JP4185312B2 - Easily dispersible copper phthalocyanine pigment composition, method for producing the same, and method for producing a colored composition - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
  The present invention relates to coloring compositions such as printing ink (offset ink, gravure ink, etc.), various paints, electrophotographic (dry or wet) toner, ink jet recording ink, thermal transfer recording ink, pigment printing agent, writing instrument ink, etc. Red dispersible copper phthalocyanine pigment composition useful as a colorant for products, plastics, color filters or cosmetics, a method for producing the same, and a color composition using the pigment composition obtained by this method It is about the method.
[0002]
[Prior art]
  In general, copper phthalocyanine pigments are, for example, urea method (Wiler method) in which phthalic acid or its derivative, urea or its derivative is heated in an organic solvent in the presence of a copper compound and a catalyst, or phthalodinitrile is present in the presence of a copper compound. It is synthesized by a method such as a nitrile method in which a reaction is performed under heating in an organic solvent. The synthesized copper phthalocyanine is called crude copper phthalocyanine, and the primary particles are very coarse (10 to 100 μm) and cannot be used as they are. Therefore, when producing a colored composition such as printing ink, the primary particles are adjusted to be fine (1 μm or less) by a method of pigmentation represented by dry milling or wet milling of crude copper phthalocyanine, Suitable as a pigmentsexThe thing which was given is used.
[0003]
  Usually, coloring compositions such as printing inks, paints, electrophotographic toners, ink jet recording inks, thermal transfer recording inks, pigment printing agents, inks for writing instruments, or coloring compositions for plastics, color filters or cosmetics, Pigmented copper phthalocyanine (copper phthalocyanine pigment) using a roll mill such as a three-roll mill, a kneader such as a kneader, or a dispersing machine such as a ball mill or a bead mill, and a resin for a coloring composition (for binder or vehicle) ( Solid) or uniformly dispersed in a resin solution.
[0004]
  Since a great amount of labor is required for the pigmentation process and the colored composition manufacturing process, a streamlined manufacturing method is required, and various proposals have been made.
  For example, Japanese Patent Publication No. 6-51846 discloses a copper phthalocyanine pigment in which crude copper phthalocyanine is dry milled in the presence of rosins, and the resulting milled product is heated in a butyl cellosolve aqueous solution to convert it into a pigment form. Manufacturing methods have been proposed. According to this method, dry milling in the presence of rosins suppresses or prevents agglomeration of the milled product, facilitating conversion to the next pigment form, and uses a specific butyl cellosolve aqueous solution for conversion. Thus, it is possible to greatly reduce the amount of solvent used for pigmentation.
[0005]
[Problems to be solved by the invention]
  However, the above method does not have sufficient pigmentation efficiency, and as a result, the copper phthalocyanine pigment obtained by this method has a problem of pigment quality such as sharpness and dispersibility when producing a colored composition. was there.
  The present invention has been made in view of such circumstances, and the object of the present invention was obtained by dry-grinding crude copper phthalocyanine in the presence of rosins described in JP-B-6-51846. In the manufacturing method of copper phthalocyanine pigment, which is obtained by heat-treating the ground product in an aqueous solution of butyl cellosolve, the pigmentation efficiency and pigment quality are improved, and it is easy to produce various colored compositions with easy dispersibility. Another object of the present invention is to provide a method for producing a copper phthalocyanine pigment composition, various colored compositions, and a method for producing the same.
[0006]
  The inventors of the present invention focused on rosins and crude copper phthalocyanine in order to achieve the above object, and as a result of intensive studies, when dry-grinding crude copper phthalocyanine, instead of rosins, pigmented copper phthalocyanine was obtained. By selecting and using a high molecular weight coloring composition resin used in the production of the desired coloring composition such as printing ink using a pigment, the pigmentation efficiency and the pigment quality are improved. I found it. In addition, since the pigmented copper phthalocyanine is coated with a resin according to the purpose of use, it is easily dispersible in the production of colored compositions such as printing inks, and various colored compositions can be produced. It has been found that a reasonably high quality colored composition can be obtained by facilitating the production of the colored composition following the pigmentation. However, the improvement by changing the resin is great, but it is still not satisfactory.
