KR102066289B1 - Photosensitive resin composition - Google Patents

Abstract

[식 (1) 중, A¹∼A⁴는, 각각 독립적으로, 수소 원자 또는 탄소수 1∼6의 알킬기를 나타낸다.]A structural unit derived from at least one selected from the group consisting of a resin, a polymerizable compound, a polymerization initiator and a compound represented by the formula (1), wherein the resin is selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, A compound containing a copolymer having a structural unit derived from a monomer having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond, wherein the polymerization initiator contains an O-acyl oxime compound and is represented by Formula (1) The photosensitive resin composition whose content is 0.25 mass part or more and 3 mass parts or less with respect to 100 mass parts of resin.

[In Formula (1), A <^1> -A <^4> respectively independently represents a hydrogen atom or a C1-C6 alkyl group.]

Description

Photosensitive resin composition {PHOTOSENSITIVE RESIN COMPOSITION}

The present invention relates to a photosensitive resin composition.

In recent liquid crystal display devices, in order to form patterned resin cured films, such as a photospacer and an overcoat, the photosensitive resin composition is used. As such a photosensitive resin composition, the copolymer of methacrylic acid and 3, 4- epoxy cyclocyclo [5.2.1.0 ^2.6 ] decyl acrylate, dipentaerythritol hexaacrylate, N-acetoxy-1- [9-ethyl- The composition which consists of 6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethane-1-imine and a solvent is known (JP2008-181087-A).

In the photosensitive resin composition conventionally proposed, when forming the patterned resin cured film from which height differs simultaneously on a same board | substrate using a halftone mask, the height difference of the patterned resin cured film obtained is small, and the patterned resin effect of desired height is carried out. There was a case where a film could not be obtained.

This invention includes the following inventions.

[1] a resin, a polymerizable compound, a polymerization initiator, and a compound represented by the formula (1);

Resin is a structural unit derived from the structural unit derived from at least 1 sort (s) chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride, and the monomer which has a C2-C4 cyclic ether structure and ethylenically unsaturated bond. It includes a copolymer having,

The polymerization initiator contains an O-acyl oxime compound,

The photosensitive resin composition whose content of the compound represented by Formula (1) is 0.25 mass part or more and 3 mass parts or less with respect to 100 mass parts of resin.

[In Formula (1), A <^1> -A <^4> respectively independently represents a hydrogen atom or a C1-C6 alkyl group.]

[2] The photosensitive resin composition according to [1], in which the resin further includes a resin having an ethylenically unsaturated bond in the side chain.

[3] A photo spacer formed from the photosensitive resin composition according to [1] or [2].

[4] A display device comprising the photospacer of [3].

According to the photosensitive resin composition of this invention, when forming the patterned resin cured film from which height differs simultaneously on a same board | substrate using a halftone mask, the height difference of the patterned resin cured film obtained is large.

In this specification, the compound illustrated as each component can be used individually or in combination of multiple types, unless there is particular notice.

The photosensitive resin composition of this invention contains resin (A), a polymeric compound (B), a polymerization initiator (C), and the compound represented by Formula (1) (hereinafter may be called "compound (1)"). do.

Moreover, it is preferable that the photosensitive resin composition of this invention contains at least 1 sort (s) chosen from the group which consists of a solvent (E) and surfactant (H).

Moreover, the photosensitive resin composition of this invention may contain at least 1 sort (s) chosen from the group which consists of an adhesion promoter (J) and a polymerization start adjuvant (C1).

<Resin (A)>

The resin (A) is a structural unit derived from at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter may be referred to as "(a)"), and has 2 to 4 carbon atoms. The copolymer which has a structural unit derived from the monomer which has a cyclic ether structure and ethylenically unsaturated bond (Hereinafter, it may be called "(b)") is included (Hereinafter, it may be called "copolymer (K).") It is resin to make. The copolymer (K) further has a structural unit that is copolymerizable with (a) and derived from a monomer (hereinafter sometimes referred to as "(c)") which does not have a cyclic ether structure having 2 to 4 carbon atoms. You may be.

As a copolymer (K), a copolymer [K1] and a copolymer [K2] are mentioned, for example.

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

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

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinyl benzoic 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-ene , 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo Bicyclo unsaturated compounds containing carboxyl groups, such as [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 dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride;

Unsaturated mono [(meth) acryloyloxyalkyl of a divalent or higher polyhydric carboxylic acid such as succinic acid mono [2- (meth) acryloyloxyethyl] and monophthalate [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, (meth) acrylic acid, maleic anhydride, etc. are preferable at the point of copolymerization reactivity and the solubility to aqueous alkali solution, and (meth) acrylic acid is more preferable.

In addition, in this specification, "(meth) acryloyl" shows 1 or more types chosen from the group which consists of acryloyl and methacryloyl. Notation, such as "(meth) acrylic acid" and "(meth) acrylate", has the same meaning.

Examples of the cyclic ether structure having 2 to 4 carbon atoms in (b) include an oxirane ring, an oxetane ring and a tetrahydrofuran ring. As for (b), the monomer which has a C2-C4 cyclic ether and a (meth) acryloyloxy group is preferable.

As (b), for example, a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)") and a monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond (hereinafter "( b2) ", and the monomer (b3) (Hereinafter, it may be called" (b3) ") which has a tetrahydrofuryl group and ethylenically unsaturated bond.

As (b1), the monomer (b1-1) (hereinafter sometimes referred to as "(b1-1)") and the unsaturated alicyclic hydrocarbon which have a structure where the linear or branched unsaturated aliphatic hydrocarbon is epoxidized are epoxidized, for example. The monomer (b1-2) (Hereinafter, it may be called "(b1-2)") which has a structure which has become, is mentioned.

Examples of (b1-1) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether and o-vinyl benzyl. Glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α -Methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxy Methyl) 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.

(b1-2) include, for example, vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane [eg, ceoxide 2000; Daicel Corporation], 3, 4- epoxycyclohexylmethyl (meth) acrylate [for example, cyclomer A400; Daicel Corporation], 3, 4- epoxycyclohexyl methyl (meth) acrylate [For example, cyclomer M100; Daicel Corporation], the compound represented by following formula (I), the compound represented by formula (II), etc. are mentioned.

[In Formula (I) and Formula (II), R <^b1> and R <^b2> represent a hydrogen atom or a C1-C4 alkyl group, and the hydrogen atom contained in this alkyl group may be substituted by the 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 with O.]

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

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

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, and more preferably a hydrogen atom and a methyl group.

Examples of alkanediyl groups include methylene, ethylene, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl and hexane-1 And a 6-diyl group.

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-, and more preferably a single bond and * -CH. ₂ CH ₂ -O- (* indicates the number of bonds with O).

As a compound represented by Formula (I), the compound etc. which are represented by either of following formula (I-1)-formula (I-15) are mentioned. Especially, Formula (I-1), Formula (I-3), Formula (I-5), Formula (I-7), Formula (I-9), or Formulas (I-11) to (I-15) ) Is preferably a compound represented by the formula (I-1), (I-7), (I-9) or (I-15).

As a compound represented by Formula (II), the compound etc. which are represented by either of following formula (II-1)-formula (II-15) are mentioned. Especially, Formula (II-1), Formula (II-3), Formula (II-5), Formula (II-7), Formula (II-9), or Formula (II-11) to Formula (II-15) ) Is preferable, and the compound represented by formula (II-1), formula (II-7), formula (II-9) or formula (II-15) is more preferable.

The compound represented by Formula (I) and the compound represented by Formula (II) may be used independently, respectively, and may use together the compound represented by Formula (I) and the compound represented by Formula (II). When using these together, the content rate of the compound represented by Formula (I) and the compound represented by Formula (II) is based on molar basis, Preferably it is 5: 95-95: 5, More preferably, it is 10: 90-90. : 10, More preferably, it is 20: 80-80: 20.

As (b2), the monomer which has an oxetanyl group and a (meth) acryloyloxy group is more preferable. Examples of (b2) include 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3- Ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacrylo Iloxy ethyl oxetane, 3-ethyl-3- acryloyloxy ethyl oxetane, etc. are mentioned.

As (b3), the monomer which has a tetrahydrofuryl group and a (meth) acryloyloxy group is more preferable. Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, biscoat V # 150, manufactured by Osaka Yuki Kagaku Kogyo Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

As (b), (b1) is preferable at the point which can raise the reliability, such as heat resistance and chemical-resistance, of the patterned resin cured film obtained or the unpatterned resin cured film more. Moreover, since it is excellent in the storage stability of the photosensitive resin composition, (b1-2) is more preferable, and the compound represented by Formula (I) or Formula (II) is still more preferable.

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-methylcyclo Hexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate [In the art, it is commonly known as "dicyclopentanyl (meth) acrylate". In addition, it may be called "tricyclodecyl (meth) acrylate.", And tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate [In the technical field, a common name is "dicish". Copenpentenyl (meth) acrylate], dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, (Meth) acrylic acid esters such as propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate and benzyl (meth) acrylate;

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

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

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 Cycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-bi Ratios of s (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene and 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene Cyclo unsaturated compounds;

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, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide And vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like.

Among them, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and the like are preferable in terms of copolymerization reactivity and heat resistance. .

