JP4572624B2 - Coloring composition for color filter, color filter, and liquid crystal display device - Google Patents

Description

  The present invention relates to a colored composition for a color filter, a color filter using the colored composition for a color filter, and a liquid crystal display device including the color filter. Specifically, for color filters that have excellent dissolution stability during development and have no problem of resist remaining in the non-image area after development and adhesion of undissolved strips of resist to the non-image area and image area. The present invention relates to a coloring composition, a color filter using the coloring composition for a color filter, and a liquid crystal display device using the color filter.

Conventionally, color filters used in liquid crystal display devices, etc., have dyes, printing methods, electrodeposition methods, pigment dispersion methods, etc., which have pixels such as red, green, and blue formed on a glass substrate. Has been used.
Among these, the color filter by the pigment dispersion method is manufactured by forming an image with a colored resist in which a pigment is dispersed in a photocurable resin, but the pigment dispersion method manufactures a color filter with high heat resistance. In addition, there is an advantage in that dyeing is unnecessary and a high-precision image can be formed.

In the pigment dispersion method, when an image is formed with a colored resist containing a large amount of pigment, there is a problem that the pigment tends to remain on the substrate and stains occur. In the production of a color filter, red, green, and blue color pixels are sequentially formed, so that the occurrence of background stains causes the color reproducibility of the color filter, the smoothness of the coating film, and the like to deteriorate.
In order to prevent such background contamination, conventionally, methods such as control of development time, adjustment of developer concentration, and removal with a brush or the like have been employed.

Also, by adding an organic carboxylic acid to the colored resist (Patent Documents 1 to 3), adding an organic carboxylic acid anhydride to the colored resist (Patent Document 4), or increasing the acid value of the binder resin. A method for improving the solubility has also been proposed.
JP-A-4-369653 Japanese Patent No. 3293171 JP 2004-117856 A JP-A-8-292316

  However, the control of the development time, adjustment of the developer concentration, and removal with a brush cannot completely remove the occurrence of background stains, resulting in problems such as reduced workability, increased costs, and waste solution treatment of the developer. Was produced. Moreover, the generation | occurrence | production of background dirt was not able to be prevented completely also by the method of adding organic carboxylic acid or organic carboxylic acid anhydride, or the method of raising the acid value of binder resin. Some organic carboxylic acids and organic carboxylic acid anhydrides have relatively low solubility in the solvent used, and a sufficient amount cannot be added to satisfy this application. Furthermore, depending on the type of organic carboxylic acid, undissolved substances are likely to be generated during development, particularly in television applications where there is a high pigment content and high color reproducibility is required. There was a problem of adhesion of undissolved peeled pieces.

The present invention has been made in view of the above circumstances, and is to achieve the following objects.
1. In the production of color filters, there is no problem of coloring composition remaining on the non-pixel part (background stain) on the substrate after development, and adhesion of undissolved strips of resist to the pixel part and non-pixel part. Disclosed is a coloring composition for a color filter which has excellent formability and stability and can form high-density color pixels uniformly with high accuracy.

2. Using the above color filter coloring composition, there is no problem of remaining undissolved coloring composition on the non-pixel portion etc. on the substrate, and high quality with high transmittance, high density and high contrast image formed. Provide color filters.
3. A high-quality liquid crystal display device using the color filter is provided.

As a result of intensive studies to solve the above problems, the present inventor achieves the above problems by including a combination of a specific organic carboxylic acid and an organic carboxylic acid anhydride as an additive of a coloring composition for a color filter. The inventors found out that a remarkable effect was achieved, and reached the present inventions 1 to 3 below.
1. A binder resin, a photopolymerization initiation system, a monomer, a coloring material, a solvent, and an organic carboxylic acid having a solubility in the solvent at 5 ° C. of 1% by weight or more, and an organic carboxylic acid anhydride, Coloring composition for color filter.
2. A color filter formed using the coloring composition according to 1 above.
3. 3. A liquid crystal display device formed using the color filter described in 2 above.

  According to the present invention, in the production of a color filter, there is no problem of resist remaining in the non-pixel portion on the substrate after development and adhesion of undissolved strips of the resist to the pixel portion and the non-pixel portion. Provided is a coloring composition for a color filter which is excellent in formability and stability and can form a high-density color pixel uniformly with high accuracy. In addition, the color filter and the liquid crystal display device formed using such a coloring composition have no problem of adhesion of undissolved strips of the resist to the pixel portion and the non-pixel portion, and the image formability and the stability thereof. The high-quality color pixels are formed with high accuracy and high quality.

The constituent requirements and the like of the present invention will be described in detail below, but these are examples of embodiments of the present invention and are not limited to these contents.
[1] Constituent Components of Color Filter Coloring Composition (Resist) Each constituent component of the color filter coloring composition of the present invention will be described below. The colored composition for a color filter of the present invention comprises a binder resin, a photopolymerization initiation system, a monomer, a coloring material, a solvent, an organic carboxylic acid having an solubility at 5 ° C. in the solvent of 0.7% by weight or more, and an organic carboxylic acid anhydride. The product is an essential component, and if necessary, an additive other than the above components such as a dispersant may be blended. Hereinafter, each component will be described.

In the following, “total solid content” refers to all components in the coloring composition for a color filter of the present invention other than the solvent components described later. In addition, “(meth) acryl”, “(meth) acrylate” and the like mean “acryl and / or methacryl”, “acrylate and / or methacrylate” and the like, for example, “(meth) acrylic acid” is “ It means “acrylic acid and / or methacrylic acid”.
[1-1] Binder Resin As the binder resin, for example, JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, JP-A-11-140144, JP-A-11- 174224, JP-A No. 2000-56118, JP-A No. 2003-233179 and the like can be used, among which a polymer compound containing no nitrogen atom is preferable. , (A): 5 to 90 mol% of epoxy group-containing (meth) acrylate, (B): obtained by copolymerizing 10 to 95 mol% of another radical polymerizable compound copolymerizable with component (A). (C) Unsaturated monobasic acid is added to 10 to 100 mol% of the epoxy group contained in the copolymer, and the hydroxyl group produced when the component (C) is added The photosensitive resin obtained by adding (D) polybasic acid anhydride to 0-100 mol% is preferable.

  (A): Examples of the epoxy group-containing (meth) acrylate include glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and 4-hydroxy Examples thereof include butyl (meth) acrylate glycidyl ether, and glycidyl (meth) acrylate is particularly preferable. These (A) components may be used individually by 1 type, and 2 or more types may be mixed and used for them.

  (A): Copolymerization ratio of epoxy group-containing (meth) acrylate (copolymerization ratio when copolymerizing (A) component and (B) component to produce a copolymer). ") Is 5 to 90 mol% as described above, preferably 20 to 80 mol%, more preferably 30 to 70 mol%. If this ratio is too large, the component (B) may be reduced and heat resistance and strength may be lowered. If it is too small, the amount of the polymerizable component and alkali-soluble component added becomes insufficient, such being undesirable.

  On the other hand, the copolymerization ratio of the other radical polymerizable compound that can be copolymerized with the component (B) :( A) is 10 to 95 mol% as described above, preferably 20 to 80 mol%, and more Preferably it is 30-70 mol%. If the proportion is too large, the amount of the component (A) is decreased, so that the addition amount of the polymerizable component and the alkali-soluble component is insufficient, and if it is too small, the heat resistance and strength are lowered, which is not preferable.

  As the other radical polymerizable compound that can be copolymerized with the component (B) :( A), one or more mono (meth) acrylates having a structure represented by the following general formula (1) are used. It is preferable.

(In formula (1), R ^{4 to} R ⁹ each represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms such as methyl, ethyl, propyl, etc., and R ¹⁰ and R ¹¹ each represent a hydrogen atom. , or a methyl group, an ethyl group, ring alkyl or a group or linked to may also form a ring .R ¹⁰ and R ^11, 1 to 3 carbon atoms such as propyl group formed by linking Is preferably an aliphatic ring, which may be saturated or unsaturated, and preferably has 5 to 6 carbon atoms.)
In the general formula (1), mono (meth) acrylate having a structure represented by the following general formula (2), (3), or (4) is preferable. By introducing these structures into the binder resin, it is possible to increase heat resistance and strength. Of course, these mono (meth) acrylates may be used alone or in combination of two or more.

  As the mono (meth) acrylate having the structure represented by the chemical formula (1), various known ones can be used, and those represented by the following chemical formula (5) are particularly preferable.

(In the formula (1), R ¹² represents a hydrogen atom or a methyl group, and R ¹³ represents the chemical formula (1)).
The content of the mono (meth) acrylate having the structure of the chemical formula (1) in the copolymerization monomer is usually 5 to 90 mol%, preferably 10 to 70 mol%, and more preferably 15 to 50 mol%. It is.

In addition, the radical polymerizable compound other than the above is not particularly limited, but as a specific example thereof,
Styrene, α-, o-, m-, p-alkyl, nitro, cyano, amide, ester derivatives of styrene;
Dienes such as butadiene, 2,3-dimethylbutadiene, isoprene, chloroprene; methyl (meth) acrylate, ethyl (meth) acrylate, (n-propyl) (meth) acrylate, iso-propyl (meth) acrylate , (Meth) acrylic acid-n-butyl, (meth) acrylic acid-sec-butyl, (meth) acrylic acid-tert-butyl, (meth) acrylic acid pentyl, (meth) acrylic acid neopentyl, (meth) acrylic acid Isoamyl, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic 2-methylcyclohexyl acid, dicyclohexyl (meth) acrylate , Isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, anthracenyl (meth) acrylate, Anthraninonyl (meth) acrylate, piperonyl (meth) acrylate, salicyl (meth) acrylate, furyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofuryl (meth) acrylate, (meth) acrylic acid Pyranyl, benzyl (meth) acrylate, phenethyl (meth) acrylate, cresyl (meth) acrylate, 1,1,1-trifluoroethyl (meth) acrylate, perfluoroethyl (meth) acrylate, ( (Meth) acrylic acid perfluoro-n-propyl, (meth) acrylic Acid perfluoro-iso-propyl, trimethylmethyl (meth) acrylate, cumyl (meth) acrylate, 3- (N, N-dimethylamino) propyl (meth) acrylate, (meth) acrylic acid-2-hydroxy (Meth) acrylic acid esters such as ethyl and (meth) acrylic acid-2-hydroxypropyl;
(Meth) acrylic acid amide, (meth) acrylic acid N, N-dimethylamide, (meth) acrylic acid N, N-diethylamide, (meth) acrylic acid N, N-dipropylamide, (meth) acrylic acid N, (Meth) acrylic amides such as N-di-iso-propylamide, (meth) acrylic acid anthracenyl amide;
(Meth) acrylic acid anilide, (meth) acryloylnitrile, acrolein,
Vinyl compounds such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate;
Unsaturated dicarboxylic acid diesters such as diethyl citraconic acid, diethyl maleate, diethyl fumarate, diethyl itaconate;
Monomaleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, N- (4-hydroxyphenyl) maleimide;
N- (meth) acryloylphthalimide and the like can be mentioned.