[0007]
  In general, copper phthalocyanine immediately after synthesis includes impurities (hereinafter referred to as reaction impurities), such as compounds and copper compounds mainly composed of phthalic acid derivatives contained in unreacted raw materials and raw materials or by-produced during synthesis. As a large amount (20 to 40% by weight). These reaction impurities are purified to some extent at the stage of crude copper phthalocyanine by methods such as acid treatment and alkali treatment, but the remaining reaction impurities (5 to 20% by weight) are effective in the pigmentation step of copper phthalocyanine. As a crude copper phthalocyanine, a high purity crude copper phthalocyanine having a purity measured by the sulfuric acid method of 97% or more is used, and a copper phthalocyanine pigment composition having a clearer and excellent dispersibility and its It has been found that a high-quality coloring composition using can be obtained. The present inventors have completed the present invention based on this knowledge and the previous knowledge.
[0008]
[Means for Solving the Problems]
  The above object is achieved by the present invention described below. That is, the present invention relates to a high purity crude copper phthalocyanine having a purity measured by the sulfuric acid method of 97% or more and, Rosin-modified phenolic resin, rosin-modified maleic resin, acrylic resin, polyester resin, alkyd resin, phthalic resin, melamine resin, polyamide resin, urethane resin, vinyl chloride resinAn easily dispersible copper phthalocyanine pigment composition and a crude copper phthalocyanine obtained by dry-grinding a dry-milled product with a coloring composition resin in butyl cellosolve or an aqueous solution thereof and dry-grinding the obtained copper phthalocyanine When the crushed material is pigmented with heating in butyl cellosolve or an aqueous solution thereof, as the crude copper phthalocyanine, a high purity crude copper phthalocyanine having a purity measured by the sulfuric acid method of 97% or more is used.Selected from rosin-modified phenolic resin, rosin-modified maleic resin, acrylic resin, polyester resin, alkyd resin, phthalic resin, melamine resin, polyamide resin, urethane resin, and vinyl chloride resinA process for producing an easily dispersible copper phthalocyanine pigment composition, characterized by dry milling in the presence of a colored composition resinAboveFollowing the above pigmentation treatment,Selected from rosin-modified phenolic resin, rosin-modified maleic resin, acrylic resin, polyester resin, alkyd resin, phthalic resin, melamine resin, polyamide resin, urethane resin, and vinyl chloride resinA method for producing a colored composition comprising mixing with a resin for a colored composition, a solvent or a vehicle, and then removing an aqueous butyl cellosolve solution.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
  The present invention is described in further detail below.
  In general, copper phthalocyanine after completion of the reaction is obtained by removing the solvent from the reaction slurry under reduced pressure, then removing the reaction impurities by a method such as acid treatment, alkali treatment, washing with warm water, washing with water, filtering and drying to obtain crude copper. Prepared as phthalocyanine.
  In the present invention, crude copper phthalocyanine can be prepared by a known method, and the preparation method is not particularly limited. As crude copper phthalocyanine, in addition to unsubstituted copper phthalocyanine, copper phthalocyanine containing 2 or less chlorine atoms or bromine atoms in the molecule, polychloro copper phthalocyanine, polychloro containing 14 or less bromine atoms in the molecule Bromine copper phthalocyanine etc. are mentioned. These crude copper phthalocyanines are preferably high-purity crude copper phthalocyanines purified to a purity of 97% or more as measured by the sulfuric acid method.
[0010]
  Components contained in reaction impurities include unreacted raw materials, phthalic acid derivatives contained in raw materials or by-produced during synthesis (eg, phthalic acid, phthalic anhydride, furimide, isoindolinone, etc.) and urea Examples of known substances include compounds and copper compounds centered on lanthanum compounds (urea or polymers thereof), free copper and residual salts (ammonium salts, etc.), but many other unknown substances are included. Yes. Although the reaction impurities adhere to the surface of the copper phthalocyanine particles or are contained inside the particles, impurities contained by incorporation into the copper phthalocyanine crystals that are difficult to remove by a normal cleaning method are particularly problematic.
