KR20120023546A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE: A photo-sensitive resin composition, and a coating film, patterns, and a display device using the same are provided to include a polymerization initiator containing a specific compound. CONSTITUTION: A photo-sensitive resin composition includes resin, polymerizable compound, a polymerization initiator, and a solvent. The polymerization initiator contains compound represented by chemical formula 1. In chemical formula 1, the R1 is C3 to C8 cycloalkyl group; the L2 is C1 to C5 alkanediyl group; the L2 is a single bond or -CO-; the R2 is methyl group, phenyl group, or benzyl group; and the R3 is phenylsulphonyl group with/without a substituted group or carbazolyl group with/without a substituted group.

Description

Photosensitive resin composition {PHOTOSENSITIVE RESIN COMPOSITION}

The present invention relates to a photosensitive resin composition.

In recent liquid crystal display panels and the like, a photosensitive resin composition is used to form a photo spacer or an overcoat. As such a photosensitive resin composition, resin, a polymeric compound, a polymerization initiator, and a solvent are contained, for example, and a polymerization initiator is N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl)- The photosensitive resin composition which is 9H-carbazol-3-yl] ethane-1-imine is known (patent document 1).

Japanese Laid-Open Patent Publication No. 2008-181087

However, in the photosensitive resin composition conventionally proposed, it may not always be satisfactory enough in view of the visible light transmittance of the coating film and pattern obtained.

The present invention is the following [1]? [6] to provide.

[1] A resin (A), a polymerizable compound (B), a polymerization initiator (C) and a solvent (D) are contained, and the polymerization initiator (C) is represented by the formula (1):

[Formula 1]

[In formula (1), R <^1> is C3? 8 cycloalkyl group;

L ¹ has 1? 5 represents an alkanediyl group;

L ² represents a single bond or -CO-;

R ² represents a methyl group, a phenyl group or a benzyl group;

R ³ represents a phenylsulfanylphenyl group which may have a substituent or a carbazolyl group which may have a substituent;

The photosensitive resin composition which is a polymerization initiator containing the compound shown by.

[2] The photosensitive resin composition according to the above [1], wherein L ² in Formula (1) represents -CO-.

[3] The content of the compound represented by Formula (1) is 30? To the total amount of the polymerization initiator (C). The photosensitive resin composition as described in said [1] or said [2] which is 100 mass%.

[4] The resin (A) has 2 to 2 carbon atoms; The above-mentioned [1] which is resin containing the structural unit derived from the monomer which has a cyclic ether structure of 4 and a carbon-carbon unsaturated double bond. The photosensitive resin composition in any one of [3].

[5] above [1]? Coating film obtained by the photosensitive resin composition in any one of [4].

[6] above [1]? The pattern obtained by the photosensitive resin composition in any one of [4].

[7] A display device comprising at least one member selected from the group consisting of the coating film according to the above [5] and the pattern according to the above [6].

According to the photosensitive resin composition of this invention, a coating film and pattern with high visible light transmittance can be formed.

Hereinafter, the present invention will be described in detail.

The photosensitive resin composition of this invention contains the polymerization initiator (C) and solvent (D) containing resin (A), a polymeric compound (B), and the compound represented by Formula (1).

[Formula 1]

[In formula (1), R <^1> is C3? 8 cycloalkyl group is shown.

L ¹ has 1? The alkanediyl group of 5 is shown.

L ² represents a single bond or -CO-.

R ² represents a methyl group, a phenyl group or a benzyl group.

R ³ represents a phenylsulfanylphenyl group which may have a substituent or a carbazolyl group which may have a substituent;

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

The photosensitive resin composition of this invention contains resin (A). As resin (A), alkali-soluble resin is preferable. Alkali-soluble resin is resin melt | dissolved in the developing solution mentioned later.

As resin (A) used for the photosensitive resin composition of this invention, it is, for example,

Resin (A-1): At least 1 sort (a) (Hereinafter, it may be called "(a)") chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride, and C2-C? A copolymer obtained by polymerizing a monomer (b) (hereinafter sometimes referred to as "(b)") having a cyclic ether structure of 4 and a carbon-carbon unsaturated double bond, and

Resin (A-2): Monomer (c) copolymerizable with (a), (b) and (a) and (b) (but does not have a cyclic ether structure having 2 to 4 carbon atoms) (c) may be referred to as &quot;

Resin (A-3): copolymer formed by superposing | polymerizing (a) and (c)

Resin (A-4): Resin obtained by making (b) react with the copolymer of (a) and (c)

Resin (A-5): Resin obtained by making (a) react with the copolymer of (b) and (c)

Etc. can be mentioned. As resin (A), resin (A-1) and resin (A-2) are preferable and resin (A-1) is more preferable.

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

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

Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hepto-2-ene, 5,6-dicarboxybicyclo [2.2.1] hepto-2- N, 5-carboxy-5-methylbicyclo [2.2.1] hepto-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hepto-2-ene, 5-carboxy-6-methyl ratio Bicyclo unsaturated compounds containing carboxyl groups such as cyclo [2.2.1] hepto-2-ene and 5-carboxy-6-ethylbicyclo [2.2.1] hepto-2-ene;

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride Unsaturated dicarboxylic anhydrides such as dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo [2.2.1] hepto-2-ene anhydride (hymic acid anhydride);

 Unsaturated mono [(meth) acryloyloxyalkyl of bivalent or more polyvalent carboxylic acids, such as monosuccinate mono [2- (meth) acryloyloxyethyl] and phthalate mono [2- (meth) acryloyloxyethyl] Esters;

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

Among these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferably used in terms of copolymerization reactivity or alkali solubility.

Here, in this specification, "(meth) acrylic acid" represents at least 1 sort (s) chosen from the group which consists of acrylic acid and methacrylic acid. Notation, such as "(meth) acryloyl" and "(meth) acrylate", has the same meaning.

(b) is C2? The polymerizable compound which has a cyclic ether structure of 4 (for example, at least 1 sort (s) chosen from the group which consists of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring (oxolane ring)). (b) has 2? It is preferable that it is a monomer which has a cyclic ether structure of 4 and a carbon-carbon unsaturated double bond, and has C2-C? More preferred are monomers having a cyclic ether structure of 4 and a (meth) acryloyloxy group.

As (b), for example, the monomer (b1) which has an oxylanyl group (hereinafter may be called "(b1)"), and the monomer (b2) which has an oxetanyl group (henceforth "(b2)" The monomer (b3) (Hereinafter, it may be called "(b3)") which has a tetrahydrofuryl group, etc. are mentioned.

The monomer (b1) which has an oxiranyl group represents the polymeric compound which has an oxiranyl group. As (b1), the monomer (b1-1) (Hereinafter, it may be called "(b1-1)") and unsaturated alicyclic which have a structure which epoxidized chain olefin, and a carbon-carbon unsaturated double bond, for example. The monomer (b1-2) (Hereinafter, it may be called "(b1-2)") which has a structure which epoxidized a formula hydrocarbon, and a carbon-carbon unsaturated double bond is mentioned.

As (b1), it is preferable that it is a monomer which has an oxilanyl group and a carbon-carbon unsaturated double bond, The monomer which has an oxilanyl group and a (meth) acryloyloxy group is more preferable, A (meth) acryloyloxy group (B1-2) which has is more preferable.

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-vinyl benzyl glycidyl ether, α-methyl-o-vinyl benzyl glycidyl ether, α-methyl-m-vinyl benzyl glycy Dyl 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 (glycidyloxymethyl) styrene, 2,3,5-tris (glycidyloxy Methyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6-tris (glycidyloxymethyl) Styrene, the compound of Unexamined-Japanese-Patent No. 7-248625, etc. are mentioned.

Examples of (b1-2) include vinylcyclohexene monooxide and 1,2-epoxy-4-vinylcyclohexane (for example, serotoside 2000; manufactured by Daicel Chemical Industry Co., Ltd.), 3,4-epoxycyclo Hexylmethyl acrylate (for example, Cychrom A400; manufactured by Daicel Chemical Industry Co., Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (for example, Cychroma M100; Daicel Chemical Industry Co., Ltd.) Production), the compound represented by Formula (I), the compound represented by Formula (II), etc. are mentioned.

[Formula 2]

[In Formula (I) and Formula (II), R ^<a> and R <^b> represent a hydrogen atom or C1-C independently of each other. The alkyl group of 4 is represented, and the hydrogen atom contained in this alkyl group may be substituted by the hydroxy group.

X ¹ and X ² independently represent a single bond, -R ^c- , * -R ^c -O-, * -R ^c -S-, * -R ^c -NH-.

R ^c has 1? The alkanediyl group of 6 is shown.

* Represents the number of bonds with O.]

Carbon number 1? As an alkyl group of 4, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert- butyl group etc. are mentioned specifically ,.

As an alkyl group substituted by the hydroxy group, a hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy A hydroxy-1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, etc. are mentioned.

As R ^<a> and R <^b> , Preferably a hydrogen atom, a methyl group, a hydroxymethyl group, 1-hydroxyethyl group, and 2-hydroxyethyl group are mentioned, More preferably, a hydrogen atom and a methyl group are mentioned.

Examples of the alkanediyl group include a methylene group, an ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, and hexane- 1, 6- diyl group etc. are mentioned.

Roneun X ¹ and X ^2, preferably a single bond, methylene group, ethylene group, * -CH ₂ -O- (* indicates the number of engagement with the O) group, * -CH ₂ CH ₂ -O- group in can and will, more preferably there may be mentioned a single bond, * -CH ₂ CH ₂ -O- group.

As a compound represented by Formula (I), it is a formula (I-1)? The compound etc. which are represented by Formula (I-15) are mentioned. Preferably, formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9), and formula (I-11)? Formula (I-15) is mentioned. More preferably, Formula (I-1), Formula (I-7), Formula (I-9), and Formula (I-15) are mentioned.

(3)

As a compound represented by Formula (II), it is a formula (II-1)? The compound etc. which are represented by Formula (II-15) are mentioned. Preferably formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9), or formula (II-11)? Formula (II-15) is mentioned.

More preferably, Formula (II-1), Formula (II-7), Formula (II-9), and Formula (II-15) are mentioned.

