KR101424811B1 - Photosensitive resin composition - Google Patents

Abstract

(A), a photopolymerizable compound (B), a photopolymerization initiator (C) and a solvent (D), wherein the binder resin (A) contains an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride And the aliphatic polycyclic epoxy compound (A2).

Description

[0001] PHOTOSENSITIVE RESIN COMPOSITION [0002]

The present invention relates to a photosensitive resin composition.

Spacers are formed between the color filter substrate and the array substrate constituting the display device, such as the liquid crystal display device and the touch panel, in order to maintain the spacing between both 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, if the spherical particles are present in the transmissive pixel portion, the scattering of the incident light causes scattering of the incident light, The contrast of the liquid crystal display element is sometimes lowered. Thus, instead of using spherical particles, it has been proposed to form a spacer with 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, there is known a composition for forming a spacer containing an acrylic copolymer having a carboxyl group and a glycidyl ether group as a binder resin (Patent Document 1). When the composition is used, a spacer having excellent solvent resistance and heat resistance A pattern can be obtained.

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

According to the study by the inventors of the present invention, it has been found that the photosensitive resin composition containing a resin having an aliphatic monocyclic epoxy group as a constituent component, which is said to have better stability than a resin having a glycidyl ether group as a constituent component, I knew something big.

In addition, development of a photosensitive resin composition which gives a fine line width pattern has been demanded.

An object of the present invention is to provide a photosensitive resin composition capable of forming a fine line width pattern with a small viscosity increase during storage.

The inventor of the present invention has conducted a study to find out a photosensitive resin composition capable of solving the above problems and found that a photosensitive resin composition containing any kind of binary copolymer has a small increase in viscosity at the time of storage and forms a fine line width pattern I found out I could.

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

[One]. (A), a photopolymerizable compound (B), a photopolymerization initiator (C) and a solvent (D), wherein the binder resin (A) contains an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride And the aliphatic polycyclic epoxy compound (A2).

[2]. The photosensitive resin composition according to [1], wherein the aliphatic polycyclic epoxy compound (A2) is a compound having an epoxy group on the ring of the aliphatic polycyclic compound and having an unsaturated bond.

[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), each R independently represents an alkyl group having 1 to 4 carbon atoms which may be substituted with a hydrogen atom or a hydroxyl group, and each X independently represents a single bond or a hetero atom- An alkylene group having 1 to 6 carbon atoms,

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

[5]. A liquid crystal display device comprising the pattern described in [4].

According to the present invention, it is possible to obtain a photosensitive resin composition capable of forming a fine line width pattern with a small viscosity increase during storage.

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) and a photopolymerization initiator (C), and optionally other additives (F) and a solvent (D).

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

The binder resin (A) used in the photosensitive resin composition of the present invention is a copolymer of an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride (A1) and a monomer (A2) having an aliphatic polycyclic epoxy group and 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 because of their high copolymerization reactivity and high 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, norbornane, isonorbornane, bicyclooctane, bicyclo-nonane, bicyclo-decane, tricyclodecane, , Tricyclododecane and the like, and a compound having a carbon number of 8 to 12 is preferable, and a compound having at least a carbon number of at least 8 selected from the group consisting of a compound represented by the formula (I) and a compound represented by the formula (II) And one kind of compound.

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

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

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

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-5), Formula (I-7), Formula (I-9), Formula (I-11) , 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), Formula (II-7), Formula (II-9) and Formula (II-11) to Formula (II- , 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 alone or in any 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.

The binder resin (A) used in the present invention is a copolymer of (A1) and (A2).

The binder resin (A) used in the present invention is a copolymer obtained by copolymerizing (A1) and (A2), and the ratio of the constituent components derived from each other is preferably within a range from the total number of moles of constituent components constituting the copolymer It is preferable that the molar fraction is in the following range.

(A1); 5 to 75 mol%

(A2); 25 to 95 mol%

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

(A1); 10 to 70 mol%

(A2); 30 to 90 mol%

When the ratio of the above components is in the above range, there is a tendency that the storage stability of the photosensitive resin composition, the resolution of the pattern obtained from the composition, developability, solvent resistance, heat resistance and mechanical strength are 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, the polymerization reaction is carried out by placing the polymerization initiator and the solvent in a predetermined amount of the units (A1) and (A2) constituting the copolymer and replacing the oxygen with nitrogen by the reaction, stirring, heating and keeping them under oxygen- . 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 hardly reduced at the time of development, and the decolorability of the non- , It is preferable since the resolution tends to be good.

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 in the above range, it is preferable because the developing property tends to be good and the resolution 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.

Examples of the photopolymerizable compound (B) contained in the photosensitive resin composition of the present invention include monofunctional monomers, bifunctional monomers, and other multifunctional monomers having three or more functionalities.

Specific examples of monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N- Ralidon, and the like.

Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) , Bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like.

Specific examples of other trifunctional or more multifunctional monomers 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, a reaction product of dipentaerythritol penta (meth) acrylate and an acid anhydride, Caprolactone-modified trifunctional or more polyfunctional monomer, and trifunctional or higher-functional polyfunctional monomer having three or more alkylene oxide-modified groups in the molecule.

