KR101692071B1 - Photosensitive resin composition and display - Google Patents

Abstract

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

The solvent (D) comprises a solvent represented by the formula (I).

R ¹ -O- (AO) _n -R ² (I)

(In the formula (I), R ¹ and R ² each independently represent a linear or branched alkyl group having 1 to 4 carbon atoms; A represents a linear or branched alkylene group having 1 to 3 carbon atoms And n represents an integer of 2 or 3, and a plurality of A's may be the same or different.

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, and in order to form a transparent film or pattern such as a coat layer on the substrate surface, the photosensitive resin composition is applied by spin coating, slit & Respectively.

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

In this background, in order to form a coating film of excellent quality, selection of a solvent species has been studied. For example, a photosensitive resin composition using a mixed solvent of propylene glycol monomethyl ether acetate, 3-ethoxyethyl propionate, 3-methoxy-1-butanol and 3-methoxybutyl acetate as a solvent is used for forming a coating film (For example, Patent Document 1).

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

DISCLOSURE OF INVENTION

However, when the photosensitive resin composition using the above-described solvent is applied on a concave-convex substrate by spin coating, which is a typical coating method, there is a problem that a radial stripe is formed on the coating surface along the concavo- ).

That is, even if applied to a spin coating method, a slit-and-spin coating method, a slit die coating method, or the like using a conventionally proposed solvent, a high-quality coating film can not always be obtained in all methods.

An object of the present invention is to provide a photosensitive resin composition capable of suppressing the occurrence of stretching and forming a uniform and high quality coating film over the whole coating film.

That is, the present invention provides the following [1] to [11].

[1] A resin composition comprising a resin (A), a polymerizable compound (B), a polymerization initiator (C), and a solvent (D)

The solvent (D) comprises a solvent represented by the formula (I).

R ¹ -O- (AO) _n -R ² (I)

(In the formula (I), R ¹ and R ² each independently represent a linear or branched alkyl group having 1 to 4 carbon atoms, and A represents an alkylene group having 1 to 3 carbon atoms in the linear or branched form And n represents an integer of 2 or 3, and a plurality of A's may be the same or different.)

[2] The photosensitive resin composition according to [1], wherein the solvent (D) comprises two or more kinds of solvents represented by formula (I).

[3] The photosensitive resin composition according to [1] or [2], wherein the solvent (D) comprises diethylene glycol ethyl methyl ether.

[4] The photosensitive resin composition according to [3], wherein the solvent (D) contains 10 to 90% by mass of diethylene glycol ethyl methyl ether based on the total amount of the solvent.

[5] The photosensitive resin composition according to any one of [1] to [4], wherein the solvent (D) comprises at least one solvent selected from the group consisting of diethylene glycol butyl methyl ether and triethylene glycol dimethyl ether.

[6] The process according to [5], wherein the solvent (D) contains 10 to 50% by mass of at least one solvent selected from the group consisting of diethylene glycol butyl methyl ether and triethylene glycol dimethyl ether with respect to the total amount of the solvent The photosensitive resin composition described above.

[7] The process according to any one of [1] to [6], wherein the solvent (D) comprises at least one solvent selected from the group consisting of diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether and triethylene glycol dimethyl ether The photosensitive resin composition according to any one of claims 1 to 5,

[8] The process for producing a photosensitive resin composition according to any one of [1] to [8], wherein the total amount of the solvent (D) is at least one solvent selected from the group consisting of diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether and triethylene glycol dimethyl ether By mass to 100% by mass or less of the total amount of the photosensitive resin composition.

[9] A coating film formed by using the photosensitive resin composition according to any one of [1] to [8].

[10] A pattern formed by using the photosensitive resin composition according to any one of [1] to [8].

[11] A display device comprising at least one selected from the group consisting of the coating film described in [9] and the pattern described in [10].

According to the present invention, occurrence of stretching is suppressed, and a uniform, high-quality coating film can be formed over the entire surface.

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

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 singly or in combination, unless otherwise specified.

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

As the resin (A1) having alkali solubility, at least one kind (a) (hereinafter also 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) include, for example, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and 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 mono [2- (meth) acryloyloxyethyl] succinate and mono [2- (meth) acryloyloxyethyl] ] Esters;

-(하이드록시메틸)아크릴산과 같은, 동일 분자 중에 하이드록시기 및 카르 복시기를 함유하는 불포화 아크릴레이트류 등을 들 수 있다.

