TWI632423B - Photosensitive resin composition - Google Patents

Abstract

The present 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) It contains a solvent (E1) having a solubility parameter of 8.0 to 9.1 (cal / cm ³ ) ^1/2 with respect to the aforementioned solvent (E), and contains 1 with respect to the aforementioned solvent (E). Solvent (E2) having a solubility parameter of 9.2 to 11.0 (cal / cm ³ ) ^1/2 to 30% by mass.

Description

Photosensitive resin composition

The present invention relates to a photosensitive resin composition.

Patterns of color filters and the like used in display devices such as liquid crystal display panels, telephone light-emitting panels, plasma display panels, and electronic paper are manufactured using a photosensitive resin composition. Specifically, a pattern is formed by applying a photosensitive resin composition on a substrate and then drying the resulting dried film after selectively exposing it to development.

As such a photosensitive resin composition, for example, Japanese Patent Application Laid-Open 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 an example of using propylene glycol monomethyl ether acetate as the aforementioned solvent is disclosed.

The dry film obtained from the aforementioned conventional photosensitive resin composition may not necessarily have a low tack, and the pattern obtained from the aforementioned conventional photosensitive resin composition may have a hardness of Situations that may not be satisfied.

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

[1] 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 ), Containing 70 to 99% by mass of the solvent (E1) with a solubility parameter of 8.0 to 9.1 (cal / cm ³ ) ^1/2 with respect to the aforementioned solvent (E), and containing 1 to the aforementioned solvent (E) A solvent (E2) having a solubility parameter of 9.2 to 11.0 (cal / cm ³ ) ^1/2 to 30% by mass.

The present invention also provides the following [2] to [10].

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

[3] The photosensitive resin composition according to the above [1] or [2], wherein the acid value of the binder resin (A) is 50 to 180 mg-KOH / g.

[4] The photosensitive resin composition according to any one of the above [1] to [3], 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 the above [1] to [4], wherein the extender pigment (D) is silicon oxide.

[6] The photosensitive resin composition according to any one of the above [1] to [5], further containing a colorant.

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

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

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

[10] A display device comprising the pattern according to the aforementioned [9].

According to the present invention, a photosensitive resin group can be provided. The finished product is provided with a dry film having a satisfactory low viscosity and a pattern having a satisfactory hardness.

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 an addition polymer (a) having a structural unit derived from an unsaturated carboxylic acid (hereinafter, referred to as "(a)") and an epoxy group. The unsaturated resin (b) (hereinafter referred to as "(b)") is a binder resin (Aa).

Examples of (a) include, for example, an unsaturated carboxylic acid (a1) (hereinafter referred to as "(a1)") and a unit having an unsaturated bond capable of addition polymerization with (a1). (A2) (hereinafter referred to as "(a2)"), an addition polymer obtained by addition polymerization.

Examples of (a1) include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, and p-vinylbenzoic acid; maleic acid, Fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1 Unsaturated dicarboxylic acids such as 2,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexene dicarboxylic acid; methyl-5-norbornene- 2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2- Ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [ 2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene, etc. Bicyclic unsaturated compounds containing carboxyl groups; mono [2- (meth) acrylfluorenyloxyethyl] succinate, mono [2- (meth) acrylfluorenyloxyethyl] phthalate Unsaturated mono-((meth) acrylfluorenyloxyalkyl] esters of polybasic carboxylic acids of 2 or more members; unsaturated compounds such as α- (hydroxymethyl) acrylic acid containing hydroxyl and carboxyl groups in the same molecule .

Among them, (meth) acrylic acid is preferably used from the viewpoint of copolymerization reactivity or the viewpoint of 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 terms "(meth) acrylfluorenyl" and "(meth) acrylate" have the same meaning.

Examples of (a2) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, secondary butyl (meth) acrylate, and (meth) acrylic acid. Tertiary butyl esters and other alkyl (meth) acrylates; cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo (meth) acrylate [5.2.1.0 ^2.6 ] decyl -8-ester (in this technical field, dicyclopentyl (meth) acrylate is used as a common name), dicyclopentyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, etc. Cycloalkyl (meth) acrylates; aryl (meth) acrylates or aralkyl esters such as phenyl (meth) acrylate, phenyl methyl (meth) acrylate; diethyl maleate, Fumar Dicarboxylic acid diesters such as diethyl acid and diethyl itaconic acid; hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; bicyclic [2.2.1 ] Hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxybicyclo [2.2.1] hept- 2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-methoxybicyclo [ 2. 2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2.1] hept-2-ene, 5,6-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-tert-butoxycarbonyl 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 (tertiary 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-maleimidebenzoate, N-succinimide Ester, 4-maleimide iminobutyric acid N-succinimide, 6-maleimide iminohexanoate N-succinimide, 3-maleimide propionate N-succinimide Derivatives such as amine esters, N- (9-acridyl) maleimide, etc. Class; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, Vinyl chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like.

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

Here, the "tricyclodecane skeleton" and "tricyclodecene skeleton" in this specification refer to the following structures (each bond is at an arbitrary point).

Examples of (a2-1) include dicyclopentyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentyloxyethyl (meth) acrylate, and (methyl) Dicyclopentenyloxyethyl acrylate. These can be used individually or in combination of 2 or more types.

Examples of (b) include a monomer (b-1) having an epoxidized structure of a chain olefin and an ethylenically unsaturated bond (hereinafter referred to as "(b-1)"), Cycloolefin epoxidized structure and ethylenically unsaturated monomer (b-2) (hereinafter referred to as "(b-2)"). As (b), (b-1) is preferred from the viewpoint of reactivity.

Examples of (b-1) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, and glycidylethylene Ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl Glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxy Methyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyl) Oxymethyl) styrene, 2,3,4-gins (glycidyloxymethyl) styrene, 2,3,5-gins (glycidyloxymethyl) styrene, 2,3, 6-gins (glycidyloxymethyl) styrene, 3,4,5-gins (glycidyloxymethyl) styrene, 2,4,6-gins (glycidyloxymethyl) Styrene, compounds described in Japanese Patent Application Laid-Open No. 7-248625, and the like.

Examples of (b-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide2000; manufactured by Daicel Corporation), and acrylic acid 3 1,4-epoxycyclohexyl methyl ester (for example, Cyclomer-A400; manufactured by Daicel (Stock) Corporation), 3,4-epoxy cyclohexyl methyl methacrylate (for example, Cyclomer-M100; Daicel (stock) Company), a compound represented by formula (I), a compound represented by formula (II), and the like.

[In the formula (I) and the formula (II), R ¹ and R ² independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group 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 alkyldiyl group having 1 to 6 carbon atoms.

* Indicates a bond with O].

The adhesive resin (Aa) can be produced through a two-step process. In this case, for example, reference may be made to the method described in the document "Experimental Method of Polymer Synthesis" (by Otsu Takayuki Publishing House; Chemical Co., Ltd., 1st edition, 1st issue, March 1, 1972), and It is manufactured by a method described in Japanese Patent Application Laid-Open No. 2001-89533.

In the production of the binder resin (Aa), first, as the first stage, (a1) and (a2) addition polymers (a) are obtained. Specifically, for example, a method of putting a predetermined amount of (a1) and (a2), a polymerization initiator, a solvent, and the like into a reaction container, replacing nitrogen with nitrogen, and stirring, heating, and holding in a deoxidized environment. . The polymerization initiator, solvent, and the like used herein are not particularly limited, and any of those skilled in the art can be used. Examples of the polymerization initiator include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), etc.) or The organic peroxide (such as benzamidine peroxide) may be any solvent as long as it can dissolve each monomer, and a solvent such as a solvent described later can be used as a solvent for the colored photosensitive resin composition.

In addition, the obtained addition polymer may be directly used as a solution after the reaction, a concentrated or diluted solution, or a solid (powder) obtained by reprecipitation or the like and taken out.

The ratio of the structural units derived from (a1) and (a2) is preferably within the following range relative to the total number of moles of all the structural units constituting the addition polymer (a).

Structural unit derived from (a1): 5 to 50 mole%, more preferably 10 to 45 mole%

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

Next, as the second stage, a part of the carboxyl group in the structural unit (a1) derived from the obtained addition polymer is reacted with (b). Because of its high reactivity, unreacted (b) is less likely to remain, so (b) is preferred as (b).

