JP3648294B2 - Manufacturing method of shaped object with sintered image and shaped object with sintered image - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a shaped article containing a sintered image and a shaped article containing a sintered image capable of forming an arbitrary image on the surface of a metal product, ceramics, stone or the like.
[0002]
[Prior art]
Conventionally, when applying a pattern to ceramics (painting), the surface of the ceramics modeled using clay is made uneven with a spatula, etc., and a three-dimensional pattern (sculpture) is applied, followed by paint (glaze) ) Is painted using a method such as handwriting or screen printing, and then fired to obtain a patterned ceramic.
In addition, as a method of directly applying a pattern to the surface of the metal body, a method such as engraving or engraving using mechanical methods such as engraving or engraving, a method such as handwriting, screen printing, or using an ink jet printer is used. ing.
[0003]
[Problems to be solved by the invention]
However, when trying to paint by hand on ceramics and metal objects, it was impossible to draw images with excellent design such as letters, figures and pictures without advanced technology. In addition, screen printing and the like should usually give a precise printed image with excellent reproducibility. However, if the printed surface, that is, the painted part of the ceramic or metal object is a curved surface, the printing operation becomes extremely difficult. The predetermined image could not be obtained. Furthermore, when an image is formed by using an ink jet printer connected to a computer, it should be possible to form a precise printed image with various reproducibility, but the painted parts of ceramics and metal objects are curved surfaces. Therefore, it is necessary to control the shape of the ceramic and the metal. Therefore, a very special technique and equipment are required, and a desired image cannot be easily formed on a ceramic or metal body. Therefore, there has been a demand for a method for forming an image that is easy and excellent in reproducibility.
Recently, a method for producing a sintered metal product such as arts and crafts and decorations using metal clay has been adopted. In particular, there are an increasing number of places instructing how to make precious metal arts and crafts, ornaments, etc. at culture centers, etc. using gold and silver clays in which gold powder or silver powder is kneaded into clay. Therefore, a method that can be easily applied to the formation of an image on the surface of these sintered metal products has been desired.
[0004]
[Means for Solving the Problems]
The present invention has been proposed in view of the above, and is imaged by a combustible sheet formed with a developer containing one or more of sinterable metals, alloys, and metal compounds, or by silver salt photography. A clay-like material obtained by kneading a development-fixed photographic film or photographic paper with a binder comprising a binder resin and a solvent thereof, and a powder comprising at least one of a sinterable metal, an alloy and a metal compound. The present invention relates to a method for producing a shaped article containing a sintered image, characterized in that a substance is bonded or adhered to the surface of a shaped article formed into a desired shape, and heated and sintered.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
First, as a first step of the present invention, a developer (toner) containing at least one of a sinterable metal, an alloy, and a metal compound is used, and an electrostatic recording method (including electrophotography) or magnetograph (MG). ) Method to form a desired image on a combustible sheet.
Specific components of sinterable metals, alloys, and metal compounds include simple metals such as Au, Pt, Pd, Ag, Fe, Cu, Ni, Sn, Pb, and Zn, alloys of these metals, or these metals These metal compounds are used, and one or more of these are mixed with a developer (toner).
In the electrostatic recording method, an electrostatic latent image is formed on an insulating layer by charging and exposing a photoconductive layer or using a multi-needle electrode. As a representative method, there are a Carlson method, an electrofax method, an NP method, a KIP method, and an electrostatic recording method using a multi-needle electrode.
In the MG method, a magnetic latent image is formed on the surface of a magnetic thin layer by using a magnetic recording head to form a magnetic latent image, and this magnetic latent image can be developed with a toner containing magnetic powder made of iron oxide or the like. This is a method of obtaining a copy print image by visualizing and transferring and fixing the visible image on paper or the like.
The toner used in the present invention includes a powder of a sinterable metal, alloy, or metal compound among the toners used in the electrostatic recording method and the MG method. Most of those used in the development method are used, and the MG method contains magnetic powder made of iron oxide, so that all can be used in the present invention.
In particular, some toners used in electrophotography include a magnetic powder such as iron oxide, and some use a one-particle magnet developing method. Toners containing iron oxide are widely used in ordinary copying machines, printers, facsimiles and the like. Further, powders of the sinterable metal, alloy, and metal compound may be mixed in a normal toner as long as the developability and fixability are not hindered. The developer used in the electrophotographic copying machine adopting the one-particle development method is a charged adhesive (for example, a dye), a thermoplastic resin or wax, a colored dye or a pigment, and a magnetic fine powder (for example, iron oxide). And is attracted to the magnet through a development sleep or the like.