[0011]
  In the present invention, the purity of the crude copper phthalocyanine conforms to the purity determined by the sulfuric acid method, but according to the sulfuric acid method, all reaction impurities including the inside of the crystal can be measured. Purity measurement by the sulfuric acid method follows the following procedure.
<Purity measurement method by sulfuric acid method>
  Crude copper phthalocyanine (5.0 gr) is dissolved by heating in 50 ml of 98 wt% sulfuric acid (90 to 100 ° C. for 40 minutes), and 150 ml of 15 wt% sulfuric acid is added to this solution for recrystallization. After allowing to cool, 250 ml of water was added to complete recrystallization, filtered and washed thoroughly, then peptized into 400 ml of water, added with 10 ml of 28% by weight aqueous ammonia and heated (at 90-100 ° C. for 30 minutes). Min). After filtering and washing with water sufficiently, it is dried at 105 to 110 ° C. for 2 hours. The mass of the crude copper phthalocyanine before and after the treatment is measured, and the purity is calculated by the following formula.
  Purity (%) = [mass after treatment (gr) / mass before treatment (gr)] × 100
[0012]
  The method for preparing high-purity crude copper phthalocyanine is, for example, a method of washing crude copper phthalocyanine after synthesis, a method of washing acid, alkali, or organic solvent, or dissolving or semi-dissolving in strong acid such as sulfuric acid, and a poor solvent such as water. It can select suitably from conventionally well-known preparation methods, such as the refinement | purification method which precipitates in and recrystallizes, It does not specifically limit.
[0013]
  As the crude copper phthalocyanine used in the present invention, it is particularly preferable to use copper phthalocyanine synthesized by performing the urea method (Weiler method) under pressure (preferably 0.1 to 0.7 MPa). Copper phthalocyanine synthesized under pressure has an advantage that the amount of reaction impurities incorporated into the copper phthalocyanine crystal is less than that synthesized under normal pressure and can be easily prepared with high purity by appropriate washing. Further, since the content of reaction impurities in the crystal is small, it is easily dispersible and can be easily pigmented.
[0014]
  In the production method of the easily dispersible copper phthalocyanine pigment composition of the present invention, first, a high purity crude copper phthalocyanine is added.belowDry milling in the presence of the resin for the coloring composition. Here, the resin for a colored composition is a resin used for producing a desired colored composition (for example, printing ink, paint, etc.) using a copper phthalocyanine pigment composition obtained by pigmentation. (For binder or vehicle), and can be used by appropriately selecting from the resin for the colored composition according to the kind of the colored composition. Examples of colored composition resins include rosin-modified phenolic resins, rosin-modified maleic resins, acrylic resins, polyester resins, alkyd resins, phthalic resins, melamine resins, polyamide resins, urethane resins, and vinyl chloride resins.Chosen fromAlthough conventionally well-known things used for manufacture of various coloring compositions are mentioned, a thing with a high softening point is desirable.
[0015]
  For example, when the colored composition is a printing ink, the resin for the colored composition includes rosin-modified phenol resin, rosin-modified acrylic resin, rosin-modified alkyd resin, rosin-modified maleic resin, rosin-modified phenol resin, rosin-modified fumarate. Various rosin-modified resins such as acid resins, rosin-modified polyamide resins, and rosin-modified polyester resins, petroleum resins, and the like may be used alone or in a mixture of two or more. A rosin-modified phenol resin is preferred.
[0016]
  In the dry grinding of the present invention, a dispersion machine using a grinding medium such as beads such as a dry attritor, a ball mill or a vibration mill; a kneader such as a twin screw extruder or a kneader; a grinding machine such as a jet mill; Any type that does not use grinding media such as a high-speed stirrer such as a Hensill mixer can be used, but the use of a dispersing machine that uses grinding media is preferred in terms of grinding efficiency.
[0017]
  The coloring composition resin used in the dry grinding is usually used in an amount of 1 to 60% by weight based on the crude copper phthalocyanine.
  The resin can be added to and mixed with the crude copper phthalocyanine at the time of dry grinding, but the surface of the crude copper phthalocyanine can be uniformly treated with the resin in advance. A method in which the resin is preliminarily treated with a crude copper phthalocyanine surface is preferable because aggregation of particles during grinding can be effectively suppressed or prevented even when a relatively small amount of resin is used.