[Formula 4]

The compound represented by Formula (I) and the compound represented by Formula (II) can be used independently, respectively. Moreover, they can be mixed in arbitrary ratios. In the case of mixing, the mixing ratio is in a molar ratio, preferably in the formula (I): formula (II), from 5:95? 95: 5, More preferably, it is 10:90? 90:10, Especially preferably, it is 20:80? It is 80:20.

The monomer (b2) which has an oxetanyl group represents the polymeric compound which has an oxetanyl group. As (b2), it is preferable that it is a monomer which has an oxetanyl group and a carbon-carbon unsaturated double bond, and the monomer which has an oxetanyl group and a (meth) acryloyloxy group is more preferable. Examples of (b2) include 3-methyl-3- (meth) acryloyloxymethyloxetane, 3-ethyl-3- (meth) acryloyloxymethyloxetane, and 3-methyl-3- ( Met) acryloyloxyethyl oxetane, 3-ethyl-3- (meth) acryloyloxyethyl oxetane, etc. are mentioned.

The monomer (b3) which has a tetrahydrofuryl group represents the polymeric compound which has a tetrahydrofuryl group. As (b3), it is preferable that it is a monomer which has a tetrahydrofuryl group and a carbon-carbon unsaturated double bond, and the monomer which has a tetrahydrofuryl group and a (meth) acryloyloxy group is more preferable.

Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, biscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

As (c), methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert- butyl (meth) acrylate, etc. are mentioned, for example. Alkyl (meth) acrylates;

Cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (in the art, dicyclopentanyl as conventional name) (Meth) acrylic acid cyclic alkyl esters such as (meth) acrylate), dicyclopentanyloxyethyl (meth) acrylate, and isobornyl (meth) acrylate;

Aryl (meth) acrylates or aralkyl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate;

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

Hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

Bicyclo [2.2.1] hepto-2-ene, 5-methylbicyclo [2.2.1] hepto-2-ene, 5-ethylbicyclo [2.2.1] hepto-2-ene, 5-hydroxybi Cyclo [2.2.1] hepto-2-ene, 5-hydroxymethylbicyclo [2.2.1] hepto-2-ene, 5- (2′-hydroxyethyl) bicyclo [2.2.1] hepto-2 -Ene, 5-methoxybicyclo [2.2.1] hepto-2-ene, 5-ethoxybicyclo [2.2.1] hepto-2-ene, 5,6-dihydroxybicyclo [2.2.1] hepto 2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hepto-2-ene, 5,6-di (2′-hydroxyethyl) bicyclo [2.2.1] hepto- 2-ene, 5,6-dimethoxybicyclo [2.2.1] hepto-2-ene, 5,6-diethoxybicyclo [2.2.1] hepto-2-ene, 5-hydroxy-5-methyl Bicyclo [2.2.1] hepto-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hepto-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] Hepto-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hepto-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hepto-2-ene, 5-phenoxy Carbonylbicycle Ro [2.2.1] hepto-2-ene, 5,6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hepto-2-ene, 5,6-bis (cyclohexyloxycarbonyl ) Bicyclo unsaturated compounds such as bicyclo [2.2.1] hepto-2-ene;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl Dicarbonylimide derivatives such as -6-maleimide caproate, N-succinimidyl-3-maleimide propionate and N- (9-acridinyl) maleimide;

Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, acetic acid Vinyl, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like.

Among them, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hepto-2-ene and the like are preferred in view of copolymerization reactivity 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 mole number of the structural unit which comprises resin (A-1).

Structural unit derived from (a): 5? 60 mol% (more preferably 10-50 mol%)

The structural unit derived from (b): 40? 95 mol% (more preferably 50-90 mol%)

If the ratio of the structural unit of resin (A-1) exists in the said range, the storage stability of the photosensitive resin composition, the developability at the time of forming a pattern from the photosensitive resin composition, and the solvent resistance, heat resistance of the coating film and pattern obtained, and The mechanical strength tends to be good.

As resin (A-1), resin whose (b) is (b1) is preferable, and resin whose (b) is (b1-2) is more preferable.

The resin (A-1) is, for example, the method described in the document "Experimental method of polymer synthesis" (Otsu Takayuki Seisen Co., Ltd., Chemical Co., Ltd., First Edition First Edition March 1, 1972) and the document. It may manufacture with reference to the cited document described in.

Specifically, a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like are put in a reaction vessel, and, for example, the oxygen is replaced with nitrogen to form a deoxygen atmosphere, and heated and kept warm while stirring. The method is illustrated. In addition, the polymerization initiator, solvent, etc. which are used here are not specifically limited, Any of the thing normally used in the said field | area can be used. For example, as a polymerization initiator, an azo compound (2,2'- azobisisobutyronitrile, 2,2'- azobis (2, 4- dimethylvaleronitrile), etc.) and an organic peroxide (benzoyl peroxide) Etc.) What is necessary is just to melt | dissolve each monomer as a solvent, The solvent (D) mentioned later as a solvent of the photosensitive resin composition can be used.

In addition, the obtained copolymer may use the solution after reaction as it is, the solution concentrated or diluted may be used, and what was taken out as solid (powder) by methods, such as reprecipitation, may be used. In particular, the solution after reaction can be used as it is by using the same solvent as the solvent (D) mentioned later as a solvent at the time of this superposition | polymerization, and a manufacturing process can be simplified.

In resin (A-2), it is preferable that the ratio of the structural unit derived from each monomer exists in the following ranges with respect to the total number of moles of all the structural units which comprise resin (A-2).

Structural unit derived from (a): 2? 40 mol% (more preferably 5-35 mol%)

Structural unit derived from (b): 2? 95 mol% (more preferably 5-80 mol%)

Structural unit derived from (c): 1? 65 mol% (more preferably 1-60 mol%)

When the ratio of the structural unit of resin (A-2) exists in the said range, the storage stability of the photosensitive resin composition, the developability at the time of forming a pattern from the photosensitive resin composition, and the solvent resistance, heat resistance of the coating film and pattern obtained, and The mechanical strength tends to be good.

As resin (A-2), resin whose (b) is (b1) is preferable, and resin whose (b) is (b1-2) is more preferable.

Resin (A-2) can be manufactured by the method similar to 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 the structural units which comprise resin (A-3).

Structural unit derived from (a): 2? 40 mol% (more preferably 5-35 mol%)

The structural unit derived from (c): 60? 98 mol% (more preferably 65-95 mol%)

When the ratio of the structural unit of resin (A-3) exists in the said range, the storage stability of the photosensitive resin composition, the developability at the time of forming a pattern from the photosensitive resin composition, and the solvent resistance and heat resistance of the coating film and pattern obtained are obtained. And mechanical strength tends to be good.

Resin (A-3) can be manufactured by the method similar to resin (A-1).

Resin (A-4) and resin (A-5) can be manufactured through a two-step process, for example. Also in this case, the method as described in the above-mentioned document "Experimental method of polymer synthesis" (Otsu Takayuki Seisen Co., Ltd. first chemical print first edition March 1, 1972), Japanese Unexamined Patent Publication No. 2001- It can manufacture with reference to the method of 89533, etc.

Resin (A-4) is first carried out as a first step, in the same manner as in the above-mentioned method for producing resin (A-1), to obtain a copolymer of (a) and (c).

In this case, similarly to the above, the obtained copolymer may use the solution after reaction as it is, the solution concentrated or diluted may be used, and what was taken out as solid (powder) by methods, such as reprecipitation, may be used.

It is preferable that the ratio of the structural unit derived from (a) and (c) exists in the following ranges with respect to the total mole number of all the structural units which comprise the said copolymer.

Structural unit derived from (a): 5? 50 mol% (more preferably 10-45 mol%)

The structural unit derived from (c): 50? 95 mol% (more preferably 55-90 mol%)

Next, as a 2nd step, some of the carboxylic acid and carboxylic anhydride of (a) derived from the obtained copolymer are made to react with the cyclic ether of (b). (B1) is preferable and (b1-1) is more preferable as (b) from the point that reactivity of a cyclic ether is high and unreacted (b) does not remain well.

Specifically, following the above, the atmosphere in the flask is replaced with nitrogen by air, and the molar number of (a) is 5? 80 mol% of (b) and the reaction catalyst of a carboxyl group and a cyclic ether (for example, tris (dimethylaminomethyl) phenol etc.) are 0.001? With respect to the total amount of (a), (b) and (c). 5 mass% and a polymerization inhibitor (for example, hydroquinone, etc.) with respect to the total amount of (a), (b), and (c) 0.001? 5 mass% was put in a flask, and 60? 1 at 130 ℃? Reaction (A-4) can be obtained by making it react for 10 hours. In addition, similarly to the polymerization conditions, the injection method and the reaction temperature can be appropriately adjusted in consideration of the amount of heat generated by the production equipment, the polymerization and the like.

In this case, the number of moles of (b) is 10? To the number of moles of (a). It is preferable to set it as 75 mol%, More preferably, it is 15? 70 mol%. By making the number-of-moles of (b) into this range, there exists a tendency for the balance of storage stability, solvent resistance, and heat resistance to become favorable.

