KR20100081931A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE: A photorsensitive resin composition, a coating film, and a pattern formed using the same, and a display device including the pattern are provided to form an uniform coating film of high quality by controlling defects and stains which are generated due to a bumping solvent. CONSTITUTION: A photosensitive resin composition contains a resin, a polymerizable monomer, a polymerization initiator, a solvent, and a surfactant. The solvent contains two or more kinds of solvent having a boiling point of 175 °C or less. The content of the surfactant is 0.0025-0.0250 weight% based on 100.0 weight% of the photosensitive resin composition excluding the surfactant. The content of a solid component is 10-30 weight%.

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, substrate size has been enlarged, and in order to form a transparent film or a pattern such as a coating layer on a substrate surface, a photosensitive resin composition is formed by spin coating, slit & spin, or the like. It is.

On the other hand, from the viewpoint of productivity improvement, response to a large screen, and the like, a method of forming a high quality uniform coating film while saving the photosensitive resin composition solution has been studied.

Against this background, the selection of solvent types has been sought to form a coating film of excellent quality. For example, when a low boiling point solvent is used, drying of a coating film is performed quickly, but on the other hand, it may cause the dolby of the micro bubble contained in the composition for coating film formation at the time of evaporation of a solvent. Such dolby appears in the surface of a coating film, and brings about crater-shaped defects.

Therefore, a high boiling point solvent has been used conventionally as a solvent. For example, the photosensitive resin composition containing high boiling point solvents, such as diethylene glycol ethyl methyl ether (boiling point 176 degreeC) and benzyl alcohol (boiling point 205 degreeC), is proposed (for example, patent document 1).

Patent document 1: Paragraph 46 of Unexamined-Japanese-Patent No. 2007-25645, Table 1

However, even if the photosensitive resin composition using the high boiling point solvent mentioned above is applied to the slit die coating method etc. which are typical coating methods, the high quality coating film which does not necessarily produce cloudy spots, a defect, etc. may not be obtained.

An object of this invention is to provide the photosensitive resin composition which can generate | occur | produce generation | occurrence | production of the defect, cloudy stains, etc. resulting from the dolby of a solvent, and can form a uniform and high quality coating film over the whole coating film.

That is, this invention provides the following [1]-[8].

[One]. As a photosensitive resin composition containing resin (A), a polymerizable monomer (B), a polymerization initiator (C), a solvent (D), and surfactant (E),

A solvent (D) is a solvent containing two or more types of solvents whose boiling point is 175 degreeC or less,

Content of surfactant (E) is 0.0025-0.0250 weight% with respect to 100 weight% of photosensitive resin compositions except surfactant,

The photosensitive resin composition whose solid amount is 10-30 weight%.

[2]. The photosensitive resin composition as described in [1] whose solvent (D) is a solvent which contains two or more types of solvents with a boiling point of 140 degreeC or more and 175 degrees C or less.

[3]. The photosensitive resin composition as described in [1] or [2] whose solvent (D) is a solvent containing a C1-C6 alcohol.

[4]. The photosensitive resin composition in any one of [1]-[3] whose solvent (D) is a solvent containing 3-methoxybutanol.

[5]. The photosensitive resin composition in any one of [1]-[4] whose surfactant (E) is at least 1 sort (s) chosen from the group which consists of a silicone type surfactant, a fluorine type surfactant, and a silicone type surfactant which has a fluorine atom.

[6]. Coating film formed using the photosensitive resin composition in any one of [1]-[5].

[7]. The pattern formed using the photosensitive resin composition in any one of [1]-[5].

[8]. The display apparatus containing the coating film as described in [6], and / or the pattern as described in [7].

This invention can provide the photosensitive resin composition which can generate | occur | produce the defects, cloudy stains, etc. which originate in the dolby of a solvent, and can form a uniform and high quality coating film over the whole coating film.

The photosensitive resin composition of this invention mainly contains resin (A), a polymerizable monomer (B), a polymerization initiator (C), a solvent (D), and surfactant (E).

Resin (A) used for the photosensitive resin composition of this invention is not specifically limited, It is preferable that it is alkali-soluble (A1), and (A2) which shows the reactivity by the action of at least one of light and heat is more preferable. desirable.

As resin (A1), at least 1 sort (Aa) (Hereinafter, it may be called "(Aa)") chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride, and the monomer copolymerizable with (Aa) Copolymers of (Ab) (except (Aa)) (hereinafter may be referred to as "(Ab)") are exemplified.

As (A-a), an aliphatic unsaturated carboxylic acid and / or aliphatic unsaturated carboxylic anhydride etc. are mentioned, for example, Specifically,

Unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid;

Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; And anhydrides of these unsaturated dicarboxylic acids;

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;

-(히드록시메틸)아크릴산 등의, 동일 분자 중에 히드록시기 및 카르복실기를 함유하는 불포화 아크릴레이트류 등을 들 수 있다.

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

Especially, acrylic acid, methacrylic acid, maleic anhydride, etc. are preferable at the point of copolymerization reactivity and alkali solubility.

You may use these individually or in combination of 2 or more types. In addition, in this specification, unless otherwise indicated, the illustrated compound, component, agent, etc. can be used individually or in combination of 2 or more types.

In addition, 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.

As (A-b),

(Meth) acrylic acid alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate and tert-butyl (meth) acrylate;

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

Cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl acrylate (also known in the art as dicyclopentanyl acrylate), dicyclopenta Acrylic acid cyclic alkyl esters such as oxyethyl acrylate and isoboroyl acrylate;

(Meth) acrylic acid aryl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate;

Acrylic acid aryl esters such as phenyl acrylate and benzyl 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-carboxybicyclo [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-dicarboxybicyclo [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-methylbicyclo [2.2.1] hepto-2-ene, 5- Hydroxy-5-ethylbicyclo [2.2.1] hepto-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hepto-2-ene, 5-carboxy-5-ethylbicyclo [2.2 .1] hepto-2-ene, 5-hydroxymethyl-5-methylbicyclo [2 .2.1] hepto-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hepto-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hepto-2-ene, 5 , 6-dicarboxybicyclo [2.2.1] hepto-2-ene anhydride (hymic acid anhydride), 5-tert-butoxycarbonylbicyclo [2.2.1] hepto-2-ene, 5-cyclohexyloxy Cycarbonylbicyclo [2.2.1] hepto-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hepto-2-ene, 5,6-di (tert-butoxycarbonyl) bicyclo [2.2 .1] bicyclo unsaturated compounds, such as hepto-2-ene and 5, 6- di (cyclohexyloxycarbonyl) 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;

-메틸스티렌, m-메틸스티렌, p-메틸스티렌, 비닐톨루엔, p-메톡시스티렌, 아크릴로니트릴, 메타크릴로니트릴, 염화비닐, 염화비닐리덴, 아크릴아미드, 메타크릴아미드, 아세트산비닐, 1,3-부타디엔, 이소프렌, 2,3-디메틸-1,3-부타디엔 등을 들 수 있다.Styrene,

-Methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 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 preferable in terms of copolymerization reactivity and alkali solubility.

Resin (A1) obtained by copolymerizing (Aa) and (Ab) is a mole fraction when the ratio of the structural component derived from each makes the total mole number of the structural component which comprises resin (A1) 100 mol%. It is preferable to be in a range.

Structural units derived from (A-a); 2-40 mol%

Structural units derived from (A-b); 60 to 98 mol%

Moreover, it is more preferable if the ratio of the said structural component is the following ranges.

Structural units derived from (A-a); 5 to 35 mol%

Structural units derived from (A-b); 65 to 95 mol%

When the above-mentioned composition ratio exists in this range, there exists a tendency for storage stability, developability, and solvent resistance to become favorable.

The resin (A1) is, for example, the method described in the document "Experimental method of polymer synthesis" (first edition, March 1, 1972, first edition of Otsu Takayuki Kogyo Co., Ltd.) and the cited document disclosed in the document. It can manufacture with reference to (the same also in resin (A2)).

Specifically, a predetermined amount of the units (Aa) and (Ab) constituting the copolymer, a polymerization initiator and a solvent are charged into the reaction vessel, oxygen is replaced by nitrogen, and stirred, heated, and warmed in the absence of oxygen. A polymer is obtained.

The polymerization initiator used here may be any of those commonly used in the art. For example, the polymerization initiator (C) etc. which are mentioned later can be used.

Moreover, 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, by using the solvent (D) mentioned later as a solvent at the time of this superposition | polymerization, the solution after reaction can be used as it is, and a manufacturing process can be simplified (same also in resin (A2)).

The weight average molecular weight of polystyrene conversion of resin (A1) becomes like this. Preferably it is 3,000-100,000, More preferably, it is 5,000-50,000. When the weight average molecular weight of resin (A1) exists in this range, applicability | paintability tends to become favorable, and film | membrane decrease does not produce easily at the time of image development, and there exists a tendency for the detachability of a non-pixel part at the time of image development to be favorable.

Dispersion degree (molecular weight distribution) of resin (A1), [weight average molecular weight (Mw) / number average molecular weight (Mn)] becomes like this. Preferably it is 1.1-6.0, More preferably, it is 1.2-4.0. When dispersion degree exists in this range, it exists in the tendency which is excellent in developability.

Content of resin (A1) which can be used for the photosensitive resin composition of this invention is mass fraction with respect to solid content in the photosensitive resin composition, Preferably it is 5-90 mass%, More preferably, it is 10-70 mass%. When the content of the resin (A1) is within this range, the solubility in the developing solution is sufficient, the development residue does not easily occur on the substrate of the non-pixel portion, and the film reduction of the pixel portion of the exposed portion at the time of development does not occur easily. There is a tendency for the missing property of the non-exposed part to be good.

As resin (A2) which shows alkali solubility and reactivity by the action of at least one of light and heat, (A2-1)-(A2-3) is illustrated.

Resin (A2-1) is a copolymer of (Aa), (Ab), and a monomer (Ac) (hereinafter may be referred to as "(Ac)") having a group having a cyclic ether bond having 2 to 4 carbon atoms. Can be mentioned.

Resin (A2-2) is a copolymer of (Aa) and (Ab), in which a part of the carboxyl groups derived from (Aa) is reacted with a group having a C 2 to C 4 cyclic ether bond derived from (Ac) The copolymer obtained by making it mention is mentioned.

Resin (A2-3) is a copolymer of (A-a) and (A-c).

