JPS626636B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing a decorative body having a novel patterned surface.

The interference colors exhibited by transparent dielectric thin films have long attracted the attention of many people, and the use of shells to make cod dens, pearls, etc.
Decorations using natural products such as inlays of fish scales are preferred, but recently, with advances in thin film manufacturing technology, many decorations are being made that utilize the interference colors of artificially created transparent dielectric thin films. It became. These decorations are made by attaching a transparent dielectric material to glass, metal plates, or metal foils as a film of appropriate thickness by vacuum evaporation, sputtering, ion plating, vapor phase growth, or other methods, so that they exhibit light interference colors. This is what I did. However, it is not always easy to make transparent dielectric thin films using this method.
It requires advanced and precise technology and takes more time than making metal thin films.

Therefore, the present applicant has developed a technology that can easily create a complex and profound optically coherent pattern layer in a short time without requiring highly precise technology, and has previously published this technology in Japanese Patent Application No. 177112/1983. I applied.

This technique is a method in which a thin metal film is formed on the glazed surface of a glazed substrate, and this is treated at high temperature in an oxygen atmosphere to form an optically coherent surface layer exhibiting an aesthetic pattern.

According to this method, an epoch-making decorative body with a complex and profound optical interference pattern layer can be obtained, but the interference pattern differs depending on the angle (direction) when viewed with respect to the film surface.
Interference colors appear particularly strongly or weakly. Although this is natural due to the nature of interference light, it was a problem.

The present invention has been made to improve this point, and by providing a concavo-convex pattern on the glaze surface, a uniform interference color appears when viewed from any angle.

That is, the first invention involves applying a glaze to the substrate surface in a finely uneven pattern, forming a thin metal film on top of the glaze, and treating this at high temperature in an oxygen atmosphere to form an optically coherent surface layer that exhibits an aesthetic pattern. The gist of this paper is a method for manufacturing a decorative body characterized by the following.

Substrates used in the present invention include copper, silver, gold,
Examples include metals such as iron, steel, stainless steel, and other alloys, and heat-resistant materials such as ceramics, ceramics, and glass.

Glazes include glazes for ceramics and glazes for metals (enamel glaze, cloisonné glaze), and an appropriate glaze is selected and used depending on the material of the substrate. The glaze may be colorless, colored, or opaque. In order to apply such a glaze in the form of fine irregularities, it is sufficient to appropriately sprinkle powder of the glaze on the surface of the substrate. Then, after firing,
The glaze surface begins to show minute irregularities such as islands, yuzu skin, or crepe. Depending on whether the glaze powder is sprinkled coarsely or densely on the base surface, and by adjusting the amount of scattering, the peaks and valleys of the unevenness on the glaze surface after firing will become shallower or deeper. It is possible to create the above-mentioned yuzu skin or crepe-like pattern, or the surface of the base that has never been glazed appears, creating a pattern in which the glaze exists in islands.

In addition, the second invention forms a finely uneven surface by scattering and firing heat-resistant fine particles on the glazed substrate surface, forming a metal thin film on top of the fine unevenness, and then exposing this in an oxygen atmosphere. The gist of the present invention is a method for producing a decorative body, which is characterized by forming a light-coherent surface layer exhibiting an aesthetic pattern through high-temperature treatment.

This method forms a glazed surface with an uneven pattern by scattering heat-resistant fine particles on the glazed substrate surface and firing them. Powder, small metal balls, or finely crushed pieces of glass, ceramics, metal, jewelry, etc. are used. These materials require heat resistance to the extent that they do not completely melt during firing.

Even with this method, the glazed surface forms irregularities, and the interference light due to the metal thin film formed on the surface is uniformly reflected over a wide range of angles.

In the above two inventions, the glazed base is
In order to produce interference colors as described above, a metal thin film is formed on the surface by any one of vacuum evaporation, sputtering, ion plating, vapor phase growth, and plating. The material of the metal thin film to be formed is Fe, Cr, Ni, Cu,
Zn, Ti, Mn, Al, Mg, Zr, Si, , Pb, Sn, In,
Various materials such as Sb, Co, Mo, W, Bi, steel, and alloys can be used, but metals that are easily oxidized in a high-temperature oxygen atmosphere are preferred.

The thickness of the metal thin film varies somewhat depending on the material, but it is preferably a thickness of 30 millimicrons or more, such as 30 millimicrons or more, at which oxidation produces light interference colors on the surface.

The glazed base coated with the metal thin film created in this way is
High temperature treatment is performed in an oxygen atmosphere. When using an electric furnace, air may be used, and there is no need to introduce oxygen. In the case of a ceramic furnace, an oxidizing flame furnace is used.

As the high-temperature treatment, in addition to treatment in a furnace, heating methods such as burner heating in air, infrared heating, induction or dielectric heating are used. The temperature of the high temperature treatment is preferably such that the metal thin film is oxidized and the glaze exhibits semi-fluidity. Although it varies depending on the type of metal thin film and glaze, a temperature range of 300 to 1600°C is sufficient in most cases.

When subjected to high-temperature treatment, the metal thin film is quickly oxidized from the surface to form an oxide thin film, which begins to exhibit interference colors, but as the oxidation progresses, the interference colors also change. This is considered to change according to the already known relationship between optical thickness and interference color for transparent dielectric thin films. In this case, at an intermediate stage, the upper layer is a metal oxide thin film and the lower layer is a metal thin film. The high-temperature treatment may be stopped at this stage, and the entire thin metal film may be completely oxidized, or a portion of the thin metal film may be completely oxidized, leaving the metal portion as an underlying layer.
In short, the degree of oxidation of the metal thin film is appropriately controlled depending on the desired pattern and color.

