KR101676871B1 - Photosensitive resin composition and display - Google Patents

Abstract

(A), a polymerizable compound (B), a polymerization initiator (C) and a solvent (D)

Wherein the solvent (D) is a solvent containing a dialkylene glycol dialkyl ether having an alkylene group having 1 to 3 carbon atoms and an alkyl group having 1 to 4 carbon atoms and an alcohol having 1 to 6 carbon atoms.

Description

[0001] PHOTOSENSITIVE RESIN COMPOSITION AND DISPLAY [0002]

The present invention relates to a photosensitive resin composition and a display device.

In recent liquid crystal display panels and the like, the size of the substrate is becoming larger. In order to form a transparent film or pattern such as a coat layer on the surface of a substrate, a photosensitive resin composition is formed by spin coating, slit & spin method or the like .

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

In this background, selection of a solvent type is sought to form a coating film of excellent quality. For example, a photosensitive resin composition using a mixture of propylene glycol monomethyl ether acetate, 3-ethoxyethyl propionate, 3-methoxy-1-butanol and 3-methoxybutyl acetate as a solvent has been disclosed For example, Patent Document 1).

[Patent Document 1] Japanese Unexamined Patent Application Publication No. 2008-181087 Paragraph 91

However, when a photosensitive resin composition using the above-described solvent is applied to a slit die coating method, which is a typical coating method, cloudy unevenness, vertical line unevenness and pin marks may occur, and a high quality coating film can not be obtained.

It is an object of the present invention to provide a photosensitive resin composition capable of forming a uniform and high quality coating film throughout the coating film by suppressing occurrence of cloudiness, vertical lines and pin marks, and a display device using the same.

That is, the present invention provides the following [1] to [8].

(1) A positive resist composition comprising a resin (A), a polymerizable compound (B), a polymerization initiator (C) and a solvent (D), wherein the solvent (D) contains an alkylene group having 1 to 3 carbon atoms and an alkyl group having 1 to 4 carbon atoms Wherein the solvent is a solvent containing a dialkylene glycol dialkyl ether and an alcohol having 1 to 6 carbon atoms.

[2] The photosensitive resin composition according to [1], wherein the solvent (D) is a solvent containing 30 to 90% by mass of a dialkylene glycol dialkyl ether based on the total amount of the solvent.

[3] The photosensitive resin composition according to [1] or [2], wherein the solvent (D) is a solvent containing 10 to 50 mass% of an alcohol having 1 to 6 carbon atoms relative to the total amount of the solvent.

[4] The photosensitive resin composition according to any one of [1] to [3], wherein the dialkylene glycol dialkyl ether is diethylene glycol ethyl methyl ether.

[5] The photosensitive resin composition according to any one of [1] to [4], wherein the alcohol having 1 to 6 carbon atoms is 3-methoxybutanol.

[6] A coated film formed by using the photosensitive resin composition according to any one of [1] to [5].

[7] A pattern formed by using the photosensitive resin composition according to any one of [1] to [5].

[8] A display device comprising at least one selected from the group consisting of the coating film of [6] and the pattern described in claim 7.

According to the present invention, it is possible to form a uniform and high-quality coating film over the entire coating film by suppressing the occurrence of cloudiness, vertical line unevenness and pin marks.

Further, by using this photosensitive resin composition, a high-quality display device or the like can be obtained.

The photosensitive resin composition of the present invention contains a resin (A), a polymerizable compound (B), a polymerization initiator (C) and a solvent (D). In the present specification, the compounds exemplified as respective components can be used alone or in combination, unless otherwise specified.

Examples of the resin (A) used in the photosensitive resin composition of the present invention include a resin (A1) having alkali solubility, a resin (A2) having an alkali solubility and at least one of the action of light and heat, and the like.

Examples of the resin (A1) having alkali solubility include (a) at least one (a) (hereinafter sometimes referred to as "(a)") selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, And a monomer (c) copolymerizable therewith (hereinafter referred to as " (c) ").

(a) specifically include, for example, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid;

Unsaturated dicarboxylic acids such as 1,4-cyclohexene dicarboxylic acid and methyl-5-norbornene-2,3-dicarboxylic acid;

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

Anhydrides of these unsaturated dicarboxylic acids;

(Meth) acryloyloxyalkyl (meth) acrylate of a divalent or higher polyvalent carboxylic acid such as succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- Esters;

-(히드록시메틸)아크릴산과 같은, 동일 분자 중에 히드록시기 및 카르복시기를 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.

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

(meth) acrylate such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, Acrylic acid alkyl esters;

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

Cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate (referred to in the art as dicyclopentanyl acrylate), dicyclopentoxy Acrylic acid cyclic alkyl esters such as ethyl acrylate and isobornyl acrylate;

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

Aryl acrylates such as phenyl acrylate and benzyl acrylate; Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconate;

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

2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 2.2.1] hept-2-ene, 5-carboxybicyclo [2.2.1] hepto-2-ene, 5-hydroxymethylbicyclo [2.2.1] 2.2.1] hepto-2-ene, 5-ethoxybicyclo [2.2.1] 2,6-dihydroxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] ) Bicyclo [2.2.1] hept-2-ene, 5,6-di (2'-hydroxyethyl) bicyclo [2.2.1] hept- 2,1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hepto-2- 2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept- 2.2.1] hepto-2-ene, 5-hydroxymethyl-5-methylbicyclo [ 2.2.1] hepto-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] 5,6-dicarboxybicyclo [2.2.1] hepto-2-ene anhydride (hydamic anhydride), 5-tert-butoxycarbonylbicyclo [2.2.1] hept- 2,6-di (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] 2.2.1] hept-2-ene, and 5,6-di (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N- Dicarbonylimide derivatives such as 6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate and N- (9-acridinyl) maleimide;

-메틸스티렌, m-메틸스티렌, p-메틸스티렌, 비닐톨루엔, p-메톡시 스티렌, 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, , 3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.

Of these, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and bicyclo [2.2.1] hept-2-ene are preferable in terms of copolymerization reactivity and alkali solubility.

(a) and (c) are used alone or in combination.

Also, in the present specification, (meth) acrylate means acrylate and / or methacrylate.

in the copolymer obtained by copolymerizing (a) and (c), the ratio of the constituent component derived from each other is in the range of the molar fraction in the range of the molar ratio of the constituent components constituting the copolymer to 100 mol% .

(a); 2 to 40 mol%

(c); 60 to 98 mol%

It is more preferable that the ratio of the constituent components is within the following range.

(a); 5 to 35 mol%

(c); 65 to 95 mol%

When the composition ratio is in the above range, storage stability, developability and solvent resistance tends to be good.

The above-mentioned alkali-soluble resin (A1) can be produced by, for example, the method described in "Experimental Method of Polymer Synthesis" (published by Otsu Takayuki Co., Ltd., 1st Edition, First Edition, March 1, 1972, Quot ;, references cited in the document, and the like.

Specifically, a predetermined amount of the units (a) and (c) constituting the copolymer, a polymerization initiator and a solvent are injected into a reaction vessel, and oxygen is substituted by nitrogen, thereby stirring, heating and keeping the mixture in the presence of oxygen A method is exemplified. The polymerization initiator and solvent used herein are not particularly limited, and any of those conventionally used in the art can be used. For example, a polymerization initiator and a solvent to be described later may be used.

The resulting copolymer may be a solution after the reaction as it is, or a concentrated or diluted solution may be used, or it may be taken out as a solid (powder) by a method such as re-precipitation. In particular, by using a solvent (D) described later as a solvent in the polymerization, the solution after the reaction can be used as it is, and the production process can be simplified (the same applies to the resin (A2)).