(Ac) is a polymerizable compound having at least one group selected from the group consisting of, for example, a group having a cyclic ether bond having 2 to 4 carbon atoms (for example, an epoxy group, an oxetanyl group, and a tetrahydrofuryl group). Say It is preferable that (A-c) is a compound which has at least 1 sort (s) of group chosen from the group which consists of group which has a C2-C4 cyclic ether bond, and has an unsaturated bond.

As (A-c), the monomer which has an epoxy group, the monomer which has an oxetanyl group, the monomer which has tetrahydrofuryl group, etc. are mentioned, for example.

The monomer which has the said epoxy group means the polymeric compound which has at least 1 sort (s) of group chosen from the group which consists of an aliphatic epoxy group and an alicyclic epoxy group, for example.

It is preferable that the monomer which has an epoxy group is a compound which has at least 1 sort (s) of group chosen from the group which consists of an aliphatic epoxy group and an alicyclic epoxy group, and has an unsaturated bond.

An aliphatic epoxy group means group which has a structure which epoxidized chain olefin.

Specific examples of the compound having an aliphatic epoxy group include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, The compound etc. which are represented by following formula (III) of Unexamined-Japanese-Patent No. 7-248625 are mentioned.

(In formula (III), R <^11> -R <^13> is a hydrogen atom or a C1-C10 alkyl group each independently, and m is an integer of 1-5.

Here, as the alkyl group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, 1-methyl-n-propyl group, 2-methyl-n-propyl group , tert-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1 , 2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, n-hexyl group, cyclohexyl group and the like are exemplified.

Moreover, in any chemical structural formula, although it changes with carbon number, unless otherwise indicated, examples of a substituent etc. can be applied similarly throughout this specification. In addition, the thing which can take both a straight chain and a branch includes all.

-메틸-o-비닐벤질글리시딜에테르,

-메틸-m-비닐벤질글리시딜에테르,

-메틸-p-비닐벤질글리 시딜에테르, 2,3-디글리시딜옥시메틸스티렌, 2,4-디글리시딜옥시메틸스티렌, 2,5-디글리시딜옥시메틸스티렌, 2,6-디글리시딜옥시메틸스티렌, 2,3,4-트리글리시딜옥시메틸스티렌, 2,3,5-트리글리시딜옥시메틸스티렌, 2,3,6-트리글리시딜옥시메틸스티렌, 3,4,5-트리글리시딜옥시메틸스티렌, 2,4,6-트리글리시딜옥시메틸스티렌 등을 들 수 있다.As a compound represented by said Formula (III), o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether,

-Methyl-o-vinylbenzylglycidyl ether,

Methyl-m-vinylbenzylglycidyl ether,

-Methyl-p-vinylbenzylglycidyl ether, 2,3-diglycidyloxymethylstyrene, 2,4-diglycidyloxymethylstyrene, 2,5-diglycidyloxymethylstyrene, 2,6 -Diglycidyloxymethylstyrene, 2,3,4-triglycidyloxymethylstyrene, 2,3,5-triglycidyloxymethylstyrene, 2,3,6-triglycidyloxymethylstyrene, 3, 4,5-triglycidyloxymethyl styrene, 2,4,6-triglycidyloxymethyl styrene, etc. are mentioned.

As a monomer which has an alicyclic epoxy group, the monomer which has an aliphatic monocyclic epoxy group, the monomer which has an aliphatic polycyclic epoxy group, etc. are mentioned, for example.

An alicyclic epoxy group means group which has a structure which epoxidized cyclic olefin. In addition, an aliphatic monocyclic epoxy group means the group which has a structure which epoxidized the monocyclic cyclic olefin, and an aliphatic polycyclic epoxy group means the group which has a structure which epoxidized polycyclic olefin.

The monomer having an aliphatic monocyclic epoxy group refers to a polymerizable compound having an epoxy group on a ring of an aliphatic monocyclic compound. It is preferable that the monomer which has an aliphatic monocyclic epoxy group is a compound which has an epoxy group on the ring of an aliphatic monocyclic compound, and has a unsaturated bond, has an epoxy group on the ring of an aliphatic monocyclic compound, and also has (meth) acryloyl jade It is more preferable that it is a compound which has timing.

As an aliphatic monocyclic compound, cyclopentane, cyclohexane, cycloheptane, cyclooctane, etc. are mentioned, for example. Especially, a C5-C7 compound is preferable.

Specific examples of the monomer having an aliphatic monocyclic epoxy group include vinylcyclohexene monooxide 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide 2000; manufactured by Daicel Chemical Industry Co., Ltd.), 3, 4-epoxycyclohexylmethyl acrylate (for example, cyclomer A400; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (for example, cyclomer M100; diecel chemistry Industrial Co., Ltd.) etc. are mentioned.

The monomer which has an aliphatic polycyclic epoxy group means the polymeric compound which has an epoxy group on the ring of an aliphatic polycyclic compound. It is preferable that the monomer which has an aliphatic polycyclic epoxy group is a compound which has an epoxy group on the ring of an aliphatic polycyclic compound, and has a unsaturated bond, has an epoxy group on the ring of an aliphatic polycyclic compound, and also has (meth) acryloyl jade It is more preferable that it is a compound which has timing.

Examples of the aliphatic polycyclic compounds include dicyclopentane, tricyclodecane, norbornane, isonorbornane, bicyclooctane, bicyclononane, bicycloundecane, tricycloundecane and bicyclododecane, Tricyclo dodecane etc. are mentioned. Especially, a C8-12 compound is preferable.

As a monomer which has the said aliphatic polycyclic epoxy group, For example, 3, 4- epoxy norbornyl acrylate, 3, 4- epoxy norbornyl methacrylate, the compound represented by Formula (I), and Formula (II) At least 1 sort (s) of compound chosen from the group which consists of a compound shown by these etc. are mentioned.

In Formula (I) and Formula (II), R <^1> and R <^2> respectively independently represents the C1-C4 alkyl group which may be substituted by the hydrogen atom or a hydroxyl group.

X <^1> and X <^2> respectively independently represents the C1-C6 alkylene group which may contain a single bond or a hetero atom.

Specific examples of R ¹ and R ² include a hydrogen atom; Alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group;

Hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxy-n-propyl group, 2-hydroxy-n-propyl group, 3-hydroxy-n-propyl group, 1-hydroxy -Isopropyl group, 2-hydroxy-isopropyl group, 1-hydroxy-n-butyl group, 2-hydroxy-n-butyl group, 3-hydroxy-n-butyl group, 4-hydroxy-n And hydroxyl-substituted alkyl groups such as -butyl group.

Preferably they are a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and 2-hydroxyethyl group, More preferably, they are a hydrogen atom and a methyl group.

Specific examples of X ¹ and X ² include a single bond; Alkylene groups such as methylene group, ethylene group and propylene group;

Hetero atom containing alkylene groups, such as an oxyalkylene group, a thioalkylene group, and an aminoalkylene group, are mentioned, Specifically, an oxymethylene group, an oxyethylene group, an oxypropylene group, a thiomethylene group, a thioethylene group, a thiopropylene group , Amino methylene group, aminoethylene group, aminopropylene group and the like are exemplified.

Preferably, a single bond, a methylene group, an ethylene group, an oxymethylene group, an oxyethylene group is mentioned, More preferably, a single bond and an oxyethylene group are mentioned.

As at least 1 type of compound chosen from the group which consists of a compound represented by Formula (I) and the compound represented by Formula (II), the group which consists of a compound represented by following formula (I ') and a compound represented by Formula (II') It is preferable that it is at least 1 type of compound chosen from.

In formula (I ') and formula (II'), R <^1>' and R <^2>' are synonymous with said R <^1> and R <^2> , respectively.

Specifically as a compound represented by Formula (I), the compound etc. which are represented by Formula (I-1)-Formula (I-15) are mentioned, Preferably Formula (I-1) and Formula (I-3) , Formula (I-5), formula (I-7), formula (I-9), formulas (I-11) to (I-15), and more preferably formula (I-1) , Formula (I-7), formula (I-9) and formula (I-15).

Specifically as a compound represented by Formula (II), the compound etc. which are represented by Formula (II-1)-Formula (II-15) are mentioned, Preferably, it is Formula (II-1), Formula (II-3) , Formula (II-5), formula (II-7), formula (II-9), formula (II-11) to formula (II-15), and more preferably formula (II-1) , Formula (II-7), formula (II-9) and formula (II-15).

The at least 1 sort (s) of compound chosen from the group which consists of a compound represented by Formula (I) and a compound represented by Formula (II) can be used individually, respectively, mixing in arbitrary ratios. In the case of mixing, the mixing ratio is in a molar ratio, preferably 5:95 to 95: 5, more preferably 10:90 to 90:10, still more preferably 20: by formula (I): formula (II). It is 80-80: 20.

The monomer which has an oxetanyl group mentioned above means the polymeric compound which has an oxetanyl group, for example. It is preferable that the monomer which has an oxetanyl group is a compound which has an oxetanyl group and has an unsaturated bond.

Specific examples of the monomer having an oxetanyl group include 3-methyl-3-methacryloxymethyloxetane, 3-methyl-3-acryloxymethyloxetane, 3-ethyl-3-methacryloxymethyloxetane, 3 -Ethyl-3-acryloxymethyloxetane, 3-methyl-3-methacryloxyethyloxetane, 3-methyl-3-acryloxyethyloxetane, 3-ethyl-3-methacryloxyethyloxetane or 3 -Ethyl-3-acryloxyethyl oxetane, etc. are mentioned.

The monomer which has said tetrahydrofuryl group means the polymeric compound which has a tetrahydrofuryl group, for example. It is preferable that the monomer which has a tetrahydrofuryl group is a compound which has a tetrahydrofuryl group and has an unsaturated bond.

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

In resin (A2-1), it is preferable that the ratio of the structural component guide | induced from each exists in the following ranges with a mole fraction with respect to the total mole number of the structural component which comprises resin (A2-1).

Structural units derived from (A-a); 2-40 mol%

Structural units derived from (A-b); 1 to 65 mol%

Structural units derived from (A-c); 2 to 95 mol%

Moreover, it is more preferable if the ratio of said structural component is the following ranges.

Structural units derived from (A-a); 5 to 35 mol%

Structural units derived from (A-b); 1 to 60 mol%

Structural units derived from (A-c); 5 to 80 mol%

When the above-mentioned composition ratio exists in this range, there exists a tendency for storage stability, developability, solvent resistance, heat resistance, and mechanical strength to become favorable.

Resin (A2-1) can be manufactured by the same manufacturing method as resin (A1) except using the compound which guide | induces the unit (A-a), (A-b), and (A-c) which comprise a copolymer.

