KR101697362B1 - A colored photo resist composition, a pattern forming method using the same and a color filter fabricated by the method - Google Patents

Abstract

(A) a colorant; (B) a binder polymer; (C) a photopolymerizable compound comprising a hyperbranched polyester amide acrylate oligomer; And (D) a photopolymerization initiator, a pattern forming method using the same, and a color filter using the same. The present invention relates to a colored photosensitive resin composition which is excellent in the linearity of a pattern and can form a coating layer for a color filter which does not cause pattern sagging, a pattern forming method using the same, and a color filter using the same.

A colored photosensitive resin composition, a color filter, a CMOS (Complementary Metal Oxide Semiconductor), a CIS (CIS)

Description

[0001] The present invention relates to a colored photosensitive resin composition, a pattern forming method using the same, and a color filter fabricated by the above method,

The present invention relates to a colored photosensitive resin composition constituting a color filter used for a photographing element and a flat panel display element, a pattern forming method using the same, and a color filter using the same. More particularly, the present invention relates to a colored photosensitive resin composition comprising a photopolymerizable compound containing a hyperbranched polyester amide acrylate oligomer, a pattern forming method using the same, and a color filter using the same.

Conventionally, as a production method of a color filter using a colored photosensitive resin composition, a dyeing method of dyeing a pattern after forming a pattern by a photosensitive resin composition, an electrodeposition method of forming a composition containing a pigment dispersed by applying a voltage to a formed pattern, A printing method in which an ink containing a thermosetting or photo-curable composition is sprayed, and a pigment dispersion method in which a pattern is formed using a photosensitive composition in which a pigment is dispersed. Further, in the production of a photographic element, a composition using a pigment such as a colored photosensitive resin composition, a composition using a pigment and a dye, or a composition using only a dye may be used.

Examples of the constituent components of the conventional colored photosensitive resin composition using the pigment and / or the dye include a colorant, a binder polymer, a photopolymerizable compound, a photopolymerization initiator, and a solvent. Such a colored photosensitive resin composition can be obtained by incorporating a mixture of a colorant and a solvent in a mixture of a binder polymer, a photopolymerizable compound and a photopolymerization initiator, usually in a clean room at room temperature. In order to effectively obtain a coloring pattern by using the colored photosensitive resin composition, it is preferable to use a colored photosensitive resin composition containing a colorant at a high concentration.

However, when a high concentration of a colorant is contained, there is a disadvantage in that the film thickness is lowered, the sensitivity is lowered, the thickening point and film thickness are increased, or the transmittance is lowered and residue is generated. In addition, the degree of the residue may be increased depending on the influence of the lower substrate. For example, in the case of a bare silicon substrate (bare silicon wafer), the degree of residue generation is not serious, but on a flattening film (overcoat, OC), a residue often occurs. In order to prevent this, the residues may be solved by a process step, but the process time is long and the processing cost is increased with an increase in the number of process steps.

It is an object of the present invention to provide a photopolymerizable composition containing a hyperbranched polyester amide acrylate oligomer having a wide process margin, good adhesion, particularly excellent linearity of pattern, A method of forming a pattern using the same, and a color filter using the same.

In order to achieve the above objects, the present invention provides a colorant composition comprising (A) a colorant; (B) a binder polymer; (C) a photopolymerizable compound comprising a hyperbranched polyester amide acrylate oligomer; And (D) a photopolymerization initiator. The present invention also provides a colored photosensitive resin composition.

Further, the present invention is characterized in that a colored photosensitive resin layer is formed on the substrate using the colored photosensitive resin composition, the colored photosensitive resin layer is selectively exposed, and the selectively exposed colored photosensitive resin layer is developed And a method of forming a coloring pattern.

The present invention also provides a color filter using the colored photosensitive resin composition.

INDUSTRIAL APPLICABILITY The colored photosensitive resin composition of the present invention is suitable for a color filter of a liquid crystal display element (LCD) and a complementary metal oxide semiconductor image sensor, has a wide process margin, is excellent in adhesion and has excellent linearity and pattern sagging It is effective.

Hereinafter, the present invention will be described in detail.

1. Colored photosensitive resin composition

The colored photosensitive resin composition of the present invention comprises (A) a colorant, (B) a binder polymer, (C) a photopolymerizable compound, (D) a photopolymerization initiator and (E) a solvent.

The colorant (A) may include one or more kinds selected from the group consisting of organic pigments, inorganic pigments, organic dyes and inorganic dyes, and may exist in the form of a mill base. The organic pigments and / or organic dyes may be synthetic or natural pigments. If necessary, the organic pigment may be subjected to a surface treatment using a pigment derivative in which a rosin treatment, an acidic group or a basic group is introduced, a graft treatment on the surface of a pigment using a polymer compound or the like, A cleaning treatment with an organic solvent or water or the like may be carried out to remove impurities. The inorganic pigment may be a metal oxide, a metal complex salt, an inorganic salt of barium sulfate (extender pigment), or the like. At this time, the main coloring layer of the mill base is the same as the pigment used in the conventional mill base.

The pigments and the dyes may be classified into pigments and dyes in the Color Index (The Society of Dyers and Colors), and the pigments and the dyes may be used alone or in combination of two or more. Can be used. Specific examples of the pigment and the dye are as follows.

