KR101498280B1 - Photosensitive resin composition - Google Patents

Abstract

1. A photosensitive resin composition comprising a binder resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C) and a solvent (D), wherein the binder resin (A) comprises an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride (A3) copolymerizable with (A1) and (A2), which is different from (A1), (A2) B) has an unsaturated double bond equivalent of 120 to 400 g / eq.

Description

[0001] PHOTOSENSITIVE RESIN COMPOSITION [0002]

The present invention relates to a photosensitive resin composition.

Spacers are formed between the color filter and the array substrate constituting the display device, such as a liquid crystal display device and a touch panel, in order to maintain a gap between the substrates. In this spacer, spherical particles such as glass beads and plastic beads are used.

However, when such spherical particles are used, since the spherical particles are scattered randomly on the glass substrate, the TFT elements and the electrodes are damaged, and if the spherical particles are present in the transmissive pixel portion, The contrast of the liquid crystal display element may be lowered. Thus, instead of using spherical particles, it has been proposed to form a spacer using a photosensitive resin composition. According to this method, since the spacer can be formed at an arbitrary place, the above-described problem can be solved.

As such a photosensitive resin composition, an acrylic copolymer having a carboxyl group and a glycidyl ether group as a binder resin, dipentaerythritol hexaacrylate (KAYARAD DPHA, manufactured by Nippon Gakuen Co., Ltd., unsaturated double bond equivalent: 105 g / (refer to Patent Document 1) discloses that a spacer pattern excellent in solvent resistance and heat resistance can be obtained when a spacer pattern is formed using the composition.

[Patent Document 1] JP-A-11-133600

However, when the photosensitive resin composition is used to form the pattern of the spacer on the transparent conductive film such as ITO (indium-tin oxide), if the pattern becomes fine, the pattern is lost in the developing and washing process, I knew there was a problem.

It is an object of the present invention to provide a photosensitive resin composition capable of forming a fine line width pattern even on a transparent conductive film such as ITO (indium-tin oxide).

The inventor of the present invention has studied a photosensitive resin composition capable of solving the above problems and found that a photosensitive resin composition containing a photopolymerizable compound having an unsaturated double bond equivalent in a certain range can form a fine line width pattern I got it.

That is, the present invention provides the following [1] to [5].

[One]. 1. A photosensitive resin composition comprising a binder resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C) and a solvent (D), wherein the binder resin (A) comprises an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride (A3) copolymerizable with (A1) and (A2), which is different from (A1), (A2) B) has an unsaturated double bond equivalent of 120 to 400 g / eq.

[2]. The photosensitive resin composition according to [1], wherein the compound having an unsaturated double bond equivalent of 120 to 400 g / eq is a compound represented by the formula (BA).

[In the formula (BA), R ^a to R ^f each independently represents a hydrogen atom or any one of groups represented by the formulas (BA-1) to (BA-3)

R ^a to R ^f (BA-1) to (BA-3), and at least four groups of R ^a to R ^f Is at least one group represented by formula (BA-2) or (BA-3)

[3]. The liquid crystal composition according to [1] or [2], wherein the monomer (A2) having an aliphatic polycyclic epoxy group is at least one compound selected from the group consisting of a compound represented by formula (I) and a compound represented by formula (II) Sensitive resin composition.

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

X represents an alkylene group having 1 to 6 carbon atoms which may contain a single bond or a hetero atom,

[4]. A pattern formed by using the photosensitive resin composition according to any one of [1] to [3].

[5]. A display device comprising a pattern according to [4].

The photosensitive resin composition of the present invention can form a pattern and a coating film excellent in storage stability, excellent in pattern shape, surface smoothness, mechanical characteristics, heat resistance and solvent resistance, and can be used as an overcoat, a photo spacer, , A coat layer for adjusting the film thickness of a colored pattern, and the like.

Hereinafter, the present invention will be described in detail.

The photosensitive resin composition of the present invention contains a binder resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C) and a solvent (D). In the photosensitive resin composition of the present invention, the binder resin (A), the photopolymerizable compound (B) and the photopolymerization initiator (C) and optionally other additives (F) are dissolved or dispersed in the solvent (D). The photosensitive resin composition of the present invention is preferably used mainly as a pattern forming material.

The binder resin (A) used in the present invention is different from the unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride (A1), the aliphatic polycyclic epoxy compound (A2) and (A1) and (A2) A1) and a monomer (A3) copolymerizable with (A2). The binder resin (A) preferably has alkali solubility.

Specific examples of the unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride (A1) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid;

Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid;

And anhydrides of said 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;

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 for copolymerization reactivity and solubility in an aqueous alkali solution. These may be used alone or in combination of two or more.

The aliphatic polycyclic epoxy compound (A2) is a compound having an epoxy group on the ring of the aliphatic polycyclic compound. The aliphatic polycyclic epoxy compound (A2) has an epoxy group on the ring of the aliphatic polycyclic compound, Bond is preferable. Examples of the aliphatic polycyclic compound include dicyclopentane, tricyclodecane, and the like.

The aliphatic polycyclic epoxy compound (A2) is preferably at least one compound selected from the group consisting of a compound represented by the formula (I) and a compound represented by the formula (II).

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

X represents an alkylene group having 1 to 6 carbon atoms which may independently contain a single bond or a hetero atom.

