11, 15, 26, 56, 77, 86; CI solvent violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60; CI solvent blue 4, 5 , 14, 18, 35, 36, 37, 45, 58, 59, 59: 1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 97, 98, 100, 101, 102 , 104, 105, 111, 112, 122, 128, 132, 136, 139; CI solvent green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35 and other CI solvent dye; CI acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113 , 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251; CI acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 50, 51, 52 , 57, 66, 73, 76, 80, 87, 88, 91, 92, 94, 95, 97, 98, 103, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151 , 155, 158, 160, 172, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270 , 274, 277, 280, 281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426; CI Acid Orange 6,6,8,10,12,26,50,51,52,56,62,63,64,74,75,94,95,107,108,169,173; CI Acid Violet 6B, 7 , 9, 15, 16, 17, 19, 21, 23, 24, 25, 30, 34, 38, 49, 72, 102; CI Acid Blue 1, 3, 5, 7, 9, 11, 13, 15, 17, 18, 22, 23, 24, 25, 26, 27, 29, 34, 38, 40, 41, 42, 43, 45, 48, 51, 54, 59, 60, 62, 70, 72, 74, 75, 78, 80, 82, 83, 86, 87, 88, 90, 9 0: 1, 91, 92, 93, 93: 1, 96, 99, 100, 102, 103, 104, 108, 109, 110, 112, 113, 117, 119, 120, 123, 126, 127, 129, 130, 131, 138, 140, 142, 143, 147, 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 182, 183, 184, 187, 192, 199, 203, 204, 205, 210, 213, 229, 234, 236, 242, 243, 256, 259, 267, 269, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340; CI Acid Green 1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 50:1, 58, 63, 65, 80 , 104, 105, 106, 109 and other CI acid dyes; CI direct yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141; CI Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172 , 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250; CI Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; CI Direct Violet 47, 52, 54, 59, 60, 65, 66 , 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104; CI direct blue 1, 2, 3, 6, 8, 15, 22, 25, 28, 29, 40, 41, 42, 47, 52, 55, 57, 71, 76, 77, 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293; CI direct green CI direct dyes such as 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82; CI disperse yellow 51, 54, 76; CI dispersion Violet 26, 27; CI disperse blue 1, 14, 56, 60 and other CI disperse dyes; CI alkaline red 1, 10; CI alkaline blue 1, 3, 5, 7, 9, 19, 21, 22, 24, 25,26,28,29,40,41,45,47,54,58,59,60,64,65,66,67,68,81,83,88,89; CI alkaline violet 2; CI base Sex red 9; CI alkaline green 1; equal CI basic dye (Basic dye); CI reactive yellow 2, 76, 116; CI reactive orange 16; CI reactive red 36; iso-CI reactive dye; Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65; CI mordant red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 29, 30, 32, 33, 36, 37, 38, 39, 41, 42, 43, 45, 46, 48, 52, 53, 56, 62, 63, 71, 74, 76, 78, 85, 86, 88, 90, 94, 95; CI mordant orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23 , 24, 28, 29, 32, 34, 35, 36, 3 7, 42, 43, 47, 48; C.I. mordant purple 1, 1:1, 2, 3, 4, 5, 6, 7, 8, 10, 11, 14, 15, 16, 17, 18, 19, 21, 22, 23, 24, 27, 28, 30, 31, 32, 33, 36, 37, 39, 40, 41, 44, 45, 47, 48, 49, 53, 58; CI mordant blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39 , 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84; CI mord green 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53 and other CI mordant dyes (Mordant dye).

C.I. Reduction of green 1, etc. C.I. vat dye (Vat dye; also known as anthraquinone dye).

These dyes may be appropriately selected in accordance with the spectral spectrum of a desired color filter.

The dye is preferably a compound containing a xanthene skeleton in the molecule.

The content of the colorant (F) is preferably from 5 to 60% by mass, more preferably from 5 to 45% by mass, based on the solid content of the photosensitive resin composition. When the content of the colorant (F) is within the above range, the desired spectral or color concentration can be obtained.

The photosensitive resin composition of the present invention may contain a surfactant. Examples of the surfactant include a ruthenium-based surfactant, a fluorine-based surfactant, and a ruthenium-based surfactant having a fluorine atom. When the surfactant is contained, the flatness at the time of coating tends to be good.

As the oxime-based surfactant, one can cite: A surfactant for the siloxane coupling. Specifically, Toray silicon DC3PA, the same SH7PA, the same DC11PA, the same SH21PA, the same SH28PA, the same SH29PA, the same SH30PA, the polyether modified oyster oil SH8400 (Toray Dow Corning (stock) system), KP321 , KP322, KP323, KP324, KP326, KP340, KP341 (Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (made by Japan Momentive Performance Materials Contracting Co., Ltd.) Wait.

As a fluorine-based surfactant, fluorocarbon can be cited Chain surfactant. Specifically, Fluorinert (registered trademark) FC430, FC431 (Sumitomo 3M (share) system), Megafac (registered trademark) F142D, F171, F172, F173, F177, F183, R30 (DIC) (share) system, EFTOP (registered trademark) EF301, EF303, EF351, EF352 (Mitsubishi Materials Electronics Co., Ltd.), Surflon (registered trademark) S381, same as S382, same as SC101, with SC105 (Asahi Glass ( Shares), E5844 (Daikin Industrial Co., Ltd.), etc.

