JP2012137745A - Photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition allowing formation of a pattern excellent in mechanical characteristics.SOLUTION: The photosensitive resin composition contains (A), (B1), (B2), (C) and (D) described in the following: (A) an alkali-soluble resin; (B1) a polymerizable compound including a cyclic ether structure with the carbon number 2-4 and an ethylenically unsaturated bond; (B2) a polymerizable compound different from (B1); (C) a polymerization initiator; and (D) a solvent.

Description

  The present invention relates to a photosensitive resin composition.

In recent liquid crystal display panels and the like, a member formed of a photosensitive resin composition or a coating film formed of a photosensitive resin composition is used as a member such as a photo spacer, an overcoat, and an inkjet partition. .
As such a photosensitive resin composition, a composition containing a resin, a polymerizable compound, a polymerization initiator and a solvent, and containing only dipentaerythritol hexaacrylate as the polymerizable compound is known (Patent Document 1). .
In particular, when a pattern formed from a photosensitive resin composition is used as a photospacer, the pattern is required to have mechanical characteristics that return to its original shape when the weight is removed, that is, flexibility. This mechanical property is represented by a recovery rate, which is a ratio of a displacement amount (elastic displacement amount) when the photo spacer is removed to a displacement amount (total displacement amount) when the photo spacer is removed. .

JP 2008-181087 A

  However, the pattern obtained from the conventionally proposed photosensitive resin composition does not always have a satisfactory recovery rate.

The present invention provides the following [1] to [9].
[1] A photosensitive resin composition comprising (A), (B1), (B2), (C) and (D).
(A) Alkali-soluble resin (B1) Polymerizable compound (C) polymerization initiator (D) different from polymerizable compound (B2) (B1) having a C2-C4 cyclic ether structure and an ethylenically unsaturated bond Solvent [2] The photosensitive resin composition according to [1], wherein (B1) is a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms and a (meth) acryloyloxy group.
[3] The photosensitive resin composition according to [1], wherein (B1) comprises a polymerizable compound having an oxiranyl group and a (meth) acryloyloxy group or a polymerizable compound having an oxetanyl group and a (meth) acryloyloxy group.
[4] The photosensitive resin composition according to any one of [1] to [3], wherein (B2) is a (meth) acrylic acid ester having no cyclic ether structure in the molecule.
[5] The composition according to any one of [1] to [4], wherein (B2) is a polymerizable compound having no cyclic ether structure in the molecule and having three or more (meth) acryloyloxy groups. Photosensitive resin composition.
[6] Any one of [1] to [5], wherein the content of (B1) is 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the total amount of (A) and (B2). The photosensitive resin composition according to Item.
[7] 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 an ethylenically unsaturated bond The photosensitive resin composition as described in any one of [1] to [6], which is an addition polymer containing a structural unit derived from a monomer having a.
[8] A pattern formed from the photosensitive resin composition according to any one of [1] to [7].
[9] A display device including the pattern according to [8].

  According to the photosensitive resin composition of the present invention, a pattern formed from the photosensitive resin composition is excellent in mechanical properties because of a high recovery rate when the load is removed.

  The photosensitive resin composition of the present invention comprises an alkali-soluble resin (A), a polymerizable compound (B1) having a C2-C4 cyclic ether structure and an ethylenically unsaturated bond (hereinafter referred to as “polymerizable compound (B1)”). Photosensitive resin containing a polymerizable compound (B2) (hereinafter sometimes referred to as “polymerizable compound (B2)”) different from (B1), a polymerization initiator (C), and a solvent (D). It is a composition. 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 present specification, the “(meth) acryloyloxy group” represents at least one selected from the group consisting of an acryloyloxy group and a methacryloyloxy group. Notations such as “(meth) acrylic acid” and “(meth) acrylate” have the same meaning.

  The resin used for the photosensitive resin composition of the present invention is an alkali-soluble resin (A). Here, alkali-soluble means the property of being dissolved in an aqueous solution of an alkali compound. As an aqueous solution of an alkali compound here, the developing solution obtained when forming a pattern from the photosensitive resin composition is mentioned.

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 a monomer (b) having an ether structure and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b)”);
Resin (A-2): Monomer (c) copolymerizable with (a) and (b) (however, different from (a) and (b)) (hereinafter referred to as “(c)”) And 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): (b) and (c) Examples thereof include a resin obtained by reacting (a) with a copolymer obtained by polymerization.
The alkali-soluble resin (A) is preferably at least one selected from the group consisting of the resin (A-1) and the resin (A-2), and more preferably the resin (A-1).

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;
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.

  (B) is an unsaturated compound 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). A compound having an ether structure and an ethylenically unsaturated double bond is preferred, and a compound having a cyclic ether structure having 2 to 4 carbon atoms and a (meth) acryloyloxy group is more preferred. Such (b) is copolymerizable with the above (a) or (c).

  Examples of (b) include a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b1)”), and a single monomer having an oxetanyl group and an ethylenically unsaturated bond. Monomer (b2) (hereinafter sometimes referred to as “(b2)”), monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b3)”), etc. Can be mentioned.

(B1) includes a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized and an ethylenically unsaturated bond (hereinafter referred to as “(b1- 1) "), a monomer (b1-2) having an epoxidized structure of an alicyclic unsaturated hydrocarbon and an ethylenically unsaturated bond (hereinafter referred to as" (b1-2) ") In some cases).
As (b1), a monomer having an oxiranyl group and a (meth) acryloyloxy group is preferable, and a monomer having a structure in which an unsaturated alicyclic hydrocarbon is epoxidized and a (meth) acryloyloxy group 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 hydrogen atom contained in the alkyl group is a hydroxy group. May be substituted.
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) or Formula (I-11) to Formula (I-15) The compound represented by these is mentioned. More preferably, the compound represented by Formula (I-1), Formula (I-7), Formula (I-9) or Formula (I-15) is 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) or Formula (II-11) to Formula (II-15) The compound represented by these is mentioned. More preferably, the compound represented by Formula (II-1), Formula (II-7), Formula (II-9), or Formula (II-15) is mentioned.

  The compound represented by the formula (I) and the compound represented by the formula (II) can be used alone as (b1-2). Moreover, they can be mixed at an arbitrary ratio and used as (b1-2). 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 It is said to be nyl (meth) acrylate.
), Tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate (referred to in the art as dicyclopentenyl (meth) acrylate as a common name.
), 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.
As (c), styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, dicyclopentenyl (meth) acrylate, bicyclo [2.2.1] hept-2-ene and the like are copolymerized. From the viewpoint of solubility and alkali solubility.

