JP2003064293A - Pigment-dispersed composition for color filter, pigment- dispersed resist and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide both of a pigment-dispersed composition for a color filter and a pigment-dispersed resist for a color filter that are superior in transparency, developing, heat resistance, light resistance and preservation stability, and a color filter using the pigment dispersing resist. SOLUTION: The pigment-dispersed composition for the color filter containing the pigment, a coupling agent, an acrylic copolymer having N,N-di-substitution amino group and acidic group and a solvent, the pigment-dispersed resist for the color filter containing the pigment-dispersed composition for the color filter and the color filter having a cured-film layer of the pigment dispersing resist for the color filter on a substrate, are provided.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a pigment dispersion composition for a color filter, a pigment dispersion resist for a color filter, and a color filter having a cured coating layer of the pigment dispersion resist for a color filter on a substrate.

[0002]

2. Description of the Related Art A color filter is a substrate on which a mesh-shaped light-shielding thin film layer called a black matrix is provided.
In the transmissive type, the three primary colors of red, green, and blue light are selectively transmitted, and in the reflective type, the three primary colors of cyan, magenta, and yellow are selectively reflected, A colored cured coating film layer corresponding to each color is formed in each mesh of the black matrix, and the mesh of each color is regularly arranged. Hereinafter, the "mesh" of the black matrix is referred to as "pixel".
Say. The color filter is a color solid-state image sensor,
It is used for color displays such as liquid crystal color displays and color CRTs. In recent years, with the increase in size of color liquid crystal display panels and diversification of applications, color filters are required to have improved reliability such as color reproducibility, heat resistance, light resistance, and chemical resistance. .

In order to meet this demand, the "dying method" in which a dye is used as a colorant was the mainstream in the manufacturing method of a color filter, but recently, heat resistance,
The "pigment dispersion method", which uses pigments with excellent light resistance and chemical resistance, has become the mainstream. Furthermore, a pigment dispersion composition in which a pigment is dispersed using a dispersant in a binder resin, a photopolymerizable monomer, a pigment dispersion resist added with a photopolymerization initiator is applied on a substrate and dried, and a photomask Generally, a photolithography method is widely used, in which a cured coating film layer of a pigment-dispersed resist is formed in a pixel portion by performing development and heat curing treatment after exposure through the through.

JP-A-7-196969 discloses an ink composition for a color filter containing a mixed resin composed of a polyester resin and a melamine resin and a coupling agent, and JP-A-10-268128 discloses a dispersion aid. As an example, a light-shielding coating composition for a color filter using a coupling agent is described. However, the composition of the color filter ink composition and the color filter light-shielding coating composition has a problem that sufficient transparency cannot be obtained. However, since the latter is a light-shielding coating composition for a color filter, there is no problem as long as it is used for a black matrix that does not require transparency.

[0005]

The problems to be solved by the present invention are excellent in transparency, developability, heat resistance and light resistance,
Another object of the present invention is to provide a pigment dispersion composition for a color filter and a pigment dispersion resist for a color filter which are excellent in storage stability, and further to provide a color filter using the pigment dispersion resist.

[0006]

The present inventors have developed a pigment for a color filter containing an acrylic copolymer containing an N, N-disubstituted amino group and an acidic group as a coupling agent and a dispersant. The dispersion composition is excellent in storage stability, the pigment dispersion resist for color filters to which it is added is excellent in storage stability and developability, and a color filter prepared by a photolithography method using the pigment dispersion resist is , And was found to be excellent in transparency, heat resistance, and light resistance.

That is, the present invention provides a pigment dispersion for a color filter containing a pigment, a coupling agent, an acrylic copolymer containing an N, N-disubstituted amino group and an acidic group in a main chain or a side chain, and a solvent. Provided is a composition and a pigment dispersion resist for a color filter containing the pigment dispersion composition for a color filter, and further a color filter having a cured coating layer of the pigment dispersion resist for a color filter on a substrate. To do.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below. Unless otherwise specified, the "pigment dispersion composition for color filter" and the "pigment dispersion resist for color filter" are simply referred to as "pigment dispersion composition". And “pigment-dispersed resist”.

