JP2011252123A - Fine organic pigment, its manufacturing method, and coloring composition using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of easily manufacturing a very fine organic pigment which is conventionally difficult to obtain.SOLUTION: The manufacturing method of a fine organic pigment which kneads a mixture of a crude organic pigment, a grinding auxiliary, and a water-soluble organic solvent by a solvent salt milling method, is characterized in that an organic matter having a metal salt of an organic acid expressed with the following general formula (I): X-(R M)n (n=1 to 3) exists at the time of kneading (wherein X denotes hydrogen, alkyl, alkenyl, alkynyl, aryl, arylalkyl, arylalkenyl, arylalkynyl, cycloalkyl or a benzene ring; R denotes a carboxylic acid group or a sulfonic acid group; M is a metal for inducing a metal salt of an organic acid, and is chosen from sodium, magnesium, potassium, calcium or barium).

Description

  The present invention relates to a method for producing a fine organic pigment, a fine organic pigment obtained by the production method, and a coloring composition containing the pigment.

Some organic pigments can produce finely sized pigment particles by selecting appropriate reaction conditions during synthesis, such as azo pigments, but they are produced during synthesis, such as copper phthalocyanine green pigments. Crude pigments in which extremely fine particles are aggregated are converted into pigments by particle (crystal) growth and particle size in the subsequent process, and coarse and irregular particles produced during synthesis, such as copper phthalocyanine blue pigment, in the subsequent process. It is known that some pigments are formed by making them finer and sized.
As a method for pigmenting coarse coarse pigment particles, currently widely used methods include a solvent salt milling method and a dry pulverization method.

  In particular, the solvent salt milling method uses coarse kneaded pigment particles in a kneader or the like in the presence of inorganic salts such as sodium chloride and sodium sulfate and highly viscous water-soluble organic solvents such as ethylene glycol, diethylene glycol and polyethylene glycol. This is a method of pulverizing and pigmenting. The solvent salt milling method is an effective method for refining and sizing, but in order to obtain a finer pigment, it is necessary to knead for a long time, which consumes a large amount of power, and per unit energy. There is a problem that productivity is poor.

Since crystal grain refinement by such grinding and crystal growth by an organic solvent proceed simultaneously, control of the type of grinding agent, amount added and mechanical shear force, control of crystal growth by the type of organic solvent, temperature, etc. Control of miniaturization and sizing is performed by taking a balance. For example, in order to refine the particles, it is necessary to knead while suppressing crystal growth, so kneading at a low temperature is effective.
Generally, a large kneading machine such as a kneader generates a large amount of heat and is difficult to knead at a low temperature.

  Regarding the particle size of the grinding aid used in the solvent salt milling method, Patent Literatures 1 and 2 disclose preferable particle size ranges. However, in the solvent salt milling method, the viewpoint of whether a fine pigment can be obtained to the limit has not been studied. Patent Document 3 discloses a method for more efficiently miniaturizing from the physical properties of the grinding aid, but a method for obtaining a pigment with a higher degree of miniaturization has been demanded.

Examples of usage of pigments with a high degree of fineness include color filters for liquid crystal color displays, video cameras, etc., and color toners for electrophotographic copying machines, but the use of organic pigments for these increases. The required quality has been increasing year by year.

JP-T-2004-502855 JP 2002-121420 A JP 2007-238852 A

  This invention is made | formed in view of this condition, Comprising: It aims at providing the method of manufacturing easily the very fine organic pigment which was difficult to obtain conventionally.

  That is, the present invention provides an organic acid represented by the following general formula (I) in a method for producing a fine organic pigment by a solvent salt milling method in which a mixture of a crude organic pigment, a grinding aid and a water-soluble organic solvent is kneaded. The present invention relates to a method for producing a fine organic pigment, characterized in that it contains an organic substance having a metal salt.

Formula (I)

X- (R · M) n (n = 1 to 3)

[Wherein X may have a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, or a substituent. Good aryl group, arylalkyl group which may have a substituent, arylalkenyl group which may have a substituent, arylalkynyl group which may have a substituent, cycloalkyl which may have a substituent Represents a group or an optionally substituted benzene ring,
Each R independently represents a carboxylic acid group or a sulfonic acid group.
Each M is independently a metal for inducing a metal salt of an organic acid, and is selected from sodium (Na), magnesium (Mg), potassium (K), calcium (Ca), and barium (Ba). ]

  The present invention also relates to a method for producing the above fine organic pigment, wherein the crude organic pigment is at least one organic pigment selected from phthalocyanine-based, quinophthalone-based, diketopyrrolopyrrole-based, and dioxazine-based pigments.

