KR101431499B1 - Colored composition and color filter therefrom - Google Patents

Abstract

The coloring composition comprises a compound (A) having an ethylenically unsaturated double bond, a pigment (B), a pigment dispersant (C), a photopolymerization initiator (D), an organic solvent having a water solubility of more than 7.0 wt% (E) containing at least 25% by weight of an organic solvent. The water content of the coloring composition is 0.3 to 2.0 wt% based on the total weight of the coloring composition. The color filter has colored pixels formed on the substrate from the coloring composition.

A coloring composition, a pigment, a dispersant, a photopolymerization initiator, and a color filter.

Description

COLORING COMPOSITION AND COLOR FILTER USING THE SAME

TECHNICAL FIELD The present invention relates to a coloring composition suitable for forming a colored image of a color filter used in a liquid crystal display element or a solid-state image pickup element (CCD, CMOS, etc.), and a color filter using the same.

Colored pixels constituting a color filter used for a color liquid crystal display device and a color (TV camera) image pickup tube device are formed as follows. A photosensitive coloring composition (colored resist material) is applied to a glass substrate, the excess solvent is dried and removed, and active energy rays are irradiated through proxy photolithography (ultraviolet light source exposure) or the like through a photomask for pixel formation. When the colored resist material is negative, the irradiated portion is cured, and when the colored resist material is positive, the alkali solubility of the irradiated portion is improved. Subsequently, the non-irradiated portion (in the case of the negative type) or the irradiated portion (in the case of the positive type) of the resist material is removed with a developer such as an alkali solution. By repeating this one-color pixel forming process for pixels of different colors, a color filter is produced.

Recently, a color liquid crystal display device has come to form a large market as a liquid crystal color television, a car navigation system, and a liquid crystal display device-integrated notebook, and has become popular as a monitor for desk top computers and a television utilizing the feature of energy saving and space saving . In addition, there is a growing demand for improving the color reproduction characteristics as they are generally supplied to the market.

In order to improve the color reproduction characteristics of the color filter, it is necessary to increase the content of the coloring agent in the photosensitive coloring composition or to increase the film thickness of the coloring composition. However, when the content of the coloring agent is increased, the sensitivity is lowered and the developability and the resolution are deteriorated. In addition, if the film thickness is increased, the exposure light does not reach the bottom of the film, resulting in a problem that the linearity and the cross-sectional shape of the colored pixel become defective.

Japanese Unexamined Patent Application, First Publication No. 2003-156842 discloses a colored photosensitive resin composition capable of giving a colored pattern at a low exposure amount even when the colorant concentration is increased. This composition contains a colorant, a binder polymer, a photopolymerization initiator and a solvent. The photopolymerization initiator contains an acetophenone compound and a triazine compound, and the photopolymerization initiator contains an amine compound.

An object of the present invention is to provide a coloring composition which is suitably used for the production of a color filter, has improved sensitivity and development speed, and has a stable viscosity.

According to the present invention, there is provided an ink composition comprising a compound (A) having an ethylenically unsaturated double bond, a pigment (B), a pigment dispersant (C), a photopolymerization initiator (D), an organic solvent having a water solubility exceeding 7.0% S) of at least 25% by weight, based on the total weight of the coloring composition, wherein the water content of the coloring composition is 0.3 to 2.0% by weight based on the total weight of the coloring composition.

According to the present invention, there is also provided a color filter having a colored pixel formed from the coloring composition of the present invention on a substrate.

(Best Mode for Carrying Out the Invention)

First, the coloring composition of the present invention will be described in detail.

The coloring composition of the present invention comprises an organic solvent (A) having an ethylenically unsaturated double bond, a pigment (B), a pigment dispersant (C), a photopolymerization initiator (D) (E) containing not less than 25% by weight of (S). And, the water content of the coloring composition is 0.3 to 2.0% by weight based on the total weight of the coloring composition.

<Water content>

The water content of the coloring composition of the present invention can be measured by a known method such as Karl Fischer's method. The Karl Fischer method is to measure the water content by using a Karl Fischer reagent (composed of a solvent such as iodine, sulfur dioxide, a base, and an alcohol (ROH)) which selectively or quantitatively reacts with water as shown in the following formula . There are total titration method and capacity titration method in this method, but any method can be used.

Equation (1):

I ₂ + SO ₂ +3 base + ROH + H ₂ O → 2 base · HI + base · HSO ₄ R

The coloring composition of the present invention preferably has a water content just before coating on the substrate is 0.3 to 2.0% by weight, preferably 0.3 to 1.5% by weight, more preferably 0.6 (by weight) based on the total weight of the coloring composition To 1.5% by weight.