As a specific example of resin (A-4), resin which made glycidyl (meth) acrylate react with the copolymer of (meth) acrylic acid / dicyclopentanyl (meth) acrylate, (meth) acrylic acid / benzyl (meth Resin which the glycidyl (meth) acrylate was made to react with the copolymer of an acrylate, resin which made glycidyl (meth) acrylate react with the copolymer of (meth) acrylic acid / cyclohexyl (meth) acrylate, ( Resin which glycidyl (meth) acrylate was made to react with the copolymer of meth) acrylic acid / styrene, resin which glycidyl (meth) acrylate was made to react with the copolymer of (meth) acrylic acid / methyl (meth) acrylate, ( Resin obtained by reacting glycidyl (meth) acrylate with a copolymer of (meth) acrylic acid / N-cyclohexylmaleimide, a copolymer of (meth) acrylic acid / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate Glycidyl (meth) acrylate Resin obtained by reacting glycidyl (meth) acrylate with a copolymer of resin (meth) acrylic acid / dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate which reacted with meth, (meth) acrylic acid / dish Glyce to a copolymer of (meth) acrylic acid / dicyclopentanyl (meth) acrylate / methyl (meth) acrylate in which glycidyl (meth) acrylate is reacted with a copolymer of clofentanyl (meth) acrylate / styrene Resin in which glycidyl (meth) acrylate was made to react with resin which made cylyl (meth) acrylate react, copolymer of (meth) acrylic acid / dicyclopentanyl (meth) acrylate / N-cyclohexyl maleimide, and croton Resin obtained by reacting glycidyl (meth) acrylate with a copolymer of acid / dicyclopentanyl (meth) acrylate;

Glycidyl (meth) acrylate is reacted with a resin obtained by reacting glycidyl (meth) acrylate with a copolymer of crotonic acid / benzyl (meth) acrylate and a copolymer of crotonic acid / cyclohexyl (meth) acrylate. Resin obtained by reacting glycidyl (meth) acrylate with a copolymer of crotonic acid / styrene and resin obtained by reacting glycidyl (meth) acrylate with a copolymer of methyl crotonic acid / crotonate, crotonic acid / Glycidyl (meth) to a copolymer of crosic acid / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate in which glycidyl (meth) acrylate is reacted with a copolymer of N-cyclohexyl maleimide Resin by reacting glycidyl (meth) acrylate with a copolymer of crotonic acid / dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate, and crotonic acid / dicyclo Glycidyl (meth) to a copolymer of resins obtained by reacting glycidyl (meth) acrylate with a copolymer of tanyl (meth) acrylate / styrene and a copolymer of crotonic acid / dicyclopentanyl (meth) acrylate / methyl crotonate Resin which made glycidyl (meth) acrylate react with the resin which made acrylate react, and the copolymer of crotonic acid / dicyclopentanyl (meth) acrylate / N-cyclohexyl maleimide;

Glycidyl (meth) acrylate is added to a copolymer of maleic acid / dicyclopentanyl (meth) acrylate with glycidyl (meth) acrylate and a copolymer of maleic acid / benzyl (meth) acrylate. Glycidyl (meth) acrylate is made to react with resin and maleic acid / styrene copolymer which made glycidyl (meth) acrylate react with the copolymer of maleic acid / cyclohexyl (meth) acrylate. Resin, Glycidyl (meth) acrylate reacted with a copolymer of maleic acid / methyl maleate, Glycidyl (meth) acrylate reacted with a copolymer of maleic acid / N-cyclohexyl maleimide , Resin obtained by reacting glycidyl (meth) acrylate with a copolymer of maleic acid / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate, maleic acid / dicyclopentanyl (meth) acrylate / cyclohexyl (Meth) acrylic Resin which made glycidyl (meth) acrylate react with the copolymer of nitrate, Resin which made glycidyl (meth) acrylate react with the copolymer of maleic acid / dicyclopentanyl (meth) acrylate / styrene, maleic acid Air of resin, maleic acid / dicyclopentanyl (meth) acrylate / N-cyclohexyl maleimide which glycidyl (meth) acrylate was made to react copolymer of / dicyclopentanyl (meth) acrylate / methyl maleate Resin which made glycidyl (meth) acrylate react with coalescence;

Resin obtained by reacting glycidyl (meth) acrylate with a copolymer of (meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate, and of (meth) acrylic acid / maleic anhydride / benzyl (meth) acrylate Resin obtained by reacting glycidyl (meth) acrylate with a copolymer, resin obtained by reacting glycidyl (meth) acrylate with a copolymer of (meth) acrylic acid / maleic anhydride / cyclohexyl (meth) acrylate, ( Glycidyl (meth) to a copolymer of (meth) acrylic acid / maleic anhydride / methyl (meth) acrylate by reacting glycidyl (meth) acrylate with a copolymer of (meth) acrylic acid / maleic anhydride / styrene Resin which the acrylate was made to react, resin which glycidyl (meth) acrylate was made to react with copolymer of (meth) acrylic acid / maleic anhydride / N-cyclohexyl maleimide, (meth) acrylic acid / maleic anhydride / dicyclo Fentanyl (Met Resin, (meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate / cyclohexyl (meth), in which a glycidyl (meth) acrylate is reacted with a copolymer of acrylate / benzyl (meth) acrylate Glycidyl (meth) acrylate to a copolymer of resin (meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate / styrene in which glycidyl (meth) acrylate is reacted with a copolymer of acrylate Resin obtained by reacting glycidyl (meth) acrylate with a copolymer of resin, (meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate / methyl (meth) acrylate, and (meth) acrylic acid / Resin obtained by reacting glycidyl (meth) acrylate with a copolymer of maleic anhydride / dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide;

Resin obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of (meth) acrylic acid / dicyclopentanyl (meth) acrylate, 3, to a copolymer of (meth) acrylic acid / benzyl (meth) acrylate Resin to which 4-epoxycyclohexyl methyl methacrylate was reacted, resin to which 3, 4- epoxycyclohexyl methyl methacrylate was reacted with the copolymer of (meth) acrylic acid / cyclohexyl (meth) acrylate, (meth) acrylic acid 3,4-epoxycyclohexylmethyl methacrylate reacted with a resin of 3,4-epoxycyclohexylmethyl methacrylate reacted with a copolymer of / styrene and a copolymer of (meth) acrylic acid / methyl (meth) acrylate Resin, a resin obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of (meth) acrylic acid / N-cyclohexylmaleimide, (meth) acrylic acid / dicyclopentanyl (meth) acrylate / benzyl (meth )Ah 3,4 to the copolymer of resin and (meth) acrylic acid / dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate which made 3, 4- epoxycyclohexyl methyl methacrylate react with the copolymer of a releasing agent -Resin reacted with epoxycyclohexyl methyl methacrylate, resin reacted with 3,4-epoxycyclohexyl methyl methacrylate with a copolymer of (meth) acrylic acid / dicyclopentanyl (meth) acrylate / styrene, (meth Resin by which 3, 4- epoxycyclohexyl methyl methacrylate was made to react the copolymer of acrylic acid / dicyclopentanyl (meth) acrylate / methyl (meth) acrylate, (meth) acrylic acid / dicyclopentanyl (meth) acrylate Resin obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of / N-cyclohexylmaleimide;

Resin obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of crotonic acid / dicyclopentanyl (meth) acrylate, and 3,4-epoxycyclo to a copolymer of crotonic acid / benzyl (meth) acrylate 3, to a copolymer of crotonic acid / styrene, a resin obtained by reacting a hexyl methyl methacrylate, a copolymer of crotonic acid / cyclohexyl (meth) acrylate, and 3,4-epoxycyclohexyl methyl methacrylate Of a resin in which 4-epoxycyclohexylmethyl methacrylate is reacted, a resin in which 3,4-epoxycyclohexylmethyl methacrylate is reacted with a copolymer of crotonic acid / methyl crotonate, and crotonic acid / N-cyclohexyl maleimide 3,4-epoxycyclohexyl to a copolymer of crotonic acid / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate in which 3,4-epoxycyclohexylmethyl methacrylate was reacted with a copolymer Resin and crotonic acid in which 3,4-epoxycyclohexylmethyl methacrylate was reacted with a copolymer of crotonic acid / dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate in which a methyl methacrylate was reacted To a copolymer of 3,4-epoxycyclohexylmethyl methacrylate and a copolymer of crotonic acid / dicyclopentanyl (meth) acrylate / methyl crotonate reacted with a copolymer of / dicyclopentanyl (meth) acrylate / styrene 3,4-epoxycyclohexylmethyl methacrylate was added to a copolymer of crotonic acid / dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide reacted with 3,4-epoxycyclohexylmethyl methacrylate. Reacted resin;

Resin obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of maleic acid / dicyclopentanyl (meth) acrylate, and 3,4-epoxycyclo to a copolymer of maleic acid / benzyl (meth) acrylate 3, to a copolymer of maleic acid / styrene and a copolymer of maleic acid / cyclohexyl (meth) acrylate, to which a hexyl methyl methacrylate was reacted, a resin of 3,4-epoxycyclohexyl methyl methacrylate, and a copolymer of maleic acid / styrene Of resin in which 4-epoxycyclohexylmethyl methacrylate is reacted, resin in which 3,4-epoxycyclohexylmethyl methacrylate is reacted with a copolymer of maleic acid / methyl maleate, and maleic acid / N-cyclohexyl maleimide 3,4-epoxycyclohexylmethyl meth to the copolymer of maleic acid / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate which made 3, 4- epoxycyclohexyl methyl methacrylate react with the copolymer Krillay Resin obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of maleic acid / dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate and maleic acid / dicyclopentanyl 3,4- to the copolymer of maleic acid / dicyclopentanyl (meth) acrylate / methyl maleate which made 3, 4- epoxycyclohexyl methyl methacrylate react with the copolymer of (meth) acrylate / styrene Resin in which 3,4-epoxycyclohexyl methyl methacrylate was reacted with a copolymer of maleic acid / dicyclopentanyl (meth) acrylate / N-cyclohexyl maleimide reacted with epoxy cyclohexyl methyl methacrylate;

Resin obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of (meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate, (meth) acrylic acid / maleic anhydride / benzyl (meth) 3,4-epoxycyclohexylmethyl to the copolymer of (meth) acrylic acid / maleic anhydride / cyclohexyl (meth) acrylate which made 3, 4- epoxycyclohexyl methyl methacrylate react with the copolymer of acrylate Resin to which methacrylate was reacted, resin to which 3,4-epoxycyclohexylmethyl methacrylate was reacted with the copolymer of (meth) acrylic acid / maleic anhydride / styrene, (meth) acrylic acid / maleic anhydride / (meth) 3,4-epoxycyclohexyl methyl methacrylate to a copolymer of (meth) acrylic acid / maleic anhydride / N-cyclohexyl maleimide by reacting 3,4-epoxycyclohexyl methyl methacrylate with a copolymer of methyl acrylate Krill Resin in which 3,4-epoxycyclohexylmethyl methacrylate was reacted with a copolymer of (meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate in which yate was reacted, Resin which (meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate reacted with 3, 4- epoxycyclohexyl methyl methacrylate, (meth) acrylic acid / Resin obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of maleic anhydride / dicyclopentanyl (meth) acrylate / styrene, (meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylic Resin which 3, 4- epoxycyclohexyl methyl methacrylate was made to react with the copolymer of a rate / methyl (meth) acrylate, (meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate / N-cyclohex The resin etc. which made 3, 4- epoxycyclohexyl methyl methacrylate react with the copolymer of silmaleimide are mentioned.