In order to impart more excellent heat resistance and strength, it is effective to use at least one selected from styrene, benzyl (meth) acrylate and monomaleimide as the component (B).
In this case, the copolymerization ratio selected from styrene, benzyl (meth) acrylate and monomaleimide is preferably 1 to 70 mol%, more preferably 3 to 50 mol%.

A known solution polymerization method is applied to the copolymerization reaction between the component (A) and the component (B). The solvent to be used is not particularly limited as long as it is inert to radical polymerization, and a commonly used organic solvent can be used.
Specific examples thereof include ethylene glycol monoalkyl ether acetates such as ethyl acetate, isopropyl acetate, cellosolve acetate, butyl cellosolve acetate;
Diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, carbitol acetate, butyl carbitol acetate; propylene glycol monoalkyl ether acetates;
Acetates such as dipropylene glycol monoalkyl ether acetates;
Ethylene glycol dialkyl ethers;
Diethylene glycol dialkyl ethers such as methyl carbitol, ethyl carbitol, butyl carbitol;
Triethylene glycol dialkyl ethers;
Propylene glycol dialkyl ethers;
Dipropylene glycol dialkyl ethers;
Ethers such as 1,4-dioxane and tetrahydrofuran;
Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone;
Hydrocarbons such as benzene, toluene, xylene, octane and decane; petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha; lactate esters such as methyl lactate, ethyl lactate and butyl lactate;
Examples include dimethylformamide and N-methylpyrrolidone.

These solvents may be used alone or in combination of two or more. The amount of these solvents used is 30 to 1000 parts by weight, preferably 50 to 800 parts by weight, with respect to 100 parts by weight of the copolymer obtained. If the amount of the solvent used is outside this range, it is difficult to control the molecular weight of the copolymer.
The radical polymerization initiator used in the copolymerization reaction is not particularly limited as long as it can initiate radical polymerization, and a commonly used organic peroxide catalyst or azo compound can be used.

Examples of the organic peroxide catalyst include those classified into known ketone peroxides, peroxyketals, hydroperoxides, diallyl peroxides, diacyl peroxides, peroxyesters, and peroxydicarbonates.
Specific examples of the radical polymerization initiator include benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, t-hexyl peroxybenzoate, and t-butyl peroxy. 2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 2,5-dimethyl-2 , 5-bis (t-butylperoxy) hexyl-3,3-isopropyl hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, dicumyl hydroperoxide, acetyl peroxide, bis (4-t- Butylcyclohexyl) peroxydicarbonate Diisopropyl peroxydicarbonate, isobutyl peroxide, 3,3,5-trimethylhexanoyl peroxide, lauryl peroxide, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1 -Bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane, azobisisobutyronitrile, azobiscarbonamide, etc., and one of radical polymerization initiators having an appropriate half-life depending on the polymerization temperature Species or two or more are selectively used.

The amount of the radical polymerization initiator used is 0.5 to 20 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the monomers used in the copolymerization reaction, that is, the components (A) and (B). Part.
The copolymerization reaction may be performed by dissolving the monomer used in the copolymerization reaction and the radical polymerization initiator in a solvent and raising the temperature while stirring. The monomer added with the radical polymerization initiator is heated and stirred. You may carry out by dripping in a solvent. Further, the monomer may be added dropwise while the radical polymerization initiator is added to the solvent and the temperature is raised. The reaction conditions can be freely changed according to the target molecular weight.

(C) component added to the epoxy group contained in the copolymer of (A) component and (B) component is an unsaturated monobasic acid. (C) As a component, a well-known thing can be used, The unsaturated carboxylic acid which has an ethylenically unsaturated double bond is mentioned, As an example, acrylic acid, methacrylic acid, crotonic acid, o-, Examples thereof include monocarboxylic acids such as m-, p-vinylbenzoic acid, α-haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, and cyano substitution. Of these, acrylic acid and / or methacrylic acid are preferred. These (C) components may be used individually by 1 type, and 2 or more types may be mixed and used for them.

Component (C) is added to 10 to 100 mol% of the epoxy group contained in the copolymer obtained by the copolymerization reaction of component (A) and component (B), preferably 30 to 100 mol%. More preferably, it is added to 50 to 100 mol%. If the addition ratio of the component (C) is too small, there are concerns about adverse effects due to residual epoxy groups such as stability over time.
As a method of adding the component (C) to the copolymer of the component (A) and the component (B), a known method can be employed.

  As the (D) polybasic acid anhydride to be added to the hydroxyl group produced when the (C) component is added to the copolymer of the (A) component and the (B) component, known ones can be used, Dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride; trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic And polybasic acid anhydrides such as acid anhydrides and biphenyltetracarboxylic acid anhydrides. Of these, tetrahydrophthalic anhydride and / or succinic anhydride are preferable. As the component (D), one type may be used alone, or two or more types may be mixed and used. By adding such components, the binder resin used in the present invention can be rendered alkali-soluble.

Component (D) is added to 10 to 100 mol% of the hydroxyl group produced when component (C) is added, preferably 20 to 90 mol%, more preferably 30 to 80 mol%. . When the addition ratio is too large, the remaining film ratio at the time of development may decrease, and when it is too small, the solubility becomes insufficient.
As a method of adding the component (D) to the hydroxyl group produced when the component (C) is added to the copolymer of the component (A) and the component (B), a known method can be adopted. .

  In the present invention, in order to further improve the photosensitivity, (D) after addition of polybasic acid anhydride, a glycidyl ether compound having a glycidyl (meth) acrylate or a polymerizable unsaturated group in a part of the generated carboxyl group is added. In order to add or improve developability, after adding (D) polybasic acid anhydride, a glycidyl ether compound having no polymerizable unsaturated group may be added to a part of the generated carboxyl group, Both of these may be added. Specific examples of the glycidyl ether compound having no polymerizable unsaturated group include a glycidyl ether compound having a phenyl group or an alkyl group (manufactured by Nagase Chemical Industries, Ltd., trade names: Denacol EX-111, Denacol EX-121, Denacol) EX-141, Denacol EX-145, Denacol EX-146, Denacol EX-171, Denacol EX-192) and the like.

These resin structures are already known, and are described, for example, in JP-A-8-297366 and JP-A-2001-89533.
As a polystyrene conversion weight average molecular weight (Mw) measured by GPC of such binder resin, 3000-100000 are preferable and 5000-50000 are especially preferable. If the molecular weight is less than 3000, the heat resistance and film strength are inferior. The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) is preferably 2.0 to 5.0.

Such binder resin may be used individually by 1 type, and may mix and use 2 or more types.
Such a binder resin is particularly excellent in adhesion to the substrate without remaining undissolved matter in the non-image area on the substrate, in combination with a urethane-based dispersant and an acrylic dispersant described later. The effect that a high density color pixel can be formed is preferable.

Such a binder resin is usually contained in the range of 10 to 80% by weight, preferably 10 to 70% by weight in the total solid content of the coloring composition for a color filter of the present invention. When the content of the binder resin is less than this range, the solubility of the unexposed portion in the developer is lowered, and it becomes easy to induce development failure. On the other hand, when the amount is larger than this range, the permeability of the developer into the exposed portion increases, and the surface smoothness and sensitivity of the pixel deteriorate.
[1-2] Photopolymerization initiator system The photopolymerization initiator is usually used as a mixture (photopolymerization initiator system) with an accelerator and an additive such as a sensitizing dye added as necessary. The photopolymerization initiator system is a component having a function of generating a polymerization active radical by directly absorbing light or being photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction.

  Examples of the photopolymerization initiator constituting the photopolymerization initiator system component include metallocene compounds including titanocene compounds described in JP-A Nos. 59-152396 and 61-151197, and JP-A-10- 39503 Hexaarylbiimidazole derivatives, halomethyl-s-triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters And the like, radical activators such as α-aminoalkylphenone compounds, and oxime ester initiators described in JP-A No. 2000-80068.

Specific examples of the polymerization initiator that can be used in the present invention are listed below.
2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2-
(4-Methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4
Halomethylated triazine derivatives such as -ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine;
2-trichloromethyl-5- (2'-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2'-benzofuryl) vinyl] -1,3,4-oxa Diazole, 2-trichloromethyl-5- [β- (2 '-(6 "-benzofuryl) vinyl)]-1,3,4-oxadiazole, 2-trichloromethyl-5 monofuryl-1,3, Halomethylated oxadiazole derivatives such as 4-oxadiazole;
2- (2'-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2'-chlorophenyl) -4,5-bis (3'-methoxyphenyl) imidazole dimer, 2- ( 2'-Fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2'-methoxyphenyl)
Imidazole derivatives such as -4,5-diphenylimidazole dimer, (4'-methoxyphenyl) -4,5-diphenylimidazole dimer;
Benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether;
2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1
-Anthraquinone derivatives such as chloroanthraquinone;
Benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone;
2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p -Isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4 '-(methylthio) phenyl) -2-morpholino-1-propanone, 1,1,1-trichloromethyl -Acetophenone derivatives such as (p-butylphenyl) ketone;
Thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2
Thioxanthone derivatives such as 1,4-diisopropylthioxanthone;
Benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate; Acridine derivatives such as 9-phenylacridine and 9- (p-methoxyphenyl) acridine; Phenazines such as 9,10-dimethylbenzphenazine Derivatives;
Anthrone derivatives such as benzanthrone;
Di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentagenyl-Ti-bis-2,3,4,5,6-pentafluorophenyl -1 monoyl, di-cyclopentagenyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, di-cyclopentagenyl-Ti-bis-2,4,6-tri Fluorophen-1-yl, di-cyclopentagenyl-Ti-2,6-dipuruolophen-1-yl, di-cyclopentagenyl-Ti-2,4-difluorophenyl-1-yl, Di-methylcyclopentaenyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, di-methylcyclopentagenyl-Ti-bis-2,6-di-fluoropheny -1-yl, di-cyclopentagenyl-Ti-2,6-di-fluoro-3- (pi 1-yl) - titanocene derivatives such as 1-yl;
2-Methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-
Dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethylbenzoate 4-dimethylaminoisoamylbenzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, Α-aminoalkylphenone compounds such as 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone;
1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole- Oxime ester compounds such as 3-yl]-, 1- (O-acetyloxime).