The weight average molecular weight of the resin (A1) having alkali solubility in terms of polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000. When the weight average molecular weight of the resin (A1) having alkali solubility is within the above range, the coating property tends to be good, the film is not easily reduced at the time of development, and the dropout of the non- It is preferable because it tends to be good.

The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the alkali-soluble resin (A1) is preferably 1.1 to 6.0, and more preferably 1.2 to 4.0. When the molecular weight distribution is within the above range, the developing property tends to be excellent.

The content of the alkali-soluble resin (A1) which can be used in the photosensitive resin composition of the present invention is preferably 5 to 90% by mass, more preferably 10 to 70% by mass, based on the solid content in the photosensitive resin composition . When the content of the resin (A1) having alkali solubility is in the above range, solubility in a developing solution is sufficient, development residues do not easily occur on the substrate of the non-pixel portion, It is preferable that the amount of the unexposed portion tends to be satisfactory.

As the resin (A2) having alkali solubility and reactivity by the action of at least one of light and heat,

(A2-1): Copolymers of (a) and (c) and a compound (b) having a cyclic ether structure having 2 to 4 carbon atoms (hereinafter may be referred to as "(b)")

Resin (A2-2): A copolymer obtained by reacting the copolymer (a) and (c) with (b)

Resin (A2-3): Copolymers of (a) and (b).

(b) is a compound having a cyclic ether structure having 2 to 4 carbon atoms, and refers to a polymerizable compound having at least one kind of group selected from the group consisting of an epoxy group, an oxetanyl group and a tetrahydrofuryl group. (b) is preferably a compound having a cyclic ether structure of 2 to 4 carbon atoms and also having an ethylenic carbon-carbon unsaturated bond, having a cyclic ether structure of 2 to 4 carbon atoms, and having an acryloyl group or a meta And more preferably a compound having a fluoroalkyl group.

(b1) having an epoxy group (hereinafter sometimes referred to as "(b1)") and an oxetanyl group-containing monomer (b2) (hereinafter referred to as "(b2)" ), A monomer having a tetrahydrofuryl group, and the like.

(b1) refers to, for example, a polymerizable compound having at least one group selected from the group consisting of an aliphatic epoxy group and an alicyclic epoxy group. The monomer having an epoxy group is preferably a compound having at least one kind of group selected from the group consisting of an aliphatic epoxy group and an alicyclic epoxy group and also having an ethylenic carbon-carbon unsaturated bond. The monomer having an aliphatic epoxy group and an alicyclic epoxy group , And more preferably a compound having an acryloyl group or a methacryloyl group.

Here, the aliphatic epoxy group means a monocyclic oxyanyl group, and the alicyclic epoxy group means a group having a structure in which a ring of an alicyclic hydrocarbon and an oxirane ring are condensed.

(B1) in the general formula (A2) include compounds having an aliphatic epoxy group and having an ethylenic carbon-carbon unsaturated bond such as glycidyl (meth) acrylate,? -Methyl glycidyl Acrylate,? -Ethylglycidyl (meth) acrylate, glycidyl vinyl ether, and compounds represented by the following formulas described in Japanese Patent Application Laid-Open No. 7-248625.

(Wherein R ¹¹ to R ¹³ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and m is an integer of 1 to 5).

-메틸-o-비닐벤질글리시딜에테르,

-메틸-m-비닐벤질글리시딜에테르,

-메틸-p-비닐벤질글리시딜에테르, 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. Examples of the compound represented by the above formula include o-vinylbenzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether,

Methyl-o-vinylbenzyl glycidyl ether,

Methyl-m-vinylbenzyl glycidyl ether,

-Methyl-p-vinylbenzyl glycidyl ether, 2,3-diglycidyloxymethylstyrene, 2,4-diglycidyloxymethylstyrene, 2,5-diglycidyloxymethylstyrene, 2, Diglycidyloxymethylstyrene, 2,3,4-triglycidyloxymethylstyrene, 2,3,5-triglycidyloxymethylstyrene, 2,3,6-triglycidyloxymethylstyrene, 3, , 4,5-triglycidyloxymethylstyrene, 2,4,6-triglycidyloxymethylstyrene, and the like.

Examples of the compound having an alicyclic epoxy group and having an ethylenic carbon-carbon unsaturated bond in the component (A2) include vinylcyclohexene monoxide 1,2-epoxy-4-vinylcyclohexane (for example, (Manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl acrylate (for example, Cyclam A 400, manufactured by Daicel Chemical Industries, Ltd.), 3,4- At least one compound selected from the group consisting of epoxy cyclohexylmethyl methacrylate (for example, Cyclam M 100, manufactured by Daicel Chemical Industries, Ltd.) or a compound represented by formula (I) and a compound represented by formula (II) And one kind of compound.

[In the formulas (I) and (II), R and R 'each independently represent an alkyl group having 1 to 4 carbon atoms which may be substituted with a hydrogen atom or a hydroxyl group.

X and X 'represents a single bond, each independently, C _1~6 alkylene group, an oxy -C _1~6 alkylene group, thio -C _1~6 alkylene group, amino -C _1~6 alkylene group, C _1~6 alkyl Oxy, C _1-6 alkylene group-thio, or C _1-6 alkylene-amino group,

Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and tert-butyl.

Examples of the hydroxyalkyl group include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxy-n-propyl group, a 2-hydroxy- Butyl group, a 2-hydroxy-n-butyl group, a 3-hydroxy-n-butyl group, A 4-hydroxy-n-butyl group and the like.

The substituents R and R 'are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, or a 2-hydroxyethyl group, more preferably a hydrogen atom or a methyl group.

Examples of the alkylene group include a methylene group, an ethylene group and a propylene group.

Examples of oxyalkylene groups include oxymethylene group, oxyethylene group, and oxypropylene group.

Examples of the alkyleneoxy group include a methyleneoxy group, an ethyleneoxy group and a propyleneoxy group.

Examples of the thioalkylene group include a thiomethylene group, a thioethylene group, and a thiopropylene group.

Examples of the alkylene thio group include a methylene thio group, an ethylene tie group and a propylene thio group.

Examples of the aminoalkylene group include an aminomethylene group, an aminoethylene group, and an aminopropylene group.

Examples of the alkyleneamino group include a methyleneamino group, an ethyleneamino group and a propyleneamino group.

The substituents X and X 'are preferably a single bond, a methylene group, an ethylene group, an oxymethylene group or an oxyethylene group, more preferably a single bond or an oxyethylene group.

Examples of the compound represented by formula (I) include compounds represented by formulas (I-1) to (I-15). (I-1), (I-3), (I-5), (I-7) ). (I-1), (I-7), (I-9) and (I-15) are more preferable.

Examples of the compound represented by the formula (II) include compounds represented by the formulas (II-1) to (II-15). (II-1), Formula (II-3), Formula (II-5), Formula (II-7), Formula ). (II-1), (II-7), (II-9) and (II-15).

At least one kind of compound selected from the group consisting of the compound represented by formula (I) and the compound represented by formula (II) may be used alone. In addition, they can be mixed at an arbitrary ratio. In the case of mixing, the mixing ratio thereof is preferably from 5:95 to 95: 5, more preferably from 10:90 to 90:10, and even more preferably from 20:10 to 90:10 in the formula (I): formula (II) : 80 to 80:20.

Examples of the compound having an oxetanyl group (b2) in the copolymers (A2-1) and (A2-2) and having an unsaturated bond include, for example, 3-methyl-3-methacryloxymethylox Cetyl, 3-methyl-3-acryloxymethyloxetane, 3-ethyl-3-methacryloxymethyloxetane, 3-ethyl-3-acryloxymethyloxetane, Cetane, 3-methyl-3-acryloxyethyl oxetane, 3-ethyl-3-methacryloxyethyl oxetane and 3-ethyl-3-acryloxyethyl oxetane.