The coloring composition having a moisture content exceeding 2.0% by weight is thickened over time and causes coating defects when coated on a substrate. In addition, the coloring composition having a water content of less than 0.3% by weight does not sufficiently improve the sensitivity and development speed.

The water content in the coloring composition may be controlled by intentionally adding water to the coloring composition at the time of preparing the coloring composition or after preservation after preparation, or in the step of applying the coloring composition to the glass substrate by the rotary rolling method. And the water content incorporated during the circulation process for recovering and applying the coloring composition that remains on the coater cup may be controlled.

<Compound (A) having an ethylenically unsaturated double bond>

The compound having an ethylenically unsaturated double bond is a compound which cures by irradiation with active energy rays, and includes a monomer, an oligomer and an active energy ray-curable resin. These compounds may be used singly or in combination of two or more.

Examples of the monomer and oligomer include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- hydroxypropyl (meth) acrylate, cyclohexyl Acrylate such as carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di , Trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, 1,6-hexane diol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (Meth) acrylate of methylolmelamine, (meth) acrylate of neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (Meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol tri (meth) acrylate and methacrylic acid ester such as styrene, epoxy Vinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.

As the active energy ray-curable resin, a (meth) acrylic compound having a reactive substituent such as an isocyanate group, an aldehyde group or an epoxy group or a cinnamic acid is reacted with a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, And a photo-crosslinking group such as a styryl group is introduced into the linear polymer. Further, a linear polymer containing an acid anhydride such as styrene-maleic anhydride copolymer or -olefin-maleic anhydride copolymer may be copolymerized with a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) Esterification is also used.

The amount of the compound having an ethylenically unsaturated double bond in the coloring composition of the present invention is preferably 50 to 2000 parts by weight, more preferably 100 to 1000 parts by weight, per 100 parts by weight of the pigment.

&Lt; Pigment (B) >

As the pigment, commercially available organic pigments can be used, and dyes, natural pigments and inorganic pigments can be used together according to the color of the formed colored pixel. As the organic pigment, those having a high coloring property and a high heat resistance, particularly a high heat decomposability are suitably used. The organic pigments and the like may be used alone or in combination of two or more. The organic pigment may be finely ground by salt milling, acid pasting or the like. Specific examples of the organic pigments usable in the coloring composition of the present invention are represented by color index (CI) numbers.

In the case of forming red pixels using the coloring composition of the present invention, CI Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 2, 81: 3, 122, 123, 146, 149, 168, 177, 178, 179, 184, 185, 187, 192, 200, 202, 208, 210, 216, 220, 223, 224, 254, 255, 264, 272 and the like can be used. A yellow pigment and an orange pigment may be used in combination in the red coloring composition.

In the case of forming a green pixel using the coloring composition of the present invention, green pigments such as C.I. Pigment Green 7, 10, 36 and 37 can be used. A yellow pigment may be used in combination with the green coloring composition.

In the case of forming a blue pixel using the coloring composition of the present invention, a blue color such as CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, Pigment can be used. A purple pigment may be used in combination with the blue coloring composition.

In the case of forming yellow pixels using the coloring composition of the present invention, CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35, 36, 36, 37, 37, 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 118, 119, 120, 123, 126, 127, 121, 123, 94, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 175, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, Yellow pigments such as 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 198, 199, 213 and 214 can be used.

Pigments such as C.I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, and 50 can be used in the case of forming a purple pixel using the coloring composition of the present invention.

When the magenta pixel is formed using the coloring composition of the present invention, CI Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: , 81: 3, 146, 177, 178, 184, 185, 187, 200, 202, 208, 210, 246, 254, 255, 264, 270 and 272 can be used. A yellow pigment may be used in combination with the magenta coloring composition.

When a cyan color pixel is formed using the coloring composition of the present invention, pigments such as CI Pigment Blue 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, have.

In the case of forming orange pixels using the coloring composition of the present invention, pigments such as C.I. Pigment Orange 36, 43, 51, 55, 59, 61, 71 and 73 can be used.

Inorganic pigments such as titanium dioxide, iron oxide, antimony pentoxide, zinc oxide, metal oxides such as silica, cadmium sulfide, calcium carbonate, barium carbonate, barium sulfate, clay, talc and chrome can also be used.

Black pigments may also be used. As the black pigment, carbon black, titanium black, aniline black, anthraquinone black pigment and perylene black pigment, specifically, CI Pigment Black 1, 6, 7, 12, 20, 31, , And the use of carbon black is preferable because of its large light shielding property. The carbon black may be surface-treated with a resin or the like.