In copolymer [K1], the ratio of the structural unit derived from each monomer is with respect to the all the structural units which comprise copolymer [K1],

structural unit derived from (a); 1 to 70 mol%

structural unit derived from (b); 30-99 mol% is preferable,

structural unit derived from (a); 10-50 mol%

structural unit derived from (b); 50-90 mol% is more preferable.

When the ratio of the structural unit constituting the copolymer [K1] is within the above range, the storage stability of the photosensitive resin composition, the chemical resistance, heat resistance and mechanical strength of the resulting patterned resin cured film or unpatterned resin cured film are Tends to be excellent.

The copolymer [K1] is, for example, the method described in the document "Experimental method of polymer synthesis" [Oct Takayuki, Otsu Chemical Co., Ltd. First Edition First Edition March 1, 1972] and the citations described in this document. It can manufacture by reference.

Specifically, a method of heating and keeping warm while stirring in a deoxygen atmosphere by putting a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like into a reaction vessel and replacing oxygen with nitrogen, for example, is mentioned. have. In addition, the polymerization initiator, 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.] and an organic peroxide (benzoyl peroxide etc.) are used. As a solvent, what is necessary is just to melt | dissolve each monomer, and the solvent etc. which are mentioned later used for the photosensitive resin composition are mentioned.

In addition, the obtained resin 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. In particular, by using the solvent used for the photosensitive resin composition of this invention as a polymerization solvent, since the solution after reaction can be used as it is for manufacture of the photosensitive resin composition of this invention, the manufacturing process of the photosensitive resin composition of this invention can be simplified. have.

In copolymer [K2], the ratio of the structural unit derived from each is in the all the structural units which comprise copolymer [K2],

structural unit derived from (a); 2-40 mol%

structural unit derived from (b); 30 to 95 mol%

structural unit derived from (c); It is preferable that it is 1-65 mol%,

structural unit derived from (a); 5 to 35 mol%

structural unit derived from (b); 35 to 80 mol%

structural unit derived from (c); It is more preferable that it is 1-60 mol%.

Moreover, as for the total amount of the structural unit derived from (a) and the structural unit derived from (b), 70-99 mol% is preferable with respect to the total mole number of all the structural units which comprise copolymer [K2], and 90-99 Mole% is more preferable.

When the ratio of the structural unit of the copolymer [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 patterned resin cured film or unpatterned resin cured film are excellent. have.

Copolymer [K2] can be manufactured by the same method as copolymer [K1].

As a specific example of copolymer [K1], the compound represented by (meth) acrylic acid / formula (I-1) may be abbreviated as "formula (I-1)" hereafter. The other is the same), the copolymer of (meth) acrylic acid / formula (I-2), the copolymer of (meth) acrylic acid / formula (I-3), (meth) acrylic acid / formula (I-4) Copolymer of (meth) acrylic acid / formula (I-5), copolymer of (meth) acrylic acid / formula (I-6), copolymer of (meth) acrylic acid / formula (I-7), Copolymer of (meth) acrylic acid / formula (I-8), copolymer of (meth) acrylic acid / formula (I-9), copolymer of (meth) acrylic acid / formula (I-10), (meth) acrylic acid / formula Copolymer of (I-11), copolymer of (meth) acrylic acid / formula (I-12), copolymer of (meth) acrylic acid / formula (I-13), (meth) acrylic acid / formula (I-14) Copolymer of (meth) acrylic acid / formula (I-15), copolymer of (meth) acrylic acid / formula (II-1), copolymer of (meth) acrylic acid / formula (II-2), ( Mat) Copolymer of methacrylic acid / formula (II-3), copolymer of (meth) acrylic acid / formula (II-4), copolymer of (meth) acrylic acid / formula (II-5), (meth) acrylic acid / formula ( II-6) copolymer, (meth) acrylic acid / copolymer of formula (II-7), (meth) acrylic acid / copolymer of formula (II-8), (meth) acrylic acid / formula (II-9) Copolymer, copolymer of (meth) acrylic acid / formula (II-10), copolymer of (meth) acrylic acid / formula (II-11), copolymer of (meth) acrylic acid / formula (II-12), (meth Copolymer of acrylic acid / formula (II-13), copolymer of (meth) acrylic acid / formula (II-14), copolymer of (meth) acrylic acid / formula (II-15), (meth) acrylic acid / formula ( I-1) / copolymer of formula (II-1), (meth) acrylic acid / copolymer of formula (I-2) / formula (II-2), (meth) acrylic acid / formula (I-3) / formula Copolymer of (II-3), copolymer of (meth) acrylic acid / formula (I-4) / formula (II-4), of (meth) acrylic acid / formula (I-5) / formula (II-5) Copolymer, (meth) acrylic acid / copolymer of formula (I-6) / formula (II-6), (meth) a Copolymer of lactic acid / formula (I-7) / formula (II-7), copolymer of (meth) acrylic acid / formula (I-8) / formula (II-8), (meth) acrylic acid / formula (I- 9) / copolymer of formula (II-9), (meth) acrylic acid / copolymer of formula (I-10) / formula (II-10), (meth) acrylic acid / formula (I-11) / formula (II -11) copolymer, (meth) acrylic acid / copolymer of formula (I-12) / formula (II-12), (meth) acrylic acid / copolymer of formula (I-13) / formula (II-13) , (Meth) acrylic acid / copolymer of formula (I-14) / formula (II-14), (meth) acrylic acid / copolymer of formula (I-15) / formula (II-15), (meth) acrylic acid / Copolymer of formula (I-1) / formula (I-7), copolymer of (meth) acrylic acid / formula (I-1) / formula (II-7), air of crotonic acid / formula (I-1) Copolymer, copolymer of crotonic acid / formula (I-2), copolymer of crotonic acid / formula (I-3), copolymer of crotonic acid / formula (I-4), crotonic acid / formula (I-5) Copolymer of crotonic acid / formula (I-6), copolymer of crotonic acid / formula (I-7), copolymer of crotonic acid / formula (I-8), crotonic acid / formula (I-) 9), public Sieve, copolymer of crotonic acid / formula (I-10), copolymer of crotonic acid / formula (I-11), copolymer of crotonic acid / formula (I-12), crotonic acid / formula (I-13) Copolymer of, crotonic acid / copolymer of formula (I-14), copolymer of crotonic acid / formula (I-15), copolymer of crotonic acid / formula (II-1), crotonic acid / formula (II- Copolymer of 2), copolymer of crotonic acid / formula (II-3), copolymer of crotonic acid / formula (II-4), copolymer of crotonic acid / formula (II-5), crotonic acid / formula ( II-6) copolymer, crotonic acid / copolymer of formula (II-7), crotonic acid / copolymer of formula (II-8), crotonic acid / copolymer of formula (II-9), crotonic acid / Copolymer of formula (II-10), copolymer of crotonic acid / formula (II-11), copolymer of crotonic acid / formula (II-12), copolymer of crotonic acid / formula (II-13), croton Copolymer of acid / formula (II-14), copolymer of crotonic acid / formula (II-15), copolymer of maleic acid / formula (I-1), copolymer of maleic acid / formula (I-2) , Maleic acid / copolymer of formula (I-3), maleic acid / formula ( I-4) copolymer, maleic acid / copolymer of formula (I-5), maleic acid / copolymer of formula (I-6), maleic acid / copolymer of formula (I-7), maleic acid / Copolymer of formula (I-8), maleic acid / copolymer of formula (I-9), maleic acid / copolymer of formula (I-10), maleic acid / copolymer of formula (I-11), male Acid / copolymer of formula (I-12), maleic acid / copolymer of formula (I-13), maleic acid / copolymer of formula (I-14), maleic acid / copolymer of formula (I-15) , Copolymer of maleic acid / formula (II-1), copolymer of maleic acid / formula (II-2), copolymer of maleic acid / formula (II-3), maleic acid / formula (II-4) Copolymer, maleic acid / copolymer of formula (II-5), maleic acid / copolymer of formula (II-6), maleic acid / copolymer of formula (II-7), maleic acid / formula (II-8) Copolymer of maleic acid / formula (II-9), copolymer of maleic acid / formula (II-10), copolymer of maleic acid / formula (II-11), maleic acid / formula (II) -12) copolymer, maleic acid / copolymer of formula (II-13), maleic acid / copolymer of formula (II-14), maleic acid / formula of formula (II-15) Polymer, copolymer of (meth) acrylic acid / maleic anhydride / formula (I-1), copolymer of (meth) acrylic acid / maleic anhydride / formula (I-2), (meth) acrylic acid / maleic anhydride / formula Copolymer of (I-3), copolymer of (meth) acrylic acid / maleic anhydride / formula (I-4), copolymer of (meth) acrylic acid / maleic anhydride / formula (I-5), (meth) Copolymer of acrylic acid / maleic anhydride / formula (I-6), copolymer of (meth) acrylic acid / maleic anhydride / formula (I-7), (meth) acrylic acid / maleic anhydride / formula (I-8) Copolymer of (meth) acrylic acid / maleic anhydride / formula (I-9), copolymer of (meth) acrylic acid / maleic anhydride / formula (I-10), (meth) acrylic acid / maleic anhydride / Copolymer of formula (I-11), (meth) acrylic acid / maleic anhydride / copolymer of formula (I-12), (meth) acrylic acid / maleic anhydride / copolymer of formula (I-13), ( (Meth) acrylic acid / maleic anhydride / copolymer of formula (I-14), (meth) acrylic acid / maleic acid Copolymer of water / formula (I-15), copolymer of (meth) acrylic acid / maleic anhydride / formula (II-1), copolymer of (meth) acrylic acid / maleic anhydride / formula (II-2), (Meth) acrylic acid / maleic anhydride / copolymer of formula (II-3), (meth) acrylic acid / maleic anhydride / copolymer of formula (II-4), (meth) acrylic acid / maleic anhydride / formula (II -5) copolymer, (meth) acrylic acid / maleic anhydride / copolymer of formula (II-6), (meth) acrylic acid / maleic anhydride / copolymer of formula (II-7), (meth) acrylic acid / Copolymer of maleic anhydride / formula (II-8), copolymer of (meth) acrylic acid / maleic anhydride / formula (II-9), air of (meth) acrylic acid / maleic anhydride / formula (II-10) Copolymer, copolymer of (meth) acrylic acid / maleic anhydride / formula (II-11), copolymer of (meth) acrylic acid / maleic anhydride / formula (II-12), (meth) acrylic acid / maleic anhydride / formula Copolymer of (II-13), (meth) acrylic acid / maleic anhydride / air of formula (II-14) A copolymer, a copolymer of (meth) acrylic acid / maleic anhydride / formula (II-15), etc. are mentioned.

