KR20110109901A - Photosensitive resin composition - Google Patents

Abstract

It contains resin (A), a photopolymerizable compound (B), a photoinitiator (C), a solvent (D), and a hydroquinone compound, and resin (A) is unsaturated with the monomer which has a C2-C4 cyclic ether, and The photosensitive resin composition which is a copolymer formed by superposing | polymerizing at least 1 sort (s) chosen from the group which consists of carboxylic acid and unsaturated carboxylic anhydride.

Description

Photosensitive resin composition {PHOTOSENSITIVE RESIN COMPOSITION}

 The present invention relates to a photosensitive resin composition.

In recent liquid crystal display panels and the like, a photosensitive resin composition is usually used to form a transparent film or a pattern such as a coating layer on a substrate surface.

As such a photosensitive resin composition, the photosensitive resin composition containing resin, a polymerizable monomer, a photoinitiator, and a solvent is disclosed, for example (patent document 1).

Japanese Laid-Open Patent Publication 2008-181087

Conventionally, the photosensitive resin composition containing the copolymer which polymerizes the monomer which has an oxiranyl group, and at least 1 sort (s) chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride, a polymerizable monomer, a photoinitiator, and a solvent is Although it is known, when forming a pattern using this composition, sensitivity may be inadequate and it was not necessarily satisfactory enough. The subject of this invention is providing the photosensitive resin composition with high sensitivity at the time of pattern formation.

This invention provides the following [1]-[5].

[1] A resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), a solvent (D) and a compound represented by the formula (1) are contained, and the resin (A) is a cyclic ether having 2 to 4 carbon atoms. The photosensitive resin composition which is a copolymer which superposes | polymerizes at least 1 sort (s) chosen from the group which consists of a monomer which has and a unsaturated carboxylic acid and unsaturated carboxylic anhydride.

[Formula 1]

[In formula (1), R ^a -R ^d Are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.]

[2] The photosensitive resin composition as described in said [1] whose content of the compound represented by Formula (1) is 0.0025 mass% or more and 0.095 mass% or less with respect to solid content of the photosensitive resin composition.

[3] The photosensitive resin composition according to the above [1] or [2], wherein the monomer having a cyclic ether having 2 to 4 carbon atoms is a monomer having an oxiranyl group.

[4] A pattern formed using the photosensitive resin composition according to any one of the above [1] to [3].

[5] A display device comprising at least one of the patterns described in [4] above.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail. In addition, in this specification, the compound illustrated as each component can be used individually or in combination unless there is particular notice.

The photosensitive resin composition of this invention contains the compound represented by Formula (1) (Hereinafter, it may be called "compound (1)."). The sensitivity can be improved because the photosensitive resin composition contains a compound (1).

[Formula 2]

[In formula (1), R ^a to R ^d independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.]

Examples of the alkyl group having 1 to 6 carbon atoms in R ^a to R ^d in the formula (1) include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group and pen Tyl group, hexyl group, etc. are mentioned.

Specific examples of the compound (1) include 2,6-dimethylhydroquinone, 2,3-dimethylhydroquinone, trimethylhydroquinone, tetramethylhydroquinone, tert-butylhydroquinone and 6-tert-butyl-2,4- Xylenol, 2,5-di-tert-butylhydroquinone, methylhydroquinone, 2,5-di-tert-amylhydroquinone and the like. Among them, hydroquinone, methylhydroquinone, tert-butylhydroquinone, and 2,5-di-tert-butylhydroquinone are preferable, and in particular, tert-butylhydroquinone and 2,5-di- because sensitivity can be improved. tert-butylhydroquinone is more preferable, and 2,5-di-tert-butylhydroquinone is more preferable.

It is preferable that content of a compound (1) is 0.0025 mass% or more and 0.095 mass% or less in solid content of the photosensitive resin composition, It is more preferable that it is 0.005 mass% or more and 0.09 mass% or less, It is further more preferable that they are 0.015 mass% or more and 0.07 mass% or less. desirable. Here, solid content of the photosensitive resin composition means the quantity remove | excluding the solvent (D) from the component in a composition. When content of a compound (1) exists in said range, since a sensitivity can be improved, it is preferable. On the other hand, when there is too much content of compound (1), there exists a possibility that adhesiveness with respect to the base of the pattern obtained from the photosensitive resin composition may fall.

The photosensitive resin composition of this invention contains resin (A).

Resin (A) is a copolymer obtained by superposing | polymerizing the monomer which has a C2-C4 cyclic ether, and at least 1 sort (s) chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride. It is especially preferable that the monomer which has a C2-C4 cyclic ether is a monomer which has an oxiranyl group. If resin (A) is said resin, it can have reliability, such as developability and the heat resistance of the hardening pattern obtained, chemical-resistance, etc.

As resin (A), it selects from the group which consists of a monomer (a) (Hereinafter, it may be called "(a)") which has a C2-C4 cyclic ether, and unsaturated carboxylic acid and unsaturated carboxylic anhydride. At least one copolymer of (b) (hereinafter may be referred to as "(b)"), and monomers (c) copolymerizable with (a) and (b) and (a) (wherein (a) And (b) are different) (hereinafter, may be referred to as "(c)").

(a) is cyclic, for example, with a cyclic ether having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring (oxolane ring)) The polymerizable compound which has a polymerizable group other than ether is said. Especially, it is preferable that (a) is a monomer which has a C2-C4 cyclic ether and ethylenic carbon-carbon double bond, and has a C2-C4 cyclic ether and a (meth) acryloyloxy group Is more preferable. Here, "(meth) acryloyl" shows at least 1 sort (s) chosen from the group which consists of acryloyl and methacryloyl in this specification. Hereinafter, notation, such as "(meth) acrylate", has the same meaning.

As (a), the monomer (a1) which has an oxiranyl group (henceforth may be called "(a1)"), and the monomer (a2) which has an oxetanyl group (henceforth "(a2)") The monomer (a3) (Hereinafter, it may be called "(a3)") which has a tetrahydrofuryl group, etc. are mentioned. Especially, the monomer (a1) which has an oxiranyl group is preferable, and the monomer (a1-2) (Hereinafter, it may be called "(a1-2)") which has a structure which epoxidized cyclic olefin is more preferable. Do.

The monomer (a1) having an oxiranyl group refers to a polymerizable compound having a polymerizable group other than an oxiranyl group and an oxiranyl group. As (a1), the monomer (a1-1) which has a structure which epoxidized the chain | strand olefin, for example (hereinafter may be called "(a1-1)"), and the structure which epoxidized the cyclic olefin, for example The monomer (a1-2) which has a is mentioned. Especially, as (a1), it is preferable that it is a monomer which has an oxiranyl group and ethylenic carbon-carbon double bond, and the monomer which has an oxiranyl group and a (meth) acryloyloxy group is more preferable.

