JP2003238838A - Resist composition with dispersed red-line pigment for color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resist composition with a dispersed red-line pigment for a color filter having very high transmittance and lightness, and giving good pigment dispersibility. <P>SOLUTION: This resist composition with the dispersed red-line pigment for the color filter comprises at least one kind of an anthraquinone derivative, a red pigment, a toning pigment, a monomer containing one or more photopolymerizable unsaturated bonds in the molecule, a photoinitiator and a solvent, or further a resin. The red pigment is salt-milling treated C.I.Pigment Red 207 and/or salt-milling treated C.I.Pigment Red 209. The toning pigment is an orange pigment of C.I.Pigment Orange 43 and/or C.I.Pigment Orange 71. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a red pigment-dispersed resist composition for color filters. More specifically, the present invention relates to a red pigment-dispersed resist composition for a color filter mainly used for manufacturing an optical color filter used for a reflective color liquid crystal display.

[0002]

2. Description of the Related Art A color filter is made of a transparent substrate such as glass having two or more kinds of fine bands (stripe) of different hues arranged in parallel on the surface thereof, or a fine pixel arranged vertically and horizontally. Has become. Pixel size is number 1
It has a minute shape of 0 to several 100 μm and is arranged in order in a predetermined order for each hue. Therefore, various methods have been proposed for manufacturing color filters.

Since a color filter is required to have high transparency, conventionally, a photolithographic method has been carried out by adding a photosensitizer such as dichromic acid to an aqueous solution of a dyeable natural polymer such as gelatin or casein to sensitize it. It is manufactured by using a so-called dyeing method, in which a pixel pattern is formed by using the above method, and the process of dyeing the pixel pattern with a desired color to obtain a color pattern is repeated three times to form a transparent colored fine pattern of three colors. It was

In recent years, with the increase in size of color liquid crystal display panels and the diversification of applications, there has been a demand for improvement in reliability such as heat resistance and light resistance. In response to this demand, as a color material for forming a color filter, an organic pigment having excellent heat resistance and light resistance has come to be used instead of a dye having excellent color characteristics but limited heat resistance and light resistance.

In the case of using an organic pigment as a color material for a color filter, the demand for higher transmittance of visible light and higher contrast for color liquid crystal display devices has been increasing in recent years, and the pigment particles have been miniaturized. Since the diameter needs to be at least less than or equal to the wavelength of visible light, the specific surface area of the pigment particles becomes larger than usual, and therefore the initial pigment dispersibility of the pigment dispersion for color filters and the dispersion stability over time are insufficient. Have the problem of being.

In red organic pigments, high transmittance,
From the point of being able to obtain high contrast, dianthraninonyl pigments, diketopyrrolopyrrole pigments, condensed azo pigments, isoindoline pigments, perinone pigments, quinacridone pigments, dibromoanthanthrone pigments, benzimidarone pigments Although it is desirable to use pigments, these pigments are difficult to disperse and have a problem that good pigment dispersibility is not obtained.

As a method for solving this problem, the present inventors use an anthraquinone derivative represented by the general formula (1) in JP-A-2002-22922 to disperse the red organic pigment. Is proposing that. With this proposal, the pigment dispersibility of the color filter pigment dispersion is improved, and it becomes possible to obtain high transmittance and contrast. However, in recent years, higher transmittance and lightness have been required.

In Japanese Patent Laid-Open No. 8-179111, in a coloring composition for a color filter in which a colorant is dispersed in a transparent resin, the colorant is an organic pigment, and the organic pigment is a water-soluble inorganic salt (A ) And (A) are mechanically kneaded together with a water-soluble organic solvent (B) which is substantially insoluble, and then (A) and (B) are removed, and a colored composition for a color filter is disclosed. It is disclosed that a color filter having a high contrast ratio can be obtained by using the sol-trimmed organic pigment. In Japanese Patent Laid-Open No. 2000-249824, (A)
In a radiation-sensitive composition for a color filter containing a colorant, (B) alkali-soluble resin, (C) polyfunctional monomer and (D) photopolymerization initiator, (A) colorant has a specific structure of quinacridone. A radiation-sensitive composition for an additive color mixture type color filter, which is used in a reflective color liquid crystal display device containing a pigment, is disclosed. Japanese Patent Laid-Open No. 11-3107
In Japanese Patent Laid-Open No. 14 and Japanese Patent Laid-Open No. 11-310715,
Red pigment and C.I. I. A red resin composition in which Pigment Orange is dispersed in a resin is disclosed, and it is disclosed that a red image formed using this red resin composition has excellent light transmittance. However, even with these techniques, the light transmittance and the brightness of the coating film formed from the resin composition are insufficiently improved, and there is room for improvement to improve the dispersibility of the pigment and further improve such characteristics. was there.