[0018]
  The surface treatment of the crude copper phthalocyanine with the resin can be performed, for example, at any stage of the copper phthalocyanine synthesis stage, the reaction slurry after the reaction is completed, or the crude copper phthalocyanine washing process. As the surface treatment method, for example, a conventionally known method such as adding a resin compound dissolved in an organic solvent can be used. In the above step, the treatment into the reaction slurry after completion of the reaction and the step of removing the solvent Is preferable because there are few restrictions on the processing amount and processing method.
[0019]
  Dry milling is usually performed at a temperature of 80 to 150 ° C. for about 0.5 to 2 hours. At that time, if necessary, dry milling can be carried out in the presence of an extender pigment together with the coloring composition resin. Extender pigments also effectively suppress or prevent agglomeration of the milled product. Any extender pigment may be used as long as it has a small refractive index and has little effect on the hue and transparency of the pigment, such as calcium carbonate, zinc oxide (zinc white), barium sulfate and barite powder, clay, talc, and alumina. Examples thereof include white and white carbon (fine silica), and calcium carbonate is preferable. The amount of extender pigment used varies depending on the amount of resin used for the colored composition, but is usually 1 to 50% by weight based on the crude copper phthalocyanine.
  Moreover, the point that an organic solvent such as a solvent for printing ink can be blended as needed during dry milling and the point that milling can be performed in a nitrogen gas atmosphere are the same as in the case of conventionally known dry milling. is there.
[0020]
  Crude copper phthalocyanine (crystal type is β type) is refined by dry milling, but at that time, due to mechanical force, part of the crystal form is changed to α type, and the milled product is α type and β type. Obtained as a mixture of molds. For this reason, in the pigmentation treatment, it is necessary to convert to a pigment form that converts the crystal form of the milled product back to the β form.
  The pigmentation treatment after dry milling of the present invention is performed by treating the milled product prepared by the above dry milling in a solvent, but the present invention is characterized by treating in butyl cellosolve or an aqueous solution thereof. Butyl cellosolve is water soluble at room temperature and mixes well with water, but becomes insoluble in water when heated to 50 ° C. or higher. Therefore, when the milled product is processed by heating to 50 ° C or higher in an aqueous solution of butyl cellosolve, butyl cellosolve separates from water and adsorbs on the surface of the milled product, efficiently promotes crystal transition and crystallization, and transfers the milled product to the pigment form. Can be made.
[0021]
  In the present invention, butyl cellosolve is usually used in a proportion of 5 to 200% by weight based on the crude copper phthalocyanine. Usually, butyl cellosolve is preferably used as an aqueous solution having a concentration of 9 to 58% by weight. The ground product and the butyl cellosolve aqueous solution are mixed at room temperature, and usually heat-treated at a temperature of 50 to 100 ° C. for about 0.5 to 5 hours.
  For heat treatment in an aqueous solution of butyl cellosolve, a known disperser such as a stirrer, a bead mill or a ball mill, or a kneader such as a kneader or a ruder can be used, but the disperser or kneader used for the heat treatment is It is not limited to these examples.
[0022]
  In the present invention, following the pigmentation treatment, various colored compositions can be produced by mixing the ground product with a colored composition resin, solvent, or vehicle. In that case, it is desirable that the pigmentation treatment is performed using a kneader such as a kneader, and the colored composition is subsequently produced.
[0023]
  In the present invention, in any step of preparation of crude copper phthalocyanine, dry grinding, and pigmentation, if necessary, conventionally known pigment derivatives, pigment dispersants such as polymer dispersants, dispersants or surfactants. It can also be treated with rosins and the like.
[0024]
  In the present invention, the copper phthalocyanine pigment composition is prepared by adding the heat treatment mixture into a large amount of water following the heat treatment in the above butyl cellosolve or an aqueous solution thereof, filtering, washing with water, drying and pulverizing as necessary. Is done.
