JP2012022304A - Photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition capable of forming a pattern excellent in both flexibility and heat resistance.SOLUTION: A photosensitive resin composition includes a resin, a polymerizable compound, a photopolymerization initiator, a silicone-based surfactant and a solvent. The resin is an addition polymer which contains a structural unit derived from at least one selected from the group composed of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, and a structural unit derived from a monomer having a cyclic ether structure of 2-4 carbon atoms and a carbon-to-carbon unsaturated double bond. The polymerizable compound contains a compound having two or more groups expressed by formula (1), the content of which is 30-100 mass% relative to the total amount of the polymerizable compound. [In formula (1), Lrepresents an ethylene group or a propane -1, 2-diyl group. p represents an integer of 1-20]

Description

  The present invention relates to a photosensitive resin composition.

In recent liquid crystal display panels and the like, a photosensitive resin composition is used to form photo spacers and overcoats.
As such a photosensitive resin composition, for example, a photosensitive resin composition containing dipentaerythritol hexaacrylate as a polymerizable compound is specifically described (Patent Document 1).

JP 2006-171160 A

  However, conventionally proposed photosensitive resin compositions have not always been sufficiently satisfactory in the flexibility and heat resistance of the resulting pattern.

［式（１）中、Ｌ^１は、エチレン基又はプロパン−１，２−ジイル基を表す。ｐは、１〜２０の整数を表す。］ The present invention provides the following [1] to [5].
[1] including a resin, a polymerizable compound, a photopolymerization initiator, a silicone-based surfactant and a solvent,
The resin has a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, a cyclic ether structure having 2 to 4 carbon atoms, and a carbon-carbon unsaturated double bond. An addition polymer containing a structural unit derived from a monomer,
The polymerizable compound includes a compound having two or more groups represented by the formula (1),
The photosensitive resin composition whose content of this compound is 30 to 100 mass% with respect to the total amount of a polymeric compound.

[In the formula (1), L ¹ represents an ethylene group or a propane-1,2-diyl group. p represents an integer of 1 to 20. ]

[2] The photosensitive resin composition according to [1], wherein the content of the silicone surfactant is 0.0001% by mass or more and 0.05% by mass or less in the photosensitive resin composition.
[3] The content of structural units derived from a monomer having a cyclic ether structure having 2 to 4 carbon atoms and a carbon-carbon unsaturated double bond is 30 mol% or more based on the total amount of structural units in the resin. The photosensitive resin composition according to [1] or [2], which is 90 mol% or less.
[4] A pattern formed from the photosensitive resin composition according to any one of [1] to [3].
[5] A display device including the pattern according to [4].

  According to the photosensitive resin composition of the present invention, a pattern excellent in both flexibility and heat resistance can be obtained.

［式（１）中、Ｌ^１は、エチレン基又はプロパン−１，２−ジイル基を表す。ｐは、１〜２０の整数を表す。］ The photosensitive resin composition of the present invention comprises a resin (A), a polymerizable compound (B), a photopolymerization initiator (C), a silicone surfactant (D), and a solvent (E). (A) is a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, a cyclic ether structure having 2 to 4 carbon atoms, and a carbon-carbon unsaturated double bond. An addition polymer containing a structural unit derived from a monomer having a polymerizable compound, wherein the polymerizable compound contains a compound having two or more groups represented by the formula (1), and the content of the compound is polymerizable It is 30 mass% or more and 100 mass% or less with respect to the total amount of a compound (B). In addition, in this specification, the compound illustrated as each component can be used individually or in combination unless there is particular notice.

[In the formula (1), L ¹ represents an ethylene group or a propane-1,2-diyl group. p represents an integer of 1 to 20. ]

  The photosensitive resin composition of this invention contains resin (A). Resin (A) is a structural unit derived from at least one (a) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (hereinafter sometimes referred to as “(a)”), and the number of carbon atoms. It is an addition polymer containing a structural unit derived from a monomer (b) having 2 to 4 cyclic ether structures and a carbon-carbon unsaturated double bond (hereinafter sometimes referred to as “(b)”).

As the resin (A) used in the photosensitive resin composition of the present invention,
Resin (A2-1): a copolymer obtained by polymerizing (a) and (b), and resin (A2-2): (a), (b), (a) and (b) Examples include a copolymer obtained by polymerizing a copolymerizable monomer (c) (however, different from (a) and (b)) (hereinafter sometimes referred to as “(c)”).

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, and p-vinylbenzoic acid;
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid;
Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo Bicyclounsaturated compounds containing a carboxy group such as [2.2.1] hept-2-ene, 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- Unsaturated dicarboxylic acid anhydrides such as tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (hymic acid anhydride);

Unsaturated mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] Kind;
Examples thereof include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) acrylic acid.
Of these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferably used from the viewpoint of copolymerization reactivity and alkali solubility.
In this specification, “(meth) acrylic acid” represents at least one selected from the group consisting of acrylic acid and methacrylic acid. Notations such as “(meth) acryloyl” and “(meth) acrylate” have the same meaning.

  (B) represents a C2-C4 cyclic ether structure (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring (oxolane ring)) and a carbon-carbon unsaturated double bond. And a monomer having a cyclic ether structure having 2 to 4 carbon atoms and a (meth) acryloyloxy group.

  Examples of (b) include a monomer (b1) having an oxiranyl group and a carbon-carbon unsaturated double bond (hereinafter sometimes referred to as “(b1)”), an oxetanyl group and carbon-carbon unsaturated. Monomer (b2) having a double bond (hereinafter sometimes referred to as “(b2)”), Monomer (b3) having a tetrahydrofuryl group and a carbon-carbon unsaturated double bond (hereinafter referred to as “(b2)”) “(B3)” in some cases).

(B1) includes a monomer (b1-1) having a structure obtained by epoxidizing a linear or branched unsaturated aliphatic hydrocarbon and a carbon-carbon unsaturated double bond (hereinafter referred to as “( b1-1) ”), a monomer (b1-2) having a structure obtained by epoxidizing a cyclic unsaturated aliphatic hydrocarbon and a carbon-carbon unsaturated double bond (hereinafter referred to as“ (b1) -2) ").
As (b1), a monomer (b1) having an oxiranyl group and a (meth) acryloyloxy group is preferable, and a structure obtained by epoxidizing a cyclic unsaturated aliphatic hydrocarbon and a (meth) acryloyloxy group The monomer (b1-2) it has is more preferable. These monomers are excellent in the storage stability of the photosensitive resin composition.

  Specific examples of (b1-1) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinyl. Benzyl 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 (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris ( Glycidyl oxime Chill) styrene, 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4, Examples thereof include 6-tris (glycidyloxymethyl) styrene and compounds described in JP-A-7-248625.

  Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide 2000; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl acrylate (for example, cyclone). Mer A400; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (for example, Cyclomer M100; manufactured by Daicel Chemical Industries, Ltd.), a compound represented by formula (I), formula (II) ) And the like.

[In Formula (I) and Formula (II), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the alkyl group may be substituted with a hydroxy group. Good.
X ¹ and X ² each independently represent a single bond, —R ³ —, * —R ³ —O—, * —R ³ —S—, or * —R ³ —NH—.
R ³ represents an alkanediyl group having 1 to 6 carbon atoms.
* Represents a bond with O. ]

Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group.
As the hydroxyalkyl group, a hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy-1-methylethyl group, Examples include 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group and the like.
R ¹ and R ² 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 the alkanediyl group include methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane- Examples include 1,6-diyl group.
X ¹ and X ² are preferably a single bond, a methylene group, an ethylene group, * —CH ₂ —O— (* represents a bond to O), or * —CH ₂ CH ₂ —O— group. More preferably, a single bond and a * —CH ₂ CH ₂ —O— group are mentioned.

  Examples of the compound represented by the formula (I) include compounds represented by the formula (I-1) to the formula (I-15). Preferably Formula (I-1), Formula (I-3), Formula (I-5), Formula (I-7), Formula (I-9), Formula (I-11) to Formula (I-15) Is mentioned. More preferably, Formula (I-1), Formula (I-7), Formula (I-9), and Formula (I-15) are mentioned.

  Examples of the compound represented by the formula (II) include compounds represented by the formula (II-1) to the formula (II-15). Preferably Formula (II-1), Formula (II-3), Formula (II-5), Formula (II-7), Formula (II-9), Formula (II-11) to Formula (II-15) Is mentioned. More preferably, Formula (II-1), Formula (II-7), Formula (II-9), and Formula (II-15) are mentioned.

  The compound represented by the formula (I) and the compound represented by the formula (II) can be used alone. They can also be mixed in any ratio. In the case of mixing, the mixing ratio is a molar ratio, preferably 5:95 to 95: 5, more preferably 10:90 to 90:10, particularly preferably 20:80 in the formula (I): formula (II). ~ 80: 20.