Specifically, continuing the above, the nitrogen gas in the ambient gas in the flask was replaced with air, (b) was set to 5 to 80 mol% relative to (a1), and the reaction catalyst (for example, reference (2) Methylaminomethyl) phenol, etc.) is set to 0.001 to 5% by mass based on the total amount of (a1), (b), and (a2), and a polymerization inhibitor (for example, hydroquinone, etc.) is set to be relative The total amount of (a1), (b), and (a2) is 0.001 to 5% by mass, and it is placed in a flask. Usually, it is reacted at 60 to 130 ° C for 1 to 10 hours to obtain an adhesive resin (Aa). In addition, similarly to the polymerization conditions, the production equipment, the amount of heat generated by polymerization, and the like can be considered, and the insertion method and reaction temperature can be appropriately adjusted.

At this time, the molar number of (b) is preferably set to 10 to 75 molar%, more preferably 15 to 70 molar% relative to the molar number of (a1). By setting the molar number of (b) within this range, there is a tendency that the balance between storage stability, solvent resistance and heat resistance becomes good.

Examples of the binder resin (Aa) include a resin in which a copolymer of (meth) acrylic acid / dicyclopentyl (meth) acrylate reacts with glycidyl (meth) acrylate, and (meth) acrylic acid / Resin reacted with copolymer of benzyl (meth) acrylate and glycidyl (meth) acrylate, copolymer of (meth) acrylic acid / cyclohexyl (meth) acrylate and (meth) acrylic acid Resin reacted with glyceride, copolymer of (meth) acrylic acid / styrene and glycidyl (meth) acrylate reacted, copolymer of (meth) acrylic acid / methyl (meth) acrylate and ( Resin reacted with glycidyl (meth) acrylate, Resin reacted with copolymer of (meth) acrylic acid / N-cyclohexylmaleimide and glycidyl (meth) acrylate, crotonic acid / (methyl) Resin reacted with a copolymer of dicyclopentyl acrylate and glycidyl (meth) acrylate, resin reacted with a copolymer of crotonic acid / benzyl (meth) acrylate and glycidyl (meth) acrylate, Crotonic acid / cyclohexyl (meth) acrylate copolymer with glycidyl (meth) acrylate Resin, crotonic acid / styrene copolymer reacted with glycidyl (meth) acrylate, resin crotonic acid / methyl crotonic acid copolymer reacted with glycidyl (meth) acrylate, croton Acid / N-cyclohexylmaleimide co-polymer reacted with glycidyl (meth) acrylate resin; maleic acid / dicyclopentyl (meth) acrylate copolymer with (meth) acrylic acid Glycidyl-resin-reactive resin, maleic acid / benzyl (meth) acrylate copolymer, and glycidyl (meth) acrylate-reactive resin, maleic acid / cyclohexyl (meth) acrylate copolymer Resin reacted with glycidyl (meth) acrylate, maleic acid / styrene copolymer and (meth) acrylic acid Resin reacted with glycidyl enoate, copolymer of maleic acid / methyl maleate reacted with glycidyl (meth) acrylate, copolymer of maleic acid / N-cyclohexylmaleimide Resin in which polymer reacts with glycidyl (meth) acrylate; resin in which (meth) acrylic acid / maleic anhydride / dicyclopentyl (meth) acrylate reacts with glycidyl (meth) acrylate Resin of (meth) acrylic acid / maleic anhydride / benzyl (meth) acrylate copolymer reacting with glycidyl (meth) acrylate, (meth) acrylic acid / maleic anhydride / (meth) Resin reacted with cyclohexyl acrylate copolymer and glycidyl (meth) acrylate, resin reacted with (meth) acrylic acid / maleic anhydride / styrene copolymer with glycidyl (meth) acrylate, ( (Meth) acrylic acid / maleic anhydride / methyl (meth) acrylate copolymer reacted with glycidyl (meth) acrylate, (meth) acrylic acid / maleic anhydride / N-cyclohexyl maleic acid Resin reacted with copolymer of imine and glycidyl (meth) acrylate; (meth) acrylic acid / (meth) propylene Dicyclopentyl ester copolymer copolymer with 3,4-epoxycyclohexyl methyl methacrylate resin, (meth) acrylic acid / benzyl (meth) acrylate copolymer and methacrylic acid 3 , 4-epoxycyclohexyl methyl ester resin, resin of (meth) acrylic acid / (meth) acrylic acid cyclohexyl co-polymer reacted with 3,4-epoxy cyclohexyl methyl methacrylate , Resins in which (meth) acrylic acid / styrene copolymers react with 3,4-epoxycyclohexyl methyl methacrylate, (meth) acrylic acid / methyl (meth) acrylate copolymers, and Resin for 3,4-epoxycyclohexyl methyl methacrylate reaction, (meth) acrylic acid / N-cyclohexyl malea Resin of amine copolymer with 3,4-epoxycyclohexyl methacrylate; crotonic acid / dicyclopentyl (meth) acrylate copolymer with 3,4-epoxy methacrylate Cyclohexyl methyl ester resin, crotonic acid / (meth) acrylic acid benzyl co-polymer and 3,4-epoxy cyclohexyl methyl methacrylate resin, crotonic acid / (methyl) Cyclohexyl acrylate copolymer with 3,4-epoxycyclohexyl methyl methacrylate resin, crotonic acid / styrene copolymer and 3,4-epoxy cyclohexyl methyl methacrylate Resin for reaction, copolymer of crotonic acid / methyl crotonic acid and 3,4-epoxycyclohexyl methacrylate, resin of crotonic acid / N-cyclohexylmaleimide Resin reacted with 3,4-epoxycyclohexyl methyl methacrylate; maleic acid / dicyclopentyl (meth) acrylate copolymer and 3,4-epoxy cyclohexyl methyl methacrylate Resin for ester reaction, resin for copolymerization of maleic acid / benzyl (meth) acrylate with 3,4-epoxycyclohexyl methacrylate, maleic acid / (meth) propyl Cyclohexyl acid copolymer copolymer with 3,4-epoxycyclohexyl methyl methacrylate resin, maleic acid / styrene copolymer and 3,4-epoxy cyclohexyl methyl methacrylate Resin for ester reaction, resin for reaction of maleic acid / methyl maleate copolymer with 3,4-epoxycyclohexyl methyl methacrylate, maleic acid / N-cyclohexyl maleimide Co-polymer with 3,4-epoxycyclohexyl methyl methacrylate resin; (meth) acrylic acid / maleic anhydride / (meth) acrylic acid dicyclopentyl ester copolymer and methacrylic acid 3,4-epoxycyclohexyl methyl ester reaction tree Resin, (meth) acrylic acid / maleic anhydride / benzyl (meth) acrylate copolymer, and 3,4-epoxycyclohexyl methyl methacrylate resin, (meth) acrylic acid / male Resins of maleic anhydride / cyclohexyl (meth) acrylate copolymer with 3,4-epoxy cyclohexyl methyl methacrylate, (meth) acrylic acid / maleic anhydride / styrene copolymer and 3,4-epoxy cyclohexyl methyl methacrylate reaction resin, (meth) acrylic acid / maleic anhydride / methyl (meth) acrylate copolymer and 3,4-epoxy methacrylate Resin for reaction with cyclohexyl methyl ester, resin for reaction of (meth) acrylic acid / maleic anhydride / N-cyclohexyl maleimide with 3,4-epoxy cyclohexyl methyl methacrylate; The binder resin (Aa) is an addition polymer obtained by copolymerizing with (a2) and (a2) other than (a1) and (a2-1) and (a2-1). ) The resin obtained by the reaction is more preferable. The adhesive resin (Aa) has the above-mentioned structure, and the obtained pattern tends to have excellent adhesion to the substrate and solvent resistance.