In the present specification, caprolactone denaturation means that a caprolactone ring-opening polymer or ring opening polymer is introduced between the alcohol-derived site of the (meth) acrylate compound and the (meth) acryloyloxy group.

Further, the alkylene oxide modification means that an alkylene glycol or a dehydration condensate thereof and a ring-opening polymer of an alkylene oxide, or a ring-opening polymer thereof, between the alcohol-derived site of the (meth) acrylate compound and the (meth) acryloyloxy group .

KAYARAD DPCA-20, KAYARAD DPCA-40, KAYARAD DPCA-60, and KAYARAD DPCA-120 (all manufactured by Nippon Gakurafu Co., Ltd.), and the like are examples of the trifunctional or more polyfunctional monomer having at least one caprolactone- NK ester AD-TMP-4CL (manufactured by Shin-Nakamura Chemical Co., Ltd.), and the like.

In the polyfunctional monomers having three or more functional groups modified with three or more alkylene oxides in the molecule, preferred alkylene oxides include ethylene oxide and propylene oxide.

Of these, polyfunctional monomers having two or more functionalities are preferably used. These photopolymerizable compounds (B) may be used alone or in combination of two or more.

The content of the photopolymerizable compound (B) is preferably 1 to 90 mass%, more preferably 10 to 80 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.

As the photopolymerization initiator (C) contained in the photosensitive resin composition of the present invention, an acetophenone-based compound, a nonimidazole-based compound, an oxime-based compound, a triazine-based compound or an acylphosphine oxide-based compound is preferably used. 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-based 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). Preferred are 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) ', 5,5'-tetraphenylbiimidazole.

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 compound 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 benzoin compounds, benzophenone compounds, Anthone compound, anthone compound, anthracene compound, and the like.

More specifically, the following compounds may be used. 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).

Further, a light and / or thermal cationic polymerization initiator may be used.

The light and / or thermal cationic polymerization initiator may be composed of an onium cation and an anion derived from a Lewis acid.

Specific examples of the onium cation include diphenyliodonium, bis (p-tolyl) iodonium, bis (p-tert-butylphenyl) iodonium, bis (P-octyloxyphenyl) iodonium, (p-octadecyloxyphenyl) iodonium, (p-tolyl) (p-iso (P-tert-butylphenyl) sulfonium, tris (2,6-dimethylphenyl) sulfonium, tris (p- (P-cyanophenyl) sulfonium, tris (p-chlorophenyl) sulfonium, dimethyl (methoxy) sulfonium, dimethyl (ethoxy) , Dimethyl (butoxy) sulfonium, dimethyl (octyloxy) sulfonium, dimethyl (octadecoxy) sulfonium, dimethyl ) Sulfonium, dimethyl (3-bromoproxy) sulfonium, dimethyl (4-cyanobutoxy) sulfonium, dimethyl (4-cyanobutoxy) sulfonium, Dimethyl (tris (trichloromethyl) methyl) diphenylsulfonium chloride, dimethyl (8-nitrooctyloxy) sulfonium, dimethyl (18- trifluoromethyloctadecaneoxy) Sulfonium, and the like.

Preferable examples of the onium cation include bis (p-tolyl) iodonium, p-tolyl (p-isopropylphenyl) iodonium, bis (p-tert- butylphenyl) iodonium, triphenylsulfonium or tris -tert-butylphenyl) sulfonium, and the like.

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

The onium cation and the anion derived from the Lewis acid may be arbitrarily combined.

Specific examples of the cationic polymerization initiator include diphenyliodonium hexafluorophosphate, bis (p-tolyl) iodonium hexafluorophosphate, bis (p-tert-butylphenyl) iodonium hexafluorophosphate, bis (P-octadecylphenyl) iodonium hexafluorophosphate, bis (p-octyloxyphenyl) iodonium hexafluorophosphate, bis (p-octadecyloxyphenyl) iodonium hexafluorophosphate, bis ) Iodonium hexafluorophosphate, phenyl (p-octadecyloxyphenyl) iodonium hexafluorophosphate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluorophosphate, methylnaphthyl iodonium hexafluoro (P-tolyl) sulfonium hexafluorophosphate, tris (p-isopropylphenyl) sulfonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, tris (P-cyanophenyl) sulfonium hexafluorophosphate, tris (2,6-dimethylphenyl) sulfonium hexafluorophosphate, tris (p-tert- butylphenyl) sulfonium hexafluorophosphate, tris Dimethyl (methoxy) sulfonium hexafluorophosphate, dimethyl (ethoxy) phosphonium hexafluorophosphate, tris (p-chlorophenyl) sulfonium hexafluorophosphate, dimethylnaphthylsulfonium hexafluorophosphate, diethylnaphthylsulfonium hexafluorophosphate, Dimethyl (octyloxy) sulfonium hexafluorophosphate, dimethyl (octyloxy) sulfonium hexafluorophosphate, dimethyl (propoxyl) sulfonium hexafluorophosphate, dimethyl (butoxy) sulfonium hexafluorophosphate, (Isopropoxy) sulfonium hexafluorophosphate, dimethyl (tert-butoxy) sulfonium hexafluorophosphate, dimethyl (cyclopentyl) sulfonium hexafluorophosphate, dimethyl (2-chloroethoxy) sulfonium hexafluorophosphate, dimethyl (cyclohexyloxy) sulfonium hexafluorophosphate, dimethyl (fluoromethoxy) sulfonium hexafluorophosphate, dimethyl (4-cyanobutoxy) sulfonium hexafluorophosphate, dimethyl (8-nitrooctyloxy) sulfonium hexafluorophosphate, dimethyl (3-bromopropoxy) sulfonium hexafluorophosphate, dimethyl (Trichloromethyl) methylsulfonium hexafluorophosphate, dimethyl (2-hydroxyisopropoxy) sulfonium hexafluorophosphate, dimethyl (tris (trichloromethyl) methyl) sulfonium hexafluorophosphate, ;

