JP4389582B2 - Photosensitive resin composition - Google Patents

Description

  The present invention relates to a photosensitive resin composition and a color filter using the same.

In recent years, various color liquid crystal display elements in which a color separation color filter is combined with a liquid crystal element have been proposed. Here, the color filter is composed of a large number of picture elements each composed of three primary colors of red, green, and blue formed on a light-transmitting substrate, and a display contrast is provided between the pixels. In some cases, a light-shielding region (black matrix) having a certain width is provided to increase the height. There are also photo spacers, transparent coating materials for adjusting the thickness of the colored pattern, and transparent electrodes.
As a resin component constituting such a pixel and a black matrix, and as a resin component used for a transparent coating material (hereinafter sometimes referred to as a transparent coating material) for adjusting the film thickness of a photo spacer and a colored pattern, Conventionally, siloxane polymers, polyimide resins, epoxy resins, acrylic resins, and the like have been used.
However, when a transparent coating material or the like is formed using a conventionally known composition containing the above resin, since the surface of the obtained transparent film may be rough, the transmittance due to light scattering As a result, there was a problem that it was difficult to function as a transparent coating material or the like, and the resolution was poor.

Furthermore, when the portion to be removed at the time of development is poor and may remain on the substrate (hereinafter, sometimes referred to as “poor detachment”), when used in a transflective color filter, The color is different at the boundary between the reflection part and the transmission part, and this deteriorates the quality of a color image displayed by the color liquid crystal display device or a color image taken by the color solid-state imaging device. Further, when the omission is poor, when used for a photospacer, the size of the photospacer is, for example, generally about several μm square to 20 μm square (Patent Document 1). There was a problem that the size of the photo spacer could not be controlled.
On the other hand, if the omission is too good, the performance is good when a fine line is drawn like a transparent resist, but if only a thin pattern such as a photo spacer is left, the adhesion becomes poor, and the pattern is not developed in the development process. There is a problem of flying.
In addition, it has excellent photocurability (no need for heat curing) and developability, excellent substrate adhesion and curability, long-term storage stability and good use environment dependence, and for LCD spacer formation Although suitable radiation-curable compositions are known, in the examples, the binder polymer specifically exemplified includes a structural unit derived from isophorone diisocyanate together with a (meth) acryloyl group. There are known ones (see Patent Document 2) and those in which the binder polymer is a styrene resin (see Patent Document 1).

JP, 2001-92128, A 3rd page right column 49th line-4th page left column 3rd line, 2nd page right column 2nd line-5th line JP, 2002-20442, A page 3 right column 6th line-31st line, page 13 left column 3rd line-39th line

  The object of the present invention is that the coating property is good, the surface is not rough and the transmittance is not lowered, and even fine patterns can be resolved, so that the omission is good, and a thin pattern such as a photo spacer is left. Another object is to provide a new photosensitive resin composition for forming a transparent film.

As a result of intensive studies on new means that can solve the above-mentioned problems, the present inventors have solved the above-mentioned problems with a photosensitive resin composition containing a specific unsaturated group-containing binder resin and a specific photopolymerization initiator. As a result, the inventors have found out that the present invention can be achieved.
That is, the present invention relates to a photosensitive resin composition comprising (A) a binder polymer, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) a photopolymerization initiation assistant, and (E) a solvent. A) The binder resin is an unsaturated group-containing resin obtained by reacting a copolymer obtained by copolymerizing the following (A1) to (A3) with (A4), and (C) light A photosensitive resin composition, wherein the polymerization initiator contains at least one acetophenone compound.
(A1); Compound (A2) having at least one skeleton selected from the group consisting of a tricyclodecane skeleton and a dicyclopentadiene skeleton and an unsaturated bond in one molecule; and (A1) and (A3) Compound (A3) having polymerizable unsaturated bond; Unsaturated carboxylic acid (A4); Compound having unsaturated bond and epoxy group in one molecule. In addition, the present invention provides the above-mentioned photosensitive resin composition, It is applied onto a substrate or a layer made of a solid content of a photosensitive resin composition previously formed, volatile components are removed from the applied photosensitive resin composition layer, and the layer is exposed through a photomask, The present invention provides a pattern to be developed, a spacer composed of the pattern, a color filter including the spacer, and a liquid crystal display device using the color filter.

  According to the photosensitive resin composition of the present invention, the coating property is good, the surface is not rough, the coating defect such as particulate foreign matter does not occur, and the fine pattern can be resolved, so that the removal property is good. Furthermore, it is possible to provide a photosensitive resin composition that can leave a thin pattern such as a photospacer, and to make the film thickness of a transparent material that constitutes a liquid crystal display device, for example, a photospacer or a colored pattern, match. It is useful for forming a transparent coat layer and the like.

