JPH10306216A - Coloring agent composition, its production thereof, electrophotographic developing agent and ink jet recording ink - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition capable of using for a coating material, an ink, an electrophotography, an ink jet recording, etc., and excellent in dispersion stability, amount of an electric charge, polarity regulating property, coloring power and transparency by containing a specific compound as a pigment and a resin. SOLUTION: This coloring agent composition is obtained by containing (A) 1-80 pts.wt. [approximately 80-10 wt.%, preferably 60-30 wt.% in the composition of a solid state, a paste state or a liquid state containing the pigment in a high concentration, and in the case of using as a coloring agent for an electrophotographic developing agent, approximately 15-2 wt.%, preferably 10-3 wt.%] pigment as a compressed by the formula (R1 to R4 are each a 1-12C alkyl or an alkoxy; R5 , R6 are each hydroxyl, carboxyl, sulfo or a halogen) and (B) a resin as a polyolefin or a copolyolefin, and produced by preferably a flushing method.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a colorant composition used for paints, printing inks, electrophotography, electrostatic printing, ink jet recording, and the like.

[0002]

2. Description of the Related Art Generally, the chargeability of a dye such as an organic pigment or a dye varies depending on its structure due to friction with a carrier used for electrophotographic development. For example, a copper phthalocyanine blue pigment, a quinacridone pigment, and the like exhibit positive chargeability due to friction with a carrier, and a copper phthalocyanine green pigment and the like exhibit negative chargeability.

[0003] In the case of a wet developing method, a wet (liquid) developer is used for visualizing an electrostatic latent image formed by an electrophotographic method such as an electrophotographic method or an electrostatic recording method. Wet developers are generally used as a carrier liquid in a high-insulating, low-dielectric organic solvent to disperse a colorant or resin called a toner, a dispersion stabilizer such as a surfactant, or a polarity controller such as a metal salt of naphthenic acid or lecithin. During use or storage, the toner is required to show a clear polarity in the developer and to be stably dispersed.

Conventionally, colorants used for coloring such toners include inorganic pigments such as carbon black, phthalocyanine blue, sky blue, rhodamine lake, malachite green lake, methyl violet lake, peacock blue lake, and naphthol. Organic pigments such as Green B, Naphthol Green Y, Naphthol Yellow S, Permanent Red 4R, Brilliant Fast Scarlet, Hansa Yellow and Benzidine Yellow are known, but many of them have poor dispersibility and have polarity controllability. Therefore, when used or stored for a long period of time in a liquid developer using these pigments, the dispersion stabilizer and the polarity controlling agent dissolve in the carrier liquid, do not lose their functions, and may cause aggregation of toner. , The polarity is unclear and the image quality There was one drawback that lead to below.

Therefore, in order to improve such disadvantages,
Proposals have been made to apply a surface treatment to the pigment or to graft carbon black to give the pigment itself dispersibility and polarity controllability, but no satisfactory results have yet been obtained. In addition, conventional colorants are inferior in transparency and tinting strength, and are not satisfactory for use in color toners.

In connection with these problems, for example, Japanese Patent Publication No. 58-9418 proposes an electrophotographic liquid developer containing a thioindigo pigment, which is a full color magenta pigment. Although it can be used for toner, it has a weak red tint and is not preferable for magenta in terms of spectral characteristics.

Further, Japanese Patent Application Laid-Open Nos. 49-99033 and 4
As described in JP-A-9-134333 and JP-A-46-1636, toners in which SiO ₂ or a resin is dyed with a dye have been proposed. However, these liquid toners have the drawbacks that the coloring power is weak and the image density is low.

[0008]

When a dye is used in a developer for an electrophotographic copying machine, the dye is dispersed in a resin dispersion medium together with other additives as required, and then finely pulverized.
Therefore, the surface of the crushed particles is inevitably affected by the pigment used. In particular, when a pigment is used, crushing occurs at the interface between the pigment and the resin, and the surface of the pigment may be exposed on the particle surface. Further, in the developer of the electrophotographic copying machine, the dye used in the developer is also limited depending on the hue and color tone of the copy image required. Therefore, for example, in a developer having a negative charge property, when a dye used in the developer has a positive charge property upon friction with a carrier, a negatively chargeable developer is exposed when the dye surface is exposed on the developer particle surface. There is a defect that positively charged portions are mixed therein and the chargeability is lacking in uniformity. The present invention has been made in view of such circumstances, and can be used for paints, inks, electrophotography, ink jet recording, and the like, and has dispersion stability, charge amount of particles, polarity controllability, coloring power, and transparency. It is an object of the present invention to obtain a colorant composition excellent in odor.