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, the storage stability of the photosensitive resin composition, the developability when forming the pattern, the solvent resistance of the pattern, the heat resistance and The mechanical strength tends 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 predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like are placed in a reaction vessel, for example, by substituting oxygen in the atmosphere with nitrogen to form a deoxygenated atmosphere, A method of heating and keeping warm while stirring 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.) As the solvent, any solvent that dissolves each monomer may be used, and a solvent described later can be used as the solvent (D) of the photosensitive resin composition. In order to adjust the molecular weight of the resin obtained, a chain transfer agent may be added during the polymerization reaction. Examples of chain transfer agents include n-butanethiol, tert-butanethiol, n-dodecanethiol, 2-sulfanylethanol, thioglycolic acid, ethyl thioglycolate, 2-ethylhexyl thioglycolate, methoxybutyl thioglycolate, 3- Thiols such as sulfanylpropionic acid and sulfanyl group-containing silicone (KF-2001: manufactured by Shin-Etsu Chemical); halogenated alkyls such as chloroform, carbon tetrachloride, carbon tetrabromide, and the like.

  The obtained copolymer may be used for the preparation of the photosensitive resin composition of the present invention as it is after the reaction, or a concentrated or diluted solution, reprecipitation, etc. You may use what was taken out as solid (powder) by the method of. In particular, by using the same solvent as the solvent contained in the photosensitive resin composition of the present invention as the solvent during the polymerization, the solution after the reaction is used as it is for the preparation of the photosensitive resin composition of the present invention. Therefore, the manufacturing process of the photosensitive resin composition of the present invention 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 (b); 2-95 mol% (more preferably 5-80 mol%)
Structural unit derived from (c): 1 to 65 mol% (more preferably 1 to 60 mol%)
When the ratio of the structural unit of the resin (A-2) is in the above range, the storage stability of the photosensitive resin composition, the developability when forming the pattern, and the solvent resistance and heat resistance of the pattern are high. There is a tendency to improve.
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 resin (A1-1).
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, the storage stability of the photosensitive resin composition, the developability when forming the pattern, and the solvent resistance of the pattern tend to be good. is there.
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 (A1-2) 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 (A1-2) 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 the storage stability of the photosensitive resin composition, the developability and sensitivity at the time of forming a pattern, and the solvent resistance and heat resistance of a pattern to become favorable.

