KR101995078B1 - Photosensitive resin composition - Google Patents

Abstract

상기 화학식 (1)에서, R¹은 탄소수 1∼6의 알킬기; A¹∼A⁴는 각각 독립적으로 수소 원자 또는 탄소수 1∼6의 알킬기를 나타낸다.The present invention provides a photosensitive resin composition comprising (A), (B), (C) and (D); (A) a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, a structural unit derived from a monomer having a cyclic ether structure having 2 to 4 carbon atoms and a monomer having an ethylenic unsaturated bond ≪ / RTI > (B) a polymerizable compound; (C) a polymerization initiator comprising an oxime compound, wherein the content of the oxime compound is 30% by mass or more and 100% by mass or less based on the total amount of the polymerization initiator; (D) A compound represented by the following formula (1).

In the above formula (1), R ¹ represents an alkyl group having 1 to 6 carbon atoms; A ^{1 to} A ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Description

[0001] PHOTOSENSITIVE RESIN COMPOSITION [0002]

The present invention relates to a photosensitive resin composition.

In recent liquid crystal displays, photosensitive resin compositions are used to form resin patterns such as photo spacers and overcoats. As such a photosensitive resin composition, a composition comprising a resin, a polymerizable compound, a polymerization initiator and a solvent is known (JP2008-181087-A).

In the conventionally proposed photosensitive resin composition, when a resin pattern having different heights is simultaneously formed on the same substrate by using a halftone mask, the height difference of the obtained resin pattern is small, and a resin pattern of a desired height can not be obtained .

The present invention includes the following inventions.

[1] A photosensitive resin composition comprising (A), (B), (C) and (D).

(A) a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, a structural unit derived from a monomer having a cyclic ether structure having 2 to 4 carbon atoms and a monomer having an ethylenic unsaturated bond ≪ / RTI >

(B) a polymerizable compound

(C) a polymerization initiator comprising an oxime compound, wherein the content of the oxime compound is from 30% by mass to 100% by mass with respect to the total amount of the polymerization initiator

(D) a compound represented by the formula (1)

[In the formula (1), R ¹ represents an alkyl group having 1 to 6 carbon atoms.

And A ^{1 to} A ⁴ independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[2] The photosensitive resin composition according to [1], wherein the content of (C) is 0.1 part by mass or more and 30 parts by mass or less based on 100 parts by mass of the total content of (A) and (B).

[3] The photosensitive resin composition according to [1] or [2], wherein the content of (D) is 0.02% by mass or more and 1% by mass or less based on 100 parts by mass of the total content of (A) and (B).

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

[5] A photo-spacer formed from the photosensitive resin composition according to any one of [1] to [3].

[6] A display device comprising at least one selected from the group consisting of the resin pattern described in [4] and the photo-spacer described in [5].

According to the photosensitive resin composition of the present invention, when a resin pattern having different heights is simultaneously formed on the same substrate by using a halftone mask, the height difference of the obtained resin pattern is large.

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

The photosensitive resin composition of the present invention comprises (A), (B), (C) and (D).

(A) a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, a structural unit derived from a monomer having a cyclic ether structure having 2 to 4 carbon atoms and a monomer having an ethylenic unsaturated bond (Hereinafter sometimes referred to as " resin (A) "),

(B) a polymerizable compound

(Hereinafter sometimes referred to as "polymerization initiator (C)") having an oxime compound content of 30 mass% or more and 100 mass% or less based on the total amount of the polymerization initiator, as the polymerization initiator containing the oxime compound (C)

(D) a compound represented by the formula (1) (hereinafter sometimes referred to as " compound (1)

The photosensitive resin composition of the present invention preferably contains at least one selected from the group consisting of a solvent (E) and a surfactant (H).

≪ Resin (A) >

The resin (A) contains a structural unit derived from at least one member selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (hereinafter also referred to as "(a)"), a structural unit derived from a cyclic (A) and a structural unit originating from a monomer having an ether structure and an ethylenically unsaturated bond (hereinafter also referred to as "(b)"), and is a copolymerizable with (a) (Hereinafter sometimes referred to as " (c) ") having no cyclic ether structure.

Examples of the resin (A) include a resin [K1] and a resin [K2].

Resin [K1]: a copolymer comprising only the structural unit derived from (a) and the structural unit derived from (b);

Resin [K2]: a copolymer comprising a structural unit derived from (a), a structural unit derived from (b), and a structural unit derived from (c)

(a) specifically include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid;

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

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

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

(Meth) acryloyloxyalkyl (meth) acrylate of a divalent or more polyvalent carboxylic acid such as mono [2- (meth) acryloyloxyethyl] succinate and mono [2- ] Esters;

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

Of these, (meth) acrylic acid and maleic anhydride are preferable from the viewpoint of copolymerization reactivity and solubility in an aqueous alkali solution, and (meth) acrylic acid is more preferable.

In the present specification, "(meth) acryloyl" represents at least one member selected from the group consisting of acryloyl and methacryloyl. The expressions such as "(meth) acrylic acid" and "(meth) acrylate" have the same meaning.

Examples of the cyclic ether structure having 2 to 4 carbon atoms in (b) include oxirane ring, oxetane ring and tetrahydrofuran ring. (b) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group.

(b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"), a monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond (hereinafter referred to as " b2) ") and a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter occasionally referred to as" (b3) ").

(b1-1) having a structure in which a linear or branched unsaturated aliphatic hydrocarbon is epoxidized (hereinafter sometimes referred to as "(b1-1)") and an unsaturated alicyclic hydrocarbon is epoxidized (Hereinafter sometimes referred to as " (b1-2) ").

(b1-1) include, for example, glycidyl (meth) acrylate,? -methyl glycidyl (meth) acrylate,? -ethyl glycidyl (meth) acrylate, glycidyl vinyl ether, Vinylbenzyl glycidyl ether,? -Methyl-o-vinylbenzyl glycidyl ether,? -Methyl-o-vinylbenzyl glycidyl ether,? Methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5- Styrenes such as 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5-tris (glycidyloxymethyl) styrene, (Glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene and 2,4,6- .

(b1-2) include, for example, vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane [e.g., Celloxide 2000; (Manufactured by Daicel Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate [e.g., CYRAMER A400; (Manufactured by Daicel Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate [for example, Cyclomer M100; (Manufactured by Daicel Co., Ltd.), a compound represented by the following formula (I) and a compound represented by the formula (II).

[In the formulas (I) and (II), R ^b1 and R ^b2 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 hydroxy group.

X ^b1 and X ^b2 represent a single bond, -R ^b3 -, * -R ^b3 -O-, * -R ^b3- S- or * -R ^b3 -NH-.

R ^b3 represents an alkanediyl group having 1 to 6 carbon atoms.

* Represents the number of bonds (bonds) with O.]

Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and tert-butyl.

Examples of the alkyl group in which the hydrogen atom is substituted with hydroxy include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, 1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group and 4-hydroxybutyl group.

R ^b1 and R ^b2 are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group, more preferably a hydrogen atom and a methyl group.

Examples of the alkanediyl group include a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, , 6-diyl group, and the like.

X ^b1 and X ^b2 are preferably a single bond, a methylene group, an ethylene group, * -CH ₂ -O- and * -CH ₂ CH ₂ -O-, more preferably a single bond, * -CH ₂ CH ₂ -O- (* represents the number of bonds with O).