Diphenyliodonium hexafluoroarsenate, diphenyliodonium hexafluoroarsenate, bis (p-tolyl) iodonium hexafluoroarsenate, bis (p-tert-butylphenyl) iodonium hexafluoroarsenate, bis ), Iodonium hexafluoroarsenate, bis (p-octadecylphenyl) iodonium hexafluoroarsenate, bis (p-octyloxyphenyl) iodonium hexafluoroarsenate, bis (P-tolyl) (p-isopropylphenyl) iodonium hexafluoroarsenate (p-phenylphenyl) iodonium hexafluoroarsenate, phenyl (p-octadecyloxyphenyl) iodonium hexafluoroarsenate, , Methyl naphthyl iodonium hexafluoroarsenate, ethyl naphthyl iodonium hexafluoroarsenate, triphenylsulfonium hexafluoroarsenate, tris (p-tolyl) sulfonium hexafluoroarsenate , Tris (p-isopropylphenyl) sulfonium hexafluoro Tris (2,6-dimethylphenyl) sulfonium hexafluoroarsenate, tris (p-tert-butylphenyl) sulfonium hexafluoroarsenate, tris (p-cyanophenyl) sulfonium hexa Dimethyl (methoxy) hexafluoroarsenate, dimethyl naphthylsulfonium hexafluoroarsenate, diethyl naphthylsulfonium hexafluoroarsenate, tris (p-chlorophenyl) sulfonium hexafluoroarsenate, (Methoxy) sulfonium hexafluoroarsenate, dimethyl (ethoxy) sulfonium hexafluoroarsenate, dimethyl (propoxy) sulfonium hexafluoroarsenate, dimethyl (butoxy) sulfonium hexafluoroarsenate , Dimethyl (octyloxy) sulfonium hexafluoroarsenate, dimethyl (octadecaneoxy) sulfonium hexafluoroarsenate, dimethyl (isopropoxy) sulfonium hexafluoroarsenate, dimethyl Ethoxy) sulfonium hexafluoro Dimethyl (cyclopentyloxy) sulfonium hexafluoroarsenate, dimethyl (cyclohexyloxy) sulfonium hexafluoroarsenate, dimethyl (fluoromethoxy) sulfonium hexafluoroarsenate, dimethyl (2-chloroethoxy) sulfonium hexafluoroarsenate, dimethyl (3-bromopropoxy) sulfonium hexafluoroarsenate, dimethyl (4-cyanobutoxy) sulfonium hexafluoroarsenate , Dimethyl (8-nitrooctyloxy) sulfonium hexafluoroarsenate, dimethyl (18-trifluoromethyloctadecaneoxy) sulfonium hexafluoroarsenate, dimethyl (2-hydroxyisopropoxy) Tetra (trichloromethyl) methyl) sulfonium hexafluoroarsenate, dimethyl (tris (trichloromethyl) methyl) sulfonium hexafluoroarsenate;

Diphenyliodonium hexafluoroantimonate, bis (p-tolyl) iodonium hexafluoroantimonate, bis (p-tert-butylphenyl) iodonium hexafluoroantimonate, bis ), Iodonium hexafluoroantimonate, bis (p-octadecylphenyl) iodonium hexafluoroantimonate, bis (p-octyloxyphenyl) iodonium hexafluoroantimonate, bis Iodonium hexafluoroantimonate, phenyl (p-octadecyloxyphenyl) iodonium hexafluoroantimonate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroantimonate , Methylnaphthyl iodonium hexafluoroantimonate, ethylnaphthyl iodonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate, tris (p-tolyl) sulfonium hexafluoroantimonate , Tris (p-isopropylphenyl) sulfonium hexafluoro (P-tert-butylphenyl) sulfonium hexafluoroantimonate, tris (p-cyanophenyl) sulfonium hexa sulphonium hexafluoroantimonate, Dimethyl (methoxy) hexafluoroantimonate, dimethyl naphthylsulfonium hexafluoroantimonate, diethyl naphthylsulfonium hexafluoroantimonate, tris (p-chlorophenyl) sulfonium hexafluoroantimonate, dimethyl naphthylsulfonium hexafluoroantimonate, (Methoxy) sulfonium hexafluoroantimonate, dimethyl (ethoxy) sulfonium hexafluoroantimonate, dimethyl (propoxy) sulfonium hexafluoroantimonate, dimethyl (butoxy) sulfonium hexafluoroantimonate , Dimethyl (octyloxy) sulfonium hexafluoroantimonate, dimethyl (octadecaneoxy) sulfonium hexafluoroantimonate, dimethyl (isopropoxy) sulfonium hexafluoroantimonate, dimethyl Ethoxy) sulfonium hexafluoro Dimethyl (cyclopentyloxy) sulfonium hexafluoroantimonate, dimethyl (cyclohexyloxy) sulfonium hexafluoroantimonate, dimethyl (fluoromethoxy) sulfonium hexafluoroantimonate, dimethyl (2-chloroethoxy) sulfonium hexafluoroantimonate, dimethyl (3-bromopropoxy) sulfonium hexafluoroantimonate, dimethyl (4-cyanobutoxy) sulfonium hexafluoroantimonate , Dimethyl (8-nitrooctyloxy) sulfonium hexafluoroantimonate, dimethyl (18-trifluoromethyloctadecaneoxy) sulfonium hexafluoroantimonate, dimethyl (2-hydroxyisopropoxy) Dimethyl (tris (trichloromethyl) methyl) sulfonium hexafluoroantimonate, tetra (trichloromethyl) methylsulfonium hexafluoroantimonate;

