KR101211493B1 - Colored composition, color filter using the same and production method thereof - Google Patents

Abstract

The present invention is difficult to produce a film thickness difference in the outer peripheral part of the substrate even when used for forming a coating film by the die coating method, providing a coloring composition capable of forming a coating film having excellent surface smoothness, and a small film thickness difference in the central part and the outer peripheral part, It is an object of the present invention to provide a method for producing a color filter having a filter segment and / or a black matrix having excellent surface smoothness.

A coloring composition comprising a transparent resin, a precursor thereof or a mixture thereof, a dye, an organic solvent, and a leveling agent, wherein the dynamic surface tension (I) at 100 ms of the coloring composition and the dynamic at 1000 ms are included. Color which surface tension (II) satisfy | fills the following relationship (1), and the said coating composition is apply | coated on a board | substrate using a coating apparatus of a die-coating system, and forms a filter segment and / or a black matrix. Method for producing a filter.

[{(I) − (II)} / (I)] × 100 ≦ 7.0... (One)

Coloring composition, color filter, dynamic surface tension

Description

Coloring composition, color filter using the same and manufacturing method therefor {COLORED COMPOSITION, COLOR FILTER USING THE SAME AND PRODUCTION METHOD THEREOF}

1 is a schematic view of a coating apparatus of a die coating method used in the embodiment.

FIG. 2 is a perspective view showing a coating state by the coating apparatus (die coater) of FIG. 1.

<Brief description of the main parts of the drawing>

1: application head 2: front lip

3: rear lip 4: manifold

5: slit 6: piping

7: valve 8: metering pump

9: filter 10: coating liquid tank

11: coating film 12: coating substrate

13: conveying stage

TECHNICAL FIELD The present invention relates to a coloring composition used in the production of color filters used in color liquid crystal display devices, color image sensor elements, and the like, color filters using the same, and methods for producing the same.

In manufacture of the color filter which comprises a liquid crystal display (LCD), a color imaging tube element (CCD), etc., a coating liquid is apply | coated on a transparent substrate, and the uniform coating film whose film thickness at the time of drying is about 1-3 micrometers is formed. Needs to be. As the coating method, a spin coating method is generally used.

In the spin coating method, the coating liquid is dropped on the transparent substrate while the transparent substrate is rotated at a constant rotational speed, the coating liquid is spread thinly by centrifugal force, and the coating film having a film thickness determined by the coating liquid viscosity, the rotation speed, or the like is transparent. It is a coating method to form on the surface of the. The spin coating method has an open air type and a closed cup type, but in any manner, there is a drawback that the thickness of the coating film of the rotating center portion and the outer circumferential portion of the transparent substrate becomes too thick as compared with the middle portion thereof.

When this defect is eliminated and the coating is applied by the spin coating method, it is possible to form a coating film having a small surface thickness difference between the central part, the outer peripheral part and the middle part, and having excellent surface smoothness, which is a pigment, a binder polymer and a radiation-sensitive compound. It is known to dissolve or disperse | distribute in this specific organic solvent (for example, refer Unexamined-Japanese-Patent No. 6-3521).

Although the film thickness difference of a coating film becomes small by using the said composition, only a few% is apply | coated to the surface of a transparent substrate among the coating liquids dripped on the transparent substrate by the spin coating method, and the remaining 90% of the coating liquid is a transparent substrate There is a drawback that there is a lot of waste because it is discharged from, and this drawback becomes a big problem with the recent increase in substrate size.

In order to alleviate the drawbacks of the spin coating method, the die coating method has recently been examined (for example, Japanese Patent Application Laid-Open No. 7-168015, Japanese Patent Application Laid-Open No. 2000-193818, and Japan). See Japanese Patent Application Laid-Open No. 2001-195004). The die coating method has an advantage that the coating liquid supply circuit is all sealed up to the tip of the coating head in addition to less waste of the coating liquid than the spin coating method.

However, in the die coating method, there is a drawback that a so-called horn is formed that the coating film on the outer peripheral portion of the substrate rises and becomes thicker than the coating film on the center portion of the substrate. With the recent increase in the size of the panel, in order to use it as a large panel up to the end of the substrate, it is not preferable that a film thickness difference occurs in the outer peripheral portion of the substrate. This problem is difficult to solve in the case of using the composition for spin coating developed so that the film thickness difference between the center part and the outer peripheral part is small and the coating film excellent in surface smoothness is used.

