JPH0130795B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing ceramic products having an uneven surface, and its purpose is to effectively utilize a glass corrosive agent and to eliminate harmful gases from the atmosphere during the manufacturing process. The objective is to manufacture ceramic products with an uneven surface to prevent diffusion.

In the present invention, ceramic products include glass products, tiles, hollow products, and the like. In the following, a method for manufacturing glass products will be described as an example of ceramic products.

Conventionally, when applying deglazing or engraving to the surface of glass products such as glass plates and glass containers, a so-called wet corrosion method using a hydrofluoric acid solution, calcium fluoride, sulfuric acid or ammonium hydrogen fluoride solution, etc. has been used. was taken. This method has disadvantages, such as the high risk of harming the health of workers since it involves handling highly toxic solutions such as hydrofluoric acid, and the fact that waste liquid treatment requires a lot of effort and expense. Under such circumstances, the applicant has conducted repeated research to improve the conventional method described above, and as a result, the present applicant applied an ink containing a relatively stable and less toxic corrosive agent that can form a solid film to the glass surface. Forms a solid film,
Invented a method of dry heating this at an appropriate temperature,
An application has already been filed (see Japanese Unexamined Patent Application Publication No. 1988-88142). However, this method also has drawbacks, such as the fact that the corrosive cannot necessarily be used effectively because the fluorinated gas generated during heating diffuses into the atmosphere, and there is a risk of contaminating the atmosphere. The present invention was completed as a result of various research and considerations aimed at solving these drawbacks. That is, the present invention uses an ink composition whose main components are a glass corrosive agent that generates a glass corrosive gas when heated and an organic substance capable of forming a solid film on a necessary portion of the surface of a ceramic substrate. A corrosive agent layer is provided, a gas diffusion prevention layer is provided to cover the corrosive agent layer, and then the glass corrosive agent is thermally decomposed and heated at a temperature such that glass corrosive gas is generated. This is a method of manufacturing a ceramic product having an uneven surface.

Hereinafter, the present invention will be explained in more detail using a case where a glass substrate is used as an example.

First, an ink composition containing a glass corrosive agent and an organic substance capable of forming a solid film as main components is coated or printed on a necessary portion of the surface of the glass substrate, that is, a portion where an uneven surface is to be formed. Provide layers. Printing means include direct printing such as screen printing and transfer printing. A glass corrosive agent is a compound that thermally decomposes when heated and generates glass corrosive gas such as hydrogen fluoride gas, such as NH ₄ F (NH ₄ ) ₃ AlF ₆ (NH ₄ ) ₂ CuF. _Four ,
NaHF ₄ (NH ₄ ) ₃ FeF ₆ , (NH ₄ ) ₂ CoF ₄ ,
(NH ₄ ) ₂ NiF ₄ KHF ₂ , etc. The organic substance capable of forming a solid film includes, for example, a polymer resin binder such as a thermosetting resin. Furthermore, if necessary,
An ink composition is obtained by mixing reaction accelerators such as KH ₂ PO ₄ and KHSO ₄ and a solvent. The content of the glass corrosive agent is adjusted appropriately depending on the degree of unevenness of the uneven surface to be formed.

Next, a gas diffusion prevention layer is provided by coating or printing to cover the glass corrosive layer. The gas diffusion prevention layer is provided to prevent the glass corrosive gas generated from the glass corrosive agent layer from diffusing into the atmosphere, and is formed of an ink using an inorganic substance and a resin binder. Inorganic substances include metal oxides, metal chlorides, metal carbides,
Silicic acid compounds, carbonic acid compounds, hydroxide compounds, etc. with metal elements are used alone or as a mixture.
Here, the metal elements include sodium, potassium,
Rubidium, cesium, magnesium, calcium, strontium, barium, scandium,
Titanium, zirconium, vanadium, chromium, molybdenum, manganese, technetium, iron, ruthenium, cobalt, rhodium, nickel, palladium, copper, silver, zinc, cadmium, aluminum, gallium, indium, hafnium, tantalum, tungsten, rhenium, These include osmium, iridium, platinum, gold, mercury, thallium, boron, carbon, silicon, germanium, tin, lead, nitrogen, phosphorus, arsenic, antimony, bismuth, sulfur, selenium, tellurium, and polonium. Further, the resin binders used include thermoplastic resins, thermosetting resins, natural resins, and heat-resistant resins. Examples include: Thermoplastic resins Polyvinyl chloride, polyvinyl acetate, polyvinyl chloride acetate, polyvinyl alcohol, polyvinyl acetal, polyacrylic acid, polyacrylic acid esters, polyamides, polyesters, rubber resins, etc. Thermosetting resins Urea Natural resins such as , phenol, epoxy, polyisocyanate, unsaturated polyester, alkyd, melamine, urethane, etc. Heat-resistant resins such as starch, cellulose resin, Niwaka, casein, etc. Polyamideimide, polybenzimidazole,
These include polyamide, aromatic polyimide, aromatic polyester, etc.