Specific examples of the resin (A-4) include a resin obtained by reacting a copolymer of (meth) acrylic acid / dicyclopentanyl (meth) acrylate with glycidyl (meth) acrylate, (meth) acrylic acid / benzyl ( Resin in which glycidyl (meth) acrylate is reacted with a copolymer of (meth) acrylate, resin in which glycidyl (meth) acrylate is reacted with a copolymer of (meth) acrylic acid / cyclohexyl (meth) acrylate, (meth) acrylic Resin obtained by reacting acid / styrene copolymer with glycidyl (meth) acrylate, resin obtained by reacting (meth) acrylic acid / methyl (meth) acrylate copolymer with glycidyl (meth) acrylate, (meth) Glycidyl (meth) acrylate was reacted with an acrylic acid / N-cyclohexylmaleimide copolymer. Fat, resin made by reacting (meth) acrylic acid / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate copolymer with glycidyl (meth) acrylate, (meth) acrylic acid / dicyclopentanyl (meta ) Resin prepared by reacting acrylate / cyclohexyl (meth) acrylate copolymer with glycidyl (meth) acrylate, and (meth) acrylic acid / dicyclopentanyl (meth) acrylate / styrene copolymer glycidyl (meth) acrylate , A resin obtained by reacting (meth) acrylic acid / dicyclopentanyl (meth) acrylate / methyl (meth) acrylate copolymer with glycidyl (meth) acrylate, (meth) acrylic acid / di Cyclopentanyl (meth) acrylate / N-cyclohexylmaleimi Copolymer glycidyl (meth) resins obtained by reacting an acrylate, glycidyl on copolymers of crotonic acid / dicyclopentanyl (meth) acrylate (meth) resins obtained by reacting acrylate;
Crotonic acid / benzyl (meth) acrylate copolymer reacted with glycidyl (meth) acrylate, crotonic acid / cyclohexyl (meth) acrylate copolymer reacted with glycidyl (meth) acrylate, crotonic acid / Styrene copolymer reacted with glycidyl (meth) acrylate, Crotonic acid / Methyl crotonic acid copolymer reacted with glycidyl (meth) acrylate, Crotonic acid / N-cyclohexylmaleimide copolymer Resin in which glycidyl (meth) acrylate was reacted with the polymer, resin in which glycidyl (meth) acrylate was reacted with the copolymer of crotonic acid / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate, crotonic acid / di Cyclopentanyl (meth) acrylate / cycle A resin obtained by reacting a copolymer of hexyl (meth) acrylate with glycidyl (meth) acrylate, a resin obtained by reacting a copolymer of crotonic acid / dicyclopentanyl (meth) acrylate / styrene with glycidyl (meth) acrylate, Crotonic acid / dicyclopentanyl (meth) acrylate / methyl crotonic acid copolymer reacted with glycidyl (meth) acrylate, copolymer of crotonic acid / dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide Resin obtained by reacting glycidyl (meth) acrylate with the coalescence;
Resin obtained by reacting maleic acid / dicyclopentanyl (meth) acrylate copolymer with glycidyl (meth) acrylate, and resin obtained by reacting maleic acid / benzyl (meth) acrylate copolymer with glycidyl (meth) acrylate , A resin obtained by reacting maleic acid / cyclohexyl (meth) acrylate copolymer with glycidyl (meth) acrylate, a resin obtained by reacting maleic acid / styrene copolymer with glycidyl (meth) acrylate, maleic acid / maleic acid Resin prepared by reacting glycidyl (meth) acrylate with a copolymer of methyl, resin obtained by reacting glycidyl (meth) acrylate with a copolymer of maleic acid / N-cyclohexylmaleimide, maleic acid / dicyclopentanyl (meth) Acrylate / benzyl (meth) acrylate copolymer Resin obtained by reacting ricidyl (meth) acrylate, resin obtained by reacting maleic acid / dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate copolymer with glycidyl (meth) acrylate, maleic acid / dicyclopenta Nyl (meth) acrylate / styrene copolymer reacted with glycidyl (meth) acrylate, maleic acid / dicyclopentanyl (meth) acrylate / methyl maleate copolymer reacted with glycidyl (meth) acrylate A resin obtained by reacting glycidyl (meth) acrylate with a copolymer of maleic acid / dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide;
Resin obtained by reacting (meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate copolymer with glycidyl (meth) acrylate, (meth) acrylic acid / maleic anhydride / benzyl (meth) Resin obtained by reacting glycidyl (meth) acrylate with a copolymer of acrylate, resin obtained by reacting glycidyl (meth) acrylate with a copolymer of (meth) acrylic acid / maleic anhydride / cyclohexyl (meth) acrylate, Resin obtained by reacting a meth) acrylic acid / maleic anhydride / styrene copolymer with glycidyl (meth) acrylate, and a glycidyl (meth) acrylic acid / maleic anhydride / methyl (meth) acrylate copolymer Resin reacted with (meth) acrylate, (meth) acrylic acid / maleic anhydride / N-cyclohexylmale Resin prepared by reacting imide copolymer with glycidyl (meth) acrylate, (meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate copolymer with glycidyl (meth) ) Acrylate-reacted resin, (meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate copolymer, and glycidyl (meth) acrylate resin ( Resin made by reacting glycidyl (meth) acrylate with a copolymer of (meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate / styrene, (meth) acrylic acid / maleic anhydride / dicyclopenta Nyl (meth) acrylate / methyl (meth) acrylate copolymer with glycidyl (meth) Resins obtained by reacting acrylate, (meth) resin obtained by reacting a copolymer glycidyl (meth) acrylate acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate / N- cyclohexyl maleimide;
Resin obtained by reacting (meth) acrylic acid / dicyclopentanyl (meth) acrylate copolymer with 3,4-epoxycyclohexylmethyl methacrylate, and (meth) acrylic acid / benzyl (meth) acrylate copolymer 3 , 4-Epoxycyclohexylmethyl methacrylate resin, (Meth) acrylic acid / cyclohexyl (meth) acrylate copolymer and 3,4-epoxycyclohexylmethyl methacrylate reaction resin, (Meth) acrylic acid / styrene A resin prepared by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of (4), a resin obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of (meth) acrylic acid / methyl (meth) acrylate, (Meth) acrylic acid / N-cyclohexyl male Resin prepared by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of imide, and 3,4-epoxy with a copolymer of (meth) acrylic acid / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate A resin obtained by reacting cyclohexylmethyl methacrylate, a resin obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of (meth) acrylic acid / dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate, (meth ) A resin obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of acrylic acid / dicyclopentanyl (meth) acrylate / styrene, (meth) acrylic acid / dicyclopentanyl (meth) acrylate / (meta ) 3, 4 in methyl acrylate copolymer A resin obtained by reacting epoxycyclohexylmethyl methacrylate, a resin obtained by reacting a copolymer of (meth) acrylic acid / dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide with 3,4-epoxycyclohexylmethyl methacrylate;
Crotonic acid / dicyclopentanyl (meth) acrylate copolymer reacted with 3,4-epoxycyclohexylmethyl methacrylate; Crotonic acid / benzyl (meth) acrylate copolymer with 3,4-epoxycyclohexylmethyl Resin in which methacrylate is reacted, Resin in which crotonic acid / cyclohexyl (meth) acrylate copolymer is reacted with 3,4-epoxycyclohexylmethyl methacrylate, Crotonic acid / styrene copolymer in 3,4-epoxycyclohexylmethyl Resin reacted with methacrylate, Crotonic acid / methyl crotonate copolymer reacted with 3,4-epoxycyclohexylmethyl methacrylate, Crotonic acid / N-cyclohexylmaleimide copolymer, 3,4-epoxycyclohexyl Methylme Resin in which acrylate was reacted, Crotonic acid / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate copolymer and 3,4-epoxycyclohexylmethyl methacrylate reacted in resin, crotonic acid / dicyclopentanyl A resin obtained by reacting a copolymer of (meth) acrylate / cyclohexyl (meth) acrylate with 3,4-epoxycyclohexylmethyl methacrylate, and a copolymer of crotonic acid / dicyclopentanyl (meth) acrylate / styrene, 3,4 -Resin reacted with epoxycyclohexylmethyl methacrylate, Resin obtained by reacting crotonic acid / dicyclopentanyl (meth) acrylate / methyl crotonic acid copolymer with 3,4-epoxycyclohexylmethyl methacrylate, crotonic acid / dicyclo Pentanyl (Me ) Acrylate / N- cyclohexyl maleimide copolymer resin obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate;
A resin obtained by reacting a maleic acid / dicyclopentanyl (meth) acrylate copolymer with 3,4-epoxycyclohexylmethyl methacrylate, and a maleic acid / benzyl (meth) acrylate copolymer with 3,4-epoxycyclohexylmethyl Resin reacted with methacrylate, Resin reacted with 3,4-epoxycyclohexylmethyl methacrylate on maleic acid / cyclohexyl (meth) acrylate copolymer, 3,4-epoxycyclohexylmethyl on maleic acid / styrene copolymer Resin reacted with methacrylate, Resin reacted with 3,4-epoxycyclohexylmethyl methacrylate on copolymer of maleic acid / methyl maleate, 3,4-epoxycyclohexyl on copolymer of maleic acid / N-cyclohexylmaleimide Methylme Resin in which acrylate is reacted, Resin in which 3,4-epoxycyclohexylmethyl methacrylate is reacted with a copolymer of maleic acid / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate, maleic acid / dicyclopentanyl Resin obtained by reacting (meth) acrylate / cyclohexyl (meth) acrylate copolymer with 3,4-epoxycyclohexylmethyl methacrylate; 3,4 for maleic acid / dicyclopentanyl (meth) acrylate / styrene copolymer -Resin obtained by reacting epoxycyclohexylmethyl methacrylate, resin obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of maleic acid / dicyclopentanyl (meth) acrylate / methyl maleate, maleic acid / dicyclohexane Pentanyl (Me ) Acrylate / N- cyclohexyl maleimide copolymer resin obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate;
(Meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate copolymer reacted with 3,4-epoxycyclohexylmethyl methacrylate, (meth) acrylic acid / maleic anhydride / benzyl Resin obtained by reacting (meth) acrylate copolymer with 3,4-epoxycyclohexylmethyl methacrylate; (meth) acrylic acid / maleic anhydride / cyclohexyl (meth) acrylate copolymer with 3,4-epoxycyclohexyl Resin in which methyl methacrylate is reacted, Resin in which 3,4-epoxycyclohexylmethyl methacrylate is reacted with a copolymer of (meth) acrylic acid / maleic anhydride / styrene, (meth) acrylic acid / maleic anhydride / Copolymer of methyl (meth) acrylate with 3,4-epoxycyclohexene Resin reacted with silmethyl methacrylate, (meth) acrylic acid / maleic anhydride / N-cyclohexylmaleimide copolymer, resin reacted with 3,4-epoxycyclohexylmethyl methacrylate, (meth) acrylic acid / maleic Resin prepared by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of acid anhydride / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate, (meth) acrylic acid / maleic anhydride / dicyclo Resin prepared by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of pentanyl (meth) acrylate / cyclohexyl (meth) acrylate, (meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate 3,4-epoxy on styrene / styrene copolymer 3,4-epoxycyclohexylmethyl methacrylate was added to a resin obtained by reacting cyclohexylmethyl methacrylate with a copolymer of (meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate / methyl (meth) acrylate. Examples include a resin obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of (meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide. It is done.

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 carboxylic acid or carboxylic acid anhydride that (a) has is added to the cyclic ether derived from (b) in the copolymer with (b). It can be obtained by reacting. 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.