Specific examples of the copolymer [K2] include a copolymer of (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate, (meth) acrylic acid / formula (I-2) / methyl (meth) acrylate Copolymer of, (meth) acrylic acid / copolymer of formula (I-3) / methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (I-4) / methyl (meth) acrylate, (meth A copolymer of acrylic acid / formula (I-5) / methyl (meth) acrylate, a copolymer of (meth) acrylic acid / formula (I-6) / methyl (meth) acrylate, (meth) acrylic acid / formula (I) -7) / copolymer of methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (I-8) / methyl (meth) acrylate, (meth) acrylic acid / formula (I-9) / methyl ( Copolymer of (meth) acrylate, copolymer of (meth) acrylic acid / formula (I-10) / methyl (meth) acrylate, and air of (meth) acrylic acid / formula (I-11) / methyl (meth) acrylate Of the copolymer, (meth) acrylic acid / formula (I-12) / methyl (meth) acrylate Polymer, copolymer of (meth) acrylic acid / formula (I-13) / methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (I-14) / methyl (meth) acrylate, (meth) acrylic acid / Copolymer of formula (I-15) / methyl (meth) acrylate, (meth) acrylic acid / copolymer of formula (II-1) / methyl (meth) acrylate, (meth) acrylic acid / formula (II-2 Copolymer of () / methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (II-3) / methyl (meth) acrylate, (meth) acrylic acid / formula (II-4) / methyl (meth) Copolymer of acrylate, copolymer of (meth) acrylic acid / formula (II-5) / methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (II-6) / methyl (meth) acrylate, Copolymer of (meth) acrylic acid / formula (II-7) / methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (II-8) / methyl (meth) acrylate, (meth) acrylic acid / formula Copolymer of (II-9) / methyl (meth) acrylate, (meth Copolymer of acrylic acid / formula (II-10) / methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (II-11) / methyl (meth) acrylate, (meth) acrylic acid / formula ( II-12) / Copolymer of methyl (meth) acrylate, (meth) acrylic acid / copolymer of formula (II-13) / methyl (meth) acrylate, (meth) acrylic acid / formula (II-14) / methyl Copolymer of (meth) acrylate, copolymer of (meth) acrylic acid / formula (II-15) / methyl (meth) acrylate, (meth) acrylic acid / formula (I-1) / dicyclopentanyl (meth) acrylic Copolymer of rate, (meth) acrylic acid / copolymer of formula (II-1) / dicyclopentanyl (meth) acrylate, (meth) acrylic acid / formula (I-1) / formula (II-1) / dicyclo Copolymer of fentanyl (meth) acrylate, copolymer of crotonic acid / formula (I-1) / dicyclopentanyl (meth) acrylate, maleic acid / formula (I-1) / dicyclopentanyl (meth) acrylate Copolymers of (meth) acrylic acid / maleic acid Copolymer of water / formula (I-1) / dicyclopentanyl (meth) acrylate, air of (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate / dicyclopentanyl (meth) acrylate Copolymer, copolymer of crotonic acid / formula (II-1) / dicyclopentanyl (meth) acrylate, copolymer of maleic acid / formula (II-1) / dicyclopentanyl (meth) acrylate, (meth) acrylic acid A copolymer of / maleic anhydride / formula (II-1) / dicyclopentanyl (meth) acrylate, (meth) acrylic acid / formula (II-1) / methyl (meth) acrylate / dicyclopentanyl (meth) acrylic Copolymer of rate, copolymer of (meth) acrylic acid / formula (I-1) / phenyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (II-1) / phenyl (meth) acrylate, ( Copolymer of methacrylic acid / formula (I-1) / formula (II-1) / phenyl (meth) acrylate, copolymer of crotonic acid / formula (I-1) / phenyl (meth) acrylate, maleic acid / Formula (I-1) / phenyl (meth) Copolymer of releasing, copolymer of (meth) acrylic acid / maleic anhydride / formula (I-1) / phenyl (meth) acrylate, (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate Copolymer of / phenyl (meth) acrylate, copolymer of crotonic acid / formula (II-1) / phenyl (meth) acrylate, copolymer of maleic acid / formula (II-1) / phenyl (meth) acrylate , Copolymer of (meth) acrylic acid / maleic anhydride / formula (II-1) / phenyl (meth) acrylate, (meth) acrylic acid / formula (II-1) / methyl (meth) acrylate / phenyl (meth) Copolymer of acrylate, copolymer of (meth) acrylic acid / formula (I-1) / maleic acid, copolymer of (meth) acrylic acid / formula (II-1) / diethyl maleate, (meth) acrylic acid / formula Copolymer of (I-1) / formula (II-1) / diethyl maleate, copolymer of crotonic acid / formula (I-1) / diethyl maleate, maleic acid / formula (I-1) / diethyl maleate Copolymers of (meth) acrylic acid / maleic anhydride / formula (I-1) / maleic acid Copolymer of ethyl, copolymer of (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate / diethyl maleate, copolymer of crotonic acid / formula (II-1) / diethyl maleate, maleic acid / Copolymer of formula (II-1) / diethyl maleate, (meth) acrylic acid / maleic anhydride / copolymer of formula (II-1) / diethyl maleate, (meth) acrylic acid / formula (II-1) / Copolymer of methyl (meth) acrylate / diethyl maleate, copolymer of (meth) acrylic acid / formula (I-1) / 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid / formula (II-1 ) / Copolymer of 2-hydroxyethyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (I-1) / formula (II-1) / 2-hydroxyethyl (meth) acrylate, croton Copolymer of acid / formula (I-1) / 2-hydroxyethyl (meth) acrylate, copolymer of maleic acid / formula (I-1) / 2-hydroxyethyl (meth) acrylate, (meth) Of acrylic acid / maleic anhydride / formula (I-1) / 2-hydroxyethyl (meth) acrylate Polymer, copolymer of (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate, crotonic acid / formula (II-1) / 2-hydroxyethyl Copolymer of (meth) acrylate, maleic acid / formula (II-1) / 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid / maleic anhydride / formula (II-1) / 2 -Copolymer of hydroxyethyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (II-1) / methyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid Copolymer of / formula (I-1) / bicyclo [2.2.1] hept-2-ene, air of (meth) acrylic acid / formula (II-1) / bicyclo [2.2.1] hept-2-ene Copolymer, copolymer of (meth) acrylic acid / formula (I-1) / formula (II-1) / bicyclo [2.2.1] hept-2-ene, crotonic acid / formula (I-1) / bicyclo [ 2.2.1] copolymer of hept-2-ene, maleic acid / formula (I-1) / bicyclo [2.2.1] copolymer of hept-2-ene, (meth) acrylic acid / maleic anhydride / formula ( I- 1) / Copolymer of bicyclo [2.2.1] hept-2-ene, (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate / bicyclo [2.2.1] hept-2-ene Copolymer of, crotonic acid / formula (II-1) / bicyclo [2.2.1] hept-2-ene, copolymer of maleic acid / formula (II-1) / bicyclo [2.2.1] hept-2 Copolymer of -ene, copolymer of (meth) acrylic acid / maleic anhydride / formula (II-1) / bicyclo [2.2.1] hept-2-ene, (meth) acrylic acid / formula (II-1) / Copolymer of methyl (meth) acrylate / bicyclo [2.2.1] hept-2-ene, copolymer of (meth) acrylic acid / formula (I-1) / N-cyclohexylmaleimide, (meth) acrylic acid / Copolymer of formula (II-1) / N-cyclohexylmaleimide, copolymer of (meth) acrylic acid / formula (I-1) / formula (II-1) / N-cyclohexylmaleimide, crotonic acid / formula Copolymer of (I-1) / N-cyclohexylmaleimide, copolymer of maleic acid / formula (I-1) / N-cyclohexylmaleimide, (meth) acrylic acid / maleic anhydride / formula (I-1 ) / N-cyclohexylmaleic Copolymer of de, copolymer of (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate / N-cyclohexylmaleimide, crotonic acid / formula (II-1) / N-cyclohexylmaleimide Copolymer of, a copolymer of maleic acid / formula (II-1) / N-cyclohexylmaleimide, a copolymer of (meth) acrylic acid / maleic anhydride / formula (II-1) / N-cyclohexylmaleimide, Copolymer of (meth) acrylic acid / formula (II-1) / methyl (meth) acrylate / N-cyclohexylmaleimide, copolymer of (meth) acrylic acid / formula (I-1) / styrene, (meth) acrylic acid Copolymer of / formula (II-1) / styrene, copolymer of (meth) acrylic acid / formula (I-1) / formula (II-1) / styrene, air of crotonic acid / formula (I-1) / styrene Copolymer of copolymer, maleic acid / formula (I-1) / styrene, copolymer of (meth) acrylic acid / maleic anhydride / formula (I-1) / styrene, (meth) acrylic acid / formula (I-1) / Copolymer of methyl (meth) acrylate / styrene, copolymer of crotonic acid / formula (II-1) / styrene, Copolymer of maleic acid / formula (II-1) / styrene, copolymer of (meth) acrylic acid / maleic anhydride / formula (II-1) / styrene, (meth) acrylic acid / formula (II-1) / methyl ( Copolymer of (meth) acrylate / styrene, copolymer of (meth) acrylic acid / formula (I-1) / N-cyclohexylmaleimide / styrene, (meth) acrylic acid / formula (II-1) / N-cyclohexyl Copolymer of maleimide / styrene, copolymer of (meth) acrylic acid / formula (I-1) / formula (II-1) / N-cyclohexylmaleimide / styrene, crotonic acid / formula (I-1) / N Copolymer of -cyclohexyl maleimide / styrene, copolymer of maleic acid / formula (I-1) / N-cyclohexyl maleimide / styrene, (meth) acrylic acid / maleic anhydride / formula (I-1) / N Copolymer of cyclohexylmaleimide / styrene, copolymer of (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate / N-cyclohexylmaleimide / styrene, crotonic acid / formula (II-1 ) / N-cyclohexylmaleimide / styrene copolymer, maleic acid / formula Copolymer of (II-1) / N-cyclohexylmaleimide / styrene, copolymer of (meth) acrylic acid / maleic anhydride / formula (II-1) / N-cyclohexylmaleimide / styrene, (meth) acrylic acid And copolymers of formula (II-1) / methyl (meth) acrylate / N-cyclohexylmaleimide / styrene.

