JPH07300382A - Image-printed ceramic and method for producing the same - Google Patents

Abstract

PURPOSE:To provide an image-printed ceramic article excellent in durability at a low cost without semi-permanently causing the fading of the image, and further to provide a method for producing the same. CONSTITUTION:An image 1 electrostatically printed with a composite powdery material on a substrate is transferred to the surface of a ceramic article 7 and subsequently baked. 10-50wt.% of an organic polymer and 50-90wt.% of an inorganic component comprising an inorganic pigment and a glass component is used for the composite powdery material. The inorganic pigment comprises the oxides of one or more metals selected from the group consisting of iron, cobalt, nickel, copper, selenium, titanium, molybdenum, chromium, and manganese, the noble metal colloid of either or both of gold and rhodium, etc. The glass component comprises the oxides of one or more elements selected from the group consisting of silicon, aluminum, calcium, magnesium boron, alkali metals, lead zinc, and zirconium. Examples of the ceramic article include a pottery and a crystal glass.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image-baked ceramic body on which an image is formed on ceramics or crystal glass, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, as a method for forming an image such as a photograph on ceramics, there are a method using an organic dye, a method using a photosensitive resin, and a method by screen printing. The method of using an organic dye is a method of forming a resin film on the surface of a ceramic and transferring an image of the organic dye to the resin film. As a method of using a photosensitive resin, for example, as shown in JP-A-5-221762, a photosensitive resin is applied to the entire surface of a ceramic substrate,
A desired portion corresponding to the image is irradiated with light to eliminate the tackiness of the photosensitive portion. Then, the pigment is sprinkled on the remaining sticky portion, and then these are baked. As a result, an image is formed on the surface of the ceramic substrate.

[0003]

However, in the above conventional image forming method, in the method using the organic dye, since the organic dye is simply attached through the resin,
Easy to fade. Therefore, it is difficult to maintain a clear image for a long period of time.

Further, in the method using a photosensitive resin and the method using screen printing, many steps are required to form an image pattern, which is troublesome. Therefore, there is a problem that the manufacturing cost becomes high. In view of such conventional problems, the present invention intends to provide an image-baked ceramic body that is semi-permanently free from image fading, has excellent durability, and is low cost, and a method for manufacturing the same.

[0005]

According to the present invention, an image electrostatically printed using a composite powder is transferred and printed on the surface of a ceramic body, and the composite powder contains an inorganic pigment and a glass component. The image-baked ceramic body is characterized by containing 50 to 90% of an inorganic component (weight ratio, the same applies hereinafter) and 10 to 50% of an organic polymer.

What is most noticeable in the present invention is that an image is electrostatically printed using a composite powder containing an inorganic component and an organic polymer, and the printed layer is transferred and baked onto a ceramic body. . The composite powder is composed of 50 to 90% of an inorganic component and 10 to 50% of an organic polymer to be described later for the reason described below.

The above-mentioned inorganic component comprises an inorganic pigment and a glass component. Examples of the inorganic pigment include oxides of one or more metals selected from the group consisting of iron, cobalt, nickel, copper, selenium, titanium, molybdenum, chromium, and manganese, and noble metals of gold and / or rhodium. There are colloids. Examples of the glass component include oxides of one or more selected from the group of silicon, aluminum, calcium, magnesium, boron, alkali metal, lead, zinc, and zirconium. The inorganic component preferably contains 10 to 90 parts by weight of the inorganic pigment and 90 to 10 parts by weight of the glass component for the reason described below.

The composite powder forms an image printing layer. The image has a form specified by visual observation, and includes, for example, photographs, paintings, characters, patterns, and the like. This print layer is
Transferred and baked on the surface of the ceramic body. Examples of the ceramic body include ceramics and crystal glass.
Ceramics are obtained by firing clay minerals as the main raw material, and have a composition of silica and alumina. Crystal glass refers to glass in which crystals are precipitated by firing. The form of the ceramic body is not particularly limited,
For example, there are dish-shaped and cup-shaped ones.

Next, as a method for producing the above image-baked ceramic body, for example, an original image to be transfer-printed on a surface of a water-soluble member formed on a base material by using a composite powder, Electrostatic printing is performed to form a print layer having the same shape as the image, and then the surface of the water-soluble member on which the print layer is formed is covered with a cover coat resin layer to prepare a transfer paper, and then, The water-soluble member is melted, the print layer and the cover coat resin layer are separated from the base material, and then the print layer and the cover coat resin layer are attached so that the print layer contacts the surface of the ceramic body. Then, these are baked to print the printed layer on the surface of the ceramic body, wherein the composite powder comprises an inorganic component 5 composed of an inorganic pigment and a glass component.
There is a method for producing an image-baked ceramic body characterized by containing 0 to 90% and an organic polymer of 10 to 50%.