  (B2) is preferably a monomer having an oxetanyl group and a (meth) acryloyloxy group. Examples of (b2) include 3-methyl-3-methacryloyloxymethyl oxetane, 3-methyl-3-acryloyloxymethyl oxetane, 3-ethyl-3-methacryloyloxymethyl oxetane, and 3-ethyl-3-acryloyloxy. Examples include methyl oxetane, 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane, and 3-ethyl-3-acryloyloxyethyl oxetane. .

(B3) is preferably a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group.
Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, Biscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

Examples of (c) include (meth) acrylic acid esters, N-substituted maleimides, unsaturated dicarboxylic acid diesters, alicyclic unsaturated compounds, styrenes, and other vinyl compounds.
Examples of (meth) acrylic acid esters include alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, and tert-butyl (meth) acrylate. ;
Cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (in this technical field, dicyclopenta Cycloalkyl esters such as dicyclopentanyloxyethyl (meth) acrylate and isobornyl (meth) acrylate;
Hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
Examples include aryl and aralkyl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate.

Examples of unsaturated dicarboxylic acid diesters include diethyl maleate, diethyl fumarate, diethyl itaconate and the like.
Examples of N-substituted maleimides include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidoca Examples include proate, N-succinimidyl-3-maleimide propionate, and N- (9-acridinyl) maleimide.

  Examples of the alicyclic unsaturated compounds include bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, and 5-ethylbicyclo [2.2. 1] hept-2-ene, 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2′-hydroxy) Ethyl) 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-methylbicyclo [2.2. 1] Hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene , 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2. 1] Hept-2-ene, 5,6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo 2.2.1] hept-2-ene bicyclo unsaturated compounds such as and the like.

Examples of styrenes include styrene, α-methyl styrene, m-methyl styrene, p-methyl styrene, vinyl toluene, and p-methoxy styrene.
Examples of other vinyl compounds include (meth) acrylonitrile, vinyl chloride, vinylidene chloride, (meth) acrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.
Examples of (c) include styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and the like from the viewpoint of copolymerization reactivity and alkali solubility. preferable.

In resin (A2-1), it is preferable that the ratio of the structural unit derived from each monomer exists in the following ranges with respect to the total number of moles of the structural unit constituting the resin (A2-1).
Structural unit derived from (a); preferably 5 to 60 mol%, more preferably 10 to 50 mol%
Structural unit derived from (b); preferably 40 to 95 mol%, more preferably 50 to 90 mol%
When the ratio of the structural unit of the resin (A2-1) is in the above range, the storage stability and developability of the photosensitive resin composition, and the solvent resistance, heat resistance and mechanical strength of the resulting pattern are good. Tend to be.

  Resin (A2-1) is, for example, a method described in the document “Experimental Methods for Polymer Synthesis” (Takayuki Otsu, published by Kagaku Dojin Co., Ltd., First Edition, First Edition, issued March 1, 1972) and It can manufacture with reference to the cited reference described in the said literature.

  Specifically, a method in which a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like are charged into a reaction vessel, and oxygen is substituted with nitrogen, thereby deoxidizing, stirring, heating, and keeping warm. Is exemplified. In addition, the polymerization initiator, the solvent, and the like used here are not particularly limited, and any of those usually used in the field can be used. For example, as polymerization initiators, azo compounds (2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.) Any solvent may be used as long as it dissolves each monomer, and a solvent (E) described later can be used as a solvent for the photosensitive resin composition.

  In addition, the obtained copolymer may use the solution after reaction as it is, a concentrated or diluted solution may be used, and it took out as solid (powder) by methods, such as reprecipitation. Things may be used. In particular, by using the same solvent as the solvent (E) described later as the solvent during the polymerization, the solution after the reaction can be used as it is, and the production process can be simplified.

In resin (A2-2), it is preferable that the ratio of the structural unit derived from each monomer exists in the following ranges with respect to the total number of moles of all structural units constituting the resin (A2-2).
Structural unit derived from (a); preferably 2 to 40 mol%, more preferably 5 to 35 mol%
Structural unit derived from (c); preferably 1 to 65 mol%, more preferably 1 to 60 mol%
Structural unit derived from (b); preferably 2 to 95 mol%, more preferably 5 to 80 mol%
When the ratio of the structural unit of the resin (A2-2) is in the above range, the storage stability and developability of the photosensitive resin composition, and the solvent resistance, heat resistance and mechanical strength of the resulting pattern are good. Tend to be.
As the resin (A2-2), a resin in which (b) is (b1) is preferable, and a resin in which (b) is (b1-1) is more preferable.
Resin (A2-2) can be manufactured by the same method as resin (A2-1).

  The resin (A) is preferably a resin (A2-1), more preferably a resin (A2-1) in which (b) is (b1), and a resin (A2-) in which (b) is (b1-2). 1) is more preferable. These resins are excellent in the storage stability and developability of the photosensitive resin composition, and the solvent resistance, heat resistance and mechanical strength of the resulting pattern.

  The polystyrene equivalent weight average molecular weight of the resin (A) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, still more preferably 5,000 to 25,000, and particularly preferably. 5,000 to 15,000. When the weight average molecular weight of the resin (A) is in the above range, the coating property tends to be excellent, the film thickness of the exposed portion is hardly generated during development, and the non-exposed portion is easily removed by development.

  The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (A) is preferably 1.1 to 6.0, more preferably 1.2 to 4.0, Preferably it is 1.5-3.0, Most preferably, it is 1.7-2.7. When the molecular weight distribution is in the above range, the developability tends to be excellent.

  The acid value of the resin (A) is preferably 20 to 150 mgKOH / g, more preferably 40 to 135 mgKOH / g, and still more preferably 50 to 135 mgKOH / g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the resin (A), and can be determined by titration with an aqueous potassium hydroxide solution.

  The content of the resin (A) is preferably 5 to 95% by mass, more preferably 20 to 80% by mass, and particularly preferably 40% with respect to the total amount of the resin (A) and the polymerizable compound (B). -60 mass%. Further, in the solid content of the photosensitive resin composition, the amount of the structural unit derived from (b) in the resin (A) and the photosensitivity so that the cyclic ether equivalent is 350 to 1500, preferably 550 to 1200. It is preferable to adjust the content of the resin (A) in the resin composition. The cyclic ether equivalent represents the mass of the photosensitive resin composition containing 1 g equivalent of cyclic ether, and can be determined, for example, according to the test method specified in JIS K7236. If the content of the resin (A) is in the above range, the developability of the photosensitive resin composition, the adhesion of the resulting pattern, the solvent resistance and the mechanical properties tend to be good. Here, solid content means the quantity remove | excluding the solvent (E) from the photosensitive resin composition.

［式（１）中、Ｌ^１は、エチレン基又はプロパン−１，２−ジイル基を表す。ｐは、１〜２０の整数を表す。］ The photosensitive resin composition of the present invention contains a polymerizable compound (B). The polymerizable compound (B) is a compound that can be polymerized by active radicals generated from the photopolymerization initiator (C). The polymerizable compound (B) includes a compound having two or more groups represented by the formula (1) (hereinafter sometimes referred to as “polymerizable compound (B1)”), and the content of the compound is a polymerizable compound. It is 30 mass% or more and 100 mass% or less with respect to the total amount of (B).

[In the formula (1), L ¹ represents an ethylene group or a propane-1,2-diyl group. p represents an integer of 1 to 20. ]

  By including the polymerizable compound (B1) in the photosensitive resin composition of the present invention, a pattern having excellent flexibility can be obtained. The flexibility of the pattern can be obtained as a total displacement measured by a micro hardness meter. When the liquid crystal display device is placed in a low-temperature environment, the internal pressure of the liquid crystal cell decreases as the volume of the liquid crystal layer shrinks, resulting in a defect that bubbles are generated in the liquid crystal cell. When a pattern having excellent flexibility is used as a photospacer, the pattern also deforms following the volume shrinkage of the liquid crystal layer, so that a decrease in the internal pressure of the liquid crystal cell can be suppressed and generation of bubbles can be suppressed. .

In group represented by Formula (1), p is 1-20, Preferably it is 1-18, More preferably, it is 1-15.
The number of groups represented by the formula (1) of the polymerizable compound (B1) is 2 or more, and preferably 3 or more. The total number of structures represented by —OL ¹ — derived from the group represented by the formula (1) is included in the groups represented by the respective formula (1) of the polymerizable compound (B1). p is the sum and is preferably 2 to 40 and more preferably 6 to 20 in the polymerizable compound (B1).