[0009]

SUMMARY OF THE INVENTION In view of the above-mentioned problems of the prior art, the present invention provides a red pigment-dispersed resist composition for a color filter which has very high transmittance and lightness and provides good pigment dispersibility. To provide.

[0010]

In order to solve such a problem, the present inventors have conducted various studies on a red pigment-dispersed resist composition for a color filter, and as a result, as a red pigment, salt-milled C was used. ． I. Pigment Red 207 and / or salt milled C.I.
I. Pigment Red 209 is a C.I.
I. Pigment Orange 43 and / or Pigment Orange 71 is used, and the sulfonic acid derivative of anthraquinone is used as a dispersant for finely dispersing the pigment, resulting in good pigment dispersibility, which is much higher than conventional products. They have found that the transmittance and the brightness can be obtained, and have completed the present invention.

That is, the present invention comprises (1) at least one anthraquinone derivative represented by the following general formula (1), a red pigment, a toning pigment, and at least one photopolymerizable unsaturated bond in the molecule. A red pigment-dispersed resist composition for a color filter, which comprises a monomer, a photoinitiator and a solvent, or further comprises a resin, wherein the red pigment is salt milled C.I. I. Pigment Red 207 and / or salt milled C.I. I.
Pigment Red 209, and the toning pigment is C.I.
I. The present invention relates to a red pigment-dispersed resist composition for a color filter, which is an orange pigment of Pigment Orange 43 and / or Pigment Orange 71.

[0012]

[Chemical 3]

In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R
⁷ and R ⁸ each independently represent a hydrogen atom, a halogen atom, —SO ₃ M, —NH ₂ or —OH. M is hydrogen atom, sodium atom, potassium atom, NH ₄ , NR ⁹
It represents a R ¹⁰ R ¹¹ R ^12. R ^9, R ^10, R ¹¹ and R ¹² each independently represent an aliphatic also be saturated or unsaturated optionally be substituted C1-10 hydrocarbon group, or 6 carbon atoms
Represents 10 optionally substituted aromatic hydrocarbon groups.
However, at least one of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ is —SO ₃ H, —SO ₃ Na and —.
It is one of SO ₃ K.

Further, in the present invention, (2) the anthraquinone derivative is at least one selected from the group of compounds represented by the following general formulas (2) to (5).
The present invention relates to the red pigment-dispersed resist composition for a color filter described above.

[0015]

[Chemical 4]

In the formula, M ¹ , M ² , M ³ , M ⁴ and M ⁵ each independently represent a hydrogen atom, a sodium atom or a potassium atom. The present invention also provides (3) the general formula (2).
To (5), wherein M ¹ is a hydrogen atom, relates to the red pigment-dispersed resist composition for a color filter according to the above (2).

The present invention also provides (4) the red pigment-dispersed resist composition for a color filter, wherein the resin is an essential component, and the resin is a basic group-containing resin, or a basic group and an acidic group. The present invention relates to the red pigment-dispersed resist composition for a color filter according to any one of (1) to (3), which comprises a resin.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The red pigment-dispersed resist composition for a color filter of the present invention comprises a salt milled C.I. I. Pigment Red 207 and / or salt milled C.I. I. Pigment Red 209 and C.I. I. Pigment Orange 43 and / or Pigment Orange 71 orange pigment,
At least one of the specific anthraquinone sulfonic acid derivatives represented by the above general formula (1) as a pigment dispersant.
By containing the seed, the pigment dispersibility is good, and higher transparency and higher brightness than conventional products can be obtained. In the present invention, one or more pigments other than these red pigments and toning pigments may be used, if necessary.

