JP2005029787A - Process for production of beta-type copper phthalocyanine pigment - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a process for production of a beta-type copper phthalocyanine pigment, with small load to equipment and environment, and have a small primary crystal aspect ratio. <P>SOLUTION: The process for the production of the beta-type copper phthalocyanine pigment comprises dry-milling a crude copper phthalocyanine having a purity of 97-100% at a temperature of 180-50°C, and then kneading in a water-miscible organic solvent, to prepare a beta-type copper phthalocyanine pigment having an average primary crystal diameter of 80±40 nm and a primary crystal aspect ratio of 2.0±1.0 and having a crystallite diameter of 22±5 nm in the direction perpendicular to a monoclinic [beta] (200) plane, a crystallite diameter of 27±5 nm in the direction perpendicular to a [beta] (001) plane and a crystallite diameter of 15±5 nm in the direction perpendicular to a [beta] (010) plane, wherein 0.1-20 wt.% of a phthaloimidemethyl group-substituted phthalocyanine compound is added to the dry-milling product before, in or after kneading in the organic solvent. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

The present invention relates to a method for producing a β-type copper phthalocyanine pigment by a dry pulverization method.

Usually, the synthesized copper phthalocyanine is called crude copper phthalocyanine, and cannot be used as it is as a pigment for printing ink because it is a large particle having a primary crystal diameter of 0.5 to 100 μm. The process of reducing the primary crystals of the crude copper phthalocyanine to about 100 ± 50 nm, which is a size that can be used as a printing ink, is called pigmentation. There are various methods for pigmentation.

The most common method is called a solvent salt milling method. This method is a method in which crude copper phthalocyanine is ground by adding a grinding aid such as salt and an organic solvent that promotes crystal transition to β-type. The β-type copper phthalocyanine pigment obtained by this method has an average primary crystal diameter of 80 ± 40 nm, and the primary crystal has an aspect ratio of 2.0 ± 0.5, and the size and shape of the primary crystal are adjusted. This physical property is advantageously reflected in suitability and is widely used because it is suitable for printing inks in terms of flow properties, coloring power and the like. However, it takes a lot of time and energy to recover the grinding aid and organic solvent in order to use a grinding aid several times the amount of the pigment and to use a high-boiling solvent with a large environmental load. In addition, there is a serious problem that the equipment is corroded by inorganic salts which are grinding aids, that is, the equipment load is large.

On the other hand, a method of treating crude copper phthalocyanine with an organic solvent after pulverizing the dry copper phthalocyanine is also known. This method is a very effective means for supplying an inexpensive β-type copper phthalocyanine pigment because the process is simplified as compared with the solvent salt milling method described above.

Now, β-type copper phthalocyanine crystallizes to α-type which is thermodynamically unstable by mechanical impact force as in the case of dry pulverization. Usually, when β type crude copper phthalocyanine is dry pulverized at a pulverization temperature of 80 to 90 ° C., the α ratio in the pulverized product is known to be 60% or more (see Patent Document 1).

On the other hand, when pulverized with a small impact force, it is naturally possible to keep the ratio of α-type crystals low. For example, Patent Document 2 discloses the inclusion of α-type crystals when pulverized at a pulverization temperature of 100 ° C. It is described that the rate is 21%. However, with such an impact force pulverization, the particle size distribution of the pigment particles obtained by the solvent salt milling method cannot be realized.

The solvent salt milling method is characterized by applying a strong grinding force to a dough formed from crude primary copper phthalocyanine, an organic solvent, and a grinding aid.

On the other hand, the method of treating the dry pulverized product with an organic solvent or the like is characterized in that the α-type is transferred to obtain β-type crystals and the strong aggregates of fine primary crystals are peptized to obtain the desired dispersed particle size. It is. However, it is known that the primary crystal grows in a needle shape in the process of transferring the α-type crystal in the dry pulverized product to the β-type, and the aspect ratio becomes larger than that in the solvent salt milling method.
JP-A-7-310024 JP-A-2-294365

The method of treating crude copper phthalocyanine with an organic solvent after dry pulverization eliminates the need for a grinding aid recovery step required by the solvent salt milling method, and the dry pulverization is efficient and the amount of powder processed. This is advantageous from the viewpoint of the above, but there is a drawback that a transition from a β-type crystal to an α-type crystal is accompanied when a mechanical force is applied. Moreover, when transitioning from α-type crystals to β-type crystals by the action of organic solvents, the pigment primary crystals grow into needles and the aspect ratio is larger than in the solvent salt milling method, so the hue based on the orientation of the dispersed particles Problems such as reddening and fluidity deterioration due to structural viscosity occur. In addition, there is a method of dry pulverization of crude copper phthalocyanine in the presence of an organic solvent to prevent the formation of α-type crystals. However, it is difficult to control the α rate based on heterogeneous processing, and is compatible with solvent processing. There is a cost problem of capital investment such as explosion-proof equipment.

