JPH0144676B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing a ceramic product having an uneven surface, and more specifically to a method for manufacturing a ceramic product having an uneven surface by using a glass surface processing technique using so-called dry glass corrosion. In a method for manufacturing a product, the object is to obtain a ceramic product in which the boundaries between uneven parts and non-irregular parts are sharp.

The glass corrosion method that the present applicant has already applied for is a method in which an ink mixed with a glass corrosive agent that can form a solid film is coated on the glass surface, printed, and then dry heated at an appropriate temperature. Showa 58-
(See Publication No. 88142). This method improves the safety of workers in the so-called wet corrosion method using conventional corrosive liquid.
This solves various problems such as waste liquid treatment, but when attempting to form characters or pictures using uneven areas, there is a problem in that the boundaries between uneven areas and other areas become unclear. In view of these problems, the present inventor has completed various research studies and has completed the present invention. That is, in the present invention, after providing a resist layer that does not allow glass corrosive gas to pass through a required portion of the surface of a ceramic base material, the glass corrosive gas is applied by heating to cover at least the portion where the resist layer is not provided. A corrosive agent layer is formed using an ink composition whose main components are a glass corrosive and an organic substance capable of forming a solid film, and then the glass corrosive is thermally decomposed to produce a glass corrosive gas. This is a method for manufacturing ceramic products having uneven portions on the surface, which is characterized by heating at a temperature such that the surface of the ceramic product is heated to such a temperature that the surface of the ceramic product is heated.

In the present invention, ceramic products include glass products, tiles, enamel products, and the like. In the following, the invention will be explained in more detail in the case of glass products.

First, a resist layer is provided on a necessary portion of the surface of a glass substrate, that is, a portion where uneven portions such as matte processing are not provided. The resist layer is for preventing glass corrosive gas from permeating, and is formed by coating or printing an ink made of an inorganic substance with a resin binder. As the inorganic substance, various metal oxides, metal chlorides, metal carbides, silicic acid compounds with metal elements, carbonate compounds, hydroxide compounds, etc. are used alone or as a mixture. Resin binders include thermoplastic resins, thermosetting resins, natural resins, etc., especially polyamideimide, polyimide,
Heat-resistant resins such as polybenzimidazole, aromatic polyimide, and aromatic polyester are preferred.

The resist layer is easy to remove after baking.
It is preferable to use an inorganic material with a high melting point that does not melt during the heating process, and in this case, a layer of an inorganic material with a low melting point may be laminated on the layer of the inorganic material with a low melting point. With this configuration, only the upper low-melting point material layer melts during heating to form a continuous film layer, which more efficiently prevents gas permeation and facilitates removal after firing.

In addition, the resist layer may be made of a material that binds to glass corrosive gas such as hydrogen fluoride, and examples of such material include CaO,
Al ₂ O ₃ , BaCO ₃ , Na ₂ CO ₃ , KHCO ₃ , SrCO ₃ ,
There are solid bases such as SiO ₂・Al ₂ O ₃ , silica gel, alkali metals or alkaline earths, metal hydrides, etc.
As a resin binder, there is a nitrogen-containing resin.

A corrosive layer is provided on top of the resist layer. The corrosive agent layer is formed by using an ink composition mainly composed of a glass corrosive that generates a glass corrosive gas such as hydrogen fluoride when heated, and an organic substance capable of forming a solid film. The resist layer is formed by coating or printing so as to cover the portions where no resist layer is provided. Examples of glass corrosives include NH ₄ F
(NH ₄ ) ₃ AlF ₆ , (NH ₄ ) ₂ CuF ₄ , (NH ₄ ) ₃ FeF ₆ ,
(NH ₄ ) ₂ CoF ₄ , NaHF ₂ , KHF ₂ (NH ₄ ) ₂ NiF ₄ and the like, and as the organic substance capable of forming a solid film, a polymeric substance such as a thermosetting resin is used. Further, if necessary, a reaction accelerator, a solvent, etc. are mixed to obtain an ink composition. Examples of reaction accelerators include:
Examples include KH ₂ PO ₄ and KHSO ₄ . The content of the glass corrosive agent is appropriately adjusted depending on the degree of unevenness of the uneven surface of the ceramic product to be formed.