Then, an object of this invention is to provide the coloring composition which can hardly produce the film thickness difference of a coating film in the outer peripheral part of a board | substrate even if it uses for coating film formation by a die-coating method, and can form the coating film excellent in surface smoothness.

It is also an object of the present invention to provide a color filter having a filter segment and / or a black matrix having a small difference in film thickness at the center and the outer circumference and having excellent surface smoothness.

In addition, an object of the present invention is to provide a method for producing a color filter having a filter segment and / or a black matrix having a small difference in film thickness at the center and the outer peripheral portion and excellent in surface smoothness.

The coloring composition of this invention is a coloring composition containing the pigment carrier which consists of a transparent resin, its precursor, or its mixture, a pigment, an organic solvent, and a leveling agent, The dynamic surface tension (I) in 100 ms of the said coloring composition. And the dynamic surface tension (II) at 1000 ms satisfy the following expression (1).

[{(I) − (II)} / (I)] × 100 ≦ 7.0... (One)

Further, the color filter of the present invention is characterized by having a filter segment and / or a black matrix formed of the coloring composition of the present invention.

In addition, the manufacturing method of the color filter of this invention is a manufacturing method of the color filter provided with a black matrix and / or a filter segment, and apply | coated the coloring composition of this invention on a board | substrate by a die-coating method, and a filter segment and // Or forming a black matrix.

The present disclosure is related to the subject matter disclosed in Japanese Patent Application No. 2005-026230, filed February 2, 2005, the disclosures of which are incorporated herein by reference.

Embodiment of the Invention

First, the coloring composition in this invention is demonstrated concretely.

The coloring composition of this invention is a coloring composition containing the pigment carrier which consists of a transparent resin, its precursor, or its mixture, a pigment, an organic solvent, and a leveling agent, The dynamic surface tension (I) in 100 ms of the said coloring composition. And the dynamic surface tension (II) at 1000 ms satisfy the following relational expression (1).

[{(I) − (II)} / (I)] × 100 ≦ 7.0... (One)

When a coating film is formed using the coloring composition whose value of a left side is larger than 7.0, the coating film of a board | substrate outer peripheral part rises thick compared with the coating film of a board | substrate center part, and an horn is produced.

As a leveling agent contained in the coloring composition of this invention, the silicone type leveling agent, especially the compound represented by following General formula (2) are used suitably.

In formula, m is 5-30, Preferably it is an integer of 10-20, n is 50-100, Preferably it is an integer of 60-90, x is 1-20, Preferably it is an integer of 5-15. .

Examples of commercially available silicone-based leveling agents composed of the compound represented by the general formula (2) include "BYK-330" manufactured by Big Chem Corporation (m is 14, n is 77, and x is 10.) Can be. In addition, examples of other commercially available silicone-based leveling agents include "BYK-320", "BYK-323" and "BYK-333" manufactured by BIC Chem. A leveling agent can be used individually by 1 type or in mixture of 2 or more types.

The leveling agent can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight based on 100 parts by weight of the dye in the coloring composition.

The dye carrier contained in the coloring composition of this invention is comprised by transparent resin, its precursor, or its mixture. The transparent resin is preferably 80% or more and more preferably 95% or more in the transmittance region of 400 to 700 nm in the visible light region. Examples of the transparent resins include thermoplastic resins, thermosetting resins, and photosensitive resins, and examples of the precursors include monomers or oligomers which are cured by radiation to produce transparent resins. Can be used.

The dye carrier can be used in an amount of 30 to 700 parts by weight, preferably 60 to 450 parts by weight based on 100 parts by weight of the dye in the coloring composition. In addition, when using a mixture of transparent resin and its precursor as a dye carrier, the transparent resin can be used in an amount of 20 to 400 parts by weight, preferably 50 to 250 parts by weight, relative to 100 parts by weight of the dye in the coloring composition. have. In addition, the precursor of transparent resin can be used in the quantity of 10-300 weight part, Preferably it is 10-200 weight part with respect to 100 weight part of pigment | dyes in a coloring composition.

As the thermoplastic resin, for example, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, polyester resin, acrylic system Resin, alkyd resin, polystyrene, polyamide resin, rubber-based resin, cyclized rubber-based resin, cellulose, polyethylene, polybutadiene, polyimide resin and the like. Moreover, as a thermosetting resin, an epoxy resin, benzoguanamine resin, rosin modified maleic acid resin, rosin modified fumaric acid resin, melamine resin, urea resin, a phenol resin etc. are mentioned, for example.