(Pentafluorophenyl) borate, bis (p-tolyl) iodonium tetrakis (pentafluorophenyl) borate, bis (p-tert- butylphenyl) iodonium tetrakis ) Borate, bis (p-octylphenyl) iodonium tetrakis (pentafluorophenyl) borate, bis (p-octadecylphenyl) iodonium tetrakis (pentafluorophenyl) Iodonium tetrakis (pentafluorophenyl) borate, phenyl (p-octadecyloxyphenyl) iodonium tetrakis (pentafluorophenyl) borate, bis (p-octadecyloxyphenyl) (Pentafluorophenyl) borate, methylnaphthyl iodonium tetrakis (pentafluorophenyl) borate, ethyl naphthyl iodonium tetrakis (pentafluorophenyl) borate, (Pentafluorophenyl) borate, (Pentafluorophenyl) borate, tris (p-tolyl) sulfonium tetrakis (pentafluorophenyl) borate, tris (p-isopropylphenyl) sulfonium tetrakis Borate, tris (2,6-dimethylphenyl) sulfonium tetrakis (pentafluorophenyl) borate, tris (p-tert- butylphenyl) sulfonium tetrakis (pentafluorophenyl) (Pentafluorophenyl) borate, tris (p-chlorophenyl) sulfonium tetrakis (pentafluorophenyl) borate, dimethylnaphthylsulfonium tetrakis (pentafluorophenyl) (Pentafluorophenyl) borate, dimethyl (methoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (ethoxy) sulfonium tetrakis ) Sulfonium tet (Pentafluorophenyl) borate, dimethyl (octyldecyloxy) borate, dimethyl (octyldecyloxy) borate, dimethyl (Pentafluorophenyl) borate, dimethyl (isopropoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (tert-butoxy) sulfonium tetrakis (Pentafluorophenyl) borate, dimethyl (cyclohexyloxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (fluoromethoxy) sulfonium tetrakis (pentafluorophenyl) ) Borate, dimethyl (2-chloroethoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (3-bromoproxy) sulfonium tetrakis (Pentafluorophenyl) borate, dimethyl (8-nitrooctyloxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (18-trifluoromethyloctadecanoxy) sulfonium tetrakis (Pentafluorophenyl) borate, dimethyl (tris (trichloromethyl) methylsulfonium tetrakis (pentafluorophenyl) borate, dimethyl (2-hydroxyisopropoxy) sulfonium tetrakis (P-tolyl) (p-isopropylphenyl) iodonium hexafluorophosphate, bis (p-tert-butylphenyl) iodonium hexafluorophosphate, (P-tert-butylphenyl) sulfonium hexafluorophosphate, bis (p-tolyl) iodonium hexafluoroarsenate, (p-tert-butylphenyl) sulfonium hexafluorophosphate, - tolyl) (p-isopropylphenyl ) Iodonium hexafluoroarsenate, bis (p-tert-butylphenyl) iodonium hexafluoroarsenate, triphenylsulfonium hexafluoroarsenate, tris (pt-butylphenyl) sulfonium hexafluoro (P-tert-butylphenyl) iodonium hexafluoroantimonate, bis (p-tolyl) iodonium hexafluoroantimonate, (P-tert-butylphenyl) sulfonium hexafluoroantimonate, bis (p-tolyl) iodonium tetrakis (pentaerythritol hexafluoroantimonate), triphenylsulfonium hexafluoroantimonate, Iodonium tetrakis (pentafluorophenyl) borate, bis (p-tert-butylphenyl) iodonium, triphenylsulfonium tetrakis (penta Fluorophenyl) borate, tris (p-tert-butylphenyl) sulfonium tetrakis (pentafluoro (P-tolyl) (p-isopropylphenyl) iodonium hexafluoroantimonate, bis (p-tolyl) hexafluoroantimonate and the like can be given. (p-tert-butylphenyl) iodonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate, tris (p-tert-butylphenyl) sulfonium hexafluoroantimonate, bis Iodonium tetrakis (pentafluorophenyl) borate, bis (p-tert-butylphenyl) iodonium tetra (pentafluorophenyl) borate, (Pentafluorophenyl) borate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, or tris (p-tert-butylphenyl) sulfonium tetrakis (pentafluorophenyl) borate.