  Examples of the accelerator constituting the photopolymerization initiator system component include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester, 2-mercaptobenzothiazole, and 2-mercaptobenzoxazole. A mercapto compound having a heterocyclic ring such as 2-mercaptobenzimidazole or an aliphatic polyfunctional mercapto compound is used.

These photopolymerization initiators and accelerators may be used alone or in combination of two or more.
Specific examples of the photopolymerization initiator component include dialkylacetophenone-based compounds described on pages 16 to 26 of “Fine Chemical” (March 1, 1991, vol. 20, No. 4). Benzoin, thioxanthone derivatives, and the like, as well as hexaarylbiimidazole series, S-trihalomethyltriazine series, and JP-A-4-221958 described in JP-A-58-403023 and JP-B-45-37377. And a combination of a titanocene and a xanthene dye, an addition-polymerizable ethylenic saturated double bond-containing compound having an amino group or a urethane group, and the like described in JP-A-4-219756. .

The blending ratio of the photopolymerization initiator component is generally 0.1 to 40% by weight, preferably 0.5 to 30% by weight, based on the total solid content of the color filter coloring composition of the present invention. If the blending ratio is extremely low, the sensitivity to the exposure light may be lowered. Conversely, if the blending ratio is extremely high, the solubility of the unexposed portion in the developer is lowered, and development failure may be induced.
If necessary, a sensitizing dye corresponding to the wavelength of the image exposure light source can be added to the photopolymerization initiator system component for the purpose of increasing the sensitivity. These sensitizing dyes include xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, coumarin dyes having a heterocyclic ring described in JP-A-3-239703 and JP-A-5-289335, and 3-ketocoumarin compounds described in Kaihei 3-239703 and 5-289335, pyromethene dyes described in JP-A-6-19240, and others, JP 47-2528, JP 54-155292, JP 45-37377, JP-A-48-84183, JP-A-52-112681, JP-A-58-15503, JP-A-60-88005, JP-A-59-56403, JP-A-2-6988, JP-A-57-168088. No. 5, JP-A-5-107761, JP-A-5-210240, and JP-A-4-288818. Mention may be made of a dye or the like having a skeleton.

  Among these sensitizing dyes, preferred are amino group-containing sensitizing dyes, and more preferred are compounds having an amino group and a phenyl group in the same molecule. Particularly preferred are, for example, 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone. Benzophenone compounds such as 3,4-diaminobenzophenone; 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl) benzo [4,5 ] Benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-oxazole, 2- (p-dimethylaminophenyl) Benzothiazole, 2- (p-diethyl Aminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-thiadiazole, (p -Dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, (p-diethylaminophenyl) pyrimidine, etc. and p-dialkylaminophenyl group-containing compounds. Of these, 4,4'-dialkylaminobenzophenone is most preferred. A sensitizing dye may also be used individually by 1 type, and 2 or more types may be mixed and used for it.

The blending ratio of the sensitizing dye in the colored composition for a color filter of the present invention is usually 0 to 20% by weight, preferably 0.2 to 15% by weight, more preferably 0.8%, based on the total solid content of the colored composition. 5 to 10% by weight.
[1-3] Monomer The monomer is not particularly limited as long as it contains a photopolymerizable low molecular weight compound that can be polymerized, and is preferably a polyfunctional monomer having a functional group. A compound capable of addition polymerization (hereinafter referred to as “ethylenic compound”) having at least one heavy bond is more preferred. Moreover, the monomer may have an acid group.

  The ethylenic compound is a compound having an ethylenic double bond that undergoes addition polymerization and cures by the action of a photopolymerization initiator described later when the colored composition for a color filter of the present invention is irradiated with actinic rays. It is. The term “monomer” in the present invention means a concept relative to a so-called polymer substance, and in addition to “monomer” in a narrow sense, “dimer”, “trimer”, “oligomer”. Means a concept that also includes

  Examples of the ethylenic compound having an acid group include an unsaturated carboxylic acid, an ester of an unsaturated carboxylic acid and a monohydroxy compound, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, an aromatic polyhydroxy compound and an unsaturated compound. Esters obtained by esterification with unsaturated carboxylic acid, unsaturated carboxylic acid and polyvalent carboxylic acid, and polyhydric hydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds, and polyisocyanate compounds Examples thereof include an ethylenic compound having a urethane skeleton obtained by reacting a (meth) acryloyl-containing hydroxy compound.

Examples of the unsaturated carboxylic acid include (meth) acrylic acid, itaconic acid, ilotonic acid, maleic acid and the like.
Esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylol ethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, penta Acrylic esters such as erythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate and the like can be mentioned. In addition, the acrylic acid part of these acrylates is a methacrylic acid ester replaced with a methacrylic acid part, an itaconic acid ester replaced with an itaconic acid part, a crotonic acid ester replaced with a crotonic acid part, or a maleic acid replaced with a maleic acid part Examples include esters.

Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, pyrogallol triacrylate, and the like.
The ester obtained by the esterification reaction of an unsaturated carboxylic acid with a polyvalent carboxylic acid and a polyvalent hydroxy compound is not necessarily a single substance but may be a mixture. Representative examples include condensates of acrylic acid, phthalic acid and ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, acrylic acid, adipic acid, butanediol and glycerin. And the like.

  Examples of the ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound and a (meth) acryloyl group-containing hydroxy compound include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; alicyclic rings such as cyclohexane diisocyanate and isophorone diisocyanate. Formula diisocyanate; aromatic diisocyanate such as toluene diisocyanate and diphenylmethane diisocyanate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxy (1,1,1-triacryloyloxymethyl) propane, 3-hydroxy (1 , 1,1-Trimethacryloyloxymethyl) propane and other (meth) acryloyl group-containing hydroxy compounds And the like.

Other examples of the ethylenic compound used in the present invention include acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate.
In the present invention, the monomer is a polyfunctional monomer and may have an acid group such as a carboxyl group, a sulfonic acid group, or a phosphoric acid group. Therefore, if the ethylenic compound has an unreacted carboxyl group as in the case of a mixture as described above, this can be used as it is. The acid group may be introduced by reacting the group with a non-aromatic carboxylic acid anhydride. In this case, specific examples of the non-aromatic carboxylic acid anhydride used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, succinic anhydride, anhydrous Maleic acid is mentioned.

  In the present invention, the monomer having an acid value is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. A polyfunctional monomer having an acid group is preferable, and in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol.

These monomers may be used alone, but since it is difficult to use a single compound in production, two or more kinds may be used in combination. Moreover, you may use together the polyfunctional monomer which does not have an acid group as a monomer, and the polyfunctional monomer which has an acid group as needed.
A preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mg-KOH / g, and particularly preferably 5 to 30 mg-KOH / g. If the acid value of the polyfunctional monomer is too low, the developing dissolution properties will be lowered, and if it is too high, the production and handling will be difficult, the photopolymerization performance will be lowered, and the curability such as the surface smoothness of the pixels will be inferior. Therefore, when two or more polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, the acid groups as the entire polyfunctional monomer should be adjusted to fall within the above range. Is essential.

  In the present invention, more preferred polyfunctional monomers having an acid group are mainly dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and succinic acid ester of dipentaerythritol pentaacrylate which are commercially available as TO1382 manufactured by Toagosei Co., Ltd. It is a mixture as a component. Other polyfunctional monomers can be used in combination with this polyfunctional monomer.

The blending ratio of these polyfunctional monomers is usually 5 to 80% by weight, preferably 10 to 70% by weight, based on the total solid content of the color filter coloring composition of the present invention. % By weight, preferably 10 to 100% by weight, more preferably 20 to 80% by weight.
As described above, as a demand on the market in recent years, in the color filter coloring composition, the weight ratio of the color material component is increasing with respect to the total solid content. In such a recent requirement level, a more preferable blending ratio of the polyfunctional monomer (ratio to the total solid content of the coloring composition) varies depending on the coloring material of the coloring composition, and in the case of a red composition, 10 to 30 wt. 10% to 25% by weight in the case of a green composition, 10% to 30% by weight in the case of a blue composition, and the acid value of the coloring composition depends on the acid value of the polyfunctional monomer used. It is determined as appropriate so as to be in the preferred range described below.
[1-4] Coloring material Coloring material refers to the coloring material for coloring composition for color filter of the present invention. As the coloring material, dyes and pigments can be used, but pigments are preferable from the viewpoint of heat resistance, light resistance and the like. As the pigment, various color pigments such as a blue pigment, a green pigment, a red pigment, a yellow pigment, a purple pigment, an orange pigment, a brown pigment, and a black pigment can be used. In addition to organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene and perylene, various inorganic pigments can be used. It is. Specific examples of pigments that can be used are shown below by pigment numbers. Note that “CI” described below means a color index (CI).

  Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 , 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267 268, 269, 270, 271, 272, 273, 274, 275, 276. Of these, C.I. I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. I. Pigment red 177, 209, 224, 254.

  Examples of blue pigments include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79. Of these, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, more preferably C.I. I. Pigment blue 15: 6.

Examples of green pigments include C.I. I. Pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55. Of these, C.I. I. And CI Pigment Green 7 and 36.
Examples of yellow pigments include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202 , 203, 204, 205, 206, 207, 208. Of these, C.I. I. Pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, more preferably C.I. I. Pigment yellow 83, 138, 139, 150, 180.

  Examples of orange pigments include C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79. Of these, C.I. I. And CI pigment oranges 38 and 71.

  Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50. Of these, C.I. I. Pigment violet 19, 23, more preferably C.I. I. And CI Pigment Violet 23.

  Moreover, when the coloring composition for color filters of this invention is the coloring composition for resin black matrices of a color filter, a black coloring material can be used as a coloring material. The black color material may be a single black color material or a mixture of red, green, blue, and the like. These color materials can be appropriately selected from inorganic or organic pigments and dyes. In the case of inorganic and organic pigments, it is preferable to use the pigment dispersed in an average particle size of 1 μm or less, preferably 0.5 μm or less.

  Color materials that can be mixed for preparing a black color material include Victoria Pure Blue (42595), Auramin O (41000), Catillon Brilliant Flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B (45170). Safranin OK 70: 100 (50240), Erioglaucine X (42080), No. 120 / Lionol Yellow (21090), Lionol Yellow GRO (21090), Shimla First Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Shimler First Red 4015 (12355), Lionol Red 7B4401 (15850), Fast Gen Blue TGR-L (74160), Lionol Blue SM (26150), Lionol Blue ES (Pigment Blue 15: 6), Lionogen Red GD (Pigment Red 168), Lionol Green 2YS (Pigment Green 36), etc. (The numbers in parentheses above mean the color index (CI)).