The salt milled C.I. used as a red pigment in the red pigment-dispersed resist composition for a color filter of the present invention. I. Pigment Red 207 and / or salt milled C.I. I. Pigment Red 209 includes, for example, C.I. I. Pigment Red 2
07 and / or C.I. I. Pigment Red 209, a water-soluble inorganic salt, a water-soluble organic solvent that does not substantially dissolve the water-soluble inorganic salt, and optionally a mixture containing at least one anthraquinone derivative represented by the general formula (1) described below ( Hereinafter, this step is referred to as salt milling processing)
A treated pigment obtained by removing the water-soluble inorganic salt and the water-soluble organic solvent after the treatment is suitable.

The orange pigment used as a toning pigment in the red pigment-dispersed resist composition for color filters of the present invention is C.I. I. Pigment Orange 43 and / or C.I.
I. Pigment Orange 71. Incidentally, C.I. I. Pigment Orange 43, C.I. I. Pigment Orange 71
May be salt milled. This allows
A red pigment-dispersed resist composition for a color filter having high light transmittance and brightness can be obtained. Among them, C.I. as a red pigment is preferred because of its high transmittance and high brightness. I. Pigment Yellow 207 and C.I. as an orange pigment. I. Pigment Orange 71 is preferably used in combination.

In the present invention, the mixing ratio of the red pigment and the orange pigment as the toning pigment is preferably red pigment / orange pigment = 99/1 to 40/60 by mass ratio,
It is appropriately selected according to the required chromaticity. When both the red pigment and the orange pigment are subjected to the salt milling treatment, the red pigment and the orange pigment may be separately performed, or the red pigment and the orange pigment may be mixed and simultaneously performed.

In the salt milling treatment, more specifically, a small amount of a pigment, a water-soluble inorganic salt and, if necessary, a mixture of at least one anthraquinone derivative represented by the general formula (1) described later as a wetting agent is used. After adding a water-soluble organic solvent and kneading with a kneader or the like, this mixture is put into water and stirred with a high speed stirrer or the like to form a slurry.
Next, this slurry is filtered and washed with water to remove the water-soluble inorganic salt and the water-soluble organic solvent, and if necessary, dried to obtain a finely treated pigment.

The water-soluble inorganic salt used in the salt milling step acts as a grinding aid and is not particularly limited as long as it dissolves in water. Sodium chloride (salt), barium chloride, potassium chloride, One or more kinds of sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of cost.
The amount of the water-soluble inorganic salt used in the salt milling step is preferably 1 to 20 times by mass, particularly 3 to 10 times by mass of the total pigment amount from the viewpoint of both treatment efficiency and production efficiency. The larger the ratio of the amount of the water-soluble inorganic salt to the amount of pigment, the higher the fine efficiency, but the smaller the amount of treatment per treatment, so the above range is preferable.

The water-soluble organic solvent used in the salt milling step acts as a lubricant, and is particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the water-soluble inorganic salt. However, since the temperature rises during the salt milling process and the water-soluble organic solvent is easily evaporated, a high-boiling point water-soluble organic solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety. Specifically, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol. Examples thereof include ethylene glycol monomethyl ether, polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether and polypropylene glycol. These may be used alone or 2
You may use together 1 or more types.

In addition, in order to suppress the crystallization and aggregation of the pigment during the salt milling process, a specific sulfonic acid derivative of anthraquinone represented by the general formula (1) described later is added. The amount of the anthraquinone sulfonic acid derivative used is not particularly limited, but is 0.3 with respect to the total pigment amount, that is, 100% by mass of the total of the red pigment and the orange pigment.
-20 mass% is preferable.

The anthraquinone derivative used in the red pigment-dispersed resist composition for a color filter of the present invention is an anthraquinone derivative represented by the general formula (1),
Preferably, one or more anthraquinone derivatives represented by the general formulas (2) to (5) are used. That is, the preferred form of the anthraquinone derivative in the present invention is
It is at least one selected from the group of compounds represented by the general formulas (2) to (5). Among them, it is preferable that M ¹ in the general formulas (2) to (5) is H (hydrogen atom).

