JP2011068958A - Method for producing decorative metal article and decorative metal article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a decorative metal article obtained by combining a composition for silver alloy sintering made of silver or a silver alloy with a composition for sintering made of copper or a copper alloy, and to provide the decorative metal article. <P>SOLUTION: The method includes: a copper-silver shaped body forming step where a copper-containing plastic composition and a silver-containing plastic composition are combined and shaped to form a decor; and a copper-silver shaped-fired body production step where the obtained decor is subjected to atmosphere firing at 660 to 770&deg;C for 3 to 40 min to obtain a decor fired body. The copper-containing plastic composition contains a powdery mixture and an organic binder, wherein the powdery mixture is one or more kinds of powders selected from copper and copper alloy and contains 25 to 75 wt.% first copper powder having an average grain size of 0.1 to 4.0 &mu;m, and the balance composed of a second copper powder having an average grain size of &gt;4.0 to 10 &mu;m. The silver-containing plastic composition contains a powdery mixture and the organic binder, wherein the powdery mixture is one or more kinds of powders selected from silver and silver alloy and contains 25 to 75 wt.% first silver powder having an average grain size of 0.1 to 4.0 &mu;m, and the balance composed of a second silver powder having an average grain size of &gt;4.0 to 40 &mu;m. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  TECHNICAL FIELD The present invention relates to a method for producing a decorative metal product and a decorative metal article obtained by combining a silver or silver alloy sintering composition and a copper or copper alloy sintering composition used in jewelry, ornaments, jewelry, and the like. .

  Conventionally, as a copper material for arts and crafts, a copper-containing plastic composition obtained by mixing copper powder or copper alloy powder and an organic binder is known. As a silver material, a silver-containing plastic composition obtained by mixing silver powder or silver alloy powder and an organic binder is also known. These copper-containing plastic composition and silver-containing plastic composition are shaped, and the copper shaped body and the silver shaped body are fired to obtain a copper shaped fired body and a silver shaped fired body. For example, Patent Documents 1 to 5 can be cited as examples.

In Patent Documents 1 and 2, the first metal particles having an average particle diameter of 3 to 8 μm of 25 wt% or more and less than 100 wt% and the second metal particles having an average particle diameter of 15 to 25 exceeding 0 wt% and 75 wt% or less are used. A plastic composition obtained by mixing a mixed powder with metal particles and an organic binder is used.
As description regarding a copper containing plastic composition, <Example 19> described in the paragraph [0028] of the said patent document 1, and the paragraph [0028] of the said patent document 2 WHEREIN: The 1st copper particle with an average particle diameter of 5 micrometers Is used in combination with 25% by weight of cupric particles having an average particle diameter of 20 μm and 75% by weight.
Then, as described in paragraph [0031] of Patent Document 1 and paragraph [0033] of Patent Document 2, the firing conditions of <Example 19> in which the two types of copper particles were mixed were as follows: It is shown that nitrogen or argon gas was introduced into the inside and fired in an inert atmosphere.
In addition, as a description relating to the silver-containing plastic composition, <Example 1> described in paragraph [0022] of Patent Document 1 and paragraph [0024] of Patent Document 2 includes a first particle having an average particle diameter of 5 μm. An example is shown in which 75% by weight of silver particles and 25% by weight of second silver particles having an average particle diameter of 20 μm are used in combination.
Then, as described in paragraph [0031] of Patent Document 1 and paragraph [0033] of Patent Document 2, the firing conditions of <Example 1> in which the two types of silver particles were mixed were as follows: It is shown that it was baked in, that is, baked in the atmosphere.
However, in Patent Document 1 and Patent Document 2, an example in which a copper-containing plastic composition and a silver-containing plastic composition are combined and shaped, and the shaped body is baked to obtain a fired body is described or suggested. It has not been. Naturally, there is no disclosure as to under what conditions a shaped body in which a copper-containing plastic composition and a silver-containing plastic composition are combined should be fired.

On the other hand, in Patent Documents 3 to 5, a copper-containing plastic composition obtained by mixing copper powder or copper alloy powder and an organic binder is combined with a different noble metal-containing plastic composition, and the molded body is fired. An example of obtaining a fired body is disclosed.
In Patent Documents 3 to 5, copper is included in noble metals, but copper is significantly more resistant to corrosion (oxidation resistance) than general noble metals which are gold, silver and white metal elements. It is well known that it has the property of being inferior.
In Patent Document 3 and Patent Document 4, a plastic composition containing pure gold powder is sintered in air, that is, in an oxidizing atmosphere, and 75.0% by weight of gold, 12.5% by weight of silver, and 12. In the case of a plastic composition containing a so-called alloy metal of K18 mixed at a ratio of 5% by weight, it is described that sintering is performed in an argon gas atmosphere. That is, it is disclosed that even a plastic composition containing an alloy metal such as K18 containing only 12.5% by weight of copper must be sintered in an inert atmosphere.
However, all of these Patent Documents 3 and 4 propose, for example, an invention in which metal powder plastic compositions having different colors are fired in a physically combined state. In a state where the plastic composition A that is fired in an atmosphere and the plastic composition B that is fired in an inert atmosphere containing copper such as K18 are combined, there is no disclosure as to under what conditions. In particular, Patent Document 5 does not allow any description of the firing atmosphere.

As described above, a copper-containing plastic composition obtained by mixing copper powder or copper alloy powder and an organic binder is fired in an inert atmosphere or a reducing atmosphere. This is because, when fired in an oxidizing atmosphere, that is, when fired in the atmosphere, the fired copper shaped fired body becomes extremely weak. In order to increase the strength, it must be sufficiently sintered, so it must naturally be fired for a long time. This is because the degree of oxidation from the surface to the inside increases further, and as a result, the fired copper shaped fired body becomes fragile and unusable.
On the other hand, a silver-containing plastic composition obtained by mixing silver powder or silver alloy powder and an organic binder is fired in the air (fired in an oxidizing atmosphere). This is because silver has an acid resistance property that is not oxidized by atmospheric firing.
A composite shaped body in which a copper-containing plastic composition containing copper or a copper alloy and a silver-containing plastic composition containing silver or a silver alloy are combined is fired “without failure” to obtain a decorative metal article. Therefore, it is not specifically known what conditions and procedures should be used in combination with what composition of the copper-containing plastic composition and what composition of the silver-containing plastic composition.

JP 2007-1131107 A JP 2007-1131106 A Japanese Patent No. 2924139 Japanese Patent No. 2932648 Japanese Patent No. 3389613

In recent years, the silver-containing plastic clay composition has been widely used in the field of jewelery, especially in culture classes, etc., because of its ease of molding, shaped into various shapes with pendant tops, rings, brooches, earrings, etc. It is used and popularized in the field of hobbies.
On the other hand, the firing of the copper-containing plastic composition needs to keep the inside of the furnace in a non-oxidizing atmosphere. For example, it is necessary to suction the air in the heating furnace to make a vacuum, or to replace the furnace by flowing argon gas, nitrogen gas, or hydrogen gas into the furnace, which is extremely complicated compared to the baking method of the silver-containing plastic clay composition. become. Such a baking method involves specialized knowledge and a large amount of money (purchasing a high-performance heating furnace), and is a factor that is not easily accepted.
If a composite shaped body combined with a copper-containing plastic composition and a silver-containing plastic composition can be baked in the atmosphere “for example” in a general-purpose heating furnace, it can be easily applied in culture classes become. In addition, the work is made of copper or copper alloys that are known in many shades, such as red bronze, bronze, white bronze, brass, etc., and silver with silvery, silvery, etc. Alternatively, it becomes possible to obtain a baked article for craft or decoration with a high contrast and a very interesting combination with a silver alloy.

  Therefore, as a result of studying in view of the above, the present inventors have determined that the copper or copper alloy powder in the copper-containing plastic composition is limited to a powder having an average particle size of 10 μm or less. The strength required for a fired article for use is found, and it can be fired in a short time, and has a good appearance and is found to be useful as a fired article for crafts and decorations. When the copper alloy powder and the silver or silver alloy powder in the silver-containing plastic composition are limited to specific mixed powders having different average particle sizes, the copper-containing plastic composition and the silver-containing plastic composition are combined. It was found that even if the composite model was fired in the air, the model could be fired “without failure”, and a highly interesting craft or decorative fired article could be obtained, resulting in the present invention. Is.