Examples of the compound represented by the formula (I) include compounds represented by any one of the following formulas (I-1) to (I-15). Among them, the compound represented by the formula (I-1), the compound represented by the formula (I-3), the compound represented by the formula (I-5), the compound represented by the formula (I- (I-1), (I-7), (I-9) or (I-15) are more preferable.

Examples of the compound represented by the formula (II) include compounds represented by any one of the following formulas (II-1) to (II-15). Among them, the compound represented by the formula (II-1), the compound represented by the formula (II-3), the compound represented by the formula (II-5), the compound represented by the formula (II- (II-1), (II-7), (II-9) or (II-15) are more preferable.

The compound represented by the formula (I) and the compound represented by the formula (II) may be used alone or in combination of the compound represented by the formula (I) and the compound represented by the formula (II). When these compounds are used in combination, the content ratio of the compound represented by formula (I) and the compound represented by formula (II) is preferably 5:95 to 95: 5, more preferably 10:90 to 90: : 10, and more preferably from 20:80 to 80:20.

(b2) is more preferably a monomer having an oxetanyl group and a (meth) acryloyloxy group. (b2) include 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3- Ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3- 3-ethyl-3-acryloyloxyethyl oxetane, and the like.

(b3) is more preferably a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group. Specific examples of the compound (b3) include tetrahydrofurfuryl acrylate [e.g., Viscot V # 150, manufactured by Osaka Yuki Kagaku Kogyo Co., Ltd.], tetrahydrofurfuryl methacrylate, and the like.

(b), it is preferable that the resin pattern or the cured film obtained is (b1) in that reliability such as heat resistance and chemical resistance can be further improved. Further, (b1-2) is more preferable in that the storage stability of the photosensitive resin composition is excellent.

(meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate, cyclohexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (Meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate [referred to in the art as "dicyclopentanyl (meth) acrylate" (Also referred to as "tricyclodecyl (meth) acrylate"), tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate (Meth) acrylate], dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) (Meth) acrylic acid esters such as propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate and benzyl (meth) acrylate;

(Meth) acrylic acid esters having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

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

2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept- Ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept- 2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept- Cyclohexyl [2.2.1] hept-2-ene, 5,6-bis 2,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene and the like such as bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept- Cyclo-unsaturated compounds;

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

But are not limited to, styrene,? -Methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide , Vinyl acetate, 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene.

Of these, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide and bicyclo [2.2.1] hept-2-ene are preferable in view of copolymerization reactivity and heat resistance.

In the resin [K1], the proportion of the structural unit derived from each monomer is preferably such that the ratio of the structural unit derived from the monomer to the total structural unit constituting the resin [K1]

(a); 1 to 70 mol%

(b); Is preferably from 30 to 99 mol%

(a); 10 to 50 mol%

(b); And more preferably 50 to 90 mol%.

When the ratio of the structural unit constituting the resin [K1] is within the above-mentioned range, there is a tendency that the storage stability of the photosensitive resin composition and the chemical resistance, heat resistance and mechanical strength of the resulting resin pattern and cured film are excellent.

The resin [K1] can be obtained by a method described in, for example, "Experimental Method of Polymer Synthesis" (published by Otsu Takayuki Co., Ltd., 1st Edition, 1st Edition, March 1, 1972), and cited documents in this document . ≪ / RTI >

Specifically, a predetermined amount of the components (a) and (b), a polymerization initiator and a solvent are placed in a reaction vessel to replace oxygen by nitrogen, for example, have. The polymerization initiator, solvent and the like to be used herein are not particularly limited and those generally used in the field can be used. Examples of the polymerization initiator include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), etc.) and organic peroxides (such as benzoyl peroxide) The solvent may be any one that dissolves the respective monomers, and may be a solvent to be described later which is used in the photosensitive resin composition.

The obtained resin may be a solution after the reaction as it is, a solution obtained by concentration or dilution, or a solid (powder) obtained by re-precipitation or the like. In particular, by using a solvent used for the photosensitive resin composition of the present invention as a polymerization solvent, the solution after the reaction can be used as it is in the production of the photosensitive resin composition, so that the production process of the photosensitive resin composition can be simplified.

In the resin [K2], the ratio of the structural units derived from each other is preferably from 1 to 100,

(a); 2 to 40 mol%

(b); 30 to 95 mol%

(c); , More preferably 1 to 65 mol%

(a); 5 to 35 mol%

(b); 35 to 80 mol%

(c); And more preferably 1 to 60 mol%.

The total amount of the structural unit derived from (a) and the structural unit derived from (b) is preferably from 70 to 99 mol%, more preferably from 90 to 99 mol% based on the total moles of all structural units constituting the resin [K2] % Is more preferable.

When the ratio of the structural unit of the resin [K2] is within the above-mentioned range, there is a tendency that the storage stability of the photosensitive resin composition and the chemical resistance, heat resistance and mechanical strength of the resulting resin pattern and cured film are excellent.

The resin [K2] can be produced by the same method as the resin [K1].