  Further, other pigments that can be used in combination are C.I. I. For example, C.I. I. Yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, C.I. I. Orange pigments 36, 43, 51, 55, 59, 61, C.I. I. Red pigments 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, C.I. I. Violet pigments 19, 23, 29, 30, 37, 40, 50, C.I. I. Blue pigment 15, 15: 1, 15: 4, 22, 60, 64, C.I. I. Green pigment 7, C.I. I. Examples thereof include brown pigments 23, 25, and 26.

Examples of the black color material that can be used alone include carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, and titanium black.
Among these, carbon black and titanium black are preferable from the viewpoints of light shielding rate and image characteristics. Examples of carbon black include the following carbon black.
Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, # 5, # 10, # 20, # 25, # 30, # 32, # 33, # 40, # 44, # 45 # 47, # 50, # 52, # 55, # 650, # 750, # 850, # 950, # 960, # 970, # 980, # 990, # 1000, # 2200, # 2300, # 2350, # 2400, # 2600, # 3050, # 3150, # 325
0, # 3600, # 3750, # 3950, # 4000, # 4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31
Made by Degussa: Printex3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Pr
intex90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V, PrintexG, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170
Manufactured by Cabot Corporation: Monarch 120, Monarch 280, Monarch 460, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch
1400, Monarch 4630, REGAL99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660
R, BLACK PEARLS 480, PEARLS 130, VULCAN XC72R, ELFTEX-8
Made by Colombian Carbon: Raven11, Raven14, Raven15, Raven16, Raven22, Raven30, Raven35, Raven40, Raven410, Raven420, Raven450, Raven500, Raven780, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10 , RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000
Titanium black will be described below.

As a method for producing titanium black, a method of heating and reducing a mixture of titanium dioxide and metallic titanium in a reducing atmosphere (Japanese Patent Laid-Open No. 49-5432), ultrafine obtained by high-temperature hydrolysis of titanium tetrachloride. A method of reducing titanium dioxide in a reducing atmosphere containing hydrogen (Japanese Patent Laid-Open No. 57-205322), a method of reducing titanium dioxide or titanium hydroxide at high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 60-65069, No. 61-201610), and a method of attaching a vanadium compound to titanium dioxide or titanium hydroxide and reducing it at high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 61-201610). It is not a thing.

Examples of commercially available titanium black products include Mitsubishi Materials Titanium Black 10S, 12S, 13R, 13M, and 13M-C.
As an example of another black pigment, aniline black, an iron oxide black pigment, and organic pigments of three colors of red, green, and blue can be mixed and used as a black pigment.
In addition, barium sulfate, lead sulfate, titanium oxide, yellow lead, bengara, chromium oxide, or the like can also be used as the pigment.

A plurality of the above-mentioned various pigments can be used in combination. For example, in order to adjust the chromaticity, a green pigment and a yellow pigment can be used in combination, or a blue pigment and a violet pigment can be used in combination.
The average particle size of these pigments is usually 1 μm, preferably 0.5 μm or less, more preferably 0.25 μm or less.

Examples of the dye that can be used as the coloring material include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.
Examples of the azo dye include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. Disperse Blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Molded Red 7, C.I. I. Moldant Yellow 5, C.I. I. Examples thereof include Moldant Black 7.

Examples of anthraquinone dyes include C.I. I. Bat Blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disper thread 60, C.I. I. Disperse Blue 56, C.I. I. Disperse Blue 60 etc. are mentioned.
Other examples of the phthalocyanine dye include C.I. I. Pad Blue 5 and the like are quinone imine dyes such as C.I. I. Basic Blue 3, C.I. I. Basic Blue 9 and the like are quinoline dyes such as C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like are nitro dyes such as C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 and the like.

The ratio of the coloring material in the coloring composition for a color filter of the present invention can be usually selected in the range of 1 to 70% by weight with respect to the total solid content in the coloring composition. In this range, 10 to 70% by weight is more preferable, and in the present invention, 25 to 60% by weight is particularly preferable. When the content ratio of the color material is too small, the film thickness for obtaining a desired color density becomes too large, which adversely affects the gap control and the like when forming a liquid crystal cell. On the other hand, when the content ratio of the color material is too large, the ratio of other components is relatively decreased, and sufficient image formability may not be obtained or the development stability may be deteriorated.
[1-5] Solvent The colored composition for a color filter of the present invention is generally prepared by dissolving or dispersing the above-described solid content in a solvent.

In the coloring composition for a color filter of the present invention, the solvent contains a binder resin, a photopolymerization initiation system, a monomer, a coloring material, an organic carboxylic acid, an organic carboxylic acid anhydride, and other components blended as necessary. Dissolves or disperses and functions to adjust viscosity.
Examples of the solvent include diisopropyl ether, mineral spirit, n-pentane, amyl ether, ethyl caprylate, n-hexane, diethyl ether, isoprene, ethyl isobutyl ether, butyl stearate, n-octane, valsol # 2, and apco #. 18 solvent, diisobutylene, amyl acetate, butyl acetate, apcocinner, butyl ether, diisobutyl ketone, methylcyclohexene, methyl nonyl ketone, propyl ether, dodecane, soak solvent no. 1 and no. 2, amyl formate, dihexyl ether, diisopropyl ketone, Solvesso # 150, (n, sec, t-) butyl acetate, hexene, shell TS28 solvent, butyl chloride, ethyl amyl ketone, ethyl benzoate, amyl chloride, ethylene glycol diethyl ether , Ethyl orthoformate, methoxymethylpentanone, methyl butyl ketone, methyl hexyl ketone, methyl isobutyrate, benzonitrile, ethyl propionate, methyl cellosolve acetate, methyl isoamyl ketone, methyl isobutyl ketone, propyl acetate, amyl acetate, Amylformate, bicyclohexyl, diethylene glycol monoethyl ether acetate, dipentene, methoxymethylpentanol, methylamino Luketone, methyl isopropyl ketone, propyl propionate, propylene glycol-t-butyl ether, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, carbitol, cyclohexanone, ethyl acetate, ethyl lactate, propylene glycol, propylene glycol monomethyl ether, propylene Glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether acetate, 3-methoxypropionic acid, 3-ethoxypropionic acid, Methyl 3-ethoxypropionate, 3 Ethyl ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, ethylene glycol acetate, ethyl carbitol, butyl carbitol, ethylene glycol mono Examples include butyl ether, propylene glycol-t-butyl ether, 3-methyl-3-methoxybutanol, tripropylene glycol methyl ether, and 3-methyl-3-methoxybutyl acetate. These solvents may be used alone or in combination of two or more.

Although there is no restriction | limiting in particular in content of the said solvent which occupies for the whole coloring composition for color filters of this invention, Usually, the upper limit shall be 99 weight% or less in the ratio for the whole coloring composition. When the proportion of the solvent exceeds 99% by weight, the coloring material and other components are too small, which is inappropriate for forming a coating film. On the other hand, the lower limit of the solvent content is usually 75% by weight or more, preferably 80% by weight or more, more preferably 82% by weight or more in consideration of viscosity suitable for coating.
[1-6] Organic Carboxylic Acid and Organic Carboxylic Anhydride The colored composition for a color filter of the present invention has a solubility at 5 ° C. in the solvent described in [1-5] in addition to the above components. It is essential to contain 0.7% by weight or more of organic carboxylic acid and organic carboxylic acid anhydride). There is no problem of resist remaining in the non-pixel portion on the substrate after development and adhesion of undissolved strips of the resist to the pixel portion and the non-pixel portion. A coloring composition for a color filter capable of forming color pixels with high accuracy and uniformity is provided.
[1-6-1] Organic carboxylic acid Examples of the organic carboxylic acid include aliphatic carboxylic acids and / or aromatic carboxylic acids. Specific examples of the aliphatic carboxylic acid include monoacids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid, glycolic acid, acrylic acid, and methacrylic acid. Carboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethyl Examples thereof include dicarboxylic acids such as succinic acid, cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, and fumaric acid, and tricarboxylic acids such as tricarbaryl acid, aconitic acid, and camphoric acid. Specific examples of aromatic carboxylic acids include benzoic acid, toluic acid, cumic acid, hemelic acid, mesitylene acid, phthalic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, and merophanic acid. , Pyromellitic acid, phenylacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidenacetic acid, coumaric acid, umbelic acid, etc. Examples thereof include carboxylic acids in which a carboxyl group is directly bonded to a group, and carboxylic acids in which a carboxyl group is bonded to a phenyl group through a carbon bond.

Among the organic carboxylic acids, monocarboxylic acids and dicarboxylic acids are preferable, and malonic acid, glutaric acid, and glycolic acid are more preferable, and malonic acid is particularly preferable.
Further, the organic carboxylic acid has a solubility in the solvent (5 ° C.) described in [1-5] above of 0.00.
It is 7% by weight or more, preferably 1% by weight or more, more preferably 5% by weight or more, and particularly preferably 10% by weight or more. If the solubility is too low, the undissolved material will hinder the production, or recrystallization will occur after the production, which is not preferable.

The molecular weight of the organic carboxylic acid is 1000 or less, and usually 50 or more. If the molecular weight of the organic carboxylic acid is too large, the effect of improving the soiling is insufficient, and if it is too small, the addition amount may be reduced or process contamination may occur due to sublimation or volatilization.
[1-6-2] Organic carboxylic acid anhydride The organic carboxylic acid anhydride includes an aliphatic carboxylic acid anhydride and / or an aromatic carboxylic acid anhydride. Specific examples of the aliphatic carboxylic acid anhydride include Includes acetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, itaconic anhydride, citraconic anhydride, glutaric anhydride, 1,2-cyclohexenedicarboxylic anhydride, n -Aliphatic carboxylic acid anhydrides such as octadecyl succinic acid and anhydrous 5-norbornene-2,3-dicarboxylic acid. Specific examples of the aromatic carboxylic acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and naphthalic anhydride.

Among the organic carboxylic acid anhydrides, maleic anhydride, succinic anhydride, itaconic anhydride, and citraconic anhydride are preferable, and maleic anhydride is more preferable.
The molecular weight of the organic carboxylic acid anhydride is usually 800 or less, preferably 600 or less, more preferably 500 or less, and usually 50 or more. If the molecular weight of the organic carboxylic acid anhydride is too large, the effect of improving background stains is insufficient.

