JP5803432B2 - Photosensitive resin composition - Google Patents

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.
Examples of such a photosensitive resin composition include a structural unit derived from an unsaturated carboxylic acid and / or an unsaturated carboxylic anhydride, a monomer having an oxiranyl group, and an ethylenically unsaturated double bond. A photosensitive resin composition containing a copolymer containing a structural unit, a photopolymerizable compound, a photopolymerization initiator, and a solvent is known (Patent Document 1).

JP 2008-181087 A

  However, the conventionally proposed photosensitive resin compositions may not always be sufficiently satisfied with respect to the mechanical characteristics of the obtained pattern.

The present invention provides the following [1] to [6].
[1] A photosensitive resin composition comprising (A), (B), (C), (D) and (E).
(A) resin (B) polymerizable compound (C) polymerization initiator (D) having at least two groups selected from the group consisting of an active methylene group and an active methine group and having a molecular weight of less than 3000 A certain compound (E) solvent

[2] The photosensitive resin composition according to [1], wherein at least one group selected from the group consisting of an active methylene group and an active methine group is an acetoacetyl group.
[3] The resin is derived from an unsaturated compound having a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride and a cyclic ether structure having 2 to 4 carbon atoms. The photosensitive resin composition according to [1] or [2], which is a copolymer containing a structural unit.
[4] The photosensitive resin composition according to any one of [1] to [3], wherein the polymerization initiator is a polymerization initiator containing an oxime ester compound.
[5] A pattern formed from the photosensitive resin composition according to any one of [1] to [4].
[6] A display device including the pattern according to [5].

  According to the photosensitive resin composition of the present invention, a pattern having excellent mechanical properties can be obtained.

The photosensitive resin composition of the present invention is a photosensitive resin composition containing (A), (B), (C), (D) and (E).
(A) resin (B) polymerizable compound (C) polymerization initiator (D) having at least two groups selected from the group consisting of an active methylene group and an active methine group and having a molecular weight of less than 3000 Certain Compound (E) Solvent In the present specification, compounds exemplified as each component can be used alone or in combination unless otherwise specified.

The photosensitive resin composition of this invention contains resin (A).
As resin (A) used for the photosensitive resin composition of this invention, it is preferable that it is resin which shows alkali solubility. Alkali solubility refers to the property of being dissolved in a developer that is an aqueous solution of an alkali compound.

As the resin showing alkali solubility,
Resin (A-1): At least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (a) (hereinafter sometimes referred to as “(a)”) and cyclic having 2 to 4 carbon atoms A copolymer obtained by polymerizing an unsaturated compound (b) having an ether structure (hereinafter sometimes referred to as “(b)”);
Resin (A-2): Monomer (c) copolymerizable with (a) and (b) (however, no cyclic ether having 2 to 4 carbon atoms is included) (hereinafter referred to as “(c)”) A copolymer obtained by polymerizing (a) and (b),
Resin (A-3): a copolymer obtained by polymerizing (a) and (c),
Resin (A-4): a resin obtained by reacting (b) with a copolymer obtained by polymerizing (a) and (c),
Resin (A-5): Resins obtained by reacting (a) with a copolymer obtained by polymerizing (b) and (c).
The resin (A) is derived from a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, and an unsaturated compound having a C2-C4 cyclic ether structure. A copolymer containing a structural unit, that is, resin (A-1) and resin (A-2) are preferable, and resin (A-1) is more preferable.

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

  Examples of (b) include a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b1)”), an oxetanyl group and an ethylenically unsaturated bond. Monomer (b2) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b3)”) ) And the like.

As (b1), a monomer (b1-1) having a structure obtained by epoxidizing an alkene and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b1-1)”) or a cycloalkene is epoxidized. And a monomer (b1-2) having a structure and an ethylenically unsaturated bond (hereinafter may be referred to as “(b1-2)”).
As (b1), a monomer (b1) having an oxiranyl group and a (meth) acryloyloxy group is preferred, and a monomer having a structure obtained by epoxidizing a cycloalkene and a (meth) acryloyloxy group (b1- 2) 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. ]

Specific 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 any one of the formulas (I-1) to (I-15). Preferably Formula (I-1), Formula (I-3), Formula (I-5), Formula (I-7), Formula (I-9) and Formula (I-11) to Formula (I-15) The compound represented by either of these is mentioned. More preferably, a compound represented by any one of formula (I-1), formula (I-7), formula (I-9) and formula (I-15) can be mentioned.