Specific examples of the resin (K1) include a compound represented by the formula (I-1): (meth) acrylic acid / (Meth) acrylic acid / copolymer of formula (I-2), copolymer of (meth) acrylic acid / formula (I-3), copolymer of (meth) acrylic acid / (Meth) acrylic acid / copolymer of formula (I-5), (meth) acrylic acid / copolymer of formula (I-6), copolymer of (meth) acrylic acid / ) Acrylic acid / copolymer of formula (I-8), a copolymer of (meth) acrylic acid / formula (I-9), a copolymer of (meth) acrylic acid / (I), a copolymer of (meth) acrylic acid / formula (I-12), a copolymer of (meth) acrylic acid / (Meth) acrylic acid / copolymer of formula (I-15), (meth) acrylic acid / (Meth) acrylic acid / (II-2), a copolymer of (meth) acrylic acid / (II-3), a copolymer of (meth) acrylic acid / (Meth) acrylic acid / copolymer of formula (II-5), copolymer of (meth) acrylic acid / formula (II-6), copolymer of (meth) acrylic acid / (Meth) acrylic acid / copolymer of formula (II-8), a copolymer of (meth) acrylic acid / formula (II-9), a copolymer of (meth) acrylic acid / Acrylic acid / copolymer of formula (II-11), copolymer of (meth) acrylic acid / formula (II-12), copolymer of (meth) acrylic acid / (Meth) acrylic acid / copolymer of formula (II-15), copolymer of (meth) acrylic acid / formula (I-1) / formula (II- (I-2) / (II-2), (meth) acrylic acid / A copolymer of (meth) acrylic acid / (I-4) / (II-4), a copolymer of (meth) acrylic acid / (Meth) acrylic acid / copolymer of formula (I-6) / (II-6), copolymer of (meth) acrylic acid / Acrylic acid / copolymer of formula (I-8) / formula (II-8), copolymer of (meth) acrylic acid / A copolymer of (meth) acrylic acid / (I-11) / (II-11), a copolymer of (meth) acrylic acid / formula (I-12) / (Meth) acrylic acid / (meth) acrylic acid / copolymer of formula (I-13) / formula (II-13), copolymer of (meth) acrylic acid / (Meth) acrylic acid / copolymer of the formula (I-1) / the formula (I-7), a copolymer of the (meth) acrylic acid / the copolymer of the formula (I-15) / (I- Copolymer of formula (I-1) / copolymer of formula (II-7), copolymer of crotonic acid / formula (I-1), copolymer of crotonic acid / (I-5), a copolymer of crotonic acid / formula (I-6), a crotonic acid / copolymer of formula (I-4) Copolymers of crotonic acid / formula (I-10), copolymers of crotonic acid / formula (I-8) Copolymers of crotonic acid / formula (I-12), copolymers of crotonic acid / formula (I-13), copolymers of crotonic acid / formula (I-14) (II-1), copolymers of crotonic acid / (II-2), copolymers of crotonic acid / formula (II-3), copolymers of crotonic acid / (II-4), a crotonic acid / copolymer of formula (II-5), a crotonic acid / Copolymers of crotonic acid / formula (II-9), copolymers of crotonic acid / formula (II-8), copolymers of formula Copolymers of crotonic acid / formula (II-13), copolymers of crotonic acid / formula (II-11) Copolymers of maleic acid / formula (I-1), copolymers of maleic acid / formula (I-2), copolymers of maleic acid / (I-4), a copolymer of maleic acid / formula (I-5), a copolymer of maleic acid / formula (I-6), a copolymer of maleic acid / / Copolymer of formula (I-7), a copolymer of maleic acid / formula (I-8), a copolymer of maleic acid / formula (I-9), a copolymer of maleic acid / Copolymers of maleic acid / formula (I-11), copolymers of maleic acid / formula (I-12), copolymers of maleic acid / (II-2), maleic acid / maleic acid / copolymer of formula (I-14), maleic acid / copolymer of formula (I-15) Copolymers of maleic acid / formula (II-3), copolymers of maleic acid / formula (II-4), copolymers of maleic acid / 6), a copolymer of maleic acid / formula (II-7), a copolymer of maleic acid / formula (II-8), a copolymer of maleic acid / formula (II-9), maleic acid / (II-10), a copolymer of maleic acid / formula (II-11), a copolymer of maleic acid / formula (II-12), a copolymer of maleic acid / (Meth) acrylic acid / maleic anhydride / copolymer of the formula (I-1), a copolymer of the (meth) acrylic acid / maleic anhydride / (Meth) acrylic acid / maleic anhydride / copolymer of formula (I-3), (meth) acrylic acid / maleic anhydride / Acrylic acid / maleic anhydride / (meth) acrylic acid / maleic anhydride / copolymer of formula (I-4), (meth) acrylic acid / maleic anhydride / copolymer of formula (I- (Meth) acrylic acid / maleic anhydride / copolymer of formula (I-7), (meth) acrylic acid / maleic anhydride / copolymer of formula (I-8), (meth) acrylic acid / maleic anhydride / (Meth) acrylic acid / maleic anhydride / copolymer of formula (I-11), (meth) acrylic acid / maleic anhydride / copolymer of formula (I- (Meth) acrylic acid / maleic anhydride / copolymer of formula (I-12), (meth) acrylic acid / maleic anhydride / copolymer of formula (I- (Meth) acrylic acid / maleic anhydride / copolymer of formula (I-15), (meth) acrylic acid / maleic anhydride / copolymer of formula (II-1) Acid anhydride / chemistry (Meth) acrylic acid / maleic anhydride / (II-4) copolymer, (meth) acrylic acid / maleic anhydride / copolymer of formula (II- (Meth) acrylic acid / maleic anhydride / copolymer of formula (II-5), (meth) acrylic acid / maleic anhydride / copolymer of formula (II- (Meth) acrylic acid / maleic anhydride / copolymer of formula (II-8), (meth) acrylic acid / maleic anhydride / copolymer of formula (II-9), (meth) acrylic acid / maleic anhydride / (Meth) acrylic acid / maleic anhydride / copolymer of formula (II-12), (meth) acrylic acid / maleic anhydride / copolymer of formula (II- (Meth) acrylic acid / maleic anhydride / copolymer of formula (II-13), copolymer of (meth) acrylic acid / maleic anhydride / 15) And the like.