And unsaturated acrylates containing a hydroxyl 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), dicyclopentoxyethyl Acrylic acid cyclic alkyl esters such as 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 diester such as diethyl maleate, diethyl fumarate, and diethyl itaconate;

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

2,2-hept-2-ene, 5-methylbicyclo [2.2.1] hepto-2-ene, 5-ethylbicyclo [2.2.1] 2.2.1] hept-2-ene, 5-carboxybicyclo [2.2.1] hepto-2-ene, 5-hydroxymethylbicyclo [ 2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hepto-2-ene, 2,6-dihydroxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] Bicyclic [2.2.1] hept-2-ene, 5,6-di (2'-hydroxyethyl) bicyclo [2.2.1] hepto-2-ene, 5,6-dimethoxybicyclo [2.2. 2,1-hept-2-ene, 5,6-diethoxybicyclo [2.2.1] 2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2 1] hepto-2-ene, 5-hydroxy 5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hepto-2-ene, 5-carboxy-6-ethylbicyclo [2.2. 1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hepto-2-ene anhydride (5-tert-butoxycarbonylbicyclo [2.2.1] 2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hepto- Cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, and the like, such as 5,6-di (cyclohexyloxycarbonyl) bicyclo [2.2.1] ;

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

-메틸스티렌, m-메틸스티렌, p-메틸스티렌, 비닐톨루엔, p-메톡시스티렌, 아크릴로니트릴, 메타크릴로니트릴, 염화 비닐, 염화 비닐리덴, 아크릴아미드, 메타크릴아미드, 아세트산 비닐, 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) may be 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 of the copolymers is such that the molar ratio of the constituent components constituting the copolymer is 100 mol% Range. ≪ / RTI >

(a); 2 to 40 mol%

(c); 60 to 98 mol%

It is more preferable that the above-mentioned ratio of the constituent components is in 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, for example, by the method described in "Experimental Method of Polymer Synthesis" (published by Otsu Takayuki Co., Ltd., And references cited in the literature.

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, Is exemplified. The polymerization initiator, solvent and the like 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 obtained copolymer 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. In particular, by using the 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 also to the resin (A2)).

The weight average molecular weight of the above-mentioned alkali-soluble resin (A1) 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 in the above range, the coating property tends to be good, the film is not easily reduced during development, and the dropout of the non- It tends to be favorable.

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-mentioned range, development tends to be excellent, which is preferable.

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 with respect to the solid content in the photosensitive resin composition % to be. 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, The film is not easily reduced and the releasability of the non-exposed portion tends to be favorable.

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) refers to a polymerizable compound having at least one structure selected from the group consisting of an epoxy group, an oxetanyl group and a tetrahydrofuryl group as a compound having a cyclic ether structure having 2 to 4 carbon atoms. (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, More preferably a compound having a methacryloyl group.

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

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

The aliphatic epoxy structure refers to a structure obtained by epoxidizing a chain-like olefin.

(meth) acrylate,? -methylglycidyl (meth) acrylate,? (meth) acrylate and? -methylglycidyl (meth) acrylate among the compounds having an aliphatic epoxy structure and having an ethylenic carbon- -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-vinyl benzyl 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.

The alicyclic epoxy structure refers to a structure obtained by epoxidizing a cyclic olefin.

Examples of the compound having an alicyclic epoxy structure and having an ethylenic carbon-carbon unsaturated bond in the component (A2) include vinylcyclohexene monoxide 1,2-epoxy-4-vinylcyclohexane (Manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl acrylate (e.g., CYROMER A400, manufactured by Daicel Chemical Industries, Ltd.), 3,4- At least one member selected from the group consisting of epoxy cyclohexylmethyl methacrylate (for example, cyclomer M100; manufactured by Daicel Chemical Industries, Ltd.) or a compound represented by formula (I) and a compound represented by formula (II) And the like.

[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 hydroxy group.

X and X 'represents a single bond, each independently, C _{1 ~ 6} alkyl group, an oxy -C _{1 ~ 6} alkyl group, a thio _{~ 1} -C ₆ alkylene group, an imino -C _{1 ~ 6} alkyl group, C _{1 ~ 6} alkylene-oxy, C _{1 ~ 6} alkylene-thio, or C _{1 ~ 6} alkylene- already represents a 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- Hydroxy-n-butyl group, 3-hydroxy-n-butyl group, 4-hydroxy-isopropyl group, -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 the oxyalkylene group 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 iminoalkylene group include an iminomethylene group, an iminoethylene group and an iminoproylene group.

Examples of the alkylene imino group include a methylenimino group, an ethyleneimino group, and a propylenimino 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 formula (II) include compounds represented by formulas (II-1) to (II-15). (II-1), II-3, II-5, II-7, I-1-9, II- ). More preferably, the formula (II-1), the formula (II-7), the formula (II-9) and the formula (II-15) can be mentioned.

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. Further, they can be mixed at an arbitrary ratio. In the case of mixing, the mixing ratio is preferably from 5:95 to 95: 5, more preferably from 10:90 to 90:10, and even more preferably from 20:90 to 90:10 in the formula (I): formula (II) : 80 to 80:20.

Examples of the compound having an oxetanyl group (b2) and having an unsaturated bond in the copolymers (A2-1) and (A2-2) include 3-methyl-3-methacryloxymethyloxetane, 3-methyl-3-acryloxymethyloxetane, 3-ethyl-3-methacryloxymethyloxetane, 3-ethyl- , 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 proportion of constituent components derived from each other is in the following range in terms of the molar 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 above-mentioned ratio of the constituent components is in 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, there is a tendency that storage stability, developability, solvent resistance, heat resistance and mechanical strength are improved.