The present inventors paid attention to the fact that the α ratio in the α / β mixed crystal copper phthalocyanine obtained by this dry pulverization affects the aspect ratio of the final pigment, and the smaller the α ratio in the ground product, the smaller the α ratio in the ground product. It was found that the aspect ratio of pigment particles obtained by treatment with an organic solvent or the like was small.

Furthermore, it has been found that the peptization property of the dry pulverized product which is a strong agglomerate depends on the α rate, and is extremely reduced when the α rate is less than 5%.

The α rate of the pulverized product obtained by dry pulverization increases with mechanical impact force and pulverization time. This phenomenon is a result of the mechanical energy breaking of the bond between the meso-position nitrogen atom in the adjacent phthalocyanine molecule coordinated in the longitudinal direction to the copper atom of the phthalocyanine central metal in β-type by the Yarn-Teller effect, and the internal energy increases. It can be explained that the crystal transitions to thermodynamically unstable α-type. Therefore, the enthalpy of ΔH _{β ← α} = -10.8 kJ / mol, that is, 10.8 kJ / mol is released from α-type by the action of heat or non-acidic organic solvent, which is directed to thermodynamic stabilization. It is thought to re-transfer to the mold.

In the dry pulverization process, in order to increase the α rate by reducing the re-transition to the β type, a substance that suppresses lattice contraction in the c-axis direction of the α type crystal may be allowed to coexist. In order to obtain a dry pulverized product, it was inferred based on crystal structure analysis that crude copper phthalocyanine with a small amount of substances that suppress lattice shrinkage in the c-axis direction may be used.

From this hypothesis, dry grinding of high-purity crude copper phthalocyanine yielded a dry pulverized product with a low α rate more easily, and this point was verified by experiments.

From the above theoretical background, if the crude copper phthalocyanine is of high purity, even if mechanical impact force is applied, the crystal transition to α-type is difficult, so the degree of heating during dry grinding can be reduced.

The dry pulverization conditions for obtaining an α / β mixed crystal copper phthalocyanine having an α ratio of 5 to 35% are such that the purity of the crude copper phthalocyanine is 97 to 100%, and the dry pulverization temperature is 180 to 50 ° C., preferably Was found to be 160-80 ° C.

The present invention was obtained by dry-pulverizing high-purity crude copper phthalocyanine for the purpose of maintaining the pigment quality obtained by the solvent salt milling method and at the same time solving the problems inherent in the process of the solvent salt milling method. The present invention provides a method for producing a β-type copper phthalocyanine pigment having a primary crystal aspect ratio of 2.0 ± 1.0 by treating a low α-rate dry pulverized product with an organic solvent. Further, 0.1 to 20% by weight of a compound represented by the following general formula (1) or (2) is added to the dry pulverized product at the time of kneading the organic solvent, to produce a β-type copper phthalocyanine pigment A method is provided.
Formula _{(1) MePc- [X- (CH} 2) kNR 1 R 2] n
(In the formula, Me represents H ₂ , Cu, Fe, Co, Ni, Zn, AlOH, FeOH, Pc represents a phthalocyanine residue, X represents —CH ₂ —, —CH ₂ NHCOCH ₂ —, —CO—. _{, -SO 2 -, - CH 2} NH -, - CH 2 NHCOCH 2 NH -, - CONH -, - SO 2 NH- _{represents, R 1,} R ₂ each independently represent a hydrogen atom or 1 to 18 carbon atoms An alkyl or alkenyl group (which may optionally have a substituent), or a 5-membered ring or 6-membered ring which may have a further nitrogen atom formed by integrating R ₁ and R ₂ ; And k represents an integer of 0 to 6, and n represents an integer of 1 to 4.)
General formula (2)