The pigments used in the present invention include commercially available pigments conventionally used for color filters and “Color Index Handbook” (Latest Pigment Handbook edited by Japan Pigment Technology Association, published in 1977) “Latest Pigment Application Technology”.
(CMC Publishing, 1986) "Printing ink technology" (C
Known publicly known pigments described in MC Publishing Co., Ltd., 1984) and the like can be mentioned. Specifically, for example, C.I. I.
Pigment Red 254, C.I. I. Pigment Red 1
77, C.I. I. Pigment Orange 71 and the like; C.I. I. Pigment Green 36, C.I. I. Pigment Green 7 and other green pigments; C.I. I. Pigment Blue 15: 6, C.I. I. Pigment Blue 22 and other blue pigments; C.I. I. Pigment Violet 23,
C. I. Pigment Violet 50 and the like; C.I. I. Pigment Yellow 138, C.I. I.
Pigment Yellow 20 and other yellow pigments; C.I. I.
Pigment Black 7 and black pigments such as carbon black.

These pigments may be used alone or in combination of two or more. The pigment content in the pigment dispersion composition is preferably 10 to 30% by mass. It is generally known that many yellow pigments are inferior in transparency, but C.I.
I. When Pigment Yellow 138 is used, high transparency is obtained. When a black pigment is used in the pigment dispersion composition for a color filter or the pigment dispersion resist for a color filter of the present invention, it can also be used for producing a black matrix.

In general, the transparency of the cured coating film of the pigment-dispersed resist increases as the particle size of the pigment contained therein decreases.
The primary particle size of the pigment used in the present invention is 10 to 8
It is preferably in the range of 0 nm, more preferably in the range of 30 to 50 nm. When the primary particle size is less than 10 nm,
It is difficult to disperse the pigment due to its high cohesiveness.
If it exceeds, the transparency will decrease. As a method of reducing the primary particle diameter of the pigment, a high-speed impact pulverization method such as jet pulverization, a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent that does not dissolve the water-soluble inorganic salt are mechanically kneaded in a kneader or the like. Salt milling method is available.

In the present invention, the coupling agent added to the pigment dispersion composition adheres to the surface of the pigment particles by the action of chemical bond, hydrogen bond, physical adsorption, etc., and enhances the affinity between the pigment and the dispersant, thereby increasing Dispersion is enabled, and at the same time, when a color filter is produced using a pigment dispersion resist containing the pigment dispersion composition, an effect of enhancing the adhesion between the substrate and the cured coating layer of the pigment dispersion resist is exhibited. To do.

Typical coupling agents include silane-based, titanium-based, and aluminum-based coupling agents. Specifically, for example, as the silane coupling agent, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N-β-aminoethyl-
γ-aminopropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) -ethyltrimethoxysilane, γ
Examples thereof include mercaptopropyltrimethoxysilane and vinyltriacetoxysilane.

As the titanium coupling agent, tetra-
i-propoxy titanium, tetra-n-butoxy titanium,
Examples thereof include tetrakis- (2-ethylhexoxy) -titanium.

Aluminum coupling agents include aluminum isopropylate, mono-sec butoxyaluminum diisopropylate, aluminum-sec.
Butyrate and the like can be mentioned.

Among these, N-β- (aminoethyl) -γ-aminopropyltris which has little deterioration in storage stability of the pigment dispersion composition and the pigment dispersion resist and the transparency of the pigment dispersion resist cured coating film layer is small. Methoxysilane,
It is preferable to use a silane coupling agent having an amino group such as N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane. These coupling agents may be used alone or in combination of two or more.

The amount of the coupling agent added to the pigment dispersion composition is preferably in the range of 0.1 to 30 parts by mass, and particularly preferably in the range of 10 to 20 parts by mass, per 100 parts by mass of the pigment. When the compounding amount of the coupling agent is less than 0.1 parts by mass, sufficient pigment dispersibility cannot be obtained, it is difficult to obtain high transparency of the pigment-dispersed resist layer, and the adhesion between the cured coating layer and the substrate is low. Is also difficult to obtain. Further, if it exceeds 30 parts by mass, the storage stability of the pigment dispersion composition and the pigment dispersion resist is lowered.

The acrylic copolymer having an N, N-disubstituted amino group and an acidic group in the main chain or side chain used as a dispersant in the present invention is, for example, a (meth) acrylic monomer. And a monomer having an N, N-disubstituted amino group and an ethylenic double bond in one molecule, and a monomer having an acidic group and an ethylenic double bond in one molecule can get.

Examples of (meth) acrylic monomers include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and β-hydroxyethyl (meth) acrylate. And known (meth) acrylic acid esters such as benzyl (meth) acrylate. Examples of the monomer having an N, N-disubstituted amino group and an ethylenic double bond in one molecule include dimethylaminoethyl (meth) acrylate, diethylaminopropyl (meth) acrylate and dimethylaminoethyl vinyl ether. To be Examples of the monomer having an acidic group and an ethylenic double bond in one molecule include (meth) acrylic acid, p-styrenesulfonic acid, p-styrenecarboxylic acid, p-hydroxystyrene, mono (2-
(Meth) acryloyloxyethyl) phosphate, di (2- (meth) acryloyloxyethyl) phosphate, tri (2- (meth) acryloyloxyethyl) phosphate and the like can be mentioned. Above all, it is preferable to use a monomer having a carboxyl group or a phenolic hydroxyl group.

