KR20090072220A - A colored photosensitive resin composition, color filter using the same, and flat panel display device comprising the color filter - Google Patents

Abstract

A coloured photosensitive resin composition, and a color filter formed by using the composition are provided to obtain a color filter with a high sensitivity and a high quality. A coloured photosensitive resin composition comprises a coloring material comprising C. I. pigment red 242; a binder resin; a photopolymerizable compound; a photopolymerization initiator; and a solvent, wherein the photopolymerization initiator is at least one selected from an acetophenone-based compound or a thioxanthone-based compound other than a multifunctional thiol compound.

Description

A colored photosensitive resin composition, color filter using the same, and flat panel display device comprising the color filter}

The present invention relates to a colored photosensitive resin composition, a color filter using the same, and a flat panel display device including the same.

Color filters are widely used in imaging devices, flat panel display devices such as liquid crystal display (LCD), organic light emitting display (OLED), and the like, and their application range is rapidly expanding. The color filter used for a flat panel display device, an image pickup device, or the like is usually uniformly coated with a coloring photosensitive resin composition containing a pigment corresponding to each color of red, green and blue on a substrate on which a black matrix is patterned, by coating. The operation of exposing and developing the coating film formed by pre-baking (hereinafter sometimes referred to as heat drying or preliminary firing) and further baking (hereinafter sometimes referred to as heat curing or post-firing) for each color may be performed. It is manufactured by forming the pixel of each color repeatedly.

In particular, liquid crystal display devices including color filters for notebook PCs and mobile devices have been required to have higher color purity and higher transmissive properties. As a color filter material, C.I. Patents using Pigment Red 242 are known and are disclosed in Japanese Patent Application Laid-Open No. 11-14824. Moreover, Japanese Laid-Open Patent Publication No. 2002-14463 discloses a colored photosensitive resin composition having excellent transmittance and leaving no residue on the substrate after development. Is disclosed.

However, if the conventional technique as described above is introduced as it is, a sensitivity decrease occurs in a composition into which a high concentration of coloring material is introduced, and high-sensitivity photopolymerization initiators or photopolymerization aids such as triazine and oxime are commonly used to compensate for this. There was a problem that the transmittance is lowered due to the use.

An object of the present invention is to provide a color photosensitive resin composition, a color filter using the same, and a color, wherein a pixel formed of the colored photosensitive resin composition can provide a high quality color filter having high sensitivity and excellent transmittance even when a high concentration of a coloring material is included. The present invention provides a flat panel display device including a filter.

The present invention for achieving the above object, (A) C.I. Pigment Red 242 includes a coloring material, (B) binder resin, (C) photopolymerizable compound, (D) photopolymerization initiator, and (E) solvent, wherein the (D) photopolymerization initiator is in addition to the polyfunctional thiol compound It provides at least one of an acetophenone type compound or a thioxanthone type compound, The coloring photosensitive resin composition characterized by the above-mentioned.

The present invention also provides a color filter comprising a colored layer formed by coating a colored photosensitive resin composition on a substrate and exposing and developing the film in a predetermined pattern, wherein the colored photosensitive resin composition is the above-mentioned colored photosensitive resin composition. It provides a color filter characterized by.

The present invention provides a flat panel display using the color filter.

According to the present invention, when forming a pixel using a colored photosensitive resin composition of the present invention with a highly concentrated coloring material, the formed pixel has an effect of providing a high quality color filter having high sensitivity and excellent transmittance.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

I. Coloring photosensitive resin composition

1. (A) Coloring material

(A) The coloring material is C.I. which is a red pigment in order to improve the transmittance. Pigment Red 242 is included as a main pigment.

The (A) coloring material is optionally C.I. Pigment other than Pigment Red 242 and other additives. Hereinafter, the expression "other pigments" is referred to as C.I. Pigment other than Pigment Red 242.

Specific examples of the other pigments include compounds classified as pigments in the color index (The Society of Dyers and Colourists), and more specifically, pigments having the following color index (CI) numbers. However, it is not necessarily limited to these.