[0009]

According to the present invention, first, in a colorant composition containing at least a dye and a resin, the dye is a compound represented by the following general formula (1). Is provided.

Embedded image (In the formula, R _{1 to} R ₄ represent an alkyl group or an alkoxy group having 1 to 12 carbon atoms, and R ₅ and R ₆ represent a hydroxyl group, a carboxyl group, a sulfo group or a halogen.) The colorant composition according to the first aspect, wherein the content of the dye is 1 to 80% by weight. Thirdly, there is provided a colorant composition according to the first aspect, wherein the resin is a polyolefin or a polyolefin copolymer. Fourthly, there is provided a method for producing a colorant composition, which comprises producing the colorant composition according to any one of the first to third aspects by a flushing method. Fifth, an electrophotographic developer characterized by containing the colorant composition described in any of the above first to third or the colorant composition produced by the production method described in the fourth above. Provided. Sixth, the first ~
An electrophotographic wet developer comprising the colorant composition described in any of the third or the colorant composition produced by the production method described in the fourth aspect is provided. Seventh, an inkjet recording ink comprising the colorant composition described in any one of the first to third aspects or the colorant composition produced by the production method described in the fourth aspect, Provided.

Hereinafter, the present invention will be described in detail. The present inventors have conducted various studies on the structure of a dye, and found that by using a dye represented by a specific structural formula as a colorant for a developer, an excellent effect can be exhibited even under the above-described conditions. Thus, the present invention has been completed. That is, the present invention is characterized in that in the colorant composition containing at least a dye and a resin, the compound represented by the general formula (1) is used as the dye.

Table 1 shows specific examples of the dye represented by the general formula (1).

[0012]

[Table 1]

Next, the preparation of the colorant composition of the present invention using the dye represented by the general formula (1) is carried out as follows.

The aqueous solution of the dye is further mixed well with the resin solution in a kneader called a flasher. As a result, water present around the pigment is replaced by the resin solution. The water is discarded from the kneader, and the dispersion of the pigment in the resin solution is dried to remove the solvent, thereby obtaining a lump.

Next, the powder of the colorant is obtained by crushing the lumps. This coloring agent is a pigment coated with a resin in a state of primary particles, and is used for printing ink, paint,
It is useful for toner for electrostatic photography. For example, to prepare a liquid developer for electrostatography using the colorant produced as described above, the colorant may be dispersed in a carrier liquid together with a binder resin.

As the carrier liquid, a high insulating property (electric resistance of 10
Petroleum aliphatic hydrocarbons having a low dielectric constant (dielectric constant of 3 or less), n-hexane, ligroin, n-heptane, n-pentane, isododecane, isooctane and the like, and halogen derivatives thereof, for example, Examples include carbon chloride and perchlorethylene. Note that commercially available petroleum aliphatic hydrocarbons include Isoper E, Isopar G, Isopar L, Isopar H, manufactured by Exxon.
Isopar K, Naphtha No. 6, Solvesso 100 and the like. These are used alone or in combination.

<Preparation Example A of Colorant Composition> 50 parts by weight of water,
25 parts by weight of the dye compound (No. 1 in Table 1) was taken with a flasher and mixed and dispersed well. Next, an ethylene-vinyl acetate copolymer (Evaflex 210 manufactured by Du Pont-Mitsui Co., Ltd.) was added to 80
And 100 parts by weight of toluene, and dispersed at 100 ° C. for 2 hours. After dispersion, the pressure was reduced to remove water and toluene, and the mixture was pulverized to obtain a flushing colorant composition.