Used as a dispersant in the present invention,
The acrylic copolymer having an N, N-disubstituted amino group and an acidic group preferably has an acid value in the range of 30 to 75 and an amine value in the range of 20 to 60.

When the acid value is less than 30, the alkali developability decreases when a color filter is prepared by the photolithography method, and when it exceeds 75, sufficient dispersibility of the pigment cannot be obtained and transparency deteriorates. If the amine value of the dispersant is less than 20, it tends to be difficult to obtain sufficient dispersibility of the pigment and the transparency tends to decrease, and if it exceeds 60, the storage stability of the pigment dispersion composition and the pigment dispersion resist decreases. To do.

Commercially available products of the dispersant usable in the present invention include "BYK-140" and "BY" manufactured by BYK Chemie.
K-2001 ”and the like. The content of the dispersant in the pigment dispersion composition is preferably 10 to 70 parts by mass, and more preferably 40 to 55 parts by mass, per 100 parts by mass of the pigment. When the blending amount of the dispersant is less than 10 parts by mass, sufficient pigment dispersibility cannot be obtained and it is difficult to obtain high transparency. On the other hand, when the amount exceeds 70 parts by mass, the alkali developability is deteriorated when the pixel pattern of the color filter is formed by the photolithography method. In the pigment dispersion composition of the present invention, an acrylic copolymer having an N, N-disubstituted amino group and an acidic group is an essential component, but other resin may be added if necessary.

As the solvent used in the pigment dispersion composition of the present invention, those capable of dissolving the above-mentioned dispersant and the resin used in the pigment dispersion resist and stably dispersing the pigment are preferable. Specific examples of such a solvent include:
For example, acetic acid ester solvents such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate, propionate solvents such as ethoxypropionate, aromatic solvents such as toluene, xylene and methoxybenzene, butyl cellosolve and propylene glycol monomethyl ether. , Ether solvents such as diethylene glycol ethyl ether and diethylene glycol dimethyl ether, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, aliphatic hydrocarbon solvents such as hexane, N, N-dimethylformamide, γ-butyrolactam, N-methyl -2-pyrrolidone, aniline, pyridine and other nitrogen compound solvents, γ-butyrolactone and other lactone solvents, Examples thereof include carbamic acid ester. These solvents may be used alone or in combination of two or more.

The above pigment, dispersant, and solvent are mixed to prepare a pigment dispersion composition. Usually, it is difficult to disperse the pigment in the liquid as primary particles, and some aggregate to form secondary particles. Therefore, when the pigment is dispersed in the liquid, it is desirable that the particle size of the secondary particles be as close as possible to the primary particle size. In order to adjust the particle size of the pigment to a desired range, it is effective to disperse the pigment using a ball mill, a sand mill, a bead mill, a three roll mill, a paint conditioner, an attritor, a dispersion stirrer, an ultrasonic wave or the like. .

The pigment-dispersed resist for a color filter of the present invention contains a pigment-dispersed composition, an alkali-soluble binder resin having an acidic group, a photocurable composition, and a solvent, to which an additive is added, if necessary. It is a thing.

The alkali-soluble binder resin having an acidic group is obtained by polymerizing a monomer having an acidic group and an ethylenic double bond in one molecule, and a typical example thereof is (meth) acrylic. The copolymer of an acid and a (meth) acrylic acid ester is mentioned. As the monomer for copolymerization, another monomer copolymerizable with the monomer having an acidic group and an ethylenic double bond in one molecule may be used in combination.

As the monomer having an acidic group and an ethylenic double bond in one molecule, in addition to the above (meth) acrylic acid, p-styrenecarboxylic acid, p-styrenesulfonic acid, p-hydroxystyrene, Maleic anhydride, 2-
(Meth) acryloyloxyethyl phosphate and the like can be mentioned. Above all, it is preferable to use a monomer having a carboxyl group or a phenolic hydroxyl group.

Examples of the (meth) acrylic acid ester include methyl (meth) acrylate and ethyl (meth).
Known monomers such as acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, β-hydroxyethyl (meth) acrylate, and benzyl (meth) acrylate can be used. Other copolymerization monomers include styrene, methyl vinyl ether, vinyl acetate, vinyl chloride, N-vinylpyrrolidone, and acrylamide. The acid value of the alkali-soluble binder resin having the acidic group varies depending on the composition of the monomer for copolymerization, but is preferably 50 to 150.