As a fluorene-based surfactant having a fluorine atom, To name: a surfactant having a siloxane chain and a fluorocarbon chain. Specific examples include Megafac (registered trademark) R08, BL30, F475, F477, and F443 (DIC). Preferably, Megafac (registered trademark) F475 is mentioned.

a surfactant, relative to the photosensitive resin composition, It is preferably 0.001% by mass to 0.2% by mass, more preferably 0.002% by mass to 0.1% by mass, particularly preferably 0.01% by mass to 0.05% by mass. By inclusion In the range of the surfactant, the flatness of the coating film can be made good.

The photosensitive resin composition of the present invention can be used as needed Further, various additives such as a filler, another polymer compound, an adhesion promoter, an antioxidant, an ultraviolet absorber, a photostabilizer, and a chain transfer agent are contained.

The photosensitive resin composition of the present invention can be mixed by The binder resin (A), the polymerizable compound (B), the polymerization initiator (C), the extender pigment (D), the solvent (E), and the necessary coloring agent (F) or other components are obtained.

Moreover, as a case where a pigment is mixed as a coloring agent (F), an example For example, it is preferable to modulate in the following order.

First, the pigment is previously mixed with the solvent (E), and the beads are used. It is dispersed by a grain mill or the like until the average particle diameter of the pigment becomes about 0.2 μm or less. At this time, a part or all of the pigment dispersant and the binder resin (A) may be blended as necessary. In the obtained pigment dispersion liquid, the remaining binder resin (A), the polymerizable compound (B), the polymerization initiator (C), the extender pigment (D), and other components used as necessary, and The solvent (E) which is added as necessary is added so as to become a predetermined concentration, and a photosensitive resin composition can be obtained.

As the photosensitive resin composition of the present invention, the substrate Examples of the coating method include an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, a CAP coating method, and a die coating method. Further, a dip coater, a roll coater, a bar coater, a spin coater, a slit & spin coater, or a slit coater (also referred to as a die coater, a curtain coater, or a spin coater) may be used. In the case of a coating device such as an inkjet. Among them, it is preferred to use a slit coater, a spin coater, a roll coater or the like.

As a result of coating a photosensitive resin composition on a substrate The method of drying the coating film may be, for example, heating, drying, natural drying, air drying, and drying under reduced pressure. It is also possible to combine a plurality of methods.

Drying temperature is preferably from 10 to 120 ° C, from 25 to 100 °C is better. Further, the heating time is preferably from 10 seconds to 60 minutes, more preferably from 30 seconds to 30 minutes.

Drying under reduced pressure is at a pressure of 50 to 150 Pa, 20 It is preferably carried out in a temperature range of up to 25 °C.

The film thickness of the dried film obtained by drying the coating film is not It is specifically limited and can be suitably adjusted by the material to be used, use, etc., and is usually 0.1 to 20 μm, and preferably 1 to 6 μm.

The dried film is exposed through the reticle used to form the target pattern Light. At this time, the shape of the pattern on the photomask is not particularly limited, and a pattern shape for the purpose of the purpose can be used. Further, in the case where a thermal polymerization initiator is used as the polymerization initiator (C), the dried film is heated by exposure, and this heat acts on the thermal polymerization initiator.

As the light source used in the exposure, to produce 250 A light source of light having a wavelength of 450 nm is preferred. For example, light having a wavelength of less than 350 nm is blocked by using a filter that blocks the wavelength region, or light having a wavelength range of around 436 nm, around 408 nm, and around 365 nm is used. Pass filter) Selectively remove. As a light source For example, mercury lamps, light-emitting diodes, metal halide lamps, halogen lamps, and the like can be cited.

In order to uniformly illuminate the entire surface of the exposure surface It is preferable to use a reticle aligner, a stepper, etc. for the wire, or to align the reticle to the correct position of the substrate.

Exposing the exposed film obtained by exposing the dried film to the developing solution By touching, a predetermined portion (for example, an unexposed portion) is dissolved, developed, whereby a pattern can be obtained. As the developer, an organic solvent can be used. However, since the exposed portion of the exposed film is less likely to be dissolved or wetted by the developing solution, and a pattern having a good shape can be obtained, an aqueous solution using a basic compound is preferred.

Development method, which can be liquid coating method, dipping method, spray method Any of the others. Furthermore, the substrate can be tilted at an arbitrary angle during development.

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

Examples of the basic compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium citrate, and potassium citrate. , inorganic basic compounds such as sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium borate, potassium borate, ammonia; tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, single An organic basic compound such as methylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine or ethanolamine.

Among them, potassium hydroxide, sodium hydrogencarbonate, tetramethylammonium hydroxide good.

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

The aqueous solution of the aforementioned basic compound may also contain a boundary Surfactant.

As a surfactant, a polyoxyethylene can be cited. Alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene/oxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene Nonionic surfactants such as sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine; An anionic surfactant such as sodium lauryl sulfate, sodium oleyl sulfate, sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate or sodium dodecyl naphthalenesulfonate; A cationic surfactant such as stearylamine hydrochloride or lauryl trimethylammonium chloride.

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

The pattern which is thermally hardened can be obtained by further baking the pattern obtained as described above. The baking temperature is usually 25 ° C or more and 230 ° C or less, preferably 25 ° C or more and 200 ° C or less, more preferably 25 ° C or more and 160 ° C or less, and still more preferably 25 ° C or more and 120 ° C or less. As the baking time, it is usually 1 to 300 minutes, preferably 1 to 180. Minutes, preferably 1 to 60 minutes.

