JP5233161B2 - Fine polyhalogenated phthalocyanine pigment, method for producing the same, and coloring composition using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyhalogenated phthalocyanine pigment having a uniform particle size. <P>SOLUTION: The fine polyhalogenated phthalocyanine pigment has a particle size distribution characterized in that the variation coefficient of the pigment particles defined by (standard deviation)/(average particle diameter) is &le;50% for particles having average particle diameter of 5-15 nm, &le;35% for particles having average particle diameter of 16-25 nm, &le;25% for particles having average particle diameter of 26-35 nm, and &le;20% for particles having average particle diameter of 36-50 nm. The method for producing the fine polyhalogenated phthalocyanine pigment comprises a solvent treating step to treat a crude pigment with a crystallization solvent for the pigment or an emulsion of the solvent to adjust the primary particle diameter of the pigment particle to &ge;20 nm and a wet crushing step to mix the pre-pigment obtained by the solvent treating step with a water-soluble inorganic salt and a water-soluble organic solvent and carry out the wet crushing at &le;90&deg;C. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a fine polyhalogenated phthalocyanine pigment, and more particularly to a polyhalogenated phthalocyanine pigment sized to a uniform particle size. The pigment of the present invention has extremely good dispersibility, and when used in a color filter used in a color liquid crystal display device and a solid-state imaging device, forms a uniform colored film having excellent viscosity characteristics and a high contrast ratio. Therefore, the color filter has excellent display quality, that is, high brightness, sharpness, and transmittance.

  Halogenated phthalocyanine pigments have hues ranging from blue to green depending on the number of halogen groups, and in particular, polyhalogenated phthalocyanine pigments have been used as colorants for paints, printing inks, and plastics as green pigments. In recent years, it has also been used as a color filter colorant for liquid crystal displays and an ink colorant for ink jet ink recording, and the required quality and required level of pigments have increased.

  The method for producing a green pigment comprises the production of a crude polyhalogenated phthalocyanine pigment by halogenation of crude phthalocyanine blue, and the formation of a pigment that makes the crude pigment clear and has high coloring power. Crude polyhalogenated phthalocyanine pigments can be produced by co-molten salts of aluminum chloride and sodium chloride, halogenated with titanium tetrachloride as a solvent, solid phase method with inorganic salt powder as a carrier, halogenated phthalimide, etc. A method using a cyclocondensation reaction is known.

  The crude polyhalogenated phthalocyanine pigment synthesized by either method has an amorphous crystal form, an extremely fine particle size, and an aggregated state. Therefore, as it is, it cannot be sufficiently dispersed in the varnish and is not suitable as a coloring material. Therefore, it is necessary to perform crystallization and pigmentization to a pigment having an optimum particle size and particle size distribution. As a pigmentation method, a wet grinding method, a sulfuric acid method, a crystallization solvent method, and the like are known.

  For example, Patent Documents 1 and 2 disclose a method of refining crude polyhalogenated phthalocyanine by wet pulverization. However, unlike other pigments, polyhalogenated phthalocyanine pigments are difficult to crystallize, so that some pigments remain without being pigmented, resulting in poor dispersion and reduced contrast.

  The sulfuric acid method is a method in which a crude polyhalogenated phthalocyanine is dissolved or suspended in sulfuric acid and then recrystallized by adding it to water to obtain a pigment. However, this method is difficult to control the particle size. Yes, the pigment has a wide particle size distribution.

  The crystallization solvent method is a method in which a crude polyhalogenated phthalocyanine pigment is treated with a crystallization solvent, and then the crystallization solvent is removed by boiling, distillation or the like to obtain a pigment. Since it is a method that makes it easy to form, the crude pigment hardly remains, but at the same time, particle growth also easily occurs, particle size control becomes difficult, and the pigment has a wide particle size distribution.

  Patent Document 3 describes a pigmentation method in which crude polyhalogenated phthalocyanine is subjected to an emulsion treatment with a crystallization solvent and then wet pulverized. However, this method was accompanied by particle growth due to the high temperature during wet pulverization, and did not become a fine pigment with a narrow particle size distribution.

With these pigmentation methods, it is difficult to achieve both crystallization and refinement. If emphasis is placed on refinement, the transmittance will improve, but the crude pigment will remain, resulting in poor dispersion and high contrast ratio. Can not. Further, if the crystallization is sufficiently performed, the crude pigment does not remain, but the particle growth cannot be controlled. As a result, a pigment having a wide particle size distribution can be obtained, and a high contrast ratio cannot be obtained.
Japanese Patent Application Laid-Open No. 7-30631 JP 2002-250812 A Japanese Unexamined Patent Publication No. 63-101458

  An object of the present invention is to provide a fine and sized polyhalogenated phthalocyanine pigment. Furthermore, the present invention has extremely good dispersibility, and when used in a color filter used in a color liquid crystal display device and a solid-state imaging device, it forms a uniform colored film having excellent viscosity characteristics and a high contrast ratio. Another object of the present invention is to provide a polyhalogenated phthalocyanine capable of obtaining a color filter having excellent display quality, that is, high brightness, sharpness, and transmittance.