Resin (A2-2) can be manufactured through a two-step process. For example, the method described in the document "Experimental method of polymer synthesis" (Issued first edition of March 1, 1972, issued by Otsu Takayuki Co., Ltd.), and Japanese Unexamined Patent Publication No. 2001-89533 It may be prepared with reference to the described method.

First, resin is obtained by the method similar to resin (A1) using the copolymer obtained by copolymerizing (A-a) and (A-b).

In this case, it is preferable that the ratio of the structural component guide | induced from each exists in the following ranges in mole fraction with respect to the total number of moles of the structural component which comprises said copolymer.

Structural units derived from (A-a); 5-50 mol%

Structural units derived from (A-b); 50 to 95 mol%

Moreover, it is more preferable if the ratio of said structural component is the following ranges.

Structural units derived from (A-a); 10 to 45 mol%

Structural units derived from (A-b); 55 to 90 mol%

The weight average molecular weight and molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of polystyrene conversion of obtained resin can be made about the same as resin (A1).

Next, in order to give reactivity by the action of light or heat, a part of the carboxylic acid and carboxylic anhydride of (Aa) derived from the copolymer obtained by copolymerizing (Aa) and (Ab) in (Ac) It reacts with the derived epoxy group, oxetanyl group, or tetrahydrofuryl group.

Therefore, the atmosphere in a flask is replaced with nitrogen by air continuously, a constituent (Ac), a reaction catalyst, a polymerization inhibitor, etc. are put in a flask, for example, reaction is carried out at 60-130 degreeC for 1 to 10 hours. Continue.

In addition, in the same manner as the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the amount of heat generated by the production equipment, polymerization, and the like.

The number of moles of (A-c) is usually 5 to 80 mol%, preferably 10 to 75 mol%, and more preferably 15 to 70 mol% with respect to the number of moles of (A-a). If the proportion is within this range, the balance of storage stability, developability, solvent resistance, heat resistance, mechanical strength and sensitivity tends to be good.

The reaction catalyst is suitably used as a reaction catalyst of, for example, a carboxyl group, an epoxy group, an oxetanyl group, or a tetrahydrofuryl group. Specifically, trisdimethylaminomethyl phenol etc. are illustrated.

The usage-amount of the reaction catalyst in this case is about 0.001 to 5% on a mass basis with respect to the total amount of monomer (A-a)-(A-c) normally.

The polymerization inhibitor may exemplify hydroquinone.

The usage-amount of a polymerization inhibitor is about 0.001 to 5% on a mass basis with respect to the total amount of monomer (A-a)-(A-c) normally.

Resin (A2-3) can be manufactured by the same manufacturing method as resin (A1) except using the compound which guide | induces the unit (A-a) and (A-c) which comprise a copolymer.

In resin (A2-3), it is preferable that the ratio of the structural component guide | induced from each exists in the following ranges with a mole fraction with respect to the total mole number of the structural component which comprises resin (A2-3).

Structural units derived from (A-a); 5 to 95 mol%

Structural units derived from (A-c); 5 to 95 mol%

Moreover, it is more preferable if the ratio of said structural component is the following ranges.

Structural units derived from (A-a); 10 to 90 mol%

Structural units derived from (A-c); 10 to 90 mol%

When the above-mentioned composition ratio exists in this range, there exists a tendency for storage stability, developability, solvent resistance, heat resistance, and mechanical strength to become favorable.

As a polymerizable monomer (B) contained in the photosensitive resin composition of this invention, a monofunctional monomer, a bifunctional monomer, or a trifunctional or more than trifunctional polyfunctional monomer etc. are mentioned.

As the monofunctional monomer, nonylphenylcarbitol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-ethylhexylcarbitol (meth) acrylate, 2-hydroxyethyl (meth ) Acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, 2- (2-ethoxyethoxy) ethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, caprolactone ( Meth) acrylate, ethoxylated nonylphenol (meth) acrylate, propoxylated nonylphenol (meth) acrylate, N-vinylpyrrolidone, and the like.

As a bifunctional monomer, 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, bisphenol A, bis (Acryloyloxyethyl) ether, ethoxylated bisphenol A di (meth) acrylate, propoxylated neopentylglycoldi (meth) acrylate, ethoxylated neopentylglycoldi (meth) acrylate or 3-methylpentanediol Di (meth) acrylate etc. are mentioned.

Examples of the trifunctional or higher polyfunctional monomer include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, and ethoxylated trimethyl. All propane 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 toltenta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritolhepta (meth) acrylate, tri Pentaerythritol octa (meth) acrylate, reactant of pentaerythritol tri (meth) acrylate and acid anhydride, dipentaerythritol penta (meth Reactant of acrylate and acid anhydride, tripentaerythritolhepta (meth) acrylate and acid anhydride caprolactone modified trimethylolpropane tri (meth) acrylate, caprolactone modified pentaerythritol tri (meth) acrylate, caprolactone Modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, caprolactone modified Dipentaerythritol hexa (meth) acrylate, caprolactone-modified tripentaerythritol tetra (meth) acrylate, caprolactone-modified tripentaerythritolpenta (meth) acrylate, caprolactone-modified tripentaerythritol hexa (meth) Acrylate, caprolactone modified tripentaerythritolhepta (meth) acrylate, caprolactone Reactant of the acidic tripentaerythritol octa (meth) acrylate, caprolactone modified pentaerythritol tri (meth) acrylate and an acid anhydride, the reactant of the caprolactone modified dipentaerythritol penta (meth) acrylate and an acid anhydride, or Caprolactone modified tripentaerythritol hepta (meth) acrylate, an acid anhydride, etc. are mentioned.

In addition, in this specification, a caprolactone modification means that the ring-opening body or ring-opening polymer of caprolactone is introduce | transduced between the alcohol origin site | part of a (meth) acrylate compound, and a (meth) acryloyloxy group.

Especially, it is preferable to use a bifunctional or more than polyfunctional monomer.

Content of a polymerizable monomer (B) is mass fraction with respect to the total amount of resin (A) and a polymerizable monomer (B), Preferably it is 1-70 mass%, More preferably, it is 5-60 mass%. When content of a polymerizable monomer (B) exists in this range, there exists a tendency for the sensitivity, the smoothness, reliability, and mechanical strength of a sensitivity, a coating film, and a pattern to become favorable.

The photosensitive resin composition of this invention may contain the at least 1 sort (s) of compound (Y) further chosen from the group which consists of a compound which has a carboxylic anhydride and at least 2 carboxyl groups. As a latter compound, polyhydric carboxylic anhydride, polyhydric carboxylic acid, etc. are mentioned, for example.

As carboxylic anhydride, the epoxy resin hardener which consists of a commercially available colorless acid anhydride can also be used preferably. Specifically, Adeka Hardner EH-700 (brand name (the following)), Asahi Denka Kogyo Co., Ltd., Recassit HH, the same MH-700 (made by Shin-Nippon Ewha Co., Ltd.), Epiki Nia 126, copper YH-306, copper DX-126 (manufactured by Yuka Shell Epoxy Co., Ltd.), and the like.

As a polyhydric carboxylic anhydride, it is, for example,

Itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarvalic acid anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, norbornene dicarboxylic acid, hymic anhydride, etc. Aliphatic dicarboxylic acid anhydrides;

Aliphatic polyhydric carboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride and cyclopentane tetracarboxylic dianhydride;

Aromatic polyhydric carboxylic acid anhydrides such as phthalic anhydride, pyromellitic anhydride, trimellitic anhydride and benzophenonetetracarboxylic anhydride;

Ester group-containing acid anhydrides such as ethylene glycol bistrimellitate and glycerin tristrimellitate.

Especially, since it is high transparency and high resolution, Preferably it is phthalic anhydride and trimellitic anhydride.

As the polyhydric carboxylic acid, for example,

Aliphatic polyhydric carboxylic acids such as succinic acid, glutaric acid, adipic acid, butanetetracarboxylic acid, maleic acid and itaconic acid;

Alicyclic polyhydric carboxylic acids such as hexahydrophthalic acid, 1,2-cyclohexanecarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid and cyclopentanetetracarboxylic acid;

And aromatic polyhydric carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, 1,4,5,8-naphthalene tetracarboxylic acid and benzophenone tetracarboxylic acid.

Especially, since it has high transparency and high resolution, Preferably it is phthalic acid and trimellitic acid.

Content of the compound (Y) in the photosensitive resin composition of this invention is a mass fraction with respect to the total amount of binder resin (A) and a polymerizable monomer (B), Preferably it is 0.1-20 mass%, More preferably, 1 It is-15 mass%. If compound (Y) exists in this range, resolution and a residual film rate can be improved.

As a polymerization initiator (C) contained in the photosensitive resin composition of this invention, the compound which starts superposition | polymerization by action of light or a heat is mentioned, For example, a biimidazole type compound, an acetophenone type compound, a triazine type compound And an acyl phosphine oxide compound or an oxime compound. Especially, since a biimidazole type compound is excellent in a sensitivity, it is preferable.

Examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,3-dichlorophenyl)- 4,4 ', 5,5'-tetraphenylbiimidazole (see, for example, JP-A-6-75372, 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-chlorophenyl)- 4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole (see, for example, Japanese Patent Application Laid-Open No. 48-38403, Japanese Patent Application Laid-Open No. 62-174204, etc.), 4,4' The imidazole compound (For example, refer Unexamined-Japanese-Patent No. 7-10913 etc.) in which the phenyl group of a 5,5'-position is substituted by the carboalkoxy group is mentioned.

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 an acetophenone type compound, diethoxy acetophenone, 2-hydroxy-2-methyl-1- phenyl propane-1-one, benzyl dimethyl ketal, 2-hydroxy-1- [4- (2-hydroxyethoxy ) Phenyl] -2-methylpropane-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl -Propan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1- (4-methylsulfanylphenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino -1- (4-morpholinophenyl) butan-1-one, 2- (2-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3- Methylbenzyl) -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-morpholi Nophenyl) -butanone, 2- (2-butylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2,3-di Tylbenzyl) -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-dimethyl Amino-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-morpholinophenyl) -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-morpholin Oligomers of nophenyl) -butanone, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one, and the like.

Examples of the triazine-based compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- ( 4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloro Rhomethyl) -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-trimethylbenzoyl diphenyl phosphine oxide etc. are mentioned as an acylphosphine oxide type initiator.

As an oxime compound, O-ethoxycarbonyl- -Oxyimino-1-phenylpropan-1-one, the compound represented by Formula (1), the compound represented by Formula (2), etc. are mentioned.