In the copolymer (A2-1), it is preferable that the ratio of the component derived from each component is in the following range in terms of the mole ratio with respect to the total number of moles of the constituent components constituting the copolymer (A2-1).

(a); 2 to 40 mol%

(c); 1 to 65 mol%

(b1) or (b2); 2 to 95 mol%

It is more preferable that the ratio of the constituent components is within the following range.

(a); 5 to 35 mol%

(c); 1 to 60 mol%

(b1) or (b2); 5 to 80 mol%

When the composition ratio is in the above range, storage stability, developability, solvent resistance, heat resistance and mechanical strength tend to be improved.

The above-mentioned alkali-soluble resin (A2-1) can be produced, for example, by a method described in "Experimental Method of Polymer Synthesis" (published by Otsu Takayuki Co., Ltd., And reference documents cited therein, and the like.

Specifically, a predetermined amount of a compound that derives units (a), (c), and (b1) or (b2) constituting the copolymer, a polymerization initiator and a solvent are injected into a reaction vessel, , And stirring, heating, and keeping the mixture in the presence of oxygen.

The resin (A2-2) can be produced, for example, by a two-step process. Also in this case, the method described in the aforementioned " Experimental Method of Polymer Synthesis " (issued by Otsu Takayuki Co., Ltd., 1st Edition, First Edition, March 1, 1972), JP-A 2001-89533 And the like.

First, as a first step, a copolymer (i.e., a resin having alkali solubility) is obtained in the same manner as in the above-described method for producing an alkali-soluble resin (A1).

In this case, it can be continuously used in various forms as described above. The weight average molecular weight and the molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] in terms of polystyrene are suitable.

However, it is preferable that the proportion of the constituent components derived from (a) and (c), respectively, falls within the following range in terms of the molar ratio with respect to the total number of moles of the constituent components constituting the copolymer.

(a); 5 to 50 mol%

(c); 50 to 95 mol%

It is more preferable that the ratio of the constituent components is within the following range.

(a); 10 to 45 mol%

(c); 55 to 90 mol%

Next, as a second step, a part of the carboxylic acid and carboxylic acid anhydride (a) derived from the obtained copolymer is reacted with an epoxy group or an oxetanyl group derived from the above-mentioned (b1) or (b2).

Concretely, the atmosphere in the flask is replaced with air in the flask, and then air is introduced into the flask so that the amount of the component (b1) or (b2) is 5 to 80 mol% based on the number of moles of the component (a), the number of the carboxyl group and the epoxy group or the oxetanyl group For example, 0.001 to 5% by mass of trisdimethylaminomethylphenol based on the total amount of the monomers (a) to (c), and a polymerization inhibitor such as hydroquinone as monomers (a) to (c) is added to the flask in an amount of 0.001 to 5% by mass based on the total amount, and the reaction is continued at 60 to 130 ° C for 1 to 10 hours. Thus, the resin (A2-2) can be obtained. In addition, as with the polymerization conditions, the injection method and the reaction temperature can be appropriately adjusted in consideration of the amount of heat generated by the production equipment or polymerization.

In this case, the number of moles of (b1) or (b2) is preferably 10 to 75 mol%, and more preferably 15 to 70 mol% based on the number of moles of (a). When the content is in this range, the balance between storage stability, developability, solvent resistance, heat resistance, mechanical strength and sensitivity tends to be good.

In the resin (A2-3), it is preferable that the ratio of the constituent component derived from each of the resins (A2-3) falls within the following range in terms of the molar ratio with respect to the total number of moles of constituent components constituting the alkali-soluble resin (A2-3).

(a); 5 to 95 mol%

(b1) or (b2); 5 to 95 mol%

It is more preferable that the ratio of the constituent components is within the following range.

(a); 10 to 90 mol%

(b1) or (b2); 10 to 90 mol%

When the composition ratio is in the above range, storage stability, developability, solvent resistance, heat resistance and mechanical strength tend to be improved.

Resin (A2-3) can be synthesized by, for example, a method described in "Experimental Method of Polymer Synthesis" (published by Otsu Takayuki Co., Ltd., 1st Edition, First Edition, March 1, 1972) Quot ;, and references cited therein.

Specifically, a predetermined amount of a compound which derives units (a) and (b1) or (b2) constituting the copolymer, a polymerization initiator and a solvent are injected into a reaction vessel and oxygen is replaced by nitrogen, Under stirring, heating, and warming, a polymer is obtained. The solution obtained after the reaction may be used as it is, or a concentrated or diluted solution may be used, or it may be taken out as a solid (powder) by re-precipitation or the like.

The polymerizable compound (B) contained in the photosensitive resin composition of the present invention is not particularly limited as far as it has polymerizability, and examples thereof include monofunctional monomers, bifunctional monomers, and multifunctional monomers having three or more functionalities.

-, o-, m-, p-메틸스티렌, p-메톡시스티렌, p-tert부톡시스티렌, 클로로메틸스티렌 등의 스티렌류 ; Examples of monofunctional monomers include nonylphenylcarbitol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-ethylhexylcarbitol (meth) acrylate, 2- (Meth) acrylates such as caprolactone (meth) acrylate, ethoxylated nonylphenol (meth) acrylate and propoxylated nonylphenol (meth) acrylate; Styrene,

-, o-, m-, p-methylstyrene, p-methoxystyrene, p-tert-butoxystyrene, chloromethylstyrene and the like;

Dienes such as butadiene, 2,3-dimethylbutadiene, and isoprene;

(Meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, sec- (Meth) acrylic acid-dicyclohexyl (meth) acrylate, stearyl (meth) acrylate, dodecyl (meth) (Meth) acrylate-dicyclohexyl, (meth) acrylic acid-adamantyl, (meth) acrylic acid-isobornyl, (Meth) acrylic acid-anthracenyl, (meth) acrylic acid-cyclopentyl, (meth) acrylic acid-naphthyl, (meth) (Meth) acrylic acid-benzene, (meth) acrylic acid-phenesil, (meth) acrylic acid-cresyl (meth) Perfluoro-n-propyl (meth) acrylate, perfluoro (meth) acrylate, perfluoro (meth) acrylate, perfluoro Acrylic acid alkyl ester such as (meth) acrylic acid-triphenylmethyl, (meth) acrylic acid-adamantyl or (meth) acrylic acid-cumyl, cycloalkyl (meth) acrylate or aryl (meth) ;

(Meth) acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

(Meth) acrylic acid amides such as (meth) acrylic acid amide, -N, N-dimethylamide and -N, N-propylamide;

Vinyl compounds such as (meth) acrylic acid anilide, (meth) acrylonitrile, acrolein, vinyl chloride, vinylidene chloride, N-vinylpyrrolidone and vinyl acetate;

Unsaturated dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate;

-에틸글리시딜(메트)아크릴레이트,

-n-프로필글리시딜(메트)아크릴레이트,

-n-부틸글리시딜(메트)아크릴레이트, 3,4-에폭시부틸(메트)아크릴레이트, 3,4-에폭시헵틸(메트)아크릴레이트,

-에틸-6,7-에폭시헵틸(메트)아크릴레이트, 알릴글리시딜에테르, 비닐글리시딜에테르 등 글리시딜 화합물 등을 들 수 있다.Glycidyl (meth) acrylate,

- ethyl glycidyl (meth) acrylate,

n-propyl glycidyl (meth) acrylate,

(meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 3,4-epoxyheptyl (meth)

-Ethyl-6,7-epoxyheptyl (meth) acrylate, allyl glycidyl ether, vinyl glycidyl ether, and the like.