&Lt; Pigment dispersant (C) >

As the pigment dispersant, a pigment derivative having a basic or acidic substituent, an anthraquinone derivative, an acridone derivative, a triazine derivative, or a resinous dispersant can be used. Among them (particularly), a pigment derivative or a resinous dispersant having a basic or acidic substituent can be suitably used because it can be used as a coloring composition having excellent dispersibility, fluidity and storage stability even when a pigment which is difficult to disperse is used have. Hereinafter, a pigment derivative having a basic or acidic substituent, and a resinous dispersant will be described in detail.

(i) a pigment derivative having a basic or acidic substituent

A pigment derivative having a basic or acidic substituent is a compound having a basic or acidic substituent introduced into an organic pigment. Examples of the organic pigments constituting the pigment derivative include azo pigments such as diketopyrrolopyrrole pigments, azo pigments, azo pigments and polyazo pigments, phthalocyanine pigments, diamino dianthraquinone, anthrapyrimidine, Anthraquinone pigments such as anthanthrone, indanthrone, pyranthrone and violanthrone, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thioindigo pigments, isoindoline pigments, isoindoline pigments, Dolinone pigments, quinophthalone pigments, trene pigments, metal complex pigments, and the like.

The basic substituent is at least one substituent selected from the group represented by the following formulas (2), (3), (4) and (5)

Equation (2):

Equation (3):

Equation (4):

Equation (5):

In the formulas (2) to (5), the symbols have the following meanings:

X is _{-SO 2 -, -CO-, -CH 2} NHCOCH 2 -, -CH 2- , or represents a direct bond;

v represents an integer of 1 to 10;

R ₈ and R ₉ each independently represent an alkyl group, an alkenyl group, an optionally substituted phenyl group, or R ₈ and R ₉ may be combined to further contain a nitrogen atom, an oxygen atom or a sulfur atom, Represents a leaving residue. The alkyl group usually has 1 to 36 carbon atoms, and the alkenyl group usually has 2 to 36 carbon atoms. Examples of the alkyl group include branched alkyl such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, nonyl, . Examples of the alkenyl group include allyl derivatives such as 1-ethylallyl and 1-butylallyl. Substituents on the phenyl group include alkyl groups, alkenyl groups and the like;

R ₁₀ represents an alkyl group, an alkenyl group or an optionally substituted phenyl group. Here, the alkyl group usually has 1 to 36 carbon atoms, and the alkenyl group usually has 2 to 36 carbon atoms. Examples of the alkyl group include branched alkyl such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, nonyl, . Examples of the alkenyl group include allyl derivatives such as 1-ethylallyl and 1-butylallyl. Substituents on the phenyl group include alkyl groups, alkenyl groups and the like;

R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each independently represent a hydrogen atom, an alkyl group, an alkenyl group or an optionally substituted phenyl group. Here, the alkyl group usually has 1 to 36 carbon atoms, and the alkenyl group usually has 2 to 36 carbon atoms. Examples of the alkyl group include branched alkyl such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, nonyl, . Examples of the alkenyl group include allyl derivatives such as 1-ethylallyl and 1-butylallyl. Substituents on the phenyl group include alkyl groups, alkenyl groups and the like;

Y represents -NR ₁₅ -Z-NR ₁₆ -or direct bond;

R ₁₅ and R ₁₆ each independently represent a hydrogen atom, an alkyl group, an alkenyl group or an optionally substituted phenyl group.

Here, the alkyl group usually has 1 to 36 carbon atoms, and the alkenyl group usually has 2 to 36 carbon atoms. Examples of the alkyl group include branched alkyl such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, nonyl, . Examples of the alkenyl group include allyl derivatives such as 1-ethylallyl and 1-butylallyl. Substituents on the phenyl group include alkyl groups, alkenyl groups and the like;

Z represents an alkylene group, an alkenylene group, or an optionally substituted phenylene group. Here, the alkylene group and the alkenylene group usually have 1 to 36 carbon atoms. Examples of these are methylene, ethylene, propylene, trimethylene, butylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, tridecamethylene , Tetradecamethylene, pentatecamethylene, and hexadecamethylene. Examples of the substituent on the phenylene group include the above-mentioned alkyl group, alkylene group and the like;

R represents a substituent represented by the following formula (6) or a substituent represented by the following formula (7);

Q represents a hydroxyl group, an alkoxyl group, a substituent represented by the following formula (6) or a substituent represented by the following formula (7). Here, the alkoxyl group usually has 1 to 36 carbon atoms.

Equation (6):

Equation (7):

In the formulas (6) and (7), R ₈ to R ₁₄ and v are as defined above.

A pigment derivative having a basic substituent can be synthesized by various synthetic routes. For example, an amine component forming a substituent represented by any of the formulas (2) to (5) and an amine component forming a substituent represented by the formulas (2) to (5) after introducing a substituent represented by the following formulas (8) For example, N, N-dimethylaminopropylamine, N-methylpiperazine, diethylamine or 4- [4-hydroxy-6- [3- (dibutylamino) propylamino] Triazin-2-ylamino] aniline, and the like.