Specific examples of (a1-1) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, and glycidyl vinyl ether. -Vinylbenzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, α-methyl-o-vinyl benzyl glycidyl ether, α-methyl-m-vinyl benzyl glycidyl Ether, α-methyl-p-vinylbenzylglycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (gly Cydyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5-tris (glycidyloxymethyl Styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6-tris (glycidyloxymethyl) styrene Etc. can be mentioned.

Examples of (a1-2) include vinylcyclohexene monooxide and 1,2-epoxy-4-vinylcyclohexane (for example, ceoxide 2000; manufactured by Daicel Chemical Industry Co., Ltd.), 3,4-epoxycyclohexyl Methyl acrylate (for example, cycloma A400; manufactured by Daicel Chemical Industry Co., Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (for example, cycloma M100; manufactured by Daicel Chemical Industry Co., Ltd.) ), The compound represented by the following formula (I), the compound represented by formula (II), etc. are mentioned.

(3)

[In Formula (I) and Formula (II), R <^1> and R <^2> represents a C1-C4 alkyl group which may have a hydrogen atom or a hydroxyl group independently of each other.

X ¹ and X ² Independently of each other, * represents a single bond, * -R ^3- , * -R ³ -O-, * -R ³ -S-, * -R ³ -NH-.

R ³ Represents alkanediyl having 1 to 6 carbon atoms.

* Represents the number of bonds with O]

As a C1-C4 alkyl group in R <^1> and R <^2> , a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert- butyl group, etc. are mentioned.

As a C1-C4 alkyl group (hydroxyalkyl group) which may have the hydroxyl group in R <^1> and R <^2> , A hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy-1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3- Hydroxybutyl group, 4-hydroxybutyl group, etc. are mentioned.

Especially, as R <^1> and R <^2> , a hydrogen atom, a methyl group, a hydroxymethyl group, 1-hydroxyethyl group, and 2-hydroxyethyl group are preferable, and a hydrogen atom and a methyl group are more preferable.

Examples of the alkanediyl group having 1 to 6 carbon atoms for X ¹ and X ² include a methylene group, an ethylene group, a 1,2-propanediyl group, a 1,3-propanediyl group, a 1,4-butanediyl group, 1 , 5-pentanediyl group, 1,6-hexanediyl group, and the like.

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

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

[Formula 4]

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

[Chemical Formula 5]

The compound represented by Formula (I) and the compound represented by Formula (II) can be used independently, respectively. Moreover, they can be mixed in arbitrary ratios. In the case of mixing, the mixing ratio is in a molar ratio, preferably in the formula (I): formula (II), 5:95 to 95: 5, more preferably 10:90 to 90:10, particularly preferably 20 : 80-80: 20.

The monomer (a2) having an oxetanyl group refers to a polymerizable compound having a polymerizable group other than an oxetanyl group and an oxetanyl group. Especially, as (a2), it is preferable that it is a monomer which has an oxetanyl group and ethylenic carbon-carbon double bond, and the monomer which has an oxetanyl group and a (meth) acryloyloxy group is more preferable. Specific examples of (a2) include 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, and 3-ethyl-3-methacryloyloxymethyl jade. Cetane, 3-ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3 -Methacryloyloxyethyl oxetane, 3-ethyl-3-acryloyloxyethyl oxetane, etc. are mentioned.

The monomer (a3) having a tetrahydrofuryl group refers to a polymerizable compound having a polymerizable group other than a tetrahydrofuryl group and a tetrahydrofuryl group. Especially, as (a3), it is preferable that it is a monomer which has a tetrahydrofuryl group and ethylenic carbon-carbon double bond, and the monomer which has a tetrahydrofuryl group and a (meth) acryloyloxy group is more preferable. Specific examples of (a3) include tetrahydrofurfuryl acrylate (for example, biscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

Specific examples of (b) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m- and p-vinylbenzoic acid;

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexenedicarboxylic acid;

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

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

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

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

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

As (c), For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert- butyl (meth) acrylate, 2 Ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2 -Methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.O ^2,6 ] decane-8-yl (meth) acrylate (in the art, it is known as dicyclopentanyl (meth) acrylate as a common name) ), Dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth ) Acrylate, naphthyl (meth) acrylate, benzyl (meth) acrylate (Meth) acrylic acid esters, such as whit;

Hydroxy group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

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

Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxybi Cyclo [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 (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (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-methyl Bicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] Hept-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxy Cycarbonyl Bicyclo [ 2.2.1] hept-2-ene, 5,6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl) ratio Bicyclo unsaturated compounds, such as cyclo [2.2.1] hept-2-ene;

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

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

Among these, styrene, N-phenylmaleimide, N-cyclohexyl maleimide, N-benzyl maleimide, bicyclo [2.2.1] hept-2-ene, etc. are preferable from a viewpoint of copolymerization reactivity and heat resistance.

In the case of the copolymer which consists only of the structural unit derived from (a) and (b), the ratio of the structural unit derived from each is in the following ranges with respect to the total mole number of all the structural units which comprise the said copolymer. It is desirable to have.

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

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

When the ratio of the structural unit of the copolymer of (a) and (b) exists in said range, there exists a tendency for storage stability, developability, and solvent resistance of a hardening pattern to become favorable, and it is preferable.

The copolymer of (a) and (b) is, for example, the method described in the document "Experimental method of polymer synthesis" (Otsu Takayuki Kogyo Co., Ltd., First Edition March 1, 1972) It can manufacture with reference to the cited document described in this document.

Specifically, the method of stirring, heating, and keeping warm in deoxygenation is illustrated by inject | pouring predetermined amount of (a) and (b), a polymerization initiator, a solvent, etc. in a reaction container, and replacing oxygen with nitrogen. In addition, the polymerization initiator, the solvent, etc. which are used here are not specifically limited, What is normally used in the said field | area can be used. For example, as a polymerization initiator, an azo compound (2,2'- azobisisobutyronitrile, 2,2'- azobis (2, 4- dimethylvaleronitrile), etc.), an organic peroxide (benzoyl peroxide, etc.) ). Moreover, what is necessary is just to melt | dissolve each monomer as a solvent, The solvent etc. which are mentioned later as a solvent of the photosensitive resin composition of this invention can be used.

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

In the case of the copolymer including the structural unit derived from (c) in addition to the structural units derived from (a) and (b), the proportion of the structural units derived from each constitutes the above copolymer. It is preferable to exist in the following ranges with respect to the total number-of-moles of all the structural units.

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

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

structural unit derived from (c); 1 to 65 mol% (more preferably 1 to 60 mol%)

When the ratio of the structural unit of the copolymer of (a) and (b) and (c) is in the above range, the storage stability, developability, solvent resistance of the curing pattern, heat resistance and mechanical strength tend to be good, which is preferable. .

The copolymer of (a) and (b) and (c) can be manufactured by the method similar to the method described as a manufacturing method of the copolymer of (a) and (b), for example.

Specifically, a method of stirring, heating and warming under deoxygenation is given by injecting predetermined amounts of (a), (b) and (c), a polymerization initiator and a solvent into a reaction vessel, and replacing oxygen with nitrogen. Can be. The obtained copolymer may use the solution after reaction as it is, may use the concentrated or diluted solution, and may use what was taken out as solid (powder) by methods, such as reprecipitation.

