JP6848610B2 - Compounds, pigment dispersants containing the compounds, coloring compositions and color filters - Google Patents

Description

The present invention is formed of a compound, a pigment dispersant, a pigment composition, a coloring composition, and a coloring composition preferably used for printing inks, paints, resin colorants, inkjet inks, color filter inks, and the like. The present invention relates to color filters used in color liquid crystal display devices, color image pickup tube elements, and the like.

In recent years, in order to realize a high contrast ratio and high brightness in a red composition for a color filter, C.I. I. Pigment Red 176, C.I. I. Pigment Red 242, and C.I. I. Azo pigments such as Pigment Orange 38 are used as the main pigment.

Generally, pigments used in inks and paints are often fine particles in order to achieve a clearer color tone, and in order to solve such problems, pigment dispersants are used, and pigments and vehicles are used. It is known to improve the affinity between pigments and stabilize the dispersion, and various pigment dispersants have been disclosed so far. For example, in a system that disperses highly fine-grained azo pigment particles such as printing inks and paints, especially inkjet inks and color filter inks, azos are used to loosen the strong cohesive force of the pigment particles and obtain stability over time. The compound is used as a pigment dispersant (Patent Documents 1 to 3). However, although this pigment dispersant is excellent in dispersibility, the dispersion has a problem that the sharpness (brightness), which is indispensable for color filter applications, is lowered. Further, Patent Document 4 discloses a naphthol azo compound having one sulfonic acid group, but the dispersibility is inferior to be applied to an ink for a color filter, and a stable dispersion cannot be obtained.

Japanese Unexamined Patent Publication No. 2015-07427 Japanese Unexamined Patent Publication No. 2015-07728 Japanese Unexamined Patent Publication No. 2011-162722 Japanese Unexamined Patent Publication No. 48-82170

An object of the present invention includes a compound having high clarity (brightness) and high heat resistance to naphthol azo pigments (surface foreign matter suppressing effect) in addition to the high dispersion performance previously required for pigment dispersants. It is to provide a pigment composition, a coloring composition, and a color filter.

That is, the present invention relates to a compound represented by the following general formula (1).
General formula (1)

[In the general formula (1), R _{1 to} R ₅ independently represent a hydrogen atom, a halogen atom, a nitro group, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, or ₆ -OR groups. Adjacent groups of R _{1 to} R ₅ may form a benzimidazolone ring. R ₆ represents an alkyl group having 1 to 4 carbon atoms. S ₁ represents a sulfonic acid group; its amine salt, its quaternary ammonium salt or its metal salt. n represents an integer of 2. ]

The present invention also relates to a pigment dispersant containing the above compound.

The present invention also relates to a pigment composition containing the above pigment dispersant and pigment.

The present invention also relates to a coloring composition for a color filter containing a coloring agent and an organic solvent, wherein the coloring agent contains the pigment dispersant or the pigment composition.

The present invention further relates to the above-mentioned coloring composition containing at least one of a photopolymerizable monomer and a photopolymerization initiator.

Furthermore, the present invention relates to a color filter formed by the above coloring composition.

According to the present invention, by using the compound represented by the general formula (1), a coloring composition for a color filter having high brightness, high fluidity and good stability can be obtained, and by using this, the color characteristics are good. It is possible to form a color filter having excellent heat resistance.

Further, since the compound represented by the general formula (1) of the present invention exhibits good dispersion performance with a smaller amount than that of the naphthol azo pigment, a color filter having excellent lightness, coloring power and heat resistance can be obtained. Can be provided. Further, the same effect can be obtained by developing it in an inkjet coloring composition, a printing ink, a resin colorant, a paint, or the like.

The present invention is a compound represented by the following general formula (1). Hereinafter, the present invention will be described in detail.
<Compound represented by the general formula (1)>
General formula (1)

[In the general formula (1), R _{1 to} R ₅ independently represent a hydrogen atom, a halogen atom, a nitro group, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, or ₆ -OR groups. Adjacent groups of R _{1 to} R ₅ may form a benzimidazolone ring. R ₆ represents an alkyl group having 1 to 4 carbon atoms. S ₁ represents a sulfonic acid group; its amine salt, its quaternary ammonium salt or its metal salt. n represents an integer of 2. ]

Substituents in the general formula (1) will be described below, but are not limited thereto.

Examples of the halogen atom in R _{1 to} R ₅ include fluorine, chlorine, bromine, and iodine, and two or more of them may be used in combination.

The alkyl group having 1 to 4 carbon atoms in R _{1 to} R ₆ may be linear or branched, and specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, or an isobutyl group. , The sec-butyl group and the tert-butyl group.

Examples of amines that form amine salts with sulfonic acid groups include (mono, di or tri) alkylamines, substituted or unsubstituted alkylenediamines and alkanolamines, and quaternary ammoniums that form quaternary ammonium salts. Examples thereof include alkylammonium chloride and the like. Examples of the metal forming the metal salt include alkali metals such as Li, Na and K, and polyvalent metals such as Ca, Ba, Al, Mn, Sr, Mg, Fe, Zn and Ni.

Examples of the "substituent" that may have include an alkyl group, an alkoxy group, a halogen, a nitro group and the like. Alkyl groups and halogens are synonymous with the substituents in the above general formula (1). An alkoxy group is a group in which an oxygen atom is bonded to an alkyl group.

<Compound manufacturing method>
As the method for producing the compound of the present invention, an industry-known production method can be used. As an example, an example of a method for producing a compound represented by the following formula (2) is given below, but the present invention is not limited to this method.

(Example of manufacturing method of compound represented by formula (2))
A naphthol azo pigment represented by the following formula (3) is added to 98% sulfuric acid and sulfonated by heating to produce a compound represented by the following formula (2). A compound having n = 2 can be selectively produced by adjusting the concentration of sulfuric acid, the heating temperature, and the heating time.

Equation (2)

Equation (3)

A sufficient dispersion effect can be obtained even if the pigment composition is prepared by mixing the pigment and the compound of the present invention, but further better results can be obtained by preparing the pigment composition by the following method. As a method for preparing a pigment composition other than the mixing method, a dissolver, a high-speed mixer, a homomixer, a kneader, a roll mill, an attritor, a sand mill, various crushers, etc. are used to mechanically prepare a pigment powder and a pigment dispersant powder. A method of adding a solution containing a pigment dispersant to a suspension system using water or an organic solvent to deposit the pigment dispersant on the surface of the pigment, a method of depositing the pigment dispersant on the surface of the pigment, an organic pigment and a pigment in a solvent having strong dissolving power such as sulfuric acid. Examples thereof include a method in which the dispersant is co-dissolved and co-precipitated with a poor solvent such as water.

<Pigment miniaturization>
In order to obtain high brightness and high contrast when the pigment composition of the present invention is used as a coloring composition, a color filter is obtained by refining the pigment particles by, if necessary, salt milling or acid pacing treatment. It can be suitably used for use. The average primary particle size of the pigment determined by TEM (transmission electron microscope) is preferably 10 nm or more in order to enhance the dispersibility in the pigment carrier. Further, in order to obtain a filter segment having high contrast, it is preferably 50 nm or less.

Salt milling is a machine that heats a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent using a kneader such as a kneader, a 2-roll mill, a 3-roll mill, a ball mill, an attritor, or a sand mill. After kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt acts as a crushing aid, and it is considered that the pigment is crushed by utilizing the high hardness of the inorganic salt during salt milling, which causes an active surface and crystal growth. There is. Therefore, during kneading, crushing of the pigment and crystal growth occur at the same time, and the primary particle size of the pigment obtained differs depending on the kneading conditions.

In order to promote the crystal growth of the pigment by heating, the heating temperature is preferably 35 to 150 ° C. The kneading time for salt milling is preferably 2 to 24 hours from the viewpoint of the balance between the particle size distribution of the primary particles of the salt milled pigment and the cost required for salt milling.

By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a very fine primary particle size, a narrow distribution width, and a sharp particle size distribution. In particular, it is preferable to use a dye derivative in combination.

Further, as the water-soluble inorganic salt used for salt milling, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of price. From the viewpoint of both treatment efficiency and production efficiency, the water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by mass, most preferably 300 to 1200 parts by mass, based on the total weight of the pigment (100% by weight).

The water-soluble organic solvent has a function of wetting the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent easily evaporates, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety. For example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by weight, most preferably 50 to 500 parts by weight, based on the total weight of the pigment (100% by weight).

When the pigment composition is subjected to salt milling treatment, a resin may be added if necessary. The type of resin used is not particularly limited, and a natural resin, a modified natural resin, a synthetic resin, a synthetic resin modified with a natural resin, or the like can be used. The resin used is preferably solid at room temperature, water-insoluble, and more preferably partially soluble in the organic solvent. The amount of the resin used is preferably in the range of 2 to 200% by weight based on the total weight of the pigment (100% by weight).