[0025]
  When producing a colored composition using a copper phthalocyanine pigment composition, it can be produced using a separated copper phthalocyanine pigment composition after the pigmentation treatment, but the above heat treatment (pigmentation) For example, it is preferable to produce a desired colored composition after separation in a kneader such as a kneader without separating the copper phthalocyanine pigment composition. In that case, the resin, solvent or vehicle suitable for the target coloring composition is appropriately selected, added to the kneader after the heat treatment and mixed, and then the aqueous butyl cellosolve solution is removed by an appropriate means, for example, reduced pressure. If necessary, it can be produced by adding and mixing a resin for a colored composition, a solvent or a vehicle, or various additives. In this case, the removal of the butyl cellosolve aqueous solution is characterized in that it is performed in parallel with the conversion of the copper phthalocyanine pigment composition from the aqueous phase to the oil phase.
[0026]
  As the colored composition resin, solvent or vehicle to be added when the colored composition is produced, any of those conventionally used for producing the desired colored composition can be used and is not particularly limited. Examples of the coloring composition include printing inks, paints, pigment printing agents, inkjet recording inks, electrophotographic toners, thermal transfer recording inks, and writing instrument inks. It can also be used as a coloring composition for plastics, color filters and cosmetics.
[0027]
  For example, when producing a printing ink as a coloring composition, for example, after heat treatment in a kneader, an appropriate amount of a printing ink solvent or printing ink varnish is subsequently added to the kneader and mixed and kneaded. After removing the separated water component, the remaining water component and butyl cellosolve are removed by heating to 50 to 100 ° C. under reduced pressure, and then varnish for printing ink, solvent, or other additives are added as necessary. Printing ink is prepared by mixing and kneading. According to this method, it is possible to produce a reasonably high-quality printing ink as compared to a conventional method of preparing a printing ink by a flushing method using an aqueous pigment presscake.
[0028]
  As a streamlined method for producing printing ink, for example, in Japanese Patent No. 3139396, crude copper phthalocyanine is dry-pulverized together with printing ink resin, and the resulting milled product is heat-treated in a printing ink solvent or varnish. Then, a method is disclosed in which a roll ink is dispersed and a varnish or a solvent is further added to the base ink to form a printing ink. This method is an excellent method for producing printing ink directly from the ground product without going through the pigment form by converting the ground material into the pigment form simultaneously with the production of the printing ink. However, as a drawback, the conversion to the pigment form in the solvent or varnish for printing ink is very inefficient, and the quality of the printing ink may not be stable, such as α-type crystals tend to remain partly unconverted, Further, in order to completely perform the conversion, there is a problem that a complicated heat treatment process is required during the ink manufacturing process.
[0029]
  On the other hand, the method of the present invention for producing a colored composition such as a printing ink subsequent to the above-mentioned pigmentation treatment efficiently converts into a pigment form in butyl cellosolve or an aqueous solution thereof, Since the coloring composition to be manufactured is manufactured, it is not necessary to carry out heat treatment again during the ink manufacturing process as described above, and a colored composition that is stable in quality can be obtained.
[0030]
【Example】
  Next, the present invention will be described more specifically with reference to pigment production examples, examples and comparative examples. In the following text, “parts” or “%” are based on weight.
[0031]
Pigment production example 1
  In a 5 liter container, 1000 parts of phthalic anhydride, 2000 parts of urea, 10 parts of ammonium molybdate, 180 parts of cuprous chloride, Hysol P (manufactured by Nippon Petrochemical Co., Ltd.) 2000 parts of an alkylbenzene solvent) was added, and the mixture was reacted by heating at 200 ° C. for 4 hours under normal pressure. After completion of the reaction, the solvent was removed under reduced pressure, and the reaction product was put into 20000 parts of 2% dilute sulfuric acid aqueous solution, stirred at 80 ° C. for 2 hours, filtered, washed with hot water, and washed with water until the filtrate became neutral. An aqueous paste of copper phthalocyanine was obtained. Next, this aqueous paste was dried at 90 ° C. to obtain 900 parts of crude copper phthalocyanine having a purity measured by a sulfuric acid method of 95.5%.
[0032]
Pigment production example 2
  890 parts of high-purity crude copper phthalocyanine having a purity measured by the sulfuric acid method of 98.5% were obtained in the same manner as in Pigment Production Example 1 except that the reaction was carried out under a pressure of 0.4 MPa in a 5-liter pressure vessel. It was.