  The present invention also relates to a miniaturized organic pigment obtained by the above production method.

  In the present invention, a baseline at a Bragg angle 2θ = 9.1 ± 0.5 ° by powder X-ray diffraction measured by CuKα ray and connected at an intensity of 2θ = 5-12 ° was used as a baseline. The present invention relates to the above-mentioned micronized organic pigment, which is a micronized phthalocyanine pigment characterized by having a net strength half-value width of 0.7 or more.

  In addition, the present invention provides a baseline at a peak at a Bragg angle 2θ = 27.8 ± 0.5 ° by powder X-ray diffraction measured by CuKα ray and connected at an intensity of 2θ = 27-29.3 °. The above-mentioned refined organic pigment, which is a refined quinophthalone pigment, has a half width of net strength of 0.8 or more.

  Further, the present invention is a peak at a Bragg angle 2θ = 28.2 ± 0.5 ° by powder X-ray diffraction measured by CuKα ray, and a straight line connected with an intensity 2θ = 23.4-34.8 °. The present invention relates to the above-mentioned refined organic pigment which is a refined diketopyrrolopyrrole pigment characterized in that the half width of the net strength as a baseline is 0.8 or more.

  In the present invention, a peak at a Bragg angle 2θ = 25.7 ± 0.5 ° by powder X-ray diffraction measured by CuKα ray and a straight line connected at an intensity of 2θ = 18 ° to 34 ° is used as a baseline. The present invention relates to the above-mentioned refined organic pigment, which is a refined dioxazine pigment characterized by having a net strength half-value width of 1.1 or more.

  The present invention also relates to a coloring composition comprising the fine organic pigment and a pigment carrier.

  The method for adding an organic substance having a metal salt of an organic acid in the present invention is not particularly limited, and it may be added as it is, may be added after being dissolved or dispersed in a water-soluble organic solvent, and an appropriate amount. It may be dissolved in water and added.

  In the method for producing a fine organic pigment of the present invention, when kneading a mixture of a crude organic pigment, a grinding aid, and a water-soluble organic solvent, an organic substance of the general formula (I) is added to the crystal of the pigment. It can act on the surface to suppress and refine crystal growth, and a pigment that is sized to have a fine and uniform particle size can be easily produced.

  Since the organic substance of the general formula (I) added in the production method of the fine organic pigment of the present invention is water-soluble, it can be separated from the pigment by filtration and washing with water. For example, the pigment can be separated like a general dye derivative. Does not affect the hue or brightness of the.

  The method for producing a finely divided organic pigment of the present invention is obtained by mechanically kneading a mixture containing a crude organic pigment, an organic substance of the general formula (I), a grinding aid, and a water-soluble organic solvent with a kneader or the like, and then in water. The slurry is put into a slurry by stirring, and the slurry is then filtered, washed with water and dried.

  The organic pigment obtained by the method for producing a finely divided organic pigment of the present invention is a pigment in which the crude organic pigment is selected from phthalocyanine, quinophthalone, diketopyrrolopyrrole, and dioxazine pigments, particularly preferably diketopyrrolo. It is a pyrrole pigment. The diketopyrrolopyrrole pigment is a red to orange pigment having a structure represented by the following general formula (II), and has excellent light resistance and heat resistance. Specific examples of diketopyrrolopyrrole pigments represented by the following general formula (II) are represented by color index numbers. I. Pigment Red 254, 255, 264, 272 and C.I. I. Pigment Orange 71, 73, 81.

［式中、ＸおよびＹはそれぞれ独立に、直接結合、ＣＮ、Ｃ（ＣＨ_３）_３、ＣＨ_３、Ｃｌ、Ｃ_６Ｈ_５、Ｈを表す。］ Formula (II)

[Wherein, X and Y each independently represent a direct bond, CN, C (CH ₃ ) ₃ , CH ₃ , Cl, C ₆ H ₅ , H. ]

  The average primary particle size of the fine organic pigment produced by the method of the present invention varies depending on the conditions of salt milling and the type of organic pigment, but by appropriately setting the conditions, it is about 0.01 to 0.5 μm. The particle size can be controlled within a range.