Specific examples of R include an alkyl group such as a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group and a tert-

Hydroxy-n-propyl group, 3-hydroxy-n-propyl group, 1-hydroxy-1-hydroxypropyl group, N-butyl group, 3-hydroxy-n-butyl group, 4-hydroxy-n-butyl group, 2-hydroxy- And a hydroxyl group-containing alkyl group such as a butyl group. Among them, a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group are preferable, and a hydrogen atom and a methyl group are more preferable.

Specific examples of X include a single bond;

Alkylene groups such as a methylene group, an ethylene group and a propylene group;

Containing alkylene groups such as a methylene group, an oxyethylene group, an oxyethylene group, an oxyethylene group, an oxypropylene group, a thiomethylene group, a thioethylene group, a thiopropylene group, an aminomethylene group, an aminoethylene group and an aminopropylene group. Among them, a single bond, a methylene group, an ethylene group, an oxymethylene group and an oxyethylene group are preferable, and a single bond and an oxyethylene group are more preferable.

Examples of the compound represented by the formula (I) include a compound represented by the formula (I-1) to formula (I-15), preferably a compound represented by the formula (I- (I-3), Formula (I-5), Formula (I-7), Formula (I-9), Formula -1), formula (I-7), formula (I-9), and formula (I-15).

Examples of the compound represented by the formula (II) include compounds represented by the formulas (II-1) to (II-15), preferably the compounds represented by the formulas (II- (II-5), the formula (II-7), the formula (II-9) and the formula (II-11) -1), formula (II-7), formula (II-9) and formula (II-15).

The at least one compound selected from the group consisting of the compound represented by the formula (I) and the compound represented by the formula (II) may be used singly or in a mixture in an arbitrary ratio. The mixing ratio thereof is preferably from 5:95 to 95: 5, more preferably from 10:90 to 90:10, even more preferably from 20:90 to 90:10 in the formula (I): formula (II) 80 to 80:20.

Examples of the monomer (A3) copolymerizable with (A1) and (A2) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (Meth) acrylic acid alkyl esters such as methyl (meth) acrylate, sec-butyl (meth) acrylate and t-butyl

Alkyl acrylates such as methyl acrylate and isopropyl acrylate;

Cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (in the art, (Meth) acrylate), dicyclopentanyloxyethyl (meth) acrylate, and isobornyl (meth) acrylate;

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

Ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- 2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5-carboxybicyclo [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] Butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-tricyclohexyl [2.2.1] hepto-2-ene anhydride 2,6-di (t-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 N-succinimidyl-3-maleimidepropionate and N- (9-acridinyl) maleimide;

And examples thereof include styrene,? -Methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, But are not limited to, vinyl, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, glycidyl acrylate, glycidyl methacrylate, glycidyl α- Dicumyl acrylate, glycidyl alpha-n-butyl acrylate, 3,4-epoxybutyl acrylate, methacrylic acid-3,4-epoxybutyl acrylate, Heptyl,? -Ethyl acrylate-6,7-epoxyheptyl, O-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether and p-vinyl benzyl glycidyl ether.

Of these, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and the like are preferable in terms of copolymerization reactivity and solubility in an aqueous alkali solution . These may be used alone or in combination of two or more.

The binder resin (A) used in the present invention is a copolymer obtained by copolymerizing (A1), (A2) and (A3), and the ratio of the constituent component derived from each of the constituent components It is preferable that the molar ratio with respect to the total molar amount falls within the following range.

(A1); 2 to 40 mol%

(A2); 2 to 95 mol%

(A3); 1 to 65 mol%

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

(A1); 5 to 35 mol%

(A2); 5 to 80 mol%

(A3); 1 to 60 mol%

When the composition ratio is in the above range, the storage stability of the photosensitive resin composition, the developability of the pattern obtained from the composition, the solvent resistance, the heat resistance, and the mechanical strength tend to be improved.

The binder resin (A) can be produced by a method described in, for example, "Experimental Method of Polymer Synthesis" (published by Otsu Takayuki Co., Ltd., 1st edition, 1st edition, published on March 1, 1972) Can be produced by referring to the cited document.

Specifically, a predetermined amount of a compound for deriving units (A1), (A2) and (A3) constituting the copolymer, a polymerization initiator and a solvent are placed in a reaction vessel and oxygen is replaced by nitrogen, The polymer is obtained by stirring, heating and warming. As the obtained copolymer, the solution after the reaction may be used as it is, or a concentrated or diluted solution may be used, or a solid (powder) extracted by a method such as re-precipitation may be used.

The weight average molecular weight of the binder resin (A) 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 binder resin (A) is within the above range, the coating property tends to be good, the film is not easily reduced during development, and the tendency of decolorization of the non- Therefore, it is desirable.

The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the binder resin (A) is preferably 1.1 to 6.0, 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 binder resin (A) used in the photosensitive resin composition of the present invention is preferably from 5 to 90 mass%, more preferably from 5 to 90 mass%, based on the solid content in the photosensitive resin composition %, More preferably from 10 to 70 mass%. When the content of the binder resin (A) is in the above range, solubility in a developing solution is sufficient, development residues do not occur on the substrate of the non-pixel portion well, and the film thickness of the pixel portion of the exposed portion And the decolorability of the non-pixel portion tends to be favorable.

The photopolymerizable compound (B) used in the present invention contains a compound having an unsaturated double bond equivalent of 120 to 400 g / eq. As the compound having an unsaturated double bond equivalent of 120 to 400 g / eq, a compound represented by the formula (BA) is preferably used.