First, specific examples of yellow pigments include C.I. Pigment Yellow 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180 and 185 Etc., and specific examples of the orange pigment are CI Pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71 and the like. Specific examples of red pigments include C.I. Pigment red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 215, 216, 224, 254, 255 and 264, and the like. Example CI Pigment violet 14, 19, 23, 29, 32, 33, 36, 37, 38 and the like. Specific examples of blue pigments include C.I. Pigment blue 15 (15: 3, 15: 4, 15: 6, etc.), 21, 28, 60, 64, and 76, and the like, and specific examples of green pigments include C.I. Pigment green 7, 10, 15, 25, 36, 47, 58 and the like. Specific examples of the brown pigment include C.I Pigment Brown 28 and the like, and specific examples of the black pigment include C.I Pigment Black 1 and 7 and the like. As said other pigment, it can be used individually or in combination of 1 or more types in the above-mentioned examples, respectively.

The coloring material (A) is C.I. Pigment Red 242 if further comprises other pigments and other additives, C.I. Pigment Red 242 is 100: 0 to 30:70 in a mass ratio with other pigments, preferably 90:10 to 50:50. If included in the above range, there is an advantage that the transmittance is improved.

The said (A) coloring material is 5-60 mass% in mass fraction with respect to solid content in colored photosensitive resin composition, Preferably it is 10-50 mass%. If the content of the coloring material (A) is in the range of 5 to 60% by mass based on the above criteria, even if a thin film is formed, the color density of the pixel is sufficient, and residues are generated because the omission of non-pixel portions is not reduced during development. It is preferable because it tends to be difficult.

2. (B) binder resin

The binder resin (B) usually makes the non-exposed portion of the colored photosensitive resin layer formed using the colored photosensitive resin composition alkali soluble and acts as a dispersion medium for the pigment.

The (B) binder resin is not particularly limited and may be selected from various polymers used in the art. It is preferable that the said (B) binder resin contains the monomer which has a (a) carboxyl group. Especially as a polymer containing the said (a) monomer, it is preferable to use the copolymer obtained from the said (a) monomer and (b) the other monomer copolymerizable with the said (a) monomer.

The monomer (a) may be, for example, an unsaturated carboxylic acid having one or more carboxyl groups in the molecule, such as unsaturated monocarboxylic acid and unsaturated dicarboxylic acid. Specific examples of the monomer (a) include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid and fumaric acid. The (a) monomers may be used alone or in combination of two or more.

(B) The other monomer is a compound having a polymerizable carbon-carbon unsaturated bond. Specific examples of the (b) other monomers include aromatic vinyl compounds such as α-methylstyrene and vinyltoluene, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and 2-hydroxyethyl Unsaturated carboxylates such as (meth) acrylate and benzyl (meth) acrylate, unsaturated aminoalkyl carboxylates such as aminoethyl acrylate, unsaturated glycidyl carboxylates such as glycidyl (meth) acrylate, Vinyl cyanide compounds, such as vinyl carboxylates, such as a vinyl acetate and a vinyl propionate, (meth) acrylonitrile, and (alpha)-chloro acrylonitrile, are mentioned. The other monomers (b) may also be used alone or in combination of two or more.

Preferred examples of the copolymer include benzyl methacrylate / methacrylic acid copolymer, benzyl methacrylate / methacrylic acid / styrene copolymer, methyl methacrylate / methacrylic acid copolymer, methyl methacrylate / methacrylate Acid / styrene copolymers and the like.

When the (B) binder resin is a copolymer obtained from the (a) monomer and (b) another monomer, in the copolymer, the (a) monomer is 10 to 50 mass% based on the total mass of the copolymer. It may be included as, preferably 15 to 40% by mass.

The (B) binder resin preferably has a weight average molecular weight of 3,000 to 100,000 measured by gel permeation chromatography converted into polystyrene, and more preferably 5,000 to 50,000. If the weight average molecular weight of the (B) binder resin is in the range of 3,000 to 100,000, film reduction is unlikely to occur at the time of development, and it is preferable because the missing property of the non-pixel portion at the time of development tends to be good.

The acid value of the (B) binder resin is preferably in the range of 30 to 150 mgKOH / g based on solid content. When the acid value satisfies the above-mentioned range, there is an advantage in that developability with respect to alkali development is excellent, residue generation is suppressed, and the adhesiveness of a pattern is improved.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the said (B) binder resin is 1.5-6.0, and it is preferable that it is 1.8-4.0. If the molecular weight distribution is 1.5 to 6.0, there is an advantage that developability is excellent.

Content of the said (B) binder resin is 5-85 mass% normally with respect to solid content in colored photosensitive resin composition, Preferably it is the range of 10-70 mass%. When the content of the binder resin (B) is 5 to 85% by mass based on the above criteria, the solubility in the developer is sufficient, and development residues are less likely to occur on the substrate of the non-pixel portion, and the film of the pixel portion of the exposed portion is reduced during development. Since the tendency to hardly occur and the missing property of a non-pixel part tends to be favorable, it is preferable.

3. (C) photopolymerizable compound

(C) A photopolymerizable compound is a compound which can superpose | polymerize by action, such as an active radical, an acid, etc. which generate | occur | produce by exposure alone or below (D) photoinitiator mentioned later. Examples of the (C) photopolymerizable compound include monofunctional monomers, bifunctional monomers, other polyfunctional monomers, and the like.

Specific examples of the monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, and N-vinyl py. A ralidone etc. are mentioned. As a specific example of the said bifunctional monomer, 1, 6- hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and triethylene glycol di (meth) acrylate And bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like. Specific examples of the other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, and pentaerythritol. Tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaeryte Lithol hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned. Of these, bifunctional or higher polyfunctional monomers are preferably used, and polyfunctional or higher functional polyfunctional monomers are particularly preferable.

The said (C) photopolymerizable compound is used in 5-50 mass% normally with respect to solid content in colored photosensitive resin composition, Preferably it is used in the range of 7-45 mass%. Since the intensity | strength and smoothness of a pixel part tend to become favorable in the said (C) photopolymerizable compound being 5-50 mass% on the said reference | standard, it is preferable.

4. (D) Photoinitiator

The photopolymerization initiator (D) plays a role of polymerizing the photopolymerizable compound (C) by generating an active radical or an acid by exposure, and a polyfunctional thiol containing two or more mercapto groups in one molecule. Compound.

The polyfunctional thiol compound is not particularly limited as long as it contains two or more mercapto groups in one molecule, and specific examples thereof include tris- (3-mercaptopropionyloxy) -ethyl-isocyanurate and trimethylolpropanetris- 3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol tetrakis-3 mercaptopropionate, etc. are mentioned.

Moreover, the said (D) photoinitiator contains 1 or more types of an acetophenone type compound compound or a thioxanthone type compound other than a polyfunctional thiol compound. In addition, a benzoin-based compound, a benzophenone-based compound, an anthracene-based compound, and a photopolymerization initiation aid may be further included alone or in combination of two or more.

Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2-hydroxy-1- [4- (2-hydroxy Hydroxyethoxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1 And oligomers of -ones and compounds represented by the following general formula (1).

<Formula 1>

In Formula 1, R ₁ to R ₄ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group unsubstituted or substituted with an alkyl group having 1 to 12 carbon atoms, or a benzyl group unsubstituted or substituted with an alkyl group having 1 to 12 carbon atoms. Or a naphthyl group unsubstituted or substituted with an alkyl group having 1 to 12 carbon atoms.

Specific examples of the compound represented by Formula 1 include 2-methyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-ethyl-2-amino (4-morpholinophenyl) ethane-1 -One, 2-propyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-butyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-methyl-2 -Amino (4-morpholinophenyl) propane-1-one, 2-methyl-2-amino (4-morpholinophenyl) butan-1-one, 2-ethyl-2-amino (4-morpholino Phenyl) propane-1-one, 2-ethyl-2-amino (4-morpholinophenyl) butan-1-one, 2-methyl-2-methylamino (4-morpholinophenyl) propan-1-one , 2-methyl-2-dimethylamino (4-morpholinophenyl) propan-1-one, 2-methyl-2-diethylamino (4-morpholinophenyl) propan-1-one, etc. may be mentioned. .

Specific examples of the thioxanthone-based compound include 2-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichloro thioxanthone, 1-chloro-4-propoxy thioxanthone, and the like. Can be mentioned.

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

Specific examples of the benzophenone compound include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert -Butyl peroxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, 4,4'-di (N, N'-dimethylamino) -benzophenone, etc. are mentioned.

Specific examples of the anthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and the like. Can be.

In addition to the compounds described above, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, phenylclinic Methyl oxylate, titanocene compound, etc. can be used as a photoinitiator.

The polyfunctional thiol compound is included in 0.1 to 50% by mass, preferably 0.5 to 30% by mass, based on the total mass of the photopolymerization initiator (D). When included in the above-described range, there is an advantage that the sensitivity and the adhesion of the pixel portion become good.

The usage-amount of the said (D) photoinitiator is 0.1-40 mass% normally in mass fraction with respect to the total amount of (B) binder resin and (C) photopolymerizable compound based on solid content, Preferably it is 1-30 mass%. When the photoinitiator (D) is in the range of 0.1 to 40% by mass based on the above criteria, the colored photosensitive resin composition is highly sensitive, and the sensitivity of the pixel portion formed using the composition and the smoothness on the surface of the pixel portion are good. This is preferable because there is.

5. (E) Solvent

The (E) solvent contained in the colored photosensitive resin composition of the present invention is not particularly limited as long as the colored photosensitive resin composition of the present invention has a suitable viscosity and can easily dissolve the remaining components, and in the field of colored photosensitive resin compositions Various organic solvents used can be used.

Specific examples of the solvent (E) include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Propylene glycol dialkyl ethers such as propylene glycol monomethyl ether; Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate; Aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin; Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; Cyclic ester, such as (gamma) -butyrolactone, etc. are mentioned.

Among the above (E) solvents, organic solvents having a boiling point of 100 ° C to 200 ° C in the solvent are preferable in terms of coating properties and drying properties, and more preferably alkylene glycol alkyl ether acetates, ketones, and 3 Esters such as ethyl ethoxypropionate and methyl 3-methoxypropionate; and more preferably propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, Ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like.

The said (E) solvent can be used individually or in mixture of 2 or more types, respectively.

Content of the (E) solvent in the coloring photosensitive resin composition of this invention is 60-90 mass% normally with a mass fraction with respect to the coloring photosensitive resin composition whole quantity containing it, Preferably it is 70-85 mass%. If the content of the solvent (E) is in the range of 60 to 90% by mass based on the above criteria, it is applied with a coating device such as a roll coater, spin coater, slit and spin coater, slit coater (sometimes referred to as die coater), inkjet, etc. It is preferable because the coating property tends to be good when used.

6. (F) Additives

In the coloring photosensitive resin composition of this invention, a filler, a polymer different from the said (B) binder resin, a hardening | curing agent, and a pigment dispersant as needed. (F) additives, such as an adhesion promoter, antioxidant, a ultraviolet absorber, and an aggregation inhibitor, may be further included.

Specific examples of the filler include glass, silica, alumina and the like. Specific examples of the other polymers include curable resins such as epoxy resins and maleimide resins, polyvinyl alcohols, polyacrylic acid, polyethylene glycol monoalkyl ethers, thermoplastic resins such as polyfluoroalkyl acrylates, polyesters, polyurethanes, and the like. Can be.

The said hardening | curing agent is used in order to raise a deep part hardening and mechanical strength, As a hardening | curing agent, an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, an oxetane compound, etc. are mentioned. Specific examples of the epoxy compound include a bisphenol A epoxy resin, a hydrogenated bisphenol A epoxy resin, a bisphenol F epoxy resin, a hydrogenated bisphenol F epoxy resin, a noblock type epoxy resin, another aromatic epoxy resin, an alicyclic epoxy resin, Glycidyl ester resins, glycidylamine resins, aliphatic, alicyclic or aromatic epoxy compounds other than the above-described brominated derivatives of epoxy resins, epoxy resins and their brominated derivatives, butadiene (co) polymer epoxides, isoprene ) Polymer epoxide, glycidyl (meth) acrylate (co) polymer, triglycidyl isocyanurate, etc. are mentioned. Specific examples of the oxetane compound include carbonate bis oxetane, xylene bis oxetane, adipate bis oxetane, terephthalate bis oxetane, and cyclohexane dicarboxylic acid bis oxetane.

The curing agent may include a curing aid compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound with the curing agent. As a hardening auxiliary compound, polyhydric carboxylic acid, polyhydric carboxylic anhydride, an acid generator, etc. are mentioned, for example. As said carboxylic anhydride, what is marketed as an epoxy resin hardener can be used. As this epoxy resin hardening | curing agent, a brand name (Adekahadona EH-700) (made by Adeka Industrial Co., Ltd.), a brand name (Rikaditdo HH) (made by Nippon Ewha Co., Ltd.), a brand name (MH-700) ( New Nippon Ewha Co., Ltd.) etc. are mentioned. The said hardening | curing agent can be used individually or in mixture of 2 or more types.

Commercially available surfactants can be used as the pigment dispersant, and specific examples thereof include surfactants such as silicone, fluorine, ester, cation, anionic, nonionic and amphoteric. These can be used individually or in combination of 2 types or more, respectively. As said surfactant, For example, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol diester, sorbitan fatty ester, fatty acid modified polyester, tertiary amine modified polyurethane , Polyethylenimine, etc., trade names include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by Tochem Products), MEGAFAC (manufactured by Dainippon Ink & Chemicals Co., Ltd.), Florard (manufactured by Sumitomo 3M Inc.), Asahi guard, Suflon (manufactured by Asahi Glass Co., Ltd.), SOLSPERSE (made by Genka Corporation), EFKA (made by EFKA Chemicals), PB 821 (made by Ajinomoto Co., Ltd.), etc. are mentioned.

Specific 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-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltri Methoxysilane, 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, and the like. The adhesion promoters may be used alone or in combination of two or more thereof. The said adhesion promoter is contained in 0.01 to 10 mass% normally with respect to solid content in colored photosensitive resin composition, Preferably it is contained in 0.05-2 mass%.

Specific examples of the antioxidant include 2,2'-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butyl-4-methylphenol, and the like. Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzothiazole, alkoxybenzophenone and the like. Specific examples of the aggregation inhibitor include sodium polyacrylate and the like.

The coloring photosensitive resin composition of this invention can be manufactured by the following methods, for example.

The said (A) coloring material is previously contained in the (E) solvent, and it disperse | distributes using a bead mill until the average particle diameter of a coloring material becomes about 0.2 micrometer or less. At this time, a pigment dispersant is used as needed, and some or all of said (B) binder resin may be mix | blended. The remainder of the said (B) binder resin, the said (C) photopolymerizable compound, the said (D) photoinitiator, the other components used as needed, as needed in the obtained dispersion liquid (it may be called a mill base hereafter). Additional solvent is further added to a predetermined concentration to obtain the desired colored photosensitive resin composition.

II. Pattern Forming Method Using Colored Photosensitive Resin Composition

The colored photosensitive resin layer using the colored photosensitive resin composition of this invention is formed on a base material. More specifically, first, the composition is applied to a substrate (not limited, usually glass or silicon wafer) or a layer containing the solids of the previously formed colored photosensitive resin composition to prebake and volatilize the solvent or the like. The component is removed to obtain a smooth coating film. The thickness of the coating film at this time is about 1-3 micrometers normally.

Subsequently, a partial region of the colored photosensitive resin layer is selectively exposed. More specifically, in order to obtain a desired pattern in the said colored photosensitive resin layer, a light ray is irradiated to a specific area | region through a mask. Under the present circumstances, it is preferable to use apparatuses, such as a mask aligner and a stepper, so that a parallel light beam may be irradiated uniformly to the whole exposure area | region, and a mask and a board | substrate exactly match.

The selectively exposed colored photosensitive resin layer is developed to remove the exposed area or the non-exposed area to form a pattern. More specifically, the desired pattern can be produced by contacting the colored photosensitive resin layer, which has been selectively exposed and cured, with an aqueous alkali solution to dissolve and develop the non-exposed areas. After development, postbaking may be performed at 150 to 230 ° C. for about 10 to 60 minutes as necessary.

The alkaline developer is usually an aqueous solution containing an alkaline compound and a surfactant. The alkaline compound may be either an inorganic or organic alkaline compound.

Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, ammonium dihydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate, hydrogen carbonate Sodium, potassium hydrogen carbonate, sodium borate, potassium borate, ammonia and the like. 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 can be used individually or in combination of 2 or more types, respectively. The concentration of the alkaline compound in the alkaline developer is in the range of 0.01 to 10% by mass, more preferably 0.03 to 5% by mass.

The surfactant in the alkaline developer may be used either among nonionic surfactants, anionic surfactants or cationic surfactants. Specific examples of the non-ionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine and the like. Specific examples of the anionic surfactants include higher alcohol sulfate ester salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzene sulfonate, Alkyl aryl sulfonates, such as sodium dodecyl naphthalene sulfonate, etc. are mentioned. Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryl trimethylammonium chloride, or quaternary ammonium salts. These surfactant can be used individually or in combination of 2 or more types, respectively.

The concentration of the surfactant in the alkaline developer is usually 0.01 to 10% by mass, preferably 0.05 to 8% by mass, more preferably 0.1 to 5% by mass.

As an example, it can apply | coat on a base material as follows, and perform a photocuring and image development to form a pattern, and can be used as a black matrix or a colored pixel (colored image).

III. Color filter using colored photosensitive resin composition

The color filter according to the present invention is characterized by comprising a color layer formed by forming the colored photosensitive resin composition of the present invention in a predetermined pattern, followed by exposure and development.

The pattern formation method of a coloring photosensitive resin composition is based on the above-mentioned, and detailed description is abbreviate | omitted. As mentioned above, the pixel or black matrix corresponded to the color of the coloring material in the photosensitive resin composition is obtained through each operation of application | coating of a coloring photosensitive resin composition solution, a front baking, patterned exposure to the obtained dry coating film, and image development. In addition, a color filter can be obtained by repeating this operation by the number of colors required for the color filter. Since the configuration and manufacturing method of the color filter are well known in the art, detailed description thereof will be omitted.

The color filter manufactured using the coloring photosensitive resin composition of this invention has little in-plane film thickness difference, For example, it can make in-plane film thickness difference 0.15 micrometer or less and further 0.05 micrometer or less with the film thickness of 1-3 micrometers. . Therefore, the color filter obtained in this way is excellent in smoothness, and it can manufacture a liquid crystal display device of excellent quality by high yield by assembling this to a color liquid crystal display device.

Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited by an Example. In addition, "%" and "part" which show content in a following example and a comparative example are a mass reference | standard unless there is particular notice.

<Example 1>

In order to obtain a red pixel, the total amount of the pigment (A) coloring material and the pigment dispersant (F) additive beforehand is 20 in each component shown in Table 1 with respect to the mixture of a pigment, a pigment dispersant, and a propylene glycol monomethyl ether acetate. The mixture was mixed to the mass% to sufficiently disperse the pigment using the bead mill, and then the bead mill was separated, and the remaining components including the remaining amount of propylene glycol monomethyl ether acetate were further added and mixed to obtain a colored photosensitive resin composition.

(A) Coloring material C.I. Pigment Red 242, C.I. Pigment Red 254 Part 5.28, Part 2.97 (B) binder resin Benzyl methacrylate / methacrylic acid copolymer (copolymer ratio 80/20, weight average molecular weight 35,000) Part 4.56 (C) photopolymerizable compound Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., "KAYARAD DPHA") Part 5.87 (D) photoinitiator Irgacure-369 (manufactured by CIBA-GEIGY), TMMP (manufactured by Sakai Kagaku) 1.21 parts, 0.23 parts (E) Solvent Propylene Glycol Monomethyl Ether Acetate Part 78.18 (F) additive Pigment Dispersant (Polyester) Part 1.70

<Example 2>

Instead of 1.21 parts of Irgacure-369 (manufactured by CIBA-GEIGY), an acetophenone compound of Example 1, 0.81 parts of Irgacure-907 (manufactured by CIBA-GEIGY), an acetophenone compound, was used and DETX- which is a thioxanthone compound. It is the same as Example 1 except using 0.4 parts of S (made by Nippon Kayaku Co., Ltd.).

Comparative Example 1

It is the same as that of Example 1 except having used EAB-F (Hodoya Co., Ltd.) which is a benzophenone type compound instead of 0.23 parts of TMMP (made by Sakai Chemical Co., Ltd.) which is the polyfunctional thiol compound of Example 1.

Comparative Example 2

It is the same as Example 1 except having used TRIAZINE EB (Pharmasynthese company) which is a triazine compound instead of 1.21 parts of Irgacure-369 (product of CIBA-GEIGY company) which is an acetophenone type compound of Example 1.

Comparative Example 3

The same procedure as in Example 1 was repeated except that Irgacure OXE02 (manufactured by Ciba Specialty Chemical), an oxime compound, was used instead of 1.21 parts of Irgacure-369 (produced by CIBA-GEIGY), an acetophenone compound.

Test Example  1: Performance Evaluation of Color Filter Using Colored Photosensitive Resin Composition

A 2 square inch glass substrate (trade name: No.1737, manufacturer: Corning) was washed sequentially with a neutral detergent, water and alcohol and dried. Post-baking when the colored photosensitive resin composition of Example 1, Example 2, and Comparative Examples 1-3 was exposed by the exposure amount (365 nm) of 100 mJ / cm <2> on the said dried glass substrate, and the image development process was skipped. It spin-coated so that the film thickness might become 2.0 micrometers. Subsequently, it baked for 3 minutes at 100 degreeC in the clean oven, and formed the coloring photosensitive resin layer. After cooling the precured colored photosensitive resin layer, the substrate on which the colored photosensitive resin layer was formed and a quartz glass photomask (a pattern for changing the transmittance stepwise in the range of 1 to 100% and a line from 1 μm to 50 μm / The space | interval was 100 micrometers, and it irradiated with the exposure amount (365 nm) of 100 mJ / cm <2> in air | atmosphere using the ultrahigh pressure mercury lamp (brand name: USH-250D) by Ushio Denki Corporation. Thereafter, the selectively exposed colored photosensitive resin layer was immersed at 26 ° C. for a predetermined time in an aqueous developer containing 0.12% of nonionic surfactant and 0.06% of potassium hydroxide, and then dried at 220 ° C. for 30 minutes after washing with water. To form a coloring pattern. Table 2 shows the minimum necessary exposure amount necessary for forming the transmittance and the surface roughness-free pattern of the colored pattern.

Color (x / y / Y) Transmittance * 1 Exposure amount * 2 (mJ / cm 2) Example 1 0.63 / 0.34 / 26.1 ○ 60 Example 2 0.63 / 0.34 / 26.5 ○ 60 Comparative Example 1 0.63 / 0.34 / 24.5 × 100 Comparative Example 2 0.63 / 0.34 / 24.8 × 80 Comparative Example 3 0.63 / 0.34 / 24.7 × 60

* 1: When the Y value representing the permeability value in the tristimulus values is excellent in the relative comparison between x and y equivalent values: ○, when falling off: represented by × (Trilateral stimulus calculation method, Sigmapress Co., Ltd. ).

* 2: The minimum required exposure amount required to form a pattern with no surface roughness even when developed.

Referring to Table 1, the pixel of Example 1 was excellent in transmittance, and the minimum required exposure amount required for forming a pattern without surface roughness after development was 60 mJ / cm 2. The pixel of Example 2 was excellent in transmittance, and the minimum required exposure amount required for forming a pattern without surface roughness after development was 60 mJ / cm 2. The pixel of Comparative Example 1 lacked transmittance, and the minimum required exposure amount necessary for forming a pattern without surface roughness after development was 100 mJ / cm 2. The pixel of Comparative Example 2 lacked transmittance, and the minimum required exposure amount necessary for forming a pattern without surface roughness after development was 80 mJ / cm 2.

From the said evaluation result, it turned out that the photosensitive resin composition of Example 1 or 2 which concerns on this invention is excellent in the transmittance | permeability, and the color filter excellent in the sensitivity is obtained. On the other hand, in the case of the colored photosensitive resin compositions of Comparative Examples 1, 2, and 3, the transmittance or sensitivity was insufficient and a high quality color filter could not be obtained.

Claims (8)

(A) C.I. Pigment Red containing a coloring material containing 242, (B) binder resin, (C) photopolymerizable compound, (D) photoinitiator, and (E) solvent, The said (D) photoinitiator is any one or more of an acetophenone type compound or a thioxanthone type compound other than a polyfunctional thiol compound, The coloring photosensitive resin composition characterized by the above-mentioned. The method according to claim 1, C.I. The mass ratio of pigment red 242 to another pigment is 100: 0-30: 70, The coloring photosensitive resin composition characterized by the above-mentioned. The method according to claim 2, C.I. Pigment Red 242 and the coloring ratio of the photosensitive resin composition, characterized in that the mass ratio of 90:10 to 50:50. The method according to claim 1, The polyfunctional thiol compound is a coloring photosensitive resin composition, characterized in that it comprises 2 to 6 mercapto groups in one molecule. The method according to claim 1, The said polyfunctional thiol compound is contained in 0.1-50 mass% with respect to the said (D) photoinitiator total mass, The coloring photosensitive resin composition characterized by the above-mentioned. The method according to claim 1, The polyfunctional thiol compound is tris- (3-mercaptopropionyloxy) -ethyl-isocyanurate, trimethylolpropanetris-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropio A colored photosensitive resin composition comprising one or two or more selected from the group consisting of a nate, and dipentaerythritol tetrakis-3-mercaptopropionate. A color filter comprising a color layer formed by applying a coloring photosensitive resin composition on a substrate and exposing and developing in a predetermined pattern, The said colored photosensitive resin composition is a colored photosensitive resin composition of any one of Claims 1-6, The color filter characterized by the above-mentioned. A flat panel display comprising the color filter of claim 7.