JPH1149864A - Production of microparticulate colored composition and microparticulate colored composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a colored composition for image recording use such as electrophotographs and electroprinting and electrostatic recording, and also for fluidized dip coating and electrostatic powder coating use, and powder coating materials or resin fine powder-type coating materials, etc. SOLUTION: This microparticulate colored composition is obtained by dissolving or dispersing a dye (and an electric charge control agent) in a polycondensation-based resin component to form a resin composition which, in turn, is pulverized; wherein the due (and the electric charge control agent) is dissolved or dispersed in the resin component by the following alternative means: addition to the stock components for producing the resin component, or addition during the time period from the beginning to ending of the polymerization for the resin component or during molten state of the resin component after ending the polymerization, and the resultant colored composition after dissolution or dispersion is cooled and then pulverized.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coloring composition for image recording such as electrophotography, electronic printing and electrostatic recording, and for fluid immersion coating, electrostatic powder coating, powder coating or resin fine powder. The present invention relates to a method for producing a coloring composition for use as a mold coating agent and the like, and a particulate coloring composition obtained by the method.

[0002]

2. Description of the Related Art Conventionally, in order to obtain a colored composition for image recording, particularly a colored composition for image recording giving an image having a uniform color tone and coloring density, first, a natural resin (raw material resin) is produced by a polymerization reaction. After being cooled to flakes, it undergoes processing such as coarse pulverization, fine pulverization, bag packing, storage, and transportation. Further, in the production of toner for electrophotography and the like, the above-mentioned stored natural resin fine powder for toner and necessary materials such as dyes and, if necessary, charge control agents are respectively weighed based on a prescribed formulation. Then, they are mixed by a mixer such as a tumbler and a Henschel mixer, and then supplied to a resin kneader such as a two-roll mill, a three-roll mill, a kneader or an extruder, and a temperature at least equal to the melting temperature of the resin, For example, a complicated and time-consuming process of melting the resin by heating to 130 to 180 ° C. and kneading and dispersing a dye or a charge control agent in the resin is required, and the heat energy consumption is enormous. It is.

[0003]

DISCLOSURE OF THE INVENTION The present inventors have found the above-mentioned problems relating to the production of a conventional particulate coloring composition, for example, a coloring composition for image recording, the production, packaging, storage and transportation of natural resins. The economical problem of the resin logistics, as well as overcoming the drawbacks such as the complexity of the production process of the particulate coloring composition and the large amount of energy consumption due to the duplication of the process, makes it possible to economically and economically produce a particulate coloring composition having excellent quality. As a result of intensive studies on a production method for mass production in a rational manner, an image having excellent dispersibility of pigments and the like, uniform color tone and coloring density is obtained by simultaneously producing a resin and a particulate coloring composition. Has been found to be economical to provide a particulate colored composition that gives The present inventors have further studied based on such knowledge, and as a result, have completed the present invention.

[0004]

That is, the present invention relates to fine particles comprising dissolving or dispersing a dye or a dye and a charge controlling agent in a condensation polymerization resin component, and forming the resulting resin composition into fine particles. In the method for producing a state coloring composition, the dye or the dye and the charge control agent, a raw material component for producing the resin component, or from the start of polymerization to the end of polymerization of the resin component, or after the end of polymerization While the resin component is in a molten state, it is added to the resin component to dissolve or disperse the dye or the dye and the charge control agent in the resulting resin component, and to obtain the coloring obtained after the dissolution or dispersion. A method for producing a particulate colored composition, comprising cooling the composition and then micronizing the cooled colored composition, and a particulate colored composition obtained by the method.

[0005] In order to use the above-mentioned particulate coloring composition as a dry or wet coloring composition for image recording, the particulate coloring composition is classified as necessary, and
A known auxiliary agent such as a fluidizing agent, a ferromagnetic carrier material or a liquid dispersion medium is mixed.

[0006] Further, the production of a resin and a particulate colored composition,
In particular, by performing the production of the coloring composition for image recording in a streamlined production process that is economically excellent, the conventional natural resin production, logistics, and the production process of the coloring composition for image recording become complicated and heat. An economical and rational fine-grained colored composition that overcomes disadvantages such as mass consumption of energy, is excellent in quality, is particularly excellent in dispersibility of a dye, and can provide an image having a uniform color tone and coloring density. Can be mass-produced.