The present invention provides a solvent treatment step in which a crude pigment is treated with a pigment crystallization solvent or an emulsion of the solvent so that the primary particle diameter of the pigment is 20 nm or more, and the pre-pigment obtained in the solvent treatment step is water-soluble. The variation coefficient represented by the standard deviation / average particle diameter of the pigment particles is characterized by comprising a wet grinding step of wet grinding at 90 ° C. or less as a mixture of an inorganic salt and a water-soluble organic solvent. 50 nm or less when the average particle size is 16 to 25 nm, 25% or less when the average particle size is 26 to 35 nm, and 20% or less when the average particle size is 36 to 50 nm. It is related with the manufacturing method of the fine polyhalogenated phthalocyanine pigment whose average particle diameter which has a particle size distribution which is 5-50 nm .

  The polyhalogenated phthalocyanine pigment obtained in the present invention is finely and highly sized, and the dispersion together with the pigment carrier has a low viscosity characteristic suitable for coating. , Have high brightness, sharpness and transmittance.

  The polyhalogenated phthalocyanine pigment obtained in the present invention has an absorption wavelength characteristic preferable as a green pigment used in a color filter used in a color liquid crystal display device or a solid-state imaging device, and is fine and sized. Therefore, a colored film having a high contrast ratio, which is important as a characteristic of the color filter, can be obtained.

  According to the present invention, a finely sized polyhalogenated phthalocyanine pigment can be obtained by the effect of crystallization in the first step of promoting crystallization of the pigment and the effect of refining the pigment in the wet pulverization step.

  The fine polyhalogenated phthalocyanine pigment of the present invention has a coefficient of variation of 50% or less when the average particle size is 5 to 15 nm, 35% or less when the average particle size is 16 to 25 nm, and 26 to 35 nm. It has a particle size distribution that is 25% or less in the case of the product, and 20% or less in the case of the average particle size of 36 to 50 nm.

  In the present invention, the standard deviation and the average particle size required for the calculation of the variable particle size are obtained by observing the obtained fine pigment with an electron microscope, and using the image analysis type particle size distribution measurement software Macview Ver. Particle size distribution analysis is performed, and the average particle size and coefficient of variation are calculated. From this, it can be determined by the variation particle size = standard deviation / average particle size.

  In the present invention, it can be determined that the sizing is progressing as the variation coefficient is smaller. For example, when the average particle size is 30 nm and the standard deviation is 10 nm, the coefficient of variation is 33.3%. In addition, when the average particle diameter becomes 20 nm and the standard deviation is 5 nm when the fine particle advances, the standard deviation is 25. However, even when the average particle diameter becomes 20 nm after the fine particle advances, the standard deviation does not change and is 10 nm. In this case, the coefficient of variation becomes 50%. This means that even if forced miniaturization is simply performed by a kneader or the like, unless the standard deviation (a measure of variation in particle diameter) is reduced, coarse particles are mixed and the contrast ratio, which is a characteristic of the color filter, is not improved.

  The crude pigment of the present invention is polychlorinated phthalocyanine, polybrominated phthalocyanine, polychlorinated brominated phthalocyanine or a mixture thereof. The number of halogen substituents is preferably 12 to 16 per molecule of phthalocyanine. In any case, it is economical to use a filter cake obtained after the synthesis reaction. The ratio of the pigment and water is 100 to 2000 parts by weight, preferably 100 to 800 parts by weight, based on 100 parts by weight of the pigment. In order to make it 100 parts by weight or less, after filtration, it is necessary to squeeze and increase the number of processes, which is disadvantageous. On the other hand, if it is 2000 parts by weight or more, the apparatus becomes large and the processing efficiency is deteriorated.

  The solvent treatment in the present invention is a step of bringing a crystallization solvent into contact with a crude polyhalogenated phthalocyanine pigment. It is preferable to contact the crude pigment and the solvent under heating. Specifically, a crude polyhalogenated phthalocyanine, which is essentially an aggregate of fine particles, is charged with a pigment crystallization solvent after being suspended and dispersed in water paste or water of a crude pigment and treated for a predetermined time. This is a method for crystal growth of a pigment. By this solvent treatment, fine pigment aggregates and amorphous pigment particles grow as the crystallization progresses and the particle diameter increases.

  The crystallization solvent used in the solvent treatment step of the present invention is not particularly limited as long as the polyhalogenated phthalocyanine is a crystal growth crystal, but an aromatic solvent is particularly preferable, and p-chlorotoluene, Aromatic solvents such as o-dichlorobenzene, trichlorobenzene, chlorobenzene, nitrobenzene, xylene, o-nitrotoluene and toluene are used. If the amount of the crystallization solvent used for the treatment is small, the pigmentation takes a long time or cannot be pigmented, but if the amount exceeds a certain amount, the pigmentation rate is saturated.