As photosensitive resin, (meth) acrylic compound and cinnamic acid which have reactive substituents, such as an isocyanate group, an aldehyde group, and an epoxy group, are made to react with the linear polymer which has reactive substituents, such as a hydroxyl group, a carboxyl group, and an amino group, Resin which introduce | transduced photocrosslinkable groups, such as acryloyl group and a styryl group, into the linear polymer is used. Moreover, half-esterification of the linear polymer containing acid anhydrides, such as a styrene maleic anhydride copolymer and an alpha olefin maleic anhydride copolymer, with the (meth) acryl compound which has hydroxyl groups, such as hydroxyalkyl (meth) acrylate, One is used.

As a monomer and oligomer which are precursors of a transparent resin, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and cyclohexyl (meth ) Acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether Di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, ester arc Various acrylic esters and methacrylic acid esters, such as (meth) acrylic acid ester of methylolated melamine, an epoxy (meth) acrylate, urethane acrylate, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene Glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile, etc. are mentioned.

As a pigment | dye contained in the coloring composition of this invention, an organic or inorganic pigment can be used individually or in mixture of 2 or more types. Among the pigments, pigments having high color development and high heat resistance, particularly pigments having high thermal decomposition resistance, are preferable, and organic pigments are usually used.

Below, the specific example of the organic pigment which can be used suitably for the coloring composition of this invention is shown by a color index number.

Red coloring compositions for forming red filter segments include, for example, C.I. Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 97, 122, 123, 146, 149, 168, 177, 178, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 246, 254, 255, 264, Red pigments, such as 272, can be used. A yellow pigment and an orange pigment can be used together in a red coloring composition.

The yellow coloring composition for forming the yellow filter segment is, for example, C.I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, Yellow pigments, such as 181, 182, 185, 187, 188, 193, 194, 199, can be used.

Orange coloring compositions for forming orange filter segments include, for example, C.I. Pigment Orange Orange pigments such as 36, 43, 51, 55, 59, 61 can be used.

Green coloring compositions for forming green filter segments include, for example, C.I. Green pigments, such as Pigment Green 7, 10, 36, 37, can be used. A yellow pigment can be used together in a green coloring composition.

Blue coloring compositions for forming blue filter segments include, for example, C.I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64 and the like can be used. Blue coloring compositions include C.I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50, etc. can use together purple pigment.

Cyan coloring compositions for forming the cyan filter segments include, for example, C.I. Pigment Blue 15: 1, 15: 2, 15: 4, 15: 3, 15: 6, 16, 81 and the like can be used.

Magenta coloring compositions for forming magenta filter segments include, for example, C.I. Pigment Violet 1, 19, C.I. Purple pigments and red pigments such as Pigment Red 144, 146, 177, 169 and 81 can be used. A yellow pigment can be used together in a magenta coloring composition.

In the black coloring composition for forming a black matrix, for example, carbon black, aniline black, anthraquinone black pigment, perylene black pigment, specifically C.I. Pigment black 1, 6, 7, 12, 20, 31 and the like can be used. In the black coloring composition, a mixture of a red pigment, a blue pigment, and a green pigment can also be used. As a black pigment, carbon black is preferable at a price and light-shielding magnitude | size, and carbon black may be surface-treated with resin etc. Moreover, in order to adjust color tone, a blue pigment and a purple pigment can be used together in a black coloring composition.

In addition, examples of the inorganic pigments include barium sulfate, zinc oxide, lead sulfate, yellow lead, zinc sulfur, bengalla (red iron (III) oxide), cadmium red, ultramarine blue, bluish blue oxide, chromium green, cobalt green, and umber ( metal oxide powders such as umber), titanium black, synthetic iron black, titanium oxide, iron tetraoxide, metal sulfide powders, and metal powders. Inorganic pigments are used in combination with organic pigments to ensure good applicability, sensitivity, developability, and the like while balancing saturation and lightness.

The coloring composition of this invention can be made to contain dye in the range which does not reduce heat resistance for coloring.