One of these organic carboxylic acids and organic carboxylic acid anhydrides may be used alone, or two or more thereof may be mixed and used.
The addition amount of these organic carboxylic acid and organic carboxylic acid anhydride is usually 0.01% by weight or more, preferably 0.03% by weight or more in the total solid content of the color filter coloring composition of the present invention, More preferably, it is 0.05 weight% or more, Usually, 10 weight% or less, Preferably it is 5 weight% or less, More preferably, it is 3 weight% or less. If the addition amount is too small, a sufficient addition effect cannot be obtained. If the addition amount is too large, surface smoothness and sensitivity are deteriorated, and undissolved peeling pieces may be generated.
Moreover, the ratio of the addition amount of the organic carboxylic acid to the organic carboxylic acid anhydride is usually 1/99 to 99/1, preferably 20/80 to 80/20, and more preferably 30/70 to 70/30.
If the ratio of the organic carboxylic acid added to the organic carboxylic acid anhydride is too large, the storage stability is insufficient, and if it is too small, the effect of improving the soiling cannot be obtained sufficiently.
[1-7] Other solid content The colored composition for a color filter of the present invention may further contain a solid content other than the above components as necessary. Examples of such components include a dispersant, a dispersion aid, a surfactant, a thermal polymerization inhibitor, a plasticizer, a storage stabilizer, a surface protective agent, an adhesion improver, and a development improver.
[1-7-1] Dispersant The dispersant is preferably a dispersant having a nitrogen-containing functional group, and more preferably an acrylic dispersant, a urethane dispersant, or a graft copolymer dispersant. .
[1-7-1-1]
Examples of urethane dispersants include (1) polyisocyanate compounds, (2) compounds having one or two hydroxyl groups in the same molecule, and (3) compounds having active hydrogen and tertiary amino groups in the same molecule. A dispersion resin obtained by reacting is preferable.
(1) Polyisocyanate compound Examples of the polyisocyanate compound include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, Aromatic diisocyanates such as tolidine diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate and other aliphatic diisocyanates, isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate) , Ω, ω'-diisocyanate dimethylcyclohexane, alicyclic diisocyanates, xylylene diisocyanate, α , Α, α ′, α′-tetramethylxylylene diisocyanate, etc., aliphatic diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, triisocyanate such as tris (isocyanatephenylmethane), tris (isocyanatephenyl) thiophosphate, and trimers thereof, water adducts, and these Examples include polyol adducts. Preferred as the polyisocyanate are trimers of organic diisocyanate, and most preferred are trimerene of tolylene diisocyanate and trimer of isophorone diisocyanate. These may be used alone or in combination of two or more.

As a method for producing an isocyanate trimer, the polyisocyanate may be formed by using an appropriate trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates, etc. And the trimerization is stopped by adding a catalyst poison, and then the unreacted polyisocyanate is removed by solvent extraction and thin-film distillation to obtain the desired isocyanurate group-containing polyisocyanate.
(2) Compound having one or two hydroxyl groups in the same molecule Examples of the compound having one or two hydroxyl groups in the same molecule include polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol, and the like. And a mixture of two or more of these having one end hydroxyl group alkoxylated with an alkyl group having 1 to 25 carbon atoms.

  Polyether glycols include polyether diols, polyether ester diols, and mixtures of two or more of these. Examples of the polyether diol include those obtained by homopolymerizing or copolymerizing alkylene oxide, such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol, and the like. The mixture of 2 or more types of these is mentioned. Polyether ester diols include those obtained by reacting a mixture of ether group-containing diols or other glycols with dicarboxylic acids or their anhydrides or reacting polyester glycols with alkylene oxides, such as poly (poly And oxytetramethylene) adipate. Most preferred as the polyether glycol is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol or a compound in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.

  Polyester glycol includes dicarboxylic acid (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or anhydrides thereof and glycol (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, Dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-2,4- Nanthanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,8-octamethylene glycol, Aliphatic glycols such as 2-methyl-1,8-octamethylene glycol and 1,9-nonanediol, alicyclic glycols such as bishydroxymethylcyclohexane, aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene, N -N-alkyl dialkanolamines such as methyldiethanolamine) obtained by polycondensation, such as polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene / propylene adipate, etc., or the diol or carbon number 1 to 25 monovalent Polylactone diol or polylactone monool obtained by using an alcohol as an initiator, for example, polycaprolactone glycol, polymethyl valerolactone and mixtures of two or more thereof. Most preferred as the polyester glycol is polycaprolactone glycol or polycaprolactone starting with an alcohol having 1 to 25 carbon atoms, more specifically, a compound obtained by ring-opening addition polymerization of ε-caprolactone to a monool. .

Examples of polycarbonate glycol include poly (1,6-hexylene) carbonate and poly (3-methyl-1,5-pentylene) carbonate. Examples of polyolefin glycol include polybutadiene glycol, hydrogenated polybutadiene glycol, and hydrogenated polyisoprene glycol. Is mentioned.
Of the compounds having one or two hydroxyl groups in the same molecule, polyether glycol and polyester glycol are particularly preferred.

The number average molecular weight of the compound having one or two hydroxyl groups in the same molecule is 300 to 10,000, preferably 500 to 6,000, and more preferably 1,000 to 4,000.
(3) Compound having active hydrogen and tertiary amino group in the same molecule The compound having active hydrogen and tertiary amino group in the same molecule used in the present invention will be described. The active hydrogen, that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom or a sulfur atom includes a hydrogen atom in a functional group such as a hydroxyl group, an amino group, and a thiol group. Of these, the hydrogen atom of the amino group is preferred. The tertiary amino group is not particularly limited. Moreover, as a tertiary amino group, the amino group which has a C1-C4 alkyl group, or a heterocyclic structure, More specifically, an imidazole ring or a triazole ring is mentioned.

  Examples of such compounds having an active hydrogen and a tertiary amino group in the same molecule include N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, N , N-dipropyl-1,3-propanediamine, N, N-dibutyl-1,3-propanediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dipropylethylenediamine, N, N -Dibutylethylenediamine, N, N-dimethyl-1,4-butanediamine, N, N-diethyl-1,4-butanediamine, N, N-dipropyl-1,4-butanediamine, N, N-dibutyl-1 , 4-butanediamine and the like.

  In addition, the tertiary amino group is a nitrogen-containing heterocycle, such as pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzotriazole ring, benzoxazole ring, benzo Examples thereof include N-containing hetero 5-membered rings such as thiazole ring and benzothiadiazole ring, nitrogen-containing hetero 6-membered rings such as pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring and isoquinoline ring. Preferred as these nitrogen-containing heterocycles are an imidazole ring or a triazole ring.

  Specific examples of these compounds having an imidazole ring and a primary amino group include 1- (3-aminopropyl) imidazole, histidine, 2-aminoimidazole, 1- (2-aminoethyl) imidazole and the like. . Further, specific examples of the compound having a triazole ring and an amino group include 3-amino-1,2,4-triazole, 5- (2-amino-5-chlorophenyl) -3-phenyl-1H-1 , 2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino-1 , 4-diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-triazole and the like. Among them, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, 1- (3-aminopropyl) imidazole, 3-amino-1,2,4-triazole preferable.

  A preferable blending ratio of the urethane-based dispersant raw material is 10 to 200 parts by weight of a compound having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the same molecule with respect to 100 parts by weight of the polyisocyanate compound. Is 20 to 190 parts by weight, more preferably 30 to 180 parts by weight, and the compound having an active hydrogen and a tertiary amino group in the same molecule is 0.2 to 25 parts by weight, preferably 0.3 to 24 parts by weight. .

  The polystyrene-converted weight average molecular weight (Mw) measured by GPC of such a urethane-based dispersant is usually 1,000 to 200,000, preferably 2,000 to 100,000, more preferably 3,000 to 50,000. Range. If the molecular weight is less than 1,000, the dispersibility and dispersion stability are poor, and if it exceeds 200,000, the solubility is lowered and the dispersibility is poor, and at the same time, it becomes difficult to control the reaction.

  The production of such a urethane-based dispersant is performed according to a known method for producing a polyurethane resin. As a solvent for production, usually, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, isophorone, esters such as ethyl acetate, butyl acetate, cellosolve acetate, benzene, toluene, xylene, hexane Hydrocarbons such as diacetone alcohol, isopropanol, sec-butanol, tert-butanol, etc., chlorides such as methylene chloride and chloroform, ethers such as tetrahydrofuran and diethyl ether, dimethylformamide, N-methyl One or more of aprotic polar solvents such as pyrrolidone and dimethyl sulfoxide are used.

In the production, a usual urethanization reaction catalyst is used. Examples of the catalyst include tin-based compounds such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctate, and stannous octoate, iron-based compounds such as iron acetylacetonate and ferric chloride, triethylamine, and triethylenediamine. Secondary amine type and the like can be mentioned.
The introduction amount of the compound having active hydrogen and tertiary amino group in the same molecule is preferably controlled in the range of 1 to 100 mg-KOH / g in terms of the amine value after the reaction. More preferably, it is the range of 5-95 mg-KOH / g. The amine value is a value expressed in mg of KOH corresponding to the acid value after neutralization titration of the basic group with an acid. When the amine value is lower than the above range, the dispersing ability tends to be lowered, and when it exceeds the above range, the developability tends to be lowered.

In addition, when an isocyanate group remains in the dispersion resin obtained by the above reaction, it is preferable to crush the isocyanate group with an alcohol or an amino compound because the stability with time of the product becomes high.
[1-7-1-2] Acrylic Dispersant As an acrylic dispersant, an AB containing an A block having a quaternary ammonium base in a side chain and a B block having no quaternary ammonium base. Block copolymers and / or B-A-B block copolymers are preferred.

The A blocks constituting the block copolymer of the acrylic dispersing agent, a quaternary ammonium base, preferably ^{_{-N + R 1a R 2a R 3a}} · Y - ( where, R _1a, R _2a and R _3a are each independently Represents a hydrogen atom or an optionally substituted cyclic or chain hydrocarbon group, or two or more of R _1a , R _2a and R _3a are bonded to each other to form a cyclic structure. Y ⁻ represents a counter anion.) And has a quaternary ammonium base. The quaternary ammonium base may be directly bonded to the main chain, but may be bonded to the main chain via a divalent linking group.