Resin (A-5) is carried out similarly to the manufacturing method of resin (A-1) mentioned above as a 1st step, and obtains the copolymer of (b) and (c).

In this case, similarly to the above, the obtained copolymer may use the solution after reaction as it is, the solution concentrated or diluted may be used, and what was taken out as solid (powder) by methods, such as reprecipitation, may be used.

It is preferable that the ratio of the structural unit derived from (b) and (c) exists in the following ranges with respect to the total mole number of all the structural units which comprise said 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%)

Moreover, the carboxylic acid or carboxylic acid which (a) has in the cyclic ether derived from (b) in the copolymer of (b) and (c) similarly to the manufacturing method of resin (A-4). It can be obtained by reacting anhydride.

The usage-amount of (a) made to react with said copolymer is 5? With respect to the number-of-moles of (b). It is preferable that it is 80 mol%. (B1) is preferable and (b1-1) is more preferable as (b) from the point that reactivity of a cyclic ether is high and unreacted (b) does not remain well.

You may make carboxylic anhydride further react with the hydroxyl group which arises by reaction of a cyclic ether, carboxylic acid, or carboxylic anhydride. An acid value can be adjusted by making carboxylic anhydride react. As carboxylic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3 , 6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hepto-2-ene anhydride (hymic acid anhydride), and the like. The use amount of carboxylic anhydride is 0.5? To 1 mol of use amount of (a). 1 mole is preferred.

As a specific example of resin (A-5), resin which made (meth) acrylic acid react with the copolymer of dicyclopentanyl (meth) acrylate / glycidyl (meth) acrylate, and benzyl (meth) acrylate / gly Resin which (meth) acrylic acid was made to react with the copolymer of cylyl (meth) acrylate, resin which (meth) acrylic acid was made to react with the copolymer of cyclohexyl (meth) acrylate / glycidyl (meth) acrylate, and styrene Resin which (meth) acrylic acid was made to react with the copolymer of / glycidyl (meth) acrylate, resin which made (meth) acrylic acid react with the copolymer of methyl (meth) acrylate / glycidyl (meth) acrylate, N Resin which (meth) acrylic acid was made to react the copolymer of cyclohexyl maleimide / glycidyl (meth) acrylate, and dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate / glycidyl (meth) acryl (Meth) arc to the copolymer of the rate Resin and dicyclopentanyl (meth) which made (meth) acrylic acid react with the copolymer of resin which made acid react, and the copolymer of dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate / glycidyl (meth) acrylate Of a resin obtained by reacting (meth) acrylic acid to a copolymer of acrylate / styrene / glycidyl (meth) acrylate and dicyclopentanyl (meth) acrylate / methyl (meth) acrylate / glycidyl (meth) acrylate Resin which (meth) acrylic acid was made to react with the copolymer of (meth) acrylic acid, and the copolymer of dicyclopentanyl (meth) acrylate / N-cyclohexyl maleimide / glycidyl (meth) acrylate;

Crotonic acid was added to a resin obtained by reacting crotonic acid with a copolymer of dicyclopentanyl (meth) acrylate / glycidyl (meth) acrylate and a copolymer of benzyl (meth) acrylate / glycidyl (meth) acrylate. Crotonic acid was made to react with the resin which made the reacted resin and the copolymer of cyclohexyl (meth) acrylate / glycidyl (meth) acrylate, and the copolymer of styrene / glycidyl (meth) acrylate reacted. Resin, the resin which made crotonic acid react with the copolymer of methyl crotonate / glycidyl (meth) acrylate, and the resin which made crotonic acid react with the copolymer of N-cyclohexyl maleimide / glycidyl (meth) acrylate Resin which made crotonic acid react with the copolymer of dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate / glycidyl (meth) acrylate, and dicyclopentanyl (meth) acrylate / cyclohexyl (meth Crotonic acid is reacted with the resin which made crotonic acid react with the copolymer of acrylate / glycidyl (meth) acrylate, and the copolymer of dicyclopentanyl (meth) acrylate / styrene / glycidyl (meth) acrylate. Resin, dicyclopentanyl (meth) acrylate / N-cyclohexyl maleimide, in which crotonic acid was reacted with a copolymer of a resin, a dicyclopentanyl (meth) acrylate / methyl crotonic acid / glycidyl (meth) acrylate Resin which made crotonic acid react with the copolymer of / glycidyl (meth) acrylate;

Maleic acid is added to a copolymer of dicyclopentanyl (meth) acrylate / glycidyl (meth) acrylate in which maleic acid is reacted and a copolymer of benzyl (meth) acrylate / glycidyl (meth) acrylate. The maleic acid was made to react with the copolymer of resin and styrene / glycidyl (meth) acrylate which made maleic acid react with the copolymer of resin and cyclohexyl (meth) acrylate / glycidyl (meth) acrylate which were made to react. Resin, maleic acid to a copolymer of methyl maleate / glycidyl (meth) acrylate, and maleic acid to a copolymer of N-cyclohexyl maleimide / glycidyl (meth) acrylate. Resin obtained by reacting maleic acid with a copolymer of dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate / glycidyl (meth) acrylate; dicyclopentanyl (meth) acrylate / cyclohexyl (meth) Acrylate / Written Resin which maleic acid was made to react with the copolymer of lycidyl (meth) acrylate, resin which maleic acid was made to react with the copolymer of dicyclopentanyl (meth) acrylate / styrene / glycidyl (meth) acrylate, and dicyclo Resin, dicyclopentanyl (meth) acrylate / N-cyclohexyl maleimide / glycidyl, in which maleic acid was reacted with a copolymer of fentanyl (meth) acrylate / methyl maleate / glycidyl (meth) acrylate Resin in which maleic acid is reacted with a copolymer of meth) acrylate;

Of resin and benzyl (meth) acrylate / glycidyl (meth) acrylate in which (meth) acrylic acid and maleic anhydride are reacted with a copolymer of dicyclopentanyl (meth) acrylate / glycidyl (meth) acrylate. Resin and (styrene) which made (meth) acrylic acid and maleic anhydride react with the copolymer of (meth) acrylic acid and maleic anhydride, and the copolymer of cyclohexyl (meth) acrylate / glycidyl (meth) acrylate, and styrene Resin obtained by reacting (meth) acrylic acid and maleic anhydride with a copolymer of / glycidyl (meth) acrylate, (meth) acrylic acid and male to a copolymer of methyl (meth) acrylate / glycidyl (meth) acrylate Resin obtained by reacting (meth) acrylic acid and maleic anhydride with a copolymer of N-cyclohexylmaleimide / glycidyl (meth) acrylate in which an acid anhydride is reacted, dicyclopentanyl (meth) acrylate Resin, dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate, in which (meth) acrylic acid and maleic anhydride are reacted with a copolymer of / benzyl (meth) acrylate / glycidyl (meth) acrylate. Resin obtained by reacting (meth) acrylic acid and maleic anhydride with a copolymer of glycidyl (meth) acrylate, and a copolymer of dicyclopentanyl (meth) acrylate / styrene / glycidyl (meth) acrylate (meth Resin which (meth) acrylic acid and maleic anhydride were made to react copolymer of dicyclopentanyl (meth) acrylate / methyl (meth) acrylate / glycidyl (meth) acrylate which made acrylic acid and maleic anhydride react Resin obtained by reacting (meth) acrylic acid and maleic anhydride with a copolymer of dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide / glycidyl (meth) acrylate;

Resin by which (meth) acrylic acid was reacted with the copolymer of dicyclopentanyl (meth) acrylate / 3,4-epoxycyclohexylmethylmethacrylate, benzyl (meth) acrylate / 3,4-epoxycyclohexylmethylmethacryl Resin in which (meth) acrylic acid was made to react with the copolymer of the rate, resin in which (meth) acrylic acid was made to react with the copolymer of cyclohexyl (meth) acrylate / 3,4-epoxycyclohexylmethylmethacrylate, styrene / 3, Resin which (meth) acrylic acid was made to react with the copolymer of 4-epoxycyclohexyl methyl methacrylate, and (meth) acrylic acid which was made to react with the copolymer of methyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate Resin and dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate / 3 which made (meth) acrylic acid react with the copolymer of resin and N-cyclohexyl maleimide / 3,4-epoxycyclohexylmethyl methacrylate ,4- Resin which (meth) acrylic acid was made to react with the copolymer of the epoxy cyclohexyl methyl methacrylate, and the air of dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate / 3,4-epoxycyclohexyl methyl methacrylate Resin which (meth) acrylic acid was made to react with copolymer, and copolymer of dicyclopentanyl (meth) acrylate / styrene / 3, 4- epoxycyclohexyl methyl methacrylate (meth) acrylic acid reacted, dicyclopentanyl ( Resin and dicyclopentanyl (meth) acrylate / N-cyclohexyl maleimide which (meth) acrylic acid was made to react the copolymer of meth) acrylate / methyl (meth) acrylate / 3,4-epoxycyclohexylmethylmethacrylate Resin which (meth) acrylic acid was made to react the copolymer of / 3, 4- epoxycyclohexyl methyl methacrylate;

Of a resin obtained by reacting crotonic acid to a copolymer of dicyclopentanyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate and benzyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate Resin which made crotonic acid react with the copolymer, the resin which made crotonic acid react with the copolymer of cyclohexyl (meth) acrylate / 3,4-epoxycyclohexylmethylmethacrylate, and styrene / 3,4-epoxycyclohexylmethyl Resin which made crotonic acid react with the copolymer of methacrylate, resin which made crotonic acid react with the copolymer of methyl crotonate / 3,4-epoxycyclohexylmethylmethacrylate, and N-cyclohexyl maleimide / 3,4 -A resin of dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate in which a crotonic acid is reacted with a copolymer of epoxycyclohexyl methyl methacrylate. Dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate resin which made crotonic acid react with the polymer, and the cyclocyclone Resin which made crotonic acid react with the copolymer of fentanyl (meth) acrylate / styrene / 3, 4- epoxycyclohexyl methyl methacrylate, dicyclopentanyl (meth) acrylate / methyl crotonate / 3, 4- epoxycyclo Crotonic acid was added to a resin obtained by reacting crotonic acid with a copolymer of hexylmethyl methacrylate and a copolymer of dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide / 3,4-epoxycyclohexylmethyl methacrylate. Reacted resin;