Equation (8) -SO ₂ Cl

(9) -COCl

Equation (10) -CH ₂ NHCOCH ₂ Cl

(11) -CH ₂ Cl

In the reaction of the substituents represented by the formulas (8) to (11) with the amine component, a part of the general formulas (8) to (11) may be hydrolyzed and the chlorine may be substituted with a hydroxyl group. In this case, the substituents represented by the formulas (8) and (9) are respectively a sulfonic acid group and a carboxylic acid group, but they may be free acid groups or salts with a mono-trivalent metal or a monoamine do.

When the organic pigment is an azo-based pigment, the substituents represented by the formulas (2) to (5) are introduced into the diazo component or the coupling component in advance and then subjected to a coupling reaction to obtain a basic substituent An azo-based pigment derivative having an azo group can be prepared.

Examples of the acidic substituent include sulfonic acid group, terephthalic acid monoamidemethyl group and the like. The sulfonic acid group can be introduced by reacting the organic pigment with sulfuric acid, and the terephthalic acid monoamidemethyl group can be introduced by chloromethylating the organic pigment, then aminomethylating the primary pigment with a primary amine, and then monoamidating it with terephthalic acid.

The pigment derivatives may be used alone or in combination of two or more.

The amount of the pigment derivative having a basic or acidic substituent in the coloring composition of the present invention is preferably 1 to 50 parts by weight, more preferably 3 to 30 parts by weight, and most preferably, 5 to 25 parts by weight. If the content of the pigment derivative relative to 100 parts by weight of the pigment is less than 1 part by weight, the dispersibility may deteriorate. If the content is more than 50 parts by weight, the heat resistance and the light resistance may be deteriorated.

(ii) a resinous dispersant

The resinous dispersant has a pigment affinity site having a property of adsorbing to a pigment and a site having compatibility with a solvent and a compound having an ethylenically unsaturated double bond and adsorbed on the pigment to have an ethylenically unsaturated double bond of the pigment And serves to stabilize the dispersion of the compound and the solvent. Examples of the resinous dispersant include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid Amide formed by the reaction of a poly (lower alkyleneimine) and a free carboxyl group-containing polyester with a carboxyl group-containing alkylamine salt, a polysiloxane, a long chain polyaminoamide phosphate, a hydroxyl group-containing polycarboxylic acid ester, (Meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol and polyvinylpyrrolidone) Water-soluble polymer compounds, polyester-based, modified polyacrylate-based, ethylene oxide / propylene oxide addition compounds, phosphate esters There may be mentioned system, etc., and these may be used either individually or in combination of two or more.

The content of the resinous dispersant in the coloring composition of the present invention is preferably 0.1 to 100 parts by weight, more preferably 0.5 to 75 parts by weight, and most preferably 1.0 to 50 parts by weight, based on 100 parts by weight of the pigment to be.

&Lt; Photopolymerization initiator (D) >

Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy- Acetophenone compounds such as 1-hydroxycyclohexyl phenyl ketone and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; Benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzyl dimethyl ketal; Benzophenone, benzoyl benzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'- methyldiphenyl sulfide, 3,3 ', 4,4'-tetra (t -Butylperoxycarbonyl) benzophenone; benzophenone-based compounds such as benzophenone; Thioxanthone compounds such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone and 2,4- ; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s- triazine, 2- (p- methoxyphenyl) (Trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho- (Trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) - (4-methoxy-naphthol- Triazine-based compounds such as 6-triazine and 2,4-trichloromethyl (4'-methoxystyryl) -6-triazine; 2- (4-phenylthio) phenyl] -, 2- (O-benzoyloxime), O- (acetyl) -Methoxy-naphthyl) ethylidene) hydroxylamine and the like; Phosphine compounds such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; Quinone compounds such as 9,10-phenanthrenequinone, camphaquinone, and ethyl anthraquinone; A borate-based compound, a carbazole-based compound, an imidazole-based compound, and a titanocene-based compound. These photopolymerization initiators may be used singly or in combination of two or more. The content of the photopolymerization initiator is preferably 5 to 200 parts by weight, more preferably 10 to 150 parts by weight, based on 100 parts by weight of the pigment.

&Lt; Solvent (E) >

The organic solvent (E) in the coloring composition of the present invention contains an organic solvent (S) having a water solubility of more than 7.0% by weight within a range of 25% by weight or more of the total solvent weight. The solvent (E) may consist solely of a solvent (S) having a water solubility of more than 7.0% by weight.