Examples of the polymerizable compound (B1) include (meth) acrylates of polyol compounds subjected to ethylene oxide modification (hereinafter sometimes referred to as “EO modification”) or propylene oxide modification (hereinafter also referred to as “PO modification”). Can be mentioned. The modification with ethylene oxide refers to addition of — (CH ₂ CH ₂ O) _p —H to a hydroxy group to give a structure represented by —O— (CH ₂ CH ₂ O) _p —H. Propylene oxide modification gives a structure represented by —O— (CH ₂ CH (CH ₃ ) O) _p —H or —O— (CH (CH ₃ ) CH ₂ O) _p —H, as described above. To do. Examples of the polyol compound include butanediol, neopentyl glycol, tricyclodecane dimethanol, bisphenol A, tris (2-hydroxyethyl) isocyanurate, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, and the like. It is done. Examples of the polymerizable compound (B1) include polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, di (meth) acrylate of EO-modified butanediol, di (meth) acrylate of EO-modified neopentyl glycol, EO-modified tricyclodecane dimethanol di (meth) acrylate, EO-modified bisphenol A di (meth) acrylate, EO-modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, EO Modified trimethylolpropane tri (meth) acrylate, EO modified pentaerythritol tri (meth) acrylate, EO modified pentaerythritol tetra (meth) acrylate, EO modified dipentaerythritol Hexa (meth) acrylate of EO, penta (meth) acrylate of tripentaerythritol modified with EO, di (meth) acrylate of PO modified butanediol, di (meth) acrylate of PO modified neopentyl glycol, PO modified Tricyclodecane dimethanol di (meth) acrylate, PO modified bisphenol A di (meth) acrylate, PO modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, PO modified Trimethylolpropane tri (meth) acrylate, EO-modified pentaerythritol tri (meth) acrylate, PO-modified pentaerythritol tetra (meth) acrylate, PO-modified dipentaerythritol hexa (meth) Acrylate, descriptor of EO-modified tripentaerythritol (meth) acrylate.
Kayrad DPEA-12 (manufactured by Nippon Kayaku Co., Ltd.), SR415, SR454, SR492, SR492, SR499, CD501, SR502, SR9020, CD9021, SR9035, SR480, CD540, SR9036 (above, manufactured by Sartomer), EBECRYL11 (Daicel) Commercially available products such as Cytec Co., Ltd., Light Acrylate 9EG-A, 4EG-A, TMP-6EO-3A (manufactured by Kyoeisha Chemical Co., Ltd.) may be used.

  The polymerizable compound (B) may contain a polymerizable compound different from the polymerizable compound (B1) (hereinafter sometimes referred to as “polymerizable compound (B2)”). The polymerizable compound (B2) is, for example, a compound having a polymerizable carbon-carbon unsaturated bond, and preferably a (meth) acrylic acid ester compound.

  Examples of the polymerizable compound (B2) having one polymerizable carbon-carbon unsaturated bond include the compounds mentioned as the above (a), (b) and (c), and among them, (meth) acrylic acid esters. Are preferred.

  Examples of the polymerizable compound (B2) having two polymerizable carbon-carbon unsaturated bonds include 1,3-butanediol di (meth) acrylate, 1,3-butanediol (meth) acrylate, and 1,6-hexane. Examples include diol di (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol A, ethoxylated bisphenol A di (meth) acrylate, and 3-methylpentanediol di (meth) acrylate.

  Examples of the polymerizable compound (B2) having three or more polymerizable carbon-carbon unsaturated bonds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and tris (2-hydroxyethyl) isocyanurate tris. (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, tripentaerythritol hepta (meth) acrylate, tripenta Lithritol octa (meth) acrylate, reaction product of pentaerythritol tri (meth) acrylate and acid anhydride, reaction product of dipentaerythritol penta (meth) acrylate and acid anhydride, tripentaerythritol hepta (meth) acrylate and Reaction product with acid anhydride, caprolactone-modified trimethylolpropane tri (meth) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate, caprolactone-modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone-modified pentaerythritol Tetra (meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate Caprolactone-modified tripentaerythritol tetra (meth) acrylate, caprolactone-modified tripentaerythritol penta (meth) acrylate, caprolactone-modified tripentaerythritol hexa (meth) acrylate, caprolactone-modified tripentaerythritol hepta (meth) acrylate, caprolactone-modified tripenta Erythritol octa (meth) acrylate, reaction product of caprolactone-modified pentaerythritol tri (meth) acrylate and acid anhydride, reaction product of caprolactone-modified dipentaerythritol penta (meth) acrylate and acid anhydride, caprolactone-modified tripentaerythritol hepta (Meth) acrylate, acid anhydride, etc. are mentioned. Among these, a tri- or higher functional monomer is preferable, and dipentaerythritol hexa (meth) acrylate is more preferable.

  Content of polymeric compound (B1) is 30 mass% or more and 100 mass% or less with respect to the total amount of polymeric compound (B), Preferably it is 50 mass% or more and 100 mass% or less, More preferably It is 75 mass% or more and 100 mass% or less. When the content of the polymerizable compound (B1) is in the above range, the resulting pattern tends to have high flexibility.

The content of the polymerizable compound (B) is preferably 5 to 95% by mass and more preferably 20 to 80% by mass with respect to the total amount of the resin (A) and the polymerizable compound (B). Further, in the solid content of the photosensitive resin composition, the content of the polymerizable compound (B) is adjusted so that the polymerizable carbon-carbon unsaturated bond equivalent is preferably 300 to 1000, more preferably 350 to 750. It is preferable to adjust. The polymerizable carbon-carbon unsaturated bond equivalent represents the mass of the solid content of the photosensitive resin composition containing 1 g equivalent of the carbon-carbon unsaturated bond. The polymerizable carbon-carbon unsaturated bond equivalent is, for example, an absorption peak derived from the carbon-carbon unsaturated bond contained in the solid content of the photosensitive resin composition using an infrared absorption spectrum (for example, 810 cm for an acrylic group). ^-1 ) can be calculated from the number of carbon-carbon unsaturated bonds determined by measuring the strength and the mass of the solid content of the photosensitive resin composition. When the content of the polymerizable compound (B) is in the above range, the sensitivity, the strength of the pattern obtained, smoothness, and reliability tend to be good.

The photosensitive resin composition of the present invention preferably contains a photopolymerization initiator (C). As a photoinitiator (C), if it is a compound which can start superposition | polymerization by the effect | action of light or a heat | fever, it will not specifically limit, A well-known photoinitiator can be used.
Examples of the photopolymerization initiator (C) include acetophenone compounds, biimidazole compounds, triazine compounds, acylphosphine oxide compounds, and oxime compounds. Moreover, you may use the cationic polymerization initiator (For example, what is comprised from the onium cation and the anion derived from a Lewis acid) described in Unexamined-Japanese-Patent No. 2008-181087. Especially, it is preferable that it is at least 1 sort (s) chosen from the group which consists of a biimidazole compound, an acetophenone compound, and an oxime compound, and it is especially preferable that it is an acetophenone compound. These photopolymerization initiators are particularly preferred because they tend to be highly sensitive.

  Examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl]- 2-methylpropan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one, 1 -Hydroxycyclohexyl phenyl ketone, 2-morpholino-1- (4-methylsulfanylphenyl) -2-methylpropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1- ON, 2-dimethylamino-2- (2-methylbenzyl) -1- (4-morpholinophenyl) Tan-1-one, 2-dimethylamino-2- (3-methylbenzyl) -1- (4-morpholinophenyl) butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholinophenyl) butan-1-one, 2-dimethylamino-2- (2-ethylbenzyl) -1- (4-morpholinophenyl) butan-1-one, 2-dimethylamino-2- (2- Propylbenzyl) -1- (4-morpholinophenyl) butan-1-one, 2-dimethylamino-2- (2-butylbenzyl) -1- (4-morpholinophenyl) butan-1-one, 2-dimethylamino -2- (2,3-dimethylbenzyl) -1- (4-morpholinophenyl) butan-1-one, 2-dimethylamino-2- (2,4-dimethylbenzyl) -1- (4- Ruphorinophenyl) butan-1-one, 2-dimethylamino-2- (2-chlorobenzyl) -1- (4-morpholinophenyl) butan-1-one, 2-dimethylamino-2- (2-bromobenzyl)- 1- (4-morpholinophenyl) butan-1-one, 2-dimethylamino-2- (3-chlorobenzyl) -1- (4-morpholinophenyl) butan-1-one, 2-dimethylamino-2- ( 4-chlorobenzyl) -1- (4-morpholinophenyl) butan-1-one, 2-dimethylamino-2- (3-bromobenzyl) -1- (4-morpholinophenyl) butan-1-one, 2- Dimethylamino-2- (4-bromobenzyl) -1- (4-morpholinophenyl) butan-1-one, 2-dimethylamino-2- (2-methoxybenzyl) -1- (4-morpholinophenyl) butan-1-one, 2-dimethylamino-2- (3-methoxybenzyl) -1- (4-morpholinophenyl) butan-1-one, 2-dimethylamino-2- (4- Methoxybenzyl) -1- (4-morpholinophenyl) butan-1-one, 2-dimethylamino-2- (2-methyl-4-methoxybenzyl) -1- (4-morpholinophenyl) butan-1-one, 2-Dimethylamino-2- (2-methyl-4-bromobenzyl) -1- (4-morpholinophenyl) butan-1-one, 2-dimethylamino-2- (2-bromo-4-methoxybenzyl)- 1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one oligomer And the like.

  Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2′-bis (2,3-dichlorophenyl) -4. , 4 ′, 5,5′-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 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 (trialkoxy) Phenyl) biimidazole (for example, see JP-B-48-38403, JP-A-62-174204, etc.), and the phenyl group at the 4,4′5,5′-position is substituted with a carboalkoxy group. Examples thereof include imidazole compounds (for example, see JP-A-7-10913). Preferably, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,3-dichlorophenyl) -4,4 ′, 5 Examples include 5'-tetraphenylbiimidazole and 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole.

  Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxy Naphthyl) -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) Sulfonyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

  Examples of the oxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-ethoxycarbonyloxy-1-phenylpropane-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-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 and the like. Commercial products such as Irgacure OXE-01, OXE-02 (manufactured by Ciba Japan), and N-1919 (manufactured by ADEKA) may be used.

  Furthermore, examples of the photopolymerization initiator (C) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4- Benzophenone compounds such as benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenance Examples include quinone compounds such as lenquinone, 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with a polymerization initiation assistant (C1) described later.

Moreover, you may use the photoinitiator described in the Japanese translations of PCT publication No. 2002-544205 gazette as a photoinitiator which has the group which can raise | generate chain transfer.
As a photoinitiator which has the group which can raise | generate the said chain transfer, the compound of following formula (a)-(f) is mentioned, for example.

  The photopolymerization initiator having a group capable of causing chain transfer can also be used as the component (c) constituting the resin (A).

  In the photosensitive resin composition of the present invention, a polymerization initiation assistant (C1) can be used together with the photopolymerization initiator (C) described above.

  As the polymerization initiation assistant (C1), it is preferable to use a compound represented by the formula (III).

［式（ＩＩＩ）中、Ｗ^１で示される点線はハロゲン原子で置換されていてもよい炭素数６〜１２の芳香環を表す。
Ｙ^１は、−Ｏ−又は−Ｓ−を表す。
Ｒ^４は、炭素数１〜６の１価の飽和炭化水素基を表す。
Ｒ^５は、ハロゲン原子で置換されていてもよい炭素数１〜１２の１価の飽和炭化水素基又はハロゲン原子で置換されていてもよい炭素数６〜１２のアリール基を表す。］

[In the formula (III), a dotted line represented by W ¹ represents an aromatic ring having 6 to 12 carbon atoms which may be substituted with a halogen atom.
Y ¹ represents —O— or —S—.
R ⁴ represents a monovalent saturated hydrocarbon group having 1 to 6 carbon atoms.
R ⁵ represents a monovalent saturated hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom or an aryl group having 6 to 12 carbon atoms which may be substituted with a halogen atom. ]

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

  Examples of the aromatic ring having 6 to 12 carbon atoms that may be substituted with a halogen atom include a benzene ring, a methylbenzene ring, a dimethylbenzene ring, an ethylbenzene ring, a propylbenzene ring, a butylbenzene ring, a pentylbenzene ring, and a hexylbenzene. Ring, cyclohexylbenzene ring, chlorobenzene ring, dichlorobenzene ring, bromobenzene ring, dibromobenzene ring, phenylbenzene ring, chlorophenylbenzene ring, bromophenylbenzene ring, naphthalene ring, chloronaphthalene ring, bromonaphthalene ring, and the like.

  Examples of the monovalent saturated hydrocarbon group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 1-methylpropyl group, 2-methylpropyl group, tert. -Butyl group, n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, n- A hexyl group, a cyclohexyl group, etc. are mentioned.

Examples of the monovalent saturated hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom include, for example, a heptyl group and an octyl group in addition to the monovalent saturated hydrocarbon group having 1 to 6 carbon atoms. , Nonyl group, decyl group, undecyl group, dodecyl group, 1-chlorobutyl group, 2-chlorobutyl group, 3-chlorobutyl group and the like.

  Examples of the aryl group having 6 to 12 carbon atoms which may be substituted with a halogen atom include phenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, dibromophenyl group, chlorobromophenyl group, biphenyl group, chlorobiphenyl group, dichloro Biphenyl group, bromophenyl group, dibromophenyl group, naphthyl group, chloronaphthyl group, dichloronaphthyl group, bromonaphthyl group, dibromonaphthyl group and the like can be mentioned.

As the compound represented by the formula (III), specifically,
2- [2-oxo-2- (2-phenyl) ethylidene] -3-methylnaphtho [2,1-d] thiazoline, 2- [2-oxo-2- (2-phenyl) ethylidene] -3-methylnaphtho [ 1,2-d] thiazoline, 2- [2-oxo-2- (2-phenyl) ethylidene] -3-methylnaphtho [2,3-d] thiazoline, 2- [2-oxo-2- (2-naphthyl) ) Ethylidene] -3-methylbenzothiazoline, 2- [2-oxo-2- (1-naphthyl) ethylidene] -3-methylbenzothiazoline, 2- [2-oxo-2- (2-naphthyl) ethylidene]- 3-methyl-5-phenylbenzothiazoline, 2- [2-oxo-2- (1-naphthyl) ethylidene] -3-methyl-5-phenylbenzothiazoline, 2- [2-oxo-2- (2-naphthyl) Ethylidene] -3-methyl-5-fluorobenzothiazoline, 2- [2-oxo-2- (1-naphthyl) ethylidene] -3-methyl-5-fluorobenzothiazoline, 2- [2-oxo-2- ( 2-naphthyl) ethylidene] -3-methyl-5-chlorobenzothiazoline, 2- [2-oxo-2- (1-naphthyl) ethylidene] -3-methyl-5-chlorobenzothiazoline, 2- [2-oxo 2- (2-naphthyl) ethylidene] -3-methyl-5-bromobenzothiazoline, 2- [2-oxo-2- (1-naphthyl) ethylidene] -3-methyl-5-bromobenzothiazoline, 2- [2-oxo-2- (4-phenylphenyl) ethylidene] -3-methylbenzothiazoline, 2- [2-oxo-2- (4-phenylphenyl) ethylidene] 3-methyl-5-phenylbenzothiazoline, 2- [2-oxo-2- (2-naphthyl) ethylidene] -3-methylnaphtho [2,1-d] thiazoline, 2- [2-oxo-2- (2 -Naphthyl) ethylidene] -3-methylnaphtho [1,2-d] thiazoline, 2- [2-oxo-2- (4-phenylphenyl) ethylidene] -3-methylnaphtho [2,1-d] thiazoline, 2- [2-oxo-2- (4-phenylphenyl) ethylidene] -3-methylnaphtho [1,2-d] thiazoline, 2- [2-oxo-2- (4-fluorophenyl) ethylidene] -3-methylnaphtho [ 2,1-d] thiazoline, 2- [2-oxo-2- (4-fluorophenyl) ethylidene] -3-methylnaphtho [1,2-d] thiazoline, 2- [2-oxo-2- (2- Phenyl) ethylidene] -3-methylnaphtho [2,1-d] oxazoline, 2- [2-oxo-2- (2-phenyl) ethylidene] -3-methylnaphtho [1,2-d] oxazoline, 2- [2 -Oxo-2- (2-phenyl) ethylidene] -3-methylnaphtho [2,3-d] oxazoline, 2- [2-oxo-2- (2-naphthyl) ethylidene] -3-methylbenzoxazoline, 2- [2-oxo-2- (1-naphthyl) ethylidene] -3-methylbenzoxazoline, 2- [2-oxo-2- (2-naphthyl) ethylidene] -3-methyl-5-phenylbenzoxazoline, 2- [2-oxo-2- (1-naphthyl) ethylidene] -3-methyl-5-phenylbenzoxazoline, 2- [2-oxo-2- (2-naphthyl) ethylidene] 3-methyl-5-fluorobenzoxazoline, 2- [2-oxo-2- (1-naphthyl) ethylidene] -3-methyl-5-fluorobenzoxazoline, 2- [2-oxo-2- (2-naphthyl) ) Ethylidene] -3-methyl-5-chlorobenzoxazoline, 2- [2-oxo-2- (1-naphthyl) ethylidene] -3-methyl-5-chlorobenzoxazoline, 2- [2-oxo-2- (2-naphthyl) ethylidene] -3-methyl-5-bromobenzoxazoline, 2- [2-oxo-2- (1-naphthyl) ethylidene] -3-methyl-5-bromobenzoxazoline, 2- [2- Oxo-2- (4-phenylphenyl) ethylidene] -3-methylbenzoxazoline, 2- [2-oxo-2- (4-phenylphenyl) ethylidene] 3-methyl-5-phenylbenzoxazoline, 2- [2-oxo-2- (1-naphthyl) ethylidene] -3-methylnaphtho [2,1-d] oxazoline, 2- [2-oxo-2- (1) -Naphthyl) ethylidene] -3-methylnaphtho [1,2-d] oxazoline, 2- [2-oxo-2- (4-phenylphenyl) ethylidene] -3-methylnaphtho [2,1-d] oxazoline, 2- [2-oxo-2- (4-phenylphenyl) ethylidene] -3-methylnaphtho [1,2-d] oxazoline, 2- [2-oxo-2- (4-fluorophenyl) ethylidene] -3-methylnaphtho [ 2,1-d] oxazoline, 2- [2-oxo-2- (4-fluorophenyl) ethylidene] -3-methylnaphtho [1,2-d] oxazoline, and the like.