When the dye of the general formula (1) is used by dispersing it in a resin, any conventionally used resin dispersion medium can be used. For example, polystyrene, styrene- (meta- ) Acrylate ester copolymer, styrene-maleate ester copolymer, (meth) acrylate ester copolymer, styrene-diene copolymer, polyethylene, polypropylene, ethylene-
Vinyl acetate copolymers, addition polymerization resins such as ethylene-acrylate copolymers, polyester resins, epoxy resins, condensation resins such as phenolic resins, rosin esters, modified resins such as maleated rosin esters, Low molecular solids such as petroleum resins, higher fatty acid waxes, higher alcohols, higher fatty acids, paraffin wax, lunava wax and shellac can be used alone or in combination. However, polyolefins or polyolefin copolymers such as polyethylene, polypropylene, ethylene-acrylate copolymer, and ethylene-maleic anhydride copolymer are preferable in view of dispersibility.

In the present invention, the content of the dye represented by the structural formula in the colorant composition containing the resin dispersion medium and other additives varies depending on the purpose of use. In a solid, paste or liquid composition containing a high concentration, about 80% by weight to 1%
0% by weight, preferably 60% to 30% by weight;
When used as a colorant in an electrophotographic developer, about 1
5% to 2% by weight, preferably 10% to 3% by weight
And the most preferred content depending on the purpose.

The colorant composition for image recording of the present invention can be used in various ways depending on the purpose. One example is to contain the pigment at a high concentration, and to make the subsequent steps easier by preliminarily kneading and dispersing or performing toning, etc., and coarse particles, coarse powder, fine powder, sheet It can be used in any form such as solid, small lump or the like, or paste or liquid.

Another example is a composition used as a final developer for image recording, which is a so-called dry developer, wet developer, electrostatic developer or the like. It is classified into a component developer and a one-component developer. A ferromagnetic material is mainly used for a one-component dry developer. These ferromagnetic materials are also added to the colorant composition of the present invention as needed, and any of ferromagnetic fine particles conventionally used for magnetic developers can be used. For example, oxides such as triiron tetroxide powder and iron sesquioxide powder, metal powders such as iron, nickel, and cobalt are not limited to a cubic shape, a needle shape and the like.

The plasticizing material to be added as required is used for, for example, a pressure fixing type developer.
Plasticizers, oils and fats, low-melting waxes, petroleum resins, liquid oligomer resins, and the like.

When the solvent is used in a paste or a liquid composition containing a pigment at a high concentration, the solvent may be selected from aliphatic, alicyclic, aromatic hydrocarbons, and the like depending on the production process or method of use. Halogenated hydrocarbons, esters, ketones, glycol ethers, alcohols,
An aqueous system or the like is used and is not particularly limited.

When used as a medium for a wet liquid developer, conventionally known high-insulating petroleum solvents such as Isopar H, Isopar G (Esso Standard Co., Ltd.), Shellsol 71 (Shell Petroleum) Co., Ltd.)
And kerosene.

When a dye is further required,
It is appropriately selected from conventionally known pigments or dyes and used together with the pigment used in the present invention. For example, organic pigments or dyes include phthalocyanine, azo, anthraquinone, perinone / perylene, indigo / thioindigo, dioxazine, quinacridone, isoindoline, aniline black, and carbon black pigments. Examples of the inorganic pigment include titanium oxide, iron oxide, calcined pigment, navy blue, metal powder pigment, extender pigment and the like.

In addition, when used as an electrophotographic developer, conventionally known charge control agents, cleaning agents,
An agent for improving the fluidity of the developer can be added.

In the colorant composition for image recording of the present invention, the pigment represented by the general formula (1) is selected as the pigment component. It is possible to reduce the variation in the chargeability between them. Even when used as a liquid developer, the interface potential is constant and the phenomenon can be stably performed for a long time.

[0028]

Next, the present invention will be described in detail with reference to examples. In the description, parts and% are based on weight unless otherwise specified.