  That is, the method for manufacturing a decorative metal article according to claim 1 of the present invention is a first powder having an average particle size of 0.1 to 4.0 μm, which is one or more powders selected from copper and copper alloys. A copper-containing plastic composition containing a copper mixed powder composed of a second powder having an average particle size of more than 4.0 μm and an average particle size of 10 μm or less, and an organic binder, and silver, One or more powders selected from silver alloys, containing 25 to 75% by weight of the first powder having an average particle size of 0.1 to 4.0 μm, and the balance exceeding the average particle size of 4.0 μm A copper-silver shaped body forming step of forming a decorative object by forming a combination of a silver-containing powder composed of a second powder having an average particle size of 40 μm or less and a silver-containing plastic composition containing an organic binder, and obtained The decoration is fired in the atmosphere at 660 to 770 ° C. for 3 to 40 minutes to obtain a decoration fired body. That copper - in which characterized in that it comprises a silver shaped fired body manufacturing process.

According to such a method for producing a decorative fired article, at least one powder selected from copper and a copper alloy in a copper-containing plastic composition is limited to a powder having an average particle size of 10 μm or less, and contains copper. The powder in the plastic composition and the silver-containing plastic composition is a specific mixed powder having different average particle diameters, and a decorative object shaped by combining the copper-containing plastic composition and the silver-containing plastic composition Even if it is fired in the air at the firing temperature and firing time, the molding can be fired “without loss”, and both the copper shaped fired part and the silver shaped fired part have a certain strength required for craft and decorative fired articles. be able to.
These copper-containing plastic composition and silver-containing plastic composition are obtained by using specific mixed powders having different average particle sizes, and the linear shrinkage rate after firing can be suppressed to the same level. In the fired body, one of the shrinkages is too large and does not peel off or lose its shape after firing.
Even if the surface of the copper molding fired portion is oxidized very thinly by air firing, it is not affected by the oxidation to the inside. Therefore, the oxide film on the surface of the copper molding fired part can be easily peeled off, and a product that can be sufficiently used as a fired article for crafts or decoration is obtained. In addition, about the silver modeling baking part, even if it carries out an air baking, it will not receive the influence of an oxidation.
Therefore, since firing in a reducing atmosphere is not performed as in the prior art, a troublesome work that must continue to flow an inert gas such as argon gas and nitrogen gas during firing and a reducing agent such as carbon together with the copper shaped body Troublesome work such as heating in the sealed container can be avoided, and it can be easily applied in culture classes.
Further, in the present invention, since a copper-containing plastic composition and a silver-containing plastic composition are combined to form an ornament and fired at the same time (at once), the firing equipment is not used many times. It is extremely efficient.

The above-described “silver alloy” of the present invention means a silver alloy that does not contain copper, and further represents an oxidation-resistant silver alloy that does not affect the shape of the fired body even when fired in the air. As such a “silver alloy”, for example, a silver-Pd alloy having improved antisulfuration performance can be mentioned.
On the other hand, the “copper alloy” of the present invention described above is a copper alloy even if the copper content is less than 50% by weight. As such an example, the 18K alloy described in the said patent documents 3-5 and the alloy whose copper content is 4 to 5 weight% are mentioned, for example. In addition, the copper alloy which does not contain copper oxide is preferable. By not containing copper oxide, it is possible to avoid becoming porous.
In the present invention, the reducing atmosphere is treated synonymously with an argon gas atmosphere or an inert atmosphere, and includes these.
Further, the “average particle diameter” of copper, copper alloy, silver, and silver alloy according to the present invention is also called a median diameter, a medium diameter, a median diameter, a median diameter, or a 50% particle diameter, and is usually represented by D50. It means the particle size corresponding to 50% of the cumulative curve. Specifically, using a laser diffraction particle size distribution measuring device (manufactured by Microtrac) having three laser scattered light detection mechanisms, the measurement conditions are [particle permeability: reflection] and [true sphere / non-spherical: non-spherical]. ] (When the particle permeability setting is set to reflection and the true / non-spherical selection is set to non-spherical), the D50 value of the particle size distribution is measured.
In the present invention, air firing means firing in the air and is synonymous with firing in an oxidizing atmosphere. The reducing atmosphere is treated synonymously with an argon gas atmosphere or an inert atmosphere and includes these.

The method for manufacturing a decorative metal article according to claim 2 is more preferable than the method for manufacturing a decorative metal article according to claim 1 of the present invention. A more preferable aspect is the method for producing a decorative metal article according to claim 3.
In the method for producing a decorative metal article according to claim 2 of the present invention, the copper-containing plastic composition contains 25 to 75% by weight of the first powder having an average particle size of 0.5 to 4.0 μm, and the balance. Includes a copper mixed powder composed of a second powder having an average particle size exceeding 4 μm and an average particle size of 10 μm or less. The silver-containing plastic composition contains 25 first powders having an average particle size of 0.5 to 4.0 μm. It is characterized in that it contains ˜75% by weight, and the balance is a silver mixed powder composed of a second powder having an average particle size exceeding 4 μm and an average particle size of 30 μm or less.

  In the method for producing a decorative metal article according to claim 3 of the present invention, the copper-containing plastic composition contains 30 to 70% by weight of the first powder having an average particle size of 2.0 to 3.0 μm, with the balance being the rest. A copper mixed powder comprising a second powder having an average particle size of 5 to 10 μm is included, and the silver-containing plastic composition contains 30 to 70 wt% of the first powder having an average particle size of 2.0 to 3.0 μm, The balance is characterized in that a silver mixed powder composed of a second powder having an average particle diameter of 5 to 20 μm is included.

  The method for producing a decorative metal article according to claim 4 of the present invention is characterized in that air baking is performed at 700 to 750 ° C. for 10 to 15 minutes.

  According to the method for producing a decorative metal article according to claim 4, in the mixed shaped body of the copper-containing plastic composition and the silver-containing plastic composition, the molding can be surely fired “without failure” Both the copper shaped fired part and the silver shaped fired part can obtain a certain strength required for a craft or decorative fired article.

  The method for producing a decorative metal article according to claim 5 of the present invention performs the surface oxide film removing step of rapidly cooling, pickling or polishing the decorative article fired body according to any one of claims 1 to 4. It is characterized by this.

  According to the method for producing a decorative metal article of claim 5, even if the surface of the copper or copper alloy copper sintered body (copper molding fired portion) is oxidized very thinly by atmospheric firing, the influence of the oxidation to the inside. Because it is not subjected to rusting, the oxide film on the surface of the copper sintered body (copper molding fired part) can be peeled off very easily by rapid cooling, pickling or polishing, and it is well-suited as a baked article for crafts and decoration. What you do is obtained.

  A decorative metal article according to claim 6 of the present invention is manufactured by the manufacturing method according to any one of claims 1 to 5.

  According to the decorative metal article of claim 6, a copper-silver shaped fired body having various shapes or patterns by combining the copper-containing plastic composition and the silver-containing plastic composition by various techniques. Baked product of copper-containing plastic composition with many shades such as red copper, bronze, white bronze, brass, etc. and silver-containing with silvery, silvery, etc. Since the contrast of the hue of the plastic composition with the fired product is clear and there is no shape limitation, it looks good as a jewelery, ornament, accessory, etc., and can be used as a fired article for crafts and decoration.

According to the method for producing a decorative metal article of the present invention, at least one powder selected from copper and a copper alloy in a copper-containing plastic composition is limited to a powder having an average particle size of 10 μm or less, and a copper-containing plastic composition. And a decorative product formed by combining the copper-containing plastic composition and the silver-containing plastic composition with a specific mixed powder having different average particle diameters, and a predetermined baking temperature. Since the firing is performed in the air for the firing time, the firing in a reducing atmosphere is not performed as in the conventional case, so that an inert gas such as argon gas or nitrogen gas must continue to flow during firing, or a reducing agent such as carbon. The troublesome work, such as heating the outside with a copper shaped body in a sealed container, can be avoided and can be easily applied in culture classes.
Decorative objects shaped by combining a copper-containing plastic composition and a silver-containing plastic composition can be baked “without losing the shape”, and both the copper shaped fired part and the silver shaped fired part can be used as fired articles for crafts and decoration. The required constant strength can be obtained, and the formed decorations are fired in the atmosphere at the same time (simultaneously), so that the firing equipment is not used many times, which is extremely efficient.