Hereinafter, an organic solvent (S) having a water solubility of more than 7.0% by weight is specifically exemplified. Exemplary braces indicate the solubility of water in a solvent, and the absence of a base specifically indicates that the solubility of water in the solvent is infinite. Cyclohexanone (11 wt.%), Isobutyl alcohol (15 wt.%), Ethylene glycol monohexyl ether (18.8 wt.%), N-butyl alcohol (20% by weight), tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diethylene Glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, ethylene Glycol monomethyl ether acetate, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol moiety Ethyl ether, ethylene glycol monoisopropyl ether,? -Butyrolactone, N, N-dimethylformamide, 1,3-butanediol, 1,3-butylene glycol, 1,4-dioxane, , 3-propanediol, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol and the like.

A solvent other than the solvent (S) in which the solubility of water is more than 7.0% by weight is selected in consideration of coatability, safety, and solubility in the case of using a transparent resin to be described later. Examples of the organic solvent other than the solvent (S) having a water solubility of more than 7.0% by weight include 1,2,3-trichloropropane, 1,3-butylene glycol diacetate, Trimethylcyclohexanone, ethyl 3-methoxypropionate, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3- Propyl acetate, N-methylpyrrolidone, N-methylpyrrolidone, N-methylpyrrolidone, N-methylpyrrolidone, Di-ethylbenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, isophorone, ethylene glycol diethyl Ether, ethylene glycol dibutyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol mono tert-butyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol Propylene glycol diisopropyl ether, propylene glycol diisopropyl ether, diisobutyl ketone, cyclohexanol acetates, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monobutyl ether, diacetone alcohol, propylene glycol diacetate, Propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ether, propyleneglycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, Butyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid ester. These are used singly or in combination.

The organic solvent (E) may be used in an amount of 800 to 4000 parts by weight based on 100 parts by weight of the pigment.

<Other additives>

The coloring composition of the present invention may optionally contain various additives such as fillers, surfactants such as nonionic, cationic and anionic surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents, ethylenically unsaturated double bonds , A sensitizer, a polyfunctional thiol that acts as a chain transfer agent, a thermal polymerization inhibitor, and the like.

Examples of the filler include glass and alumina.

As the adhesion promoter, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4 -Epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc. .

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.

These additives may be used in an amount of preferably from 0.05 to 20 parts by weight, more preferably from 0.1 to 10 parts by weight, based on 100 parts by weight of the pigment.

The transparent resin having no ethylenically unsaturated double bond is preferably a resin having a transmittance of preferably 80% or more, more preferably 95% or more, in the entire wavelength range of 400 to 700 nm in the visible light region, and the transparent resin may include a thermoplastic resin, .

Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyvinyl alcohol, polyacrylic acid, polyethylene (HDPE, LDPE), polybutadiene, polyimide resin, and the like may be added to the resin composition of the present invention, for example, a glycol monoalkyl ether, a polyurethane resin, a polyester resin, an acrylic resin, an alkyd resin, a polystyrene resin, . Examples of the thermosetting resin include an epoxy resin, a benzoguanamine resin, a rosin-modified maleic resin, a rosin-modified fumaric acid resin, a melamine resin, a urea resin, and a phenol resin. The transparent resin having no ethylenically unsaturated double bond is preferably 50 to 2000 parts by weight, more preferably 100 to 1000 parts by weight, per 100 parts by weight of the pigment.

Examples of the sensitizer include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, (Ethylamino) benzophenone, 4,4'-bis (ethylmethylamino) benzophenone, 4,4'-bis ) Benzophenone, and the like. These sensitizers may be used alone or in combination of two or more. The content of the sensitizer is preferably 0.1 to 60 parts by weight based on 100 parts by weight of the photopolymerization initiator.

The multifunctional thiol may be any compound having two or more thiol groups. Examples of the multifunctional thiol include hexanedithiol, decanedithiol, 1,4-butanediol bisstiouropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bis Trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthioglycolate, Pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethyl mercaptobenzene, 2,4,6-trimercapto-s-triazine , 2- (N, N-dibutylamino) -4,6-dimercapto-s-triazine, and the like. These multifunctional thiols may be used alone or in combination of two or more. The content of the polyfunctional thiol is preferably 0.05 to 100 parts by weight, more preferably 0.1 to 60 parts by weight, based on 100 parts by weight of the pigment.

Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'- -Butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzoimidazole and the like are useful. The content of the thermal polymerization inhibitor is preferably 0.01 to 10 parts by weight based on 100 parts by weight of the pigment.