The weight average molecular weight of polystyrene conversion of resin (A) becomes like this. Preferably it is 3,000-100,000, More preferably, it is 5,000-50,000. When the weight average molecular weight of resin (A) exists in the said range, applicability | paintability tends to become favorable, film | membrane decrease does not generate | occur | produce well at the time of image development, and peelability of a non-exposed part tends to be favorable at the time of image development.

The molecular weight distribution [weight average molecular weight (kPa) / number average molecular weight (Mn)] of the resin (A) is preferably 1.1 to 6.0, more preferably 1.2 to 4.0. When molecular weight distribution exists in the said range, it exists in the tendency which is excellent in developability.

The acid value of resin (A) becomes like this. Preferably it is 20-150, More preferably, it is 40-135, Especially preferably, it is 50-135. The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (A), and can be obtained by titration using an aqueous potassium hydroxide solution.

Content of resin (A) is 5-95 mass% with respect to the total amount of resin (A) and a photopolymerizable compound (B), More preferably, it is 20-80 mass%, Especially preferably, it is 40- 60 mass%. When content of resin (A) exists in said range, there exists a tendency for developability, adhesiveness, solvent resistance of a hardening pattern, and a mechanical characteristic to become favorable.

The photosensitive resin composition of this invention may contain resin (AX) other than resin (A). As resin (AX), resin obtained by making (a) react with the copolymer of (b) and (c), and the copolymer of (b) and (c), etc. are mentioned, for example. When the photosensitive resin composition contains resin (AX) in combination with resin (A), it is preferable that content of resin (AX) is 0-50 mass% with respect to resin whole quantity, and it is more preferable that it is 0-30 mass% desirable.

The photosensitive resin composition of this invention contains a photopolymerizable compound (B). A photopolymerizable compound (B) is a compound which can superpose | polymerize with the active radical, the acid, etc. which generate | occur | produced from the polymerization initiator (C), For example, the compound etc. which have a polymerizable carbon-carbon unsaturated bond are mentioned, Preferably it is (Meth) acrylic acid ester compound is mentioned.

As a photopolymerizable compound (B) which has one polymerizable carbon-carbon unsaturated bond, the compound illustrated as said (a), (b) and (c) is mentioned, Especially, (meth) acrylic acid ester is preferable. Do.

As a photopolymerizable compound (B) which has two polymerizable carbon-carbon unsaturated bonds, 1, 3- butanediol di (meth) acrylate, 1, 3- butanediol (meth) acrylate, and 1, 6- hexanediol di ( Meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth ) Acrylate, polyethyleneglycol diacrylate, bis (acryloyloxyethyl) ether of bisphenol A, ethoxylated bisphenol A di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, ethoxylated neo Pentyl glycol di (meth) acrylate, 3-methylpentanediol di (meth) acrylate, and the like.

Examples of the polymerizable compound (B) having three or more polymerizable carbon-carbon unsaturated bonds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and tris (2-hydroxyethyl) isocyte. Anurate tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta ( Meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tri Pentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, pentaerythritol tri (meth) acrylate and acid anhydride Reactant, reactant of dipentaerythritol penta (meth) acrylate and acid anhydride, tripentaerythritolhepta (meth) acrylate and acid anhydride caprolactone modified trimethylolpropanetri (meth) acrylate, caprolactone modified pentaerythritol Tri (meth) acrylate, caprolactone modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol penta (Meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, caprolactone modified tripentaerythritol tetra (meth) acrylate, caprolactone modified tripentaerythritol penta (meth) acrylate, caprolactone Modified tripentaerythritol hexa (meth) acrylate, caprolactone modified tripentaerythritol Reactant of other (meth) acrylate, caprolactone modified tripentaerythritol octa (meth) acrylate, caprolactone modified pentaerythritol tri (meth) acrylate, and acid anhydride, caprolactone modified dipentaerythritol penta (meth) The reaction product of an acrylate and an acid anhydride, a caprolactone modified tripentaerythritol hepta (meth) acrylate, an acid anhydride, etc. are mentioned. Especially, a trifunctional or more than trifunctional monomer is preferable and dipentaerythritol hexa (meth) acrylate is more preferable.

Content of a photopolymerizable compound (B) becomes like this. Preferably it is 5-95 mass%, More preferably, it is 20-80 mass% with respect to the total amount of resin (A) and a photopolymerizable compound (B). When content of a polymeric compound (B) exists in the said range, there exists a tendency for the intensity | strength, smoothness, reliability, and mechanical strength of a sensitivity and a hardening pattern to become favorable.

The photosensitive resin composition of this invention contains a photoinitiator (C). As a photoinitiator (C), if it is a compound which starts superposition | polymerization by action of light, it will not specifically limit, A well-known photoinitiator can be used.

As a photoinitiator (C), a biimidazole compound, an acetophenone compound, a triazine compound, an acylphosphine oxide compound, an oxime compound is mentioned, for example. Moreover, you may use the optical and / or thermal cationic polymerization initiator (for example, what consists of onium cation and an anion derived from Lewis acid) of Unexamined-Japanese-Patent No. 2008-181087. Especially, it is preferable that it is at least 1 sort (s) chosen from the group which consists of a biimidazole compound, an acetophenone compound, and an oxime compound, and it is more preferable that it is 2 or more types chosen from the group which consists of a biimidazole compound, an acetophenone compound, and an oxime compound. Do. If it is these polymerization initiators, there exists a tendency which becomes especially high sensitivity and is preferable.

As said biimidazole compound, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetraphenylbiimidazole, 2,2'-bis (2,3-dichloro Phenyl) -4,4 ', 5,5'-tetraphenylbiimidazole (see, eg, JP-A-6-75372, JP-A-6-75373, etc.), 2,2' -Bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra ( Alkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chloro Phenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole (see, for example, Japanese Patent Application Laid-Open No. 48-38403, Japanese Patent Application Laid-open No. 62-174204, etc.), 4 The imidazole compound (For example, Unexamined-Japanese-Patent No. 7-10913 etc.) etc. which the phenyl group of the 4'5,5'-position are substituted by the carboalkoxy group are mentioned. Preferably 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole.

As said acetophenone type compound, diethoxy acetophenone, 2-hydroxy-2-methyl-1- phenyl propane- 1-one, benzyl dimethyl ketal, 2-hydroxy-1- [4- (2-hydroxy) Hydroxyethoxy) phenyl] -2-methylpropane-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2 -Methyl-propane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethyl Amino-1- (4-morpholinophenyl) butan-1-one, 2- (2-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (3- Methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2 -(2-ethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (2-propylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) Butanone, 2- (2-butylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) moiety Non, 2- (2,3-dimethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (2,4-dimethylbenzyl) -2-dimethylamino-1- ( 4-morpholinophenyl) butanone, 2- (2-chlorobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (2-bromobenzyl) -2-dimethyl Amino-1- (4-morpholinophenyl) butanone, 2- (3-chlorobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (4-chlorobenzyl) 2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (3-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- ( 4-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (2-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) Butanone, 2- (3-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (4-methoxybenzyl) -2-dimethylamino-1- (4 -Morpholinophenyl) butanone, 2- (2-methyl-4-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (2-meth Methyl-4-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (2-bromo-4-methoxybenzyl) -2-dimethylamino-1- ( And oligomers of 4-morpholinophenyl) butanone and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one.

