JPH0961979A - Production of sintered image-containing molding and sintered image-containing molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make it possible to form arbitrary images on the surfaces of metallic products, pottery and porcelain, stone materials, etc., by adhering or sticking a sinterable sheet formed with images by using a developer contg. sinterable metals or a photographic film, etc., which are taken by a silver salt photographic method and are subjected to developing and fixing onto the surface of a molding and heating and sintering the sheet or film. SOLUTION: The desired images are formed on the sinterable sheet by an electrostatic recording method, etc., by using the developer contg. >=1 kinds of the sinterable metals, alloys and metal compds. as a first stage. The photographic film or photographic paper which is taken by the silver photographic method and is subjected to developing and fixing in place of this stage may be used. Namely, the photographic film or photographic paper which is photographed with the images by known method and is subjected to developing and fixing may be used. The sheet or photographic film or photographic paper obtd. by the first stage is adhered or stuck to the surface of the molding formed to a desired shape as a second stage. The sheet, film or paper is sintered in an electric furnace, etc., in a third stage. The metals, alloys and metal oxides constituting the images by heating up are adhered or stuck on the molding, by which the images are transferred thereon and are sintered.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a molded product with a sintered image and a molded product with a sintered image, which can form an arbitrary image on the surface of metal products, ceramics, stones and the like.

[0002]

2. Description of the Related Art Conventionally, when a pattern is applied to ceramics (painting), a three-dimensional pattern (engraving) is made by using a spatula or the like to make irregularities on the surface of the ceramics made of clay. After that, paint (glaze) is painted by using a method such as handwriting or screen printing, and baked to obtain a patterned ceramic. In addition, as a method of directly applying a pattern to the surface of the metal body, a method of making unevenness by a mechanical method such as engraving or engraving, a method of handwriting, screen printing, using an ink jet printer, or the like is used. ing.

[0003]

However, when attempting to paint by hand on a ceramic or a metal body, an image with excellent design such as characters, figures, and pictures is drawn without advanced technology. I couldn't do that. Also, in screen printing, etc., a precise printed image with excellent reproducibility should normally be obtained, but if the printing surface, that is, the painted part of the ceramic or metal body is a curved surface, the printing work becomes extremely difficult. , The desired image was not obtained. Furthermore, when an image is formed using an inkjet printer connected to a computer, it should be possible to form a precise printed image with excellent reproducibility, but the painted portion of the ceramic or metal body is a curved surface. Since it is also necessary to control the shape thereof, very special technology and equipment are required, and a desired image cannot be easily formed on a ceramic or a metal body. Therefore, a method for easily forming an image with excellent reproducibility has been desired. In addition, recently, a method of manufacturing metal-sintered products such as arts and crafts and ornaments using metal clay has been adopted. In particular, an increasing number of culture centers are teaching how to make precious metal arts and crafts and ornaments using gold clay and silver clay in which gold powder and silver powder are kneaded. Therefore, a method that can be easily applied to form an image on the surface of these sintered metal products has been desired.

[0004]

