JP3314004B2 - Image recording coloring composition and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording agent in image recording such as electrophotography, electronic printing, electrostatic recording, ink jet recording and thermal transfer recording, or a high-density coloring composition used for the production thereof, and to the image recording. The present invention relates to a coloring composition for image recording used in a recording agent and a method for producing the same. More specifically, the present invention provides a recording agent for image recording containing a pigment and a resin, which comprises a dichloroquinacridone pigment having excellent fastness and a fine particle diameter as a pigment and a γ-type unsubstituted quinacridone red pigment. It is an object of the present invention to provide a magenta colored composition for image recording and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, red pigments used in magenta recording agents used for image recording such as full-color or mono-color electrophotography, electrostatic printing, electrostatic recording, ink jet recording and thermal transfer recording are red. Oil-soluble dyes, dispersible dyes, thioindigo pigments, soluble azo lake pigments,
Insoluble azo pigments, dichloroquinacridone pigments and the like have been used.

[0003]

As the red pigment used in the above-mentioned magenta color image recording agent, a dichloroquinacridone pigment which is well-known as a magenta color pigment is often used. However, the magenta color alone is bluish. Because it is too intense, in many cases, a yellow pigment having a yellow tint is mixed and used as a desired magenta color.

However, regarding the red dyes used in these, oil-soluble dyes, dispersible dyes, and the like can be dissolved in a resin medium, so that they have high coloring power,
There is a disadvantage that it is inferior in various fastnesses such as heat resistance, solvent resistance and chemical resistance. Also, thioindigo pigments, soluble azo lake pigments, insoluble azo pigments are also superior to dyes,
Various fastnesses such as light fastness and heat resistance are insufficient. Therefore,
Dyes and pigments as described above are insufficient as dyes used for magenta colors for recording agents requiring various fastnesses, and are used for magenta colors for recording agents having excellent physical properties. There is a need for the development of pigments.

The present inventors have conducted various studies on the development of a red pigment capable of solving the above-mentioned defects of the conventional dyes for magenta color recording agents and satisfying various fastnesses. As a result, a γ-type unsubstituted quinacridone pigment was obtained. It has been found that it has a yellowish red hue and high fastness suitable for this use, and a specific range of dichloroquinacridone pigments and γ-type unsubstituted quinacridone pigments as pigments used in magenta color recording agents. The mixture has an appropriate magenta hue and is excellent in various fastnesses such as light resistance, solvent resistance, heat resistance, chemical resistance, etc., and is used for applications such as conventional paint and plastic coloring. By making the particle size smaller than that of the pigment, it is possible to exhibit excellent properties such as sharpness of hue, sharpness, transparency, etc., and by using this as a coloring agent, an excellent recording agent can be obtained. See that The present invention has been completed.

[0006]

That is, the present invention relates to a coloring composition for image recording containing a pigment and a resin, wherein a dichloroquinacridone pigment and a .gamma.-type unsubstituted quinacridone pigment are each crushed individually or as a mixture or as a solid solution. A dichloroquinacridone pigment having an average particle diameter of about 200 nm or less and a γ-type unsubstituted quinacridone pigment alone obtained by impact grinding or grinding with a medium and / or grinding aid and post-treatment with water;
A dichloroquinacridone pigment is obtained by using a solid, paste or liquid high-concentration coloring composition in which a mixed or solid solution pigment is dispersed in a resin binder or a resin solution for image recording at a high concentration at a processing temperature of 120 ° C. or less. The γ-type unsubstituted quinacridone pigment is contained in a ratio of 99: 1 to 1:99, diluted and redispersed in a resin binder or a resin solution,
According to a conventional method of producing a coloring composition for image recording, a conventionally known charge control agent, a fluidizing agent, a ferromagnetic material, a solvent medium, an aqueous medium and the like may be added and processed as necessary. It is a coloring composition for image recording which is a feature.

