JP2001089682A - Composite pigment, coloring composition and image recording agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new bluish green composite pigment capable of forming a clear and transparent image, furthermore without causing environmental problems, and to provide a coloring composition and an image-recording agent using the same. SOLUTION: The subject bluish green composite pigment comprises copper phthalocyanine and aluminum phthalocyanine. The coloring composition comprises at least the above pigment. The image recording agent is prepared using this coloring composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a composite pigment comprising copper phthalocyanine (hereinafter abbreviated as "CuPc") and aluminum phthalocyanine (hereinafter abbreviated as "AlPc").
The present invention relates to a coloring composition and an image recording agent using the composite pigment.

[0002]

2. Description of the Related Art CuPc pigments are one of the excellent pigments having a clear blue color tone and excellent fastness, and have been used as one of the three primary colors of process printing.
However, in addition to the conventional printing method using a printing plate,
The use of pigments as colorants is expanding in various image recording systems, including electrophotographic recording systems, ink jet recording systems, and thermal transfer recording systems. With these recording methods,
In order to realize better color reproducibility when forming an image, there is an increasing demand for a pigment having a blue-green color tone and a clear and transparent image recording agent using the pigment instead of the blue CuPc pigment. .

[0003] Blue-green pigments are generally prepared by mixing CuPc pigments and chlorinated CuPc pigments.
JP-A-5-26300 is an improved type of this mixed pigment.
No. 6 discloses a high chlorinated CuPc pigment and a low chlorinated CuPc pigment.
and c) a solid solution pigment (blue-green) obtained therefrom. Japanese Patent Application Laid-Open No. 9-68607 discloses CuP
A medium chlorinated CuPc pigment (blue-green) in which the number of chlorine atoms bonded to CuPc is adjusted in the synthesis stage of c is described.

[0004]

Another important problem in the use of pigments is the effect of the use of pigments on the global environment. From such a viewpoint, all of the above blue-green CuPc-based pigments are premised on the use of chlorinated CuPc pigments, and are not desirable in that the pigments contain chlorine atoms. Also, from the standpoint of heavy metal regulations, CuP containing heavy metal copper in its structure
There are also attempts to limit the use of c-based pigments themselves. Accordingly, an object of the present invention is to provide a novel blue-green composite pigment, which forms a clear and transparent image and is environmentally friendly, a blue-green coloring composition, and a blue-green image recording agent using the same.

[0005]

The above object is achieved by the present invention described below. That is, the present invention relates to CuPc and A
a blue-green composite pigment (hereinafter, the “composite pigment” may be simply referred to as a “pigment”), a coloring composition using the pigment, and an image recording agent using the composition. I do.

The present inventors have solved the above-mentioned problems of the conventional blue-green pigment mainly composed of a chlorinated CuPc-based pigment, and have pigments, coloring compositions and images having excellent properties similar to the chlorinated CuPc-based pigment. As a result of various studies to develop a recording agent,
A mixed pigment or solid solution pigment composed of CuPc and AlPc having no chlorine atom is a pigment that does not contain chlorine atoms, has a low copper content as a whole, and does not destroy the environment. It has been found that it has good properties, forms an image having a clear color tone, and is useful as a colorant for an image recording agent in various applications.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be described in more detail with reference to embodiments of the present invention. The pigment of the present invention comprises CuPc
And AlPc. Further, the coloring composition of the present invention is characterized in that it contains at least a pigment and a resin, and the pigment comprises CuPc and AlPc.
Further, the image recording agent of the present invention is characterized in that it contains the pigment composed of CuPc and AlPc.

[0008] CuPc used in the present invention is a compound known per se and has substantially no chlorine atom in its structure. AlPc used in the present invention is also a compound known per se, and generally, for example, phthalonitrile or 1,3-diiminoisoindoline is
It is produced by reacting in a high boiling organic solvent such as 1-chloronaphthalene or quinoline in the presence of aluminum chloride. The manufacturing method is not particularly limited. AlPc is
Depending on the difference between the synthesis method and the pigmentation method, structures such as chloro-AlPc, hydroxy-AlPc, and AlPc dimer are usually used, and these are usually used alone or as a mixture. In the present invention, it is preferable to use an AlPc dimer having the most excellent robustness, but it is not limited thereto.

The method for producing the composite pigment of the present invention includes
A method of mixing uPc and AlPc, a method of synthesizing both at the same time, a method of synthesizing another compound in the presence of any one compound, and the like can be given. In any method, a mixture or solid solution of CuPc and AlPc is subjected to a pigmentation treatment as necessary. In the above, CuPc and Al
In the method of mixing Pc, the mixture may be subjected to a pigmentation treatment after the mixing, or the pigmented CuPc and the pigmented AlPc may be mixed. The mixing may be before the pigmentation treatment or after the pigmentation treatment. Also, mixing
Mixing of powders, mixing of aqueous presscakes, and mixing in other states may be used. Further, CuPc and AlPc may be mixed in the step of producing the coloring composition of the present invention. In the above simultaneous synthesis method, when synthesizing a metal phthalocyanine by a conventionally known method, CuPc and Al are used by using a mixture of a copper salt and an aluminum salt in a desired ratio as a metal source.
A mixture with Pc is synthesized. Also, CuPc or AlPc
To synthesize AlPc or CuPc in the presence of
And a mixture of AlPc.

