JPH10115948A - Electrostatic image-developing color toner, color image forming material therefor, and method for painting on ceramic product by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a color image forming material high in color density, and a color toner for developing an electrostatic charge image and useful for obtaining this color image forming material, by incorporating an inorganic pigment, a glass component, and a thermoplastic resin, and specifying the grain diameter. SOLUTION: The color toner contains the inorganic pigment, the glass components, and the thermoplastic resin and it is regulated to have the grain diameter range of 20-60μm. As the metal oxide, such as Indian red, chrome green and the like, and as the solid solution of the metal oxide, such as mangan pink or chrome alumina green, and as double oxides, (Zn, Co)OAl2 O3 and the like, and as the solid solution of the composite, such as antimony yellow, are enumerated. As the glass components, the hydroxide of alakali metals, or alkaline earth metals, such as lithium hydroxide and the like, and glasslets are enumerated as fundamental materials alone or in combination of them, and as the thermoplastic resin, polyesters and polystyrenes, such as a copolymer of polyester, copolymers, such as styrene and ethyl acrylate copolymers are enumerated.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color toner for developing an electrostatic image, an image forming body obtained by using the toner, and a ceramic, glass, enamel, tile and other ceramic products (hereinafter referred to as "ceramic products"). ") In some cases).

[0002]

2. Description of the Related Art Pattern formation of ceramic products is obtained by handwriting with a brush or the like, applying an inorganic pigment, a glass component or the like, and then firing. According to this method, a skilled technician is required even for a simple pattern to obtain a plurality of ceramic products having the same pattern. When a plurality of ceramic products having the same pattern are formed, a method using offset printing, screen printing, or the like is generally used. In addition, recently, a method using electrophotography has been proposed in patent publications and the like.

As a method for forming a plurality of identical patterns, a method utilizing a screen printing method disclosed in Japanese Patent Application Laid-Open No. 49-35407 is widely used. This is because the screen printing method allows more ink to be applied on transfer paper than the offset printing method, and can form a so-called high-quality image such as gloss, gloss, and clear color tone.
In the screen printing method, an image is formed on the upper surface of a transfer paper comprising a water-soluble glue layer and a vinyl-based or cellulose-based resin layer on a substrate using an ink containing an inorganic pigment or the like by a screen printing method. After a resin layer is coated on the ink image, the transfer paper is immersed in water to dissolve the adhesive layer of the transfer paper, thereby obtaining a resin layer having an image using an inorganic pigment.
If this resin layer is attached to a ceramic product fabric and then fired, a plurality of ceramic products having the same pattern can be obtained. But,
In the case of the screen printing method, the plate making process is complicated and requires considerable time and labor. For this reason, not only lack of immediacy, but also no problem in the case of a very large number of products, but in the case of a not so large amount or in the case of a small lot and many kinds, the unit price per product becomes high. In addition, since an organic solvent is used at the time of printing, there is a problem that the working environment is deteriorated.

In order to solve the problems of the screen printing method, Japanese Patent Application Laid-Open Nos. Hei 4-135798 and Hei 7 have been disclosed.
As disclosed in JP-A-199540, JP-A-7-214890, and JP-A-7-228037, a technique using a dry copying machine (hereinafter sometimes referred to as "electrophotographic method") has been proposed. As described in these publications, image formation on transfer paper by electrophotography is a method suitable for obtaining a plurality of identical images or for producing a small lot multi-product product. Further, since the conventionally required plate formation becomes unnecessary, the process is greatly simplified as compared with the screen printing method. However, since the developer described in Japanese Patent Application Laid-Open No. 4-135798 uses a one-component developer containing a magnetic material, it is suitable for obtaining a plurality of identical images or for producing small lots and many kinds of products. However, the color development is limited to brown or black caused by iron oxide, so that the versatility as a ceramic product is extremely low.

[0005] Therefore, in order to solve such problems, JP-A-7-199540, JP-A-7-214890 and JP-A-7-228037 suggest the possibility of coloring using an inorganic pigment, and have industrial significance. Proposals have been made to expand. That is, it is an attempt to improve the time and labor of plate making by screen printing and the working environment by obtaining a transfer paper in which an inorganic pigment-containing composite powder is formed on a transfer paper by electrophotography. . However, images on transfer paper using the composite powders described in these publications are not good high-density images with low coloring degrees.