The coloring composition of the present invention comprises a compound (A) having an ethylenically unsaturated double bond, a pigment (B), a pigment dispersant (C), an organic solvent (E) and, if necessary, a transparent resin having no ethylenically unsaturated double bond , Various additives, and the like and dispersed in a horizontal type sand mill, a vertical type sand mill, an annular type bead mill, an aerator and the like, and adding a photopolymerization initiator (D). The coloring composition of the present invention may be prepared by dispersing only the pigment and the pigment dispersant in a solvent first, then adding another component, and then dispersing again.

Next, the color filter of the present invention will be described.

In the color filter of the present invention, the coloring composition of the present invention is coated on a substrate by a coating method such as rotation coating, cast coating and roll coating, followed by drying, irradiating ultraviolet rays through a predetermined mask pattern , Developing with a developer, and forming colored pixels. As the ultraviolet ray to be used at this time, g line, h line, i line and the like are particularly preferable.

Examples of the substrate include a soda glass, a Pyrex (registered trademark) glass, a quartz glass, and a photoelectric conversion element substrate used for an image pickup device or the like in which a transparent conductive film is attached thereto, Substrate, a complementary metal oxide semiconductor (CMOS), and the like. These substrates may be formed with black stripes for isolating each pixel. If necessary, a subbing layer may be formed on these substrates in order to improve adhesion with the upper layer, prevent diffusion of the material, or planarize the surface of the substrate.

As the developer, any composition may be used as long as it dissolves the coloring composition of the ultraviolet ray unexposed portion and does not dissolve the coloring composition of the ultraviolet ray irradiation portion. Specifically, various organic solvents or alkaline aqueous solutions can be used. Examples of the organic solvent include the above-mentioned solvents contained in the coloring composition of the present invention.

Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide Alkaline compounds such as benzoyl peroxide, benzoyl peroxide, benzoyl peroxide, benzoyl peroxide, benzoyl peroxide, benzoyl peroxide, benzoyl peroxide, %, Is used. When a developer comprising such an alkaline aqueous solution is used, it is generally washed with water after development.

The color filter of the present invention can be used for a solid-state image pickup device such as a liquid crystal display device or a CCD.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the following Examples and Comparative Examples, "part (s)" means "part (s) by weight". The total weight of the organic solvent in the proportion of the solvent (S) in which the solubility of water in the total weight of the organic solvent exceeds 7.0% by weight is not more than the total weight of the organic solvent, It is the total weight of the solvent.

First, a production example of an acrylic resin solution and a production example of a pigment dispersion used in Examples and Comparative Examples will be described.

<Preparation of acrylic resin solution>

The reaction vessel was charged with 650 parts of cyclohexanone, and the mixture was heated to 100 DEG C while nitrogen gas was being injected into the vessel. At the same temperature, 70.0 parts of styrene, 70.0 parts of methacrylic acid, 75.0 parts of methyl methacrylate, 75.0 parts of butyl methacrylate And 10.0 parts of azobisisobutyronitrile were added dropwise over 1 hour to carry out a polymerization reaction.

After dropwise addition, the mixture was further reacted at 100 DEG C for 3 hours, and then a solution of 2.0 parts of azobisisobutyronitrile in 50 parts of cyclohexanone was added and the reaction was further continued at 100 DEG C for 1 hour to obtain a solution having a weight average molecular weight of about 40000 To obtain a solution of an acrylic resin.

After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C for 20 minutes to measure the nonvolatile content. Based on these measured values, cyclohexanone And an acrylic resin solution was prepared.

<Production Example of Yellow Pigment Dispersion>

(a) Salt milling treatment

, 107 g of a maleic acid resin ("Malcide No.3002" manufactured by Arakawa Chemical Industries, Ltd., acid value: 100 mgKOH / g) and 300 g of polyethylene glycol (CI Pigment Yellow 139; "Pallitol Yellow D1819" (Manufactured by Tokyo Kasei Co., Ltd.) was introduced into a stainless steel first gallon kneader (manufactured by INOUE SAKUSHO CO., LTD.) And kneaded for 3 hours. Then, this mixture was charged into about 3 liters of hot water and stirred with a high-speed mixer for about one hour while heating at about 80 DEG C to form a slurry, which was then filtered and washed with water to remove sodium chloride and solvent, And dried in an oven for about 24 hours to obtain a &quot; salt milled PY 139 pigment &quot;.

(b) Preparation of pigment dispersion

The mixture of the following composition was uniformly stirred and then dispersed in an Eiger mill for 10 hours using zirconia beads having a diameter of 0.5 mm and then filtered with a filter of 1.0 탆 to prepare a yellow pigment dispersion.

