JP3486438B2 - Glaze composition and inorganic substrate provided with the composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a glaze composition, and more particularly to a glaze composition which enables metal plating on an arbitrary inorganic substrate and an inorganic substrate provided with the composition.

[0002]

2. Description of the Related Art Forming a metallized film on the surface of a substrate made of an inorganic material (hereinafter referred to as "inorganic substrate") not only gives a metallic appearance but also wear resistance, mechanical strength, conductivity,
It can be used in a wide range of fields such as ornaments, daily necessities, electronic substrate materials, etc., because it can impart various properties such as chemical properties that are not possessed by an inorganic substrate alone.

Various methods are known for metalizing (forming a metallized film) on an inorganic substrate. For example, a solid phase-gas phase system such as an ion plating method, a sputtering method, or a CVD method requires expensive equipment, equipment, etc., which increases the cost in terms of equipment and process, and metalizing of large products is not possible. Have difficulty.

The method using an organic adhesive is simple and easy.
Although it is low in price, it has the disadvantage of poor heat resistance and weather resistance, and it has the drawback that it is hard to become completely airtight due to its minute holes, which hardens due to the loss of water during heating during bonding operation. is there.

Other methods include a refractory metal method, a pressure bonding method, a DC voltage application method, and a reduction method, all of which are accompanied by a change in the base material, a decrease in dimensional accuracy, and an increase in residual stress. There are drawbacks such as a decrease in bonding strength and an increase in cost.

[0006]

Under these circumstances, plating an inorganic base material is a simple and low-priced process at about room temperature, and it is necessary to cover a base material with a complicated shape. Is possible, and so on. However, it is difficult to form the surface of the inorganic base material that can be plated (roughened surface), and a special technique is required. It is difficult to perform rational mechanical etching on a hard inorganic substrate such as sandblast and tumbler polishing, and in many cases, the surface smoothness of the substrate is impaired and it is difficult to plate in a uniform state. Is. In addition, the inorganic base material is likely to be subjected to stress concentration due to the influence of a slight surface scratch, which may cause a decrease in reliability as a structural material.

Even in the case of chemical etching, it is difficult to form a roughened surface. That is, the inorganic base material is generally a material having high chemical resistance, and even if it is a chemical that can be etched, it is limited by the material of the inorganic base material. In any case, since the plating film is sensitive to the etching conditions, it can be applied to various inorganic base materials that are hard and have high chemical resistance.
Mass production is difficult because it is not easy to obtain a roughened surface with good reproducibility. Moreover, the partial plating of the inorganic base material requires a special masking for etching, resulting in low productivity and high cost. The purpose of the present invention is not limited to the material of the inorganic substrate, and the etching operation is not required,
It is an object of the present invention to provide a glaze composition that can be plated at high adhesion strength at low cost and can be easily given a delicate design.

[0008]

In order to achieve the above object, the present invention has been made, and is a glaze composition characterized by containing 5 to 95% by weight of alkali titanate in a glaze component. . In addition, after applying the above glaze composition and baking,
Characterized by the solidification of alkali titanate on the surface
It is an inorganic base material. In addition, the above-mentioned inorganic substrate is
With a metal plating layer characterized by being applied
It is an organic base material.

As the base glaze to which the alkali titanate is mixed, a glaze suitable for the material of the target inorganic base material can be selected, and a low-grade glaze that does not deteriorate the alkali titanate is preferable. For example, alkaline glaze, boric acid glaze,
Examples include frit glaze and lead glaze. Then, by firing, the alkali titanate is solidified on the inorganic base material by the bonding of the glass bond. The amount of alkali titanate compounded is 5
The range is from 95 to 95% by weight, preferably from 30 to 70% by weight. If it is less than 5% by weight, the effect of alkali titanate is not sufficient, and if it exceeds 95% by weight, the effect of the glaze component is reduced and the adhesion to the inorganic base material is lowered. Therefore, it is important to select from the above range. is there.

Examples of the inorganic base material to which the present invention can be applied include glass, ceramics, tiles, new ceramics, and composite materials using a matrix as an inorganic material.

The alkali titanate used in the present invention is
A complex oxide of M ₂ O (M is an alkali metal) and TiO ₂ and its hydrate, which are TiO ₆ octahedron or Ti
O ₅ has a characteristic of having a crystal structure consisting of a triangular bipyramidal chain. The shape of the powdered alkali titanate is not restricted by the shape such as fibrous, plate-like, spherical, and amorphous, but in order to support delicate designs, fine-grained alkali titanate should be used. Suitable.