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

Among the addition polymers obtained by copolymerizing (a1) with (a2-1) and (a2) other than (a2-1), resins obtained by reacting with (b) include: (methyl ) Acrylic acid / (meth) acrylic acid dicyclopentyl ester / (meth) acrylic acid Resin reacted with copolymer of benzyl acid and glycidyl (meth) acrylate, copolymer of (meth) acrylic acid / dicyclopentyl (meth) acrylate / cyclohexyl (meth) acrylate and Resin reacted with (meth) glycidyl, resin reacted with (meth) acrylic acid / dicyclopentyl / (meth) acrylate / styrene and glycidyl (meth) acrylate, ) Resin reacted with acrylic acid / dicyclopentyl (meth) acrylate / methyl (meth) acrylate copolymer and glycidyl (meth) acrylate, (meth) acrylic acid / (meth) acrylic acid bicyclic Resin reacted with amyl ester / N-cyclohexyl maleimide copolymer and glycidyl (meth) acrylate; crotonic acid / dicyclopentyl (meth) acrylate / benzyl (meth) acrylate Resins reacted with glycidyl (meth) acrylate, copolymers of crotonic acid / dicyclopentyl (meth) acrylate / cyclohexyl (meth) acrylate, and glycidyl (meth) acrylate Ester reaction resin, crotonic acid / dicyclopentyl (meth) acrylate / styrene copolymer and glycidyl (meth) acrylate Resin, crotonic acid / dicyclopentyl (meth) acrylate / methyl crotonate copolymer and glycidyl (meth) acrylate reacting resin, crotonic acid / dicyclopentyl (meth) acrylate / Resin of N-cyclohexylmaleimide co-polymer reacted with glycidyl (meth) acrylate; co-polymer of maleic acid / dicyclopentyl (meth) acrylate / benzyl (meth) acrylate Resin reacting polymer with glycidyl (meth) acrylate, copolymer of maleic acid / dicyclopentyl (meth) acrylate / cyclohexyl (meth) acrylate, and glycidyl (meth) acrylate Resin, maleic acid / dicyclopentyl (meth) acrylate / styrene copolymer and (meth) propylene Resin reacted with glycidyl acid, resin reacted with maleic acid / dicyclopentyl (meth) acrylate / methyl maleate and glycidyl (meth) acrylate reacted, maleic acid / (formaldehyde) (Resin) copolymer of dicyclopentyl acrylate / N-cyclohexylmaleimide and glycidyl (meth) acrylate; (meth) acrylic acid / maleic anhydride / (meth) acrylic acid di Resin for the reaction of cyclopentyl ester / benzyl (meth) acrylate copolymer with glycidyl (meth) acrylate, (meth) acrylic acid / maleic anhydride / dicyclopentyl (meth) acrylate / ( Copolymer of cyclohexyl methacrylate copolymer with glycidyl (meth) acrylate, copolymer of (meth) acrylic acid / maleic anhydride / dicyclopentyl (meth) acrylate / styrene Resin reacted with glycidyl (meth) acrylate, copolymer of (meth) acrylic acid / maleic anhydride / dicyclopentyl (meth) acrylate / (meth) acrylate, and (meth) acrylic acid Resin of glycidyl ester, copolymer of (meth) acrylic acid / maleic anhydride / dicyclopentyl (meth) acrylate / N-cyclohexylmaleimide, and ( Base) glycidyl acrylate resin; (meth) acrylic acid / dicyclopentyl (meth) acrylate / benzyl (meth) acrylate copolymer with 3,4-epoxy methacrylate Hexyl methyl ester resin, copolymer of (meth) acrylic acid / dicyclopentyl (meth) acrylate / cyclohexyl (meth) acrylate, and 3,4-epoxy cyclohexyl methyl methacrylate Resin for reaction, resin for (meth) acrylic acid / dicyclopentyl (meth) acrylate / styrene copolymer with 3,4-epoxy cyclohexyl methyl methacrylate, (meth) acrylic acid / (Meth) acrylate dicyclopentyl ester / (meth) acrylate copolymer and 3,4-epoxy methacrylate ring Hexyl methyl ester resin, copolymer of (meth) acrylic acid / dicyclopentyl (meth) acrylate / N-cyclohexylmaleimide, and 3,4-epoxycyclohexyl methacrylate Resin for ester reaction; resin for crotonic acid / dicyclopentyl (meth) acrylate / benzyl (meth) acrylate reacted with 3,4-epoxycyclohexyl methacrylate, croton Acid / dicyclopentyl (meth) acrylate / cyclohexyl (meth) acrylate copolymer, 3,4-epoxycyclohexyl methyl methacrylate resin, crotonic acid / (meth) Copolymer of dicyclopentyl acrylate / styrene copolymer with 3,4-epoxycyclohexyl methyl methacrylate, co-polymer of crotonic acid / dicyclopentyl (meth) acrylate / methyl crotonic acid Resin in which polymer reacts with 3,4-epoxycyclohexyl methyl methacrylate, co-polymer of crotonic acid / dicyclopentyl (meth) acrylate / N-cyclohexylmaleimide and methyl 3,4-epoxy cyclohexyl methyl acrylate resin; maleic acid / dicyclopentyl (meth) acrylate / benzyl (meth) acrylate copolymer with 3,4-methacrylic acid Epoxy cyclohexyl Resin for methyl ester reaction, resin for maleic acid / dicyclopentyl (meth) acrylate / cyclohexyl (meth) acrylate copolymer and 3,4-epoxycyclohexyl methyl methacrylate Resin of maleic acid / dicyclopentyl (meth) acrylate / styrene copolymer reacted with 3,4-epoxycyclohexyl methyl methacrylate, maleic acid / (meth) acrylic acid dipolymer Resin for the reaction of cyclopentyl ester / methyl maleate copolymer with 3,4-epoxy cyclohexyl methyl methacrylate, maleic acid / dicyclopentyl (meth) acrylate / N-cyclohexyl Resin in which the copolymer of maleimide and 3,4-epoxycyclohexyl methyl methacrylate is reacted; (meth) acrylic acid / maleic anhydride / (meth) acrylic acid dicyclopentyl ester / Resin for the copolymer of benzyl (meth) acrylate and 3,4-epoxycyclohexyl methyl methacrylate, (meth) acrylic acid / maleic anhydride / (meth) acrylic acid dicyclopentyl ester / (Meth) acrylic acid cyclohexyl copolymer copolymer with 3,4-epoxycyclohexyl methyl methacrylate resin, (meth) acrylic acid / maleic anhydride / (meth) acrylic acid dicyclopentyl Ester / styrene copolymer with 3,4-epoxycyclohexyl methyl methacrylate resin, (meth) acrylic acid / maleic anhydride / (meth) acrylic acid dicyclopentyl ester / (methyl Resin of methyl acrylate copolymer reacted with 3,4-epoxy cyclohexyl methacrylate, (meth) acrylic acid / maleic anhydride / (meth) acrylic acid dicyclopentyl ester / N-cyclo Hexyl maleimide copolymers with 3,4-epoxy cyclohexyl methyl methacrylate resins; these binder resins (A) can be used individually or in combination of two or more use.

The polystyrene equivalent weight average molecular weight (Mw) of the binder resin (A) is preferably 8 × 10 ³ to 100 × 10 ³ , and more preferably 10 × 10 ³ to 50 × 10 ³ . When the weight average molecular weight (Mw) of the binder resin (A) is within the aforementioned range, the coatability of the photosensitive resin composition and the low viscosity of the dry film tend to change well, and the film is unlikely to occur during development. Decreasing, and furthermore, there is a tendency that the removal property of the non-pixel portion is good during 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, and even more preferably 50 to 180 mg-KOH / g. The acid value is a value for measuring the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the binder resin (A), and can be obtained by titration using an aqueous potassium hydroxide solution.

Although the binder resin (A) is preferably composed of only the above-mentioned binder resin (Aa), it may contain other resins. Examples of such a resin include epoxy resin, acrylic resin, urethane resin, polyester resin, polyimide resin, polyolefin resin, novolac resin, and polyamine resin.

In the case where the binder resin (A) contains a resin other than the binder resin (Aa), the content of the binder resin (Aa) is preferably 20 to 99% by mass relative to the binder resin (A), and is preferably 50 to 50% by mass. It is more preferably 99% by mass.

The polymerizable compound (B) is not particularly limited as long as it is a compound capable of starting polymerization by an active radical, an acid, or the like generated from the polymerization initiator (C) by the action of light or heat. Examples of the polymerizable compound (B) include compounds having a polymerizable carbon-carbon unsaturated bond, and a monofunctional monomer, a bifunctional monomer, and a trifunctional or higher polyfunctional monomer are preferably used. As the polymerizable compound (B), a compound having no acidic group is preferably used.