[Example 1] Dye 2
8 parts of a styrene-methacrylic copolymer (softening point of about 11
The mixture was sufficiently kneaded with 75 parts of 8 ° C, glass transition point of about 58 ° C, GPC method weight average molecular weight of about 70,000) using a three-roll mill to disperse the dye. After cooling, the mixture was crushed to obtain a coarse powder of the colorant composition of the present invention containing a pigment at a concentration of 20%. Next, 20 parts of the colorant composition containing the coloring matter obtained above was kneaded with 80 parts of the styrene-methacrylic copolymer used above according to a conventional method, pulverized after cooling, finely pulverized with a jet mill, and classified. As a result, a fine powder of the colorant composition of the present invention having a size of 5 to 30 microns was obtained. When the triboelectric charge of this colorant composition was measured, it was -12.3 μc / g. Colloidal silica was added as a fluidizing agent to the above red resin fine powder, and mixed well according to a conventional method to obtain an electrophotographic dry developer. Then, the mixture was mixed with a magnetic iron powder of a carrier and copied with an electrophotographic copying machine for negative charge developer.
5. A stable copy image with uniform negative polarity was obtained.

Example 2 Colorant composition 2 containing the dye compound used in Example 1 (No. 2 in Table 1) at a concentration of 35%
5 parts were added to 100 parts of Isopar H together with 15 parts of an acrylic ester resin soluble in an aliphatic hydrocarbon-based solvent, and dispersed in a ball mill for 20 hours to prepare a thick colored liquid of the present invention. 5 parts of this concentrated coloring liquid was added and dispersed in 1 liter of Isopar H to obtain an electrophotographic wet developer of the present invention. When this was copied with a wet electrophotographic copying machine,
The image density was 1.20, the OHP color reproducibility was good, and a clear and calm color image was obtained stably.

Example 3 Colorant composition 28 of Example 1
The colorant composition of Production Example A produced by the flushing method was used in place of the part. Similarly, when a dry toner was prepared and evaluated, the triboelectric charge was −16.4 μc / g. The image density was 1.30, indicating a uniform negative polarity.
A sharper image was obtained than in Example 1.

Example 4 A wet toner was prepared in the same manner as in Example 2, except that 25 parts of the colorant composition was replaced by the colorant composition of Production Example A prepared by a flushing method. Upon evaluation, the image density was 1.2.
7, a deep magenta image could be obtained.

Example 5 When the wet toners obtained in Examples 2 and 4 were used as inks for ink jet recording, an image having a higher image density and less bleeding was obtained as compared with the conventional aqueous ink. . Further, since the wet toner of the present invention has a small particle size of 0.1 to 0.5 μm and has good dispersibility, it can be used to produce a glossy high-brightness coating film or printed matter even when used as a paint or printing ink. it can.

[0034]

As described above, according to the colorant composition using the compound represented by the general formula (1) as a coloring matter and the method for producing the same by a flushing method, the charge amount is high as an electrophotographic dry toner. In addition, an excellent dry toner such as a sharp copy can be obtained. Further, even as a wet toner, a toner having a high copy density and excellent color reproducibility by OHP can be obtained. Further, it can be used as an ink for ink-jet recording and other paints and inks.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI G03G 9/09 C07D 471/04 112Z // B41J 2/01 G03G 9/08 361 C07D 471/04 112 B41J 3/04 101Y (72 Inventor Aiko Ishikawa 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Co., Ltd.

Claims (7)

[Claims] 1. A colorant composition comprising at least a dye and a resin, wherein the dye is a compound represented by the following general formula (1). Embedded image (In the formula, R _{1 to} R ₄ represent an alkyl group or an alkoxy group having 1 to 12 carbon atoms, and R ₅ and R ₆ represent a hydroxyl group, a carboxyl group, a sulfo group or a halogen.) 2. The colorant composition according to claim 1, wherein the content of the coloring matter is 1 to 80% by weight. 3. The colorant composition according to claim 1, wherein the resin is a polyolefin or a polyolefin copolymer. 4. A method for producing a colorant composition, comprising producing the colorant composition according to claim 1 by a flushing method. 5. An electrophotographic dry developer comprising the colorant composition according to claim 1 or the colorant composition produced by the production method according to claim 4. Description: 6. An electrophotographic wet developer comprising the colorant composition according to claim 1 or the colorant composition produced by the production method according to claim 4. Description: 7. An ink jet recording ink comprising the colorant composition according to claim 1 or the colorant composition produced by the production method according to claim 4. Description: