JPS5825073B2 - Precious metal paste formulation for high temperature firing - Google Patents

Description

[Detailed description of the invention] The present invention relates to noble metal paste formulations for high temperature firing.

Conventionally, a mixture of organic binders of metals containing organic binders of gold called mizukin has been used for gold and silver decorations on ceramics.

However, in this composition, the main color forming agent is gold, and when a silver color is to be formed, palladium, platinum, or silver is added therein as a metal powder or in the form of an organic compound.

For this reason, when these preparations are fired on a ceramic shaft at a temperature higher than the melting point of gold, the gold melts, evaporates, and reacts with the glaze, resulting in fine particle formation due to surface tension and dissolution in the glaze. It was not possible to obtain a smooth surface with a metallic color without destroying the painted shape.

Therefore, the decoration is generally done by firing at around 800°C, which is called overglazing, and using bismuth as the main binder.

However, in recent years, with the development of cleaning agents and the spread of dishwashers, ceramic decorations have become required to be more durable.For this reason, even decorations using paint are fired at a high temperature of 11003 or higher, which softens the glaze. A firing method called inglaze or sink-in, in which paint is soaked into the glaze, is rapidly becoming popular.

According to these conventional methods, it is currently not possible to decorate with gold and silver at the same time as decoration with paint, but with the present invention, it is possible to decorate at the same time even when firing at a temperature higher than the melting point of gold, 1063°C. It provides a composition for gold and silver decoration.

Water gold uses gold, platinum, and palladium as coloring sources, and organic combinations of each are used to obtain a mirror surface. When trying to obtain a matte surface or forming a thick metal film surface, They are added and used in the form of metal powder depending on the purpose.

In this application, fine inorganic powder is added to gold powder and an organic combination of gold (if a silver color is desired, an organic combination of palladium, palladium metal powder, or an organic combination of platinum is added). It prevents the formation of particles in the gold-containing metal film at high temperatures, leaving a metal film covered with an oxide film on the surface of the glaze, and the surface oxide film can be easily rubbed off with zircon sand to create a beautiful finish. Forms gold and silver metal surfaces.

The organic combination of metals such as gold as used in the present invention refers to noble metal combinations of metal resinates and resin sulfurized balsams.

As the inorganic fine powder, fine powders of zirconium silicate, zirconium oxide, a compound containing aluminum oxide and silicic acid, titanium oxide, and tin oxide are used.

For example, a mixture containing 10 to 40 parts of zirconium silicate, 8 to 40 parts of zirconium oxide, or aluminum oxide and silicic acid is added to 150 parts by weight of gold powder with an average particle size of 2 μm to 100 parts of a gold resinate solution with a metal content of 20 parts. A formulation containing a compound (depending in this case on the proportions of silicic acid and aluminum oxide), for example 5 to 50 parts in the case of kaolin, or 8 to 40 parts in the case of titanium oxide, or 8 to 40 parts in the case of tin oxide. Created, completely transferred onto the ceramic glaze surface,
Or, paint with a brush and bake at 1100-1300℃ depending on the amount and type of metal oxide powder, and after baking 80℃
By polishing the surface with mesh zircon sand, you can obtain a beautiful golden metallic surface.

Regarding the color-forming compounding ratios of gold and silver colors (palladium color, platinum color), the component ratios are shown in the triangular diagram in the attached figure.

In the same figure, ■ is a golden colored area, and ■ is a silver colored area (
Palladium color) and ■ indicate a silver colored region (platinum color).

It goes without saying that the coloring formulation range must be within the above ranges I to (3), but examples of prescription standards for each coloring formulation range are as follows.

(1) Golden color tone prescription standard range Gold powder (99.8% Au content, average particle size, e.g. 1.0μ)
40-53 parts Organic combination of gold (containing 15% Au) 30-40 parts Inorganic fine powder (e.g. tin oxide, silica powder) 30-10 parts
Part (2) Silver color formulation standard range (palladium color) Gold powder (contains 99.8% Au) 30-45 parts organic combination of gold (contains AulO) 30-40 parts Pd powder (contains 98.0% Pd) ) 10 to 5 parts Palladium binder (contains 8% Pd) 5 to 0 parts Inorganic fine powder (e.g. titanium oxide) 25 to 10 parts (3) Standard range for silver color formulation prescription (platinum color) Gold powder (Au
99.8% content average particle size e.g. 0.5μ) 0-45
Organic bond of metal (contains 10% Au) 0-40 parts Pi powder (contains 98% Pi, average particle size e.g. 2.0 μ) 45-40 parts
5 parts Organic combination of platinum (containing 5% Pt) 30-0 parts Inorganic fine powder (e.g. zirconium silicate, alumina powder) 25-10 parts Example 1 Gold powder (average particle size 1μ) 50 (parts by weight) Gold resinate solution (metal content) 15) 35 Zirconium oxide (average particle size 2μ) 15 Stir the above mixture for 30 minutes with an Ishikawa stirrer, make it into a paste, create a slide transfer by screen printing, and paste it on the glazed surface of a fired white ceramic fabric, or Alternatively, use a brush to draw contour lines on the mixture, heat and dry it, and then fire it at a high temperature under different conditions depending on the softening point of the glaze. You can get it.