The above-mentioned alkali-soluble resin (A2-1) can be produced, for example, by the method described in "Experimental Method of Polymer Synthesis" (published by Otsu Takayuki Co., Ltd., 1st edition, 1st edition, March 1, 1972) Can be produced by referring to the described method and the literature cited therein.

Specifically, a predetermined amount of a compound capable of forming the units (a), (c) and (b1) or (b2) constituting the copolymer, a polymerization initiator and a solvent are introduced into a reaction vessel, , And stirring, heating and keeping the temperature in the absence of oxygen by substitution.

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, similarly to the above, various forms can be continuously used. 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) is in 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 above-mentioned ratio of the constituent components is in the following range.

(a); 10 to 45 mol%

(c); 55 to 90 mol%

Next, as a second step, a part of the carboxylic acid (a) and the carboxylic acid anhydride 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 from the atmosphere, and the content of the component (b1) or (b2) is 5 to 80 mol%, the amount of the component (b1) As the reaction catalyst of the silyl group, for example, trisdimethylaminomethylphenol may be used in an amount of 0.001 to 5% by mass based on the total amount of the monomers (a) to (c), and a polymerization inhibitor such as hydroquinone ) To (c) is put in a flask in an amount of 0.001 to 5% by mass, 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, the injection method and the reaction temperature can be appropriately adjusted in consideration of the production facility or the amount of heat generated by polymerization, as in the case of the polymerization conditions.

In this case, the number of moles of (b1) or (b2) is preferably 10 to 75 mol%, and more preferably 15 to 70 mol% with respect to 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 improved.

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

(a); 5 to 95 mol%

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

It is more preferable that the above-mentioned ratio of the constituent components is in the following range.

(a); 10 to 90 mol%

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

When the composition ratio is in the above range, there is a tendency that storage stability, developability, solvent resistance, heat resistance and mechanical strength are improved.

Resin (A2-3) can be produced by a method described in, for example, "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 the units (a) and (b1) or (b2) constituting the copolymer, a polymerization initiator and a solvent are introduced into a reaction vessel and oxygen is replaced by nitrogen, Stirring, heating, and warming in the presence of a polymerization initiator. The solution obtained after the reaction may be used as it is, or a concentrated or diluted solution may be used, or a solution obtained as a solid (powder) by re-precipitation or the like may be used.

The polymerizable compound (B) contained in the photosensitive resin composition of the present invention is not particularly limited as long as it has polymerizability, and examples thereof include monofunctional monomers, bifunctional monomers, and trifunctional or higher functional polyfunctional monomers.

Examples of monofunctional monomers include nonylphenylcarbitol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-ethylhexylcarbitol (meth) acrylate, 2- (Meth) acrylates such as propyl (meth) acrylate, ethyl (meth) acrylate, ethyl (meth) acrylate, ethyl

-, o-, m-, p-메틸스티렌, p-메톡시스티렌, p-tert 부톡시스티렌, 클로로메틸스티렌 등의 스티렌류 ; 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-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert- (Meth) acrylate, stearyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, (meth) acrylic acid dodecyl (Meth) acrylate, propyl (meth) acrylate, propyl (meth) acrylate, isobutyl (meth) acrylate, isobutyl (meth) acrylate, (Meth) acrylate, phenyl (meth) acrylate, anthracenyl (meth) acrylate, cyclopentyl (meth) acrylate, furyl methacrylate, tetrahydrofuryl (Meth) acrylate, (meth) acrylic acid Propyl (meth) acrylate, perfluoro (meth) acrylate, 1,1,1-trifluoroethyl (meth) acrylate, perfluoroethyl (meth) acrylate, perfluoro- (Meth) acrylic acid alkyl esters such as triphenylmethyl (meth) acrylate and cumyl (meth) acrylate, cycloalkyl (meth) acrylates or aryl (meth) acrylates;

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

Vinyl compounds such as (meth) acrylic acid amide, (meth) acryl ananilide, (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, Acrylate, ethoxylated bisphenol A di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, 3- Methylpentanediol di (meth) acrylate, and the like.