In the general formula (1), examples of the halogen atom represented by R ^{1 to} R ⁸ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Saturated or unsaturated, optionally substituted aliphatic hydrocarbon group having 1 to 10 carbon atoms represented by R ^{9 to} R ¹² or 6 to 10 carbon atoms
Examples of the optionally substituted aromatic hydrocarbon group of are, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl,
Pentyl, hexyl, octyl, 2-ethylhexyl,
Linear or branched alkyl groups such as nonyl and decyl; substituted alkyl groups such as methoxyethyl, ethoxyethyl, methoxypropyl, aminoethyl, chloroethyl and hydroxyethyl; alkenyl groups such as propenyl, butenyl, pentenyl and hexenyl. Can be mentioned. Examples of the optionally substituted aromatic hydrocarbon group having 6 to 10 carbon atoms represented by R ^{9 to} R ¹² include phenyl, methylphenyl, ethylphenyl, hydroxyphenyl, chlorophenyl, nitrophenyl, naphthyl and the like. To be

The sulfonic acid derivative of anthraquinone represented by the general formulas (2) to (5) used in the present invention can be easily obtained, for example, by the following method. General formula (2)
The compound (1) can be obtained, for example, by a method of sulfonating 1-aminoanthraquinone with fuming sulfuric acid and then reacting it with bromine (PB Report, FIAT 1313214). The compound of general formula (3) can be obtained by a method of isolating the compound of general formula (2) by reacting it with an alkali such as caustic soda. The compounds of the general formulas (4) and (5) can be obtained in a free acid state by a method of sulfonating anthraquinone with fuming sulfuric acid. Sodium or potassium salts are prepared by dissolving or suspending these free acids in water or the like,
It can be easily obtained by neutralizing with an alkali such as caustic soda or caustic potash.

In the present invention, the amount of the sulfonic acid derivative of anthraquinone used is the total amount of the pigment used, that is, the red pigment and orange pigment in the red pigment-dispersed resist composition for a color filter, and if necessary. It is usually 30% by mass or less, preferably 0.1 to 20% by mass, based on 100% by mass of the total amount of other pigments. Even if the amount of the sulfonic acid derivative of anthraquinone used exceeds the above range, the effect of dispersing the pigment tends not to be further improved.

The resin used as required in the red pigment-dispersed resist composition for a color filter of the present invention includes:
As long as it has pigment dispersibility, a basic group-containing resin or a resin containing a basic group and an acidic group can be used.

As such a resin, a polyester having an amino group and / or an imino group and a free carboxyl group of a polyamine compound (for example, poly (lower alkyleneamine) such as polyallylamine, polyvinylamine, polyethylenepolyimine, etc.) , A reaction product with at least one selected from the group consisting of polyamide and polyesteramide; a reaction product obtained by reacting a low molecular weight amino compound such as N, N′-dimethylaminopropylamine with a polyester having a free carboxyl group. Reaction product obtained by reacting a polyepoxy compound with a linear polymer having a free carboxyl group and an organic amine compound having one secondary amino group; an isocyanate group of a polyisocyanate compound, an alcohol such as methoxypolyethylene glycol And capro Polyesters having one hydroxyl group such as clon polyester, compounds having 2-3 isocyanate group-reactive functional groups, aliphatic or heterocyclic hydrocarbons having isocyanate group-reactive functional groups and tertiary amino groups A reaction product obtained by sequentially reacting compounds; a reaction product of a polycarbonate compound having a functional group capable of reacting with an amino group at one end and a polyamine compound; methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, stearyl methacrylate, At least one selected from methacrylic acid esters or acrylic acid esters such as benzyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, stearyl acrylate, and benzyl acrylate. And at least one basic group-containing polymerizable monomer such as acrylamide, methacrylamide, N-methylolamide, vinylimidazole, vinylpyridine, and a monomer having an amino group and a polycaprolactone skeleton, and a styrene or styrene derivative , A copolymer of at least one other polymerizable monomer; a reaction product obtained by reacting a polymer of an acrylate having an alcoholic hydroxyl group with a polyisocyanate compound and a hydrocarbon compound having an amino group; hydroxyethyl cellulose, etc. Cellulose-based resin, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, alkyd resin, phenol resin, epoxy resin, urethane resin, polyester resin and the like can be exemplified, and these can be used alone or in combination.

Among these, at least one resin selected from a basic group-containing resin, a basic group and an acidic group-containing resin is used because good initial pigment dispersibility and dispersion stability over time can be obtained. Preferably. The amount of the above resin used is 0 to 2 with respect to 100 parts by weight of all pigments used.
00 parts by weight, preferably 5 to 100 parts by weight, more preferably 10 to 100 parts by weight. The amount of resin used is 20
If it is more than 0 parts by weight, the developability of the obtained color resist will be poor.

As the solvent used in the red pigment-dispersed resist composition for a color filter of the present invention, the pigment can be stably dispersed in the dispersion, and the resin used can be dissolved if necessary. Solvents are preferred. Specific examples of such a solvent include (poly) alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether. (Poly) alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate and propylene glycol monomethyl ether acetate; ethers such as diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether and tetrahydrafuran; Methyl ethyl ketone, Chill isobutyl ketone, cyclohexanone, 2-heptanone, ketones such as 3-heptanone; 2
-Lactic acid alkyl esters such as methyl hydroxypropionate and ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate and 3-methyl-
3-methoxybutyl propionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3
-Ethyl compounds such as methyl ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, hydroxyacetic acid ester, ethyl acetate, n-amyl formate and ethyl pyruvate; aromatic hydrocarbons such as toluene and xylene; N- Examples thereof include amides such as methylpyrrolidone, N, N-dimethylformamide and N, N-dimethylacetamide. These solvents may be used alone or in admixture of two or more. The amount of these solvents used is preferably 40 to 80% by mass based on 100% by mass of the red pigment-dispersed resist composition for color filters.

The monomer containing at least one photopolymerizable unsaturated bond used in the red pigment-dispersed resist composition for a color filter used in the present invention will be described below. Among the monomers having one or more photopolymerizable unsaturated bonds in the molecule, examples of the monomer having one photopolymerizable unsaturated bond in the molecule include methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, Alkyl methacrylates or acrylates such as methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate; aralkyl methacrylates or acrylates such as benzyl methacrylate, benzyl acrylate;
Alkoxyalkyl methacrylates or acrylates such as butoxyethyl methacrylate, butoxyethyl acrylate; aminoalkyl methacrylates or acrylates such as N, N-dimethylaminoethyl methacrylate, N, N-dimethylaminoethyl acrylate; diethylene glycol ethyl ether, triethylene glycol butyl ether, diester Methacrylic acid or acrylic ester of polyalkylene glycol alkyl ether such as propylene glycol methyl ether; Methacrylic acid or acrylic ester of polyalkylene glycol aryl ether such as hexaethylene glycol phenyl ether; Isobornyl methacrylate or acrylate;
Glycerol methacrylate or acrylate; 2-hydroxyethyl methacrylate or acrylate and the like can be exemplified.

Among the monomers having at least one photopolymerizable unsaturated bond in the molecule, the number of photopolymerizable unsaturated bonds in the molecule is 2
Examples of the monomer having more than one are bisphenol A dimethacrylate, 1,4-butanediol dimethacrylate, 1,3-butylene glycol dimethacrylate, diethylene glycol dimethacrylate, glycerol dimethacrylate, neopentyl glycol dimethacrylate, polyethylene glycol dimethacrylate. , Polypropylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentamethacrylate, bisphenol A Diacrylate, , 4-butanediol diacrylate, 1,3-butylene glycol diacrylate, diethylene glycol diacrylate, glycerol diacrylate, neopentyl glycol diacrylate,
Polyethylene glycol diacrylate, polypropylene glycol diacrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol penta Acrylate etc. are mentioned. Monomers containing one or more of these photopolymerizable unsaturated bonds in the molecule may be used alone or
Combinations of more than one species can be used.

The photoinitiator (photopolymerization initiator) used in the red pigment-dispersed resist composition for a color filter of the present invention is not particularly limited, and examples thereof include benzophenone, N,
N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, benzyl, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, α- Hydroxyisobutylphenone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl phenyl ketone, t-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-
Examples thereof include chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 1,2-benzanthraquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, and a triazine-based photopolymerization initiator. These photoinitiators may be used alone or in combination of two or more.

The red pigment-dispersed resist composition for a color filter of the present invention may further contain a developer, particularly preferably an alkali developer, which is used in the developing treatment step when producing the color filter, if necessary. On the other hand, an alkali-soluble resin having solubility, but not limited to, one or more alkali-soluble resins having a carboxyl group can be used.