  In addition, the decorative metal article of the present invention is a composite shaped body obtained by combining a silver-containing plastic composition and a copper-containing plastic composition, which have been conventionally known as noble metal plastic compositions that can be fired in the atmosphere, and is fired in the air. Yes, as copper or copper alloys are already known in many shades such as bronze, bronze, white, brass, etc. By combining with silver having a silvery color It can be used as a baked article for crafts or decorations with high contrast and high interest.

It is a front view which shows the copper rod-shaped body and silver bar-shaped body which were obtained at the rod-shaped body formation process in the marble pattern technique. It is a front view which shows the state which accommodates a copper rod-shaped body and a silver rod-shaped body in a syringe in the mixing rod-shaped body formation process in a marble pattern technique. It is a perspective view which shows the state which injected and formed the rod-shaped body from the syringe in the mixing rod-shaped body formation process in the marble pattern technique. It is a front view which shows the state which rolled the rod-shaped body in the mixing rod-shaped body formation process in the marble pattern technique, and formed in the column shape. It is a perspective view which shows the state which obtains a mixing rod-shaped body in the mixing rod-shaped body formation process in a marble pattern technique. It is a front view which shows the state which wound and mixed the mixing rod-shaped body in the plane spiral shape in the decoration formation process in a marble pattern technique. It is a front view which shows the state planarized in the ornament formation process in the marble pattern technique. It is a front view which shows the state made into plate shape in the ornament formation process in a marble pattern technique. It is a perspective view which shows the state shape | molded in the ring shape in the ornament formation process in a marble pattern technique. It is a perspective view which shows the state which shapes a modeling body with the file in a decoration formation process in a marble pattern technique. It is a perspective view which shows the state cooled rapidly in the surface oxide film removal process in a marble pattern technique. It is a perspective view which shows the state of pickling in the surface oxide film removal process in a marble pattern technique. It is a perspective view which shows the decoration metal goods (ring) obtained in the marble pattern technique. It is a front view which shows the copper rod-shaped body in a technique according to marble pattern, and a silver rod-shaped body. It is a front view which shows the state which twists together in the mixing rod-shaped body formation process in the technique according to a marble pattern, and forms in a column shape. It is a front view which shows the state extended in the length direction in the mixing rod-shaped body formation process in the technique according to marble pattern. It is a front view which shows the state which divided the mixing rod-shaped body in the mixing rod-shaped body formation process in the technique according to marble pattern. It is a front view which shows the state which sticks together the rod-shaped body parted in the mixing rod-shaped body formation process in the technique according to marble pattern, and forms in a column shape. It is a front view which shows the state which wound the mixing rod-shaped body in the plane spiral shape in the decoration formation process in the technique according to a marble pattern. It is a front view which shows the state which wound and mixed the mixing rod-shaped body in the plane spiral shape in the decoration formation process in another technique of the technique according to a marble pattern. It is a front view which shows the plate-shaped ornament obtained in the ornament formation process in another technique of the technique according to marble pattern. It is a front view which shows the decorative metal article (brooch) obtained in the technique according to marble pattern. It is a front view which shows the state which extended the silver containing plastic composition flatly in the main body formation process in the inlay technique A. It is a front view which shows the plate-shaped main body modeling body obtained at the main body formation process in the inlay technique A. It is a perspective view which shows the state which is performing the dry surface groove | channel formation process in the inlay technique A with the medium file. It is a perspective view which shows the state which embeds a copper containing plastic composition in the groove | channel dried in the copper-silver modeling body formation process in the inlay technique A. FIG. It is a perspective view which shows the deletion grinding | polishing process in the inlay technique A. It is a perspective view which shows the state which opens a hole with a drill blade in the inlay technique A. FIG. It is a perspective view which shows the state cooled rapidly in the surface oxide film removal process in the inlay technique A. It is a perspective view which shows the state of pickling in the surface oxide film removal process in the inlay technique A. It is a perspective view which shows the decorative metal goods (pendant) obtained in the inlay technique A. It is a front view which shows the state which extended the copper containing plastic composition used for the indentation shaping body in the inlay technique B, and the silver containing plastic composition used for a main body shaping body, respectively. It is a perspective view which shows the state which forms the indentation modeling body in the inlay technique B. FIG. It is a perspective view which shows the state which forms the main body modeling body in the inlay technique B. It is a perspective view which shows the state which pushes in and integrates the press molding body dried to the main body modeling body of the clay state in the copper-silver modeling body formation process in the inlay technique B. It is a perspective view which shows the copper-silver molded object grinding | polishing process in the inlay technique B. FIG. It is a perspective view which shows the state cooled rapidly in the surface oxide film removal process in the inlay technique B. It is a perspective view which shows the state of pickling in the surface oxide film removal process in the inlay technique B. It is a perspective view which shows the decorative metal goods (brooch) in the inlay technique B. It is a perspective view which shows the copper plate obtained at the plate formation process in a grain metal technique. It is a perspective view which shows the silver plate obtained at the plate formation process in a grain metal technique. It is a perspective view which shows the state which makes a small amount of water adhere to a joint surface in the multilayering adhesion | attachment process in a grain metal technique. It is a perspective view which shows the composite plate obtained by the multilayering contact | adherence process in a grain metal technique. It is a perspective view which shows the state which divided the composite plate obtained in the multilayer contact | adherence process in a grain metal technique into two equal parts. It is a perspective view which shows the multilayer plate obtained at the decoration formation process in a grain metal technique. It is a perspective view which shows the state which wound the multilayer plate around the wood core stick in the ornament formation process in the wood grain technique. It is a perspective view which shows the state which formed the notch part with the file of the medium grain in the grain pattern formation process in the grain metal technique. It is a perspective view which shows the state cooled rapidly in the surface oxide film removal process in a grain metal technique. It is a perspective view which shows the state of pickling in the surface oxide film removal process in a grain metal technique. It is a perspective view which shows a decorative metal article (ring) in the wood grain technique.

The copper-containing plastic composition used in claim 1 of the present invention is at least one powder selected from copper and a copper alloy, and a first copper powder having an average particle size of 0.1 to 4.0 μm. Is contained in an amount of 25 to 75% by weight, and the balance contains a copper mixed powder composed of a second copper powder having an average particle size of more than 4.0 μm and an average particle size of 10 μm or less, and an organic binder.
The silver-containing plastic composition used in claim 1 of the present invention is one or more powders selected from silver and a silver alloy, and has a first average particle diameter of 0.1 to 4.0 μm. The silver powder is contained in an amount of 25 to 75% by weight, and the balance contains a silver mixed powder composed of a second silver powder having an average particle size exceeding 4.0 μm and an average particle size of 40 μm or less, and an organic binder.

As described above, copper has a bronze color, and copper alloys include bronze, which is a copper alloy with tin, white copper, which is a copper alloy with nickel, and zinc. Many shades are known, such as brass, which is a copper alloy.
Further, silver has a white silver color, and the silver alloy is a silver alloy that does not contain copper as described above, and is an oxidation-resistant silver that does not affect the shape of the fired body even when fired in the air. It means an alloy. Specifically, a silver-Pd alloy to which 1% of Pd is added can be used.
These copper powder, copper alloy powder, silver powder, and silver alloy powder are not particularly specified for production methods such as atomized powder and reduced powder, but it is preferable that the particles have a nearly spherical shape.
A decorative object formed by combining a copper-containing plastic composition and a silver-containing plastic composition containing specific mixed powders each having a different average particle diameter can be fired in the atmosphere, and both the copper shaped fired part and the silver shaped fired part A certain strength required for a craft or decorative sintered article can be obtained, and the shrinkage of each fired body (modeled fired part) after firing can be approximated. It is too large to peel off or lose its shape after firing.
Moreover, even if the surface of a copper shaping | molding baking part oxidizes very thinly by air | atmosphere baking, it will not receive the influence of oxidation to the inside. Therefore, the oxide film on the surface of the copper molding fired part can be easily peeled off by rapid cooling, pickling, polishing, etc., and a product that can be sufficiently used as a sintered article for crafts and decoration can be obtained.