Specific examples of the bifunctional monomer include 1,3-butanediol di (meth) acrylate, 1,3-butanediol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, ethylene glycol di Acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol diacrylate, Bis (acryloyloxyethyl) ether of bisphenol A, ethoxylated bisphenol A di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) -Methylpentanediol di (meth) acrylate, and the like.

Examples of the multifunctional monomer having three or more functional groups include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, (Meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, (Meth) acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol Pentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate and acid anhydride, dipentaerythritol penta (meth) acrylate, (Meth) acrylate, caprolactone-modified caprolactone-modified trimethylolpropane tri (meth) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate, caprolactone-modified (Meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate, caprolactone-modified di Caprolactone-modified tripentaerythritol tetra (meth) acrylate, caprolactone-modified tripentaerythritol penta (meth) acrylate, caprolactone-modified tripentaerythritol hexa (meth) acrylate, caprolactone- Acrylate, caprolactone-modified tripentaerythritol hepta (meth) acrylate, caprolactone-modified (Meth) acrylate, a reaction product of caprolactone-modified pentaerythritol tri (meth) acrylate and an acid anhydride, a reaction product of caprolactone-modified dipentaerythritol penta (meth) acrylate and an acid anhydride, caprolactone Modified tripentaerythritol hepta (meth) acrylate and acid anhydride. Of these, monofunctional or higher functional monomers are preferably used.

The content of the polymerizable compound (B) is preferably 1 to 70% by mass, more preferably 5 to 60% by mass, based on the total amount of the resin (A) and the polymerizable compound (B). When the content of the polymerizable compound (B) is within the above range, the sensitivity and the strength, smoothness, reliability, and mechanical strength of the coating film and pattern tend to be favorable.

The polymerization initiator (C) contained in the photosensitive resin composition of the present invention is not particularly limited as far as it is a compound that initiates polymerization by the action of light or heat, and a known polymerization initiator can be used.

As the polymerization initiator (C), for example, a nonimidazole-based compound, an acetophenone-based compound, a triazine-based compound, an acylphosphine oxide-based compound or an oxime-based compound is preferable. It is also possible to use the photo- and / or thermal cationic polymerization initiator described in JP-A-2008-181087 (for example, an onium cation and an anion derived from Lewis acid). Among them, a nonimidazole-based compound is more preferable because of its excellent sensitivity.

Examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- ) -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'-tetra (alkoxy) Phenyl) imidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) ) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole (see, for example, Japanese Patent Publication No. 48-38403, Japanese Patent Application Laid-open No. 62-174204, Imidazole compounds in which the phenyl group at the 4'5,5'-position is substituted by a carboalkoxy group (see, for example, JP-A-7-10913). Preferred are 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole.

Examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy- 1- [4- Phenyl} -2-methylpropan-1-one, 2-hydroxy-1- {4- [4- (2- Methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino 1- (4-morpholinophenyl) -butanone, 2- (3-methylphenyl) butan- (4-morpholinophenyl) -butanone, 2- (4-methylbenzyl) -2-dimethylamino-1- , 2- (2-ethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) 2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2,3- Dimethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- 2- (2-chlorobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) 2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4-chlorobenzyl) -2-dimethyl 2- (4-morpholinophenyl) -butanone, 2- (3-bromobenzyl) -2-dimethylamino- (4-morpholinophenyl) -butanone, 2- (2-methoxybenzyl) -2-dimethylamino-1- Butanone, 2- (3-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) (4-morpholinophenyl) -butanone, 2- (2-methoxybenzyl) -2-methylamino- (2-bromo-4-methoxybenzyl) -2-dimethylamino-1- ( Oligomers of 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one.

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (Trichloromethyl) -6- [2- (5-methylfuran-2-yl) -1,3,5-triazine, ) Ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] Bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

Examples of the acylphosphine oxide-based initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like.

-옥시이미노-1-페닐프로판-1-온, 식 (Ⅲ) 으로 나타내는 화합물, 식 (Ⅳ) 로 나타내는 화합물 등을 들 수 있다. As the oxime compound, 0-ethoxycarbonyl-

-Oxyimino-1-phenylpropan-1-one, a compound represented by the formula (III) and a compound represented by the formula (IV).

It is also preferable to use the polymerization initiator (C-1) together with the polymerization initiator (C) described above. Examples of the polymerization initiation aid (C-1) include compounds represented by the formula (V).

[In the formula (V), the dotted line X represents an aromatic ring having 6 to 12 carbon atoms which may be substituted with a halogen atom.

Y represents an oxygen atom or a sulfur atom.

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

R ² represents an alkyl group having 1 to 12 carbon atoms which may be substituted with a halogen atom or an aryl group which may be substituted with a halogen atom;

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

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

Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a 1-methyl- butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-butyl group, -Propyl group, 2,2-dimethyl-n-propyl group, n-hexyl group, cyclohexyl group and the like.

Examples of the alkyl group having 1 to 12 carbon atoms which may be substituted with a halogen atom include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 1-methyl- butyl group, a 1-methyl-n-butyl group, a 1-methyl-n-propyl group, a 1-methyl- N-propyl group, a 2-dimethyl-n-propyl group, an n-hexyl group, a cyclohexyl group, Chloro-n-butyl group and the like.

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 chlorobenzophenyl group, a biphenyl group, a chlorobiphenyl group, a dichlorobiphenyl group, a bromophenyl group, A phenyl group, a naphthyl group, a chloronaphthyl group, a dichloronaphthyl group, a bromonaphthyl group, and a dibromonaphthyl group.

In the present specification, any of the chemical structural formulas is different depending on the number of carbon atoms. Unless otherwise specified, the examples given above apply to the respective substituents. Incidentally, all that can take both of a linear chain and a branch are included.

As the compound represented by the formula (V), 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.

Among them, 2- (2-naphthoylmethylene) -3-methylbenzothiazoline represented by the formula (V-1) and 2-benzoylmethylene-3-methylnaphtho [1,2-d] thiazoline and 2- (4-biphenoylmethylene) -3-methyl-naphtho [1,2-d] thiazoline represented by the formula (V-3).

The sensitivity of the photosensitive resin composition obtained by using these compounds becomes higher. It is preferable to form a coating film or a pattern by using the obtained photosensitive resin composition because the productivity of the coating film and the pattern can be improved. The compound represented by the formula (V) is preferable because it is not sublimated by the post-baking heat of the coating film but is discolored by the action of at least one of light and heat to improve transparency.

As the polymerization initiator (C-1), a compound represented by at least one kind selected from the group consisting of the formulas (VI) and (VII) may be used.

In the formulas (VI) and (VII), the rings X ¹ and X ² each independently represents an aromatic ring or heterocyclic ring having 6 to 12 carbon atoms which may be substituted with a halogen atom. Y ¹ and Y ² represent an oxygen atom or a sulfur atom. R ¹ and R ² represent an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms. These alkyl groups and aryl groups may be substituted with a halogen atom, a hydroxy group or an alkoxy group having 1 to 6 carbon atoms.

Examples of the aromatic ring or heterocyclic ring which may be substituted with a halogen atom include a benzene ring, a methylbenzene ring, a dimethylbenzene ring, an ethylbenzene ring, a propylbenzene ring, a butylbenzene ring, a pentylbenzene ring, a hexylbenzene ring, a cyclohexylbenzene ring, A chlorobenzene ring, a chlorobenzene ring, a dichlorobenzene ring, a bromobenzene ring, a dibromobenzene ring, a phenylbenzene ring, a chlorophenylbenzene ring, a bromophenylbenzene ring, a naphthalene ring, a chloronaphthalene ring, a bromanaphthalene ring, A chrysene ring, a fluoranthene ring, a benzo [a] pyrene ring, a benzo [e] pyrene ring, a perylene ring and derivatives thereof.