As said triazine type compound, 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1, 3, 5- triazine, 2, 4-bis (trichloromethyl) -6 -(4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (Trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2- Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl ) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine, etc. are mentioned.

2,4,6-trimethylbenzoyldiphenylphosphine oxide etc. are mentioned as said acylphosphine oxide type initiator.

Examples of the oxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-ethoxycarbonyloxy-1-phenylpropan-1-one-2 -Imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H -Carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-dioxacyclopentanyl Methyloxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine and the like. You may use commercial items, such as Irgacure OXE-01, OXE-02 (made by Chiba Japan Co., Ltd.), and N-1919 (made by ADEKA Corporation).

Moreover, as a polymerization initiator (C), Benzoin type compounds, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; Benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone Benzophenone compounds such as 2,4,6-trimethylbenzophenone; Quinone compounds such as 9,10-phenanthrene quinone, 2-ethylanthraquinone and camphor quinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compound, etc. are mentioned. It is preferable to use these in combination with the polymerization start adjuvant (C1) mentioned later.

Moreover, you may use the photoinitiator described in Unexamined-Japanese-Patent No. 2002-544205 as a photoinitiator which has group which can cause chain transfer.

As a photoinitiator which has group which can cause said chain transfer, the photoinitiator of following formula (a)-(f) is mentioned, for example.

[Formula 6]

The photoinitiator which has group which can cause said chain transfer can be used also as a component (c) which comprises resin (A).

Moreover, it is preferable to use a photoinitiator adjuvant (C1) with the polymerization initiator (C) mentioned above. As a photopolymerization start adjuvant (C1) used for the photosensitive resin composition of this invention, a thioxanthone compound is preferable. When a thioxanthone compound is used as a photoinitiator adjuvant (C1), there exists a tendency for a sensitivity to become high.

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

As a polymerization start adjuvant (C1), the compound represented by Formula (III) can also be used.

[Formula 7]

[In the formula (III), the dotted line represented by W ¹ represents an aromatic ring having 6 to 12 carbon atoms which may be substituted with a halogen atom.

Y ¹ Represents -O- or -S-.

R ⁴ Represents a C1-C6 monovalent saturated hydrocarbon group.

R ⁵ Represents a saturated hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom or an aryl group having 6 to 12 carbon atoms which may be substituted with a halogen atom]

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, etc. are mentioned. Examples of the aromatic ring having 6 to 12 carbon atoms include a benzene ring and a naphthalene ring.

As a C6-C12 aromatic ring which may be substituted by the halogen atom, For example, a benzene ring, a methylbenzene ring, a dimethylbenzene ring, an ethylbenzene ring, a propylbenzene ring, a butylbenzene ring, a pentylbenzene ring, a hexylbenzene ring, Cyclohexylbenzene ring, chlorobenzene ring, dichlorobenzene ring, bromobenzene ring, dibromobenzene ring, phenylbenzene ring, chlorophenylbenzene ring, bromophenylbenzene ring, naphthalene ring, chloronaphthalene ring, bromonaphthalene ring Etc. can be mentioned.

As a C1-C6 saturated hydrocarbon group, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, 1-methylpropyl group, 2-methylpropyl group, tert- butyl group, n- Pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, n-hexyl group, Cyclohexyl group etc. are mentioned.

As a C1-C12 saturated hydrocarbon group which may be substituted by the halogen atom, for example, in addition to the said C1-C6 saturated hydrocarbon group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, 1 -Chlorobutyl group, 2-chlorobutyl group, 3-chlorobutyl group, etc. are mentioned.

Examples of the aryl group having 6 to 12 carbon atoms that may be substituted with a halogen atom include phenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, dibromophenyl group, chlorobromophenyl group, biphenyl group, chlorobiphenyl group, dichlorobiphenyl group and bromo. A phenyl group, a dibromophenyl group, a naphthyl group, a chloro naphthyl group, a dichloro naphthyl group, a bromonaphthyl group, a dibromonaphthyl group, etc. are mentioned.

Specifically as a compound represented by Formula (III),

2- [2-oxo-2- (2-phenyl) ethylidene] -3-methylnaphtho [2,1-d] thiazoline, 2- [2-oxo-2- (2-phenyl) ethylidene] 3-methylnaphtho [1,2-d] thiazoline, 2- [2-oxo-2- (2-phenyl) ethylidene] -3-methylnaphtho [2,3-d] thiazoline, 2 -[2-oxo-2- (2-naphthyl) ethylidene] -3-methylbenzothiazoline, 2- [2-oxo-2- (1-naphthyl) ethylidene] -3-methylbenzothiazoline , 2- [2-oxo-2- (2-naphthyl) ethylidene] -3-methyl-5-phenylbenzothiazoline, 2- [2-oxo-2- (1-naphthyl) ethylidene]- 3-methyl-5-phenylbenzothiazoline, 2- [2-oxo-2- (2-naphthyl) ethylidene] -3-methyl-5-fluorobenzothiazoline, 2- [2-oxo-2 -(1-naphthyl) ethylidene] -3-methyl-5-fluorobenzothiazoline, 2- [2-oxo-2- (2-naphthyl) ethylidene] -3-methyl-5-chlorobenzo Thiazolin, 2- [2-oxo-2- (1-naphthyl) ethylidene] -3-methyl-5-chlorobenzothiazoline, 2- [2-oxo-2- (2-naphthyl) ethylidene ] -3-methyl-5-bromobenzothiazoline, 2- [2-oxo-2- (1-naphthyl) ethylidene] -3-methyl-5-bromobenzo Thiazolin, 2- [2-oxo-2- (4-phenylphenyl) ethylidene] -3-methylbenzothiazoline, 2- [2-oxo-2- (4-phenylphenyl) ethylidene] -3- Methyl-5-phenylbenzothiazoline, 2- [2-oxo-2- (2-naphthyl) ethylidene] -3-methylnaphtho [2,1-d] thiazoline, 2- [2-oxo- 2- (2-naphthyl) ethylidene] -3-methylnaphtho [1,2-d] thiazoline, 2- [2-oxo-2- (4-phenylphenyl) ethylidene] -3-methylnaph To [2,1-d] thiazoline, 2- [2-oxo-2- (4-phenylphenyl) ethylidene] -3-methylnaphtho [1,2-d] thiazoline, 2- [2- Oxo-2- (4-fluorophenyl) ethylidene] -3-methylnaphtho [2,1-d] thiazoline, 2- [2-oxo-2- (4-fluorophenyl) ethylidene]- 3-methylnaphtho [1,2-d] thiazoline, 2- [2-oxo-2- (2-phenyl) ethylidene] -3-methylnaphtho [2,1-d] oxazoline, 2- [2-oxo-2- (2-phenyl) ethylidene] -3-methylnaphtho [1,2-d] oxazoline, 2- [2-oxo-2- (2-phenyl) ethylidene] -3 -Methylnaphtho [2,3-d] oxazoline, 2- [2-oxo-2- (2-naphthyl) ethylidene] -3-methylbenzooxazoline, 2- [2-oxo-2- ( 1-naphthyl) ethyl ] -3-methylbenzooxazoline, 2- [2-oxo-2- (2-naphthyl) ethylidene] -3-methyl-5-phenylbenzooxazoline, 2- [2-oxo-2- (1 -Naphthyl) ethylidene] -3-methyl-5-phenylbenzooxazoline, 2- [2-oxo-2- (2-naphthyl) ethylidene] -3-methyl-5-fluorobenzooxazoline, 2- [2-oxo-2- (1-naphthyl) ethylidene] -3-methyl-5-fluorobenzooxazoline, 2- [2-oxo-2- (2-naphthyl) ethylidene]- 3-methyl-5-chlorobenzooxazoline, 2- [2-oxo-2- (1-naphthyl) ethylidene] -3-methyl-5-chlorobenzooxazoline, 2- [2-oxo-2- (2-naphthyl) ethylidene] -3-methyl-5-bromobenzooxazoline, 2- [2-oxo-2- (1-naphthyl) ethylidene] -3-methyl-5-bromobenzo Oxazoline, 2- [2-oxo-2- (4-phenylphenyl) ethylidene] -3-methylbenzooxazoline, 2- [2-oxo-2- (4-phenylphenyl) ethylidene] -3- Methyl-5-phenylbenzooxazoline, 2- [2-oxo-2- (1-naphthyl) ethylidene] -3-methylnaphtho [2,1-d] oxazoline, 2- [2-oxo- 2- (1-naphthyl) ethylidene] -3-methylnaphtho [1,2-d] oxazoline, 2- [2-jade -2- (4-phenylphenyl) ethylidene] -3-methylnaphtho [2,1-d] oxazoline, 2- [2-oxo-2- (4-phenylphenyl) ethylidene] -3-methyl Naphtho [1,2-d] oxazoline, 2- [2-oxo-2- (4-fluorophenyl) ethylidene] -3-methylnaphtho [2,1-d] oxazoline, 2- [ 2-oxo-2- (4-fluorophenyl) ethylidene] -3-methylnaphtho [1,2-d] oxazoline etc. are mentioned.