Specific examples of the pigment include C.I. Pigment Yellow No. 1, C.I. Pigment yellow No. 12, C.I. Pigment yellow No. 13, C.I. Pigment yellow No. 14, C.I. Pigment yellow No. 15, C.I. Pigment yellow No. 16, C.I. Pigment yellow No. 17, C.I. Pigment yellow No. 20, C.I. Pigment yellow No. 24, C.I. Pigment yellow No. 31, C.I. Pigment Yellow No. 53, C.I. Pigment Yellow 83, C.I. Pigment Yellow No. 86, C.I. Pigment yellow 93, C.I. Pigment Yellow 94, C.I. Pigment yellow No. 109, C.I. Pigment Yellow No. 110, C.I. Pigment yellow No. 117, C.I. Pigment Yellow No. 125, C.I. Pigment yellow No. 128, C.I. Pigment yellow No. 137, C.I. Pigment yellow 138, C.I. Pigment yellow No. 139, C.I. Pigment yellow No. 147, C.I. Pigment yellow No. 148, C.I. Pigment Yellow No. 150, C.I. Pigment yellow 153, C.I. Pigment yellow 154, C.I. Pigment yellow 166, C.I. Pigment yellow No. 173, C.I. Pigment Orange No. 13, C.I. Pigment Orange No. 31, C.I. Pigment orange No. 36, C.I. Pigment Orange No. 38, C.I. Pigment orange No. 40, C.I. Pigment orange No. 42, C.I. Pigment orange No. 43, C.I. Pigment Orange No. 51, C.I. Pigment orange No. 55, C.I. Pigment Orange No. 59, C.I. Pigment Orange No. 61, C.I. Pigment orange No. 64, C.I. Pigment orange No. 65, C.I. Pigment orange No. 71, C.I. Pigment Orange No. 73, C.I. Pigment Red No. 9, C.I. Pigment red No. 97, C.I. Pigment red No. 105, C.I. Pigment Red 122, C.I. Pigment Red 123, C.I. Pigment red No. 144, C.I. Pigment red No. 149, C.I. Pigment Red 166, C.I. Pigment Red No. 168, C.I. Pigment Red 176, C.I. Pigment Red 177, C.I. Pigment red No. 180, C.I. Pigment red No. 192, C.I. Pigment Red 215, C.I. Pigment Red 216, C.I. Pigment Red 224, C.I. Pigment Red 242, C.I. Pigment Red 254, C.I. Pigment Red No. 264, C.I. Pigment red No. 265, C.I. Pigment Blue No. 15, C.I. Pigment Blue 15: 3, C.I. Pigment Blue 15: 4, C.I. Pigment Blue 15: 6, C.I. Pigment Blue No. 60, C.I. Pigment Violet No. 1, C.I. Pigment purple No. 19, C.I. Pigment Purple No. 23, C.I Pigment Purple No. 29, C.I Pigment Purple No. 32, C.I Pigment Purple No. 36, C.I Pigment Purple No. 38, C.I. Pigment Green No. 7, C.I. Pigment green No. 36, C.I. Pigment Brown 23, C.I. Pigment brown No. 25, and the like.

The above (A) colorant is contained in an amount of 10% by weight to 50% by weight, based on the solid content after volatile components in the colored photosensitive resin composition of the present invention are volatilized. When the above-mentioned range is satisfied, the ratio of the colorant (A) to the binder polymer (B) is appropriately included in the colored photosensitive resin composition, thereby preventing oxidation of the colorant in the heating process. In addition, there is an advantage of exhibiting excellent coloring power.

The binder polymer (B) may be prepared by dispersing a colorant in a colored photosensitive resin composition to remove non-exposed areas of the colored photosensitive resin layer formed using the colored photosensitive resin composition during the development process in the photoresist process, And the like.

The binder polymer (B) preferably has a weight average molecular weight (MW) measured by gel permeation chromatography (GPC) using polystyrene as a standard substance of 5,000 to 400,000 and preferably 10,000 to 300,000.

The binder polymer (B) preferably includes a polymer containing a monomer having a carboxyl group.

Examples of the monomer having a carboxyl group include unsaturated carboxylic acids having at least one carboxyl group in the molecule, such as unsaturated monocarboxylic acids and unsaturated dicarboxylic acids. Specific examples thereof include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid. The monomer having a carboxyl group is a compound having a carbon-carbon unsaturated bond, and each may be used alone or in combination of two or more.

The binder polymer (B) may be a homopolymer composed of a monomer having a carboxyl group, but the binder polymer may be a copolymer composed of a monomer having a carboxyl group and another monomer. Here, the other monomer is a monomer having a carbon-carbon unsaturated bond and capable of copolymerizing with the monomer having a carboxyl group.

Specific examples of the other monomer include an aromatic vinyl compound, an unsaturated carboxylate compound, an unsaturated aminoalkyl carboxylate compound, an unsaturated glycidyl carboxylate compound, a vinyl carboxylate compound, a vinyl cyanide compound and an unsaturated oxetanecarboxylic acid And the like.

Specific examples of the vinyl compound include styrene,? -Methylstyrene, vinyltoluene, and the like. Specific examples of the unsaturated carboxylate compound include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl Methacrylate, benzyl acrylate, benzyl methacrylate, and the like. Specific examples of the unsaturated aminoalkyl carboxylate compound include aminoethyl acrylate and the like. Specific examples of the unsaturated glycidyl carboxylate compound include glycidyl methacrylate and the like. Specific examples of the vinyl carboxylate compound include vinyl acetate and vinyl propionate. Specific examples of the vinyl cyanide compound include acrylonitrile, methacrylonitrile,? -Chloroacrylonitrile, and the like. Specific examples of the unsaturated oxetanecarboxylate compound include 3-methyl-3-acryloxymethyloxetane, 3-methyl-3-methacryloxymethyloxetane, 3-ethyl- Methyl-3-acryloxyethyl oxetane, 3-methyl-3-acryloxyethyl oxetane, 3-methyl- Methyl-3-methacryloxyethyloxetane and the like. These other monomers may be used alone or in combination of two or more.