Specific examples of the resin (K2) include copolymers of (meth) acrylic acid / (I-1) / methyl (meth) acrylate, copolymers of (meth) acrylic acid / Copolymers of (meth) acrylic acid / (I-3) / methyl (meth) acrylate, copolymers of (meth) acrylic acid / (I-4) / methyl (meth) acrylate, (Meth) acrylic acid / copolymer of formula (I-5) / methyl (meth) acrylate, copolymer of (meth) acrylic acid / (Meth) acrylate, a copolymer of (meth) acrylic acid / (I-8) / methyl (meth) acrylate, a copolymer of (meth) acrylic acid / ) Copolymer of (meth) acrylic acid / (I-10) / methyl (meth) acrylate, copolymer of (meth) acrylic acid / (I-11) / methyl (meth) , (Meth) Copolymers of (meth) acrylic acid / (I-13) / methyl (meth) acrylate, copolymers of (meth) acrylic acid / (meth) acrylate / A copolymer of (meth) acrylic acid / (I-15) / methyl (meth) acrylate, a copolymer of (meth) acrylic acid / (II-1) / methyl Copolymer of (meth) acrylic acid / (II-2) / methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (II-3) / methyl (meth) acrylate (Meth) acrylic acid / copolymer of formula (II-4) / methyl (meth) acrylate, copolymer of (meth) acrylic acid / (Meth) acrylic acid / (II-7) / methyl (meth) acrylate copolymer, (meth) acrylic acid / ) / Me (Meth) acrylate, a copolymer of (meth) acrylic acid / (II-9) / methyl (meth) acrylate, a copolymer of (meth) acrylic acid / Copolymers of (meth) acrylic acid / (II-11) / methyl (meth) acrylate, copolymers of (meth) acrylic acid / (II-12) / methyl (meth) acrylate, (Meth) acrylic acid / copolymer of formula (II-13) / methyl (meth) acrylate, copolymer of (meth) acrylic acid / A copolymer of (meth) acrylic acid / (I-1) / dicyclopentanyl (meth) acrylate, (meth) acrylic acid / (II-1) / Copolymers of (meth) acrylic acid / (I-1) / (II-1) / dicyclopentanyl (meth) acrylate, copolymers of (Meth) acrylic acid / maleic acid / copolymer of formula (I-1) / dicyclopentanyl (meth) acrylate, copolymer of maleic acid / (Meth) acrylic acid / copolymer of formula (I-1) / methyl (meth) acrylate / dicyclopentanyl (meth) acrylate, Copolymers of maleic acid / (II-1) / dicyclopentanyl (meth) acrylate, copolymers of (meth) acrylic acid (II) (Meth) acrylic acid / (II-1) / methyl (meth) acrylate / dicyclopentanyl (meth) acrylate / maleic anhydride / copolymer of formula (II- (Meth) acrylic acid / copolymer of formula (I-1) / phenyl (meth) acrylate, copolymer of (meth) acrylic acid / Copolymers of (meth) acrylic acid / (I-1) / (II-1) / phenyl (meth) acrylate, crotonic acid / (Meth) acrylate, a copolymer of maleic acid / (I-1) / phenyl (meth) acrylate, (meth) acrylic acid / maleic anhydride / Copolymers of (meth) acrylic acid / (I-1) / methyl (meth) acrylate / phenyl (meth) acrylate, crotonic acid / (II-1) / phenyl (Meth) acrylate, a copolymer of maleic acid / (II-1) / phenyl (meth) acrylate, (meth) acrylic acid / maleic anhydride / A copolymer of (meth) acrylic acid / (II-1) / methyl (meth) acrylate / phenyl (meth) acrylate, a copolymer of (meth) acrylic acid / Copolymers, (Meth) acrylic acid / copolymer of formula (II-1) / diethyl maleate, copolymer of (meth) acrylic acid / formula (I-1) / formula (II-1) / diethyl maleate, crotonic acid / A copolymer of maleic acid / (I-1) / diethyl maleate, (meth) acrylic acid / maleic anhydride / copolymer of formula (I-1) / diethyl maleate (Meth) acrylic acid / copolymer of formula (I-1) / methyl (meth) acrylate / diethyl maleate, crotonic acid / copolymer of formula (II-1) / diethyl maleate, maleic acid / (Meth) acrylic acid / (II-1) / methyl (meth) acrylic acid / maleic anhydride / copolymer (II-1) / diethyl maleate, A copolymer of (meth) acrylic acid / (I-1) / 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid / (II-1) / 2 - hydroxyethyl (meth) acrylate Copolymers of (meth) acrylic acid / (I-1) / (II-1) / 2-hydroxyethyl (meth) acrylate, crotonic acid / (Meth) acrylic acid / maleic anhydride / copolymer of formula (I-1) / 2-hydroxyethyl (meth) acrylate, a copolymer of maleic acid / ) / 2-hydroxyethyl (meth) acrylate, copolymers of (meth) acrylic acid / (I-1) / methyl (meth) acrylate / (Meth) acrylate, a copolymer of maleic acid / (II-1) / 2-hydroxyethyl (meth) acrylate, a copolymer of maleic acid / Acrylic acid / maleic anhydride / copolymer of formula (II-1) / 2-hydroxyethyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (II-1) / methyl (meth) acrylate / Ethyl (meth) acrylate Copolymers of (meth) acrylic acid / (I-1) / bicyclo [2.2.1] hept-2-ene, (meth) acrylic acid / (II-1) / bicyclo [2.2. Copolymers of (meth) acrylic acid / (I-1) / (II-1) / bicyclo [2.2.1] hept-2-ene, crotonic acid / (I-1) / bicyclo [2.2.1] hept-2-ene, copolymers of maleic acid / Acrylic acid / maleic anhydride / copolymer of formula (I-1) / bicyclo [2.2.1] hept-2-ene, copolymer of (meth) acrylic acid / (II-1) / bicyclo [2.2.1] hept-2-ene, maleic acid / copolymer of formula (II-1) Copolymer of (meth) acrylic acid / maleic anhydride / (II-1) / bicyclo [2.2.1] hept-2-ene, (meth) acrylic acid / maleic anhydride / Methacrylic acid / (II-1) / methyl (meth) acrylate Copolymers of (meth) acrylic acid / (I-1) / N-cyclohexylmaleimide, (meth) acrylic acid / (II-1) Copolymers of (meth) acrylic acid / (I-1) / (II-1) / N-cyclohexylmaleimide, crotonic acid / (I-1) / N-cyclohexylmaleimide copolymer, (I-1) / N-cyclohexylmaleimide copolymer, (meth) acrylic acid / maleic anhydride / copolymer of formula (I-1) / N-cyclohexylmaleimide, Copolymers of (meth) acrylic acid / (I-1) / methyl (meth) acrylate / N-cyclohexylmaleimide, crotonic acid / (II-1) / N-cyclohexyl Copolymers of maleic acid / maleic acid / (II-1) / N-cyclohexyl maleimide, (meth) acrylic acid / maleic anhydride / copolymer of formula (II-1) / N-cyclohexyl maleimide (Meth) acrylate, (Meth) acrylic acid / copolymer of formula (I-1) / styrene, (meth) acrylic acid / copolymer of formula (II-1) / methyl (meth) acrylate / N-cyclohexylmaleimide (Meth) acrylic acid / copolymer of formula (I-1) / (II-1) / styrene, crotonic acid / copolymer of formula (I-1) / styrene, male (Meth) acrylic acid / (I-1) / methyl (meth) acrylic acid / maleic anhydride / copolymer of formula (I- (Meth) acrylic acid / maleic anhydride / (meth) acrylate / styrene copolymer, crotonic acid / copolymer of formula (II-1) / styrene, maleic acid / (Meth) acrylic acid / (meth) acrylic acid / copolymer of formula (II-1) / styrene, copolymer of (meth) acrylic acid / Copolymers of maleimide / styrene, (Meth) acrylic acid / (I-1) / (II-1) / N-cyclohexylmaleimide / styrene copolymer of formula (II-1) / N-cyclohexylmaleimide / styrene Copolymers of maleic acid / formula (I-1) / N-cyclohexylmaleimide / styrene, copolymers of (meth) acrylic acid, Acrylic acid / maleic anhydride / copolymer of formula (I-1) / N-cyclohexylmaleimide / styrene, (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate / N-cyclohexylmaleimide / Styrene copolymer, crotonic acid / copolymer of formula (II-1) / N-cyclohexylmaleimide / styrene, maleic acid / copolymer of formula (II-1) / N-cyclohexylmaleimide / styrene, (Meth) acrylic acid / maleic anhydride / copolymer of formula (II-1) / N-cyclohexylmaleimide / styrene, (meth) acrylic acid / Copolymers of cyclohexylmaleimide / styrene, and the like.

The weight average molecular weight of the resin (A) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, still more preferably 5,000 to 20,000, and particularly preferably 5,000 to 15,000. When the weight average molecular weight of the resin (A) is within the above range, the coating property of the photosensitive resin composition tends to be good.

The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the resin (A) is preferably 1.1 to 6.0, more preferably 1.2 to 4.0. When the molecular weight distribution is within the above range, the obtained resin pattern or cured film tends to have excellent chemical resistance.

The acid value of the resin (A) is preferably 30 mg-KOH / g to 180 mg-KOH / g, more preferably 40 mg-KOH / g to 150 mg-KOH / g, 50 mg-KOH / g to 135 mg-KOH / g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the resin, and can be determined by titration using an aqueous solution of potassium hydroxide. When the acid value of the resin (A) is within the above range, the resin pattern or the cured film obtained tends to have an excellent adhesion with the substrate.

The content of the resin (A) is preferably 30 to 90 mass%, more preferably 35 to 80 mass%, and still more preferably 40 to 70 mass% with respect to the solid content of the photosensitive resin composition of the present invention, Particularly preferably 52 to 70% by mass. When the content of the resin (A) is within the above range, the resin pattern or the cured film obtained is excellent in heat resistance and tends to have excellent adhesion with the substrate and chemical resistance. Here, the solid content of the photosensitive resin composition means the amount excluding the content of the solvent (E) in the total amount of the photosensitive resin composition of the present invention.

≪ Polymerizable compound (B) >

The polymerizable compound (B) is a compound capable of polymerizing by an active radical generated from the polymerization initiator (C), such as a compound having a polymerizable ethylenically unsaturated bond, and is preferably a (meth) acrylic acid ester compound .

Examples of the polymerizable compound (B) having one ethylenically unsaturated bond include the same compounds as the compounds (a), (b) and (c) above, and among them, a (meth) acrylate ester is preferable.