The pattern obtained as described above, for example, may have A photo spacer used for a liquid crystal display device, a patternable protective coating film, and a color filter. Further, the photosensitive resin composition of the present invention can be suitably used for forming a film or a pattern of a pixel which is a liquid crystal display device or an image sensor, and can be utilized in such a film or A color filter or an array substrate provided as a part of the components, and a display device including such a color filter and/or an array substrate, for example, a liquid crystal display device or an organic EL device, solid state imaging device, and the like.

(Example)

Hereinafter, the colored photosensitive resin composition of the present invention will be described in more detail by way of examples. The "%" and "parts" in the examples are % and mass parts unless otherwise stated.

<Synthesis of Binder Resin (A1) Solution>

In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 67 parts of propylene glycol monomethyl ether acetate and 33 parts of propylene glycol monomethyl ether were placed, and the mixture was stirred while being replaced with nitrogen. Warm up to 120 °C. Next, in a monomer mixture of 11 parts of dicyclopentanyl acrylate, 31 parts of benzyl methacrylate, and 23 parts of methacrylic acid, it is added in a ratio of 1 part by weight relative to 100 parts of the monomer mixture. Perbutyl O. This was dropped from the dropping funnel for 2 hours into a flask, and further stirred at 120 ° C for 2 hours to obtain a copolymer. Next, the flask was replaced with air, and 10 parts of glycidyl methacrylate, 0.46 parts of triphenylphosphine, and 0.08 parts of methylhydroquinone were put into the solution of the above copolymer, and the reaction was continued at 120 ° C until solid content. When the acid value became 150 mg-KOH/g, the reaction was stopped, and 75 parts of propylene glycol monomethyl ether acetate and 5 parts of propylene glycol monomethyl ether were added, whereby a weight average molecular weight (Mw) of 30% by mass was obtained. 30 × 10 ³ , a solution of the binder resin (A1) having an acid value of 150 mg-KOH/g. The binder resin (A1) is one having the following structural unit.

<Synthesis of Binder Resin (A2) Solution>

In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 67 parts of propylene glycol monomethyl ether acetate and 33 parts of propylene glycol monomethyl ether were placed, and the mixture was stirred while being replaced with nitrogen gas. To 120 ° C. Next, in a monomer mixture of 10 parts of dicyclopentanyl acrylate, 34 parts of benzyl methacrylate, and 20 parts of methacrylic acid, Perbutyl is added in a ratio of 1 part by weight relative to 100 parts of the monomer mixture. O. This was dropped from the dropping funnel for 2 hours into a flask, and further stirred at 120 ° C for 2 hours to obtain a copolymer. Next, the flask was replaced with air, and 10 parts of glycidyl methacrylate, 0.44 parts of triphenylphosphine, and 0.08 parts of methylhydroquinone were put into the solution of the above copolymer, and the reaction was continued at 120 ° C until solid content. When the acid value was changed to 130 mg-KOH/g, the reaction was stopped, and 74 parts of propylene glycol monomethyl ether acetate and 5 parts of propylene glycol monomethyl ether were added, whereby a weight average molecular weight (Mw) of 30% by mass was obtained. 30 × 10 ³ , a solution of the binder resin (A2) having an acid value of 130 mg-KOH/g. The binder resin (A2) is one having the following structural unit.

<Synthesis of Binder Resin (A3) Solution>

In a flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel, and a gas introduction tube, 413 parts of propylene glycol monomethyl ether acetate was placed. Thereafter, nitrogen gas was introduced into the flask through a gas introduction tube, the atmosphere in the flask was replaced with nitrogen, and 144 parts of benzyl methacrylate, 30 parts of dicyclopentyl acrylate, 35 parts of methacrylic acid, and 5.2 parts were added. Azobisisobutyronitrile was stirred at 100 ° C for 5 hours. Thereafter, the mixture was cooled to room temperature to obtain a solution containing 33.6 mass% of a binder resin (A3) having a weight average molecular weight (Mw) of 10 × 10 ³ and an acid value of 110 mg-KOH/g. The resin (A3) is one having the following structural unit.

<Synthesis of Binder Resin (A4) Solution>

In a 1 L flask equipped with a reflux cooling tube, a dropping funnel, and a stirrer, an appropriate amount of nitrogen gas was introduced to replace the nitrogen atmosphere, and 371 parts of propylene glycol monomethyl ether acetate was placed, and the mixture was heated to 85 ° C while stirring. Next, 54 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decane-8-acrylate and 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decane-acrylic acid- A mixed solution of 225 parts of a 9-ester mixture, 81 parts of a vinyl toluene (isomer mixture), and 80 parts of propylene glycol monomethyl ether acetate was dropped for 4 hours. On the other hand, a solution in which 30 parts of the polymerization initiator 2,2-azobis(2,4-dimethylvaleronitrile) was dissolved in 160 parts of propylene glycol monomethyl ether acetate was dropped for 5 hours. After the completion of the dropwise addition of the starter solution, the temperature was maintained at the same temperature for 4 hours, and after cooling to room temperature, the weight average molecular weight (Mw) containing 37.5 mass% was 10×10 ³ and the acid value was 115 mg-KOH/g. Binder resin (A4), and B type viscosity (23 ° C) is a solution of 246 mPas. The binder resin (A4) is one having the following structural unit.

The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin obtained in the synthesis example was carried out under the following conditions using a GPC method.