The binder resin (A) used in the photosensitive resin composition of the present invention generally has reactivity and alkali solubility due to the action of light and heat, and acts as a dispersion medium for coloring materials. The binder resin (A) used in the photosensitive resin composition of the present invention is unsaturated obtained by further reacting (A4) with a copolymer obtained by copolymerizing the following (A1) to (A3). It is a group-containing resin.
(A1); Compound (A2) having at least one skeleton selected from the group consisting of a tricyclodecane skeleton and a dicyclopentadiene skeleton and an unsaturated bond in one molecule; and (A1) and (A3) Compound (A3) having polymerizable unsaturated bond; Unsaturated carboxylic acid (A4); Compound having unsaturated bond and epoxy group in one molecule

  Specific examples of the compound (A1) having an unsaturated bond and a tricyclodecane skeleton and / or a dicyclopentadiene skeleton in one molecule include dicyclopentanyl (meth) acrylate and dicyclopentenyl (meth). Examples include acrylate, dicyclopentanyloxyethyl (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate. These can be used alone or in combination. Here, description of (meth) acrylate in this specification represents an acrylate and / or a methacrylate.

Specific examples of the compound (A2) having an unsaturated bond copolymerizable with (A1) and (A3) include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, Unsubstituted or substituted alkyl esters of unsaturated carboxylic acids such as 2-hydroxyethyl (meth) acrylate and aminoethyl (meth) acrylate;
Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl (meth) acrylate, menthyl (meth) acrylate, cyclopentenyl (meth) acrylate, cyclohexenyl (meta) ) Acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (meth) acrylate, mentadienyl (meth) acrylate, isobornyl (meth) acrylate, pinanyl (meth) acrylate, adamantyl (meth) acrylate, norbornenyl (meth) acrylate, pinenyl (meth) acrylate An ester compound containing an alicyclic group of an unsaturated carboxylic acid such as
Monosaturated carboxylic acid ester compounds of glycols such as oligoethylene glycol monoalkyl (meth) acrylate;
Ester compounds containing an aromatic ring of an unsaturated carboxylic acid such as benzyl (meth) acrylate and phenoxy (meth) acrylate;
Aromatic vinyl compounds such as styrene, α-methylstyrene and vinyltoluene;
Carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate;
Vinyl cyanide compounds such as (meth) acrylonitrile and α-chloroacrylonitrile;
Examples thereof include maleimide compounds such as N-cyclohexylmaleimide and N-phenylmaleimide. These can be used alone or in combination.

  Specific examples of the unsaturated carboxylic acid (A3) include acrylic acid and methacrylic acid. Acrylic acid and methacrylic acid can be used alone or in combination. In addition to these acrylic acid and methacrylic acid, other acids can be used. Specifically, as the other acid, at least one carboxylic acid selected from other unsaturated carboxylic acids such as crotonic acid, itaconic acid, maleic acid and fumaric acid can be used in combination. A monomer containing a hydroxy group and a carboxyl group in the same molecule, such as α- (hydroxymethyl) acrylic acid, can also be used in combination.

First, in the copolymer obtained by copolymerizing (A1) to (A3) in the present invention, the ratio of the components derived from each of (A1) to (A3) constitutes the copolymer. It is preferable to be in the following range in terms of mole fraction with respect to the total number of moles of the constituent components.
Structural units derived from (A1); 2 to 30 mol%
Structural units derived from (A2); 2 to 95 mol%
Structural units derived from (A3); 2 to 70 mol%
Moreover, it is more preferable in the ratio of the said structural component being the following ranges.
Structural units derived from (A1); 5 to 25 mol%
Structural units derived from (A2); 5 to 80 mol%
Structural units derived from (A3); 5 to 60 mol%
When the composition ratio is in the above range, the balance of developability, flexibility and heat resistance is good, and a preferable trunk polymer is obtained.
Furthermore, next, (A4) can be added to the copolymer to impart photo / thermosetting properties to the binder resin.
Specific examples of the compound (A4) having an unsaturated bond and an epoxy group in one molecule include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, and 3,4-epoxycyclohexylmethyl. (Meth) acrylate and methyl glycidyl (meth) acrylate are mentioned. Preferably, glycidyl (meth) acrylate is used. These can be used alone or in combination of two or more.
The amount of (A4) added is 5 to 90 mol%, preferably 10 to 80 mol%, based on the carboxyl group (derived from the A3 component) in the resin obtained by polymerizing (A1) to (A3). It is.
When the composition ratio of (A4) is within the above range, sufficient photocurability and thermosetting are obtained, both sensitivity and pencil hardness are achieved, and reliability is preferable.

The binder resin (A) preferably has a polystyrene-equivalent weight average molecular weight in the range of 3,000 to 100,000, and more preferably in the range of 5,000 to 50,000. When the weight average molecular weight of the binder resin (A) is in the range of 3,000 to 100,000, film loss is unlikely to occur during development, and non-pixel portion omission tends to be good during development, which is preferable. .
The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the binder resin (A) is preferably 1.5 to 6.0, more preferably 1.8 to 4.0. preferable. A molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of 1.5 to 6.0 is preferable because of excellent developability.
The binder resin (A) used in the colored photosensitive resin composition of the present invention is usually in the range of 5 to 90% by mass, preferably 10 to 70% by mass, based on the total solid content in the colored photosensitive resin composition. Contained. When the content of the binder resin (A) is 5 to 90% by mass on the basis of the above, the solubility in the developer is sufficient, and a development residue is hardly generated on the non-pixel portion of the substrate. It is sometimes preferable because the film thickness of the pixel portion of the exposed portion is less likely to occur, and the non-pixel portion tends to be easily removed.