The photopolymerization initiator may be used in combination with the photopolymerization initiator (C-1), or a plurality of photopolymerization initiators may be used in combination.

Examples of the photopolymerization initiator include amine compounds, carboxylic acid compounds, polyfunctional thiol compounds, and compounds represented by the formula (III). As the amine compound, an aromatic amine compound is preferable. As the photopolymerization initiator, an amine compound, a polyfunctional thiol, and a compound represented by the formula (III) are preferable.

Examples of the photopolymerization initiation auxiliary (C-1) include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine; aliphatic amine compounds such as methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, Amyl, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone Aromatic amine compounds such as bis (diethylamino) benzophenone;

Phenylthioacetic acid, methylphenylthioacetic acid, methylphenylthioacetic acid, methylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine , Aromatic acetoacetic acids such as phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid;

Hexanediol diol, hexanediol diol, hexanediol diol, hexanediol, hexanediol, decanediol, hexanediol, decanediol, hexanediol, decanediol, decanediol, hexanediol, Pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthiopropionate, Multifunctional thiol compounds such as lithol tetrakis (3-mercaptobutyrate) and 1,4-bis (3-mercaptobutyryloxy) butane;

And compounds represented by the following formula (III).

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

Y represents an oxygen atom or a sulfur atom.

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

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

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

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

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

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

Examples of the aryl group which may be substituted with a halogen atom include a phenyl group, a chlorophenyl group, a dichlorophenyl group, a bromophenyl group, a dibromophenyl group, a chlorobenzophenyl group, a biphenyl group, a chlorobiphenyl group, a dichlorobiphenyl group, a bromophenyl group, A phenyl group, a naphthyl group, a chloronaphthyl group, a dichloronaphthyl group, a bromonaphthyl group, and a dibromonaphthyl group.

As the compound represented by the formula (III), 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

And the like.

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

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 Therefore, it is preferable.

The photosensitive resin composition of the present invention contains a solvent (D). Examples of the solvent (D) include various organic solvents used in the field of the photosensitive resin composition, and specific examples thereof include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol Ethylene glycol monoalkyl ethers such as monobutyl ether;

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

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

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

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

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

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

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 and butoxybutyl acetate;

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

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

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

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

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

Examples of the solvent include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxypropionate, methylhydroxyacetate, Hydroxypropionate, propyl 3-hydroxypropionate, propyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, 2-hydroxybutyl 3-hydroxypropionate, Methyl methoxyacetate, methyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethoxyacetate, ethoxyacetate, ethoxyacetate, and the like. , Methyl propoxyacetate, ethyl propoxyacetate, propoxypropylacetate, butyl propoxyacetate, methyl butoxyacetate, Methoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-methoxypropionate, Ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 3-butoxypropionate, Ethoxypropionate, propyl 3-ethoxypropionate, propyl 3-methoxypropionate, propyl 3-methoxypropionate, methyl 3-methoxypropionate, Ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, Esters such as ethyl butoxypropionate, propyl 3-butoxypropionate and butyl 3-butoxypropionate;

Cyclic ethers such as tetrahydrofuran and pyran;

and cyclic esters such as? -butyrolactone.

In view of coatability and dryness, an organic solvent having a boiling point of 100 ° C to 200 ° C is preferably used in the above solvent, more preferably an alkylene glycol alkyl ether acetate, a ketone, a butanediol alkyl ether acetate Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexane monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate, and more preferably, Methoxybutyl acetate, methoxybutanol, ethyl 3-ethoxypropionate, and methyl 3-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.

The photosensitive resin composition of the present invention may optionally contain additives (F) such as fillers, other polymer compounds, leveling agents, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents, chain transfer agents and the like.

Specific examples of the filler include glass, silica and alumina.

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 leveling agent, a commercially available surfactant can be used, and examples thereof include surfactants such as silicon-based, fluorine-based, ester-based, cationic, anionic, nonionic and amphoteric surfactants. A combination of two or more species may be used. 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.).

As the adhesion promoter, silane compounds are preferable, and specific examples thereof include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3 Aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3- (3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3- Trimethoxysilane, 3-mercaptopropyltrimethoxysilane, and the like.

Specific examples of the antioxidant include 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4- methylphenyl acrylate, 2- [1- (3-tert-butyl-4-hydroxy-5-methylphenyl) ethyl] -4,6-di- Propoxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [1,3,2] dioxaphosphperine, 3,9-bis [2- {3- methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 4,4'-butylidenebis (6-tert- -Methylphenol), 2,2'-thiobis (6-tert-butyl-4-methylphenol), dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropion (3-laurylthiopropionate), 1,3,5-tris (3,5-di-tert-butylphenyl) 3,3 ', 3' ', 5,5', 5 ', 5'-triene, -Hexa-tert-butyl-a, a ', a "- (mesitylene-2,4,6-triyl) tri-p-cresol, pentaerythritol tetrakis [3- -tert-butyl-4-hydroxyphenyl) propionate], 2,6-di-tert-butyl-4-methylphenol and the like.