In the present invention, the solid solution pigment comprising CuPc and AlPc refers to a solution in which CuPc and AlPc are dissolved in concentrated sulfuric acid or polyphosphoric acid, and the solution is poured into water to obtain CuPc.
a method of precipitating a solid solution of c and AlPc into fine particles,
Mixing CuPc and AlPc with concentrated sulfuric acid or polyphosphoric acid to form a mixture of CuPc sulfate and AlPc sulfate,
A method of injecting this mixture into water to precipitate a solid solution of CuPc and AlPc into fine particles (acid paste method);
It can be obtained by a method in which uPc and AlPc are simultaneously ground to form solid solution fine particles. These solid solution fine particles are preferably treated with an organic solvent or the like, if necessary, to crystallize the fine particles to an appropriate particle size, thereby obtaining a solid solution composite pigment. The solid solution composite pigment obtained by such solid solution and pigmentation gives an image with improved hue clarity, sharpness, transparency and the like.

[0011] CuPc and Al in the composite pigment of the present invention
The ratio with Pc is appropriately determined depending on the desired blue-green color tone, and is not particularly limited. Usually, CuPc is 95 to 5% by weight and AlPc is 5 to 95% by weight.
CuPc is 70 to 30% by weight and AlPc is 30 to 70% by weight. The more AlPc is used, the more a composite pigment having a greenish color tone can be obtained. It has been conventionally known that AlPc pigments are inferior in sharpness, coloring power, light resistance, and the like, as compared with CuPc pigments. However, the composite pigment of the present invention, particularly a composite pigment in the form of a solid solution of CuPc and AlPc, has sharpness due to blending of AlPc,
It is useful as a colorant for a blue-green image recording agent because it exhibits a bluish green color having excellent clarity, coloring power, and weather resistance without pigment properties such as coloring power and weather resistance.

An image recording agent is prepared by using the coloring composition of the present invention described below, and when an image is formed with the image recording agent, the image is improved in sharpness, sharpness, transparency and the like. In order to achieve this, CuPc or Al
Processing such as adjusting the crystallinity of Pc or adjusting the shape and particle size of the crystal particles to a desired range can be performed according to a conventionally known method. Also, for the same purpose as above,
After the preparation of the composite pigment or at the time of dispersion of the pigment, rosin, an aliphatic amine, a derivative of CuPc or AlPc, a conventionally known pigment treatment agent such as a polymer dispersant, a dispersant or a surfactant is used to prepare the composite pigment. May be processed.

Conventional pigments generally used for coloring paints, plastics, and the like, have a weight-average particle size of the pigment particles so as to have excellent opacity, weather resistance, heat resistance, dispersibility in a medium, and the like. The diameter (hereinafter, simply referred to as the average particle diameter) is large, and is adjusted to, for example, a particle diameter of 500 to 700 nm. However, when a pigment composed of such coarse particles is used as a colorant for an image recording agent, the transparency, sharpness, sharpness, and the like of the hue of the formed image are reduced. Therefore, particularly when a pigment is used as a coloring agent of a full-color recording agent, it is preferable to use a pigment which is excellent in hue transparency, sharpness, sharpness and the like of an image to be formed.
Therefore, the composite pigment comprising CuPc and AlPc of the present invention has an average particle diameter of particles in a normal dispersion method such as a flashing treatment, a heat kneading treatment, or a wet dispersion when producing the composite pigment of the present invention. It is preferable to disperse the resin in a resin so as to have a thickness of 200 nm or less, preferably 150 nm or less. Therefore, in the production of the coloring composition of the present invention, it is preferable to use a pigment which has been previously finely divided so that the pigment particles to be used have the above-mentioned dispersed particle diameter.

In the present invention, the method for making the pigment particles fine is not particularly limited, and can be carried out according to a conventionally known method. For example, the above-mentioned acid paste method, a method by impact pulverization or grinding, and the like can be mentioned. The impact milling method includes a dry milling method using a ball mill or a vibration mill.
Grinding media such as steel balls and steel rods are used, and if necessary, inorganic salts such as anhydrous sodium sulfate, sodium chloride, and aluminum sulfate are used as grinding aids. The grinding method includes a salt milling method and a solvent salt milling method, and the above-mentioned inorganic salt is used as a grinding aid. For finer particles of other pigments, at the same time as grinding and kneading the pigment particles using a high shear bead mill, etc.
There is also a so-called direct conversion method for directly producing the coloring composition and the image recording agent of the present invention. The fine-particle pigment thus obtained has sharpness, clearness, transparency, etc., and is excellent in various fastnesses such as light resistance, heat resistance, solvent resistance, chemical resistance, and water resistance. give.

Since the composite pigment of the present invention as described above has excellent pigment properties as described above, it can be used in various applications such as printing inks, paints, plastics, fine powder dry developers, liquid wet It is useful as a developer, ink for ink jet, ink for thermal transfer ink ribbon, resist for color filter, and blue-green colorant for other uses.