Examples of the monofunctional monomer include nonylphenylcarbitol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and 2-ethylhexylcarbitol ( (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, N-vinylpyrrolidone and the like.

Examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and Ethylene glycol di (meth) acrylate, bis (propyleneoxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylic acid Esters, tricyclodecanedimethanol di (meth) acrylate, and the like.

Examples of the trifunctional or higher polyfunctional monomer include trimethylolpropane tri (meth) acrylate, neopentaerythritol tri (meth) acrylate, neopentaerythritol tetra (meth) acrylate Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, reactant of neopentaerythritol tri (meth) acrylate and anhydride, dipentaerythritol penta Reactant of (meth) acrylic acid ester and anhydride, V # 1000, V # 802, STAR-501 made by Osaka Organic Chemical Industry Co., Ltd., and UA-306H, UA-306T made by Kyoeisha Chemical Co., Ltd. , UA-306I, New Frontier R-1150 manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd. and other urethane acrylates. Among them, it is preferable to use a bifunctional monomer and a trifunctional or higher polyfunctional monomer.

As the polymerizable compound (B), the following polymerizable compounds can also be used.

These polymerizable compounds (B) may be used alone or in combination of two or more kinds.

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

Here, the solid content means a total component excluding a solvent contained in the photosensitive resin composition.

When the content of the binder resin (A) is in the aforementioned range, the viscosity of the dried film is more suppressed, and a color filter having colorless unevenness is more likely to be obtained.

The polymerization initiator (C) is a compound for starting the polymerization of the polymerizable compound (B) to generate active radicals, acids, and the like, and can be used for photopolymerization to generate active radicals, acids, and the like by the action of light. The initiator may also be a thermal polymerization initiator that generates active radicals, acids, and the like by the action of heat, but a photopolymerization initiator is preferred in order to generate the free radicals by the action of light. A radical polymerization initiator is more preferred.

The polymerization initiator (C) is preferably an oxime compound. By using such a polymerization initiator, the photosensitive resin composition becomes more sensitive, and The film formed by these methods has a good pattern with excellent resolution and solvent resistance. Further, it is preferable that the photosensitive resin composition obtained by using the polymerization initiation aid (C-1) in combination has a high sensitivity, and productivity is improved when a color filter is formed by using these.

Examples of the oxime compound include N-benzyloxy-1- (4-phenylthiophenyl) butane-1-one-2-imine, and N-ethoxyl-1- [9-Ethyl-6- (2-methylbenzylfluorenyl) -9H-carbazol-3-yl] ethane-1-imine, N-ethoxyl-1- [9-ethyl -6- {2-methyl-4- (3,3-dimethyl-2,4-dioxolylmethyloxy) benzyl} -9H-carbazol-3-yl] Ethane-1-imine and the like. Commercially available products such as Irgacure (registered trademark) OXE-01, OXE-02 (above, made in Japan by BASF (stock)), N-1919 (made by ADEKA (stock)) can also be used. Among them, N-benzyloxy-1- (4-phenylthiophenyl) octan-1-one-2-imine (the following formula) is preferred.

Examples of the polymerization initiator other than the oxime compound include a biimidazole compound, an alkylphenone compound, and Compounds, fluorenylphosphine oxide compounds, and the like.

Examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,3- Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole (for example, refer to Japanese Patent Laid-Open No. 6-75372, Japanese Patent Laid-Open No. 6-75373, etc.), 2,2'- Bis (2-chlorobenzene Phenyl) -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-chloro Phenyl) -4,4 ', 5,5'-tetrakis (trialkoxyphenyl) biimidazole (for example, refer to Japanese Patent Publication No. 48-38403, Japanese Patent Publication No. 62-174204, etc.), The phenyl group at the 4,4 ', 5,5'-position is an imidazole compound substituted with an alkoxycarbonyl group (for example, refer to Japanese Patent Application Laid-Open No. 7-10913). Preferred examples include: 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 .

Examples of the phenalkyl ketone compound include diethoxyacetophenone, 2-methyl-2- (N-morpholinyl) -1- (4-methylthiophenyl) propane-1- Ketone, 2-dimethylamino-1- (4- (N-morpholinyl) phenyl) -2-benzylbutane-1-one, 2-dimethylamino-1- (4 -(N-morpholinyl) phenyl) -2- (4-methylphenylmethyl) butane-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1-one, Benzyl dimethyl acetal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propane-1-one, 1-hydroxycyclohexylphenyl ketone, 2 -Hydroxy-2-methyl-1- (4-isopropenylphenyl) propane-1-one, etc., preferably 2-methyl-2- (N-morpholinyl) -1- (4-methylthiophenyl) propane-1-one, 2-dimethylamino-1- (4- (N-morpholinyl) phenyl) -2-benzylbutane-1- Ketones, etc. Commercial products such as Irgacure (registered trademark) 369, 907 (above, made by Japan BASF (stock)) can also be used.

As three Examples of compounds include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-tris , 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-tris , 2,4-bis (trichloromethyl) -6-piperyl-1,3,5-tri , 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) vinyl] -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) vinyl] -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) vinyl] -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) vinyl] -1,3,5-tris Wait.

Examples of the fluorenylphosphine oxide compound include 2,4,6-trimethylbenzylidenediphenylphosphine oxide and the like. Commercial products such as Irgacure (registered trademark) 819 (manufactured by BASF (Japan)) can also be used.

In addition, as an oxime compound, a biimidazole compound, a benzoyl ketone compound, Examples of the polymerization initiator (C) other than the compound and the fluorenylphosphine oxide include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin Benzoin compounds such as isobutyl ether; benzophenone, o-benzylidene methyl benzoate, 4-phenylbenzophenone, 4-benzylidene-4'-methyldiphenyl Sulfides, benzophenone compounds such as 3,3 ', 4,4'-tetrakis (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9 ,, 10-phenanthrenequinone, 2-ethylanthraquinone, camphorquinone and other quinone compounds; 10-butyl-2-chloroacridone, benzophenone, methyl phenylglyoxylate, titanocene compound and the like.

These polymerization initiators (C) may be used alone or in combination of two or more kinds.

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

The polymerization initiator (C) is preferably used in combination with a polymerization initiator (C-1) (especially an amine). The polymerization initiation aid (C-1) is a compound or a sensitizer used to promote the polymerization of a polymerizable compound that is polymerized by the polymerization initiator (C).

Examples of the polymerization initiation aid (C-1) include amine compounds, thiazoline compounds, alkoxyanthracene compounds, thioxanthone compounds, carboxylic acid compounds, and thiol compounds.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethylamine. Isoamylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethyl-p-toluidine, 4, 4'-bis (dimethylamine) benzophenone (commonly known as Michler's ketone), 4,4'-bis (diethylamine) benzophenone, 4,4'-bis (ethylmethyl) Among them, 4,4'-bis (diethylamine) benzophenone is preferred. Commercial products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can also be used.

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

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

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1 -Chloro-4-propoxythioxanthone and the like.

Examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, Methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthio Acetic acid, N-naphthyl glycine, naphthyloxyacetic acid, and the like.

Examples of the thiol compound include: 2-thio group Azole, 2-thiothiazole, 2-thiobenzimidazole, 2-thiobenzothiazole, 2-thiobenzo Azole, 2-thionicotinic acid, 2-thiopyridine, 2-thiopyridine-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-thio-1-methylimidazole, 4-amino-3-diamino-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-thio -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-tetrazol-5-thiol, 2-quinoline thiol, 2-thio 5-methylbenzimidazole, 2-thio-5-nitrobenzimidazole, 6-amino-2-thiobenzothiazole, 5-chloro-2-thiobenzothiazole, 6- Ethoxy-2-thiobenzothiazole, 6-nitro-2-thiobenzothiazole, 2-thionaphthoimidazole, 2-thionaphtho Azole, 3-thio-1,2,4-triazole, 4-amino-6-thiopyrazolo [2,4-d] pyridine, 2-amino-6-purinethiol, 6- Thiopurine, 4-thio-1H-pyrazolo [2,4-d] pyrimidine, hexanedithiol, decanedithiol, 1,4-bis (methylthio) benzene, butane Alcohol bis (3-thiopropionate), butanediol bis (3-thioacetate), ethylene glycol bis (3-thioacetate), trimethylolpropane ginseng (3-thiopropionate) Methyl acetate), butanediol bis (3-thiopropionate), trimethylolpropane ginseng (3-thiopropionate), trimethylolpropane ginseng (3-thioacetate) ), Neopentaerythritol (3-thiopropionate), neopentaerythritol (3-thioacetate), hydroxyethyl ginseng (3-thiopropionate), neopentyl Alcohol (3-thiobutyrate), 1,4-bis (3-thiobutyloxy) butane, and the like.