Examples of the copolymer include 3-ethyl-3-methacryloxymethyloxetane / benzyl methacrylate / methacrylic acid copolymer, 3-ethyl-3-methacryloxymethyloxetane / benzyl methacrylate / Ethyl-3-methacryloxymethyloxetane / methyl methacrylate / methacrylic acid copolymer, 3-ethyl-3-methacryloxymethyl oxetane / methyl methacrylate / methacrylic acid / Acid / styrene copolymer and the like.

When the binder polymer (B) is the copolymer, the amount of the monomer having a carboxyl group is preferably 5 wt% to 50 wt%, more preferably 10 wt% to 40 wt%, based on the total weight of the copolymer Is most preferable. If the monomer unit having a carboxyl group is contained in an amount of less than 5% by weight, the light-irradiated region of the colored photosensitive resin composition may not remain when the developing process is carried out, and if it contains more than 50% by weight, A problem may arise in which the film is not formed.

The binder polymer (B) is contained in an amount of 10% by weight to 50% by weight based on the solid content after volatile components in the colored photosensitive resin composition of the present invention are volatilized. When the above-mentioned range is satisfied, there is an advantage that an excellent pattern can be formed by giving a capability of removing the light non-irradiated area and remaining the light irradiated area at the time of development.

The photopolymerizable compound (C) is a compound which can be polymerized by an active radical, an acid, or the like generated from the photopolymerization initiator (D) by exposure and includes a hyperbranched polyester amide (meth) acrylate oligomer .

The polymerized polyester amide (meth) acrylate oligomer of the present invention is preferably a compound represented by the following general formula (1), which is a second generation or more.

≪ Formula 1 >

X - [- A] _l

In Formula 1,

X represents a central component of a hyperbranched polyester amide acrylate oligomer and is a functional group having 2 to 4 carbonyl groups at the ends of the aliphatic or aromatic residue having 2 to 20 carbon atoms,

l is 2 to 4,

A is a group of the following formula (2) bonded to the carbonyl group.

(2)

-B-C

In Formula 2,

B is a divalent or higher-valent organic group containing at least one ester bond and at least one amide bond,

C is -CO-CR ₁ = CH _2,

R ₁ is H or CH ₃ .

B is preferably a divalent or higher-valent organic group containing at least one ester and amide bond and having at least one oxide group at the terminal.

More specifically, the highly branched polyester amide acrylate oligomer represented by Formula 1 is reacted with an anhydride to form a compound having four hydroxyl groups, This compound serves as a core of the highly branched polyester amide acrylate represented by the above formula (1). Subsequently, a compound in which one diethanolamine is reacted with the anhydride is added to the core to form a branch.

The hyperbranched polyester amide acrylate oligomer preferably has a weight average molecular weight of 400 to 10,000 as measured by gel permeation chromatography (GPC) using polystyrene as a standard, and preferably 1,000 to 6,000. When the molecular weight is in the above range, there is an advantage that synthesis is easy.

The hyperbranched polyester amide acrylate oligomer can be directly prepared and used.

The above-mentioned (C) photopolymerizable compound may further include the above-mentioned hyperbranched polyester amide acrylate oligomer alone, but may further include a compound having a polymerizable carbon-carbon unsaturated bond and the like. The compound may be a monofunctional photopolymerizable compound, a bifunctional photopolymerizable compound, or a trifunctional or more multifunctional photopolymerizable compound.

Examples of the monofunctional photopolymerizable compound include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N-vinyl Pyrrolidone and the like. Examples of the bifunctional photopolymerizable compound include 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, neopentyl glycol diacrylate , Neopentyl glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol diacrylate, 3-methylpentane Diol dimethacrylate, and the like. Examples of the polyfunctional acryl oligomer and polyfunctional acrylic monomer include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetra Methacrylate, dipentaerythritol pentaacrylate, dipentaerythritol penta methacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexa methacrylate, and the like.

When the (C) photopolymerizable compound contains a compound other than the hyperbranched polyester amide acrylate as described above, the (Hyperbranched) polyester amide acrylate may be added to the total weight of the photopolymerizable compound (C) By weight, and 5 to 100% by weight. When included in the above-mentioned range, there is an advantage in the residue and pattern straightness and pattern sagging.

The (C) photopolymerizable compound is contained in an amount of 10% by weight to 50% by weight based on the solid content after volatile components in the colored photosensitive resin composition of the present invention are volatilized. When the above-mentioned range is satisfied, an excellent pattern can be formed without causing pattern peeling, and the colored photosensitive resin composition of the present invention can be uniformly applied during the process, and reverse taper and residue generation can be prevented .

Examples of the photopolymerization initiator (D) include an active radical generator that generates an active radical upon irradiation with light or an acid generator that generates an acid. Examples of the active radical generator include an acetophenone photopolymerization initiator, a benzoin photopolymerization initiator, a benzophenone photopolymerization initiator, a thioxanthone photopolymerization initiator, and a triazine photopolymerization initiator.

Examples of the acetophenone photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2- Methyl-1- [4- (1-methylvinyl) phenyl] propane-1-one and 2-hydroxy-2-methyl- -One oligomers, and the like.

Examples of the benzoin-based photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether. Examples of the benzophenone photopolymerization initiator include benzophenone, methyl o-benzoyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3 ', 4,4'-tetra (t -Butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like. Examples of the thioxanthone (D) photopolymerization initiator include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, -4-propoxyoctanoic acid, and the like.

Examples of the triazine photopolymerization initiator include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6 - (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, (Trichloromethyl) -6- [2- (5-methylfuran-2- (4-methoxystyryl) -1,3,5-triazine, Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan- , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- ) -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'-tetra Phenyl-1,2'-bimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methylphenylglyoxylate, Etc. may be used.