When the pigment composition is subjected to salt milling treatment, a dye derivative may be added if necessary. As the dye derivative, a compound having an organic pigment as a parent skeleton and having a basic group, an acidic group, or a phthalimide methyl group introduced into the organic pigment by a known method can also be used. Specific examples of the organic pigments include quinacridone pigments, phthalocyanine pigments, azo pigments, quinophthalone pigments, isoindolin pigments, isoindolinone pigments, quinoline pigments, diketopyrrolopyrrole pigments, benzoimidazolone pigments and the like. Can be mentioned. In addition, pale yellow aromatic polycyclic compounds such as phthalimide-based, naphthalene-based, naphthoquinone-based, anthracene-based, and anthraquinone-based compounds, which are not generally called dyes, are also included. Examples of the dye derivative include Japanese Patent Application Laid-Open No. 63-305173, Japanese Patent Application Laid-Open No. 57-15620, Japanese Patent Application Laid-Open No. 59-40172, Japanese Patent Application Laid-Open No. 63-17102, Japanese Square Root 5-2469, Japanese Patent Application Laid-Open No. 06- Those described in JP-A-306301, JP-A-2001-220520, JP-A-2003-238842, etc. can be used, and these can be used alone or in combination of two or more.

The amount of the dye derivative used is preferably in the range of 2 to 200% by weight based on the total weight of the pigment (100% by weight).

<Coloring composition for color filters>
The coloring composition of the present invention contains a coloring agent and an organic solvent containing a pigment composition composed of a compound represented by the general formula (1) of the present invention (including a pigment if necessary), and if necessary, a binder. Pigments other than resins, dispersion aids and colorants can also be included.

<Organic solvent>
In the coloring composition of the present invention, the pigment composition is sufficiently dispersed in the pigment composition carrier, and the filter segment is applied onto a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. An organic solvent can be included to facilitate the formation. The organic solvent is selected in consideration of the solubility of each component of the coloring composition and the safety in addition to the good coatability of the coloring composition.

Examples of the organic solvent include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, and 1,4-dioxane. , 2-Heptanone, 2-Methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexene-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3- Methyl-1,3-butanol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene , O-Dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, Ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotersial butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol Monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol Diethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethylate , Dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene Glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl Cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid ester and the like can be mentioned.

Among them, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, etc. It is preferable to use aromatic alcohols such as glycol acetate and benzyl alcohol, and ketones such as cyclohexanone.

These organic solvents may be used alone or in admixture of two or more. Further, since the organic solvent can adjust the coloring composition to an appropriate viscosity and form a filter segment having a desired uniform film thickness, 500 to 4000 based on the total mass of the pigment composition (100% by mass). It is preferably used in an amount of mass%.

<Binder resin>
The binder resin contained in the coloring composition of the present invention disperses the pigment composition, and examples thereof include conventionally known thermoplastic resins and thermosetting resins.

Examples of the thermoplastic resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, and polyurethane resin. , Polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, celluloses, polyethylene (HDPE, LDPE), polybutadiene, polyimide resin and the like.

When used as a color filter application, a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region is preferable. When used in the form of an alkali-developable colored resist, it is preferable to use an alkali-soluble vinyl-based resin in which an acidic group-containing ethylenically unsaturated monomer is copolymerized. Further, in order to further improve the photosensitivity, an energy ray-curable resin having an ethylenically unsaturated active double bond can also be used.

Examples of the alkali-soluble resin obtained by copolymerizing an acidic group-containing ethylenically unsaturated monomer include a resin having an acidic group such as a carboxyl group and a sulfone group. Specifically, the alkali-soluble resin includes an acrylic resin having an acidic group, an α-olefin / (maleic anhydride) maleic anhydride copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or Isobutylene / (maleic anhydride) maleic anhydride copolymer and the like can be mentioned. Among them, an acrylic resin having an acidic group and at least one resin selected from a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic group, is preferably used because of its high heat resistance and transparency.

As an energy ray-curable resin having an ethylenically unsaturated active double bond, a polymer having a reactive substituent such as a hydroxyl group, a carboxyl group or an amino group is substituted with a reactive substituent such as an isocyanate group, an aldehyde group or an epoxy group. A resin is used in which a (meth) acrylic compound having a group or silicic acid is reacted to introduce a photocrosslinkable group such as a (meth) acryloyl group or a styryl group into the polymer. Further, a polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is half-esterled with a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. The modified one is also used.

As the thermoplastic resin, one having both alkali-soluble performance and energy ray curing performance is also preferable for color filter applications.

Examples of the monomer constituting the thermoplastic resin include the following. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-Ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) (Meta) acrylates such as acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, or ethoxypolyethylene glycol (meth) acrylate,

Alternatively, (meth) such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, or acryloylmorpholin. Acrylamides, styrene, styrenes such as α-methylstyrene, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether, vinyl acetate, or fatty acid vinyl such as vinyl propionate. Kind is mentioned.

Alternatively, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimideethane 1,6-bismaleimidehexane, 3-maleimide propionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide Kumarin, 4,4'-bismaleimidediphenylmethane, bis (3-ethyl-5-methyl-4-maleimidephenyl) methane, N, N'-1,3-phenylenedimaleimide, N, N'-1,4- Phenylened maleimide, N- (1-pyrenyl) maleimide, N- (2,4,6-trichlorophenyl) maleimide, N- (4-aminophenyl) maleimide, N- (4-nitrophenyl) maleimide, N-benzyl Maleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-3-maleimidepropionate, N-succinimidyl-4-maleimidebutyrate, N-succinimidyl-6-maleimide Examples thereof include N-substituted maleimides such as hexanoate, N- [4- (2-benzoimidazolyl) phenyl] maleimide, and 9-maleimide acrydin.

Examples of the thermosetting resin include epoxy resin, benzoguanamine resin, rosin-modified maleic acid resin, rosin-modified fumaric acid resin, melamine resin, urea resin, and phenol resin. Of these, epoxy resins and melamine resins are more preferably used from the viewpoint of improving heat resistance.

The weight average molecular weight (Mw) of the binder resin is preferably in the range of 5,000 to 80,000, more preferably in the range of 7,000 to 50,000 in order to preferably disperse the pigment composition. The number average molecular weight (Mn) is preferably in the range of 2,500 to 40,000, and the value of Mw / Mn is preferably 10 or less.

Here, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are determined by connecting four separation columns in series in gel permeation chromatography "HLC-8120GPC" manufactured by Tosoh Corporation, and using Tosoh stocks as fillers in order. It is a polystyrene-equivalent molecular weight measured using tetrahydrofuran as the mobile phase using "TSK-GEL SUPER H5000", "H4000", "H3000", and "H2000" manufactured by the company.

When the binder resin is used for color filters, it is a carboxyl group that acts as an alkali-soluble group during adsorption and development to the pigment composition, an aliphatic group and an aromatic group that act as an affinity group for the pigment composition carrier and solvent. The balance of groups is important for the dispersibility, developability, and durability of the pigment composition, and it is preferable to use a resin having an acid value of 20 to 300 mgKOH / g. If the acid value is less than 20 mgKOH / g, the solubility in a developing solution is poor, and it may be difficult to form a fine pattern. If it exceeds 300 mgKOH / g, fine patterns may not remain in development.

The binder resin can be used in an amount of 20 to 500% by mass based on the total mass of the pigment composition. If it is less than 20% by mass, the film forming property and various resistances are insufficient, and if it is more than 500% by mass, the pigment concentration is low and the color characteristics may not be exhibited.

<Dispersion aid>
When the pigment composition is dispersed in the pigment composition carrier, a dispersion aid such as a pigment derivative, a resin-type dispersant, or a surfactant can be appropriately used. Since the dispersion aid is excellent in dispersing the pigment composition and has a great effect of preventing the reaggregation of the pigment composition after dispersion, the pigment composition is dispersed in the pigment composition carrier using the dispersion aid. When a coloring composition is used, a color filter having high spectral transmittance (brightness) can be obtained.

(Dye derivative)
As the dye derivative used in the present invention, a compound having an organic pigment as a parent skeleton and having a basic group, an acidic group, or a phthalimide methyl group introduced into the organic pigment by a known method can also be used. Specifically, the organic pigments include quinacridone pigments, phthalocyanine pigments, azo pigments, quinophthalone pigments, isoindolin pigments, isoindolinone pigments, quinoline pigments, diketopyrrolopyrrole pigments, benzoimidazolone pigments and the like. Can be mentioned. In addition, pale yellow aromatic polycyclic compounds such as phthalimide-based, naphthalene-based, naphthoquinone-based, anthracene-based, and anthraquinone-based compounds, which are not generally called dyes, are also included. Examples of the dye derivative include Japanese Patent Application Laid-Open No. 63-305173, Japanese Patent Application Laid-Open No. 57-15620, Japanese Patent Application Laid-Open No. 59-40172, Japanese Patent Application Laid-Open No. 63-17102, Japanese Square Root 5-1469, JP-A-06- Those described in JP-A-306301, JP-A-2001-220520, JP-A-2003-238842, etc. can be used, and these can be used alone or in combination of two or more.