Of a resin obtained by reacting maleic acid with a copolymer of dicyclopentanyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate and benzyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate Resin which maleic acid was made to react with copolymer, resin which maleic acid was made to react with copolymer of cyclohexyl (meth) acrylate / 3,4-epoxycyclohexylmethylmethacrylate, and styrene / 3,4-epoxycyclohexylmethyl Resin obtained by reacting maleic acid with a copolymer of methacrylate, Resin obtained by reacting maleic acid with a copolymer of methyl maleate / 3,4-epoxycyclohexylmethylmethacrylate, N, cyclohexylmaleimide / 3,4 To a copolymer of dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate in which a maleic acid is reacted with a copolymer of epoxycyclohexyl methyl methacrylate. Male Resin and dicyclopentanyl (meth) which made maleic acid react with the copolymer of resin which made this reaction, the copolymer of dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate / 3, 4- epoxycyclohexyl methyl methacrylate Resin obtained by reacting maleic acid with a copolymer of acrylate / styrene / 3,4-epoxycyclohexylmethylmethacrylate, dicyclopentanyl (meth) acrylate / methyl maleate / 3,4-epoxycyclohexylmethylmethacryl Resin which maleic acid was made to react the copolymer of maleic acid with the copolymer of a rate, and the copolymer of dicyclopentanyl (meth) acrylate / N-cyclohexyl maleimide / 3,4-epoxycyclohexyl methyl methacrylate;

Resin, benzyl (meth) acrylate / 3,4-epoxycyclo, in which (meth) acrylic acid and maleic anhydride are reacted with a copolymer of dicyclopentanyl (meth) acrylate / 3,4-epoxycyclohexylmethylmethacrylate (Meth) acrylic acid and a copolymer of cyclohexyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate in which a (meth) acrylic acid and maleic anhydride were reacted with a copolymer of hexylmethyl methacrylate. Resin obtained by reacting maleic anhydride, a copolymer of styrene / 3,4-epoxycyclohexylmethyl methacrylate, a resin (meth) acrylic acid and maleic anhydride reacted, methyl (meth) acrylate / 3,4-epoxycyclo (Meth) acryl to a copolymer of N-cyclohexyl maleimide / 3,4-epoxycyclohexylmethyl methacrylate in which a (meth) acrylic acid and maleic anhydride are reacted with a copolymer of hexyl methyl methacrylate. (Meth) acrylic acid and maleic anhydride were added to a copolymer of resin and dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate reacted with lylic acid and maleic anhydride. Resin which reacted (meth) acrylic acid and maleic anhydride to the copolymer of resin which was made to react, dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate / 3, 4- epoxycyclohexyl methyl methacrylate, and dish A resin obtained by reacting (meth) acrylic acid and maleic anhydride with a copolymer of clofentanyl (meth) acrylate / styrene / 3,4-epoxycyclohexylmethylmethacrylate, dicyclopentanyl (meth) acrylate / (meth) Resin, dicyclopentanyl (meth) acrylate / N-cyclohex, in which (meth) acrylic acid and maleic anhydride were reacted with a copolymer of methyl acrylate / 3,4-epoxycyclohexylmethyl methacrylate Maleimide can be given a mid / 3,4-epoxycyclohexylmethyl methacrylate to a copolymer of acrylate (meth) acrylic resin is reacted with maleic anhydride and the like.

The weight average molecular weight of polystyrene conversion of resin (A) becomes like this. Preferably it is 3,000? 100,000, more preferably 5,000? 50,000. When the weight average molecular weight of resin (A) exists in the said range, there exists a tendency for the applicability | paintability of the photosensitive resin composition to become favorable, and the film | membrane reduction of the pixel part of the uncured coating film by the phenomenon at the time of forming a pattern is favorable. It does not occur, and there exists a tendency for the omission property of the non-pixel part of an uncured coating film at the time of image development (namely, solubility to a developing solution) to be favorable.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of resin (A) becomes like this. 6.0, more preferably 1.2? 4.0. When molecular weight distribution exists in the said range, it exists in the tendency which is excellent in developability.

The acid value of resin (A) is 20? 150 mg-KOH / g, preferably 40? 135 mg-KOH / g, more preferably 50? 135 mg-KOH / g. The acid value is a value measured as the amount (mg) of potassium hydroxide required for neutralizing 1 g of the resin (A), and can be obtained by titration using an aqueous potassium hydroxide solution.

The content of the resin (A) is preferably 5? To the total amount of the resin (A) and the polymerizable compound (B). 95 mass%, More preferably, it is 20? 80 mass%, Especially preferably, it is 40? 60 mass%. When content of resin (A) exists in said range, there exists a tendency for developability, adhesiveness, solvent resistance, and a mechanical characteristic to become favorable.

The photosensitive resin composition of this invention contains a polymeric compound (B).

The polymerizable compound (B) is a compound which can be polymerized by an active radical generated from the polymerization initiator (C), for example, a compound having a polymerizable carbon-carbon unsaturated double bond, or the like, and preferably (meth) acrylic acid ester The compound can be mentioned.

As a polymeric compound (b) which has one polymerizable carbon-carbon unsaturated double bond, the compound illustrated as said (a), (b) and (c) is mentioned, Especially, (meth) acrylic acid esters Is preferred.

As a polymeric compound (b) which has two polymerizable carbon-carbon unsaturated double bonds, 1, 3- butanediol di (meth) acrylate, 1, 3- butanediol (meth) acrylate, 1, 6- hexanediol di (Meth) 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 (meth) acrylate, 3-methylpentanediol di (meth) acrylate, etc. are mentioned.

Examples of the polymerizable compound (b) having three or more polymerizable carbon-carbon unsaturated double bonds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and tris (2-hydroxyethyl) iso. Cyanurate 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, tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, Tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, pentaerythritol tri (meth) acrylate and acid free Reactant of water, reactant of dipentaerythritol penta (meth) acrylate and acid anhydride, tripentaerythritolhepta (meth) acrylate and acid anhydride caprolactone modified trimethylolpropanetri (meth) acrylate, caprolactone modified penta Erythritol tri (meth) acrylate, caprolactone modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerytate Ritol penta (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, caprolactone modified tripentaerythritol tetra (meth) acrylate, caprolactone modified tripentaerythritol penta (meth) acrylate, Caprolactone modified tripentaerythritol hexa (meth) acrylate, caprolactone modified tripentaery Litholhepta (meth) acrylate, caprolactone modified tripentaerythritol octa (meth) acrylate, caprolactone modified pentaerythritol tri (meth) acrylate and a reaction product of an acid anhydride, caprolactone modified dipentaerythritol penta (meth The reactant of an acrylate and an acid anhydride, a caprolactone modified tripentaerythritol hepta (meth) acrylate, an acid anhydride, etc. are mentioned. Especially, a trifunctional or more than trifunctional monomer is preferable and dipentaerythritol hexa (meth) acrylate is more preferable.

The content of the polymerizable compound (B) is preferably 5? To the total amount of the resin (A) and the polymerizable compound (B). 95 mass%, More preferably, it is 20? 80 mass%. When content of a polymeric compound (B) exists in the said range, there exists a tendency for the sensitivity, the smoothness, the reliability, and mechanical strength of a hardened pattern to become favorable.

The photosensitive resin composition of this invention contains a polymerization initiator (C), and a polymerization initiator (C) contains the compound represented by Formula (1) (hereinafter may be called "compound (1)"). A polymerization initiator is a compound which starts superposition | polymerization by action of light or heat.

[Chemical Formula 5]

[In formula (1), R <^1> is C3? 8 cycloalkyl group is shown.

L ¹ has 1? The alkanediyl group of 5 is shown.

L ² represents a single bond or -CO-.

R ² represents a methyl group, a phenyl group or a benzyl group.

R ³ represents a phenylsulfanylphenyl group which may have a substituent or a carbazolyl group which may have a substituent;

Carbon number 3? As a cycloalkyl group of 8, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, etc. are mentioned. Especially, cyclopentyl group is preferable.

Carbon number 1? As an alkanediyl group of 5, a methylene group, an ethylene group, a propanediyl group, butanediyl group, a pentanediyl group, etc. are mentioned. Especially, methylene group and ethylene group are preferable.

As L ² , -CO- is preferable. When L <^2> is -CO-, there exists a tendency for the visible light transmittance of the coating film and pattern obtained to be high.

As compound (1), it is a formula (1-1)? The compound represented by Formula (1-3) is preferable. If it is these compounds, there exists a tendency for the visible light transmittance of the coating film and pattern obtained to become high.

[Formula 6]

The photosensitive resin composition of this invention is a polymerization initiator different from a compound (1) as a polymerization initiator (C) (henceforth "polymerization initiator (C0)" may be called.) It may contain. As a polymerization initiator (C0), if it is a compound which starts superposition | polymerization by action of light or a heat | fever, it will not specifically limit, A well-known polymerization initiator can be used.

As a polymerization initiator (C0), a biimidazole compound, an acetophenone compound, a triazine compound, an acylphosphine oxide compound, an oxime compound is mentioned, for example. Moreover, you may use the optical and / or thermal cationic polymerization initiator (for example, what consists of onium cation and an anion derived from Lewis acid) of Unexamined-Japanese-Patent No. 2008-181087. Especially, it is preferable that it is at least 1 sort (s) chosen from the group which consists of a biimidazole compound, an acetophenone compound, and an oxime compound, and it is especially preferable that it is a biimidazole compound. Since a polymerization initiator (C0) uses the said compound with compound (1), it exists in the tendency to become high sensitivity, and is preferable.

As said biimidazole compound, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl biimidazole, 2,2'-bis (2,3-dichloro Phenyl) -4,4 ', 5,5'-tetraphenylbiimidazole (see, for example, JP-A-6-75372, JP-A-6-75373, etc.), 2,2' -Bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra ( Alkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chloro Phenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole (see, for example, Japanese Patent Application Laid-Open No. 48-38403, Japanese Laid-Open Patent Publication No. 62-174204, etc.), 4 And imidazole compounds in which the phenyl group at the 4′5,5′-position is substituted with a carboalkoxy group (see, for example, JP-A-7-10913). Preferably 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4 ＇, 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole.