Moreover, about the 1 or more types of powder selected from copper and a copper alloy, About the 1 or more types of powder selected from silver and a silver alloy, Preferably, the copper used in Claim 2 of this invention is preferable. Mixed powder and silver mixed powder are preferable. More preferably, the copper mixed powder and the silver mixed powder used in claim 3 of the present invention are preferable.
According to claim 2 of the present invention, the first copper powder having an average particle size of 0.5 to 4.0 μm is contained in an amount of 25 to 75% by weight, and the remainder exceeds the average particle size of 4.0 μm and has an average particle size of 10 μm or less. A copper mixed powder composed of two copper powders was used.
Moreover, in Claim 2 of this invention, 25 to 75 weight% of 1st silver powder with an average particle diameter of 0.5-4.0 micrometers is contained, and the remainder exceeds average particle diameter 4.0 micrometers, and average particle diameter is 30 micrometers or less. A silver mixed powder made of the second silver powder was used.
In Claim 3 of this invention, the copper mixed powder which contains 30 to 70weight% of 1st copper powder with an average particle diameter of 2.0-3.0 micrometers, and remainder consists of 2nd copper powder with an average particle diameter of 5-10 micrometers. Was used.
Moreover, in Claim 3 of this invention, the silver which consists of 30-70weight% of 1st silver powder with an average particle diameter of 2.0-3.0 micrometers, and the remainder consists of 2nd silver powder with an average particle diameter of 5-20 micrometers. Mixed powder was used.

  Although it does not specifically limit as said organic binder, Cellulose type | system | groups, such as methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, carmellose (carboxymethylcellulose), carboxymethylcellulose sodium, carboxymethylcellulose potassium, carboxymethylcellulose calcium Alginate binders such as binder and sodium alginate, polysaccharide binders such as starch, wheat flour, British gum, xanthan gum, dextrin, dextran and pullulan, animal binders such as gelatin, vinyl binders such as polyvinyl alcohol and polyvinylpyrrolidone, poly Acrylic vines such as acrylic acid and polyacrylic acid ester , Polyethylene oxide, polypropylene oxide, is preferably used by selecting one or more binders from such other resin-based binder such as polyethylene glycol. In the cellulose binder, it is most preferable to use a water-soluble cellulose binder.

When these copper-containing plastic compositions and silver-containing plastic compositions are appropriately combined to form a decorative article as a composite shaped body, the temperature is 660 to 770 ° C. for 3 to 40 minutes, preferably 700 to 750 ° C. It is necessary to bak in the air for 10 to 15 minutes, and baked in the air at a lower temperature and in a shorter time than when the shaped body of the copper-containing plastic composition is baked in the air.
By the way, as the conditions for the atmospheric firing of the shaped article of only the copper-containing plastic composition, the firing temperature of the copper-containing plastic composition whose powder is pure copper is 990 ° C. × 3 minutes to 6 minutes, 980 ° C. × 4 minutes to 15 Minutes, 970 ° C. × 5-30 minutes, 950 ° C. × 5-40 minutes, 850 ° C. × 10-50 minutes, 800 ° C. × 30-60 minutes, preferably 850 ° C.-980 ° C. More preferably, it is 950 to 970 ° C.

Furthermore, if necessary, the following substances may be added to the organic binder as an additive to the copper-containing plastic composition or the silver-containing plastic composition. That is, the additives include organic acids (oleic acid, stearic acid, phthalic acid, palmitic acid, sepacic acid, acetylcitric acid, hydroxybenzoic acid, lauric acid, myristic acid, caproic acid, enanthic acid, butyric acid, capric acid, citric acid. Acid), organic acid esters such as phthalic acid-n-dioctyl, phthalic acid-n-dipyl (methyl group, ethyl group, propyl group, butyl group, octyl group, hexyl group, dimethyl group, diethyl group, isopropyl group, isobutyl Organic acid ester having a group), higher alcohol (octanol, nonanol, decanol), polyhydric alcohol (glycerin, arabit, sorbitan, diglycerin, isoprene glycol, 1,3 butylene glycol), ether (dioctyl ether, didecyl ether) Bones, phenylpropane Or a mixture of two or more selected from the group consisting of lignin, liquid paraffin, and oils and fats (for example, olive oil rich in oleic acid). . These additives are added for the purpose of improving plasticity, or added for the purpose of preventing the copper-containing plastic composition and the silver-containing plastic composition from adhering to the hand during molding. Furthermore, the above additives, lignin and glycerin, provide appropriate water retention.
Further, examples of the additive include anionic, cationic, and nonionic surfactants. The surfactant has an effect of improving the mixing property of silver powder or copper powder and an organic binder and an effect of improving water retention.

Among the organic binders, the water-soluble cellulose binder serves to impart plasticity. Of the organic binders, polyethylene oxide has a function of improving the adhesion in a liquid state by giving a high viscosity at a low concentration. Moreover, although sodium alginate gives moderate water retention like the said glycerol, it contributes also to the contact | adherence improvement effect | action. Furthermore, the polyacrylic acid ester and the polyacrylic acid serve to strengthen the adhesiveness.
The water-soluble cellulose binder serves to impart plasticity as described above, but the water-soluble cellulose binder includes methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose sodium, carboxymethyl cellulose. Potassium, carboxymethylcellulose calcium and the like are used, and are used by dissolving in water.

As the amount of the organic binder in the copper-containing plastic composition and the silver-containing plastic composition using the water-soluble cellulose-based binder described above as an organic binder, as a more preferable aspect, the total amount of the organic binder is a solid content excluding water. It is desirable that it is within a range of 0.1 to 4 wt% in terms of display. In this case, if the amount of the organic binder is less than 0.1 wt%, it is difficult to obtain a homogeneous copper-containing plastic composition and silver-containing plastic composition. In addition, there is a disadvantage that the strength after coating and drying is weakened. When the amount of the organic binder exceeds 4 wt%, the shrinkage rate increases and cracks are likely to occur. Therefore, the amount of the organic binder is desirably 0.1 to 4 wt%.
When polyethylene oxide is used, it is desirable to use polyethylene oxide having a molecular weight of 100,000 to several million within the range of 0.1 to 3 wt%.
Moreover, when using surfactant, it is desirable to exist in the range of 0.03 to 3 wt%, and when using fats and oils, it is desirable to be within the range of 0.1 to 3 wt%.

Furthermore, water is added in a required amount. If it is too small, it becomes hard and difficult to form, and if it is too much, the shape cannot be maintained. The copper-containing plastic composition and silver-containing plastic composition used in the present invention can be prepared in the form of clay, paste, or slurry depending on the water content.
In the above preferred composition, the metal powder is 75 to 99 wt% in any plastic composition. However, if the amount is too small, the shrinkage becomes large and the sintering also becomes troublesome. In addition, the ratio of water is reduced, which hinders modeling.

Moreover, you may add Bi, Se, Sb, In, Sn, Zn powder, or those alloy powders as a sintering promoter.
Furthermore, you may add the metal compound powder or glass powder chosen from lead carbonate, lithium carbonate, zinc oxide, phosphoric acid, sodium carbonate, vanadium oxide, sodium silicate, phosphate etc. as an adhesive improvement agent.
Further, for the purpose of improving plasticity, a network polymer formed by condensation of structural units having a skeleton of phenylpropane such as lignin, glycerin, diglycerin, isoprene glycol, 1,3 butylene glycol, liquid paraffin, alcohols, Fats and oils, phthalic acid, phthalic acid-n-dioctyl, phthalic acid-n-dibutyl, and polyvinyl alcohol may be added, and a surfactant and a surfactant may be added as necessary.

  The copper-containing plastic composition having the above-described configuration and the silver-containing plastic composition can be combined and fired in the atmosphere to obtain a copper-silver shaped fired body. Four techniques to get are introduced below.

As a first technique, a method for manufacturing an ornament including a marble pattern (a marble pattern technique) will be exemplified.
In this method, the copper-containing plastic composition and the silver-containing plastic composition are each formed into a columnar shape to form a copper rod-shaped body and a silver rod-shaped body [bar-shaped body forming step];
A mixed rod-shaped body is formed by entanglement and mixing of the copper rod-shaped body and silver rod-shaped body that have undergone the rod-shaped body forming step;
Flattening at least part of the mixed rod-shaped body that has undergone the mixed rod-shaped body forming step to form a decorative object [decorative object forming step];
[Baked body manufacturing step] to obtain a decorative fired body by firing the obtained decorative object to the atmosphere;
Is included.