  The amount of the crystallization solvent used is preferably 10 to 500 parts by weight, more preferably 50 to 350 parts by weight, and still more preferably 100 to 300 parts by weight with respect to 100 parts by weight of the crude pigment. is there. Since the crystallization speed varies depending on the type of crystallization solvent, an amount and a type that are easy to control, and an economical and highly safe solvent are selected. Anionic, cationic or nonionic surfactants are preferably used to facilitate the formation of an oily phase pigment suspension in water. In particular, an anionic active agent is preferable. Further, when the amount of the crystallization solvent used is large, the transition to the oil phase is not required with the aid of the surfactant, and thus the pigment may be formed without using the surfactant.

  It is preferable to use a stirrer in the solvent treatment step. The stirrer is not particularly limited, and various types of apparatuses can be used according to the viscosity of the object to be treated, such as a normal stirrer and a stirrer for low-viscosity slurry, a kneader or a kneader for a high-viscosity paste. . The heating temperature in the solvent treatment step is 50 ° C. or higher, preferably the azeotropic point of the crystallization solvent and water. If it is 50 ° C. or lower, the pigmentation speed becomes slow, which is disadvantageous. Depending on the case, treatment above the azeotropic point by pressurization is also possible. The heating time varies depending on the type and composition of the crystallization solvent and the processing temperature, and is determined depending on economic considerations. After heating and stirring for the required time, it is preferable to remove the used crystallization solvent by steam distillation or the like and return the pigment to the aqueous phase again. Thereafter, the pre-pigment is taken out through filtration, washing with water and drying.

  The pre-pigment obtained in the solvent treatment step of the present invention has a primary particle size of 20 nm or more, preferably 30 nm or more. If the primary particle size of the pre-pigment is smaller than this, the crude pigment is not sufficiently crystallized, and pigment particles having a coefficient of variation below a predetermined value cannot be obtained even if the next wet pulverization treatment is performed. When used as a filter, a high contrast ratio cannot be obtained.

  The wet kneading step in the present invention is a step of kneading the crude pigment at 90 ° C. or higher in the presence of a water-soluble organic solvent. The apparatus used for the kneading is not particularly limited as long as the mixture of the crude pigment and the water-soluble organic solvent is uniformly stirred so that the heat distribution of the mixture is not biased. Is preferably used as it is.

  Water-soluble organic solvents include methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, ethylene glycol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol, propylene Examples include goricol monomethyl ether acetate, acetone, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone and the like.

  If it is added to the above water-soluble organic solvent and used in a small amount, it will be adsorbed on the pigment and will not be washed away in the wastewater. Isopropyl acetate, butyl acetate, hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclohexane, methylcyclohesasan, halogenated hydrocarbons, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. may be used. Accordingly, two or more kinds of solvents may be mixed and used.

  The amount of the water-soluble organic solvent used in the wet kneading process is in the range of 50% by weight to 500% by weight with respect to the pigment, and preferably in the range of 100% by weight to 300% by weight.

  In the wet kneading treatment, a water-soluble inorganic salt such as sodium chloride, potassium chloride, calcium chloride, barium chloride, or sodium sulfate may be added to the mixture of the pigment and the water-soluble organic solvent. When a water-soluble inorganic salt is used, it is preferably 0.5 to 3 times the weight of the pigment.

  In the present invention, the wet kneading treatment is performed at 90 to 150 ° C., preferably 90 to 130 ° C. If the temperature during wet pulverization is lower than 90 ° C., the crystallization of the crude pigment is difficult to proceed, and the primary particle diameter of the pre-pigment does not become 20 nm or more.

  The pre-pigment obtained in the wet kneading treatment step of the present invention has a primary particle size of 20 nm or more, preferably 30 nm or more. If the primary particle size of the pre-pigment is smaller than this, the crude pigment is not sufficiently crystallized, and pigment particles having a coefficient of variation below a predetermined value cannot be obtained even if the next wet pulverization treatment is performed. When used as a filter, a high contrast ratio cannot be obtained.

  The wet pulverization step of the present invention is a step of pulverizing the pre-pigment obtained in the solvent treatment step or the wet kneading treatment as a viscous liquid composition together with the water-soluble organic solvent and the water-soluble inorganic salt at a temperature of 90 ° C. or less. is there.

  The water-soluble organic solvent used in the wet pulverization step can be the same as that used in the wet kneading step. The amount of the water-soluble organic solvent used is in the range of 50 to 500% by weight, preferably in the range of 100 to 300% by weight, based on the pigment.

  The water-soluble inorganic salt is a pulverizing medium, and preferably sodium chloride, potassium chloride, calcium chloride, barium chloride, sodium sulfate and the like. The water-soluble inorganic salt preferably has a pulverized particle size of 5 to 50 μm, a sharp and small particle size distribution, and a spherical shape.

  The amount of the water-soluble inorganic salt used is preferably 5 to 30 times the weight of the pigment. Although the grinding effect is improved by using a large amount, the preferred amount is 6 to 20 times the weight from the viewpoint of productivity. The water content in the water-soluble inorganic salt is preferably 1% by weight or less.