  In the method for producing a fine organic pigment of the present invention, when kneading a mixture of a crude organic pigment, a grinding aid and a water-soluble organic solvent, a dye is used for the purpose of preventing crystal growth and crystal dislocation of the organic pigment. Derivatives may be added. The pigment derivative to be added is preferably a pigment derivative having the same structure as that of the crude organic pigment to be finely pulverized, but may be a pigment derivative having a structure different from the matrix. Examples of the substituent of the dye derivative include a hydroxyl group, a carboxyl group, a carbamoyl group, a sulfonic acid group, a sulfonic acid amide group, and a phthalimidomethyl group. Organic dyes also include light yellow aromatic polycyclic compounds such as naphthalene and anthraquinone that are not generally called dyes. In particular, a pigment derivative having a basic group is preferably used because it has a large pigment dispersion effect. These can be used alone or in admixture of two or more.

  As the grinding aid used at the time of kneading, a water-soluble inorganic salt is desirable, and the pigment is crushed during salt milling using the high hardness, and the primary particles of the pigment are refined. Although it will not specifically limit if it melt | dissolves in water, For example, it is a metal chloride, salt (sodium chloride), potassium chloride, sodium sulfate, zinc chloride, calcium chloride, magnesium chloride, or these mixtures etc. Sodium chloride is preferably used from the viewpoint of price.

  The particle diameter of the water-soluble inorganic salt used in the present invention is not particularly limited, but is water-soluble with a volume-based median particle diameter (D50) of 1 to 50 μm and a 95% particle diameter (D95) of 80 μm or less. Inorganic salts are desirable. Furthermore, when a fine organic pigment is desired, the water-soluble inorganic salt used as a grinding aid must also be fine, and the volume-based median particle diameter (D50) is 1 to 10 μm, 95 A water-soluble inorganic salt having a% particle diameter (D95) of 20 μm or less is preferably used. The particle diameter of the water-soluble inorganic salt can be determined using a dry-type laser diffraction particle size distribution analyzer.

  The water content is also important as the quality of the water-soluble inorganic salt. Industrial average salt usually contains 1.0% by weight or more of water, and if salt with a water content of 1.0% by weight or more is pulverized as it is without drying, adhesion of the crushed water-soluble inorganic salt It is strong and often hardens immediately if left unattended. The water-soluble inorganic salt is preferably dried to a water content of 0.5% by weight or less, more preferably 0.3% by weight or less. Particularly preferably, the water-soluble inorganic salt is sintered at a high temperature so that the water content is 0.2% by weight or less.

  The amount of the water-soluble inorganic salt varies depending on the type of the crude organic pigment, but is preferably 1 to 30 parts by weight, more preferably the water-soluble inorganic salt 5 to 1 part by weight of the crude organic pigment. ~ 15 parts by weight. The larger the ratio of the water-soluble inorganic salt to the crude organic pigment, the greater the effect of miniaturization.

  The water-soluble organic solvent used in the present invention is for moistening a mixture of a crude organic pigment and a water-soluble inorganic salt into a dough having an appropriate hardness to increase the grinding effect and promote the refinement of the pigment. Although there will be no restriction | limiting in particular if it is a thing, A water-soluble organic solvent is preferable. Particularly preferred are highly viscous water-soluble organic solvents such as ethylene glycol, diethylene glycol, and polyethylene glycol.

  The amount of the water-soluble organic solvent used varies depending on the type of the crude organic pigment and the amount of the water-soluble inorganic salt, but is generally 0.1 to 5 parts by weight, preferably 1 part by weight of the crude organic pigment. 1 to 2 parts by weight.

Examples of water-soluble organic solvents include 2- (methoxymethoxy) ethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono Butyl 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, low Molecular weight polypropylene glycol,
Aniline, pyridine, tetrahydrofuran, dioxane, methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, ethylene glycol, propylene glycol, propylene glycol monomethyl ether acetate, ethyl acetate, isopropyl acetate, acetone, methyl ethyl ketone, dimethylformamide, Examples thereof include a solvent having a hydroxyl group such as dimethyl sulfoxide and N-methylpyrrolidone, a carbonyl group, a carboxyl group, an amide group and a hetero atom. If necessary, two or more of these water-soluble organic solvents may be mixed and used.