The weight average molecular weight of polystyrene conversion of the copolymer (K) becomes like this. Preferably it is 3,000-100,000, More preferably, it is 5,000-50,000, More preferably, it is 5,000-20,000, Especially preferably, it is 5,000-15,000. When the weight average molecular weight of a copolymer (K) exists in the said range, there exists a tendency for the applicability | paintability of the photosensitive resin composition to become favorable.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the copolymer (K) is preferably 1.1 to 6.0, and more preferably 1.2 to 4.0. When the molecular weight distribution of a copolymer (K) exists in the said range, the patterned resin cured film obtained and the uncured resin cured film tend to be excellent in chemical resistance.

The acid value of the copolymer (K) is preferably 30 mg-KOH / g or more and 180 mg-KOH / g or less, more preferably 40 mg-KOH / g or more and 150 mg-KOH / g or less, particularly preferably Is 50 mg-KOH / g or more and 135 mg-KOH / g or less. The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin, and can be obtained by titrating with an aqueous potassium hydroxide solution. If the acid value of copolymer (K) exists in the said range, the patterned resin cured film obtained or the uncured resin cured film tends to be excellent in adhesiveness with a board | substrate.

It is preferable that resin (A) contains resin other than a copolymer (K). As resin other than copolymer (K), resin which has an ethylenically unsaturated bond in a side chain (hereinafter may be called "resin (M)") is preferable. As resin which has an ethylenically unsaturated bond in such a side chain, resin [M1]-resin [M3] are mentioned, for example.

Resin [M1]; Resin which (b) was made to react the copolymer of (a) and (c);

Resin [M2]; Resin which (a) was made to react the copolymer of (b) and (c);

Resin [M3]; Resin which (a) was made to react with the copolymer of (b) and (c), and carboxylic anhydride was made to react further.

Resin [M1] obtains the copolymer of (a) and (c), and adds the C2-C4 cyclic ether which (b) has to carboxylic acid and / or carboxylic anhydride which (a) has It can manufacture.

First, the copolymer of (a) and (c) is manufactured similarly to the method described as a manufacturing method of copolymer [K1]. In this case, the ratio of the structural unit derived from each of the all the structural units which comprise resin [M1],

structural unit derived from (a); 2 to 60 mol%

structural unit derived from (c); 40-98 mol%

Is preferably,

structural unit derived from (a); 10-50 mol%

structural unit derived from (c); 50 to 90 mol%

It is more preferable that is.

Next, the C2-C4 cyclic ether which (b) has is made to react with a part of carboxylic acid and / or carboxylic anhydride derived from (a) in the said copolymer.

Subsequent to the preparation of the copolymers of (a) and (c), the atmosphere in the flask was replaced with nitrogen to air, and (b) a reaction catalyst of carboxylic acid or carboxylic anhydride with a cyclic ether (e.g. tris (dimethylamino Resin [M1] can be manufactured by making methyl) phenol etc.) and a polymerization inhibitor (for example, hydroquinone etc.) into a flask, and making it react, for example at 60-130 degreeC for 1 to 10 hours.

As for the usage-amount of (b), 5-80 mol is preferable with respect to 100 mol of (a), More preferably, it is 10-75 mol. By setting it as this range, there exists a tendency for the balance of the storage stability of the coloring photosensitive resin composition, the developability at the time of forming a pattern, and the solvent resistance, heat resistance, mechanical strength, and the sensitivity of the patterned resin cured film obtained to become favorable. Since the reactivity of a cyclic ether is high and it is hard to remain unreacted (b), as (b) used for resin [M1], (b1) is preferable and (b1-1) is more preferable.

As for the usage-amount of the said reaction catalyst, 0.001-5 mass parts is preferable with respect to 100 mass parts of total amounts of (a), (b) and (c). As for the usage-amount of the said polymerization inhibitor, 0.001-5 mass parts is preferable with respect to 100 mass parts of total amounts of (a), (b) and (c).

Reaction conditions, such as an injection | throwing-in method, reaction temperature, and time, can be adjusted suitably in consideration of heat generation amount by a manufacturing facility, superposition | polymerization, etc. In addition, in the same manner as the polymerization conditions, the injection method and the reaction temperature can be appropriately adjusted in consideration of the amount of heat generated by the production facility, polymerization, and the like.

Resin [M2] is obtained as a 1st step similarly to the manufacturing method of copolymer [K1] mentioned above, and obtains the copolymer of (b) and (c). In the same manner as described above, the obtained copolymer may be used as it is, or a concentrated or diluted solution may be used, or one obtained as a solid (powder) by reprecipitation or the like may be used.

The ratio of the structural unit derived from (b) and (c) is respectively with respect to the total number of moles of all the structural units which comprise the said copolymer,

structural unit derived from (b); 5 to 95 mol%

structural unit derived from (c); 5 to 95 mol%

Is preferably,

structural unit derived from (b); 10 to 90 mol%

structural unit derived from (c); 10 to 90 mol%

It is more preferable that is.

Moreover, the carboxylic acid or carboxylic anhydride which (a) has in the cyclic ether derived from (b) which the copolymer of (b) and (c) has on the same conditions as the manufacturing method of resin [M1] By reacting, resin [M2] can be obtained.

As for the usage-amount of (a) made to react with the said copolymer, 5-80 mol is preferable with respect to 100 mol of (b). Since the reactivity of a cyclic ether is high and it is hard to remain unreacted (b), as (b) used for resin [M2], (b1) is preferable and (b1-1) is more preferable.

Resin [M3] is resin which made carboxylic anhydride react with resin [M2] further.

Carboxylic anhydride is made to react with the hydroxyl group which arises by reaction of a cyclic ether and carboxylic acid or carboxylic anhydride.

As carboxylic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3 , 6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride, and the like. As for the usage-amount of carboxylic anhydride, 0.5-1 mol is preferable with respect to 1 mol of usage-amounts of (a).

Specifically as resin (M), resin to which glycidyl (meth) acrylate was added to the benzyl (meth) acrylate / (meth) acrylic acid copolymer, tricyclodecyl (meth) acrylate / styrene / (meth) Glycidyl (meth) acrylate is added to the resin which added glycidyl (meth) acrylate to the acrylic acid copolymer, and tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer. Resins [M1], such as resin made; Resin obtained by reacting (meth) acrylic acid to a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate, and of tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate Resins [M2] such as resins obtained by reacting (meth) acrylic acid with a copolymer; Resin [M3], such as resin which made tetrahydrophthalic anhydride react with resin which (meth) acrylic acid reacted with the copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate, etc. are mentioned. .

The weight average molecular weight of polystyrene conversion of resin (M) becomes like this. Preferably it is 5,000-100,000, More preferably, it is 8,000-50,000, More preferably, it is 10,000-30,000.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of resin (M) becomes like this. Preferably it is 1.1-6.0, More preferably, it is 1.2-4.0.