In addition, commercially available active radical generating agents may be used. Commercially available photopolymerization initiators include, for example, " Irgacure-907 " (trade name, type: acetophenone-based photopolymerization initiator;

Examples of the acid generator include an onium salt such as 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p- Benzenesulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenylsulfonium p-toluenesulfonate, Toluene sulfonate, diphenyl iodonium hexafluoroantimonate and the like, nitrobenzyl tosylate, and benzoin tosylate.

Among the above-mentioned compounds, a compound capable of generating an acid simultaneously with an active radical as an active radical generator may also be included. For example, the triazine-based photopolymerization initiator can be used as an acid generator. These photopolymerization initiators may be used alone or in combination of two or more.

The photopolymerization initiator (D) is contained in an amount of 0.01% by weight to 10% by weight, preferably 0.1% by weight to 5% by weight, based on the solid content after volatilization of the volatile components in the colored photosensitive resin composition of the present invention . When the above-mentioned range is satisfied, an excellent pattern can be formed without occurrence of pattern peeling, and there is an advantage that residue can be prevented from being generated during the process.

The photopolymerization initiator (D) may further comprise a photopolymerization initiator. The photopolymerization initiation assistant is a compound used together with the photopolymerization initiator (D) for promoting polymerization of the photopolymerizable compound (C) initiated by the photopolymerization initiator (D). Examples of the photopolymerization initiator include amine-based photopolymerization initiators, alkoxyanthracene photopolymerization initiators, and the like.

Examples of the amine photopolymerization initiation auxiliary include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylamino N, N-dimethyl p-toluidine, 4,4'-bis (dimethylamino) benzophenone (generic name: Michler's ketone), 4, 4'-bis (diethylamino) benzophenone, and 4,4'-bis (ethylmethylamino) benzophenone.

Examples of the alkoxyanthracene-based photopolymerization initiator include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, etc. .

Commercially available photopolymerization initiators may also be used. Examples of such commercially available photopolymerization initiators include " EAB-F " (trade name, product of Hodogaya Chemical Co., Ltd.) and the like.

When such a photopolymerization initiator is used, the photopolymerization initiator may be contained in an amount of 0.01 to 10 mol, preferably 0.1 to 5 mol per mol of the photopolymerization initiator (D). If the amount of the photopolymerization initiator is less than 0.01 mol, the effect due to the photopolymerization initiator can not be achieved. If the amount of the photopolymerization initiator is more than 10 mol, the production cost may increase.

The solvent (E) contained in the colored photosensitive resin composition of the present invention has an appropriate viscosity and can easily dissolve the remaining components. The solvent (E) is preferably contained in an amount of 50 to 90% by weight based on the total weight of the colored photosensitive resin composition of the present invention.

The solvent (E) may be the same solvent as that used in conventional colored photosensitive compositions. 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 Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, alkylene glycol alkyl ethers such as ethylene glycol diethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; Ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, methoxypentyl acetate, etc., aromatic hydrocarbons, examples Methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, Glycerin and the like, esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, and cyclic esters such as? -Butyrolactone. The above (E) solvents may be used alone or in combination of two or more.

The colored photosensitive resin composition of the present invention may further comprise (F) an additive. Examples of the additive (F) include fillers, polymers other than the binder polymer (B), surfactants, adhesion promoters, antioxidants, ultraviolet Absorbing agents, anti-aggregation agents, organic acids, organic amino compounds, and curing agents.