Specific examples of the resin (A-5) include a resin obtained by reacting a copolymer of dicyclopentanyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid, benzyl (meth) acrylate / glycidyl ( Resin in which (meth) acrylic acid is reacted with a copolymer of (meth) acrylate, resin in which (meth) acrylic acid is reacted with a copolymer of cyclohexyl (meth) acrylate / glycidyl (meth) acrylate, styrene / glycidyl ( Resin obtained by reacting (meth) acrylic acid with a copolymer of (meth) acrylate, resin obtained by reacting (meth) acrylic acid with a copolymer of methyl (meth) acrylate / glycidyl (meth) acrylate, N-cyclohexyl A resin obtained by reacting (meth) acrylic acid with a maleimide / glycidyl (meth) acrylate copolymer Resin obtained by reacting clopentanyl (meth) acrylate / benzyl (meth) acrylate / glycidyl (meth) acrylate copolymer with (meth) acrylic acid, dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate / glycidyl ( Resin in which (meth) acrylic acid is reacted with a copolymer of (meth) acrylate, and (meth) acrylic acid is reacted with a copolymer of dicyclopentanyl (meth) acrylate / styrene / glycidyl (meth) acrylate , (Dicyclopentanyl (meth) acrylate / Methyl (meth) acrylate / Glycidyl (meth) acrylate copolymer) Resin obtained by reacting (meth) acrylic acid, Dicyclopentanyl (meth) acrylate / N- Copolymerization of cyclohexylmaleimide / glycidyl (meth) acrylate Body (meth) resins obtained by reacting an acrylic acid;
Resin obtained by reacting crotonic acid with dicyclopentanyl (meth) acrylate / glycidyl (meth) acrylate copolymer, resin obtained by reacting crotonic acid with benzyl (meth) acrylate / glycidyl (meth) acrylate copolymer , A resin obtained by reacting crotonic acid with a copolymer of cyclohexyl (meth) acrylate / glycidyl (meth) acrylate, a resin obtained by reacting styrene / glycidyl (meth) acrylate copolymer with crotonic acid, methyl crotonate / glycidyl Resin obtained by reacting crotonic acid with copolymer of (meth) acrylate, resin obtained by reacting crotonic acid with copolymer of N-cyclohexylmaleimide / glycidyl (meth) acrylate, dicyclopentanyl (meth) acrylate / benzyl (Meth) acrylate / Glycidyl (Meth) Ac Resin obtained by reacting crotonic acid with a copolymer of a rate, resin obtained by reacting crotonic acid with a copolymer of dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate / glycidyl (meth) acrylate, dicyclopenta Resin obtained by reacting crotonic acid with a copolymer of nyl (meth) acrylate / styrene / glycidyl (meth) acrylate, croton into a copolymer of dicyclopentanyl (meth) acrylate / methyl crotonic acid / glycidyl (meth) acrylate A resin obtained by reacting an acid, a resin obtained by reacting crotonic acid with a copolymer of dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide / glycidyl (meth) acrylate;
Resin made by reacting maleic acid with dicyclopentanyl (meth) acrylate / glycidyl (meth) acrylate copolymer, resin made by reacting maleic acid with benzyl (meth) acrylate / glycidyl (meth) acrylate copolymer , A resin in which maleic acid is reacted with a copolymer of cyclohexyl (meth) acrylate / glycidyl (meth) acrylate, a resin in which maleic acid is reacted with a copolymer of styrene / glycidyl (meth) acrylate, methyl maleate / glycidyl Resin in which maleic acid is reacted with copolymer of (meth) acrylate, resin in which maleic acid is reacted with copolymer of N-cyclohexylmaleimide / glycidyl (meth) acrylate, dicyclopentanyl (meth) acrylate / benzyl (Meth) acrylate / Glycidyl (Meth) Ac Resin in which maleic acid is reacted with a copolymer of a rate, resin in which maleic acid is reacted with a copolymer of dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate / glycidyl (meth) acrylate, dicyclopenta Nyl (meth) acrylate / styrene / glycidyl (meth) acrylate copolymer maleic resin, dicyclopentanyl (meth) acrylate / methyl maleate / glycidyl (meth) acrylate copolymer A resin obtained by reacting an acid, a resin obtained by reacting a dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide / glycidyl (meth) acrylate copolymer with maleic acid;
Resin obtained by reacting dicyclopentanyl (meth) acrylate / glycidyl (meth) acrylate copolymer with (meth) acrylic acid and maleic anhydride, benzyl (meth) acrylate / glycidyl (meth) acrylate copolymer Resin in which (meth) acrylic acid and maleic anhydride are reacted with, cyclohexyl (meth) acrylate / glycidyl (meth) acrylate copolymer in which (meth) acrylic acid and maleic anhydride are reacted, styrene Resin prepared by reacting (meth) acrylic acid and maleic anhydride with a copolymer of glycidyl / glycidyl (meth) acrylate, and (meth) acrylic acid and a copolymer of methyl (meth) acrylate / glycidyl (meth) acrylate Resin reacted with maleic anhydride, (N-cyclohexylmaleimide / glycidyl A resin obtained by reacting a (meth) acrylate copolymer with (meth) acrylic acid and maleic anhydride, a dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate / glycidyl (meth) acrylate copolymer ( Resin obtained by reacting meth) acrylic acid and maleic anhydride, (meth) acrylic acid and maleic anhydride into dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate / glycidyl (meth) acrylate copolymer , A resin obtained by reacting (meth) acrylic acid and maleic anhydride with a copolymer of dicyclopentanyl (meth) acrylate / styrene / glycidyl (meth) acrylate, dicyclopentanyl (meth) Acrylate / methyl (meth) acrylate / glycidyl (meth) acrylate Resin obtained by reacting polymer with (meth) acrylic acid and maleic anhydride, dimethypentanyl (meth) acrylate / N-cyclohexylmaleimide / glycidyl (meth) acrylate copolymer with (meth) acrylic acid and maleic A resin reacted with an acid anhydride;
Resin obtained by reacting (meth) acrylic acid with a copolymer of dicyclopentanyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate, copolymer of benzyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate Resin in which (meth) acrylic acid is reacted with the polymer, Resin in which (meth) acrylic acid is reacted with the copolymer of cyclohexyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate, styrene / 3,4-epoxy A resin obtained by reacting (meth) acrylic acid with a copolymer of cyclohexylmethyl methacrylate, a resin obtained by reacting (meth) acrylic acid with a copolymer of methyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate, N-cyclohexylmaleimide / 3,4-epo A resin obtained by reacting a copolymer of cyclocyclohexylmethyl methacrylate with (meth) acrylic acid, a copolymer of dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate (meta ) A resin obtained by reacting acrylic acid, a resin obtained by reacting (meth) acrylic acid with a copolymer of dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate, Resin prepared by reacting a copolymer of pentanyl (meth) acrylate / styrene / 3,4-epoxycyclohexylmethyl methacrylate with (meth) acrylic acid, dicyclopentanyl (meth) acrylate / methyl (meth) acrylate / 3 , 4-Epoxycyclohexylmethyl Resin of (meth) acrylic acid reacted with a copolymer of methacrylate, (meth) acrylic acid to a copolymer of dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide / 3,4-epoxycyclohexylmethyl methacrylate Reacted resin;
A resin obtained by reacting a copolymer of dicyclopentanyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate with crotonic acid, a copolymer of benzyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate and croton Acid-reacted resin, cyclohexyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate copolymer, crotonic acid-reacted resin, styrene / 3,4-epoxycyclohexylmethyl methacrylate copolymer, croton Acid-reacted resin, Crotonic acid methyl / 3,4-epoxycyclohexylmethyl methacrylate copolymer, Crotonic acid-reacted resin, N-cyclohexylmaleimide / 3,4-epoxycyclohexylmethyl methacrylate copolymer A resin obtained by reacting crotonic acid, a resin obtained by reacting crotonic acid with a copolymer of dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate, dicyclopentanyl (meta ) A resin obtained by reacting crotonic acid with a copolymer of acrylate / cyclohexyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate, dicyclopentanyl (meth) acrylate / styrene / 3,4-epoxycyclohexylmethyl methacrylate Resin obtained by reacting crotonic acid with copolymer, resin obtained by reacting crotonic acid with copolymer of dicyclopentanyl (meth) acrylate / methyl crotonic acid / 3,4-epoxycyclohexylmethyl methacrylate, dicyclopentanyl (Meta) acryle Resin obtained by reacting crotonic acid with a copolymer of carbonate / N-cyclohexylmaleimide / 3,4-epoxycyclohexylmethyl methacrylate;
Dicyclopentanyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate copolymer with maleic acid reacted, benzyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate copolymer with maleic acid Acid-reacted resin, cyclohexyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate copolymer, maleic acid-reacted resin, styrene / 3,4-epoxycyclohexylmethyl methacrylate copolymer Resin in which acid is reacted, Resin in which maleic acid is reacted with copolymer of methyl maleate / 3,4-epoxycyclohexylmethyl methacrylate, Copolymer of N-cyclohexylmaleimide / 3,4-epoxycyclohexylmethyl methacrylate A resin reacted with maleic acid, a resin obtained by reacting maleic acid with a copolymer of dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate, dicyclopentanyl (meta ) Resin prepared by reacting maleic acid with a copolymer of acrylate / cyclohexyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate, dicyclopentanyl (meth) acrylate / styrene / 3,4-epoxycyclohexylmethyl methacrylate Resin obtained by reacting maleic acid with copolymer, resin obtained by reacting maleic acid with copolymer of dicyclopentanyl (meth) acrylate / methyl maleate / 3,4-epoxycyclohexylmethyl methacrylate, dicyclopentanyl (Meta) acryle A resin obtained by reacting maleic acid with a copolymer of carbonate / N-cyclohexylmaleimide / 3,4-epoxycyclohexylmethyl methacrylate;
Resin obtained by reacting (meth) acrylic acid and maleic anhydride with a copolymer of dicyclopentanyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate, benzyl (meth) acrylate / 3,4-epoxycyclohexyl Resin obtained by reacting (meth) acrylic acid and maleic anhydride with a copolymer of methyl methacrylate, (meth) acrylic acid and maleic acid with a copolymer of cyclohexyl (meth) acrylate / 3,4-epoxycyclohexyl methyl methacrylate Resin in which anhydride is reacted, Resin in which (meth) acrylic acid and maleic anhydride are reacted with a copolymer of styrene / 3,4-epoxycyclohexylmethyl methacrylate, methyl (meth) acrylate / 3,4- Copolymerization of epoxycyclohexylmethyl methacrylate. A resin obtained by reacting (meth) acrylic acid and maleic anhydride, and a copolymer obtained by reacting a copolymer of N-cyclohexylmaleimide / 3,4-epoxycyclohexylmethyl methacrylate with (meth) acrylic acid and maleic anhydride. , A resin obtained by reacting a copolymer of dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate with (meth) acrylic acid and maleic anhydride, dicyclopentanyl ( Resin of (meth) acrylate / cyclohexyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate copolymer reacted with (meth) acrylic acid and maleic anhydride, dicyclopentanyl (meth) acrylate / styrene / 3,4-epoxycyclohexylmethyl Resin obtained by reacting (meth) acrylic acid and maleic anhydride with a copolymer of tacrylate, copolymer of dicyclopentanyl (meth) acrylate / methyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate (Meth) acrylic acid and maleic anhydride, and a copolymer of dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide / 3,4-epoxycyclohexylmethyl methacrylate to (meth) acrylic acid and Examples include resins reacted with maleic anhydride.