  The photopolymerizable compound (B) used in the photosensitive resin composition of the present invention is a compound that can be polymerized by an active radical, an acid, or the like generated from a photopolymerization initiator when irradiated with light, for example, Examples thereof include a compound having a polymerizable carbon-carbon unsaturated bond.

  The (B) photopolymerizable compound is preferably a tetrafunctional or higher polyfunctional photopolymerizable compound. Examples of the tetrafunctional or higher polyfunctional photopolymerizable compound include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate and the like. Is mentioned. These photopolymerizable compounds are used alone or in combination of two or more, and the content thereof is usually 5% by mass or more and 90% by mass or less, preferably 10% by mass or more in terms of the mass fraction of the photosensitive resin composition. It is used in the range of 80% by mass or less, particularly preferably 20% by mass or more and 70% by mass or less.

The photopolymerization initiator (C) used in the photosensitive resin composition of the present invention contains at least one acetophenone compound. Examples of the acetophenone compound include diethoxyacetophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-methyl-2-morpholino-1- (4-methylthiophenyl). ) Propan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propane -1-one, 1-hydroxycyclohexyl phenyl ketone, oligomers of 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one, and the like, preferably 2-methyl -2-morpholino-1- (4-methylthiophenyl) propan-1-one and the like
A plurality of acetophenone-based and other photopolymerization initiators may be used in combination.
Examples of photopolymerization initiators other than acetophenone are active radical generators and sensitizers that generate active radicals when irradiated with light.
Examples of the active radical generator include benzoin compounds, benzophenone compounds, thioxanthone compounds, and triazine compounds.

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

  Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (t-butyl). Peroxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

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

  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- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl ] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- Bis (trichloromethyl) ) Such -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  Examples of the active radical generator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2 '-Biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compound and the like can also be used.

  Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenyl, Onium salts such as methyl benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, and nitrobenzyl tosylate And benzoin tosylate.

  Among the compounds described above as active radical generators, there are also compounds that generate an acid simultaneously with active radicals. For example, triazine photopolymerization initiators are also used as acid generators.

The (D) photopolymerization initiation assistant used in the present invention is a compound that is used in combination with a photopolymerization initiator and is used to promote polymerization of a photopolymerizable compound that has been polymerized by the photopolymerization initiator. is there. The photopolymerization initiation assistant includes at least one amine system.
Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylbenzoate. Aminoethyl, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 4, Examples thereof include 4′-bis (ethylmethylamino) benzophenone, and among these, 4,4′-bis (diethylamino) benzophenone is preferable. Further, a plurality of amines and other photopolymerization initiation assistants may be used in combination. Examples of other photopolymerization initiation assistants include alkoxyanthracene compounds and thioxanthone compounds.

  Examples of the alkoxyanthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and the like. Can be mentioned.

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

  Commercially available photopolymerization initiation assistants can also be used, and examples of commercially available photopolymerization initiation assistants include trade name “EAB-F” (manufactured by Hodogaya Chemical Co., Ltd.).

  Examples of the combination of (C) the photopolymerization initiator and (D) the photopolymerization initiation assistant in the photosensitive resin composition of the present invention include diethoxyacetophenone / 4,4′-bis (diethylamino) benzophenone, 2-methyl-2. -Morpholino-1- (4-methylthiophenyl) propan-1-one / 4,4'-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one / 4,4'- Bis (diethylamino) benzophenone, benzyldimethyl ketal / 4,4′-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one / 4 4′-bis (diethylamino) benzophenone, 1-hydroxycyclohexyl phenyl ketone / , 4′-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one oligomer / 4,4′-bis (diethylamino) benzophenone, Examples include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one / 4,4′-bis (diethylamino) benzophenone, and preferably 2-methyl-2-morpholino- A combination of 1- (4-methylthiophenyl) propan-1-one / 4,4′-bis (diethylamino) benzophenone may be mentioned.

  The total amount of (C) photopolymerization initiator and (D) photopolymerization initiation assistant used in the photosensitive resin composition of the present invention is the total amount of (A) binder polymer and (B) photopolymerizable compound. The amount is usually 0.1 to 20 parts by mass, preferably 0.5 to 15 parts by mass, and more preferably 1 to 10 parts by mass with respect to 100 parts by mass. The amount of the (D) photopolymerization initiation auxiliary used is preferably 0.6 parts by mass or more and 10 parts by mass or less, and more preferably 1 part by mass or more and 8 parts by mass or less per 1 part by mass of the (C) photopolymerization initiator. In particular, it is preferably 1.5 parts by mass or more and 5 parts by mass or less.

  Examples of the (E) solvent used in the present invention include ethers, aromatic hydrocarbons, ketones, alcohols, esters, amides and the like.