As the combustible sheet, a paper or film, a seal type paper or film in which an adhesive or an adhesive is applied on one side, an OHP sheet, or the like is used. As a special one, a so-called ceramic transfer paper having a structure in which a water-soluble resin such as dextrin is coated on the surface of a paper substrate that easily contains water may be used.
In the first step, general-purpose and high-functional office equipment such as a copying machine, a printer, and a facsimile can be used, so that a precise image can be arbitrarily formed easily.
[0006]
In place of the first step, a photographic film or photographic paper which is copied and developed and fixed by a silver salt photographic method may be used. That is, a photograph taken by a known method and a photographic film developed and fixed by a known method may be used in the subsequent second step.
[0007]
As the second step of the present invention, the combustible sheet on which the image obtained in the first step is drawn or the photographic film or photographic paper on which the development is fixed is adhered or adhered to the surface of the shaped article formed in a desired shape. To do.
As a shaped article formed into a desired shape, at least a metal (noble metal, base metal, metal) having a melting point higher than the sintering temperature of the metal, alloy, or metal compound constituting the image formed on the combustible sheet in the first step. These alloys) products (may be just raw cut metal plates), minerals (including rocks and processed products), ceramics and the like.
In this second step, the method of bonding or sticking the combustible sheet or the development-fixed photographic film or photographic paper is not particularly limited. For example, a seal type in which an adhesive or an adhesive is applied on one side in advance. The sheet may be pressure-bonded or hot-melt bonded as it is, and an unprocessed sheet, photographic film, or photographic paper is coated with an adhesive or a pressure-sensitive adhesive on either or both of the modeled object and the sheet. Adhering or sticking. The transfer paper sheet for ceramics may be transferred to the surface of the modeled object according to a conventional method, that is, wetted with water. Further, an appropriately cut portion such as a portion where an image is formed may be adhered or adhered. Note that the surface on which the image of the sheet is formed is preferably a surface to be applied to the modeled object, and for this purpose, the image is reversed (mirror image) and drawn.
[0008]
In addition, it was obtained by kneading a binder made of a binder resin and a solvent such as water and a powder made of one or more of a sinterable metal, an alloy and a metal compound as a shaped article used in the second step. You may use the molded article produced using the clay-like substance.
Specific examples of the sinterable metal, alloy, and metal compound used in the clay-like material include noble metals such as Au, Pt, Pd, and Ag, base metals such as Fe, Cu, Ni, Sn, and Pb, and Those alloys and metal compounds are used. Further, it is preferable that the powder has a particle size of 1 to 100 micrometers and closes 90% or more of the whole. In particular, those having an average particle diameter of 5 to 30 micrometers and being appropriately distributed are desirable. This is because a small particle is mixed between large particles, and the fine particles fill the voids between the large particles, whereby a high-density, and thus low-shrinkage, metal sintered shaped article can be obtained. Further, the particle shape of the powder is not particularly limited, such as a spherical shape, a lump shape, or a teardrop shape, and it is desirable to use a high-density powder having a low porosity inside the powder. For example, when powder produced by a wet method is used, there are many voids inside the powder, particles are thermally melted by sintering, and when trying to become spherical due to surface tension, the voids are filled with molten metal and densely packed. Try to become. Therefore, the apparent volume is reduced and the shrinkage rate is increased.
Moreover, as a binder resin, a component in particular is not limited, For example, starch and water-soluble cellulose resin can also be used.
[0009]
As a third step of the present invention, a combustible sheet on which an image obtained in the first step is drawn, or a development-fixed photographic film or photographic paper is adhered or adhered to the surface of a shaped object in the second step Is sintered in an electric furnace or the like.
Sintering atmosphere is the nature of the components that make up the image on the combustible sheet or development-fixed photographic film or photographic paper, or the clay-like material if the model is made from a clay-like material. Judging from the properties of the components to be carried out, it is performed under conditions such as a low oxygen concentration (non-oxidizing) atmosphere or a reducing atmosphere as necessary. In the temperature rising process, when the sheet body (or photographic film or photographic paper), the toner, and the modeled object are made from a clay-like substance, the organic substances and solvents contained in the clay-like substance burn. Disappears by decomposition, evaporation, etc. Further, by raising the temperature, the metal, alloy, or metal compound that constitutes the image adheres to or adheres to the shaped object, and the image is transferred to the surface of the shaped object and sintered.