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

Examples of the polymerizable compound having three or more ethylenic unsaturated bonds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tri (meth) acrylate, (Meth) acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (Meth) acrylate, a reaction product of pentaerythritol tri (meth) acrylate and an acid anhydride, A reaction product of erythritol penta (meth) acrylate and an acid anhydride, a reaction product of tripentaerythritol hepta (meth) acrylate and an acid anhydride, caprolactone-modified trimethylolpropane tri (meth) acrylate, caprolactone-modified pentaerythritol tri (Meth) acrylate, caprolactone-modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone-modified pentaerythritol tetra (Meth) acrylate, caprolactone-modified tripentaerythritol tetra (meth) acrylate, caprolactone-modified tripentaerythritol penta (meth) acrylate, caprolactone-modified tripentaerythritol hexa (meth) acrylate, caprolactone-modified tripentaerythritol tetra ) Acrylate, caprolactone-modified tripentaerythritol hepta (Meth) acrylate, caprolactone-modified tripentaerythritol octa (meth) acrylate, a reaction product of caprolactone-modified pentaerythritol tri (meth) acrylate and an acid anhydride, caprolactone-modified dipentaerythritol penta (meth) A reaction product with an acid anhydride, and a reaction product of caprolactone-modified tripentaerythritol hepta (meth) acrylate and an acid anhydride.

Among them, a polymerizable compound having three or more ethylenic unsaturated bonds is preferable, and dipentaerythritol hexa (meth) acrylate is more preferable.

The weight average molecular weight of the polymerizable compound (C) is preferably 150 or more and 2,900 or less, and more preferably 250 to 1,500 or less.

The content of the polymerizable compound (B) is preferably 5 to 95 mass%, more preferably 20 to 80 mass%, and still more preferably 40 to 80 mass%, based on the total amount of the resin (A) By mass to 80% by mass, particularly preferably from 46 to 70% by mass. When the content of the polymerizable compound (B) is within the above range, there is a tendency that the sensitivity at the time of producing the resin pattern and the strength, smoothness and reliability of the obtained resin pattern and the cured film become good.

≪ Polymerization initiator (C) >

The oxime compound is, for example, an O-acyloxime compound and has a partial structure represented by the following formula (d1). Herein, * represents the number of bonds.

Examples of the O-acyloxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy- 2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan- Yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3 -Dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethan- 1-imine, N- acetoxy- 1- [ Benzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropan- 1-imine, N-benzoyloxy- -Yl] -3-cyclopentylpropan-1-one-2-imine and the like. Commercially available products such as Irgacure (registered trademark) OXE01, OXE02 (manufactured by BASF) and N-1919 (manufactured by ADEKA) may be used.

The polymerization initiator (C) may contain a polymerization initiator other than an oxime compound. Such a polymerization initiator is not particularly limited as long as it is a compound capable of generating an active radical, an acid, or the like by the action of light or heat and capable of initiating polymerization, and a known polymerization initiator can be used. Examples thereof include alkylphenone compounds, Compounds, acylphosphine oxide compounds and nonimidazole compounds.

The alkylphenone compound is a compound having a partial structure represented by the following formula (d2) or a partial structure represented by the following formula (d3). Of these partial structures, the benzene ring may have a substituent.

Examples of the compound having a partial structure represented by the formula (d2) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan- (4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butane- 1-on. And commercially available products such as Irgacure (registered trademark) 369, 907 and 379 (manufactured by BASF) may be used. A polymerization initiator having a group capable of chain transfer described in JP2002-544205-A may also be used.

Examples of the compound having a partial structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2- Hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, an oligomer of 2-hydroxy- ,? -diethoxyacetophenone, benzyldimethylketal, and the like.

From the viewpoint of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by the general formula (d2).

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

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

Examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl ) -4,4 ', 5,5'-tetraphenylbiimidazole (see JPH06-75372-A, JPH06-75373-A and the like), 2,2'-bis (2-chlorophenyl) 4 ', 5,5'-tetra (alkoxyphenyl) biimidazole, 2,2'-bis (4-chlorophenyl) Bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis -Tetra (trialkoxyphenyl) biimidazole (see, for example, JPS48-38403-B, JPS62-174204-A and the like), the phenyl group at the 4,4'5,5'- position is substituted by a carboalkoxy group (See JPH07-10913-A and the like), and the like.

Examples of the polymerization initiator include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; Benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert- butylperoxycarbonyl) benzophenone Benzophenone compounds such as 2,4,6-trimethylbenzophenone; Quinone compounds such as 9,10-phenanthrenequinone, 2-ethyl anthraquinone, and campquinone; Butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with a polymerization initiator (C1) (particularly amines) to be described later.

Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4- Triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p- And iodonium hexafluoroantimonate; and nitrobenzyl tosylates, benzoin tosylates, and the like.

As the polymerization initiator to be combined with the oxime compound, an alkylphenone compound and a nonimidazole compound are preferable.

The content of the oxime compound is 30 mass% or more and 100 mass% or less, preferably 50 mass% or more and 100 mass% or less, and more preferably 70 mass% or more and 100 mass% or less, with respect to the total amount of the polymerization initiator (C) . When the oxime compound is combined with the above compound or the content of the oxime compound is within the above range, in addition to the effect of the present invention, a resin mask having different heights can be formed on the same substrate The height difference of the obtained resin pattern becomes large.

The content of the oxime compound is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 6 parts by mass, based on 100 parts by mass of the total amount of the resin (A) and the polymerizable compound (B) 0.3 to 3 parts by mass.

The content of the polymerization initiator (C) is preferably 0.1 parts by mass or more and 30 parts by mass or less, more preferably 0.2 parts by mass or more and 15 parts by mass or less, based on 100 parts by mass of the total amount of the resin (A) and the polymerizable compound (B) More preferably not less than 0.3 parts by mass and not more than 8 parts by mass, and particularly preferably not less than 0.5 parts by mass and not more than 3 parts by mass. When the content of the polymerization initiator (C) is within the above-mentioned range, productivity is improved because the sensitivity and the exposure time are shortened in addition to the effect of the present invention, and the visible light transmittance of the obtained resin pattern tends to be high have.

≪ Polymerization initiator (C1) >

The polymerization initiator (C1) is used together with the polymerization initiator (C), and a compound or a sensitizer used for accelerating the polymerization of the compound (for example, the polymerizable compound (B) to be.

Examples of the polymerization initiator (C1) include a thiazoline compound, an amine compound, an alkoxyanthracene compound, a thioxanthone compound and a carboxylic acid compound.

Examples of the thiazoline compound include compounds represented by the following formulas (III-1) to (III-3) and compounds described in JP2008-65319-A.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, (Diethylamino) benzophenone, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'- 4'-bis (ethylmethylamino) benzophenone, and the like, among which 4,4'-bis (diethylamino) benzophenone is preferable. EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) and the like may be used.

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

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

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

When the photosensitive resin composition of the present invention contains the polymerization initiator (C1), the content thereof is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 30 parts by mass based on 100 parts by mass of the total content of the resin (A) and the polymerizable compound (B) More preferably 0.2 to 10 parts by mass. When the amount of the polymerization initiator (C1) is in the above range, there is a tendency that the sensitivity becomes higher when the resin pattern is formed.

≪ Compound (1) >

The compound (1) is represented by the following formula (1).

[In the formula (1), R ¹ represents an alkyl group having 1 to 6 carbon atoms.

And A ^{1 to} A ⁴ independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Examples of the alkyl group represented by R ¹ and A ^{1 to} A ⁴ include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, .