The acid value of resin (M) becomes like this. Preferably it is 30 mg-KOH / g or more and 180 mg-KOH / g or less, More preferably, it is 40 mg-KOH / g or more and 150 mg-KOH / g or less.

The content of the copolymer (K) is preferably 10 to 100% by mass, more preferably 20 to 90% by mass, still more preferably 35 to 75% by mass relative to the total amount of the resin (A).

Content of resin (A) is 15-80 mass% with respect to solid content, More preferably, it is 20-70 mass%, More preferably, it is 20-50 mass%. When content of resin (A) exists in the said range, the patterned resin cured film obtained or the uncured resin cured film tends to be excellent in heat resistance, and excellent in adhesiveness with a board | substrate, and chemical-resistance. Here, "solid content" means the quantity remove | excluding content of a solvent (E) from the total amount of the photosensitive resin composition of this invention.

<Polymeric Compound (B)>

A polymerizable compound (B) is a compound which can superpose | polymerize with the active radical which generate | occur | produced from the polymerization initiator (C), For example, it is a compound etc. which have a polymerizable ethylenically unsaturated bond, Preferably it is a (meth) acrylic acid ester compound. .

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

Polymerizable compounds having two ethylenically unsaturated bonds include 1,3-butanedioldi (meth) acrylate, 1,3-butanediol (meth) acrylate, 1,6-hexanedioldi (meth) acrylate, and ethylene Glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol Diacrylate, bis (acryloyloxyethyl) ether of bisphenol A, ethoxylated bisphenol A di (meth) acrylate, propoxylated neopentylglycol di (meth) acrylate, ethoxylated neopentylglycol di (meth) Acrylate, 3-methylpentanediol di (meth) acrylate, and the like.

Examples of the polymerizable compound having three or more ethylenically unsaturated bonds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and tris (2-hydroxyethyl) isocyanurate tri (meth) acrylic acid. 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, tripentaerythritolhepta (meth) acrylate, tripentaerythritol octa (Meth) acrylate, reactant of pentaerythritol tri (meth) acrylate with acid anhydride, diphene Reaction of erythritol penta (meth) acrylate with acid anhydride, reaction product of tripentaerythritol hepta (meth) acrylate with acid anhydride, caprolactone modified trimethylolpropane tri (meth) acrylate, caprolactone modified pentaerythritol tree ( Meth) acrylate, caprolactone modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylic Latex, 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 tripentaerythritolhepta (Meth) acrylate, caprolactone modified tripentaerythritol octa (meth) acrylate, caprolactone modified pentaerythritol tri (meth) acrylate and a reaction product of an acid anhydride, caprolactone modified dipentaerythritol penta (meth) acrylate The reactant with an acid anhydride, the reactant with caprolactone modified tripentaerythritol hepta (meth) acrylate, and an acid anhydride, etc. are mentioned.

Especially, the polymeric compound which has three or more ethylenically 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, more preferably 250 or more and 1,500 or less.

Content of a polymeric 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 polymeric compound (B), More preferably, it is 40- 80 mass%, Especially preferably, it is 55-75 mass%. When content of a polymeric compound (B) exists in the said range, the tendency for the sensitivity at the time of preparation of a patterned resin cured film, the strength, smoothness, and reliability of the patterned resin cured film obtained or the unpatterned resin cured film to become favorable will be favorable. There is this.

<Polymerization Initiator (C)>

A polymerization initiator (C) is a compound which can generate an active radical, an acid, etc. by the action of light or heat, and can start superposition | polymerization, and contains an O-acyl oxime compound. Thereby, when forming the patterned resin cured film from which height differs simultaneously on a same board | substrate using a halftone mask, the height difference of the patterned resin cured film obtained is large, and the patterned resin cured film of desired height can be formed.

It is the said O-acyl oxime compound, It is a compound which has a partial structure represented by Formula (d1), Preferably it is a compound represented by Formula (d2). Hereinafter, * represents a bond number.

[In formula (d2), R <^d1> represents a C1-C12 saturated hydrocarbon group.

R ^d2 represents a methyl group, a phenyl group or a benzyl group.

L ^d1 represents a single bond or -CO-.

R ^d3 represents a phenylsulfanylphenyl group which may have a substituent or a carbazolyl group which may have a substituent.]

As a saturated hydrocarbon group, an alkyl group, an alicyclic saturated hydrocarbon group, and group which combined these are mentioned.

Examples of the alkyl group include linear alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and dodecyl group; And branched chain alkyl groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group, and 2-ethylhexyl group.

Examples of the alicyclic saturated hydrocarbon group include cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, tricyclodecyl group, and adamantyl group.

As group which combined these, a cyclopentyl methyl group, a cyclopentyl ethyl group, a cyclohexyl methyl group, a cyclohexyl ethyl group, a methylcyclohexyl group, etc. are mentioned, for example.

As a substituent which the phenylsulfanylphenyl group and carbazolyl group may have, the benzoyl group which may have a C1-C6 alkyl group and a C1-C10 saturated hydrocarbon group is mentioned, for example, It contains in the said alkyl group and the said saturated hydrocarbon group. The hydrogen atom to be mentioned may be substituted by the hydroxy group, and the methylene group contained in the said alkyl group and the said saturated hydrocarbon group may be substituted by the oxygen atom.

The alkyl group and the saturated hydrocarbon group are the same as the above.

As such a substituent, the said alkyl group; 2-hydroxyethyl group, 2-hydroxyethoxy group, ethoxyethyl group; Benzoyl group, 2-methylbenzoyl group, (3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl group, etc. are mentioned.

The compound represented by the formula (d2) is preferably a compound represented by the formula (d3) or a formula (d4), more preferably a compound represented by the formula (d3).

[In formula (d3) and formula (d4), R <^d1> and R <^d2> represent the same meaning as the above.

R <^d4> represents a hydrogen atom or a C1-C6 alkyl group, the hydrogen atom contained in the said alkyl group may be substituted by the hydroxy group, and the methylene group contained in the said alkyl group may be substituted by the oxygen atom.

R <^d5> represents the benzoyl group which may have a C1-C10 saturated hydrocarbon group, a hydrogen atom, or a C1-C6 alkyl group, and the hydrogen atom contained in the said alkyl group and the said saturated hydrocarbon group may be substituted by the hydroxy group, The methylene group contained in an alkyl group and the said saturated hydrocarbon group may be substituted by the oxygen atom.

R ^d6 represents an alkyl group having 1 to 6 carbon atoms.]

The alkyl group and the saturated hydrocarbon group are the same as the above.

Examples of the O-acyl oxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane -1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-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-dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- (2-methyl Benzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3 -Yl] -3-cyclopentylpropane-1-one-2-imine and the like; O-acyl oxime compound of JP2001-233842-A, JP2004-534797-A, or JP2011-132215-A, etc. are mentioned. You may use commercially available products, such as Irgacure OXE01, OXE02 (above BASF Corporation), and N-1919 (ADEKA Corporation). Especially, O-acyl oxime compound is N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) At least one selected from the group consisting of octane-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine is preferable, And N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine is more preferable.

The polymerization initiator (C) may contain a polymerization initiator other than the O-acyl oxime compound. As such a polymerization initiator, a well-known polymerization initiator can be used, For example, an alkylphenone compound, a biimidazole compound, an acyl phosphine oxide compound, and a triazine compound are mentioned.

The alkylphenone compound is a compound having a partial structure represented by the following formula (d5) or a partial structure represented by the formula (d6). In these partial structures, the benzene ring may have a substituent.

Examples of the compound having a partial structure represented by formula (d5) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one and 2-dimethylamino-1- (4 -Morpholinophenyl) -2-benzylbutan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butane- 1-one etc. are mentioned. You may use commercially available products, such as Irgacure (trademark) 369, 907, 379 (above, BASF Corporation make). In addition, a polymerization initiator having a group capable of causing chain transfer described in JP2002-544205-A may be used.

Examples of the compound having a partial structure represented by formula (d6) include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-hydroxy-2-methyl-1- [4- (2- Oligomer of hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α and? -diethoxyacetophenone, benzyl dimethyl ketal and the like.

In view of sensitivity, a compound having a partial structure represented by the formula (d5) is preferable as the alkylphenone compound.

The said biimidazole compound is a dimer of an imidazole compound, and the compound represented by a formula (d7) is preferable.

[In formula (d7), R <^3> -R <^8> represents the C6-C10 aryl group which may have a substituent.]

Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, toluyl group, xylyl group, ethylphenyl group, naphthyl group, and the like, and preferably a phenyl group.

As a substituent, a halogen atom, a C1-C4 alkoxy group, etc. are mentioned, for example. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, for example, Preferably it is a chlorine atom. As a C1-C4 alkoxy group, a methoxy group, an ethoxy group, a propoxy group, butoxy group etc. are mentioned, for example, Preferably it is a methoxy group.

Examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,3-dichlorophenyl ) -4,4 ', 5,5'-tetraphenylbiimidazole (see eg JPH06-75372-A, JPH06-75373-A, 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-chlorophenyl) -4,4', 5,5 '-Tetra (trialkoxyphenyl) biimidazole (see, eg, JPS48-38403-B, JPS62-174204-A, etc.), wherein the phenyl group at the 4,4'5,5'-position is substituted by a carboalkoxy group An imidazole compound (for example, see JPH07-10913-A etc.) etc. are mentioned. Especially, the compound represented by the following formula or its mixture is preferable.