The photocurable composition used in the present invention is a compound having a photopolymerizable or photocurable functional group,
And a photopolymerization initiator. The compound having a photopolymerizable or photocurable functional group is polymerized by irradiation with ultraviolet rays or visible rays, or cured by crosslinking. As a typical example of such a compound, a photocrosslinking resin having a cinnamic acid residue or an azide group in a side chain, radical polymerization by light, or an ionically polymerizable monomer, etc., are all known. Compounds.

Examples of such a monomer include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and 2-ethylhexyl (meth).
In addition to monofunctional monomers such as acrylate and β-hydroxyethyl (meth) acrylate, for example, trimethylolpropane tri (meth) acrylate, trimethylolpropane di (meth) acrylate, neopentyl glycol di (meth) acrylate, Examples thereof include polyfunctional monomers such as pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.

Among these monomers, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate and the like are polyfunctional. Moreover, it is preferable to use the one having low volatility. These monomers may be used alone or in combination of two or more.

The compounding ratio of the compound having a photopolymerizable or photocurable functional group is preferably 25 to 150% by mass with respect to the alkali-soluble binder resin. Even if the compound itself having a photopolymerizable or photocurable functional group is insoluble in alkali, it is mixed with an alkali-soluble binder resin together with the pigment dispersion composition, and a photopolymerization initiator is further added to the pigment dispersion resist. When prepared and used in the photolithography method, the portion of the pigment-dispersed resist coating film irradiated with ultraviolet rays or visible light is photocured and becomes insoluble in an alkali developing solution, but the unirradiated portion is alkaline. It is dissolved and removed in a developing solution and developed. If the compounding ratio of the compound having a photopolymerizable or photocurable functional group is more than 150% by mass with respect to the alkali-soluble binder resin, the developability tends to decrease. Curing tends to be insufficient.

As the photopolymerization initiator, known general photopolymerization initiators can be used. Specifically, for example, benzophenone, 4,4′-bismethylaminobenzophenone,
Benzophenos such as Michler's ketone; xanthone,
Xanthones such as thioxanthone, p-dimethylaminoacetophenone, benzyl-4-dimethylaminobenzoate, 4-bis-trichloromethyl-6, etc.
Examples include-(4-ethoxy) phenyl-S-triazine, 2-amylanthraquinone and β-chloroanthraquinone.

Examples of commercially available photopolymerization initiators include:
"Irgacure-" manufactured by Ciba Specialty Chemicals
184 "," Irgacure-369 "," Darocur-
1173 ", BASF's" Lucirin-TPO ", Nippon Kayaku's" Kayacure DETX "," Kayacure O "
"A", "Vicure 10" manufactured by STAUFER,
"Vicure 55", "Trigonal PI" made by AKUZO, "Sandray 1000" made by Sand Co., APJO
There is "Deep" manufactured by HN.

A known and commonly used photosensitizer may be used in combination with the photopolymerization initiator. Examples of the photosensitizer include amines, ureas, compounds having a sulfur atom, compounds having a phosphorus atom, compounds having a chlorine atom, nitriles and other compounds having a nitrogen atom. These may be used alone or in combination of two or more.

The mixing ratio of the photopolymerization initiator is not particularly limited, but is preferably in the range of 0.1 to 30% by mass with respect to the compound having a photopolymerizable or photocurable functional group. If the amount used is less than 0.1% by mass, the sensitivity tends to decrease, and if it exceeds 30% by mass, when the coating film of the pigment-dispersed resist is dried, crystals of the photopolymerization initiator are precipitated, Physical properties such as strength and transparency of the cured coating film tend to deteriorate.

As the solvent used for the pigment-dispersed resist,
For example, acetic acid ester solvents such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate, propionate solvents such as ethoxypropionate, aromatic solvents such as toluene and xylene, ether solvents such as butyl cellosolve, and methyl ethyl ketone. The ketone-based solvent and the like can be mentioned. These solvents may be used alone or in combination of two or more.

The pigment-dispersed composition and the pigment-dispersed resist may be added to the pigment-dispersed composition, if necessary, within a range not impairing the effects of the present invention.
Known and commonly used additives such as pigment derivatives, dyes, resins, leveling agents, defoaming agents, antioxidants and stabilizers can be added.