R ¹ is preferably a methyl group or an ethyl group, more preferably a methyl group.

A ^{1 to} A ⁴ are preferably each independently a hydrogen atom or a tert-butyl group.

Examples of the compound (1) include methoxyphenol, ethoxyphenol, 2,5-tert-butylmethoxyphenol and the like.

The photosensitive resin composition of the present invention exerts the effects of the present invention by containing the compound (1) and the polymerization initiator (C) containing an oxime compound together.

The content of the compound (1) is preferably 0.02 parts by mass or more and 1 part by mass or less, more preferably 0.03 parts by mass or more and 0.4 parts by mass or less, based on 100 parts by mass of the total amount of the resin (A) and the polymerizable compound (B) Or less. When the content of the compound (1) is within the above range, the height difference of the resin pattern obtained when simultaneously forming the resin patterns having different heights on the same substrate using the halftone mask is large, and a resin pattern of a desired height can be formed . If the content of the compound (1) is in excess of the above range, the sensitivity may be significantly lowered and it may be difficult to obtain a resin pattern of a desired line width. If the content of the compound (1) is smaller than the above range, There is a fear that it will not be enough.

≪ Surfactant (H) >

Examples of the surfactant (H) include a silicone surfactant, a fluorine surfactant, and a silicon surfactant having a fluorine atom.

Examples of the silicone surfactant include a surfactant having a siloxane bond. Specific examples include DC3PA, Dowrene silicone SH7PA, Dowrene silicone DC11PA, Dowrene silicone SH21PA, Dowrene silicone SH28PA, Dowrene silicone SH29PA, Dowrene silicone SH30PA, Dowry silicone SH8400 (Manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (manufactured by Shinetsu Kagaku Kogyo Co., Ltd.)), KP321, KP323, KP324, KP326, KP340 and KP341 Momentive Performance Materials Japan Co., Ltd.).

Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain. Specific examples thereof include Fluorad (registered trademark) FC430, Fluorad FC431 (manufactured by Sumitomo 3M Ltd.), Megapack (registered trademark) F142D, Megapack F171, Megapack F172, Megapack F173, Megapack F177, , Megapack F554, Megapack R30, Megapack RS-718-K [manufactured by DIC Corporation], FEPTOPE (registered trademark) EF301, FEPTOP EF303, FEPTOP EF351, FEPTOP EF352 (manufactured by Mitsubishi Materials Corporation, (Manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Co., Ltd.), and the like, and the like, .

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

When the photosensitive resin composition of the present invention contains the surfactant (H), its content is 0.001% by mass or more and 0.2% by mass or less, preferably 0.002% by mass or more and 0.1% by mass or less, relative to the total amount of the photosensitive resin composition of the present invention. Or less, more preferably 0.01 mass% or more and 0.05 mass% or less. When the content of the surfactant (H) is within the above range, the flatness of the composition layer can be improved, so that the height deviation of the resin pattern tends to be small and the flatness of the cured film tends to be high.

≪ Solvent (E) >

The solvent (E) is not particularly limited, and a solvent commonly used in the field can be used. For example, an ester solvent (a solvent containing -COO- in the molecule and not containing -O-), an ether solvent (a solvent containing -O- and no -COO- in the molecule), an ether ester solvent ( A solvent containing -COO- and -O- in a molecule), a ketone solvent (a solvent containing -CO- in the molecule and not including -COO-), an alcohol solvent (containing OH in the molecule, -O- , A solvent not containing -CO- and -COO-), an aromatic hydrocarbon solvent, an amide solvent, dimethylsulfoxide, and the like.

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, Butyl propionate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetone, and γ-butyrolactone.

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene Propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetol, methyl anisole And the like.

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

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

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

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

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

Among the above-mentioned solvents, an organic solvent having a boiling point of 120 占 폚 or more and 180 占 폚 or less at 1 atm is preferable from the viewpoint of coatability and drying property. Among these, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol methyl ethyl ether, 3-methoxybutyl acetate and 3-methoxy-1-butanol are preferable as the organic solvent. The solvent (E) is preferably a mixed solvent containing them.

The content of the solvent (E) is preferably 60 to 95% by mass, and more preferably 70 to 95% by mass, based on the total amount of the photosensitive resin composition of the present invention. In other words, the solid content of the photosensitive resin composition of the present invention is preferably 5 to 40% by mass, and more preferably 5 to 30% by mass. When the content of the solvent (E) is within the above range, the composition layer formed of the photosensitive resin composition of the present invention tends to have a high degree of flatness, so that the resin pattern tends to have a small height deviation and a high flatness in the cured film have.

≪ Other components >

The photosensitive resin composition of the present invention may contain additives known in the art, such as fillers, other polymer compounds, thermal radical generators, ultraviolet absorbers, chain transfer agents, and adhesion promoters, if necessary.

Examples of the filler include glass, silica and alumina.

Other polymeric compounds include thermosetting resins such as maleimide resins, and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane.

Specific examples of the thermal radical generator include 2,2'-azobis (2-methylvaleronitrile) and 2,2'-azobis (2,4-dimethylvaleronitrile).

Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole and alkoxybenzophenone.

Examples of the chain transfer agent include dodecanethiol, 2,4-diphenyl-4-methyl-1-pentene and the like.

Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxy Silane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-sulfanylpropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, N Aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, N-2- (aminoethyl) N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3- Aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane and the like.

The photosensitive resin composition of the present invention contains substantially no coloring agent such as pigment and dye. That is, in the photosensitive resin composition of the present invention, the content of the coloring agent in the entire composition is, for example, less than 1% by mass, preferably less than 0.5% by mass.

When the photosensitive resin composition of the present invention is packed in a quartz cell having an optical path length of 1 cm and the transmittance is measured under the condition of a measurement wavelength of 400 to 700 nm using a spectrophotometer, the average transmittance is preferably 70 % Or more, and more preferably 80% or more.

The photosensitive resin composition of the present invention preferably has an average transmittance of 90% or more, more preferably 95% or more, of the cured film as a cured film. The average transmittance is obtained by measuring a cured film having a thickness of 2 占 퐉 after heat curing (e.g., 100 占 폚 to 250 占 폚, 5 minutes to 3 hours) under a condition of a measurement wavelength of 400 to 700 nm using a spectrophotometer It is the average value. Thus, it is possible to provide a resin pattern or a cured film excellent in transparency in the visible light region.

≪ Method of producing photosensitive resin composition >

The photosensitive resin composition of the present invention comprises a resin (A), a polymerizable compound (B), a polymerization initiator (C) and a compound (1), a solvent (E) to be used if necessary, a surfactant (H) By a known method. After mixing, it is preferable to filter with a filter having a pore diameter of about 0.05 to 1.0 mu m.

≪ Resin pattern production method >

The resin pattern formed by the photosensitive resin composition of the present invention can be produced, for example, by the following steps (1) to (4). Step (5) is preferably performed after step (4).

Step (1) Step of applying the photosensitive resin composition of the present invention to a substrate

Step (2) Step of drying the applied photosensitive resin composition to form a composition layer

Step (3) Step of exposing the composition layer through a photomask

Step (4) Step of developing the composition layer after exposure

Step (5) Step of heating the composition layer after development

Step (1) is a step of applying the photosensitive resin composition of the present invention to a substrate.