As a means for applying the glaze composition of the present invention to the surface of the inorganic base material, a known method such as a transfer method, a screen printing method, a spraying method, or a brush coating method can be adopted, and it is particularly limited. Not a thing. After being applied by the required means, it is usually dried at 100 to 200 ° C. and baked at a temperature depending on the type of glaze to be solidified on the inorganic base material, whereby an arbitrary design can be formed. When the plating is performed after the solidification, the known method can be used without changing the conventional plating equipment. That is, after degreasing, cleaning, sensitizing, and activating, electroless plating is performed. If necessary, electroless plating, or electrolytic plating or brazing is further performed.

[0013]

In the glaze composition of the present invention, the contained alkali titanate is solidified on the surface of the inorganic base material, so that plating having excellent adhesion strength can be performed. The high adhesion strength and airtightness with the metal are due to the above-mentioned crystal structure consisting of the chain pattern of the TiO ₆ octahedron of the alkali titanate or the TiO ₅ triangular bipyramid, and the formed tunnel or layer side,
Alternatively, the zigzag-shaped connecting part that shares the ridge plays an important role, and the micro concave part provides a strong anchor effect (anchor effect). For the purpose of increasing the surface exposure amount of alkali titanate, chemical or mechanical etching can be performed as a pretreatment, but this etching operation is performed depending on the type of glaze and the blending amount of alkali titanate. Is unnecessary.

[0014]

[Examples 1 to 3] As shown in Table 1, alkali titanate powder and base glaze powder were blended, mixed into each blend, and an appropriate amount of auxiliary material was added according to the painting method, and after painting After drying and firing, the glaze composition was solidified on each inorganic substrate. Then, after degreasing the surface with a surfactant, electroless plating was performed according to a conventional method. In each of the examples, a plating layer was selectively obtained on the painted portion and the adhesion strength was high.

[0015]

[Table 1]

[0016]

[Examples 4 to 8] Frit glaze powder and K ₂ O · 6TiO ₂
The powder was prepared as shown in Table 2, an appropriate amount of auxiliary material was added, and the mixture was sprayed onto an alumina substrate and dried at 1050 ° C.
After solidifying with, and degreasing with a 3% potassium hydroxide solution, electroless copper plating and an electroless nickel plating layer were obtained according to a conventional method. The results of the adhesion strength test of the obtained film are shown in Table 2. Incidentally, in Comparative Example 2, at a firing temperature of 1050 ° C., K
_{Since 2} O · 6 TiO ₂ did not solidify, a plating layer could not be obtained. In Comparative Example 3, the firing temperature was 13
By setting the temperature to 10 ° C., K ₂ O.6TiO was formed on the alumina substrate.
_{Since 2} was solidified, a plating layer could be obtained,
The adhesion strength was lower than in the examples.

[0017]

[Table 2]

In the above-mentioned embodiment, the auxiliary material is a liquid suitable for the painting method, such as water, a water-soluble solvent or an oily liquid, in order to control the tackiness, adhesiveness and drying property of the inorganic substrate, and Known sizing agents corresponding thereto are used, and all are materials that disappear by firing. In addition, the painting method corresponds to a delicate design, and when the plating film is selectively obtained at the painting place, transfer is performed in order to form a uniform alkali titanate composition with a constant coating thickness on the surface of the inorganic substrate. Method and screen method are suitable. Further, for complicated curved surfaces such as a cubic curved surface, a transfer method or brush coating is suitable, and the painting method can be appropriately selected according to the design shape. It is also an advantage of the present invention that such a method can be adopted.

[0019]

As described above, in the glaze composition of the present invention, a metal film having high adhesion strength can be formed on an inorganic base material by an arbitrary painting means by a usual plating method and is delicate. Since it can also be designed, various properties not possessed by the inorganic base material alone can be easily imparted as necessary. Therefore, it can be used not only in daily necessities but also in a wide range of fields such as various electronic base materials, and its effect is extremely large.

Claims (3)

(57) [Claims] 1. A glaze component containing 5 to 9 alkali titanates.
A glaze composition characterized by containing 5% by weight . 2. An inorganic base material, characterized in that the glaze composition according to claim 1 is applied and baked to solidify alkali titanate on the surface. 3. An inorganic base material having a metal plating layer, characterized in that the inorganic base material according to claim 2 is plated with a metal.