JP2012025920A - Method for producing fine organic pigment, the fine organic pigment, and fine organic pigment colored composition - Google Patents

Abstract

An object of the present invention is to provide a method for producing a very fine organic pigment, which can be processed in a shorter time than before, has good productivity per unit energy. Furthermore, it is providing the fine organic pigment manufactured by the said manufacturing method, and the fine organic pigment coloring composition using a fine organic pigment.
A method for producing a finely divided organic pigment, characterized in that a finer step is carried out in the presence of an alkaline substance.
[Selection figure] None

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 milling agent, amount added and mechanical shear force, control of crystal growth by 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 refining from the physical properties of the grinding aid, but there has been a demand for a method for obtaining a pigment having a higher degree of fineness more efficiently.

  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

  The present invention has been made in view of such a situation, and an object of the present invention is to provide a method for producing a very fine organic pigment in a shorter time and with higher productivity per unit energy. Furthermore, it aims at providing the fine organic pigment manufactured by the said manufacturing method and the fine organic pigment coloring composition using a fine organic pigment.

  That is, the present invention relates to a method for producing a fine organic pigment, wherein the fine organic pigment is refined in the presence of an alkaline substance in the method for producing a fine organic pigment.

  The present invention also relates to a method for producing a fine organic pigment, wherein the method for producing a fine organic pigment is 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 also relates to a method for producing the fine organic pigment, wherein the crude organic pigment is a quinophthalone pigment or / and a diketopyrrolopyrrole pigment.

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

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

  The present invention also relates to the above-mentioned fine organic pigment coloring composition comprising a non-aqueous solvent.

  In the method for producing a fine organic pigment of the present invention, when a mixture of a crude organic pigment, a grinding aid and a water-soluble organic solvent is kneaded, an alkaline substance is added to act on the crystal surface of the crude organic pigment. , Improve the affinity between the crude organic pigment and the water-soluble organic solvent. By improving the affinity, the pigment can be efficiently ground and the miniaturization can be promoted. For this reason, it is possible to produce a pigment that is sized in a fine and uniform particle size with a high productivity per unit energy in a shorter time than before.

  In addition, the method for producing a fine organic pigment by adding an alkaline substance according to the present invention produces a pigment that is sized to a fine and uniform particle size at a very low cost compared to the conventional method by adding an expensive dye derivative. can do.

  Furthermore, the alkaline substance added in the method for producing a fine organic pigment of the present invention can be separated from the pigment by filtration and washing with water, and does not affect the hue or brightness of the pigment, for example, as in general dye derivatives. .

  The method for producing a fine organic pigment according to the present invention is a method in which a mixture containing a crude organic pigment, an alkaline substance, a grinding aid, and a water-soluble organic solvent is mechanically kneaded with a kneader or the like and then poured into water and stirred to obtain a slurry. And then the slurry is filtered, washed with water and dried.

  The organic pigment obtained by the method for producing a fine organic pigment of the present invention is a pigment in which the crude organic pigment is selected from quinophthalone-based and diketopyrrolopyrrole-based pigments. Particularly preferred are quinophthalone pigments.

  The quinophthalone pigment is a yellow pigment having a structure represented by the following general formula (I), and has excellent light resistance and heat resistance. Specific examples of quinophthalone pigments are indicated by color index numbers. I. Pigment Yellow 138 and the like.

［式中、Ｘは塩素原子、または、臭素原子を表す。］ Formula (I)

[Wherein, X represents a chlorine atom or a bromine atom. ]

  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 are indicated by color index numbers. I. Pigment RED 254, 255, 264, 272, or C.I. I. Pigment Orange 71, 73, 81 and the like.

［式中、ＸおよびＹはそれぞれ独立に、−ＣＮ、−Ｃ（ＣＨ₃）₃、−ＣＨ₃、−Ｃｌ、−Ｃ₆Ｈ₅、または、−Ｈを表す。］ Formula (II)

[Wherein, X and Y each independently represent —CN, —C (CH ₃ ) ₃ , —CH ₃ , —Cl, —C ₆ H ₅ , or —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 pigment derivative is used for the purpose of preventing crystal growth and crystal dislocation of the organic pigment. 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 a grinding aid used at the time of kneading, a water-soluble inorganic salt is desirable, and the pigment is crushed during salt milling by utilizing 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, salt (sodium chloride), potassium chloride, sodium sulfate, zinc chloride, calcium chloride, magnesium chloride, or these mixtures etc. can be mentioned, It is preferable to use sodium chloride 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 used varies depending on the type of the crude organic pigment, but it is preferably 100 to 3000 parts by weight, more preferably the water-soluble inorganic salt 500 with respect to 100 parts by weight of the crude organic pigment. ˜1500 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 to obtain a dough having an appropriate hardness, thereby increasing the grinding effect and promoting 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 10 to 500 parts by weight, preferably 100 to 100 parts by weight based on 100 parts by weight of the crude organic pigment. 250 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, eta Alcohol, isopropanol, n-propanol, isobutanol, n-butanol, ethylene glycol, propylene glycol, propylene glycol monomethyl ether acetate, ethyl acetate, isopropyl acetate, acetone, methyl ethyl ketone, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, etc. Can be mentioned. If necessary, two or more of these water-soluble organic solvents may be mixed and used.