As an organic solvent contained in the coloring composition of this invention, 2-heptanone, 4-heptanone, cyclohexanone, n-butyl acetate, isobutyl acetate, isoamyl acetate, n-amyl acetate, methyl isobutyl ketone, n-butyl alcohol, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, N, N-dimethylformamide, 1,2,3-trichloropropane, o-chlorotoluene, o-xylene, m-xylene, 3-methoxy-3-methyl-1-butanol, 1,3-butanediol, 3-methyl-1,3-butanedi , 2-methyl-1,3-propanediol, diisobutyl ketone, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, di Ethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monoisopropyl ether, propylene glycol monobutyl ether, propylene glycol diacetate, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono Propyl ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, 3-ethoxy propionate, 3-methoxybutyl acetate, 3-methoxy-3-methylbutyl acetate, γ-butyrolactone, N, N -Dimethylacetamide, N-methylpyrrolidone, p-chlorotoluene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene , o-dichlorobenzene, m-dichlorobenzene, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, cyclohexanol, methylcyclohexanol, etc. are mentioned. These are used individually or in mixture of 2 or more types. The organic solvent can be used in an amount of 800 to 4000 parts by weight, preferably 1000 to 2500 parts by weight, based on 100 parts by weight of the dye in the coloring composition.

When hardening the said composition by light irradiation, such as an ultraviolet-ray, to the coloring composition of this invention, a photoinitiator is added.

As a photoinitiator, 4-phenoxy dichloro acetophenone, 4-t-butyl- dichloro acetophenone, diethoxy acetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one Acetophenone photoinitiators such as 1-hydroxycyclohexylphenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, benzoin, benzoin methyl ether , Benzoin photopolymerization initiators such as benzoin ethyl ether, benzoin isopropyl ether, benzyl dimethyl ketal, benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl Benzophenone type photoinitiators, such as -4'-methyl diphenyl sulfide, a thioxanthone, 2-chloro thioxanthone, 2-methyl thioxanthone, isopropyl thioxanthone, 2, 4- diisopropyl Thioxanthone photopolymerization initiators such as thioxanthone, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis ( Richloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6 -Bis (trichloromethyl) -s-triazine, 2-piphenyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl- s-triazine, 2- (naphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphtho-1-yl) -4, 6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4-trichloromethyl- (4'-methoxystyryl) Triazine type photoinitiators, such as -6-triazine, a borate type photoinitiator, a carbazole type photoinitiator, an imidazole type photoinitiator, etc. are used. A photoinitiator can be used in 5-200 weight part with respect to 100 weight part of pigment | dyes in a coloring composition, Preferably it can be used in the quantity of 10-150 weight part.

Although the said photoinitiator can be used individually or in mixture of 2 or more types, As a sensitizer, (alpha)-acyl oxime ester, acyl phosphine oxide, methylphenylglyoxylate, benzyl, 9,10- phenanthrene quinone, camphor quinone, ethyl Anthraquinone, 4,4'-diethylisophthalophenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 4,4'-diethylaminobenzophenone You may use a compound together. A sensitizer can be used in the quantity of 0.1-60 weight part with respect to 100 weight part of photoinitiators in a coloring composition.

The coloring composition of the present invention comprises one or two or more pigments in combination with a leveling agent and, if necessary, the photopolymerization initiator, three roll mills, two roll mills, a sand mill, a kneader and an attritor (in a dye carrier and an organic solvent). It can be produced by finely dispersing using a variety of dispersing means such as attritor). The leveling agent may be added after the pigment is dispersed in the dye carrier and the organic solvent. Moreover, the coloring composition containing 2 or more types of pigments can also be manufactured by mixing what disperse | distributed finely each pigment | dye separately in a pigment carrier and an organic solvent. When disperse | distributing a pigment | dye in a pigment | dye carrier and an organic solvent, dispersion adjuvant, such as a resinous pigment dispersing agent, surfactant, and a pigment derivative, can be contained suitably. Dispersion aids are excellent in dispersion of pigments and have a great effect of preventing re-agglomeration of pigments after dispersion. Therefore, in the case of using a coloring composition obtained by dispersing a pigment in a dye carrier and an organic solvent using a dispersion aid, it is excellent in transparency. A color filter is obtained. Dispersion adjuvant is 0.1-40 weight part with respect to 100 weight part of pigment | dyes in a coloring composition, Preferably it can be used in the quantity of 0.1-30 weight part.

The resinous pigment dispersant is a resin having a pigment affinity site having a property of adsorbing to the pigment and a site compatible with the pigment carrier, and is a function of adsorbing the pigment to stabilize dispersion of the pigment into the dye carrier. Specifically as a resin pigment dispersant, Polycarboxylic acid esters, such as polyurethane and polyacrylate other than resin used as the said transparent resin, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) amine salt , Polycarboxylic acid ammonium salt, polycarboxylic acid alkylamine salt, polysiloxane, long chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified substances thereof, poly (lower alkyleneimine) and glass Oily dispersing agents, such as an amide and its salt formed by reaction with the polyester which has a carboxyl group of (iii), (meth) acrylic- styrene copolymer, (meth) acrylic-acid ((meth) acrylic acid ester copolymer, styrene-maleic acid air Water-soluble resins such as copolymer, polyvinyl alcohol, polyvinylpyrrolidone, water-soluble high molecular compounds, polyesters, modified polyacrylates, ethylene An oxide / propylene oxide addition compound, a phosphate ester type, etc. are used, These can be used individually or in mixture of 2 or more types.

