KR101899290B1 - Colored photosensitive resin composition, color filter and display device - Google Patents

Abstract

[PROBLEMS] To provide a colored photosensitive resin composition excellent in stability of viscosity and patterning characteristics over time, a color filter formed using the colored photosensitive resin composition, and a display device provided with a color filter.
[Solution] The colored photosensitive resin composition according to the present invention contains an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, an inorganic pigment and a solvent, and the solvent includes a solvent having an amide structure. The solvent having an amide structure is preferably represented by the following formula. In the formulas, R ¹ , R ² and R ³ each independently represent a hydrogen atom or an alkyl group, and n represents an integer of 1 to 3.

Description

TECHNICAL FIELD [0001] The present invention relates to a colored photosensitive resin composition, a color filter and a display device,

The present invention relates to a colored photosensitive resin composition, a color filter, and a display device.

Generally, a color filter is manufactured by a lithography method. In this lithography method, first, a black colored photosensitive resin composition is coated on a substrate, followed by exposure and development to form a black matrix. Then, coating, drying, exposure, and development are repeated for each colored photosensitive resin composition of each color of red, green, and blue to form a pixel region of each color at a predetermined position to produce a color filter.

The colored photosensitive resin composition used for the color filter is generally prepared by first dispersing a pigment and a pigment dispersant in a solvent to prepare a pigment dispersion, then adding other components such as a resin to the pigment dispersion, and mixing them.

As the solvent, those having high solubility for each component contained in the conventional colored photosensitive resin composition or those having excellent coatability and evaporability when the colored photosensitive resin composition is applied to a substrate or the like are used, and an ester type or ketone type solvent is used It is widely used. However, in the case of a colored photosensitive resin composition containing an organic pigment and a pigment dispersant, since the pigment dispersant is hardly soluble in an ester or ketone solvent and the particle diameter of the pigment can not be made fine, the use of such a colored photosensitive resin composition provides a high contrast There is a problem in that a color filter having a branch can not be manufactured. On the other hand, when a solvent having an amide structure is used as the solvent, the solubility of the pigment dispersant can be increased, the pigment particle diameter can be reduced, and a colored photosensitive resin composition having a high transmittance can be prepared. It is reported that a filter can be fabricated (see Patent Document 1).

Japanese Patent Application Laid-Open No. 2003-330165

On the other hand, when an ester-based or a ketone-based solvent is used as a solvent in a colored photosensitive resin composition using an inorganic pigment as a pigment, there is a problem that a large viscosity change is caused by long-term storage and the patterning property is deteriorated. For this reason, a colored photosensitive resin composition excellent in storage stability is desired.

An object of the present invention is to provide a colored photosensitive resin composition excellent in viscosity and patterning characteristics with a lapse of time stability, a color filter formed using the colored photosensitive resin composition, and a display device provided with a color filter.

As a result of intensive studies, the present inventors have found out that the above problems can be solved by containing a specific solvent, and have reached the completion of the present invention.

A first aspect of the present invention is a colored photosensitive resin composition comprising an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, an inorganic pigment and a solvent, wherein the solvent comprises a solvent having an amide structure .

A second aspect of the present invention is a color filter formed using the colored photosensitive resin composition according to the present invention, and the third aspect of the present invention is a display device having a color filter according to the present invention.

According to the present invention, it is possible to obtain a colored photosensitive resin composition excellent in stability with time and stability of viscosity and patterning characteristics. Therefore, the colored photosensitive resin composition according to the present invention can be suitably used for various color filter fabrication and display devices equipped with the same.

The colored photosensitive resin composition according to the present invention contains an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, an inorganic pigment and a solvent. First, these constituent components will be described.

<Alkali-soluble resin>

The alkali-soluble resin used in the present invention is not particularly limited, and conventionally known alkali-soluble resins can be used. In this specification, the alkali-soluble resin means a resin film having a thickness of 1 占 퐉 formed on a substrate with a resin solution (solvent: propylene glycol monomethyl ether acetate) having a resin concentration of 20% by weight and a 2.38% by weight tetramethyl Means that the film thickness is dissolved by 0.01 m or more when immersed in an aqueous solution of ammonium hydroxide (TMAH) for 1 minute.