Examples of the alkali-soluble resin having a carboxyl group include unsaturated monomers containing a carboxyl group such as acrylic acid and methacrylic acid, and styrene and 2-
At least one selected from the group of hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, glycerol monoacrylate, glycerol methacrylate, N-phenylmaleimide, polystyrene macromonomer and polymethylmethacrylate macromonomer. Copolymers with seeds can be used.

Further, the red pigment-dispersed resist composition for a color filter of the present invention comprises a substrate, a thermal polymerization inhibitor such as hydroquinone, pyrogallol, t-butylcatechol, etc., for controlling the dark reaction, if necessary. Additives such as silane coupling agents, titanate coupling agents, ultraviolet absorbers, antioxidants, etc. for improving the adhesiveness of
One kind or two or more kinds can be appropriately used.

The red pigment dispersion resist composition for a color filter of the present invention is generally a pigment dispersion prepared by dispersing an orange pigment as a toning pigment in a pigment dispersion prepared by dispersing a salt milled red pigment. And a monomer having at least one photopolymerizable unsaturated bond in the molecule, and a photoinitiator. It should be noted that a red pigment-dispersed resist composition for a color filter of the present invention can also be obtained by adding and dispersing a salt-milled red pigment and an orange pigment together, and a red pigment and an orange pigment can be salt-milled together. It is also possible to obtain the red pigment-dispersed resist composition for a color filter of the present invention by dispersing the above.

The method for producing the red pigment-dispersed resist composition for a color filter of the present invention is not particularly limited, but the following method is preferably applied. First, a red pigment and / or an orange pigment as a toning pigment, a sulfonic acid derivative of anthraquinone, a solvent and, if necessary, a resin are mixed, and an ultrasonic disperser, a bead mill, three rolls, a ball mill, a sand mill, a homogenizer, and a kneader. A pigment dispersion is obtained by kneading and dispersing using the above.

Next, the pigment dispersion obtained by subjecting the red pigment and the orange pigment to the dispersion treatment together contains a monomer containing at least one photopolymerizable unsaturated bond in the molecule, a photoinitiator, and if necessary. Accordingly, a resin, a solvent, and other additives are added to obtain the red pigment-dispersed resist composition for a color filter of the present invention. Also, when separately dispersing the red pigment and the orange pigment,
An orange pigment dispersion as a toning pigment is added to the obtained red pigment dispersion for toning, and further, a monomer containing at least one photopolymerizable unsaturated bond in the molecule, a photoinitiator, necessary. According to the above, a resin, a solvent, and other additives are added to obtain a red pigment-dispersed resist composition for a color filter of the present invention.

The red pigment-dispersed resist composition for a color filter of the present invention has good pigment dispersibility and can form a coating film having extremely high transmittance and lightness, and thus is particularly suitable for a reflective color liquid crystal display. It can be suitably applied to the production of optical color filters used.

[0044]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "parts" in the present examples represent "parts by weight".

Examples 1 to 4 and Comparative Examples 1 to 10 [Preparation of Pigment Dispersion] C.V. having a specific surface area of 107 m ² / g subjected to salt milling so as to have the composition shown in Table 1. I. Pigment Red 209, salt milled C.I. having a specific surface area of 88 m ² / g. I. Pigment Red 207,
C. I. Pigment Red 209, C.I. I. Pigment Red 207, C.I. I. Pigment Orange 43, C.I.
I. Pigment Orange 71, C.I. I. Pigment Yellow 139, anthraquinone derivative, resin, propylene glycol monomethyl ether acetate (PMAC)
Was dispersed in a bead mill all day and night to obtain pigment dispersions 1 to 9. In Table 1, in the pigment dispersion,
Each numerical value means part by weight.

[0046]

[Table 1]

[Preparation of Red Pigment Dispersion Resist Composition for Color Filter] Pigment dispersions 1 to 6 in which a red pigment was dispersed so as to have the composition shown in Table 2 had a C.I. I. Pigment Orange 43, Pigment Dispersion 7, C.I. I. Pigment Orange 73, Pigment Dispersion 8, C.I. I. Pigment Yellow 139 Pigment Dispersion 9 is added and uniformly mixed. Further, acrylic resin, dipentaerythritol hexaacrylate, Irgacure 907 (trade name, manufactured by Ciba Geigy), and PMAC are uniformly mixed, and then filtered with a filter having a pore size of 3 μm. Then, red pigment-dispersed resist compositions for color filters of Examples 1 to 4 and Comparative Examples 1 to 10 were obtained. In Table 2, in the pigment dispersion, the numerical value in each formulation means parts by weight.