[Bar-shaped body forming step]
In this step, the copper rod-shaped body and the silver rod-shaped body to be formed do not necessarily have the same thickness (diameter), and the length does not necessarily have to be the same length. You may form in sheath length.
[Mixed rod forming step]
In this step, the mixed rod-shaped body is formed by entanglement and mixing of the copper rod-shaped body and the silver rod-shaped body that have been subjected to the [bar-shaped body forming step]. The specific method for forming the mixed rod-shaped body by entanglement and mixing the copper rod-shaped body and the silver rod-shaped body is not particularly limited, and may be formed in any way. The mixed rod-shaped body should just be the state which the copper rod-shaped body and silver rod-shaped body which are comprised are each extended | stretched thinly in the length direction, and are entangled and mixed.
[Decoration process]
In this step, at least a part of the mixing rod-like body is flattened to form an ornament. A specific method for forming the decoration from the mixed rod-like body is not particularly limited, and any method may be used.
[Firing body manufacturing process]
In this step, the decorative object obtained is fired in the air to obtain a decorative fired body, but firing is performed at a lower temperature and in a shorter time than firing of a copper shaped body alone or a silver shaped body alone. To do.

  And according to this marble pattern technique, the copper rod-shaped body made of the copper-containing plastic composition and the silver rod-shaped body made of the silver-containing plastic composition are stretched thinly in the length direction, and are in an intertwined state. The mixed rod-shaped body was formed, and the flattened decoration was fired in the atmosphere, resulting in a complex shaped body in which the color of copper or copper alloy and the color of silver or silver alloy were intertwined. It is possible to form a pattern as if it was melted in a state where copper fine wires and silver fine wires were entangled and bundled together, and it could not be obtained by any other method. A decorative metal article with a pattern can be formed.

As a 2nd technique, the manufacturing method (inlay technique A) of an ornament provided with an inlaid pattern is illustrated.
In this method, a main body shaped body is formed with any one of the copper-containing plastic composition and the silver-containing plastic composition [main body forming step];
[Main body drying step] for drying the main body shaped body,
[Dry surface groove forming step] in which grooves are provided on the surface of the obtained dry main body shaped body,
[Copper-silver shaped body forming step] in which the other plastic composition is embedded and integrated in the groove of the dried body shaped body,
[Copper-silver shaped body drying step] for drying the obtained copper-silver shaped body,
Deleting or polishing a portion of the other plastic composition raised from the surface of one plastic composition of the dried copper-silver shaped body [Delete polishing step];
[Circuit body manufacturing step] to obtain a decorative body fired body by firing the deleted or polished copper-silver shaped body in the atmosphere.

[Main body formation process]
In this step, the main body shaped body is formed from either one of the copper-containing plastic composition and the silver-containing plastic composition.
[Main body drying process]
In this step, the main body molded body obtained is dried by natural drying (1 day or more) or by drying with a drying temperature of 80 to 180 ° C. and a drying time of 10 to 60 minutes using a dryer, electric furnace, dryer or the like. .
[Dry surface groove forming process]
In this step, it is possible to easily and finely form a fine groove on the surface of the dried main body molded body using a file or the like, and finally a beautiful and fine inlaid pattern can be obtained. .
[Copper-silver model forming process]
In this step, the other plastic composition is embedded and integrated in the groove of the obtained dried main body molded body. When embedding the other plastic composition, it may be applied in the form of a slurry by diluting with water or with a brush or the like even in a clay state.
[Copper-silver model drying process]
In this step, the obtained copper-silver model is dried by the aforementioned heat drying or natural drying.
[Delete polishing process]
In this step, the portion of the other plastic composition raised from the surface of the one plastic composition of the obtained dried copper-silver model is removed or polished.
[Firing body manufacturing process]
In this step, the removed or polished copper-silver shaped body obtained is fired in the atmosphere to obtain a decorative fired body, but at a lower temperature than the firing of the copper shaped body alone or the silver shaped body alone. Firing is performed in a short time.

  And according to this inlaying technique A, after forming a main body modeling body and drying with any one plastic composition among a copper containing plastic composition and a silver containing plastic composition, dried main body modeling Since a groove is provided on the surface of the body, and the other plastic composition is embedded in the groove and integrated to form a copper-silver shaped body and fired in the atmosphere, a decorative metal article having a beautiful and fine inlaid pattern can be obtained. It can be obtained very easily.

As a third technique, a method for manufacturing an inlaid ornament (inlay technique B) will be exemplified.
In this method, an indented shaped body is formed with any one of the copper-containing plastic composition and the silver-containing plastic composition [indented shaped body forming step];
Indentation [modeling body drying process] for drying the indentation model,
[Copper-silver model body forming step], in which a main body shaped body is formed with the other plastic composition, and the indented shaped body is pressed into the main body shaped body and integrated.
[Copper-silver shaped body drying step] for drying the obtained copper-silver shaped body,
Polishing so that the surface of one plastic composition and the surface of the other plastic composition of the dried copper-silver model may be integrated with each other [copper-silver model polishing step];
And bake the polished copper-silver shaped body in the atmosphere to obtain a decorative fired body [fired body manufacturing step].

[Indented body forming process]
In this step, an indentation molded body is formed with either one of the copper-containing plastic composition and the silver-containing plastic composition, but there is no particular limitation on the shape, so how to form it. May be.
[Dry body drying process]
In this process, the obtained indented shaped body is dried by the aforementioned heat drying or natural drying.
[Copper-silver model forming process]
In this step, the main body shaped body is shaped with the other plastic composition, and the dried indented shaped body is pushed into and integrated with the main body shaped body. In addition, since there is no restriction | limiting in particular in a main body modeling body, you may form in that way.
[Copper-silver model drying process]
In this step, the obtained copper-silver model is dried by the aforementioned heat drying or natural drying.
[Copper-silver model polishing process]
In this step, polishing is performed using a file or the like so that the surface of one plastic composition of the dried copper-silver model and the surface of the other plastic composition are integrated.
[Firing body manufacturing process]
In this step, the dried copper-silver shaped body is fired in the atmosphere to obtain a decorative fired body, which is fired at a lower temperature and in a shorter time than the firing of the copper shaped body alone or the silver shaped body alone. To implement.

  And according to this inlay technique B, after forming an indentation model and drying with any one plastic composition among a copper content plastic composition and a silver content plastic composition, the other plastic composition Since the main body shaped body is formed and the dry shaped body to be pushed in is pushed in and integrated to form a copper-silver shaped body and fired in the atmosphere, an inlaid decorative metal article can be obtained very easily.

As a fourth technique, an example of a method for manufacturing an ornament having a wood grain pattern (wood grain technique) is illustrated.
In this method, a copper-containing plastic composition and a silver-containing plastic composition are each formed into a plate shape to produce a copper plate and a silver plate [plate forming step]
The copper plate and the silver plate are overlapped with each other with water applied to the joint surface, and then a load is applied, and the overlapped thickness with the play is stretched and adhered to each other by 10% or more. Chemical adhesion process],
Forming a copper-silver multilayer ornament using the multilayer plate that has undergone the multilayering step [decoration forming step];
Drying the copper-silver multilayer ornament [copper-silver multilayer ornament drying step];
Cutting or polishing the surface of the dried copper-silver multilayer ornament so that a grain pattern appears, and forming a notch [grain pattern forming step];
And bake the decorative object in which the notch is formed in the air to obtain a decorative fired body [fired body manufacturing step].

[Plate formation process]
In this step, a copper plate and a silver plate are produced by forming a copper-containing plastic composition and a silver-containing plastic composition into a plate shape, respectively.
[Multilayer adhesion process]
In this process, the copper plate and the silver plate are overlapped with each other by adding water to the joint surface, and then the load is applied and stretched so that the overlapped thickness of the plate is reduced by 10% or more. Paste together.
[Decoration process]
In this step, a copper-silver multilayer ornament is formed using the multilayer plate.
[Copper-silver multilayer decoration drying process]
In this step, the copper-silver multilayer ornament is dried by the above-mentioned heat drying or natural drying.
[Wood grain pattern forming process]
In this step, the surface of the dried copper-silver multilayer decorative article is cut or polished so that a grain pattern appears, thereby forming a notch.
[Firing body manufacturing process]
In this step, the decorative object in which the notch is formed is fired in the atmosphere to obtain a decorative fired body, which is fired at a lower temperature and in a shorter time than the firing of the copper shaped body alone or the silver shaped body alone. To implement.

  Then, according to this wood grain technique, the surface of a copper-silver multilayer decorative article in which a copper plate made of a copper-containing plastic composition and a silver plate made of a silver-containing plastic composition are stacked in layers and adhered is cut. Or the decoration provided with the grain metal pattern can be obtained very easily by air-baking the decoration formed by polishing and forming the notch.