Moreover, as a polymerization start adjuvant (C1), you may use the compound represented by Formula (IV) or Formula (V).

[Formula 8]

Of the formula (Ⅳ) and formula (Ⅴ), ring W ^2, W ³ and W ⁴ ring Represents a C6-C12 aromatic ring or C2-C10 heterocyclic ring which may be substituted independently with each other. Y ² -Y ⁵ Are independently from each other, -O- or -S-. R ⁶ To R ⁹ Represents a C1-C12 monovalent saturated hydrocarbon group or a C6-C12 aryl group, and the hydrogen atom contained in this saturated hydrocarbon group and this aryl group is substituted by a halogen atom, a hydroxyl group, or a C1-C6 alkoxy group. You may be.

As an aromatic ring, the aromatic ring similar to what was illustrated by Formula (III) is mentioned, The hydrogen atom contained in the aromatic ring may be substituted by the halogen atom illustrated above.

As a hetero ring which may be substituted by the halogen atom, a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, a pyran ring, etc. are mentioned.

Examples of the monovalent hydroxy group-substituted saturated hydrocarbon group include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group and a hydroxybutyl group.

Examples of the hydroxy group-substituted aryl group include a hydroxyphenyl group and a hydroxy naphthyl group.

Examples of the monovalent alkoxy group substituted saturated hydrocarbon group include methoxymethyl group, methoxyethyl group, methoxypropyl group, methoxybutyl group, butoxymethyl group, ethoxyethyl group, ethoxypropyl group, propoxybutyl group and the like. .

As an alkoxy group substituted aryl group, a methoxyphenyl group, an ethoxy naphthyl group, etc. are mentioned.

As a compound represented by Formula (IV) and Formula (V), specifically,

Dialkoxy naphthalenes such as dimethoxynaphthalene, diethoxynaphthalene, dipropoxynaphthalene, diisopropoxynaphthalene and dibutoxynaphthalene;

9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, dipropoxycanthracene, diisopropoxycanthracene , Dibutoxy anthracene, dipentyloxy anthracene, dihexyloxy anthracene, methoxy ethoxy anthracene, methoxy propoxy thracene, methoxy isopropoxy canthracene, methoxy butoxy anthracene, ethoxy propoxy thracene, ethoxy isopro Dialkoxy anthracenes such as oxycanthracene, ethoxy butoxy anthracene, propoxy isopropoxy anthracene, propoxy butoxy anthracene and isopropoxy butoxy anthracene;

Dialkoxy naphthacenes such as dimethoxynaphthacene, diethoxy naphthacene, dipropoxynaphthacene, diisopropoxy naphthacene and dibutoxynaphthacene; Etc. can be mentioned.

Moreover, an amine compound, a carboxylic acid compound, etc. are mentioned as a photoinitiation start adjuvant (C1).

Examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 4-dimethylaminobenzoic acid. 2-ethylhexyl, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (collectively; Michler's ketone), 4,4'-bis (diethylamino Aromatic amine compounds, such as) benzophenone, are mentioned.

Examples of the carboxylic acid compound include phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, And aromatic heteroacetic acids such as chlorophenylsulfanyl acetic acid, dichlorophenylsulfanyl acetic acid, N-phenylglycine, phenoxy acetic acid, naphthylthioacetic acid, N-naphthylglycine and naphthoxy acetic acid.

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

When content of a photoinitiator (C) exists in the said range, the photosensitive resin composition will become high sensitivity, the intensity | strength of the coating film and pattern formed using this photosensitive resin composition, and the smoothness in the surface of a coating film or a pattern will be It is preferable because it tends to be good.

The amount of the photopolymerization initiation assistant (C1) to be used is preferably 0.01 to 50 mass%, more preferably 0.1 to 40 mass%, based on the total amount of the resin (A) and the polymerizable compound (B).

When the quantity of a polymerization start adjuvant (C1) exists in the said range, since the sensitivity of the photosensitive resin composition obtained becomes higher and the productivity of the patterned substrate formed using this photosensitive resin composition tends to improve, it is preferable.

Moreover, the photosensitive resin composition of this invention may contain the polyfunctional thiol compound (T) further. A polyfunctional thiol compound (T) means the compound which has a 2 or more sulfanyl group in a molecule | numerator. In particular, when the compound which has 2 or more sulfanyl groups couple | bonded with the carbon atom derived from an aliphatic hydrocarbon group is used, since the sensitivity of the photosensitive resin composition becomes high, it is preferable.