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

Specific examples of the anti-aggregation agent include sodium polyacrylate 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 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 made of a solid component of a previously formed photosensitive resin composition, and pre-baked from the applied photosensitive resin composition layer to remove volatile components such as a solvent 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 application method is, for example, a spin coating method, a flexible coating method, a roll coating method, a slit and spin coating method, a slit coating method, or the like. After the application, the photosensitive resin composition layer is formed by heating and drying (pre-baking) or heating under reduced pressure and drying to volatilize the volatile components such as a solvent. Here, the heating temperature is usually 70 to 200 占 폚, preferably 80 to 130 占 폚. The photosensitive resin composition layer contains little volatile components. The thickness of the photosensitive resin composition layer is usually about 1.5 to 8 mu m.

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 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.

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 laurylsulfate and ammonium laurylsulfate, And alkylarylsulfonic acid salts such as sodium sulfonate and 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 singly or in combination of two or more kinds.

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. Further, at the time of exposure to a dry film, a transparent film can be formed only by full-surface exposure, heat curing, or heat curing without using a photomask, and this transparent film is useful as an overcoat and can also be used as a touch panel .

Therefore, 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 is capable of forming a pattern or a coating film having a small change in viscosity at the time of storage, resolving to a fine pattern, and excellent in solvent resistance and heat resistance.

The photosensitive resin composition of the present invention is preferably used as a material for forming a transparent film constituting a part of a color filter such as an overcoat, a photo spacer, an insulating film, a projection for controlling liquid crystal alignment, a coat layer for adjusting the thickness of a coloring pattern Lt; / RTI >

Example

Hereinafter, the present invention will be described in more detail with reference to Examples, but it goes without saying that the present invention is not limited by 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, 60 parts by mass of methacrylic acid, the molar ratio of the compound represented by the formula (I-1) and the compound represented by the formula (II-1), 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl acrylate 50: 50) and 140 parts by mass of 3-methoxybutyl acetate to prepare a solution, and the solution was dropped into a flask heated to 70 DEG C over 4 hours using a dropping funnel . On the other hand, a solution prepared by dissolving 30 parts by mass of polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in 225 parts by mass of 3-methoxybutyl acetate was added to a flask / RTI > After the dropwise addition of the polymerization initiator solution was completed, the solution was kept at 70 占 폚 for 4 hours and then cooled to room temperature to obtain a copolymer (solid content: 32.6 mass%, acid value: 110 mg-KOH / g ) Was obtained. The weight average molecular weight Mw of the obtained resin Aa was 13,400 and the degree of dispersion was 2.50.

Synthesis Example 2

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. Subsequently, 55 parts by mass of methacrylic acid, the molar ratio of the compound represented by the formula (I-1) and the compound represented by the formula (II-1), 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl acrylate 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 reaction mixture over 4 hours using a dropping funnel Lt; RTI ID = 0.0 > 70 C < / RTI > On the other hand, a solution prepared by dissolving 30 parts by mass of polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in 225 parts by mass of 3-methoxybutyl acetate was added to a flask / RTI > After the dropwise addition of the polymerization initiator solution was completed, the solution was maintained at 70 DEG C 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 mass% and an acid value of 105 mg-KOH / g . The weight average molecular weight Mw of the obtained resin Ab was 13,600 and the degree of dispersion was 2.54.

Synthesis Example 3

In the same manner as in Synthesis Example 1 of JP-A-11-133600, 7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 20 parts by mass of diethylene glycol And 200 parts by mass of dimethyl ether. Subsequently, 30 parts by mass of styrene, 20 parts by mass of methacrylic acid and 50 parts by mass of glycidyl methacrylate were purged with nitrogen, and stirring was started slowly. The temperature of the solution was raised to 70 캜 and maintained at this temperature for 5 hours to obtain a polymer solution containing the resin Ac. The weight average molecular weight of the resin Ac obtained in terms of polystyrene was 24,000.

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

169 parts (55 parts in terms of solid content) of a resin solution (A) containing the resin Aa obtained in Synthesis Example 1, 45 parts of dipentaerythritol hexaacrylate (B), 2,2'-bis (2-chlorophenyl) 4 parts of 4,4 ', 5,5'-tetraphenylbiimidazole (C), 0.5 parts of 2- (2-naphthoylmethylene) -3-methylbenzothiazoline (C-1), 0.5 parts of pentaerythritol tetrakis 3 parts of thiopropionate (C-1), 0.8 parts of IRGANOX 3141 (Ciba Specialty Chemicals) (F), 58 parts of propylene glycol monomethyl ether acetate, 42 parts of 3-ethoxyethyl propionate, 3 parts of 1-butanol and 2 parts of 3-methoxybutyl acetate were mixed to obtain Photosensitive Resin Composition 1.