The coloring composition of the present invention comprises CuPc and AlP
c (or a mixed pigment or solid solution pigment thereof) and a resin. The resin is mixed. If the pigment can be uniformly dispersed in the resin, any mixing method can be used. The production method is not particularly limited.

The method for producing the coloring composition includes, for example, the following method. (A) CuPc and AlPc are individually pulverized independently to form a composite pigment by mixing the pigment and the resin with a heating kneader such as a roll mill or an extruder to uniformly disperse the pigment in the resin. And (B) mixing an aqueous presscake of CuPc and an aqueous presscake of AlPc, drying the resulting mixture, pulverizing the dried product to form a composite pigment, and combining the pigment and the resin with the above-described resin. Kneading with a heating kneader to uniformly disperse the pigment in the resin, (C) CuPc
(D) CuPc: a method of finely pulverizing a mixture composed of AlPc and AlPc to form a composite pigment, kneading the pigment and the resin with a heating kneader as described above to uniformly disperse the pigment in the resin,
Aqueous presscake and an aqueous presscake of AlPc (or a mixture of both, or an aqueous presscake of a composite pigment composed of CuPc and AlPc) and a resin are charged into a heating kneader or the like, and kneaded by a melt flushing method or the like, and kneaded into the resin. A method of uniformly dispersing a pigment, (E) a finely pulverized product of CuPc (pigment), a finely pulverized product of AlPc (pigment), a resin and a small amount of water are charged into a heating kneader or the like, and kneaded by a melt flushing method or the like. A method of uniformly dispersing the pigment therein, (F) a composite pigment comprising CuPc and AlPc,
Examples thereof include a method of uniformly dispersing in a monomer mixture constituting a resin, polymerizing the monomer, and dispersing the composite pigment in the resin.

As the resin used for producing the coloring composition of the present invention, for example, a thermoplastic resin or wax is used. These resins function as a pigment dispersing medium in a coloring composition used in a solid form, and function as a pigment dispersing agent in a coloring composition used in a liquid form. When actually used as a recording agent, it functions as a fixing agent for the pigment. Examples of resins used for such purposes include dry and wet developers for electrophotography, electrostatic printing, and electrostatic recording, and image recording agents such as oil-based and aqueous ink jet inks, and inks for thermal transfer ink ribbons. Any conventionally used resin can be used without any particular limitation. In addition, in accordance with each of the above applications, if necessary, conventionally known additives, for example, a charge control agent, a fluidizing agent or the like, or an organic solvent or an aqueous medium as a medium is added to the coloring composition of the present invention. be able to.

The coloring composition of the present invention may be produced from the beginning so as to have a pigment concentration suitable for the intended use, or may be produced as a high-concentration coloring composition containing a pigment at a high concentration. Good. The high-concentration coloring composition contains the pigment in a high concentration, and is sufficiently kneaded with the resin in advance to sufficiently disperse the pigment, or by adding another pigment as necessary to perform toning. Production of an image recording agent after using these coloring compositions becomes easy. The form of the high-concentration colored composition may be, for example, any of solid, paste, and liquid forms such as coarse particles, coarse powder, fine powder, sheets, and small lumps. The content of the pigment in the high-concentration coloring composition is usually 1
It is about 0 to 70% by weight, preferably about 20 to 60% by weight.

As a method for producing a high-concentration coloring composition, there are, for example, a dry heating kneading dispersion method and a wet dispersion method using ceramic beads, glass beads, steel balls and the like and a dispersion medium. In particular, as a method of dispersing a pigment in a resin in a high concentration in a dry manner, usually, a kneading and dispersing machine such as a twin roll, a triple roll, a heating kneader, a pressure heating kneader, a single screw extruder, and a twin screw extruder is used. Then, a method is used in which the resin is brought into a molten state and the pigment particles are dispersed in the resin. In any of these methods, the kneading and dispersion of the pigment and the resin are desirably performed at a temperature of 120 ° C. or lower. By dispersing at a relatively low temperature, the particle diameter of the pigment particles prepared in advance is kept as it is in the obtained coloring composition, and the subsequent production of the recording agent is also 120. By performing at a temperature below ℃
As described above, the particle diameter of the pigment particles is maintained as it is.
As a result, it is possible to obtain an image recording agent which gives an image having excellent hue clarity, sharpness, transparency and the like. In addition, the above temperature is set to 12
When the temperature exceeds 0 ° C., the aggregation of the pigment particles and the crystal growth of the particles grow, and the sharpness, sharpness, transparency and the like are reduced.

A more preferable method for dispersing the pigment in the resin at a high concentration is a method of flushing an aqueous paste of the pigment with a molten resin (normal pressure melting flushing method). There is a method proposed in Japanese Patent No. 175770. Specifically, the aqueous presscake of the pigment and the resin are charged into a steam-heated kneader or flasher without using any solvent, and kneaded at normal pressure at a temperature close to the melting point or softening point of the resin to form an aqueous phase. This is a method in which the pigment of (press cake) is transferred to the resin phase, water separated at that time is removed, and remaining water is removed by evaporation. By using an aqueous presscake of pigment,
Since the pigment can be transferred into the resin while keeping the particle diameter of the fine pigment in the press cake as it is, and the kneading dispersion temperature can be kept at 100 ° C. or less while water is present,
It has the characteristic that aggregation or crystal growth of pigment particles due to high temperature can be suppressed.