  The weight average molecular weight in terms of polystyrene of the alkali-soluble resin (A) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000. If the weight average molecular weight of the alkali-soluble resin (A) is in the above range, the photosensitive resin composition tends to have excellent coatability, and the exposed area is less likely to be reduced during development when producing a pattern. Further, the non-exposed part is easily removed by development.

  The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the alkali-soluble 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, there is a tendency that the developability when producing a pattern is excellent.

  The acid value of the alkali-soluble resin (A) is 20 to 150 mgKOH / g, preferably 40 to 135 mgKOH / g, more preferably 50 to 135 mgKOH / g.

  The content of the alkali-soluble resin (A) is preferably 5 to 95% by mass, more preferably 20 with respect to the total amount of the alkali-soluble resin (A), the polymerizable compound (B1) and the polymerizable compound (B2). It is -80 mass%, More preferably, it is 40-60 mass%. When the content of the alkali-soluble resin (A) is in the above range, the pattern can be formed with high sensitivity and the developability is excellent.

  The photosensitive resin composition of the present invention contains a polymerizable compound (B1) and a polymerizable compound (B2). The polymerizable compound (B1) is a polymerizable compound having a C2-C4 cyclic ether and an ethylenically unsaturated double bond. As the polymerizable compound (B1), for example, a polymerizable compound having a C2-C4 cyclic ether structure and a (meth) acryloyloxy group is preferable.

  Examples of the polymerizable compound (B1) include a polymerizable compound (B1-1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(B1-1)”), an oxetanyl group, and an ethylenically unsaturated group. A polymerizable compound (B1-2) having a saturated bond (hereinafter sometimes referred to as “(B1-2)”) and a polymerizable compound (B1-3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter referred to as “( B1-3) ”may be mentioned.

  (B1-1) includes a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized, a polymerizable compound having an ethylenically unsaturated bond, and an alicyclic unsaturated hydrocarbon And a polymerizable compound having an epoxidized structure and an ethylenically unsaturated bond. Moreover, as (B1-1), the polymeric compound which has an oxiranyl group and a (meth) acryloyloxy group is preferable. As the polymerizable compound having a structure obtained by epoxidizing a linear or branched unsaturated aliphatic hydrocarbon and a (meth) acryloyloxy group, glycidyl (meth) acrylate is particularly preferable. The polymerizable compound having an epoxidized structure of an unsaturated alicyclic hydrocarbon and an ethylenically unsaturated bond is selected from the group consisting of the compound represented by the formula (I) and the compound represented by the formula (II). Particularly preferred is at least one selected.

  As (B1-2), a polymerizable compound having an oxetanyl group and a (meth) acryloyloxy group is preferable, and 3-ethyl-3-acryloyloxymethyloxetane is particularly preferable.