The substrate may be glass, metal, plastic, or the like, and a color filter, an insulating film, a conductive film, a driving circuit, or the like may be formed on the substrate.

The application onto the substrate is preferably performed using a coating apparatus such as a spin coater, a slit & spin coater, a slit coater, an ink jet, a roll coater or a dip coater.

Step (2) is a step of drying the applied photosensitive resin composition to form a composition layer. By carrying out this step, volatile components such as a solvent in the photosensitive resin composition are removed. Examples of the drying method include heat drying (prebaking) and drying under reduced pressure.

In the case of heating and drying, the drying temperature is preferably 30 to 120 占 폚, more preferably 50 to 110 占 폚, and the drying time is preferably 10 seconds to 60 minutes, It is 30 minutes. The heating and drying is usually carried out using a heating apparatus such as an oven and a hot plate.

In the case of performing the reduced-pressure drying, it is preferably carried out at a temperature of 20 ° C to 25 ° C under a pressure of 50 to 150 Pa.

Step (3) is a step of exposing the composition layer formed by the step (2) through a photomask. In this photomask, a light shielding portion is formed corresponding to a portion of the composition layer to be removed. The shape of the light-shielding portion is not particularly limited and may be selected according to the intended use. Particularly, by using a halftone mask or a gray scale mask, resin patterns having different heights can be simultaneously formed on the same substrate. The halftone mask is preferably a photomask having two or more kinds of transmissive portions having different transmissivity from each other and has a transmissive portion with a transmittance of 100% and a transmissive portion with a transmittance of 10 to 60%. By using such a halftone mask, it is possible to form a resin pattern having high dimensional accuracy and height.

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

It is preferable to use an exposure apparatus such as a mask aligner or a stepper because it is possible to uniformly irradiate the entire surface of the exposure surface with parallel rays or to precisely align the photomask with the composition layer.

Step (4) is a step of developing the composition layer after exposure. The exposed composition layer is brought into contact with a developing solution and developed, whereby the unexposed portion of the composition layer is dissolved and removed in the developing solution to form a resin pattern on the substrate.

As the developer, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate, tetramethylammonium hydroxide or the like is preferable. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, and more preferably 0.03 to 5% by mass. In addition, the developer may contain a surfactant.

The developing method may be any of a puddle method, a dipping method, and a spraying method. Further, the substrate may be inclined at an arbitrary angle at the time of development.

It is preferable to rinse after development.

Step (5) is a step of heating (post-baking) the composition layer after development. By heating, the durability of the resin pattern, such as heat resistance, chemical resistance and mechanical properties, is improved. Heating is usually carried out using a heating apparatus such as an oven and a hot plate. The heating temperature is preferably 120 ° C to 250 ° C, more preferably 150 ° C to 235 ° C. The heating time is preferably from 1 to 180 minutes, more preferably from 10 to 60 minutes.

From the photosensitive resin composition of the present invention, a cured film that is not patterned can also be produced by the following process. Preferred conditions of each step are the same as those of the resin pattern.

Step (1) Step of applying the photosensitive resin composition of the present invention to a substrate

Step (2) Step of drying the applied photosensitive resin composition to form a composition layer

Step (5) Step of heating the composition layer after development

If necessary, a step of exposing the process (3 ') composition layer after the step (2) without exposing the photomask may be performed. When the step (3 ') is carried out,

Step (4) The step of developing the composition layer after exposure may be performed.

The resin pattern obtained in this manner can be applied to a touch panel such as a color filter substrate and / or a photo-spacer constituting a part of an array substrate, a patternable overcoat, an interlayer insulating film, a projection for controlling liquid crystal orientation, a microlens, A color filter substrate, and / or an overcoat constituting a part of an array substrate. Particularly, since the height control when the resin patterns having different heights are simultaneously formed on the same substrate is excellent, when the photo spacers having different heights are simultaneously formed on the same substrate, the protrusions for controlling the liquid crystal alignment and the photo- Which is advantageous in simultaneous formation. The color filter substrate and the array substrate described above are suitably used for a liquid crystal display, an organic EL display, an electronic paper, and the like.

Example

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

Synthesis Example 1

In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at a flow rate of 0.02 l / min to make a nitrogen atmosphere, 200 parts by mass of 3-methoxy-1-butanol and 105 parts by mass of 3-methoxybutyl acetate were added and stirred And heated to 70 deg. Subsequently, 60 parts by mass of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl acrylate (content of the compound represented by the formula (I-1) and the content of the compound represented by the formula (Molar ratio) of 50:50) was dissolved in 140 parts by mass of 3-methoxybutyl acetate to prepare a solution. This solution was added dropwise into a flask heated to 70 ° C over 4 hours using a dropping funnel Respectively.

On the other hand, a solution prepared by dissolving 30 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator in 225 parts by weight of 3-methoxybutyl acetate was placed in a flask over 4 hours using a separate dropping funnel . (Resin Aa) having a solid content of 32.6% by mass and an acid value of 110 mg-KOH / g (in terms of solid content) was obtained by heating the solution of the polymerization initiator at 70 캜 for 4 hours. Solution. The resin Aa thus obtained had a weight average molecular weight (Mw) of 13,400 and a molecular weight distribution of 2.50. Resin Aa has the following structural units.

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

Apparatus: K2479 (manufactured by Shimadzu Corporation)

Column: SHIMADZU Shim-pack GPC-80M

Column temperature: 40 DEG C

Solvent: THF (tetrahydrofuran)

Flow rate: 1.0 ml / min

Detector: RI

Calibration standards; TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 [

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

Example  1 ~ Example  7 and Comparative Example  One

≪ Preparation of Photosensitive Resin Composition >

Each component shown in Table 1 was mixed in the ratios shown in Table 1 to obtain a photosensitive resin composition.

In Table 1, the number of parts contained in the resin (A) represents the part by mass in terms of solid content.

Resin (A); Resin Aa

Polymerizable compound (B); Dipentaerythritol hexaacrylate [KAYARAD TM DPHA; Manufactured by Nippon Kayaku Co., Ltd.]

A polymerization initiator (C); Ca; N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethan- 1-imine [Irgacure OXE 02; Manufactured by BASF; O-acyloxime compound]

A polymerization initiator (C); Cb; N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine [Irgacure (R) OXE 01; Manufactured by BASF; O-acyloxime compound]

A polymerization initiator (C); Cc; 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one [Irgacure (R) 369; Manufactured by BASF Japan Co., Ltd.; Alkylphenone compound]

A polymerization initiator (C); CD; 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole [B-CIM; Manufactured by Hodogaya Kagaku Co., Ltd.; Nonimidazole compound]

Compound (1); 1a; 4-methoxyphenol (manufactured by Tokyo Kasei Kogyo Co., Ltd.)

Surfactant (H); Polyether-modified silicone oil (Dowrel silicone SH8400; Manufactured by Dow Corning Toray Co., Ltd.]

Solvent (E); Ea; Diethylene glycol ethyl methyl ether

Solvent (E); Eb; Propylene glycol monomethyl ether acetate

Solvent (E); Ec; 3-Methoxy-1-butanol

Solvent (E); Ed; 3-methoxybutylacetate

Solvent (E); Ee; 3-ethoxyethyl propionate

The solvent (E) was mixed so that the solid content of the photosensitive resin composition was the " solid content (%) " The values of the respective components Ea to Ee in the solvent (E) represent a mass ratio (%) in the solvent (E).