≪ Pattern formation >

A glass substrate (Eagle 2000; manufactured by Corning) having an aspect ratio of 2 inches was sequentially washed with a neutral detergent, water and alcohol, and then dried. The photosensitive resin composition 1 was exposed to an exposure amount (405 nm) of 100 mJ / cm 2 on the glass substrate, spin-coated so as to have a film thickness of 3.0 μm when developed, washed and post-baked, And prebaked at 90 DEG C for 3 minutes. After cooling, the space between the substrate coated with this photosensitive resin composition and the quartz glass photomask was set to 10 mu m and an exposure amount of 100 mJ / cm < 2 > was formed in an atmosphere of an atmosphere using an exposure machine (TME-150RSK; Topcon Co., 405 nm). The irradiation of the polymerizable resin composition at this time was carried out by passing the radiation from the ultra-high pressure mercury lamp through an optical filter (LU0400; manufactured by Asahi Spectroscopy), and cutting light having a wavelength of 400 nm or less.

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

- A light-transmitting portion (pattern) having a square of 10 mu m in one side, and the interval of the square is 100 mu m.

- A light-transmitting portion (pattern) having a square of 15 mu m per side, and the interval of the square is 100 mu m.

After the light irradiation, the substrate was developed by immersing the coating film in an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 25 캜 for 100 seconds, rinsed and then rinsed in an oven at 220 캜 for 20 minutes Post-baking was carried out. After the cooling, the film thickness of the obtained cured film was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.), and it was 3.0 탆.

<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.).

<Line width, sectional shape>

The line width and shape (cross section) of the cured film were observed and measured using a scanning electron microscope (S-4000, manufactured by Hitachi, Ltd.).

The line width measured in the pattern corresponding to the 10 mu m pattern on the photomask was 10.0 mu m.

The cross-sectional shape was an angle of the pattern with respect to the substrate was less than 90 degrees, and was a net taper. When the angle of the pattern with respect to the substrate was 90 degrees or more, it was judged as an inverse taper.

A net taper is preferable because disconnection of the ITO wirings hardly occurs at the time of forming the liquid crystal display device.

<Mechanical Characteristics> (Total Displacement and Recovery Rate)

The total amount of displacement (占 퐉) and the amount of elastic displacement (占 퐉) were measured using a dynamic ultra-microhardness tester (DUH-W201; Shimadzu Corporation). Recovery rates (%) were obtained from these figures. The total displacement amount was 0.57 탆 and the recovery rate was 92.9%.

-Measuring conditions-

Test mode; Load - unloading test

Test force; 5gf [SI conversion value; 49.0 mN]

Load speed; 0.45 gf / sec [SI unit conversion value; 4.41 mN / sec]

Retention time; 5sec

Indenter; Conical indenter indenter (diameter 50 탆)

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

<Solvent resistance>

In the exposure step, except that a photomask was not used, the same operation was carried out to prepare a coating film, and the film thickness thereof was measured. The resulting coating film was immersed in N-methylpyrrolidone at 40 占 폚 for 40 minutes, and the film thickness after immersion was measured. The change in film thickness was determined according to the following formula, and this was taken as an index of the solvent resistance. The value obtained was 103.9%.

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

The film thickness change is preferably 104% or less.

<Heat resistance>

In the exposure process, the same operation was carried out except that the photomask was not used, and a coating film was produced. The coated film thus prepared was allowed to stand in a clean oven at 240 캜 for 1 hour. The film thickness before and after heating was measured, and the film thickness change was determined according to the following formula, which was regarded as an index of heat resistance. The value obtained was 98.2%.

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

The film thickness change is preferably 97% or more.

Example 2

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

Example 3

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

Comparative Example 1

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

Comparative Example 2

The photosensitive resin composition 5 was obtained so as to have the composition shown in Table 1. The storage stability was measured in the same manner as in Example 1, and the evaluation was stopped because it was thickened.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Photosensitive resin composition One 2 3 4 5 bookbinder
Resin (A) Resin Aa 55 50 45 - - Resin Ab - - - 55 - Resin Ac - - - - 60 Photopolymerizable compound (B);
Dipentaerythritol hexaacrylate
(KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) 45 50 55 45 40 Light curing
Initiator (C); Bis (o-chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole (B-CIM manufactured by Hodogaya Chemical Co., Ltd.) 4 4 4 4 - 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one (Irgacure-907, manufactured by Ciba Specialty Chemicals) - - - - 6 A photopolymerization initiation auxiliary (C-1); 2- (2-naphthoylmethylene) -3-methylbenzothiazoline 0.5 0.5 0.5 0.5 - Pentaerythritol tetrakisthiopropionate (PEMP; manufactured by Sakai Chemical Industry Co., Ltd.) 3 3 3 3 - Solvent (D); Propylene glycol monomethyl ether acetate 58 58 58 58 - 3-ethoxyethyl propionate 42 42 42 42 - 3-Methoxy-1-butanol 3 7 10 3 - 3-methoxybutylacetate 2 9 17 2 - Diethylene glycol dimethyl ether - - - - 197 Additive (F) Antioxidants; 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) Irganox 3114 (manufactured by Ciba Specialty Chemicals) 0.8 0.8 0.8 0.8 -

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Photosensitive resin composition One 2 3 4 5 Storage stability (%) 100 101 100 101 107 pattern Line width (탆) 10.0 8.9 8.2 11.6 - shape Sun Taper Sun Taper Sun Taper Sun Taper - Mechanical properties Total displacement (㎛) 0.57 0.73 0.67 0.50 - Recovery Rate (%) 92.9 77.9 75.6 88.3 - Solvent resistance (%) 103.9 102.2 103.0 105.3 - Heat resistance (%) 98.2 98.1 98.0 98.0 -

Example 4

The photosensitive resin composition 6 was obtained so as to have the composition shown in Table 3.