As described above, in order to solve the drawbacks of the screen printing method, it has been proposed to use an electrophotographic method to form a pattern on a ceramic product.
At present, the image density is low and a full-color image cannot be obtained.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a color image forming body having a high degree of coloring and a color toner for developing an electrostatic image useful for obtaining the same. It is another object of the present invention to provide a method for forming a high-density and vivid pattern on a small lot and many kinds of ceramic products.

[0008]

According to the present invention, (1)
A color toner for developing an electrostatic image, containing at least an inorganic pigment, a glass component, and a thermoplastic resin, and having a particle size in a range of 20 to 60 μm; (3) A full-color image is formed on a substrate sheet having a water-soluble adhesive layer on at least the top surface of the mount by the electrostatic image developing method using the color toner of (1). And (4) immersing the image-formed body of (3) in water to form a full-color image-formed body having the sheet image surface covered with a water-insoluble glue layer. After dissolving the glue layer, a method for impressing a ceramic product is provided, in which the separated image forming film is attached to a ceramic product and fired.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. As the inorganic pigment used in the present invention, red iron oxide as a metal oxide, chrome green, etc., as a solid solution of the metal oxide, manganese pink, chromium alumina green, chromium titanium yellow, vanadium tin yellow, antimony tin ashy blue, lilac, (Zn, Co) O.Al as double oxide such as vanadium zirconium yellow
_{2 O 3, ZnO · (Al} , Cr) 2 O 3, (Zn, Co) O
・ (Al, Cr) ₂ O ₃ , ZnO ・ (Al, Cr, Fe)
₂ O ₃ , (Mn, Co) O. (Cr, Fe) ₂ O ₃ , CuO
Etc. · Cr ₂ O _3, antimony yellow and the like as a solid solution of mixed oxide. In addition, silicates such as cobalt oripin, nickel oripin, and ubalobite; silicate solid solutions such as chrome tin pink, vanadium blue, turkish blue, praseodymium yellow, and coral red; sulfides such as cadmium orange; and sulfides such as cadmium sulfate. Red, selenium red, mandarin and the like.

As the glass component, the following compounds can be mentioned as those which improve the fusion property of the inorganic pigment. Hydroxides of alkali metals and alkaline earth metals such as lithium hydroxide, carbonates of alkali metals and alkaline earth metals such as lithium carbonate, chlorides of alkali metals and alkaline earth metals, aluminum chloride, boric acid, and alkali Metal or alkaline earth metal chloride borate, alkali metal or alkaline earth metal chloride metaborate, alkali metal or alkaline earth metal phosphate, alkali metal or alkaline earth metal pyrophosphate Salt, alkali metal or alkaline earth metal silicate, alkali metal or alkaline earth metal metasilicate, zirconium silicate, bone ash, borax,
Metal oxides such as ammonium metavanadate, tungsten oxide, vanadium pentoxide, tin oxide, zirconium oxide, cerium oxide, and molybdenum oxide; metal fluorides such as calcium fluoride and aluminum fluoride; and glasslets as basic materials. Singly or in combination.

[0011] In addition, feldspars such as lime feldspar, potassium feldspar, soda feldspar, betalite (lithium feldspar), kaolin, quartzite, alumina, silica, quartz, titanium oxide, chamotte, etc. are used to strengthen the binding of glass components. As the basic material, a single material or a mixture thereof may be used. In addition, natural or minerals such as lime, limestone, magnesite, talc, and dolomite, and barium carbonate, zinc oxide, strontium carbonate, and the like are used as basic materials as adjusters for the saturation, hue, and lightness of the fired image. A mixture is given. The above-mentioned glass components may be mixed in advance or melted after mixing to produce a so-called frit.