Device: K2479 (Shimadzu Corporation (stock) system)

Column: SHIMADZU Shim-pack GPC-80M

Column temperature: 40 ° C

Solvent: THF (tetrahydrofuran)

Flow rate: 1.0ml/min

Detector: RI

<Synthesis of a compound represented by the formula (F1)>

40.5 parts of the compound of the formula (IV-1) and 60.5 parts of 2,6-dimethylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed under light-shielding conditions, and 200 parts of N-methylpyridone at 150 parts. Stir at °C for 8 hours. After the obtained reaction liquid was cooled to room temperature, it was added to a mixed liquid of 1200 parts of water and 75 parts of 35% hydrochloric acid, and when it was stirred at room temperature for 1 hour, crystals were precipitated. The precipitated crystal was obtained as a residue for suction filtration, washed with 100 parts of methanol, and then dried under reduced pressure at 60 ° C for one night to obtain 49 parts of the compound of the formula (IV-2). The yield was 85%.

Next, 28.8 parts of the compound represented by (IV-2), and 1- 21.6 parts of bromopropane and 24.2 parts of potassium carbonate were added to 144 parts of N-methylpyridone, and stirred at 90 ° C for 4 hours, and the obtained reaction liquid was cooled to room temperature, concentrated, and added to 560 parts of water, at 10 to When stirred at 15 ° C for 1 hour, crystals were precipitated. The resulting crystal was taken as a residue for suction filtration, dried, and washed with 1000 parts of ion-exchanged water, and then dried under reduced pressure at 60 ° C for 1 night to obtain 30.0 parts of a compound represented by the formula (F1). The yield was 91%.

Identification of compounds represented by formula (F1)

(mass analysis) ionization mode = ESI +: m / z = [M + H] ⁺ 659.3 accurate mass (Exact Mass): 658.3

Example 1 [Modulation of Photosensitive Resin Composition 1]

The following are mixed: colorant (F): CI Pigment Red 242 15 parts Colorant (F): CI Pigment Red 177 20 parts Acrylic Pigment Dispersant 14 parts Binder Resin (A1) Solution 33.3 parts (Binder Resin (A1) 10 parts) and solvent (E): 191 parts of propylene glycol monomethyl ether acetate, and the pigment dispersion liquid is fully dispersed by using a bead mill, and the pigment dispersion liquid is mixed with the following. Photosensitive resin composition 1: 254 parts of a binder resin (A1) solution (76.2 parts of a binder resin (A1)); a polymerizable compound (B): 1,3-diglyceride diacrylate (GDDA; Aldrich Co., Ltd.) System) 37 copies; Polymerization initiator (C): N-benzylideneoxy-1-(4-phenylthiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; Japan BASF (manufactured by BASF) 3.7 parts; polymerization initiator (C): bis(2,4,6-trimethylbenzylidene) phenylphosphine oxide (Irgacure (registered trademark) 819; Japan BASF (share) 7.4 parts: polymerization starting aid (C): diethyl thioxanthone (KAYACURE (registered trademark) DETX-S; manufactured by Nippon Chemical Co., Ltd.) 3.7 parts; extender pigment (D) dispersion: PMA -ST; Nissan Chemical Co., Ltd. (30% by mass of cerium oxide, hexadecyl propylene monoethyl ether acetate, and 6.5% by mass of methanol) (the same applies hereinafter) 41 parts; solvent (E): propylene glycol monomethyl ether 398 parts of acetate; and surfactant: Polyether modified oyster sauce (Toray silicon SH8400: manufactured by Toray Dow Corning Co., Ltd.) 0.5 parts.

The ratio of propylene glycol monomethyl ether acetate (solvent (E1)) which is contained in the total solvent (E) in the obtained photosensitive resin composition 1 was 93.3 mass%, propylene glycol monomethyl ether (solvent (E2) The ratio is 6.7% by mass. Further, the mass ratio of the binder resin (A1) to the polymerizable compound (B) (the binder resin (A1) / the polymerizable compound (B)) was 70/30.

Example 2 [Modulation of Photosensitive Resin Composition 2]

Mix the following: colorant (F): C.I. Pigment Green 58 43 parts Colorant (F): C.I. Pigment Yellow 138 24 parts Acrylic Pigment Dispersant 12 parts 86.7 parts of binder resin (A1) solution (26 parts of binder resin (A1)), and solvent (E): 390 parts of propylene glycol monomethyl ether acetate, and the pigment was dispersed by using a bead mill to obtain pigment dispersion. The pigment dispersion liquid was mixed with the following to obtain a photosensitive resin composition 2: 117 parts of a binder resin (A1) solution (35.1 parts of a binder resin (A1)); a polymerizable compound (B): two new Pentaerythritol hexaacrylate (KAYARAD (registered trademark); DPHA; manufactured by Nippon Chemical Co., Ltd.) 41 parts; polymerization initiator (C): N-benzylideneoxy-1-(4-phenylsulfide) Phenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF Co., Ltd.) 10 parts; polymerization initiator (C): double (2, 4, 6 -Trimethyl benzhydryl)phenylphosphine oxide (Irgacure (registered trademark) 819; manufactured by BASF Co., Ltd.) 8.1 parts: polymerization starting aid (C): diethyl thioxanthone (KAYACURE (registered) Trademark) DETX-S; Nippon Chemical Co., Ltd.) 10 parts; Body pigment (D) dispersion: PMA-ST; Nissan Chemical Co., Ltd. 34 parts; Solvent (E): Propylene glycol monomethyl ether acetate 307 parts ester; and surfactant: polyether modified oyster sauce (T Oray silicon SH8400: Toray Road Corning (stock) system 0.5 parts.