Specific examples of the polyfunctional thiol compound (T) include hexanedithiol, decandithiol, 1,4-bis (methylsulfanyl) benzene, butanediolbis (3-sulfanylpropionate) and butanediolbis (3-sulfur). Panyl acetate), ethylene glycol bis (3-sulfanyl acetate), trimethylol propane tris (3-sulfanyl acetate), butanediol bis (3-sulfanyl propionate), trimethylol propane tris (3-sulfanyl propio) Nate), trimethylol propane tris (3-sulfanyl acetate), pentaerythritol tetrakis (3-sulfanyl propionate), pentaerythritol tetrakis (3-sulfanyl acetate), trishydroxyethyl tris (3 Sulfanyl propionate), pentaerythritol tetrakis (3-sulfanylbutylate), 1,4-bis (3-sulfanylbutyloxy) butane and the like.

Content of a polyfunctional thiol compound (T) is a weight fraction with respect to a photoinitiator (C), Preferably it is 0.5-20 mass%, More preferably, it is 1-15 mass%. When content of a polyfunctional thiol compound (T) exists in this range, since a sensitivity will become high and developability tends to become favorable, it is preferable.

The photosensitive resin composition of this invention contains a solvent (D). It does not specifically limit as a solvent (D), The solvent normally used in the said field | area can be used. For example, ester solvent (solvent containing -COO-), ether solvent other than ester solvent (solvent containing -O-), ether ester solvent (solvent containing -COO- and -O-), ester Ketone solvents other than solvents (solvents containing -CO-), alcohol solvents, aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide and the like can be selected and used.

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

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

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

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

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

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

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

You may use these solvents individually or in combination of 2 or more types.

The organic solvent whose boiling point in 1 atm is 120 degreeC or more and 180 degrees C or less is preferable from a viewpoint of applicability | paintability and dryness among the said solvents. Especially, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol methyl ethyl ether, 3-methoxy butyl acetate, 3-methoxy-1- butanol, etc. are preferable.

Content of a solvent (D) becomes like this. Preferably it is 60-95 mass% with respect to 100 mass% of photosensitive resin compositions, More preferably, it is 70-90 mass%. In other words, solid content of the photosensitive resin composition becomes like this. Preferably it is 5-40 mass%, More preferably, it is 10-30 mass%. Here, solid content means the quantity remove | excluding the solvent (D) from the photosensitive resin composition. When content of a solvent (D) exists in said range, there exists a tendency for the flatness at the time of application | coating to become favorable.

It is preferable that the photosensitive resin composition of this invention contains surfactant (E). As surfactant, silicone type surfactant, a fluorochemical surfactant, silicone type surfactant which has a fluorine atom, etc. are mentioned, for example.

As silicone type surfactant, surfactant which has a siloxane bond is mentioned. Specifically, Toray silicone DC3PA, copper SH7PA, copper DC11PA, copper SH21PA, copper SH28PA, copper SH29PA, copper SH30PA, polyether modified silicone oil SH8400 (trade name: manufactured by Toray Dow Corning), KP321, KP322 , KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (Momental Performance Materials Japan) Joint company manufacture) etc. are mentioned.

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

As silicone type surfactant which has a fluorine atom, surfactant which has a siloxane bond and a fluorocarbon chain | strand is mentioned. Specifically, Mega Fox R08, BL20, F475, F477, F443 (manufactured by DIC Corporation), and the like can be given. Preferably, megafax (trademark) F475 is mentioned.

Surfactant (E) is 0.001 mass% or more and 0.2 mass% or less with respect to 100 mass% of photosensitive resin compositions, Preferably they are 0.002 mass% or more and 0.1 mass% or less, More preferably, they are 0.01 mass% or more and 0.05 mass% or less. . By containing surfactant in this range, flatness of a coating film can be made favorable.

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

Examples of the filler include glass, silica, alumina and the like.

As another high molecular compound, For example, thermoplastic resins, such as curable resin polyvinyl alcohol, polyacrylic acid, polyethyleneglycol monoalkyl ether, polyfluoroalkylacrylate, polyester, polyurethane, such as an epoxy resin and a maleimide resin, are mentioned, for example. Can be mentioned.

Examples of the adhesion promoter include vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane , 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3 -Sulfanyl propyl trimethoxysilane, etc. are mentioned.

As antioxidant, it is, for example, 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenylacrylate, 2- [1- (2-hydroxy -3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenylacrylate, 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) prop Foxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [1,3,2] dioxaphosphine, 3,9-bis [2- {3- (3-tert -Butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 2,2'-methylenebis ( 6-tert-butyl-4-methylphenol), 4,4'-butylidenebis (6-tert-butyl-3-methylphenol), 4,4'-thiobis (2-tert-butyl-5- Methylphenol), 2,2'-thiobis (6-tert-butyl-4-methylphenol), 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1 , 3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 3,3 ', 3' ', 5,5', 5 ''-hexa-tert-butyl-a, a ', a' '-(mesitylene-2,4,6-triyl) tri-p-cresol, pentaerythritol tetrakis [3- (3,5-di-tert- Butyl-4-hydroxyphenyl) propionate], it is different from 2,6-di -tert- butyl-4 compound represented by the phenol-based antioxidant (In this formula (1), such as methyl phenol); Bis (dodecyloxycarbonylethyl) sulfane, bis (tetradecyloxycarbonylethyl) sulfane, bis (octadecyloxycarbonylethyl) sulfane, pentaerythritoltetrakis (3-dodecylsulfanylpropionate) Sulfur type antioxidants, such as these, etc. are mentioned.

As a ultraviolet absorber, it is 2- (2-hydroxy-5-tert- butylphenyl) -2H-benzotriazole, octyl-3- [3-tert- butyl- 4-hydroxy-5- (5, for example). -Chloro-2H-benzotriazol-2-yl) phenyl] propionate, 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4, 6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [4-[(2-hydroxy-3- (2'-ethyl) hexyl) oxy] -2-hydroxy Phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-butyloxyphenyl) -6- (2,4 -Bis-butyloxyphenyl) -1,3,5-triazine, 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl ) -1,3,5-triazine, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazole -2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2- (3-tert-butyl-2-hydroxy- 5-methylphenyl) -5-chlorobenzotriazole, alkoxybenzophenone, etc. are mentioned There.

As an optical stabilizer, for example, a polymer composed of succinic acid and (4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yl) ethanol, N, N ', N' ', N' '' -Tetrakis (4,6-bis (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) triazin-2-yl) -4,7 -Diazadecane-1,10-diamine, decandioic acid, bis (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester, 1,1- Reactant of dimethylethyl hydroperoxide, bis (1,2,2,6,6-pentamethyl-4-piperidinyl)-[[3,5-bis (1,1-dimethylethyl) -4-hydroxy Phenyl] methyl] butyl malonate, 2,4-bis [N-butyl-N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) amino] -6 -(2-hydroxyethylamine) -1,3,5-triazine, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, methyl (1,2,2 , 6,6-pentamethyl-4-piperidinyl) sebacate and the like.