In -N ⁺ R _1a R _2a R _3a , as a cyclic structure formed by combining two or more of R _1a , R _2a and R _3a with each other, for example, a 5- to 7-membered nitrogen-containing heterocyclic monocycle or A condensed ring formed by condensing two of these may be mentioned. The nitrogen-containing heterocycle preferably has no aromaticity, more preferably a saturated ring. Specific examples include the following.

(In the above formula, R represents any group of R _{1a to} R _3a .)
These cyclic structures may further have a substituent.
As R _1a to R _3a in the ^{_{-N + R 1a R 2a R 3a}} , and more preferably may have an alkyl group, or a substituent having carbon atoms of 1 to 3 may have a substituent It is a benzyl group which may have a phenyl group or a substituent.

  As the A block, those containing a partial structure represented by the following general formula (6) are particularly preferable.

(In the general formula (6), R _1a , R _2a and R _3a each independently represent a hydrogen atom or an optionally substituted cyclic or chain hydrocarbon group. Alternatively, R _1a , R _2a And two or more of R _3a may be bonded to each other to form a cyclic structure, R _4a represents a hydrogen atom or a methyl group, X represents a divalent linking group, and Y ⁻ represents Represents a counter anion.)
In the general formula (6), examples of the divalent linking group X include, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group, —CONH—R _5a —, —COO—R _6a — (provided that R _5a and R _6a represents a direct bond, an alkylene group having 1 to 10 carbon atoms, or an ether group having 1 to 10 carbon atoms (—R _7a —O—R _8a —: R _7a and R _8a are each independently an alkylene group). And the like, preferably —COO—R _6a —.

Further, Y ⁻ of the counter anion includes Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , CH ₃ CO.
O ^-, PF ₆ ^-, and the like.
Two or more kinds of partial structures containing the specific quaternary ammonium base as described above may be contained in one A block. In that case, two or more quaternary ammonium base-containing partial structures may be contained in the A block in any form of random copolymerization or block copolymerization. Moreover, the partial structure which does not contain this quaternary ammonium base may be contained in the A block, and examples of the partial structure include a partial structure derived from a (meth) acrylic acid ester monomer described later. It is done. The content of the partial structure containing no quaternary ammonium base in the A block is preferably 0 to 50% by weight, more preferably 0 to 20% by weight. Most preferably, it is not included in the A block.

  On the other hand, as the B block constituting the block copolymer of the dispersant, for example, styrene monomers such as styrene and α-methylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate (propyl) methacrylate , Isopropyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate (Meth) acrylate monomers such as glycidyl ethyl acrylate and N, N-dimethylaminoethyl (meth) acrylate; (meth) acrylate monomers such as (meth) acrylic chloride; (meth) acrylamide, N-methylolacrylamide, , N-dimethylacrylamide, (meth) acrylamide monomers such as N, N-dimethylaminoethylacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonic acid glycidyl ether; and N-methacryloylmorpholine Examples include polymer structures.

  The B block is particularly preferably a partial structure derived from a (meth) acrylic acid ester monomer represented by the following general formula (7).

(In the general formula (7), R _9a represents a hydrogen atom or a methyl group. R _10a may have a cyclic or chain alkyl group which may have a substituent, or a substituent. Represents a good allyl group or an aralkyl group which may have a substituent.)
Two or more kinds of the partial structure derived from the (meth) acrylic acid ester monomer may be contained in one B block. Of course, the B block may further contain a partial structure other than these. When a partial structure derived from two or more monomers is present in a B block that does not contain a quaternary ammonium base, each partial structure is contained in the B block in any form of random copolymerization or block copolymerization. May be. When the B block contains a partial structure other than the partial structure derived from the (meth) acrylic acid ester monomer, the content of the partial structure other than the (meth) acrylic acid ester monomer in the B block is preferably Is 0 to 50% by weight, more preferably 0 to 20% by weight, but it is most preferable that a partial structure other than the (meth) acrylic acid ester monomer is not contained in the B block.

The acrylic dispersant used in the present invention is an AB block or a B-A-B block copolymer type polymer compound composed of such an A block and a B block, and such a block copolymer. Is prepared, for example, by the living polymerization method shown below.
The living polymerization method includes an anion living polymerization method, a cation living polymerization method, and a radical living polymerization method. In the anion living polymerization method, the polymerization active species is an anion, for example, shown in the following scheme.

  In the radical living polymerization method, the polymerization active species is a radical, and is represented by the following scheme, for example.

In synthesizing such an acrylic dispersant, JP-A-9-62002, P. Lutz, P. Masson et al, Polym. Bull. 12, 79 (1984), BC Anderson, GD Andrews et al. , Macromolecules, 14, 1601 (1981), K. Hatada, K. Ute, et al, Polym. J. 17, 977 (1985), 18, 1037 (1986), Koichi Right Hand, Koichi Hatada, Polymer Processing, 36 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Polymer Journal, 46, 189 (1989), M. Kuroki, T. Aida, J. Am. Chem. Sic, 109, 4737 (1987), Takuzo Aida Inoue Shohei, Synthetic Organic Chemistry, 43, 300 (1985), DY Sogoh, WR Hertler et al., Macromolecules, 20, 1473 (1987), and the like can be employed.

  Whether the dispersant used in the present invention is an AB block copolymer or a B-A-B block copolymer, the A block / B block ratio (weight ratio) constituting the copolymer. Is usually in the range of 1/99 or more, especially 5/95 or more, and usually 80/20 or less, especially 60/40 or less. Outside this range, it may not be possible to combine good heat resistance and dispersibility.

In addition, the amount of the quaternary ammonium base in 1 g of the AB block copolymer and the BAB block copolymer according to the present invention is preferably 0.1 to 10 mmol, and outside this range. In some cases, good heat resistance and dispersibility cannot be combined.
Such a block copolymer usually contains an amino group produced in the production process, but its amine value is about 1 to 100 mg-KOH / g. The amine value is a value expressed in mg of KOH corresponding to the acid value after neutralization titration of a basic amino group with an acid.

  Moreover, although the acid value of this block copolymer depends on the presence and type of the acid group that is the basis of the acid value, it is generally preferable that the acid value is low, and is usually 100 mg-KOH / g or less, and its molecular weight is The weight average molecular weight (Mw) in terms of polystyrene measured by GPC is usually in the range of 1000 or more and 100,000 or less. When the molecular weight of the block copolymer is too small, the dispersion stability is lowered, and when it is too large, the developability and the resolution tend to be lowered.

In the present invention, as the dispersant, a commercially available urethane-based and / or acrylic-based dispersant having a structure similar to that described above can also be applied.
[1-7-1-3] Graft Copolymer Dispersant The graft copolymer dispersant preferably has a repeating unit containing a nitrogen atom in the main chain. Especially, it is preferable to have a repeating unit represented by Formula (I) or / and a repeating unit represented by Formula (II).

(In the formula, R ₁ represents an alkylene group having 1 to 5 carbon atoms, and A represents a hydrogen atom or any one of the following formulas (III) to (V).)
In the above formula (I), R ₁ represents a linear or branched alkylene group having 1 to 5 carbon atoms such as methylene, ethylene or propylene, preferably 2 to 3 carbon atoms, more preferably ethylene. It is a group. A represents a hydrogen atom or any one of the following formulas (III) to (V), preferably formula (III).

In the formula (II), R _1, A has the same meaning as R _1, A of formula (I).

In the above formula (III), W ₁ represents a linear or branched alkylene group having 2 to 10 carbon atoms, and an alkylene group having 4 to 7 carbon atoms such as butylene, pentylene and hexylene is particularly preferable. p represents an integer of 1 to 20, preferably an integer of 5 to 10.

In the above formula (IV), Y ₁ represents a divalent linking group. Among them, an alkylene group having 1 to 4 carbon atoms such as ethylene and propylene and an alkyleneoxy group having 1 to 4 carbon atoms such as ethyleneoxy and propyleneoxy are included. preferable. W ₂ represents a linear or branched alkylene group having 2 to 10 carbon atoms such as ethylene, propylene, or butylene, and among them, an alkylene group having 2 to 3 carbon atoms such as ethylene or propylene is preferable. Y ₂ represents a hydrogen atom or —CO—R ₂ (R ₂ represents an alkyl group having 1 to 10 carbon atoms such as ethyl, propyl, butyl, pentyl, hexyl, etc., among which carbon number 2 such as ethyl, propyl, butyl, pentyl, etc. ~ 5 alkyl groups are preferred). q represents the integer of 1-20, Preferably it is an integer of 5-10.

In the above formula (V), W ₃ represents an alkyl group having 1 to 50 carbon atoms or a hydroxyalkyl group having 1 to 50 carbon atoms having 1 to 5 hydroxyl groups, among which an alkyl group having 10 to 20 carbon atoms such as stearyl, A C10-20 hydroxyalkyl group having 1-2 hydroxyl groups such as monohydroxystearyl is preferred.
The content of the repeating unit represented by formula (I) or (II) in the graft copolymer of the present invention is preferably as high as possible, usually 50 mol% or more, and preferably 70 mol% or more. The repeating unit represented by the formula (I) and the repeating unit represented by the formula (II) may both be present, and the content ratio is not particularly limited. It is preferable to contain more repeating units. The total number of repeating units represented by formula (I) or formula (II) is usually 1 to 100, preferably 10 to 70, and more preferably 20 to 50. Moreover, repeating units other than formula (I) and formula (II) may be included, and examples of other repeating units include an alkylene group and an alkyleneoxy group. The graft copolymer of the present invention preferably has a terminal of —NH ₂ and —R ₁ —NH ₂ (R ₁ is as defined above for R ₁ ).

In the graft copolymer of the present invention, the main chain may be linear or branched.
The amine value of the graft copolymer of the present invention is usually from 5 to 100 mgKOH / g, preferably from 10 to 70 mgKOH / g, and more preferably from 15 to 40 mgKOH / g. If the amine value is too low, the dispersion stability may decrease and the viscosity may become unstable. Conversely, if the amine value is too high, the residue may increase or the electrical characteristics after the liquid crystal panel is formed may deteriorate.

  As a weight average molecular weight measured by GPC of the said dispersing agent, 3000-100000 are preferable and 5000-50000 are especially preferable. When the weight average molecular weight is less than 3000, the color material cannot be prevented from agglomerating and may become highly viscous or gelled. When the weight average molecular weight exceeds 100000, the material itself becomes highly viscous and dissolved in an organic solvent. It is not preferable because of lack of properties.