The composition of the pigment-dispersed resist is pigments 4-10.
% By mass, 0.6 to 1.5% by mass of coupling agent, 1.0 to 4.0% by mass of an acrylic copolymer having an N, N-disubstituted amino group and an acidic group in the main chain or side chain. Alkali-soluble binder resin 5 to 10% by mass, photocurable composition 5 to 10% by mass, solvent added to make nonvolatile content 20 to 30%
It is preferably in the range of mass%.

Generally, the color filter is manufactured through the following steps. That is, the pigment-dispersed resist is applied to the entire surface of the color filter substrate on which the black matrix is provided, heated and dried (pre-baked), and then irradiated with ultraviolet rays or visible light through a photomask to develop the pixel. A photocurable coating film layer of a pigment-dispersed resist is formed on the area. The same operation is repeated three times for each color to create a color filter having red, green, and blue (or cyan, magenta, and yellow) pixels at predetermined positions. Thereafter, if necessary, the entire color filter may be heat-treated (after-baked) to further heat-cure the photocurable coating film layer of the pigment-dispersed resist. Hereinafter, the method for manufacturing the color filter of the present invention will be described in more detail in the order of steps by taking the above general manufacturing method as an example, but the present invention is not limited thereto.

The method for applying the pigment-dispersed resist on the surface of the color filter substrate is not particularly limited. As a coating method, a known method such as a printing method, a spray method, a roll coating method, a bar coating method, a curtain coating method or a spin coating method can be used.

The drying conditions of the coating film of the pigment-dispersed resist applied to the color filter substrate are usually 50 to 150 ° C. and 1 to 50 ° C., although they vary depending on the kind and mixing ratio of each component.
It is about 15 minutes. This heat treatment is generally called "pre-bake". As the light used for photocuring the pigment-dispersed resist coating, it is preferable to use ultraviolet light or visible light in the wavelength range of 200 to 500 nm. Above all, it is preferable to use ultraviolet rays having a short wavelength and high energy. As the light source of ultraviolet rays or visible light, those widely used in the field of photofabrication can be used. Specifically, for example, a low pressure mercury lamp,
High-pressure mercury lamp, ultra-high-pressure mercury lamp, metal halide lamp, chemical lamp, black light lamp, mercury-
Examples thereof include a xenon lamp, an excimer lamp, a short arc lamp, a helium / cadmium laser, an argon laser, and a THG or FHQ light laser using an Nd-YAG laser. When a laser is used as a light source, a pixel pattern can be directly drawn on the pigment-dispersed resist coating film without using a photomask.
The pigment-dispersed resist of the present invention is not limited to the above light,
Since it also has sensitivity to an electron beam, it is also possible to draw a pixel pattern directly on the pigment-dispersed resist coating film with an electron beam, similar to a laser. In this case, it is not always necessary to add a photopolymerization initiator to the photocurable composition.

As the alkali developing solution used for developing after the pixel pattern is baked by irradiating the coating film of the pigment-dispersed resist with light, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, trimethylammonium hydroxide, etc. Aqueous solution and the like can be used. A suitable amount of a water-soluble organic solvent such as methanol, ethanol and isopropanol, and a surfactant may be added to the alkaline developer.

The developing method includes a puddle method, a dipping method,
Any of a spray method and the like may be used. After development, it is washed with water and dried. The above operation is repeated three times for each color to form a color filter having a photo-curing coating layer of a pigment dispersion resist of red, green and blue (or cyan, magenta and yellow) on the pixel portion at a predetermined position. . The obtained color filter is heated with a heating device such as a hot plate or an oven at 100 to 280 ° C. for a predetermined time (after-baking) to remove volatile components in the coating film, and at the same time, to disperse the pigment dispersion resist. The photo-cured coating film is further cured by heat to complete a color filter having excellent heat resistance and chemical resistance. The color filter of the present invention obtained through the above steps is excellent in transparency, heat resistance, chemical resistance, solvent resistance, and light resistance.

[0045]

EXAMPLES The present invention will be described in more detail below with reference to examples. In addition, "part" and "%" represent "part by mass" and "% by mass", respectively, unless otherwise specified.

<Example 1> A high-speed disperser "TS" manufactured by Igarashi Kikai Seisakusho Co., Ltd., in which zirconia beads having a diameter of 0.5 mm were charged.
G-6H ”has a primary particle size of C.I. I.
Pigment Yellow 138 15 parts, Shin-Etsu Chemical Co., Ltd. aminosilane coupling agent "KBM-602" (N-β
2.3 parts of (aminoethyl) γ-aminopropylmethyldimethoxysilane), 4.5 parts of BYK-2001 acrylic dispersant manufactured by BYK-Chemie, and propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMAc) 78.2. Parts were charged and stirred at 2000 rpm for 8 hours to obtain a yellow pigment dispersion composition (Y-1).

Next, the yellow pigment dispersion composition (Y-1) 1
00 parts, Dainippon Ink and Chemicals Inc. acidic group-containing alkali-soluble binder resin "EXECEDIC Binder LC-295" 17.5 parts, dipentaerythritol hexaacrylate (hereinafter abbreviated as DPHA).
7.0 parts, and 0.3 parts of a photopolymerization initiator "Irgacure # 369" manufactured by Ciba Specialty Chemicals, P
After mixing 78.2 parts of GMAc, the mixture was filtered using a filter having a pore size of 1.0 μm to obtain a yellow pigment-dispersed resist.

<Example 2> In Example 1, "C.
I. Pigment Yellow 138 "instead of 15 parts, C.I. I. A yellow pigment dispersion composition (Y-2) and a yellow pigment dispersion resist were obtained in the same manner as in Example 1 except that 15 parts of Pigment Yellow 150 was used.

<Third Embodiment> In the first embodiment, "KBM"
-602 ", instead of 2.3 parts, γ-methacryloxypropyltrimethoxysilane" KBM-50 "manufactured by Shin-Etsu Chemical Co., Ltd.
3 "5 parts, and in place of 7.0 parts of DPHA, 7.0 parts of pentaerythritol triacrylate (hereinafter abbreviated as PETA) was used in the same manner as in Example 1, except that a yellow pigment dispersion composition (Y -3) and a yellow pigment dispersion resist were obtained.

<Example 4> In Example 1, "CI Pigment Yellow 1" having a primary particle diameter of 35 to 45 nm was used.
38 "instead of 15 parts, the primary particle size is 100 to 120.
nm C. I. Pigment Yellow 138, 15 copies,
A yellow pigment dispersion composition (Y) was prepared in the same manner as in Example 1 except that 4.5 parts of "BYK-140" acrylic dispersant "BYK-140" manufactured by BYK-Chemie was used. -4) and a yellow pigment dispersion resist were obtained.

<Example 5> A high-speed disperser "TS" manufactured by Igarashi Machinery Co., Ltd., in which zirconia beads having a diameter of 0.5 mm were charged.
G-6H ”, C.I. I. Pigment Green 36 to 15
, Shin-Etsu Chemical γ-methacryloxysilane “KBM-5
03 "4.0 parts," BYK-2001 "4.0 parts, PG
78.2 parts of MAc was charged and stirred at 2000 rpm for 8 hours to obtain a green pigment dispersion composition (G-1).

Next, the above green pigment dispersion composition (G-1) 7
0 part, yellow pigment dispersion composition (Y-1) 30 parts, "EXECEDIC Binder LC-295" 17.5 parts, D
PHA 7.0 parts and "Irgacure # 369"
After adding 0.3 parts and 78.2 parts of PGMAc and mixing,
Filtration was performed using a filter having a pore size of 1.0 μm to obtain a green pigment-dispersed resist.

<Example 6> A high-speed disperser "TS" manufactured by Igarashi Kikai Seisakusho Co., Ltd., in which zirconia beads having a diameter of 0.5 mm were charged.
G-6H ”, C.I. I. Pigment Red 254 15
Part, "KBM-602" 3 parts, "BYK-140" part 4.5 parts, PGMAc 78.2 parts, 200 minutes per minute
The red pigment dispersion composition (R-
1) was obtained.

Next, the above red pigment dispersion composition (R-1) 8
0 part, yellow pigment dispersion composition (Y-1) 20 parts, "EXECEDIC Binder LC-295" 17.5 parts, D
PHA 7.0 parts and "Irgacure # 369"
After adding 0.3 parts and 78.2 parts of PGMAc and mixing,
A red pigment-dispersed resist was obtained by filtering with a filter having a pore size of 1.0 μm.

<Comparative Example 1> A high-speed disperser "TS" manufactured by Igarashi Kikai Seisakusho Co., Ltd., in which zirconia beads having a diameter of 0.5 mm were charged.
G-6H ”has a primary particle diameter of C.I. I. Pigment Yellow 138 (15 parts), BYK-2001 "BYK-2001" (4.5 parts) and PGMAc (78.2 parts) were charged, and the mixture was stirred at 2000 rpm for 8 hours to obtain a yellow pigment dispersion composition (Y-5). It was

Next, the above yellow pigment dispersion composition (Y-5) 1
For 00 parts, "Exedic Binder LC-2
95 "17.5 parts, DPHA 7.0 parts, and" Irgacure # 369 "0.3 parts and PGMAc 78.2 parts were added and mixed, and then filtered using a filter having a pore size of 1.0 µm to give a yellow pigment. A dispersed resist was obtained.