X in the general formula (I) used in the present invention is a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an alkynyl group that may have a substituent. An aryl group which may have a substituent, an arylalkyl group which may have a substituent, an arylalkenyl group which may have a substituent, an arylalkynyl group which may have a substituent, a substituent Or a benzene ring which may have a substituent. The substituent here is a halogen atom, a hydroxyl group, an alkyl group having 6 or less carbon atoms, an alkyloxy group having 6 or less carbon atoms, a nitro group, an amino group, an alkylamino group having 6 or less carbon atoms, or a dialkyl having 6 or less carbon atoms. It is an amino group. The organic acid salt of the general formula (I) has 1 to 3 carboxylates or sulfonates in X. The metal M for deriving the organic acid metal salt is selected from sodium (Na), magnesium (Mg), potassium (K), calcium (Ca), and barium (Ba).
For example, organic acids for deriving metal salts of organic acids are formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, Oleic acid, linoleic acid, linolenic acid, cyclohexanecarboxylic acid, phenylacetic acid, benzoic acid, o-toluic acid, m-toluic acid, p-toluic acid, o-chlorobenzoic acid, m-chlorobenzoic acid, p-chlorobenzoic acid Acid, o-bromobenzoic acid, m-bromobenzoic acid, p-bromobenzoic acid, o-nitrobenzoic acid, m-nitrobenzoic acid, p-nitrobenzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, p -Hydroxybenzoic acid, anthranilic acid, m-aminobenzoic acid, p-aminobenzoic acid, o-methoxybenzoic acid, m-methoxybenzoic acid P-methoxybenzoic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, hemimellitic acid, trimellitic acid, trimesic acid, apple Examples include acids, citric acid, methanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, and branched isomers and halogen-substituted derivatives thereof.
Preferably, an acid having a benzene ring, formic acid, an aliphatic acid having 6 or less carbon atoms (where X is an alkyl group), specifically, phthalic acid, benzoic acid, benzenesulfonic acid, benzene Examples include disulfonic acid, formic acid, acetic acid, and propanoic acid. If necessary, two or more of these organic substances may be mixed and used.

  The amount of the organic compound of the general formula (I) used in the present invention is not particularly limited, but is preferably 0.001 to 0.5 parts by weight with respect to 1 part by weight of the crude organic pigment. Particularly preferred is 0.005 to 0.1 parts by weight.

  As a device for mechanically kneading the kneaded mixture, a kneader, a planetary mixer, a trimix (manufactured by Inoue Seisakusho), a two-roll, a three-roll, a multi-axis roll, an extruder, a KRC kneader (Kurimoto Steel Works) Manufactured), Miracle KCK (manufactured by Asada Tekko Co., Ltd.) and the like, but are not particularly limited, as long as mechanical shearing force can be efficiently applied to the kneaded material, regardless of batch type or continuous type. Can be used.

  The temperature at which the kneaded mixture is mechanically kneaded is not particularly limited, but is preferably treated at 20 to 60 ° C, more preferably at 30 to 50 ° C. When the temperature exceeds 60 ° C., the crystal growth rate of the pigment particles increases as compared with the rate at which the crude pigment particles are crushed and refined, so the refinement rate is reduced and the degree of refinement reached is reduced. Further, when the temperature is lower than 20 ° C., it is difficult to remove the thermal energy generated during kneading, and the operation such as reducing the mechanical energy applied, reducing the processing amount of the kneaded mixture, or reducing the viscosity of the kneaded mixture, or A combination of these actions is required and productivity is reduced.

  The refined organic pigment after kneading is treated by a conventional method. That is, it is obtained by treating the kneaded composition with water or an aqueous mineral acid solution, filtering, washing with water and isolating the pigment. The finely divided organic pigment can be used in a wet state as it is, or in a powder state by drying and pulverization. If necessary, a pigment derivative, a dispersant, a surfactant, or other additives may be added during kneading.

  Next, the coloring composition of the present invention containing the fine organic pigment, the pigment carrier, and the non-aqueous solvent thus obtained will be described.

  The pigment carrier contained in the coloring composition of the present invention is for dispersing a fine organic pigment and is composed of a binder resin, a precursor thereof, or a mixture thereof. The binder resin is a resin having a 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. Binder resins include thermoplastic resins, thermosetting resins, and active energy ray curable resins, and precursors thereof include monomers or oligomers that cure upon irradiation with active energy rays to form binder resins. These can be used alone or in admixture of two or more.

  The pigment carrier can be used in an amount of 30 to 700 parts by weight, preferably 60 to 450 parts by weight with respect to 100 parts by weight of the pigment in the coloring composition. Moreover, when using the mixture of binder resin and its precursor as a pigment carrier, binder resin is 20-400 weight part with respect to 100 weight part of pigments in a coloring composition, Preferably it is 50-250 weight part. Can be used. The precursor of the binder resin can be used in an amount of 10 to 300 parts by weight, preferably 10 to 200 parts by weight, with respect to 100 parts by weight of the pigment in the coloring composition.

  Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. Acrylic resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, polyimide resins, and the like. Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.

  Active energy ray-curable resins include (meth) acrylic having a reactive substituent such as an isocyanate group, an aldehyde group, or an epoxy group on a polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, or an amino group. A resin in which a photocrosslinkable group such as a (meth) acryloyl group or a styryl group is introduced by reacting a compound or cinnamic acid 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 products are also used.