2,4,6-trimethylbenzoyldiphenylphosphine oxide etc. are mentioned as said acylphosphine oxide compound. You may use a commercial item, such as Irgacure (trademark) 819 (made by BASF Corporation).

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

Moreover, as a polymerization initiator, Benzoin 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-phenanthrenequinone, 2-ethylanthraquinone and camphor quinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compound, etc. are mentioned. It is preferable to use these in combination with the polymerization start adjuvant (C1) (especially amines) mentioned later.

As the acid generator, for example, 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4- Acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyl iodonium p-toluenesulfonate, diphenyl Onium salts such as iodonium hexafluoroantimonate, nitrobenzyl tosylates, benzointosylates and the like.

As a polymerization initiator combined with an O-acyl oxime compound, an alkylphenone compound or a biimidazole compound is preferable, and a biimidazole compound is more preferable.

When the polymerization initiator (C) contains a polymerization initiator other than the O-acyl oxime compound, the content of the O-acyl oxime compound is preferably 30 mass% or more and 90 mass% or less with respect to the total amount of the polymerization initiator (C). More preferably, they are 40 mass% or more and 80 mass% or less. If the O-acyl oxime compound is combined with the compound or the content of the O-acyl oxime compound is in the above range, in addition to the effect of the present invention, the sensitivity at the time of pattern formation, the pattern shape, the adhesion between the patterned resin cured film and the substrate This is preferable because it tends to be good.

Content of a polymerization initiator (C) becomes like this. Preferably it is 0.1 mass part or more and 30 mass parts or less with respect to 100 mass parts of total content of resin (A) and a polymeric compound (B), More preferably, it is 0.2 mass part or more and 15 It is mass parts or less, More preferably, it is 0.3 mass parts or more and 8 mass parts or less. When content of a polymerization initiator (C) exists in the said range, in addition to the effect of this invention, since there exists a tendency to become high sensitivity and shorten an exposure time, productivity improves and the visible light transmittance of the patterned resin cured film obtained is high. There is a tendency.

<Polymerization start preparation (C1)>

The polymerization initiation assistant (C1) is used together with the polymerization initiator (C) and is a compound or sensitizer used to promote the polymerization of a compound (eg, a polymerizable compound (B)) in which polymerization is initiated by the polymerization initiator (C). to be.

As a polymerization start adjuvant (C1), a thiazoline compound, an amine compound, an alkoxy anthracene compound, a thioxanthone compound, and a carboxylic acid compound are mentioned, for example. Especially, a thioxanthone compound is preferable.

As said thiazoline compound, the compound represented by following formula (III-1)-formula (III-3), the compound of JP2008-65319-A, etc. are mentioned.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, and 4-dimethyl Aminobenzoic acid 2-ethylhexyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (collectively Michler's ketone), 4,4'-bis (diethylamino) benzophenone, 4, 4'-bis (ethylmethylamino) benzophenone etc. are mentioned, Especially, 4,4'-bis (diethylamino) benzophenone is preferable. You may use a commercial item, such as EAB-F (made by Hodogaya Kagaku Kogyo Co., Ltd.).

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

As the thioxanthone compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxy Citioxanthone etc. are mentioned.

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

When the photosensitive resin composition of this invention contains a polymerization start adjuvant (C1), the content becomes like this. Preferably it is 0.1-30 mass parts with respect to a total of 100 mass parts of resin (A) and a polymeric compound (B). Preferably it is 0.2-10 mass parts. When the amount of the polymerization initiation assistant (C1) is within the above-described range, there is a tendency to become more sensitive when the patterned resin cured film is formed.

<Compound (1)>

Compound (1) is represented by Formula (1).

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

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

Examples of the compound (1) include hydroquinone, tert-butylhydroquinone and 2,5-di-tert-butylhydroquinone.

Content of compound (1) is 0.25 mass part or more and 3 mass parts or less with respect to 100 mass parts of resin (A), Preferably they are 0.25 mass part or more and 2 mass parts or less. When content of the compound (1) exists in the said range, when forming the patterned resin cured film from which height differs simultaneously on a same board | substrate using a halftone mask, the height difference of the patterned resin cured film obtained is large and the pattern of a desired height The height difference of the patterned resin cured film obtained becomes large also when forming a cured resin cured film and simultaneously forming the patterned resin cured film from which height differs using the binary mask which has the light-transmitting part of a different size on the same board | substrate. If the content of the compound (1) is more than the above-mentioned range, the sensitivity is significantly lowered, so that the patterned resin cured film of the desired line width may be difficult to be obtained, and if the content of the compound (1) is less than the above-mentioned range, There exists a possibility that the effect of this invention may not be fully acquired.

<Surfactant (H)>

As surfactant (H), silicone type surfactant, a fluorochemical surfactant, silicone type surfactant which has a fluorine atom, etc. are mentioned, for example.

Examples of the silicone-based surfactants include surfactants having a siloxane bond. Specifically, doyle silicon (brand name) DC3PA, doyle silicon SH7PA, doyle silicon DC11PA, doyle silicon SH21PA, doyle silicon SH28PA, doyle silicon SH29PA, doyle silicon SH30PA, doyle silicon SH8400 [Doray silicon Do84 Corning] Co., Ltd.], KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsukagaku Kogyo Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 ( Momentive Performance Materials Japan Co., Ltd.).

As said fluorine-type surfactant, surfactant etc. which have a fluorocarbon chain | strand are mentioned. Specifically, fluoride (trademark) FC430, fluoride FC431 (manufactured by Sumitomo 3M Co., Ltd.), megapack (registered trademark) F142D, megapack F171, megapack F172, megapack F173, megapack F177, megapack F183 , Megapack F554, Megapack R30, Megapack RS-718-K (manufactured by DIC Corporation), FTop® EF301, Ftop EF303, Ftop EF351, Ftop EF352 [Mitsubishi Material Denshi Kasei Ltd.], Supron (registered trademark) S381, Supron S382, Supron SC101, Supron SC105 (manufactured by Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Fine Chemical Co., Ltd.) Can be mentioned.

Examples of the silicone-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain. Specifically, Mega Pack (R) R08, Mega Pack BL20, Mega Pack F475, Mega Pack F477, Mega Pack F443 (manufactured by DIC Corporation), and the like.

When the photosensitive resin composition of this invention contains surfactant (H), the content is 0.001 mass% or more and 0.2 mass% or less with respect to the total amount of the photosensitive resin composition of this invention normally, Preferably it is 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. When content of surfactant (H) exists in the said range, since the flatness of a composition layer can be improved, height deviation will become small in a patterned resin cured film, and flatness will increase in a resin cured film.

<Adhesive Promoter (J)>

As the adhesion promoter (J), for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidoxy Propylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropyl Methyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-sulfanylpropyltrimethoxysilane, 3-isocyanate Propyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimeth Sisilran, and 3-aminopropyl the silane, N- phenyl-3-aminopropyltrimethoxysilane, N- phenyl-3-amino propyl silane in the tree.

Content of adhesion promoter (J) is 0.1 mass% or more and 5 mass% or less with respect to solid content, More preferably, they are 0.2 mass% or more and 2 mass% or less. When content of adhesion promoter (J) exists in the said range, adhesiveness of a patterned resin cured film and a board | substrate can be made favorable.

<Solvent (E)>

Solvent (E) is not specifically limited, The solvent normally used in the said field | area can be used. For example, an ester solvent (solvent containing -COO- in a molecule and no -O-), an ether solvent (solvent containing -O- in a molecule and not containing -COO-), an ether ester solvent ( A solvent containing -COO- and -O- in a molecule, a ketone solvent (a solvent containing -CO- in a molecule and no -COO-), an alcoholic solvent (containing OH in a molecule, -O- , -CO- and -COO- free solvents), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide and the like can be used.

As the ester solvent, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, 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 anisole Etc. can be mentioned.

As an ether ester solvent, methyl methoxy acetate, ethyl methoxy acetate, butyl acetate, methyl ethoxy acetate, ethyl ethoxy acetate, methyl 3-methoxy propionate, ethyl 3-methoxy propionate, and methyl 3-ethoxy propionate , 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 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.

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

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

Benzene, toluene, xylene, mesitylene etc. are mentioned as an aromatic hydrocarbon solvent.

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

Among the solvents described above, organic solvents having a boiling point of 120 ° C. or higher and 180 ° C. or lower at 1 atm are preferable in view of coatability and dryness. Especially, as said organic solvent, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol methyl ethyl ether, 3-methoxy butyl acetate, and 3-methoxy- 1-butanol are preferable. The solvent (E) is preferably a mixed solvent containing these.

Content of a solvent (E) becomes like this. Preferably it is 60-95 mass% with respect to the total amount of the photosensitive resin composition of this invention, More preferably, it is 70-95 mass%. In other words, solid content of the photosensitive resin composition of this invention becomes like this. Preferably it is 5-40 mass%, More preferably, it is 5-30 mass%. When content of a solvent (E) exists in the said range, since the flatness of the composition layer formed from the photosensitive resin composition of this invention tends to be high, height deviation becomes small in a patterned resin cured film, and flatness in a resin cured film This tends to be high.