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

[In Formula (IV) and Formula (V), Rings W ² , W ³ and Ring W ⁴ are each independently an aromatic ring having 6 to 12 carbon atoms which may be substituted with a halogen atom, or 2 to 2 carbon atoms. 10 heterocycles are represented. Y ^{2 to} Y ⁵ each independently represent —O— or —S—. R ^{6 to} R ⁹ represent a monovalent saturated hydrocarbon group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group and the aryl group is a halogen atom. , May be substituted with a hydroxy group or an alkoxy group having 1 to 6 carbon atoms.

Examples of the aromatic ring having 6 to 12 carbon atoms include the same aromatic rings as those mentioned in formula (III), and the hydrogen atom contained in the aromatic ring is optionally substituted with the halogen atoms mentioned above. May be.
Examples of the heterocyclic ring having 2 to 10 carbon atoms that may be substituted with a halogen atom include a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, and a pyran ring.

Examples of the monovalent hydroxy group-substituted saturated hydrocarbon group include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, and a hydroxybutyl group.
Examples of the hydroxy group-substituted aryl group include a hydroxyphenyl group and a hydroxynaphthyl group.
Examples of the monovalent alkoxy group-substituted saturated hydrocarbon group include a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, a methoxybutyl group, a butoxymethyl group, an ethoxyethyl group, an ethoxypropyl group, and a propoxybutyl group.
Examples of the alkoxy group-substituted aryl group include a methoxyphenyl group and an ethoxynaphthyl group.

Specific examples of the compounds represented by formula (IV) and formula (V) include
Dialkoxynaphthalenes such as dimethoxynaphthalene, diethoxynaphthalene, dipropoxynaphthalene, diisopropoxynaphthalene, dibutoxynaphthalene;
9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, dipropoxyanthracene, diisopropoxyanthracene, dibutoxyanthracene , Dipentyloxyanthracene, dihexyloxyanthracene, methoxyethoxyanthracene, methoxypropoxyanthracene, methoxyisopropoxyanthracene, methoxybutoxyanthracene, ethoxypropoxyanthracene, ethoxyisopropoxyanthracene, ethoxybutoxyanthracene, propoxyisopropoxyanthracene, propoxybutoxyanthracene, propoxybutoxyanthracene Dialkoxyanthracenes such as butoxyanthracene;
Dialkoxynaphthacenes such as dimethoxynaphthacene, diethoxynaphthacene, dipropoxynaphthacene, diisopropoxynaphthacene, dibutoxynaphthacene;
Etc.

  Moreover, a thioxanthone compound can also be used as a polymerization initiation assistant (C1). Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.

Furthermore, examples of the polymerization initiation assistant (C1) include amine compounds and carboxylic acid compounds.
Examples of amine compounds include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4-dimethylamino. Of 2-ethylhexyl benzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (common name; Michler's ketone), 4,4′-bis (diethylamino) benzophenone Such aromatic amine compounds are mentioned.

  Carboxylic acid compounds 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 -Aromatic heteroacetic acids such as phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine and naphthoxyacetic acid.

Preferable combinations of the photopolymerization initiator (C) and the polymerization initiation assistant (C1) include an acetophenone compound and a thioxanthone compound, an acetophenone compound and an aromatic amine compound, and specifically, 2-morpholino-1- (4-Methylsulfanylphenyl) -2-methylpropan-1-one and 2,4-diethylthioxanthone, 2-dimethylamino-2-benzyl-1- (4-morpholinophenyl) butan-1-one and 2,4 -Diethylthioxanthone, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholinophenyl) butan-1-one and 2,4-diethylthioxanthone, 2-morpholino-1- (4-methylsulfanyl) Phenyl) -2-methylpropan-1-one, 2-isopropylthioxanthone and 4-isopro Ruthioxanthone, 2-morpholino-1- (4-methylsulfanylphenyl) -2-methylpropan-1-one and 4,4′-bis (diethylamino) benzophenone, 2-dimethylamino-2-benzyl-1- (4 -Morpholinophenyl) butan-1-one and 4,4'-bis (diethylamino) benzophenone, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholinophenyl) butan-1-one and 4 , 4′-bis (diethylamino) benzophenone and the like.
As a combination of the photopolymerization initiator (C) and the polymerization initiation assistant (C1), a combination of an acetophenone compound and a thioxanthone compound is preferable, and 2-morpholino-1- (4-methylsulfanylphenyl) -2-methylpropane More preferred are -1-one and 2,4-diethylthioxanthone, 2-morpholino-1- (4-methylsulfanylphenyl) -2-methylpropan-1-one, 2-isopropylthioxanthone and 4-isopropylthioxanthone. With these combinations, a pattern with high sensitivity and high visible light transmittance can be obtained.

  The content of the photopolymerization initiator (C) is preferably 0.5 to 30% by mass, more preferably 1 to 20% by mass with respect to the total amount of the resin (A) and the polymerizable compound (B). More preferably, it is 1-10 mass%. When the content of the photopolymerization initiator (C) is in the above range, a pattern can be obtained with high sensitivity.

  The amount of the polymerization initiation assistant (C1) used is preferably 0.1 to 10% by mass, more preferably 0.3 to 7% by mass, based on the total amount of the resin (A) and the polymerizable compound (B). It is. When the amount of the polymerization initiation assistant (C1) is in the above range, a pattern can be obtained with high sensitivity, and the resulting pattern has a good shape.

The photosensitive resin composition of the present invention contains a silicone surfactant (D).
Examples of the silicone surfactant include surfactants having a siloxane bond.
Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH29PA, SH30PA, polyether-modified silicone oil SH8400 (trade name: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322 , KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (Momentive Performance Materials Japan GK) Manufactured) and the like.

  The silicone-based surfactant (D) is 0.0001% by mass or more and 0.05% by mass or less, preferably 0.0005% by mass or more and 0.04% by mass or less, based on the photosensitive resin composition. Preferably they are 0.001 mass% or more and 0.03 mass% or less. By containing the surfactant in this range, the flatness of the coating film can be improved by suppressing unevenness during coating and unevenness during development. When the flatness of the coating film is good, when a plurality of patterns are produced on the same substrate, variation in height between patterns can be reduced.

The photosensitive resin composition of the present invention contains a solvent (E).
Examples of the solvent that can be used in the present invention include ester solvents (solvents containing —COO—), ether solvents other than ester solvents (solvents containing —O—), ether ester solvents (—COO— and —O— and Selected from the group consisting of ketone solvents other than ester solvents (solvents containing —CO—), alcohol solvents, aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like.

  As ester solvents, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, 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.

  Ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene 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, diethyl Glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, and the like methyl anisole.

  Examples of ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, Ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, and the like diethylene glycol monobutyl ether acetate.

  Examples of ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone. Etc.

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

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

Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.
These solvents may be used alone or in combination of two or more.

  Among the above-mentioned solvents, an organic solvent having a boiling point at 1 atm of 120 ° C. or higher and 180 ° C. or lower is preferable from the viewpoints of coating properties and drying properties. Of these, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, diethylene glycol methyl ethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol and the like are preferable. When the solvent (E) is any of these solvents, unevenness during coating can be suppressed and the flatness of the coating film can be improved.

  The content of the solvent (E) in the photosensitive resin composition is preferably 60 to 95% by mass and more preferably 70 to 90% by mass with respect to the photosensitive resin composition. In other words, the solid content of the photosensitive resin composition is preferably 5 to 40% by mass, and more preferably 10 to 30% by mass. When the content of the solvent (E) is in the above range, the flatness of the film coated with the photosensitive resin composition tends to be high.