[0048]

[Table 2]

The anthraquinone derivatives, polyallylamine derivatives, basic group-containing acrylic resins, acrylic resins and polyurethane resins shown in Tables 1 and 2 are shown below. Anthraquinone derivative

[0050]

[Chemical 5]

Polyallylamine derivative A reaction product PB821 (trade name, manufactured by Ajinomoto Co., Inc.) obtained by reacting a polyester having a free carboxyl group with polyallylamine Basic group-containing acrylic resin Disperbyk-2001 (trade name, Big Chemie Japan) Polyester resin having one hydroxyl group in the isocyanate group of the polyurethane resin polyisocyanate compound, a compound having two to three isocyanate group-reactive groups, a fat having an isocyanate group-reactive functional group and a tertiary amino group Reaction product Disperbyk-161 (trade name, BYK Che, which is obtained by sequentially reacting a group or heterocyclic hydrocarbon compound
Acrylic resin benzyl methacrylate / methacrylic acid copolymer (weight average molecular weight: 20000, acid value 100)

<Test Evaluation> (Pigment Dispersibility) Regarding the red pigment-dispersed resist compositions for color filters of Examples 1 to 4 and Comparative Examples 1 to 10, B
The viscosity at 25 ° C. was measured using a type viscometer (trade name RE100L type viscometer, manufactured by Toki Sangyo Co., Ltd.) to evaluate the pigment dispersibility.

(Applicability) Examples 1 to 4, Comparative Examples 1 to 1
The red pigment-dispersed resist composition for a color filter of No. 0 was coated on a glass substrate for a color filter by a spin coater, and the coating film surface was visually evaluated. The evaluation results are shown in Table 3. Evaluation results A: No coating unevenness B: No coating unevenness Evaluation results are shown in Table 3.

<Color characteristics> Example 1 having good pigment dispersibility
~ 4, the red pigment-dispersed resist composition for each color filter of Comparative Examples 2, 3, 4, 5, 7, 8, 9, 10 is applied on a glass substrate for color filter by a spin coater.
It was dried at 0 ° C. for 3 minutes to obtain a red coating film. Then, each unexposed coating film was exposed through a photomask using a high-pressure mercury lamp at an exposure dose of ultraviolet rays of 300 mJ / cm ² . About each coated film after exposure, spectrophotometer 2500P
C (trade name, manufactured by Shimadzu Corporation), spectral transmittance, C
The chromaticity (x value, y value) and Y value in the IE display system were measured. The results are shown in Table 3, FIG. 1 and FIG. Note that FIG.
2 is a transmission spectrum at (x, y = 0.393, 0.296).

[0055]

[Table 3]

From Tables 2 and 3 and FIGS. 1 and 2, salt milled C.I. I. Pigment Red 207 is C.I. I. Pigment Orange 43 (Example 4) or C.I.
I. Pigment Orange 71 (Example 3), the red pigment-dispersed resist composition for a color filter is C.I. I. Pigment Red 207 is C.I. I. Pigment Orange 43 (Comparative Example 1)
0), C.I. I. Pigment Orange 71 (Comparative Example 7),
C. I. Pigment Yellow 139 (Comparative Example 9), a red pigment-dispersed resist composition for a color filter,
Salt milled C.I. I. Pigment Red 2
07 to C.I. I. (X, y) = (0.393, 0.296) as compared with the red pigment-dispersed resist composition for a color filter toned with Pigment Yellow 139 (Comparative Example 8).
It can be seen that the brightness at time and the transmittance at 470 nm or less are very high.

Next, referring to Tables 2 and 3 and FIGS. 1 and 2, salt milled C.I. I. Pigment Red 20
9 to C.I. I. Pigment Orange 71, a red pigment-dispersed resist composition for a color filter (Example 1)
C. which has not been subjected to salt milling. I. Pigment Red 209 is C.I. I. Pigment Orange 71 (Comparative Example 2), C.I. I. Pigment Yellow 139 (Comparative Example 4), a red pigment-dispersed resist composition for a color filter, a salt milled C.I. I. Pigment Red 209 is C.I. I. Pigment Yellow 139
Compared with the red pigment-dispersed resist composition for a color filter toned in (Comparative Example 3), (x, y) = (0.393,
It can be seen that the brightness at 0.296) and the transmittance at 470 nm or less are very high.