In the formula (BA), R ^a to R ^f each independently represents a hydrogen atom or any one of the groups represented by the formulas (BA-1) to (BA-3).

However, R ^a to R ^f (BA-1) to (BA-3), and at least four of R ^a to R ^f At least one of them is a group represented by the formula (BA-2) or (BA-3).

The compound represented by the formula (BA) is preferably a compound wherein two of R ^a to R ^f are hydrogen atoms, three are groups represented by the formula (BA-1), and one is a group represented by the formula (BA-2) Gt; Two are hydrogen atoms, three are groups represented by the formula (BA-1), and one is a group represented by the formula (BA-3); Two are hydrogen atoms, two are groups represented by formula (BA-1), and two are groups represented by formula (BA-2); (BA-2), and one of them is a group represented by the formula (BA-3); a group represented by the formula (BA-1); Two are hydrogen atoms, two are groups represented by formula (BA-1), and two are groups represented by formula (BA-3); Two are hydrogen atoms, one is a group represented by the formula (BA-1), and three are a group represented by the formula (BA-2); 2 are hydrogen atoms, one is a group represented by the formula (BA-1), two are groups represented by the formula (BA-2), and one is a group represented by the formula (BA-3); (BA-1), one group is a group represented by the formula (BA-2), and two groups are a group represented by the formula (BA-3); Two are hydrogen atoms, one is a group represented by the formula (BA-1) and three are groups represented by the formula (BA-3); Two are hydrogen atoms, and four are groups represented by formula (BA-2); Two are hydrogen atoms, three are groups represented by formula (BA-2), and one is a group represented by formula (BA-3); Two are hydrogen atoms, two are groups represented by formula (BA-2), and two are groups represented by formula (BA-3); Two are hydrogen atoms, one is a group represented by the formula (BA-2), and three are a group represented by the formula (BA-3); Two are hydrogen atoms, and four are groups represented by formula (BA-3); 1 is a hydrogen atom, 4 are groups represented by the formula (BA-1), and 1 is a group represented by the formula (BA-2); 1 is a hydrogen atom, 4 are groups represented by the formula (BA-1), and 1 is a group represented by the formula (BA-3); 1 is a hydrogen atom, 3 are groups represented by the formula (BA-1), and 2 are groups represented by the formula (BA-2): one hydrogen atom, three groups represented by the formula (BA- One is a group represented by the formula (BA-2), and one is a group represented by the formula (BA-3); 1 is a hydrogen atom, 3 are groups represented by the formula (BA-1), and 2 are groups represented by the formula (BA-3); One is a hydrogen atom, two are groups represented by the formula (BA-1), and three are a group represented by the formula (BA-2); (BA-1), two of them are groups represented by the formula (BA-2), and one group is a group represented by the formula (BA-3); (BA-1), one group is a group represented by the formula (BA-2), and two groups are a group represented by the formula (BA-3); 1 are hydrogen atoms, two of them are groups represented by the formula (BA-1), and three are groups represented by the formula (BA-3); One is a hydrogen atom, one is a group represented by the formula (BA-1), and four are a group represented by the formula (BA-2); 1 is a hydrogen atom, one is a group represented by the formula (BA-1), the other is a group represented by the formula (BA-2), and one is a group represented by the formula (BA-3); One is a hydrogen atom, one is a group represented by the formula (BA-1), two are groups represented by the formula (BA-2), and two are a group represented by the formula (BA-3); 1 is a hydrogen atom, one is a group represented by the formula (BA-1), one is a group represented by the formula (BA-2), and three are a group represented by the formula (BA-3); One is a hydrogen atom, one is a group represented by the formula (BA-1), and four are a group represented by the formula (BA-3); One is a hydrogen atom, and five are a group represented by the formula (BA-2); 1 is a hydrogen atom, 4 are groups represented by the formula (BA-2), and 1 is a group represented by the formula (BA-3); 1 is a hydrogen atom, 3 are groups represented by the formula (BA-2), and 2 are groups represented by the formula (BA-3); One is a hydrogen atom, the other is a group represented by the formula (BA-2), and the other is a group represented by (BA-3); One is a hydrogen atom, one is a group represented by the formula (BA-2), and four are a group represented by (BA-3); 1 is a hydrogen atom, and 5 are a group represented by the formula (BA-3);