That is, when the method of the present invention is applied to the production of a colored composition for image recording, simultaneously with the polymerization reaction of a resin component as a binder, a finely dispersed pigment such as a pigment or a charge controlling agent is added. Since the mixture is mixed, a coloring composition for image recording which does not contain coarse particles of the dye and has excellent dispersibility of the dye is provided. Therefore, the image formed by the coloring composition is excellent in clarity and transparency, and the coloring composition for image recording according to the present invention is suitable for copying not only on paper but also on a film for an overhead projector. . In addition to the quality, the method of the present invention has great advantages in the production process and economically. That is, regarding the resin component, all the conventional steps following the polymerization reaction, that is, cooling, crushing, fine pulverization, bagging, storage, transportation, etc. become unnecessary, and a colorant composition for image recording is produced as a developer. In this case, a powder premixing step of a resin component and a colorant or a charge controlling agent, and a subsequent melt-kneading step are not required, so that the manufacturing process is greatly shortened, heat energy is saved, and economically. It has been found that it can greatly contribute to cost reduction.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described below in more detail with reference to preferred embodiments. In the method of the present invention, in producing the particulate coloring composition, it is necessary to dissolve or finely disperse a dye or a charge control agent (hereinafter referred to as a dye) in the resin. By performing the dispersion step during the condensation polymerization step of the resin,
The purpose of the present invention is to rationalize the production process of the particulate coloring composition. Specific examples in which the dissolving or dispersing step is performed during the condensation polymerization step of the resin will be described below.

(1) A method of preliminarily dissolving or finely dispersing a dye or the like in a raw material of a condensation polymerization resin and proceeding a condensation polymerization reaction in the presence of the dye or the like. (2) During the polymerization reaction of the condensation polymerization resin, a dye or the like is added and mixed, for example, the dye or the like is dissolved or finely dispersed in the resin at the oligomer stage, and the polymerization reaction is further advanced to completion. Method. (3) A method in which after the polymerization reaction of the condensation polymerization resin is completed, a dye or the like is added and mixed into the molten resin of the polymerization reaction apparatus, and the dye or the like is dissolved or finely dispersed in the resin. (4) The polymerization reaction is completed, and the condensation-polymerized resin in a molten state is supplied to, for example, an extruder attached to an automatic measuring device, and while the pigment and the like are automatically measured through the automatic measuring device,
Injected and added by the side feeder of the extruder,
A method in which a dye or the like is kneaded and diffused with a resin component in a molten state to dissolve or finely disperse the dye or the like. Etc., which are very preferable methods.

The extruder used in the above method (4) is, for example, a single screw extruder of a screw type, a twin screw extruder rotating in the same direction or a different direction, a multi-screw extruder, or a rotor type extruder. A twin-screw kneader, a single-screw or multi-screw continuous kneader, and the like can be given. In these extruders, various segments such as a screw, a kneading disk, and a rotor can be freely rearranged, and the length and shape of the cylinder may be changed. Further, these extruders may be used in combination. Further, the extruder may be provided with a vent port as necessary, and in some cases, may be evacuated.

The dye or the like added in the above method is a high-concentration composition in which the dye or the like is finely dispersed in a high concentration in advance in a part of the resin component raw material, an oligomer of the resin component and / or a part of the resin component. Can be used as This is preferable in that it is kneaded with a resin component in a molten state, diffuses a dye or the like into the resin component, and dissolves or finely disperses the dye or the like in the resin component. In the above method, the condensation polymerization resin in which a dye or the like is added and dispersed can be made into fine particles by selecting a conventionally known fine pulverizing method appropriate for each purpose of use of the fine particle colored composition.

When the particulate coloring composition is used in a dry developer or the like, the pulverization is often performed by a pulverization method using a dry jet pulverizer. The particle size of the dry developer is about 3 to 20 μm, preferably about 5 to 10 μm in average particle diameter.
m. In the case of a wet developer, that is, in the case of finely pulverizing with an aqueous system and then drying to obtain a wet developer, the fine particles are formed by a fine pulverization method using a wet medium disperser. The average particle size of the wet developer is about 0.5 to 10 μm
m, preferably about 1-5 μm. Even in the case of finely pulverizing with an aqueous wet medium dispersing machine and drying to obtain a dry developer, the particle size of the finely pulverized product is also about 3 to 3 in average particle diameter.
It is 20 μm, preferably about 5 to 10 μm.