Examples of the ethers include tetrahydrofuran, tetrahydropyran, 1,4-dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether. , Diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate Over DOO, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate, methoxybutyl acetate, methoxy pentyl acetate, anisole, phenetole, and the like methyl anisole.
Examples of the aromatic hydrocarbons include benzene, toluene, xylene, mesitylene and the like.
Examples of the ketones include acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, and cyclohexanone.
Examples of the alcohols include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin.
Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, Ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, 3 -Methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, Methyl methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, 2-oxy-2- Ethyl methyl propionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-oxobutane Examples include methyl acid, ethyl 2-oxobutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, and γ-butyrolactone.
Examples of the amides include N, N-dimethylformamide and N, N-dimethylacetamide.
Examples of other solvents include N-methylpyrrolidone and dimethyl sulfoxide.

  Among the above (E) solvents, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, ethyl carbitol acetate, Butyl carbitol acetate, propylene glycol methyl ether acetate, 2-heptanone and the like are preferably used.

  These solvents can be used alone or in combination of two or more, and the amount used thereof is usually 50% by mass to 90% by mass, preferably 60% by mass in terms of the content in the photosensitive resin composition. % Or more and 85% by mass or less.

  The photosensitive resin composition of the present invention includes a filler, (A) a polymer compound other than the binder polymer, an adhesion promoter, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, an organic acid, an organic amino compound, a curing agent, and the like. The additive may be contained.

  Examples of the filler include fine particles such as glass and alumina.

Examples of the polymer compound other than the (A) binder polymer include polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, and a dispersant.
Examples of the dispersing agent include Disperbyk-115, Disperbyk-160, Disperbyk-161, Disperbyk-162, Disperbyk-163, Disperbyk-164, Disperbyk-166, Disperbyk-167, DisperDyb69- -171, Disperbyk-174, Disperbyk-182 (all manufactured by BYKChemie).

  Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2 -Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxymethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) Examples include ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane.

  Examples of the antioxidant include 4,4'-thiobis (6-tert-butyl-3-methylphenol), 2,6-di-tert-butyl-4-methylphenol, and the like.

  Examples of the ultraviolet absorber include benzotriazoles such as 2- (2-hydroxy-3-t-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2-hydroxy-4-octyloxybenzophenone, and the like. Benzophenone series, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, and other benzoate series, 2- (4,6-diphenyl-1,3,5-triazine And triazines such as -2-yl) -5-hexyloxyphenol.

  Examples of the aggregation preventing agent include sodium polyacrylate.

Examples of the organic acid include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, and caprylic acid;
Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid Aliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, mesaconic acid;
Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoric acid;
Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelic acid, mesitylene acid;
Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid;
Aromatic polycarboxylic acids such as trimellitic acid, trimesic acid, merophanic acid, and pyromellitic acid are listed.

Examples of the organic amine compound include n-propylamine, i-propylamine, n-butylamine, i-butylamine, sec-butylamine, t-butylamine, n-pentylamine, n-hexylamine, and n-heptylamine. Monoalkylamines such as n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine;
Monocycloalkylamines such as cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine;
Methyl ethylamine, diethylamine, methyl n-propylamine, ethyl n-propylamine, di-n-propylamine, di-i-propylamine, di-n-butylamine, di-butylamine, disec-butylamine, di-t-butylamine, di dialkylamines such as n-pentylamine and di-n-hexylamine;
Monoalkylmonocycloalkylamines such as methylcyclohexylamine and ethylcyclohexylamine;
Dicycloalkylamines such as dicyclohexylamine;
Dimethylethylamine, methyldiethylamine, triethylamine, dimethyl n-propylamine, diethyl n-propylamine, methyldi-n-propylamine, ethyldi-n-propylamine, tri-n-propylamine, tri-i-propylamine, tri-n-butylamine, tri trialkylamines such as i-butylamine, trisec-butylamine, tri-t-butylamine, tri-n-pentylamine, tri-n-hexylamine;
Dialkylmonocycloalkylamines such as dimethylcyclohexylamine and diethylcyclohexylamine;
Monoalkyldicycloalkylamines such as methyldicyclohexylamine, ethyldicyclohexylamine, tricyclohexylamine;
Monoalkanolamines such as 2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, and 6-amino-1-hexanol Kind;
Monocycloalkanolamines such as 4-amino-1-cyclohexanol;
Dialkanolamines such as diethanolamine, di-n-propanolamine, di-i-propanolamine, di-n-butanolamine, dii-butanolamine, di-n-pentanolamine, di-n-hexanolamine;
Dicycloalkanolamines such as di (4-cyclohexanol) amine;
Trialkanolamines such as triethanolamine, tri-n-propanolamine, tri-i-propanolamine, tri-n-butanolamine, tri-i-butanolamine, tri-n-pentanolamine, tri-n-hexanolamine; -Cyclocycloalkanolamines such as cyclohexanol) amine;
3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol, 4-amino-1,3-butanediol, 3-dimethylamino-1 , 2-propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino-1,3-propanediol, aminoalkanediols such as 2-diethylamino-1,3-propanediol;
Aminocycloalkanediols such as 4-amino-1,2-cyclohexanediol and 4-amino-1,3-cyclohexanediol;
Amino group-containing cycloalkanone methanols such as 1-aminocyclopentanone methanol and 4-aminocyclopentanone methanol;
Amino group-containing cycloalkanemethanols such as 1-aminocyclohexanone methanol, 4-aminocyclohexanone methanol, 4-dimethylaminocyclopentanemethanol, 4-diethylaminocyclopentanemethanol, 4-dimethylaminocyclohexanemethanol, 4-diethylaminocyclohexanemethanol;
β-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisoacetic acid, 3-aminoisoacetic acid, 2-aminovaleric acid, 5-aminovaleric acid, 6-aminocaproic acid, 1-aminocyclo Aminocarboxylic acids such as propanecarboxylic acid, 1-aminocyclohexanecarboxylic acid, 4-aminocyclohexanecarboxylic acid;
Aniline, o-methylaniline, m-methylaniline, p-methylaniline, p-ethylaniline, pn-propylaniline, pi-propylaniline, pn-butylaniline, pt-butylaniline, Aromatic amines such as 1-naphthylamine, 2-naphthylamine, N, N-dimethylaniline, N, N-diethylaniline, p-methyl-N, N-dimethylaniline;
aminobenzyl alcohols such as o-aminobenzyl alcohol, m-aminobenzyl alcohol, p-aminobenzyl alcohol, p-dimethylaminobenzyl alcohol, p-diethylaminobenzyl alcohol;
aminophenols such as o-aminophenol, m-aminophenol, p-aminophenol, p-dimethylaminophenol, p-diethylaminophenol;
Examples include aminobenzoic acids such as m-aminobenzoic acid, p-aminobenzoic acid, p-dimethylaminobenzoic acid, and p-diethylaminobenzoic acid.

  As said hardening | curing agent, the compound which can react with the carboxyl group in (A) binder polymer by being heated, and can bridge | crosslink (A) binder polymer is mentioned, for example. Moreover, the compound which can superpose | polymerize independently and harden | cure a pattern is also mentioned. Examples of the compound include an epoxy compound and an oxetane compound.

  Examples of the epoxy compound include bisphenol A type epoxy resins, hydrogenated bisphenol A type epoxy resins, bisphenol F type epoxy resins, hydrogenated bisphenol F type epoxy resins, novolac type epoxy resins, other aromatic type epoxy resins, Other than alicyclic epoxy resins, heterocyclic epoxy resins, glycidyl ester resins, glycidylamine resins, epoxidized oils, brominated derivatives of these epoxy resins, epoxy resins and brominated derivatives thereof Aliphatic, alicyclic or aromatic epoxy compounds, butadiene (co) polymer epoxidized products, isoprene (co) polymer epoxidized products, glycidyl (meth) acrylate (co) polymers, triglycidyl isocyanate Examples include nurate.

  Examples of the oxetane compound include carbonate bisoxetane, xylylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and bisoxetane cyclohexanedicarboxylate.

  When the photosensitive composition of the present invention contains an epoxy compound, an oxetane compound, or the like as a curing agent, it may contain a compound capable of ring-opening polymerization of the epoxy group of the epoxy compound or the oxetane skeleton of the oxetane compound. Examples of the compound include polyvalent carboxylic acids, polyvalent carboxylic acid anhydrides, and acid generators.

Examples of the polyvalent carboxylic acids include phthalic acid, 3,4-dimethylphthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 3 Aromatic polycarboxylic acids such as 3,3 ', 4,4'-benzophenonetetracarboxylic acid;
Aliphatic polycarboxylic acids such as succinic acid, glutaric acid, adipic acid, 1,2,3,4-butanetetracarboxylic acid, maleic acid, fumaric acid, itaconic acid;
Hexahydrophthalic acid, 3,4-dimethyltetrahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, 1,2,4-cyclopentanetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, cyclopentanetetracarboxylic acid And alicyclic polyvalent carboxylic acids such as 1,2,4,5-cyclohexanetetracarboxylic acid.

Examples of the polyvalent carboxylic acid anhydrides include aromatic phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, and 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride. Carboxylic anhydrides;
Aliphatic polycarboxylic anhydrides such as itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarballylic anhydride, maleic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride Kind;
Hexahydrophthalic anhydride, 3,4-dimethyltetrahydrophthalic anhydride, 1,2,4-cyclopentanetricarboxylic anhydride, 1,2,4-cyclohexanetricarboxylic anhydride, cyclopentanetetracarboxylic dianhydride Alicyclic polycarboxylic acid anhydrides such as 1,2,4,5-cyclohexanetetracarboxylic dianhydride, hymic anhydride, and nadic anhydride;
Examples include ester group-containing carboxylic acid anhydrides such as ethylene glycol bistrimellitic acid and glycerin tristrimellitic anhydride.

  As said carboxylic acid anhydride, you may use what is marketed as an epoxy resin hardening | curing agent. Examples of the epoxy resin curing agent include a trade name “Adeka Hardener EH-700” (manufactured by Asahi Denka Kogyo Co., Ltd.), a trade name “Rikacid HH” (manufactured by Shin Nippon Rika Co., Ltd.), and a trade name “MH-”. 700 "(manufactured by Shin Nippon Rika Co., Ltd.).

  The said hardening | curing agent can be used individually or in combination of 2 types or more, respectively.

  As a method for forming a pattern using the photosensitive resin composition of the present invention, specifically, a solid colored photosensitive resin obtained by previously forming the photosensitive resin composition of the present invention on a substrate or a substrate. It is applied onto a composition layer (hereinafter sometimes referred to as a substrate), and volatile components such as a solvent are removed from the applied photosensitive resin composition layer, and the volatile components are removed through a photomask. And a method of developing after exposing the exposed layer.

  Examples of the substrate include flat substrates such as a glass substrate, a silicon substrate, a polycarbonate substrate, a polyester substrate, an aromatic polyamide substrate, a polyamideimide substrate, a polyimide substrate, an Al substrate, and a GaAs substrate. These substrates may be subjected to pretreatment such as chemical treatment with chemicals such as a silane coupling agent, plasma treatment, ion plating treatment, sputtering treatment, gas phase reaction treatment, and vacuum deposition treatment. When a silicon substrate or the like is used as the substrate, a charge coupled device (CCD), a thin film transistor (TFT, Thin Film Transistor), or the like may be formed on the surface of the silicon substrate.

  In order to apply the photosensitive resin composition on the substrate, for example, the photosensitive resin composition of the present invention can be applied by spin coating (spin coating), casting coating, roll coating, slit coating, It coat | covers on a board | substrate etc. by normal coating methods, such as a slit & spin coat method, and forms the layer of the photosensitive resin composition on a board | substrate etc. Next, volatile components such as a solvent may be removed by heating or drying under reduced pressure. In this way, a layer made of the solid content of the photosensitive resin composition is formed on the substrate or the like.

  Subsequently, the layer (henceforth a photosensitive resin composition layer) which consists of solid content of the photosensitive resin composition is exposed. For exposure, for example, light may be irradiated through a photomask. As light rays, ultraviolet rays called g-line (wavelength 436 nm) and i-line (wavelength 365 nm) are usually used. The light beam is irradiated through a photomask. Here, for example, the photomask is provided with a light shielding layer that shields the light beam on the surface of a glass plate. The portion of the glass plate that is not provided with the light-shielding layer is a light-transmitting portion that transmits light. The photosensitive resin composition layer is exposed in a pattern according to the pattern of the light-transmitting portion, and the light is irradiated. An unirradiated region that has not been irradiated and an irradiated region that has been irradiated with the light beam are generated. The irradiation amount of the light in the irradiation region is as follows: (A) binder polymer weight average molecular weight, monomer ratio, content, type and content of photopolymerizable compound, type and content of photopolymerization initiator, photopolymerization start It is appropriately selected depending on the type and content of the auxiliary agent.

  Develop after exposure. In order to develop, for example, the exposed photosensitive resin composition layer may be brought into contact with the developer, and specifically, the substrate having the photosensitive resin composition layer formed on the surface thereof is developed into the developer. What is necessary is just to immerse in. Examples of the developer include aqueous solutions of alkaline compounds such as sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, and tetramethylammonium hydroxide. By the development, an unirradiated area of the photosensitive resin composition layer that has not been irradiated with the light beam is removed. On the other hand, the light irradiation area remains as it is to form a pattern.

  After development, the desired pattern can be obtained usually by washing with water and drying. You may heat after drying. When the pattern is cured by heating, its mechanical strength tends to improve, and when a photosensitive resin composition containing a curing agent is used, the mechanical strength can be further improved. . The heating temperature is usually 180 ° C. or higher, preferably 200 ° C. or higher, and usually 250 ° C. or lower.

  The color filter having a transparent pattern thus obtained can be suitably used for display devices such as liquid crystal display devices, plasma displays, and organic EL display devices.

  Although the embodiments of the present invention have been described above, the embodiments of the present invention disclosed above are merely examples, and the scope of the present invention is not limited to these embodiments. The scope of the present invention is defined by the terms of the claims, and includes the meaning equivalent to the description of the claims and all modifications within the scope. EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by these Examples. In the examples, “%” and “part” representing the content or amount used are based on mass unless otherwise specified.

<Synthesis of Resin A>
After introducing 182 g of propylene glycol monomethyl ether acetate into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introduction tube, and changing the atmosphere in the flask from air to nitrogen, the temperature was raised to 100 ° C., 70.5 g (0.40 mol) of benzyl methacrylate, 43.0 g (0.5 mol) of methacrylic acid, 22.0 g (0.10 mol) of monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) ) And propylene glycol monomethyl ether acetate (136 g) in a solution obtained by adding 3.6 g of azobisisobutyronitrile to the flask from the dropping funnel over 2 hours, and further stirring at 100 ° C. for 5 hours. Next, the atmosphere in the flask was changed from nitrogen to air, and 35.5 g of glycidyl methacrylate [0.25 mol, (50 mol% with respect to the carboxyl group of methacrylic acid used in this reaction)], trisdimethylaminomethylphenol, 0.5%. 9 g and 0.145 g of hydroquinone were charged into the flask, and the reaction was continued at 110 ° C. for 6 hours to obtain a resin A having a solid content acid value of 79 mgKOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 13,000, and the molecular weight distribution (Mw / Mn) was 2.1.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the binder polymer were measured using the GPC method under the following conditions.
Equipment: HLC-8120GPC (manufactured by Tosoh Corporation)
Column; TSK-GELG4000HXL + TSK-GELG2000HXL (series connection)
Column temperature: 40 ° C
Solvent; THF
Flow rate: 1.0 ml / min
Injection volume: 50 μl
Detector; RI
Measurement sample concentration: 0.6 mass% (solvent: THF)
Standard material for calibration; TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)
The ratio of the weight average molecular weight and the number average molecular weight obtained above was defined as molecular weight distribution (Mw / Mn).

The components used in this example are as follows, and may be omitted below.
(A-1) Resin A
(A-2) Binder polymer: Copolymer of methacrylic acid and benzyl methacrylate [ratio of methacrylic acid unit and benzyl methacrylate unit is 30:70 by mass ratio (molar ratio), acid value is 113, polystyrene equivalent weight The average molecular weight is 25,000
(B) Photopolymerizable compound: Dipentaerythritol hexaacrylate (C) Photopolymerization initiator: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (D) Photopolymerization initiation assistant Agent: 4,4′-bis (diethylamino) benzophenone (E-1) Solvent: Propylene glycol monomethyl ether acetate (E-2) Solvent: Ethyl epoxy compound of 3-ethoxypropionate: Orthocresol novolac type epoxy resin, “SUMI Epoxy ESCN” -195XL-80 "(manufactured by Sumitomo Chemical Co., Ltd.)

Example 1
[Preparation of photosensitive resin composition 1]
(A-1) 1.982 parts by mass,
(B) 2.972 parts by mass,
(C) 0.149 parts by mass,
(D) 0.050 part by mass,
(E-1) 8.637 parts by mass,
(E-2) A photosensitive resin composition 1 was obtained by mixing 0.960 parts by mass and 0.248 parts by mass of an epoxy compound.

[Formation of pattern]
The photosensitive resin composition obtained above was applied on a glass substrate [Corning, “# 7059”] by spin coating, and then dried at 100 ° C. for 3 minutes to volatilize the volatile components. A functional resin composition layer was formed.
After cooling, the photosensitive resin composition layer was exposed by irradiating with i-line [wavelength 365 nm] through a photomask. As an i-line light source, an ultra-high pressure mercury lamp was used, and the irradiation light quantity was 150 mJ / cm ² . As the photomask, a photomask for forming dot-like pixels having line widths of 3 μm, 5 μm, 7 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 40 μm, and 50 μm was used.

  Next, the exposed glass substrate was developed by immersing it in a developer (an aqueous solution containing 0.05% potassium hydroxide and 0.2% sodium butylnaphthalenesulfonate by mass fraction) and washed with pure water. Then, it heated at 230 degreeC for 20 minute (s), and formed the transparent pattern. In the obtained pattern, no particulate foreign matter or coating unevenness was observed, and the coating property was good.

[Evaluation]
As a result of investigating whether or not 20 μm necessary as a photospacer can be resolved, defects such as pattern peeling due to poor adhesion at the time of development and surface roughness were not observed, and the 20 μm pattern was resolved without tailing. .

Example 2
[Preparation of photosensitive resin composition 2]
(A-1) 1.946 parts by mass,
(B) 2.919 parts by mass,
(C) 0.150 parts by mass,
(D) 0.025 parts by mass,
(E-1) 8.637 parts by mass,
(E-2) 0.960 mass parts and 0.243 mass parts of epoxy compound were mixed, and the photosensitive resin composition 2 was obtained.
A pattern was obtained in the same manner as in Example 1 except that the photosensitive resin composition 1 of Example 1 was replaced with the photosensitive resin composition 2.
[Evaluation]
As in Example 1, it was investigated whether 20 μm necessary as a photospacer could be resolved or not. As a result, defects such as pattern peeling due to poor adhesion during development and surface roughness were not observed, and the 20 μm pattern was tailed. It was resolving without.

Example 3
[Preparation of photosensitive resin composition 3]
(A-1) 1.846 parts by mass,
(B) 2.769 parts by mass,
(C) 0.150 parts by mass,
(D) 0.012 parts by mass,
(E-1) 8.637 parts by mass,
(E-2) 0.960 mass parts and 0.231 mass parts of epoxy compound were mixed, and the photosensitive resin composition 3 was obtained.
A pattern was obtained in the same manner as in Example 1 except that the photosensitive resin composition 1 of Example 1 was replaced with the photosensitive resin composition 3.
[Evaluation]
As in Example 1, it was examined whether 20 μm necessary for the photospacer could be resolved or not. As a result, defects such as pattern skipping and surface roughness were not observed, and the 20 μm pattern was resolved without tailing.

Example 4
[Preparation of photosensitive resin composition 4]
(A-1) 1.756 parts by mass,
(B) 2.634 parts by mass,
(C) 0.150 parts by mass,
(E-1) 8.637 parts by mass,
(E-2) A photosensitive resin composition 4 was obtained by mixing 0.960 parts by mass and 0.220 parts by mass of an epoxy compound.
A pattern was obtained in the same manner as in Example 1 except that the photosensitive resin composition 1 of Example 1 was replaced with the photosensitive resin composition 4.
[Evaluation]
As in Example 1, it was investigated whether 20 μm necessary as a photospacer could be resolved or not. As a result, defects such as pattern peeling due to poor adhesion during development and surface roughness were not observed, and the 20 μm pattern was tailed. It was resolving without.

Comparative Example 1
[Preparation of photosensitive resin composition 5]
(A-2) 1.982 parts by mass,
(B) 2.972 parts by mass,
(C) 0.149 parts by mass,
(D) 0.050 part by mass,
(E-1) 8.637 parts by mass,
(E-2) 0.960 mass parts and 0.248 mass parts of epoxy compound were mixed, and the photosensitive resin composition 5 was obtained.
A pattern was obtained in the same manner as in Example 1 except that the photosensitive resin composition 1 of Example 1 was replaced with the photosensitive resin composition 5.
[Evaluation]
As in Example 1, it was investigated whether 20 μm necessary as a photospacer could be resolved or not. As a result, defects such as pattern peeling due to poor adhesion at the time of development were not observed, but due to poor omission, 20 μm The pattern did not resolve. Moreover, the transmittance | permeability fall by surface roughness was seen.

Comparative Example 2
[Preparation of photosensitive resin composition 6]
(A-2) 1.756 parts by mass,
(B) 2.634 parts by mass,
(C) 0.150 parts by mass,
(E-1) 8.637 parts by mass,
(E-2) 0.960 mass part and 0.220 mass part of epoxy compounds were mixed, and the photosensitive resin composition 6 was obtained.
A pattern was obtained in the same manner as in Example 1 except that the photosensitive resin composition 1 of Example 1 was replaced with the photosensitive resin composition 6.
[Evaluation]
As in Example 1, it was investigated whether 20 μm necessary as a photospacer could be resolved or not. As a result, defects such as pattern peeling due to poor adhesion at the time of development were not observed, but due to poor omission, 20 μm The pattern did not resolve. Moreover, the transmittance | permeability fall by surface roughness was seen.

The photosensitive resin composition of the present invention can provide a photosensitive resin composition capable of leaving a thin pattern such as a photospacer, and can provide a transparent material constituting a liquid crystal display device such as a photospacer or a colored pattern. This is useful for forming a transparent coat layer for adjusting the film thickness.

Claims (6)

In the photosensitive resin composition containing (A) a binder polymer, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) a photopolymerization initiation assistant, and (E) a solvent, (A) the binder resin is , A copolymer obtained by copolymerizing the following (A1) to (A3), and an unsaturated group-containing resin obtained by further reacting (A4), and (C) a photopolymerization initiator, see contains at least one acetophenone compounds, (a) a binder resin, (A1) the ratio of the components derived from each of the ~ (A3) is the mole fraction of the total number of moles of components constituting And a binder resin obtained by reacting 5 to 80 mol% of (A4) with respect to (A3) contained in the copolymer in the following range and the copolymer. A photosensitive resin composition.
(A1); Compound (A2) having at least one skeleton selected from the group consisting of a tricyclodecane skeleton and a dicyclopentadiene skeleton and an unsaturated bond in one molecule; and (A1) and (A3) Compound (A3) having polymerizable unsaturated bond; Unsaturated carboxylic acid (A4); Compound having unsaturated bond and epoxy group in one molecule
Structural units derived from (A1); 2 to 30 mol%
Structural units derived from (A2); 2 to 95 mol%
Structural units derived from (A3); 2 to 70 mol%   (C) The acetophenone-based compound as the photopolymerization initiator is 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one and / or 2-methyl-2-morpholino-1- The photosensitive compound according to claim 1, which is (4-methylthiophenyl) propan-1-one, and (D) the amine compound which is a photopolymerization initiation assistant is 4,4'-bis (diethylamino) benzophenone. Resin composition. 3. The photosensitive resin composition according to claim 1 or 2 is applied on a substrate or a layer made of a solid content of a colored photosensitive resin composition previously formed, and volatilized from the applied photosensitive resin composition layer. A pattern obtained by removing the components, exposing the layer through a photomask, and developing. A spacer comprising the pattern according to claim 3 . A color filter comprising the spacer according to claim 4 . A liquid crystal display device using the color filter according to claim 5 .