  Monomers and oligomers that are precursors of the binder resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 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 (meth) acrylate, trimethylolpropane tri (Meth) acrylate, pentaerythritol tri (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di ( (Meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, (meth) acrylic acid ester of methylolated melamine, epoxy ( Various acrylic esters and methacrylic esters such as (meth) acrylate and urethane acrylate, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxy Examples include methyl (meth) acrylamide, N-vinylformamide, acrylonitrile, and the like. These may be used alone or in admixture of two or more. It is possible.

  When the composition is cured by ultraviolet irradiation, a photopolymerization initiator or the like is added to the colored composition of the present invention.

  Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane Acetophenone photopolymerization initiators such as -1-one, benzoin photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4 Benzophenone photopolymerization initiators such as phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2 Thioxanthone photopolymerization initiators such as 2,4-diisopropylthioxanthone, 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 (tri (Loromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -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, etc. A polymerization initiator, a borate photopolymerization initiator, a carbazole photopolymerization initiator, an imidazole photopolymerization initiator, or the like is used. A photoinitiator can be used in the amount of 5-200 weight part with respect to 100 weight part of pigments in a coloring composition, Preferably it is 10-150 weight part.

  The above photopolymerization initiators are used alone or in combination of two or more. As sensitizers, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl-9,10-phenanthrenequinone are used. , Camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4,4′-diethylaminobenzophenone, etc. It can also be used together. The sensitizer can be used in an amount of 0.1 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator in the pigment coloring composition.

  The pigment coloring composition of the present invention can be adjusted in the form of a solvent developing type or alkali developing type colored resist. The colored resist is obtained by dispersing a pigment in a pigment carrier containing a thermoplastic resin, a thermosetting resin, or an active energy ray curable resin and a monomer, and one or more kinds of the above-mentioned fine organic pigments are added. If necessary, it can be produced together with a photopolymerization initiator in a pigment carrier using various dispersing means such as a three roll mill, a two roll mill, a sand mill, a kneader, and an attritor. The colored composition of the present invention can also be produced by mixing several types of fine organic pigments separately dispersed in a pigment carrier.

  When the fine organic pigment is dispersed in the pigment carrier, a dispersion aid such as a resin-type pigment dispersant, a surfactant, or a dye derivative can be appropriately used. Since the dispersion aid is excellent in dispersing the pigment and has a great effect of preventing re-aggregation of the pigment after dispersion, a coloring film is formed using a coloring composition in which the pigment is dispersed in the pigment carrier using the dispersion aid. When is prepared, it is excellent in transparency. The dispersion aid can be used in an amount of 0.1 to 40 parts by weight, preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the pigment in the coloring composition.

Among these, the dye derivatives are excellent in preventing fine organic pigments from agglomerating and maintaining the finely dispersed state of the organic pigments. By using a coloring composition containing these derivatives, the color purity can be achieved with a high contrast ratio. A colored film having a high thickness can be produced, which is preferable as a dispersion aid.

  The resin-type pigment dispersant added in the coloring composition of the present invention has a pigment-affinity part having the property of adsorbing to the pigment and a part compatible with the pigment carrier, and is adsorbed to the pigment to give the pigment of the pigment It serves to stabilize dispersion in the carrier. Specific examples of resin-type pigment dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamines. Salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, their modified products, amides formed by the reaction of poly (lower alkyleneimines) with polyesters having free carboxyl groups, and the like Water-based dispersants such as oily dispersants such as salts, (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone Resin, water-soluble polymer, polyester Modified polyacrylate, ethylene oxide / propylene oxide adduct, phosphoric ester or the like is used, it can be used alone or in admixture of two or more.

  As the surfactant to be added in the coloring composition of the present invention, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Anionic surfactants such as esters; polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonyl Nonionic surfactants such as phenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate; chaotic interfaces such as alkyl quaternary ammonium salts and their ethylene oxide adducts Activators: Examples include alkylbetaines such as alkyldimethylaminoacetic acid betaines and amphoteric surfactants such as alkylimidazolines, and these can be used alone or in admixture of two or more.

  In the colored composition of the present invention, a pigment is sufficiently dispersed in a pigment carrier and applied on a transparent substrate such as a glass substrate so as to have a dry film thickness of 0.2 to 5 μm to form a colored film. In order to facilitate this, a non-aqueous solvent can be contained.