Examples of the other polymer include polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate. Examples of the surfactant include a polyester polymer dispersant, an acrylic polymer dispersant, a polyurethane polymer dispersant, a cationic surfactant, an anionic surfactant, and a nonionic surfactant. These surfactants may be used alone or in combination of two or more Used in combination. The pigment dispersant is contained in an amount of 0.01 part by weight or more, preferably 0.05 part by weight or more, based on 1 part by weight of the colorant. Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- ( 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- Ethoxy silane, and the like. Examples of the antioxidant include 2,2-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol and the like. Examples of the ultraviolet absorber include 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenone. Examples of the anti-aggregation agent include sodium polyacrylate and the like. Examples of the organic acid include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, capronic acid, diethylacetic acid, enanthic acid, caprylic acid, etc., aliphatic dicarboxylic acids Such as 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, Aliphatic tricarboxylic acids such as tricarboxylic acid, aconitic acid, camphoronic acid, etc., such as methylsuccinic acid, tetramethylsuccinic acid, cyclohexanedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, , Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumenic acid, hemelitic acid and mesitylenic acid, aromatic dicarboxylic acids, phthalic acid, isophthalic acid and terephthalic acid, aromatic polycarboxylic acids such as trimellitic acid, Trieste, Melodic acid, pyromellitic acid, and the like, and other acids. Examples of the organic amino compound include mono (cyclo) alkylamines such as n-propylamine, i-propylamine, n-butylamine, i-butylamine, s-butylamine, heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, cyclohexylamine, 2-methylcyclohexylamine, 3- Methylcyclohexylamine, 4-methylcyclohexylamine and the like, di (cyclo) alkylamines such as methylethylamine, diethylamine, methylnopropylamine, ethylnopropylamine, di- Butylamine, di-n-butylamine, di-n-pentylamine, di-n-hexylamine, methylcyclohexylamine, ethylcyclohexylamine, dicyclopentylamine (Cyclo) alkylamines such as dimethylethylamine, methyldiethylamine, triethylamine, dimethyl n-propylamine, diethyl n-propylamine, methyl propylamine, tri-n-butylamine, tri-i-butylamine, tri-s-butylamine, tri-t-butylamine, tri Mono (cyclo) alkanolamines such as pentylamine, trihexylamine, dimethylcyclohexylamine, diethylcyclohexylamine, methyldicyclohexylamine, ethyldicyclohexylamine and tricyclohexylamine, Amino-1-pentanol, 6-amino-1-hexanol, 4-amino-1-butanol, -Cyclohexanol, di (cyclo) alkanolamines such as diethanolamine, di-propanolamine, di-propanolamine, di-n-butanolamine, di-butanolamine, di- Tri (cyclo) alkanolamines such as triethanolamine, tri-n-propanolamine, tri-i-propanol Amino (cyclo) alkanediols such as triethanolamine, tri-n-butanolamine, tri-n-pentanolamine, Amino-1,2-butanediol, 4-amino-1, 3-butanediol, 4-amino-1,2-cyclohexanediol 1,3-cyclohexanediol, 3-dimethylamino-1,2-propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino- 2-diethylamino-1,3-propanediol, and the like, amino group-containing cycloalkane methanol such as 1-aminocyclopentanone methanol, 4-aminocyclopentanone methanol, 1-aminocyclohexanone methanol, 4-aminocyclohexane Dimethylaminocyclopentanemethanol, 4-dimethylaminocyclopentanemethanol, 4-dimethylaminocyclopentanemethanol, 4-dimethylaminocyclohexanemethanol and 4-diethylaminocyclohexanemethanol, aminocarboxylic acid, Aminobutyric acid, 2-aminobutyric acid, 3-aminoisobutyric acid, 2-aminobutyric acid, 5-aminobutyric acid, 6-aminocaproic acid, Aminocyclohexanecarboxylic acid, and 4-aminocyclohexanecarboxylic acid; aromatic amines such as aniline, o-methylaniline, m-methylaniline, p-methylaniline, p N-dimethylaniline, N, N-diethylaniline, N, N-dimethylaniline, N, N-dimethylaniline, aminobenzyl alcohol, m-aminobenzyl alcohol, p-aminobenzyl alcohol, p-dimethylaminobenzyl alcohol, p-diethylaminobenzyl alcohol, Alcohols and the like, aminophenols such as o-aminophenol, m-aminophenol, p-aminophenol, p-dimethylaminophenol, p -Diethylaminophenol, aminobenzoic acids such as m-aminobenzoic acid, p-aminobenzoic acid, p-dimethylaminobenzoic acid, p-diethylaminobenzoic acid and the like, and other acids. The curing agent is used in the process for pattern formation to improve its mechanical strength by curing the coloring pattern due to crosslinking with the binder polymer by post-development baking treatment. The curing agent is a compound capable of reacting with a carboxyl group in the binder polymer by post-baking to crosslink the binder polymer, and examples thereof include an epoxy compound and an oxetane compound.

Examples of the epoxy compound include epoxy resins such as bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolac epoxy resin, Based epoxy resins, heterocyclic epoxy resins, glycidyl ester-based resins, glycidylamine-based resins, and epoxidized oils. Brominated derivatives of the above epoxy resins; Aliphatic, alicyclic or aromatic epoxy compounds other than epoxy resins and brominated derivatives thereof; An epoxidation material of (co) polymer of butadiene, an epoxidation material of (co) polymer of isoprene, (co) polymer of glycidyl (meth) acrylate, and triglycidyl isocyanurate.

Examples of the oxetane compound include carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and cyclohexanedicarboxylic acid bisoxetane.

The colored photosensitive resin composition of the present invention may contain a compound capable of causing ring-opening polymerization of an oxetane skeleton in an epoxy compound and an oxetane compound in an epoxy compound together with a curing agent. Examples of such compounds include polycarboxylic acids, polycarboxylic acid anhydrides, acid generators, and the like.

Examples of the polyvalent carboxylic acid include aromatic polycarboxylic acids such as phthalic acid, 3,4-dimethylphthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimethylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 3,3 ', 4,4'-benzophenonetetracarboxylic acid, and the like. Alicyclic polyvalent carboxylic acids such as succinic acid, glutaric acid, adipic acid, 1,2,3,4-butanetetracarboxylic acid, maleic acid, fumaric acid and itaconic acid, which are aliphatic polycarboxylic acids, Hydroxycarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, cyclopentanetetracarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,2-cyclohexanetricarboxylic acid, Carboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid and the like, and other acids can be mentioned.

Examples of the polycarboxylic acid anhydrides include aromatic polycarboxylic anhydrides such as phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic acid dianhydride, Aliphatic polycarboxylic acid anhydrides such as itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenylsuccinic anhydride, tricarbalic anhydride, maleic anhydride, 1,2,3,4-butanetetracarboxylic acid dianhydride Water and the like, and examples thereof include hexahydrophthalic anhydride which is an alicyclic polycarboxylic anhydride, 3,4-dimethyltetrahydrophthalic anhydride, 1,2,4-cyclopentanetricarboxylic anhydride, 1,2,4 Cyclohexanetricarboxylic acid dianhydride, cyclic pentanetricarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, hymic anhydride, nadic anhydride, etc., ester group-containing Carboxylic acid Anhydrides such as ethylene glycol bistrimellitic acid and glycerin tristrimellitic acid anhydride, and other acids.

Commercially available ones as the epoxy resin curing agent may be used. Commercially available epoxy resin curing agents include, for example, 'Adeka Hardener EH-700' (trade name, available from Asahi Denka Kogyo K.K.) and 'Rickacid HH' (trade name, New Japan Chemical Co., Ltd.) and 'MH-700' (New Japan Chemical Co., Ltd.).

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

The (F) additive may be previously dissolved in the mixture if it can be contained in the form of a solution in a composition of a colorant and a solvent. Generally, the (F) additive is premixed with (B) the binder polymer, (C) the photopolymerizable compound and (D) the photopolymerization initiator.

The colored photosensitive resin composition of the present invention is advantageous for achieving high resolution, high sensitivity and wide margin, and is excellent in adhesion, and therefore is useful as a raw material for forming a coloring pattern constituting a color filter.