<Other ingredients>

In the photosensitive resin composition of the present invention, additives known in the art, such as fillers, other polymer compounds, thermal radical generating agents, ultraviolet absorbers, chain transfer agents, etc. You may contain it.

Glass, silica, alumina, etc. are mentioned as a filler.

As another high molecular compound, thermosetting resins, such as a maleimide resin, thermoplastic resins, such as polyvinyl alcohol, polyacrylic acid, polyethyleneglycol monoalkyl ether, polyfluoroalkylacrylate, polyester, and polyurethane, etc. are mentioned.

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

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

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

The photosensitive resin composition of this invention does not contain coloring agents, such as a pigment and dye, substantially. That is, in the photosensitive resin composition of this invention, the content of the coloring agent with respect to the whole composition is for example less than 1 mass%, Preferably it is less than 0.5 mass%.

Moreover, when the photosensitive resin composition of this invention is filled into the quartz cell whose optical path length is 1 cm, and the transmittance | permeability was measured on the conditions of 400-700 nm of measurement wavelengths using the spectrophotometer, average transmittance becomes like this. It is% or more, More preferably, it is 80% or more.

When the photosensitive resin composition of this invention is set as the resin cured film, the average transmittance of a resin cured film becomes like this. Preferably it is 90% or more, More preferably, it is 95% or more. When this average transmittance is measured on the resin cured film whose thickness after heat-hardening (for example, 100 degreeC-250 degreeC, 5 minutes-3 hours) is 2 micrometers using the spectrophotometer on the conditions of the measurement wavelength 400-700 nm. Is the average value. Thereby, the patterned resin cured film excellent in transparency in visible region, or the uncured resin cured film can be provided.

<The manufacturing method of the photosensitive resin composition>

The photosensitive resin composition of this invention is resin (A), a polymeric compound (B), a polymerization initiator (C), and a compound (1), the solvent (E), surfactant (H), and other components used as needed. It can manufacture by mixing by a well-known method. After mixing, it is preferable to filter with a filter having a pore diameter of about 0.05 to 1.0 m.

<Method for producing patterned resin cured film>

The patterned resin cured film formed with the photosensitive resin composition of this invention can be manufactured, for example by performing following process (1)-(4). It is preferable to perform process (5) further after process (4).

Process (1) Process of apply | coating the photosensitive resin composition of this invention to a board | substrate

Process (2) The process of drying the photosensitive resin composition after application | coating and forming a composition layer

Process (3) Process of exposing composition layer through photomask

Process (4) The process of developing the composition layer after exposure

Process (5) Process of heating composition layer after image development

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

Glass, metal, plastic, etc. are mentioned as a board | substrate, A color filter, an insulating film, a conductive film, and / or a drive circuit etc. may be formed on the board | substrate.

Application | coating on a board | substrate is performed using coating apparatuses, such as a spin coater, a slit & spin coater, a slit coater, an inkjet, a roll coater, and a dip coater.

Step (2) is a step of drying the photosensitive resin composition after application to form a composition layer. By performing this process, volatile components, such as a solvent in the photosensitive resin composition, are removed. As a method of drying, heat drying (prebaking) and reduced pressure drying are mentioned.

When carrying out heat drying, the drying temperature is preferably in the range of 30 ° C to 120 ° C, more preferably 50 ° C to 110 ° C, and the drying time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes. Heat drying is normally performed using heating apparatuses, such as an oven and a hotplate.

When drying under reduced pressure, it is preferable to carry out in the temperature range of 20 degreeC-25 degreeC under the pressure of 50-150 Pa.

Step (3) is a step of exposing the composition layer formed by step (2) through a photomask. This photomask uses the thing in which the light shielding part was formed corresponding to the part to remove of a composition layer. The shape of the light shielding portion is not particularly limited and can be selected according to the intended use. In particular, when a halftone mask or a gray scale mask is used, a patterned resin cured film having a different height can be simultaneously formed on the same substrate. A halftone mask is a photomask which has 2 or more types of transmissive parts of mutually different transmittance | permeability, It is preferable to have a transmissive part of 100% of transmittance | permeability, and a transmissive part of the range of 10 to 60% of transmittance | permeability. By using such a halftone mask, the patterned resin cured film with high precision of a dimension and a height can be formed.

As a light source used for exposure, the light source which produces the light of 250-450 nm wavelength is preferable. For example, light of less than 350 nm is selectively blocked using a filter that blocks this wavelength range, or light around 436 nm, 408 nm, and 365 nm is selectively used by using a bandpass filter to select these wavelength ranges. You may pick out one. Specifically, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp etc. are mentioned.

Since it is possible to irradiate the parallel light beam uniformly on the entire exposure surface or to accurately position the photomask and the composition layer, it is preferable to use an exposure apparatus such as a mask aligner and a stepper.

Process (4) is a process of developing the composition layer after exposure. By developing the composition layer after exposure in contact with a developer, the unexposed portion of the composition layer is dissolved in the developer and removed, thereby forming a patterned resin cured film on the substrate.

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

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

It is preferable to wash with water after image development.

Process (5) is a process of heating (post-baking) the composition layer after image development. By heating, durability of the patterned resin cured film, for example, heat resistance, chemical resistance, mechanical properties, and the like is improved. Heating is usually performed using heating apparatuses, such as an oven and a hotplate. 120 to 250 degreeC is preferable and 150 to 235 degreeC of heating temperature is more preferable. 1 to 180 minutes are preferable and, as for a heat time, 10 to 60 minutes are more preferable.

From the photosensitive resin composition of this invention, the resin cured film which is not patterned can also be manufactured by the following process. Preferable conditions of each process are the same as the manufacturing method of a patterned resin cured film.

Process (1) Process of apply | coating the photosensitive resin composition of this invention to a board | substrate

Process (2) The process of drying the photosensitive resin composition after application | coating and forming a composition layer

Process (5) Process of heating composition layer after image development

Behind the process (2) as required

Process (3 ') Process of exposing composition layer without passing through photomask

May be performed. In addition, when performing a process (3 '),

Process (4) The process of developing the composition layer after exposure

May be performed.

The patterned resin cured film thus obtained may be, for example, a photo spacer constituting part of a color filter substrate and / or an array substrate, a patternable overcoat, an interlayer insulating film, a projection for controlling liquid crystal orientation, a microlens, a coating layer for adjusting film thickness, and the like, It is useful as an overcoat which comprises a part for a touch panel member, a color filter substrate, and / or an array substrate. In particular, since the height control at the time of simultaneously forming the patterned resin cured film with a different height on the same board | substrate is excellent, when forming photospacers with a different height on the same board | substrate simultaneously, the photospacer and the liquid crystal orientation control protrusion are the same. It is useful for simultaneous formation on a substrate. The color filter substrate and the array substrate described above are suitably used for liquid crystal display devices, organic EL display devices, electronic paper and the like.

Example

Hereinafter, an Example demonstrates this invention in more detail. In the examples, "%" and "parts" are% by mass and parts by mass unless otherwise specified.

Synthesis Example  One

In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to make a nitrogen atmosphere, and 140 parts of diethylene glycol ethylmethyl ether was added and heated to 70 ° C while stirring. 40 parts methacrylic acid subsequently; And mixture of monomer (I-1) and monomer (II-1) {molar ratio of monomer (I-1): monomer (II-1) in mixture = 50:50} 360 parts of diethylene glycol ethylmethyl ether 190 parts The solution dissolved in was prepared, and this solution was dripped in the flask kept at 70 degreeC over 4 hours using the dropping funnel.

On the other hand, the solution which melt | dissolved 30 parts of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 240 parts of diethylene glycol ethyl methyl ethers was dripped in the flask over 5 hours using the other dropping pump. It was. After dripping of the polymerization initiator solution 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 A1a) of 42.3% of solid content. As for the weight average molecular weight (Mw) of obtained resin A1a, 8,000 and molecular weight distribution (Mw / Mn) were 1.91, and the acid value was 60 mg-KOH / g. Resin A1a has the following structural units.

Synthesis Example  2

In a 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 by mass of 3-methoxy-1-butanol and 105 parts by mass of 3-methoxybutyl acetate were added thereto while stirring. Heated to 70 ° C. Subsequently, 60 parts by mass of methacrylic acid and the content ratio (molar ratio) of 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (monomer (I-1) and monomer (II-1) were 50:50. ) Was dissolved in 240 parts by mass and 140 parts by mass 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 mass parts of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 225 mass parts of 3-methoxybutyl acetates in the flask over 4 hours using the separate dropping funnel. It dripped. After completion of the dropwise addition of the solution of the polymerization initiator, the mixture was kept at 70 ° C for 4 hours, and then cooled to room temperature to obtain a copolymer of the resin (resin A1b) having a solid content of 32.6 mass% and an acid value of 110 mg-KOH / g (solid content). A solution was obtained. The weight average molecular weight (Mw) of obtained resin A1b was 13,400, and molecular weight distribution was 2.50.

Synthesis Example  3

182 parts of propylene glycol monomethyl ether acetate were introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen inlet tube, and the atmosphere in the flask was changed from nitrogen to air. Azobisisobutyro in the mixture which consists of 70.5 parts of acrylates, 43.0 parts of methacrylic acid, 22.0 parts of monomethacrylates (FA-513M by Hitachikasei Co., Ltd.) of a tricyclodecane skeleton, and 136 parts of propylene glycol monomethyl ether acetate. The solution to which 1.4 parts of nitriles was added was dripped at the flask over 2 hours from the dropping funnel, and it stirred further at 100 degreeC for 5 hours. Next, the atmosphere in the flask was changed from nitrogen to air, 35.5 parts of glycidyl methacrylate, 0.9 part of trisdimethylaminomethylphenol and 0.145 part of hydroquinone were charged into the flask, and the reaction was continued at 110 ° C. for 6 hours to give a solid content of 29.0. A solution of% resin A2a was obtained. As for the weight average molecular weight (Mw) of obtained resin A2a, 2.4 and the acid value of 32,000 and molecular weight distribution (Mw / Mn) were 79 mg-KOH / g. Resin A2a has the following structural units.

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

Apparatus: K2479 [manufactured by Shimadzu Seisakusho Corporation]

Column: SHIMADZU Shim-pack GPC-80M

Column temperature: 40 ℃

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 (manufactured by Tosoh Corporation)

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

Example  1 to Example  9 and Comparative example  One

<Preparation of the photosensitive resin composition>

Each component shown in Table 1 was mixed in the ratio shown in Table 1, and the photosensitive resin composition was obtained.

In addition, in Table 1, the containing number of resin (A) shows the mass part of solid content conversion.

Resin (A); A1a; Resin A1a

Resin (A); A1b; Resin A1b

Resin (A); A2a; Resin A2a

Polymerizable compound (B); Dipentaerythritol hexaacrylate [KAYARAD® DPHA; Nihon Kayaku Co., Ltd.]

Polymerization initiator (C); Ca; N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (irgacure® OXE 01; manufactured by BASF; O-acyl oxime compound)

Polymerization initiator (C); Cb; N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethane-1-imine [Irgacure® OXE 02; Manufactured by BASF Corporation; O-acyl oxime compound]

Polymerization initiator (C); Cc; 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole [B-CIM; Hodogaya Kagaku Co., Ltd. product; Biimidazole compound]

Polymerization initiation aid (C1); 2,4-diethyl thioxanthone (KAYACURE® DETX-S; Nihon Kayaku Co., Ltd .; thioxanthone compound)

Compound (1); 1a; 2,5-di-tert-butylhydroquinone (nonflex alba; manufactured by Seiko Kagaku Co., Ltd.)

Adhesion promoter (J); 3-glycidyloxypropyltrimethoxysilane (KBM-403; manufactured by Shin-Etsu Chemical Co., Ltd.)

Surfactant (H); Fluorine-based surfactants (MEGAFACE® F554; manufactured by DIC Corporation)

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-methoxybutyl acetate

Solvent (E); Ee; 3-ethoxyethylpropionate

The solvent (E) was mixed so that solid content of the photosensitive resin composition might be "solid content (%)" of Table 1. The value of each component Ea-Ee in a solvent (E) shows the mass ratio in a solvent (E).

<Patternized resin cured film formation 1>

A square glass substrate (Eagle XG; manufactured by Corning Co., Ltd.) having one side of 2 inches was washed sequentially with a neutral detergent, water, and isopropanol, and dried. The photosensitive resin composition was spin-coated on this glass substrate, and then pressure-reduced until it became 66 Pa in the pressure reduction dryer, and it prebaked at 90 degreeC on a hotplate for 80 second, and formed the composition layer. After cooling, the space | interval of the board | substrate with which this composition layer was formed, and the quartz glass photomask was 150 micrometers, and the exposure machine [TME-150RSK; Topcon Co., Ltd. light source; Ultra-high pressure mercury lamp] was used to irradiate light with an exposure dose of 60 mJ / cm 2 (365 nm standard) under an atmospheric atmosphere. In addition, the irradiation to the composition layer at this time is carried out by the optical filter [UV-31; Asahi Bunko Co., Ltd.] was passed through. As the photomask, a halftone mask having a shape of a light transmitting portion having a square of 10 mu m in one side, which is arranged at intervals of 100 mu m, and having a transmittance of 100% and 25% of two kinds of light transmitting portions was used.

After irradiation with light, the coating film was immersed and developed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide while shaking at 23 ° C. for 60 seconds, and further washed with water. Then, it post-baked for 15 minutes at 235 degreeC in oven, and obtained the patterned resin cured film.

Evaluation; Measurement of Width and Height of Patterned Resin Cured Film>

The width and height of the obtained patterned resin cured film were measured by a three-dimensional non-contact surface shape measurement system (Micromap MM527N-PS-M100; manufactured by Ryoka System Co., Ltd.). The width of the patterned resin cured film was measured at a height position of 5% of the height of the patterned resin cured film with respect to the substrate surface.

Patterning the resin in the cured film formed. 1, (hereinafter referred to as "H ₁₀₀ ') patterned resin cured film in height formed by the light-transmitting portion of the transmittance 100% and a pattern formed by the transparent portion of the transmittance 25% resin cured film height from the measured value (hereinafter referred to as "H _25"), was calculated for both the car [H ₁₀₀ -H _25]. When forming patterned resin cured film from which height differs simultaneously on the same board | substrate, it is advantageous that this height difference is large. The results are shown in Table 2.

<Patternized Resin Cured Film Formation 2>

A square glass substrate (Eagle XG; manufactured by Corning Corporation) having one side of 2 inches was washed sequentially with a neutral detergent, water, and isopropanol, and dried. The photosensitive resin composition was spin-coated on this glass substrate, and it pressure-reduced until it became 66 Pa by the pressure reduction dryer, and then prebaked at 90 degreeC on a hotplate for 80 second to form a composition layer. After cooling, the space | interval of the board | substrate with which this composition layer was formed, and the quartz glass photomask was 150 micrometers, and the exposure machine [TME-150RSK; Topcon Co., Ltd. light source; Ultra-high pressure mercury lamp] was used for exposure at an exposure dose of 60 mJ / cm 2 (365 nm standard) under an atmospheric atmosphere. In addition, the exposure to the composition layer at this time is carried out by the optical filter [UV-31; Asahi Bunko Co., Ltd.] was passed through. As the photomask, a binary mask having a square of 10 μm on one side and a square of 8 μm on one side was arranged at intervals of 100 μm, and the transmittance of the transmissive portion was 100%.

After irradiation with light, the coating film was immersed and developed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide while shaking at 23 ° C. for 60 seconds, and further washed with water. Then, it post-baked for 15 minutes at 235 degreeC in oven, and obtained the patterned resin cured film.

Evaluation; Measurement of Width and Height of Patterned Resin Cured Film>

The width and height of the obtained patterned resin cured film were measured using a three-dimensional non-contact surface shape measurement system [Micromap MM527N-PS-M100; Manufactured by Ryoka Systems Co., Ltd.]. The width of the patterned resin cured film was measured at a height position of 5% of the height of the patterned resin cured film with respect to the substrate surface.

The patterned resin cured film formation 2 WHEREIN: The height of the patterned resin cured film formed by the square transmissive part of one side of 10 micrometers (henceforth " _HS10 "), and the square transmissive part of 1 side to 8 micrometers The difference [H _S10 -H _S8 ] of both was calculated | required from the measured value of the height (henceforth "H _S8 ") of the formed patterned resin cured film. In the case where the patterned resin cured films having different heights are formed simultaneously on the same substrate, the larger the height difference is, the better. The results are shown in Table 3.

From the said result, according to the photosensitive resin composition of this invention, it was confirmed that it is advantageous when simultaneously forming a patterned resin cured film from which height differs using a halftone mask on the same board | substrate.

According to the photosensitive resin composition of this invention, when simultaneously forming a patterned resin cured film from which height differs using the halftone mask, the height difference of the patterned resin cured film obtained is large.

Claims (4)

Including resin, a polymeric compound, a polymerization initiator, and the compound represented by Formula (1),
Resin is a structural unit derived from the structural unit derived from at least 1 sort (s) chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride, and the monomer which has a C2-C4 cyclic ether structure and ethylenically unsaturated bond. It includes a copolymer having,
The polymerization initiator contains an O-acyl oxime compound,
O-acyl oxime compound is a compound represented by formula (d3),

[In formula (d3), R <^d1> represents a C1-C12 saturated hydrocarbon group, R <^d2> represents a methyl group, a phenyl group, or a benzyl group, R <^d4> represents a hydrogen atom or a C1-C6 alkyl group, and is contained in the said alkyl group. The hydrogen atom to be mentioned may be substituted by the hydroxy group, and the methylene group contained in the said alkyl group may be substituted by the oxygen atom.]
The photosensitive resin composition whose content of the compound represented by Formula (1) is 0.25 mass part or more and 3 mass parts or less with respect to 100 mass parts of resin.

[In Formula (1), A <^1> -A <^4> respectively independently represents a hydrogen atom or a C1-C6 alkyl group.] The photosensitive resin composition of Claim 1 in which resin further contains resin which has an ethylenically unsaturated bond in a side chain. The photospacer formed from the photosensitive resin composition of Claim 1 or 2. A display device comprising the photospacer according to claim 3.