  Moreover, the photosensitive resin composition of this invention may contain the polyfunctional thiol compound (T) further. The polyfunctional thiol compound (T) refers to a compound having two or more sulfanyl groups in the molecule. In particular, when a compound having two or more sulfanyl groups bonded to a carbon atom derived from an aliphatic hydrocarbon group is used, the sensitivity of the photosensitive resin composition of the present invention tends to increase.

  Specific examples of the polyfunctional thiol compound (T) include hexanedithiol, decanedithiol, 1,4-bis (methylsulfanyl) benzene, butanediol bis (3-sulfanylpropionate), butanediol bis (3- Sulfanyl acetate), ethylene glycol bis (3-sulfanyl acetate), trimethylolpropane tris (3-sulfanyl acetate), butanediol bis (3-sulfanylpropionate), trimethylolpropane tris (3-sulfanylpropionate), Trimethylolpropane tris (3-sulfanyl acetate), pentaerythritol tetrakis (3-sulfanylpropionate), pentaerythritol tetrakis (3-sulfanyl acetate), trishydro Shiechirutorisu (3-sulfanyl propionate), pentaerythritol tetrakis (3-sulfanyl butyrate), 1,4-bis (3-sulfanyl-butyloxy) include butane and the like.

  The content of the polyfunctional thiol compound (T) is preferably 0.1 to 10% by mass, more preferably 0.5 to 7% by mass with respect to the photopolymerization initiator (C). When the content of the polyfunctional thiol compound (T) is in the above range, the sensitivity of the photosensitive resin composition is increased and the developability tends to be favorable, which is preferable.

  In the photosensitive resin composition of the present invention, various additives such as fillers, other polymer compounds, adhesion promoters, antioxidants, ultraviolet absorbers, light stabilizers, chain transfer agents, etc., are optionally added. May be used in combination.

  The photosensitive resin composition of the present invention does not substantially contain colorants such as pigments and dyes. That is, in the photosensitive resin composition of the present invention, the content of the colorant with respect to the entire composition is preferably less than 1% by mass, more preferably less than 0.5% by mass.

  The photosensitive resin composition of the present invention preferably has an average transmittance when filling a quartz cell having an optical path length of 1 cm and measuring the transmittance under a measurement wavelength of 400 to 700 nm using a spectrophotometer. Is 70% or more, more preferably 80% or more.

  When the photosensitive resin composition of the present invention is formed into a coating film, the average transmittance of the coating film is preferably 90% or more, and more preferably 95% or more. This average transmittance is measured at a wavelength of 400 to 700 nm using a spectrophotometer on a coating film having a thickness of 3 μm after heat curing (for example, curing at 100 to 250 ° C. for 5 minutes to 3 hours). It is an average value when measured under conditions. Thereby, the coating film excellent in transparency in the visible light region can be provided.

  The photosensitive resin composition of the present invention is formed as a coating film by, for example, coating on a substrate made of glass, metal, plastic, etc., a color filter, various insulating or conductive films, a drive circuit, etc. can do. The coating film is preferably dried and cured. Moreover, the obtained coating film can be patterned into a desired shape and used as a pattern. Furthermore, these coating films or patterns may be formed and used as part of a component such as a display device.

First, the photosensitive resin composition of the present invention is applied on a substrate.
As described above, the coating can be performed using various coating apparatuses such as a spin coater, a slit & spin coater, a slit coater, an ink jet, a roll coater, and a dip coater.

Then, it is preferable to dry or pre-bake to remove volatile components such as a solvent. Thereby, a smooth uncured coating film can be obtained.
The film thickness of the coating film in this case is not particularly limited, and can be appropriately adjusted depending on the material used, application, etc. For example, about 1 to 6 μm is exemplified.

Further, the obtained uncured coating film is irradiated with light, for example, ultraviolet rays generated from a mercury lamp or a light emitting diode through a photomask for forming a target pattern. The shape of the photomask at this time is not particularly limited, and the shape and size may be selected according to the application of the pattern.
In recent exposure machines, light of less than 350 nm is cut using a filter that cuts this wavelength range, or light near 436 nm, 408 nm, and 365 nm is used using a bandpass filter that extracts these wavelength ranges. It is possible to selectively take out and irradiate parallel light uniformly on the entire exposure surface. At this time, an apparatus such as a mask aligner or a stepper may be used to accurately align the mask and the substrate.

A desired pattern shape can be obtained by bringing the exposed coating film into contact with a developer to dissolve a predetermined portion, for example, a non-exposed portion, and developing.
The developing method may be any of a liquid piling method, a dipping method, a spray method, and the like. Further, the substrate may be inclined at an arbitrary angle during development.

The developer used for development is preferably an aqueous solution of a basic compound.
The basic compound may be either an inorganic or organic basic compound.
Specific examples of inorganic basic compounds include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, silicic acid. Examples include potassium, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate, and ammonia.

Examples of organic basic compounds include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, and ethanolamine. Is mentioned.
The concentration of these inorganic and organic basic compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass.

The developer may contain a surfactant.
The surfactant may be any of a nonionic surfactant, an anionic surfactant, or a cationic surfactant.
Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene Examples include ethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, and polyoxyethylene alkylamine.

  Examples of the anionic surfactant include higher alcohol sulfates such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, and dodecyl sodium sulfate. And alkylaryl sulfonates such as sodium naphthalene sulfonate.

Examples of the cationic surfactant include amine salts or quaternary ammonium salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride.
The concentration of the surfactant in the alkali developer is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, and more preferably 0.1 to 5% by mass.

A pattern can be obtained by washing with water after development. Furthermore, you may post-bake as needed. Post bake is preferably performed at a temperature range of 150 to 240 ° C. for 10 to 180 minutes.
When exposing an uncured coating film, it is possible to obtain a coating film having no pattern by irradiating the entire surface with light and / or omitting development without using a photomask on which a pattern is formed. it can.

According to the present invention, it is possible to obtain a pattern excellent in both flexibility and heat resistance.
In this way, the pattern obtained from the photosensitive resin composition of the present invention is, for example, a photo spacer constituting a part of a color filter substrate and / or an array substrate, a patternable overcoat, an interlayer insulating film, and a liquid crystal alignment control. A coating film that is useful as a member for a touch panel, such as a projection for projection, a microlens, and a coating layer for adjusting a film thickness, and having no pattern obtained as described above is used for a color filter substrate and / or an array substrate. It is useful as an overcoat that constitutes a part. The color filter substrate and the array substrate are suitably used for a liquid crystal display device, an organic EL display device, electronic paper, and the like.

  Hereinafter, the present invention will be described in more detail with reference to examples. Unless otherwise specified, “%” and “parts” in the examples are% by mass and parts by mass.

Synthesis example 1
In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was allowed to flow 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. Heat to 70 ° C. with stirring. Subsequently, 55 parts by mass of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (a compound represented by the formula (I-1) and a formula (II-1) The compound to be prepared is a mixture of 50:50 in a molar ratio.) A solution is prepared by dissolving 175 parts by mass and 70 parts by mass of N-cyclohexylmaleimide in 140 parts by mass of 3-methoxybutyl acetate. It was dripped in the flask kept at 70 degreeC over 4 hours using the dripping pump. On the other hand, a solution obtained by dissolving 30 parts by mass of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 225 parts by mass of 3-methoxybutyl acetate was added to a flask over another 5 hours using another dropping pump. It was dripped in. After completion of dropping of the solution of the polymerization initiator, the temperature was kept at 70 ° C. for 4 hours, and then cooled to room temperature. The solid content was 32.6% by mass, and the acid value of the solution was 34.3 mg-KOH / g. A coalesced (resin Aa) solution was obtained. The obtained resin Aa had a weight average molecular weight (Mw) of 13,600, a number average molecular weight (Mn) of 5,400, and a molecular weight distribution of 2.5.

Synthesis example 2
In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was allowed to flow 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. Heat to 70 ° C. with stirring. Subsequently, 60 parts by mass of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (a compound represented by the formula (I-1) and a formula (II-1) The compound to be mixed is mixed at a molar ratio of 50:50.) A solution is prepared by dissolving in 240 parts by mass and 140 parts by mass of 3-methoxybutyl acetate. And dropped in a flask kept at 70 ° C. On the other hand, a solution in which 30 parts by mass of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) was dissolved in 225 parts by mass of 3-methoxybutyl acetate was added to a flask over another 4 hours using another dropping funnel. It was dripped in. After completion of the dropwise addition of the polymerization initiator solution, the mixture was kept at 70 ° C. for 4 hours, and then cooled to room temperature, so that the solid content was 32.6% by mass and the acid value was 110 mg-KOH / g (solid content conversion). A polymer (resin Ab) solution was obtained. The obtained resin Aa had a weight average molecular weight Mw of 13,400 and a molecular weight distribution of 2.50.