（式中、Ｍｅ、Ｐｃおよびｎは上記と同様の意味を表し、Ｙはハロゲン原子、アルキル基、ニトロ基、アミノ基、スルホン基またはカルボキシル基を表し、ｍは０〜４の整数を表す。）

(In the formula, Me, Pc and n represent the same meaning as described above, Y represents a halogen atom, an alkyl group, a nitro group, an amino group, a sulfone group or a carboxyl group, and m represents an integer of 0 to 4. )

The compound represented by the general formula (1) or (2) can be added before, during or after the organic solvent kneading, but is preferably added before or during the mixing. The reason is that the compound represented by the general formula (1) is considered to contribute to the stabilization of dispersion of the organic solvent dispersion of the copper phthalocyanine pigment and to promote the peptization of the aggregate. The remarkable improvement in the fluidity of the dispersion supports the hypothesis.

The present invention relates to an obtained α / β mixed crystal copper obtained by dry-grinding crude copper phthalocyanine having a purity of 97 to 100% based on a sulfuric acid dissolution method and a primary crystal diameter of 0.5 to 100 μm at a temperature of 180 to 50 ° C. By treating phthalocyanine in an organic solvent or a mixture of an organic solvent and water, α-type crystals are transferred to β-type crystals, the average primary crystal diameter is 80 ± 40 nm, and the primary crystal has an aspect ratio of 2.0. ± 1.0, and the crystallite diameter is 22 ± 5 nm in the vertical direction of the monoclinic β (200) plane, 27 ± 5 nm in the vertical direction of the β (001) plane, and in the vertical direction of the β (010) plane. In the method for producing a β-type copper phthalocyanine pigment characterized by being 15 ± 5 nm, 0.1 to 20% by weight of the following general formula (following general formula ( 1) or ( The present invention relates to a method for producing a β-type copper phthalocyanine pigment, which comprises adding the compound represented by 2).
Formula _{(1) MePc- [X- (CH} 2) kNR 1 R 2] n
(In the formula, Me represents H ₂ , Cu, Fe, Co, Ni, Zn, AlOH, FeOH, Pc represents a phthalocyanine residue, X represents —CH ₂ —, —CH ₂ NHCOCH ₂ —, —CO—. _{, -SO 2 -, - CH 2} NH -, - CH 2 NHCOCH 2 NH -, - CONH -, - SO 2 NH- _{represents, R 1,} R ₂ each independently represent a hydrogen atom or 1 to 18 carbon atoms An alkyl or alkenyl group (which may optionally have a substituent), or a 5-membered or 6-membered ring which may have a further nitrogen atom formed by integrating R ₁ and R ₂ ; And k represents an integer of 0 to 6, and n represents an integer of 1 to 4.)

Furthermore, this invention relates to the manufacturing method of the said beta-type copper phthalocyanine pigment whose alpha ratio of a dry-type grind | pulverized product is 5-35%. General formula (2)

The present invention can produce a β-type copper phthalocyanine pigment having a small primary crystal aspect ratio. Compared to commonly used solvent salt milling pigments, it has the same or better quality in terms of coloring power, gloss, fluidity, etc., but has higher salt and COD values as grinding aids. Since a high boiling point solvent is not used, it is possible to provide a β-type copper phthalocyanine pigment having a small load on facilities and the environment.

(In the formula, Me, Pc and n represent the same meaning as described above, Y represents a halogen atom, an alkyl group, a nitro group, an amino group, a sulfone group or a carboxyl group, and m represents an integer of 0 to 4. )

Hereinafter, the present invention will be described in detail. In the dry pulverization of the present invention, crude copper phthalocyanine 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. Moreover, you may dry-grind by making nitrogen gas etc. flow into the dry-type grinding | pulverization apparatus inside a deoxygenation atmosphere as needed.

As the dry pulverization apparatus, a known method such as a dry attritor capable of heating with steam or oil, a ball mill, a vibration mill, or the like can be used, and the pulverization time is set according to the apparatus or to a desired pulverized particle size. It can be set arbitrarily according to the requirements. In general, dry pulverization is carried out while the temperature is reduced to 80 to 100 ° C. because the inside generates heat. In the present invention, the internal temperature is 180 to 50 ° C., preferably 160 ° C. By adjusting the temperature to ˜80 ° C., a pulverized product having a target α rate is obtained. If the temperature exceeds 180 ° C., the quality of the pigment will be affected.