Salt Milling Treatment P. Y. 139 Pigment 10.0 parts

1.0 part of a resin type dispersant ("Soap Spaz 20000" manufactured by Nippon Lubrizol Corporation)

Acrylic resin solution 30.0 parts

Propylene glycol monomethyl ether acetate 59.0 parts

<Production Example of Red Pigment Dispersion α>

A mixture having the following composition was uniformly stirred and then dispersed for 10 hours in an Eiger mill using zirconia beads having a diameter of 0.5 mm and then filtered with a filter having a thickness of 1.0 탆 to prepare a red pigment dispersion α.

Red pigment (CI Pigment Red 254; "Chromophthal Red B-CF" manufactured by Chiba Specialty Chemicals Co., Ltd.) 10.0 parts

1.0 part of a resin type dispersant ("Soap Spaz 20000" manufactured by Nippon Lubrizol Corporation)

Acrylic resin solution 30.0 parts

Propylene glycol monomethyl ether acetate 59.0 parts

<Production example of red pigment dispersion β>

177 pigment of salt milling treatment "was prepared in the same manner as in the above-mentioned salt milling treatment except that the yellow pigment was changed to a red pigment (C. I. Pigment Red 177;" Lionol Red 2B FG3300 "manufactured by Toyo Ink SEIZO Co., Ltd.).

A red pigment dispersion β was prepared in the same manner as in the preparation of the red pigment dispersion α except that the red pigment was changed to "Salt milled P. R. 177 pigment".

<Production Example of Green Pigment Dispersion α>

A green pigment dispersion α was prepared in the same manner as in the preparation of the red pigment dispersion α except that the red pigment was changed to a green pigment (C. I. Pigment Green 36; "Lionol Green 6Y-501" available from Toyo Ink and Chemicals Inc.).

<Production Example of Green Pigment Dispersion β>

A green pigment dispersion β was prepared in the same manner as in the preparation of the red pigment dispersion α except that the red pigment was changed to a green pigment (C. I. Pigment Green 7; "Paste Green Green S" available from Dainippon Ink and Chemicals, Inc.).

<Production Example of Blue Pigment Dispersion>

A mixture having the following composition was uniformly mixed and stirred, and dispersed in a sand mill for 10 hours using zirconia beads having a diameter of 0.5 mm, followed by filtration with a filter of 1.0 탆 to prepare a blue pigment dispersion.

Blue pigments (C. I. Pigment Blue 15: 6; &quot; Heliogen Blue L-6700F &quot;

9.0 part

Copper phthalocyanine pigment derivative 1.0 part

Phosphoric acid ester-based pigment dispersant (BYK111 manufactured by Big Chemie Co., Ltd. 2.0 parts

Acrylic resin solution 27.0 parts

Propylene glycol monomethyl ether acetate 61.0 parts

Copper phthalocyanine pigment derivatives:

<Production Example of Purple Pigment Dispersion Material>

A mixture having the following composition was uniformly mixed and stirred, dispersed in a sand mill for 10 hours using zirconia beads having a diameter of 0.5 mm, and then filtered with a filter of 1.0 탆 to prepare a purple pigment dispersion.

Purple pigment (C.I. Pigment Violet 23)

(&Quot; Rio Nogen Violet R6200 &quot; manufactured by Toyo Ink and Chemicals, Inc.) 9.0 parts

Had dioxazine pigment derivative 1.0 part

Resin type dispersant ("Soap Spaz 24000GR" manufactured by Nippon Lubrizol Corporation)

2.0 parts

Acrylic resin solution 27.0 parts

Propylene glycol monomethyl ether acetate 61.0 parts

Dioxazine pigment derivatives:

The composition of the pigment dispersion is shown in Table 1 below.

Examples 1 to 9 and Comparative Examples 1 to 6

Each of the compositions shown in Table 2 below was stirred and mixed so as to be uniform, and then filtered through a filter of 0.6 mu m to obtain each colored composition (resist). Table 2 also shows the ratio (% by weight) of the solvent (S) to the total solvent in each coloring composition and the color of the coloring composition.

For each coloring composition obtained, the water content was measured by the following method, and the stability of the sensitivity, the developing speed, the coating property and the viscosity were evaluated. The results are shown in Table 3.

<Water content measurement method>

The water content (mg) was measured using a Karl Fischer titration apparatus (Model KF-06, manufactured by Mitsubishi Chemical Corporation) and the water content (%) was calculated by the following formula.

Water content (%) = [Water content (mg) / Amount of sample to be measured (mg)] × 100

<Sensitivity evaluation>

The colored compositions obtained in Examples 1 to 9 and Comparative Examples 1 to 6 were coated on a glass substrate by spin coating using a spin coater so as to have a dry film thickness of 1.2 占 퐉 and prebaked at 120 占 폚 for 120 seconds. Subsequently, the substrate was cooled to room temperature, and ultraviolet rays were exposed through a photomask using an ultra-high pressure mercury lamp. Thereafter, this substrate was spray-developed using an aqueous solution of sodium carbonate at 23 캜, washed with ion-exchanged water, air-dried, post-baked at 230 캜 for 30 minutes in a clean oven, Pixel.