[0013] The resin component used in the present invention is preferably a resin mainly composed of a polyester resin, particularly a polyester resin mainly composed of an aromatic diol component or an alicyclic diol component and a dicarboxylic acid component. Is particularly preferred because it has a high glass transition point, a relatively low melting point and a low melt viscosity. The high glass transition point of the resin is in the summer season, hot area or hot workplace, etc.
It exhibits excellent durability against the blocking phenomenon that solidifies during storage or use of the particulate coloring composition (eg, toner) in a high-temperature use environment, and has a relatively low melting point and low melt viscosity of the resin. Is inconsistent with its properties, but is excellent in properties such as fixing and sharpness of color development when an image is formed on a substrate such as paper or film. In addition, this property is such that a low-viscosity molten state is produced in a condensation polymerization apparatus or an extruder, and an added dye or the like is uniformly dissolved or finely dispersed in a molten resin component. be able to.

The diol component as a main raw material of the polyester resin used in the present invention includes an alkylene oxide adduct such as bisphenol A, bisphenol F, bisphenol AF or bisphenol S (provided that the alkylene chain is C ₂ -C ₄ ), Hydrogenated alkylene oxide adducts, bis (hydroxymethyl)
Naphthalene, bis (hydroxymethyl) deurene, p
-Xylylene glycol, bis (hydroxyethoxy)
It is at least one selected from the group consisting of benzene, bis (α-hydroxyisopropyl) benzene, and bis (hydroxymethyl) cyclohexane. Further, if necessary, a known diol component such as ethylene glycol, diethylene glycol, propylene glycol, or dipropylene glycol may be used in combination.

The dicarboxylic acid component as a main raw material of the polyester resin includes terephthalic acid, isophthalic acid,
4,4'-biphenyldicarboxylic acid, naphthalene-2,
Aromatic, alicyclic and aliphatic dicarboxylic acids such as 6-dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,2-cyclohexenedicarboxylic acid, methylnadic acid, fumaric acid and maleic acid It is at least one selected from the group consisting of acids and their lower alkyl esters, acid halides, and acid anhydrides.

Among the above-mentioned dicarboxylic acids, a dicarboxylic acid which is particularly preferable as a raw material of the polyester resin of the present invention is an aromatic or alicyclic compound having properties such as a high glass transition point and a sharp melt property resulting from the high crystallinity of the resin. 1,4
And dicarboxylic acids having symmetrical positions, such as dicarboxylic acids, and aliphatic low molecular weight dicarboxylic acids having 2 to 3 carbon atoms.

The production of a polyester resin using the aromatic diol component and the dicarboxylic acid component as main raw materials is carried out according to a usual method for producing a polyester resin. To give an example, an aromatic diol component and a dicarboxylic acid are added to a condensation polymerization reactor equipped with a raw material inlet, a stirrer, a thermometer, a nitrogen gas inlet pipe, and a moisture meter with a cooling condenser connected to a pressure reducing device. Ingredients are charged, heated and stirred, and while being dehydrated, 100 ° C to 250 ° C.
A dehydration condensation reaction is carried out at about 5 ° C. for about 5 to 7 hours, and if necessary, a condensation polymerization reaction is further continued under a reduced pressure for 1 to 3 hours to complete the reaction, thereby obtaining a polyester resin used in the present invention. Conventionally known condensation catalysts can be used, but zinc acetate, antimony trioxide, tetrabutyl titanate and the like are preferred.

Preferred characteristics of the resin component used in the method for producing the particulate colored composition of the present invention include a glass transition point of about 50 ° C. or higher, and particularly preferably 50 to 65 ° C.
° C, the softening point is about 100-150 ° C, preferably 100-150 ° C.
It is a solid resin at room temperature with a sharp melt property of 130 ° C. Also, the average molecular weight is about 1,000 to 50,000, preferably about 5,000 to 10,000, so that the viscosity of the melt is markedly lower than that of ordinary thermoplastic resins.