<Comparative Example 2> High-speed disperser charged with zirconia beads having a diameter of 0.5 mm "TS TS manufactured by Igarashi Machinery Co., Ltd."
G-6H ”has a primary particle diameter of C.I. I. Pigment Yellow 138 15 parts, Ajinomoto Co. ester-based dispersant "Azisper PB-814" 4.5 parts, PG
A dispersion consisting of 78.2 parts of MAc was charged, and 20 minutes per minute
The yellow pigment dispersion composition (Y-
6) was obtained.

Then, the above yellow pigment dispersion composition (Y-6) 1
For 00 parts, "Exedic Binder LC-2
95 "17.5 parts, DPHA 7.0 parts, and" Irgacure # 369 "0.3 parts and PGMAc 78.2 parts were added and mixed, and then filtered using a filter having a pore size of 1.0 µm to give a yellow pigment. A dispersed resist was obtained.

<Comparative Example 3> A high-speed disperser "TS" manufactured by Igarashi Kikai Seisakusho Co., Ltd. in which zirconia beads having a diameter of 0.5 mm were charged
G-6H ”, C.I. I. Pigment Green 36 to 15
Part, "Azisper PB-814" 4.5 parts, PGMAc
A dispersion liquid consisting of 80.5 parts was charged and stirred at 2000 rpm for 8 hours to obtain a green pigment dispersion composition (G-2).

Next, the green pigment dispersion composition (G-2) 7
0 part, yellow pigment dispersion composition (Y-5) 30 parts, "EXECEDIC Binder LC-295" 17.5 parts, D
PHA 7.0 parts, and "Irgacure # 369"
After adding 0.3 parts and 78.2 parts of PGMAc and mixing,
Filtration was performed using a filter having a pore size of 1.0 μm to obtain a green pigment-dispersed resist.

<Comparative Example 4> In Comparative Example 3, "C.
I. Pigment Green 36 "instead of 15 parts,
Comparative Example 3 except that 15 parts of "CI Pigment Red 254" and 30 parts of the yellow pigment dispersion composition (Y-5) were used instead of 30 parts of the yellow pigment dispersion composition (Y-6). Similarly, a red pigment dispersion composition (R-2) and a red pigment dispersion resist were obtained.

The following tests were conducted on the pigment dispersion compositions and the pigment dispersion resists obtained in the above Examples and Comparative Examples, and the results and evaluations thereof are shown in Tables 1 to 3. <Preparation of test sample> After the color pigment dispersion resist was dropped on a glass plate and spin coated at 1000 rpm for 9 seconds using a spin coater, preliminary drying was performed at 60 ° C for 5 minutes and prebaking was performed to obtain a film thickness. A 1.5 μm pigment-dispersed resist coating was formed. The coating film was irradiated with light of 0.1 J / cm ² through a color filter photomask using a high pressure mercury lamp to obtain a cured coating film of a pigment-dispersed resist. Then, stock solution of alkaline developer "ID19A1" manufactured by AITES
(Tetramethylammonium hydroxide type) was diluted 30 times with pure water, and an alkaline developer having a pH of 10.8 was used.
The temperature was maintained at 0 ° C., and the test sample after light irradiation was immersed in this to elute the pigment-dispersed resist coating film in the unexposed area and developed. It was washed with pure water until the washing liquid became neutral and air dried. The test sample was heated at 280 ° C. for 30 minutes and post-baked to obtain “development” of the pigment-dispersed resist, “transparency” and “heat resistance” of the pigment-dispersed resist cured coating layer formed on the color filter pixel portion. , A test sample for evaluating the “light resistance”.

<Pigment Dispersibility Test of Pigment Dispersion Composition> LE
Made by EDS & NORTHRUP "MicrotracU
PA "was used to measure the 50% average particle size of the pigment dispersed in the pigment dispersion composition.

<Storage Stability Test of Pigment Dispersion Composition and Pigment Dispersion Resist> The initial viscosity of the pigment dispersion composition and the pigment dispersion resist was measured with an E-type viscometer manufactured by Tokimec. Separately, 25 g of each of the pigment dispersion composition and the pigment dispersion resist is sealed in a glass container in a sealed state.
After standing still at 0 ° C. for 24 hours, the viscosity was measured by the same method as above. For each sample, the change rate of the viscosity after standing for 24 hours at 40 ° C. with respect to the initial viscosity was calculated. Those with a viscosity change rate of less than 10% were evaluated as “◯”, and those with a viscosity change rate of 10% or more were evaluated as “x”.