 As said acetophenone compound, diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2-hydroxy-1- [4- (2-hydroxy Ethoxy) phenyl] -2-methylpropan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2- Methyl-propane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino -1- (4-morpholinophenyl) butan-1-one, 2- (2-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (3-methyl Benzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (2-ethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (2-propylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) buta Paddy, 2- (2-butylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (2,3-dimethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (2,4-dimethylbenzyl) -2-dimethylamino-1- (4- Morpholinophenyl) butanone, 2- (2-chlorobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (2-bromobenzyl) -2-dimethylamino- 1- (4-morpholinophenyl) butanone, 2- (3-chlorobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (4-chlorobenzyl) -2 -Dimethylamino-1- (4-morpholinophenyl) butanone, 2- (3-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (4- Bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (2-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone , 2- (3-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (4-methoxybenzyl) -2-dimethylamino-1- (4-mor Polynophenyl) butanone, 2- (2-methyl-4-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (2-methyl-4- Lomobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (2-bromo-4-methoxybenzyl) -2-dimethylamino-1- (4-morpholino And oligomers of phenyl) butanone and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one.

As said triazine compound, 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1, 3, 5- triazine, 2, 4-bis (trichloromethyl) -6 -(4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (Trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2- Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl ) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like.

2,4,6-trimethylbenzoyldiphenylphosphine oxide etc. are mentioned as said acylphosphine oxide compound.

Examples of the oxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-ethoxycarbonyloxy-1-phenylpropan-1-one-2 -Imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H -Carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-dioxacyclopentanyl Methyloxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine and the like. You may use commercial items, such as Irgacure OXE-01, OXE-02 (above, Chiba Japan Corporation), and N-1919 (made by ADEKA Corporation).

Moreover, as a polymerization initiator (C0), Benzoin compounds, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; Benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone Benzophenone compounds such as 2,4,6-trimethylbenzophenone; Quinone compounds, such as 9,10- phenanthrene quinone, 2-ethyl anthraquinone, and camphor quinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compound, etc. are mentioned. It is preferable to use these in combination with the polymerization start adjuvant (C1) mentioned later.

Moreover, as a polymerization initiator (C0), you may use the polymerization initiator which has group which can cause chain transfer as described in Unexamined-Japanese-Patent No. 2002-544205. As a polymerization initiator which has group which can cause said chain transfer, it is following formula (a)? The compound of (f) is mentioned.

[Formula 7]

The polymerization initiator which has group which can cause said chain transfer can be used also as a component (c) which comprises resin (A).

In the photosensitive resin composition of this invention, a polymerization start adjuvant (C1) can be used with the polymerization initiator (C) mentioned above.

As a polymerization start adjuvant (C1), the compound represented by Formula (III) is mentioned, for example.

[Formula 8]

[In the formula (III), the dotted line represented by W ¹ has 6 to 6 carbon atoms which may be substituted with a halogen atom. 12 aromatic rings.

Y ¹ represents -O- or -S-.

R ⁴ has 1? 6 monovalent saturated hydrocarbon group is shown.

R ⁵ may be substituted with a halogen atom. C 6? Which may be substituted with a saturated hydrocarbon group of 12 or a halogen atom? 12 represents an aryl group]

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, etc. are mentioned. 6 carbon atoms? As an aromatic ring of 12, a benzene ring, a naphthalene ring, etc. are mentioned.

Carbon number which may be substituted by halogen atom; Examples of the 12 aromatic ring include a benzene ring, a methylbenzene ring, a dimethylbenzene ring, an ethylbenzene ring, a propylbenzene ring, a butylbenzene ring, a pentylbenzene ring, a hexylbenzene ring, a cyclohexylbenzene ring, and a chlorobenzene ring. , Dichlorobenzene ring, bromobenzene ring, dibromobenzene ring, phenylbenzene ring, chlorophenylbenzene ring, bromophenylbenzene ring, naphthalene ring, chloronaphthalene ring, bromonaphthalene ring and the like.

Carbon number 1? As a saturated hydrocarbon group of 6, a methyl group, an 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-hexyl group, cyclohex Practical skills etc. are mentioned.

Carbon number which may be substituted by halogen atom; As a saturated hydrocarbon group of 12, it is the said C1-C, for example. In addition to the saturated hydrocarbon group of 6, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, 1-chlorobutyl group, 2-chlorobutyl group, 3-chlorobutyl group, etc. are mentioned.

Carbon number which may be substituted by halogen atom; As the aryl group of 12, a phenyl group, a chlorophenyl group, a dichlorophenyl group, a bromophenyl group, a dibromophenyl group, a chlorobromo phenyl group, a biphenyl group, a chlorobiphenyl group, a dichlorobiphenyl group, a bromophenyl group, a dibromophenyl group, a naphthyl group And chloronaphthyl group, dichloronaphthyl group, bromonaphthyl group, dibromonaphthyl group and the like.

Specifically as a compound represented by Formula (III),

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-chlorobenzo Thiazolin, 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-bromobenzo Thiazolin, 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-methylnaph To [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-methylbenzooxazoline, 2- [2-oxo-2- ( 1-naphthyl) ethyl ] -3-methylbenzooxazoline, 2- [2-oxo-2- (2-naphthyl) ethylidene] -3-methyl-5-phenylbenzooxazoline, 2- [2-oxo-2- (1 -Naphthyl) ethylidene] -3-methyl-5-phenylbenzooxazoline, 2- [2-oxo-2- (2-naphthyl) ethylidene] -3-methyl-5-fluorobenzooxazoline, 2- [2-oxo-2- (1-naphthyl) ethylidene] -3-methyl-5-fluorobenzooxazoline, 2- [2-oxo-2- (2-naphthyl) ethylidene]- 3-methyl-5-chlorobenzooxazoline, 2- [2-oxo-2- (1-naphthyl) ethylidene] -3-methyl-5-chlorobenzooxazoline, 2- [2-oxo-2- (2-naphthyl) ethylidene] -3-methyl-5-bromobenzooxazoline, 2- [2-oxo-2- (1-naphthyl) ethylidene] -3-methyl-5-bromobenzo Oxazoline, 2- [2-oxo-2- (4-phenylphenyl) ethylidene] -3-methylbenzooxazoline, 2- [2-oxo-2- (4-phenylphenyl) ethylidene] -3- Methyl-5-phenylbenzooxazoline, 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-jade -2- (4-phenylphenyl) ethylidene] -3-methylnaphtho [2,1-d] oxazoline, 2- [2-oxo-2- (4-phenylphenyl) ethylidene] -3-methyl Naphtho [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 etc. are mentioned.

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

[Formula 9]

[In Formula (IV) And (V), Ring W ² , Ring W ³ And Ring W ⁴ Are independently of each other the carbon number which may be substituted by halogen atom? 12 aromatic rings or 2? 10 heterocyclic rings are shown. Y ² ? Y ⁵ independently of one another represents —O— or —S—. R ⁶ ? R ⁹ has 1? 12 monovalent saturated hydrocarbon groups or carbon atoms? The aryl group of 12 is represented, and the hydrogen atom contained in this saturated hydrocarbon group and this aryl group is a halogen atom, a hydroxyl group, or a C1-C? May be substituted with 6 alkoxy groups]

As an aromatic ring, the aromatic ring similar to what was illustrated by Formula (III) is mentioned, The hydrogen atom contained in the aromatic ring may be substituted by the halogen atom illustrated above.

As a hetero ring which may be substituted by the halogen atom, a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, a pyran ring, etc. are mentioned.

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 hydroxy naphthyl group.

Examples of the monovalent alkoxy group substituted saturated hydrocarbon group include methoxymethyl group, methoxyethyl group, methoxypropyl group, methoxybutyl group, butoxymethyl group, ethoxyethyl group, ethoxypropyl group, propoxybutyl group and the like. .

As an alkoxy group substituted aryl group, a methoxyphenyl group, an ethoxy naphthyl group, etc. are mentioned.

As a compound represented by Formula (IV) and Formula (V), specifically,

Dialkoxy naphthalenes such as dimethoxynaphthalene, diethoxynaphthalene, dipropoxynaphthalene, diisopropoxynaphthalene and dibutoxynaphthalene;

9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, dipropoxycanthracene, diisopropoxycanthracene , Dibutoxy anthracene, dipentyloxy anthracene, dihexyloxy anthracene, methoxy ethoxy anthracene, methoxy propoxy thracene, methoxy isopropoxy canthracene, methoxy butoxy anthracene, ethoxy propoxy thracene, ethoxy isopro Dialkoxy anthracenes such as oxycanthracene, ethoxy butoxy anthracene, propoxy isopropoxy anthracene, propoxy butoxy anthracene and isopropoxy butoxy anthracene;

Dialkoxy naphthacenes such as dimethoxynaphthacene, diethoxynaphthacene, dipropoxynaphthacene, diisopropoxynaphthacene and dibutoxynaphthacene; Etc. can be mentioned.

Moreover, a thioxanthone compound can also be used as a polymerization start adjuvant (C1). As a thioxanthone compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-4 -Propoxy thioxanthone, etc. are mentioned.

Moreover, an amine compound, a carboxylic acid compound, etc. are mentioned as a polymerization start adjuvant (C1).

Examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 4-dimethylaminobenzoic acid. 2-ethylhexyl, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (collectively; Michler's ketone), 4,4'-bis (diethylamino Aromatic amine compounds, such as) benzophenone, are mentioned.

Examples of the carboxylic acid compound include phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, And aromatic heteroacetic acids such as chlorophenylsulfanyl acetic acid, dichlorophenylsulfanyl acetic acid, N-phenylglycine, phenoxy acetic acid, naphthylthioacetic acid, N-naphthylglycine and naphthoxy acetic acid.

The content of the compound (1) is preferably 30? To the total amount of the polymerization initiator (C). 100 mass%, More preferably, it is 50? 100 mass%. If content of a compound (1) exists in said range, a pattern can be obtained with high sensitivity.

The content of the polymerization initiator (C) is preferably 0.5? To 100 parts by mass of the content of the resin (A) and the polymerizable compound (B). 30 parts by mass, more preferably 1? It is 20 mass parts, More preferably, it is 1? 10 parts by mass. When content of a polymerization initiator (C) exists in the said range, a pattern can be obtained with high sensitivity and there exists a tendency for the visible light transmittance of the pattern obtained to be high.