Examples of the hydroxy-substituted alkyl group include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, and a hydroxybutyl group.

Examples of the hydroxyl group-substituted aryl group include a hydroxyphenyl group and a hydroxynaphthyl group.

Examples of the alkoxy-substituted alkyl group include a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, a methoxybutyl group, a butoxymethyl group, an ethoxyethyl group, an ethoxypropyl group, and a propoxybutyl group.

Examples of the alkoxy-substituted aryl group include a methoxyphenyl group and an ethoxynaphthyl group.

Specifically, the compounds represented by the formulas (VI) and (VII)

Dialkoxynaphthalenes such as dimethoxynaphthalene, diethoxynaphthalene, dipropoxynaphthalene, diisopropoxynaphthalene, dibutoxynaphthalene and the like

But are not limited to, dimethoxyanthracene, dimethoxyanthracene, diethoxyanthracene, dipropoxyanthracene, diisopropoxyanthracene, dibutoxyanthracene, dipentaoxyanthracene, dihexaooxyanthracene, methoxyethoxyanthracene, methoxypropoxyanthracene, methoxyisopropoxy Examples of the alkoxy include alkoxy groups such as anthracene, methoxybutoxyanthracene, ethoxypropoxyanthracene, ethoxyisopropoxyanthracene, ethoxybutoxyanthracene, propoxyisopropoxyanthracene, propoxybutoxyanthracene, isopropoxybutoxyanthracene, Anthracene

And dialkoxynaphthacenes such as dimethoxynaphthacene, diethoxynaphthacene, dipropoxynaphthacene, diisopropoxynaphthacene, dibutoxynaphthacene, and the like.

A photopolymerization initiator may be used as the polymerization initiator (C) described above.

Examples of the photopolymerization initiator include a benzoin-based compound, a benzophenone-based compound, a thioxanthone-based compound, and an anthracene-based compound.

Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

Examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

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

Examples of the anthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene And the like.

Further, 10-butyl-2-chloroacridone, 2-ethyl anthraquinone, benzyl, 9,10-phenanthrenequinone, camphaquinone, methyl phenylglyoxylate, a titanocene compound and the like may be used as a photopolymerization initiator.

As a photopolymerization initiator having a group capable of causing chain transfer, a photopolymerization initiator described in JP-A-2002-544205 may be used.

Examples of the photopolymerization initiator having a group capable of causing chain transfer include photopolymerization initiators represented by the following formulas (1) to (6).

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

It is also preferable to use the polymerization initiator (C-2) together with the above-mentioned polymerization initiator

Examples of the polymerization initiator (C-2) include an amine compound and a carboxylic acid compound.

Examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine; aliphatic amine compounds such as methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl benzoate, 2-dimethylaminoethyl benzoate, N, N-dimethyl paratoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'- ) Benzophenone. ≪ / RTI >

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

The content of the polymerization initiator (C) is preferably 0.1 to 40% by mass, more preferably 1 to 30% by mass, based on the total amount of the resin (A) and the polymerizable compound (B).

When the total amount of the polymerization initiator (C) is within this range, the photosensitive resin composition becomes highly sensitive, and the strength of the coating film or pattern formed by using the photosensitive resin composition and the smoothness of the surface of the coating film or pattern become good It is preferable because there is a tendency.

The amount of the polymerization initiator (C-1) and / or the polymerization initiator (C-2) to be used is preferably 0.01 to 50% by mass, more preferably 0.01 to 50% by mass, based on the total amount of the resin (A) 0.1 to 40% by mass.

When the amount of the polymerization initiator (C-1) and / or the amount of the polymerization initiator (C-2) is within the above range, the sensitivity of the resulting photosensitive resin composition is further increased and productivity of the pattern substrate formed using the photosensitive resin composition is improved It is preferable because there is a tendency.

Particularly, when the compound represented by the formula (V) is used, the content thereof is preferably 50 to 100%, more preferably 60 to 100%, even more preferably 60 to 100% based on the content of the polymerization initiator (C-1) Is set at 65 to 100%. When the content of the compound represented by the formula (V) is within the above range, transparency of the coating film is favorable when the coating film is formed using the photosensitive resin composition containing the compound.

The photosensitive resin composition of the present invention may further contain a polyfunctional thiol compound (T). The polyfunctional thiol compound (T) is a compound having two or more sulfanyl groups in the molecule. Among them, when a compound having two or more sulfanyl groups bonded to carbon atoms of two or more aliphatic hydrocarbon groups is used, the sensitivity of the photosensitive resin composition of the present invention is high, which is preferable.

Specific examples of the polyfunctional thiol compound (T) include hexane dithiol, decane dithiol, 1,4-dimethyl mercaptobenzene, butanediol bis-thiophosphate, butanediol bis-thioglycolate, ethylene glycol bis- Trimethylolpropane trisphosphate, trimethylolpropane tristhioglycolate, butanediol bisthiouropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate , Trishydroxyethyl tris thiopropionate, pentaerythritol tetrakis (3-mercaptobutyrate), and 1,4-bis (3-mercaptobutyryloxy) butane.

The content of the polyfunctional thiol compound (T) is preferably 0.5 to 100% by mass, more preferably 1 to 90% by mass, based on the mass of the polymerization initiator (C). The content of the polyfunctional thiol compound is preferably 0.1 to 20% by mass, more preferably 1 to 10% by mass, based on the total amount of the binder resin (A) and the photopolymerizable compound (C). When the content of the polyfunctional thiol compound (T) is within this range, the sensitivity is preferably high and the developing property tends to be good.

The solvent (D) used in the photosensitive resin composition of the present invention preferably dissolves the components such as the resin (A), the polymerizable compound (B) and the polymerization initiator (C) uniformly and does not react with each component Do. It is more preferable that the solvent (D) is a solvent containing at least both of a specific dialkylene glycol dialkyl ether and a specific alcohol. The dialkylene glycol dialkyl ether and the alcohol may be used alone or in combination of two or more.

As the dialkylene glycol dialkyl ether, a solvent containing two or more alkylene groups each having 1 to 3 carbon atoms and an alkyl group having 1 to 4 carbon atoms, the alkylene group and the alkyl group may be the same or different.

Examples of such dialkylene glycol dialkyl ethers include diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-propyl ether, diethylene glycol isopropyl Methyl ethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol ethyl methyl ether, dipropylene glycol diethyl ether, dipropylene glycol methyl propyl ether, dipropylene glycol butyl methyl ether , Dipropylene glycol ethyl propyl ether, dipropylene glycol butyl ethyl ether, dipropylene glycol butyl propyl ether, and dipropylene glycol dibutyl ether. Among them, diethylene glycol ethyl methyl ether is preferable.

The dialkylene glycol dialkyl ether is contained preferably in an amount of 30 to 90 mass%, more preferably 30 to 80 mass%, and still more preferably 30 to 70 mass%, based on the total amount of the solvent (D). By setting this range, drying non-uniformity of the coating film can be suppressed. In short, when the coated film is dried, the solvent is usually dried by reduced pressure drying, and the pressure is reduced in a short time because the drying time is shortened. At this time, the solvent causes sudden boiling and causes drying non-uniformity. By using the dialkylene glycol dialkyl ether in this range, it is possible to effectively prevent drying non-uniformity of the coating film.

As the alcohol, an alcohol having 1 to 6 carbon atoms is preferable. The alcohol may be a monoalcohol or a polyhydric alcohol having two or more hydroxyl groups.