The blending amount of the pigment derivative is preferably 0.5% by weight or more, more preferably 1% by weight or more, most preferably 1% by weight or more, based on the total amount of the pigment composition (100% by weight) from the viewpoint of improving the dispersibility of the pigment composition. It is preferably 3% by weight or more. Further, from the viewpoint of heat resistance and light resistance, the total amount of the pigment composition is preferably 40% by weight or less, more preferably 35% by weight or less, based on the total amount (100% by weight).

(Resin type dispersant)
The resin-type dispersant has an affinity site for the pigment composition having a property of adsorbing to the pigment composition and a site compatible with the pigment composition carrier, and is adsorbed on the pigment composition to adsorb the pigment composition. It works to stabilize the dispersion on the carrier. Specifically, as the resin type dispersant, polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts. , Polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products of these, amides and salts thereof formed by the reaction of poly (lower alkyleneimine) with polyester having a free carboxyl group. Oil-based dispersants such as, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, water-soluble such as polyvinylpyrrolidone. Resins, water-soluble polymer compounds, polyester-based, modified polyacrylate-based, ethylene oxide / propylene oxide-added compounds, phosphoric acid ester-based, etc. are used, and these can be used alone or in admixture of two or more. It is not necessarily limited to these.

Among the above dispersants, the acid-base interaction with the pigment dispersant of the present invention is fully utilized, and the viscosity of the coloring composition is lowered with a small amount of addition, and high spectral transmittance is exhibited. A polymer dispersant having a basic functional group is more preferable. In particular, a graft copolymer containing an amino group, a basic functional group-containing acrylic block copolymer having an amino group in the side chain, a urethane-based polymer dispersant, and the like are preferable.

Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170 manufactured by Big Chemie Japan. , 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 6919, or Anti-Terra-U, 203, 204, Or BYK-P104, P104S, 220S, 21116, or Lactimon, Lactimon-WS or Bykuman, etc., SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000 , 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., EFKA-46, 47, manufactured by BASF. 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc. , PB824 and the like.

(Surfactant)
Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalin sulfonate, sodium alkyldiphenyl ether disulfonate. , Anionic surfactants such as monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; alkyl Chaotic surfactants such as quaternary ammonium salts and their ethylene oxide adducts; alkyl betaines such as alkyldimethylaminoacetic acid betaine and amphoteric surfactants such as alkylimidazolin, which may be used alone or in combination of two or more. They can be mixed and used, but are not necessarily limited to these.

When the resin type dispersant and the surfactant are added, the blending amount is preferably 0.1 to 55% by weight, more preferably 0.1 to 45% by weight, based on the total amount of the pigment composition (100% by weight). %. When the blending amount of the resin type dispersant and the surfactant is less than 0.1% by weight, it is difficult to obtain the effect of addition, and when the blending amount is more than 55% by weight, the dispersion is adversely affected by the excessive dispersant. May affect.

<Colorants (other pigments)>
The following pigments or dyes may be used in combination with the coloring composition of the present invention as a coloring agent as long as the effects of the present invention are not impaired, for the purpose of adjusting the chromaticity or the like.

For example, C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 122, 146, 168, 169, 176, 177, 178, 179, 184, 185, 187, 200, 202, 208, 210, 246, 254, 255, 264, 270, 272, 273, 274, 276, 277, 278, 279, Red pigments such as 280, 281, 282, 283, 284, 285, 286, 287 or brominated diketopyrrolopyrrole pigments can be mentioned. Examples of the red dye include xanthene type, azo type (pyridone type, barbituric acid type, metal complex type, etc.), disazo type, anthraquinone type, cyanine type, and the like. Xanthene dyes are particularly preferable.

Specifically, the xanthene-based oil-soluble dyes include CI Solvent Red 35, CI Solvent Red 36, CI Solvent Red 42, CI Solvent Red 43, and CI Solvent Red. Red 44, CI Solvent Red 45, CI Solvent Red 46, CI Solvent Red 47, CI Solvent Red 48, CI Solvent Red 49, CI Solvent Red 72 , CI Solvent Red 73, CI Solvent Red 109, CI Solvent Red 140, CI Solvent Red 141, CI Solvent Red 237, CI Solvent Red 246, C. .I. Solvent Violet 2, CI Solvent Violet 10, etc.

Examples of xanthene-based acid dyes include C.I. I. Acid Red 51, C.I. I. Acid Red 52, C.I. I. Acid Red 87, C.I. I. Acid Red 92, C.I. I. Acid Red 289, C.I. I. Acid Red 388, Rose Bengal B, Acid Rhodamine G, C.I. I. Acid Violet 9 etc.

Examples of the xanthene-based basic dye include C.I. I. Basic Red 1, C.I. I. Basic Red 8, C.I. I. Basic Violet 10 and the like.

In addition, C.I. I. Pigment Orange 38, 43, 71, or 73 or other orange pigments or C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, Yellow pigments such as 193, 194, 198, 199, 213, 214, 218, 219, 220, or 221 can be used in combination. Examples of the orange dye or the yellow dye include quinoline dyes, azo dyes (pyridone dyes, barbituric acid dyes, metal complex dyes, etc.), disazo dyes, methine dyes, and the like.

Preferred dyes to be used in combination include azo-based, naphthol-azo-based, diketopyrrolopyrrole-based, anthraquinone-based, quinophthalone-based, and perylene-based dyes from the viewpoint of color characteristics. Specifically, C.I. I. Pigment Red 254, brominated diketopyrrolopyrrole pigment, C.I. I. Pigment Yellow 138, 139, 150, 185.

<Manufacturing method of coloring composition>
In the coloring composition of the present invention, the pigment composition is mixed with an organic solvent and, if necessary, a binder resin, a dispersion aid, or other dye, and then a kneader, a 2-roll mill, a 3-roll mill, a ball mill, etc. It can be produced by finely dispersing using various dispersion means such as a horizontal sand mill, a vertical sand mill, an annual bead mill, or an attritor. Further, in the coloring composition of the present invention, the pigment composition and other pigments and the like may be dispersed in the pigment composition carrier at the same time, or separately dispersed in the pigment composition carrier may be mixed.

<Photosensitive coloring composition>
The coloring composition of the present invention can be used as a photosensitive coloring composition by further containing at least one of a photopolymerizable monomer and a photopolymerization initiator.

<Photopolymerizable monomer>
The photopolymerizable monomer that may be added to the photosensitive coloring composition of the present invention contains a monomer or oligomer that is cured by ultraviolet rays, heat, or the like to produce a transparent resin, and these may be used alone or in 2). More than seeds can be mixed and used.

Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce a transparent resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. , Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di ( Meta) Acrylate, Trimethylol Propanetri (Meta) Acrylate, Pentaerythritol Tri (Meta) Acrylate, Pentaerythritol Tetra (Meta) Acrylate, 1,6-hexanediol Diglycidyl Ether Di (Meta) Acrylate, Bisphenol A Diglycidyl Etherdi (Meta) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, methylolated melamine (Meta) acrylic acid ester, epoxy (meth) acrylate, various acrylic acid esters such as urethane acrylate and methacrylic acid ester, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol tri Examples thereof include, but are not limited to, vinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, and acrylonitrile. These photopolymerizable compounds may be used alone or in admixture of two or more at any ratio as required.

The blending amount of the photopolymerizable monomer is preferably 5 to 400 parts by weight, and more preferably 10 to 300 parts by weight from the viewpoint of photocurability and developability with respect to 100 parts by weight of the pigment composition. preferable.

<Photopolymerization initiator>
The photosensitive coloring composition of the present invention is cured by ultraviolet irradiation, and a photopolymerization initiator is added as necessary to form a filter segment by a photolithography method, and solvent-developed or alkaline-developed. It can be prepared in the form of a type photosensitive coloring composition.

Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-. Hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 -Acetophenone compounds such as 4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one; benzoin, benzoin Benzoin compounds such as methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylicized benzophenone, 4-benzoyl-4' -Methyldiphenyl sulfide, or benzophenone compounds such as 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorthioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4 Thioxanthone compounds such as −diisopropylthioxanthone or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2-( p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6- Bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho-1-yl) -4,6-bis (trichloromethyl) -s- Triazine, 2- (4-methoxy-naphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4- Triazine compounds such as trichloromethyl- (4'-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)) ], Or an oxime ester compound such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4'-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6-trimethyl) Benzoyl) phenylphosphine oxide, or phosphine compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrene quinone, camphorquinone, ethylanthraquinone; borate compounds; carbazole Compounds; imidazole compounds; or titanosen compounds are used. These photopolymerization initiators can be used alone or in admixture of two or more at any ratio as required.

The content of the photopolymerization initiator is preferably 2 to 200 parts by weight, and more preferably 3 to 150 parts by weight from the viewpoint of photocurability and developability with respect to 100 parts by weight of the pigment composition.

<Sensitizer>
Further, the photosensitive coloring composition of the present invention may contain a sensitizer.
Examples of the sensitizer include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, and anthraquinone derivatives. , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonoal derivatives and other polymethine dyes, acrydin derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indolin derivatives, Azulene derivative, azurenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin derivative, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalyloporphyrazine derivative , Naphthalocyanine derivative, Subphthalocyanine derivative, Pyrylium derivative, Thiopyrylium derivative, Tetraphyllin derivative, Anuren derivative, Spiropyran derivative, Spiroxazine derivative, Thiospiropirane derivative, Metal allene complex, Organic ruthenium complex, or Michler ketone derivative, α-Acyloxy ester , Acylphosphine oxide, methylphenylglycolate, benzyl, 9,10-phenanthrene quinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalofenone, 3,3', or 4,4' -Tetra (t-butylperoxycarbonyl) benzophenone, 4,4'-diethylaminobenzophenone and the like can be mentioned. These sensitizers can be used alone or in admixture of two or more at any ratio, if necessary.

More specifically, Ogawara Nobu et al., "Dye Handbook" (1986, Kodansha), Ogawara Nobu et al., "Functional Dye Chemistry" (1981, CMC), Ikemori Chuzaburo et al., And " The sensitizers described in "Special Functional Materials" (1986, CMC) can be mentioned, but are not limited thereto. In addition, a sensitizer that absorbs light from the ultraviolet to the near infrared region can also be contained.

The content of the sensitizer is preferably 3 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator contained in the photosensitive coloring composition, and is 5 to 50 from the viewpoint of photocurability and developability. It is more preferably a part by weight.

<Amine compounds>
Further, the photosensitive coloring composition of the present invention may contain an amine compound having a function of reducing dissolved oxygen. Examples of such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylaminobenzoate. Examples thereof include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethylparatoluidine.

<Leveling agent>
It is preferable to add a leveling agent to the photosensitive coloring composition of the present invention in order to improve the leveling property of the composition on the transparent substrate. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of the dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning Co., Ltd. and BYK-333 manufactured by Big Chemie Co., Ltd. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by Big Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can also be used in combination. The content of the leveling agent is usually preferably 0.003 to 0.5% by weight based on the total weight of the photosensitive coloring composition (100% by weight).

A particularly preferable leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, which has a hydrophilic group but has low solubility in water and is added to a photosensitive coloring composition. , It has a feature of low surface tension lowering ability, and it is useful to have good wettability to the glass plate despite its low surface tension lowering ability, and addition that does not cause defects in the coating film due to foaming. Those capable of sufficiently suppressing chargeability in terms of amount can be preferably used. As a leveling agent having such preferable properties, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. The polyalkylene oxide unit includes a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

The bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the polyalkylene oxide unit is bonded to the terminal of dimethylpolysiloxane, and dimethylpolysiloxane. It may be any of the linear block copolymer types that are alternately and repeatedly bonded. Didimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ. 2207, but is not limited to these.

Anionic, cationic, nonionic, or amphoteric surfactants can be added as an adjunct to the leveling agent. Two or more kinds of surfactants may be mixed and used. Anionic surfactants to be added as an auxiliary to the leveling agent include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalin sulfonate, and alkyldiphenyl ether disulfonic acid. Sodium, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include ester.

Examples of the chaotic surfactant added as a supplement to the leveling agent include alkyl quaternary ammonium salts and ethylene oxide adducts thereof. Nonionic surfactants to be added to the leveling agent include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, and polyoxyethylene sorbitan monostearate. , Polyethylene glycol monolaurate and the like; alkyl betaines such as alkyldimethylaminoacetic acid betaine, amphoteric surfactants such as alkyl imidazoline, and fluorine-based and silicone-based surfactants.

<Curing agent, curing accelerator>
Further, the photosensitive coloring composition of the present invention may contain a curing agent, a curing accelerator, or the like, if necessary, in order to assist the curing of the thermosetting resin. Phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective as the curing agent, but the curing agent is not particularly limited to these, and is a thermosetting resin. Any curing agent may be used as long as it can react with. Further, among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine-based curing agent are preferably mentioned. Examples of the curing accelerator include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl). -N, N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (eg, triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (eg, dimethylamine, etc.), imidazole derivative bicyclic amidin compounds and salts thereof (eg, eg). Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2- Ethyl-4-methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), guanamine compounds (eg, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (eg, 2,4-diamino-6, etc.) -Methacryloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6- Methacryloyloxyethyl-S-triazine, isocyanuric acid adduct, etc.) and the like can be used. These may be used alone or in combination of two or more. The content of the curing accelerator is preferably 0.01 to 15 parts by weight with respect to 100 parts by weight of the thermosetting resin.

<Other additive ingredients>
The photosensitive coloring composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity over time. Further, an adhesion improver such as a silane coupling agent can be contained in order to improve the adhesion with the transparent substrate.

Examples of the storage stabilizer include quaternary ammonium chloride such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and phosphorous acid and their methyl ethers, t-butylpyrocatechol, tetraethylphosphine, tetraphenylphosphine and the like. Examples thereof include organic phosphine and phosphite. The storage stabilizer can be used in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the colorant.

Adhesion improvers include vinylsilanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylic silanes such as γ-methacryloxypropyltrimethoxysilane, and β- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino) Ethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysisilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-amino Examples thereof include aminosilanes such as propyltrimethoxysilane and N-phenyl-γ-aminopropyltriethoxysilane, and silane coupling agents such as thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the colorant in the photosensitive coloring composition.

<Removal of coarse particles>
The coloring composition and the photosensitive coloring composition of the present invention have coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, and more preferably 0. It is preferable to remove coarse particles of 5 μm or more and mixed dust. As described above, it is preferable that the coloring composition and the photosensitive coloring composition do not substantially contain particles having a size of 0.5 μm or more. More preferably, it is 0.3 μm or less.

<Color filter>
Next, the color filter of the present invention will be described. The color filter of the present invention includes a red filter segment, a green filter segment, and a blue filter segment, in which the red filter segment is a coloring composition or a photosensitive coloring composition containing the compound of the present invention. Formed from.

The green filter segment can be formed by using a conventional green coloring composition containing a green pigment and a pigment carrier or a green photosensitive coloring composition. Examples of the green pigment include C.I. I. Pigment Green 7, 10, 36, 37, 58 and the like are used. In addition, blue pigments such as aluminum phthalocyanine can also be used.

Further, a yellow pigment can be used in combination with the green coloring composition or the green photosensitive coloring composition. Examples of the yellow pigment that can be used in combination include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, Yellow pigments such as 193, 194, 198, 199, 213, 214, 218, 219, 220, or 221 can be mentioned. It is also possible to use a salt-forming compound of a basic dye or an acid dye that exhibits yellow color in combination.

The blue filter segment can be formed by using a conventional blue coloring composition or a blue photosensitive coloring composition containing a blue pigment and a pigment carrier. Examples of the blue pigment include C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64 and the like are used. Further, a purple pigment can be used in combination with the blue coloring composition or the blue photosensitive coloring composition. Examples of the purple pigment that can be used in combination include C.I. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50 and other purple pigments can be mentioned. Further, a salt-forming compound of a basic dye or an acid dye exhibiting blue or purple can also be used. When a dye is used, a xanthene dye is preferable in terms of heat resistance and brightness.

<Manufacturing method of color filter>
The color filter of the present invention can be manufactured by a printing method or a photolithography method. The formation of the filter segment by the printing method can be patterned only by repeating printing and drying of the coloring composition prepared as the printing ink, and therefore, as a manufacturing method of the color filter, it is excellent in mass productivity at low cost. Further, with the development of printing technology, it is possible to print a fine pattern having high dimensional accuracy and smoothness. In order to perform printing, it is preferable that the composition is such that the ink does not dry or solidify on the printing plate or on the blanket. It is also important to control the fluidity of the ink on the printing machine, and the viscosity of the ink can be adjusted with a dispersant or an extender pigment.

When the filter segment is formed by the photolithography method, the coloring composition prepared as the solvent-developable or alkali-developable colored resist material is applied onto a transparent substrate by spray coating, spin coating, slit coating, roll coating or the like. By the method, the coating is applied so that the dry film thickness is 0.2 to 5 μm. If necessary, the dried film is exposed to ultraviolet rays through a mask having a predetermined pattern provided in contact with or without contact with the film. Then, after immersing in a solvent or an alkaline developer or spraying the developer with a spray or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to manufacture a color filter. be able to. Further, in order to promote the polymerization of the colored resist material, heating can be applied as needed. According to the photolithography method, a color filter having higher accuracy than the above printing method can be manufactured.

At the time of development, an aqueous solution of sodium carbonate, sodium hydroxide or the like is used as the alkaline developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Further, an antifoaming agent or a surfactant can be added to the developing solution. In order to increase the ultraviolet exposure sensitivity, the colored resist was applied and dried, and then a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin was applied and dried to form a film for preventing polymerization inhibition by oxygen. After that, ultraviolet exposure can also be performed.

The color filter of the present invention can be produced by an electrodeposition method, a transfer method, or the like in addition to the above methods, but the coloring composition or the photosensitive coloring composition of the present invention can be used in any of the methods. The electrodeposition method is a method of manufacturing a color filter by electrodepositing each color filter segment on the transparent conductive film by electrophoresis of colloidal particles using the transparent conductive film formed on the substrate. .. The transfer method is a method in which a filter segment is formed in advance on the surface of a peelable transfer base sheet, and the filter segment is transferred to a desired substrate.