As surfactant, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, the alkali salt of a styrene-acrylic acid copolymer, sodium alkylnaphthalin sulfonate, sodium alkyldiphenyl ether disulfonate, lauryl sulfate monoethanolamine, lauryl sulfate Anionic surfactants such as triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, and polyoxyethylene alkyl ether phosphate ester; Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate; Cationic surfactants such as alkyl quaternary ammonium salts and ethylene oxide adducts thereof; Amphoteric surfactants, such as alkyl betaine, such as alkyl dimethylaminoacetic acid betaine, and alkyl imidazoline, are mentioned, These can be used individually or in mixture of 2 or more types.

A dye derivative is a compound which introduced the substituent into the organic pigment. Such organic dyes also include light yellow aromatic polycyclic compounds such as naphthalenes and anthraquinones, which are not generally called dyes. As a dye derivative, Japanese Patent Publication No. 63-305173, Japanese Patent Publication No. 57-15620, Japanese Patent Publication No. 59-40172, Japanese Patent Publication No. 63-17102, Japan What is described in Unexamined-Japanese-Patent No. 5-9469 etc. can be used, These can be used individually or in mixture of 2 or more types.

The coloring composition of this invention can contain a storage stabilizer in order to stabilize the viscosity with time of a composition. Moreover, in order to improve adhesiveness with a transparent substrate, you may contain adhesive improvers, such as a silane coupling agent.

Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butyl pyrocatechol, tetraethylphosphine and tetraphenylphosphine. Organic phosphines, phosphites, etc. are mentioned. A storage stabilizer can be used in the quantity of 0.1-10 weight part with respect to 100 weight part of pigment | dyes in a coloring composition.

As a silane coupling agent, (meth) acrylsilanes, such as vinyl silanes, such as a vinyl tris ((beta) -methoxyethoxy) silane, a vinyl ethoxysilane, and a vinyl trimethoxysilane, and (gamma) -methacryloxypropyl trimethoxysilane. , Β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrie Epoxysilanes, such as (beta)-(3, 4- epoxycyclohexyl) methyltriethoxysilane, (gamma)-glycidoxy propyl trimethoxysilane, (gamma)-glycidoxy propyl triethoxysilane, and N- (beta) -Aminoethyl-γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropyltriethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldiethoxysilane, γ-aminopropyltri Ethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltriethoxysil Amino silanes such as, γ- mercaptopropyltrimethoxysilane, γ- mercaptopropyl the tree, and the like thio silanes such as silane. The silane coupling agent can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight based on 100 parts by weight of the dye in the coloring composition.

The coloring composition of this invention can be prepared as a gravure offset printing ink, anhydrous offset printing ink, silkscreen printing ink, a solvent developing type or an alkali developing type coloring resist material. A solvent developing type or an alkali developing type colored resist material is obtained by dispersing a dye in a composition containing a thermoplastic resin, a thermosetting resin or a photosensitive resin, which is a dye carrier, a monomer, a photopolymerization initiator, and an organic solvent.

The coloring composition of the present invention is a coarse particle of 5 μm or more, preferably coarse particle of 1 μm or more, more preferably 0.5 μm or more of coarse particles by means of centrifugation, a sintering filter, a membrane filter, or the like. And it is preferable to remove the mixed dust.

In addition, the coloring composition of this invention adjusts so that the viscosity in 25 degreeC measured at the rotation speed of 20 rpm using an E-type viscometer may be 6 mPa * s or less, in order to obtain a uniform coating film without generating a coating unevenness. It is preferable to adjust so that it may become 2 mPa * s or more and 6 mPa * s or less.

Next, the manufacturing method of the color filter using the coloring composition of this invention is demonstrated.

The color filter of the present invention includes a filter segment and / or a black matrix on a substrate, and may include, for example, a black matrix and filter segments of red, green, and blue. The filter segment and / or black matrix is formed on a substrate by applying the coloring composition of the present invention by a die coating method.