As a chain transfer agent, dodecane thiol, 2, 4- diphenyl-4-methyl-1- pentene, etc. are mentioned, for example.

The photosensitive resin composition of this invention can be formed as a coating film, for example by apply | coating on the board | substrate, such as glass, a metal, a plastic, or the board | substrate which arrange | positioned a color filter, various insulating films, an electrically conductive film, a drive circuit, etc., for example. It is preferable that a coating film is what dried and hardened | cured. Moreover, the obtained coating film can also be patterned in a desired shape and used as a pattern. In addition, you may form and use these coating films or patterns as a part of component parts, such as a display apparatus.

First, the photosensitive resin composition of this invention is apply | coated on a base material.

Application | coating can be performed using various coating apparatuses, such as a spin coater, a slit & spin coater, a slit coater, an inkjet, a roll coater, and a dip coater. Among them, it is preferable to apply coating by the spin coating method, that is, coating using a slit & spin coater, spin coater, or the like, in the solubility, drying prevention, foreign matter generation prevention, and the like.

Subsequently, it is preferable to dry or prebake to remove volatile components, such as a solvent. Thereby, a smooth uncured coating film can be obtained.

The film thickness of the coating film in this case is not specifically limited, It can adjust suitably according to the material to be used, a use, etc., for example, about 1-6 micrometers is illustrated.

Further, light, for example, mercury lamp, ultraviolet light generated from a light emitting diode, or the like is irradiated to the obtained uncured coating film through a mask for forming a target pattern. The shape of the mask at this time is not particularly limited, and various shapes can be used. The line width and the like can also be appropriately adjusted according to the mask size and the like.

In a recent exposure machine, the light of 350 nm or less is cut using the filter which cuts this wavelength range, or the bandpass filter which extracts the light of 4 nm, 408 nm, and 365 nm vicinity is these wavelength ranges, It can selectively take out and irradiates a parallel light beam uniformly to the whole exposure surface. At this time, in order to perform accurate alignment of a mask and a base material, you may use apparatuses, such as a mask aligner and a stepper.

After that, the coating film is brought into contact with an aqueous alkali solution to dissolve and develop a predetermined portion, for example, a non-exposed portion, to obtain a target pattern shape.

The developing method may be any of liquid mounting, dipping, spraying and the like. In addition, you may tilt the base material at arbitrary angles at the time of image development.

As for the developing solution used for image development, the aqueous solution of an alkaline compound is preferable.

The alkaline compound may be either an inorganic or organic alkaline compound.

Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, sodium hydrogen phosphate, sodium dihydrogen phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate And sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate, ammonia and the like.

Moreover, as an organic alkaline compound, for example, tetramethylammonium hydroxide, 2-hydroxyethyl trimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine , Monoisopropylamine, diisopropylamine, ethanolamine and the like.

The density | concentration in the developing solution of these inorganic and organic alkaline compounds becomes like this. Preferably it is 0.01-10 mass%, More preferably, it is 0.03-5 mass%.

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

The surfactant in the alkaline developer may be any of nonionic surfactants, anionic surfactants, or cationic surfactants.

As nonionic surfactant, For example, polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivative, oxyethylene / oxypropylene block copolymer, sorbitan fatty acid ester, Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine and the like.

Examples of the anionic surfactants include higher alcohol sulfate ester salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, and sodium dodecylbenzene sulfonate. And alkyl aryl sulfonates such as sodium dodecyl naphthalene sulfonate.

As cationic surfactant, amine salt, quaternary ammonium salt, etc., such as stearylamine hydrochloride and lauryl trimethylammonium chloride, etc. are mentioned, for example.

The density | concentration of surfactant in a developing solution becomes like this. Preferably it is 0.01-10 mass%, More preferably, it is 0.05-8 mass%, More preferably, it is 0.1-5 mass%.

After image development, you may wash with water and you may perform post-baking as needed. It is preferable to perform a postbaking for 10 to 180 minutes, for example in the temperature range of 150-240 degreeC.

The coating film or pattern obtained in this way is useful as a photo spacer used for a liquid crystal display device, and a patternable overcoat, for example. In addition, by using the photomask for hole formation at the time of patterning exposure with respect to an uncured coating film, a hole can be formed and it is useful as an interlayer insulation film. In addition, a transparent film can be formed by performing whole surface exposure and heat-hardening or heat-hardening, without using a photomask at the time of exposure to an uncured coating film. This transparent film is useful as an overcoat. Moreover, it can also be used for display apparatuses, such as a touch panel. Thereby, the display apparatus provided with a high quality coating film or a pattern can be manufactured with high production rate.

According to the present invention, a pattern can be obtained with high sensitivity.

The photosensitive resin composition of this invention is a material for forming various film | membrane and patterns, for example, a transparent film | membrane, especially the transparent film | membrane which comprises a part of a color filter, a pattern, a photo spacer, an overcoat, an insulating film, the projection for liquid-crystal orientation control , A microlens, a coloring pattern in which different film thicknesses are combined, and a coating layer can be preferably used. In addition, display devices including these color filters and / or array substrates, such as color filters and array substrates having these coating films or patterns as part of the component parts thereof, for example, liquid crystal displays, organic EL devices, and the like. It is available.

Example

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

Synthesis Example 1

Into a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to form a nitrogen atmosphere, and 140 parts by mass of diethylene glycol ethylmethyl ether was added and heated to 70 ° C while stirring. Subsequently, 40 mass parts of methacrylic acid, a mixture of 3, 4- epoxy cyclocyclo [5.2.1.0 ^2.6 ] decyl acrylate (a compound represented by the formula (I-1) and a compound represented by the formula (II-1), molar ratio = 50:50) 360 parts by mass were dissolved in 190 parts by mass of diethylene glycol ethylmethyl ether to prepare a solution. The obtained solution was dripped over 4 hours in the flask heated at 70 degreeC using the dropping pump.

On the other hand, the solution which melt | dissolved 30 mass parts of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 240 mass parts of diethylene glycol ethyl methyl ethers in the flask over 5 hours using the other dropping pump. It dripped. After dripping of the solution of a polymerization initiator was complete | finished, it hold | maintained at 70 degreeC for 4 hours, it cooled to room temperature after that, and obtained the solution of the copolymer (resin Aa) of 42.6 mass% of solid content and the acid value 60 mg-KOH / g. . The weight average molecular weight (Mw) of obtained resin Aa was 8.0 * 10 <^3> , and molecular weight distribution (Mn / Mw) was 1.91.

[Formula 9]

Synthesis Example 2

Into a 1 L flask equipped with a reflux cooler, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to form a nitrogen atmosphere, and 200 parts of 3-methoxy-1-butanol and 105 parts of 3-methoxybutyl acetate were added thereto while stirring. Heated to 70 ° C. Subsequently, molar ratio 50:50 of 60 parts of methacrylic acid and 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (compound represented by formula (I-1) and compound represented by formula (II-1)) Mixture)) 240 parts was dissolved in 140 parts of 3-methoxybutyl acetate to prepare a solution, and the solution was added dropwise into a flask kept at 70 ° C. over 4 hours using a dropping funnel.