Crude copper phthalocyanine having a purity of 97 to 100% based on the sulfuric acid dissolution method is used. If it is less than 97%, it becomes a pulverized product with a high α rate.

The purity of the crude copper phthalocyanine in the present invention based on the sulfuric acid dissolution method is measured as follows.
5 g of a sample is added little by little to 100 g of 98% sulfuric acid while stirring at room temperature, stirred for 2 hours after the addition is completed, and poured into 500 ml of distilled water with stirring. After heating and stirring at 90 ° C., after 0.5 hours, after drying and constant weight at 100 ° C., using a weighed 17G4 glass filter, suction filtration, washing with water until acid free, and after drying constant weight at 100 ° C. together with the glass filter Weigh. Purity is calculated | required by the following formula | equation.
Purity /% = weight after treatment × 100 / weight before treatment

The α ratio of the pulverized product is 5 to 35%, preferably 10 to 30%. The upper limit of the α ratio is limited by an increase in the aspect ratio of the pigment primary crystal, and the lower limit is limited by the peptization of the strong aggregate.

The obtained ground product is treated with an organic solvent alone or a mixed system of an organic solvent and water.

The type of the solvent is a water-miscible organic solvent, for example, an alcohol compound such as isopropanol, butanol, isobutanol, ethyl cellosolve, butyl cellosolve, cyclohexanol, or one or a mixture of two or more ketone compounds such as acetone and methyl ethyl ketone. Can be used.

In the solvent treatment step, a bead mill such as an Eiger mill, a sand mill, a ball mill, a pearl mill (such as “DCP mill” manufactured by Eirich), a Cosmo mill, a Z mill, a disperse mat, or a basket mill can be used.

In the solvent treatment step, a medialess disperser such as a wet jet mill (“Genus PY” manufactured by Genus, “Nanomizer” manufactured by Nanomizer), a homomixer, or the like can be used.

In the present invention, the pigment can be subjected to a resin treatment in order to impart suitability to the application. The treatment method may be performed at the time of the step (A) or may be performed at the time of the step (B). It may be added at the time of dry grinding or at the time of solvent treatment. The resin can be freely selected as long as it is suitable for printing inks, paints, or colored resins, such as rosins represented by polymerized rosin, hydrogenated rosin, disproportionated rosin, and rosin-modified phenolic resin. .

In the present invention, the pigment can be treated with a surfactant in order to impart suitability to the application. The treatment method may be performed at the time of the step (A) or may be performed at the time of the step (B). The surfactant can be freely selected from nonionic surfactants, anionic surfactants and cationic surfactants as long as they are suitable for printing inks, paints or colored resins.

The vehicle to be used is not particularly limited, and may contain auxiliary agents and extender pigments. When a vehicle for offset ink is produced using the copper phthalocyanine pigment produced by the method according to the present invention, the vehicle to be used is not particularly limited, and rosin-modified phenolic resin, petroleum resin, alkyd resin, or these Examples include a resin such as a dry oil-modified resin and vegetable oils such as linseed oil, tung oil, soybean oil, and solvents such as n-paraffin, I-paraffin, aromatic, naphthene, α-olefin, and water. .

Examples of paint vehicles include acrylic resins, alkyd resins, epoxy resins, chlorinated rubber, vinyl chloride, synthetic resin emulsions, silicone resins, polyurethane resins, polyester resins, melamine resins, urea resins, or mixtures thereof, or the above resins. The case where it consists of water-soluble water-soluble resin or emulsion resin, and solvents, such as hydrocarbon, alcohol, ketone, ether alcohol, ether, ester, water, is mentioned.

Vehicles for gravure printing ink include gum rosin, wood rosin, tall oil rosin, lime rosin, rosin ester, maleic acid resin, polyamide resin, vinyl resin, nitrocellulose, cellulose acetate, ethyl cellulose, chlorinated rubber, cyclized rubber, ethylene-vinyl acetate Copolymer resin, polyurethane resin, polyester resin, alkyd resin, acrylic resin, gilsonite, dammar, shellac, or a mixture thereof, or a water-soluble resin or emulsion resin obtained by water-solubilizing the above resin, and hydrocarbon , Alcohol, ketone, ether alcohol, ether, ester, water and the like.