Examples of such alcohols include methanol, ethanol, propanol, butanol, pentanol, hexanol, cyclohexanol, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol Propylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, methyl lactate, ethyl lactate, propyl lactate, methyl 2-methyl lactate, diacetone alcohol, 3-methoxybutanol, glycerin, Methyl 2-hydroxypropionate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, methylhydroxyacetate, hydroxy Ethyl acetate, butyl hydroxyacetate, and the like. Among them, 3-methoxybutanol is preferred.

The content of the alcohol is preferably 10 to 50 mass%, more preferably 10 to 45 mass%, and still more preferably 15 to 40 mass% with respect to the total amount of the solvent (D).

By containing the alcohol in this range, the solubility of the resin and the like can be sufficiently obtained, and the uniformity of the coating film obtained by adjusting the viscosity to an appropriate level can be achieved. In addition, even when the photosensitive resin composition is applied using a slit die coater, the drying of the tip of the nozzle is prevented to prevent the foreign matter from being precipitated by the dried material, and the generation of vertical lines caused by the foreign matter can be reliably prevented .

Further, if necessary, the following solvents may be used in combination.

For example, 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 having 7 or more carbon atoms such as 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;

Butanediol monoalkyl ethers having 7 or more carbon atoms such as propoxybutanol and butoxybutanol;

Butanediol monoalkyl ether acetates such as methoxybutyl acetate, ethoxybutyl acetate, propoxybutyl acetate and butoxybutyl acetate;

Butanediol monoalkyl ether propionates such as methoxy butyl propionate, ethoxy butyl propionate, propoxy butyl propionate and butoxy butyl propionate;

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

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

And examples thereof include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, ethoxyacetate, ethoxyacetate, ethoxyacetate, Propoxyacetic acid, propoxyacetic acid, propoxyacetic acid, propoxyacetic acid, propoxyacetic acid, butoxyacetic acid, butoxyacetic acid, butoxyacetic acid, butoxyacetic acid, Ethoxypropionate, propyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, ethyl 2- methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, Butoxy propionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, 3-methoxy Ethoxypropionate, propyl 3-ethoxypropionate, propyl 3-ethoxypropionate, propyl 3-ethoxypropionate, propyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, Propoxy propionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, butyl 3-propoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, Esters such as propyl propionate and butyl 3-butoxy propionate;

Esters having a hydroxyl group having 7 or more carbon atoms such as butyl lactate, butyl 3-hydroxypropionate and methyl 2-hydroxy-3-methylbutanoate;

Cyclic ethers such as tetrahydrofuran and pyran;

and cyclic esters such as? -butyrolactone.

Among these solvents, an organic solvent having a boiling point of 100 占 폚 to 200 占 폚 is preferable from the viewpoint of coatability and drying property. Among them, esters such as alkylene glycol alkyl ether acetates, ketones, butanediol alkyl ether acetates, butanediol monoalkyl ethers having 7 or more carbon atoms, ethyl 3-ethoxypropionate and methyl 3-methoxypropionate are more preferable, More preferred are propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, methoxybutyl acetate, ethyl 3-ethoxypropionate and methyl 3-methoxypropionate.

However, it is preferable to use only the above-mentioned dialkylene glycol dialkyl ether and alcohol.

The content of the solvent (D) in the photosensitive resin composition of the present invention is preferably 60 to 90% by mass, more preferably 65 to 85% by mass, based on the mass of the photosensitive resin composition. When the content of the solvent (D) is within this range, in the various coating devices such as a spin coater, a slit & spin coater, a slit coater (also referred to as a die coater or a curtain flow coater), an ink jet, a roll coater, , A good coating property can be expected.

The photosensitive resin composition of the present invention contains substantially no coloring agent such as pigment and dye. That is, in the photosensitive resin composition of the present invention, the content of the colorant in the entire composition is, for example, less than 1% by mass, preferably less than 0.5% by mass.

For example, the photosensitive resin composition of the present invention is substantially free from the following colorants used in the art.

A compound classified as a pigment by the color index (published by The Society of Dyers and Colourists), specifically,

C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139 , 147, 148, 150, 153, 154, 166, 173, 194 and 214;

C.I. Orange pigments such as Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;

C.I. Red pigments such as Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, ;

C.I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, and 60;

C.I. Violet pigments such as Pigment Violet 1, 19, 23, 29, 32, 36, 38;

C.I. Green pigments such as Pigment Green 7, 36;

C.I. Brown pigments such as Pigment Brown 23 and 25;

C.I. Pigment Black 1, 7 black pigments.

Various additives such as fillers, other polymer compounds, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, light stabilizers, and chain transfer agents may be used in combination in the photosensitive resin composition of the present invention.

Examples of the filler include glass, silica, alumina and the like.

Examples of the other polymer compound include thermoplastic resins such as curable resin polyvinyl alcohol such as epoxy resin and maleimide resin, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, polyurethane and the like .

The surfactant may be any of a silicone surfactant, a fluorine surfactant, an ester surfactant, a cationic surfactant, an anionic surfactant, a nonionic surfactant, and an amphoteric surfactant. Specific examples include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, polyethyleneimines and the like , Commercially available surfactants can be used. (Manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoei Chemical Co., Ltd.), F-top (manufactured by Mitsubishi Materials Corporation), Megapack (manufactured by DIC Corporation) (Manufactured by Sumitomo 3M Ltd.), Safron (manufactured by AGC Seiyam Chemical Co., Ltd.), Solsperse (manufactured by Zeneca), EFKA (manufactured by CIBA), Ajisera PB821 Ltd.) and the like.

Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2 (aminoethyl) - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3- Tripropyl trimethoxysilane, and the like.

Examples of the antioxidant include 2-tert-butyl-6- (3- tert -butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- -3,5-di-tert-butylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 6- [3- (3- Bis [2- {3- [3- tert -butyl] benzo [d, f] [1,3,2] dioxaphospepine, 3,9- -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- Methylphenol), 2,2'-thiobis (6-tert-butyl-4-methylphenol), dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate , Distearyl 3,3'-thiodipropionate, pentaerythrityl tetrakis (3-laurylthiopropionate), 1,3,5-tris (3,5-di-tert- 4- 3,3 ', 3 ", 5,5', 5" -hexa-tert-butoxycarbonylamino) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) Butyl-a, a ', a "- (mesitylene-2,4,6-triyl) tri-p-cresol, pentaerythritol tetrakis [3- (3,5- Hydroxyphenyl) propionate], 2,6-di-tert-butyl-4-methylphenol and the like.

Examples of the ultraviolet absorber include 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole, octyl-3- [3- Phenyl] propionate, 2- [4 - [(2-hydroxy-3-dodecyloxypropyl) oxy] -2- (2,4-dimethylphenyl) -1,3,5-triazine, 2- [4 - [(2-hydroxy-3- Phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine, ) -1,3,5-triazine, 2- (2H-benzotriazol-2-yl) -4,6-bis 2- (3-tert-butyl-2-hydroxy-phenyl) -4- (1,1,3,3-tetramethylbutyl) 5-methylphenyl) -5-chlorobenzotriazole, and alkoxybenzophenone.

Examples of the light stabilizer include a polymer comprising succinic acid and (4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yl) ethanol, N, N ', N " -Tetrakis (4,6-bis (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4- yl) amino) triazin- (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester and 1,1-dimethylethylhydroxy ester of diazadecane-1,10- (1,2,2,6,6-pentamethyl-4-piperidinyl) - [[3,5-bis (1,1-dimethylethyl) -4- hydroxyphenyl] methyl ] Butyl malonate, 2,4-bis [N-butyl-N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin- - (hydroxyethylamine) -1,3,5-triazine, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, methyl Pentamethyl-4-piperidinyl) sebacate, and the like.