  Although there is no restriction | limiting in particular in the apparatus used by the wet grinding process of this invention, Trimix (made by Inoue Seisakusho), supermix (made by Shinei Machine), a kneader, etc. can be used. The operating conditions of the wet pulverizer need to make grinding with grinding media effective, and the operating conditions when the apparatus is a kneader are such that the rotation speed of the blade in the apparatus is high and the biaxial rotation ratio is high. A relatively large one is preferable because the grinding effect is large. The internal temperature of the apparatus needs to be 30 to 80 ° C., and more preferably 50 to 80 ° C., since the temperature affects the particle growth of the pigment.

  In the second wet pulverization step, since the pigment needs to be made fine efficiently, pulverization is performed at 90 ° C. or less, preferably 20 ° C. to 90 ° C., more preferably 30 ° C. to 80 ° C. When the pulverization temperature exceeds 90 ° C., pigment particle growth increases and fine pigment particles having a predetermined coefficient of variation cannot be obtained.

  In the present invention, a pigment such as a phthalocyanine pigment, an azo pigment, a quinophthalone pigment, an isoindoline pigment, or an azo metal complex pigment is mixed for the purpose of toning in each step of the solvent treatment step, the wet kneading step and the wet grinding step. May be used. The pigment to be mixed is not particularly limited, and examples thereof include quinacridone, diketopyrrolopyrrole, dianthraquinone, perylene, and dioxazine.

  In the present invention, in each step of the solvent treatment step, the wet kneading step, and the wet pulverization step, a resin, a surfactant, a dye derivative, and the like are added in addition to other pigments, organic solvents, and higher fatty acids as necessary. Also good. Resin used is not particularly limited, but rosin, rosin derivative, rosin modified maleic resin, rosin modified phenolic resin, rubber derivative, protein derivative, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, polyvinyl acetate, epoxy resin , Acrylic resin, maleic resin, styrene resin, styrene-maleic acid copolymer resin, butyral resin, polyester resin, melamine resin, phenol resin, polyurethane resin, polyamide resin, polyimide resin, alkyd resin, rubber resin, celluloses, Examples thereof include benzoguanamine resins, urea resins, and oligomers and monomers of the above resins. The surfactant to be used is not particularly limited, but any one of anionic, neutral and cationic may be used. As the dye derivative, a phthalocyanine pigment, an azo pigment, a quinophthalone pigment, an isoindoline pigment, or an azo metal complex pigment skeleton having a basic or acidic group added to the terminal can be used.

  The fine polyhalogenated phthalocyanine pigment of the present invention is dispersed in a resin solution for dispersion to provide offset printing ink, gravure printing ink, waterless offset printing ink, silk screen printing ink, solvent development type or alkali development type. A colored resist agent is obtained. Various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, and a kneader can be used for dispersing the pigment in the resin solution for dispersion. Moreover, in order to make these dispersion | distribution favorable, dispersion | distribution adjuvants, such as various surfactant and a pigment derivative, can be added suitably. The dispersion aid is excellent in pigment dispersion and has a great effect of preventing reaggregation of the pigment after dispersion. These printing inks, coloring resist agents and the like are coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more, and coarse particles by means of centrifugation, sintered filter, membrane filter and the like. It is manufactured by removing the mixed dust.

  Moreover, the coloring composition used for manufacture of a color filter is obtained by disperse | distributing in the photosensitive transparent resin solution. The pigment and the photosensitive transparent resin solution are blended in a weight ratio of 1: 4 to 10: 1. Various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, and a kneader can be used for dispersing the pigment in the photosensitive transparent resin solution. Moreover, in order to make these dispersion | distribution favorable, dispersion | distribution adjuvants, such as various surfactant and a pigment derivative, can be added suitably. The dispersion aid is excellent in pigment dispersion and has a great effect of preventing reaggregation of the pigment after dispersion. Therefore, when a coloring composition is used in which the pigment is dispersed in the photosensitive transparent resin solution using the dispersion aid. Provides a color filter with excellent transparency.

The transparent resin contained in the photosensitive transparent resin solution is a resin having a transmittance of 80% or more, preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Transparent resins include thermosetting resins, thermoplastic resins, photosensitive resins, and monomers, oligomers, etc. that are cured by irradiation to form the same coating film as the resin. Use these alone or in combination of two or more. Can do. However, since a high-temperature heating process is performed in the subsequent steps in the production of the color filter, it is necessary to use a resin having good resistance in the heat treatment. Thermosetting resins and thermoplastic resins are, for example, butyral resin, styrene- Maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polyurethane resin, phenol resin, polyester resin, acrylic resin, alkyd resin, styrene resin, polyamide Resins, rubber resins, cyclized rubbers, epoxy resins, celluloses, polybutadiene resins, polyimide resins, benzoguanamine resins, melamine resins, urea resins and the like can be mentioned.

  As the photosensitive resin, a (meth) acrylic compound, cinnamic acid, or the like is bonded to a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, or an amino group via an isocyanate group, an aldehyde group, an epoxy group, or the like. A resin into which a photocrosslinkable group is introduced is used. Further, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is converted into a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. Half-esterified polymers can also be used.