5 are groups represented by the formula (BA-1) and one is a group represented by the formula (BA-2); (BA-1) and two compounds in which one of them is a group represented by the formula (BA-3), four of them are represented by the formula (BA-1) A group represented by the formula (BA-1), one group represented by the formula (BA-2) and one group represented by the formula (BA-3); 4 groups are groups represented by the formula (BA-1), and two groups are groups represented by the formula (BA-3); 3 are groups represented by the formula (BA-1), and three are groups represented by the formula (BA-2); 3, a group represented by the formula (BA-1), two groups represented by the formula (BA-2), and a group in which one is a group represented by the formula (BA-3); 3 are groups represented by the formula (BA-1), one is a group represented by the formula (BA-2), and two are a group represented by the formula (BA-3); 3 are groups represented by the formula (BA-1), and three are groups represented by the formula (BA-3); Two groups represented by the formula (BA-1), and four groups represented by the formula (BA-2); Two groups represented by the formula (BA-1), three groups represented by the formula (BA-2), and one group represented by the formula (BA-3); Two groups represented by the formula (BA-1), two groups represented by the formula (BA-2), and two groups represented by the formula (BA-3); Two groups represented by the formula (BA-1), one group represented by the formula (BA-2) and three groups represented by the formula (BA-3); Two groups represented by the formula (BA-1), and four groups represented by the formula (BA-3); One is a group represented by the formula (BA-1), and five are a group represented by the formula (BA-2); 1 is a group represented by the formula (BA-1), four are groups represented by the formula (BA-2), and one is a group represented by the formula (BA-3); 1, a group represented by the formula (BA-1), three groups represented by the formula (BA-2), and two groups represented by the formula (BA-3); 1 is a group represented by the formula (BA-1), two groups represented by the formula (BA-2), and three groups represented by the formula (BA-3); 1 is a group represented by the formula (BA-1), one is a group represented by the formula (BA-2), and the other is a group represented by the formula (BA-3); One is a group represented by the formula (BA-1), and five are a group represented by the formula (BA-3); 6 is a group represented by the formula (BA-2); 5 groups are groups represented by the formula (BA-2), and one group is a group represented by the formula (BA-3); 4 groups are groups represented by the formula (BA-2), and two groups are groups represented by the formula (BA-3); 3 are groups represented by the formula (BA-2), and three are groups represented by the formula (BA-3); Two groups represented by the formula (BA-2), and four groups represented by the formula (BA-3); One is a group represented by the formula (BA-2), and five are a group represented by the formula (BA-3); 6 are compounds represented by the formula (BA-3).

Among them, the compound having an unsaturated double bond equivalent of 200 to 350 g / eq is more preferable, and the compound is a compound having 6 groups represented by the formula (BA-2) BA-3). ≪ / RTI >

Examples of the compound represented by the formula (BA) include KAYARAD DPCA-20, which is a compound represented by the formula (BA-2) in two of R ^a to R ^f , and KAYARAD KAYARAD DPCA-60, which is a compound represented by the formula (BA-2), and KAYARAD DPCA-120 (all manufactured by Nippon Kayaku Co., Ltd.), which is a compound represented by the formula (BA-3) And those commercially available.

Examples of the photopolymerizable compound other than the compound represented by the formula (BA) contained in the photopolymerizable compound (B) include trifunctional or more polyfunctional monomers.

Specific examples of the trifunctional or more multifunctional monomer include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) Acrylate, dipentaerythritol hexa (meth) acrylate, a reaction product of pentaerythritol tri (meth) acrylate and an acid anhydride, and a reaction product of dipentaerythritol penta (meth) acrylate and an acid anhydride. Of these, polyfunctional monomers having four or more functionalities are preferably used. These photopolymerizable compounds may be used alone or in combination of two or more.

The content of the photopolymerizable compound (B) is preferably 1 to 70 mass%, more preferably 5 to 60 mass%, based on the total amount of the binder resin (A) and the photopolymerizable compound (B). When the content of the photopolymerizable compound (B) is within the above range, the strength, smoothness and reliability of the pixel portion tends to be improved.

The content of the compound represented by the formula (BA) is preferably from 3 to 100 mass%, more preferably from 3 to 100 mass%, based on the total amount of the photopolymerizable compound other than the compound represented by the formula (BA) %, Preferably 3 to 70 mass%, more preferably 3 to 50 mass%, and still more preferably 5 to 40 mass%. When the content of the compound represented by the formula (BA) is in the above range, it is preferable because the balance of the sensitivity and the development adhesion tends to be good.

Examples of the photopolymerization initiator (C) contained in the photosensitive resin composition of the present invention include acetophenone, nonimidazole, oxime, triazine, and acylphosphine oxide initiators. When the photopolymerization initiator (C) is used in combination with the photopolymerization initiator (C-1), the resultant photosensitive resin composition has a higher sensitivity. Therefore, when a pattern is formed using the photopolymerization initiator, the productivity of the pattern is improved.

Examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2- 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1- 2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2- ) -Butanone, 2- (3-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) (4-morpholinophenyl) -butanone, 2- (2-propylbenzyl) -2-dimethylamino- (2-butylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- Dimethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2,4- 2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2 (2-chlorobenzyl) - (4-morpholinophenyl) -butanone, 2- (3-chlorobenzyl) -2-dimethylamino- Phenyl) -butanone, 2- (4-chlorobenzyl) -2-dimethylamino-1- - (4-morpholinophenyl) -butanone, 2- (2-methoxybenzyl) -2-dimethylamino- Butanone, 2- (3-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) 2- (4-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) (4-morpholinophenyl) -butanone, 2- (2-methyl-4-bromobenzyl) Bromo-4 2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1, 2- -One oligomers, and the like.

Examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis 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 Tetra (alkoxyphenyl) biimidazole, 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- , 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) Is 2,2'-bis (2-chlorophenyl ) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4', 5,5'- .

Examples of the oxime compound include O-ethoxycarbonyl- [alpha] -oxyimino-1-phenylpropan-1-one, a compound represented by formula (3), a compound represented by formula (4) .

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

Further, as long as the effect of the present invention is not impaired, a photopolymerization initiator and the like commonly used in this field can be further used in combination. Examples of the photopolymerization initiator include a benzoin-based compound, a benzophenone-based compound, a thioxanthone-based compound, and an anthracene-based compound.

More specifically, the following compounds may be used, and these may be used alone or in combination of two or more.

Examples of the benzoin 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- -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, etc. .

In addition, examples of the photopolymerization initiator include 10-butyl-2-chloroacridone, 2-ethyl anthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate and titanocene compounds.

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

Examples of the photopolymerization initiator having a group capable of causing chain transfer include photopolymerization initiators represented by the following formulas (5) to (10).

The photopolymerization initiator having a group capable of causing chain transfer can also be used as the constituent component (A3) of the copolymer. The obtained copolymer may be used as a binder resin of the photosensitive resin composition of the present invention, or may be used in combination with a binder resin.

The photopolymerization initiator may be used in combination with the photopolymerization initiator (C-1). As the photopolymerization initiation auxiliary, an amine compound and a carboxylic acid compound are preferably used, and as the amine compound, an aromatic amine compound is preferably used.

Specific examples of the photopolymerization initiation auxiliary include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine; aliphatic amine compounds such as methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4- N, N-dimethyl paratoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis Diethylamino) benzophenone, and the like.

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

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

The content of the photopolymerization initiation auxiliary (C-1) is preferably 0.01 to 50% by mass, more preferably 0.1 to 40% by mass on the same basis as described above.

When the total amount of the photopolymerization initiator (C) is within the above range, the photosensitive resin composition becomes highly sensitive, and the strength of the pixel portion formed using the photosensitive resin composition and the smoothness of the surface of the pixel tends to be favorable, Do. In addition to the above, when the amount of the photopolymerization initiator (C-1) is in the above range, the sensitivity of the obtained photosensitive resin composition becomes higher, and the productivity of the pattern substrate formed using the photosensitive resin composition tends to be improved .

Examples of the solvent (D) used in the present invention include various organic solvents commonly used in the field of photosensitive resin compositions.

Specific examples of the solvent (D) include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether;

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

Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve 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;

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

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

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

Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; and cyclic esters such as? -butyrolactone.

Among the above-mentioned solvents, organic solvents having a boiling point of 100 ° C to 200 ° C in the solvent are preferably used from the viewpoint of coatability and dryness, more preferably alkylene glycol alkyl ether acetates, ketones, 3- Ethoxypropionate, ethyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate and the like. More preferred are propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, And methyl methoxypropionate.

These solvents (D) may be used alone or in combination of two or more.

The content of the solvent (D) in the photosensitive resin composition of the present invention is preferably 60 to 90 mass%, more preferably 70 to 85 mass%, based on the mass of the photosensitive resin composition. When the content of the solvent (D) is within the above range, the coating property becomes good when the coating composition is applied by a spin coater, a slit & spin coater, a slit coater (sometimes referred to as a die coater or a curtain flow coater) This is preferable because there is a possibility.

(F) such as a filler, another polymer compound, a pigment dispersant, an adhesion promoter, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, a chain transfer agent, etc. may be used in combination in the photosensitive resin composition of the present invention.

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

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

As the pigment dispersant, commercially available surfactants can be used, and examples thereof include surfactants such as silicone, fluorine, ester, cationic, anionic, nonionic, and amphoteric surfactants. Two or more species may be used in combination. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, (Manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoei Chemical Co., Ltd.), F-top (manufactured by TOKEM PRODUCTS CO., LTD.), Megapak (manufactured by Dainippon Ink Chemical Industry Co., (Manufactured by Asahi Glass Co., Ltd.), SORPARS (manufactured by Zeneca), EFKA (manufactured by EFKA CHEMICALS Co., Ltd.), FERRAD (manufactured by Sumitomo 3M Ltd.) , And PB821 (manufactured by Ajinomoto Co., Ltd.).

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 2,2'-thiobis (4-methyl-6-tert-butylphenol) and 2,6-di-tert-butyl-4-methylphenol.

Examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole and alkoxybenzophenone.

The anti-aggregation agent includes, for example, sodium polyacrylate.

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

The photosensitive resin composition can be applied on a substrate, for example, as described below, and photo-cured and developed to form a pattern. First, this composition is applied on a substrate (usually glass) or a layer comprising a solid content of a previously formed photosensitive resin composition, or a substrate on which ITO (indium-tin oxide) or IZO (indium-zinc oxide) By pre-baking the applied photosensitive resin composition layer, volatile components such as a solvent are removed to obtain a smooth coated film. The thickness of the coating film at this time is usually about 1 to 6 mu m. Ultraviolet rays are applied to the thus obtained coating film through a mask for forming a desired pattern. At this time, it is preferable to use an apparatus such as a mask aligner or a stepper so as to uniformly irradiate a parallel light beam onto the entire exposed portion and accurately align the mask and the substrate. Thereafter, the coated film, which has been cured, is brought into contact with an aqueous alkaline solution to dissolve the unexposed portion and then developed, thereby obtaining a desired pattern shape. The developing method may be any of a liquid addition method, a dipping method, and a spraying method. Further, the substrate may be inclined at an arbitrary angle during development.

The developing solution used for development after patterning exposure 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 hydrogen phosphate, sodium dihydrogen phosphate, ammonium dihydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, Potassium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate, and ammonia.

Specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine , Monoisopropylamine, diisopropylamine, ethanolamine, and the like. These inorganic and organic alkaline compounds may be used alone or in combination of two or more. The concentration of the alkaline compound in the alkaline developer is preferably 0.01 to 10% by mass, and more preferably 0.03 to 5% by mass.

The surfactant in the alkali developing solution may be any of a nonionic surfactant, an anionic surfactant and a cationic surfactant.

Specific examples of the 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.

Specific 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 lauryl sulfate and ammonium lauryl sulfate, And alkylarylsulfonic acid salts such as sodium or sodium dodecylnaphthalenesulfonate.

Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, and quaternary ammonium salts.

These surfactants may be used alone or in combination of two or more.

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 development, it is washed with water, and post baking at 150 to 230 캜 for 10 to 60 minutes may be carried out if necessary.

Using the photosensitive resin composition of the present invention, a pattern can be formed on a substrate or a color filter substrate through each of the steps described above. This pattern is useful as a photo spacer used in a liquid crystal display device. When a photomask for hole formation is used for patterning exposure of a dry coating film, a hole can be formed and is useful as an interlayer insulating film. The shape, size and pitch of the pattern layout of the photomask can be arbitrarily changed. Further, when exposed to a dry film, a transparent film can be formed only by full-surface exposure, heat curing or heat curing without using a photomask. This transparent film is useful as an overcoat and can also be used for a touch panel.

By attaching the thus obtained pattern to a display device such as a liquid crystal display device, a display device of excellent quality can be manufactured with a high yield.

The photosensitive resin composition of the present invention can be formed even on a transparent conductive film such as ITO (indium-tin oxide) without missing a fine line width pattern, and the pattern is excellent in solvent resistance and heat resistance.

The photosensitive resin composition of the present invention is preferably used for forming a transparent film such as a transparent film constituting a part of a color filter, for example, an overcoat, a photo spacer, an insulating film, a projection for controlling liquid crystal orientation, And the obtained transparent film is preferably used for a color filter or a display device having the color filter.

Example

Hereinafter, the present invention will be described in more detail based on examples, but needless to say, the present invention is not limited to these examples. In the examples,% and parts representing the content or amount are based on mass unless otherwise specified.

Synthesis Example 1

A 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer was charged with nitrogen at a flow rate of 0.02 L / min to give a nitrogen atmosphere. 200 parts by mass of 3-methoxy-1-butanol and 105 parts by mass of 3-methoxybutyl acetate , And the mixture was heated to 70 DEG C while stirring. Then, 55 parts by mass 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 70 parts by mass of N-cyclohexylmaleimide were dissolved in 140 parts by mass of 3-methoxybutyl acetate to prepare a solution, and the solution was added dropwise to the mixture at 4 hours Lt; RTI ID = 0.0 > 70 C < / RTI > On the other hand, a solution in which 30 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator was dissolved in 225 parts by mass of 3-methoxybutyl acetate was added to a flask / RTI > After the dropping of the solution of the polymerization initiator was completed, the solution was maintained at 70 캜 for 4 hours and then cooled to room temperature to obtain a copolymer having a viscosity of 234 캜 at 114 캜, a solid content of 32.6% by mass, and an acid value of 34.3 mg- (Resin Aa) was obtained. The weight average molecular weight Mw of the obtained resin Aa was 13,600 and the degree of dispersion was 2.54.

The viscosity of the copolymer solution was measured by a B-type viscometer.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the binder polymer 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).

Example 1

≪ Preparation of Photosensitive Resin Composition >

40 parts of dipentaerythritol hexaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) and 40 parts of caprolactone-modified polyfunctional acrylate (manufactured by Nippon Kayaku Co., Ltd.) were added to a resin solution portion (55 parts in solid content) containing the resin Aa obtained in Synthesis Example 1 , 6 parts of 2-methyl-2-morpholino (4-thiomethylphenyl) propane-1-one, 53 parts of propylene glycol monomethyl ether acetate, 3 parts of 3-ethoxyethyl 20 parts of propionate, 37 parts of 3-methoxy-1-butanol and 87 parts of 3-methoxybutyl acetate were mixed to obtain Photosensitive Resin Composition 1.

≪ Formation of pattern &

An ITO film (having a thickness of 1500 ANGSTROM and a resistance value of 10 OMEGA / sq) was sequentially cleaned with a neutral detergent, water and alcohol on a glass substrate (# 1737; Corning Inc.) having a width of 2 inches and dried. The photosensitive resin composition 1 was exposed on this glass substrate at an exposure amount (365 nm) of 100 mJ / cm 2, spin-coated so as to have a film thickness of 3.5 μm after being subjected to each step of development, washing and post-baking, Pre-baked on a hot plate at 75 캜 for 2 minutes. After cooling, an exposure apparatus (TME-150RSK; manufactured by TOPKON CO., LTD.) Was used with an interval of 10 mu m between the substrate coated with this photosensitive resin composition and a quartz glass photomask, and an exposure amount of 100 mJ / (Based on 365 nm).

A photomask in which the following pattern was formed on the same plane was used as the photomask.

A photomask having 5600 light-projecting portions (patterns) each having a side of 7 占 퐉 and having a square interval of 100 占 퐉.

After the light irradiation, the coating film was immersed in an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.05% of potassium hydroxide at 23 DEG C for 80 seconds and developed. After washing with an ultrasonic cleaner (frequency: 38 kHz) for 20 minutes, Post-baking was performed at 230 占 폚 for 20 minutes. After cooling down, the film thickness was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.).