SUMMARY OF THE INVENTION The present invention has been proposed in view of the above, and is one of sinterable metals, alloys and metal compounds.
A combustible sheet on which an image is formed by using a developer containing one or more kinds, or a photographic film or photographic paper imaged and developed and fixed by a silver salt photographic method, is adhered to the surface of a molded object formed into a desired shape. Alternatively, the present invention relates to a method for producing a molded article with a sintered image, which is characterized in that it adheres and is heated and sintered.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION First, as the first step of the present invention,
Using a developer (toner) containing one or more types of sinterable metals, alloys, and metal compounds, it is possible to burn desired images by electrostatic recording methods (including electrophotography) and magnetograph (MG) methods. It is formed on a sheet. Specific components of sinterable metals, alloys, and metal compounds include Au, Pt, and P.
A simple metal such as d, Ag, Fe, Cu, Ni, Sn, Pb, or Zn, an alloy of these metals, a metal compound of these metals, or the like is used, and one or more of these are mixed with a developer (toner). Let it be used. The electrostatic recording method forms an electrostatic latent image on the insulating layer by charging and exposing the photoconductive layer or using a multi-needle electrode, and the electrostatic latent image is a toner of opposite polarity or the same polarity. A typical method for obtaining a visible image by developing with Carlson method, electrofax method, NP
Method, KIP method, and electrostatic recording method using a multi-needle electrode. In the MG method, a magnetic latent image is formed on a surface of a magnetic thin layer by using a magnetic recording head to form a magnetic latent image, and the magnetic latent image can be developed with a toner containing magnetic powder such as iron oxide. In this method, a visible image is formed, and this visible image is transferred and fixed on paper or the like to obtain a copy print image. The toner used in the present invention includes, among the toners used in the electrostatic recording method and the MG method, a powder of a sinterable metal, an alloy, or a metal compound, and in the electrostatic recording method, one particle is mainly used. Most of those used in the developing method are used, and in the MG method, since magnetic powder containing iron oxide is contained, all of them can be used in the present invention. Especially for toner used in electrophotography,
Some contain magnetic powders such as iron oxide, and some use the one-particle magnet development method. The toner containing iron oxide is often used in ordinary copying machines, printers, facsimiles and the like. Further, powder of the above-mentioned sinterable metal, alloy, or metal compound may be mixed with an ordinary toner within a range that does not impair the developability and fixability. The developers used in the electrophotographic copying machine adopting the one-particle developing method are charging adhesives (for example, dyes), thermoplastic resins or waxes, colored dyes or pigments, and magnetic fine powders (for example, iron oxide). And is attracted to the magnet through the developing sleep or the like. Examples of combustible sheets include paper and film, seal-type paper and film coated with adhesive or adhesive on one side, and OHP.
Sheets or the like are used. As a special one, so-called transfer paper for ceramics may be used which has a structure in which a water-soluble resin such as dextrin is applied to the surface of a paper base material which easily contains water. In the first step, since a general-purpose and highly functional office equipment such as a copying machine, a printer or a facsimile can be used, it is possible to extremely easily form a precision image or the like.

Instead of the first step, a photographic film or photographic paper imaged by the silver salt photographic method and developed and fixed may be used. That is, a photograph is taken by a known method, and a photographic film is developed and fixed by a known method.
You may use it for a process.

As the second step of the present invention, the combustible sheet on which the image obtained in the first step or the photographic film or printing paper on which development and fixing have been carried out is formed on the surface of a molded article formed into a desired shape. Adhere or stick. The shaped article molded into a desired shape includes at least a metal having a melting point higher than the sintering temperature of the metal, alloy, or metal compound forming the image formed on the combustible sheet in the first step (noble metal, base metal, These alloys) products (it may be a simple uncut metal plate), minerals (including rocks and processed products), ceramics and the like. In this second step, the method for adhering or adhering the combustible sheet or the photographic film or photographic paper on which development and fixing has been carried out is not particularly limited, and for example, a seal type of which one side is previously coated with an adhesive or an adhesive is used. The sheet may be pressure-sensitive adhesive or hot-melt adhesive as it is.For a sheet, a photographic film or a photographic paper which is not treated in any way, an adhesive or a pressure-sensitive adhesive is applied to either one or both of the molded article and the sheet. It may be adhered or tacked. Further, the sheet of transfer paper for ceramics may be transferred in accordance with a standard method, that is, by wetting with water to transfer an image onto the surface of the modeled object. Further, an appropriately cut product such as a portion on which an image is formed may be adhered or adhered. In addition, it is preferable that the surface of the sheet on which the image is formed is a surface to be attached to the modeled object, and for that purpose, the image is inverted (mirror image) and drawn.

As the modeled object used in the second step,
A molded object produced by using a clay-like substance obtained by kneading a binder composed of a binder resin and a solvent such as water, and a powder composed of at least one of a sinterable metal, an alloy, and a metal compound. You may use. Specific examples of sinterable metals, alloys, and metal compounds used for this clay-like substance include Au and P.
Noble metals such as t, Pd, Ag, Fe, Cu, Ni, S
Base metals such as n and Pb, and alloys and metal compounds thereof are used. The size of the powder is preferably such that the particle size is 1 to 100 micrometers and 90% or more of the entire powder is closed. In particular, those having an average particle size of 5 to 30 micrometers and being appropriately distributed are desirable. This is because small particles are mixed between large particles, and the voids between giant particles are filled with fine particles, so that a high-density, therefore low-shrinkage, metal-sintered shaped article can be obtained. Furthermore, the particle shape of the powder is not particularly limited, such as spherical shape, lump shape, and teardrop shape, and it is desirable to use high-density powder having a low porosity inside the powder. For example, when a powder produced by a wet method is used, there are many voids inside the powder, and when the particles are heat-melted by sintering and try to be spherical due to surface tension, the voids are filled with molten metal inside, and Trying to become. Therefore, the apparent volume is reduced and the shrinkage rate is increased. In addition, the binder resin is not particularly limited in its components, and for example, starch or water-soluble cellulose resin can be used.

As a third step of the present invention, the combustible sheet having the image obtained in the first step or the photographic film or photographic paper on which development and fixing have been performed is adhered to the surface of the molded article in the second step. The adhered one is sintered in an electric furnace or the like. The sintering atmosphere constitutes the nature of the components that make up the image on a combustible sheet or photographic film or photographic paper that has been developed and fixed, or the clay-like material if the model is made from a clay-like material. Judging from the properties of the components to be added, it is carried out under the conditions of a low oxygen concentration (non-oxidizing) atmosphere or a reducing atmosphere, if necessary. When the sheet body (or photographic film or photographic paper), toner, or modeled object is made of a clay-like substance during the temperature raising process, organic substances, solvents, etc. contained in this clay-like substance are burned. , Disappears due to decomposition, evaporation, etc. By further raising the temperature, the metal, alloy, or metal compound that is a component of the image adheres or sticks to the modeled object, and the image is transferred to the surface of the modeled object and sintered.

As described above, according to the present invention,
Any sintered image can be formed very easily.
That is, it is possible to extremely easily produce a molded article with a sintered image on which an arbitrary image is formed. Since a copying machine, a printer, a facsimile, a photographic machine or the like can be used for the image formation in the first step which is the basis of the sintered image, any
Complex images can be produced with good reproducibility. In a copying machine using a single particle developer, a character, figure, or drawing drawn by a designer, calligrapher, or general creator is copied using a writing instrument with a thin line drawing such as a pencil or a pen, or a writing instrument with a thick line drawing such as a writing brush. It is also possible to provide excellent reproducibility, especially when a large number of shaped articles having the same image are produced, and is industrially useful. Further, since a printer can be used, it is possible to connect to a computer and variously process and create an image on a computer screen, or variously combine and output and display. Further, since a facsimile can be used, it is possible to faithfully reproduce the original image of the creator at a distance. Even if the painted part of the modeled object has a curved surface, it suffices to sinter a combustible sheet, photographic film, or photographic paper along the curved shape of the painted part, so there is no hindrance to the work. Does not happen.

Further, in the present invention, an image is formed by an electrostatic recording method (including an electrophotographic method) or a magnetograph method using a developer containing at least one kind of a sinterable metal, an alloy and a metal compound. The clay-like substance is attached to a combustible sheet or a photographic film or photographic paper printed by a silver salt photography method, or a paste-like substance obtained by diluting the clay-like substance is applied, dried, and then baked by heating. The present invention also proposes a method for producing a molded article with a sintered image, which is characterized by being bonded.

Since the clay-like substance has adhesiveness, the first-mentioned clay-like substance is not required to intervene.
It can be attached to the surface of the combustible sheet, photographic film or photographic paper obtained in the step, dried and brought into close contact. Further, the paste-like substance obtained by diluting the clay-like substance with a solvent such as water is a brush or a brush on the surface of the combustible sheet, photographic film or photographic paper obtained in the first step, or screen printing, ink jet type. It can be applied by using a printing machine, dried and brought into close contact. By subjecting this state to the above-mentioned third step, a molded article with a sintered image can be produced.

[0013]

Examples of the present invention will be described below. Example 1 Silver powder (particle size 1 to 100 μm, average particle size 10)
~ 30 μm) 80 wt%, methylcellulose 1 wt%,
The silver slurry obtained by kneading 19 wt% of water was printed on one side by a laser printer (using a single particle developer containing iron oxide) connected to a general-purpose personal computer. The printing surface of 100 mm printer paper was uniformly applied with a thickness of about 100 μm and dried at 50 ° C. for 30 minutes. Put this in an electric furnace and let it reach the ambient temperature (oxidation) from room temperature to 800 ° C over 60 minutes.
After the temperature was raised in the atmosphere, the temperature was kept at 800 ° C. for 30 minutes for sintering. After that, the heating is stopped and the inside of the electric furnace is heated to 10
As a result of standing to cool to 0 ° C. or lower, a satin-finished silver thin plate on which a sintered image of iron oxide (image in which the star marks were uniformly transferred) was formed was obtained.

Example 2 A monochrome photograph of a landscape photograph was copied onto paper by a copying machine using a one-particle developer containing iron oxide. A copied portion of the landscape was cut out and attached to the outer surface of a cup-shaped container made of an alloy of 75 wt% gold and 25 wt% silver with an adhesive mixture of an epoxy resin, an acrylic resin and a solvent.
This was placed in an electric furnace, and the temperature was raised from room temperature to 800 ° C over 60 minutes in the atmosphere (oxidizing), and then at 800 ° C for 3 minutes.
It was held for 0 minutes to perform sintering. After that, the heating was stopped, and the mixture was allowed to cool to 100 ° C. or lower in an electric furnace. As a result, a cup-shaped container made of gold alloy was obtained in which the sintered image (landscape image) of iron oxide was transferred to the outer surface. It was

[Example 3] A pictorial pattern was copied onto a slightly thick paper containing no clay by using an electrophotographic copying machine adopting the one-particle developing method. A conical shape was formed with the surface on which the picture pattern was copied inside, and the silver clay used in Example 4 was thinly stretched into a plate shape, and the conical shape was formed inside so that the picture pattern and the clay surface were in firm contact. Paste it on and shape it,
It was dried at about 100 ° C. for about 1 hour with the paper and the silver clay stuck together. Then, it was put in an electric furnace and heated up to 800 ° C. After holding at 800 ° C. for 30 minutes, heating was stopped, the mixture was allowed to cool as in Example 4, and then taken out of the furnace. When the temperature is raised, the binder components in the paper and silver clay and the organic substances in the toner have disappeared due to burning, decomposition and evaporation, etc., and are contained in the toner (developer) for the electrophotographic copying machine drawn on the paper. The magnetic powder was deposited and sintered on the surface of the silver conical object. A silver cone-shaped article was obtained in which a black picture was copied on the surface of white pear surface, and the picture pattern was firmly attached and transferred without rubbing.

Example 4 8 g of a binder obtained by dissolving 14 g of methyl cellulose in 70 g of water and silver powder produced by the atomizing method (particle size 1 to 100 μm, average particle size 10 to 10 μm).
20 μm) 100 g was kneaded to prepare silver clay. Using this silver clay, a cup-shaped container was modeled. Then, the pattern to be transferred to the surface of the drinking water was copied on paper by an electrophotographic copying machine adopting the single particle developing method. This desired pattern portion is cut out, attached to the surface of the silver clay molded article, dried at 80 ° C. for about 30 minutes, and then heated in an electric furnace from room temperature to 800 ° C. for about 1 hour, and then at 800 ° C. for 20 minutes. Hold and sinter. After that, heating was stopped and the product was taken out when the temperature in the furnace reached 300 ° C. As a result, a silver-molded article having a black sintered image (picture) formed on shirashi satin was obtained.