When the polymerization initiation aid (C-1) is used, the content thereof is preferably 0.01 to 50 parts by mass, more preferably 100 parts by mass relative to the total amount of the resin (A) and the polymerizable compound (B). 0.1 to 40 parts by mass. In addition, 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 initiator (C-1) is within this range, a pattern can be formed with higher sensitivity, and the productivity of the pattern tends to be improved.

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

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

The photosensitive resin composition of the present invention contains 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 dry film having a satisfactory low viscosity can be obtained, and a pattern having a satisfactory hardness can be obtained.

As a solvent (E1) having a solubility parameter of 8.0 to 9.1 (cal / cm ³ ) ^1/2 , when the solubility parameter ((cal / cm ³ ) ^1/2 ) is described in parentheses, the following can be enumerated: 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 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 mono-n-butyl ether 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, acylate of a glycol monoether such as propylene glycol monomethyl ether acetate is preferable, and e.g., butanediol, dialkylene glycol, or trialkylene is preferred. Alkanoates of monoalkyl ethers of glycols are more preferred.

As a solvent (E2) having a solubility parameter of 9.2 to 11.0 (cal / cm ³ ) ^1/2 , when the solubility parameter ((cal / cm ³ ) ^1/2 ) is included in the parentheses, the following can be enumerated: 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 monobenzyl ether (10.8), ethylene glycol monoallyl ether (9.8), diethylene glycol monomethyl ether (10.7), diethylene glycol mono-n-butyl ether 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-tertiary 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 (also known as 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 preferable, and a diol monoether such as propylene glycol monomethyl ether or a hydroxy ketone such as 4-hydroxy-4-methyl-2-pentanone is more preferable. It is more preferable to use alkylene glycol, dialkylene glycol, or monoalkyl ether of trialkylene glycol, or hydroxyalkanone.

The content of the solvent (E1) having a 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 with respect to 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, and preferably 3 to 30% by mass, with respect to 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 good. The solvent (E) may contain solvents other than the solvent (E1) and the solvent (E2), but its content is usually 20% by mass or less, and preferably 10% by mass or less, based on the solvent (E). .

The solubility parameter is obtained from the following formula.

Solubility parameter = (ΔE / V) ^1/2

ΔE: agglutination energy (enthalpy), V: mole volume

The solvent (E) can be used when synthesizing the binder resin (A).

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

The photosensitive resin composition of the present invention preferably further contains a colorant (F). Examples of such a coloring agent (F) include pigments and dyes, but from the viewpoint of heat resistance and light resistance of a pattern, it is preferable to contain a pigment.

Examples of pigments include organic pigments and inorganic pigments, and compounds classified as pigments in the Color Index (published by The Society of Dyers and Colourists) can be cited.

For organic pigments, the series includes: CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125 , 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214 and other yellow pigments; CI Pigment Orange 13, 31, 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 pigments; CI Pigment Green 7, 36, 58 and other green pigments; CI Pigment Brown 23 and 25 and other brown pigments; CI Pigment Black 1, 7 and other black pigments Pigments, etc.

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, and C.I. Pigment Green 7, 36, 58 are preferred.

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

The aforementioned pigments may be subjected to the following treatments, if necessary: surface treatment with a pigment derivative or pigment dispersant introduced with an acidic or basic group, or grafting of the pigment surface with a polymer compound or the like Treatment, micronization treatment by a sulfuric acid micronization method, etc., or cleaning treatment by an organic solvent or water, etc. to remove impurities, and removal treatment by an ion exchange method such as an ionic impurity. The pigment preferably has a uniform particle size. By performing a dispersion treatment containing a pigment dispersant, a pigment dispersion liquid in a state where the pigment is uniformly dispersed in the solution can be obtained.

As the pigment dispersant, a commercially available surfactant can be used, and examples thereof include silica-based, fluorine-based, ester-based, cationic, anionic, non-ionic, amphoteric, polyester-based, polyamine-based, and acrylic acid. Department of surfactants and so on. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, and fatty acid modified polyesters. , Grade 3 amine modified polyurethanes, polyethyleneimines, etc. Examples include KP (Shin-Etsu Chemical Industry Co., Ltd.), Flowlen (Kyoeisha Chemical Co., Ltd.), Solsperse (Zeneca (Stock)), EFKA (Japan BASF (Stock)), Ajisper (registered trademark) (Ajinomoto Exquisite Technology Co., Ltd.), Disperbyk (by BYK), etc. These can be used individually or in combination of 2 or more types.

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

As a colorant (F), a well-known dye can be used, and as a dye, an oil-soluble dye, an acid dye, etc. can be mentioned.

These dyes are appropriately selected depending on the solubility in a solvent and the light fading resistance or the spectral spectrum when a pattern of a color filter is formed using a coloring curable resin composition containing the dye.

The dye is not particularly limited, and known dyes can be used, and examples thereof include solvent dyes, acid dyes, direct dyes, and mordant dyes. Examples of the dyes include compounds classified as colored people other than pigments in the color index (published by The Society of Dyers and Colourists), and conventional dyes described in dyeing notes (color dyeing companies). Depending on the chemical structure, examples include azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, and quinoneimine dyes. , Methine dye, azomethine dye, Squarylium Dyes, acridine dye, styryl dye, coumarin dye, quinoline dye, and nitro dye 料 等。 Waiting. Among them, organic solvent-soluble dyes are preferred.

Specific examples include: 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 dyes; 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, 7, 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, 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, 90: 1, 91, 92, 93, 9 3: 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 Purple 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 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, CI direct dyes such as 68, 69, 72, 77, 79, 82; CI disperse yellow 51, 54, 76; CI disperse violet 26, 27; CI disperse blue 1, 14, 56, 60 and other CI disperse dyes; CI basic Red 1, 10; CI Basic 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 basic violet 2; CI basic red 9; CI basic green 1; etc. CI basic dyes; CI reactivity Yellow 2, 76, 116; CI reactive orange 16; CI reactive red 36; etc. CI reactive dyes; CI mordant yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 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, 37, 42, 43, 47, 48; CI Mordant Violet 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 Mordant 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.

C.I. reduced green 1 and the like C.I. reduced dye (Vatdye; also known as vat dye) and the like.

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

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

The content of the colorant (F) is preferably 5 to 60% by mass, and more preferably 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 aforementioned range, a desired spectroscopic or color density can be obtained.

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

Examples of the siloxane-based surfactant include a surfactant having a siloxane bond. Specifically, it can be listed: Toray silicon DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, polyether modified silicone oil SH8400 (manufactured by Toray Dow Corning (stock)), KP321, KP322, KP323, KP324, KP326 , KP340, KP341 (made by Shin-Etsu Chemical Industry Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (made by Japan Momentive Performance Materials contract company), etc.

Examples of the fluorosurfactant include a fluorocarbon chain surfactant. Specific examples include: Fluorinert (registered trademark) FC430, same as FC431 (Sumitomo 3M (shares)), Megafac (registered trademark) F142D, same F171, same F172, same F173, same F177, same F183, same R30 (DIC (Stock) system), EFTOP (registered trademark) EF301, same EF303, same EF351, same EF352 (Mitsubishi Materials Electronics Co., Ltd.), Surflon (registered trademark) S381, same S382, same SC101, same SC105 (Asahi Glass (Asahi Glass) Share) system), E5844 (Daikin Industrial (shares) system), etc.

Examples of the siloxane surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain. Specific examples include Megafac (registered trademark) R08, same BL20, same F475, same F477, and F443 (DIC (shares) system). Preferable examples include Megafac (registered trademark) F475.