Further, another preferred method of dispersing the pigment is as follows:
Add water as a dispersant to the powdery pigment and resin, and forcibly at a temperature of 120 ° C. or less and a temperature close to the melting point or softening point of the resin at normal pressure in the absence of a solvent in the same manner as described above. In this method, the pigment is transferred to the resin phase by kneading, the separated water is removed, and the remaining water is evaporated. As described above, the use of the coloring composition of the present invention is the same as the use of the composite pigment of the present invention, and can be more easily used in various uses than using the composite pigment.

Various image recording agents of the present invention can be prepared by adding various additives and solvents conventionally used to the coloring composition of the present invention according to the intended use. Examples of the image recording agent of the present invention include so-called fine powder dry developers, liquid wet developers, electrostatic recording agents, ink jet inks, and thermal transfer ink ribbon inks.

The content of the pigment in the image recording agent of the present invention is as follows:
Depending on the intended use of the recording agent, the content of the pigment in the entire recording agent including the blue-green pigment, resin, other additives or medium of the present invention is usually about 2 to 20% by weight. When used as a dry recording agent for electrophotography, the pigment concentration is about 2 to 15% by weight, preferably 3 to 10% by weight.
When it is used as a wet recording agent for electrostatic recording, the pigment concentration is about 1 to 20% by weight, preferably about 3 to 10% by weight, and usually about 10 to 10% by weight. Use it after diluting it up to 30 times. When the image recording agent is a thermal transfer ink ribbon ink, the pigment concentration is about 4 to 15% by weight, preferably about 6 to 10% by weight. About 20% by weight, preferably 5 to 10% by weight
And the most preferred pigment concentration according to the purpose of use.

Dry and wet developers for electrophotography, electrostatic printing, electrostatic recording, etc., aqueous, oily and solid ink jet inks, and thermal transfer ink ribbons produced using the coloring composition of the present invention. Image recording agents such as inks for
It can be manufactured by using a coloring composition prepared so as to have a pigment concentration suitable for a desired use from the beginning. Alternatively, the high-concentration coloring composition can be produced by dispersing or diluting and dispersing it in a resin, a resin solution or an addition-polymerizable monomer. In the production thereof, a conventionally known charge control agent, fluidizing agent, ferromagnetic material, organic solvent medium, aqueous medium and the like can be added as necessary.

For example, image recording agents used for electrophotography, electrostatic printing, electrostatic recording and the like are described. Dry recording agents include a pulverization method or a polymerization method (suspension polymerization method, emulsion polymerization aggregation method). And the like. In the pulverization method, a pigment, a resin, a charge control agent and the like are heated and kneaded, and after cooling, the kneaded material is pulverized and classified to a predetermined particle size. In the above suspension polymerization method, a pigment, a charge control agent, and the like are dispersed in an addition polymerizable monomer, and the monomer is formed into an O / W emulsion to control the particle diameter of a droplet, and is colored by suspension polymerization. The recording agent is in the form of fine particles. Also, in the emulsion polymerization liquid aggregation method,
Mix the emulsion polymerization solution with a fine dispersion such as a pigment or a charge control agent,
The obtained colored emulsion polymerization solution is polymerized, and the polymer particles are fused and aggregated to cause the pigment and the charge control agent to co-precipitate or adsorb to the polymer particles. Fine particles to the particle size. If necessary, conventionally known materials such as a fluidizing agent and a ferromagnetic agent can be added.

The wet recording agent is prepared by dispersing a pigment together with a resin, a dispersion stabilizer and a charge controlling agent in a solvent medium using a wet medium dispersing machine, or by coloring a pigment, a resin, a charge controlling agent and the like. It is produced by a method of dispersing resin fine particles together with a dispersion stabilizer or a charge control agent in a solvent medium using a wet medium disperser. The image recording agent using the coloring composition of the present invention is a blue-green image recording agent, and can be used alone, or as a cyan color of a multicolor or full-color recording agent, magenta, yellow or even black. It can be used as a set with a color image recording agent.

[0028]

Next, the present invention will be described more specifically with reference to examples. In the text, parts or% are based on weight.
The average particle diameter of the pigment particles and the average particle diameter of the pigment particles in the composition in the following examples are the average particle diameters measured by the following methods. (1) Method for measuring average particle diameter of pigment particles 0.5 g of pigment was dispersed in a dispersant of 0.5 g using a Hoover-type muller.
After dispersing in 7 g and diluting to a measured concentration with water, a test solution prepared by applying ultrasonic waves for 1 minute is used to prepare a Coulter submicron particle analyzer (manufactured by Coulter) MODE
It measured using LN-4. (2) Measurement method of average particle diameter of pigment particles in coloring composition 0.1 g of coloring composition was dissolved in 10 cc of xylene, diluted with xylene to a measured concentration, and then prepared by applying ultrasonic waves for 1 minute. The test liquid was measured as described above.