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

The photosensitive resin composition of the present invention can be applied to a substrate such as a substrate such as glass, metal, and plastic, a color filter, various insulating films or conductive films, a driving circuit, etc., Whereby a coating film can be formed. The coating film is preferably dried and cured. The obtained coating film may be patterned into a desired shape and used as a pattern. These coating films and / or patterns may also be formed and used as part of component parts such as display devices.

When the curable resin composition of the present invention is packed in a quartz cell having an optical path length of 1 cm and the transmittance is measured under the condition of a measurement wavelength of 400 to 700 nm using a spectrophotometer, the average transmittance is preferably 70% or more , And more preferably at least 75%. This makes it possible to form a transparent pattern or a coating film in the visible light region.

First, the photosensitive resin composition of the present invention is applied onto a substrate.

The application can be carried out using various coating apparatuses such as a spin coater, a slit & spin coater, a slit coater, an ink jet, a roll coater and a dip coater as described above. Among them, it is preferable to apply coating using a slit coating method, that is, coating using a slit & spin coater, a slit coater or the like, in terms of solubility, prevention of drying, prevention of generation of foreign matter,

Then, it is preferable to remove the volatile components such as a solvent by drying and / or prebaking. Thus, a smooth uncured coating film can be obtained.

The film thickness of the coating film in this case is not particularly limited and can be appropriately adjusted depending on the material to be used, the use, and the like, and is, for example, about 1 to 6 mu m.

Further, ultraviolet rays or the like generated from light-emitting diodes or the like is irradiated to the obtained uncured coating film through a mask for forming a desired pattern. The shape of the mask at this time is not particularly limited, and various shapes can be cited. In addition, the line width and the like can be appropriately adjusted in accordance with the mask size or the like.

In recent exposures, light having a wavelength of less than 350 nm is cut using a filter that cuts this wavelength region, or light having wavelengths around 436 nm, around 408 nm, and around 365 nm is extracted by a band- So that the parallel rays can be uniformly irradiated onto the entire exposure surface. In this case, a mask aligner, a stepper, or the like may be used to accurately align the mask and the substrate.

Thereafter, a desired pattern shape can be obtained by bringing the coating film into contact with an aqueous alkali solution to dissolve and develop a predetermined portion, for example, an unexposed portion.

The developing method may be any of a liquid mounting method, a dipping method, and a spraying method. Also, the base material may be inclined at an arbitrary angle during development.

The developing solution used for development is usually an aqueous solution containing an alkaline compound and a surfactant.

The alkaline compound may be any of inorganic and organic alkaline compounds.

Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogenphosphate, sodium dihydrogenphosphate, ammonium dihydrogenphosphate, ammonium dihydrogenphosphate, potassium dihydrogenphosphate, sodium silicate, sodium silicate, sodium carbonate, potassium carbonate , Sodium hydrogencarbonate, potassium hydrogencarbonate, sodium borate, potassium borate, and ammonia.

The organic alkaline compound includes, for example, tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine , Monoisopropylamine, diisopropylamine, ethanolamine, and the like.

The concentration of these inorganic and organic alkaline compounds in the alkali developer is preferably 0.01 to 10% by mass, and more preferably 0.03 to 5% by mass.

The surfactant may be any of a nonionic surfactant, an anionic surfactant, and a cationic surfactant.

Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, Polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene alkylamines.

Examples of the anionic surfactant include higher alcohol sulfuric acid ester salts such as sodium lauryl alcohol sulfate ester and sodium oleyl alcohol sulfate ester, alkylsulfates such as sodium laurylsulfate and ammonium laurylsulfate, sodium dodecylbenzenesulfonate And alkylarylsulfonic acid salts such as sodium dodecylnaphthalenesulfonate.

Examples of cationic surfactants include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, and quaternary ammonium salts.

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

After the development, washing with water may be carried out, and further post baking may be carried out if necessary. The post bake is suitable, for example, in a temperature range of 150 to 230 DEG C for 10 to 180 minutes.

The curable resin composition of the present invention has a transmittance of 3 占 퐉 thick after heat curing (for example, at 150 to 250 占 폚 for 0.1 to 3 hours) under a condition of a wavelength of 400 to 700 nm using a spectrophotometer When measured, the transmittance is preferably 90% or more, and more preferably 95% or more. This makes it possible to form a transparent pattern or a coating film in the visible light region.

The coating film or pattern thus obtained is useful as, for example, a photo-spacer used in a liquid crystal display device, a patternable overcoat. In the patterning exposure of the uncured coating film, holes can be formed by using a photomask for forming a hole, which is useful as an interlayer insulating film. Further, at the time of exposure for the uncured coating film, the transparent film can be formed by performing only the entire surface exposure and heat curing or heat curing without using a photomask. This transparent film is useful as an overcoat. It can also be used for a display device such as a touch panel. Thus, a display device having a high-quality coating film or pattern can be manufactured at a high yield.

The photosensitive resin composition of the present invention can be used for various films and materials for forming a pattern, for example, a transparent film, a transparent film constituting a part of a color filter, a pattern, a photo spacer, an overcoat, A microstructure, a projection, a micro lens, a coloring pattern combining a different film thickness, a coat layer, and the like. In addition, a color filter, an array substrate, and the like having these coating films or patterns as a part of their constituent parts, display devices including these color filters and / or array substrates, for example, liquid crystal display devices, organic EL devices And the like.

Example

Hereinafter, the photosensitive resin composition of the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the following Examples and Comparative Examples,% and parts representing the content or amount are based on mass unless otherwise specified.

Synthesis Example 1

In a one liter 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, 140 parts of diethylene glycol ethyl methyl ether was added, and the mixture was heated to 70 DEG C with stirring. Subsequently, 40 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl acrylate (the compound represented by formula (I-1) and the compound represented by formula (II-1) 50: 50) and 190 parts of diethylene glycol ethyl methyl ether to prepare a solution, and the obtained solution was dropped into a flask maintained at 70 캜 for 4 hours by using a dropping pump.

On the other hand, a solution prepared by dissolving 30 parts of polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in 240 parts of diethylene glycol ethyl methyl ether was dropped into a flask over 5 hours using another dropping pump Respectively. After completion of the dropwise addition of the polymerization initiator solution, the solution was maintained at 70 占 폚 for 4 hours and then cooled to room temperature to obtain a solution of a copolymer (resin Aa) having a solid content of 42.6% and an acid value of 60 mg-KOH / g. The weight average molecular weight (Mw) of the obtained resin Aa was 8000 and the degree of dispersion was 1.91.

Synthesis Example 2

In a 1 liter 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 305 parts of diethylene glycol ethyl methyl ether was added and heated to 70 deg. C with stirring. Subsequently, a mixture of 60 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl acrylate (the compound represented by formula (I-1) and the compound represented by formula (II- 50: 50) was dissolved in 140 parts of diethylene glycol ethyl methyl ether to prepare a solution. The solution was dropped into a flask maintained at 70 캜 for 4 hours using a dropping funnel. On the other hand, a solution prepared by dissolving 30 parts of polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in 225 parts of diethylene glycol ethyl methyl ether was added dropwise to the flask over 4 hours using another dropping funnel Respectively. After the dropwise addition of the polymerization initiator solution was completed, the solution was kept at 70 캜 for 4 hours and then cooled to room temperature to obtain a copolymer (resin Ab) solution having a solid content of 32.6% and an acid value of 110 mg-KOH / g . The weight average molecular weight Mw of the obtained resin Ab was 13,600 and the degree of dispersion was 2.49.