Examples of polyfunctional monomers having three or more functional groups include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethoxylated trimethyl (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, (Meth) acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol (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 pentaerythritol hexa (meth) acrylate, caprolactone-modified tripentaerythritol tetra (meth) acrylate, caprolactone-modified tripentaerythritol penta (meth) acrylate, caprolactone-modified tripentaerythritol hexa (meth) 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, a 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 with respect to the total amount of the resin (A) and the polymerizable compound (B). When the content of the polymerizable compound (B) is in the above-mentioned range, the sensitivity and the strength, smoothness, reliability and mechanical strength of the coating film and pattern tends 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. The light and / or thermal cation polymerization initiator described in JP-A-2008-181087 (for example, one composed of onium cation and anion derived from Lewis acid) may be used. 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'-tetraphenylbimidazole, 2,2'-bis (2,3- Phenyl) -4,4 ', 5,5'-tetraphenylbiimidazole (see, for example, JP-A-6-75372, JP-A-6-75373, '- bis (2-chlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis (Alkoxyphenyl) imidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra Chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole (see, for example, Japanese Patent Publication No. 48-38403, Japanese Patent Application Laid-Open No. 62-174204, etc.) , Imidazole compounds in which the phenyl group at the 4,4 ', 5,5'-position is substituted by a carboalkoxy group (see, for example, JP-A 7-10913, etc.). 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 compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2- 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-butylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) - 2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2,4-dimethylbenzyl) (4-morpholinophenyl) -butanone, 2- (2-bromobenzyl) - butanone, 2- (4-morpholinophenyl) -butanone, 2- (3-chlorobenzyl) -2-dimethylamino-1- 2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3-bromobenzyl) -Butanone, 2- (2-methoxybenzyl) -2-dimethylamino-1- (4-fluorophenyl) (4-morpholinophenyl) -butanone, 2- (3-methoxybenzyl) -2-dimethylamino- (4-morpholinophenyl) -butanone, 2- (2-methyl-4-methoxybenzyl) -2-dimethylamino- part 2- (2-bromo-4-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) Oligomers of 2-dimethylamino-1- (4-morpholinophenyl) -butanone and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan- .

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis - (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, (Trichloromethyl) -6- [2- (5-methylfuran-2- (4-methoxystyryl) -1,3,5-triazine, Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan- , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- L-methylethyl) -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.Examples of the oxime compounds include O-ethoxycarbonyl-

-Oxyimino-1-phenylpropan-1-one, a compound represented by formula (III) and a compound represented by 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, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl- 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, in any of the chemical structural formulas, the number varies depending on the number of carbon atoms, and unless otherwise stated, the above examples apply to each substituent. 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).

When these compounds are used, the resultant photosensitive resin composition has a high sensitivity. Therefore, when a coating film or a pattern is formed by using such a compound, the productivity of a coating film or a pattern is 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 formula (VI) and the formula (VII) may be used.

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

[In the formulas (VI) and (VII), the rings X ¹ and X ² each independently represent 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 hydroxyl 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 hydroxy group-substituted aryl group include a hydroxyphenyl group and a hydroxy naphthyl 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.

The compounds represented by 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.

As the above-mentioned polymerization initiator (C), a photopolymerization initiator may be used.

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 compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and the like.

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- Chloro-4-propoxyoctanoic acid and the like.

Examples of the anthracene 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 the photopolymerization initiators represented by the following formulas (1) to (6).

The above-mentioned photopolymerization initiator having a group capable of 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 polymerization initiator described above.

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, benzoic acid 2-dimethylaminoethyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'- And aromatic amine compounds such as phenanone.

Examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthio And aromatic heteroacetic acids such as acetic 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 with respect to 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 sensitivity of the photosensitive resin composition becomes high, and the strength of the coating film or pattern formed by using the photosensitive resin composition and the smoothness on the surface of the coating film or pattern are satisfactory It tends to disappear.

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) And preferably 0.1 to 40% by mass.

When the amount of the polymerization initiator (C-1) and / or the polymerization initiator (C-2) is within the above range, the sensitivity of the obtained photosensitive resin composition becomes higher and productivity of the pattern substrate formed using the photosensitive resin composition is improved Tends to be preferable.

Particularly, when the compound represented by the formula (V) is used, the content thereof is preferably 50% by mass to 100% by mass, more preferably 60% by mass to 60% by mass with respect to the content of the polymerization initiator (C- 100% by mass, and more preferably 65% by mass to 100% by mass. When the content of the compound represented by the formula (V) is within this range, it is preferable that the transparency of the coated film becomes good when the coated 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 increased, 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- Pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthioglycolate, Pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, and the like.

The content of the polyfunctional thiol compound (T) is preferably from 0.5 to 100 mass%, more preferably from 1 to 90 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 tends to be high and the developability tends to be good, which is preferable.

The solvent (D) used in the photosensitive resin composition of the present invention is a solvent which uniformly dissolves the components such as the resin (A), the polymerizable compound (B) and the polymerization initiator (C) .

In addition, the solvent (D)

R ¹ -O- (AO) _n -R ² (I)

(In the formula (I), R ¹ and R ² each independently represent a linear or branched alkyl group having 1 to 4 carbon atoms.) A is an alkylene group having 1 to 3 carbon atoms in the linear or branched form N represents an integer of 2 or 3. A plurality of A's may be the same or different.)

Lt; / RTI >

Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, 1-methyl-n-propyl, 2-methyl-n-propyl and tert-butyl.

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

As the compound of the formula (I), specifically,

Dimethylene glycol dimethyl ether, trimethylene glycol dimethyl ether,

Diethylene glycol dimethyl ether, triethylene glycol dimethyl ether,

Dipropylene glycol dimethyl ether, tripropylene glycol dimethyl ether,

Dimethylene glycol methyl ethyl ether, trimethylene glycol methyl ethyl ether,

Diethylene glycol methyl ethyl ether, triethylene glycol methyl ethyl ether,

Dipropylene glycol methyl ethyl ether, tripropylene glycol methyl ethyl ether,

Dimethylene glycol methyl propyl ether, trimethylene glycol methyl propyl ether,

Diethylene glycol methyl propyl ether, triethylene glycol methyl propyl ether,

Dipropylene glycol methyl propyl ether, tripropylene glycol methyl propyl ether,

Dimethylene glycol methyl butyl ether, trimethylene glycol methyl butyl ether,

Diethylene glycol methyl butyl ether, triethylene glycol methyl butyl ether,

Dipropylene glycol methyl butyl ether, tripropylene glycol methyl butyl ether,

Dimethylene glycol diethyl ether, trimethylene glycol diethyl ether,

Diethylene glycol diethyl ether, triethylene glycol diethyl ether,

Dipropylene glycol diethyl ether, tripropylene glycol diethyl ether,

Dimethylene glycol ethyl propyl ether, trimethylene glycol ethyl propyl ether,

Diethylene glycol ethyl propyl ether, triethylene glycol ethyl propyl ether,

Dipropylene glycol ethyl propyl ether, tripropylene glycol ethyl propyl ether,

Dimethylene glycol ethyl butyl ether, trimethylene glycol ethyl butyl ether,

Diethylene glycol ethyl butyl ether, triethylene glycol ethyl butyl ether,

Dipropylene glycol ethyl butyl ether, tripropylene glycol ethyl butyl ether,

Dimethylene glycol dipropyl ether, trimethylene glycol dipropyl ether,

Diethylene glycol dipropyl ether, triethylene glycol dipropyl ether,

Dipropylene glycol dipropyl ether, tripropylene glycol dipropyl ether,

Dimethylene glycol propyl butyl ether, trimethylene glycol propyl butyl ether,

Diethylene glycol propyl butyl ether, triethylene glycol propyl butyl ether,

Dipropylene glycol propyl butyl ether, tripropylene glycol propyl butyl ether,

Dimethylene glycol dibutyl ether, trimethylene glycol dibutyl ether,

Diethylene glycol dibutyl ether, triethylene glycol dibutyl ether,

Dipropylene glycol dibutyl ether, tripropylene glycol dibutyl ether, and the like.

Among them, diethylene glycol methyl ethyl ether, diethylene glycol methyl butyl ether and triethylene glycol dimethyl ether are preferable.

In addition, it is preferable to use a combination of two or more solvents of the formula (I). By using these solvents in combination, it is possible to ensure compatibility with each component of the photosensitive resin composition, and even when coating is carried out on uneven substrates by various coating methods, particularly spin coating methods, .

The solvent of the formula (I) is preferably contained in an amount of 50 to 100 mass%, more preferably 70 to 100 mass%, further preferably 90 to 100 mass%, based on the total amount of the solvent Do. When the content of the solvent of the formula (I) falls within this range, various applications 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, In the apparatus, good application properties can be expected.

Particularly, when the solvent (D) contains diethylene glycol ethyl methyl ether, the content of diethylene glycol ethyl methyl ether is preferably 10 to 100 mass%, more preferably 10 to 90 mass% , More preferably from 30 to 90 mass%.

When the solvent (D) contains diethylene glycol butyl methyl ether and / or triethylene glycol dimethyl ether, the amount of diethylene glycol butyl methyl ether and / or triethylene glycol dimethyl ether is preferably 0 to 50 By mass, more preferably 10 to 50% by mass.

By setting this range, in particular, in the spin coating method, it is possible to more effectively prevent the stretching.

The solvent (D) is preferably composed of only a solvent other than those described above, but may contain other solvents.

Examples of the other solvent include alcohols such as monoalcohol and polyhydric alcohol, ethers, aromatic hydrocarbons, ketones, esters and the like exemplified below.

These alcohols include alcohols such as 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 mono Ethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, methyl lactate, ethyl lactate, methyl 2-methyl lactate, diacetone alcohol, 3-methoxybutanol, glycerin and the like. Among them, 3-methoxybutanol is preferred.

The amount of the alcohols is preferably 0 to 50 mass%, more preferably 10 to 50 mass%, further preferably 10 to 45 mass%, still more preferably 10 to 40 mass%, based on the total amount of the solvent (D) %.

When the alcohol is contained in this range, the solubility of the resin and the like can be sufficiently obtained, and the viscosity of the resulting film can be adjusted to be uniform. In addition, even when the photosensitive resin composition is applied using a slit die coater, it is possible to prevent drying of the tip of the nozzle and suppress the precipitation of foreign matter by the dried material, thereby preventing occurrence of vertical stripes caused by foreign matter .