[0010]
Thus, in the present invention, an arbitrary sintered image can be very easily formed on the surface of the modeled object. That is, it is possible to very easily produce a shaped article containing a sintered image on which an arbitrary image is formed.
For image formation in the first step, which is the basis of the sintered image, a copier, printer, facsimile, camera, etc. can be used, so that any complex image can be produced with good reproducibility. . Copiers that use single-particle developers copy characters, figures, and pictures drawn by designers, calligraphers, or general creators using thin writing tools such as pencils and pens, and thick writing tools such as brushes. In particular, it has excellent reproducibility when, for example, a large number of shaped articles having the same image are produced, and industrial utility value is high. In addition, since a printer can be used, the image can be connected to a computer and various images can be processed and created on the computer screen, or can be output and displayed in various combinations. Furthermore, since a facsimile can be used, it is possible to faithfully reproduce an image created by a distant creator.
Also, even if the painted part of the model is a curved surface, it is only necessary to sinter the combustible sheet, photographic film, or photographic paper along the curved surface shape of the painted part, so there is no hindrance to the work. Does not occur.
[0011]
Furthermore, the present invention is combustible in which an image is formed by electrostatic recording methods (including electrophotography) or magnetograph methods using a developer containing one or more of sinterable metals, alloys and metal compounds. Paste the clay-like substance on a sheet or photographic film or photographic paper copied by silver salt photography, or apply a paste-like substance diluted with this clay-like substance, dry, and then heat-sinter A method for producing a shaped article containing a sintered image is also proposed.
[0012]
Since the clay-like substance has adhesiveness, it is affixed to the surface of the combustible sheet, photographic film or photographic paper obtained in the first step without any adhesive or adhesive. It can be 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, brush, screen printing, or ink jet type on the surface of the combustible sheet, photographic film or photographic paper obtained in the first step. It can be applied and dried using a printing machine.
The thing of this state can be used for the said 3rd process, and a molded article containing a sintered image can be produced.
[0013]
【Example】
Examples of the present invention are shown below.
[Example 1]
A laser printer (containing iron oxide) in which a silver slurry obtained by kneading 80% by weight of silver powder (particle size 1 to 100 μm, average particle size 10 to 30 μm), 1% by weight of methylcellulose and 19% by weight of water is connected to a general-purpose personal computer Using a one-particle developer) ★ is applied evenly to a printing paper surface of 100 mm in length and breadth 100 mm on each side, and dried at 50 ° C. for 30 minutes. I let you.
This was put into an electric furnace, heated from room temperature to 800 ° C. in the atmosphere (oxidation) over 60 minutes, and then held at 800 ° C. for 30 minutes for sintering.
After this, heating was stopped, and after cooling to 100 ° C. or lower in an electric furnace, a satin-like silver thin plate on which a sintered image of iron oxide (an image in which the ★ marks were uniformly transferred) was formed. Obtained.
[0014]
[Example 2]
A landscape photograph printed in monochrome was copied on paper by a copying machine using a one-particle developer containing iron oxide.
The copied portion of the landscape was cut out and attached to the outer surface of an alloy cup type container made of 75 wt% gold and 25 wt% silver with an adhesive mixed with an epoxy resin, an acrylic resin and a solvent.
This was put in an electric furnace, heated from room temperature to 800 ° C. in the atmosphere (oxidation) over 60 minutes, and then held at 800 ° C. for 30 minutes for sintering.
After this, the heating was stopped and the product was allowed to cool to 100 ° C. or lower in the electric furnace. As a result, a cup-shaped container made of a gold alloy with a sintered image (landscape image) of iron oxide transferred to the outer surface was obtained. It was.
[0015]
[Example 3]
Using an electrophotographic copying machine that employs the one-particle development method, the pattern was copied onto a slightly thicker paper that did not contain clay.
The conical shape is made with the surface on which the picture pattern is copied inside, and the silver clay used in Example 4 is thinly stretched into a plate shape. The inside of the conical shape so that the picture pattern and the clay surface are in good contact The paper and silver clay were stuck and dried at about 100 ° C. for about 1 hour.