As the thermoplastic resin, polyester-based resins,
Resin systems such as polystyrene, polyethylene, polyamide, epoxy, epoxy polyol, and terpene resins, such as polystyrene, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, and styrene-acrylic acid Examples thereof include n-butyl copolymers, which can be used alone or as a mixture. The thermoplastic resin used in the present invention is not limited to these, and a binder resin component used in a conventionally known toner can be used.

The toner of the present invention may contain a charge control agent, if necessary. As such a charge control agent, any of conventionally known charge control agents can be used. For example, nigrosine dyes, quaternary ammonium salts, Cr-containing dyes, Zn-containing dyes, Fe-containing dyes, molybdate chelate dyes, fluorine-modified quaternary An ammonium salt or the like is appropriately selected and used according to the charging polarity. In the present invention, the amount of the charge control agent used is determined by the type of the binder resin (thermoplastic resin), the presence or absence of additives used as necessary, and the toner manufacturing method including the method of dispersion in the toner. Therefore, it is not necessarily limited, but preferably the thermoplastic resin 10
It is used in the range of 0.1 to 10 parts by weight with respect to 0 parts by weight. More preferably, 2 to 6 parts by weight is preferable.
If the amount is less than 0.1 parts by weight, the charge amount of the toner becomes insufficient, and problems such as toner scattering and background contamination occur. When the amount exceeds 10 parts by weight, the electrostatic adhesion to the carrier is increased, which causes problems such as a decrease in the fluidity of the developer and a decrease in the development amount.

In addition, additives can be used as needed to improve the fluidity of the toner. As the additives, conventionally known additives such as hydrophobic silica, zinc stearate, aluminum stearate, and titanium oxide may be added to the toner surface.

The content of the inorganic pigment among the components constituting the toner described above largely depends on the density of the toner image to be formed. In order to fix an image on the surface of the intended ceramic product by printing, the glass component in the toner is essential. At this time, the weight ratio of the inorganic pigment to the glass component is 1/9 to inorganic pigment / glass component. 4/6 is preferred. More preferably, the ratio of inorganic pigment / glass component is 2/8 to 3/7. When the amount of the glass component is larger than 1/9, the printing can be performed well, but the density of the obtained image becomes low and the image becomes poor. On the other hand, when the amount of the inorganic pigment is more than 4/6, the inorganic pigment cannot be effectively fixed on ceramic products at the time of baking.

Therefore, in the toner of the present invention, by setting the particle diameter to 20 to 60 μm, a large amount of the inorganic pigment can be contained in the image without reducing the glass component. This makes it possible to form a high-density and clear picture on a ceramic product. For example, when the ratio of inorganic pigment / glass component is 2/8, the preferred toner particle diameter is 20 to
It is 60 μm, more preferably 30 to 40 μm. 2
When the thickness is less than 0 μm, the density of the obtained image becomes low,
If it is larger than 0 μm, the development amount decreases and the toner transfer rate on the substrate sheet decreases, and a clear image cannot be obtained. This is because the specific gravity of the inorganic pigment and the glass component is 2
It is considered that this is because the movement of the toner powder due to the electrostatic force is hindered due to the large size of 大 き い 5.

In the present invention, the toner is used alone as a developer to visualize the electrostatic latent image. The development may be performed by a so-called one-component development method, or may be performed by a two-component development method in which an electrostatic latent image is visualized using a two-component developer obtained by mixing a toner and a carrier. As the carrier used in the two-component developing method, iron powder, ferrite, glass beads and the like are the same as those in the related art. The carrier may be coated with a resin. In this case, the resin used is polyfluorocarbon, polyvinyl chloride, polyvinyl chloride, polyvinylidene chloride, phenol resin, polyvinyl acetal, silicone resin, or the like. The mixing ratio of the toner and the carrier is 100
The appropriate amount is about 1 to 7 parts by weight of the toner with respect to parts by weight.

A transfer sheet as a transfer medium used in the present invention has a glue layer on the upper surface of the backing paper. This can be used as it is, which is generally commercially available for ceramics, for example, used as screen printing. The glue layer at this time is water-soluble, and dexton, polyvinyl alcohol, or the like is used. An image is formed on the base sheet by using a copying machine or a printer for developing an electrostatic latent image for developing an electrostatic latent image. Thereafter, the upper surface of the image is coated with a water-insoluble material such as an acrylic paint or a polystyrene resin to obtain a color image or a full-color image formed body. Attaching the image forming body obtained in this manner to a target ceramic product by a water transfer method and baking it at 800 to 850 ° C. for about 5 hours to obtain a ceramic product having a color or full-color pattern Can be.

[0019]

Next, the present invention will be described in detail with reference to examples. However, the present invention is not limited to these examples.

(Adjustment of Glass Components) As shown in Table 1,
The compounds were pulverized with a stamp mill and then mixed with a Henschel mixer to prepare prepared glass component powder mixtures A to D. The numbers in Table 1 are polymerization parts.

[Table 1]

(Toner Production Example) (a) Yellow toner 100 parts by weight of polyester resin (Tg = 60 ° C.) 20 parts by weight of chromium titanium yellow 80 parts by weight of glass component powder mixture A 4 parts by weight of zinc salicylate derivative (Bontron E84, Orient Was mixed with a mixer and melt-kneaded with a two-roll mill. After the mixture was rolled and cooled, it was subjected to pulverization classification to produce seven types of yellow toners having different volume average particle diameters as shown in Table 2. Further, 0.5% by weight of hydrophobic silica (R972, manufactured by Nippon Aerogel Co., Ltd.) was added to toners having different particle diameters, and the mixture was stirred with a mixer.

(B) Magenta toner polyester resin (Tg = 60 ° C.) 100 parts by weight ZnO. (Al, Cr) ₂ O ₃ 20 parts by weight Glass component powder mixture B 80 parts by weight Zinc salicylate derivative 4 parts by weight (Bontron E84 Magenta toners having different particle diameters were prepared in the same manner as in the case of the yellow toner.
Table 2 summarizes the volume average particle size at this time.

(C) Cyan toner 100 parts by weight of polyester resin (Tg = 60 ° C.) 20 parts by weight of vanadium blue 80 parts by weight of glass component powder mixture C 4 parts by weight of zinc salicylate derivative (Bontron E84, manufactured by Orient Chemical Co., Ltd.) Using these materials, seven types of cyan toners having different particle diameters were prepared in the same manner as in the case of the yellow toner. Table 2 summarizes the volume average particle size at this time.

The (d) The black toner polyester resin (Tg = 60 ℃) 100 parts by weight (Mn, Co) O · ( Cr, Fe) 2 O 3 20 parts by weight glass component powder mixture D 80 parts by weight of zinc salicylate derivative 4 Using a material consisting of parts by weight (Bontron E84, manufactured by Orient Chemical Co., Ltd.), seven kinds of black toners having different particle diameters were prepared in the same manner as in the case of the yellow toner.
Table 2 summarizes the volume average particle size at this time.

[0025]

[Table 2] * Measured with a Coulter Multisize 100μm aperture tube

(Example of Carrier Production) The following compound was dispersed with a homomixer for 30 minutes to prepare a coating layer forming solution. Carrier A was prepared by forming a coating layer on the surface of a spherical ferrite carrier having a volume average particle diameter of 150 μm on the surface of 1000 parts by weight of a coating liquid for forming a lake using a fluidized bed type coating apparatus. Silicon resin solution (KR50, manufactured by Shin-Etsu Chemical Co., Ltd.) 100 parts by weight Carbon black (BP2000, manufactured by Cabot Corporation) 3 parts by weight Toluene 100 parts by weight

Examples 1 to 4 950 g of the above carrier and 50 g of a yellow toner (volume average particle size: 20.4 μm: 3 groups in Table 2) were placed in a ball mill and stirred for 30 minutes to prepare a developer. The obtained developer was placed in an electrophotographic copier (Imagio 530) manufactured by Ricoh Co., Ltd.
An image was formed on the transfer sheet. Next, a polystyrene resin was applied to the upper surface of the image, dried and then attached to a tile by a water transfer method, and baked at 800 ° C. for 5 hours. Table 3 summarizes the results of measuring the image density of the solid image portion of the fired product using a Macbeth densitometer. Similarly, developers were prepared for toners having different volume average particle diameters in groups 4 to 6 of the yellow toner in Table 2, and the solid image density was measured in the same manner. Table 3 summarizes the results.