Other solvents include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl 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;

Butyldiol monoalkyl ethers such as methoxybutyl alcohol, ethoxybutyl alcohol, propoxybutyl alcohol and butoxybutyl alcohol;

Butanediol monoalkyl ether acetates such as methoxybutyl acetate, ethoxybutyl acetate, propoxybutyl acetate, butoxybutyl acetate, and the like:

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

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

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

Examples of the solvent include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy- , Hydroxybutyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, Methyl methoxyacetate, methyl methoxyacetate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, ethoxyacetate, ethoxyacetate, ethoxyacetate, ethoxyacetate, propoxy Methyl acetate, ethyl propoxyacetate, propoxy acetic acid propyl, propoxyacetic acid Methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, butyl 2-methoxypropionate, butyl 2-methoxypropionate, Ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, 2- Methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, Propoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, 3- Ethoxy-propionic acid methyl, 3-butoxy-ethyl, 3-butoxy-propionic acid propyl esters such as 3-butoxy-propionic acid butyl;

Cyclic ethers such as tetrahydrofuran and pyran;

and cyclic esters such as? -butyrolactone.

Among the above-mentioned 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, ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, and propylene glycol monomethyl Ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, methoxybutyl acetate, ethyl 3-ethoxypropionate, and methyl 3-methoxypropionate are preferable.

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 preferably less than 1% by mass, more preferably less than 0.5% by mass.

The photosensitive resin composition of the present invention contains substantially no the following colorants used in the art.

A compound classified as a pigment in 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, if necessary.

As the filler, for example, glass, silica, alumina and the like are exemplified.

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 a 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, Commercially available surfactants can be used. (Manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyowa Chemical Industry Co., Ltd.), F-top (manufactured by Mitsubishi Materials Corporation), Megapack (manufactured by DIC Corporation) (Manufactured by Sumitomo 3M Ltd.), Sulfur (manufactured by AGC Seiyaku 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- Tripropyltrimethoxysilane, 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-pentylphenyl) ethyl] -4,6-di-tert-pentylphenylacrylate, 6- [3- (3-tert- butyl-4-hydroxy- ) Propoxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [1,3,2] dioxaphosphepin, 3,9-bis [2- {3- butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 2,2'-methylene Bis (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'-thiodipropane (3-laurylthiopropionate), 1,3,5-tris (3,5-di-tert-butylphenyl) propionate, pentaerythrityl tetrakis (3H, 3H, 5H) -triene, 3,3 ', 3 ", 5,5' , 5 '' - hexa-tert-butyl-a, a ', a' '- (mesitylene-2,4,6-triyl) tri-p-cresol, pentaerythritol tetrakis [3- Di-tert-butyl-4-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 (1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2- (3- tert- 5-methylphenyl) -5-chlorobenzotriazole, alkoxybenzophenone, etc. .

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, 1,1-diazabicyclo [ The reaction product of dimethylethyl hydroperoxide, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) - [[3,5-bis (1,1-dimethylethyl) Phenyl] methyl] butyl malonate, 2,4-bis [N-butyl-N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin- - (2-hydroxyethylamine) -1,3,5-triazine, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, methyl , 6,6-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 glass substrate, a metal substrate, a plastic substrate, a color filter, various insulating films, a conductive film, a driving circuit, Thereby forming a coating film. It is preferable that the coating film is one that has been dried and cured. The obtained coating film may be patterned into a desired shape and used as a pattern. Further, these coating films and / or patterns may be formed and used as a part of constituent parts such as a display device.

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 75% or more. Thus, a transparent pattern or a coating film can be formed 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 devices 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 by spin coating, that is, coating using a slit & spin coater, a spin coater or the like, in terms of solubility, prevention of drying, prevention of generation of foreign matter,

Next, it is preferable to dry and / or pre-bake to remove volatile components such as solvents. 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.

The obtained uncured coating film is irradiated with light, for example, a mercury lamp, ultraviolet rays generated from the light emitting diode, or the like, through a mask for forming a desired pattern. In this case, the shape of the mask is not particularly limited, and may be various shapes. In addition, the line width and the like can be appropriately adjusted according to the mask size and the like.

In recent exposures, light having a wavelength of less than 350 nm is cut using a filter that cuts the wavelength band, or a band-pass filter for extracting light in the vicinity of 436 nm, around 408 nm, and around 365 nm, So that it is possible to uniformly irradiate the entire exposed surface with a parallel light beam. In this case, a device such as a mask aligner or a stepper 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 alkaline solution and dissolving a predetermined portion, for example, an unexposed portion, to develop.

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 either an inorganic or an organic alkaline compound.

Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogenphosphate, sodium dihydrogenphosphate, ammonium dihydrogenphosphate, ammonium dihydrogenphosphate, potassium dihydrogenphosphate, sodium silicate, potassium 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 alkylaryl 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, alkylsulfuric acid salts such as sodium laurylsulfate and ammonium laurylsulfate, dodecylbenzenesulfonic acid And alkylarylsulfonic acid salts such as sodium or 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 developing solution is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, and still more preferably 0.1 to 5% by 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 the temperature range of 150 to 230 DEG C for 10 to 180 minutes.

The curable resin composition of the present invention can be obtained by coating a coating film having a thickness of 3 占 퐉 after heat curing (for example, at 150 to 250 占 폚 for 0.1 to 3 hours) using a spectrophotometer under the condition of a measurement wavelength of 400 to 700 nm When the transmittance is measured, the transmittance is preferably 90% or more, and more preferably 95% or more. Thus, a transparent pattern or a coating film can be formed 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, and 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 to 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. As a result, a display device having a high-quality coating film or pattern can be produced with high productivity.