Application | coating of the coloring composition by a die-coating system can be performed using a well-known die coater, and what is necessary is just to select suitably the coating conditions at that time according to the composition of a coloring composition, the kind of color filter to manufacture, etc. For example, it is preferable that the lip width of a nozzle tip is 50-500 micrometers, and the space | interval of a nozzle tip and a board | substrate surface shall be 30-300 micrometers. In order to adjust the coating film thickness, what is necessary is just to adjust a lip running speed and the amount of extraction | drawing from a lip.

As a substrate of a color filter, glass plates, such as soda-lime glass, low alkali borosilicate glass, and alkali-free alumino borosilicate glass which have high transmittance | permeability with respect to visible light, and resin plates, such as polycarbonate, polymethyl methacrylate, and a polyethylene terephthalate, are used. . Moreover, the transparent electrode which consists of indium oxide, a tin oxide, etc. may be formed in the surface of a glass plate or a resin plate for liquid crystal drive after panelization.

Formation of each color filter segment and black matrix by the photolithography method is performed by the following method. That is, the coloring composition of this invention prepared as a solvent developing type or an alkali developing type coloring resist material is apply | coated on a board | substrate so that a dry film thickness may be set to 0.2-10 micrometers using the coating apparatus of a die-coating system. The film dried as needed is subjected to ultraviolet exposure through a mask having a predetermined pattern formed in contact or non-contact state with the film. Thereafter, the developer is sprayed with a solvent or an alkaline developer, or sprayed with a spray or the like to remove the uncured portion to form a desired pattern, and the same operation is repeated for the required color to form each color filter segment and a black matrix. Can be. Moreover, in order to accelerate superposition | polymerization of a coloring resist material, you may heat as needed. According to the photolithography method, a color filter with higher precision than the printing method can be manufactured.

It is preferable that the dry film thickness of a filter segment and a black matrix is 0.2-10 micrometers, More preferably, it is 0.2-5 micrometers. When drying a coating film, you may use a pressure reduction dryer, a convection oven, an IR oven, a hotplate, etc.

At the time of image development, aqueous solution, such as sodium carbonate and sodium hydroxide, is used as alkaline developing solution, Organic alkali, such as dimethylbenzylamine and triethanolamine, can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.

As the developing treatment method, a shower developing method, a spray developing method, a dip (immersion) developing method, a paddle (liquid stacking) developing method, or the like can be applied.

On the other hand, in order to increase the ultraviolet exposure sensitivity, after coating and drying the colored resist material, a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film to prevent polymerization inhibition by oxygen. After that, ultraviolet light exposure may be performed.

Since the change rate of the dynamic surface tension in 100 ms and the dynamic surface tension in 1000 ms is 7.0% or less, since the coloring composition of this invention has no horn in a board | substrate outer peripheral part, the difference in the film thickness of a board | substrate outer peripheral part and a board | substrate center part is different. It is possible to form a small, uniform coating film with no coating unevenness.

Therefore, by forming a filter segment and / or a black matrix using the coloring composition of this invention, it becomes possible to manufacture a color filter with high yield.

<Examples>

Although an Example demonstrates this invention more concretely below, this invention is not limited to a following example, unless the summary is exceeded.

In addition, in an Example and a comparative example, "part" and "%" mean "weight part" and "weight%", respectively.

First, preparation of the acrylic resin solution used by the Example and the comparative example is demonstrated. The molecular weight of resin is the weight average molecular weight of polystyrene conversion measured by GPC (Gel Permeation Chromatography).

(Preparation of acrylic resin solution)

370 parts of cyclohexanone were put into the reaction container, heated to 80 degreeC, injecting nitrogen gas into the container, and the mixture of the following monomers and a thermogravimetric initiator was dripped over 1 hour at the same temperature, and polymerization reaction was performed.

Methacrylic acid 20.0 parts

Methyl methacrylate 10.0 parts

Butyl methacrylate 55.0 parts

2-hydroxyethyl methacrylate 15.0 parts

Azobisisobutylonitrile 4.0 parts

After dripping and further reacting at 100 degreeC for 3 hours, the thing which melt | dissolved 1.0 part of azobisisobutyronitrile in 50 parts of cyclohexanone was added, and also the reaction was continued at 100 degreeC for 1 hour, and the solution of acrylic resin was obtained. The weight average molecular weight of the acrylic resin was about 40000.

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, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20%. It prepared.

Example 1

After the mixture of the following composition was stirred and mixed uniformly, it disperse | distributed with the sand mill for 5 hours using the glass beads of diameter 1mm, and it filtered with the filter of 5 micrometers, and produced the copper phthalocyanine dispersion.

ε-type copper phthalocyanine pigment (C.I. Pigment Blue 15: 6) 12.0 parts

(BASF "Heriogen Blue L-6700F")

Dispersing agent (Gensol Corp. "Sol Spas 20000") 2.4 parts

Acrylic resin solution 28.1 parts

57.5 parts cyclohexanone

Subsequently, the mixture of the following composition was stirred and mixed so that it might become uniform, and it filtered with the 1 micrometer filter and obtained the coloring composition adjusted as a blue resist material. The composition (weight ratio which made the coloring composition whole quantity 100) 100 weights with respect to 100 weight part of pigments in a coloring composition of a coloring composition is shown in Table 1.

Copper phthalocyanine dispersion 45.0 parts

12.5 parts acrylic resin solution

Trimethylolpropane triacrylate 4.8 parts

("NK ester ATMPT" from Shinnakamura Kagaku Corporation)

Photopolymerization initiator ("Irucure 907" from Chiba, Specialty, Chemicals)

Part 2.5

0.2 parts of sensitizers ("EAB-F" manufactured by Hodogaya Kagaku Corporation)

Of silicone-based leveling agent (BIC Chem Corporation "BYK-330)

1.0% 2% ethylene glycol monoethyl ether acetate dilution solution)

Cyclohexanone 34.0 parts

[Examples 2 to 7 and Comparative Example 1]

The composition of a pigment, a dispersing agent, an acrylic resin, a monomer, a photoinitiator, a sensitizer, a solvent, and a leveling agent was changed to the ratio shown in Table 1 (weight ratio of the coloring composition whole quantity 100 to the weight with respect to 100 weight part of pigments). A coloring composition adjusted in the same manner as in Example 1 except for each color resist material was obtained.

On the other hand, the transmittance | permeability of the visible light region (400-700 nm) of the pigment carrier used by the Example and the comparative example was 95% or more.

Blue pigment: 5.40 parts of ε-type copper phthalocyanine pigment (C.I. Pigment Blue 15: 6)

             (BASF "Heriogen Blue L-6700F")

Pigment for red: diketopyrrolopyrrole pigment (C.I. Pigment Red 254) 5.08 parts

             (Ilgafored B-CF, manufactured by Chiba, Specialty, and Chemicals)

             0.82 parts of anthraquinone pigment (C.I.Pigment Red 177)

             (Chiva, Specialty and Chemicals, Inc. "Chromophthaled A2B")

             0.20 part of anthraquinone pigment (C.I.Pigment Yellow 199)

             (Chiva, Specialty, Chemicals, Inc. "Chromophthal Yellow GT-AD")

                                                           6.10 total

Green pigments: halogenated copper phthalocyanine pigments (C.I. Pigment Green 36)

             (Toyo Inkisei Research Product "Rionol Green 6YK")

             2.35 parts of monoazo pigment (C.I.Pigment Yellow 150)

             (Fanchon Fast Yellow, manufactured by Bayer, Inc.)

              Y-5688 ")

                                                           5.60 copies in total

Black Pigment: Carbon Black

           ("Tex" "Printex 75") 5.50

Dispersant: "Senpass 20000" from Geneca

Monomer: Trimethylolpropane triacrylate ("NK ester ATMPT" manufactured by Shin-Nakamura Kagaku Corporation)

Photopolymerization initiator: "Irucure 907" from Chiba Specialty Chemicals

Sensitizer: Hodogaya Kagaku Corporation "EAB-F"

Silicone Leveling Agent A: Dilution solution of 2% ethylene glycol monoethyl ether acetate from Vicchemy's "BYK-330"

Silicone leveling agent B: 1% cyclohexanone dilution solution of BYK-323 manufactured by BIC Chem.

Silicone leveling agent C: 1% cyclohexanone dilution solution of BYK-333 manufactured by BIC Chem Corporation

Silicone leveling agent D: 1% cyclohexanone dilution solution of BYK-320 manufactured by BIC Chem.

Fluorine leveling agent E: "BL-20" 5% ethylene glycol monoethyl ether acetate dilution solution from Dainippon Inky Kagaku Kogyo Co., Ltd.

The dynamic surface tension (I) at 100 ms and the dynamic surface tension (II) at 1000 ms of each of the color resist materials obtained in Examples 1 to 7 and Comparative Example 1 were measured by a dynamic surface tension meter (Crus Corporation). The value of [{(I)-(II)} / (I)] × 100 was calculated. In addition, the viscosity at 25 degrees C of each obtained color resist material was measured at the rotation speed of 20 rpm using the E-type viscosity meter (the Tokimek company). Moreover, each obtained color resist material is apply | coated so that average film thickness may be set to 2.0 micrometers on the glass substrate of 360 mm x 465 mm size as shown in FIG. 2 using the coating apparatus of the die-coating system shown in FIG. The board | substrate was pre-baked at 70 degreeC for 20 minutes, and the dry coating film was obtained. The film thickness was measured at 5 mm intervals from the center of the short side of the obtained dry coating film to 10 cm in the coating direction. The maximum film thickness at that time is called T _max , the minimum film thickness is T _min , and the average film thickness is called T _avg . Uniformity U (Uniformity) of the film thickness is evaluated by following formula (3) as less than 1% A, 1% or more and less than 2%, B, 2% or more and less than 5% as C, 5% or more as D Was performed.

U [%] = (T _max -T _min ) / (T _avg × 2)... (3)

Moreover, application | coating spot | dye evaluation was performed with the white transmitted light about the said coating board | substrate. A case where there was no coating stain and visual observation was visually observed by eye, and a case where coating stain was slightly observed was B, and a case where coating stain was certainly observed was C. Table 2 shows the results of film thickness uniformity and coating unevenness.

1 or 2, 1 is an application head, 2 is a front lip, 3 is a rear lip, 4 is a manifold, 5 is a slit, 6 is a pipe, 7 a valve, 8 a metering pump, 9 a filter, 10 The silver coating liquid tank, 11 is a coating film, 12 is a coating substrate, and 13 is a conveyance stage.

The coating film formed using the resist material of Examples 1-7, especially the coating film formed using the resist material of Examples 1-4 containing the silicone type leveling agent represented by said Formula (2), is a film of a board | substrate end surface part and a board | substrate center part. The thickness difference was small and it was a uniform coating film. On the other hand, the coating film formed using the resist material of Comparative Example 1 had a large difference in film thickness between the substrate end surface portion and the substrate central portion.

Moreover, although the coating unevenness was not seen in the coating film formed using the resist material of Examples 1-7, the coating unevenness was observed in the coating film formed using the resist material of Comparative Example 1.

The resist material obtained in Examples 1-7 was apply | coated on the glass substrate of 360 mmx465 mm size by the die-coating method, and the color filter was manufactured by the photolithographic method shown above. It was possible to obtain a color filter having no horns and no coating unevenness on the outer periphery of the substrate.

According to the present invention, even when used for forming a coating film by the die coating method, it is difficult to produce a difference in the film thickness of the coating film on the outer peripheral portion of the substrate, and a coloring composition capable of forming a coating film having excellent surface smoothness can be provided.

Further, according to the present invention, it is possible to provide a color filter having a filter segment and / or a black matrix having a small difference in film thickness at the central portion and the outer peripheral portion and excellent in surface smoothness.

In addition, according to the present invention, it is possible to provide a method for producing a color filter having a filter segment and / or a black matrix having a small film thickness difference at the central portion and an outer peripheral portion, and having excellent surface smoothness.

Claims (7)

A coloring composition comprising a transparent resin, a precursor thereof or a mixture thereof, a dye, an organic solvent, and a leveling agent, wherein the dynamic surface tension (I) at 100 ms of the coloring composition and the dynamic at 1000 ms are included. Surface tension (II) satisfies the following relation (1), The leveling agent is a silicone-based leveling agent, characterized in that. [{(I) − (II)} / (I)] × 100 ≦ 7.0... (One) delete The coloring composition according to claim 1, wherein the silicone leveling agent is a compound represented by the following formula (2).

(In formula, m is an integer of 5-30, n is an integer of 50-100, and x is an integer of 1-20.) The viscosity in 25 degreeC is 6 mPa * s or less, The coloring composition of Claim 1 or 3 characterized by the above-mentioned. The color filter provided with the filter segment and / or black matrix formed from the coloring composition of Claim 1 or 3. A method for producing a color filter having a black matrix and / or a filter segment, wherein the coloring composition according to claim 1 or 3 is coated on a substrate by a die coating method to form a filter segment and / or a black matrix. The manufacturing method of the color filter characterized by the above-mentioned. The coloring composition of Claim 1 or 3 used for manufacture of the color filter by a die-coating system.

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