[0007] The coloring composition for image recording of the present invention uses a dichloroquinacridone pigment and a γ-type unsubstituted quinacridone pigment as its pigment components. Solvent resistance, chemical resistance,
Excellent fastness such as water resistance, higher coloring power, sharpness,
It is clear, transparent, and can be produced stably in the process of producing colored products by employing a dispersion processing method such as processing at a processing temperature of 120 ° C. or less when producing a high-concentration colored composition. Further, even when finally used as a coloring composition for image recording, a clear, clear, and highly transparent image can be stably recorded. Also, when used as a liquid recording agent,
It can record stably for a long time. Therefore, the obtained image is excellent in hue and sharp, and exhibits the above-mentioned properties in various fastnesses.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in more detail.
The mixture of the dichloroquinacridone pigment and the γ-type unsubstituted quinacridone pigment used in the present invention and mainly characterizing the present invention is a mixture of pigments having an average particle diameter of about 200 nm or less, and is used in an image recording agent finally used. The ratio of the dichloroquinacridone pigment to the γ-type unsubstituted quinacridone pigment is determined from the color tone of the image, and is in a range of approximately 99: 1 to 1:99, preferably 90:
The range is from 10 to 30:70.

[0009] The mixed toning of the dichloroquinacridone pigment and the γ-type unsubstituted quinacridone pigment is carried out in various forms in each step of the production. As a mixture of pigments dried and pulverized independently, an aqueous presscake of both pigments is mixed, and as a mixture of dried and pulverized pigments, an aqueous presscake of each pigment is charged into a heating kneader or the like, and a melt flushing method described later. By mixing the high concentration colorant obtained by
An aqueous presscake of both pigments is charged into a heating kneader or the like, and as a high-concentration colorant of the mixed pigment by a melt flushing method or the like, and at the stage of pigment production, dichloroquinacridone and γ
A non-substituted quinacridone is mixed and treated to form a solid solution, but dried, ground pigment, and an aqueous presscake of the solid solution pigment are also used as a high-concentration colorant by a melt flushing method or the like.

Post-treatments such as adjusting the crystal of the pigment and adjusting the shape and particle size of the particles to a desired range are carried out in the same manner according to a usual method. When dichloroquinacridone pigments and γ-type unsubstituted quinacridone pigments are used for applications such as coloring of paints, plastics, and synthetic fibers, hiding power, ease of dispersion in a medium, weather resistance, heat processing resistance, etc. In general, the average particle diameter is large, for example, about 500 to 700 nm in order to have the performance described above. However, when this coarse pigment is used as a colorant for an image recording agent, there is a problem that the hue is lacking in sharpness, sharpness, and transparency. In particular, when used as a colorant for a full-color recording agent, it is preferable that the colorant has sharpness, sharpness, and transparency, and for this purpose, the dichloroquinacridone pigment and γ when dispersed are used. The average particle size of the unsubstituted quinacridone pigment is about 200 n.
m or less, preferably about 150 nm or less.

As a method for making the pigment fine particles, a method by impact pulverization, a method by attrition, and the like are mentioned. As the impact crushing method, a dry milling method using a ball mill or a vibration mill is a typical method.A conventionally known crushing medium such as a steel ball or a steel rod is used, and an inorganic salt is used as a grinding aid in combination. Is preferred. Typical examples of the grinding method include a salt milling method and a solvent salt milling method, and grinding aids such as anhydrous sodium sulfate, sodium chloride, and aluminum sulfate are used together. As a post-treatment of the pulverization or attrition step, the substrate is washed with a dilute acid aqueous solution and then sufficiently washed with water to remove metallic impurities, or sufficiently washed with water after removing water-soluble salts with water. The fine particle pigment thus obtained has sharpness of hue, clearness, transparency,
In addition, it exhibited properties excellent in various fastnesses such as light resistance, heat resistance, solvent resistance, chemical resistance, and water resistance.

A mixed pigment of a dichloroquinacridone pigment and a γ-type unsubstituted quinacridone pigment is subjected to a pigmentation treatment as described below to form a solid solution, thereby further improving the sharpness, clarity and transparency of the hue. I can do it. The method of converting the mixed pigment into a solid solution is achieved by blending a pigment to be a solid solution, obtaining a solid solution coarse crystal through an acid paste treatment or a grinding step, and treating with an organic solvent or the like.