A black matrix can be formed in advance before each color filter segment is formed on the transparent substrate or the reflective substrate. As the black matrix, a multilayer film of chromium or chromium / chromium oxide, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but the black matrix is not limited thereto. It is also possible to form a thin film transistor (TFT) on the transparent substrate or the reflective substrate in advance, and then form each color filter segment. Further, an overcoat film, a transparent conductive film, or the like is formed on the color filter of the present invention, if necessary.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. In the examples,% and parts represent mass% and parts by mass.

(Weight average molecular weight of binder resin)
A method for calculating the weight average molecular weight (Mw) of the resin type dispersant and the binder resin will be described.

In gel permeation chromatography "HLC-8120GPC" manufactured by Tosoh Corporation, four separation columns are connected in series, and the fillers are "TSK-GEL SUPER H5000", "H4000", "H3000" manufactured by Tosoh Corporation in order. , And "H2000", and the polystyrene-equivalent molecular weight measured using tetrahydrofuran as the mobile phase.

(Acid value of resin)
80 ml of acetone and 10 ml of water are added to 0.5 to 1.0 part of the resin solution and stirred to uniformly dissolve the solution. Using a 0.1 mol / L KOH aqueous solution as a titrator, an automatic titrator (“COM-555”” The acid value of the resin solution was measured by titration using (manufactured by Hiranuma Sangyo). Then, the acid value per solid content of the resin was calculated from the acid value of the resin solution and the solid content concentration of the resin solution.
(LC-MASS (mass spectrometry))
An LC-MS spectrum was used to identify the pigment derivative used in the present invention. The measurement of the LC-MS spectrum was performed under the following conditions.

Equipment: UPLC H-Class / XevoTQD manufactured by Japan Waters Corp.
Column: Symmetry C185 micron (Japan Waters Corp.)
Eluent:
(A) H ₂ O
(B) DMF
Eluent conditions: (A): (B) = 10:90 (volume ratio)
Flow velocity: 0.400 ml / min Injection volume: 1 μl
Column temperature: 40 ° C
Measurement wavelength: 300 nm

The obtained compound was identified based on the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation.

<Manufacturing method of binder resin solution>
(Preparation of acrylic resin solution 1)
196 parts of cyclohexanone was charged into a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer in a separable 4-neck flask, the temperature was raised to 80 ° C., the inside of the reaction vessel was replaced with nitrogen, and then dropped. From the tube, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, paracumylphenol ethylene oxide-modified acrylate (“Aronix M110” manufactured by Toa Synthetic Co., Ltd.) 20.7 A mixture of 1.1 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropping, the reaction was continued for another 3 hours to obtain a solution of acrylic resin. After cooling to room temperature, about 2 parts of the resin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and methoxypropyl acetate is added so that the non-volatile content is 20% by mass in the previously synthesized resin solution. Was added to prepare an acrylic resin solution 1. The weight average molecular weight (Mw) was 26000.

(Preparation of acrylic resin solution 2)
207 parts of cyclohexanone was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer in a separable 4-neck flask, the temperature was raised to 80 ° C., the inside of the reaction vessel was replaced with nitrogen, and then dropped. From the tube, 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide-modified acrylate (Aronix M110 manufactured by Toa Synthetic Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2'-azobis. A mixture of 1.33 parts of isobutyronitrile was added dropwise over 2 hours. After completion of the dropping, the reaction was continued for another 3 hours to obtain a copolymer resin solution. Next, for the entire amount of the obtained copolymer solution, nitrogen gas was stopped, dry air was injected for 1 hour, and the mixture was stirred, cooled to room temperature, and then 2-methacryloyloxyethyl isocyanate (Karens manufactured by Showa Denko Co., Ltd.) A mixture of 6.5 parts of MOI), 0.08 parts of dibutyltin laurate and 26 parts of cyclohexanone was added dropwise at 70 ° C. over 3 hours. After completion of the dropping, the reaction was continued for another 1 hour to obtain a solution of acrylic resin. After cooling to room temperature, about 2 parts of the resin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and cyclohexanone is added to the previously synthesized resin solution so that the non-volatile content is 20% by mass. Acrylic resin solution 2 was prepared. The weight average molecular weight (Mw) was 18,000.

<Compound synthesis>
Examples 1 to 7 and Comparative Examples 1 to 4 are obtained by reacting compound a and compound b as described below. The following compounds (a-1) to (a-3) were used as the reactants a, and the following compounds (b-1) to (b-5) were used as the reactants b, respectively.

[Example 1] (Production of compound (A-1))
27 parts of compound (b-1) and 96 parts of a 25% sodium hydroxide aqueous solution were dissolved in 208 parts of methanol to prepare a coupler solution. On the other hand, 20 parts of compound (a-1) was dispersed in 320 parts of water, ice was added to adjust the temperature to 5 ° C., 36.3 parts of a 35% aqueous hydrochloric acid solution was added, and the mixture was stirred for 1 hour. An aqueous solution prepared by adding 7 parts to 19.2 parts of water was added, and the mixture was stirred for 2 hours. An aqueous solution consisting of 93 parts of an 80% acetic acid aqueous solution, 106 parts of a 25% sodium hydroxide aqueous solution, and 112 parts of water was added to prepare a diazonium salt aqueous solution.
The coupler solution was poured into the diazonium salt aqueous solution at 5 ° C. over 30 minutes to carry out a coupling reaction. After stirring for 2 hours and confirming the disappearance of the diazonium salt, the mixture was heated to 60 ° C., filtered, washed with water, and dried at 80 ° C. for 24 hours to obtain 46 parts of the pigment represented by the formula (3). In 100 parts of 98% sulfuric acid, 5 parts of the pigment of the formula (3) were pulverized and charged at 15 ° C. or lower. Then, the temperature was raised to 50 ° C., the mixture was stirred for 2 hours, and slowly added dropwise to 2000 parts of cold acetone prepared separately. The precipitate was filtered, washed twice with 1000 parts of cold acetone and dried at 80 ° C. for 24 hours to give 6.1 parts of red compound. As a result of mass spectrometry by LC-MS, it was identified that the following compound (A-1) was the main component.

Equation (3)

Compound (A-1)

[Example 2] (Production of compound (A-2))
30 parts of compound (b-2) and 96 parts of a 25% sodium hydroxide aqueous solution were dissolved in 208 parts of methanol to prepare a coupler solution. On the other hand, 20 parts of compound (a-1) was dispersed in 320 parts of water, ice was added to adjust the temperature to 5 ° C., 36.3 parts of a 35% aqueous hydrochloric acid solution was added, and the mixture was stirred for 1 hour. An aqueous solution prepared by adding 7 parts to 19.2 parts of water was added, and the mixture was stirred for 2 hours. An aqueous solution consisting of 93 parts of an 80% acetic acid aqueous solution, 106 parts of a 25% sodium hydroxide aqueous solution, and 112 parts of water was added to prepare a diazonium salt aqueous solution.
The coupler solution was poured into the diazonium salt aqueous solution at 5 ° C. over 30 minutes to carry out a coupling reaction. After stirring for 2 hours and confirming the disappearance of the diazonium salt, the mixture was heated to 60 ° C., filtered, washed with water, and dried at 80 ° C. for 24 hours to obtain 49 parts of the pigment represented by the formula (4). In 100 parts of 98% sulfuric acid, 5 parts of the pigment of the formula (4) were pulverized and charged at 15 ° C. or lower. Then, the temperature was raised to 50 ° C., the mixture was stirred for 2 hours, and slowly added dropwise to 2000 parts of cold acetone prepared separately. The precipitate was filtered, washed twice with 1000 parts of cold acetone and dried at 80 ° C. for 24 hours to give 6.0 parts of red compound. As a result of mass spectrometry by LC-MS, it was identified that the following compound (A-2) was the main component.

Equation (4)

Compound (A-2)

[Example 3] (Production of compound (A-3))
27 parts of compound (b-3) and 96 parts of a 25% sodium hydroxide aqueous solution were dissolved in 208 parts of methanol to prepare a coupler solution. On the other hand, 20 parts of compound (a-1) was dispersed in 320 parts of water, ice was added to adjust the temperature to 5 ° C., 36.3 parts of a 35% aqueous hydrochloric acid solution was added, and the mixture was stirred for 1 hour. An aqueous solution prepared by adding 7 parts to 19.2 parts of water was added, and the mixture was stirred for 2 hours. An aqueous solution consisting of 93 parts of an 80% acetic acid aqueous solution, 106 parts of a 25% sodium hydroxide aqueous solution, and 112 parts of water was added to prepare a diazonium salt aqueous solution.
The coupler solution was poured into the diazonium salt aqueous solution at 5 ° C. over 30 minutes to carry out a coupling reaction. After stirring for 2 hours and confirming the disappearance of the diazonium salt, the mixture was heated to 60 ° C., filtered, washed with water, and dried at 80 ° C. for 24 hours to obtain 45 parts of the pigment represented by the formula (5). In 100 parts of 98% sulfuric acid, 5 parts of the pigment of the formula (5) were pulverized and charged at 15 ° C. or lower. Then, the temperature was raised to 60 ° C., the mixture was stirred for 2 hours, and slowly added dropwise to 2000 parts of cold acetone prepared separately. The precipitate was filtered, washed twice with 1000 parts of cold acetone and dried at 80 ° C. for 24 hours to give 6.1 parts of red compound. As a result of mass spectrometry by LC-MS, it was identified that the following compound (A-3) was the main component.