[0033]
Comparative Example 1
  100 parts of the crude copper phthalocyanine obtained in Pigment Production Example 1 and 10 parts of hydrogenated rosin were added to a dry attritor, and dry milling was performed at 100 ° C. for 40 minutes. The content of β-type crystals determined from the X-ray diffraction spectrum of this crude copper phthalocyanine ground product was 43%. Next, 100 parts of the obtained ground product is put into a 0.5 liter container, 30 parts of butyl cellosolve and 200 parts of water are added thereto, and the mixture is stirred and mixed at room temperature for 30 minutes. The contents are further heated to 90 ° C. for 4 hours. Stir and mix. This mixture was added to 1000 parts of a 1.0% dilute sulfuric acid aqueous solution, heated at 80 ° C. for 1 hour, filtered, washed with water, dried and pulverized to obtain powdered β-type copper phthalocyanine pigment (CI Pigment). Blue 15: 3) A composition was obtained.
[0034]
  18 parts of the β-type copper phthalocyanine pigment obtained above is mixed with 67 parts of varnish for printing ink (rosin-modified phenolic resin varnish, non-volatile content 70%), and kneaded 3 times with 3 rolls to give a particle size of 7. A base ink of 5 μm or less was obtained. To this base ink, 19 parts of the above varnish for printing ink, 6 parts of No. 7 solvent (petroleum solvent manufactured by Nippon Oil Co., Ltd.) and 10 parts of compound (ink adjustment aid) were added to obtain a blue printing ink.
  This blue ink was mixed with white ink so that the weight ratio of copper phthalocyanine pigment / titanium oxide was 1/10 to obtain a light-color ink for determining the coloring power.
  The blue ink and the light color ink were used as comparative inks according to a conventional method.
[0035]
Example 1
  In Pigment Production Example 2, 178 parts of rosin-modified phenolic resin (weight average molecular weight: 123,000, acid value: 20) was added to the slurry after the heat reaction, and the reaction solvent was reduced in pressure after stirring at 60 ° C. for 1 hour. Removed. Thereafter, in the same manner as in Pigment Production Example 2, crude copper phthalocyanine surface-treated with 20% by weight of rosin-modified phenol resin was prepared.
  To the dry attritor, 120 parts of the above surface-treated crude copper phthalocyanine, 10 parts of calcium carbonate, and 10 parts of a resin for printing ink (the above-mentioned rosin-modified phenolic resin) were added and dry-ground at 100 ° C. for 1 hour. The content of β-type crystals in the obtained ground product was 49%.
[0036]
  Next, 100 parts of the obtained ground product is put in a 0.5 liter container, 30 parts of butyl cellosolve and 200 parts of water are added thereto, mixed at room temperature for 30 minutes, and the contents are further heated to 90 ° C. and stirred for 4 hours. Mixed. The mixture is added to 1000 parts of water, heat-treated at 80 ° C. for 1 hour, filtered, washed with water, dried and pulverized, and the copper phthalocyanine pigment of the present invention for printing ink (CI Pigment Blue 15: 3). A composition was obtained.
[0037]
  50 parts of the above copper phthalocyanine pigment composition, 118 parts of varnish for printing ink (rosin-modified phenolic resin varnish: non-volatile content 70%) and 4.5 parts of No. 7 solvent are stirred and mixed in a dissolver, and the mixture is mixed in three rolls. The base ink having a particle size of 7.5 μm or less was obtained by kneading once. To this base ink, 33 parts of the above printing ink varnish, 13 parts of No. 7 solvent, and 20 parts of compound (ink adjusting aid) were added to prepare a blue printing ink.
  This blue ink was mixed with white ink so that the weight ratio of copper phthalocyanine pigment / titanium oxide was 1/10 to obtain a light color ink.
  The obtained blue ink and light color ink were clear in hue and excellent in coloring power as compared with the ink prepared by the conventional method of Comparative Example 1. Further, the copper phthalocyanine pigment composition of the present invention is very easy to disperse, and in Comparative Example 1, three times of kneading were performed with three rolls to obtain a base ink. Meat was enough.