The method of manufacturing the image-baked ceramic body will be described below in detail. First, the original image is electrostatically printed on the surface of the water-soluble member formed on the base material by using the composite powder. The composite powder contains 50 to 90% of an inorganic component composed of an inorganic pigment and a glass component, and 10 to 50% of an organic polymer. 90% inorganic component
If it exceeds, it becomes difficult to electrostatically print the composite powder. In addition, the bond between the composite powder and the ceramic body may be weakened. On the other hand, when the content of the inorganic component is less than 50%, there is a problem in that the amount of the scattered component is too large during the firing, and the final product becomes less colored.

The above-mentioned inorganic component contains an inorganic pigment and a glass component. The inorganic pigment is a material for displaying an image on the surface of the ceramic body. Inorganic pigments include iron, cobalt, nickel, copper, selenium, titanium, molybdenum, chromium, manganese, tin, zirconium, and oxides of one or more metals selected from the group of antimony, iron chromate, and silicic acid. There are salts, precious metal colloids of gold and / or rhodium, or both.

The above glass component is used to fuse the inorganic pigment to the ceramic body. Glass components include silicon, aluminum, calcium, magnesium,
There are oxides of one or more selected from the group consisting of boron, alkali metals, lead, zinc, and zirconium.

The inorganic component is 10 to 90% of inorganic pigment,
It preferably contains 90 to 10% of a glass component. If the content of the inorganic pigment is less than 10%, or if the content of the glass component exceeds 90%, the final product may be colored poorly. On the other hand, if the inorganic pigment exceeds 90%,
Alternatively, if the glass component is less than 10%, the fixation of the inorganic pigment may be deteriorated.

As the organic polymer, for example, one or more selected from the group consisting of homopolymers or copolymers of styrene or methacrylic acid lower alkyl ester, polyester, polyamide, polyurethane, and epoxy resin can be used. . The polyester is a polymer in which a dibasic acid such as terephthalic acid or adipic acid and a glycol such as butylene glycol or bisphenol A ethylene oxide adduct are crosslinked by an ester bond.

The above organic polymer is preferably used in combination with an azo metal-containing dye or paraffin wax in order to improve printability. The amount used is generally 5% or less based on the weight of the organic polymer. The average particle size of the composite powder is 1 to
It is preferably 20 μm. If it is less than 1 μm, crushing may be difficult. If it exceeds 20 μm, the sharpness of the transferred image may be poor.

In producing the above composite powder, for example, powders of glass component and inorganic pigment having an average particle size of 0.5 to 10 μm and an organic polymer are mixed by a heating kneader or the presence of an organic solvent. Mix with 3 rolls below.
Next, this mixture is roughly pulverized and further finely pulverized by a ball mill, a jet mill or the like until a desired particle size is obtained. Then, the pulverized product is classified to obtain the above composite powder.

The composite powder is electrostatically printed on the surface of the water-soluble member formed on the base material. This electrostatic printing method is one of the electrostatic latent image methods using the above composite powder. That is, the above-mentioned composite powder has an inorganic pigment in the center and its surface is covered with an organic polymer.
Therefore, the composite powder is easily charged and behaves as a toner.

First, the composite powder is subjected to a treatment such as mixing and stirring to give an electric charge to the entire composite powder. In addition, separately, a light beam or other means irradiates the charged photosensitive drum with light corresponding to an image to locally reduce or eliminate the electrostatic charge to form an electrical latent image.

Next, the toner is adsorbed to this electric latent image to form a visible image, which is transferred onto the surface of the water-soluble member formed on the substrate and baked. As a result, a print layer having the same shape as the original image is formed on the surface of the water-soluble member. For the electrostatic printing, it is preferable to use a printer capable of changing the number of halftone dots according to the shade of the printing layer.

The water-soluble member is, for example, a water-soluble polymer or water-soluble film. When the water-soluble member is a water-soluble polymer, the surface of the base material is coated with the water-soluble polymer in advance, and the composite powder is dry-printed on the coated surface. As the water-soluble polymer, polyvinyl alcohol, starch, dextrin or the like is used. Paper, synthetic paper, polyvinyl alcohol, or the like is used as the base material. On the other hand, when the water-soluble member is a water-soluble film, the water-soluble film itself can be used as a base material without using the base material. In this case, the composite powder is directly printed on the surface of the water-soluble film. A polyvinyl alcohol film or the like can be used as the water-soluble film.

Next, the surface of the water-soluble member on which the printing layer is formed is covered with a cover coat resin layer to prepare a transfer paper. As the cover coat resin layer, an alkyl methacrylate ester resin or the like is used. Next, the water-soluble member is melted, the print layer and the cover coat resin layer are separated from the base material, and these are attached to the ceramic body so that the print layer contacts the surface of the ceramic body. . Then, these are baked and the above image is baked on the surface of the ceramic body. Firing is performed at a firing temperature of 600 to 1200 ° C. in the presence of air, for example.

[0022]

In the image-baked ceramic body of the present invention, an image is formed on its surface with an inorganic pigment. The inorganic pigment is fused to the surface of the ceramic body by the glass component. Therefore, the image is strongly fixed to the ceramic body. Therefore, the image does not fade and the durability is excellent.

In the method for producing an image-baked ceramic body of the present invention, an image is formed on the transfer paper by using the inorganic pigment and the glass component. This image is transferred to the surface of the ceramic body and fired. During this firing, the glass component melts and the inorganic pigment fuses to the ceramic body. Therefore, the inorganic pigment is strongly fixed to the ceramic body. Therefore, it is possible to produce an image-baked ceramic body that is free from image fading and has excellent durability.

Further, in the present invention, the inorganic pigment is easily charged and behaves as a toner. Therefore, an image can be formed by using a general office-use dry copier. Therefore, it is easy to form an image, and a desired image can be arbitrarily formed. According to the present invention, it is possible to provide a low-cost image-baking ceramic body that is semi-permanently free from image fading, has excellent durability, and a method for manufacturing the same.

[0025]

【Example】

Example 1 An image-baked ceramic body according to an example of the present invention will be described with reference to FIGS. The image-baked ceramics body 9 of this example is a dish, and the image 1 of a black-and-white photograph electrostatically printed using the composite powder is transferred and burned onto the surface of the ceramics body 7. The composite powder comprises an inorganic component composed of an inorganic pigment and a glass component, and an organic polymer.

Next, a method of manufacturing the above image-baked ceramic body will be described with reference to FIGS. First,
Inorganic component 70% by weight and polystyrene-based organic polymer 30
% By weight with toluene. The inorganic component is
It comprises 30 parts by weight of an inorganic pigment and 70 parts by weight of a glass component.

The inorganic pigment is a black pigment whose main component is iron oxide. The glass component is a glass frit having an average particle size of 3 μm, and its constituent elements include lead oxide, silicon oxide, aluminum oxide, alkali metal oxide, alkaline earth metal oxide, or the like.

The organic polymer is a polystyrene resin having an acid value of 5. 120 parts by weight of toluene is added to 100 parts by weight of the total weight of the inorganic component and the organic polymer. These are mixed using a triple roll.

Next, this mixture is put into ethanol to elute toluene and air-dried. Next, this is roughly crushed, put in a ball mill, and finely crushed. Next, the pulverized product is dried to obtain a composite powder having an average particle size of 13 μm.

Next, as shown in FIG. 2, the electrostatic dry copying machine electrostatically prints the image 1 on the surface of the water-soluble member 2 using the above composite powder. The image is a photograph of the landscape. The water-soluble member 2 is dextrin as a water-soluble polymer and is formed on the surface of the paper as the base material 20 in advance.

Next, as shown in FIG. 3, the water-soluble member 2
The image forming surface is covered with the cover coat resin layer 3 to prepare the transfer paper 5. The cover coat resin layer 3 is a methacrylic acid resin. Next, the transfer paper 5 is immersed in water to dissolve the water-soluble member 2. Next, the print layer on which the image is formed and the cover coat resin layer 3 are separated from the base material 20.

Next, as shown in FIG. 4, the print layer and the cover coat resin layer 3 are attached to the surface of the ceramic body 7 whose image surface is to be transferred. The ceramic body 7 is a dish-type ceramics. Next, these are fired to burn the image 1 on the surface of the ceramic body 7. The firing is performed in the air at a maximum temperature of 800 ° C. As a result, the image-baked ceramic body 9 shown in FIG. 1 is obtained.

In the image-baked ceramic body obtained by the above-mentioned manufacturing method, the image was strongly adhered to the surface of the ceramic body. This landscape image was semi-permanently clear without fading.

Example 2 In the method for producing an image-baked ceramic body of this example, a composite powder containing 60% by weight of an inorganic component and 40% by weight of a styrenic organic polymer was used. In making the inorganic component, the mixture of the inorganic component and the organic polymer is
After elution with toluene, air-drying, coarse pulverization, and fine pulverization with a jet mill, a composite powder having an average particle size of 10 μm was obtained. Others are the same as in the first embodiment. Also in this example, the black and white image of the photograph clearly adhered to the ceramic body,
A clear and beautiful pattern was formed. Moreover, this image was semi-permanently clear without fading.