<Storage stability>

The viscosity of the photosensitive resin composition 1 obtained above was measured. Then, the photosensitive resin composition 1 was sealed in a light-shielding container, and the container was stored in a thermostatic chamber at 23 DEG C for 2 weeks.

The viscosity of the photosensitive resin composition 1 after storage was measured. The viscosity change obtained on the basis of the following formula was 100%.

Viscosity change = [(viscosity of photosensitive resin composition after storage for 2 weeks at 23 占 폚] / [viscosity of photosensitive resin composition before storage] 占 100%

The smaller the viscosity change is, for example, the range of 100 to 103% is preferable. The measurement of the viscosity was carried out as follows.

The viscosity was measured at 23 캜 using a viscometer (VISCOMETER TV-30, manufactured by Toray Industries, Ltd.).

<Transmittance>

The same operation as described above was carried out except that the photomask was not used and the film thickness was made to be 2.9 to 3.1 mu m in the exposure step in the pattern formation, and the film thickness was measured by film thickness measurement (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.).

Subsequently, the transmittance (%) of the cured film obtained at 400 nm was measured using a brown spectrometer (OSP-SP200, manufactured by OLYMPUS CO., LTD.) And the transmittance was 96.3% .

<Surface smoothness>

A cured film was produced in the same manner as above except that the photosensitive resin composition 1 was used and a photomask was not used. The obtained cured films were evaluated for the items shown in Table 2.

The surface of the obtained cured film was observed using a scanning electron microscope (S-4000; manufactured by Hitachi, Ltd.).

The case where the surface of the cured film was smooth was evaluated as &amp; cir &amp;

<Pattern shape>

The line width of the pattern used for measurement in the surface smoothness was measured using a scanning electron microscope (S-4000; manufactured by Hitachi, Ltd.), and found to be 7.9 mu m.

The shape was observed from the side of the pattern. In the case of the line width of the bottom floor is larger than that of the upper floor, the line taper is divided into the rectangle when the line width is equal to the line width of the upper floor and the bottom floor.

If the pattern shape is a rectangle, development adhesion tends to be good, which is preferable.

&Lt; Development adhesion &

In the pattern formation step, the developed substrate was immersed in a 1 L glass beaker containing 500 mL of pure water, and the substrate was immersed in an ultrasonic cleaner (US-4, measurement frequency: 38 kHz, manufactured by SENNED Co., Ltd.) under the condition of 23 to 25 캜 After washing for 10 minutes and 20 minutes, the number of peeled patterns of 5600 patterns was counted. The number of peels was 0, and peeling was not observed at all. The smaller the number of peeled off, the better the adhesion to the development.

<Mechanical properties (total displacement and recovery rate)>

The total amount of displacement (占 퐉) and the amount of elastic displacement (占 퐉) were measured with respect to one cured pattern obtained in the pattern formation using a dynamic ultra microhardness tester (DUH-W201; manufactured by Shimadzu Corporation) %).

-Measuring conditions-

Test mode; Load - unloading test

Test force; 20 mN

Load speed; 4.4 mN / sec

Retention time; 5sec

Indenter; Conical indenter indenter (diameter 50 탆)

Recovery rate (%); [Elastic displacement amount (占 퐉) / total displacement amount (占 퐉)] 占 100

As for the mechanical characteristics, when the film thickness is 3 to 5 탆 and the line width is 7 to 10 탆, the total displacement amount is 0.90 탆 or more and the recovery rate is 45% or more.

<Solvent resistance>

In the exposure step in the pattern formation, a coating film was produced by the same operation except that a photomask was not used, and the film thickness and the transmittance were measured. The coating film thus prepared was immersed in N-methylpyrrolidone at 30 占 폚 for 30 minutes, and the film thickness and the transmittance after immersion were measured, and their changes were determined according to the following formula.

Film thickness change (%); [Film thickness after immersion (占 퐉) / Film thickness before immersion (占 퐉)] 占 100

Transmittance change (%); [Transmittance (%) after immersion / Transmittance (%) before immersion] × 100

It can be said that the film thickness change and the transmittance change are 90% to 103%, respectively.

Solvent resistance;

On the coated film after immersion in the solvent resistance test, 100 commercially available cutter knives were used to produce squares with 1 mm side by side. A commercially available cellophane tape was used and subjected to a peeling test to evaluate the following numerical values.

[(Number of squares remaining on the substrate without peeling) / 100]

The larger the value, the better the adhesion.

<Heat resistance>

In the exposure step in the pattern formation, a coating film was produced by the same operation except that a photomask was not used. The coated film thus prepared was allowed to stand in a clean oven at 240 ° C for 1 hour, and the film thickness and transmittance (measured wavelength: 400 nm) before and after heating were measured and their changes were determined according to the following formula. As a result, the film thickness change was 92.4%. The transmittance change was 96.3%.

Film thickness change (%); [Film thickness after heating (占 퐉) / Film thickness before heating (占 퐉)] 占 100

Transmittance change (%); [Transmittance (%) after heating / Transmittance (%) before heating] × 100

It is preferable that the film thickness change and the transmittance change are 90 to 103%, respectively.

Heat resistance; On the coated film after heating in the heat resistance test, 100 commercially available cutter knives were used to produce squares with 1 mm side by side. A commercially available cellophane tape was used and subjected to a peeling test to evaluate the following numerical values.

[(Number of squares remaining on the substrate without peeling) / 100]

The larger the number is, the better the adhesion is.