Equation (5)

Compound (A-3)

[Example 4] (Production of compound (A-4))
26 parts of compound (b-4) and 96 parts of a 25% sodium hydroxide aqueous solution were dissolved in 208 parts of methanol to prepare a coupler solution. On the other hand, 20 parts of compound (a-1) was dispersed in 320 parts of water, ice was added to adjust the temperature to 5 ° C., 36.3 parts of a 35% aqueous hydrochloric acid solution was added, and the mixture was stirred for 1 hour. An aqueous solution prepared by adding 7 parts to 19.2 parts of water was added, and the mixture was stirred for 2 hours. An aqueous solution consisting of 93 parts of an 80% acetic acid aqueous solution, 106 parts of a 25% sodium hydroxide aqueous solution, and 112 parts of water was added to prepare a diazonium salt aqueous solution.
The coupler solution was poured into the diazonium salt aqueous solution at 5 ° C. over 30 minutes to carry out a coupling reaction. After stirring for 2 hours and confirming the disappearance of the diazonium salt, the mixture was heated to 60 ° C., filtered, washed with water, and dried at 80 ° C. for 24 hours to obtain 45 parts of the pigment represented by the formula (6). In 100 parts of 98% sulfuric acid, 5 parts of the pigment of the formula (6) were pulverized and charged at 15 ° C. or lower. Then, the temperature was raised to 60 ° C., the mixture was stirred for 2 hours, and slowly added dropwise to 2000 parts of cold acetone prepared separately. The precipitate was filtered, washed twice with 1000 parts of cold acetone and dried at 80 ° C. for 24 hours to give 6.1 parts of red compound. As a result of mass spectrometry by LC-MS, it was identified that the following compound (A-4) was the main component.

Equation (6)

Compound (A-4)

[Example 5] (Production of compound (A-5))
26 parts of compound (b-5) and 96 parts of a 25% sodium hydroxide aqueous solution were dissolved in 208 parts of methanol to prepare a coupler solution. On the other hand, 20 parts of compound (a-1) was dispersed in 320 parts of water, ice was added to adjust the temperature to 5 ° C., 36.3 parts of a 35% aqueous hydrochloric acid solution was added, and the mixture was stirred for 1 hour. An aqueous solution prepared by adding 7 parts to 19.2 parts of water was added, and the mixture was stirred for 2 hours. An aqueous solution consisting of 93 parts of an 80% acetic acid aqueous solution, 106 parts of a 25% sodium hydroxide aqueous solution, and 112 parts of water was added to prepare a diazonium salt aqueous solution.
The coupler solution was poured into the diazonium salt aqueous solution at 5 ° C. over 30 minutes to carry out a coupling reaction. After stirring for 2 hours and confirming the disappearance of the diazonium salt, the mixture was heated to 60 ° C., filtered, washed with water, and dried at 80 ° C. for 24 hours to obtain 45 parts of the pigment represented by the formula (7). In 100 parts of 98% sulfuric acid, 5 parts of the pigment of the formula (7) were pulverized and charged at 15 ° C. or lower. Then, the temperature was raised to 60 ° C., the mixture was stirred for 2 hours, and slowly added dropwise to 2000 parts of cold acetone prepared separately. The precipitate was filtered, washed twice with 1000 parts of cold acetone and dried at 80 ° C. for 24 hours to give 6.1 parts of red compound. As a result of mass spectrometry by LC-MS, it was identified that the following compound (A-5) was the main component.

Equation (7)

Compound (A-5)

[Example 6] (Production of compound (A-6))
In 100 parts of 98% sulfuric acid, 5 parts of the pigment of the formula (4) were pulverized and charged at 15 ° C. or lower. Then, the temperature was raised to 60 ° C., the mixture was stirred for 2 hours, and slowly added dropwise to 2000 parts of cold acetone prepared separately. The precipitate was filtered and washed twice with 1000 parts of cold acetone to obtain a paste of the compound represented by compound (A-2). The compound paste was mixed with 60 parts of water, and caustic soda was added until the pH became 10 or more. Further, 40 parts of 24 aqueous acetamine solution (10% aqueous solution) was added, and the mixture was stirred at 50 ° C. for 1 hour. The product was filtered, washed with water and dried at 80 ° C. As a result, 8.8 parts of the compound (A-6) which is an amine salt of A-2 was obtained.

[Example 7] (Production of compound (A-7))
In 100 parts of 98% sulfuric acid, 5 parts of the pigment of the formula (4) were pulverized and charged at 15 ° C. or lower. Then, the temperature was raised to 60 ° C., the mixture was stirred for 2 hours, and slowly added dropwise to 2000 parts of cold acetone prepared separately. The precipitate was filtered and washed twice with 1000 parts of cold acetone to obtain a paste of the compound represented by compound (A-2). The compound paste was mixed with 60 parts of water, and caustic soda was added until the pH became 10 or more. Further, 12 parts of a sulfuric acid band solution (8% aqueous solution) was added, and the mixture was stirred at 50 ° C. for 1 hour. The product was filtered, washed with water and dried at 80 ° C. As a result, 6.1 parts of compound (A-7), which is an aluminum salt of compound (A-2), was obtained.

[Comparative Example 1] (Production of Compound (A-8))
30 parts of compound (b-2) and 96 parts of a 25% sodium hydroxide aqueous solution were dissolved in 208 parts of methanol to prepare a coupler solution. On the other hand, 26.6 parts of compound (a-2) was dispersed in 320 parts of water, ice was added to adjust the temperature to 5 ° C., 36.3 parts of a 35% aqueous hydrochloric acid solution was added, and the mixture was stirred for 1 hour, and then sodium nitrite. The prepared aqueous solution was added by adding 6.7 parts to 19.2 parts of water, and the mixture was stirred for 2 hours. An aqueous solution consisting of 93 parts of an 80% acetic acid aqueous solution, 106 parts of a 25% sodium hydroxide aqueous solution, and 112 parts of water was added to prepare a diazonium salt aqueous solution.
The coupler solution was poured into the diazonium salt aqueous solution at 5 ° C. over 30 minutes to carry out a coupling reaction. After stirring for 2 hours and confirming the disappearance of the diazonium salt, the mixture was heated to 60 ° C., filtered, washed with water, and dried at 80 ° C. for 24 hours to obtain 55 parts of a red compound. As a result of mass spectrometry by LC-MS, it was identified that the following compound (A-8) was the main component.

Compound (A-8)

[Comparative Example 2] (Production of Compound (A-9))
30 parts of compound (b-2) and 96 parts of a 25% sodium hydroxide aqueous solution were dissolved in 208 parts of methanol to prepare a coupler solution. On the other hand, 26.6 parts of compound (a-3) was dispersed in 320 parts of water, ice was added to adjust the temperature to 5 ° C., 36.3 parts of a 35% aqueous hydrochloric acid solution was added, and the mixture was stirred for 1 hour, and then sodium nitrite. The prepared aqueous solution was added by adding 6.7 parts to 19.2 parts of water, and the mixture was stirred for 2 hours. An aqueous solution consisting of 93 parts of an 80% acetic acid aqueous solution, 106 parts of a 25% sodium hydroxide aqueous solution, and 112 parts of water was added to prepare a diazonium salt aqueous solution.
The coupler solution was poured into the diazonium salt aqueous solution at 5 ° C. over 30 minutes to carry out a coupling reaction. After stirring for 2 hours and confirming the disappearance of the diazonium salt, the mixture was heated to 60 ° C., filtered, washed with water, and dried at 80 ° C. for 24 hours to obtain 46 parts of a red compound. As a result of mass spectrometry by LC-MS, it was identified that the following compound (A-9) was the main component.

Compound (A-9)

[Comparative Example 3] (Production of Compound (A-10))
In 100 parts of 98% sulfuric acid, 5 parts of C.I. I. Pigment Red 2 was charged at 15 ° C. or lower. Then, the temperature was raised to 60 ° C., the mixture was stirred for 2 hours, and slowly added dropwise to 2000 parts of cold acetone prepared separately. The precipitate was filtered, washed twice with 1000 parts of cold acetone and dried at 80 ° C. for 24 hours to give 6.5 parts of red compound. As a result of mass spectrometry by LC-MS, it was identified that the following compound (A-10) was the main component.

Compound (A-10)

[Comparative Example 4] (Production of Compound (A-11))
5 parts of the compound (A-8) synthesized in Comparative Example 1 was mixed with 60 parts of water, and caustic soda was added until the pH became 10 or more. Further, 5.1 parts of an 8% aqueous aluminum sulfate solution (liquid sulfuric acid band) was added, and the mixture was stirred at 50 ° C. for 1 hour. The product was filtered, washed with water and dried at 80 ° C. As a result, 5.1 parts of compound (A-11), which is an aluminum salt of compound (A-8), was obtained.