The pigments used in the present invention include conventionally used chromatic or black oil-soluble dyes, disperse dyes, organic pigments, carbon black pigments, inorganic pigments, fine ferromagnetic materials, and white organic pigments and inorganic pigments. A pigment selected from pigments. As the pigment used in the present invention, conventionally known chromatic colors and black or white pigments are used.
Pigments such as perylene, indigo / thioindigo, dioxazine, quinacridone, isoindolinone, aniline black and iron oxide pigments, fine ferromagnetic materials,
Spinel structure pigments, carbon black pigments, titanium oxide pigments and the like.

Particularly preferred pigments include cyan pigments such as C.I. I. Pigment Blue 15: 3, C.I.
I. Pigment Blue 16, phthalimidomethyl-substituted copper phthalocyanine blue, etc. I. Pigment Red 122, γ-type unsubstituted quinacridone, solid solutions thereof and the like, and yellow pigments such as C.I. I.
Pigment Yellow 93, 94, 128, 166, 16
7, 139, 185, disanthraquinonyl-monophenylamino-s-triazine and the like. I. Pigment Black 7, 6, JP-A-4-275
No. 47, azomethine azo black pigments, etc., and these pigments are used alone or in combination.
The ferromagnetic material is a conventionally known ferromagnetic material selected from chromatic or black magnetic iron oxide, magnetic metal, magnetic chromium oxide and the like.

As the charge control agent, those conventionally used are also used in the present invention. As the negative charge control agent, salicylic acid or its derivatives chromium, aluminum,
Examples of positive charge control agents such as metal complex salts such as zinc and azo complex dyes include nigrosine, tertiary amino compounds and quaternary amino compounds.

The content of the coloring matter and the charge controlling agent in the particulate coloring composition varies depending on the type of the particulate coloring composition, but may be the same as the content of each conventionally known particulate coloring composition. When the particulate coloring composition of the present invention is used as a dry developer for electrophotography, the content of the dye is about 1% to 20% by weight, preferably about 2% to 8% by weight. The content of the control agent is about 1% by weight or more.
It is 10% by weight, preferably about 2% to 6% by weight.
When the particulate coloring composition of the present invention is used in a wet developer for electrostatic recording, the content of the dye is about 1 in a concentrated stock solution.
% To 20% by weight, preferably 3% to 10% by weight
Usually, it is used after diluting with a diluent to a volume of 10 to 30 times.

As described above, a high-concentration composition in which a coloring material or the like to be used is dissolved or finely dispersed at a high concentration in a resin component such as the above-mentioned polyester-based resin or a resin easily compatible therewith is used. Use in form is also a very preferred method. Such a high-concentration composition contains a pigment and the like in a high concentration, and disperses the pigment and the like by sufficiently kneading the components in advance, or by toning, thereby facilitating the subsequent steps. Yes, it may be in the form of solid such as coarse particles, coarse powder, fine powder, sheet, or small lump, or any form of paste or liquid. The content of the pigment and the like in the high concentration composition is about 10% by weight to 70% by weight, preferably 2% by weight.
It is about 0% to 60% by weight.

As a method for producing the above-mentioned high-concentration composition such as a dye, a dry heat-kneading dispersion method and ceramic beads,
There is a method using a wet medium dispersion method using glass beads, steel balls, or the like. In particular, as a method of dispersing a pigment or the like at a high concentration in a resin, a two-roll, three-roll, heating kneader, a pressure heating kneader, a single-screw extruder, using a kneading and dispersing machine such as a twin-screw extruder to reduce the resin. A method of melting and kneading and dispersing a dye or the like is preferable.

The most preferred method for dispersing the dye or the like at a high concentration is a method of flushing an aqueous paste of the dye or the like with a molten resin (melt flushing method), for example, a method proposed in JP-A-2-175770. And so on. Specifically, the aqueous press cake of the dye and the resin are charged into a kneader or flasher capable of steam heating without using any solvent, and kneaded at normal pressure to transfer the dye and the like in the aqueous phase to the resin phase, and separated. In this method, the remaining water is removed, and the remaining water is kneaded and evaporated.