The ratio of propylene glycol monomethyl ether acetate (solvent (E1)) which is contained in the total solvent (E) in the obtained photosensitive resin composition 2 is 96.9 mass%, propylene glycol monomethyl ether (solvent (E2) The ratio is 3.1% by mass. Further, the mass ratio of the binder resin (A1) to the polymerizable compound (B) (adhesive resin (A1) The /polymerizable compound (B)) is 60/40.

Example 3 [Modulation of Photosensitive Resin Composition 3]

Mix the following: Colorant (F): CI Pigment Blue 15: 6 27 parts Colorant (F): CI Pigment Violet 23 0.5 part Acrylic Pigment Dispersant 10 parts Binder Resin (A1) Solution 27.7 parts (bonding Resin (A1) 8.3 parts) and solvent (E): 140 parts of propylene glycol monomethyl ether acetate, and fully disperse the pigment using a bead mill to obtain a pigment dispersion; the pigment dispersion is mixed with Thus, a photosensitive resin composition 3: 227 parts of a binder resin (A1) solution (68.1 parts of a binder resin (A1)); a polymerizable compound (B): dipentaerythritol hexaacrylate (KAYARAD (registered trademark)) DPHA; manufactured by Nippon Chemical Co., Ltd.) 32 parts; polymerization initiator (C): N-benzylideneoxy-1-(4-phenylthiophenyl)octane-1-one-2- Imine (Irgacure (registered trademark) OXE-01; manufactured by BASF Co., Ltd.) 5.4 parts; polymerization initiator (C): bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide (Irgacure (registered trademark) 819; Japan BASF Co., Ltd.) 8.6 parts: polymerization starting aid (C): diethyl thioxanthone (KAYACURE (registered trademark) DETX-S; Nippon Chemical Co., Ltd. ) 4.3 parts; body pigment (D) dispersion: PMA- ST; Nissan Chemical (share) system 36; Solvent (E): 497 parts of propylene glycol monomethyl ether acetate; and surfactant: Polyether modified eucalyptus oil (Toray silicon SH8400: manufactured by Toray Dow Corning Co., Ltd.) 0.5 parts.

The ratio of propylene glycol monomethyl ether acetate (solvent (E1)) in the total solvent (E) of the obtained photosensitive resin composition 3 was 94.2% by mass, and propylene glycol monomethyl ether (solvent (E2)) The ratio is 5.8 mass%, and the mass ratio of the binder resin (A1) to the polymerizable compound (B) (the binder resin (A1) / the polymerizable compound (B)) is 70/30.

Example 4 [Modulation of Photosensitive Resin Composition 4]

Mix the following: Colorant (F): CI Pigment Blue 15: 6 27 parts Colorant (F): CI Pigment Violet 23 0.5 part Acrylic Pigment Dispersant 10 parts Binder Resin (A2) Solution 24.7 parts (bonding Resin (A2) 7.4 parts) and solvent (E): 140 parts of propylene glycol monomethyl ether acetate, and fully disperse the pigment using a bead mill to obtain a pigment dispersion; the pigment dispersion is mixed with Thus, a photosensitive resin composition 4: 191 parts of a binder resin (A2) solution (57.3 parts of a binder resin (A2)); a polymerizable compound (B): dipentaerythritol hexaacrylate (KAYARAD (registered trademark)) DPHA; manufactured by Nippon Chemical Co., Ltd.) 43 parts; polymerization initiator (C): N-benzylideneoxy-1-(4-phenylthiophenyl)octane-1- Ketone-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF Co., Ltd.) 5.4 parts; polymerization initiator (C): bis(2,4,6-trimethylbenzylidene) Benzene phosphine oxide (Irgacure (registered trademark) 819; manufactured by BASF Co., Ltd.) 8.6 parts: polymerization starting aid (C): diethyl thioxanthone (KAYACURE (registered trademark) DETX-S; Nippon Chemical (share) system) 4.3 parts; body pigment (D) dispersion: PMA-ST; Nissan Chemical Co., Ltd. 36 parts; solvent (E): propylene glycol monomethyl ether acetate 530 parts; and surfactant: Polyether modified oyster sauce (Toray silicon SH8400: manufactured by Toray Silicon Corning Co., Ltd.) 0.5 parts.

The ratio of propylene glycol monomethyl ether acetate (solvent (E1)) in the total solvent (E) in the obtained photosensitive resin composition was 95.1% by mass, and propylene glycol monomethyl ether (solvent (E2)) The ratio is 4.9 mass%. Further, the mass ratio of the binder resin (A2) to the polymerizable compound (B) (the binder resin (A2) / the polymerizable compound (B)) was 60/40.