[0038]
Example 2
  Add 100 parts of the crude copper phthalocyanine obtained in Pigment Production Example 2 and 40 parts of a resin for printing ink (rosin-modified phenol resin, weight average molecular weight: 123,000, acid value: 20) to a dry attritor. Dry grinding for hours. The content of β-type crystals in the obtained ground product was 50%.
  Next, 100 parts of the obtained ground product is put in a 0.5 liter container, 30 parts of butyl cellosolve and 200 parts of water are added thereto, mixed at room temperature for 30 minutes, and the contents are further heated to 90 ° C. and stirred for 4 hours. Mixed. The mixture is added to 1000 parts of 1.0% dilute sulfuric acid aqueous solution, heated at 80 ° C. for 1 hour, filtered, washed with water, dried and pulverized, and the copper phthalocyanine pigment composition of the present invention for printing ink is used. Got.
[0039]
  50 parts of the above copper phthalocyanine pigment composition, 112.5 parts of varnish for printing ink (rosin-modified phenolic resin varnish: 70% non-volatile content), and 6.2 parts of No. 7 solvent are stirred and mixed in a dissolver, and the mixture is rolled into three rolls. The base ink was obtained by kneading once. To this base ink, 38 parts of the above printing ink varnish, 12 parts of No. 7 solvent, and 20 parts of compound (ink adjustment aid) were added to prepare a blue printing ink.
  In the same manner as in Example 1, the blue ink and the light color ink of the present invention were obtained.
  The obtained blue ink and light-colored ink were clearer in red than inks obtained by conventional methods, and were excellent in ink suitability such as viscoelasticity and emulsification characteristics. Further, as in Example 1, the obtained copper phthalocyanine pigment composition was very easily dispersible at the time of printing ink preparation.
[0040]
Example 3
  Add 100 parts of the crude copper phthalocyanine obtained in Pigment Production Example 2 and 40 parts of a resin for printing ink (rosin-modified phenol resin, weight average molecular weight: 123,000, acid value: 20) to a dry attritor. Dry grinding for hours.
  Next, 100 parts of the obtained ground product, 30 parts of butyl cellosolve and 200 parts of water were added to a kneader, mixed at room temperature for 30 minutes, and the contents were further heated to 90 ° C. and stirred for 4 hours.
[0041]
  Subsequently, 420 parts of printing ink varnish (rosin-modified phenolic resin varnish: 70% non-volatile content) and 50 parts of No. 7 solvent were added to the copper phthalocyanine pigment composition for printing ink of the present invention and kneaded at 90 ° C. for 1 hour. Then, the mixture was heated and kneaded at 90 ° C. under reduced pressure until the butyl cellosolve aqueous solution disappeared. After cooling, 56 parts of a compound (ink adjusting agent) was added to prepare the blue printing ink of the present invention. The blue ink and the white ink were mixed in the same manner as in the other examples to obtain a light color ink.
  The obtained blue ink and light color ink were clear in hue and excellent in coloring power as compared with the inks prepared by the conventional method of Comparative Example 1.
[0042]
Example 4
  100 parts of the crude copper phthalocyanine obtained in Pigment Production Example 2 and 20 parts of a styrene / methacrylate copolymer resin (GPC method weight average molecular weight of about 50,000, softening point of about 110 ° C., glass transition point of about 56 ° C.) in a dry attritor In addition, dry grinding was performed at 100 ° C. for 1 hour. The content of β-type crystals in the ground product was 48%.
  Next, 100 parts of the obtained ground product, 30 parts of butyl cellosolve and 200 parts of water were added to a kneader, mixed at room temperature for 30 minutes, and the contents were further heated to 90 ° C. and stirred for 4 hours. Subsequently, 213 parts of the above styrene / methacrylate copolymer resin was added to the copper phthalocyanine pigment composition for an electrophotographic toner of the present invention, and the mixture was heated and kneaded at 90 ° C. until no butyl cellosolve aqueous solution disappeared. After cooling, a coarse powder of a cyan high-concentration coloring composition containing a pigment content of 30% was obtained.