Example 2 Gold powder (average particle size 1μ) 40 (parts by weight) Gold resinate solution (metal content 15%) 35 Palladium powder 5 Titanium oxide powder (average particle size 2μ) 15 The above formulation was applied to a slide transfer mount using a 250 mesh Tetron screen. and apply Degussa 80454 top coat enamel to create a slide transfer.

Paste the slide transfer on the glazed surface of the porcelain, and
By firing at 0°C and polishing the entire transfer surface with zircon sand, a silver metallic surface can be obtained.

Example 3 A silver metallic surface can be obtained using the following formulation and following the same procedure as in Example 1.

Gold powder (average particle size 0.5μ) 45 parts Platinum powder (average particle size 1.0μ) 7 parts Resin sulfurized balsam (
Au10%) 33 parts titanium oxide
15 parts Example 4 A silver metallic surface can be obtained using the following formulation and following the same procedure as in Example 1.

Platinum powder (average particle size 20μ) 45 parts Platinum resin sulfide/<) L/Sam (pt 5%) 30 parts Zirconium silicate 20 parts Alumina powder
Part 5 Example 5 A golden metallic surface can be obtained using the following formulation and following the same procedure as in Example 1.

Gold powder (average particle size 1.0μ) 45 parts Fat sulfide 7 sum (A1115%) 35 parts Tin oxide
10 parts silica powder 10 parts additional relationship Regarding a noble metal paste formulation for high temperature firing that exhibits a golden or silver decorative surface after high temperature firing, most of the components are based on the prior patent application No. 1127440 (Special Patent No. The composition is the same as that of Publication No. 57-15069).

However, the earlier application contains (1) gold powder and (2) organic combinations of gold, rhodium, and chromium as precious metal sources in both gold and silver cases, and in addition, in the case of gold, it also contains organic combinations of silver. While silver color further contains an organic compound of palladium and palladium powder as essential components, in this application, neither gold nor silver color contains organic compounds of rhodium and chromium as essential components, and silver color (palladium color) ), the object can also be achieved by using only a small amount of platinum powder and an organic combination of platinum as the noble metal.

In addition to the above, in the binder component, the earlier application has silica,
While one or more of the three components of alumina and zircon are used, the present invention is different in that in addition to these three components, dillhnium silicate, titanium oxide, and tin oxide are also used.

Therefore, the claimed invention is an invention that uses the main parts of the essential elements of the earlier claimed invention as essential parts of its composition, and aims to achieve the same purpose as the earlier claimed invention. It is something.

[Brief explanation of drawings]

The attached figure is a triangular diagram showing the coloring ratio of precious metals of gold and silver (palladium color, platinum color).

Claims (1)

[Claims] 1(1) Gold powder (as containing 99.8% Au) 40-53
Part (2) Organic bond of gold (as containing 15% Au) 30~
40 parts (3) A noble metal paste composition for high-temperature firing that exhibits a golden metallic surface after painting on a porcelain glaze surface and firing at a high temperature, characterized by comprising 30 to 10 parts of inorganic fine powder. 2 (1) Gold powder (assuming 99.8% Au content) 30-4
5 parts (2) organic bond of gold (assuming 10% Au content) 30~
40 parts (3) Palladium powder (as containing 98.0% Pd) 10
~5 parts (4) Palladium organic combination (assuming 8% Pd content) 5 to 0 parts (5) Inorganic fine powder 25 to 10 parts Painted on porcelain glaze surface After high temperature firing, palladium A noble metal paste formulation for high temperature firing that exhibits a silvery metallic surface. 3(1) Gold powder (Au 99. B% content) 0~
45 parts (2) Organic bond of gold (assuming 10% Au content) 0 to 4
0 parts (3) Platinum powder (assuming 98% Pt content) 45-5 parts (4) Organic bond of platinum (assuming 5% Pt content) 30-5 parts
0 parts (5) A noble metal paste preparation for high-temperature firing, which exhibits a platinum-colored silvery metal surface after being painted on a porcelain glaze surface and fired at a high temperature, characterized by comprising 25 to 10 parts of inorganic fine powder.