The following photoinitiators etc. may contain in the polymerization initiator (C) of the photosensitive resin composition of this invention.

As a photoinitiator, a benzoin compound, a benzophenone type compound, a thioxanthone type compound, etc. are mentioned, for example.

As a benzoin type compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. are mentioned, for example.

As a benzophenone type compound, for example, benzophenone, methyl o-benzoyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3 ', 4,4'- tetra ( tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, etc. are mentioned.

As a thioxanthone type compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, and 1-chloro-4 Propoxy city oxanthone etc. are mentioned.

In addition, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphor quinone, methyl phenylglyoxylate or titanocene compound may be used as the photopolymerization initiator.

Moreover, the photoinitiator described in Unexamined-Japanese-Patent No. 2002-544205 can be used as a photoinitiator which has group which can cause chain transfer.

As a photoinitiator which has group which can cause said chain transfer, the photoinitiator of following formula (3)-(8) is mentioned, for example.

It is also possible to use light and / or thermal cationic polymerization initiators.

As an optical and / or thermal cationic polymerization initiator, the thing comprised from onium cation and an anion derived from Lewis acid can also be used.

As a specific example of onium cation, diphenyl iodonium, bis (p-tolyl) iodonium, bis (p-tert- butylphenyl) iodonium, bis (p-octylphenyl) iodonium, bis (p-octadecylphenyl Iodide, bis (p-octyloxyphenyl) iodium, bis (p-octadecyloxyphenyl) iodium, phenyl (p-octadecyloxyphenyl) iodium, (p-tolyl) (p-isopropylphenyl Iodide, triphenylsulfonium, tris (p-tolyl) sulfonium, tris (p-isopropylphenyl) sulfonium, tris (2,6-dimethylphenyl) sulfonium, tris (p-tert-butylphenyl) Sulfonium, tris (p-cyanophenyl) sulfonium, tris (p-chlorophenyl) sulfonium, dimethyl (methoxy) sulfonium, dimethyl (ethoxy) sulfonium, dimethyl (propoxy) sulfonium, dimethyl ( Butoxy) sulfonium, dimethyl (octyloxy) sulfonium, dimethyl (octadecaneoxy) sulfonium, dimethyl (isopropoxy) sulfonium, dimethyl (tert-butoxy) sulfonium, dimethyl (cyclopentyloxy) sulfonium , Dimethyl (cyclohex Oxy) sulfonium, dimethyl (fluoromethoxy) sulfonium, dimethyl (2-chloroethoxy) sulfonium, dimethyl (3-bromopropoxy) sulfonium, dimethyl (4-cyanobutoxy) sulfonium, dimethyl ( 8-nitrooctyloxy) sulfonium, dimethyl (18-trifluoromethyloctadecaneoxy) sulfonium, dimethyl (2-hydroxyisopropoxy) sulfonium, or dimethyl (tris (trichloromethyl) methyl) sulfonium Etc. can be mentioned.

Preferred onium cations include bis (p-tolyl) iodium, (p-tolyl) (p-isopropylphenyl) iodium, bis (p-tert-butylphenyl) iodium, triphenylsulfonium or tris (p -tert- butylphenyl) sulfonium etc. are mentioned.

Specific examples of the Lewis acid-derived anion include hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate, tetrakis (pentafluorophenyl) borate, and the like. Preferred anions derived from Lewis acids include hexafluoroantimonate or tetrakis (pentafluorophenyl) borate.

These onium cations and anions derived from Lewis acid can be arbitrarily combined.

As a specific example of a cationic polymerization initiator, diphenyl iodonium hexafluoro phosphate, bis (p-tolyl) iodonium hexafluoro phosphate, bis (p-tert- butylphenyl) iodonium hexafluoro phosphate, bis (p- Octylphenyl) iodonium hexafluorophosphate, bis (p-octadecylphenyl) iodonium hexafluorophosphate, bis (p-octyloxyphenyl) iodonium hexafluorophosphate, bis (p-octadecyloxyphenyl) iodine Nium hexafluorophosphate, phenyl (p-octadecyloxyphenyl) iodonium hexafluorophosphate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluorophosphate, methylnaphthyl iodonium hexafluorophosphate , Ethylnaphthyl iodonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, tris (p-tolyl) sulfonium hexafluorophosphate, tris (p-isopropylphenyl) sulfonium hexa Fluorophosphate, tris (2,6-dimethylphenyl) sulfonium hexafluorophosphate, tris (p-tert-butylphenyl) sulfonium hexafluorophosphate, tris (p-cyanophenyl) sulfonium hexafluorophosphate , Tris (p-chlorophenyl) sulfonium hexafluorophosphate, dimethylnaphthylsulfonium hexafluorophosphate, diethylnaphthylsulfonium hexafluorophosphate, dimethyl (methoxy) sulfonium hexafluorophosphate, dimethyl (ethoxy ) Sulfonium hexafluorophosphate, dimethyl (propoxy) sulfonium hexafluorophosphate, dimethyl (butoxy) sulfonium hexafluorophosphate, dimethyl (octyloxy) sulfonium hexafluorophosphate, dimethyl (octadecanoxy) Sulfonium hexafluorophosphate, dimethyl (isopropoxy) sulfonium hexafluorophosphate, dimethyl (tert-butoxy) sulfonium hexafluorophosphate, dimethyl (ci Lopentyloxy) sulfonium hexafluorophosphate, dimethyl (cyclohexyloxy) sulfonium hexafluorophosphate, dimethyl (fluoromethoxy) sulfonium hexafluorophosphate, dimethyl (2-chloroethoxy) sulfonium hexafluoro Phosphate, dimethyl (3-bromopropoxy) sulfonium hexafluorophosphate, dimethyl (4-cyanobutoxy) sulfonium hexafluorophosphate, dimethyl (8-nitrooctyloxy) sulfonium hexafluorophosphate, dimethyl (18-trifluoromethyloctadecaneoxy) sulfonium hexafluorophosphate, dimethyl (2-hydroxyisopropoxy) sulfonium hexafluorophosphate, dimethyl (tris (trichloromethyl) methyl) sulfonium hexafluoro Phosphate;

Diphenyl iodonium hexafluoroarsenate, bis (p-tolyl) iodonium hexafluoroarsenate, bis (p-tert-butylphenyl) iodonium hexafluoroarsenate, bis (p-octylphenyl Iodide hexafluoroarsenate, bis (p-octadecylphenyl) iodine hexafluoroarsenate, bis (p-octyloxyphenyl) iodonium hexafluoroarsenate, bis (p-octadecyl Oxyphenyl) iodonium hexafluoroarsenate, phenyl (p-octadecyloxyphenyl) iodonium hexafluoroarsenate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroarsenate , Methylnaphthyl iodonium hexafluoroarsenate, ethylnaphthyl iodonium hexafluoroarsenate, triphenylsulfonium hexafluoroarsenate, tris (p-tolyl) sulfonium hexafluoroarsenate Tris (p-isopropylphenyl) sulfonium hexafluoro Recetate, tris (2,6-dimethylphenyl) sulfonium hexafluoroarsenate, tris (p-tert-butylphenyl) sulfonium hexafluoroarsenate, tris (p-cyanophenyl) sulfonium hexa Fluoroarsenate, tris (p-chlorophenyl) sulfoniumhexafluoroarsenate, dimethylnaphthylsulfonium hexafluoroarsenate, diethylnaphthylsulfonium hexafluoroarsenate, dimethyl (methoxy) Sulfonium hexafluoroarsenate, dimethyl (ethoxy) sulfonium hexafluoroarsenate, dimethyl (propoxy) sulfonium hexafluoroarsenate, dimethyl (butoxy) sulfonium hexafluoroarsenate , Dimethyl (octyloxy) sulfonium hexafluoroarsenate, dimethyl (octadecaneoxy) sulfonium hexafluoroarsenate, dimethyl (isopropoxy) sulfonium hexafluoroarsenate, dimethyl (tert-part Methoxy) sulfonium hexafluoro Recetate, dimethyl (cyclopentyloxy) sulfonium hexafluoroarsenate, dimethyl (cyclohexyloxy) sulfonium hexafluoroarsenate, dimethyl (fluoromethoxy) sulfonium hexafluoroarsenate, dimethyl (2-chloroethoxy) sulfonium hexafluoroarsenate, dimethyl (3-bromopropoxy) sulfonium hexafluoroarsenate, dimethyl (4-cyanobutoxy) sulfonium hexafluoroarsenate , Dimethyl (8-nitrooctyloxy) sulfonium hexafluoroarsenate, dimethyl (18-trifluoromethyloctadecaneoxy) sulfonium hexafluoroarsenate, dimethyl (2-hydroxyisopropoxy) sulphate Phonium hexafluoroarsenate, dimethyl (tris (trichloromethyl) methyl) sulfonium hexafluoroarsenate;

Diphenyliodonium hexafluoroantimonate, bis (p-tolyl) iodonium hexafluoroantimonate, bis (p-tert-butylphenyl) iodonium hexafluoroantimonate, bis (p-octylphenyl Iodide hexafluoroantimonate, bis (p-octadecylphenyl) iodine hexafluoroantimonate, bis (p-octyloxyphenyl) iodonium hexafluoroantimonate, bis (p-octadecyl Oxyphenyl) iodonium hexafluoroantimonate, phenyl (p-octadecyl oxyphenyl) iodonium hexafluoroantimonate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroantimonate , Methylnaphthyl iodonium hexafluoroantimonate, ethylnaphthyl iodonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate, tris (p-tolyl) sulfonium hexafluoroantimonate Tris (p-isopropylphenyl) sulfonium hexafluoro Antimonate, tris (2,6-dimethylphenyl) sulfoniumhexafluoroantimonate, tris (p-tert-butylphenyl) sulfonium hexafluoroantimonate, tris (p-cyanophenyl) sulfonium Hexafluoroantimonate, tris (p-chlorophenyl) sulfonium hexafluoroantimonate, dimethylnaphthylsulfonium hexafluoroantimonate, diethylnaphthylsulfonium hexafluoroantimonate, dimethyl (methoxy Sulfonium hexafluoroantimonate, dimethyl (ethoxy) sulfonium hexafluoroantimonate, dimethyl (propoxy) sulfonium hexafluoroantimonate, dimethyl (butoxy) sulfonium hexafluoroantimo Nate, dimethyl (octyloxy) sulfonium hexafluoroantimonate, dimethyl (octadecaneoxy) sulfonium hexafluoroantimonate, dimethyl (isopropoxy) sulfonium hexafluoroantimonate, dimethyl (tert- Butoxy) sulfonium hexafluoro Timonate, dimethyl (cyclopentyloxy) sulfonium hexafluoroantimonate, dimethyl (cyclohexyloxy) sulfonium hexafluoroantimonate, dimethyl (fluoromethoxy) sulfonium hexafluoroantimonate, dimethyl (2-Chloroethoxy) sulfonium hexafluoroantimonate, dimethyl (3-bromopropoxy) sulfonium hexafluoroantimonate, dimethyl (4-cyanobutoxy) sulfonium hexafluoroantimonate , Dimethyl (8-nitrooctyloxy) sulfonium hexafluoroantimonate, dimethyl (18-trifluoromethyloctadecaneoxy) sulfonium hexafluoroantimonate, dimethyl (2-hydroxyisopropoxy) sulphate Phonium hexafluoro antimonate, dimethyl (tris (trichloromethyl) methyl) sulfonium hexafluoroantimonate;