  Monomers and oligomers that are cured by radiation irradiation to form a coating film similar to a resin include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, polyethylene glycol di (meth) ) Acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, hexa (meth) acrylate of caprolactone adduct of dipentaerythritol hexa (meth) acrylate, etc. Acrylic acid ester and methacrylic acid ester, acrylic acid, methacrylic acid, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, styrene, vinyl acetate, acrylonitrile Melamine (meth) acrylate, an epoxy (meth) acrylate prepolymer, and the like.

  Moreover, when hardening a coloring composition by ultraviolet irradiation, a photoinitiator etc. are used. As photoinitiators, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1one, 1-hydroxycyclohexyl Acetophenone photoinitiators such as phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl Benzoin series such as dimethyl ketal, benzophenone series photoinitiator, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4 Benzophenone photoinitiators such as benzoyl-4'-methyldiphenyl sulfide, thioxanthone photoinitiators such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone Agent, 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-pienyl-4,6-bis (trichloromethyl) -s-triazine, 2,4- -Bis (trichloromethyl) -6-styryl s-triazine, 2- (naphth-1-yl) -4,6-bis (to Chloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine , 2,4-trichloromethyl (4′-methoxystyryl) -6-triazine and other compounds such as triazine photoinitiators and carbazole photoinitiators and imidazole photoinitiators are used.

  The photoinitiator may be used alone or in combination of two or more. As a sensitizer, α-acyloxime ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, Combined use of compounds such as camphorquinone, ethylanthraquinone, 4,4'-diethylisophthalophenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 4,4'-diethylaminobenzophenone You can also

  In the coloring composition for a color filter, a solvent can be used in order to sufficiently disperse the coloring agent and apply it on the glass substrate so that the dry film thickness is 0.2 to 5 μm. Examples of the solvent include cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxy-2-propyl acetate, diethylene glycol dimethyl ether, ethylbenzene, ethylene glycol diethyl ether, xylene, ethyl cellosolve, methyl-n amyl ketone, propylene glycol monomethyl ether toluene, methyl ethyl ketone. , Ethyl acetate, methanol, ethanol, isopropyl alcohol, butanol, isobutyl ketone, petroleum solvent and the like, and these are used alone or in combination.

  Currently, a color filter is produced mainly by a method called a pigment dispersion method using a pigment having excellent weather resistance and heat resistance as a colorant. The color filter is produced mainly by the following two methods. . In the first method, a pigment dispersed in a photosensitive transparent resin solution is applied to a transparent substrate such as glass and the solvent is removed by drying, followed by pattern exposure of one filter color, and then development of unexposed areas. A color filter can be manufactured by forming the first color pattern after removing in the process, adding a treatment such as heating if necessary, and then repeating the same operation sequentially for all the filter colors.

  The second method is to apply a dispersion of a pigment in a transparent resin solution to a transparent substrate such as glass, remove the solvent by drying, and then apply a resist such as a positive resist on the coating film to obtain one filter. After exposing and developing to form a resist pattern, using this as an edging resist, the pigment-dispersed coating film without the resist pattern is peeled to form a first color pattern, and if necessary, treatment such as heating is applied, A color filter can be manufactured by sequentially repeating the same operation for all filter colors. The resist development and the pigment-dispersed coating edging can be performed simultaneously.

  The organic pigment produced by the method of the present invention is refined and sized into a uniform particle shape. Therefore, when the organic pigment obtained by the present invention is uniformly dispersed in a photosensitive transparent resin solution while maintaining a fine particle state, a color filter coloring composition, that is, a resist ink, has stable viscosity characteristics. A color filter having high brightness, sharpness, and transmittance can be realized.

[Example]
EXAMPLES Next, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited to a following example.

[Example 1]
A cake containing 100 parts of crude polychlorinated copper phthalocyanine (15.5 chlorine substituents) was reslurried in water to give 600 parts of a crude pigment slurry. Next, 100 parts of xylene, 5 parts of a cationic surfactant (Farmin DM0898, manufactured by Kao) and 3 parts of acetic acid were added, stirred at room temperature for 1 hour, heated to 90 to 100 ° C., stirred for 2 hours and solvent. Was removed. Furthermore, it was filtered, washed with water, and dried to obtain a polychlorinated copper phthalocyanine pigment. When the primary particle diameter of this polychlorinated copper phthalocyanine pigment was observed with an electron micrograph, it was in the range of 72 nm (50 to 100 nm). Next, 100 parts of this polychlorinated copper phthalocyanine pigment, 500 parts of salt (5 times the amount of the pigment) and 300 parts of diethylene glycol were mixed in a kneader and polished at 50 ° C. for 5 hours. It was poured into a 5% sulfuric acid aqueous solution, stirred at 80 to 90 ° C. for 1 hour, filtered, washed with water and dried to obtain a phthalocyanine green pigment.

[Example 2]
The same operation as in Example 1 was carried out except that the salt was changed to 1000 parts of Example 1 (10 times the amount of pigment).