In addition to oxidizing the metal thin film as described above to form a transparent metal oxide thin film that exhibits interference colors, the purpose of high-temperature treatment is to make the glaze semi-fluid and to form a metal layer or metal oxide layer. It can also cause changes in the pattern by creating cracks, wrinkles, striations, and bubbles. In other words, when the metal oxides and metal layers in the metal thin film formed on the glaze surface by the above method are observed under a microscope, they show irregular cracks ranging from thick to thin cracks, wrinkles, streaks, and bubble holes. , the underlying glaze may appear due to the bumps. This is presumed to be caused by the relationship between the rapid volume change that occurs when the glaze reaches the glass transition point and the mechanical strength of the thin film.

The metal thin film is rarely dissolved in the glaze, which becomes semi-fluid at high temperatures, but the metal oxide layer is easily dissolved in the glaze and loses its interference color.

Therefore, the temperature conditions of high-temperature treatment, temperature unevenness,
The above effects are intricately intertwined depending on the thickness of the thin film, uneven thickness, etc., and the degree of oxidation (processing time), resulting in complex cracks and cracks in the metal oxide layer and metal layer of the metal thin film on the surface of the substrate. Wrinkles and streaks occur, and the metal oxide layer dissolves into the glaze and disappears, forming the base pattern of the glaze, causing bubbles and bumps, and the effects of uneven glaze surfaces on the base. Together, an interference color pattern with a complex and profound taste different from the conventional simple interference color pattern can be obtained.

Furthermore, the high temperature treatment allows the metal thin film to be firmly bonded to the glaze, making it resistant to friction and wear.

The high-temperature treatment time may be set at a time at which the desired pattern appears, taking into account the above-mentioned complex effects.

Examples will be described below.

Example 1 A heat-resistant ceramic board (material: aluminum oxide, dimensions 50.8 x 50.8 x 0.6 mm) was coated with porosilicate glaze powder (passed through a 40-mesh sieve) at a firing temperature of 850°C, and was coarsely sprinkled over the board using a sieve. (Scattering thickness 0.00
~0.02 mm, amount: 0.1 g) and placed in a furnace at 870°C for 3 minutes to obtain a glazed ceramic plate with a crepe-like pattern on the surface. This was placed in a sputtering device targeting titanium metal, and DC discharged in a 5Pa low-pressure argon flow (current 1A, voltage 500V).
This was carried out for 50 seconds to form a metallic titanium thin film (film thickness 2200±330 Å) on a ceramic plate with a glazed surface.
Place this in an electric furnace (air bath) at 700℃ for 80 seconds,
We created an oxide film and obtained a ceramic plate that exhibits a golden interference color. The thickness of the oxide film is estimated to be 1300-1400 Å. In this board, a golden interference color was seen from the uneven surface of the crepe pattern, and the strength or weakness of the interference color depending on the viewing direction was extremely small, resulting in a ceramic board with an optically coherent surface layer with an aesthetic golden crepe pattern. .

Example 2 A heat-resistant ceramic plate (material: aluminum oxide, dimensions: 50.8 x 50.8 x 0.6 mm) was coated with 0.2 g of porosilicate glaze (passed through a 40-mesh sieve) at a firing temperature of 850°C, and further glazed with a diameter of 0.2 to 0.8 mm. Using a sieve, coarsely scatter 0.8 g of glass beads of 870 mm size over the entire board.
The material was fired by placing it in a furnace at ℃ for 3 minutes to obtain a plate having a finely uneven surface. This was placed in a sputtering device that targets titanium metal, and DC discharge (current 1A, voltage 500V) was performed for 50 seconds in a low-pressure argon flow of 5Pa, and a thin metal titanium film ( Thin film thickness 2200±330Å)
I made it. Place this in an electric furnace (air bath) at 700℃ for 120 minutes.
I left it there for a second to create an oxide film. The thickness of the oxide film is
It is estimated to be 1700-1800Å. This board has a finely uneven surface in the shape of an orange skin, and a blue interference color can be seen from that surface, and the strength or weakness of the interference color depending on the viewing direction is extremely small. A board was obtained.

As described above, according to the present invention, a decorative body having a novel patterned surface can be obtained, which is extremely useful as ornaments, tableware, building materials, crafts, etc.

Claims (1)

[Claims] 1. A glaze is applied to the substrate surface in a finely uneven shape, a thin metal film is formed on the glaze, and this is treated at high temperature in an oxygen atmosphere to form a light interference surface layer exhibiting an aesthetic pattern. A method for manufacturing a decorative body characterized by: 2. A finely uneven surface is formed by scattering heat-resistant fine particles on the glazed substrate surface and firing, forming a thin metal film on top of the surface, and treating this at high temperature in an oxygen atmosphere. A method for producing a decorative body characterized by forming a light interference surface layer exhibiting an aesthetic pattern. 3. The method for producing a decorative body according to claim 1 or 2, wherein the metal thin film is formed by any one of vacuum deposition, sputtering, ion plating, vapor phase growth, and plating. 4. The method for producing a decorative body according to claim 1 or 2, wherein the high temperature treatment is carried out at a temperature at which the metal thin film is oxidized and the glaze becomes semi-fluid.