Example 1 50.0 parts of phthalonitrile, 1-chloronaphthalene 30
0.0 parts and 13.0 parts of aluminum chloride were charged into a reaction vessel and reacted at 230 ° C. for 5 hours. After the reaction product was separated by filtration, the reaction product was successively and thoroughly washed with methanol and a 2% dilute sulfuric acid aqueous solution, followed by filtration and drying. Next, the obtained reaction product was subjected to 500.
After dissolving in 0 parts of concentrated sulfuric acid, the mixture was poured into 3,000 parts of ice water at a temperature of 10 ° C. or less to precipitate and crystallize AlPc fine particles. Obtained. Subsequently, water was adjusted to 1,000 parts together with the water in the press cake, 20 parts of butyl cellosolve was added, and the mixture was stirred and mixed at 90 ° C. for 6 hours. The mixture was filtered, washed with water, dried and ground to 38.2 parts of Al
A Pc pigment was obtained. The average particle size of the pigment particles is 200 n.
m or less, and the hue showed bluish green.

Example 2 The amount of 1-chloronaphthalene used was changed to 600.0 parts,
Add 40 parts of CuPc powder to synthesize AlPc with CuP
A composite pigment of the present invention was obtained in the same manner as in Example 1 except that the operation was performed in the presence of c. Powder 100 of the obtained composite pigment
Was added to 400 parts of the varnish for offset ink, and after sufficient premixing, the mixture was kneaded with a three-roll mill to obtain a blue-green offset ink. When printing was performed on paper using this ink, a clear and clear blue-green printed matter was obtained.

Example 3 The aqueous slurry of CuPc pigment obtained by a known method and the aqueous slurry of AlPc obtained in Example 1 were mixed at a pigment weight ratio of 1
/ 1, filtered, washed with water, dried and pulverized to obtain a blue-green composite pigment of the present invention. Using this composite pigment, a blue-green offset ink was obtained in the same manner as in Example 2. This ink had a clear, clear blue-green color.

Example 4 A ball mill was charged with 10 parts of CuPc, 100 parts of sodium chloride, and 1 part of a high-boiling alicyclic hydrocarbon, and ground for 10 hours to form a pigment. Subsequently, post-treatments such as filtration and washing were performed according to a conventional method to obtain a press cake of a CuPc pigment. The solid content as a CuPc pigment was 40%.
Further, the obtained press cake is dried and pulverized to obtain powder Cu.
It was a Pc pigment. The average particle diameter of the particles of the CuPc pigment thus produced was 200 nm or less, and the hue was blue (cyan).

Next, the aqueous presscake of the above-mentioned CuPc pigment and the aqueous presscake of the AlPc pigment of Example 1 were mixed at a solid content weight ratio of 1/1, dried and pulverized to obtain a CuPc pigment and an AlPc pigment. A composite pigment consisting of The average particle size of the pigment particles was 200 nm or less, and the hue was bluish green.

Example 5 6 parts of CuPc used in Example 4 and 4 parts of AlPc obtained in Example 1 were mixed and ground to obtain fine particles of a solid solution of CuPc / AlPc. , And filtered and washed to obtain a press cake. This is dried and crushed to obtain CuP
A solid solution composite pigment of c / AlPc (weight ratio 6/4) was obtained. The average particle size of the pigment particles was 200 nm or less, and the hue was bluish green.

Example 6 The CuPc obtained in Example 4 was obtained according to the normal-pressure melt flushing method of the pigment proposed in JP-A-2-175770.
37.5 parts (solid content 40%) of a pigment press cake, 39.5 parts (solid content 38%) of an AlPc pigment press cake obtained in Example 1, and a styrene / methacrylic ester copolymer (softening About 110 ° C, glass transition point about 56
70 ° C., GPC method weight average molecular weight: about 50,000) was charged into a heating kneader, and the mixture was heated with steam while being mixed, and subjected to melt flushing. The temperature of the kneaded resin was set to 90 to 95 ° C., flushing was continued, and water was separated. The separated water was discharged, and the remaining water was removed by evaporation while heating and kneading. After the kneading was further continued, the kneaded material was taken out of the kneader, cooled and pulverized to obtain a coarse powder of a blue-green high-concentration coloring composition (pigment content: 30%). The average particle size of the pigment particles in the coarse powder was 200 nm or less.

Next, 11.7 parts of the high-concentration coloring composition thus obtained and 3 parts of the chromium complex-based negative charge control agent were used in the above-mentioned styrene / methacrylic acid ester-based copolymer 8
The mixture was kneaded with 5.3 parts according to a conventional method, cooled, pulverized, finely pulverized with a jet mill, and further classified to obtain a blue-green fine powder of 5 to 20 μm. Subsequently, colloidal silica was added as a fluidizing agent according to a conventional method, mixed well, and then mixed with a carrier (magnetic iron powder) to obtain a blue-green electrophotographic dry developer.