The resin used in the present invention is a dispersing medium in a coloring composition in a solid form, and functions as a dispersant for a pigment in a liquid coloring composition. When actually used as a recording agent, it acts as a fixing agent for the pigment. Resins used for such purposes include dry and wet developers such as electrophotography, electrostatic printing, and electrostatic recording, oil-based and aqueous inkjet inks, and image recording agents such as thermal transfer ink ribbons and films. Any resin used may be used. In addition, conventionally known additives such as a charge controlling agent, a fluidizing agent, and the like, or a solvent and an aqueous medium as a medium are used as necessary according to each application.

The coloring composition for image recording of the present invention can be used in various ways depending on the purpose. One of them is a high-concentration coloring composition, which contains pigment at a high concentration, and is used for facilitating the subsequent steps by preliminarily kneading and dispersing or toning. It can be used in the form of solids such as coarse particles, coarse powders, fine powders, sheets and small lumps, or any form of paste or liquid. Examples of the coloring composition for image recording according to the present invention include compositions used as a target image recording agent, and include so-called fine powder dry developers, liquid wet developers, electrostatic recording agents, and inkjet recording. Thermal transfer ink ribbons and films applied to substrates such as inks, films, and paper.

The content of the mixed pigment of dichloroquinacridone and γ-quinacridone toned to magenta used in the present invention in the coloring composition containing the resin and other additives or the medium is as described above. It depends on the purpose of use. In pigmented high-concentration coloring compositions, the content is approximately 70% to 10%, preferably 6%.
It is about 0% to 20%.

The content of the pigment in the target image recording agent varies depending on the type of the recording agent. In an electrophotographic dry developer or the like, the content of the pigment is about 15% to
2%, preferably about 10% to 3%, and about 1% to 20% for a concentrated undiluted solution in a wet developer for electrostatic recording.
%, Preferably about 3% to 10%, and is usually used after being diluted 10 to 30 times with a diluent. When used as a colorant for thermal transfer ink ribbons and films, 15
% To 4%, preferably about 10% to 6%, and 3% to 20%, preferably 5% for an ink jet recording ink.
% To about 10%, and each is used at the most preferable content depending on the purpose of use.

As a method for producing the above-mentioned pigment-concentrated coloring composition, there are a dry heat kneading dispersion method and a wet medium dispersion method using ceramic beads, glass beads, steel balls and the like. In particular, as a method for dispersing the pigment in the resin at a high concentration, the resin is melted using a kneading and dispersing machine such as a two-roller, a three-roller, a heating kneader, a pressure heating kneader, a single-screw extruder, and a twin-screw extruder. And then kneading and dispersing the pigment. In any of these cases, the kneading and dispersion processing is desirably performed at a temperature of 120 ° C. or less. By performing the process under the relatively low processing temperature conditions, the particle diameter of the finely prepared pigment is kept as it is, and by performing the same in the subsequent processing step of the recording agent production, the image recording agent is used. Hue clarity, sharpness, and transparency are shown.

The most preferable method for dispersing the pigment at a high concentration is a method of flushing an aqueous paste of the pigment with a molten resin (melt flushing method), for example, a method proposed in Japanese Patent Application Laid-Open No. 2-175770. is there. Specifically, the aqueous presscake of the pigment and the resin binder are charged into a steam-heater or a flasher without using any solvent, and kneaded at normal pressure at a temperature lower than the melting point or softening point of the resin to form an aqueous phase. Is transferred to the resin phase, the separated water is removed, and the remaining water is kneaded and evaporated. By using an aqueous press cake, the pigment particles of the press cake can be transferred directly into the resin, and the kneading and dispersing temperature can be reduced to 100 ° C. or less while water is present. I have.

Further, the colored composition for image recording of the present invention is used as a magenta image recording agent in individual colors such as mono-color, two-color, multi-color, etc., and in addition to cyan and yellow as a full-color recording system. Of course, it can be used together with a black image recording agent as a set. Examples of these organic pigments and inorganic pigments include phthalocyanine, azo, polycondensed azo, azomethine azo, anthraquinone, perinone / perylene, indigo / thioindigo, dioxazine, quinacridone, and isoindolinone-based pigments. And carbon black pigments such as pyrrolopyrrole-based pigments, titanium oxide-based pigments, iron oxide-based pigments, calcined pigment-based pigments, and extender pigments.