Photosensitive
Resin tank
Religious 1 Photosensitive
Resin tank
Religious 2 Photosensitive
Resin tank
Religious 3 Photosensitive
Resin composition 4 The binder resin (A)

Photopolymerization
The compound (B) Resin Aa (solids only)
55 55 55 55 Dipentaerythritol hexaacrylate
(Unsaturated double bond equivalent: 105 g / eq)
KAYARAD DPHA manufactured by Nippon Gunpaku Co., Ltd. 40 40 40 45 Caprolactone-modified polyfunctional acrylate (unsaturated double bond equivalent: 134 g / eq)
KAYARAD DPCA-20 manufactured by Nippon Gunpaku Co., Ltd. 0 0 5 0 Caprolactone-modified polyfunctional acrylate (unsaturated double bond equivalent: 210 g / eq)
KAYARAD DPCA-60 manufactured by Nippon Gunpaku Co., Ltd. 0 5 0 0 Caprolactone-modified polyfunctional acrylate (unsaturated double bond equivalent 324 g / eq)
KAYARAD DPCA-120 manufactured by Nippon Gunpaku Co., Ltd. 5 0 0 0 The photopolymerization initiator (C) Methyl-2-morpholino (4-thiomethylphenyl) propan-1-one (Irgacure-907 manufactured by CIBA SPECIALTY CHEMICALS) 6 6 6 6 Solvent (D) Propylene glycol monomethyl ether acetate 53 53 53 53 3-ethoxyethyl propionate 20 20 20 20 3-Methoxy-1-butanol 37 37 37 37 3-methoxybutylacetate 87 87 87 87

Example 2

The photosensitive resin composition 2 was obtained in the same manner as in Example 1 so as to have the composition shown in Table 1, and the evaluation was carried out. The results are shown in Table 2.

Example 3

The photosensitive resin composition 3 was obtained in the same manner as in Example 1 so as to have the composition shown in Table 1, and the evaluation was carried out. The results are shown in Table 2.

Comparative Example 1

The photosensitive resin composition 4 was obtained in the same manner as in Example 1 so as to have the composition shown in Table 1, and the evaluation was carried out. The results are shown in Table 2.

Example 1 Example 2 Example 3 Comparative Example 1 Photosensitive resin composition One 2 3 4 Storage stability 100 101 100 100 Transmittance 96.3 96.2 97.0 97.3 Surface smoothness ○ ○ ○ ○ pattern Line width ㎛ 7.9 8.2 8.4 8.8 shape Rectangle Rectangle Rectangle Rectangle Close Ultrasonic wave 10 minutes - 0 0 0 50 Ultrasonic 20 min - 0 0 0 86 Mechanical properties Total displacement ㎛ 1.02 0.99 0.98 0.94 Recovery rate % 52.5 53.6 53.9 54.1 Solvent resistance Transmittance change % 100 100 100 100 Film thickness change % 100 100 101 101 Adhesiveness - 100/100 100/100 100/100 100/100 Heat resistance Transmittance change % 92.4 92.5 92.5 92.6 Film thickness change % 96.3 96.4 96.4 96.5 Adhesiveness - 100/100 100/100 100/100 100/100

From the results of Examples 1 to 3 shown in Table 2, when the photosensitive resin composition of the present invention is used, even when a fine pattern is formed, a pattern having excellent developing adhesion can be formed, and thus the process margin is wide. Further, it can be seen that the pattern formed, the pattern shape, the surface smoothness, the mechanical characteristics, the heat resistance, the excellent solvent resistance, and the coating film are obtained.

On the other hand, the photosensitive resin composition of Comparative Example 1, which did not contain a compound having an unsaturated double bond equivalent of 120 to 400 g / eq, was poor in developing adhesion.

The photosensitive resin composition of the present invention can form a pattern and a coating film excellent in storage stability, excellent in pattern shape, surface smoothness, mechanical characteristics, heat resistance and solvent resistance, and can be used as an overcoat, a photo spacer, , A coat layer for adjusting the film thickness of a colored pattern, and the like.

Claims (5)

1. A photosensitive resin composition comprising a binder resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C) and a solvent (D), wherein the binder resin (A) comprises an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride (A3) copolymerizable with (A1) and (A2), which is different from (A1), (A2) B) is a compound having an unsaturated double bond equivalent of 120 to 400 g / eq, which is a compound represented by the formula (BA).

[In the formula (BA), R ^a to R ^f each independently represents a hydrogen atom or any one of groups represented by the formulas (BA-1) to (BA-3)

R ^{a f} ~R at least four groups of the formula (BA-1) ~ a group represented by any one of ^{(BA-3), R a} ~R f at least one group is formulas (BA-2) or of the formula (BA-3) delete The method according to claim 1, Wherein the monomer (A2) having an aliphatic polycyclic epoxy group is at least one compound selected from the group consisting of a compound represented by the formula (I) and a compound represented by the formula (II) Resin composition.

[In the formulas (I) and (II), R represents, independently of each other, an alkyl group having 1 to 4 carbon atoms which may be substituted with a hydrogen atom or a hydroxyl group, X represents an alkylene group having 1 to 6 carbon atoms which may contain a single bond or a hetero atom, A pattern for a photo-spacer formed by using a photosensitive resin composition for forming a pattern for a photo-spacer according to claim 1 or 3. A display device comprising the pattern for a photo spacer according to claim 4.