Examples of the non-aqueous solvent include 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2 -Methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3- Butanediol, 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, N-methyl Rupyrrolidone, 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 monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl Ether, ethylene glycol monohexyl ether, ethylene glycol Ether 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 dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopro 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, include dibasic acid esters such as, used alone or in combination. The solvent can be used in an amount of 800 to 4000 parts by weight, preferably 1000 to 2500 parts by weight, with respect to 100 parts by weight of the pigment in the pigment dispersion and coloring composition.

  In addition, the colored composition of the present invention can contain a storage stabilizer in order to stabilize the viscosity with time of the composition. Examples of the storage stabilizer include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and organic acids such as methyl ether, t-butylpyrocatechol, triethylphosphine, and triphenylphosphine. Examples thereof include 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 pigment in the coloring composition.

  The coloring composition of the present invention can be prepared in the form of gravure offset printing ink, waterless offset printing ink, silk screen printing ink, solvent development type or alkali development type color resist. The colored resist is obtained by dispersing a dye in a composition containing a thermoplastic resin, a thermosetting resin or a photosensitive resin, a monomer, a photopolymerization initiator, and an organic solvent.

  The fine organic pigment is preferably contained in a proportion of 5 to 70% by weight based on the total solid content of the colored composition (100% by weight). A ratio of 20 to 50% by weight is more preferable.

  Moreover, the coloring composition of this invention can be made to contain a dye within the range which does not reduce heat resistance for color matching.

  The coloring composition of the present invention is mixed with 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 or the like. It is preferable to remove dust.

  In the present invention, if necessary, a resin, a surfactant, or the like may be added before or during the step of kneading the mixture of the crude organic pigment, the grinding aid, and the water-soluble organic solvent. The resin to be used is not particularly limited, but rosin, rosin derivative, rosin modified maleic acid 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, cellulose , Benzoguanamine resins, urea resins, and oligomers and monomers of the above resins.

  The refined organic pigment produced by the method of the present invention is refined and sized into a uniform particle shape, so that it is uniformly dispersed in an aqueous or non-aqueous vehicle while maintaining the fine particle state. When the pigment dispersion is used, a good dispersion having stable viscosity characteristics is obtained. When the dispersion is used as an inkjet ink, excellent flight stability, sharpness of recorded matter, and various resistances can be realized.

  Moreover, when a color filter is prepared using the dispersion, a color filter having high brightness, sharpness, and transmittance is obtained.

  The average primary particle diameter of the resulting fine organic pigment is preferably 30 nm or less, more preferably 20 nm or less. Moreover, it is preferable that an average primary particle diameter is 5 nm or more. When the average primary particle diameter of the pigment is larger than the upper limit value, the transparency of the colored film is lowered. Moreover, when smaller than a lower limit, pigment dispersion | distribution becomes difficult, it becomes difficult to maintain stability as a coloring composition and to ensure fluidity | liquidity. Moreover, as a calculation method of a primary particle diameter, the following are mentioned as an example. The projected area of each particle is obtained by, for example, image processing of an image of a fine organic pigment image taken with a transmission electron microscope (TEM), and the diameter of a circle corresponding to the projected area is calculated. A value obtained by dividing the sum of the diameters of individually calculated particle circles by the number can be used as the average primary particle size.

  EXAMPLES The present invention will be described in more detail with reference to the following examples. However, the following examples do not limit the scope of rights of the present invention. In the examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.

Example 1 Diketopyrrolopyrrole Pigment A kneaded material having the following composition was put into a 3000 volume part kneader and kneaded at a rotation speed of 45 rpm and a processing temperature of 60 ° C. for 6 hours. (Disodium phthalate was used as the organic substance of the general formula (I).)
IRGAFOR RED B-CF (manufactured by Ciba Specialty Chemicals) 135 parts Diketopyrrolopyrrole pigment derivative (structure is represented by formula (III)) 15 parts Disodium phthalate 10 parts Sodium chloride 1500 parts Diethylene glycol 240 parts The obtained kneaded material was taken out in 10,000 parts of 70 ° C. water and stirred while keeping it warm for 1 hour, followed by filtration, washing with water, drying and pulverization to obtain a fine diketopyrrolopyrrole pigment.