[Effect of particle size of copper powder in copper fired body]
<Raw materials used>
The copper powder constituting the copper-containing plastic composition is pure copper, and is a copper mixture in which 50% by weight of a first copper powder having an average particle diameter of 2.5 μm and 50% by weight of a second copper powder having an average particle diameter of 10 μm are mixed. Powder was prepared. 90% by weight of this copper mixed powder, 1.20% by weight of methylcellulose as an organic binder, 0.30% by weight of sodium carboxymethylcellulose and 8.50% by weight of water were mixed thoroughly to form a clay, and the length was 50 mm. A test piece having a thickness of 10 mm and a thickness of 1.5 mm was prepared, dried at 80 ° C. × 30 min, the length was measured, and the shrinkage was determined. And it baked in air | atmosphere (oxidizing atmosphere) at 970 degreeC for 30 minutes using the electric furnace, and the surface of the obtained copper modeling baking body was polished and it was set as the test piece.
The bending strength was obtained by the following equation by bending the center of the test piece to a depth of 10 mm with an indenter (speed: 50 mm / min) and measuring the load value at that time.
Bending strength = 3 Pl / 2bd ²
P: Load value,
l: Distance between supporting points b: Specimen width d: Specimen thickness In addition, as a reference example, instead of the copper mixed powder, a powder having the powder composition shown in Table 1 was formed in the same manner to make a specimen. Then, it was dried and fired under the same conditions, and the surface of the obtained copper molded fired body was polished and pickled to obtain a test piece. The two types of mixed powders in the table were blended equally (50 wt% each), and the three types of mixed powder were also blended equally (100/3 wt% each).

<result>

<Discussion>
In the copper-containing plastic compositions of Examples A to C containing a copper mixed powder having an average particle size of 10 μm or less, it was confirmed that a beautiful surface state would be obtained by subsequent polishing and pickling even after firing in the atmosphere. It was.
On the other hand, the copper-containing plastic compositions of Comparative Examples A and B to which copper powder having an average particle size of 40 μm is added have a low bending strength and are not suitable as a copper shaped fired body.
In addition, the copper-containing plastic composition of Example A containing 50% by weight of a first powder having an average particle size of 2.5 μm and 50% by weight of a second powder having an average particle size of 10.0 μm is the most. The result was desirable.
Incidentally, the copper-containing plastic compositions of Comparative Examples A and B had the above-mentioned results when fired in the atmosphere. However, when this copper-containing plastic composition was fired in an argon gas atmosphere, it could be used as a decorative article. A copper shaped fired body was obtained.

[Evaluation of firing conditions in copper-silver fired body]
<Raw materials used>
The copper powder constituting the copper-containing plastic composition is pure copper, and the first copper powder having an average particle diameter of 2.5 μm is 50% by weight (45 wt%) and the second copper powder having an average particle diameter of 10 μm is 50% by weight (45 wt. %) Was prepared. The copper mixed powder 90 wt%, 1.20 wt% methylcellulose as an organic binder, 0.30 wt% sodium carboxymethylcellulose and 8.50 wt% water were thoroughly mixed to form a clay to obtain a copper-containing plastic composition.
The silver powder constituting the silver-containing plastic composition is pure silver, and 50 wt% (46 wt%) of the first silver powder having an average particle diameter of 2.5 μm and 50 wt% (46 wt%) of the second silver powder having an average particle diameter of 20 μm. %) Was prepared. A clay-like silver-containing plastic composition was prepared by sufficiently mixing 92% by weight of this silver mixed powder, 0.7% by weight starch as an organic binder, 0.8% by weight cellulose, and the remaining water as a water-soluble binder.

<Create test piece>
The silver-containing plastic composition and the copper-containing plastic composition are weighed so as to have a predetermined ratio, and are formed into a columnar shape having a width of about 3 mm with a finger to produce a silver bar and a copper bar, respectively. did.
The stretched silver bar and copper bar were put into an empty syringe without being twisted. When either one was long, the end was folded back and accommodated, and a columnar mixing rod-like body was ejected from the syringe.
As the syringe, a 2.0 ml syringe having a cylinder inner length of 8 cm, an inner diameter of 6 mm, and an extrusion port inner diameter of 1.4 mm (manufactured by Top Co., Ltd., medical device notification number 13B1 × 00085000023) was used.
The obtained mixing rod-shaped body was folded in half, and the two were twisted four times to form a columnar shape, which was then accommodated in the syringe, and the mixing rod-shaped body was ejected from the syringe.
This operation was repeated three times to obtain a mixed rod-like body in which the linear shape of the copper-containing plastic composition and the linear shape of the silver-containing plastic composition were intertwined in an intricate manner.
The obtained mixed rod-like body was injected onto a work table and wound into a plane spiral shape, and the upper surface thereof was flattened to form a plate shape, and the plate was pressed from the outside to form a flat plate shape.
Next, it was flattened with a roller (1.5 mm thickness), and a test piece (modeled body) of about 15 mm in length and 15 mm in width was created with a cutter.
After drying the obtained test piece, it was fired in the atmosphere under the conditions of 650 ° C. × 30 minutes to 850 ° C. × 5 minutes, and the firing time was shortened as the temperature became higher.
In addition, the atmospheric firing was performed by preheating the electric furnace to the above temperature, putting it in the electric furnace maintained at the set temperature, and maintaining a predetermined temperature and time.
After firing, it was quenched in water. The oxide film was removed well.
Next, it was immersed in a solid acid material for pickling (trade name: Pickling Compound, manufactured by GROBET FULE CO. OF AMERICA, INC., Main component: sodium hydrogen sulfate) to remove the oxide film on the surface of the sintered body.
The surface became glossy by polishing with a stainless steel brush or the like as necessary.
As a result, a test piece having a marbled surface layer pattern of two types (two colors) of silver and copper was obtained.

The firing conditions were changed, and the ratio of the copper-containing plastic composition to the silver-containing plastic composition was changed within the range of copper 83 wt%: silver 17 wt% to copper 17 wt%: silver 83 wt%. 2 to Table 7 were obtained.
Test 1 is a baking condition of 650 ° C. × 30 minutes, and Table 2 shows the result.
Test 2 was baking conditions at 700 ° C. for 15 minutes, and Table 3 shows the results.
Test 3 is a baking condition at 750 ° C. × 10 minutes, and Table 4 shows the result.
Test 4 is a baking condition of 780 ° C. × 5 minutes, and Table 5 shows the result.
Test 5 is a baking condition of 800 ° C. × 5 minutes, and Table 6 shows the result.
Test 6 is a baking condition of 850 ° C. × 5 minutes, and Table 7 shows the result.
In Tables 2 to 7, “◯” and “Δ” in the evaluation column are usable evaluations, and “×” is an unusable evaluation. The “△” evaluation was an apparent problem that it was difficult to understand the marble pattern aesthetically, and it was not a problem for decorations with different designs, and had sufficient strength in use.

<result>

<Discussion>
In Test 1 (Table 2), Test 4 (Table 5), Test 5 (Table 6), and Test 6 (Table 7), regardless of the ratio of the copper-containing plastic composition and the silver-containing plastic composition, no good results were obtained. Only obtained.
In contrast, in Test 2 (Table 3) and Test 3 (Table 4), conversely, good results were obtained regardless of the ratio of the copper-containing plastic composition and the silver-containing plastic composition, and 700 ° C. × 15 It was confirmed that minutes to 750 ° C. × 10 minutes are conditions under which good atmospheric firing can be performed in firing this copper-silver mixed shaped body.
From this result, when a decorative object is formed as a composite shaped body by appropriately combining a copper-containing plastic composition and a silver-containing plastic composition, it can be air-fired at 700 to 750 ° C. for 10 to 15 minutes. In particular, it was possible to make an ornament with a design in which copper and silver were well-balanced.