Synthesis Example 3

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, 200 parts of 3-methoxy-1-butanol and 105 parts of 3-methoxybutyl acetate were added, Lt; 0 > C. Subsequently, a mixture of 60 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl acrylate (the compound represented by formula (I-1) and the compound represented by formula (II- 50: 50) was dissolved in 140 parts of 3-methoxybutyl acetate to prepare a solution. The solution was dropped into a flask maintained at 70 캜 for 4 hours using a dropping funnel. On the other hand, a solution prepared by dissolving 30 parts of polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in 225 parts of 3-methoxybutyl acetate was dropped into a flask over 4 hours using another dropping funnel Respectively. After the dropwise addition of the polymerization initiator solution was completed, the solution was kept at 70 캜 for 4 hours and then cooled to room temperature to obtain a copolymer (Resin Ac) solution having a solid content of 32.6% and an acid value of 110 mg-KOH / g . The weight average molecular weight Mw of the obtained resin Ac was 13,400 and the degree of dispersion was 2.50.

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the copolymers (Resins Aa to Ac) were measured by the GPC method under the following conditions.

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 the number average molecular weight in terms of polystyrene obtained as described above was determined as the degree of dispersion (Mw / Mn).

Examples 1 to 9, Comparative Example 1

The compositions of Table 1 were mixed to obtain photosensitive resin compositions 1 to 10.

<Evaluation of cloudy smudge>

Using a slit die coater (Takuda-100, manufactured by Itochu-Kagaku Co., Ltd.), the solution of the photosensitive resin composition obtained in the examples and the comparative examples was applied onto the ITO film-formed glass substrate of 15 cm in length and 15 cm, To a thickness of 5.5 m.

Thereafter, the reduced pressure was dried under reduced pressure to 0.5 torr with a vacuum dryer (VCD Microtech Co., Ltd.). And then prebaked on a hot plate at 90 DEG C for 2 minutes to form a coating film.

After cooling, the surface of the coating film was visually observed by irradiating the film surface with an Na lamp.

When cloudy unevenness (cloud-shaped unevenness) was clearly confirmed, it was determined as &quot; C &quot;, when it was slightly confirmed, &amp;

<Pin Mark Evaluation>

Similarly to the above, a coating film was formed and then dried under reduced pressure. Thereafter, a stainless steel plate having a hole of 60 mm in diameter and having a thickness of 20 mm was mounted on a hot plate set at 90 占 폚, and then prebaked thereon for 2 minutes to form a coating film.

After cooling, the surface of the coating film was visually observed by irradiating the film surface with an Na lamp.

When the pin marks were clearly identified, the marks were marked as &quot; x &quot;, when the pin marks were slightly identified, and when the pin marks were hardly identified, &quot;

<Slit nozzle dryness evaluation>

A coating film was formed in the same manner as described above.

Thereafter, the tip of the nozzle was left without being cleaned. After one minute, the same application was carried out without cleaning the tip of the nozzle.

Subsequently, the reduced pressure was reduced to a pressure of 0.5 torr with a vacuum dryer (VCD Microtech) and prebaked on a hot plate at 90 DEG C for 2 minutes to form a coating film.

After cooling, the surface of the coating film was visually observed by irradiating the film surface with an Na lamp.

When the vertical line unevenness was clearly identified, it was determined as &quot; C &quot;, when it was slightly confirmed, &quot; DELTA, &quot;

&Lt; Average transmittance of the composition >

The average transmittance (%) at 400 to 700 nm was measured for each photosensitive resin composition using an ultraviolet visible near infrared spectrophotometer (V-650; Nippon Spectroscopy) (quartz cell, optical path length: Were measured.

&Lt; Average transmittance of pattern >

Each of the photosensitive resin compositions was used to produce a cured film in such a manner that the film thickness after curing was 3 占 퐉.

A glass substrate of 5 cm in length and width was sequentially washed with a neutral detergent, water and 2-propanol, and then dried. On this substrate, the composition was applied by spin-coating so that the post-baked pattern had a film thickness of 3 占 퐉. Next, the reduced pressure was reduced to 0.5 torr with a vacuum dryer (VCD Microtech Co., Ltd.) and dried to form a coating film. This coated film was prebaked in a hot plate at 90 캜 for 2 minutes. (Based on 405 nm) of 100 mJ / cm &lt; 2 &gt; in an atmospheric environment using an exposure apparatus (TME-150RSK; manufactured by Topcon Co., , The coated film after pre-baking was exposed. In this exposure, the light emitted from the ultra-high pressure mercury lamp was irradiated through an optical filter (LU0400, manufactured by Asahi Spectroscopy). A photomask for forming a line-and-space pattern of 100 mu m was also used. After exposure, the substrate was immersed in an aqueous solution of tetramethylammonium hydroxide (containing 2.38 parts of tetramethylammonium hydroxide in 100 parts of an aqueous solution) at 23 占 폚 for 60 seconds, developed and washed with water, and then transferred to a hot plate at 235 占 폚 for 11 minutes Baked to form a line and space pattern.

The average transmittance (%) at 400 to 700 nm was measured for each obtained pattern using a microscopic spectrophotometric apparatus (OSP-SP200, manufactured by OLYMPUS CO., LTD.).

The higher the transmittance means the smaller the absorption.

The components in Table 1 are as follows.

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

Polymerization initiator (C) Ca; Dioxo-2-oxime-O-benzoate (OXE 01; manufactured by Chiba Japan K.K.) was added to a solution of 1- (4-phenylsulfanylphenyl)

Polymerization initiator (C) Cb; 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole (B-CIM; manufactured by Hodogaya Chemical Co.,

Initiation aid C2a; Pentaerythritol tetrakispropionate (PEMP manufactured by SC Organic Chemicals Co., Ltd.)

Initiation aid C2b; 2- (2-naphthoylmethylene) -3-methylbenzothiazoline

Solvent Da; 3-Methoxy-1-butanol

Solvent Db; Propylene glycol monomethyl ether

Solvent Dc; Diethylene glycol ethyl methyl ether

Solvent Dd; Propylene glycol monomethyl ether acetate

Solvent De; 3-methoxybutylacetate

Solvent Df; 3-ethoxyethyl propionate

As described above, even when a coating film is formed using the photosensitive resin composition of the present invention and a comparatively thick film is formed thereon, cloudiness, vertical line unevenness and pin marks are not generated, and evenness over the entire coating film And a smooth, high-quality coating film can be formed. In other words, since it has a relatively low boiling point, it is possible to shorten the coating drying time and to improve the productivity, while suppressing the drying of the tip of the slit nozzle and to prevent the generation of foreign substances caused by drying, Can be prevented.

In addition, the solubility of the resin and various components is good, and the storage stability can be improved.

By using such a photosensitive resin composition, a coating film or a pattern is formed, and the yield can be improved by manufacturing a display device using them.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to form a uniform and high-quality coating film over the entire coating film without causing cloudiness, vertical line unevenness and pin marks.

Further, by using the photosensitive resin composition of the present invention, it becomes possible to obtain a high-quality display device or the like.

Claims (8)

(A), a polymerizable compound (B), a polymerization initiator (C) and a solvent (D) Wherein the solvent (D) is a solvent containing a dialkylene glycol dialkyl ether having an alkylene group of 1 to 3 carbon atoms and an alkyl group of 1 to 4 carbon atoms, and 3-methoxybutanol. The method according to claim 1, Wherein the solvent (D) is a solvent containing 30 to 90% by mass of a dialkylene glycol dialkyl ether based on the total amount of the solvent. The method according to claim 1, Wherein the solvent (D) is a solvent containing 10 to 50 mass% of 3-methoxybutanol based on the total amount of the solvent. The method according to claim 1, Wherein the dialkylene glycol dialkyl ether is diethylene glycol ethyl methyl ether. A coating film formed by using the photosensitive resin composition according to any one of claims 1 to 4. A pattern formed by using the photosensitive resin composition according to any one of claims 1 to 4. A display device comprising the coating film of claim 5. A display device comprising the pattern according to claim 6.