Next, the mixture of the following composition containing the obtained fine diketopyrrolopyrrole pigment was uniformly stirred, dispersed with a bead mill for 10 hours using zirconia beads having a diameter of 0.5 mm, and then filtered through a 1 μm filter. A red pigment dispersion was prepared.
Diketopyrrolopyrrole pigment 17.4 parts Diketopyrrolopyrrole pigment derivative (structure shown in formula (III)) 2.4 parts Methoxypropyl acetate 68.8 parts Cyclohexanone 17.2 parts Resin solution 53.9 parts

Formula (III)

Furthermore, after stirring and mixing the mixture of the following composition containing the obtained red pigment dispersion uniformly, it filtered with a 1 micrometer filter, and produced the red coloring composition.
Red pigment dispersion 44.0 parts Resin solution 27.2 parts Methoxypropyl acetate 29.0 parts The red colored composition was applied on a glass plate and dried to prepare a colored film.

[Example 2]
A refined diketopyrrolopyrrole pigment was obtained in the same manner as in Example 1 except that disodium benzenedisulfonate was used instead of disodium phthalate. Subsequently, the obtained fine diketopyrrolopyrrole pigment was stirred, dispersed, mixed, filtered and applied in the same manner as in Example 1 to produce a colored film of a red colored composition.

[Example 3]
A refined diketopyrrolopyrrole pigment was obtained in the same manner as in Example 1 except that sodium benzoate was used instead of disodium phthalate. Subsequently, the obtained fine diketopyrrolopyrrole pigment was stirred, dispersed, mixed, filtered and applied in the same manner as in Example 1 to produce a colored film of a red colored composition.

Example 4 Kinophthalone Pigment A kneaded material having the following composition was put into a 3000 volume part kneader and kneaded at a rotational speed of 63 rpm and a processing temperature of 60 ° C. for 10 hours. (Disodium phthalate was used as the organic substance of the general formula (I).)
Paliotol yellow K0961HD (manufactured by BASF) 135 parts Benzimidarone dye derivative (structure shown in formula (IV)) 15 parts Disodium phthalate 10 parts Sodium chloride 1500 parts Diethylene glycol 330 parts The kneaded product obtained here is 70 ° C The mixture was taken out to 10,000 parts of water, stirred for 1 hour, and then filtered, washed with water, dried and pulverized to obtain a fine quinophthalone pigment.

Next, the obtained mixture of the following composition containing the fine quinophthalone pigment was uniformly stirred, dispersed with a bead mill for 13.5 hours using zirconia beads having a diameter of 0.5 mm, and then filtered with a 1 μm filter. A yellow pigment dispersion was prepared.
Quinophthalone pigment 17.4 parts Benzimidazolone dye derivative 3.0 parts Methoxypropyl acetate 125.0 parts Cyclohexanone 7.5 parts Resin solution 34.5 parts

Formula (IV)

Furthermore, after stirring and mixing the mixture of the following composition containing the obtained yellow pigment dispersion uniformly, it filtered with a 1 micrometer filter, and produced the yellow coloring composition.
Yellow pigment dispersion 45.0 parts Resin solution 5.0 parts

The yellow colored composition was applied on a glass plate and dried to prepare a colored film.

[Comparative Example 1]
A kneaded material having the following composition was put into a 3000 volume part kneader and kneaded at a rotational speed of 53 rpm and a processing temperature of 60 ° C. for 12 hours.
IRGAFOR RED B-CF (manufactured by Ciba Specialty Chemicals) 135 parts Diketopyrrolopyrrole dye derivative (structure is represented by formula (III)) 15 parts Sodium chloride 1500 parts Diethylene glycol 240 parts The kneaded product obtained here is carried out By treating in the same manner as in Example 1, a fine diketopyrrolopyrrole pigment was obtained. Subsequently, the obtained fine diketopyrrolopyrrole pigment was stirred, dispersed, mixed, filtered and applied in the same manner as in Example 1 to produce a colored film of a red colored composition.
[Comparative Example 2]
A kneaded material having the following composition was put into a 3000 volume part kneader and kneaded at a rotation speed of 63 rpm and a processing temperature of 60 ° C. for 10 hours.
Pariol Yellow K0961HD (BASF) 135 parts Benzimidarone pigment derivative 15 parts Sodium chloride 1500 parts Diethylene glycol 330 parts The kneaded product obtained here is taken out in 10,000 parts of 70 ° C. water, heated and stirred for 1 hour, filtered, washed with water, Drying and pulverization gave a fine quinophthalone pigment. Subsequently, the resulting fine quinophthalone pigment was stirred, dispersed, mixed, filtered and applied in the same manner as in Example 4 to produce a colored film of a yellow colored composition.