The sensitivity of the colored composition was evaluated by the lowest exposure dose at which the pattern of the formed colored pixels was finished in accordance with the image size of the photomask. The rating is as follows.

?: Less than 100 mJ / cm ²

?: Not less than 100 and not more than 150 mJ / cm ²

×: 150 mJ / cm ² or more

&Lt; Evaluation of development speed &

The colored compositions obtained in Examples 1 to 9 and Comparative Examples 1 to 6 were spin coated on a glass substrate using a spin coater so that the dry film thickness became 1.0 占 퐉 and dried at 70 占 폚 for 20 minutes.

2 ml of a 2 wt% aqueous solution of potassium hydroxide was added dropwise to the coating film to measure the time until the coating film was no longer dissolved, and the developing rate of the colored composition was evaluated. The rating is as follows.

○: Less than 10 seconds

B: 10 seconds or more, less than 15 seconds

×: more than 15 seconds

<Evaluation of Coating Property>

The coloring compositions obtained in Examples 1 to 9 and Comparative Examples 1 to 6 were coated on a glass substrate by spin coating using a spin coater and the state of the coating film was visually observed to evaluate the coating properties of the colored composition. The rating is as follows.

○: A uniform film was formed

△: There is a little porcelain stain but it is coated.

X: Coating uneven or uncoated

&Lt; Evaluation of stability of viscosity &

The viscosity (initial viscosity) of the coloring composition obtained in Examples 1 to 9 and Comparative Examples 1 to 6 immediately after preparation and the viscosity (the viscosity at the time of storage) after storage for one week in an environment of 40 占 폚 after preparation were measured at 25 占 폚 for E type The viscosity change was measured at 20 rpm using a viscometer ("ELD type viscometer" manufactured by Toki Sangyo Co., Ltd.). The rating is as follows.

○: Viscosity change is less than 0.5 mPa · s

?: Viscosity change of 0.5 mPa · s or more, less than 1.5 mPa · s

X: Change in viscosity of 1.5 mPa 占 퐏 or more

The coloring compositions of Examples 1 and 4 were good in terms of developing speed, coatability, and viscosity stability. However, since the water content was less than 0.6 to 1.5 wt%, which is a more preferable range of the present invention, .

The coloring compositions of Examples 2, 5, 7, and 8 were satisfactory in sensitivity, development rate, coatability, and viscosity stability because the water content was 0.6 to 1.5 wt%, which is a more preferable range of the present invention.

The coloring compositions of Examples 3, 6 and 9 showed good results in sensitivity, developing speed and coatability. However, since the water content exceeds 0.6 to 1.5% by weight, which is a more preferable range of the present invention, Results.

The color compositions of Comparative Examples 1 and 3 had a low water sensitivity and a slow development rate because the water content was 0.1 wt%.

The coloring compositions of Comparative Examples 2 and 4 had a moisture content of more than 2.0% by weight, so that the coating properties were slightly poor and the viscosity stability was poor.

Since the coloring composition of Comparative Example 5 had a water content of 0.2% by weight, the sensitivity was low and the developing speed was slightly slower.

Since the coloring composition of Comparative Example 6 had a water content as high as 2.7% by weight, the coating properties were poor and the viscosity stability was poor.

As is apparent from the above results, the coloring composition of the present invention having a water content of 0.3 to 2.0 wt% in a coloring composition in which the proportion of the solvent (S) having a water solubility of 7.0 wt% or more in the solvent is 25 wt% The stability of development speed, coating speed and viscosity was improved as compared with the coloring composition which was not in the range of 0.3 to 2.0 wt%.

As described in detail above, the coloring composition of the present invention has a high sensitivity because it contains an appropriate amount of water and has a high developing speed. Further, since the coloring composition of the present invention contains the solvent (S) having a water solubility of more than 7.0% by weight in the range of 25% by weight or more of the total solvent weight, the viscosity is stable even though it contains water.

Claims (4)

(B), a pigment dispersant (C), a photopolymerization initiator (D), and an organic solvent (S) having a solubility in water of more than 7.0 wt% % Or more of an organic solvent (E), wherein the water content of the coloring composition is 0.3 to 2.0% by weight based on the total weight of the coloring composition. The coloring composition according to claim 1, wherein the water content of the coloring composition is 0.6 to 1.5% by weight. The coloring composition according to claim 1, wherein the pigment dispersant (C) comprises a pigment derivative having a basic or acidic substituent, or a resinous dispersant. A color filter comprising a coloring pixel formed from the coloring composition according to claim 1 on a substrate.