In particular, the pigment used in the full color recording agent is a phthalocyanine blue pigment as a cyan pigment, and each of an azo type, a polycondensed azo type, an anthraquinone type and an isoindolinone type as a yellow color. Typical examples of the black color include a carbon black pigment, an azomethine azo black pigment, and a black pigment obtained by toning a pigment of each color.

[0021]

Now, the present invention will be described in further detail with reference to Synthesis Examples and Examples. It should be noted that “part” or “%” in the text is based on weight. Synthesis Example 1 A ball mill was charged with 10 parts of a crude pigment of dichloroquinacridone, 100 parts of sodium chloride, and 1 part of a high-boiling alicyclic hydrocarbon, followed by grinding for 10 hours. Post-treatments such as pigmentation, filtration, and washing were performed to obtain a press cake. The solid content of the dichloroquinacridone pigment was 30%. The obtained press cake was dried and pulverized to obtain a dichloroquinacridone pigment. The average particle size when the pigment thus produced was dispersed was about 30 nm or less, and the hue was bluish red.

Separately, crude pigment of γ-type unsubstituted quinacridone 10
Parts, 90 parts of anhydrous sodium sulfate and 1 part of chlorinated aliphatic hydrocarbon were charged into a ball mill and ground for 10 hours. Post-treatments such as pigmentation, filtration, and washing were performed to obtain a press cake. γ
The solid content of the unsubstituted quinacridone pigment was 30%. The obtained press cake was dried and pulverized to obtain a γ-type unsubstituted quinacridone pigment. When the pigment thus produced was dispersed, the average particle diameter was about 200 nm or less, and the hue was yellowish red.

Synthesis Example 2 An aqueous presscake of dichloroquinacridone pigment obtained in the same manner as in Synthesis Example 1 was taken at a solid content of 60 parts and mixed with 40 parts of an aqueous presscake of a γ-type unsubstituted quinacridone pigment at a solid content of 40 parts. After drying and pulverizing, a mixture pigment of dichloroquinacridone and gamma-quinacridone pigment was obtained. The hue showed a magenta color. The average particle size when the mixture pigment was dispersed was about 200 nm or less.

Synthesis Example 3 To 50 parts of dichloroquinacridone pigment, 50 parts of crude γ-type unsubstituted quinacridone pigment was added, and the mixture was ground to obtain a solid solution crude crystal, which was treated with an organic solvent, converted to a pigment, and filtered. After washing, drying and pulverization, a solid solution pigment of dichloroquinacridone and γ-quinacridone was obtained. The hue showed a magenta color. The average particle diameter when the magenta solid solution pigment was dispersed was about 200 nm or less.

Example 1 21 parts of the dichloroquinacridone pigment obtained in Synthesis Example 1 and γ
9 parts of an unsubstituted quinacridone pigment of styrene-methacrylic copolymer resin (softening point: about 110 ° C., glass transition point: about 56
The mixture was kneaded sufficiently with 70 parts of a GPC method weight average molecular weight of about 90,000) using a three-roll mill to disperse the pigment. After cooling, the mixture was crushed to obtain a coarse powder of a magenta high-concentration coloring composition containing a pigment component at a concentration of 30%.

Next, 14.7 parts of the high-concentration coloring composition containing the magenta mixed pigment thus obtained and 3 parts of the chromium complex-based negative charge control agent were used in the above-mentioned styrene-methacrylic copolymer resin 82. .3 parts, kneaded according to a conventional method, cooled, coarsely crushed, finely crushed by a jet mill, and classified to obtain a fine powder of a magenta resin composition of 5 to 20 μm.
Next, colloidal silica was added as a fluidizing agent according to a conventional method and mixed well to obtain a magenta electrophotographic dry developer.

This was mixed with the magnetic iron powder of the carrier, and a monochromatic copy was performed by a negative charge full-color developing electrophotographic copying machine. As a result, a clear magenta image was obtained. The image exhibited a clear and clear magenta color, and exhibited fastness excellent in various physical properties such as light fastness. Further, when copied on a polyester sheet for an overhead projector (hereinafter referred to as OHP), a transparent image was exhibited, and a clear magenta color image was displayed on the OHP screen.