2. Manufacturing method of colored photosensitive resin composition

One embodiment of the method for producing the colored photosensitive resin composition of the present invention will be described.

The binder polymer (B), the photopolymerizable compound (C), and the photopolymerization initiator (D) are added to the solvent containing the colorant (A) in the solvent (E) To thereby prepare the colored photosensitive resin composition of the present invention. The colorant (A) may be dissolved or dispersed in the solvent (E). In addition, the (F) additive may further include a pigment dispersant, which may be included in advance if the pigment dispersant can be present in the form of a solution.

Further, another embodiment of the method for producing the colored photosensitive resin composition of the present invention will be described.

A first mixture is prepared by incorporating the colorant (A) in a part of the solvent (E). A second mixture is prepared by adding the binder polymer (B), the photopolymerizable compound (C), and the photopolymerization initiator (D) to the remainder of the solvent (E). The colored photosensitive resin composition of the present invention can be prepared by incorporating the second mixture into the first mixture or by incorporating the first mixture into the second mixture.

3. Pattern formation method of colored photosensitive resin composition

1 to 9 are diagrams for explaining a method for producing a color filter which is an example of a pattern forming method of the colored photosensitive resin composition according to the present invention.

Referring to FIG. 1, a substrate 2 made of glass or a silicon wafer is provided, and a first colored photosensitive resin layer 1 is formed on the substrate 2 using the colored photosensitive resin composition of the present invention . When the substrate 2 is a silicon wafer, a charge coupled device (CCD) and a complementary metal oxide semiconductor image sensor (CIS) may be formed on the surface of the silicon wafer. The first colored photosensitive resin layer 1 is formed by coating a colored photosensitive resin composition diluted with a solvent F on a substrate by a coating method such as spin, slit, spin, slit, or inkjet method . In addition, a soft-bake may be performed to volatilize the volatile components such as the solvent (E).

2, the first colored photosensitive resin layer 1 is irradiated with ultraviolet light such as i-line (wavelength: 436 nm) or KrF-Eximer (wavelength: 248 nm) using a photomask 3 4).

Here, the photomask 3 may be formed by providing a glass plate 31 including a light-shielding layer 32 for shielding the light ray 4 and a light-transmitting portion 33 for transmitting the light ray 4. The colored photosensitive resin layer 1 can be exposed according to the pattern of the transparent portion 33. [ The dose of the light is appropriately selected depending on the type and content of the binder polymer (B), the color and the content of the colorant (C), the type and content of the photopolymerizable compound (D), the type and content of the photopolymerization initiator . After the colored photosensitive resin layer is exposed, post exposure bake (PEB) may be performed.

Referring to FIG. 3, the exposed first colored photosensitive resin layer 1 is developed to form a first colored pattern 5. The development can be performed by a dipping method. Examples of the developer used in the dipping method include aqueous solutions such as alkali compounds such as sodium carbonate, sodium hydroxide, potassium hydroxide, potassium carbonate, and tetramethylammonium hydroxide. At this time, the first colored pattern 5 formed by the development is the exposed area 12 of the first colored photosensitive resin layer 1. [ Further, after the development, the substrate can be cleaned and dried. Subsequently, hard bake may be performed after drying. By the hard bake, the first colored pattern 5 is cured and the mechanical strength is improved. The temperature at which the hard bake is carried out is usually 180 ° C or higher, preferably 200 ° C to 250 ° C.

Referring to FIG. 4, a second colored photosensitive resin layer 1 'using the colored photosensitive resin composition of the present invention is formed on a substrate 2 having the first colored pattern 5 formed thereon.

Referring to FIG. 5, the second colored photosensitive resin layer 1 'is selectively exposed in the same manner as in FIG.

Referring to FIG. 6, the selectively exposed second colored photosensitive resin layer 1 'is developed to form a second colored pattern 5'. The developer used in the developing process has been described in detail with reference to FIG. 1C and therefore will not be described. Here, the second coloring pattern 5 'has a different color from the first coloring pattern 5.

7, a third colored photosensitive resin layer 1 "is formed on a substrate on which the first and second colored patterns 5 and 5 'are formed. The third colored photosensitive resin layer 1" Is the same as the method of forming the first and second colored photosensitive resin layers (1, 1 ').

8, the third colored photosensitive resin layer 1 "is selectively exposed. Since the above-mentioned exposure method has been described above, it will be omitted.

Referring to Fig. 9, the exposed third colored photosensitive resin layer 1 "is developed to form a third colored pattern 5 ". At this time, the third coloring pattern 5 '' is different from the first and second coloring patterns 5 and 5 '.

Figs. 10 and 11 are views showing color pixels manufactured by the method shown in Figs. 1 to 9. Fig.

Referring to Fig. 10, a color pixel including a mosaic color filter is shown. Referring to Fig. 11, a color pixel including a stripe-matrix color filter is shown.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by these Examples.