[Evaluation method]
The obtained fine diketopyrrolopyrrole pigment and quinophthalone pigment were subjected to X-ray diffraction spectrum measurement under the following conditions.
Equipment: Rigaku Ultima2001
X-ray source: CuKα
Voltage: 40kV
Current: 40mA
Measurement range: 3.0 ° to 35.0 °
Step angle: 0.02 °

<Half width>
From this measurement result, the data was processed under the following conditions to determine the peak half width. Here, the half-value width is a black angle value defined by a peak width at an intensity position that is a half intensity of the X-ray diffraction intensity at a certain 2θ peak.

  The half width was obtained as follows. First, the X-ray diffraction intensity of 2θ = x was set to a moving average of x ± 0.2, and the data was smoothed. In the vicinity of the target peak value, the position where the intensity is the maximum is the peak position, and then the background is removed using the straight line drawn from before and after the peak position as the baseline, and the half-value width (△ 2θ) from the net value Asked.

  The half-value width (Δ2θ) obtained here corresponds to the size of the crystal, and the half-value width becomes larger as the crystal becomes smaller.

<Contrast ratio>
A colored film was prepared by the following method using the obtained colored composition. That is, the obtained colored composition was applied on a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater at a rotation speed such that the chromaticity (x) of the colored film was 0.640. did. Next, it was dried at 85 ° C. for 10 minutes and at 230 ° C. for 60 minutes. And the brightness (Y) and contrast ratio (CR ratio) of the colored film were measured. The brightness (Y) was measured with a spectrophotometer (“U-3500” manufactured by Hitachi, Ltd.). The contrast ratio (CR ratio) was measured with a contrast tester (“CT-1BF” manufactured by Aisaka Electric Co., Ltd.).

Table 1 shows the half width and the contrast ratio measured by the method of the above example.

  As shown in Table 1, each of the pigments of Examples 1 to 3 has a larger half-value width and a higher contrast ratio as compared with Comparative Example 1. It can be seen that the pigment of Example 4 has a larger half-value width than that of Comparative Example 2, and further refinement. By preparing the pigment by adding the organic substance of general formula (I) as in the examples, it is possible to provide a fine organic pigment and a coloring composition that are very fine and have a high contrast ratio.

Claims (8)

In a method for producing a fine organic pigment in which a mixture of a crude organic pigment, a grinding aid and a water-soluble organic solvent is kneaded by a solvent salt milling method, a metal salt of an organic acid represented by the following general formula (I) is added during kneading: The manufacturing method of the refined organic pigment characterized by the organic substance which has.
Formula (I)

X- (R · M) n (n = 1 to 3)

[Wherein X may have a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, or a substituent. Good aryl group, arylalkyl group which may have a substituent, arylalkenyl group which may have a substituent, arylalkynyl group which may have a substituent, cycloalkyl which may have a substituent Represents a group or an optionally substituted benzene ring,
Each R independently represents a carboxylic acid group or a sulfonic acid group.
Each M is independently a metal for inducing a metal salt of an organic acid, and is selected from sodium (Na), magnesium (Mg), potassium (K), calcium (Ca), and barium (Ba). ]   The method for producing a fine organic pigment according to claim 1, wherein the crude organic pigment is at least one organic pigment selected from the group consisting of phthalocyanine, quinophthalone, diketopyrrolopyrrole, and dioxazine pigments.   A refined organic pigment obtained by the production method according to claim 1.   The peak at Bragg angle 2θ = 9.1 ± 0.5 ° by powder X-ray diffraction measured by CuKα ray, and the half-value width of net intensity based on the straight line connecting with 2θ = 5-12 ° intensity is 0.7 or more The refined organic pigment according to claim 4, which is a refined phthalocyanine pigment.   The peak at Bragg angle 2θ = 27.8 ± 0.5 ° by powder X-ray diffraction measured by CuKα ray, and the half-value width of net intensity based on the straight line connected with the intensity of 2θ = 27-29.3 ° is 0.8 or more 5. The refined organic pigment according to claim 4, which is a refined quinophthalone pigment.   The half-value width of the net intensity with a peak at a Bragg angle of 2θ = 28.2 ± 0.5 ° by powder X-ray diffraction measured with CuKα rays, with the intensity of 2θ = 23.4-34.8 ° as the baseline, is 0.8 or more. 5. The refined organic pigment according to claim 4, which is a refined diketopyrrolopyrrole pigment.   The peak at Bragg angle 2θ = 25.7 ± 0.5 ° by powder X-ray diffraction measured by CuKα ray, and the half-value width of net intensity is 1.1 or more based on the straight line connecting with 2θ = 18-34 ° intensity. The refined organic pigment according to claim 4, which is a refined dioxazine-based pigment.   A coloring composition comprising the finely divided organic pigment according to claim 3 and a pigment carrier.