[Example 3]
The same operation as in Example 1 was carried out except that the salt was changed to 1500 parts of Example 1 (15 times the amount of pigment).
(Comparative Example 1)
A cake containing 100 parts of crude polychlorinated copper phthalocyanine (14.7 chlorine atoms) was reslurried in water to give 600 parts of a crude pigment slurry. Next, 100 parts of xylene, 5 parts of a cationic surfactant (Farmin DM0898, manufactured by Kao) and 3 parts of acetic acid were added, stirred at room temperature for 1 hour, heated to 90 to 100 ° C., stirred for 2 hours and solvent. Remove. Furthermore, it was filtered, washed with water, and dried to obtain a polychlorinated copper phthalocyanine pigment.

(Comparative Example 2)
After mixing 100 parts of crude polychlorinated copper phthalocyanine (15.2 chlorine atoms), 1500 parts of sodium chloride (15 times the amount of pigment) and 300 parts of diethylene glycol in a kneader, polishing at 50 ° C. for 5 hours, This mixture was put into a 0.5% aqueous sulfuric acid solution, stirred at 80 to 90 ° C. for 1 hour, filtered, washed with water and dried to obtain a phthalocyanine green pigment.

[Example 4]
A cake containing 100 parts of crude polybrominated copper phthalocyanine (bromine group number of 13.2 and chlorine number of 2.0) was reslurried in water to give 600 parts of crude pigment as slurry. Next, 200 parts of chlorobenzene, 5 parts of an anionic surfactant (oleic acid, manufactured by Soken Chemical) and 3 parts of sodium hydroxide were added and stirred for 1 hour at room temperature, then heated to 90 to 100 ° C. and stirred for 2 hours. To remove the solvent. Furthermore, it was filtered, washed with water, and dried to obtain a polybrominated phthalocyanine pigment. When the primary particle diameter of this polybrominated copper phthalocyanine pigment was observed with an electron micrograph, it was in the range of 58 nm (25 to 80 nm). 100 parts of this polybrominated phthalocyanine pigment, 500 parts of salt (5 times the amount of pigment) and 300 parts of diethylene glycol were mixed in a kneader and polished at 90 ° C. for 5 hours. The solution was put into an aqueous sulfuric acid solution, stirred at 80 to 90 ° C. for 1 hour, filtered, washed with water and dried to obtain a phthalocyanine green pigment.

[Example 5]
The same operation as in Example 4 was carried out except that the salt was changed to 1000 parts of Example 4 (10 times the amount of pigment).
[Example 6]

The same operation as in Example 4 was carried out except that the salt was changed to 1000 parts of Example 4 (15 times the amount of pigment).
(Comparative Example 3)
A cake containing 100 parts of crude polybrominated copper phthalocyanine (13.5 bromine groups and 2.0 chlorine atoms) was reslurried in water to give 600 parts of crude pigment as slurry. Next, 50 parts of chlorobenzene, 5 parts of an anionic surfactant (oleic acid, manufactured by Soken Chemical) and 3 parts of sodium hydroxide were added and stirred for 1 hour at room temperature, then heated to 90 to 100 ° C. and stirred for 2 hours. To remove the solvent. Further, filtration, washing with water and drying were performed to obtain a phthalocyanine green pigment.
(Comparative Example 4)
After mixing 100 parts of crude polybrominated copper phthalocyanine (13.5 bromine groups, 2.0 chlorine atoms) with 500 parts of sodium chloride and 300 parts of diethylene glycol in a kneader and polishing at 90 ° C. for 5 hours, The solution was put into a 0.5% aqueous sulfuric acid solution, stirred at 80 to 90 ° C. for 1 hour, filtered, washed with water and dried to obtain a phthalocyanine green pigment.

[Example 7]
100 parts of crude polychlorinated copper phthalocyanine (15.2 chlorine substituents) 100 parts of sodium chloride (1 times the amount of pigment) and 100 parts of diethylene glycol were mixed in a kneader and wet-kneaded at 100 ° C. for 3 hours. This mixture was put into water, stirred at 80 to 90 ° C. for 1 hour, filtered, washed with water and dried to obtain a phthalocyanine green pigment. When the primary particle diameter of this polychlorinated copper phthalocyanine pigment was observed with an electron micrograph, it was in the range of 93 nm (70 to 120 nm). Next, 100 parts of this polychlorinated copper phthalocyanine pigment, 700 parts of sodium chloride (7 times the amount of the pigment) and 300 parts of diethylene glycol are mixed in a kneader and wet-ground at 50 ° C. for 5 hours. The mixture was stirred at 80 to 90 ° C. for 1 hour, filtered, washed with water and dried to obtain a phthalocyanine green pigment.