Synthesis Example 1: Hyperbranched polyester amide Acrylate C-2 Synthesis

165.16 g of diisopropanolamine (manufacturer: Merck) and 139.25 g of succinic anhydride (Merck, manufacturer) were added to a 1 L reactor equipped with an azototropic cooling condenser equipped with a thermometer, a stirrer and a temperature controller And the temperature was raised to 140 캜. The condensed dehydrate starts to escape at 140 ° C. When the temperature of the azototropic condenser drops to 50 ° C. or lower, the reactor temperature is increased by 10 ° C. to raise the reaction temperature to 180 ° C. When the condenser temperature did not rise at 180 ° C, 80 g of toluene was added to the reaction mixture, and 18.02 g of dehydrated product was obtained. The reaction was terminated and the temperature was lowered to room temperature. (Manufactured by Eastman Chemical Co., Ltd., trade name: BHT) in an amount of 119.14 g of acrylic acid (manufactured by LG Chemie), 200 g of toluene, 2.5 g of para toluenesulfonic acid, 0.04 g of nitrobenzene and 0.4 g of butylated hydroxytoluene And the temperature was raised to the boiling point of toluene while air bubbling was carried out to carry out the ester condensation reaction again. When 29.8 g of dehydrated water was obtained, the reaction was stopped. The reaction mixture was put into a fractionator and washed with 500 g of distilled water. The reaction mixture was stirred while 10% sodium hydroxide aqueous solution was added thereto to a pH of 6 to 7 to remove unreacted acrylic acid . 500 g of 5% brine was added to purify the reaction substance again, and then 50 g of magnesium sulfide was added to remove residual moisture. The remaining water was removed by filtration using a filter paper. 0.2 parts by weight of methoxyphenol (manufactured by Eastman Corporation, trade name: HQMME) was added and the toluene was removed at a temperature of 60 ° C and a pressure of 1,000 mbar while stirring to obtain a hyperbranched poly Ester amide acrylic oligomer was prepared.

Examples 1 to 8, Comparative Examples 1 and 2: Preparation of colored photosensitive resin composition

A mill base containing a colorant, an additive and a solvent at a composition ratio shown in Table 1 was obtained. A mixture containing a binder polymer, a photopolymerizable compound, a photopolymerization initiator and a solvent was added dropwise over a period of one hour to the mill base at 23 占 폚 under stirring to prepare a colored photosensitive resin composition. Here, all components except solvent are solid.

coloring agent
(Parts by weight) Binder polymer
(Parts by weight) Photopolymerizable compound
(Parts by weight) Photopolymerization initiator
(Parts by weight) menstruum
(Parts by weight) additive
(Parts by weight) Example 1 A-1 / A-2 5.23 / 1.07
= 6.30 B-1 7.55 C-2 5.03 D-1 1.01 E-1 79 F-1 1.11 Example 2 A-1 / A-2 5.23 / 1.07
= 6.30 B-1 7.55 C-1 / C-2 3.77 / 1.26
= 5.03 D-1 1.01 E-1 79 F-1 1.11 Example 3 A-1 / A-2 5.23 / 1.07
= 6.30 B-1 7.55 C-1 / C-2 2.52 / 2.51
= 5.03 D-1 1.01 E-1 79 F-1 1.11 Example 4 A-1 / A-2 5.23 / 1.07
= 6.30 B-1 7.55 C-1 / C-2 1.26 / 3.77
= 5.03 D-1 1.01 E-1 79 F-1 1.11 Example 5 A-1 / A-2 5.23 / 1.07
= 6.30 B-1 6.29 C-2 6.29 D-1 1.01 E-1 79 F-1 1.11 Example 6 A-1 / A-2 5.23 / 1.07
= 6.30 B-1 6.29 C-1 / C-2 4.72 / 1.57
= 6.29 D-1 1.01 E-1 79 F-1 1.11 Example 7 A-1 / A-2 5.23 / 1.07
= 6.30 B-1 6.29 C-1 / C-2 3.15 / 3.14
= 6.29 D-1 1.01 E-1 79 F-1 1.11 Example 8 A-1 / A-2 5.23 / 1.07
= 6.30 B-1 6.29 C-1 / C-2 1.57 / 4.72
= 6.29 D-1 1.01 E-1 79 F-1 1.11 Comparative Example 1 A-1 / A-2 6.53 / 1.43
= 7.96 B-1 7.55 C-1 5.03 D-1 1.01 E-1 79 F-1 1.11 Comparative Example 2 A-1 / A-2 6.53 / 1.43
= 7.96 B-1 6.29 C-1 3.70 D-1 1.01 E-1 79 F-1 1.11

A-1: Blue pigment (CI Pigment blue 15: 6)

A-2: Purple pigment (CI Pigment violet No. 23)

B-1: Copolymer of methacrylic acid and benzyl methacrylate (molar ratio of methacrylic acid unit to benzyl methacrylate unit: 3: 7, weight average molecular weight: 25,000)

C-1: dipentaerythritol hexaacrylate

C-2: Hyperbranched polyester amide acrylate prepared in Synthesis Example 1

D-1: Photopolymerization initiator IGACURE-907 (trade name, manufactured by Shiba-Kagi)

E-1: Propylene glycol monomethyl ether acetate

F-1: Non-ionic pigment dispersant

Test Example: Performance Evaluation of Colored Photosensitive Resin Composition

The colored photosensitive resin compositions of Examples 1 to 8 and Comparative Examples 1 and 2 were spun on the surface of a glass substrate (manufacturer: Corning, product name: No.1737, thickness: 0.7 mm) Coating method. Thereafter, the resultant was dried at 90 DEG C for 90 seconds to volatilize the volatile components to form a colored photosensitive resin layer. The colored photosensitive resin layer thus formed was cooled to 23 캜 and selectively exposed to i-line (wavelength: 365 nm) using a photomask. At this time, an ultra-high pressure mercury lamp was used as a light source of the i-line, and the irradiation light amount was set to 150 mJ / cm 2. As the photomask, a line width of 1 占 퐉, 2 占 퐉, 3 占 퐉, 4 占 퐉, 5 占 퐉, 6 占 퐉, 7 占 퐉, 8 占 퐉, 9 占 퐉, 10 占 퐉, 20 占 퐉, 30 占 퐉, A photomask for forming color pixels in the form of lines and dots having a diameter of 占 퐉 was used.