  Examples of the compound represented by the formula (II) include compounds represented by any one of the formulas (II-1) to (II-15). Preferably Formula (II-1), Formula (II-3), Formula (II-5), Formula (II-7), Formula (II-9) and Formula (II-11) to Formula (II-15) The compound represented by either of these is mentioned. More preferably, a compound represented by any one of formula (II-1), formula (II-7), formula (II-9) and formula (II-15) can be 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- (meth) acryloyloxymethyl oxetane, 3-ethyl-3- (meth) acryloyloxymethyl oxetane, 3-methyl-3- (meth) acryloyloxyethyl oxetane, Examples include 3-ethyl-3- (meth) 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 (A-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 (A-1).
Structural unit derived from (a); 5 to 60 mol% (more preferably 10 to 50 mol%)
Structural unit derived from (b); 40 to 95 mol% (more preferably 50 to 90 mol%)
When the ratio of the structural unit of the resin (A-1) is in the above range, storage stability, developability, solvent resistance, heat resistance and mechanical strength tend to be good.
As the resin (A-1), a resin (A-1) in which (b) is (b1) is preferable, and a resin (A-1) in which (b) is (b1-2) is more preferable.

  Resin (A-1) is, for example, a method described in the document “Experimental Method 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 (A-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 (A-2).
Structural unit derived from (a); 2 to 40 mol% (more preferably 5 to 35 mol%)
Structural unit derived from (c): 1 to 65 mol% (more preferably 1 to 60 mol%)
Structural unit derived from (b); 2-95 mol% (more preferably 5-80 mol%)
When the ratio of the structural unit of the resin (A-2) is in the above range, storage stability, developability, solvent resistance, heat resistance and mechanical strength tend to be good.
As the resin (A-2), a resin (A-2) in which (b) is (b1) is preferable, and a resin (A-2) in which (b) is (b1-2) is more preferable.
Resin (A-2) can be manufactured by the same method as resin (A-1).

In resin (A-3), 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 (A-3).
Structural unit derived from (a); 2 to 40 mol% (more preferably 5 to 35 mol%)
Structural unit derived from (c); 60 to 98 mol% (more preferably 65 to 95 mol%)
When the ratio of the structural unit of the resin (A-3) is in the above range, storage stability, developability, and solvent resistance tend to be good.
Resin (A-3) can be manufactured by the same method as resin (A-1).

Resin (A-4) is a resin obtained by reacting (b) with a copolymer of (a) and (c).
Resin (A-4) can be manufactured through a two-step process, for example. In this case as well, the method described in the above-mentioned document “Experimental Methods for Polymer Synthesis” (Takayuki Otsu Publishing Co., Ltd., Chemical Dojin Co., Ltd., 1st edition, 1st edition, published on March 1, 1972), JP-A-2001-2001 It can be produced with reference to the method described in JP 89533.

First, as a first step, a copolymer of (a) and (c) is obtained in the same manner as in the method for producing the resin (A-1) described above.
In this case, in the same manner as described above, the obtained copolymer may be used as it is as the solution after the reaction, or may be a concentrated or diluted solution, or a solid ( You may use what was taken out as a powder. Moreover, it is preferable to set it as the polystyrene conversion weight average molecular weight and molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] similar to the above.
However, it is preferable that the ratio of the structural units derived from (a) and (c) is in the following range with respect to the total number of moles of all structural units constituting the copolymer.
Structural unit derived from (a); 5-50 mol% (more preferably 10-45 mol%)
Structural unit derived from (c); 50 to 95 mol% (more preferably 55 to 90 mol%)