&Lt; Pattern formation >

A glass substrate (Eagle 2000; manufactured by Corning) having an aspect ratio of 2 inches was sequentially washed with a neutral detergent, water and alcohol, and then dried. The photosensitive resin composition 1 was exposed to an exposure dose (365 nm) of 40 mJ / cm 2 on the glass substrate, spin-coated so as to have a film thickness of 3.0 μm when developed, washed and post-baked, , And pre-baked at 85 캜 for 3 minutes. After cooling, the distance between the substrate coated with this photosensitive resin composition and the quartz glass photomask was 10 mu m, and an exposure amount of 40 mJ / cm &lt; 2 &gt; was measured under an atmospheric environment using an exposure apparatus (TME-150RSK; Topcon Co., 365 nm). The irradiation of the polymerizable resin composition at this time was carried out by passing the radiation from the ultra-high pressure mercury lamp through an optical filter (UV-31; manufactured by Asahi Spectroscopy).

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

- A light-transmitting portion (pattern) having a square of 10 mu m in one side, and the interval of the square is 100 mu m.

- A light-transmitting portion (pattern) having a square of 15 mu m per side, and the interval of the square is 100 mu m.

After light irradiation, the substrate was developed by immersing the coating film in an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23 DEG C for 40 seconds. After washing with water, the substrate was dried in an oven at 220 DEG C for 20 minutes Post-baking was carried out. After the cooling, the film thickness of the obtained cured film was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.), and it was 3.0 탆.

Evaluation after pattern formation was evaluated in the same manner as in Example 1.

Comparative Example 3

The photosensitive resin composition 7 was obtained so as to have the composition shown in Table 3. And evaluated in the same manner as in Example 4.

Example 4 Comparative Example 3 Polymerizable
Resin composition 6 Polymerizable
Resin composition 7 Resin (A) Resin Aa (solids only) 60 Resin Ab (solids only) 60 Resin Ac (solids only) The polymerizable compound (B) Dipentaerythritol hexaacrylate
KAYARAD DPHA manufactured by Nippon Gunpaku Co., Ltd. 40 40 Initiator (C) 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -, 1- (O-acetyloxime)
OXE-02 manufactured by CIBA SPECIALTY CHEMICALS 2 2 Solvent (D) Propylene glycol monomethyl ether acetate 41 41 3-ethoxyethyl propionate 37 37 3-Methoxy-1-butanol 4 4 3-methoxybutylacetate 0 0 3-Methoxy-1-butanol
+ 3-methoxybutyl acetate
The inflow from the resin (A) 124 124

Example 4 Comparative Example 3 Photosensitive resin composition 6 7 Storage stability 100 101 pattern Line width ㎛ 13.1 20.0 shape Sun Taper Sun Taper

From the results of Examples 1 to 3 shown in Table 2, the photosensitive resin composition of the present invention containing a binder resin containing an aliphatic polycyclic epoxy compound is excellent in storage stability. It is also understood that when the photosensitive resin composition of the present invention is used, a pattern and a coating film having good pattern shape, mechanical properties, solvent resistance, and heat resistance can be obtained. Compared with the comparative example 1, it can be understood that even a fine pattern can be resolved.

From the results of Example 4 shown in Table 4, the photosensitive resin composition of the present invention containing a binder resin containing an aliphatic polycyclic epoxy compound is excellent in storage stability. It is also understood that when the photosensitive resin composition of the present invention is used, a pattern and a coating film having a good pattern shape can be obtained. Compared with Comparative Example 3, it can be seen that a fine pattern can be resolved.

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, an insulating film, And a coat layer for adjusting the film thickness of the colored pattern.

Claims (5)

(A), a photopolymerizable compound (B), a photopolymerization initiator (C) and a solvent (D), wherein the binder resin (A) contains an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride (A2) alone, and the ratio of the constitutional units derived from the unsaturated carboxylic acid and / or the unsaturated carboxylic acid anhydride (A1) in the copolymer is not particularly limited as long as the ratio of the constituent units constituting the copolymer And the proportion of the constituent unit derived from the aliphatic polycyclic epoxy compound (A2) relative to the total molar number of the constituent units constituting the copolymer is from 25 to 95 mol% Sensitive resin composition. The method according to claim 1, The aliphatic polycyclic epoxy compound (A2) is a compound having an epoxy group on the ring of an aliphatic polycyclic compound and having an unsaturated bond. 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).

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