Diphenyl iodonium tetrakis (pentafluorophenyl) borate, bis (p-tolyl) iodonium tetrakis (pentafluorophenyl) borate, bis (p-tert-butylphenyl) iodonium tetrakis (pentafluorophenyl) ) Borate, bis (p-octylphenyl) iodium tetrakis (pentafluorophenyl) borate, bis (p-octadecylphenyl) iodium tetrakis (pentafluorophenyl) borate, bis (p-octyloxyphenyl) Iodonium tetrakis (pentafluorophenyl) borate, bis (p-octadecyloxyphenyl) iodonium tetrakis (pentafluorophenyl) borate, phenyl (p-octadecyloxyphenyl) iodonium tetrakis (pentafluoro Phenyl) borate, (p-tolyl) (p-isopropylphenyl) iodium tetrakis (pentafluorophenyl) borate, methylnaphthyl iodonium tetrakis (pentafluorophenyl) borate, ethylnaphthyl iodonium tetrakis (Pentafluorophenyl) borate, Triphenylsulfonium tetrakis (pentafluorophenyl) borate, tris (p-tolyl) sulfonium tetrakis (pentafluorophenyl) borate, tris (p-isopropylphenyl) sulfonium tetrakis (pentafluorophenyl) Borate, tris (2,6-dimethylphenyl) sulfoniumtetrakis (pentafluorophenyl) borate, tris (p-tert-butylphenyl) sulfoniumtetrakis (pentafluorophenyl) borate, tris (p-cyano Phenyl) sulfonium tetrakis (pentafluorophenyl) borate, tris (p-chlorophenyl) sulfonium tetrakis (pentafluorophenyl) borate, dimethylnaphthylsulfonium tetrakis (pentafluorophenyl) borate, diethylnaph Tyl sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (methoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (ethoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (propoxy Sulfonium Tet Kis (pentafluorophenyl) borate, dimethyl (butoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (octyloxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (octadecanoxy) sulphate Phosphorium tetrakis (pentafluorophenyl) borate, dimethyl (isopropoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (tert-butoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl ( Cyclopentyloxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (cyclohexyloxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (fluoromethoxy) sulfonium tetrakis (pentafluorophenyl ) Borate, dimethyl (2-chloroethoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (3-bromopropoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (4-cyanobu Methoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (8-nitrooctyloxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (18-trifluoromethyloctadecaneoxy) sulfonium tetrakis (Pentafluorophenyl) borate, dimethyl (2-hydroxyisopropoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (tris (trichloromethyl) methyl) sulfonium tetrakis (pentafluorophenyl) Borate etc. are mentioned.

Preferably, bis (p-tolyl) iodonium hexafluorophosphate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluorophosphate, bis (p-tert-butylphenyl) iodonium hexafluoro Phosphate, triphenylsulfonium hexafluorophosphate, tris (p-tert-butylphenyl) sulfonium hexafluorophosphate, bis (p-tolyl) iodonium hexafluoroarsenate, (p-tolyl) (p- Isopropylphenyl) iodonium hexafluoroarsenate, bis (p-tert-butylphenyl) iodonium hexafluoroarsenate, triphenylsulfonium hexafluoroarsenate, tris (pt-butylphenyl) sulfonium Hexafluoroarsenate, bis (p-tolyl) iodonium hexafluoroantimonate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroantimonate, bis (p-tert-butyl Phenyl) iodonium hexafluoroantimonate, triphenylsulfonium hexafluoro Timonate, tris (p-tert-butylphenyl) sulfoniumhexafluoroantimonate, bis (p-tolyl) iodoniumtetrakis (pentafluorophenyl) borate, (p-tolyl) (p-isopropylphenyl Iodide tetrakis (pentafluorophenyl) borate, bis (p-tert-butylphenyl) iodium, triphenylsulfonium tetrakis (pentafluorophenyl) borate, tris (p-tert-butylphenyl) sulfonium Tetrakis (pentafluorophenyl) borate and the like.

More preferably, bis (p-tolyl) iodonium hexafluoroantimonate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroantimonate, bis (p-tert-butylphenyl) Iodonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate, tris (p-tert-butylphenyl) sulfonium hexafluoroantimonate, bis (p-tolyl) iodonium tetrakis (penta Fluorophenyl) borate, (p-tolyl) (p-isopropylphenyl) iodium tetrakis (pentafluorophenyl) borate, bis (p-tert-butylphenyl) iodium tetrakis (pentafluorophenyl) borate And triphenylsulfonium tetrakis (pentafluorophenyl) borate, tris (p-tert-butylphenyl) sulfonium tetrakis (pentafluorophenyl) borate, and the like.

Content of a polymerization initiator (C) is mass fraction with respect to the total amount of resin (A) and a polymerizable monomer (B), Preferably it is 0.1-40 mass%, More preferably, it is 1-30 mass%.

When content of a polymerization initiator (C) exists in this range, the photosensitive resin composition will become high sensitivity, the intensity | strength of the coating film or pattern formed using the said photosensitive resin composition, and smoothness in the surface of the said coating film or pattern It tends to be good.

Moreover, you may use for the photosensitive resin composition of this invention combining the polymerization start adjuvant (C-1) with a polymerization initiator (C) so that the effect of this invention may not be impaired.

As a polymerization start adjuvant (C-1), an amine compound, a carboxylic acid compound, a polyfunctional thiol compound, the compound represented by Formula (IV), the compound represented by Formula (V) or Formula (VI), etc. are mentioned.

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 (common name: Mihiler ketone), 4,4'-bis (diethylamino) Aromatic amine compounds, such as benzophenone, are mentioned.

Examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid and dichlorophenylthioacetic acid. And aromatic heteroacetic acids such as acetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine or naphthoxyacetic acid.

Multifunctional thiol compounds are compounds having two or more sulfanyl groups in the molecule.

Specific examples of the polyfunctional thiol compound include hexanedithiol, decandithiol, 1,4-dimethyl mercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate and trimethylolpropane tris. Thioglycolate, butanediol bisthio propionate, trimethylol propane tristyopiothionate, trimethylolpropane tristhioglycolate, pentaerythritol tetraquistiopionopionate, pentaerythritol tetrakisthioglycolate, trishydroxy Ethyl tristyropropionate, pentaerythritol tetrakis (3-mercapto butyrate), 1, 4-bis (3- mercapto butyryloxy) butane, etc. are mentioned.

Especially, the compound which has 2 or more of sulfanyl groups couple | bonded with the carbon atom of an aliphatic hydrocarbon group is more preferable because the sensitivity of the photosensitive resin composition of this invention becomes high.

The compound represented by Formula (IV) is the following compound.

In formula (IV), the ring represented by X represents the C6-C12 aromatic ring which may be substituted by the halogen atom.

Y represents an oxygen atom and a sulfur atom.

R ²¹ represents an alkyl group having 1 to 6 carbon atoms.

R <^22> represents the C1-C12 alkyl group which may be substituted by the halogen atom, or the aryl group which may be substituted by the halogen atom.

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, etc. are mentioned.

Examples of the aromatic ring having 6 to 12 carbon atoms include benzene ring, methylbenzene ring, dimethylbenzene ring, ethylbenzene ring, propylbenzene ring, butylbenzene ring, pentylbenzene ring, hexylbenzene ring, cyclohexylbenzene ring, chlorobenzene ring and dichloro Benzene ring, bromobenzene ring, dibromobenzene ring, phenylbenzene ring, chlorophenylbenzene ring, bromophenylbenzene ring, naphthalene ring, chloronaphthalene ring, bromonaphthalene ring, phenanthrene ring, chrysene ring, fluoro Lanten ring, benzo [a] pyrene ring, benzo [e] pyrene ring, perylene ring, derivatives thereof and the like. Especially, a benzene ring, a naphthalene ring, etc. are preferable.

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

Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 1-methyl-n-propyl group, 2-methyl-n-propyl group, tert-butyl group, n -Pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n- A propyl group, a 2, 2- dimethyl- n-propyl group, n-hexyl group, a cyclohexyl group, etc. are mentioned.

As a C1-C12 alkyl group which may be substituted by the halogen atom, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, 1-methyl-n-propyl group, 2-methyl-n-propyl group, tert-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1, 2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, n-hexyl group, cyclohexyl group, 1-chloro-n-butyl group, 2-chloro-n-butyl group, 3-chloro -n-butyl group etc. are mentioned.

Examples of the aryl group which may be substituted with a halogen atom include a phenyl group, a chlorophenyl group, a dichlorophenyl group, a bromophenyl group, a dibromophenyl group, a chlorobromophenyl group, a biphenyl group, a chlorobiphenyl group, a dichlorobiphenyl group, a bromophenyl group, and a dibromo group. A phenyl group, a naphthyl group, a chloro naphthyl group, a dichloro naphthyl group, a bromonaphthyl group, a dibromonaphthyl group, etc. are mentioned.

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

2-benzoylmethylene-3-methyl-naphtho [2,1-d] thiazoline,

2-benzoylmethylene-3-methyl-naphtho [1,2-d] thiazoline,

2-benzoylmethylene-3-methyl-naphtho [2,3-d] thiazoline,

2- (2-naphthoylmethylene) -3-methylbenzothiazoline,

2- (1-naphthoylmethylene) -3-methylbenzothiazoline,

2- (2-naphthoylmethylene) -3-methyl-5-phenylbenzothiazoline,

2- (1-naphthoylmethylene) -3-methyl-5-phenylbenzothiazoline,

2- (2-naphthoylmethylene) -3-methyl-5-fluorobenzothiazoline,

2- (1-naphthoylmethylene) -3-methyl-5-fluorobenzothiazoline,

2- (2-naphthoylmethylene) -3-methyl-5-chlorobenzothiazoline,

2- (1-naphthoylmethylene) -3-methyl-5-chlorobenzothiazoline,

2- (2-naphthoylmethylene) -3-methyl-5-bromobenzothiazoline,

2- (1-naphthoylmethylene) -3-methyl-5-bromobenzothiazoline,

2- (4-biphenoylmethylene) -3-methylbenzothiazoline,

2- (4-biphenoylmethylene) -3-methyl-5-phenylbenzothiazoline,

2- (2-naphthoylmethylene) -3-methyl-naphtho [2,1-d] thiazoline,

2- (2-naphthoylmethylene) -3-methyl-naphtho [1,2-d] thiazoline,

2- (4-biphenoylmethylene) -3-methyl-naphtho [2,1-d] thiazoline,

2- (4-biphenoylmethylene) -3-methyl-naphtho [1,2-d] thiazoline,

2- (p-fluorobenzoylmethylene) -3-methyl-naphtho [2,1-d] thiazoline,

2- (p-fluorobenzoylmethylene) -3-methyl-naphtho [1,2-d] thiazoline,

2-benzoylmethylene-3-methyl-naphtho [2,1-d] oxazoline,

2-benzoylmethylene-3-methyl-naphtho [1,2-d] oxazoline,

2-benzoylmethylene-3-methyl-naphtho [2,3-d] oxazoline,

2- (2-naphthoylmethylene) -3-methylbenzooxazoline,

2- (1-naphthoylmethylene) -3-methylbenzooxazoline,

2- (2-naphthoylmethylene) -3-methyl-5-phenylbenzooxazoline,

2- (1-naphthoylmethylene) -3-methyl-5-phenylbenzooxazoline,

2- (2-naphthoylmethylene) -3-methyl-5-fluorobenzooxazoline,

2- (1-naphthoylmethylene) -3-methyl-5-fluorobenzooxazoline,

2- (2-naphthoylmethylene) -3-methyl-5-chlorobenzooxazoline,

2- (1-naphthoylmethylene) -3-methyl-5-chlorobenzooxazoline,

2- (2-naphthoylmethylene) -3-methyl-5-bromobenzooxazoline,

2- (1-naphthoylmethylene) -3-methyl-5-bromobenzooxazoline,

2- (4-biphenoylmethylene) -3-methylbenzooxazoline,

2- (4-biphenoylmethylene) -3-methyl-5-phenylbenzooxazoline,

2- (2-naphthoylmethylene) -3-methyl-naphtho [2,1-d] oxazoline,

2- (2-naphthoylmethylene) -3-methyl-naphtho [1,2-d] oxazoline,

2- (4-biphenoylmethylene) -3-methyl-naphtho [2,1-d] oxazoline,

2- (4-biphenoylmethylene) -3-methyl-naphtho [1,2-d] oxazoline,

2- (p-fluorobenzoylmethylene) -3-methyl-naphtho [2,1-d] oxazoline,

2- (p-fluorobenzoylmethylene) -3-methyl-naphtho [1,2-d] oxazoline, etc. are mentioned.

Especially, 2-benzoylmethylene-3-methyl-naphtho [1,2-d represented by 2- (2-naphthoylmethylene) -3-methylbenzothiazoline represented by Formula (9), and Formula (10). ] Thiazoline and 2- (4-biphenoylmethylene) -3-methyl-naphtho [1,2-d] thiazoline represented by formula (11) are preferable.

The compound represented by Formula (V) and Formula (VI) is the following compound.

In Formulas (V) and (VI), Ring X ³¹ and Ring X ³² each independently represent an aromatic ring having 6 to 12 carbon atoms. Y ³¹ and Y ³² represent an oxygen atom or a sulfur atom. R <^31> and R <^32> represents a C1-C12 alkyl group or a C6-C12 aryl group.

The carbon atoms contained in these aromatic rings, alkyl groups or aryl groups may be substituted with oxygen atoms, nitrogen atoms or sulfur atoms, and the hydrogen atoms contained in these aromatic rings, alkyl groups or aryl groups may be substituted with halogen atoms. In addition, the hydrogen atom contained in an aryl group may be substituted by the hydroxyl group or the alkoxy group.

As a hydroxyl-substituted aryl group, a hydroxyphenyl group, a hydroxy naphthyl group, etc. are mentioned.

As an alkoxy group, a C1-C6 alkoxy group is mentioned, for example. Specifically, methoxy, ethoxy, propoxy, butoxy, etc. are mentioned.

Examples of the alkoxy group substituted aryl group include methoxyphenyl, ethoxyphenyl, propoxyphenyl, methoxynaphthyl, ethoxynaphthyl, propoxynaphthyl and the like.

As a compound represented by Formula (V) or Formula (VI), specifically,

Dialkoxynaphthalenes such as dimethoxynaphthalene, diethoxynaphthalene, dipropoxynaphthalene, diisopropoxynaphthalene, dibutoxynaphthalene,

Dimethoxy anthracene, diethoxy anthracene, dipropoxy canthracene, diisopropoxy canthracene, dibutoxy anthracene, dipentaoxy anthracene, dihexaoxy anthracene, methoxyethoxy anthracene, methoxy propoxy canthracene, methoxy isopropoxy Dialkoxy such as anthracene, methoxybutoxy anthracene, ethoxy propoxycanthracene, ethoxy isopropoxy canthracene, ethoxy butoxy anthracene, propoxy isopropoxy thracene, propoxy butoxy anthracene, isopropoxy butoxy anthracene Anthracene,

And dialkoxy naphthacenes such as dimethoxynaphthacene, diethoxy naphthacene, dipropoxynaphthacene, diisopropoxynaphthacene and dibutoxynaphthacene.

Content of a polymerization start adjuvant (C-1) is mass fraction with respect to the total amount of resin (A) and a polymerizable monomer (B), Preferably it is 0.01-50 mass%, More preferably, it is 0.1-40 mass%.

In particular, when using a polyfunctional thiol compound as a polymerization start adjuvant (C-1), the content is a mass fraction with respect to a polymerization initiator (C), Preferably it is 0.5-20 mass%, More preferably, 1- 15 mass%.

Moreover, content of the compound represented by at least 1 sort (s) chosen from the group which consists of Formula (V) and Formula (VI) becomes like this. Preferably it is 50-100 mass% with respect to content of a polymerization start adjuvant (C-1), More preferably Preferably it is 60-100 mass%, More preferably, it is 65-100 mass%. When content of these compounds exists in this range, when the coating film is formed using the photosensitive resin composition containing this, transparency of a coating film becomes favorable and it is preferable.

When the amount of the polymerization initiation assistant (C-1) is in the above-described range, the sensitivity of the photosensitive resin composition obtained becomes higher, developability becomes good, and the tendency that the productivity of the pattern formed by using the photosensitive resin composition is improved. have.

The photosensitive resin composition of this invention contains a solvent (D). Examples of the solvent (D) include various organic solvents used in the field of the photosensitive resin composition.

Specific examples include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether;

Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether;

Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol monoethyl ether acetate;

Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate;

Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether;

Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol ethyl methyl ether, propylene glycol dipropyl ether, propylene glycol propyl methyl ether and propylene glycol ethyl propyl ether;

Propylene glycol alkyl ether propionates such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate and propylene glycol butyl ether propionate;

Butyl diol monoalkyl ethers such as methoxy butyl alcohol, ethoxy butyl alcohol, propoxy butyl alcohol and butoxy butyl alcohol;

Butanediol monoalkyl ether acetates, such as methoxy butyl acetate, ethoxy butyl acetate, propoxy butyl acetate, and butoxy butyl acetate:

Butanediol monoalkyl ether propionate, such as a methoxy butyl propionate, an ethoxy butyl propionate, a propoxy butyl propionate, butoxy butyl propionate;

Dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, and dipropylene glycol methyl ethyl ether;

Aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene;

Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone;

Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin;

Methyl acetate, ethyl acetate, propyl acetate, butyl acetate, 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate , Butyl hydroxy acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, 2-hydroxy 3-Methyl methyl butyrate, methyl methoxy acetate, ethyl methoxy acetate, methoxy acetate propyl, butyl acetate, ethoxy acetate methyl, ethoxy acetate, ethoxy acetate propyl, butyl ethoxy acetate, propoxy Methyl acetate, ethyl propoxy acetate, propyl propoxy acetate, butyl propoxy acetate, methyl butoxy acetate, ethyl butoxy acetate, Propyl acetate, butyl butoxy acetate, methyl 2-methoxypropionate, 2-methoxy ethylpropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate Propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, 3-methoxy ethylpropionate, 3-methoxy propylpropionate, 3-methoxy propylpropionate, 3-ethoxy propylpropionate, 3-ethoxy propylpropionate, 3-ethoxy propylpropionate, 3-ethoxy propylpropionate, 3 Methyl propoxypropionate, 3-propoxy propionate, 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, 3-butoxypropionic acid Esters such as ropil, 3-butoxy-propionic acid butyl;

Cyclic ethers such as tetrahydrofuran and pyran;

Cyclic ester, such as (gamma) -butyrolactone, etc. are mentioned.

The said solvent (D) contains the solvent whose boiling point is 140 degreeC or more and 175 degrees C or less from a viewpoint of applicability | paintability and dryness. As a solvent whose boiling point is 175 degreeC or less, Alkylene glycol alkyl ether acetates; Alcohols such as methoxybutanol and ethoxybutanol, ketones such as cyclohexanone; Ester, such as 3-ethoxy propionate ethyl, 3-methoxy methyl propionate, 3-ethoxy acetate ethyl, 3-methoxy butyl acetate, and 3-ethoxy acetate butyl, is mentioned, Preferably it is methoxy butanol And methoxy butyl acetate, ethyl 3-ethoxypropionate and methyl 3-methoxypropionate.

These solvents (D) can be used individually or in mixture of 2 or more types, respectively, It is preferable to mix 2 or more types. Moreover, the thing of boiling point exceeding 175 degreeC may contain in the solvent (D).

Moreover, it is preferable that a C1-C6 alcohol is contained in a solvent (D). Such alcohol can be suitably selected from the above-mentioned solvent. It is preferable that boiling point of this alcohol is 175 degreeC or less, but it may exceed boiling point 175 degreeC.