Synthesis example 3
Nitrogen was allowed to flow at 0.02 L / min in a flask equipped with a reflux condenser, a dropping funnel and a stirrer to form a nitrogen atmosphere, and 140 parts by mass of diethylene glycol ethyl methyl ether was added and heated to 70 ° C. with stirring.
Subsequently, 40 parts by mass of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (a compound represented by the formula (I-1) and a formula (II-1) 340 parts by mass of a mixture of compounds to be prepared, molar ratio = 50: 50) and 20 parts by mass of dicyclopentenyl acrylate (compound represented by the following formula (x1)) are dissolved in 190 parts by mass of diethylene glycol ethyl methyl ether to obtain a solution. Was prepared.

The obtained solution was dropped into a flask kept at 70 ° C. for 4 hours using a dropping pump.
On the other hand, a solution prepared by dissolving 30 parts by mass of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 240 parts by mass of diethylene glycol ethyl methyl ether was added to a flask over another 5 hours using another dropping pump. It was dripped in.
After completion of the dropwise addition of the polymerization initiator solution, the solution was kept at 70 ° C. for 4 hours, and then cooled to room temperature to obtain a copolymer (resin Ac) solution having a solid content of 41.8%. The weight average molecular weight (Mw) of the obtained resin Ac was 9.6 × 10 ³ , the molecular weight distribution (Mw / Mn) was 2.02, and the acid value in terms of solid content was 60 mg-KOH / g.

Synthesis example 4
Nitrogen was allowed to flow at 0.02 L / min in a flask equipped with a reflux condenser, a dropping funnel and a stirrer to form a nitrogen atmosphere, and 140 parts by mass of diethylene glycol ethyl methyl ether was added and heated to 70 ° C. with stirring.
Subsequently, 40 parts by mass of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (a compound represented by the formula (I-1) and a formula (II-1) A mixture of compounds to be dissolved, 320 parts by mass of a molar ratio = 50: 50), 40 parts by mass of dicyclopentanyl acrylate (a compound represented by the following formula (x2)) are dissolved in 190 parts by mass of diethylene glycol ethyl methyl ether, A solution was prepared.

The obtained solution was dropped into a flask kept at 70 ° C. for 4 hours using a dropping pump.
On the other hand, a solution prepared by dissolving 30 parts by mass of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 240 parts by mass of diethylene glycol ethyl methyl ether was added to a flask over another 5 hours using another dropping pump. It was dripped in.
After dropping of the polymerization initiator solution was completed, the solution was kept at 70 ° C. for 4 hours and then cooled to room temperature to obtain a copolymer (resin Ad) solution having a solid content of 41.8%. The weight average molecular weight (Mw) of the obtained resin Ad was 7.9 × 10 ³ , the molecular weight distribution (Mw / Mn) was 1.82, and the acid value in terms of solid content was 60 mg-KOH / g.

Synthesis example 5
Nitrogen was allowed to flow at 0.02 L / min in a flask equipped with a reflux condenser, a dropping funnel and a stirrer to form a nitrogen atmosphere, 60 parts by mass of diethylene glycol ethyl methyl ether was added, and the mixture was heated to 90 ° C. with stirring. Next, 13 parts by weight of methyl methacrylate, 7 parts by weight of methacrylic acid, 14 parts by weight of n-butyl methacrylate, 6 parts by weight of 2-ethylhexyl acrylate, 0.4 parts by weight of azobisvaleronitrile, 0.8 parts by weight of n-dodecyl mercaptan The portion was continuously added dropwise over 3 hours. Then, after maintaining at 90 ° C. for 30 minutes, the temperature was raised to 105 ° C. and maintained for 3 hours, and then cooled to room temperature to obtain a copolymer (resin Ae) solution having a solid content of 40.1%. Obtained. The obtained resin Ae had a weight average molecular weight (Mw) of 1.6 × 10 ⁴ and a molecular weight distribution (Mw / Mn) of 2.02.

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained resins Aa to Ae were measured under the following conditions using the GPC method.
Apparatus; K2479 (manufactured by Shimadzu Corporation)
Column; SHIMADZU Shim-pack GPC-80M
Column temperature: 40 ° C
Solvent; THF (tetrahydrofuran)
Flow rate: 1.0 mL / min
Detector; RI
The ratio of the weight average molecular weight and number average molecular weight obtained in the above-mentioned manner was defined as the molecular weight distribution (Mw / Mn).

Examples and Comparative Examples <Preparation of Photosensitive Resin Composition>
The components of Table 1 were mixed to obtain photosensitive resin compositions 1-8.

重合性化合物（Ｂ１）；Ｂ１ｂ：ポリエチレングリコールジアクリレート（ＥＢＥＣＲＹＬ１１；ダイセルサイテック（株）製；アクリロイルオキシ基２個、−ＯＣＨ_２ＣＨ_２−を化合物中に１１個含有）
重合性化合物（Ｂ１）；Ｂ１ｃ：テトラデカエチレングリコールジアクリレート（ライトアクリレート１４ＥＧ−Ａ：共栄社化学製；アクリロイルオキシ基２個、−ＯＣＨ_２ＣＨ_２−を化合物中に１４個含有）
重合性化合物（Ｂ２）；Ｂ２ａ：ジペンタエリスリトールヘキサアクリレート（ＫＡＹＡＲＡＤ ＤＰＨＡ；日本化薬（株）製）
重合性化合物（Ｂ２）；Ｂ２ｂ：トリメチロールプロパントリアクリレート（ＮＫエステルＡ−ＴＭＰＴ；新中村化学工業製）
光重合開始剤（Ｃ）；Ｃａ：２−モルホリノ−１−（４−メチルスルファニルフェニル）−２−メチルプロパン−１−オン（イルガキュア９０７；ＢＡＳＦジャパン製）
光重合開始剤（Ｃ）；Ｃｂ：２−ベンジル−２−ジメチルアミノ−１−（４−モルホリノフェニル）ブタン−１−オン（イルガキュア３６９；ＢＡＳＦジャパン製）
重合開始助剤（Ｃ１）；Ｃ１ａ：２，４−ジエチルチオキサントン（ＤＥＴＸ−Ｓ；日本化薬（株）製）
熱架橋剤；Ｈａ；イソシアネート化合物（デュラネートＥ−４０２−Ｂ８０Ｔ：旭化成ケミカルズ製）
多官能チオール（Ｔ１）；ペンタエリスリトールテトラキス（３−スルファニルプロピオネート）（ＰＥＭＰ；ＳＣ有機化学（株）製）
シリコーン系界面活性剤（Ｄ）；ＳＨ８４００；東レダウコーニング製
溶剤（Ｅ）；Ｅａ；プロピレングリコールモノメチルエーテルアセテート
溶剤（Ｅ）；Ｅｂ；３−エトキシプロピオン酸エチル
溶剤（Ｅ）；Ｅｃ；３−メトキシ１−ブタノール
溶剤（Ｅ）；Ｅｄ；３−メトキシブチルアセテート
溶剤（Ｅ）；Ｅｅ；ジエチレングリコールジメチルエーテル
溶剤（Ｅ）は、感光性樹脂組成物の固形分量が表１の「固形分量（％）」となるように混合し、溶剤（Ｅ）中の溶剤成分（Ｅａ）〜（Ｅｅ）の値は、溶剤（Ｅ）中での質量比を表す。 Each component in Table 1 is as follows. In Table 1, the number of parts of the resin (A) represents a mass part in terms of solid content.
Resin (A); Aa: Resin Aa obtained in Synthesis Example 1
Resin (A); Ab: Resin Ab obtained in Synthesis Example 2
Resin (A); Ac: Resin Ac obtained in Synthesis Example 3
Resin (A); Ad: Resin Ad obtained in Synthesis Example 4
Resin (A); Ae: Resin Ae obtained in Synthesis Example 5
Polymerizable compound (B1); B1a: ethylene oxide-modified dipentaerythritol hexaacrylate (compound represented by the following formula) (KAYARAD DPEA12; manufactured by Nippon Kayaku Co., Ltd.)