The photosensitive resin composition of the present invention can be used for various films and materials for forming patterns such as a transparent film, a transparent film constituting a part of a color filter, a pattern, a photo spacer, an overcoat, an insulating film, A micro lens, a coloring pattern combining different film thicknesses, 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, liquid crystal display devices, Can be used.

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 on a mass basis 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. Next, 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) ) And 190 parts of diethylene glycol ethyl methyl ether to prepare a solution, and this solution was dropped into a flask maintained at 70 DEG C for 4 hours 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 added dropwise to the flask using another dropping pump for 5 hours. After the dropping of the polymerization initiator solution was completed, the temperature 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 obtained resin Aa had a weight average molecular weight (Mw) of 8,000 and a degree of dispersion of 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. Next, a solution of 60 parts of methacrylic acid, 3,4-epoxy tricyclo [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) was dissolved in 140 parts of diethylene glycol ethyl methyl ether to prepare a solution, and this 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 using another dropping funnel for 4 hours. After the dropping of the polymerization initiator solution was completed, the solution was maintained at 70 캜 for 4 hours and then cooled to room temperature to obtain a solution of a copolymer (resin Ab) having a solid content of 32.6% and an acid value of 110 mg-KOH / g ≪ / RTI > 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. Next, a solution of 60 parts of methacrylic acid, 3,4-epoxy tricyclo [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) was dissolved in 140 parts of 3-methoxybutyl acetate to prepare a solution, and this solution was dropped into a flask kept at 70 캜 for 4 hours by using a dropping funnel.

On the other hand, a solution obtained by dissolving 30 parts of polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in 225 parts of 3-methoxybutyl acetate was added dropwise to the flask using another dropping funnel for 4 hours. After the dropping 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 solution of a copolymer (resin Ac) having a solid content of 32.6% and an acid value of 110 mg-KOH / g ≪ / RTI > 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 the number average molecular weight (Mn) of the obtained 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 to the weight average molecular weight in terms of polystyrene obtained above was determined as the degree of dispersion (Mw / Mn).

Examples 1 to 10, Comparative Example 1

The compositions of Table 1 were mixed to obtain Photosensitive Resin Compositions 1 to 11.

The components in Table 1 are as follows.

Polymerizable compound (B): dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Yakuza Co., Ltd.)

A polymerization initiator (Ca); 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole (B-CIM; manufactured by Hodogaya Chemical Co.,

Initiation aid (C2a); 9,10-dibutoxyanthracene (DBA; manufactured by Kawasaki Chemical Industry Co., Ltd.)

Initiator aid (C2b); Pentaerythritol tetrakis (3-sulfanyl propionate) (PEMP; SC Organic Chemicals Co., Ltd.)

Initiation aid (C2c); 2- (2-naphthoylmethylene) -3-methylbenzothiazoline

Solvent (Da); Diethylene glycol ethyl methyl ether

Solvent (Db); Diethylene glycol butyl methyl ether

Solvent (Dc); Triethylene glycol dimethyl ether

Solvent (Dd): Propylene glycol monomethyl ether acetate

Solvent (De); 3-ethoxyethyl propionate

Solvent (Df); 3-Methoxy-1-butanol

Solvent (Dg); 3-methoxybutylacetate

Solvent (Dh); Dipropylene glycol dimethyl ether

Additive 1; Polyether-modified silicone oil (SH8400 manufactured by Toray Dow Corning Co., Ltd.)

Additive 2; IRGANOX3114 (manufactured by Chiba Japan)

 ≪ Striation evaluation >

The components shown in Table 2 were mixed in the ratios shown in Table 2 to obtain colored photosensitive resin composition 1.

C.I. Pigment Blue 15: 6 5.48 part C.I. Pigment Violet 23 0.35 part Pigment dispersant 2.04 part Benzyl methacrylate / methacrylic acid copolymer (mass composition ratio: 65/35, weight average molecular weight in terms of polystyrene: 25000) 7.38 part Dipentaerythritol hexaacrylate
(KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) 7.38 part 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone (Irgacure 369 manufactured by Chiba, 1.77 part 4,4'-diethylaminobenzophenone
(EAB-F manufactured by Hodogaya Chemical Co., Ltd.) 0.59 part Polyether-modified silicone oil
(SH8400 manufactured by Toray Dow Corning Co., Ltd.) 0.01 part Ethyl 3-ethoxypropionate 15.0 parts Propylene glycol monomethyl ether acetate 60.0 parts

A 4-inch silicon substrate was washed sequentially with a neutral detergent, water and alcohol, and then dried. On this silicon substrate, the colored photosensitive resin composition 1 was exposed at an exposure amount (365 nm) of 100 mJ / cm 2 and spin-coated so as to have a film thickness after development, water washing and post-baking to 3.0 탆. Next, it was pre-baked in a clean oven at 90 캜 for 3 minutes. After cooling, the space between the substrate coated with the colored photosensitive resin composition 1 and the quartz glass photomask was set at 100 탆, and an atmosphere of air (TME-150RSK; manufactured by Topcon Co., Ltd., light source: super high pressure mercury lamp) At an exposure amount of 100 mJ / cm < 2 > (based on 365 nm). The irradiation of the colored photosensitive resin composition at this time was conducted by passing the radiation from the ultra-high pressure mercury lamp through an optical filter (UV-35, manufactured by Asahi Techno Glass Co., Ltd.). As a photomask, a photomask having a pattern (having a light-transmitting portion having a square of 10 mm in each side and a space of 100 mm in the square) was formed on the same plane was used.