  Examples of the alkaline substance used in the present invention include alkali metal hydroxides, alkaline earth metal hydroxides, basic oxides, alkali metal carbonates, alkaline earth metal carbonates, bicarbonates, and alkali metal phosphates. Examples thereof include, but are not limited to, salts, alkaline earth metal phosphates, ammonia or amines.

  Examples of the alkali metal or alkaline earth metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, beryllium hydroxide, magnesium hydroxide, calcium hydroxide, and strontium hydroxide. And barium hydroxide.

  Examples of the basic oxide include calcium oxide, magnesium oxide, sodium oxide and the like.

  Examples of the alkali metal or alkaline earth metal carbonate include lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, beryllium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, and barium carbonate.

  Examples of the hydrogen carbonate include ammonium hydrogen carbonate, sodium hydrogen carbonate, and potassium hydrogen carbonate.

  Examples of the alkali metal or alkaline earth metal phosphate include trisodium phosphate, tripotassium phosphate, trirubium phosphate, and tricalcium phosphate.

  Examples of amines include dimethylamine, diethylamine, methylethylamine, N, N-ethylisopropylamine, N, N-ethylpropylamine, N, N-methylbutylamine, N, N-methylisobutylamine, N, N-butyl. Ethylamine, N, N-tert-butylethylamine, diisopropylamine, dipropylamine, N, N-sec-butylpropylamine, dibutylamine, di-sec-butylamine, diisobutylamine, N, N-isobutyl-sec-butylamine, Diamylamine, diisoamylamine, dihexylamine, dicyclohexylamine, di (2-ethylhexyl) amine, dioctylamine, N, N-methyloctadecylamine, didecylamine, diallylamine, N, N-ethyl-1,2- Methylpropylamine, N, N-methylhexylamine, dioleylamine, distearylamine, N, N-dimethylaminomethylamine, N, N-dimethylaminoethylamine, N, N-dimethylaminoamylamine, N, N-dimethyl Aminobutylamine, N, N-diethylaminoethylamine, N, N-diethylaminopropylamine, N, N-diethylaminohexylamine, N, N-diethylaminobutylamine, N, N-diethylaminopentylamine, N, N-dipropylaminobutylamine, N, N-dibutylaminopropylamine, N, N-dibutylaminoethylamine, N, N-dibutylaminobutylamine, N, N-diisobutylaminopentylamine, N, N-methyl-laurylaminopropylamine, N, N- Tylhexylaminoethylamine, N, N-distearylaminoethylamine, N, N-dioleylaminoethylamine, N, N-distearylaminobutylamine, piperidine, 2-pipecoline, 3-pipecholine, 4-pipecholine, 2,4- Lupetidine, 2,6-lupetidine, 3,5-lupetidine, 3-piperidinemethanol, pipecolic acid, isonipecotic acid, methyl isonipecotate, ethyl isonipecotate, 2-piperidineethanol, pyrrolidine, 3-hydroxypyrrolidine, N-aminoethyl Piperidine, N-aminoethyl-4-pipecholine, N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropyl-2-pipecholine, N-aminopropyl-4-pipecholine, N-aminopropylmorpholine, - methylpiperazine, N- butyl piperazine, N- methyl homopiperazine, 1-cyclopentylpiperazine, mention may be made of 1-amino-4-methylpiperazine, or 1-cyclopentyl piperazine.

  Among these, alkali metal hydroxides, alkaline earth metal hydroxides, and basic oxides are particularly preferable. If necessary, two or more of these alkaline substances may be mixed and used.

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

  The addition amount of the alkaline substance used in the present invention is not particularly limited, but is preferably 0.05 to 5 parts by weight, particularly preferably 0.1 to 100 parts by weight of the crude organic pigment. -2.5 parts by weight. When the amount exceeds 5 parts by weight, the crude organic pigment may be altered, and an organic pigment having a desired hue and brightness cannot be obtained. On the other hand, if it is lower than 0.05, the desired effect of promoting the refinement of the organic pigment cannot be obtained.

  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 70 ° C, more preferably at 30 to 60 ° C. When the temperature exceeds 70 ° 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 fine 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 fine 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.

  The production method of the present invention is not limited to the solvent salt milling method. Other examples include dry salt milling and dry pulverization.