The surfactant is preferably 0.001% by mass to 0.2% by mass, more preferably 0.002% by mass to 0.1% by mass, and particularly preferably 0.01% by mass to 0.05% by mass with respect to the photosensitive resin composition. By containing a surfactant in this range, the The flatness becomes good.

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

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

When a pigment is mixed as the colorant (F), for example, it is preferably prepared in the following order.

First, the pigment is mixed with the solvent (E) in advance, and dispersed using a bead mill or the like until the average particle diameter of the pigment becomes about 0.2 μm or less. In this case, 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), polymerizable compound (B), polymerization initiator (C), extender pigment (D), and other components used as necessary, and The solvent (E) added as necessary is added so as to have a predetermined concentration, and a photosensitive resin composition can be obtained.

Examples of the method for coating the substrate with the photosensitive resin composition of the present invention include an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, a CAP coating method, and a die coating method. In addition, a dip coater, a roll coater, a bar coater, a spin coater, a slit & spin coater, a slit coater (also referred to as a die coater, a curtain coater, and a spinless coater) can also be used. (Case)), coating by inkjet and other coating devices. Among them, coating using a slit coater, a spin coater, a roll coater, or the like is preferred.

Examples of a method for drying a coating film obtained by applying a photosensitive resin composition to a substrate include methods such as heat drying, natural drying, ventilation drying, and reduced pressure drying. It is also possible to combine plural methods.

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

Drying under reduced pressure is preferably performed at a temperature of 20 to 25 ° C under a pressure of 50 to 150 Pa.

The film thickness of the dried film obtained by drying the coating film is not particularly limited, and can be appropriately adjusted depending on the materials used, applications, and the like. Usually, it is 0.1 to 20 μm, and preferably 1 to 6 μm.

The dry film is exposed through a mask for forming a desired pattern. In this case, the shape of the pattern on the photomask is not particularly limited, and a pattern shape according to the intended use can be used. When 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, a light source that generates light with a wavelength of 250 to 450 nm is preferred. For example, use a filter that cuts off this wavelength range to cut light below 350 nm, or use a band-pass filter (band) that removes these wavelengths around 436 nm, 408 nm, and 365 nm. pass filter). As a light source Examples thereof include a mercury lamp, a light emitting diode, a metal halide lamp, and a halogen lamp.

In order to uniformly radiate parallel light to the entire exposure surface, or to align the photomask and the substrate at the correct position, it is preferable to use a device such as a photomask aligner and a stepper.

The exposed film obtained by exposing the dried film is brought into contact with a developing solution, and a predetermined portion (for example, an unexposed portion) is dissolved and developed, whereby a pattern can be obtained. As the developer, an organic solvent can be used, but since the exposed portion of the exposure film is not easily dissolved or swollen by the developer, and a well-shaped pattern can be obtained, an aqueous solution of a basic compound is preferably used.

The development method may be any of a liquid coating method, a dipping method, and a spray method. Furthermore, the substrate can be tilted at an arbitrary angle during development.

After 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 silicate, and potassium silicate. , Sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium borate, potassium borate, ammonia and other inorganic basic compounds; tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, mono Organic basic compounds such as methylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, and ethanolamine.

Among them, potassium hydroxide, sodium bicarbonate, and tetramethylammonium hydroxide are used as good.

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

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

Examples of the surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, and oxyethylene / oxypropylene block copolymers. , Sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, etc. Ionic surfactants; anionic interfacial activities such as sodium lauryl sulfate, sodium oleyl sulfate, sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium dodecylnaphthalenesulfonate Agents; cationic surfactants such as stearylamine hydrochloride, lauryltrimethylammonium chloride, etc.

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

By further baking the pattern obtained as described above, a heat-hardened pattern can be obtained. The baking temperature is usually 25 ° C to 220 ° C, preferably 25 ° C to 200 ° C, more preferably 25 ° C to 160 ° C, and even more preferably 25 ° C to 120 ° C. As the baking time, usually 1 to 300 minutes, preferably 1 to 180 Minutes, more preferably from 1 to 60 minutes.

The pattern obtained as described above may include, for example, a photo spacer, a patternable protective coating film, and a color filter used in a liquid crystal display device. In addition, the photosensitive resin composition of the present invention can be suitably used for forming a film or a pattern of pixels as a liquid crystal display device or an image sensor, and can be used for such a film or The pattern includes a color filter, an array substrate, and an array substrate, which are part of the components, and can be used in a display device having such a color filter and / or an array substrate, such as a liquid crystal display device, an organic substrate, and the like. EL devices, solid-state imaging devices, etc.

(Example)

Hereinafter, the coloring photosensitive resin composition of this invention is demonstrated in detail using an Example. In the examples, "%" and "part" indicate mass% and mass parts unless otherwise specified.

<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, put 67 parts of propylene glycol monomethyl ether acetate and 33 parts of propylene glycol monomethyl ether, and stir while replacing with nitrogen. The temperature was raised to 120 ° C. Secondly, in a monomer mixture of 11 parts of dicyclopentyl acrylate, 31 parts of benzyl methacrylate, and 23 parts of methacrylic acid, a ratio of 1 part to 100 parts of the monomer mixture was added. Perbutyl O. The self-driving funnel was dropped into the flask over 2 hours, and further stirred at 120 ° C for 2 hours to obtain a copolymer. Next, the inside of the flask was replaced with air, 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 the 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 to obtain a weight average molecular weight (Mw) containing 30% by mass. A solution of 30 × 10 ³ binder resin (A1) having an acid value of 150 mg-KOH / g. The binder resin (A1) is one having the following structural units.

<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 stirred while replacing with nitrogen, and the temperature was raised. To 120 ° C. Next, Perbutyl was added to a monomer mixture of 10 parts of dicyclopentyl acrylate, 34 parts of benzyl methacrylate, and 20 parts of methacrylic acid at a ratio of 1 part to 100 parts of the monomer mixture. O. The self-driving funnel was dropped into the flask over 2 hours, and further stirred at 120 ° C for 2 hours to obtain a copolymer. Next, the inside of the flask was replaced with air, 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 the solid content When the acid value became 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 to obtain a weight average molecular weight (Mw) containing 30% by mass. A solution of 30 × 10 ³ binder resin (A2) having an acid value of 130 mg-KOH / g. The binder resin (A2) is one having the following structural units.

<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. After that, nitrogen was introduced into the flask through a gas introduction tube, and the environment 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 of Azobisisobutyronitrile was stirred at 100 ° C for 5 hours. After cooling to room temperature, a solution containing a binder resin (A3) having a weight-average molecular weight (Mw) of 33.6% by mass of 10 × 10 ³ and an acid value of 110 mg-KOH / g was obtained. The resin (A3) is one having the following structural units.

〈Synthesis of Binder Resin (A4) Solution)

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

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin obtained in the synthesis example were measured using the GPC method under the following conditions.

Installation: K2479 (made by Shimadzu Corporation)

Column: SHIMADZU Shim-pack GPC-80M

Column temperature: 40 ℃

Solvent: THF (tetrahydrofuran)

Flow rate: 1.0ml / min

Detector: RI

<Synthesis of compound represented by formula (F1)>

40.5 parts of the compound represented by 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 were mixed at 150 Stir at 8 ° C for 8 hours. After the resulting reaction solution was cooled to room temperature, it was added to a mixed solution of 1200 parts of water and 75 parts of 35% hydrochloric acid, and when stirred at room temperature for 1 hour, crystals were precipitated. The precipitated crystal was taken as a residue by 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 a compound represented by formula (IV-2). The yield was 85%.

Next, 28.8 parts of the compound shown in (IV-2), 21.6 parts of 1-bromopropane and 24.2 parts of potassium carbonate were added to 144 parts of N-methylpyridone, and the resulting reaction solution was stirred at 90 ° C for 4 hours. After cooling to room temperature, it was concentrated, added to 560 parts of water, and crystals were precipitated when stirred at 10 to 15 ° C for 1 hour. The resulting crystals were taken as a residue for suction filtration, and then dried, washed with 1,000 parts of ion-exchanged water, and dried under reduced pressure at 60 ° C. for one night to obtain 30.0 parts of a compound represented by formula (F1). The yield was 91%.