Content of the solvent (D) in the photosensitive resin composition of this invention is a mass fraction with respect to the photosensitive resin composition, Preferably it is 60-90 mass%, More preferably, it is 65-85 mass%. If content of a solvent (D) exists in this range, applicability | paintability becomes favorable, when apply | coating with the various coating apparatuses mentioned later. Moreover, when the boiling point contains the solvent exceeding 175 degreeC, such a solvent is preferable about 30 mass% or less in all the solvents.

Surfactant (E) in the photosensitive resin composition of this invention is not specifically limited, For example, silicone type surfactant, a fluorochemical surfactant, silicone type surfactant which has a fluorine atom, etc. are mentioned. Especially, silicone type surfactant which has a fluorine atom is preferable. By using such surfactant (E), generation | occurrence | production of the microbubble contained in a composition can be prevented with the other component in its photosensitive resin composition and its content. As a result, the dolby at the time of solvent evaporation can be suppressed effectively.

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), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (made by Shin-Etsu Silicone), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (made by GE Toshiba Silicone Co., Ltd.), etc. are mentioned.

As a fluorine type surfactant, surfactant which has a fluorocarbon chain | strand is mentioned. Specifically, Furolinato (trademark) FC430, copper FC431 (manufactured by Sumitomo 3M Co., Ltd.), mega pack (trademark) F142D, copper F171, copper F172, copper F173, copper F177, copper F183, copper R30 ( Dainippon Ink & Chemicals Co., Ltd.), F-Top (registered trademark) EF301, East EF303, East EF351, East EF352 (manufactured by Shin-Akita Chemical Co., Ltd.) And SC105 (manufactured by Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Fine Chemical Research Institute Co., Ltd.), BM-1000, and BM-1100 (all manufactured by BM Chemie Co., Ltd.).

As silicone type surfactant which has a fluorine atom, surfactant which has a siloxane bond and a fluorocarbon chain | strand is mentioned. Specifically, Megapack (registered trademark) R08, Copper BL20, Copper F475, Copper F477, Copper F443 (manufactured by Dainippon Ink Chemical Industries, Ltd.), and the like can be given. Preferably Megapack (trademark) F475 is mentioned.

Surfactant (E) is 0.0025-0.0250 mass% normally with respect to 100 mass% of photosensitive resin compositions except surfactant, Preferably it is 0.0025-0.0200 mass%, More preferably, it is 0.05-0.0100 mass%. By containing surfactant in this range, flatness can be made favorable and it becomes possible to prevent Dolby effectively as mentioned above.

In the photosensitive resin composition of this invention, you may use together additives, such as a filler, polymeric compounds other than resin (A), an adhesion promoter, antioxidant, a ultraviolet absorber, a light stabilizer, an aggregation inhibitor, and a chain transfer agent.

Moreover, it is suitable that the photosensitive resin composition of this invention does not contain coloring agents, such as a pigment and dye, substantially. In short, in the photosensitive resin composition of this invention, the content of the coloring agent with respect to the whole composition is a mass fraction, less than 1 mass% is suitable, Preferably it is less than 0.5 mass%.

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

As polymer compounds other than the resin (A), curable resins such as epoxy resins and maleimide resins and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ethers, polyfluoroalkyl acrylates, polyesters and polyurethanes Etc. can be mentioned.

As an adhesion promoter, a silane type compound is preferable. Specifically, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2 -Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimeth Oxysilane, etc. are mentioned.

As antioxidant, 2-tert- butyl-6- (3-tert- butyl- 2-hydroxy-5- methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-3, 5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenylacrylate, 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy]- 2,4,8,10-tetra-tert-butyldibenz [d, f] [1,3,2] dioxaphosphine, 3,9-bis [2- {3- (3-tert-butyl- 4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 2,2'-methylenebis (6-tert -Butyl-4-methylphenol), 4,4'-butylidenebis (6-tert-butyl-3-methylphenol), 4,4'-thiobis (2-tert-butyl-5-methylphenol) , 2,2'-thiobis (6-tert-butyl-4-methylphenol), dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distea Reel 3,3'- thiodipropionate, pentaerythritol tetrakis (3-laurylthiopropionate), 1,3,5-tris (3,5-di-tert-butyl-4-hydride rock Benzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 3,3 ', 3' ', 5,5', 5 ''-hexa-tert- Butyl-a, a ', a' '-(mesitylene-2,4,6-triyl) tri-p-cresol, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4 -Hydroxyphenyl) propionate], 2,6-di-tert-butyl-4-methylphenol and the like.

As a ultraviolet absorber, 2- (2-hydroxy-5-tert- butylphenyl) -2H-benzotriazole, octyl-3- [3-tert- butyl- 4-hydroxy-5- (5-chloro- 2H-benzotriazol-2-yl) phenyl] propionate, 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [4-[(2-hydroxy-3- (2'-ethyl) hexyl) oxy] -2-hydroxyphenyl]- 4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-butyloxyphenyl) -6- (2,4-bis- Butyloxyphenyl) -1,3,5-triazine, 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1 , 3,5-triazine, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazole-2- Yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl ) -5-chlorobenzotriazole, alkoxybenzophenone, etc. are mentioned.

As a light stabilizer, a polymer consisting of succinic acid and (4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yl) ethanol, N, N ', N' ', N' ''- Tetrakis (4,6-bis (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) triazin-2-yl) -4,7-diaza Decane-1,10-diamine, decandioic acid, bis (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester, 1,1-dimethylethylhydro Reactant of peroxide, bis (1,2,2,6,6-pentamethyl-4-piperidinyl)-[[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl ] Butylmalonate, 2,4-bis [N-butyl-N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) amino] -6- (2 Hydroxyethylamine) -1,3,5-triazine, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate or methyl (1,2,2,6, 6-pentamethyl-4-piperidinyl) sebacate and the like.

Examples of the aggregation inhibitor include sodium polyacrylate.

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

It is preferable that solid content of the photosensitive resin composition of this invention is about 10-30 weight%, More preferably, it is 12-28 weight%, More preferably, it is 15-25 weight%. By setting it as this range, even a various coating method, especially the slit method, does not generate | occur | produce a defect, cloudy stain, etc., and can form a uniform coating film.

Moreover, when the photosensitive resin composition of this invention is filled into the quartz cell whose optical path length is 1 cm, and transmittance | permeability is measured on the conditions of 400-700 nm of measurement wavelengths using a spectrophotometer, a transmittance | permeability is usually 70% or more, Preferably it is Is 80% or more.

When the photosensitive resin composition of this invention is used as a coating film, it is preferable that the transmittance | permeability of a coating film is 90% or more, and it is more preferable to be 95% or more. This transmittance | permeability was measured on the coating film whose thickness after heat-hardening (for example, 100-250 degreeC and 5 minutes-3 hours) is 3 micrometers using the spectrophotometer on the conditions of the measurement wavelength 400-700 nm. Value. Thereby, the coating film excellent in transparency can be provided.

The photosensitive resin composition of this invention is a base material, for example, as mentioned later; Substrates such as glass, metal and plastics; A coating film can be formed by apply | coating on these board | substrates which formed the color filter, various insulated or electrically conductive films, a drive circuit, etc. It is preferable that a coating film was dried and hardened | cured. Moreover, the obtained coating film can also be patterned in a desired shape, and can also be used as a pattern. In addition, you may form these coating films or patterns as a part of component parts, such as a display apparatus.

First, the photosensitive resin composition of this invention is apply | coated on the base material or the layer which consists of solid content of the photosensitive resin composition previously formed.

A coating method is not specifically limited, For example, coating apparatuses, such as a spin coater, a slit & spin coater, a slit coater (it may be called a die coater, a curtain flow coater)), an inkjet, a roll coater, a dip coater, are used, for example. Can be carried out. Among them, it is preferable to use coating by the slit coating method, that is, a slit & spin coater, a slit coater, etc. in view of solubility, drying prevention, and foreign matter generation.

Subsequently, it is preferable to dry or prebak and remove volatile components, such as a solvent. Thereby, a smooth uncured coating film can be obtained. In particular, drying under reduced pressure is preferable. The reduced-pressure drying here should just be removed to the extent that it does not become an obstacle in a subsequent process by removing at least one part of a solvent, It does not necessarily need to remove all the solvent from a coating film. It is preferable to carry out drying under reduced pressure at room temperature (25 degreeC) conditions, and normal pressure in the range of 10-500 Pa of arrival pressure, More preferably, it is 30-400 Pa, More preferably, it is 50-300 Pa. There is no restriction | limiting in vacuum drying time, and it can set suitably in consideration of a film thickness, the magnitude | size of a board | substrate, the solvent amount of the photosensitive resin composition, etc. Usually, 10 to 60 second is preferable. In order to apply such relatively strict pressure-reduced drying conditions, the decompression rate may be changed in multiple stages until the final attained pressure is reached. For example, a smoother uncured film can be obtained by controlling the depressurization rate in two stages for about 10 seconds for the time from 130 to 10 Pa for 130 seconds to 66 Pa for 10 seconds.

The film thickness of the coating film in this case is not specifically limited, It can adjust suitably according to the material, a use, etc. to use, Usually it is about 0.1-30 micrometers, Preferably it is about 1-20 micrometers, More preferably, it is 1-6 micrometers The degree is illustrated.

And the obtained uncured coating film is irradiated with light, for example, the ultraviolet-ray generate | occur | produced in a mercury lamp, a light emitting diode, etc. via the mask for forming the target pattern. The mask shape at this time is not specifically limited, Various shapes are mentioned. The line width and the like can also be appropriately adjusted according to the mask size and the like.

In a recent exposure machine, the bandpass filter which cuts the light of less than 350 nm using the filter which cuts this wavelength range, or extracts these wavelength ranges the light of 436 nm vicinity, 408 nm vicinity, and 365 nm vicinity is used. It can take out selectively using, and can irradiate a parallel light beam uniformly to the whole 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.

After that, the coating film is brought into contact with an aqueous alkali solution to dissolve and develop a predetermined portion, for example, a non-exposed portion, to obtain a target pattern shape.

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

The developing solution used for image development is an aqueous solution containing an alkaline compound and surfactant normally.

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

As an inorganic alkaline compound, 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, potassium carbonate, sodium bicarbonate And potassium hydrogen carbonate, sodium borate, potassium borate, ammonia and the like.

Moreover, as an organic alkaline compound, tetramethylammonium hydroxide, 2-hydroxyethyl trimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropyl Amine, diisopropylamine, ethanolamine, etc. are mentioned.

The concentration of the alkaline compound in the alkaline developer is preferably 0.01 to 10 mass%, more preferably 0.03 to 5 mass%.

The surfactant in the alkaline developer may be any of nonionic surfactants, anionic surfactants, or cationic surfactants.