<Transparency Test of Pigment Dispersion Resist Cured Coating Film> The post-baking pigment dispersion resist cured coating film layer of the test sample was measured using an Olympus spectroscopic spectrophotometer “OSP-SP-200”. Colorimetric, transparency (Y
Value) and chromaticity (x, y values) in the CIE color system.

<Development Test of Pigment-Dispersed Resist Coating Film> The pixel pattern of the post-baked pigment-dispersed resist cured coating layer of the test sample and the pixel pattern of the photomask were visually observed using a microscope. For comparison, the pattern reproducibility was evaluated as “⊚”, the good pattern was evaluated as “◯”, and the bad pattern was evaluated as “x”.

<Heat Resistance Test of Pigment-Dispersed Resist Cured Coating Film> Regarding the pigment-dispersed resist cured coating film layer before and after post-baking of the test sample, a microscopic spectrophotometer “OSP-SP-200” manufactured by Olympus Corporation was used. Was used to calculate the amount of change in transparency (Y value) ΔY due to post-baking. A having a ΔY of less than 0.3 is “◎”, 0.3 to
Less than 0.5 "○", more than 0.5 "x"
It was evaluated.

<Light resistance test> A post-baking pigment-dispersed resist cured coating layer of a test sample and a xenon fade meter "WEL-25AX-" manufactured by Suga Test Instruments Co., Ltd.
The cured coating layer after light irradiation with "HC-B-EL" for 300 hours is made by Olympus "OS"
P-SP-200 "was used for color measurement, and the color difference ΔEab ^* was calculated. Those having ΔEab ^* of less than 2 were evaluated as “⊚”, those of less than 2 to 3 were evaluated as “◯”, and those of 3 or more were evaluated as “x”.

[0069]

[Table 1]

[0070]

[Table 2]

[0071]

[Table 3]

From the results shown in Tables 1 to 3, the pigment dispersion composition for a color filter of the present invention has good pigment dispersibility and excellent storage stability. The pigment dispersion resist for color filters of the invention is
It is clear that the developability in the photolithography method is excellent, and the pixel of the color filter formed by using the pigment-dispersed resist is also excellent in transparency, heat resistance, and light resistance.

[0073]

The pigment dispersion composition for a color filter of the present invention comprises a pigment, a coupling agent, N in the main chain or side chains,
By containing an acrylic copolymer having an N-disubstituted amino group and an acidic group, and a solvent, the following effects are exhibited. That is, in the pigment dispersion composition, the dispersibility of the pigment is good and the storage stability is excellent. The pigment-dispersed resist for color filters of the present invention containing the pigment-dispersed composition for color filters has excellent developability in the process of forming a pixel pattern of a color filter by a photolithography method. Furthermore, the pigment-dispersed resist for a color filter is used, and the pigment-dispersed resist cured coating layer formed on the color filter pixel portion by a photolithography method has, among others, transparency, heat resistance, chemical resistance, solvent resistance, and Has excellent light resistance.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G03F 7/004 505 G03F 7/004 505 // C08L 33:00 C08L 33:00 (72) Inventor Masaaki Kishimoto 3-7-19 Ayukawa, Ibaraki-shi, Osaka (reference) 2H025 AB13 AC01 AD01 BC13 BC42 CA00 CB13 CB14 CB42 CC12 CC20 2H048 BA45 BA47 BA48 4F070 AA32 AC31 AC54 AE04 AE22 FA05 FB03 A05 CB06 FC02 4J037 CB03 A05A29A29A2902 DD11 DD23 EE28 FF03 FF13 FF22 FF23 4J038 CG141 CG142 CH201 CH202 FA121 FA122 GA06 GA09 GA14 JA23 JC35 KA03 KA06 KA08 PA17

Claims (6)

[Claims] 1. A pigment for a color filter comprising a pigment, a coupling agent, an acrylic copolymer having an N, N-disubstituted amino group and an acidic group in a main chain or a side chain, and a solvent. Dispersion composition. 2. The primary particle size of the pigment is 10 to 80 nm.
The pigment dispersion composition for a color filter according to claim 1, which is in the range of 1. 3. The pigment is C.I. I. Pigment Yellow 138, The pigment dispersion composition for a color filter according to claim 1. 4. The pigment dispersion composition for a color filter according to claim 1, wherein the coupling agent is an aminosilane coupling agent. 5. A pigment-dispersed resist for color filters, which comprises the pigment-dispersed composition for color filters according to claim 1. 6. A color filter comprising a cured coating film layer of the pigment-dispersed resist for a color filter according to claim 5 on a substrate.