<Manufacturing method of pigment composition>
[Production Example 1] (Production of Pigment Composition R-1)
A mixture of 150 parts of the pigment represented by the formula (3), 1500 parts of sodium chloride, and 250 parts of diethylene glycol was kneaded at 60 ° C. for 10 hours using a stainless steel 1-gallon kneader (Inoue Seisakusho). Next, this kneaded product was put into 5000 parts of warm water and stirred for 1 hour while heating at 70 ° C. to form a slurry. After repeating filtration and washing with water to remove sodium chloride and diethylene glycol, the mixture was dried and pulverized to obtain 134 parts of the pigment composition R-1.

[Production Examples 2 to 3] (Production of Pigment Compositions R-2 to 3)
132 parts of the pigment composition R-2 and 134 parts of the pigment composition were similar to the pigment composition R-1, except that the pigment represented by the formula (3) was changed to the pigment shown in Table 4. The thing R-3 was obtained respectively.

[Example 8] (Production of pigment composition R-4)
A mixture of 135 parts of the pigment represented by the formula (3), 15 parts of the compound (A-1), 1500 parts of sodium chloride, and 250 parts of diethylene glycol was mixed with 60 parts using a stainless steel 1 gallon kneader (Inoue Seisakusho). Kneaded at ° C. for 10 hours. Next, this kneaded product was put into 5000 parts of warm water and stirred for 1 hour while heating at 70 ° C. to form a slurry. After repeating filtration and washing with water to remove sodium chloride and diethylene glycol, the mixture was dried and pulverized to obtain 132 parts of a pigment composition R-4.

[Examples 9 to 12] (Production of Pigment Compositions R-5 to 8)
132 parts of the pigment composition R- in the same manner as the pigment composition R-4, except that the pigment represented by the formula (3) and the compound (A-1) were changed to the pigments shown in Table 4, respectively. 5, 131 parts of the pigment composition R-6 and 132 parts of the pigment composition R-7 and 133 parts of the pigment composition R-8 were obtained, respectively.

<Manufacturing method of other fine pigments>
(Manufacturing of fine pigment PR254-1)
150 copies of C.I. I. A mixture of Pigment Red 254, sodium chloride 1500 parts and diethylene glycol 250 parts was kneaded at 60 ° C. for 10 hours using a stainless steel 1 gallon kneader (Inoue Seisakusho). Next, this kneaded product was put into 5000 parts of warm water and stirred for 1 hour while heating at 70 ° C. to form a slurry. After repeating filtration and washing with water to remove sodium chloride and diethylene glycol, the mixture was dried and pulverized to obtain 135 parts of a fine pigment PR254-1.

(Manufacturing of fine pigment PR177-1)
150 parts of a dianthraquinone pigment (CI Pigment Red 177), 1500 parts of sodium chloride, and 250 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 10 hours. Next, the kneaded mixture was put into warm water, stirred for 1 hour while heating at about 70 ° C. to form a slurry, filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours. By pulverization, 138 parts of anthraquinone-based fine pigment PR177-1 was obtained.

<Method for producing coloring composition for color filter>
[Example 13] (Preparation of coloring composition (RP-1))
The mixture having the composition shown below is uniformly stirred and mixed, dispersed with a picomill (manufactured by Asada Iron Works Co., Ltd.) for 8 hours using zirconia beads having a diameter of 0.1 mm, and then filtered through a 5 μm filter to obtain a coloring composition (colored composition). RP-1) was prepared.
Pigment composition (R-1): 9.5 parts Compound (A-1): 0.5 parts Disperbyk-2000 (NV40%): 18.0 parts Propylene glycol monomethyl ether acetate: 72.0 parts

[Examples 14 to 22, 28, Comparative Examples 4 to 9] (Preparation of coloring compositions (RP-2 to 10, 16 to 22))
The pigment composition (R-1) and the compound (A-1) were prepared in the same manner as the coloring composition (RP-1) except that the materials shown in Table 5 and the addition amounts thereof were changed. (RP-2 to 10, 16 to 22) were prepared.

[Example 23] (Preparation of coloring composition (RP-11))
The mixture having the composition shown below is uniformly stirred and mixed, dispersed with a picomill (manufactured by Asada Iron Works Co., Ltd.) for 8 hours using zirconia beads having a diameter of 0.1 mm, and then filtered through a 5 μm filter to obtain a coloring composition (colored composition). RP-11) was prepared.
Pigment composition (R-4): 10.0 parts Disperbyk-2000 (NV 40%): 18.0 parts Propylene glycol monomethyl ether acetate: 72.0 parts

[Examples 24-28] (Preparation of coloring composition (RP-12-15))
A coloring composition (RP-12-15) was prepared in the same manner as the coloring composition (RP-11) except that the pigment composition (R-4) was changed to the materials shown in Table 5.

<Evaluation of coloring composition>
The obtained coloring composition was evaluated by the following method. The results are shown in Table 3.

(Dispersibility: initial viscosity, stability)
For the viscosity of the coloring composition, the initial viscosity at 25 ° C. was measured using an E-type viscometer (“ELD-type viscometer” manufactured by Toki Sangyo Co., Ltd.). Separately, 25 g of the coloring composition was allowed to stand at 40 ° C. for 24 hours in a sealed state in a glass container, and then the viscosity was measured by the same method as described above to obtain the viscosity over time. The stability was judged as follows.
◯: When the viscosity change rate is less than ± 10% and no sediment is formed.
Δ: When the viscosity change rate is ± 10% or more and less than 20%, and no sediment is formed.
X: When a sediment is formed even if the viscosity change rate is ± 20% or more, or the viscosity change rate is less than ± 20%.

From the results shown in Table 5, it was found that the pigment composition using the compound of the present invention had good viscosity measurement values and stability, and was excellent in dispersibility in the preparation of the coloring composition. Furthermore, by comparing Examples 14, 19 and 20, it was found that the compound of the present invention has excellent dispersion performance because the dispersion stability is good even if the amount of the derivative added is small.

<Method for producing other coloring compositions>
(Preparation of other coloring composition (PR177-1P))
The mixture having the composition shown below is uniformly stirred and mixed, dispersed with a picomill for 8 hours using zirconia beads having a diameter of 0.1 mm, and then filtered through a filter of 5 μm to prepare a colored composition (PR177-1P). did.
Fine pigment (PR177-1): 12.0 parts Disperbyk-2000 (NV40%): 20.0 parts Propylene glycol monomethyl ether acetate: 68.0 parts

(Preparation of other coloring composition (PR254-1P))
The mixture having the composition shown below is uniformly stirred and mixed, dispersed with a picomill for 8 hours using zirconia beads having a diameter of 0.1 mm, and then filtered through a filter of 5 μm to prepare a colored composition (PR254-1P). did.
Fine pigment (PR254-1): 12.0 parts Disperbyk-2000 (NV40%): 20.0 parts Propylene glycol monomethyl ether acetate: 68.0 parts

<Method for producing photosensitive coloring composition>
[Example 29] (Preparation of photosensitive coloring composition (RR-1))
The mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare a photosensitive coloring composition (RR-1).
Coloring composition (RP-1): 12.6 parts Coloring composition (PR254-1P): 29.4 parts Acrylic resin solution 2: 13.2 parts Photopolymerizable monomer ("Aronix M400" manufactured by Toa Synthetic Co., Ltd. " ): 2.8 parts Photopolymerization initiator (BASF's "Irgacure 907"): 2.0 parts sensitizer (Hodogaya Chemical Co., Ltd. "EAB-F"): 0.4 parts ethylene glycol monomethyl ether Acetate: 39.6 parts

[Examples 30 to 44, Comparative Examples 10 to 16] (Preparation of photosensitive coloring compositions (RR-2 to 23))
Photosensitivity in the same manner as the photosensitive coloring composition (RR-1), except that the coloring composition (RP-1) and the coloring composition (PR254-1P) were changed to the coloring compositions shown in Table 4, respectively. Sex colored compositions (RR-2 to 23) were prepared. The blending amounts of the two types of coloring compositions were fixed at a total of 42 parts, and the ratio was changed so that the chromaticity of x = 0.640 and y = 0.328 was obtained with the C light source when the coating film was formed. did.

<Evaluation of photosensitive coloring composition>
The lightness, foreign matter in the coating film, and heat resistance of the obtained photosensitive coloring composition were evaluated by the following methods. The results are shown in Table 4.

(Brightness Y (C) evaluation)
A photosensitive coloring composition is applied on a glass substrate having a thickness of 100 mm × 100 mm and 0.7 mm to a thickness such that x = 0.640 and y = 0.328 with a C light source, and after drying, ultra-high pressure mercury is applied. A lamp was used ^{to irradiate 300 mJ / cm 2} of ultraviolet light. Further, a red coating film was obtained by heating at 230 ° C. for 60 minutes. Then, the brightness Y (C) of the obtained coating film was measured with a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). Regarding the brightness Y (C), if it is 0.2 points or more, it can be said that there is a clear difference.