Subsequently, the selectively exposed colored photosensitive resin layer was immersed in an aqueous solution containing 0.04% by weight of tetramethylammonium hydroxide as a developer at 23 占 폚. Thereafter, it was washed with pure water and then baked at 220 캜 for 90 seconds to form a colored pattern. The thickness of the obtained color pattern was 0.8 mu m, and the minimum line width (resolution) was 1 mu m. The linearity of the obtained coloring pattern and the residue and pattern sagging were observed and are shown in Table 2 below.

Pattern linearity Pattern sagging Example 1 5 4 Example 2 5 4 Example 3 5 4 Example 4 4 4 Example 5 5 5 Example 6 5 5 Example 7 5 5 Example 8 5 5 Comparative Example 1 One 2 Comparative Example 2 2 3

※ Linearity of pattern> 1: Severe defect, 2: Bad, 3: Normal, 4: Good, 5: Very good

※ Pattern sagging> 1: Severe defect, 2: Bad, 3: Normal, 4: Good, 5: Very good

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a diagram showing that a color photosensitive resin composition (red) is applied on a substrate when the steps are red-green-blue in the process of manufacturing a color filter and a photographic element.

FIG. 2 is a view showing that a colored photosensitive resin composition in an exposed portion is reacted by selectively passing light through a substrate using the photomask of FIG. 1.

FIG. 3 is a view showing that the unexposed portion of the substrate of FIG. 2 is removed using a developing solution and the exposed portion remains.

Fig. 4 is a view showing that the substrate of Fig. 3 is coated with a colored photosensitive resin composition (green).

FIG. 5 is a view showing that a colored photosensitive resin composition is reacted with an exposed portion by selectively passing light through a substrate using the photomask of FIG. 4.

FIG. 6 is a view showing that the unexposed portion of the substrate of FIG. 5 is removed using a developing solution and the exposed portion remains.

Fig. 7 is a view showing that the substrate of Fig. 6 is coated with a colored photosensitive resin composition (blue).

FIG. 8 is a view showing that a colored photosensitive resin composition is reacted with an exposed portion by selectively passing light through a substrate using the photomask of FIG. 7; FIG.

FIG. 9 is a view showing that the unexposed portion of the substrate of FIG. 7 is removed using a developing solution and the exposed portion remains.

10 is a view showing a mosaic matrix type color filter.

11 is a diagram showing a stripe matrix type color filter.

[Description of the Drawings]

1: first colored photosensitive resin layer 1 ': second colored photosensitive resin layer

1 ": third colored photosensitive resin layer 2: substrate

3: Photomask 31: Glass plate

32: light shielding layer 33:

4: light ray 5: first coloring pattern

5 ': second colored pattern 5' ': third colored pattern

5R: red pixel 5G: green pixel

5B: blue pixel 6: color filter

Claims (14)

(A) a colorant; (B) a binder polymer; (C) a photopolymerizable compound comprising a hyperbranched polyester amide acrylate oligomer; (D) a photopolymerization initiator; And (E) a solvent. The method according to claim 1, Based on the solid content after the volatile component is volatilized in the colored photosensitive resin composition, 10 to 50% by weight of the above (A) colorant; 10 to 50% by weight of the binder polymer (B); 10 to 50% by weight of the (C) photopolymerizable compound; And (D) 0.01 to 10% by weight of a photopolymerization initiator. The method according to claim 1, On the basis of the colored photosensitive resin composition, And the solvent is contained in an amount of 50 to 90% by weight. The method according to claim 1, Wherein the hyperbranched polyester amide acrylate oligomer is a second generation or more. The method of claim 4, Wherein the hyperbranched polyester amide acrylate oligomer is represented by the following Formula 1: ≪ Formula 1 > X - [- A] _l In Formula 1, X represents a central component of a hyperbranched polyester amide acrylate oligomer and is a functional group having 2 to 4 carbonyl groups at the end of an aliphatic or aromatic hydrocarbon group having 6 to 20 carbon atoms and having 2 to 20 carbon atoms, l is 2 to 4, A is a group of the following formula (2) bonded to the carbonyl group. (2) -B-C In Formula 2, B is a divalent or higher-valent organic group containing at least one ester bond and at least one amide bond, C is -CO-CR ₁ = CH _2, R ₁ is H or CH ₃ . The method according to claim 1, Wherein the hyperbranched polyester amide acrylate oligomer has a weight average molecular weight of 400 to 5,000. The method according to claim 1, Wherein the colorant (A) comprises one or more kinds selected from the group consisting of an inorganic pigment, an organic pigment and a dye. The method according to claim 1, Wherein the binder polymer (B) comprises a monomer having a carboxyl group. The method according to claim 1, The photopolymerization initiator (D) is one or more selected from the group consisting of an acetophenone photopolymerization initiator, a benzoin photopolymerization initiator, a benzophenone photopolymerization initiator, a thioxanthone photopolymerization initiator, and a triazine photopolymerization initiator By weight. The method according to claim 1, The solvent (E) is selected from the group consisting of a glycol monoalkyl ether compound, a diethylene glycol dialkyl ether compound, a glycol alkyl ether acetate compound, an alkylene glycol alkyl ether acetate compound, an aromatic hydrocarbon compound, an alcohol compound and a cyclic ester compound Wherein the coloring photosensitive resin composition is one or two or more of the following. The method according to claim 1, Wherein the colored photosensitive resin composition further comprises an additive. The method of claim 11, The additive may be one or more selected from the group consisting of a filler, a polymer other than the binder polymer (B), a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, an organic acid, an organic amino compound, Wherein the coloring photosensitive resin composition is at least two kinds. A colored photosensitive resin layer is formed on a substrate using the colored photosensitive resin composition according to claim 1, Selectively exposing the colored photosensitive resin layer, Wherein the selectively exposed colored photosensitive resin layer is developed. A color filter produced by the method according to claim 13.

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