The content of the polymerization start aid (C1) is preferably 0? To 100 parts by mass of the content of the resin (A) and the polymerizable compound (B). 10 parts by mass, more preferably 0? 7 parts by mass. When the quantity of a polymerization start adjuvant (C1) exists in said range, a pattern can be obtained with high sensitivity, and the pattern obtained has favorable shape.

The photosensitive resin composition of this 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 a molecule and no -O-), an ether solvent (-O- in a molecule, and -COO). Solvent without-), ether ester solvent (solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- in the molecule and no -COO-), alcohol It can be used, selecting from a solvent, an aromatic hydrocarbon solvent, an amide solvent, and dimethyl sulfoxide.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate and ethyl butyrate Butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, γ-butyrolactone, and the like.

As an ether solvent, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran , 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phentol, methyl an Or a brush.

As an ether ester solvent, methyl methoxy acetate, ethyl methoxy acetate, methoxy acetate, methyl ethoxy acetate, ethyl ethoxy acetate, 3-methoxy propionate, ethyl 3-methoxy propionate, 3-ethoxy propionic acid Methyl, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-methoxy-2 -Methyl methyl propionate, 2-ethoxy-2-methyl ethyl propionate, 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 , Di, and the like ethylene glycol monobutyl ether acetate.

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

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

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

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

These solvents may be used independently or may be used in combination of 2 or more type.

Among the above solvents, an organic solvent having a boiling point of 120 ° C. or higher and 180 ° C. or lower at 1 atm is preferable from the viewpoint of applicability and drying properties. Especially, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol methyl ethyl ether, 3-ethoxy propionate, 3-methoxy butyl acetate, 3-methoxy-1- butanol, etc. are preferable.

Content of the solvent (D) in the photosensitive resin composition becomes like this. 95 mass%, More preferably, it is 70? 90 mass%. In other words, the solid content of the photosensitive resin composition becomes like this. 40 mass%, More preferably, it is 10? 30 mass%. Here, solid content means the quantity remove | excluding the solvent (D) from the photosensitive resin composition. When content of a solvent (D) exists in the said range, there exists a tendency for the flatness of the film | membrane which applied the photosensitive resin composition to be high.

Moreover, the photosensitive resin composition of this invention may contain the polyfunctional thiol compound (T) further. A polyfunctional thiol compound (T) means the compound which has 2 or more sulfanyl group (-SH) in a molecule | numerator. In particular, when the compound which has 2 or more of sulfanyl groups couple | bonded with the carbon atom derived from an aliphatic hydrocarbon group, there exists a tendency for the sensitivity of the photosensitive resin composition of this invention to become high.

Specific examples of the polyfunctional thiol compound (T) include hexanedithiol, decandithiol, 1,4-bis (methylsulfanyl) benzene, butanediolbis (3-sulfanylpropionate) and butanediolbis (3-sulfur). Panyl acetate), ethylene glycol bis (3-sulfanyl acetate), trimethylol propane tris (3-sulfanyl acetate), butanediol bis (3-sulfanyl propionate), trimethylol propane tris (3-sulfanyl propio) Nate), trimethylol propane tris (3-sulfanyl acetate), pentaerythritol tetrakis (3-sulfanyl propionate), pentaerythritol tetrakis (3-sulfanyl acetate), trishydroxyethyl tris (3 Sulfanyl propionate), pentaerythritol tetrakis (3-sulfanylbutylate), 1,4-bis (3-sulfanylbutyloxy) butane and the like.

The content of the polyfunctional thiol compound (T) is preferably 0.1? To 100 parts by mass of the polymerization initiator (C). 10 parts by mass, more preferably 0.5? 7 parts by mass. When content of a polyfunctional thiol compound (T) exists in the said range, since the sensitivity of the photosensitive resin composition becomes high and developability at the time of forming a pattern becomes favorable, it is preferable.

It is preferable that the photosensitive resin composition of this invention contains surfactant (E). As surfactant, silicone type surfactant, a fluorochemical surfactant, silicone type surfactant which has a fluorine atom, etc. are mentioned, for example.

As silicone type surfactant, surfactant which has a siloxane bond is mentioned.

Specifically, Toray silicone DC3PA, copper SH7PA, copper DC11PA, copper SH21PA, copper SH28PA, copper SH29PA, copper 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 (Momental Performance Materials Japan) Joint company manufacture) etc. are mentioned.

As a fluorine type surfactant, surfactant which has a fluorocarbon chain | strand is mentioned.

Specifically, Fluorine Nut (registered trademark) FC430, Copper FC431 (manufactured by Sumitomo 3M Co., Ltd.), Mega Fox (registered trademark) F142D, Copper F171, Copper F172, Copper F173, Copper F177, Copper F183, Copper R30 ( DIC Co., Ltd.), F-Top (registered trademark) EF301, copper EF303, copper EF351, copper EF352 (manufactured by Mitsubishi Material Electronics Hwaseong Co., Ltd.), Sufron (trademark) S381, copper S382, copper SC101, copper SC105 (made by Asahi Glass Co., Ltd.), E5844 (made by Daikin Fine Chemical Research Institute), etc. are mentioned.

As silicone type surfactant which has a fluorine atom, surfactant which has a siloxane bond and a fluorocarbon chain | strand is mentioned. Specifically, Mega Fox R08, BL20, F475, F477, F443 (manufactured by DIC Corporation), and the like can be given. Preferably, megafax (trademark) F475 is mentioned.

Content of surfactant (E) is 0.001 mass% or more and 0.2 mass% or less with respect to the photosensitive resin composition, Preferably they are 0.002 mass% or more and 0.1 mass% or less, More preferably, they are 0.01 mass% or more and 0.05 mass% or less. . By containing surfactant in said range, flatness of a coating film can be made favorable.

The photosensitive resin composition of this invention may contain various additives, such as a filler, another high molecular compound, an adhesion promoter, antioxidant, a ultraviolet absorber, a light stabilizer, a chain transfer agent, as needed.

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

The photosensitive resin composition of this invention is filled into the quartz cell whose optical path length is 1 cm, and uses a spectrophotometer, and measures wavelength 400? The average transmittance when the transmittance is measured under the conditions of 700 nm is preferably 70% or more, and more preferably 80% or more.

When the photosensitive resin composition of this invention is used as a coating film, the average transmittance of a coating film becomes like this. Preferably it is 90% or more, and it is more preferable to become 95% or more. This average transmittance | permeability measures the wavelength 400-degree using a spectrophotometer with respect to the coating film whose thickness after heat-hardening (for example, 100-250 degreeC, 5 minutes-3 hours) is 3 micrometers. It is the average value when it measures on conditions of 700 nm. Thereby, the coating film excellent in transparency in visible region can be provided.

In the coating film manufactured from the resin composition which does not contain the conventionally known coloring agent, the transmittance | permeability in 400 nm vicinity of measurement wavelength falls, and it is colored in yellow or brown in many cases. However, the photosensitive resin composition of this invention can provide the coating film and pattern which show high transmittance | permeability in the whole visible region (400-700 nm).

The photosensitive resin composition of this invention can form a coating film by apply | coating on these board | substrates which formed board | substrates, such as a glass, a metal, a plastic, a color filter, various insulation or an electrically conductive film, a drive circuit, etc., for example. It is preferable that a coating film dried and hardened | cured. After coating on the substrate, it can be patterned into a desired shape to form a pattern.

First, the photosensitive resin composition of this invention is apply | coated on a board | substrate.

Application | coating can be performed using various coating apparatuses, such as a spin coater, a slit & spin coater, a slit coater, an inkjet, a roll coater, and a dip coater.

Next, it is preferable to dry or prebak, to remove volatile components, such as a solvent, and to dry. Thereby, a smooth uncured coating film can be obtained.

The film thickness of the coating film in this case is not specifically limited, It can adjust suitably according to the material to be used, a use, etc., for example, 1? About 6 micrometers is illustrated.

In addition, light, for example, mercury lamp, ultraviolet rays generated from a light emitting diode, or the like is irradiated to the obtained uncured coating film through a photo mask for forming a target pattern. The shape of the photomask at this time is not specifically limited, What is necessary is just to select a shape and a size according to a use of a pattern.

In recent exposure machines, the light of 350 nm or less is cut using the filter which cuts this wavelength range, or the bandpass filter which extracts the light area of about 436 nm, 408 nm, and 365 nm vicinity is used for this wavelength range. Can be taken out selectively, and the parallel light beam can be irradiated uniformly to the entire exposure surface. At this time, in order to perform accurate alignment of a mask and a base material, you may use apparatuses, such as a mask aligner and a stepper.

The target pattern shape can be obtained by making the coating film after exposure contact with a developing solution, melt | dissolving and developing a predetermined part, for example, a non-exposed part (namely, a non-pixel part).

The developing method may be any of liquid mounting, dipping and spraying. In addition, during development, the substrate may be tilted at any angle.

As for the developing solution used for image development, the aqueous solution of a basic compound is preferable.

The basic compound may be either an inorganic or organic basic compound.

Specific examples of the inorganic basic compound include sodium hydroxide, potassium hydroxide, sodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, and carbonic acid. Potassium, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium borate, potassium borate, ammonia, etc. are mentioned.

As an organic basic compound, For example, tetramethylammonium hydroxide, 2-hydroxyethyl trimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, Monoisopropylamine, diisopropylamine, ethanolamine and the like.

The concentration in the aqueous solution of these inorganic and organic basic compounds becomes like this. 10 mass%, More preferably, it is 0.03? 5 mass%.

The developing solution may contain a surfactant.

The surfactant may be any of nonionic surfactants, anionic surfactants, or cationic surfactants.

As nonionic surfactant, For example, polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivative, oxyethylene / oxypropylene block copolymer, sorbitan fatty acid ester, Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine and the like.

Examples of the anionic surfactants include higher alcohol sulfate ester salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, and sodium dodecylbenzene sulfonate. And alkyl aryl sulfonates such as sodium dodecyl naphthalene sulfonate.

As cationic surfactant, amine salt, quaternary ammonium salt, etc., such as stearylamine hydrochloride and lauryl trimethylammonium chloride, etc. are mentioned, for example.