  In the dry pulverization method, a crude organic pigment is pulverized by using a pulverizer having a built-in pulverization medium such as beads without substantially interposing a liquid substance. The pulverization is performed by using a pulverization force and a destructive force caused by collision between the pulverization media. As the dry pulverizer, known methods such as a dry attritor, a ball mill, and a vibration mill can be used.

  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 fine organic pigments 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 requires one or more of the above-mentioned fine organic pigments. Depending on the condition, it can be produced in a pigment carrier together with a photopolymerization initiator 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- Tylpyrrolidone, 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 Recall 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 mono Propyl 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, methylcyclohexanol, n-amyl acetate, n-butyl acetate Le, 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 wt%, more preferably 20 to 50 wt%, based on the total solid content of the colored composition (100 wt%).

  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.

  Since the fine organic pigment produced by the method of the present invention is refined and sized into a uniform particle shape, it is uniformly dispersed in an aqueous or non-aqueous vehicle while maintaining a fine particle state. When a 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 obtained 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 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.

[Adjustment of acrylic resin solution]
700 parts of cyclohexanone was added to a separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, and a stirring device, and heated to 80 ° C. After substituting the inside of the reaction vessel with nitrogen, from the dropping tube, 133 parts of N-butyl methacrylate, 46 parts of 2-hydroxyethyl methacrylate, 43 parts of methacrylic acid, paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.) ) 74 parts, a mixture of 2,2'-azobisisobutyronitrile 4 parts was added dropwise over 2 hours. After completion of dropping, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight of 26000. After cooling to room temperature, 2 parts of the resin solution was taken out, dried by heating at 180 ° C. for 20 minutes, and the nonvolatile content was measured. Cyclohexanone was added so that the nonvolatile content of the resin solution was 20% by weight to obtain an acrylic resin solution.

[Example 1]
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 6 hours. (Sodium hydroxide aqueous solution was used as the alkaline substance.)
Paliotol yellow K0961HD (manufactured by BASF) 147 parts Benzimidarone dye derivative (structure shown in formula (III)) 3 parts Sodium hydroxide aqueous solution 3 parts Sodium chloride 1500 parts Diethylene glycol 330 parts The kneaded product obtained here is 70 ° C It was taken out in 10,000 parts of water, heated and stirred for 1 hour, 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, filtered through a 1 μm filter, and yellow. A pigment dispersion was prepared.
Quinophthalone pigment 16.9 parts Quinophthalone dye derivative (structure shown in formula (IV)) 3.0 parts Methoxypropyl acetate 124.0 parts Cyclohexanone 7.6 parts Acrylic resin solution 38.1 parts

Formula (III)

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 Acrylic resin solution 5.0 parts The yellow colored composition was coated on a glass plate and dried to prepare a colored film.

[Example 2]
A kneaded material having the following composition was put into a 3000 volume part kneader and kneaded for 4 hours at a rotational speed of 63 rpm and a processing temperature of 60 ° C. (Sodium hydroxide aqueous solution was used as the alkaline substance.)
Paliotol yellow K0961HD (manufactured by BASF) 147 parts Benzimidarone dye derivative 3 parts Sodium hydroxide aqueous solution 6 parts Sodium chloride 1500 parts Diethylene glycol 330 parts By treating the kneaded mixture obtained in the same manner as in Example 1, fine quinophthalone A pigment was obtained. Subsequently, the obtained fine quinophthalone pigment was stirred, dispersed, mixed, filtered and applied in the same manner as in Example 1 to prepare a colored film of a yellow colored composition.

[Example 3]
A kneaded material having the following composition was put into a 3000 volume part kneader and kneaded for 8 hours at a rotation speed of 63 rpm and a processing temperature of 60 ° C. (Magnesium oxide was used as the alkaline substance.)
Paliotol yellow K0961HD (manufactured by BASF) 147 parts Benzimidarone dye derivative 3 parts Magnesium oxide 0.2 parts Sodium chloride 1500 parts Diethylene glycol 330 parts By treating the kneaded mixture obtained in the same manner as in Example 1, fine quinophthalone A pigment was obtained. Subsequently, the obtained fine quinophthalone pigment was stirred, dispersed, mixed, filtered and applied in the same manner as in Example 1 to prepare a colored film of a yellow colored composition.

[Example 4]
A kneaded material having the following composition was put into a 3000 volume part kneader and kneaded for 5 hours at a rotation speed of 45 rpm and a processing temperature of 60 ° C. (Sodium hydroxide aqueous solution was used as the alkaline substance.)
IRGAFOR RED B-CF (manufactured by Ciba Specialty Chemicals) 135 parts Diketopyrrolopyrrole pigment derivative (structure is represented by formula (V)) 15 parts Sodium hydroxide aqueous solution 1 part Sodium chloride 1500 parts Diethylene glycol 240 parts The obtained kneaded material was taken out to 10,000 parts of 70 ° C. water, stirred for 1 hour with heat, filtered, washed with water, dried and pulverized to obtain fine diketopyrrolopyrrole pigment.

Next, the obtained mixture of the following composition containing the 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 with a 1 μm filter. A red pigment dispersion was prepared.
Diketopyrrolopyrrole pigment 17.4 parts Diketopyrrolopyrrole pigment derivative 2.4 parts Methoxypropyl acetate 66.1 parts Cyclohexanone 17.2 parts Acrylic resin solution 53.9 parts

Formula (V)

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 45.3 parts Acrylic resin solution 18.1 parts Methoxypropyl acetate 28.9 parts The above red coloring composition was applied onto 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 rotation speed of 63 rpm and a processing temperature of 60 ° C. for 10 hours.
Paliotol yellow K0961HD (manufactured by BASF) 147 parts benzimidarone dye derivative 3 parts sodium chloride 1500 parts diethylene glycol 330 parts The kneaded material obtained here was treated in the same manner as in Example 1 to obtain a fine quinophthalone pigment. Subsequently, the obtained fine quinophthalone pigment was stirred, dispersed, mixed, filtered and applied in the same manner as in Example 1 to prepare a colored film of a yellow colored composition.

[Comparative Example 2]
A kneaded material having the following composition was put into a 3000 volume part kneader and kneaded for 6 hours at a rotation speed of 45 rpm and a processing temperature of 60 ° C.
IRGAFOR RED B-CF (manufactured by Ciba Specialty Chemicals) 135 parts Diketopyrrolopyrrole pigment derivative 15 parts Sodium chloride 1500 parts Diethylene glycol 240 parts Finely treating the kneaded material obtained here in the same manner as in Example 4 A diketopyrrolopyrrole pigment was obtained. The resulting fine diketopyrrolopyrrole pigment was then stirred, dispersed, mixed, filtered and applied in the same manner as in Example 4 to produce a colored film of a red colored composition.

[Evaluation method]
The obtained fine quinophthalone pigment and fine diketopyrrolopyrrole 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, data processing was performed under the following conditions to determine the peak half-value width. Here, the half-value width is a Bragg angle value defined by a peak width at an intensity position that is half 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.

  For the peak at 2θ = 27.8 ± 0.5 ° for quinophthalone pigment, the background is removed using the straight line connecting 2θ = 27.0 and 2θ = 29.3 as the baseline, and for diketopyrrolopyrrole pigment, it is 2θ = 28.2 ± 0.5 °. The background was removed from the peak using the straight line connecting 2θ = 23.4 and 2θ = 34.8 as the base line.

  The half width (Δ2θ) obtained here corresponds to the size of the crystal. The smaller the crystal is, the larger the half width is.

<Contrast ratio>
A colored film was prepared by the following method using the obtained colored composition. That is, using a spin coater on a 100 mm × 100 mm, 1.1 mm thick glass substrate, the chromaticity (x) of the colored film is 0.415 for the quinophthalone pigment and 0.640 for the diketopyrrolopyrrole pigment. The obtained colored composition was applied at such a rotational speed. Next, the quinophthalone pigment was dried at 140 ° C. for 5 minutes, the diketopyrrolopyrrole pigment was dried at 85 ° C. for 10 minutes, and 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 kneading time of the organic pigment and the half width, contrast ratio, and brightness measured by the method of the above example.

Table 1

  As shown in Table 1, all of the pigments of Examples 1 to 3 can obtain the same half-value width and contrast ratio by kneading in a short time as compared with Comparative Example 1. Compared with Comparative Example 2, the pigment of Example 4 was able to obtain the same half width and contrast ratio by kneading in a short time. Providing a method for producing very fine organic pigments with a higher productivity per unit energy in a shorter time than before by preparing pigments by adding alkaline substances described in this patent as in the examples. can do.

Claims (6)

  In the manufacturing method of a fine organic pigment, it refines | miniaturizes in coexistence of an alkaline substance, The manufacturing method of the fine organic pigment characterized by the above-mentioned.   The method for producing a fine organic pigment according to claim 1, wherein the method for producing a fine organic pigment is 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 method for producing a fine organic pigment according to claim 1 or 2, wherein the crude organic pigment is a quinophthalone pigment or / and a diketopyrrolopyrrole pigment.   A fine organic pigment obtained by the production method according to claim 1.   A fine organic pigment coloring composition comprising the fine organic pigment according to claim 4 and a pigment carrier.   The fine organic pigment coloring composition according to claim 5, further comprising a non-aqueous solvent.