On the other hand, the solution which melt | dissolved 30 parts of polymerization initiators 2,2'- azobis (2, 4- dimethyl vareronitrile) in 225 parts of 3-methoxybutyl acetates was dripped in the flask over 4 hours using the other dropping funnel. After completion of the dropwise addition of the solution of the polymerization initiator, the mixture was kept at 70 ° C for 4 hours, and then cooled to room temperature, followed by a solution of a copolymer (resin Ab) having a solid content of 32.6% and an acid value of 110 mg-KOH / g (solid content conversion). Got. As for the weight average molecular weight Mw of obtained resin Ab, 1.34 * 10 <^4> and molecular weight distribution (Mn / Mw) were 2.50.

<Measurement of molecular weight>

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

Equipment: K2479 (manufactured by Shimadzu Corporation)

Column: SHIMADZU Shim-pack GPC-80M

Column temperature: 40 DEG C

Solvent: THF (Tetrahydrofuran)

Flow rate: 1.0 ml / min

Detector: RI

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

Examples 1-4, Comparative Example 1

Each component was mixed so that it might become the composition shown in Table 1, and the photosensitive resin compositions 1-5 and the composition 1 of the comparative example were obtained.

In Table 1,

Resin (Aa) and resin (Ab) represent the mass part of solid content conversion.

Polymeric compound (B); Dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Gunpowder Co., Ltd.)

Photoinitiator (Ca); 2,2'-bis (o-chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole (B-CIM; manufactured by Hodogaya Chemical Industry Co., Ltd.)

Photoinitiator (Cb); 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (IRGACURE 379EG; manufactured by Chiba Japan Co., Ltd.)

Photoinitiator (Cc); N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethane-1-imine (IRGACURE OXE02; manufactured by Chiba Japan)

Photopolymerization start adjuvant (Cd); 2,4-diethyl thioxanthone (KAYACURE DETX-S; manufactured by Nippon Gunpowder Co., Ltd.)

Photopolymerization start adjuvant (Ce); 2- [2-oxo-2- (2-naphthyl) ethylidene] -3-methylbenzothiazoline (compound represented by formula (III-1))

Polyfunctional thiol compound (T); Pentaerythritol tetrakis (3-sulfanylpropionate) (PEMP; manufactured by Sakai Chemical Industries, Ltd.)

Compound (1) (a); 2,5-di-tert-butylhydroquinone (manufactured by Seko Chemical Co., Ltd .; Nonflex Alba)

Compound (1) (b); tert-butylhydroquinone (manufactured by Seko Chemical Co., Ltd .; TBH)

Compound (1) (c); Methylhydroquinone (manufactured by Seko Chemical Co., Ltd .; MH)

Solvent (Da); 3-methoxy-1-butanol

Solvent (Db); Diethylene glycol ethyl methyl ether

Solvent (Dc); Propylene Glycol Monomethyl Ether Acetate

Solvent (Dd); Ethyl 3-ethoxypropionate

Solvent (De); 3-methoxybutyl acetate

Surfactant (E); Polyether modified silicone oil (Toray Dow Corning Co., Ltd. product; SH8400)

The solvent (D) is mixed so that the solid content of the photosensitive resin composition becomes "solid content [%]" in Table 1, and the values of the solvent components (Da) to (De) in the solvent (D) are the mass ratios in the solvent (D). Indicates.

Content of surfactant (E) shows the mass ratio (%) with respect to 100 mass% of photosensitive resin compositions.

[Formula 10]

<Pattern formation>

A 2 inch square glass substrate (# 1737; manufactured by Corning) was washed sequentially with a neutral detergent, water, and alcohol, and then dried. The photosensitive resin composition was exposed on this glass substrate at an exposure amount of 60 mJ / cm 2 (365 nm standard), spin-coated so that the film thickness after developing, washing with water, and postbaking was 3.0 µm, and then, 80 ° C in a clean oven. Prebaked for 2 minutes at. After cooling, the space | interval of the board | substrate which apply | coated this photosensitive resin composition and the photomask made from quartz glass was set to 200 micrometers, and 60 degreeC was used under atmospheric atmosphere using the exposure machine (TME-150RSK; Topcon Co., Ltd. light source, ultrahigh pressure mercury lamp). The light was irradiated with an exposure amount of mJ / cm 2 (365 nm standard). In addition, irradiation with the photosensitive resin composition at this time used the radiation light from an ultrahigh pressure mercury lamp through the optical filter (UV-33; Asahi Techno Glass Co., Ltd. product). In addition, as a photomask, the photomask in which the pattern (having a square transmissive part whose one side is 13 micrometers and the said space | interval of said square is 100 micrometers) was formed on the same plane was used.

After irradiation with light, the coating film was immersed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 25 ° C. for 60 seconds, and developed after washing with water in an oven at 235 ° C. for 15 minutes. A pattern was obtained.

<Measurement of pattern width>

About the obtained pattern, the width | variety of the pattern was measured with the three-dimensional non-contact surface shape measurement system (Micromap MM527N-PS-M100; Ryoka system make). In addition, the value measured in the part of 5% height with respect to the height of a pattern from the board | substrate surface was made into the pattern width. The larger the pattern width, the higher the sensitivity. The results are shown in Table 2.

As shown in Table 2, it was confirmed that the photosensitive resin composition containing the compound (1) has a large pattern width and high sensitivity.

Productivity can be improved by forming a coating film or a pattern using such a photosensitive resin composition, and manufacturing a display apparatus using them.

According to the present invention, a coating film or a pattern can be formed with high sensitivity.

The photosensitive resin composition of this invention is a material for forming various film | membrane and patterns, for example, a transparent film | membrane, especially the transparent film | membrane which comprises a part of a color filter, a pattern, a photo spacer, an overcoat, an insulating film, the projection for liquid-crystal orientation control , A microlens, a coloring pattern in which different film thicknesses are combined, and a coating layer can be preferably used. In addition, display devices including these color filters and / or array substrates, such as color filters and array substrates having these coating films or patterns as part of the component parts thereof, for example, liquid crystal displays, organic EL devices, and the like. It is available.

Claims (5)

A monomer containing a resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), a solvent (D) and a compound represented by the formula (1), and the resin (A) having a cyclic ether having 2 to 4 carbon atoms. And a photosensitive resin composition which is a copolymer formed by superposing | polymerizing at least 1 sort (s) chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride.
(11)

[In formula (1), R ^a -R ^d Are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.] The method of claim 1,
The photosensitive resin composition whose content of the compound represented by Formula (1) is 0.0025 mass% or more and 0.095 mass% or less with respect to solid content of the photosensitive resin composition. The method of claim 1,
The photosensitive resin composition whose monomer which has a C2-C4 cyclic ether is a monomer which has an oxiranyl group. The pattern formed using the photosensitive resin composition of Claim 1. The display device containing at least 1 sort (s) of the pattern of Claim 4.