(Contrast ratio evaluation of coating film)
The light emitted from the backlight unit for a liquid crystal display passes through a polarizing plate, is polarized, passes through a dry coating film of a coloring composition applied on a glass substrate, and reaches the polarizing plate. If the polarizing plate and the polarizing planes of the polarizing plate are parallel, light passes through the polarizing plate, but if the polarizing planes are orthogonal, the light is blocked by the polarizing plate. However, when the light polarized by the polarizing plate passes through the dry coating film of the coloring composition, scattering by pigment particles or the like occurs and a part of the polarizing surface is displaced. When the polarizing plates are parallel, the polarized light is polarized. The amount of light transmitted through the plate is reduced, and when the polarizing plate is orthogonal, part of the light is transmitted through the polarizing plate. This transmitted light was measured as the brightness on the polarizing plate, and the ratio (contrast ratio) between the brightness when the polarizing plates were parallel and the brightness when the polarizing plates were orthogonal was calculated. When scattering occurs due to the pigment in the coating film, the brightness when parallel is reduced and the brightness when orthogonal is increased, so that the contrast ratio is lowered.
(Contrast ratio) = (Brightness when parallel) / (Brightness when orthogonal)
A color luminance meter (“BM-5A” manufactured by Topcon Corporation) was used as the luminance meter, and a polarizing plate (“NPF-G1220DUN” manufactured by Nitto Denko Corporation) was used as the polarizing plate. At the time of measurement, a black mask having a 1 cm square hole was applied to the measurement portion in order to block unnecessary light. Further, for the contrast ratio measurement, a red coating film obtained by the same method as in the evaluation of brightness Y (C) was used.

(Evaluation of foreign matter on the coating film)
A glass substrate having a thickness of 100 mm × 100 mm and 1.1 mm is coated with a spin coater so that the dry film thickness is 2.0 μm, then dried at 70 ° C. for 20 minutes, and using an ultra-high pressure mercury lamp. A coated substrate was prepared by subjecting to ultraviolet exposure at an integrated light amount of 150 mJ / cm ² and developing with an alkaline developer at 23 ° C., and then heating and allowing to cool at 230 ° C. for 60 minutes. The evaluation was carried out by observing the surface using a metallurgical microscope "BX60" manufactured by Olympus System Corporation. The magnification was set to 500 times, and the number of particles that could be observed in any five fields of view by transmission was counted. It was evaluated in the following three stages. ○ indicates that the number of foreign substances is small and is good, Δ indicates that the number of foreign substances is large but there is no problem in use, and × corresponds to a state in which it cannot be used because coating unevenness (spots) occurs due to foreign substances.
◯: The number of foreign substances is less than 10 Δ: The number of foreign substances is 10 or more and less than 60 ×: The number of foreign substances is 60 or more

(Evaluation of coating film heat resistance)
A glass substrate having a thickness of 100 mm × 100 mm and 1.1 mm is coated with a spin coater so that the dry film thickness is 2.0 μm, then dried at 70 ° C. for 20 minutes, and using an ultra-high pressure mercury lamp. A coated substrate was prepared by subjecting to ultraviolet exposure at an integrated light amount of 150 mJ / cm ² and developing with an alkaline developer at 23 ° C., and then heating and allowing to cool at 230 ° C. for 60 minutes. Use a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.) to measure the chromaticity ([L * (1), a * (1), b * (1)]) of the obtained coating film at the C light source. Measured using. After that, as a heat resistance test, the mixture was heated at 250 ° C. for 1 hour, the chromaticity ([L * (2), a * (2), b * (2)]) with a C light source was measured, and the following formula was used. , Color difference ΔEab * was obtained and evaluated in the following three stages.
ΔEab * = √ ((L * (2) -L * (1)) 2+ (a * (2) -a * (1)) 2+ (b * (2) -b * (1)) 2)
◯: ΔEab * is less than 2.5
Δ: ΔEab * is 2.5 or more and less than 5.0 ×: ΔEab * is 5.0 or more

From the results shown in Table 6, it was found that the photosensitive coloring composition using the compound of the present invention was excellent in lightness and heat resistance in forming a color filter. In particular, from Examples 30, 35 and 36, it was found that a photosensitive coloring composition having higher brightness and excellent heat resistance was obtained by reducing the amount of the derivative added with the compound of the present invention.

<Making color filters>
A green photosensitive coloring composition and a blue photosensitive coloring composition used for producing a color filter were produced. For red color, the photosensitive coloring composition (RR-2) of the present invention was used.

(Preparation of Green Coloring Composition 1 (GP-1))
The mixture having the composition shown below is uniformly stirred and mixed, dispersed with a picomill for 8 hours using zirconia beads having a diameter of 0.1 mm, and then filtered through a 5 μm filter to obtain a green coloring composition (GP-1). Made.
Green pigment (CI Pigment Green 36): 6.8 parts Yellow pigment (CI Pigment Yellow 150): 5.2 parts Resin type dispersant (BASF "EFKA4300"): 1.0 part Acrylic Resin solution 1: 35.0 parts propylene glycol monomethyl ether acetate: 52.0 parts

(Preparation of Green Photosensitive Coloring Composition (GR-1))
The mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare a green photosensitive coloring composition (GR-1).
Green coloring composition (GP-1): 42.0 parts Acrylic resin solution 2: 13.2 parts Photopolymerizable monomer ("Aronix M400" manufactured by Toa Synthetic Co., Ltd.): 2.8 parts Photopolymerization initiator (BASF) "Irgacure 907" manufactured by Irgacure 907): 2.0 parts Sensitizer ("EAB-F" manufactured by Hodoya Chemical Industry Co., Ltd.): 0.4 parts Ethylene glycol monomethyl ether acetate: 39.6 parts

(Preparation of Blue Coloring Composition 1 (BP-1))
The mixture having the composition shown below is uniformly stirred and mixed, dispersed with a picomill for 8 hours using zirconia beads having a diameter of 0.1 mm, and then filtered through a 5 μm filter to obtain a blue coloring composition (BP-1). Made.
Blue pigment (CI Pigment Blue 15: 6): 7.2 parts Purple pigment (CI Pigment Violet 23): 4.8 parts Resin type dispersant (BASF "EFKA4300"): 1.0 Part Acrylic resin solution 1: 35.0 part propylene glycol monomethyl ether acetate: 52.0 part

(Preparation of Blue Photosensitive Coloring Composition 1 (BR-1))
The mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare a blue photosensitive coloring composition (BR-1).
Blue coloring composition (BP-1): 34.0 parts Acrylic resin solution 2: 15.2 parts Photopolymerizable monomer ("Aronix M400" manufactured by Toa Synthetic Co., Ltd.): 3.3 parts Photopolymerization initiator (BASF) "Irgacure 907" manufactured by Irgacure 907): 2.0 parts Sensitizer ("EAB-F" manufactured by Hodoya Chemical Industry Co., Ltd.): 0.4 parts Ethylene glycol monomethyl ether acetate: 45.1 parts

(Making a color filter)
A black matrix is patterned on a glass substrate, and the photosensitive coloring composition (RR-2) of the present invention is coated on the substrate with a spin coater to a thickness such that x = 0.640 and y = 0.328. It was applied to form a colored film. The coating film was irradiated with ultraviolet rays of ^{300 mJ / cm 2} using an ultra-high pressure mercury lamp via a photomask. Next, the unexposed portion was removed by spray development with an alkaline developer consisting of a 0.2 wt% sodium carbonate aqueous solution, washed with ion-exchanged water, and the substrate was heated at 230 ° C. for 20 minutes to obtain a red filter segment. Was formed. By the same method, the green photosensitive coloring composition (GR-1) was applied to a film thickness such that x = 0.300 and y = 0.600, and the blue photosensitive coloring composition (BR-1) was used. The mixture was applied to a thickness such that x = 0.150 and y = 0.060, respectively, to form a green filter segment and a blue filter segment to obtain a color filter.

By using the photosensitive coloring composition (RR-2) of the present invention, a color filter having high brightness and high contrast could be produced.

Claims (6)

A compound represented by the following general formula (1).
General formula (1)

[In the general formula (1), R _{1 to} R ₅ independently represent a hydrogen atom, a halogen atom, a nitro group, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, or ₆ -OR groups. Adjacent groups of R _{1 to} R ₅ may form a benzimidazolone ring. R ₆ represents an alkyl group having 1 to 4 carbon atoms. S ₁ represents a sulfonic acid group; its amine salt, its quaternary ammonium salt or its metal salt. n represents an integer of 2. ] A pigment dispersant containing the compound according to claim 1. A pigment composition containing the pigment dispersant and the pigment according to claim 2. A coloring composition for a color filter containing a colorant and an organic solvent, wherein the coloring agent contains the pigment dispersant according to claim 2 or the pigment composition according to claim 3. .. The coloring composition for a color filter according to claim 4, further containing at least one of a photopolymerizable monomer and a photopolymerization initiator. A color filter formed by the coloring composition for a color filter according to claim 4 or 5.