Next, as a second stage, the carboxylic acid (a) and a part of the carboxylic anhydride derived from the obtained copolymer are reacted with the cyclic ether (b) described above. Since (b) used in the resin (A-4) is preferably (b1) or (b2) because the reactivity of the cyclic ether is high and unreacted (b) hardly remains, (b1-1) Is more preferable.
Specifically, following the above, the atmosphere in the flask was replaced from nitrogen to air, and 5 to 80 mol% (b) of a reaction catalyst of a carboxy group and a cyclic ether with respect to the number of moles of (a) ( For example, tris (dimethylaminomethyl) phenol) is 0.001 to 5% by mass with respect to the total amount of (a), (b) and (c), and a polymerization inhibitor (such as hydroquinone) is (a), 0.001-5 mass% is put in a flask with respect to the total amount of (b) and (c), and it is made to react at 60-130 degreeC for 1 to 10 hours, and resin (A-4) is obtained. it can. In addition, like the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, and the like.
In this case, the number of moles of (b) is preferably 10 to 75 mole%, more preferably 15 to 70 mole%, with respect to the number of moles of (a). By setting it as this range, there exists a tendency for the balance of storage stability, developability, solvent resistance, heat resistance, mechanical strength, and sensitivity to become favorable.

Resin (A-5) obtains a copolymer of (b) and (c) as the first step in the same manner as in the method for producing resin (A-1) described above.
In this case, in the same manner as described above, the obtained copolymer may be used as it is as the solution after the reaction, or may be a concentrated or diluted solution, or a solid ( You may use what was taken out as a powder.
The ratio of the structural units derived from (b) and (c) is preferably in the following range with respect to the total number of moles of all the structural units constituting the copolymer.
Structural unit derived from (b); 5-95 mol% (more preferably 10-90 mol%)
Structural unit derived from (c); 5-95 mol% (more preferably 10-90 mol%)

Further, in the same manner as in the production method of the resin (A-4), the cyclic ether derived from (b) in the copolymer of (b) and (c) is added to the carboxylic acid or carboxylic acid that (a) has. It can be obtained by reacting an anhydride. A carboxylic acid anhydride may be further reacted with a hydroxy group generated by the reaction of a cyclic ether with a carboxylic acid or a carboxylic acid anhydride.
The amount of (a) used to react with the copolymer is preferably 5 to 80 mol% with respect to the number of moles of (b). Since the reactivity of the cyclic ether is high and unreacted (b) hardly remains, (b1) is preferable as (b), and (b1-1) is more preferable.

  The weight average molecular weight in terms of polystyrene of the resin (A) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000. 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, and more preferably 1.2 to 4.0. When the molecular weight distribution is in the above range, the developability tends to be excellent.

  The acid value of the resin (A) is 20 to 150 mgKOH / g, preferably 40 to 135 mgKOH / g, 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%. 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.

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 polymerization initiator (C), and is, for example, a compound having a polymerizable ethylenically unsaturated bond, preferably (meth). Acrylic ester compound.

  Examples of the polymerizable compound (B) having one ethylenically unsaturated bond include the same compounds as those described above as (a), (b) and (c), and among them, (meth) acrylic acid esters Is preferred.

  Examples of the polymerizable compound (B) having two ethylenically unsaturated bonds include 1,3-butanediol di (meth) acrylate, 1,3-butanediol (meth) acrylate, and 1,6-hexanediol di (meta). ) Acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol diacrylate, Bis (acryloyloxyethyl) ether of bisphenol A, ethoxylated bisphenol A di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (me ) Acrylate, 3-methyl-pentanediol di (meth) acrylate.

  Examples of the polymerizable compound (B) having three or more ethylenically unsaturated bonds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate. , Ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri Pentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaery Ritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, reaction product of pentaerythritol tri (meth) acrylate and acid anhydride, reaction product of dipentaerythritol penta (meth) acrylate and acid anhydride, tripenta Erythritol hepta (meth) acrylate and 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 dipenta Lithritol 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 tripentaerythritol 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, Examples include caprolactone-modified tripentaerythritol hepta (meth) acrylate and acid anhydrides. Among these, a tri- or higher functional photopolymerizable compound (B) is preferable, and dipentaerythritol hexa (meth) acrylate is more preferable.

  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). 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 polymerization initiator (C). As a polymerization initiator (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 polymerization initiator can be used.
Examples of the polymerization initiator (C) include alkylphenone compounds, biimidazole compounds, triazine compounds, acylphosphine oxide compounds, and oxime ester compounds. Moreover, you may use the light and / or thermal 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 alkylphenone compound, and an oxime ester compound, and it is especially preferable that it is an oxime ester compound. A polymerization initiator containing these compounds is particularly preferred because it tends to be highly sensitive.