Example 5 [Modulation of Photosensitive Resin Composition 5]

Mix the following: Colorant (F): CI Pigment Blue 15: 6 27 parts Colorant (F): CI Pigment Violet 23 0.5 part Acrylic Pigment Dispersant 10 parts Binder Resin (A1) Solution 24.7 parts (bonding Resin (A1) 7.4 parts) and solvent (E): 140 parts of propylene glycol monomethyl ether acetate And using a bead mill to sufficiently disperse the pigment to obtain a pigment dispersion; the pigment dispersion is mixed with the following to obtain a photosensitive resin composition 5: 245 parts of a binder resin (A1) solution (adhesive resin (A1) 73.5 parts); polymerizable compound (B): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Chemical Co., Ltd.) 27 parts; polymerization initiator (C): N-benzene Methoxy-1-(4-phenylthiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF Co., Ltd.) 5.4 parts; Starting agent (C): bis(2,4,6-trimethylbenzylidene) phenylphosphine oxide (Irgacure (registered trademark) 819; manufactured by BASF Co., Ltd.) 8.6 parts: polymerization starting aid ( C): diethyl thioxanthone (KAYACURE (registered trademark) DETX-S; manufactured by Nippon Chemical Co., Ltd.) 4.3 parts; body pigment (D) dispersion: PMA-ST; Nissan Chemical Co., Ltd. 36 parts Solvent (E): 307 parts of propylene glycol monomethyl ether acetate; and surfactant: Polyether modified eucalyptus oil (Toray silicon SH8400: manufactured by Toray Dow Corning Co., Ltd.) 0.5 parts.

The ratio of propylene glycol monomethyl ether acetate (solvent (E1)) in the total solvent (E) in the obtained photosensitive resin composition was 93.8 mass%, and propylene glycol monomethyl ether (solvent (E2)) The ratio is 6.2% by mass, and the mass ratio of the binder resin (A1) to the polymerizable compound (B) (the binder resin (A1) / the polymerizable compound (B)) is 75/25.

Example 6 [Modulation of Photosensitive Resin Composition 6]

Mix the following: Colorant (F): CI Pigment Blue 15: 6 27 parts Colorant (F): CI Pigment Violet 23 0.5 part Acrylic Pigment Dispersant 10 parts Binder Resin (A1) Solution 27.7 parts (bonding Resin (A1) 8.3 parts) and solvent (E): 140 parts of propylene glycol monomethyl ether acetate, and fully disperse the pigment using a bead mill to obtain a pigment dispersion; the pigment dispersion is mixed with Thus, a photosensitive resin composition 6: 227 parts of a binder resin (A1) solution (68.1 parts of a binder resin (A1)); a polymerizable compound (B): dipentaerythritol hexaacrylate (KAYARAD (registered trademark)) DPHA; manufactured by Nippon Chemical Co., Ltd.) 32 parts; polymerization initiator (C): N-benzylideneoxy-1-(4-phenylthiophenyl)octane-1-one-2- Imine (Irgacure (registered trademark) OXE-01; manufactured by BASF Co., Ltd.) 5.8 parts; polymerization initiator (C): bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide (Irgacure (registered trademark) 819; Japan BASF Co., Ltd.) 9.4 parts: polymerization starting aid (C): diethyl thioxanthone (KAYACURE (registered trademark) DETX-S; Nippon Chemical Co., Ltd. ) 4.7 parts; body pigment (D) dispersion: PMA- ST; Nissan Chemical Co., Ltd. 36 parts; solvent (E): propylene glycol monomethyl ether 190 parts; solvent (E): propylene glycol monomethyl ether acetate 317 parts; and surfactant: polyether modified eucalyptus oil (Toray silicon SH8400: Toray Dow Corning (share) system) 0.5 parts.

The ratio of propylene glycol monomethyl ether acetate (solvent (E1)) in the total solvent (E) in the obtained photosensitive resin composition 6 was 71.2% by mass, and propylene glycol monomethyl ether (solvent (E2) The ratio of the binder resin (A1) to the polymerizable compound (B) (the binder resin (A1) / the polymerizable compound (B)) is 70/30.

Comparative example 1 [Modulation of Photosensitive Resin Composition 7]

The photosensitive resin composition 7 was obtained in Example 1 of JP-A-2011-221310.

Example 7 [Modulation of Photosensitive Resin Composition 8]

The following were mixed: colorant (F): CI Pigment Blue 15: 6 26 parts of colorant (F): Compound of formula (F1) 6.4 parts of acrylic pigment dispersant 9.0 parts of binder resin (A4) solution 26.7 Parts (10 parts of binder resin (A4)) Solvent (E): 4-hydroxy-4-methyl-2-pentanone 31 parts and solvent (E): 282 parts of propylene glycol monomethyl ether acetate, and used The bead mill sufficiently disperses the pigment to obtain a pigment dispersion; the pigment dispersion is mixed with the following to obtain a photosensitive resin composition 8: 108 parts of a binder resin (A3) solution (adhesive resin (A3) 36.3 parts) ); Polymerizable compound (B): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Chemical Co., Ltd.) 47 parts; polymerization initiator (C): N-benzyl methoxy group- 1-(4-phenylthiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF Co., Ltd.) 9.3 parts; polymerization initiator (C) : 2-methyl-2-(N-morpholinyl)-1-(4-methylthiophenyl)propan-1-one (Irgacure 907; manufactured by BASF, Japan) 1.9 parts; polymerization initiation Additive (C): diethyl thioxanthone (KAYACURE (registered trademark) DETX-S; manufactured by Nippon Chemical Co., Ltd.) 5.6 parts; extender pigment (D) dispersion: PMA-ST; Nissan Chemical Co., Ltd. 37 parts; solvent (E): 4-hydroxy-4-methyl-2-pentanone 168 parts solvent (E): propylene glycol monomethyl ether acetate 260 parts; and surfactant: polyether modified eucalyptus oil (Toray silicon SH8400: Toray Silicon Corning Co., Ltd.) 0.1 parts.