Polymerizable compound (B1); B1b: Polyethylene glycol diacrylate (EBECRYL11; manufactured by Daicel Cytec Co., Ltd .; 2 acryloyloxy groups and 11 —OCH ₂ CH ₂ — contained in the compound)
Polymerizable compound (B1); B1c: tetradecaethylene glycol diacrylate (light acrylate 14EG-A: manufactured by Kyoeisha Chemical; 2 acryloyloxy groups, 14 —OCH ₂ CH ₂ — contained in the compound)
Polymerizable compound (B2); B2a: dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)
Polymerizable compound (B2); B2b: trimethylolpropane triacrylate (NK ester A-TMPT; manufactured by Shin-Nakamura Chemical Co., Ltd.)
Photopolymerization initiator (C); Ca: 2-morpholino-1- (4-methylsulfanylphenyl) -2-methylpropan-1-one (Irgacure 907; manufactured by BASF Japan)
Photopolymerization initiator (C); Cb: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (Irgacure 369; manufactured by BASF Japan)
Polymerization initiation assistant (C1); C1a: 2,4-diethylthioxanthone (DETX-S; manufactured by Nippon Kayaku Co., Ltd.)
Thermal crosslinking agent; Ha; Isocyanate compound (Duranate E-402-B80T: manufactured by Asahi Kasei Chemicals)
Multifunctional thiol (T1); pentaerythritol tetrakis (3-sulfanylpropionate) (PEMP; manufactured by SC Organic Chemical Co., Ltd.)
SH8400; manufactured by Toray Dow Corning; solvent (E); Ea; propylene glycol monomethyl ether acetate solvent (E); Eb; ethyl 3-ethoxypropionate solvent (E); Ec; 3-methoxy 1-butanol solvent (E); Ed; 3-methoxybutyl acetate solvent (E); Ee; diethylene glycol dimethyl ether The solvent (E) has a solid content of the photosensitive resin composition of “solid content (%)” in Table 1. The values of the solvent components (Ea) to (Ee) in the solvent (E) represent mass ratios in the solvent (E).

<Average transmittance of composition>
About the obtained photosensitive resin compositions 1-8, respectively 400-400 using an ultraviolet-visible near-infrared spectrophotometer (V-650; JASCO Corporation make) (quartz cell, optical path length: 1 cm). The average transmittance (%) at 700 nm was measured. The results are shown in Table 1.

<Membrane average transmittance>
Using the obtained photosensitive resin compositions 1 to 7, films were prepared under the following conditions so that the film thickness after curing was 3 μm, respectively.
A 2-inch square glass substrate (# 1737; manufactured by Corning) was sequentially washed with a neutral detergent, water and alcohol and then dried. The photosensitive resin composition was spin-coated on this glass substrate so that the film thickness after post-baking was 3.0 μm, and then pre-baked at 90 ° C. for 10 minutes in a clean oven. After cooling, the distance between the substrate coated with the photosensitive resin composition and the quartz glass photomask is set to 100 μm, and the exposure apparatus (TME-150RSK; manufactured by Topcon Corporation, light source: ultrahigh pressure mercury lamp) is used to form the atmosphere. Under an atmosphere, light with an exposure amount of 100 mJ / cm ² (based on 365 nm) was irradiated. In addition, irradiation to the photosensitive resin composition at this time was performed by passing the radiated light from the ultra-high pressure mercury lamp through an optical filter (UV-35; manufactured by Asahi Spectroscopic Co., Ltd.). After light irradiation, the coating film was developed by immersing and shaking at 23 ° C. for 60 seconds in an aqueous developer solution containing 0.12% nonionic surfactant and 0.04% potassium hydroxide, and then 150 ° C. And heated for 180 minutes to obtain a film.
About the obtained film | membrane, the average transmittance | permeability (%) in 400-700 nm was measured using the microspectrophotometer (OSP-SP200; OLYMPUS company make). Higher transmittance means less absorption. The results are shown in Table 1.

<Pattern formation>
A 2-inch square glass substrate (# 1737; manufactured by Corning) was sequentially washed with a neutral detergent, water and alcohol and then dried. On this glass substrate, the photosensitive resin composition was spin-coated so that the film thickness after post-baking was 4.5 μm. Next, it was pre-baked at 90 ° C. for 10 minutes in a clean oven. After cooling, the distance between the substrate coated with the photosensitive resin composition and the quartz glass photomask is set to 100 μm, and the exposure apparatus (TME-150RSK; manufactured by Topcon Corporation, light source: ultrahigh pressure mercury lamp) is used to form the atmosphere. Under an atmosphere, light with an exposure amount of 100 mJ / cm ² (based on 365 nm) was irradiated. In addition, irradiation to the photosensitive resin composition at this time was performed by passing the radiated light from the ultra-high pressure mercury lamp through an optical filter (UV-35; manufactured by Asahi Spectroscopic Co., Ltd.). Further, a photomask having a pattern (having a square light-transmitting portion with one side of 10 μm and a space between the squares of 100 μm) (that is, the light-transmitting portion) formed on the same plane was used as the photomask.
After light irradiation, the coating film was developed by immersing and shaking at 23 ° C. for 60 seconds in an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide, washed with water, Inside, post-baking was performed at 150 ° C. for 180 minutes to obtain a pattern.

<Measurement of pattern width>
The width of the obtained pattern was measured with a three-dimensional non-contact surface shape measurement system (Micromap MM527N-PS-M100; manufactured by Ryoka System Co., Ltd.). A pattern width of 5% higher than the substrate surface was measured with respect to the pattern height. The results are shown in Table 4.

<Mechanical properties (total displacement and recovery rate)>
About the obtained pattern, the total displacement (μm) and the elastic displacement (μm) were measured using a dynamic ultra-micro hardness meter (DUH-W201; manufactured by Shimadzu Corporation), and the recovery rate (%) Was calculated. It can be determined that the greater the total displacement, the higher the flexibility. The results are shown in Table 4.
-Measurement conditions-
Test mode: Load-unloading test force: 20 mN
Load speed: 4.41 mN / sec
Holding time: 5 sec
Indenter: truncated cone indenter (diameter 50 μm)
Recovery rate (%); (elastic displacement (μm) / total displacement (μm)) × 100

<Coating formation>
A 2-inch square glass substrate (# 1737; manufactured by Corning) was sequentially washed with a neutral detergent, water and propan-2-ol and then dried. On this glass substrate, the photosensitive resin composition was spin-coated so that the film thickness after post-baking was 3 μm. Next, it was pre-baked at 100 ° C. for 3 minutes in a clean oven. After cooling, using an exposure machine (TME-150RSK; manufactured by Topcon Corp., light source: ultrahigh pressure mercury lamp), irradiation was performed with an exposure amount of 100 mJ / cm ² (365 nm reference) in an air atmosphere. In addition, irradiation to the photosensitive resin composition at this time was performed by passing the radiated light from the ultra-high pressure mercury lamp through an optical filter (UV-35; manufactured by Asahi Spectroscopic Co., Ltd.). Further, no photomask was used.
After light irradiation, the coating film was developed by immersing and shaking at 23 ° C. for 60 seconds in an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide, washed with water, Inside, post-baking was performed at 220 ° C. for 20 minutes to obtain a pattern.
<Heat resistance evaluation>
The obtained coating film was heated at 240 ° C. for 1 hour in a clean oven, and the film thickness was measured. From the film thickness before and after heating, the rate of change was determined according to the following equation.
Film thickness change rate (%) = film thickness after heating (μm) / film thickness before heating (μm)
If the heat resistance in the coating film is good, the heat resistance is good even in a pattern formed using the same photosensitive resin composition. The results are shown in Table 2.

It was confirmed that the pattern obtained from the photosensitive resin composition of the present invention was excellent in flexibility. Furthermore, it was confirmed that the coating film obtained from the photosensitive resin composition of the present invention also has excellent heat resistance.
By forming a coating film or pattern using such a photosensitive resin composition and applying them to a liquid crystal display device as a photospacer, by suppressing foaming in a liquid crystal layer generated in a low temperature environment, liquid crystal The durability of the display device can be improved.

  The photosensitive resin composition of the present invention provides a pattern having excellent flexibility and heat resistance.

Claims (5)

Resin, polymerizable compound, photopolymerization initiator, silicone surfactant and solvent,
The resin has a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, a cyclic ether structure having 2 to 4 carbon atoms, and a carbon-carbon unsaturated double bond. An addition polymer containing a structural unit derived from a monomer,
The polymerizable compound includes a compound having two or more groups represented by the formula (1),
The photosensitive resin composition whose content of this compound is 30 to 100 mass% with respect to the total amount of a polymeric compound.

[In the formula (1), L ¹ represents an ethylene group or a propane-1,2-diyl group. p represents an integer of 1 to 20. ]   The photosensitive resin composition according to claim 1, wherein the content of the silicone surfactant is 0.0001 mass% or more and 0.05 mass% or less in the photosensitive resin composition.   The content of the structural unit derived from the monomer having a cyclic ether structure having 2 to 4 carbon atoms and a carbon-carbon unsaturated double bond is 30 mol% or more and 90 mol% with respect to the total amount of the structural unit in the resin. The photosensitive resin composition of Claim 1 or 2 which is the following.   The pattern formed with the photosensitive resin composition in any one of Claims 1-3.   A display device comprising the pattern according to claim 4.