As a method for synthesizing the dispersant, a known method can be employed, and for example, a method described in JP-B-63-30057 can be used.
In the coloring composition for a color filter of the present invention, the content of the dispersant is usually 10 to 300% by weight, preferably 20 to 100% by weight, and particularly preferably 30 to 80% by weight with respect to the color material. %. If the content of the dispersant is too small, adsorption to the coloring material is insufficient, aggregation cannot be prevented, and viscosity or gelation may occur. On the other hand, if the content is too large, the film thickness increases. Therefore, when used in a color filter, cell gap control failure may occur in the liquid crystal cell forming step, which is not preferable in either case.
[1-7-2] Dispersion aid Examples of the dispersion aid include pigment derivatives. As pigment derivatives, azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole, dioxazine And derivatives such as pigments. As the substituent of the pigment derivative, a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a phthalimidomethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, an amide group, etc. are directly present on the pigment skeleton or an alkyl group, aryl group, complex Examples thereof include those bonded via a ring group and the like, preferably a sulfonamide group and a quaternary salt thereof, and a sulfonic acid group, and more preferably a sulfonic acid group. In addition, a plurality of these substituents may be substituted on one pigment skeleton, or a mixture of compounds having different numbers of substitutions. Specific examples of pigment derivatives include azo pigment sulfonic acid derivatives, phthalocyanine pigment sulfonic acid derivatives, quinophthalone pigment sulfonic acid derivatives, anthraquinone pigment sulfonic acid derivatives, quinacridone pigment sulfonic acid derivatives, and diketopyrrolopyrrole pigment sulfonic acid. Derivatives, sulfonic acid derivatives of dioxazine pigments and the like.

The addition amount of the pigment derivative is usually 0.1 to 30% by weight, preferably 0.1 to 20% by weight or less, more preferably 0.1 to 10% by weight, based on the coloring material in the colored composition of the present invention. Most preferably, it is 0.1 to 5% by weight. This is because if the added amount is small, the effect is not sufficiently exhibited, and conversely if the added amount is too large, dispersibility and dispersion stability are deteriorated.
[1-7-3] Surfactant A variety of surfactants such as anionic, cationic, nonionic and amphoteric surfactants can be used as surfactants, but they are unlikely to adversely affect various properties. In this respect, it is preferable to use a nonionic surfactant.

The addition amount of the surfactant is usually 0.001 to 10% by weight, preferably 0.005 to 1% by weight, and more preferably 0.01 to 0. 0% by weight with respect to the total solid content in the colored composition of the present invention. 5% by weight, most preferably 0.03 to 0.3% by weight. If the addition amount of the surfactant is less than the above range, the smoothness and uniformity of the coating film cannot be expressed. .
[1-7-4] Thermal polymerization inhibitor Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6-t-butyl-p-cresol, β-naphthol, and the like. . The addition amount of the thermal polymerization inhibitor is preferably in the range of 0 to 3% by weight with respect to the total solid content of the colored composition of the present invention.
[1-7-5] Plasticizer Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin and the like. Is used. The amount of these plasticizers added is preferably 10% by weight or less based on the total solid content of the colored composition of the present invention.
[1-7-6] Others In addition, a storage stabilizer, a surface protective agent, an adhesion improver, a development improver and the like can be added as necessary. The amount of these components added is preferably 20% by weight or less based on the total solid content of the colored composition of the present invention.
[2] Preparation of Colored Composition (Color Filter Coating Liquid) Next, a method for preparing the color composition for color filter according to the first invention of the present invention will be described.

  First, a predetermined amount of each of the coloring material, the solvent, and the dispersant is weighed, and in the dispersion treatment step, the coloring material is dispersed to obtain a liquid colored composition (ink-like liquid). In this dispersion treatment step, a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like can be used. By carrying out this dispersion treatment, the color material is made into fine particles, so that the coating characteristics of the colored composition are improved and the transmittance of the product color filter substrate is improved.

  When the colorant is subjected to a dispersion treatment, it is preferable to appropriately use the binder resin or the dispersion aid. For example, when the dispersion treatment is performed using a sand grinder, it is preferable to use glass beads or zirconia beads having a diameter of 0.1 to several mm. The temperature for the dispersion treatment is usually set in the range of 0 ° C to 100 ° C, preferably in the range of room temperature to 80 ° C. The dispersion time varies depending on the composition of the ink-like liquid (coloring material, solvent, dispersant, etc.), the size of the sand grinder apparatus, etc., and therefore needs to be adjusted as appropriate.

The ink-like liquid obtained by the above dispersion treatment is mixed with a solvent, a binder resin, a polyfunctional monomer, a photopolymerization initiator system component, and other components blended as necessary to obtain a uniform dispersion solution. . In each of the dispersion treatment step and the mixing step, fine dust may be mixed, and thus the obtained color filter coating solution is preferably filtered with a filter or the like.
[3] Production of Color Filter Next, a method for producing a color filter according to the second invention of the present invention will be described.

The color filter is usually manufactured by forming a black matrix on a transparent substrate and then sequentially forming red, green, and blue pixel images.
The coloring composition for a color filter of the present invention is used as at least one pixel image forming coating liquid of black, red, green, and blue. For black resists, for red, green, and blue color resists, the resin black matrix forming surface formed on the transparent substrate, or a metal formed using a chromium compound or other light shielding metal material A pixel image of each color is formed on the black matrix forming surface by performing respective processes of coating, heat drying, image exposure, development and thermosetting.
[3-1] Transparent substrate (support)
The transparent substrate of the color filter is not particularly limited as long as it is transparent and has an appropriate strength. Examples of the material include polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, thermoplastic resin sheets such as polycarbonate, polymethyl methacrylate, and polysulfone, epoxy resins, unsaturated polyester resins, and poly (meth). Examples thereof include thermosetting resin sheets such as acrylic resins, and various glasses. Among these, glass and heat resistant resin are preferable from the viewpoint of heat resistance.

Thin film formation of various resins such as corona discharge treatment, ozone treatment, silane coupling agent, and urethane-based resin is necessary on transparent substrates and black matrix forming substrates described later for improving surface properties such as adhesion. Processing may be performed.
The thickness of the transparent substrate is usually 0.05 to 10 mm, preferably 0.1 to 7 mm. Moreover, when performing the thin film formation process of various resin, the film thickness is 0.01-10 micrometers normally, Preferably it is the range of 0.05-5 micrometers.
[3-2] Black matrix The black matrix is formed on a transparent substrate using a light-shielding metal thin film or a photosensitive black composition for black matrix. As the light-shielding metal material, chromium compounds such as metal chromium, chromium oxide and chromium nitride, nickel and tungsten alloy, etc. are used, and these may be laminated in a plurality of layers.

  These metal light shielding films are generally formed by a sputtering method, and after forming a desired pattern in a film shape with a positive photoresist, ceric ammonium nitrate, perchloric acid and / or nitric acid are added to chromium. Other materials are etched using an etchant according to the material, and finally a positive photoresist is stripped with a dedicated stripper to form a black matrix. be able to.

  In this case, first, a thin film of the metal or metal / metal oxide is formed on the transparent substrate by vapor deposition or sputtering. Next, after forming a coating film of the colored composition on the thin film, the coating film is exposed and developed using a photomask having a repetitive pattern such as a stripe, a mosaic, and a triangle to form a resist image. Thereafter, this coating film can be etched to form a black matrix.

On the other hand, when the black composition for black matrix is used, a black matrix is formed using a coloring composition containing a black color material. For example, single or plural black color materials such as carbon black, graphite, iron black, aniline black, cyanine black, titanium black, or red, green, blue, etc., appropriately selected from inorganic or organic pigments and dyes A black matrix can be formed in the same manner as described below for forming a red, green, and blue pixel image using a coloring composition containing a black color material by mixing the above.
[3-3] Formation of pixels [3-3-1] Formation of coating film On a transparent substrate provided with a black matrix, a coloring composition containing one color material of red, green, and blue is applied and dried. After that, a photomask is overlaid on the formed coating film, and image exposure, development, and thermal curing or photocuring are performed as necessary through this photomask to form a pixel image, and a colored layer of the pixel image Create A color filter image can be formed by performing this operation for each of the three colored compositions of red, green, and blue.

  The coloring composition for the color filter can be applied by a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method, or the like. In particular, the die coating method significantly reduces the amount of coating solution used, and has no influence from mist adhering to the spin coating method. To preferred.

If the thickness of the coating film is too thick, pattern development becomes difficult, and gap adjustment in the liquid crystal cell forming process may be difficult. Expression may be impossible. The thickness of the coating film is usually preferably in the range of 0.2 to 20 μm as the film thickness after drying, more preferably in the range of 0.5 to 10 μm, and still more preferably in the range of 0.8 to 5 μm. It is a range.
[3-3-2] Drying of Coating Film The coating film formed by applying the coloring composition to the transparent substrate is preferably dried by a drying method using a hot plate, IR oven, or convection oven. Usually, after preliminary drying, two-stage drying is performed by heating again and drying. The conditions for the preliminary drying can be appropriately selected according to the type of the solvent component, the performance of the dryer to be used, and the like. The drying time is usually selected in the range of 15 to 5 minutes at a temperature of 40 to 80 ° C., preferably 30 to 50 to 70 ° C., depending on the type of solvent component, the performance of the dryer used, and the like. It is selected in the range of seconds to 3 minutes.

The reheat drying temperature condition is 50 to 200 ° C higher than the predrying temperature, preferably 70 to 160 ° C, particularly preferably 70 to 130 ° C. The drying time is preferably 10 seconds to 10 minutes, and more preferably 15 seconds to 5 minutes, depending on the heating temperature. The higher the drying temperature, the better the adhesion to the transparent substrate. However, if the drying temperature is too high, the binder resin is decomposed, and thermal polymerization may be induced to cause development failure. The coating film may be dried by a reduced pressure drying method in which the temperature is not increased and drying is performed in a reduced pressure chamber.
[3-3-3] Exposure Step Image exposure is performed by overlaying a negative matrix pattern on the dried coating film of the colored composition and irradiating an ultraviolet or visible light source through the mask pattern. At this time, if necessary, exposure may be performed after an oxygen blocking layer such as a polyvinyl alcohol layer is formed on the colored composition film in order to prevent a decrease in sensitivity of the colored composition film due to oxygen.

The light source used for image exposure is not particularly limited. For example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a fluorescent lamp. And lamp light sources such as argon ion laser, YAG laser, excimer laser, nitrogen laser, helium cadmium laser, and semiconductor laser. An optical filter can also be used when used by irradiating light of a specific wavelength.
[3-3-4] Development Step After the image exposure, development can be performed using an organic solvent or an aqueous solution containing a surfactant and an alkaline compound. This aqueous solution may further contain an organic solvent, a buffering agent, a complexing agent, a dye or a pigment.

  Alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate Inorganic alkaline compounds such as sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-di- or triethanolamine, mono-di- or trimethyl Ami, mono-di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline, etc. And alkali compounds. These alkaline compounds may be used individually by 1 type, and 2 or more types may be mixed and used for them.

  Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, and alkylbenzene sulfonic acids. Examples include anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, sulfosuccinate esters, amphoteric surfactants such as alkylbetaines, amino acids, etc. They may be used alone or in combination of two or more.

Examples of the organic solvent include one or more of isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol, and the like. The organic solvent may be used alone or in combination with an aqueous solution.
There are no particular limitations on the conditions for the development treatment, and usually the development temperature is in the range of 10 to 50 ° C., especially 15 to 45 ° C., particularly preferably 20 to 40 ° C. The development methods are immersion development, spray development, brush Any of a developing method, an ultrasonic developing method and the like can be used.
[3-3-5] Thermosetting treatment The developed color filter substrate is usually subjected to a thermosetting treatment or a photocuring treatment, preferably a thermosetting treatment.

As for the thermosetting treatment conditions, the temperature is selected in the range of 100 to 280 ° C, preferably in the range of 150 to 250 ° C, and the time is selected in the range of 5 to 60 minutes.
Through these series of steps, the patterning image formation for one color is completed. This process is sequentially repeated to pattern (black,) red, green, and blue to form a color filter. Note that the patterning order of the three colors red, green, and blue is not limited to the order described above.
[3-3-6] Formation of transparent electrode The color filter according to the present invention forms a transparent electrode such as ITO on the image as it is, and is used as a part of components such as a color display and a liquid crystal display device. However, in order to improve surface smoothness and durability, a top coat layer such as polyamide or polyimide can be provided on the image as necessary.

Further, in some applications such as a planar alignment type drive system (IPS mode), the transparent electrode may not be formed.
[4] Liquid crystal display device (panel)
Next, a method for manufacturing a liquid crystal display device (panel) according to the third aspect of the present invention will be described.
In the liquid crystal display device of the present invention, an alignment film is usually formed on the color filter of the present invention, spacers are dispersed on the alignment film, and then bonded to a counter substrate to form a liquid crystal cell. It is manufactured by injecting liquid crystal into the cell and connecting it to the counter electrode.

As the alignment film, a resin film such as polyimide is suitable. For the formation of the alignment film, a gravure printing method and / or a flexographic printing method is usually employed, and the thickness of the alignment film is usually several tens of nm. The alignment film is cured by thermal baking, and then surface-treated by irradiation with ultraviolet rays or a rubbing cloth to process the surface state so that the tilt of the liquid crystal can be adjusted.
A spacer having a size corresponding to a gap (gap) with the counter substrate is used, and a spacer of 2 to 8 μm is usually preferable. A photo spacer (PS) of a transparent resin film can be formed on the color filter substrate by photolithography, and this can be used instead of the spacer.

As the counter substrate, an array substrate is usually used, and a TFT (thin film transistor) substrate is particularly preferable.
The gap for bonding to the counter substrate varies depending on the use of the liquid crystal display device, but is usually selected in the range of 2 to 8 μm. After being bonded to the counter substrate, portions other than the liquid crystal injection port are sealed with a sealing material such as an epoxy resin. The sealing material is cured by ultraviolet (UV) irradiation and / or heating, and the periphery of the liquid crystal cell is sealed.

The liquid crystal cell whose periphery is sealed is cut into panel units, then decompressed in a vacuum chamber, the liquid crystal injection port is immersed in liquid crystal, and then the liquid crystal is injected into the liquid crystal cell by leaking in the chamber. . The degree of reduced pressure in the liquid crystal cell is usually 1 × 10 ⁻² to 1 × 10 ⁻⁷ Pa, preferably 1 × 10 ⁻³ to 1 × 10 ⁻⁶ Pa. Moreover, it is preferable to heat a liquid crystal cell at the time of pressure reduction, and heating temperature is 30-100 degreeC normally, More preferably, it is 50-90 degreeC. The warming hold during decompression is usually in the range of 10 to 60 minutes, and then immersed in the liquid crystal. The liquid crystal cell into which the liquid crystal is injected has a liquid crystal display device (panel) completed by sealing the liquid crystal injection port by curing the UV curable resin.

  The type of liquid crystal is not particularly limited, and conventionally known liquid crystals such as aromatic, aliphatic, and polycyclic compounds are used, and any of lyotropic liquid crystals, thermotropic liquid crystals, and the like may be used. As the thermotropic liquid crystal, nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal and the like are known, but any of them may be used.

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. In addition, this invention is not limited to description of a following example, unless the summary is exceeded.
[1] Synthesis Example 1: Production of urethane-based dispersant [2] Preparation of red pigment dispersion A I. 20 parts by weight of Pigment Red 177, 70 parts by weight of propylene glycol monomethyl ether acetate as a solvent, and 10 parts by weight of the urethane-based dispersant synthesized in the above [1] were used together with 300 parts by weight of zirconia beads having a diameter of 0.5 mm and stainless steel. The container was filled and dispersed in a paint shaker for 6 hours to prepare a red pigment dispersion A.
[3] Preparation of blue pigment dispersion B I. 20 parts by weight of Pigment Red 115: 6, 70 parts by weight of propylene glycol monomethyl ether acetate as a solvent, and 10 parts by weight of a urethane-based dispersant similar to the above [2] were used, and 300 parts by weight of zirconia beads having a diameter of 0.5 mm. In addition, the mixture was filled in a stainless steel container and dispersed in a paint shaker for 6 hours to prepare a red pigment dispersion B.
[4] Preparation of coloring composition (resist) Next, the pigment dispersion and each component shown in the following table were blended to prepare a coloring composition.

[5] Solubility in solvents Using propylene glycol monomethyl ether acetate as a solvent, the organic carboxylic acid and the organic carboxylic acid anhydride used in the colored composition were each 1% by weight, and the solubility at 5 ° C was examined. Undissolved material was visually observed and evaluated according to the following criteria. The results are shown in Tables 2 and 3.

○: Undissolved material is not observed. ×: Undissolved material is observed. [6] Developability of colored composition Spin the colored composition on a glass substrate (AN100 manufactured by Asahi Glass Co., Ltd.) having a 5 cm square and a thickness of 0.7 mm. Coated and prebaked for 3 minutes on a hot plate at 80 ° C. At the time of application, the rotation speed was adjusted so that the film thickness after drying was 2.5 μm.

As a developer, a 0.04% by weight aqueous potassium hydroxide solution is prepared in a beaker, and the glass substrate is immersed in the developer while stirring with a stirrer, and the development state of the dried film of the colored composition is visually observed. The evaluation was based on the following criteria. The results are shown in Tables 2 and 3.
○: No peeling piece is observed. ×: The peeling piece is recognized. [7] Soil stain and scum stability The colored composition stored at 23 ° C. for 1 month immediately after preparation and 23 months after preparation on a chromium-deposited glass substrate. Each was spin-coated and pre-baked on an 80 ° C. hot plate for 3 minutes. At the time of application, the rotation speed was adjusted so that the film thickness after drying was 2.5 μm.

Next, the sample was exposed at 60 mj / cm 2 through a mask pattern with a high-pressure mercury lamp, and then developed with the same developer as described above. After development, the substrate was rinsed with sufficient water and then dried with clean air.
The non-image area (on the color filter) of the developed sample was wiped 10 times with a dustless cloth (Toraysee MK Clean Cloth manufactured by Toray Industries, Inc.) soaked with 100% by weight ethanol. The dust-free cloth was fixed to the tip of a 1 cm × 1 cm resin square and impregnated with 0.1 cc of ethanol using a dropper. The pigment adhesion to the dust-free cloth was visually observed, and the presence or absence of the colored composition remaining in the non-image area after development was evaluated according to the following criteria. The results are shown in Tables 2 and 3.

○: No pigment adhesion to the dust-free cloth was observed.
(Triangle | delta): The pigment adhesion to a dust-free cloth was recognized very slightly.
X: Pigment adhesion to a dust-free cloth was clearly observed.
[8] Line width stability Immediately after preparation and / or after preparation, the coloring compositions of Examples and Comparative Examples stored at 23 ° C. for 1 month were applied on a glass substrate to a dry film thickness of 2.0 μm, and 80 After heating and drying at 3 ° C. for 3 minutes, using a test mask having a linear opening with a line width of 1 μm and exposing at a gap of 150 μm and an exposure amount of 300 mJ / cm ² , a 0.04 wt% potassium hydroxide aqueous solution performed developed for 60 seconds at a liquid pressure of 0.2 kg / cm ² at a temperature of the developer 23 ° C. in, followed when forming a 3 kg / cm ² pattern for 30 seconds spray water washing treatment with water pressure, as a linear image The remaining minimum pattern width was measured. The results are shown in Tables 2 and 3.

○: Minimum pattern width is 10 μm or less ×: Minimum pattern width exceeds 10 μm

From Tables 2 and 3, it was confirmed that the present invention has good developability, no soiling, and good storage stability.

The coloring composition for color filter of the present invention is used in the production of a color filter. Residue of a non-pixel part on the substrate after development and adhesion of undissolved strips of the resist to the pixel part and the non-pixel part. There is no problem, the image formability and stability are excellent, and high-density color pixels can be formed accurately and uniformly. In addition, the color filter and the liquid crystal display device formed using such a coloring composition have no problem of adhesion of undissolved strips of the resist to the pixel portion and the non-pixel portion, and the image formability and the stability thereof. And high quality color pixels with high density are formed with high accuracy and uniformity.

  From two or more, the present invention has extremely high industrial applicability in the fields of the color filter coloring composition, the color filter, and the liquid crystal display device.

Claims (5)

Binder resin, photopolymerization initiating system, monomer, colorant, solvent, and propylene glycol monomethyl ether acetate as the solvent, the solubility at 5 ° C. in propylene glycol monomethyl ether acetate is 0.7% by weight or more A coloring composition for a color filter, comprising an organic carboxylic acid and an organic carboxylic acid anhydride.   The coloring composition for a color filter according to claim 1, wherein the organic carboxylic acid according to claim 1 is a monocarboxylic acid and / or a dicarboxylic acid.   The colored composition for a color filter according to claim 2, wherein the monocarboxylic acid and / or dicarboxylic acid according to claim 2 is one or more selected from malonic acid, glutaric acid, and glycolic acid.   A color filter formed using the colored composition according to claim 1.   A liquid crystal display device formed using the color filter according to claim 4.