  Examples of the alkylphenone 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-dimethylamino-2-benzyl-1- (4-morpholinophenyl) butane-1 -One, 2-dimethylamino-2- (2-methylbenzyl) -1- (4-morpholinophenyl) Butan-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 Morpholinophenyl) 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) Oligomers of -1- (4-morpholinophenyl) butan-1-one and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one Etc. The.

  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 ester 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, as the polymerization initiator (C), 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 Benzophenone compounds such as -4'-methyldiphenyl sulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrene Examples include quinone compounds such as quinone, 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compounds and the like. These are preferably used in combination with a polymerization initiation assistant (C1) described later.

In addition, as a polymerization initiator having a group capable of causing chain transfer, a photopolymerization initiator described in JP-T-2002-544205 may be used.
Examples of the polymerization initiator having a group capable of causing the chain transfer include compounds represented by the following formulas (a) to (f).

  The polymerization initiator having a group capable of causing chain transfer can 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 polymerization initiator (C) described above. The polymerization initiation assistant (C1) is a compound or sensitizer that is used in combination with the polymerization initiator (C) and is used to accelerate the polymerization of the polymerizable compound that has been polymerized by the polymerization initiator. . Examples of the polymerization initiation assistant (C1) include compounds represented by the following formulas (III) to (V), thioxanthone compounds, amine compounds, and carboxylic acid compounds.

［式（ＩＩＩ）中、環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また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), the dashed line indicated by the ring 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.

[In Formula (IV) and Formula (V), Ring W ² , Ring W ³ and Ring W ⁴ each independently represent an aromatic ring having 6 to 12 carbon atoms or a heterocyclic ring having 2 to 10 carbon atoms, The hydrogen atom contained in the aromatic ring and the heterocyclic ring may be substituted with a halogen atom. 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.

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

  Examples of 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.

  Examples of the combination of the polymerization initiator (C) and the polymerization initiation assistant (C1) include an acetophenone compound and a thioxanthone compound, and an acetophenone compound and an aromatic amine compound. 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-diethyl Thioxanthone, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholinophenyl) butan-1-one and 2,4-diethylthioxanthone, 2-morpholino-1- (4-methylsulfanylphenyl) 2-methylpropan-1-one, 2-isopropylthioxanthone and 4-isopropylthioxone N, 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 can be mentioned.

  Among them, a combination of an acetophenone compound and a thioxanthone compound is preferable, and 2-morpholin-1- (4-methylsulfanylphenyl) -2-methylpropan-1-one, 2,4-diethylthioxanthone, 2-morpholino-1- ( 4-methylsulfanylphenyl) -2-methylpropan-1-one, 2-isopropylthioxanthone and 4-isopropylthioxanthone are more preferred. With these combinations, a pattern with high sensitivity and high visible light transmittance can be obtained.

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

  The amount of the photopolymerization 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). %. 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 comprises a compound having at least two groups selected from the group consisting of an active methylene group and an active methine group and having a molecular weight of less than 3000 (hereinafter referred to as “compound (D)”). In some cases). The active methylene group refers to a methylene group having a reaction activity with respect to a nucleophilic reagent, and the active methine group refers to a methine group having a reaction activity with respect to a nucleophilic reagent. The at least one group selected from the group consisting of an active methylene group and an active methine group is preferably a group represented by the formula (VI).
^{-X a -CHR k -R m (VI} )
Wherein (VI), ^{X a} is, -CO -, - SO- or -SO ₂ - represents a.
R ^{m represents} a ^{-CO-R n, -CO-O} -R n, -CO-NR p -R n, -SO-R n, -SO 2 -R n, a cyano group or a nitro group.
R ^k , R ⁿ and R ^p each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ^k and R ^m may be bonded to each other to form a ring. ]

  Examples of the group represented by the formula (VI) include groups represented by the formula (VI-1) to the formula (VI-9).

  Examples of the compound (D) include acetoacetic acid esters of polyhydric alcohols such as trimethylolpropane, pentaerythritol, and dipentaerythritol.