Identification of compound represented by formula (F1)

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

Example 1 [Preparation of photosensitive resin composition 1]

Mix the following:

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

Example 2 [Preparation of photosensitive resin composition 2]

Mix the following:

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

Example 3

[Preparation of photosensitive resin composition 3]

Mix the following: Colorant (F): C.I. Pigment Blue 15: 6 27 parts

Colorant (F): C.I. Pigment Violet 23 0.5 parts

10 parts of acrylic pigment dispersant

27.7 parts of binder resin (A1) solution

(8.3 parts of binder resin (A1)) and solvent (E): 140 parts of propylene glycol monomethyl ether acetate, and the pigment was sufficiently dispersed using a bead mill to obtain a pigment dispersion; the pigment dispersion was mixed with the following To obtain a photosensitive resin composition 3: 227 parts of a binder resin (A1) solution

(68.1 parts of binder resin (A1)); polymerizable compound (B): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.); polymerization initiator ( C): N-benzyloxy-1- (4-phenylthiophenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF Japan) ) 5.4 parts; polymerization initiator (C): bis (2,4,6-trimethylbenzyl) phenylphosphine oxide (Irgacure (registered trademark) 819; made by Japan BASF (stock)) 8.6 parts: Polymerization initiation aid (C): 4.3 parts of diethylthioxanthone (KAYACURE (registered trademark) DETX-S; manufactured by Nippon Kayaku Co., Ltd.); physical pigment (D) dispersion: PMA-ST; Nissan Chemical 36 shares; Solvent (E): 497 parts of propylene glycol monomethyl ether acetate; and surfactant: 0.5 part of polyether modified silicone oil (Toray silicon SH8400: manufactured by Toray Dow Corning Co., Ltd.).

The ratio of propylene glycol monomethyl ether acetate (solvent (E1)) occupied 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 was 5.8% by mass, and the mass ratio of the binder resin (A1) to the polymerizable compound (B) (binder resin (A1) / polymerizable compound (B)) was 70/30.

Example 4

[Preparation of photosensitive resin composition 4]

Mix the following: Colorant (F): C.I. Pigment Blue 15: 6 27 parts

Colorant (F): C.I. Pigment Violet 23 0.5 parts

10 parts of acrylic pigment dispersant

Adhesive resin (A2) solution 24.7 parts

(7.4 parts of binder resin (A2)) and solvent (E): 140 parts of propylene glycol monomethyl ether acetate, and the pigment was sufficiently dispersed using a bead mill to obtain a pigment dispersion liquid; the pigment dispersion liquid was as follows To obtain a photosensitive resin composition 4: 191 parts of a binder resin (A2) solution

(57.3 parts of binder resin (A2)); polymerizable compound (B): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.); polymerization initiator ( C): N-benzyloxy-1- (4-phenylthiophenyl) octane-1-

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 was 4.9% by mass. The mass ratio of the binder resin (A2) to the polymerizable compound (B) (binder resin (A2) / polymerizable compound (B)) was 60/40.

Example 5 [Preparation of photosensitive resin composition 5]

Mix the following:

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

Example 6 [Preparation of photosensitive resin composition 6]

Mix the following: Colorant (F): C.I. Pigment Blue 15: 6 27 parts

Colorant (F): C.I. Pigment Violet 23 0.5 parts

10 parts of acrylic pigment dispersant

27.7 parts of binder resin (A1) solution

(8.3 parts of binder resin (A1)) and solvent (E): 140 parts of propylene glycol monomethyl ether acetate, and the pigment was sufficiently dispersed using a bead mill to obtain a pigment dispersion; the pigment dispersion was mixed with the following To obtain a photosensitive resin composition 6: 227 parts of a binder resin (A1) solution

(68.1 parts of binder resin (A1)); polymerizable compound (B): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.); polymerization initiator ( C): N-benzyloxy-1- (4-phenylthiophenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF Japan) ) 5.8 parts; polymerization initiator (C): bis (2,4,6-trimethylbenzyl) phenylphosphine oxide (Irgacure (registered trademark) 819; made by Japan BASF (stock)) 9.4 parts: Polymerization initiation aid (C): Diethylthioxanthone (KAYACURE (registered trademark) DETX-S; manufactured by Nippon Kayaku Co., Ltd.); 4.7 parts; constitution pigment (D) dispersion: PMA-ST; 36 parts (stock); solvent (E): 190 parts of propylene glycol monomethyl ether; solvent (E): 317 parts of propylene glycol monomethyl ether acetate; and surfactant: polyether modified silicone oil (Toray silicon SH8400 : Toray Dow Corning Co., Ltd.) 0.5 copies.

The ratio of propylene glycol monomethyl ether acetate (solvent (E1)) occupied 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) is 28.9% by mass, and the mass ratio of the binder resin (A1) to the polymerizable compound (B) (binder resin (A1) / polymerizable compound (B)) is 70/30.

Comparative Example 1

[Preparation of photosensitive resin composition 7]

According to Example 1 of Japanese Patent Application Laid-Open No. 2011-221310, a photosensitive resin composition 7 was obtained.

Example 7

[Preparation of photosensitive resin composition 8]

Mix the following: Colorant (F): C.I. Pigment Blue 15: 6 26 parts

Colorant (F): 6.4 parts of the compound represented by formula (F1)

Acrylic pigment dispersant 9.0 parts

Adhesive resin (A4) solution 26.7 parts

(10 parts of adhesive resin (A4))

Solvent (E): 31 parts of 4-hydroxy-4-methyl-2-pentanone and solvent (E): 282 parts of propylene glycol monomethyl ether acetate, and the pigment was sufficiently dispersed using a bead mill to obtain pigment dispersion This pigment dispersion was mixed with the following to obtain a photosensitive resin composition 8: 108 parts of a binder resin (A3) solution

(36.3 parts of binder resin (A3)); Polymerizable compound (B): 47 parts of dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.); polymerization initiator (C): N-benzyloxy- 9.3 parts of 1- (4-phenylthiophenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF (Japan)); polymerization initiator (C) : 1.9 parts of 2-methyl-2- (N-morpholinyl) -1- (4-methylthiophenyl) propan-1-one (Irgacure 907; manufactured by BASF Japan); polymerization initiation Auxiliary agent (C): 5.6 parts of diethylthioxanthone (KAYACURE (registered trademark) DETX-S; manufactured by Nippon Kayaku Co., Ltd.); physical pigment (D) dispersion: PMA-ST; 37 parts; solvent (E): 168 parts of 4-hydroxy-4-methyl-2-pentanone; solvent (E): 260 parts of propylene glycol monomethyl ether acetate; and surfactant: polyether modified silicone oil (Toray silicon SH8400: Toray Dow Corning Co., Ltd.) 0.1 part.

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

Example 8

[Preparation of photosensitive resin composition 9]

Mix the following: Colorant (F): C.I. Pigment Blue 15: 6 26 parts

Colorant (F): 6.4 parts of the compound represented by formula (F1)

Acrylic pigment dispersant 9.0 parts

Adhesive resin (A4) solution 26.7 parts

(10 parts of adhesive resin (A4))

Solvent (E): 31 parts of 4-hydroxy-4-methyl-2-pentanone and solvent (E): 282 parts of propylene glycol monomethyl ether acetate, and the pigment was sufficiently dispersed using a bead mill to obtain pigment dispersion This pigment dispersion was mixed with the following to obtain a photosensitive resin composition 9: 97 parts of a binder resin (A4) solution

(36.4 parts of binder resin (A4)); polymerizable compound (B): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.); polymerization initiator ( C): N-benzyloxy-1- (4-phenylthiophenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF Japan) ) 9.3 parts; polymerization initiator (C): 2-methyl-2- (N-morpholinyl) -1- (4-methylthiophenyl) propane-1-one (Irgacure 907; Japan BASF 1.9 parts; manufactured by Co., Ltd .; polymerization initiator (C): diethylthioxanthone (KAYACURE (registered trademark) DETX-S; manufactured by Nippon Kayaku Co., Ltd.); 5.6 parts; dispersion of constitution pigment Liquid: PMA-ST; 37 parts made by Nissan Chemical Co., Ltd .; solvent (E): 168 parts of 4-hydroxy-4-methyl-2-pentanone

Solvent (E): 272 parts of propylene glycol monomethyl ether acetate; and surfactant: 0.1 part of polyether modified silicone oil (Toray silicon SH8400: manufactured by Toray Dow Corning Co., Ltd.).