As the carrier resin for producing the high-concentration composition such as the above-mentioned pigments, resins having the same or the same kind as well as resins compatible with these polyester resins can be used. For example, polystyrene, styrene
(Meth) acrylic acid ester copolymers, styrene-maleic acid ester copolymers, (meth) acrylic acid ester polymers and addition polymerization resins such as copolymers, epoxy resins and various waxes. . Preferred among the above resins are those having a glass transition point of about 50 ° C. or higher and a softening point of about 90 ° C. to 150 ° C., preferably 100 ° C. to 130 ° C.
It is a resin that is solid at room temperature.

The condensation polymer-based resin containing the coloring matter and the like obtained as described above is then cooled, turned into fine particles, and when used as a coloring composition for image recording (toner or developer), it is necessary to use a conventional method. And a known auxiliary such as a fluidizing agent, a ferromagnetic material of a carrier or a liquid dispersion medium is added and mixed.

The particulate colored composition obtained according to the present invention may be used in addition to a colored composition for image recording, for fluid immersion coating,
It is also useful as a colored coating coloring composition for electrostatic powder coating, powder coating or resin fine powder type coating agent. In particular, it is suitable for use in JP-A-10-120945 "Powder coating, powder coating method, and powder coated article".

[0029]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the following description, “parts” and “%” are based on weight unless otherwise specified.

Example 1 (1) Preparation of High Concentration Blue Pigment-Diol Dispersion A copper phthalocyanine blue pigment (CI pigment blue 15: 3) was added to 80 parts of a propylene oxide adduct of bisphenol A (hydroxyl number: 321). After adding 17 parts and 3 parts of phthalimidomethylated copper phthalocyanine blue (the number of phthalimidomethyl groups, average 2 / mol), stirring and mixing, the pigment is finely dispersed using a three-roll mill to obtain a high-concentration blue pigment dispersion. Was prepared. As a result of observing this with a microscope, all the pigment particles are finely dispersed,
No coarse particles were found. (2) Production of high concentration charge control agent-resin composition 70 parts of fine powder of polyester resin (number average molecular weight: about 6,000) obtained by condensation polymerization of propylene oxide adduct of dimethyl terephthalate and bisphenol A, and a chromium complex salt The mixture was preliminarily mixed with 30 parts of a system negative charge control agent by a high-speed mixer, kneaded by a heated three-roll mill, cooled, and pulverized to prepare a fine powder of a high-concentration charge control agent composition.

(3) Condensation Polymerization Reaction of Polyester Resin Bisphenol was added to a moisture meter equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, a flexible tube condenser connected to a pressure reducing device, and a condensation polymerization reactor equipped with a raw material inlet. A propylene oxide adduct (hydroxyl number: 321) 7
83 parts were charged and, with stirring, 315 parts of the high-concentration blue pigment-diol dispersion obtained in the above (1) was added, and then 536 parts of dimethyl terephthalate and 0.27 parts of zinc acetate were charged. The mixture was stirred and heated to carry out a condensation reaction at 230 ° C. to 240 ° C. for about 6 hours, and further continued the condensation reaction under reduced pressure for 2 hours to complete the reaction. Further, 150 parts of the fine powder of the high concentration charge control agent-resin composition obtained in the above (2) was added and mixed to uniformly disperse the charge control agent. The softening point of the polyester resin component of the obtained blue colored polymer is about 10
The glass transition point was 5 ° C., about 59 ° C., and the number average molecular weight was about 6,000.

(4) Production of Blue Image Recording Agent Next, the blue colored polyester resin is taken out from the polymerization reactor, formed into a thin film by a cooling roll, cooled by a cooling belt, crushed into flakes, and finely crushed by a jet mill. It was pulverized and classified to obtain fine powder of a blue resin composition having an average particle diameter of about 7 μm. Colloidal silica was added as a fluidizing agent according to a conventional method, and mixed with magnetic iron powder as a carrier to obtain a cyan electrophotographic dry developer. Using the cyan electrophotographic dry developer obtained above and copying with a negative charge two-component dry electrophotographic copying machine, a clear cyan image was obtained.

Example 2 (1) Production of a high-concentration diol dispersion of red, yellow, and black pigments According to the method described in Example 1, (1), using the materials shown in Table 1, the pigment content was 20%. % Of a high concentration diol dispersion of red, yellow and black pigments was prepared.