The ratio of propylene glycol monomethyl ether acetate (solvent (E1)) in the total solvent (E) in the obtained photosensitive resin composition 8 was 75.7 mass%, 4-hydroxy-4-methyl-2 - the ratio of the pentanone (solvent (E2)) is 24.3% by mass, and the mass ratio of the binder resin (A3) to the binder resin (A4) to the polymerizable compound (B) (adhesive resin (A3) / bonding The resin (A4) / the polymerizable compound (B)) was 11/39/50.

Example 8 [Modulation of Photosensitive Resin Composition 9]

Mix the following: colorant (F): C.I. Pigment Blue 15: 6 26 parts Colorant (F): Compound of formula (F1): 6.4 parts of acrylic pigment dispersant 9.0 parts of binder resin (A4) solution 26.7 parts (binder resin (A4) 10 parts) Solvent (E): 4-hydroxy- 31 parts of 4-methyl-2-pentanone and solvent (E): 282 parts of propylene glycol monomethyl ether acetate, and the pigment dispersion liquid was sufficiently dispersed by using a bead mill to obtain a pigment dispersion; The photosensitive resin composition 9 was obtained by mixing as described above: 97 parts of a binder resin (A4) solution (36.4 parts of a binder resin (A4)); a polymerizable compound (B): dipentaerythritol hexaacrylate (KAYARAD ( Registered trademark) DPHA; Nippon Chemical Co., Ltd.) 47 parts; polymerization initiator (C): N-benzylideneoxy-1-(4-phenylthiophenyl)octane-1-one -2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF Co., Ltd.) 9.3 parts; polymerization initiator (C): 2-methyl-2-(N-morpholinyl)-1- (4-methylthiophenyl)propan-1-one (Irgacure 907; manufactured by BASF Co., Ltd.) 1.9 parts; polymerization starting aid (C): diethyl thioxanthone (KAYACURE (registered trademark) DETX-S; Nippon Chemical Co., Ltd.) 5.6 parts; Body pigment (D) dispersion: PMA-ST; Chemical (stock) 37 parts; solvent (E): 4-hydroxy-4-methyl-2-pentanone 168 parts solvent (E): propylene glycol monomethyl ether acetate 272 parts; and surfactant: poly Ether modified oyster sauce (Toray silicon SH8400: manufactured by Toray Silicon Corning Co., Ltd.) 0.1 part. The ratio of propylene glycol monomethyl ether acetate (solvent (E1)) in the total solvent (E) in the obtained photosensitive resin composition 9 was 75.7 mass%, 4-hydroxy-4-methyl-2 The ratio of pentanone (solvent (E2)) was 24.3% by mass. Further, the mass ratio of the binder resin (A4) to the polymerizable compound (B) (adhesive resin (A4) / polymerizable compound (B)) was 50/50.

Comparative example 2 [Modulation of Photosensitive Resin Composition 10]

The following were mixed: colorant (F): CI Pigment Blue 15: 6 26 parts of colorant (F): Compound of formula (F1) 6.4 parts of acrylic pigment dispersant 4.3 parts of binder resin (A4) solution 32 Parts (Binder Resin (A4) 12 parts) Solvent (E): 4-hydroxy-4-methyl-2-pentanone 29 parts and solvent (E): propylene glycol monomethyl ether acetate 243 parts, and used The bead mill sufficiently disperses the pigment to obtain a pigment dispersion liquid; and the pigment dispersion liquid is mixed with the following to obtain a photosensitive resin composition 10: 121 parts of a binder resin (A4) solution (45.4 parts of a binder resin (A4)) ); polymerizable compound (B): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 52 parts; polymerization initiator (C): N-benzonitrile 1-(4-phenylthiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF Co., Ltd.) 11 parts; Polymerization initiator (C): 2-methyl-2-(N-morpholinyl)-1-(4-methylthiophenyl)propan-1-one (Irgacure 907; manufactured by BASF Japan) ) 2.1 parts; polymerization starting aid (C): diethyl thioxanthone (KAYACURE (registered trademark) DETX-S; manufactured by Nippon Chemical Co., Ltd.) 6.3 parts; solvent (E): 4-hydroxy-4 -Methyl-2-pentanone 168 parts solvent (E): 320 parts of propylene glycol monomethyl ether acetate; and surfactant: polyether modified oyster sauce (Toray silicon SH8400: manufactured by Toray Dow Corning Co., Ltd.) 0.1 Share.

The ratio of propylene glycol monomethyl ether acetate (solvent (E1)) in the total solvent (E) in the obtained photosensitive resin composition 10 was 75.8 mass%, 4-hydroxy-4-methyl-2 The ratio of the pentanone (solvent (E2)) is 24.2% by mass, and the mass ratio of the binder resin (A4) to the polymerizable compound (B) (the binder resin (A4) / the polymerizable compound (B)) is 50/50.

<Production of patterns>

The photosensitive resin composition was applied onto a glass substrate of 2 square meters by spin coating, and then prebaked at 100 ° C for 3 minutes to form a dried film. After cooling, the dried film formed on the substrate was exposed to a quartz glass mask which was placed at a distance of 100 μm from the dried film, and an exposure machine (TME-150RSK; TOPCON) was used. Light irradiation was performed at an exposure amount of 50 mJ/cm ² (based on 365 nm) in an atmospheric environment. As the reticle, those having a line pattern of 50 μm line and space were used. After the light irradiation, the obtained exposed film was immersed and imaged at 24 ° C for 60 seconds in a water-based developing solution containing 0.12% of a nonionic surfactant and 2% of sodium carbonate, washed with water, and then baked in a baking oven. After baking at 230 ° C for 30 minutes, a pattern was obtained.