Further, C.I. I. Pigment Blue 15: 3, C.I. I. Pigment Yellow 93, C.I. I. Pigment Black 7 having a mean particle diameter of 0.2 μm or less, respectively, to obtain a cyan developer, a yellow developer, and a black developer in the same manner as described above, respectively, together with the magenta developer obtained above. Color full-color copying was performed to obtain a clear full-color image. Further, the image was copied on an OHP sheet to obtain a full-color image showing a clear full-color image on an OHP screen.

Example 2 According to the pigment melt-flushing method proposed in JP-A-2-175770, 84 parts of a dichloroquinacridone pigment press cake obtained in Synthesis Example 1 (pigment solid content: 25%),
30 parts of a γ-type unsubstituted quinacridone pigment presscake (30% pigment solids) and 70 parts of the styrene-methacrylic copolymer resin used in Example 1 were charged into a heating kneader, mixed, heated with steam, and melted. Flushing was performed. 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 evaporated and removed while heating and kneading. After the kneading was further continued, the kneaded product was taken out of the kneader, cooled and crushed to obtain a coarse powder of a magenta high-concentration coloring composition containing a pigment content of 30%.

Next, 14.7 parts of the high-concentration coloring composition containing the magenta mixed pigment thus obtained and 3 parts of a chromium complex-based negative charge control agent were used in accordance with the method described in Example 1. 82. Styrene-methacrylic copolymer resin
Kneaded with 3 parts, cooled, coarsely crushed, then finely crushed with a jet mill, and classified to obtain a fine powder of a magenta resin composition of 5 to 20 μm, to which colloidal silica was added, mixed, and mixed. A photographic dry developer was used. As a result of mixing with the magnetic iron powder of the carrier and performing monochromatic copying with a negative charge full-color developing electrophotographic copying machine, a clear magenta image was obtained. The image had a clear and clear magenta color. Also, OH
When copied on a polyester sheet for P, a transparent image was exhibited, and a clear magenta image was displayed on the OHP screen.

Further, C.I. I. Pigment Blue 15: 3, C.I. I. Pigment Yellow 93,
C. I. Pigment Black 7 having a mean particle diameter of 0.2 μm or less was used to prepare a cyan developer, a yellow developer, and a black developer, respectively, and four-color full-color copying was performed together with the magenta developer obtained above. And
A clear full-color image was obtained. Further, the image was copied on an OHP sheet to obtain a full-color image showing a clear full-color image on an OHP screen.

Example 3 According to the method of melt-flushing the pigment shown in Example 2, 107 parts (28% of pigment solids) of a solid solution pigment of dichloroquinacridone and γ-quinacridone obtained in Synthesis Example 3 were obtained. 70 parts of the styrene-methacrylic copolymer resin used in Example 1 and a heating type kneader were charged, mixed, and subjected to melt flushing. The separated water was discharged, and the remaining water was removed while heating and kneading to disperse the pigment. The kneaded material was taken out of the kneader, cooled and coarsely crushed to obtain a coarse powder of a magenta high-concentration colored composition containing a pigment content of 30%.

Next, 14.7 parts of the high-concentration coloring composition containing the magenta mixed pigment thus obtained and 3 parts of the chromium complex-based negative charge control agent were used in accordance with the method described in Example 1. 82. Styrene-methacrylic copolymer resin
Knead with 3 parts, cool, coarsely crush, finely crush and classify
A fine powder of a 0 μm magenta resin composition was obtained, and colloidal silica was added and mixed to obtain a magenta electrophotographic dry developer. As a result of mixing with the magnetic iron powder of the carrier and performing monochromatic copying with a negative charge full-color developing electrophotographic copying machine, a clear magenta image was obtained. The image had a clear and clear magenta color. The image was copied on an OHP polyester sheet, and a clear magenta image was displayed on the OHP screen.

Similarly, C.I. I. Pigment Blue 1
5: 3, C.I. I. Pigment Yellow 93, C.I. I. Pigment Black 7 having a mean particle diameter of 0.2 μm or less, respectively, to obtain a cyan developer, a yellow developer, and a black developer in the same manner as described above. Color full-color copying was performed to obtain a clear full-color image. Further, the image was copied on an OHP sheet to obtain a full-color image showing a clear full-color image on an OHP screen.

Example 4 According to the method of melt-flushing the pigment shown in Example 2, 107 parts of a solid solution pigment of dichloroquinacridone obtained in Synthesis Example 3 and γ-quinacridone (pigment solid content: 28%) and Bisphenol type polyester resin for negative charge (softening point approx. 100 ° C) and heated kneader
Mixing and melt flushing were performed. The separated water was discharged, and the remaining water was removed while heating and evaporating to disperse the pigment. The kneaded material was taken out of the kneader, cooled and coarsely crushed to obtain a coarse powder of a magenta high-concentration colored composition containing a pigment content of 30%.

Next, 14.7 parts of the high-concentration coloring composition containing the magenta mixed pigment thus obtained and 3 parts of the chromium complex-based negative charge control agent were used in accordance with the method described in Example 1. 82. Bisphenol-type polyester resin
Knead with 3 parts, cool, coarsely crush, finely crush and classify
A fine powder of a 0 μm magenta resin composition was obtained, and colloidal silica was added as a fluidizing agent and mixed well to obtain a magenta electrophotographic dry developer. As a result of mixing with the magnetic iron powder of the carrier and performing monochromatic copying with a negative charge full-color developing electrophotographic copying machine, a clear magenta image was obtained.
The image had a clear and clear magenta color. The image was copied on an OHP polyester sheet, and a clear magenta image was displayed on the OHP screen.

Similarly, C.I. I. Pigment Blue 1
5: 3, C.I. I. Pigment Yellow 93, C.I. I. Pigment Black 7 having a mean particle diameter of 0.2 μm or less, respectively, to obtain a cyan developer, a yellow developer, and a black developer in the same manner as described above, respectively, together with the magenta developer obtained above. Color full-color copying was performed to obtain a clear full-color image. Further, the image was copied on an OHP sheet to obtain a full-color image showing a clear full-color image on an OHP screen.

Example 5 According to the pigment melt-flushing method described in Example 2, 107 parts of a solid solution pigment presscake of dichloroquinacridone and γ-type unsubstituted quinacridone obtained in Synthesis Example 3 (pigment solid content: 28% ) And 70 parts of a styrene-methacrylic copolymer resin having a tertiary amino group for positive charge and a heating-type kneader, mixed, and subjected to melt flushing.
The separated water was discharged, and the remaining water was removed while heating and kneading to disperse the pigment. The kneaded material was taken out of the kneader, cooled and coarsely crushed to obtain a coarse powder of a magenta high-concentration colored composition containing a pigment content of 30%.

Next, according to the method described in Example 1, 14.7 parts of the high-concentration coloring composition containing the magenta mixed pigment thus obtained and the styrene-methacrylic copolymer resin 85. Kneaded with 3 parts, cooled, coarsely crushed, finely crushed and classified to obtain a fine powder of a magenta resin composition of 5 to 20 μm, to which colloidal silica was added as a fluidizing agent and mixed well. A dry developer was used. As a result of mixing with the magnetic iron powder of the carrier and performing monochromatic copying with a positive charge full-color developing electrophotographic copying machine, a clear magenta color image was obtained. The image had a clear and clear magenta color. The image was copied on an OHP polyester sheet, and a clear magenta image was displayed on the OHP screen.

Similarly, C.I. I. Pigment Blue 1
5: 3, C.I. I. Pigment Yellow 93, C.I. I. Pigment Black 7 having a mean particle diameter of 0.2 μm or less was used to prepare a cyan developer, a magenta developer, and a black developer, respectively, in the same manner as described above, and together with the yellow developer obtained above, Four-color full-color copying was performed by an electrophotographic copying machine for charge full-color development to obtain a clear full-color image. Also, copy it to an OHP sheet,
A full-color image showing a clear full-color image on the HP screen was obtained.

Example 6 30 parts of a magenta mixed pigment of the dichloroquinacridone pigment and the γ-type unsubstituted quinacridone pigment obtained in Synthesis Example 2 were kneaded with 70 parts of a styrene-methacrylic copolymer resin having a tertiary amino group. Thus, a high-concentration colored composition containing a pigment at a concentration of 30% was obtained. Next, this was cooled, coarsely crushed and finely crushed. 10 parts of the obtained magenta resin powder is added to 75 parts of Isopar G together with 15 parts of a methacrylic ester resin soluble in an aliphatic hydrocarbon solvent, glass beads are added, and the mixture is shaken with a paint shaker for 20 hours to be dispersed. A thick colored liquid was prepared. 200 g of this concentrated solution was added and dispersed in 1 liter of Isopar G to obtain an electrophotographic wet developer.

This was copied by a full-color wet electrophotographic copying machine to obtain a clear magenta color copied image. This image showed fastness excellent in various physical properties such as light fastness. or,
C. I. Pigment Blue 15: 3, C.I. I. Pigment Yellow 93, C.I. I. Pigment Black 7 having a mean particle diameter of 0.2 μm or less, respectively, in the same manner as described above, to obtain a cyan wet developer, a magenta wet developer, and a black wet developer, respectively, together with the yellow wet developer obtained above. Then, four-color full-color copying was performed to obtain a clear full-color image. Using the four-color full-color developer described above, a clear full-color image was output by a four-color full-color wet electrostatic plotter.

Example 7 10 parts of the solid solution pigment of dichloroquinacridone and γ-quinacridone obtained in Synthesis Example 3 were combined with 41 parts of ester wax,
41 parts of paraffin wax, 5 parts of styrene-methacrylic copolymer resin and 3 parts of silica were applied as binders to a polyethylene film according to a conventional method to prepare an ink film for magenta thermal transfer recording. This was copied by a full-color thermal transfer copying machine to obtain a clear magenta color copied image. This image showed fastness excellent in various physical properties such as light fastness. Further, when copied on a polyester sheet for OHP, a transparent image was obtained and a clear image was shown on the OHP screen.

Further, C.I. I. Pigment Blue 15: 3,
C. I. Pigment Yellow 93, C.I. I. Pigment Black 7 each having a mean particle diameter of 0.2 μm or less, in the same manner as described above, to obtain cyan, yellow and black thermal transfer ink films, respectively, together with the magenta thermal transfer ink film obtained above, Four-color full-color copying was performed to obtain a clear full-color copied image. Further, the image was copied onto a polyester sheet for OHP to obtain a full-color image showing a transparent full-color image on an OHP screen.

Example 8 5 parts of a magenta mixed pigment of dichloroquinacridone pigment and γ-type unsubstituted quinacridone pigment obtained in Synthesis Example 1, 3 parts of styrene-acrylate-diethanolamine methacrylate copolymer, 22 parts of ethylene glycol, An aqueous pigment dispersion of 8 parts of glycerin and 62 parts of water was prepared, and the pigment coarse particles that could not be dispersed by an ultracentrifuge were removed to obtain an aqueous magenta ink for inkjet. With an on-demand type ink jet printer having a piezo oscillator, image information is printed using the above magenta ink,
A clear magenta image was obtained.

In addition, C.I. I. Pigment Blue 15: 3,
C. I. Pigment Yellow 93, C.I. I. Pigment Black 7 having a mean particle diameter of 0.2 μm or less, respectively, to obtain cyan, yellow and black inkjet inks in the same manner as described above, respectively, together with the magenta inkjet ink obtained above. Color full-color printing was performed to obtain a clear full-color copy image.

[0047]