Subsequently, it put into the electric furnace and heated up to 800 degreeC. After holding at 800 ° C. for 30 minutes, the heating was stopped, the mixture was allowed to cool in the same manner as in Example 4, and then taken out from the furnace. During heating, the binder components in the paper and silver clay and the organic matter in the toner disappear due to combustion, decomposition and evaporation, etc., and are contained in the toner (developer) for electrophotographic copying machines drawn on the paper. The magnetic powder to be adhered and sintered on the surface of the silver cone-shaped product. A silver cone-shaped object with a black picture copied on white pear on the surface was obtained, and the pattern was firmly attached and transferred without rubbing.
[0016]
[Example 4]
Silver clay was prepared by kneading 8 g of a binder obtained by dissolving 14 g of methylcellulose in 70 g of water and 100 g of silver powder (particle size: 1 to 100 μm, average particle size: 10 to 20 μm) produced by the atomizing method. Using this silver clay, a cup-shaped container was shaped.
Next, the pattern to be transferred onto the surface of the cup was copied on paper by an electrophotographic copying machine employing a one-particle development method. This desired pattern portion is cut out, pasted on the surface of the silver clay shaped article, dried at 80 ° C. for about 30 minutes, then heated from room temperature to 800 ° C. for about 1 hour by an electric furnace, and at 800 ° C. for 20 minutes. Hold and sinter. Thereafter, heating was stopped and the furnace was taken out when the furnace temperature reached 300 ° C. As a result, a silver shaped article was obtained in which a black sintered image (picture) was formed on white pear.
[0017]
[Example 5]
A photographic film in which a human image is developed and fixed in a range of 40 mm in length and 35 mm in width on a brass plate with a thickness of 1.5 mm and length and width of 50 mm each consisting of 70 wt% copper and 30 wt% zinc is coated with epoxy resin, acrylic resin and solvent It stuck with the mixed adhesive.
This was put in an electric furnace, heated from room temperature to 400 ° C. over 120 minutes in the atmosphere (oxidation) atmosphere, and then heated to 700 ° C. over 30 minutes in an ammonia decomposition gas (reduction) atmosphere. Sintering was carried out at 20 ° C. for 20 minutes.
Thereafter, the heating was stopped, and the product was allowed to cool to 100 ° C. or lower in an electric furnace. As a result, a shaped article in which a sintered silver image (person image) was transferred to the surface of the brass plate was obtained.
[0018]
【The invention's effect】
As described above, the present invention can be combusted by electrostatic recording (including electrophotography) or magnetography using a developer containing a sinterable metal, alloy, or metal compound on the surface of a model. An image formed on a transparent sheet and an image developed and fixed on a photographic film or photographic paper by silver salt photography can be easily transferred.
In particular, 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.
Also, even if the painted part of the model is a curved surface, it is only necessary to sinter the combustible sheet, the development-fixed photographic film or the photographic paper along the curved shape of the painted part. There will be no trouble.

Claims (3)

A combustible sheet having an image formed using a developer containing one or more of sinterable metals, alloys, and metal compounds, or a photographic film or photographic paper that has been developed and fixed by silver salt photography. On the surface of a shaped object obtained by molding a clay-like substance obtained by kneading a binder resin and its solvent, and a powder made of one or more of sinterable metal, alloy, and metal compound into a desired shape A method for producing a shaped article containing a sintered image, characterized in that it is bonded or adhered, heated and sintered. A sinterable metal, an alloy, a combustible sheet having an image formed using a developer containing one or more metal compounds, or a photographic film or photographic paper that has been developed and fixed by silver salt photography. Paste a clay-like material obtained by kneading a binder resin and its solvent binder and a powder of one or more of a sinterable metal, alloy, or metal compound, or dilute this clay-like material A method for producing a shaped article with a sintered image, characterized in that a shaped substance is applied, dried and then heated and sintered. A combustible sheet having an image formed using a developer containing one or more of sinterable metals, alloys, and metal compounds, or a photographic film or photographic paper that has been developed and fixed by silver salt photography. A shaped article obtained by molding a clay-like substance obtained by kneading a binder resin and a binder thereof and a powder made of one or more of sinterable metal, alloy, and metal compound into a desired shape, or this It is characterized in that a sintered image is formed on the surface of the modeled object by heating and sintering in a state of being interposed on the surface of the modeled object prepared using a paste-like substance diluted with a clay-like substance. A model with a sintered image.