  Moreover, as a compound (D), a compound (D-1)-a compound (D-12) etc. are mentioned, for example. The compound (D-1) is a compound represented by the following formula (D-1).

  Content of a compound (D) becomes like this. Preferably it is 0.1-50 mass% with respect to the total amount of resin (A) and polymeric compound (B), More preferably, it is 1-30 mass%. When the content of the compound (D) is in the above range, the developability is excellent during pattern formation, and the resulting pattern tends to be excellent in mechanical properties.

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 an ester solvent (a solvent containing —COO— in the molecule and not containing —O—), an ether solvent (containing —O— in the molecule, —COO—). Solvent not containing)), ether ester solvent (solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- in the molecule and not -COO-), alcohol solvent, It can be selected from 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 polymerization 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.

  The photosensitive resin composition of the present invention may contain a surfactant (F). Examples of the surfactant include a silicone surfactant, a fluorine surfactant, a silicone surfactant having a fluorine atom, and the like.

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.

Examples of the fluorosurfactant include surfactants having a fluorocarbon chain.
Specifically, Florinart (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), MegaFac (registered trademark) F142D, F171, F172, F173, F177, F183, R183 (DIC) ), Ftop (registered trademark) EF301, EF303, EF351, EF351, EF352 (manufactured by Mitsubishi Materials Denkasei), Surflon (registered trademark) S381, S382, SC101, SC105 (Asahi Glass) And E5844 (manufactured by Daikin Fine Chemical Laboratory Co., Ltd.).

  Examples of the silicone-based surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain. Specifically, Megafac (registered trademark) R08, BL20, F475, F477, F443 (manufactured by DIC Corporation) and the like can be mentioned. Preferably, MegaFac (registered trademark) F475 is used.

  Surfactant (F) is 0.001 mass% or more and 0.2 mass% or less with respect to the photosensitive resin composition, Preferably it is 0.002 mass% or more and 0.1 mass% or less, More preferably It is 0.01 mass% or more and 0.05 mass% or less. By containing the surfactant in this range, the flatness of the coating film can be improved.

  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 relative to the entire composition is, for example, 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 this invention can form a coating film by apply | coating on a board | substrate. The coating film is preferably dried and cured. Moreover, a pattern can also be formed by patterning the obtained coating film into a desired shape. 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. Examples of the substrate include glass, metal, plastic and the like. In these, a color filter, various insulating or conductive films, a driving circuit, and the like may be formed in advance.
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.

Next, it is preferable to dry or pre-bake to remove volatile components such as a solvent and dry. 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 substantially parallel rays uniformly over the entire exposed surface. If an apparatus such as a mask aligner or a stepper is used, accurate alignment between the mask and the substrate can be performed at this time.

The exposed pattern is brought into contact with a developer to dissolve a predetermined portion, for example, a non-exposed portion (that is, a non-pixel portion), and development is performed, whereby a target pattern shape can be obtained.
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 in the range of 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. The post-baking is preferably, for example, a temperature range of 150 to 240 ° C. and 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.

  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 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.

一方、重合開始剤２，２’−アゾビス（２，４−ジメチルバレロニトリル）３０質量部を３−メトキシブチルアセテート２２５質量部に溶解した溶液を、別の滴下ロートを用いて４時間かけてフラスコ内に滴下した。重合開始剤の溶液の滴下が終了した後、４時間、７０℃に保持し、その後室温まで冷却して、固形分３２．６質量％、酸価１１０ｍｇ−ＫＯＨ／ｇ（固形分換算）の共重合体（樹脂Ａａ）の溶液を得た。得られた樹脂Ａａの重量平均分子量Ｍｗは、１３，４００、分子量分布は２．５０であった。樹脂Ａａは、以下の構造単位を有する。

(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. Next, 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 the solution is added using a dropping funnel over 4 hours. 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 solution of the polymer (resin Aa) was obtained. The obtained resin Aa had a weight average molecular weight Mw of 13,400 and a molecular weight distribution of 2.50. Resin Aa has the following structural units.

(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, 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 Ab) solution was obtained. The obtained resin Ab 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. Resin Ab has the following structural units.

一方、重合開始剤２，２’−アゾビス（２，４−ジメチルバレロニトリル）３０質量部をジエチレングリコールエチルメチルエーテル２４０質量部に溶解した溶液を、別の滴下ポンプを用いて、５時間かけてフラスコ内に滴下した。
重合開始剤の溶液の滴下が終了した後、４時間、７０℃に保持し、その後室温まで冷却して、固形分４１.８％の共重合体（樹脂Ａｃ）の溶液を得た。得られた樹脂Ａｃの重量平均分子量（Ｍｗ）は９．６×１０^３、分子量分布（Ｍｗ／Ｍｎ）は２．０２であり、固形分換算した酸価は６０ｍｇ−ＫＯＨ／ｇであった。樹脂Ａｃは、以下の構造単位を有する。

(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 weight of a mixture of the compounds represented by formula (x1) and a mixture of the compounds represented by formula (x2), molar ratio = 50: 50 ) 20 parts by mass was dissolved in 190 parts by mass of diethylene glycol ethyl methyl ether to prepare a solution. 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. Resin Ac has the following structural units.

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained resin Aa to resin Ac 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 polystyrene-converted weight average molecular weight and number average molecular weight ratio (Mw / Mn) obtained above was defined as molecular weight distribution.

(Examples 1-5 and Comparative Example 1)
<Adjustment of photosensitive resin composition>
The components of Table 4 were mixed to obtain photosensitive resin compositions 1-6.

Each component in Table 4 is as follows. In Table 4, 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
Polymerizable compound (B); dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)
Compound (D); trimethylolpropane tris (acetoacetate) (compound (D-1)) (molecular weight: 386) (manufactured by Nippon Synthetic Chemical Co., Ltd.)
Polymerization initiator (C); N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethane-1-imine (Irgacure OXE02; manufactured by BASF Japan Ltd.) )
Surfactant (F); polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.)
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 methyl ethyl ether The solvent (E) was mixed so that the solid content of the photosensitive resin composition was “solid content (%)” in Table 1, and the solvent (E) The values of the solvent components (Ea) to (Ee) represent the mass ratio in the solvent (E).

<Average transmittance of composition>
About the obtained photosensitive resin compositions 1-3, respectively, using an ultraviolet-visible near-infrared spectrophotometer (V-650; manufactured by JASCO Corporation) (quartz cell, optical path length: 1 cm), 400- The average transmittance (%) at 700 nm was measured. The results are shown in Table 4.

<Membrane average transmittance>
Using the obtained photosensitive resin compositions 1 to 3, films were prepared under the following conditions so that the film thickness after curing was 3 μm, respectively.
A 2-inch square glass substrate (Eagle XG; manufactured by Corning) was sequentially washed with a neutral detergent, water and alcohol and then dried. On this glass substrate, the photosensitive resin composition is spin-coated so that the film thickness after post-baking is 3.0 μm, and until the degree of vacuum reaches 66 kPa with a vacuum dryer (manufactured by Microtech Co., Ltd.). After drying under reduced pressure, it was dried by prebaking at 80 ° C. for 2 minutes on a hot plate. After cooling, using an exposure machine (TME-150RSK; manufactured by Topcon Corporation, light source: ultrahigh pressure mercury lamp), the light was irradiated with an exposure amount of 60 mJ / cm ² (based on 365 nm) in an air atmosphere. In addition, irradiation to the photosensitive resin composition at this time was performed by passing the radiated light from an ultrahigh pressure mercury lamp through an optical filter (UV-33; manufactured by Asahi Spectroscopy Co., Ltd.). After the 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, and then in an oven. A film was obtained by heating at 235 ° C. for 15 minutes.
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 4.

<Pattern formation>
A 2-inch square glass substrate (Eagle XG; manufactured by Corning) was sequentially washed with a neutral detergent, water and alcohol and then dried. On this glass substrate, the photosensitive resin composition is spin-coated so that the film thickness after post-baking is 3.5 μm, and the pressure reduction degree becomes 66 kPa with a vacuum dryer (manufactured by Microtech Co., Ltd.). After drying under reduced pressure, it was dried by prebaking at 80 ° C. for 2 minutes on a hot plate. After cooling, the distance between the substrate coated with the photosensitive resin composition and the quartz glass photomask was set to 10 μm, and the exposure apparatus (TME-150RSK; manufactured by Topcon Corporation, light source: ultrahigh pressure mercury lamp) Under an atmosphere, light with an exposure amount of 60 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-33; manufactured by Asahi Spectroscopic Co., Ltd.). In addition, a photomask having a pattern (having a square light-transmitting portion with one side of 13 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 is developed by immersing and shaking for 100 seconds at 25 ° C. in an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide. Inside, post-baking was performed at 235 ° C. for 15 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.). Measurement was performed at a position 5% higher than the substrate surface with respect to the pattern height. The results are shown in Table 5.

<Mechanical properties (total displacement and recovery rate)>
About the obtained pattern, a total amount of displacement (μm) and an amount of elastic displacement (μm) were measured using a dynamic ultra-micro hardness meter (DUH-W201; manufactured by Shimadzu Corporation), and a recovery rate (%) Was calculated. As the recovery rate is higher, it is possible to produce a liquid crystal panel having higher strength. The results are shown in Table 5.
-Measurement conditions-
Test mode: Load-unloading test force: 50 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

<Sensitivity>
A 2-inch square glass substrate (Eagle XG; manufactured by Corning) was sequentially washed with a neutral detergent, water and alcohol and then dried. On this glass substrate, the photosensitive resin composition is spin-coated so that the film thickness after post-baking is 3.5 μm, and the pressure reduction degree becomes 66 kPa with a vacuum dryer (manufactured by Microtech Co., Ltd.). After drying under reduced pressure, it was dried by prebaking at 80 ° C. for 2 minutes on a hot plate. After cooling, the distance between the substrate coated with the photosensitive resin composition and the quartz glass photomask was set to 10 μm, and the exposure apparatus (TME-150RSK; manufactured by Topcon Corporation, light source: ultrahigh pressure mercury lamp) atmosphere, exposure was irradiated with light of 200mJ ^/ cm 2 (365nm reference). 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-33; manufactured by Asahi Spectroscopic Co., Ltd.). In addition, a photomask having a pattern (having a square light-transmitting portion with one side of 13 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 is developed by immersing and shaking for 100 seconds at 25 ° C. in an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide. Inside, post-baking was performed at 235 ° C. for 15 minutes to obtain a pattern.
Patterns were obtained in the same manner as described above except that the exposure dose was changed to 100, 50, 25 mJ / cm ² (365 nm reference). In addition, when producing these patterns, spin coating was performed under the same conditions as those for producing patterns with an exposure amount of 200 mJ / cm ² .

The film thickness of the obtained pattern was measured with a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.), and the remaining film ratio was calculated by the following formula. It can be said that the higher the remaining film ratio at a low exposure amount, the higher the sensitivity. The results are shown in Table 5.
(Height at exposure dose D ⁰ mJ / cm ² )
Remaining film rate (%) = ―――――――――――――――――――― × 100
(Height at an exposure amount of 200 mJ / cm ² )
[Wherein the exposure dose D ⁰ represents 100, 50 or 25. ]

  From the results of Examples shown in Table 5, it can be seen that according to the photosensitive resin composition of the present invention containing the compound (D), a pattern having excellent mechanical properties can be obtained without lowering the sensitivity.

  According to the photosensitive resin composition of the present invention, a pattern having excellent mechanical properties can be obtained.

Claims (5)

A photosensitive resin composition comprising (A), (B), (C), (D) and (E).
(A) a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, and a structural unit derived from an unsaturated compound having a C2-C4 cyclic ether structure; resin is a copolymer comprising (B) a polymerizable compound (C) polymerization initiator (D) at least one group selected from the group consisting of active methylene groups and active methine group two or more, and a molecular weight (E) solvent in which is less than 3000   The photosensitive resin composition according to claim 1, wherein at least one group selected from the group consisting of an active methylene group and an active methine group is an acetoacetyl group. The photosensitive resin composition according to claim 1 or 2, wherein the polymerization initiator is a polymerization initiator containing an oxime ester compound. Pattern formed by the photosensitive resin composition according to any one of claims 1 to 3.
A display device comprising the pattern according to claim 4 .