The ratio of propylene glycol monomethyl ether acetate (solvent (E1)) occupied in the total solvent (E) in the obtained photosensitive resin composition 9 was 75.7 mass%, and 4-hydroxy-4-methyl-2 The ratio of -pentanone (solvent (E2)) was 24.3% by mass. The mass ratio of the binder resin (A4) to the polymerizable compound (B) (binder resin (A4) / polymerizable compound (B)) was 50/50.

Comparative Example 2

[Preparation of photosensitive resin composition 10]

Mix the following: Colorant (F): C.I. Pigment Blue 15: 6 26 parts

Colorant (F): 6.4 parts of the compound represented by formula (F1)

4.3 parts of acrylic pigment dispersant

Adhesive resin (A4) solution 32 parts

(12 parts of adhesive resin (A4))

Solvent (E): 29 parts of 4-hydroxy-4-methyl-2-pentanone and solvent (E): 243 parts of propylene glycol monomethyl ether acetate, and the pigment was sufficiently dispersed using a bead mill to obtain pigment dispersion This pigment dispersion was mixed with the following to obtain a photosensitive resin composition 10: 121 parts of a binder resin (A4) solution

(45.4 parts of binder resin (A4)); polymerizable compound (B): 52 parts of dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.); polymerization initiator ( C): N-benzyloxy-1- (4-phenylthiophenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF Japan) ) 11 copies; Polymerization initiator (C): 2-methyl-2- (N-morpholinyl) -1- (4-methylthiophenyl) propane-1-one (Irgacure 907; manufactured by BASF Japan) ) 2.1 parts; polymerization initiation aid (C): diethylthioxanthone (KAYACURE (registered trademark) DETX-S; manufactured by Nippon Kayaku Co., Ltd.) 6.3 parts; solvent (E): 4-hydroxy-4 -168 parts of methyl-2-pentanone solvent (E): 320 parts of propylene glycol monomethyl ether acetate; and surfactant: polyether modified silicone oil (Toray silicon SH8400: manufactured by Toray Dow Corning Co., Ltd.) 0.1 Serving.

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

<Making a Pattern>

A photosensitive resin composition was applied on a 2-inch square glass substrate by a spin coating method, and then dried at 100 ° C. for 3 minutes to form a dry film. After being allowed to cool, an exposure machine (TME-150RSK; manufactured by TOPCON) was used with a dry mask formed on the substrate through a quartz glass photomask arranged so that the interval between the dry film and the dry film became 100 μm. Under the atmospheric environment, light irradiation was performed with an exposure amount of 50 mJ / cm ² (365 nm as a reference). As the photomask, a 50 μm line and space pattern was used. After light irradiation, the obtained exposure film was immersed in a water-based imaging solution containing 0.12% of a non-ionic surfactant and 2% of sodium carbonate for development for 60 seconds at 24 ° C. After washing with water, it was placed in a baking oven. After 30 minutes at 230 ° C, a pattern was obtained.

<Resolution Evaluation>

The obtained pattern was observed using a laser microscope (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.

<Unevenness evaluation>

The obtained pattern was observed with a laser microscope (Axio Imager MAT Zeiss), and those with no water stains on the pattern were evaluated as ○ (no unevenness in development was observed), and those with water stains were evaluated as × (when the image was not visible) Both). When the development unevenness is seen, color unevenness occurs when it is used for manufacturing a color filter.

〈Solvent Resistance Evaluation〉

In the pattern formed on the substrate, 1 ml of propylene glycol monomethyl ether acetate was dropped, and after standing for 30 seconds, the spin coater was used to rotate at 1000 rpm for 10 seconds to rotate the propylene glycol monomethyl ether ethyl on the pattern The acid ester vibrates. By measuring the film thickness value before and after 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 rate, the better the hardenability. When used in the manufacture of color filters, it can prevent color mixing and improve uneven development.

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

〈Production of comprehensive exposure imaging film〉

A PET film (Lumirror 75-T60, manufactured by Toray Corporation) was attached to a 2-inch square glass plate to prepare a substrate. On the PET film side of the substrate, a photosensitive resin composition was applied by a spin coating method, and pre-baked at 80 ° C for 2 minutes on a hot plate. After cooling, the entire surface of the dry film formed on the substrate was exposed using an exposure machine (TME-150RSK; manufactured by TOPCON Co., Ltd.) at an exposure of 150mJ / cm ² (based on 365nm) in the atmospheric environment. Light exposure. After light irradiation, it was immersed in an aqueous imaging solution containing 0.12% of non-ionic surfactant and 0.04% of potassium hydroxide at 23 ° C for 50 seconds for development and washed with pure water to obtain a comprehensive exposure imaging film. . When the obtained full-exposure imaging film was measured using a film thickness measuring device (DEKTAK3; manufactured by ULVAC Corporation), it was 2 μm.

<Cross cut test>

With respect to the obtained fully exposed developing film, a tape peeling test (cross cutting test) was performed 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>

The obtained full-exposure imaging film was subjected to pencil hardness measurement using a pencil scratch hardness tester (manufactured by Yasuda Seiki Seisakusho Co., Ltd.) in accordance with JIS-K5400. The load was set to 1,000 g.

<Viscosity Evaluation>

A 5 cm square PET film (Lumirror 75-T60 manufactured by Toray Industries Co., Ltd.) was applied with a photosensitive resin composition using a film applicator (AP75 manufactured by Taiyou Machinery Co., Ltd.), and applied on a hot plate at 80 Pre-bake at 2 ° C for 2 minutes. After leaving to cool, a 5 cm square PET film (Lumirror 75-T60 manufactured by Toray Co., Ltd.) was laminated with the dried film formed on the aforementioned 5 cm square PET film, and the laminated PET film was peeled off. A non-uniform and peeled PET film with no unevenness on the dried film was evaluated as ○ (tackiness was not observed), and a non-uniform and peeled PET film with unevenness on the dried film was evaluated as × (see Get sticky Sex). It can be seen that there is stickiness. When it is used for manufacturing a color filter, color unevenness may occur.

According to the present invention, it is possible to provide a photosensitive resin composition provided with a dry film having a satisfactory low viscosity and a pattern having a satisfactory hardness.

By using the photosensitive resin composition of the present invention, it is possible to obtain a pattern with high resolution that improves uneven 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 containing a binder resin (A), a polymerizable compound (B), a polymerization initiator (C), an extender pigment (D), and a solvent (E); wherein the extender pigment (D) 1 to 30 parts by mass based on 100 parts by mass of the total amount of the resin (A) and the polymerizable compound (B); the solvent (E) contains a solubility of 70 to 99% by mass relative to the solvent (E) The solvent (E1) having a parameter of 8.0 to 9.1 (cal / cm ³ ) ^1/2 and containing a solubility parameter of 1 to 30% by mass relative to the aforementioned solvent (E) is 9.2 to 11.0 (cal / cm ³ ) ^{1 / 2} solvent (E2). The photosensitive resin composition according to item 1 of the scope of patent application, wherein the polymerization initiator (C) is an oxime compound. The photosensitive resin composition according to item 1 or 2 of the scope of patent application, wherein the acid value of the binder resin (A) is 50 to 180 mg-KOH / g. The photosensitive resin composition according to claim 1 or claim 2, wherein the content of the binder resin (A) is relative to the total amount of the binder resin (A) and the polymerizable compound (B). 100 parts by mass, from 30 to 80 parts by mass. The photosensitive resin composition according to item 1 or 2 of the scope of patent application, wherein the extender pigment (D) is silica. The photosensitive resin composition according to item 1 or 2 of the patent application scope further contains a colorant. The photosensitive resin composition as described in Claim 6 of a patent application range whose coloring agent is a coloring agent containing a pigment. The photosensitive resin composition according to item 6 of the scope of patent application, wherein the colorant is a coloring agent containing a dye. A pattern formed by a photosensitive resin composition as described in item 1 or 2 of the scope of patent application. A display device includes a pattern as described in item 9 of the scope of patent application.