This was charged in an electrophotographic copying machine for negative charge full-color development, and an image was formed on paper. As a result, the image showed a clear and clear blue-green color and was excellent in various physical properties such as light resistance.
When an image was formed on a polyester sheet for an overhead projector (hereinafter abbreviated as OHP), the image showed high transparency, and a clear blue-green image was displayed on the OHP screen. In addition, C.I. I. Pi
gment Red 122, C.I. I. Pigment Yellow 93, C.I. I. Pigment Black
7 were respectively dispersed in a magenta color developer (pigment content: 4.4%) and a yellow color developer (pigment content: (4.4%) and a black developer (pigment content: 3.5%), and a four-color full-color image was formed together with the blue-green developer obtained above to obtain a clear full-color image. Further, a full-color image in which a clear full-color image was projected on an OHP screen was obtained.

Example 7 16 parts of the CuPc powder pigment obtained in Example 4, 14 parts of the AlPc powder pigment obtained in Example 1, and 70 parts of the styrene-methacrylic acid ester copolymer used in Example 6 And 100 parts of water were charged into a heating-type kneader, steam-heated while mixing, and sufficiently kneaded. The temperature of the kneaded resin was adjusted to 90 to 95 ° C. to separate water. The separated water was discharged, and the remaining water was removed by evaporation while heating and kneading.
After further kneading, remove the kneaded material from the kneader,
After cooling and pulverizing, the bluish-green high-concentration coloring composition (pigment 3
(0%). The average particle size of the pigment particles in the coarse powder was 200 nm or less.

Next, a high-concentration coloring composition and a chromium complex-based negative charge controlling agent were kneaded with a styrene-methacrylic copolymer in the same manner as in Example 6, cooled, pulverized and classified to give a particle size of 5 to 20 μm. Was obtained, colloidal silica was added, and mixed with magnetic iron powder to obtain a blue-green electrophotographic dry developer. When this developer was used to form an image on paper with a negative charge full color developing electrophotographic copier, the image showed a clear and clear blue-green color, and exhibited robustness with excellent physical properties such as light resistance. Was. Further, when an image was formed on a polyester sheet for an overhead projector, the image showed high transparency and a clear blue-green image was shown on the OHP screen. Further, when a four-color full-color image was formed in the same manner as in Example 6, the image was a clear full-color image.

Example 8 The CuPc pigment obtained in Example 4 and the Al obtained in Example 1
30 parts of the composite pigment with the Pc pigment was sufficiently kneaded with 70 parts of the styrene-methacrylic acid ester-based copolymer used in Example 6 using a three-roll mill to disperse the pigment. After cooling, the mixture is coarsely pulverized to obtain a blue-green high-concentration coloring composition (pigment content 30%).
%) Of a coarse powder. The average particle size of the pigment particles in the coarse powder was 200 nm or less. Subsequently, a blue-green electrophotographic dry developer was used in the same manner as in Example 6, and an image was formed on paper with an electrophotographic copying machine for negative charge full-color development. The image was a blue-green clear and sharp image. Met.

Example 9 75 parts of the composite pigment presscake obtained in Example 5 (solid content: 40%) and 70 parts of a bisphenol type polyester resin for negative charge (softening point: about 100 ° C.) were charged into a heating kneader. The melt flushing was performed in the same manner as in Example 6. The separated water was discharged, and the remaining water was removed by evaporation while heating and kneading. After continuing the kneading to disperse the pigment, the kneaded product was taken out of the kneader, cooled and coarsely pulverized to obtain a coarse powder of a blue-green high-concentration colored composition (pigment content: 30%). Next, a blue-green electrophotographic dry developer was prepared in the same manner as in Example 6.
When an image was formed on paper using an electrophotographic copying machine for negative charge full-color development, the image was a blue-green clear and sharp image. Further, a four-color full-color image was formed in the same manner as in Example 6, and a clear full-color image was obtained.

Example 10 30 parts of the composite pigment obtained in Example 4 and a styrene / methacrylic copolymer having a tertiary amino group for positive charge (Tg57
70 ° C.) with a three-roll mill to sufficiently disperse the pigment. After cooling, the mixture was coarsely pulverized to obtain a coarse powder of a blue-green high-concentration colored composition (pigment content: 30%). The average particle size of the pigment particles in the coarse powder was 200 nm or less. Next, Example 6
14.7 parts of the above-mentioned high-concentration coloring composition was mixed with the same styrene / methacrylic acid ester-based copolymer as described above.
3 parts, and after cooling, coarsely pulverized, finely pulverized and classified to obtain a fine powder having a particle size of 5 to 20 μm. Colloidal silica is added as a fluidizing agent, mixed with magnetic iron powder and mixed with a blue-green electrophotographic dry method. A developer was used. When an image was formed on paper using an electrophotographic copying machine for positive charge full-color development, the image was a clear and clear blue-green image.

Example 11 50 parts of diethyl maleate was placed in a container, 20 parts of a styrene / benzyl methacrylate / 2-ethylhexyl methacrylate (weight ratio: 7/2/1) copolymer was added and dissolved therein. 30 parts of the composite pigment obtained in Example 5 was mixed and sufficiently finely dispersed using a continuous horizontal wet bead medium disperser to obtain a blue-green pigment monomer dispersion. The average particle size of the pigment particles in the dispersion was 200 nm or less. Similarly, 50 parts of diethyl maleate was dissolved in 20 parts of the styrene / methacrylic acid ester copolymer of Example 6, and 30 parts of a chromium complex-based negative charge control agent was added and mixed. A monomer dispersion of the charge control agent was obtained.

16.7 parts of the pigment dispersion obtained above, 10.0 parts of the negative charge control agent dispersion and butyl methacrylate 1
2.6 parts, 60.7 parts of styrene, 1.5 parts of lauryl mercaptan and 2.0 parts of azoisobutyronitrile were sufficiently and uniformly mixed. Next, 4% colloidal silica aqueous dispersion 2
While stirring 00 parts with a high-shear high-speed stirrer, 103.5 parts of this mixed liquid was gradually added to prepare an oil-in-water emulsion.

A polymerization reactor was charged with 200 parts of an aqueous dispersion of 4% colloidal silica and about one third of the emulsion obtained above, and was subjected to a polymerization reaction at 75 to 80 ° C. for 2 hours. Then, the remaining about two-thirds of the emulsion was added dropwise from the dropping funnel over 3 hours and stirred for another 1 hour.
The temperature was raised to 5 ° C. and the mixture was stirred for 1 hour to complete the polymerization reaction.
The produced polymer was separated by filtration, washed with an aqueous sodium hydroxide solution to remove silica, sufficiently washed with water, and dried to obtain a fine powder of a blue-green polymer having an average particle diameter of about 8 μm. . Subsequently, this was mixed with colloidal silica and magnetic iron powder to obtain an electrophotographic dry developer. The image formed on the paper by the electrophotographic copying machine for negative charge full-color development exhibited a clear and clear blue-green color.

Example 12 Heating 75 parts (40% solids) of a presscake of the composite pigment obtained in Example 5 and 70 parts of a styrene / methacrylic ester copolymer having a tertiary amino group (Tg 57 ° C.) The mixture was charged into a mold kneader, and a coarse powder of a high-concentration coloring composition was obtained in the same manner as in Example 6. Next, 10 parts of this blue-green coarse powder were added to 75 parts of Isopar G together with 15 parts of a methacrylic acid ester resin (Tg of 48 ° C.) soluble in an aliphatic hydrocarbon solvent, glass beads were added, and a paint conditioner was used for 20 hours. It was dispersed by shaking to prepare a thick colored liquid. The average particle diameter of the pigment particles in the concentrated coloring liquid is 200 n.
m or less. 200 parts of this concentrated liquid is
In addition, the mixture was dispersed in 00 parts to obtain an electrophotographic wet developer. Using this, an image was formed with a full-color wet electrophotographic copying machine, and a clear blue-green image was obtained. This image showed fastness excellent in various physical properties such as light fastness.

Example 13 5 parts of a conventionally known CuPc powder pigment and Al obtained in Example 1
5 parts of Pc powder pigment, 41 parts of ester wax, 41 parts of paraffin wax, 5 parts of styrene / methacrylic ester copolymer (Tg 56 ° C.), 3 parts of silica as a binder, and 50 parts of water as a dispersant are added. The separated water was removed by kneading under normal pressure at a temperature close to the melting point or softening point of the resin, and the remaining water was evaporated. The obtained coloring composition was applied to a polyethylene film according to a conventional method to obtain a blue-green heat transfer ink ribbon. Using this, an image was formed with a full-color thermal transfer printer to obtain a clear blue-green image. This image showed fastness excellent in various physical properties such as light fastness.
When an image is formed on a polyester sheet for OHP,
A transparent image was obtained and a clear image was shown on the screen.

In the same manner as above, magenta, yellow and black thermal transfer ink ribbons were obtained using the magenta, yellow and black pigments used in Example 6, respectively. Used with a blue-green thermal transfer ink ribbon to form a four-color full-color image,
A clear full-color image was obtained. Further, when an image was formed on a polyester sheet for OHP, a full-color image showing a transparent full-color image on a screen was obtained.

Example 14 12.5 parts (40% pigment content) of an aqueous presscake of the composite pigment obtained in Example 5, 3 parts of a styrene / butyl acrylate / ethyl methacrylate copolymer, 22 parts of ethylene glycol, and glycerin 8 Part, and make an aqueous pigment dispersion liquid consisting of 50 parts of water, remove the pigment coarse particles with an ultracentrifuge,
An ink for ink jet was obtained. Using this ink, image information was printed by an on-demand type ink jet printer having a piezo oscillator, and a clear blue-green image was obtained. The same magenta, yellow, and black pigments as used in Example 6 were used as magenta, yellow, and black ink jet inks, respectively, and four-color full-color printing was performed together with the blue-green ink obtained above. To obtain a clear full-color image.

[0050]

According to the present invention as described above, it is possible to provide a novel blue-green composite pigment, a blue-green coloring composition and a blue-green image recording agent using the same which are clear, transparent and environmentally friendly. Can be.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08J 3/20 CER C08K 5/00 3/22 CER C08L 101/00 C08K 5/00 C09B 67/22 F C08L 101/00 67/46 A C09B 67/22 C09D 11/00 67/46 G03G 9/12 311 C09D 11/00 B41J 3/04 101Y G03G 9/09 B41M 5/26 K 9/12 311 G03G 9/08 361 (72) Inventor Kazutaka Aoki 1-7-6 Nihombashi Bakurocho, Chuo-ku, Tokyo Dai Nippon Kagaku Kogyo Co., Ltd. (72) Inventor Naotoku Takami 1-7-6 Nihonbashi Bakurocho, Chuo-ku, Tokyo Dainippon Kagaku Kogyo Co., Ltd. (72) Inventor Masahiko Aoba 1-7-6 Nihombashi Bakurocho, Chuo-ku, Tokyo Dai Nippon Seika Industry Co., Ltd. (72) Inventor Yukio Kamihara 1-7-6, Nihonbashi Bakurocho, Ward Nissei Chemical Industry Co., Ltd. (72) Inventor Shigeru Takarada 1-7-6, Nihonbashi Bakurocho Nihonbashi, Chuo Ward, Tokyo Dainippon Chemical Co., Ltd. (72) Inventor Keiji Nakajima Chuo, Tokyo 1-7-6, Nihonbashi Bakurocho, Ward Inside Nissei Chemical Industry Co., Ltd.

Claims (21)

[Claims] 1. A blue-green composite pigment comprising copper phthalocyanine and aluminum phthalocyanine. 2. The composite pigment according to claim 1, wherein copper phthalocyanine and aluminum phthalocyanine are in a mixture or a solid solution. 3. The ratio of copper phthalocyanine to aluminum phthalocyanine is 95 to 5% by weight of the former, and 5 to 95% by weight of the latter.
The composite pigment according to claim 1, which is in weight%. 4. A method for producing a composite pigment, comprising mixing copper phthalocyanine and aluminum phthalocyanine and then pigmenting the mixture. 5. Synthesis of copper phthalocyanine and aluminum phthalocyanine in the presence of a copper salt and an aluminum salt,
A method for producing a composite pigment, which comprises pigmentating a product. 6. A method for producing a composite pigment, comprising simultaneously synthesizing another phthalocyanine in the presence of copper phthalocyanine or aluminum phthalocyanine, and pigmentating the product. 7. A method for producing a composite pigment, which comprises mixing a pigmented copper phthalocyanine (or a press cake thereof) with a pigmented aluminum phthalocyanine (or a press cake thereof). 8. A coloring composition comprising at least a pigment and a resin, wherein the pigment comprises copper phthalocyanine and aluminum phthalocyanine. 9. The coloring composition according to claim 8, wherein the pigment is a mixed pigment or a solid solution pigment composed of copper phthalocyanine and aluminum phthalocyanine. 10. The colored composition according to claim 9, wherein the weight average particle diameter of the mixed pigment or solid solution pigment particles is 200 nm or less. 11. The coloring composition according to claim 8, wherein the pigment is a solid, paste, or liquid dispersed in a resin or a resin solution at a high concentration. 12. A coloring composition comprising a mixture of finely pulverized copper phthalocyanine and aluminum phthalocyanine alone to form a composite pigment, kneading the pigment and a resin, and dispersing the pigment in the resin. Method of manufacturing a product. 13. An aqueous presscake of copper phthalocyanine and an aqueous presscake of aluminum phthalocyanine are mixed, and the resulting mixture is dried. The dried product is finely pulverized into a composite pigment, and the pigment and the resin are kneaded. A method for producing a colored composition, comprising dispersing a pigment in a resin. 14. A method for producing a coloring composition, comprising: pulverizing a mixture of copper phthalocyanine and aluminum phthalocyanine to form a composite pigment; kneading the pigment with a resin to disperse the pigment in the resin. . 15. An aqueous presscake of copper phthalocyanine and an aqueous presscake of aluminum phthalocyanine (or a mixture thereof, or an aqueous presscake of a composite pigment comprising copper phthalocyanine and aluminum phthalocyanine) and a resin at a temperature of 120 ° C. or lower. A method for producing a colored composition, comprising kneading and dispersing a pigment in a resin. 16. A pigment is dispersed in a resin by kneading a finely pulverized copper phthalocyanine (pigment), a finely pulverized aluminum phthalocyanine (pigment), a resin and a small amount of water at a temperature of 120 ° C. or lower. A method for producing a coloring composition. 17. A composite pigment comprising copper phthalocyanine and aluminum phthalocyanine is uniformly dispersed in a monomer mixture constituting the resin, and the monomer is polymerized to disperse the composite pigment in the resin. A method for producing a coloring composition. 18. An image recording agent comprising at least a pigment and a resin, wherein the pigment is produced using a coloring composition that is a mixed pigment or a solid solution pigment composed of copper phthalocyanine and aluminum phthalocyanine. 19. The image recording agent according to claim 18, which is a fine powder dry developer or a liquid wet developer. 20. The image recording agent according to claim 18, which is an ink for an ink jet. 21. The image recording agent according to claim 18, which is an ink for a thermal transfer ink ribbon applied to a film or sheet substrate.