<Resolution rating>

The obtained pattern was observed using a laser microscope (manufactured by Axio Imager MAT Zeiss), and the minimum size of the image was taken as the resolution. The higher the resolution, the more it can be used in the manufacture of high-definition color filters.

<Inconsistent evaluation of imaging>

The obtained pattern was observed using a laser microscope (manufactured by Axio Imager MAT Zeiss), and it was evaluated as ○ on the pattern without water staining (no uneven imaging was observed), and those with water stains were evaluated as × (seeing the image is not observed) All). In the case where the development unevenness is observed, color unevenness occurs when used for manufacturing a color filter.

<Solvent resistance evaluation>

In the pattern formed on the substrate, propylene glycol monomethyl ether acetate 1 ml was dropped, and after standing for 30 seconds, the pattern was propylene glycol monomethyl ether B by using a spin coater at a rotation of 1000 rpm for 10 seconds. Acid ester shake-off. From the film thickness values before and after the contact with propylene glycol monomethyl ether acetate, the film thickness retention ratio was calculated according to the following formula. The higher the film thickness retention ratio, the better the hardenability, and when used in the production of a color filter, color mixing can be prevented, and development unevenness can be improved.

(film thickness retention ratio) (%) = (film thickness after contact) / (film thickness before contact) <production of full-exposure development film>

A PET film (Lumirror 75-T60 manufactured by Toray Industries, Inc.) was adhered to a glass plate of 2 square meters to prepare a substrate. On the PET film side of the substrate, the photosensitive resin composition was applied by a spin coating method, and prebaked on a hot plate at 80 ° C for 2 minutes. After cooling, the entire surface of the dried film formed on the substrate was subjected to an exposure apparatus (TME-150RSK; TOPCON) to conduct an exposure amount of 150 mJ/cm ² (based on 365 nm) in an atmosphere. Light irradiation. After light irradiation, the image was immersed in a water-based developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23 ° C for 50 seconds, and washed with pure water to obtain a full-exposure developing film. . The obtained full-exposure development film was 2 μm when measured by a film thickness measuring device (DEKTAK 3; manufactured by ULVAC Co., Ltd.).

<cross cut test>

With respect to the obtained full-exposure development film, a tape peeling test (cross-cut test) was carried out in accordance with JIS K5600-5-6, and the adhesion to the PET film was evaluated. The results are shown in Table 1.

<pencil hardness>

For the obtained full-exposure development film, pencil hardness measurement was performed according to JIS-K5400 using a pencil scratch hardness tester (manufactured by Yasuda Seiki Co., Ltd.). Also, the load is set to 1,000g.

<Adhesion Assessment>

The photosensitive resin composition was coated on a 5 cm square PET film (Lumirror 75-T60, manufactured by Toray Industries, Inc.) using a film applicator (AP75 manufactured by Taiyo Kogyo Co., Ltd.) on a hot plate at 80 Pre-bake for 2 minutes at °C. After cooling, the dried film formed on the above-mentioned 5 cm square PET film was pressed with another 5 cm square PET film (Lumirror 75-T60 manufactured by Toray Co., Ltd.), and the pressed PET film was peeled off. In the non-uniform and peeled PET film on the dried film, no transfer was evaluated as ○ (viscosity was not observed), and unevenness on the dried film and peeling on the PET film was evaluated as × (see Getting sticky Sex). When the viscosity is observed, color unevenness occurs when used to manufacture a color filter.

According to the invention, it can be provided that the assignment can be full A low-viscosity dry film of the foot, and a photosensitive resin composition having a pattern having a hardness that can be satisfied.

By using the photosensitive resin composition of the present invention, In order to obtain a pattern with high resolution which improves the unevenness of development. The pattern obtained by the present invention is useful as a color filter for display used in a liquid crystal display device, an organic EL display device, or an electronic paper display device.

Claims (10)

A photosensitive resin composition comprising a binder resin (A), a polymerizable compound (B), a polymerization initiator (C), an extender pigment (D), and a solvent (E), wherein the solvent (E) is The solvent (E1) having a solubility parameter of from 8.0 to 9.1 (cal/cm ³ ) ^1/2 with respect to the solvent (E) of 70 to 99% by mass, and containing 1 to 30 by mass with respect to the aforementioned solvent (E) The solubility parameter of % is 9.2 to 11.0 (cal/cm ³ ) ^1/2 of solvent (E2). The photosensitive resin composition according to claim 1, wherein the polymerization initiator (C) is an anthracene compound. The photosensitive resin composition according to claim 1 or 2, wherein the binder resin (A) has an acid value of 50 to 180 mg-KOH/g. The photosensitive resin composition according to any one of claims 1 to 3, wherein the content of the binder resin (A) is relative to the binder resin (A) and the polymerizable compound (B). The total amount of 100 parts by mass is 30 to 80 parts by mass. The photosensitive resin composition according to any one of claims 1 to 4, wherein the extender pigment (D) is cerium oxide. The photosensitive resin composition as described in any one of Claims 1 to 5 further contains a coloring agent. The photosensitive resin composition according to claim 6, wherein the colorant is a pigment-containing coloring agent. The photosensitive resin composition according to claim 6 or 7, wherein the colorant is a dye-containing coloring agent. A pattern formed by the photosensitive resin composition according to any one of claims 1 to 8. A display device comprising the pattern as described in claim 9 of the patent application.