As nonionic surfactant, polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbent Non-fatty fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, etc. are mentioned.

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, sodium dodecylbenzene sulfonate and dodecyl naphthalene. Alkyl aryl sulfonates, such as sodium sulfonate, etc. are mentioned.

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

The concentration of the surfactant in the alkaline developer is preferably in the range of 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, still more preferably 0.1 to 5% by mass.

After image development, you may wash with water and post-bake as needed. Post-baking is suitable for the temperature range of 150-230 degreeC for 10 to 180 minutes.

In particular, it is preferable to use the photosensitive resin composition of this invention in order to manufacture a coating film by apply | coating the photosensitive resin composition of this invention using a slit coater on a board | substrate, forming a film, and drying the film formed on the board | substrate under reduced pressure.

In addition, it is preferable to use the obtained coating film in order to manufacture a pattern by exposing through a photomask and developing the exposed coating film.

The coating film or pattern obtained in this way is useful as a photospacer used for a liquid crystal display device, and a patternable overcoat, for example. In addition, during patterning exposure to an uncured coating film, a hole can be formed by using a hole forming photomask, which is useful as an interlayer insulating film. And at the time of exposing to an uncured coating film, a transparent film can be formed by performing whole surface exposure and heat hardening or heat hardening without using a photomask. This transparent film is useful as an overcoat. It can also be used for display devices such as touch panels. Thereby, it is possible to manufacture a display apparatus provided with a high quality coating film or a pattern with high yield.

The photosensitive resin composition of the present invention is a material for forming various films and patterns, for example, a transparent film, in particular a transparent film constituting a part of a color filter, a pattern, a photo spacer, an overcoat, an insulating film, a projection for controlling the alignment of liquid crystals. , A microlens, a coloring pattern combining different film thicknesses, and a coating layer can be preferably used. Moreover, a color filter, an array substrate, etc. which comprise these coating films or patterns as a part of its component parts, Furthermore, the display apparatus provided with such a color filter and / or an array substrate, etc., for example, a liquid crystal display device, an organic EL device, etc. It is available.

According to the photosensitive resin composition of this invention, generation | occurrence | production of defects, cloudy stains, etc. resulting from the dolby of a solvent are suppressed, and it can form a uniform, high quality coating film over the whole coating film.

Moreover, a high quality display device can be obtained by using such a photosensitive resin composition.

Example

Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by these Examples. In addition, in the following examples and comparative examples,% and part which show content or usage-amount are a mass reference | standard unless there is particular notice.

Synthesis Example 1

In a 1 L flask equipped with a reflux cooler, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min in a nitrogen atmosphere, 200 parts by mass of 3-methoxy-1-butanol and 105 parts by mass of 3-methoxybutyl acetate were added thereto. It heated to 70 degreeC, stirring.

Next, 60 parts by mass of methacrylic acid, a mixture of 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl acrylate (a compound represented by formula (I-1) and a compound represented by formula (II-1), Molar ratio = 50:50) 240 parts by mass were dissolved in 140 parts by mass of 3-methoxybutyl acetate to prepare a solution.

The obtained solution was dripped in the flask kept warm at 70 degreeC over 4 hours using the dropping funnel.

On the other hand, the solution which melt | dissolved 45 mass parts of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 225 mass parts of 3-methoxybutyl acetates in the flask over 4 hours using another dropping funnel. It dripped.

After completion of the dropwise addition of the polymerization initiator solution, the mixture was kept at 70 ° C for 4 hours, and then cooled to room temperature to obtain a resin solution of a copolymer (resin Aa) having a solid content of 32.3% by mass and an acid value of 35.6 mg-KOH / g. . The weight average molecular weight (Mw) of obtained resin Aa was 9.1 * 10 <^3> , and dispersion degree was 2.02.

Synthesis Example 2

In a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to make a nitrogen atmosphere, and 140 parts by mass of diethylene glycol ethylmethyl ether was added and heated to 70 ° C while stirring.

Next, a mixture of 40 parts by mass of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl acrylate (a compound represented by formula (I-1) and a compound represented by formula (II-1)) Molar ratio = 50:50) 360 parts by mass was dissolved in 190 parts by mass of diethylene glycol ethylmethyl ether to prepare a solution.

The obtained solution was dripped in the flask kept warm at 70 degreeC over 4 hours using the dropping pump.

On the other hand, the solution which melt | dissolved 30 mass parts of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 240 mass parts of diethylene glycol ethyl methyl ethers in the flask over 5 hours using another dropping pump. It dripped.

After completion of the dropwise addition of the polymerization initiator solution, the mixture was maintained at 70 ° C for 4 hours, and then cooled to room temperature, thereby obtaining a solution of a copolymer (resin Ab) having a solid content of 42.6 mass% and an acid value of 60 mg-KOH / g. The weight average molecular weight (Mw) of obtained resin Ab was 8.0x10 <^3> , and dispersion degree was 1.91.

About the measurement of the weight average molecular weight (Mw) and number average molecular weight (Mn) of the said binder polymer, it carried out 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 of the weight average molecular weight and number average molecular weight of polystyrene conversion obtained above was made into dispersion degree (Mw / Mn).

Examples 1-8, Comparative Examples 1-3

Each component was mixed with the composition of Table 1, and the photosensitive resin composition was obtained.

In addition, in Table 1,

Polymerizable monomer (B); Dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Gunpowder Co., Ltd.)

Polymerization initiator (C); 2-methyl-1- (4-methylsulfanylphenyl) -2-morpholinopropane-1-one (irgacure 907; manufactured by Chiba Specialty Chemicals)

Solvent (Da); 3-methoxy-1-butanol (boiling point 161 ° C.)

Solvent (Db); Ethyl 3-ethoxypropionate (boiling point 170 캜)

Solvent (Dc); 3-methoxybutyl acetate (boiling point 171 ° C)

Solvent (Dd); Diethylene glycol ethyl methyl ether (boiling point: 176 ° C)

Solvent (De); Propylene glycol monomethyl ether acetate (boiling point 146 ℃)

Solvent (Df); Benzyl Alcohol (boiling point 205 ℃)

Solvent (Dg); Ethylene Glycol Monobutyl Ether Acetate (boiling point 192 ℃)

Surfactant (E); It is polyether modified silicone oil (SH8400 manufactured by Toray Dow Corning Co., Ltd.).

A solvent (D) mixes so that solid content of a composition may become "solid content (%)" of Table 1, and the value of the solvent component in a solvent (D) shows the mass ratio in a solvent (D). Content of surfactant (E) shows the mass ratio with respect to 100 mass% of photosensitive resin compositions except surfactant.

<Evaluation of Dolby and Blurry Spots>

The composition solution prepared on the 15-cm-thick ITO film-formed glass substrate was apply | coated on the conditions which the film thickness after hardening will be 3.0 micrometers using the slit die coater (made by Takudai-100 Itutochugi Co., Ltd. product). Thereafter, the reduced pressure was dried under reduced pressure to 0.5 torr with a reduced pressure drier (manufactured by VCD Microtech Co., Ltd.), and prebaked at 90 ° C for 2 minutes on a hot plate to form a coating film A.

The obtained coating film A was cooled, the surface was illuminated with Na lamp, and the coating film surface was visually confirmed.

When the defect resulting from Dolby was clearly able to be confirmed, it was X, and when it was barely able to confirm, it was set as (triangle | delta), and when it was hardly confirmed, it was set as (circle).

In the case where the cloudy spots could be clearly identified, ×, in the case of barely confirmed, △, and in the case of almost no confirmation, it was set as ○.

<Evaluation of Uniformity>

About the obtained coating film A, the film thickness in the measuring point which aligned within the distance of 12.5 mm from the end part on the matrix by 12.5 mm interval was measured. The maximum film thickness, the minimum film thickness, and the average film thickness were calculated | required and evaluated by Formula (1).

Unity (%) = (Maximum Film Thickness × Min Film Thickness) / (2 × Average Film Thickness) × 100 (1)

When uniformity was less than 3%, it was set as (circle), and in the case of 3 to 5%, (triangle | delta) and 5% or more.

<Evaluation of reduced pressure drying time>

The prepared composition solution was applied onto the ITO film-forming glass substrate having a width of 15 cm by using a slit die coater (manufactured by Takudai-100 Itochu Sangi Co., Ltd.) under conditions such that the film thickness after curing was 3.0 µm. Then, the time until a pressure reduction degree reaches 66 Pa under conditions of 1800 rpm, booster pump rotation speed 3600 rpm, and normal temperature 25 degreeC with a rotary pump rotation speed by a pressure reduction dryer (made by VCD Microtech Co., Ltd.) (following, VCD time) was measured.

The shorter the VCD time is, the better.

[Industry availability]

The photosensitive resin composition of this invention can apply | coat uniformly over the whole surface of a large area, and generation | occurrence | production of defects, cloudy stains, etc. resulting from the dolby of a solvent are suppressed. In addition, excellent resolution can be exhibited and a pattern of high transmittance can be formed. Therefore, it can use suitably for formation of the coating film and pattern used for a display apparatus, such as an overcoat, a photo spacer, an insulating film, the processus | protrusion for liquid crystal orientation control, and the coating layer for adjusting the film thickness of a coloring pattern.

Claims (8)

As a photosensitive resin composition containing resin (A), a polymerizable monomer (B), a polymerization initiator (C), a solvent (D), and surfactant (E), A solvent (D) is a solvent containing two or more types of solvents whose boiling point is 175 degreeC or less, Content of surfactant (E) is 0.0025-0.0250 weight% with respect to 100 weight% of photosensitive resin compositions except surfactant, The photosensitive resin composition whose solid amount is 10-30 weight%. The method of claim 1, The photosensitive resin composition whose solvent (D) is a solvent containing two or more types of solvents with a boiling point of 140 degreeC or more and 175 degrees C or less. The method according to claim 1 or 2, The photosensitive resin composition whose solvent (D) is a solvent containing a C1-C6 alcohol. 4. The method according to any one of claims 1 to 3, The photosensitive resin composition whose solvent (D) is a solvent containing 3-methoxybutanol. The method according to any one of claims 1 to 4, The photosensitive resin composition whose surfactant (E) is at least 1 sort (s) chosen from the group which consists of a silicone type surfactant, a fluorine type surfactant, and a silicone type surfactant which has a fluorine atom. The coating film formed using the photosensitive resin composition of any one of Claims 1-5. The pattern formed using the photosensitive resin composition of any one of Claims 1-5. A display device comprising the coating film of claim 6 and / or the pattern of claim 7.