After the light irradiation, the coating film was immersed in an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23 캜 for 80 seconds and developed, and post-baking was performed in an oven at 220 캜 for 20 minutes Thus, a silicon substrate having a color pattern of 10 mm square was produced.

The photosensitive resin compositions of Examples 1 to 6 and Comparative Example 1 were applied to a silicon substrate having a color pattern of 10 mm square using a spin coater under the condition that the film thickness after curing became 2.0 占 퐉. Thereafter, the reduced pressure was dried under reduced pressure to 1.0 torr with a vacuum dryer (VCD Microtech Co., Ltd.). Subsequently, the wafer was mounted on a hot plate set at 95 DEG C, and then baked on the wafer for 2 minutes to form a coating film. After cooling, the film surface was irradiated with a Na lamp, and the surface of the coating film was visually observed.

As a result, in Examples 1 to 6, almost no striation was observed along the coloring pattern. The results are shown in Table 3.

Here, the term "stretching" refers to nonuniformity of the radiation shape resulting from the step of the coloring pattern.

<Average Transmittance of Photosensitive Resin Composition>

(%) At 400 to 700 nm was measured using an ultraviolet visible spectrophotometer (V-650DS, manufactured by Nippon Bunko K.K.) (quartz cell, optical path length: 1 cm) Respectively. The results are shown in Table 3.

&Lt; Average transmittance of coated film &

The same operation as described above was carried out except that the photomask was not used at the time of light irradiation to prepare a coating film so that the film thickness after post-baking was 2.0 占 퐉. The average transmittance (%) of the prepared coated film at a wavelength of 400 to 700 nm was measured using a microscopic spectrometer (OSP-SP200; manufactured by OLYMPUS). The results are shown in Table 3.

Example Comparative Example One 2 3 4 5 6 7 8 9 10 One Photosensitive resin composition One 2 3 4 5 6 7 8 9 10 11 Streaming ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ × The average transmittance (%) of the composition 84.1 84.2 84.1 84.3 84.1 84.1 84.1 84.4 84.4 83.7 84.3 The average transmittance (%) of the coated film 99.8 99.8 99.8 99.8 99.8 99.8 99.8 99.8 99.8 99.7 99.8

As described above, when a coating film is formed using the photosensitive resin composition of the present invention, no stretching occurs even when a relatively thick film is formed, and a uniform, smooth, high-quality coating film is formed over the entire film can do.

Further, the coating and drying time can be shortened, productivity can be improved, and drying of the tips of the slit nozzles can be suppressed, so that generation of foreign matter due to drying, mixing with the coating film and vertical stripes 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 to form a coating film or a pattern, and manufacturing a display device using them, the productivity can be improved.

According to the present invention, occurrence of stretching is suppressed, and a uniform and high-quality coating film can be formed over the entire coating film.

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 (11)

(A), a polymerizable compound (B), a polymerization initiator (C) and a solvent (D) Wherein the solvent (D) comprises at least one solvent selected from the group consisting of diethylene glycol butyl methyl ether and triethylene glycol dimethyl ether. The method according to claim 1, A photosensitive resin composition comprising two or more kinds of solvents represented by formula (I) wherein the solvent (D) is different from each other. The method according to claim 1, Wherein the solvent (D) further comprises diethylene glycol ethyl methyl ether. The method of claim 3, Wherein the solvent (D) contains 10 to 90% by mass of diethylene glycol ethyl methyl ether with respect to the total amount of the solvent. The method according to claim 1, Wherein the solvent (D) contains 10 to 50 mass% of at least one solvent selected from the group consisting of diethylene glycol butyl methyl ether and triethylene glycol dimethyl ether with respect to the total solvent amount. The method according to claim 1, Wherein the solvent (D) comprises at least one solvent selected from the group consisting of diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether and triethylene glycol dimethyl ether. The method according to claim 6, Wherein the total amount of the solvent (D) is at least 60% by mass or more, based on the total amount of the solvent, of at least one solvent selected from the group consisting of diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether and triethylene glycol dimethyl ether 100% by mass or less.        A coating film formed using the photosensitive resin composition according to any one of claims 1 to 7. A pattern formed by using the photosensitive resin composition according to any one of claims 1 to 7. A display device comprising the coating film according to claim 8. A display device comprising the pattern according to claim 9.