In addition, salt milled C.I. I.
Pigment Red 209 is C.I. I. The red pigment-dispersed resist composition for a color filter toned with Pigment Orange 43 (Example 2) was treated with or without salt milling. I. Pigment Red 209
To C. I. Pigment Yellow 139 (Comparative Example 3 and Comparative Example 4) (x, y) = (0.393, 0.
It can be seen that the brightness at 296) is high and the transmittance is 470 nm or less.

In addition, salt milled C.I. I.
Pigment Red 209 is C.I. I. The red pigment-dispersed resist composition for a color filter (Example 2) toned with Pigment Orange 43 is C.I. I. Pigment Red 209 is C.I. I. Pigment Orange 43 is less effective than the red pigment-dispersed resist composition for color filters (Comparative Example 5), but the brightness at (x, y) = (0.393, 0.296), 420 nm High transmittance below 550nm-60
It can be seen that the rise of the curve at 0 nm is high.

[0060]

EFFECTS OF THE INVENTION The red pigment dispersion for color filters of the present invention has the above-mentioned constitution, and even if the salt-milled pigment is used, the pigment dispersibility is good and the transmittance and the lightness are very high. Since it is possible to form an extremely high coating film, it can be suitably applied particularly to the production of optical color filters and the like used in reflective color liquid crystal displays.

[Brief description of drawings]

FIG. 1 shows a chromaticity (x value, y value) of (x, y = 0.393, 0) of a coating film formed from a red pigment-dispersed resist composition for a color filter toned in Examples and Comparative Examples. .29
It is a transmission spectrum at the time of 6).

FIG. 2 shows the chromaticity (x value, x value of a coating film formed from a red pigment-dispersed resist composition for a color filter toned in Comparative Example.
It is a transmission spectrum when (y value) is (x, y = 0.393, 0.296).

Claims (4)

[Claims] 1. At least one anthraquinone derivative represented by the following general formula (1), a red pigment, a toning pigment,
A red pigment-dispersed resist composition for a color filter, comprising a monomer having at least one photopolymerizable unsaturated bond in the molecule, a photoinitiator and a solvent, or further comprising a resin. The red pigment is a salt-milled C.I. I. Pigment Red 207 and / or salt milled C.I. I. Pigment Red 209, and the toning pigment is C.I. I. Pigment Orange 43 and / or Pigment Orange 71 orange pigment, a red pigment-dispersed resist composition for a color filter. [Chemical 1] In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are
Independently of each other, hydrogen atom, halogen atom, -SO
It represents a ₃ M, -NH ₂ or -OH. M is a hydrogen atom, sodium atom, potassium atom, NH ₄ , NR ⁹ R ¹⁰ R ¹¹ R
Represents ¹² . R ^9, R ^10, R ¹¹ and R ¹² are each independently substituted aliphatic hydrocarbon group or a C 6-10 substituted saturated or may be or unsaturated 1 to 10 carbon atoms Represents an aromatic hydrocarbon group. However, R
^1, at least one of ^{R 2, R 3, R 4} , R 5, R 6, R 7 and R ⁸ _is either -SO ₃ H, -SO 3 Na and -SO ₃ K. 2. The red pigment for a color filter according to claim 1, wherein the anthraquinone derivative is at least one selected from the group of compounds represented by the following general formulas (2) to (5). Dispersed resist composition. [Chemical 2] In the formula, M ¹ , M ² , M ³ , M ⁴ and M ⁵ each independently represent a hydrogen atom, a sodium atom or a potassium atom. 3. M ¹ in the general formulas (2) to (5) is
The red pigment-dispersed resist composition for a color filter according to claim 2, which is a hydrogen atom. 4. The red pigment-dispersed resist composition for a color filter is characterized in that a resin is an essential component and the resin comprises a basic group-containing resin or a basic group- and acidic group-containing resin. The red pigment-dispersed resist composition for a color filter according to any one of claims 1 to 3.