[Example 8]
After mixing 100 parts of crude polychlorinated copper phthalocyanine (15.2 chlorine substituents) with 200 parts of salt (2 times the amount of pigment) and 100 parts of diethylene glycol in a kneader and wet kneading at 100 ° C. for 5 hours, This mixture was put into water, stirred at 80 to 90 ° C. for 1 hour, filtered, washed with water and dried to obtain a phthalocyanine green pigment. When the primary particle diameter of this polychlorinated copper phthalocyanine pigment was observed with an electron micrograph, it was in the range of 77 nm (50 to 95 nm). Next, 100 parts of this polychlorinated copper phthalocyanine pigment, 1500 parts of sodium chloride (15 times the amount of the pigment) and 300 parts of diethylene glycol were mixed in a kneader and wet-ground at 50 ° C. for 5 hours. The mixture was stirred at 80 to 90 ° C. for 1 hour, filtered, washed with water and dried to obtain a phthalocyanine green pigment.
(Comparative Example 5)
100 parts of crude polychlorinated copper phthalocyanine (15.2 chlorine atoms), 700 parts of sodium chloride (7 times the amount of pigment) and 100 parts of diethylene glycol were mixed in a kneader and wet-kneaded at 100 ° C. for 5 hours. This mixture was put into water, stirred at 80 to 90 ° C. for 1 hour, filtered, washed with water and dried to obtain a phthalocyanine green pigment.
(Comparative Example 6)
After 100 parts of crude polychlorinated copper phthalocyanine (15.2 chlorine atoms), 700 parts of sodium chloride (7 times the amount of pigment) and 300 parts of diethylene glycol were mixed in a kneader and wet-kneaded at 100 ° C. for 5 hours, This mixture was put into water, stirred at 80 to 90 ° C. for 1 hour, filtered, washed with water and dried to obtain a phthalocyanine green pigment.

[Example 9]
Crude polybrominated copper phthalocyanine (13.2 bromine groups, 2.0 chlorine atoms) 100 parts of sodium chloride (1 part of the pigment) and 100 parts of diethylene glycol were mixed in a kneader at 120 ° C. After grinding for a period of time, the mixture was poured into water, stirred at 80 to 90 ° C. for 1 hour, filtered, washed with water and dried to obtain a polybrominated phthalocyanine pigment. When the primary particle diameter of this polychlorinated copper phthalocyanine pigment was observed with an electron micrograph, it was in the range of 50 nm (30 to 65 nm). 100 parts of this polybrominated phthalocyanine pigment, 700 parts of sodium chloride (7 times the amount of pigment) and 300 parts of diethylene glycol were mixed in a kneader and ground at 50 ° C. for 5 hours, and then this mixture was poured into water. The mixture was stirred at 80 to 90 ° C. for 1 hour, filtered, washed with water, and dried to obtain a phthalocyanine green pigment.

[Example 10]
Crude polybrominated copper phthalocyanine (13.2 bromine groups, 2.0 chlorine atoms) 100 parts salt 200 parts (2 times the amount of pigment), diethylene glycol 100 parts mixed in a kneader at 120 ° C. 3 After grinding for a period of time, the mixture was poured into water, stirred at 80 to 90 ° C. for 1 hour, filtered, washed with water and dried to obtain a polybrominated phthalocyanine pigment. When the primary particle diameter of this polychlorinated copper phthalocyanine pigment was observed with an electron micrograph, it was in the range of 52 nm (35 to 70 nm). After 100 parts of this polybrominated phthalocyanine pigment, 1500 parts of sodium chloride (15 times the amount of the pigment) and 300 parts of diethylene glycol were mixed in a kneader and ground at 50 ° C. for 5 hours, the mixture was poured into water, The mixture was stirred at 80 to 90 ° C. for 1 hour, filtered, washed with water, and dried to obtain a phthalocyanine green pigment.
(Comparative Example 7)
100 parts of crude polybrominated copper phthalocyanine (13.2 bromine groups, 2.0 chlorine atoms), 200 parts of sodium chloride (twice the amount of pigment) and 100 parts of diethylene glycol were mixed in a kneader at 50 ° C. After grinding for 5 hours, this mixture was poured into water, stirred at 80 to 90 ° C. for 1 hour, filtered, washed with water and dried to obtain a phthalocyanine green pigment.
(Comparative Example 8)
Crude polybrominated copper phthalocyanine (13.2 bromine groups, 2.0 chlorine atoms), 1500 parts of sodium chloride (15 times the amount of pigment) and 300 parts of diethylene glycol were mixed in a kneader at 50 ° C. After grinding for 5 hours, this mixture was poured into water, stirred at 80 to 90 ° C. for 1 hour, filtered, washed with water and dried to obtain a phthalocyanine green pigment.
(Comparative Example 9)
A cake containing 100 parts of crude polychlorinated copper phthalocyanine (15.5 chlorine substituents) was reslurried in water to give 600 parts of a crude pigment slurry. Next, 100 parts of xylene, 5 parts of a cationic surfactant (Farmin DM0898, manufactured by Kao) and 3 parts of acetic acid were added, stirred at room temperature for 1 hour, heated to 90 to 100 ° C., stirred for 2 hours and solvent. Was removed. Furthermore, it was filtered, washed with water, and dried to obtain a polychlorinated copper phthalocyanine pigment. When the primary particle diameter of this polychlorinated copper phthalocyanine pigment was observed with an electron micrograph, it was in the range of 72 nm (50 to 100 nm). Next, 100 parts of this polychlorinated copper phthalocyanine pigment, 100 parts of sodium chloride (1 times the amount of the pigment) and 300 parts of diethylene glycol were mixed in a kneader and polished at 100 ° C. for 5 hours. It was poured into a 5% sulfuric acid aqueous solution, stirred at 80 to 90 ° C. for 1 hour, filtered, washed with water and dried to obtain a phthalocyanine green pigment.
(Comparative Example 10)
A cake containing 100 parts of crude polybrominated copper phthalocyanine (bromine group number of 13.2 and chlorine number of 2.0) was reslurried in water to give 600 parts of crude pigment as slurry. Next, 200 parts of chlorobenzene, 5 parts of an anionic surfactant (oleic acid, manufactured by Soken Chemical) and 3 parts of sodium hydroxide were added and stirred for 1 hour at room temperature, then heated to 90 to 100 ° C. and stirred for 2 hours. To remove the solvent. Furthermore, it was filtered, washed with water, and dried to obtain a polybrominated phthalocyanine pigment. When the primary particle diameter of this polybrominated copper phthalocyanine pigment was observed with an electron micrograph, it was in the range of 58 nm (25 to 80 nm). After 100 parts of this polybrominated phthalocyanine pigment, 200 parts of sodium chloride (2 times the amount of pigment) and 300 parts of diethylene glycol were mixed in a kneader and polished at 120 ° C. for 5 hours, this mixture was mixed with 0.5% The solution was put into an aqueous sulfuric acid solution, stirred at 80 to 90 ° C. for 1 hour, filtered, washed with water and dried to obtain a phthalocyanine green pigment.