Note that a gas diffusion prevention layer may be provided to cover the corrosive layer. The gas diffusion prevention layer can prevent the glass corrosive gas generated from the glass corrosive agent from diffusing into the atmosphere, making handling operations safer and allowing the glass corrosive agent to be used more efficiently. can. This gas diffusion prevention layer is provided by coating or printing an ink made using an inorganic substance and a resin binder that can be applied to the resist layer described above.

Next, the glass substrate is heated at a temperature such that the corrosive layer thermally decomposes and generates a glass corrosive gas such as hydrogen fluoride gas. If the above-mentioned corrosive agent is used, it may be heat-treated in a temperature range of 250°C to 550°C. By this heat treatment, the glass substrate in the part where the corrosive agent layer is provided in contact with the surface of the glass substrate, that is, the part where the corrosive agent layer is provided except for the part where the resist layer is provided, is corroded, and the uneven parts are corroded. is formed.

Residues generated by the heat treatment are washed and removed by appropriate means.

Since the present invention is a method for manufacturing a ceramic product having an uneven part as described above, by applying the present invention, an uneven part forming a delicate pattern can be easily and safely obtained. It is.

Examples of the present invention will be described below.

Example A floral pattern was printed on the surface of a soda glass plate with a thickness of 1 mm using a resist ink having the composition shown below, and then a glass corrosive agent having the composition shown below was coated over the entire surface of the glass plate by spraying. Furthermore, a gas diffusion inhibitor of the same composition was applied over the entire surface by screen printing. As a result, on the surface of the glass plate, a 20μ thick glass corrosive agent layer is applied on top of a 15μ thick resist layer.
A 15 μm gas diffusion prevention layer was formed.

Resist agent composition High melting point glass frit OC-790 (manufactured by Okuno Pharmaceutical Co., Ltd.) 40 parts Polyamic acid SP-510 (manufactured by Toray Industries, Inc.) 30 parts N-methyl-2-pyrrolidone 30 parts Glass corrosive composition Aluminum ammonium fluoride salt (NH ₄ ) ₃ AlF ₆ 30 parts Potassium hydrogen phosphate KH ₂ PO ₄ 8 parts Coponyl 4906 (manufactured by Nippon Gosei Kagaku Co., Ltd.)
15 parts toluene 45 parts Duomine TDO (manufactured by Lion Akzo)
2 parts Gas diffusion inhibitor composition High melting point frit OG-15 (manufactured by Nippon Fellow Co., Ltd.) 40 parts Almatex 762/LV55A (manufactured by Mitsui Toatsu Chemical Co., Ltd.) 14 parts Euban 203E60 (manufactured by Mitsui Toatsu Chemical Co., Ltd.) 4 parts Epicote 1009 (manufactured by Mitsui Toatsu Chemical Co., Ltd.) (Manufactured by Ciel) 2 parts Solbetsuso #100 (Manufactured by Etsuso) 40 parts The glass plate was then heat treated at 450℃ for 20 minutes, and the residue was removed by washing with water, resulting in a beautiful pine part without floral patterns. A formed glass plate could be obtained.

Claims (1)

[Scope of Claims] 1. After providing a resist layer that does not allow glass corrosive gas to pass through the necessary portions of the surface of the ceramic substrate, the glass is corroded by heating so as to cover at least the portions where the resist layer is not provided. A corrosive agent layer is formed using an ink composition whose main components are a glass corrosive agent that generates a toxic gas and an organic substance capable of forming a solid film, and then the glass corrosive agent thermally decomposes and corrodes the glass. A method for manufacturing a ceramic product having an uneven surface, the method comprising heating at a temperature that generates a toxic gas. 2. The method for manufacturing a ceramic product having an uneven surface on the surface as set forth in claim 1, wherein the resist layer is made of a high melting point inorganic substance. 3. A resist layer having an uneven portion on the surface as set forth in claim 1, wherein the resist layer is composed of a layer made of a low melting point inorganic material laminated on a layer made of a high melting point inorganic material. A method for manufacturing ceramic products. 4. Having an uneven portion on the surface according to claim 1, wherein the resist layer is mainly composed of a solid base and/or a nitrogen-containing resin that chemically bonds with glass corrosive gas. Method of manufacturing ceramic products. 5. The method for manufacturing a ceramic product having an uneven surface as claimed in claim 1, wherein the corrosive layer is covered with a gas diffusion prevention layer made of an inorganic substance.