[Example 5] 70 wt% copper, 30 wt% zinc
%, A brass plate with a thickness of 1.5 mm and a length and width of 50 mm, and a photographic film on which a human image is developed and fixed within a length of 40 mm and a width of 35 mm is attached with an adhesive mixture of epoxy resin, acrylic resin and solvent. I attached it. This was placed in an electric furnace and heated from room temperature to 400 ° C. in the atmosphere (oxidizing) atmosphere for 120 minutes, and then to 700 ° C. in the ammonia decomposing gas (reducing) atmosphere for 30 minutes.
It hold | maintained at 00 degreeC for 20 minutes, and sintered. After that, the heating was stopped, and the mixture was allowed to cool to 100 ° C. or lower in an electric furnace, and as a result, a molded product in which a silver sintered image (person image) was transferred to the surface of the brass plate was obtained.

[0018]

INDUSTRIAL APPLICABILITY As described above, according to the present invention, the electrostatic recording method (including the electrophotographic method) or the magneto-resistive method using the developer containing the sinterable metal, alloy or metal compound on the surface of the modeled object. An image formed on a combustible sheet by the graph method,
An image developed and fixed on a photographic film or photographic paper can be easily transferred by the silver salt photographic method. Especially when an image copied by a copying machine using a one-particle developer is used, a complicated image pattern or the like can be transferred very easily. Even if the painted part of the shaped object is a curved surface, it is sufficient to sinter a combustible sheet or photographic film or photographic paper that has been developed and fixed along the curved shape of the painted part. There is no hindrance to.

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Shinichi Ishigaki 6-28-3 Minamimachi, Fuchu-shi, Tokyo Aida Chemical Industry Co., Ltd.

Claims (5)

[Claims] 1. A sinterable metal, alloy or metal compound.
A combustible sheet on which an image is formed by using a developer containing one or more kinds, or a photographic film or photographic paper imaged and developed and fixed by a silver salt photographic method, is adhered to the surface of a molded object formed into a desired shape. Alternatively, a method for producing a molded article containing a sintered image, which comprises sticking, heating and sintering the same. 2. The molded product is a clay-like substance obtained by kneading a binder composed of a binder resin and a solvent thereof and a powder composed of at least one of a sinterable metal, an alloy and a metal compound. The method for producing a molded article with a sintered image according to claim 1, characterized in that it is produced by 3. A sinterable metal, alloy or metal compound.
A combustible sheet on which an image is formed using a developer containing one or more kinds, or a photographic film or photographic paper which has been transferred by a silver salt photographic method and developed and fixed, and a binder comprising a binder resin and a solvent thereof, A clay-like substance kneaded with a powder of at least one of a sinterable metal, an alloy, and a metal compound is applied, or a paste-like substance obtained by diluting the clay-like substance is applied, dried, and then baked by heating. A method for producing a molded article containing a sintered image, which is characterized by being bonded. 4. One of sinterable metals, alloys and metal compounds.
A combustible sheet on which an image is formed using a developer containing one or more kinds, or a photographic film or photographic paper imaged by a silver salt photographic method and developed and fixed, is heated with the surface of the modeled object interposed, A molded article with a sintered image, characterized by forming a sintered image on the surface of the molded article by sintering. 5. The molded product is a clay-like substance obtained by kneading a binder composed of a binder resin and a solvent thereof and a powder composed of at least one of a sinterable metal, an alloy and a metal compound, or The molded product with a sintered image according to claim 4, which is produced by using a paste-like substance obtained by diluting the clay-like substance.