[0043]
  Next, 81.7 parts of a styrene / methacrylate copolymer resin using 11.7 parts of the cyan high-concentration coloring composition thus obtained and 3 parts of a chromium complex-based negative charge control agent as described above and a conventional method. Kneaded in accordance with the above, cooled, pulverized, finely pulverized with a jet mill, and further classified to obtain a fine powder of cyan resin composition of 5 to 20 μm, followed by adding colloidal silica as a fluidizing agent according to a conventional method. After sufficiently mixing, it was mixed with the carrier magnetic iron powder to obtain a cyan electrophotographic dry developer.
  When this was copied to paper with an electrophotographic copying machine for negative charge full color development, the copied image was copied using a cyan electrophotographic dry developer similarly produced from the copper phthalocyanine pigment of Comparative Example 1. Compared with, it had a reddish and bright blue color and excellent density.
[0044]
【The invention's effect】
  According to the present invention described above, when crude copper phthalocyanine is dry milled in the presence of a resin, and the resulting milled product is pigmented under heating in an aqueous butyl cellosolve solution, (1) high purity as crude copper phthalocyanine Using crude copper phthalocyanine, (2) As a resin, depending on the type of color composition (printing ink, paint, etc.) produced using the resulting copper phthalocyanine pigment composition, it is usually used in that color composition By appropriately selecting and using a resin (for binder or vehicle), the pigmentation efficiency and further the pigment quality can be improved, and the copper phthalocyanine pigment composition can be used as a coloring composition produced using the same. Copper phthalocyanine which is very easily dispersible in the production of the colored composition and can be easily produced in various colored compositions since it is coated with the corresponding resin. Sweetener composition is provided. In addition, the pigmentation treatment is performed in a kneader, followed by the addition and mixing of the colored composition resin, solvent or vehicle, and then the aqueous butyl cellosolve solution is removed to produce a highly rational colored composition. can do.

Claims (8)

High purity crude copper phthalocyanine with a purity measured by sulfuric acid method of 97% or more , rosin modified phenolic resin, rosin modified maleic resin, acrylic resin, polyester resin, alkyd resin, phthalic resin, melamine resin, polyamide resin, urethane An easily dispersible copper phthalocyanine pigment composition obtained by subjecting a dry milled product with a coloring composition resin selected from a resin and a vinyl chloride resin to a pigmentation treatment in butyl cellosolve or an aqueous solution thereof.   The easily dispersible copper phthalocyanine pigment composition according to claim 1, wherein the high-purity crude copper phthalocyanine is produced by performing the Weiler method under pressure. Crude copper phthalocyanine is dry-milled, and when the resulting milled product is pigmented under heating in butyl cellosolve or an aqueous solution thereof, high-purity crude copper having a purity measured by the sulfuric acid method of 97% or more as crude copper phthalocyanine A phthalocyanine- based resin for coloring compositions selected from rosin-modified phenolic resins, rosin-modified maleic resins, acrylic resins, polyester resins, alkyd resins, phthalic resins, melamine resins, polyamide resins, urethane resins, and vinyl chloride resins. A process for producing an easily dispersible copper phthalocyanine pigment composition, characterized by dry-grinding in the presence.   The method for producing an easily dispersible copper phthalocyanine pigment composition according to claim 3, wherein the high-purity crude copper phthalocyanine is produced by performing the Weiler method under pressure.   The method for producing an easily dispersible copper phthalocyanine pigment composition according to claim 3 or 4, wherein the pigmentation treatment is carried out by kneading in a kneader. The easily dispersible copper phthalocyanine pigment composition according to claim 1 or the easily dispersible copper phthalocyanine pigment composition obtained by the method according to claim 3 is used as a rosin-modified phenol resin, rosin-modified maleic acid resin, acrylic resin, polyester. Coloring characterized by mixing with resin, solvent or vehicle for coloring composition selected from resin, alkyd resin, phthalic resin, melamine resin, polyamide resin, urethane resin, vinyl chloride resin, and then removing butyl cellosolve aqueous solution A method for producing the composition.   The method for producing a colored composition according to claim 6, wherein the colored composition is a printing ink.   7. The coloring composition is for an application selected from paints, pigment printing agents, ink for ink jet recording, toner for electrophotography, ink for thermal transfer recording, ink for writing instruments, plastic, color filters and cosmetics. The manufacturing method of coloring composition.