Resins for molded plastics include polyethylene, polypropylene, ethylene / propylene copolymer, ethylene / acrylic acid copolymer, ethylene / maleic acid copolymer, α-olefin / acrylic acid copolymer, α-olefin / maleic acid Copolymer, ethylene / vinyl acetate copolymer, polyvinyl chloride, polyvinyl acetate, polyvinyl formal, polybutyral, polyacrylonitrile, polymethacryl, polystyrene, acrylonitrile / butadiene / styrene copolymer, polyethylene terephthalate, polyurethane, polycarbonate, Examples include 6-nylon, 6,6-nylon, unsaturated polyester, epoxy resin, urea resin, melamine resin, and cellulose resin.

When a copper phthalocyanine pigment, a phthalocyanine derivative, or a mixture thereof is mixed or dispersed in a vehicle to produce a printing ink, paint or colored resin composition according to the present invention, a dissolver, a high speed mixer, a homomixer is used as a dispersing machine. Good mixing or dispersion can be achieved by using a kneader, flasher, roll mill, sand mill, attritor, single-screw or multi-screw rotary screw extruder or the like.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. In addition, what is used as the standard pigment in the examples is that the crude copper phthalocyanine having the same quality as that used in each example is pigmented by a solvent salt milling method (5 times the amount of salt) and used in each example. It is a pigment containing the same amount of the same phthalocyanine derivative.

The aspect ratio of the primary crystal was calculated from a photograph taken with a transmission electron microscope. The α rate and crystallite diameter were determined from an X-ray diffraction profile.
The α rate was calculated based on the following equation.
α rate /% = {(integrated intensity of diffraction angle 14.3 ° to 16.0 °) − (integrated intensity of diffraction angle 13.8 °)} × 100 / {(diffraction angle 12.2 °, 14.3 ° to 16.0 °, the sum of the integrated intensities of 18.0 °)-(integrated intensities at the diffraction angle of 13.8 °)}.
The crystallite diameter is calculated using the Scherrer equation from the value of the integral width based on the diffraction planes of β (001), β (200), β (010) at diffraction angles of 7.0 °, 10.5 °, and 18.5 °. Calculated.

Add 500 parts by weight of crude copper phthalocyanine having a purity of 99% based on the sulfuric acid dissolution method and a primary crystal diameter of 1 to 10 μm to a 5 L dry attritor, grind it at 115 ° C. for 1 hour, and grind the milled product containing 15% α-type crystal form. Obtained. 48 parts by weight of the obtained ground product was added to 100 parts by weight of isobutanol and 50 parts by weight of water, and stirred at 80 ° C. for 1 hour using a high speed mixer. It was confirmed that the α ratio was 1% or less by this premixing operation. To confirm the α ratio, the slurry after the premixing treatment was poured into an equal amount of methanol, filtered through No. 5C filter paper manufactured by Toyo Filter Paper Co., Ltd., further sprinkled with 3 times the amount of isobutanol, and air-dried. A sample was used. Next, 200 parts by weight of isobutanol, 100 parts by weight of water, 2 parts by weight of phthalimidomethylated copper phthalocyanine (the number of substitution of phthalimidomethyl group is 1 / mol) and 0.8 mmφ steel beads in an Eiger mill with a mill volume of 200 ml Was circulated and dispersed at 50 ° C. for 1 hour. Next, 200 parts by weight of water was added, distilled and spray dried. The pigment particles thus obtained had an aspect ratio of 2.2 and an α ratio of 1% or less. The crystallite diameter was 22 nm in the vertical direction of the monoclinic β (200) plane, 30 nm in the vertical direction of the β (001) plane, and 16 nm in the vertical direction of the β (010) plane.
When this pigment and the standard pigment were compared in the offset ink test, the offset printing ink obtained using the pigment of this example was obtained using the standard pigment in terms of coloring power, fluidity, and the like. It had the same or better quality as the ink, and the hue was green.
The offset ink test was performed as follows (the same applies to the following examples). 100 parts of a pigment was added to 400 parts of an offset ink vehicle composed of a rosin-modified phenolic resin and a solvent and dispersed using a three roll, and an offset ink was prepared by further adding an offset ink vehicle and a solvent. Color printing was performed using a simple printing machine to create a color sample.
Next, when the pigment obtained in this example and the standard pigment were compared in a colored resin test, the colored resin obtained using the pigment of this example was standard in terms of color developability and coloring power. It had the same or better quality as the colored resin obtained using the pigment.
The colored resin test was conducted as follows (the same applies to the following examples).
A color paste was prepared by dispersing 0.8 part of pigment and 1.2 part of plasticizer with a Hoovermarler. 0.5 parts of this color paste was mixed with two rolls adjusted to 155 ° C. together with 50 parts of transparent vinyl chloride compound to prepare a dark sheet. Further, 0.1 part of the color paste was subjected to the same operation together with 50 parts of the opaque vinyl chloride compound to prepare a light-colored sheet. A dark color sheet and a light color sheet were heated and pressed to prepare a color sample.

Add 500 parts by weight of a crude copper phthalocyanine having a purity of 97% based on the sulfuric acid dissolution method and a primary crystal diameter of 1 to 10 μm to a 5 L dry attritor, pulverize it at 90 ° C. for 1 hour, and obtain a milled product containing 27% α-type crystal form. Obtained. 48 parts by weight of the obtained ground product is added to 150 parts by weight of isobutanol, 50 parts by weight of water, and 0.7 parts by weight of PELEX OT-P (an anionic activator manufactured by Kao Corporation), and 80 parts by weight using a high speed mixer. The mixture was stirred at ℃ for 1.5 hours, and it was confirmed that the α ratio became 1% or less. Next, 225 parts by weight of isobutanol, 75 parts by weight of water, and 2 parts by weight of phthalimidomethylated copper phthalocyanine (the number of substitution of phthalimidomethyl group is 1 / mol) were added, and 0.8 mmφ steel beads were used in an Eiger mill with a mill volume of 200 ml Was circulated and dispersed at 60 ° C. for 1 hour. Next, 260 parts by weight of water was added, distilled and spray dried. The pigment particles thus obtained had an aspect ratio of 2.6 and an α ratio of 1% or less. The crystallite diameter was 20 nm in the vertical direction of the monoclinic β (200) plane, 25 nm in the vertical direction of the β (001) plane, and 18 nm in the vertical direction of the β (010) plane. When this pigment and the standard pigment were compared in the offset ink test, the offset printing ink obtained using the pigment of this example was of the same or better quality than the standard pigment ink in terms of coloring power, fluidity, etc. The hue was green.
Next, when the pigment obtained in this example and the standard pigment were compared in a colored resin test, the colored resin obtained using the pigment of this example was standard in terms of color developability and coloring power. It had the same or better quality as the colored resin obtained using the pigment.

Add 500 parts by weight of crude copper phthalocyanine having a purity of 98% based on the sulfuric acid dissolution method and a primary crystal diameter of 1 to 10 μm to a 5 L dry attritor, and pulverize it at 140 ° C. for 1 hour to obtain a milled product containing 8% α-type crystal form. Obtained. 48 parts by weight of the obtained ground product is added to 75 parts by weight of isobutanol, 175 parts by weight of water, and 0.5 parts by weight of ester gum AT (Arakawa Chemical Co., Ltd. rosin ester resin), using a high speed mixer. After stirring at 80 ° C. for 1 hour, it was confirmed that the α ratio was 1% or less. Next, 175 parts by weight of isobutanol, 75 parts by weight of water, CuPc—CH ₂ N An additional 2 parts by weight of HCOCH ₂ NH (CH ₂ ) ₃ N (C ₂ H ₅ ) ₂ was added and circulated and dispersed at 60 ° C. for 1.5 hours using 0.8 mmφ steel beads in an Eiger mill with a mill volume of 200 ml. Next, 75 parts by weight of water was added, distilled and spray dried. The pigment particles thus obtained had an aspect ratio of 2.1 and an α ratio of 1% or less. The crystallite diameter was 23 nm in the vertical direction of the monoclinic β (200) plane, 24 nm in the vertical direction of the β (001) plane, and 16 nm in the vertical direction of the β (010) plane. When this pigment and a standard pigment were compared in a paint test, the paint obtained using the pigment of this example was equivalent to the paint obtained using the standard pigment in terms of coloring power, fluidity, etc. It had the above quality.
The paint test was conducted as follows. Disperse the glass beads as a dispersion medium together with 6 parts of pigment, 56 parts of alkyd resin varnish with a solid content of 60%, 28 parts of melamine resin varnish with a solid content of 50%, and 10 parts of xylene. It was created. For comparison of coloring power, a light paint was prepared by mixing a white paint consisting of 1 part of pigment and 10 parts of titanium dioxide. A 6 mil applicator was used to develop the color on art paper and baked at 130 ° C. for 30 minutes to prepare a color sample.

Add 500 parts by weight of crude copper phthalocyanine having a purity of 99% based on the sulfuric acid dissolution method and a primary crystal diameter of 1 to 10 μm to a 5 L dry attritor, grind it at 115 ° C. for 1 hour, and grind the milled product containing 15% α-type crystal form. Obtained. 48 parts by weight of the obtained ground product was added to 75 parts by weight of ethyl cellosolve and 75 parts by weight of water, and the mixture was stirred at 80 ° C. for 1 hour using a high speed mixer, and it was confirmed that the α ratio was 1% or less. Next, 150 parts by weight of ethyl cellosolve, 150 parts by weight of water, CuPc—SO ₂ N An additional 2 parts by weight of H (CH ₂ ) ₃ N (C ₂ H ₅ ) ₂ was added and circulated and dispersed at 50 ° C. for 1 hour using 0.8 mmφ steel beads in an Eiger mill with a mill volume of 200 ml. Next, 70 parts by weight of water was added, distilled and spray dried. The pigment particles thus obtained had an aspect ratio of 2.3 and an α ratio of 1% or less. The crystallite diameter was 23 nm in the vertical direction of the monoclinic β (200) plane, 26 nm in the vertical direction of the β (001) plane, and 14 nm in the vertical direction of the β (010) plane. When this pigment and a standard pigment were compared in a water-based paint test, the water-based paint obtained using the pigment of this example was obtained using the standard pigment in terms of coloring power, gloss, fluidity, and the like. The quality was equivalent to or better than that of water-based paint.
(Comparative Example 1)

Add 500 parts by weight of crude copper phthalocyanine having a purity of 93% based on the sulfuric acid dissolution method and a primary crystal diameter of 1 to 10 μm to a 5 L dry attritor, grind it at 130 ° C. for 1 hour, and grind the milled product containing 45% α-type crystal form. Obtained. 48 parts by weight of the obtained ground product was added to 100 parts by weight of isobutanol and 50 parts by weight of water, and stirred at 80 ° C. for 2 hours using a high speed mixer, and it was confirmed that the α ratio was 1% or less. Next, 200 parts by weight of isobutanol, 100 parts by weight of water, 2 parts by weight of phthalimidomethylated copper phthalocyanine (the number of substitution of phthalimidomethyl group is 1 / mol) and 0.8 mmφ steel beads in an Eiger mill with a mill volume of 200 ml Was circulated and dispersed at 50 ° C. for 1 hour. Next, 200 parts by weight of water was added, distilled and spray dried. The pigment particles thus obtained had an aspect ratio of 4.0 and an α ratio of 1% or less. The crystallite diameter was 21 nm in the vertical direction of the monoclinic β (200) plane, 26 nm in the vertical direction of the β (001) plane, and 16 nm in the vertical direction of the β (010) plane. When this pigment and the standard pigment were compared in the offset ink test, the offset printing ink obtained using the pigment of this comparative example was obtained using the standard pigment in terms of coloring power, fluidity, and the like. It was inferior to ink.
(Comparative Example 2)

Add 500 parts by weight of crude copper phthalocyanine having a purity of 98% based on the sulfuric acid dissolution method and a primary crystal diameter of 1 to 10 μm to a 5 L dry attritor, and pulverize it at 120 ° C. for 1 hour in the presence of 15 parts by weight of xylene. A grind containing 3% was obtained. 48 parts by weight of the obtained ground product was added to 75 parts by weight of isobutanol and 175 parts by weight of water, and stirred at 80 ° C. for 1 hour using a high speed mixer, and it was confirmed that the α ratio was 1% or less. Next, 175 parts of isobutanol, 75 parts of water, CuPc—SO ₂ N An additional 2 parts by weight of H (CH ₂ ) ₃ N (C ₂ H ₅ ) ₂ was added and circulated and dispersed at 60 ° C. for 1.5 hours using 0.8 mmφ steel beads in an Eiger mill with a mill volume of 200 ml. Next, 75 parts by weight of water was added, distilled and spray dried. The pigment particles thus obtained had an aspect ratio of 2.0 and an α ratio of 1% or less. The crystallite diameter was 20 nm in the vertical direction of the monoclinic β (200) plane, 27 nm in the vertical direction of the β (001) plane, and 14 nm in the vertical direction of the β (010) plane. When this pigment and a standard pigment were compared in a paint test, the paint obtained using the pigment of this comparative example was inferior to the ink obtained using the standard pigment in terms of coloring power, fluidity and the like. It was.
(Comparative Example 3)

Add 500 parts by weight of crude copper phthalocyanine having a purity of 99% based on the sulfuric acid dissolution method and a primary crystal diameter of 1 to 10 μm to a 5 L dry attritor, grind it at 115 ° C. for 1 hour, and grind the milled product containing 15% α-type crystal form. Obtained. 50 parts by weight of the obtained ground product was added to 100 parts by weight of isobutanol and 50 parts by weight of water, and stirred at 80 ° C. for 1 hour using a high speed mixer. It was confirmed that the α ratio was 1% or less by this premixing operation. Next, 200 parts by weight of isobutanol and 100 parts by weight of water were added, and the mixture was circulated and dispersed for 1 hour at 50 ° C. using 0.8 mmφ steel beads in an Eiger mill having a mill volume of 200 ml. Next, 200 parts by weight of water was added, distilled and spray dried. The pigment particles thus obtained had an aspect ratio of 2.3 and an α ratio of 1% or less. The crystallite diameter was 23 nm in the vertical direction of the monoclinic β (200) plane, 26 nm in the vertical direction of the β (001) plane, and 15 nm in the vertical direction of the β (010) plane. When this pigment and the pigment obtained in Example 1 were compared in an offset ink test, the ink obtained using the pigment of this comparative example was found to be in Example 1 in terms of coloring power, gloss, fluidity, and the like. Was inferior to the ink obtained using this pigment.

Claims (4)

An α / β mixed crystal having a purity of 97 to 100% based on a sulfuric acid dissolution method and dry pulverizing crude copper phthalocyanine having a primary crystal diameter of 0.5 to 100 μm at a temperature of 180 to 50 ° C. and an α ratio of 5 to 35%. A primary crystal having an average primary crystal diameter of 80 ± 40 nm comprising a step (A) of forming copper phthalocyanine and a step (B) of treating the dry pulverized product obtained in step (A) in a water-miscible organic solvent. Has an aspect ratio of 2.0 ± 1.0, a crystallite diameter of 22 ± 5 nm in the direction perpendicular to the monoclinic β (200) plane, 27 ± 5 nm in the direction perpendicular to the β (001) plane, β ( In the method for producing a β-type copper phthalocyanine pigment, which is 15 ± 5 nm in the direction perpendicular to the (010) plane, 0.1 to 20 weights with respect to the dry pulverized product before, during or after step (B) % Of the following general formula (1) or (2 Method for producing a β type copper phthalocyanine pigment, which comprises adding in compound represented by.
Formula _{(1) MePc- [X- (CH} 2) kNR 1 R 2] n
(In the formula, Me represents H ₂ , Cu, Fe, Co, Ni, Zn, AlOH, FeOH, Pc represents a phthalocyanine residue, X represents —CH ₂ —, —CH ₂ NHCOCH ₂ —, —CO—. _{, -SO 2 -, - CH 2} NH -, - CH 2 NHCOCH 2 NH -, - CONH -, - SO 2 NH- _{represents, R 1,} R ₂ each independently represent a hydrogen atom or 1 to 18 carbon atoms An alkyl or alkenyl group (which may optionally have a substituent), or a 5-membered ring or 6-membered ring which may have a further nitrogen atom formed by integrating R ₁ and R ₂ ; And k represents an integer of 0 to 6, and n represents an integer of 1 to 4.)
General formula (2)

(In the formula, Me, Pc and n represent the same meaning as described above, Y represents a halogen atom, an alkyl group, a nitro group, an amino group, a sulfone group or a carboxyl group, and m represents an integer of 0 to 4. ) The method for producing a β-type copper phthalocyanine pigment according to claim 1, wherein the water-miscible organic solvent is a mixed solution with water. The method for producing a β-type copper phthalocyanine pigment according to claim 1, wherein the step (B) is performed using a bead mill. A printing ink, paint or colored resin composition comprising a β-type copper phthalocyanine pigment obtained by the production method according to claim 1 and a printing ink vehicle, a paint vehicle or a molded plastic resin.