  The obtained fine pigment is observed with an electron microscope, and the particle diameter is visually observed. At the same time, the primary particle size distribution analysis is performed with the image analysis type particle size distribution measurement software Macview Ver. A coefficient of variation was calculated and used as an index of the degree of sizing.

  The photosensitive coloring composition was prepared by the following method. That is, 4.5 parts of pigment, 24.0 parts of acrylic resin solution, 5.4 parts of trimethylolpropane triacrylate (“NK ester ATMPT” manufactured by Shin-Nakamura Chemical Co., Ltd.), photoinitiator (“Irgacure 907” manufactured by Ciba Geigy) A mixture of 0.3 parts, 0.2 parts of a sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.), and 65.1 parts of cyclohexanone was uniformly stirred and mixed, and then filtered through a 1 µm filter for alkali development. Type photosensitive coloring composition was produced.

  The viscosity of the obtained photosensitive coloring composition was measured. Moreover, the color filter was created with the following method using the photosensitive coloring composition. That is, the obtained photosensitive coloring composition was applied on a glass substrate having a thickness of 100 mm × 100 mm and a thickness of 1.1 mm using a spin coater at a rotation speed of 500 rpm, 1000 rpm, 1500 rpm, 2000 rpm, and the film thickness of the color material layer. Four types of coated substrates having different values were obtained. Next, after drying at 70 ° C. for 20 minutes, an ultrahigh pressure mercury lamp was used to perform ultraviolet exposure with an integrated light amount of 150 mJ to form a color filter. The contrast ratio was measured. The above results are shown in Table 1.

  Looking at the results of Example 1 in Table 1, compared to the kneader product of the comparative example, the average particle size and the coefficient of variation (standard deviation / average particle size, it can be determined that the smaller the value, the better the sizing) Is small, fine and more sized. In addition, since the sizing is advanced, the viscosity is small and the transmittance is improved, so that the contrast ratio is also improved. Other examples had similar results.

The average particle size (unit: nm) and coefficient of variation (%) were calculated by analyzing an electron micrograph from image analysis type particle size distribution measurement software Macview Ver.
The viscosity was measured with a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd., unit: mPa · s).
The CR ratio (contrast ratio) was measured with a luminance meter DM-5A manufactured by TOPCON.

Claims (5)

A crude pigment is treated with a pigment crystallization solvent or an emulsion of the solvent to give a pigment particle primary particle diameter of 20 nm or more, and the pre-pigment obtained in the solvent treatment step is converted into a water-soluble inorganic salt. The variation coefficient represented by the standard deviation / average particle size of pigment particles, characterized in that it comprises a wet pulverization step of wet pulverization at 90 ° C. or less as a mixture of water-soluble organic solvents , the average particle size is 5 to 15 nm The average particle size is 35% or less when the average particle size is 16 to 25 nm, 25% or less when the average particle size is 26 to 35 nm, and 20% or less when the average particle size is 36 to 50 nm. A method for producing a fine polyhalogenated phthalocyanine pigment having an average particle size of 5 to 50 nm having a distribution . The process according to claim 1, wherein the crystallization solvent is an aromatic solvent. The production method according to claim 1 or 2 , wherein the crystallization solvent is used in an amount of 50% by weight or more based on the pigment. The production method according to any one of claims 1 to 3 , wherein the water-soluble inorganic salt is used in an amount of 5 to 30 times the weight of the pigment. It claims 1 to colored composition which comprises a fine polyhalogenated phthalocyanine pigment and a pigment carrier obtained by the 4 The method according to any one.