[Manufacture of copper-silver decorative metal products with complex marble pattern 1 (Marble pattern technique)]
<Raw materials used>
The same silver-containing plastic composition and copper-containing plastic composition as used in <Raw material used> in [Evaluation of firing conditions in copper-silver fired body] were used.
<Bar-shaped body formation process>
6 g of the silver-containing plastic composition and 3 g of the copper-containing plastic composition are formed by extending them into pillars having a width of about 3 mm with fingers, respectively, and as shown in FIG. 1, 70 mm silver rods 2 and 35 mm copper A rod-shaped body 1 was formed.
<Mixed rod forming process>
The obtained silver rod-like body 2 and copper rod-like body 1 were put in an empty syringe 21 as shown in FIG. In this case, since the silver rod-shaped body 2 was long, the end portion was folded back and accommodated, and the columnar mixed rod-shaped body 3 was injection-formed from the syringe 21 as shown in FIG.
As the syringe 21, a 2.0 ml syringe (manufactured by Top Co., Ltd., medical device notification number 13B1 × 00085000023) having a cylinder inner length of 8 cm, an inner diameter of 6 mm, and an extrusion port inner diameter of 1.4 mm was used.
The obtained mixed rod-shaped body 3 is folded in half, and the two are crushed four times as shown in FIG. 4 and accommodated in the syringe again. The rod-shaped body is formed by injection from the syringe, and this operation is repeated three times. As shown in FIG. 5, a single mixed rod 4 was obtained in which a large number of copper rods elongated in the lengthwise direction and a large number of silver rods were intricately entangled and mixed. .
<Decoration process>
The obtained mixed rod-shaped body was ejected onto a work table, and the injected mixed rod-shaped body was wound into a flat spiral shape, wound slightly elongated, and pressed and integrated from the outside to obtain a shaped body 5 shown in FIG. .
Next, the upper surface is flattened with a roller (1.5 mm thick) to form a shaped body 6 shown in FIG. 7, and the periphery is further cut to a width of about 1 cm with a cutter, and the plate-like shaped body 7 shown in FIG. did.
As shown in FIG. 9, the plate-shaped shaped body 7 is wound around a wood core bar 22 of No. 16 to obtain a ring-shaped shaped body 8.
The shaped body 8 was put into a dryer set at a drying temperature of 100 ° C. and dried for a drying time of 30 minutes.
After drying, the ring-shaped shaped body 8 was shaped with a file 23 as shown in FIG.
<Firing body manufacturing process>
The resulting shaped body (decorated object) was air-fired at 750 ° C. for 10 minutes.
In addition, the atmospheric firing was performed by preheating the electric furnace to the above temperature, putting it in the electric furnace maintained at that temperature, and maintaining a predetermined temperature and time.
<Surface oxide film removal process>
After firing, the fired body 9 was placed in water 24 and rapidly cooled as shown in FIG. The oxide film was well removed in water.
Next, as shown in FIG. 12, the fired body 9 is immersed in an aqueous solution 25 of a solid acid material for pickling (trade name: Pickling Compound, manufactured by GROBET FULE CO. OF AMERICA, INC.). The oxide film was removed.
The surface became glossy by polishing with a stainless steel brush or the like as necessary.
As a result, a decorative metal article (ring) 10 having a complicated marble pattern made of two kinds (two colors) of silver and copper shown in FIG. 13 was completed. The obtained ring 10 was attached as a reference photograph (A). This marble pattern was a pattern as if it were formed by melting two types of ultrafine metal wires that were tangled and bundled together.

[Manufacture of Decorative Metal Products with Complex Marble Patterns 2 (Technique Based on Marble Patterns)]
<Raw materials used>
The same silver-containing plastic composition and copper-containing plastic composition as used in <Raw material used> in [Evaluation of firing conditions in copper-silver fired body] were used.
<Bar-shaped body formation process>
Using the silver-containing plastic composition and the copper-containing plastic composition, each is formed by extending it into a column having a width of about 3 mm with a finger to form a silver rod-like body 32 and a copper rod-like body 31 having a length of 70 mm shown in FIG. did.
<Mixed rod forming process>
The obtained silver bar 32 and copper bar 31 are twisted together to form a column as shown in FIG. 15, stretched in the length direction as shown in FIG. 16, and then mixed bar 33 as shown in FIG. The mixed rod-like bodies 33, 33 were crushed together as shown in FIG. 18 and repeatedly formed into a columnar shape to form a mixed rod-like body.
<Decoration process>
The obtained mixed rod-shaped body is wound in a plane spiral shape as shown in FIG. 19 to form a shaped body 34, and the upper surface thereof is flattened with a roller to form a shaped body 35 shown in FIG. 20, and the surroundings are further cut with a cutter. A plate-like ornament 36 shown in FIG. 21 was obtained.
The decoration 36 was placed in a dryer set at a drying temperature of 100 ° C. and dried for a drying time of 30 minutes.
After drying, it was calcined at 750 ° C. for 10 minutes.
<Surface oxide film removal process>
After firing, the substrate was immersed in a dilute sulfuric acid aqueous solution or the like to remove the oxide film in the direction of the copper fired portion.
The surface became glossy by polishing with a stainless steel brush or the like as necessary.
As shown in FIG. 22, a decorative metal article (brooch) 37 having a complicated marble pattern made of two kinds (two colors) of silver and copper was completed. Although the shapes were different, a ring obtained in substantially the same manner was attached as a reference photograph (B).

[Manufacture of copper-silver decorative metal products with beautiful and fine inlay patterns (inlay technique A)]
<Raw materials used>
The same silver-containing plastic composition and copper-containing plastic composition as used in <Raw material used> in [Evaluation of firing conditions in copper-silver fired body] were used.
<Main body formation process>
The silver-containing plastic composition and the copper-containing plastic composition were used.
The silver-containing plastic composition 10 g was flattened to a thickness of about 1.5 mm with a roller to obtain a shaped body 41 having an equal thickness shown in FIG. Furthermore, the periphery was cut with a cutter, and a rectangular plate-shaped shaped body 42 having a length of 35 mm and a width of 15 mm shown in FIG. 24 was created.
<Main body drying process>
The obtained main body shaped body 42 was put into a drier set at a drying temperature of 100 ° C. to obtain a dried main body shaped body 43 with a drying time of 30 minutes.
<Dry surface groove forming process>
A groove 44 was formed on the surface of the dried main body shaped body 43 using a medium mesh file 26 as shown in FIG. In addition, although it may be dented with a spatula in the clay state, in the case of forming a sharp groove, it is desirable to form the groove in the main body shaped body 43 thus dried.
The groove 44 to be cut was formed in a reverse wedge shape so as to become wider toward the inside.
<Copper-silver structure forming process>
The copper-containing plastic composition 46 is embedded in a groove 44 formed on the surface of the dried main body modeling body 43 as shown in FIG. Formed.
<Copper-silver shaped body drying process>
The obtained copper-silver shaped body 45 was put into a dryer set at a drying temperature of 100 ° C. and dried for a drying time of 30 minutes.
<Deleted polishing process>
As shown in FIG. 27, the surface of the obtained copper-silver shaped body 45 is a sponge abrasive (trade name: 3M sponge abrasive, manufactured by Sumitomo 3M Co., Ltd., model: Superfine # 320 to # 600) 28. Sharpened until the pattern was visible, and the sides were trimmed with a medium file. Reference numeral 47 denotes a decorative body that has been shaved until a pattern is visible.
<Firing body manufacturing process>
In order to make the obtained shaped body (decorative object) 47 into a pendant, a hole was made with a drill blade 29 as shown in FIG. 28, and the ornamental object was baked in the atmosphere at 750 ° C. for 10 minutes.
In addition, the atmospheric firing was performed by preheating the electric furnace to the above temperature, putting it in the electric furnace maintained at that temperature, and maintaining a predetermined temperature and time.
<Surface oxide film removal process>
After firing, the fired body 48 was placed in water 24 and rapidly cooled as shown in FIG. The oxide film was removed well.
Next, as shown in FIG. 30, the fired body 48 is dipped in an aqueous solution 25 of a solid acid material for pickling (trade name: Pickling Compound, manufactured by GROBET FULE CO. OF AMERICA, INC) to oxidize the surface of the sintered body 48. The membrane was removed.
The surface became glossy by polishing with a stainless steel brush or the like as necessary.
As a result, as shown in FIG. 31, a decorative metal article (pendant) 49 having a beautiful and fine inlaid pattern made of two kinds (two colors) of silver and copper was easily obtained.
In this example, copper was inlaid on the base of silver, but silver could be inlaid on the base of copper.