Comparative Examples 1 to 3 Solid toner image densities of the toners having different volume average particle diameters of groups 1, 2 and 7 in Table 2 were measured in the same manner as in Example 1. Table 3 summarizes the results.

Examples 5 to 8 In place of the yellow toner, 3 of the magenta toners in Table 2 was used.
The image density of the solid portion was measured in the same manner as in Example 1 for the toners having different volume average particle diameters in groups 6 to 6, and the results are summarized in Table 3.

Comparative Examples 4 to 6 Solid toner image densities were measured in the same manner as in Example 1 for toners having different volume average particle diameters of groups 1, 2, and 7 of magenta toners in Table 2, and the results were measured. Table 3 summarizes the results.

Examples 9 to 12 Instead of the yellow toner, 3 to 3 of the cyan toners in Table 2 were used.
Example 1 Regarding Six Groups of Toners with Different Volume Average Particle Sizes
The image density of the solid portion was measured in the same manner as in the above, and the results are summarized in Table 3.

Comparative Examples 7 to 9 Solid toner image densities of groups 1, 2 and 7 of Table 2 having different volume average particle diameters were measured in the same manner as in Example 1. Table 3 summarizes the results.

Examples 13 to 16 Instead of the yellow toner, 3 of the black toner in Table 2 was used.
The image density of the solid portion was measured in the same manner as in Example 1 for the toners having different volume average particle diameters in groups 6 to 6, and the results are summarized in Table 3.

Comparative Examples 10 to 13 Solid toner image densities were measured in the same manner as in Example 1 for toners having different volume average particle diameters in groups 1, 2 and 7 of the cyan toners in Table 2, and the results were obtained. Table 3 summarizes the results.

[0035]

[Table 3]

Example 17 475 g of carrier A and four groups of yellow toner 25 in Table 2
g was placed in a ball mill and stirred for 30 minutes to prepare a developer.
Similarly, 475 g of the carrier A and 25 g of the magenta toners of the four groups in Table 2 were placed in a ball mill and stirred for 30 minutes to prepare a developer. Similarly, 475 g of the carrier A and 25 g of the four groups of cyan toner in Table 2 were placed in a ball mill and stirred for 30 minutes to prepare a developer. Similarly, 475 g of carrier A and 4 in Table 2
25 g of the black toner of the group was put into a ball mill and stirred for 30 minutes to prepare a developer. These developers were placed in a developing section of a color copying machine (PRETER550) manufactured by Ricoh Co., Ltd. to form a full-color image on a transfer sheet. Next, a polystyrene resin was applied to the upper surface of the image, dried and then attached to a tile by a water transfer method, and baked at 800 ° C. for 5 hours. Observation after cooling revealed that the tile had a glossy, high density and clear image.

[0037]

According to the first and second aspects of the invention, a high-density and clear color image is formed. According to the third aspect of the present invention, a ceramic product painting material can be easily obtained by a commercially available electrophotographic copying machine. According to the invention of claim 4,
Painting on small lots and many kinds of ceramics can be done easily.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03G 9/09 G03G 9/08 361 (72) Inventor Shinichi Kuramoto 1-3-6 Nakamagome, Ota-ku, Tokyo RICOH Company, Limited Inside

Claims (4)

[Claims] 1. A color toner for developing an electrostatic image, comprising at least an inorganic pigment, a glass component and a thermoplastic resin, and having a particle size in the range of 20 to 60 μm. 2. An image forming body obtained by using at least one kind of the color toner according to claim 1. 3. A full-color image of the color toner according to claim 1 is formed on a substrate sheet having a water-soluble glue layer on at least the upper surface of the mount by an electrostatic image developing method, and the sheet image surface is formed with a water-insoluble glue. A full-color image forming body characterized by being coated with a layer. 4. The image forming body according to claim 3, which is immersed in water to dissolve the water-soluble glue layer of the substrate sheet, and then the separated image forming film is attached to a ceramic product and fired. And painting method of ceramic products.