  (B1-3) is preferably a compound having a tetrahydrofuryl group and a (meth) acryloyloxy group.

  Specific examples of the polymerizable compound (B1) include the same compounds as those described above as (b).

  The amount of the polymerizable compound (B1) used is preferably 1 to 20 parts by mass, more preferably 2 to 15 parts by mass with respect to 100 parts by mass of the total amount of the alkali-soluble resin (A) and the polymerizable compound (B2). It is. When the amount of the polymerizable compound (B1) is in the above range, the mechanical properties are even better.

  The amount of the polymerizable compound (B1) used is preferably 1 to 40 parts by mass, more preferably 2 to 30 parts by mass, particularly preferably 5 to 10 parts per 100 parts by mass of the polymerizable compound (B2). % By weight. When the amount of the polymerizable compound (B1) is in the above range, the mechanical properties are even better.

  The polymerizable compound (B2) is a polymerizable compound different from the polymerizable compound (B1). The polymerizable compound (B2) is a compound that can be polymerized by active radicals generated from the polymerization initiator (C), and has, for example, a compound having no cyclic ether structure in the molecule and having an ethylenically unsaturated bond. It is.

  As a polymeric compound (B2), the same thing as the compound quoted as said (a) and (c) is mentioned, for example. Examples of the polymerizable compound (B2) include (meth) acrylic acid esters having no cyclic ether structure in the molecule.

  Examples of the polymerizable compound (B2) 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 ( Data) acrylate, 3-methyl-pentanediol di (meth) acrylate.

  Examples of the polymerizable compound (B2) 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, tripentae Thritol 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, Reaction product of tripentaerythritol 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, caprolact 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 tripentaerythritol octa (meth) acrylate, reaction product of caprolactone-modified pentaerythritol tri (meth) acrylate and acid anhydride, reaction of caprolactone-modified dipentaerythritol penta (meth) acrylate and acid anhydride Products, reaction products of caprolactone-modified tripentaerythritol hepta (meth) acrylate and acid anhydrides, etc. Is mentioned.

Further, as the polymerizable compound (B2), a (meth) acrylate of a polyol compound subjected to ethylene oxide modification (hereinafter sometimes referred to as “EO modification”) or propylene oxide modification (hereinafter also referred to as “PO modification”). Examples thereof include acrylates having urethane bonds, epoxy acrylate resins produced by reaction of epoxy resins and acrylic acid, and acrylic compounds having siloxane bonds.
Examples of the polyol compound subjected to EO modification include EO-modified trimethylolpropane triacrylate, EO-modified pentaerythritol tetraacrylate, EO-modified dipentaerythritol pentaacrylate, and EO-modified dipentaerythritol hexaacrylate.

  Among these, the polymerizable compound (B2) is preferably a polymerizable compound having no cyclic ether structure in the molecule and having three or more ethylenically unsaturated bonds, and having no cyclic ether structure in the molecule. In addition, a polymerizable compound having three or more (meth) acryloyloxy groups is more preferable, (meth) acrylic acid ester of dipentaerythritol is more preferable, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate Is particularly preferred.

  The content of the polymerizable compound (B2) is preferably 5 to 95% by mass, more preferably 20 with respect to the total amount of the alkali-soluble resin (A), the polymerizable compound (B1) and the polymerizable compound (B2). It is -80 mass%, More preferably, it is 30-70 mass%, Most preferably, it is 40-55 mass%. When the content of the polymerizable compound (B2) is in the above range, the sensitivity, smoothness and reliability tend to be good.

The photosensitive resin composition of the present invention 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 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. Among these, at least one selected from the group consisting of a biimidazole compound, an alkylphenone compound and an oxime ester compound is preferable, and at least one selected from the group consisting of a biimidazole compound and an oxime ester compound is particularly preferable. . 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 (registered trademark) OXE-01, OXE-02 (manufactured by Ciba Japan), 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 alkali-soluble 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、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.

[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 each independently represent a monovalent saturated hydrocarbon group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group and the aryl group May be substituted with a halogen atom, 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, and 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 parts by mass with respect to 100 parts by mass of the total amount of the alkali-soluble resin (A), the polymerizable compound (B1) and the polymerizable compound (B2). More preferably, it is 1-20 mass parts, More preferably, it is 1-10 mass parts. 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 polymerization initiation assistant (C1) used is preferably 0.1 to 10 mass with respect to 100 mass parts of the total amount of the alkali-soluble resin (A), the polymerizable compound (B1) and the polymerizable compound (B2). Part, more preferably 0.3 to 7 parts by mass. 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 solvent (D).
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, and —COO—). Solvent), ether ester solvent (solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- in the molecule and not -COO-), alcohol solvent, aromatic It can be selected from 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, methyl anisole, and the like.

  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, diethylene glycol monobutyl ether acetate and the like.

  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, glycerin and the like.

  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 (D) 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 (D) in the photosensitive resin composition is preferably 60 to 95% by mass, more preferably 63 to 90% by mass, with respect to the total amount of components contained in the photosensitive resin composition. is there. In other words, the solid content of the photosensitive resin composition is preferably 5 to 40% by mass, more preferably 10 to 37% by mass. When the content of the solvent (D) is in the above range, the flatness of the film coated with the photosensitive resin composition tends to be high. Here, solid content means the quantity remove | excluding the solvent (D) from the photosensitive resin composition.

  Moreover, it is preferable that the photosensitive resin composition of this invention contains a polyfunctional thiol compound (T) further. The polyfunctional thiol compound (T) refers to a compound having two or more sulfanyl groups (—SH) 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 with respect to 100 parts by mass of the total amount of the alkali-soluble resin (A), the polymerizable compound (B1) and the polymerizable compound (B2). Part by mass, more preferably 0.5 to 7 parts by mass. 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 preferably contains a surfactant (E). 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.

  Content of surfactant (E) is 0.001 mass% or more and 0.2 mass% or less with respect to the total amount of the component contained in the photosensitive resin composition, Preferably it is 0.002 mass% or more. It is 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.

The photosensitive resin composition of the present invention preferably contains an antioxidant (F).
Examples of the antioxidant (F) include phenol-based antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, and amine-based antioxidants. Among these, a phenolic antioxidant is preferable in that the pattern and the coating film are less colored.

Examples of phenolic antioxidants include 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy -3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5) -Methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 2,2′-methylenebis (6-tert-butyl-4-methyl) Phenol), 4,4′-butylidenebis (6-tert-butyl-3-methylphenol), 4,4′-thiobis (2-tert-butyl-5-methyl) Ruphenol), 2,2′-thiobis (6-tert-butyl-4-methylphenol), 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3 , 5-Triazine-2,4,6 (1H, 3H, 5H) -trione, 3,3 ', 3 ", 5,5', 5" -hexa-tert-butyl-a, a ', a "- (Mesitylene-2,4,6-triyl) tri-p-cresol, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,6-di-tert- Butyl-4-methylphenol and 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [ 1, , 2] dioxaphosphepin and the like.
A commercial item may be used as said phenolic antioxidant. Commercially available phenolic antioxidants include, for example, Sumilizer (registered trademark) BHT, GM, GS, GP (all manufactured by Sumitomo Chemical Co., Ltd.), Irganox (registered trademark) 1010, 1076, 1330, 3114 (all are manufactured by BASF).

  Examples of the sulfur-based antioxidant include dilauryl 3,3′-thiodipropionate, dimyristyl 3,3′-thiodipropionate, distearyl 3,3′-thiodipropionate, pentaerythrityl tetrakis (3 -Lauryl thiopropionate) and the like. A commercially available product may be used as the sulfur-based antioxidant. Examples of commercially available sulfur-based antioxidants include Sumilizer (registered trademark) TPL-R and TP-D (all manufactured by Sumitomo Chemical Co., Ltd.).

  Examples of phosphorus antioxidants include trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, tris (nonylphenyl) phosphite, distearyl pentaerythritol diphosphite, tetra (tridecyl) -1,1, Examples include 3-tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butane diphosphite. A commercially available product may be used as the phosphorus-based antioxidant. Examples of commercially available phosphorus antioxidants include Irgaphos (registered trademark) 168, 12, and 38 (all manufactured by BASF), Adeka Stub 329K, Adeka Stub PEP36 (all manufactured by ADEKA), and the like.

  Examples of amine-based antioxidants include N, N′-di-sec-butyl-p-phenylenediamine, N, N′-di-isopropyl-p-phenylenediamine, and N, N′-dicyclohexyl-p-phenylene. Examples include diamine, N, N′-diphenyl-p-phenylenediamine, and N, N′-bis (2-naphthyl) -p-phenylenediamine. A commercially available product may be used as the amine-based antioxidant. Examples of commercially available amine-based antioxidants include Sumilizer (registered trademark) BPA, BPA-M1, 4ML (all manufactured by Sumitomo Chemical Co., Ltd.) and the like.

  The content of the antioxidant (F) is 0.1 parts by mass or more and 5 parts by mass or less, and preferably 0.5 parts by mass or more and 3 parts by mass or less with respect to 100 parts by mass of the alkali-soluble resin (A). There exists a tendency which is excellent in the heat resistance of a pattern or a coating film as content of antioxidant (F) exists in the said range. When content of antioxidant (F) exceeds the said range, there exists a possibility that a sensitivity may fall.

  In the photosensitive resin composition of the present invention, various additives such as fillers, other polymer compounds, adhesion promoters, ultraviolet absorbers, light stabilizers, chain transfer agents and the like may be used in combination as necessary. Also good.

  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.

  The photosensitive resin composition of the present invention includes, for example, an alkali-soluble resin (A), a polymerizable compound (B1), a polymerizable compound (B2), a polymerization initiator (C), a solvent (D), and as necessary. It can be prepared by mixing the polymerization initiation assistant (C1), surfactant (E), antioxidant (F), polyfunctional thiol compound (T) and other components used. The mixed photosensitive resin composition is preferably filtered with a filter having a pore size of about 0.01 to 10 μm.

  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.

Examples of the method for producing a pattern from the photosensitive resin composition of the present invention include a photolithographic method, an ink jet method, and a printing method. Of these, the photolithographic method is preferable. The photolithographic method is a method in which the photosensitive resin composition is applied to a substrate, dried to form an uncured coating film, and the uncured coating film is exposed and developed through a photomask. In the photolithographic method, a coating film that is a cured product of the uncured coating film can be formed by not using a photomask and / or not developing during exposure.
These coating films or patterns may be formed and used as a part of components such as a display device.

  Examples of the substrate include a substrate made of glass, metal, plastic, and the like, and a color filter, various insulating or conductive films, a drive circuit, and the like may be formed on the substrate.

Formation of the pattern by the photolithographic method can be performed by a known or conventional apparatus or conditions. For example, it can be formed as follows.
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 to be used, the use, etc.

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, the mask and the substrate can be accurately aligned at this time.

By bringing the uncured coating film after exposure into contact with a developer to dissolve a predetermined portion, for example, an unexposed portion, and developing it, a desired 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 tilted 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.

  Thus, the pattern and coating film obtained from the photosensitive resin composition of the present invention can be obtained by photo spacers and overcoats that form part of the color filter substrate and / or array substrate, overcoatable patternable, and ink jet methods. It is useful as a partition used for producing a color filter, an ITO electrode of a liquid crystal display element, an organic EL display element, a circuit wiring board, etc. Among them, the pattern obtained from the photosensitive resin composition of the present invention is excellent. Since it has mechanical properties, it is particularly useful as a photospacer.

  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（Ｍｗ／Ｍｎ）は２．５０であった。樹脂Ａａは、下記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. 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 the solution is added using a dropping funnel for 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. 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 (Mw / Mn) of 2.50. Resin Aa 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Ａｂ）の溶液を得た。得られた樹脂Ａｂ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Ａｂは、下記の構造単位を有する。

(Synthesis Example 2)
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 the dropping of the polymerization initiator solution was completed, the temperature was maintained at 70 ° C. for 4 hours, and then cooled to room temperature to obtain a copolymer (resin Ab) solution having a solid content of 41.8%. The weight average molecular weight (Mw) of the obtained resin Ab 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 Ab has the following structural units.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin obtained in the synthesis example 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
Standard material for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)
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, Comparative Example 1
<Preparation of photosensitive resin composition>
The components of Table 1 were mixed to obtain photosensitive resin compositions 1-6.

表１中各成分は以下のとおりである。樹脂の部数は、固形分換算の質量部を表す。
アルカリ可溶性樹脂（Ａ）；
Ａａ：合成例１で得られた樹脂Ａａ
Ａｂ：合成例２で得られた樹脂Ａｂ
重合性化合物（Ｂ１）；
Ｂ１ａ：３−エチル−３−アクリロイルオキシメチルオキセタン（ＯＸＥ−１０；大阪有機化学（株）製）
Ｂ１ｂ：グリシジルメタクリレート（和光純薬（株）製）
Ｂ１ｃ：３，４−エポキシトリシクロ［５．２．１．０^２．６］デシルアクリレート（式（Ｉ−１）で表される化合物及び式（ＩＩ−１）で表される化合物の混合物、モル比＝５０：５０）
重合性化合物（Ｂ２）；ジペンタエリスリトールヘキサアクリレート（ＫＡＹＡＲＡＤ（登録商標）ＤＰＨＡ；日本化薬（株）製）
重合開始剤（Ｃ）；２，２'−ビス（２−クロロフェニル）−４，４'，５，５'−テトラフェニル−１，２'−ビイミダゾール（Ｂ−ＣＩＭ；保土谷化学（株）製）
重合開始助剤（Ｃ１）；Ｃ２ａ：２−［２−オキソ−２−（２−ナフチル）エチリデン］−３−メチルベンゾチアゾリン（式（ＩＩＩ−１）で表される化合物）

多官能チオール化合物（Ｔ）：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）（SC有機化学(株)製；ＰＥＭＰ)
溶剤（Ｄ）；
Ｄａ：プロピレングリコールモノメチルエーテルアセテート
Ｄｂ：３−エトキシプロピオン酸エチル
Ｄｃ：３−メトキシ１−ブタノール
Ｄｄ：３−メトキシブチルアセテート
Ｄｅ：ジエチレングリコールメチルエチルエーテル
界面活性剤（Ｅ）；
ポリエーテル変性シリコーンオイル（トーレシリコーンＳＨ８４００；東レダウコーニング（株）製）
酸化防止剤（Ｆ）；１，３，５−トリス（４−ヒドロキシ−３，５−ジ−ｔｅｒｔ−ブチルベンジル）−１，３，５−トリアジン−２，４，６（１Ｈ，３Ｈ，５Ｈ）−トリオン（ＩＲＧＡＮＯＸ（登録商標）３１１４；チバ・ジャパン社製）
溶剤（Ｄ）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（Ｄ）中の溶剤成分（Ｄａ）〜（Ｄｅ）の値は、溶剤（Ｄ）中での質量比を表す。

Each component in Table 1 is as follows. The number of parts of resin represents a mass part in terms of solid content.
Alkali-soluble resin (A);
Aa: Resin Aa obtained in Synthesis Example 1
Ab: Resin Ab obtained in Synthesis Example 2
Polymerizable compound (B1);
B1a: 3-ethyl-3-acryloyloxymethyl oxetane (OXE-10; manufactured by Osaka Organic Chemical Co., Ltd.)
B1b: Glycidyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
B1c: 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (a mixture of a compound represented by the formula (I-1) and a compound represented by the formula (II-1); (Molar ratio = 50: 50)
Polymerizable compound (B2); dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)
Polymerization initiator (C); 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole (B-CIM; Hodogaya Chemical Co., Ltd.) Made)
Polymerization initiation aid (C1); C2a: 2- [2-oxo-2- (2-naphthyl) ethylidene] -3-methylbenzothiazoline (compound represented by formula (III-1))

Multifunctional thiol compound (T): Pentaerythritol tetrakis (3-sulfanylpropionate) (manufactured by SC Organic Chemical Co., Ltd .; PEMP)
Solvent (D);
Da: propylene glycol monomethyl ether acetate Db: ethyl 3-ethoxypropionate Dc: 3-methoxy 1-butanol Dd: 3-methoxybutyl acetate De: diethylene glycol methyl ethyl ether surfactant (E);
Polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.)
Antioxidant (F); 1,3,5-tris (4-hydroxy-3,5-di-tert-butylbenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) ) -Trion (IRGANOX (registered trademark) 3114; manufactured by Ciba Japan)
The solvent (D) is mixed so that the solid content of the photosensitive resin composition is “solid content (%)” in Table 1, and the values of the solvent components (Da) to (De) in the solvent (D) are Represents a mass ratio in the solvent (D).

<Average transmittance of composition>
About each of the obtained photosensitive resin compositions 1 to 4, an ultraviolet-visible near-infrared spectrophotometer (V-650; manufactured by JASCO Corporation) (quartz cell, optical path length: 1 cm) was used. The average transmittance (%) at 700 nm was measured. The results are shown in Table 2.

<Average transmittance of coating film>
Using the obtained photosensitive resin compositions 1 to 4, coating 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. 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 prebaked at 80 ° C. for 2 minutes on a hot plate and dried to form an uncured coating film. After standing to cool, the substrate on which this uncured coating film was formed was exposed to an exposure amount of 100 mJ / cm ² (in an air atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon Corporation, light source: ultrahigh pressure mercury lamp). 405 nm reference). In addition, irradiation to the uncured coating film (photosensitive resin composition) at this time was performed by passing the radiated light from the ultra-high pressure mercury lamp through an optical filter (LU0400; manufactured by Asahi Spectrometer Co., Ltd.). After light irradiation, the uncured coating film was immersed in an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 25 ° C. for 100 seconds and developed, A coating film was obtained by heating at 235 ° C. for 15 minutes.
About the obtained coating film, 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 2.

<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 is spin-coated so that the film thickness after post-baking is 4.0 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 prebaked at 80 ° C. for 2 minutes on a hot plate and dried to form an uncured coating film. After cooling, the distance between the substrate on which the uncured coating film is formed and the photomask made of quartz glass is 10 μm, and using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd., light source: ultrahigh pressure mercury lamp) Under an atmosphere, light with an exposure amount of 100 mJ / cm ² (405 nm reference) was irradiated. In addition, irradiation to the uncured coating film (photosensitive resin composition) at this time was performed by passing the radiated light from the ultra-high pressure mercury lamp through an optical filter (LU0400; manufactured by Asahi Spectrometer Co., Ltd.). In addition, a photomask in which a pattern (having a square light-transmitting portion with one side of 19 μm and an interval of the square of 100 μm) formed on the same plane was used as the photomask.
After light irradiation, the uncured coating film was 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, and then washed with water. In the oven, 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.). A pattern width of 5% higher than the substrate surface was measured with respect to the pattern height. The results are shown in Table 2.

<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 said that the higher the pattern recovery rate, the higher the flexibility, and the more useful the photo spacer. When such a pattern is used as a photo spacer, a liquid crystal panel having excellent strength can be manufactured. The results are shown in Table 2. Patterns and coating films formed from the same photosensitive resin composition exhibit similar mechanical properties.
-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

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

Claims (9)

A photosensitive resin composition containing (A), (B1), (B2), (C) and (D).
(A) Alkali-soluble resin (B1) Polymerizable compound (C) polymerization initiator (D) different from polymerizable compound (B2) (B1) having a C2-C4 cyclic ether structure and an ethylenically unsaturated bond solvent   The photosensitive resin composition according to claim 1, wherein (B1) is a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms and a (meth) acryloyloxy group.   The photosensitive resin composition according to claim 1 or 2, wherein (B1) comprises a polymerizable compound having an oxiranyl group and a (meth) acryloyloxy group or a polymerizable compound having an oxetanyl group and a (meth) acryloyloxy group.   The photosensitive resin composition according to any one of claims 1 to 3, wherein (B2) is a (meth) acrylic acid ester having no cyclic ether structure in the molecule.   The photosensitive resin composition according to any one of claims 1 to 4, wherein (B2) is a polymerizable compound having no cyclic ether structure in the molecule and having three or more (meth) acryloyloxy groups. .   The photosensitivity according to any one of claims 1 to 5, wherein the content of (B1) is 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the total amount of (A) and (B2). Resin composition.   (A) is a single unit 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, a cyclic ether structure having 2 to 4 carbon atoms, and an ethylenically unsaturated bond. The photosensitive resin composition according to claim 1, which is an addition polymer containing a structural unit derived from a monomer.   The pattern formed from the photosensitive resin composition as described in any one of Claims 1 thru | or 7.   A display device comprising the pattern according to claim 8.