[Manufacture of inlaid copper-silver decorative metal products (inlay technique B)]
<Raw materials used>
The same silver-containing plastic composition and copper-containing plastic composition as used in <Raw material used> in [Evaluation of firing conditions in copper-silver fired body] were used.
<Indented body forming process>
The copper-containing plastic composition 51 is flattened to a thickness of 1 mm with a roller as shown on the left side of FIG. 32, and cut into a desired shape with a cookie mold for home cooking as shown in FIG. .
<Model body drying process>
The obtained indented shaped body 53 was put into a dryer set at a drying temperature of 100 ° C. and dried for a drying time of 30 minutes.
<Copper-silver structure forming process>
The silver-containing plastic composition 52 is flattened to a pressure of 3 mm with a roller as shown in the right of FIG. 32, and cut out with a mold that is slightly larger than the cut-out mold 53 as shown in FIG. 54.
While the main body shaped body 54 was soft, the dried indented shaped body 53 was pushed into a copper-silver shaped body 55 as shown in FIG.
<Copper-silver shaped body drying process>
The obtained copper-silver model was put into a dryer set at a drying temperature of 100 ° C. and dried for a drying time of 30 minutes.
<Copper-silver molding body polishing process>
36. As shown in FIG. 36, the surface is made of a sponge abrasive (trade name: 3M sponge) so that the surface of the dried shaped body 53 and the surface of the body shaped body 54 are integrated. Abrasive material, manufactured by Sumitomo 3M Co., Ltd., model: Superfine # 320 to # 600) 23.
Furthermore, a 2 mm hole was made with a drill blade to make a pendant or the like.
<Firing body manufacturing process>
The dried copper-silver shaped body 55 was air-fired at 750 ° C. for 10 minutes.
In addition, the atmospheric firing was performed by preheating the electric furnace to the above temperature, putting it in the electric furnace maintained at that temperature, and maintaining a predetermined temperature and time.
<Surface oxide film removal process>
After firing, the fired body 56 obtained was placed in water 24 and rapidly cooled as shown in FIG. 37 to remove the oxide film.
Next, as shown in FIG. 38, the fired body 56 is immersed in an aqueous solution 25 of a solid acid material for pickling (trade name: Pickling Compound, manufactured by GROBET FULE CO. OF AMERICA, INC), and the surface of the sintered body 56 is oxidized. The membrane was removed.
The surface became glossy by polishing with a stainless steel brush or the like as necessary.
As a result, as shown in FIG. 39, an inlaid decorative metal article (brooch) 57 in which two types (two colors) of silver and copper were integrated could be obtained very easily.

[Manufacture of copper-silver decorative metal products with wood grain pattern (wood grain technique)]
<Raw materials used>
The same silver-containing plastic composition and copper-containing plastic composition as used in <Raw material used> in [Evaluation of firing conditions in copper-silver fired body] were used.
<Plate formation process>
The silver-containing plastic composition and the copper-containing plastic composition were used.
The copper-containing plastic composition was flattened to a thickness of about 1.5 mm with a roller to produce a copper plate 61 shown in FIG.
The silver-containing plastic composition was flattened to a thickness of about 1.5 mm with a roller to produce a silver plate 62 shown in FIG.
<Multilayer adhesion process>
When the copper plate 61 and the silver plate 62 are overlapped and joined together, as shown in FIG. 42, a small amount of water is applied to the joining surface and the surface is stretched flat with a roller until the thickness reaches about 3 mm. A composite plate 63 shown in FIG. 43 was obtained.
The extended composite plate 63 was divided into two equal parts as shown in FIG.
When the bipartite composite plates 64, 64 were overlapped and joined, a small amount of water was applied to the joining surface in the same manner as described above, and the layers of the copper plate 61 and the silver plate 62 were placed alternately. . In this state, the film was flattened using a roller and stretched to a thickness of about 3 mm.
Such an operation was repeated three times to obtain a multilayer plate 65 in which the copper plate 61 layer and the silver plate 62 layer shown in FIG.
<Decoration process>
The excess portion of the multilayer plate 65 finally extended to a thickness of 3 mm in the above process is cut with a cutter and wound around a wood core bar 22 as shown in FIG. 46 to form a ring-shaped copper-silver multilayer ornament 66. Was shaped.
<Copper-silver multilayer decoration drying process>
The obtained ring-shaped copper-silver multilayer decoration 66 was put into a dryer set at a drying temperature of 100 ° C. and dried for a drying time of 30 minutes.
<Wood grain pattern formation process>
A portion of the dried copper-silver multi-layer ornament 66 is cut with a medium file 19 to form a notch so that a wood grain pattern appears as shown in FIG. (Product name: 3M sponge abrasive, manufactured by Sumitomo 3M Co., Ltd., model: Superfine # 320 to # 600) was prepared to obtain an ornament 67 having a notch.
<Firing body manufacturing process>
The decorative object 67 having the notch thus obtained was baked in the air at 750 ° C. for 10 minutes.
In addition, the atmospheric firing was performed by preheating the electric furnace to the above temperature, putting it in the electric furnace maintained at that temperature, and maintaining a predetermined temperature and time.
<Surface oxide film removal process>
After firing, the fired body 68 was placed in water 24 and rapidly cooled as shown in FIG. The oxide film was removed well.
Next, as shown in FIG. 49, the fired body 68 is immersed in an aqueous solution 25 of a solid acid material for pickling (trade name: Pickling Compound, manufactured by GROBET FULE CO. OF AMERICA, INC), and the surface of the sintered body 68 is oxidized. The membrane was removed.
The surface became glossy by polishing with a stainless steel brush or the like as necessary.
As a result, as shown in FIG. 50, it is very easy to obtain a decorative metal article (ring) 69 having a grain pattern that is difficult even in the engraving technique in which two types (two colors) of silver and copper are integrated. I was able to.

10 Decorative metal articles with a marble pattern (rings)
37 Decorative metal articles with marble pattern (brooch)
49 Decorative Metal Articles (Pendants) with Inlaid Patterns
57 Inlaid decorative metal articles (brooch)
69 Decorative metal objects with wood grain pattern (rings)

Claims (6)

One or more powders selected from copper and a copper alloy, containing 25 to 75% by weight of a first powder having an average particle size of 0.1 to 4.0 μm, and the balance having an average particle size of 4.0 μm A copper-containing plastic composition containing a copper mixed powder composed of a second powder having an average particle size of 10 μm or less and an organic binder;
One or more powders selected from silver and a silver alloy, containing 25 to 75% by weight of a first powder having an average particle size of 0.1 to 4.0 μm, and the balance having an average particle size of 4.0 μm A copper-silver shaped body forming step of forming a decorative article by combining a silver-containing plastic composition containing a silver mixed powder composed of a second powder having an average particle size of 40 μm or less and an organic binder;
A process for producing a decorative metal article, comprising: a copper-silver shaped fired body manufacturing step of firing the obtained decorative object in the atmosphere at 660 to 770 ° C. for 3 to 40 minutes to obtain a fired decorative article. One or more kinds of powders selected from copper and copper alloy, containing 25 to 75% by weight of a first powder having an average particle size of 0.5 to 4.0 μm, and the balance having an average particle size of 4.0 μm A copper-containing plastic composition containing a copper mixed powder composed of a second powder having an average particle size of 10 μm or less and an organic binder;
One or more powders selected from silver and a silver alloy, containing 25 to 75% by weight of a first powder having an average particle size of 0.5 to 4.0 μm, and the balance having an average particle size of 4.0 μm A copper-silver shaped body forming step of forming a decorative article by combining a silver-containing plastic composition containing a silver mixed powder composed of a second powder having an average particle size of 30 μm or less and an organic binder;
A process for producing a decorative metal article, comprising: a copper-silver shaped fired body manufacturing step of firing the obtained decorative object in the atmosphere at 660 to 770 ° C. for 3 to 40 minutes to obtain a fired decorative article. One or more kinds of powders selected from copper and copper alloy, containing 30 to 70% by weight of a first powder having an average particle size of 2.0 to 3.0 μm, and the balance having an average particle size of 5 to 10 μm A copper-containing plastic composition containing a copper mixed powder comprising the second powder and an organic binder;
One or more kinds of powders selected from silver and a silver alloy, containing 30 to 70% by weight of a first powder having an average particle size of 2.0 to 3.0 μm, and the balance having an average particle size of 5 to 20 μm A copper-silver shaped body forming step of forming a decorative object by shaping a combination of a silver-containing powder composed of the second powder and a silver-containing plastic composition containing an organic binder;
A process for producing a decorative metal article, comprising: a copper-silver shaped fired body manufacturing step of firing the obtained decorative object in the atmosphere at 660 to 770 ° C. for 3 to 40 minutes to obtain a fired decorative article.   The method for producing a decorative metal article according to any one of claims 1 to 3, wherein air baking is performed at 700 to 750 ° C for 10 to 15 minutes.   The method for producing a decorative metal article according to any one of claims 1 to 4, wherein a surface oxide film removing step of pickling or polishing the decorative article fired body is performed.   A decorative metal article manufactured by the manufacturing method according to any one of claims 1 to 5.

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