The coloring composition for image recording according to the present invention uses, as its pigment component, a fine particle pigment of a mixture of a specific range of dichloroquinacridone pigment and γ-type unsubstituted quinacridone pigment. The mixed pigment and the solid solution pigment of the dichloroquinacridone pigment and the γ-type unsubstituted quinacridone pigment are very excellent as a magenta color pigment of a coloring composition for full-color image recording, and have light resistance, heat resistance, solvent resistance, Excellent in various fastnesses such as chemical resistance and water resistance,
Since it has high coloring power, sharpness, sharpness, and transparency, it can be stably manufactured under specific conditions even in the process of manufacturing colored products, and as a result, magenta color image recording finally Even when used as a coloring composition for use, it is possible to stably record a clear, clear, and highly transparent image. Further, even when used as a liquid recording agent, stable recording can be performed for a long period of time. Therefore, the obtained image is clear and shows excellent properties in the above-mentioned fastnesses related to the pigment.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yukio Kamihara 1-7-6 Nihombashi Bakurocho, Chuo-ku, Tokyo Inside Dainippon Seika Kogyo Co., Ltd. (72) Keiji Nakajima 1-7-6 Nihonbashi Bakurocho, Chuo-ku, Tokyo Inside Daiichi Seika Industry Co., Ltd. (72) Inventor Ken Okura 1-7-6 Nihombashi Bakurocho, Chuo-ku, Tokyo Inside Daiichi Seika Industry Co., Ltd. (72) Michie Nakamura 1-7- Nihonbashi Bakurocho, Chuo-ku, Tokyo 6 Dainichi Seika Kogyo Co., Ltd. (56) References JP-A-2-38463 (JP, A) JP-A-55-116758 (JP, A) JP-A-10-219166 (JP, A) JP-A-8 JP-A-34934 (JP, A) JP-A-2-175770 (JP, A) JP-B-37-12832 (JP, B1) JP-B-43-28014 (JP, B1) (58) Fields investigated (Int. . ^7, DB name) C09B 67/20 C09D 11/00 C09D 17/00

Claims (7)

(57) [Claims] An image recording coloring composition comprising a pigment and a resin, wherein a dichloroquinacridone pigment and a γ-type unsubstituted quinacridone pigment are used alone, mixed or in a solid solution together with a grinding medium and / or a grinding aid. A dichloroquinacridone pigment having an average particle size of about 200 nm or less and a γ-type unsubstituted quinacridone pigment having an average particle diameter of about 200 nm or less obtained by impact crushing or grinding alone or mixed or solid-solution pigment is processed at a processing temperature of 120 ° C. or less for image recording. A dichloroquinacridone pigment and γ are obtained by using a solid, paste or liquid high-concentration coloring composition dispersed in a resin binder or a resin solution at a high concentration.
The unsubstituted quinacridone pigment is contained in a ratio of 99: 1 to 1:99, diluted and redispersed in a resin binder or a resin solution, and according to a conventional method for producing a coloring composition for image recording, where necessary. A coloring composition for image recording, characterized by being processed by adding a conventionally known charge control agent, fluidizing agent, ferromagnetic material, solvent medium, aqueous medium and the like. 2. A high-concentration pigment dispersing step at a processing temperature of 120 ° C. or less is performed by kneading the resin binder and the resin at a temperature lower than the melting point or softening point of the resin at normal pressure in the absence of a solvent to convert the aqueous phase pigment into the resin phase. The colored composition for image recording according to claim 1, wherein the method is a method of removing separated water and kneading and evaporating residual water. 3. The coloring composition for image recording according to claim 1, which is a fine powdery dry developer. 4. The coloring composition for image recording according to claim 1, which is a liquid wet developer. 5. The colored composition for image recording according to claim 1, which is an ink for inkjet recording. 6. The colored composition for image recording according to claim 1, which is a thermal transferable image recording agent applied to a substrate such as a film or paper. 7. A dichloroquinacridone pigment and a γ-type unsubstituted quinacridone pigment, each alone, mixed or made into a solid solution, are subjected to impact grinding or grinding with a grinding medium and / or a grinding aid and post-treated with water. Average particle size is about 200nm
The following dichloroquinacridone pigments and γ-type unsubstituted quinacridone pigments are used alone, mixed or in the form of a solid solution, and dispersed at a processing temperature of 120 ° C. or less at a high concentration in a resin binder or a resin solution for image recording to form a solid. , Paste-like or liquid high-concentration coloring composition, using it to contain a dichloroquinacridone pigment and a γ-type unsubstituted quinacridone pigment in a ratio of 99: 1 to 1:99, in a resin binder or a resin solution. Diluted and redispersed, according to a conventional method of producing a color composition for image recording, at that time, if necessary, a conventionally known charge control agent, a fluidizing agent, a ferromagnetic material, a solvent medium, an aqueous medium and the like are added, A method for producing a coloring composition for image recording, which comprises processing.