[0034]

[Table 1] Table 1

(2) Condensation Polymerization Reaction of Colored Polyester Resin and Production of Image Recording Agent According to the method described in (3) of Example 1, condensation polymerization was carried out using the materials shown in Table 2 for each color, and the reaction was carried out. After completion, the high-concentration charge control agent-resin composition of (1) of Example 1 was added and mixed uniformly. Next, the colored polyester resin was taken out in the same manner as in (4) of Example 1, cooled, crushed and finely pulverized, and a fluidizing agent and magnetic iron powder were added.
Magenta, yellow and black electrophotographic dry developers were prepared.

Using the three-color dry developer of Example 2 obtained above, each was copied by a negative charge two-component dry electrophotographic copying machine, and clear color images shown in Table 2 were obtained. Further, using the cyan developer prepared in Example 1 and the magenta, yellow, and black developers of Example 2 to make a copy using a negative-charge two-component full-color developer copier, a clear image was obtained. Four full-color images were obtained. In the same manner, when a copy was made on a transparent polyester film for an overhead projector, a four-color full-color image showing a clear image on a screen was obtained. Similarly, a clear full-color copy image was output using a four-color full-color dry electrostatic plotter using the four-color full-color dry developer.

[0037]

[Table 2] Table 2: Materials used in the production of image recording agents and colors of images

Example 3 (1) Production of High Concentration Pigment-Resin Composition According to the formulation shown in Table 3 below for each color, the fine powder of the bisphenol-type polyester resin used in (2) of Example 1 was prepared. After pre-mixing the corresponding pigment with a high-speed mixer, the mixture is sufficiently kneaded with a heated three-roll mill, cooled and pulverized to obtain a high-concentration pigment content containing a total of 30% pigment-fine powder of a resin composition. I got This was placed on a slide glass, heated and melted, and observed with a microscope. As a result, all the pigment particles were finely dispersed, and no coarse particles were observed.

[0039]

[Table 3] Table 3

(2) Condensation Polymerization Reaction of Colored Polyester Resin and Production of Image Recording Agent For each color, the condensation polymerization reaction apparatus used in (3) of Example 1 was used to prepare a bisphenol type resin according to the formulation shown in Table 4 below. Charge the raw materials of polyester resin and stir 2
The condensation reaction was performed at 30 ° C. to 240 ° C. for about 6 hours, and further continued for 2 hours under reduced pressure. The polymerization reactor was returned to normal pressure, and the molten polymer was charged with the high-concentration pigment dispersion-resin composition obtained in (1) and the high-concentration charge control agent-resin composition obtained in (2) of Example 1. The fine powder was added, thoroughly stirred and mixed to uniformly disperse the pigment and the charge control agent.

Next, the colored polyester resin was taken out of the polymerization reactor in the same manner as in (4) of Example 1, formed into a thin film with a cooling roll, cooled with a cooling belt, crushed into flakes, and finely crushed with a jet mill. It was pulverized and classified to obtain a fine powder of a colored resin composition having an average particle diameter of about 7 μm. Colloidal silica was added as a fluidizing agent according to a conventional method, and mixed with the magnetic iron powder of the carrier. As described above, electrophotographic dry developers of cyan, magenta, yellow and black were obtained, respectively.

Examples 1 and 2 using the cyan, magenta, yellow and black electrophotographic dry developers obtained above.
When a copying machine was used in a copying machine for a two-component full-color developer with negative charge in the same manner as described above, clear single-color and four-color full-color images were obtained. When a transparent polyester film for an overhead projector was copied in the same manner, a four-color full-color image showing a clear image on a screen was obtained. Similarly, a clear full-color copy image was output using a four-color full-color dry electrostatic plotter using the four-color full-color dry developer.

[0043]

[Table 4] Table 4

Example 4 (1) Production of Polyester Resin The propylene oxide adduct of bisphenol A 1,113 was added to the condensation polymerization reactor used in (3) of Example 1.
Parts, 577 parts of dimethyl terephthalate and 0.1 part of zinc acetate.
29 parts were charged and a condensation reaction was carried out at 230 to 240 ° C. for about 6 hours with stirring, and further continued for 2 hours under reduced pressure to complete the reaction. The obtained bisphenol-type polyester resin had a number average molecular weight of about 7,000, a softening point of 105 ° C, a glass transition point of 55 ° C, and a viscosity of the molten resin at 125 ° C of about 1,600 poise.

(2) Production of developer by kneading of extruder In order to produce a full-color dry developer for electrophotography using a twin-screw extruder equipped with a side feeder, the amount of polyester resin discharged from the extruder was determined in advance. Is set, and the automatic weighing device of the side feeder is adjusted so as to have the following blending amount according to the setting.

For each color, the bisphenol type polyester resin obtained in the above (1) is supplied to the above twin screw extruder from a hopper through an automatic metering device in a molten state from a condensation polymerization reactor. In addition, the pigment high-concentration dispersion-resin composition of the corresponding color obtained in Example 1 (1) by an automatic weighing device from the middle of the extruder cylinder so that the materials are as shown in Table 5 below. And the powder of the high-concentration charge control agent-resin composition obtained in (2) of Example 1 were respectively automatically supplied in a fixed amount, injected and added by a side feeder, and kneaded with the polyester resin component in a molten state. In this way, a coloring composition for image recording having a good dispersibility of the dye and having a uniform color tone and density could be obtained.

[0047]

[Table 5] Table 5

Example 5 The phenol oxide adduct of bisphenol A and dimethyl terephthalate used in place of the bisphenol-type polyester resin used in accordance with the method described in the method for producing the developer in Examples 1 to 4 described above. Blue, magenta, yellow, and black electrophotographic dry developers were similarly produced using bisphenol-type polyester resins obtained using the materials shown in Table 6. When a four-color dry developer obtained by using each bisphenol-type polyester resin was used to copy using a negative-charged two-component full-color developer copier, the images were sharp as in Examples 1-4. A single-color image and a four-color full-color image were obtained. Similarly, when the image was copied on a transparent polyester film for an overhead projector, an image showing a clear image on the screen was obtained. Similarly, a clear full-color copy image was output using a four-color full-color dry electrostatic plotter using the four-color full-color dry developer.

[0049]

[Table 6] Table 6

Example 6 A blue polyester resin was taken out from the polymerization reactor of Example 1 (3), formed into a thin film with a cooling roll, cooled with a cooling belt, crushed into flakes, and finely crushed with a crusher. did. 10 parts of the obtained blue resin powder was added to 87 parts of Isopar G (trade name, manufactured by Exxon) together with 3 parts of a methacrylic ester-based resin soluble in an aliphatic hydrocarbon-based solvent, and a continuous horizontal type using ceramic beads as a rotating medium. After adding to the disperser, the mixture obtained above was dispersed therein to prepare a concentrated blue stock solution having an average particle diameter of about 3 μm. This concentrated undiluted solution 20
0 volume parts was added to 1000 volume parts of Isopar G to obtain an electrophotographic wet developer.

Similarly, the magenta, yellow and black polyester resins were respectively taken out from the polymerization reactor of Example 2 (2), formed into a thin film with a cooling roll, cooled with a cooling belt, and then roughly crushed into flakes. And pulverized with a pulverizer. For each color, the resulting resin powder 10
Parts were added to 87 parts of Isopar G along with 3 parts of a methacrylic ester-based resin soluble in an aliphatic hydrocarbon-based solvent, and ceramic beads were added to a continuous horizontal dispersing machine as a rotating medium. Dispersed. In this way, concentrated magenta, yellow and black stock solutions each having an average particle size of about 3 μm were prepared. 200 parts by volume of this concentrated stock solution
Magenta, yellow and black electrophotographic wet developers were obtained in addition to 1000 parts by volume of Isopar G, respectively.

When this was copied by a wet electrophotographic copying machine, clear cyan, magenta, yellow and black copied images were obtained. Using the above-described cyan, magenta, yellow, and black wet developers, a 4-color full-color wet electrophotographic copying machine was used to obtain a clear full-color copied image. Similarly, a clear full-color copy image was output by a four-color full-color wet electrostatic plotter using the four-color full-color wet developer described above.

[0053]

According to the present invention, a coloring composition for image recording such as electrophotography, electronic printing and electrostatic recording, and a fluid immersion coating, an electrostatic powder coating, a powder coating or a resin fine powder. It is possible to provide a particulate colored composition useful for a mold coating agent and the like.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C09D 167/02 C09D 167/02 G03G 5/08 331 G03G 5/08 331 9/087 9/08 381 9/12 9/12 / / C08L 67:00 (72) Inventor Masayuki Takahashi 1-7-6 Nihombashi Bakurocho, Chuo-ku, Tokyo Dai-Nissei Chemical Industry Co., Ltd. (72) Inventor Yukio Kamihara 1-7-6 Nihonbashi Bakurocho, Chuo-ku, Tokyo Daisei Chemical Industry Co., Ltd. (72) Inventor Masayuki Kanno 1-7-6 Nihombashi Bakurocho, Chuo-ku, Tokyo Dai-Nippon Kagaku Kogyo Co., Ltd. (72) Yoshimasa Nakamura 1-7-6 Nihonbashi Bakurocho, Chuo-ku, Tokyo Large Inside Nissei Chemical Industry Co., Ltd. (72) Inventor Keiji Nakashima Inside Nisashi Chemical Industry Co., Ltd.

Claims (11)

[Claims] 1. A method for producing a particulate colored composition, comprising dissolving or dispersing a dye or a dye and a charge control agent in a condensation polymerization resin component, and forming the resulting resin composition into fine particles. A dye or a dye and a charge control agent, a raw material component for producing the resin component, or from the start of polymerization to the end of polymerization of the resin component, or while the resin component is in a molten state after completion of the polymerization. , Added to the above resin component, the dye or the dye and the charge control agent are dissolved or dispersed in the resin component to be formed, and the coloring composition obtained after the dissolution or dispersion is cooled, and then cooled to be colored. A method for producing a particulate colored composition, comprising forming the composition into fine particles. 2. The method according to claim 1, wherein the fine particles are formed by a dry jet pulverizer or a wet medium disperser. 3. The method according to claim 1, further comprising adding at least one additive selected from a fluidizing agent, a ferromagnetic carrier material, and a liquid dispersion medium at any time. 4. A dye or a dye and a charge controlling agent are dissolved or finely dispersed in a high concentration in advance in a part of the raw material component of the resin component, a part of an intermediate of the resin component, and a part of the resin component. The method for producing a particulate coloring composition according to claim 1, wherein the composition is a highly concentrated composition. 5. The method according to claim 1, wherein the pigment is selected from the group consisting of oil-soluble dyes, disperse dyes, organic pigments, inorganic pigments, carbon black pigments, and ferromagnetic materials. 6. The method for producing a particulate colored composition according to claim 1, wherein the resin component is a resin mainly composed of a polyester resin. 7. A diol component, which is a raw material of a polyester resin, is an alkylene oxide adduct of bisphenol A, bisphenol F, bisphenol AF or bisphenol S (where the alkylene chain is C ₂ -C ₄ ), From the group consisting of hydrogenated products, bis (hydroxymethyl) naphthalene, bis (hydroxymethyl) deurene, p-xylylene glycol, bis (hydroxyethoxy) benzene, bis (α-hydroxyisopropyl) benzene, bis (hydroxymethyl) cyclohexane At least one selected compound; wherein the dicarboxylic acid component is terephthalic acid, isophthalic acid, 4,4'-biphenyldicarboxylic acid, naphthalene-
2,6-dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,2
7. The fine particle according to claim 6, which is at least one compound selected from the group consisting of cyclohexenedicarboxylic acid, methylnadic acid, fumaric acid, maleic acid and lower alkyl esters thereof, acid halides and acid anhydrides. 8. A method for producing a coloring composition. 8. A particulate coloring composition produced by the method according to claim 1. Description: 9. The particulate coloring composition according to claim 8, which is a dry or wet coloring composition for image recording. 10. The particulate coloring composition according to claim 8, which is a recording agent for dry or wet electrophotography, electronic printing or electrostatic recording. 11. The particulate colored composition according to claim 8, which is used for fluid immersion coating, electrostatic powder coating, powder coating, or resin fine powder type coating agent.