Example 3 In the method for producing an image-baked ceramic body of this example, a polyester composed of a bisphenol A ethylene oxide adduct having an acid value of 3 and adipic acid was used as the organic polymer. Then, 30% by weight of this polyester and 70% by weight of an inorganic component were kneaded with a kneader. The inorganic component comprises 30 parts by weight of an inorganic pigment and 40 parts by weight of a glass component.

Next, this kneaded material was roughly pulverized and then finely pulverized by a jet mill to obtain a composite powder having an average particle size of 10 μm. Others are the same as in the first embodiment. Also in this example, as in Example 1, it was possible to obtain an image-baked ceramic body which was free from discoloration, was clear, and had excellent durability.

[Brief description of drawings]

FIG. 1 is a perspective view of an image-baked ceramic body according to a first embodiment.

FIG. 2 is an explanatory diagram of a water-soluble member of Example 1 in which an image is dry-printed.

FIG. 3 is an explanatory diagram of a transfer paper according to the first embodiment.

FIG. 4 is an explanatory diagram showing an image transfer method according to the first embodiment.

[Explanation of symbols]

 1. ． ． Image, 2. ． ． Water-soluble member, 20. ． ． Base material, 3. ． ． Cover coat resin layer, 5. ． ． Transfer paper, 7. ． ． Ceramics body, 9. ． ． Image-baked ceramics body,

Claims (11)

[Claims] 1. An image electrostatically printed using a composite powder is transferred and baked onto the surface of a ceramic body, and the composite powder comprises inorganic components 50 to 90 containing an inorganic pigment and a glass component. % (Weight ratio, the same applies hereinafter) and 10 to 50% of an organic polymer, an image-baked ceramic body. 2. The inorganic pigment according to claim 1, wherein:
Iron, cobalt, nickel, copper, selenium, titanium, molybdenum, chromium, manganese, tin, zirconium, and oxides of one or more metals selected from the group of antimony, iron chromate, silicate, or gold or An image-baked ceramic body characterized by being a noble metal colloid of either or both of rhodium. 3. The oxide of claim 1, wherein the glass component is one or more selected from the group consisting of silicon, aluminum, calcium, magnesium, boron, alkali metal, lead, zinc and zirconium. An image-baked ceramic body characterized by being a product. 4. The inorganic component according to claim 1, 2 or 3, wherein the inorganic component contains 10 to 90 parts (weight ratio, the same applies hereinafter) of an inorganic pigment and 90 to 10 parts of a glass component. An image-baked ceramic body characterized in that 5. The image-baked ceramic body according to claim 1, wherein the ceramic body is ceramics or crystal glass. 6. A printing layer having the same shape as the above-mentioned image, which is obtained by electrostatically printing an original image to be transferred and printed on the surface of a water-soluble member formed on a substrate by using a composite powder. Then, the surface of the water-soluble member on which the printing layer has been formed is covered with a cover coat resin layer to prepare a transfer paper, and then the water-soluble member is melted to remove the printing layer and the printing layer from the substrate. The cover coat resin layer is peeled off, and then the printed layer and the cover coat resin layer are attached so that the printed layer comes into contact with the surface of the ceramic body, and then these are baked to form the printed layer on the ceramic body. The method of baking on the surface of
50-90% inorganic component consisting of inorganic pigment and glass component
And an organic polymer in an amount of 10 to 50%. 7. The inorganic pigment according to claim 6,
Iron, cobalt, nickel, copper, selenium, titanium, molybdenum, chromium, manganese, tin, zirconium, and oxides of one or more metals selected from the group of antimony, iron chromate, silicate, or gold or A method for producing an image-baked ceramic body, which is a precious metal colloid of either or both of rhodium. 8. The glass component according to claim 6, wherein the glass component is
A method for producing an image-baked ceramic body, which is an oxide of one or more selected from the group consisting of silicon, aluminum, calcium, magnesium, boron, alkali metals, lead, zinc, and zirconium. 9. The image baking ceramic according to claim 6, wherein the inorganic component contains 10 to 90 parts of an inorganic pigment and 90 to 10 parts of a glass component. Body manufacturing method. 10. The organic polymer according to claim 6, wherein the organic polymer is a homopolymer or copolymer of styrene or a methacrylic acid lower alkyl ester, or a dibasic acid such as terephthalic acid or adipic acid, and butylene. A method for producing an image-baked ceramic body, comprising at least one selected from the group consisting of polyesters, polyamides, polyurethanes, and epoxy resins consisting of glycols such as glycols and bisphenol A ethylene oxide adducts. 11. The method for producing an image-baked ceramic body according to claim 6, wherein the ceramic body is ceramics or crystal glass.