As the alkali-soluble resin, for example, a resin obtained by reacting a reaction product of an epoxy compound and an unsaturated carboxylic acid with a polybasic acid anhydride may be used.

Among them, a resin represented by the following formula (a-1) is preferable. The resin represented by the formula (a-1) is preferable because of its high photocurability.

In the above formula (a-1), X ^a represents a group represented by the following formula (a-2).

In formula (a-2), R ^a1 independently represents a hydrogen atom, a hydrocarbon group of 1 to 6 carbon atoms, or a halogen atom, R ^a2 each independently represents a hydrogen atom or a methyl group, and W ^a represents ^a single bond or Represents a group represented by the following formula (a-3).

In the formula (a-1), Y ^a represents a residue obtained by removing an acid anhydride group (-CO-O-CO-) from ^a dicarboxylic acid anhydride. Examples of the dicarboxylic acid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylene tetrahydrophthalic anhydride, chlorenedic anhydride, methyltetrahydrophthalic anhydride, And glutaric acid.

In the above formula (a-1), Z ^a represents a residue obtained by subtracting two acid anhydride groups from ^a tetracarboxylic acid dianhydride. Examples of the tetracarboxylic acid dianhydride include pyromellitic dianhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, and biphenyl ether tetracarboxylic dianhydride.

In the above formula (a-1), m represents an integer of 0 to 20.

Examples of the alkali-soluble resin having an ethylenic unsaturated group include polyester (meth) acrylate obtained by reacting a (meth) acrylic acid with a polyester prepolymer obtained by condensing a polyhydric alcohol with a monobasic acid or a polybasic acid; Polyurethane (meth) acrylate obtained by reacting a polyol with a compound having two isocyanate groups and then reacting with (meth) acrylic acid; Bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol or cresol novolak type epoxy resin, resol type epoxy resin, triphenol methane type epoxy resin, polycarboxylic acid polyglycidyl ester, An epoxy (meth) acrylate resin obtained by reacting an epoxy resin such as a cydyl ester, an aliphatic or alicyclic epoxy resin, an amine epoxy resin, or a dihydroxybenzene type epoxy resin with (meth) acrylic acid may be used.

In the present specification, "(meth) acrylic acid" means both acrylic acid and methacrylic acid. Likewise, "(meth) acrylate" means both acrylate and methacrylate.

The weight average molecular weight of the alkali-soluble resin is preferably from 1,000 to 400,000, more preferably from 2,000 to 30,000. Within this range, satisfactory developability can be obtained, and sufficient heat resistance and film strength can be obtained.

The content of the alkali-soluble resin is preferably 5 to 80% by weight, more preferably 15 to 50% by weight based on the solid content of the colored photosensitive resin composition. The solid content referred to herein is a component other than the solvent. When the amount is in the above range, the balance of developability tends to be easily obtained.

&Lt; Photopolymerizable monomer &gt;

The colored photosensitive resin composition according to the present invention contains a photopolymerizable monomer. The photopolymerizable monomers include monofunctional monomers and polyfunctional monomers.

Examples of the monofunctional monomer include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxy (Meth) acrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, maleic anhydride, maleic anhydride, Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, (Meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl ) Acrylate, 2-phenoxy-2-hydroxypropyl (meth) (Meth) acrylate, glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylamino (meth) acrylate, glycidyl (Meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, and half . These monofunctional monomers may be used alone or in combination of two or more.

Examples of the polyfunctional monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (Meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, butyleneglycol di (meth) acrylate, neopentyl glycol di (Meth) acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol penta (Meth) acryloxypolyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxy diethoxyphenyl) propane, (Meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (Meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (meth) acrylate, urethane (meth) acrylate (i.e., tolylene diisocyanate), trimethylhexamethylene diisocyanate, (Meth) acrylamide, (meth) acrylamide methylene ether, polyhydric alcohol and N-methylol (meth) acrylamide, a reaction product of methylene diisocyanate and 2-hydroxyethyl There may be mentioned polyfunctional monomer and, triacrylate formal such as in the compounds and the like. These multifunctional monomers may be used alone or in combination of two or more.

The content of the photopolymerizable monomer is preferably 1 to 30% by weight, more preferably 5 to 20% by weight, based on the solid content of the colored photosensitive resin composition. When the concentration is in the above range, the balance of sensitivity, developability and resolution tends to be easily adjusted.

<Photopolymerization initiator>

The colored photosensitive resin composition according to the present invention contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited, and conventionally known photopolymerization initiators can be used.

Specific examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2- hydroxyethoxy) Methyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy- 2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis (4-dimethylaminophenyl) 2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, ethanone, 1 - [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl], 1- (o-acetyloxime), 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4- Benzyl-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4- Dimethylamino-2-isoamylbenzoic acid, Ben Ethyl-1,2-propanediol-2- (o-ethoxycarbonyl) oxime, methyl o-benzoylbenzoate, 2,4-diethylthioxane 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthone, 2- , 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethyl anthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile , Benzoyl peroxide, cumene peroxide, 2-mercaptobenzoimidal, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2- (o-chlorophenyl) -4,5-diphenylimidazole (O-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- A dimer of 2- (o-methoxyphenyl) -4,5-diphenylimidazolyl, a dimer of 2- (p-methoxyphenyl) -4,5- Triallyl (I.e., Michler's ketone), 4,4'-bisdiethylaminobenzophenone (that is, bisphenol) , Ethylhexyl ketone), 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, Benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloro Butyl acetoacetophenone, p-tert-butyl acetophenone, p-tert-butyl acetoacetophenone, p-tert-butyl acetoacetophenone, , Thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl-4-dimethylaminobenzoate, 9 (9-acridinyl) heptane, 1,5-bis- (9-acridinyl) pentane, 1,3-bis- triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2 (Trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6 (Trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (Trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloro 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) Bis-trichloromethyl-6- (3-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis- Trichloromethyl-6- (2-bromo-4-methoxy ) Phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4- methoxy) styrylphenyl- IRGACURE OXE02, IRGACURE OXE01, IRGACURE 369, IRGACURE 651, IRGACURE 907 (trade name: BASF) NCI-831 &quot; (trade name, manufactured by ADEKA), and the like. Among them, it is particularly preferable to use a photopolymerization initiator of oxime type in terms of sensitivity, and it is particularly preferable to use oxime-based photopolymerization initiator as the carbazole skeleton. These photopolymerization initiators may be used alone or in combination of two or more.

The content of the photopolymerization initiator is preferably 0.5 to 20% by weight based on the solid content of the colored photosensitive resin composition. When the content is in the above range, sufficient heat resistance and chemical resistance can be obtained, and the coating film forming ability can be improved and the hardening failure can be suppressed.

<Inorganic pigment>

The colored photosensitive resin composition according to the present invention contains an inorganic pigment. The inorganic pigment is not particularly limited, and conventionally known inorganic pigments can be used.

Specific examples of the inorganic pigments include carbon black, titanium black, Cu, Fe, Mn, Cr, Co, Ni, V, Zn, Se, Mg, Ca, Sr, Ba, Pd, Ag, Cd, In, Sn, Sb, Various metal oxides, complex oxides, metal sulfides, metal sulfates, metal carbonates, etc. of Hg, Pb, Bi, Si and Al.

When the black matrix is formed, it is preferable to use carbon black having high light shielding properties. As carbon black, known carbon blacks such as channel black, furnace black, thermal black and lamp black can be used, but it is particularly preferable to use channel black having excellent light shielding properties. Resin-coated carbon black may also be used.

Since resin-coated carbon black has low conductivity compared to carbon black without resin coating, leakage of current is small when used as a black matrix of a liquid crystal display element such as a liquid crystal display, and a display with low power consumption with high reliability is manufactured can do.

In order to uniformly disperse the inorganic pigment, a dispersant may be further used. As such a dispersing agent, it is preferable to use a polyethyleneimine-based, urethane resin-based, acrylic resin-based polymeric dispersing agent. Particularly, when carbon black is used as the inorganic pigment, it is preferable to use an acrylic resin dispersant.

The content of the inorganic pigment is preferably 5 to 70% by weight, more preferably 25 to 55% by weight, based on the solid content of the colored photosensitive resin composition. By setting the thickness within the above range, a black matrix or each colored layer can be formed with a desired pattern, which is preferable. In particular, in the case of forming a black matrix, it is preferable to adjust the amount of the inorganic pigment in the colored photosensitive resin composition so that the OD value in the vicinity of 1 mu m in film thickness becomes 4 or more. When the OD value in the vicinity of 1 mu m in film thickness in the black matrix is 4 or more, sufficient display contrast can be obtained when the black matrix is used for a black matrix of a liquid crystal display.

<Solvent>

The colored photosensitive resin composition according to the present invention contains a solvent, and the solvent includes a solvent having an amide structure. Here, the solvent having an amide structure is a solvent having a bond of a carbonyl group and nitrogen, and means a carboxylic acid amide, an imide, an urea and a derivative thereof. By including a solvent having an amide structure, stability over time of viscosity and stability over time of patterning characteristics are improved.

As the solvent having the amide structure, it is preferable to use one represented by the following formula (1) or (2).

In the formula (1), each R ¹ independently represents a hydrogen atom or an alkyl group, and X represents a hydrogen atom, an alkyl group or an amino group.

In the formula (2), R ² and R ³ each represent a hydrogen atom or an alkyl group, and n represents an integer of 1 to 3.

R ¹ , R ² and R ³ are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. N is preferably 1 or 2.

The solvent having the amide structure preferably has a boiling point of 150 to 250 캜. When the color photosensitive resin composition is applied to a substrate in the above-described range, it is difficult to cause surface defects or surface roughness since it is sufficiently volatilized from the coating film without causing boiling during drying after coating the substrate.

Examples of the solvent having an amide structure represented by the above formula (1) or (2) and having a boiling point of 150 to 250 ° C include 1,1,3,3-tetramethylurea, 1,1,3,3-tetraethylurea , Dimethylformamide, diethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidone, 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) N, N-dimethylpropionamide, N-methylacetamide, N-methylformamide and the like.

The solvent having the amide structure is generally used in combination with other solvents used in the colored photosensitive resin composition. Other commonly used solvents include those which disperse or dissolve an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, and an inorganic pigment, do not react with these components, and those having appropriate volatility may be used, and polyalkylene glycol mono Alkyl ethers, polyalkylene glycol monoalkyl ether acetates, ketones, esters, and aromatic hydrocarbons.

Specific examples include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono- , Propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl Ether, tripropylene glycol monoethyl ether and the like ) Alkylene glycol monoalkyl ether; (Poly) alkylene ethers such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate. Glycol monoalkyl ether acetates; Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and tetrahydrofuran; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone; Lactic acid alkyl esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; Methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, Methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n- Butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyl butyrate, ethyl pyruvate, n-propyl pyruvate, Other esters such as methyl, ethyl acetate and ethyl 2-oxobutanoate; And aromatic hydrocarbons such as toluene and xylene. These solvents may be used alone or in combination of two or more.

Among these solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 3- Methoxybutyl acetate, ethyl lactate, and ethylene glycol monoethyl ether are preferable because they can improve the dispersibility of the inorganic pigment, and propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate are particularly preferably used.

The solvent and the solvent having the amide structure are preferably combined to form a solvent for the colored photosensitive resin composition. The solvent having the amide structure is preferably contained in an amount of 1 to 90 wt%, more preferably 1 to 50 wt% %.

The content of the solvent is preferably such that the total concentration of the total solid content of the colored photosensitive resin composition is from 1 to 50% by weight, preferably from 5 to 30% by weight, from the viewpoint of coatability and stability of the obtained colored photosensitive resin composition More preferable.

The colored photosensitive resin composition according to the present invention may contain various additives as required.

Examples of the additive include fillers such as glass and alumina; High molecular compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylate); Surfactants such as fluorine-based surfactants and silicone-based surfactants; Vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclo Hexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like Adhesion promoters; Antioxidants such as 2,2-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butylphenol; Ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; An anti-aggregation agent such as sodium polyacrylate; Amino-1-propanol, 5-amino-1-pentanol, 3-amino-1, 2-pentanone, Propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol, and the like.

In the present invention, the colored photosensitive resin composition can be prepared by an appropriate method. As a method for preparing a preferable colored photosensitive resin composition, there may be mentioned, in some cases, a method in which an inorganic pigment is added in a solvent in the presence of other dispersing agent, if necessary, , A method of preparing a dispersion by mixing and dispersing while pulverizing, and then adding an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator and, if necessary, a solvent and an additive to the dispersion, have.

The thus-prepared colored photosensitive resin composition is excellent in viscosity and patterning characteristics with respect to time-course stability.

«Color filter, display device»

The color filter according to the present invention comprises a colored layer formed using the colored photosensitive resin composition according to the present invention. A coating film is formed on a substrate or on a substrate on which a light-shielding layer with a desired pattern is formed in advance by using a colored photosensitive resin composition, and the coating film is irradiated with radiation in a predetermined pattern shape and developed, A pixel of the filter or a black matrix can be formed.

The display device according to the present invention is provided with such a color filter, and a liquid crystal display display, an organic EL display, or the like can be given as a display device.

Example

Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these embodiments.

&Lt; Preparation of colored photosensitive resin composition &gt;

[Example 1]

The following components were mixed and the mixture was stirred for 1 hour and then filtered through a membrane filter of 5 占 퐉 to prepare a colored photosensitive resin composition.

· Alkali-soluble resin

Resin A (solid content: 55%, solvent: 3-methoxybutyl acetate) 60 parts by weight

· Photopolymerizable monomer

Dipentaerythritol hexaacrylate (manufactured by Nippon Yakuzaku Co., Ltd.) ... 25 parts by weight

· Photopolymerization initiator

(Trade name: BASF), 1- (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol- ... 15 parts by weight

· Inorganic pigments

Carbon dispersion "CF Black" (trade name: 25% solids by Mikuni Color Co., Ltd. Solvent: 3-methoxybutyl acetate 400 parts by weight

·solvent

3-methoxybutyl acetate / 1,1,3,3-tetramethylurea / propylene glycol monomethyl acetate = 55/10/35 (by weight) 300 parts by weight

The synthesis method of the resin A is as follows.

First, 235 g of bisphenol fluorene type epoxy resin (epoxy equivalent 235), 110 mg of tetramethylammonium chloride, 100 mg of 2,6-di-tert-butyl-4-methylphenol and 72.0 g of acrylic acid were introduced into a 500 ml four- And heated and dissolved at 90 to 100 占 폚 while blowing air at a rate of 25 ml / min. Then, the solution was slowly heated in a cloudy state, and completely dissolved by heating at 120 占 폚. At this time, the solution became gradually transparent (viscous), but stirring was continued. During this period, the acid value was measured, and heating and stirring were continued until the concentration was less than 1.0 mg KOH / g. It took 12 hours until the acid value reached the target value. The mixture was cooled to room temperature to obtain a bisphenol fluorene-type epoxy acrylate represented by the following formula (a-4) as a colorless transparent solid.

Subsequently, 600 g of 3-methoxybutyl acetate was further dissolved in 307.0 g of the bisphenol fluorene-type epoxy acrylate thus obtained, and then 80.5 g of benzophenone tetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were mixed , The temperature was gradually raised, and the reaction was carried out at 110 to 115 ° C for 4 hours. After disappearance of the acid anhydride group was confirmed, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 DEG C for 6 hours to obtain a resin A. The disappearance of the acid anhydride group was confirmed by IR spectrum.

This resin A corresponds to the compound represented by the above formula (a-1).

[Examples 2 to 10 and Comparative Examples 1 to 9]

A colored photosensitive resin composition was prepared in the same manner as in Example 1 except that the mixing ratio (weight ratio) of the solvent was changed as shown in Table 1.

[Table 1]

MBA: 3-methoxybutylacetate

PGMEA: Propylene glycol monomethyl ether acetate

EL: ethyl lactate

Ethyl Cellosolve: Ethylene glycol monoethyl ether

AN: cyclohexanone

? -BL:? -butyrolactone

? -VL:? -valerolactone

? -CL:? -caprolactone

TMU: 1,1,3,3-tetramethylurea

DMF: methylformamide

DMAC: Dimethylacetamide

DMI: 1,3-dimethyl-2-imidazolidone

&Lt; Evaluation of colored photosensitive resin composition &gt;

[Evaluation of viscosity stability]

After the colored photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 1 to 9 were stored at the initial stage of preparation and at 25 ° C for 7 days, the viscosity was measured using an E-type viscometer to determine the viscosity difference between the initial stage and after storage. The evaluation indexes were evaluated as &amp; cir &amp; The results are shown in Table 2.

[Table 2]

As can be seen from Table 2, it was confirmed that 1,1,3,3-tetramethylurea, dimethylformamide, dimethylacetamide and 1,3-dimethyl-2-imidazolidinone, which are solvents having an amide structure in the solvent, , The difference from the initial viscosity was 0.03 to 0.04 even after storage for 7 days, and the stability of the viscosity over time was excellent.

Even when the solvent contains 隆 -valerolactone and 竜 -caprolactone, the viscosity stability over time is excellent.

[Evaluation of Stability of Patterning Characteristics]

After the colored photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 1 to 9 were stored at the initial stage of preparation and at 25 占 폚 for 7 days, a spin coater (Eagle Co., -XG), and prebaked on a hot plate at 90 DEG C for 120 seconds to form a coating film having a thickness of 1.0 mu m. Next, this coating film was irradiated with 50 mJ / cm &lt; 2 &gt; using a mirror projection aligner (TME-150 RTO) (Exposure gap: 50 mu m). And exposed through respective masks having line widths of 4, 6, 8, 10, 12, 14, 16, 18, and 20 탆. After the exposure, the resist film was developed with a 0.04% by weight KOH aqueous solution at 26 캜 for 60 seconds, and the presence or absence of each line width was confirmed by an optical microscope to confirm the patterned thinning line. The difference between the initial value and the patterned line width after storage was obtained. The difference was evaluated as? When the difference was 0 占,? When the difference was 2 to 4 占 퐉, and? When the difference was 6 占 퐉 or more. The results are shown in Table 3.

[Table 3]

As can be seen from Table 3, both of the colored photosensitive resin compositions showed good minute patterning characteristics at the beginning of preparation. When the solvent contains 1,1,3,3-tetramethylurea, dimethylformamide, dimethylacetamide and 1,3-dimethyl-2-imidazolidinone, which are solvents having an amide structure, And good micropatterning characteristics. Thus, the patterning characteristics were excellent over time and stability. On the other hand, in other cases, deterioration of the patterning characteristics was observed. Particularly, in Comparative Examples 8 and 9, in which stability of viscosity over time was excellent, deterioration of the patterning property was remarkable.

As described above, when a solvent having an amide structure is contained in a solvent in a colored photosensitive resin composition containing an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, an inorganic pigment, and a solvent, .

Claims (6)

A colored photosensitive resin composition comprising an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, an inorganic pigment, and a solvent, wherein the solvent comprises a solvent having an amide structure,
The solvent having an amide structure may be 1,1,3,3-tetramethylurea, 1,1,3,3-tetraethylurea, 1,3-dimethyl-2-imidazolidone, 1,3- At least one coloring selected from the group consisting of 3,4,5,6-tetrahydro-2 (1H) -pyrimidinone, N, N-dimethylpropionamide, N-methylacetamide, Sensitive resin composition. The method according to claim 1,
Wherein the solvent having the amide structure has a boiling point of 150 to 250 캜. 1. A colored photosensitive resin composition comprising an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, an inorganic pigment, and a solvent,
Wherein the solvent contains at least one selected from the group consisting of a solvent having an amide structure and propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate and ethylene glycol monoethyl ether,
Wherein the solvent having the amide structure is at least one selected from the group consisting of 1,1,3,3-tetramethylurea, dimethylformamide and 1,3-dimethyl-2-imidazolidone. The method according to any one of claims 1 and 3,
The proportion of the solvent having the amide structure is 1 to 90% by weight of the total solvent. A color filter formed using the colored photosensitive resin composition according to any one of claims 1 to 3. A display device comprising the color filter according to claim 5.