The concentration of the surfactant in the alkaline developer is preferably 0.01? 10 mass%, More preferably, it is 0.05? 8 mass%, More preferably, it is 0.1? 5 mass%.

After image development, a pattern can be obtained by performing water washing. In addition, you may post-bake as needed. Post-baking, for example, 150? Temperature range of 240 ℃, 10? 180 minutes is preferred.

When exposing an uncured coating film, the coating film which does not have a pattern can be obtained by performing light irradiation to the whole surface, and / or omitting image development, without using the photomask in which the pattern was formed.

Thus, the pattern obtained from the photosensitive resin composition of this invention is a photo spacer which comprises a part of color filter board | substrate and / or an array board | substrate, a patternable overcoat, an interlayer insulation film, the processus | protrusion for liquid crystal orientation control, a micro lens, a film | membrane, for example. It is useful as a member for touch panels, such as a coating layer for thickness adjustment, and the coating film which does not have the pattern obtained by the above is useful as an overcoat which comprises a part of color filter substrate and / or an array substrate. Said color filter substrate and an array substrate are used suitably for a liquid crystal display device, an organic electroluminescence display, an electronic paper, etc.

Example

Hereinafter, an Example demonstrates this invention in more detail. "%" And "part" in an example are the mass% and a mass part, unless there is particular notice.

Synthesis Example 1

Into a flask equipped with a reflux cooler, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to a nitrogen atmosphere, 200 parts by mass of 3-methoxy-1-butanol and 105 parts by mass of 3-methoxybutyl acetate were added thereto, and stirred. Heated to 70 ° C. Subsequently, 60 mass parts of methacrylic acid, the molar ratio of 3, 4- epoxy cyclocyclo [5.2.1.0 ^2.6 ] decyl acrylate (compound represented by Formula (I-1) and a compound represented by Formula (II-1), 50: A mixture of 50) 240 parts by mass was dissolved in 140 parts by mass of 3-methoxybutyl acetate to prepare a solution, and the solution was added dropwise into a flask kept at 70 ° C. over 4 hours using a dropping funnel. On the other hand, the solution which melt | dissolved 30 mass parts of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 225 mass parts of 3-methoxybutyl acetates was dripped in the flask over 4 hours using another dropping funnel. It was. After completion of the dropwise addition of the solution of the polymerization initiator, the mixture was kept at 70 ° C for 4 hours, and then cooled to room temperature, followed by copolymerization of a solid content of 32.6 mass% and an acid value of 110 mg-KOH / g (solid content conversion) (resin Aa). A solution of was obtained. The weight average molecular weight Mw of obtained resin Aa was 13,400, and molecular weight distribution (Mw / Mn) was 2.50.

[Formula 10]

Synthesis Example 2

Into a flask equipped with a reflux cooler, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to a nitrogen atmosphere, 200 parts by mass of 3-methoxy-1-butanol and 105 parts by mass of 3-methoxybutyl acetate were added thereto, and stirred. Heated to 70 ° C. Next, 55 parts by mass of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (compound represented by formula (I-1) and compound represented by formula (II-1) in a molar ratio of 50: Mixed with 50) 175 parts by mass and 70 parts by mass of N-cyclohexylmaleimide are dissolved in 140 parts by mass of 3-methoxybutyl acetate to prepare a solution, and the solution is dropped over 4 hours using a dropping pump. It dripped in the flask kept warm at ° C. On the other hand, the solution which melt | dissolved 30 mass parts of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 225 mass parts of 3-methoxybutyl acetates was dripped in the flask over 5 hours using another dropping pump. It was. After completion of the dropwise addition of the solution of the polymerization initiator, the mixture was kept at 70 ° C for 4 hours, and then cooled to room temperature, followed by viscosity (23 ° C) 114 mPa · s, solid content 32.6 mass%, acid value 34.3 mg-KOH / g A solution of a copolymer (resin Ab) of (acid value 105.2 mg-KOH / g in terms of solid content) was obtained. The weight average molecular weight Mw of obtained resin Ab was 13,600, and molecular weight distribution (Mw / Mn) was 2.54. In addition, the viscosity of the copolymer solution was measured with the Brookfield viscometer.

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

Device ; K2479 (manufactured by Shimadzu Corporation)

column ; SHIMADZU Shim-pack GPC-80M

Column temperature; 40 ℃

Solvent; THF (tetrahydrofuran)

Flow rate; 1.0 ml / min

Detector; RI

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

(Examples 1-4 and Comparative Example 1)

<Preparation of the photosensitive resin composition>

The components of Table 1 were mixed, respectively, and the photosensitive resin composition was obtained.

In Table 1, each component is as follows.

Resin (A); Resin Aa obtained in Synthesis Example 1. The number of copies in Table 1 shows the mass part of solid content conversion.

Polymeric compound (B); Dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)

Compound (1); 1? 1; Compound represented by formula (1-1) (TR-PBG-304; manufactured by Joshu Strong Electronic Materials, Inc.)

Compound (1); 1 to 2; Compound represented by formula (1 ~ 3) (TR-PBG-305; manufactured by Joshu Strong Electronic Materials, Inc.)

Compound (1); 1 to 3; Compound represented by formula (1-2) (TR-PBG-309; manufactured by Joshu Strong Electronic Materials, Inc.)

Polymerization initiator (C0); N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethane-1-imine (IRGACURE OXE 02; manufactured by BASF Japan)

Solvent (D); (Da); 3-methoxy-1-butanol

Solvent (D); (Db); Propylene Glycol Monomethyl Ether Acetate

Solvent (D); (Dc); Ethyl 3-ethoxypropionate

Solvent (D); (Dd); 3-methoxybutyl acetate

The solvent (D) is mixed so that the solid content of the photosensitive resin composition becomes "solid content (%)" of Table 1, and the solvent component (Da) in a solvent (D)? The value of (Dd) shows the mass ratio in a solvent (D).

[Formula 11]

<Average transmittance of the composition>

About the obtained photosensitive resin composition, it was 400? Using an ultraviolet-visible near-infrared spectrophotometer (V-650; Nippon Spectroscopy Co., Ltd. product) (quartz cell, optical path length; 1 cm), respectively. The average transmittance (%) at 700 nm was measured. The results are shown in Table 2.

<Formation of Coating Film>

A 2-inch square glass substrate (Eagle XG; manufactured by Corning) was washed sequentially with a neutral detergent, water, and alcohol, and then dried. On this glass substrate, the photosensitive resin composition obtained above was spin-coated so that the film thickness after postbaking might be set to 3.0 micrometers, and then prebaked for 3 minutes at 90 degreeC in a clean oven. Then, it heated at 230 degreeC for 20 minutes, and obtained the coating film.

<Transmittance of Coating Film>

About the obtained coating film, the transmittance | permeability (%) in 400 nm and 400? Using a microscopic spectrophotometer (OSP-SP200; manufactured by OLYMPUS). The average transmittance (%) at 700 nm was measured. Higher transmittance at 400 nm indicates less yellow coloring. Moreover, when the transmittance | permeability of a coating film is high, the pattern formed as follows also has a high transmittance | permeability. The results are shown in Table 2.

<Formation of Pattern>

A glass substrate 2 inches wide (Eagle XG; manufactured by Corning) was washed sequentially with a neutral detergent, water, and alcohol, and then dried. On this glass substrate, the photosensitive resin composition was spin-coated so that the film thickness after postbaking might be set to 3.0 micrometers, and it prebaked for 2 minutes at 80 degreeC with a hotplate, and dried. After cooling, the gap between the substrate coated with the photosensitive resin composition and the quartz glass photomask was set to 200 µm, and the exposure dose was measured under an atmospheric atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd. Light of 60 mJ / cm 2 (365 nm) was irradiated. In addition, irradiation with respect to the photosensitive resin composition at this time was performed through the optical filter (UV-33; Asahi Spectrum Co., Ltd. make) the emission light from an ultrahigh pressure mercury lamp. As a photomask, a photomask was used in which a pattern (a square light-transmitting portion of one side was 13 μm, and the interval of the square was 100 μm) (that is, a light-transmitting portion) was formed on the same plane.

After light irradiation, the coating film was immersed and stirred for 25 seconds at 25 ° C. for 60 seconds in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide. Was carried out to form a pattern. It was set as (circle) when a pattern remained without peeling. The results are shown in Table 2.

Since the coating film and pattern obtained from the photosensitive resin composition of this invention show the above results, the display apparatus is manufactured by manufacturing a display apparatus using the coating film and / or pattern formed from the photosensitive resin composition of this invention. It is possible to improve the display characteristics.

(Examples 5-8)

<Preparation of the photosensitive resin composition>

Each component of Table 3 is mixed and a photosensitive resin composition is obtained. In addition, each component of Table 3 is a component similar to Table 1.

<Formation of pattern>

Example 5 In the photosensitive resin composition of 8, operation similar to Example 1 is performed and the coating film and pattern with high transmittance | permeability in 400 nm are obtained.

The photosensitive resin composition of this invention has high visible light transmittance of the coating film and pattern obtained.

Claims (7)

Resin (A), a polymeric compound (B), a polymerization initiator (C), and a solvent (D) are contained, and a polymerization initiator (C) is a formula (1):
[Formula 1]

[In formula (1), R <^1> is C3? 8 cycloalkyl group;
L ¹ has 1? 5 represents an alkanediyl group;
L ² represents a single bond or -CO-;
R ² represents a methyl group, a phenyl group or a benzyl group;
R ³ represents a phenylsulfanylphenyl group which may have a substituent or a carbazolyl group which may have a substituent;
The photosensitive resin composition which is a polymerization initiator containing the compound shown by. The method of claim 1,
Photosensitive resin composition whose L <^2> in Formula (1) shows -CO-. The method according to claim 1 or 2,
Content of the compound represented by Formula (1) is 30? With respect to the total amount of the polymerization initiator (C). The photosensitive resin composition which is 100 mass%. The method of claim 1,
Resin (A) has 2 carbon atoms? The photosensitive resin composition which is resin containing the structural unit derived from the monomer which has a cyclic ether structure of 4 and a carbon-carbon unsaturated double bond. The coating film obtained by the photosensitive resin composition of Claim 1. The pattern obtained by the photosensitive resin composition of Claim 1. The display device containing at least 1 sort (s) chosen from the group which consists of a coating film of Claim 5, and the pattern of Claim 6.