<Measurement of Transmittance of Composition>

The obtained photosensitive resin composition was subjected to ultraviolet visible near infrared spectrophotometer [V-650; The average transmittance (%) at 400 to 700 nm was measured using a quartz cell (optical path length: 1 cm, manufactured by Nihon Bunko Co., Ltd.). The results are shown in Table 2.

&Lt; Preparation of cured film &

A square glass substrate (Eagle XG; manufactured by Corning) having a side of 2 inches was washed sequentially with a neutral detergent, water and alcohol, and then dried. The photosensitive resin composition was spin-coated on the glass substrate so that the film thickness after post-baking was 3.0 占 퐉 and dried under reduced pressure in a vacuum dryer (manufactured by Microtec Co., Ltd.) until the vacuum degree became 66 Pa. At 90 占 폚 for 80 seconds and dried to form a composition layer. After cooling down, an exposure machine [TME-150RSK; A light source manufactured by Topcon Co., Ltd.; Ultra-high pressure mercury lamp] at an exposure dose of 60 mJ / cm 2 (based on 365 nm) under the atmosphere. The irradiation of the composition layer at this time was carried out by irradiating the radiation from the ultra-high pressure mercury lamp with an optical filter [UV-33; (Manufactured by Asahi Bunko Co., Ltd.). After light irradiation, the composition layer after exposure was immersed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide while being rocked at 25 캜 for 60 seconds, and further washed with water. Thereafter, the film was heated in an oven at 235 DEG C for 15 minutes to obtain a cured film.

<Measurement of Transmittance of Cured Film>

The obtained cured film was measured for an average transmittance (%) at 400 to 700 nm using a microscopic spectroscopic photometry apparatus (OSP-SP200, manufactured by OLYMPUS CO., LTD.). The results are shown in Table 2.

&Lt; Resin pattern formation 1 &

A square glass substrate (Eagle XG; manufactured by Corning) having a side length of 2 inches was sequentially washed with a neutral detergent, water and isopropanol, and then dried. The photosensitive resin composition was spin-coated on the glass substrate, then reduced in pressure in a vacuum dryer to 66 Pa, and then prebaked on a hot plate at 90 DEG C for 80 seconds to form a composition layer. After cooling, the space between the substrate on which the composition layer was formed and the quartz glass photomask was set to 150 mu m, and an exposure machine (TME-150RSK; A light source manufactured by Topcon Co., Ltd.; High-pressure mercury lamp] was used to irradiate light with an exposure dose of 60 mJ / cm 2 (based on 365 nm) in an air atmosphere. Further, irradiation of the composition layer at this time was performed by irradiating the radiation from the ultra-high pressure mercury lamp with an optical filter [UV-33; (Manufactured by Asahi Bunko Co., Ltd.). The photomask used was a halftone mask in which the shape of the transmissive portion was a square with 20 占 퐉 in one side, the square was arranged at 100 占 퐉 intervals, and the transmissivity of the transmissive portion was 100% and 25%.

After the light irradiation, the coating film was immersed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide while shaking the coating film at 23 캜 for 60 seconds, and developed and further washed. Thereafter, post-baking was performed in an oven at 235 DEG C for 15 minutes to obtain a resin pattern.

&Lt; Resin pattern formation 2 >

A square glass substrate (Eagle XG; manufactured by Corning) having a side length of 2 inches was sequentially washed with a neutral detergent, water and isopropanol, and then dried. The photosensitive resin composition was spin-coated on the glass substrate, then reduced in pressure in a vacuum dryer to 66 Pa, and then prebaked on a hot plate at 90 DEG C for 80 seconds to form a composition layer. After cooling, the distance between the substrate on which the composition layer was formed and the quartz glass photomask was set to 200 mu m, exposure was performed with an exposure machine (TME-150RSK; A light source manufactured by Topcon Co., Ltd.; Ultra-high pressure mercury lamp] at an exposure dose of 60 mJ / cm 2 (based on 365 nm) under the atmosphere. Exposure to the composition layer at this time was performed by irradiating the radiation from the ultra-high pressure mercury lamp with an optical filter [UV-33; (Manufactured by Asahi Bunko Co., Ltd.). The photomask used was a binary mask in which the shape of the light transmitting portion was a square having one side of 20 占 퐉 and one side of 12 占 퐉 square, each square being arranged at an interval of 100 占 퐉, and the transmittance of the light transmitting portion being 100%.

After the light irradiation, the coating film was immersed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide while shaking the coating film at 23 캜 for 60 seconds, and developed and further washed. Thereafter, post-baking was performed in an oven at 235 DEG C for 15 minutes to obtain a resin pattern.

<Evaluation; Measurement of width and height of resin pattern >

The width and height of the obtained resin pattern were measured using a three-dimensional non-contact surface shape measuring system [Micromap MM527N-PS-M100; (Manufactured by Ryoka System Co., Ltd.). The width of the resin pattern was measured at a height of 5% of the height of the resin pattern with respect to the substrate surface.

In the resin Pattern 1, the height of resin pattern formed by the transparent portion of the transmittance 100% (hereinafter referred to as "H _100") and a height of resin pattern formed by the transparent portion of the transmittance 25% (hereinafter referred to as "H _25" , The difference [H ₁₀₀ -H ₂₅ ] between the measured values was obtained. When resin patterns having different heights are simultaneously formed on the same substrate, the larger the height difference is, the more advantageous it is.

(Hereinafter referred to as &quot; _H20 &quot;) formed by a square transparent portion having a side of 20 mu m and a height of a resin pattern formed by a transparent portion of a square having one side of 12 mu m (Hereinafter referred to as "H _S12 "), the difference [H _S20 -H _S12 ] between them was obtained. When resin patterns having different heights are simultaneously formed on the same substrate, the larger the height difference is, the more advantageous it is. The results are shown in Table 2.

From the results shown in Table 2, it was confirmed that the photosensitive resin composition of the present invention is advantageous when a resin pattern having different heights is simultaneously formed on the same substrate using a halftone mask.

According to the photosensitive resin composition of the present invention, when a resin pattern having different heights is simultaneously formed on the same substrate by using a halftone mask, the height difference of the obtained resin pattern is large.

Claims (6)

A photosensitive resin composition comprising (A), (B), (C) and (D) below, wherein the content of (D) is 0.03 parts by mass or more and 0.4 parts by mass or more based on 100 parts by mass of the total of Parts by mass or less:
(A) a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, a structural unit derived from a monomer having a cyclic ether structure having 2 to 4 carbon atoms and a monomer having an ethylenic unsaturated bond &Lt; / RTI &gt;
(B) a polymerizable compound;
(C) a polymerization initiator comprising an oxime compound, wherein the content of the oxime compound is 30% by mass or more and 100% by mass or less based on the total amount of the polymerization initiator;
(D) A compound represented by the following formula (1).

[In the formula (1), R ¹ represents an alkyl group having 1 to 6 carbon atoms. And A ^{1 to} A ⁴ independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The photosensitive resin composition according to claim 1, wherein the content of (C) is 0.1 part by mass or more and 30 parts by mass or less based on 100 parts by mass of the total content of (A) and (B). delete A resin pattern formed from the photosensitive resin composition according to claim 1 or 2. A photo-spacer formed from the photosensitive resin composition according to claim 1 or 2. A display device comprising the resin pattern according to claim 4.