In addition, the gas diffusion prevention layer may be made of a material that binds to glass corrosive gases such as hydrogen fluoride, and examples of such materials include inorganic materials such as CaO,
Al ₂ O ₃ , BaCO ₃ , Na ₂ CO ₃ , KHCO ₃ , SrCO ₃ ,
Solid bases such as SiO ₂ Al ₂ O ₃ , silica gel, alkali metal or alkaline earth metal hydrides,
As a resin binder, there is a nitrogen-containing resin.

Further, the gas diffusion prevention layer is preferably one that can be easily removed after firing, and for this purpose, an inorganic substance with a high melting point that will not melt in the subsequent heating step can be used. Furthermore, when a high melting point inorganic substance is used, if a layer made of a low melting point inorganic substance is laminated on top of it to form a gas diffusion prevention layer, only the upper layer will melt when heated to form a continuous film layer. The effect of preventing gas diffusion more efficiently can be obtained.

Next, the surface of the glass substrate is heated. Heating is carried out in a temperature range where the glass corrosive agent thermally decomposes and generates glass corrosive gas such as hydrogen fluoride gas, and in the case of the above-mentioned corrosive agent, the heating temperature is 250°C to 550°C.
Heat treatment may be performed at ℃. By this heat treatment, the portion of the glass substrate provided with the corrosive agent layer is corroded. Furthermore, glass corrosive gas such as hydrogen fluoride gas generated from the glass corrosive agent is prevented from diffusing into the atmosphere by the gas diffusion prevention layer, and the corrosive agent can be used more effectively to corrode glass. .

After firing, the remaining gas diffusion prevention layer and the like are washed and removed by an appropriate means.

Since the present invention is a method for manufacturing a ceramic product having an uneven surface as described above, by applying the manufacturing method according to the present invention, it is easy to prevent glass corrosive gas from diffusing into the atmosphere. Therefore, glass corrosive agents can be used effectively, there is little need for air pollution, and the process is simple, so it is expected to be widely used.

Examples of the present invention will be described below.

Example 1 A floral pattern was printed on the surface of a 1 mm thick soda glass plate using a glass corrosive agent with the following composition by screen printing, and then a first gas diffusion prevention layer with the following composition was sprayed over the entire surface of the glass plate. Then, a second gas diffusion inhibitor having a different composition was applied to the entire surface by screen printing. As a result, the thickness of the glass plate surface
A first gas diffusion prevention layer with a thickness of 20μ and a second gas diffusion prevention layer with a thickness of 15μ were formed on the glass corrosive layer with a thickness of 20μ.

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 Co., Ltd.) 15 parts Toluene 45 parts Duomine TDO (Lion Akzo) (manufactured by Toray Industries) 2 parts First gas diffusion inhibitor composition High melting point glass frit OC-790 (manufactured by Okuno Pharmaceutical Co., Ltd.) 50 parts Polyamic acid SP-510 (manufactured by Toray Industries, Inc.) 20 parts N. Methyl 2. Pyrrolidone 30 parts Second gas Diffusion inhibitor composition Low melting point glass frit OC-410 (manufactured by Okuno Pharmaceutical Co., Ltd.) 35 parts Metrose SM100 (manufactured by Shin-Etsu Chemical Co., Ltd.) 5 parts Water 60 parts After that, the glass plate was heat-treated at 500°C for 30 minutes, and the remainder remained. As a result of removing things by washing with water,
It was possible to obtain a glass plate having a concavo-convex pine shape with a beautiful floral pattern.

Example 2 On the surface of a 2.5 mm thick glass plate, the following glass corrosive agent was printed in a letter pattern with a film thickness of 10 μm, and then a gas diffusion inhibitor with the same composition was screen printed on top of this. A gas diffusion prevention layer with a thickness of 20 μm was formed to cover the glass corrosive layer.

Glass corrosive composition Iron ammonium fluoride salt (NH ₄ ) ₃ FeF ₆ 30 parts Potassium hydrogen sulfate KHSO ₄ 5 parts Coponyl 4906 (manufactured by Nippon Gosei Kagaku Co., Ltd.) 15 parts Toluene 48 parts Duomin TDO (manufactured by Lion Akzo Co., Ltd.) 2 Part Gas diffusion inhibitor composition High melting point Fritz OG-15 (manufactured by Nippon Fellow Co., Ltd.)
40 parts Almatex 762LV55A (manufactured by Mitsui Toatsu Chemical Co., Ltd.)
14 parts Yuban 203E60 (manufactured by Mitsui Toatsu Chemical Co., Ltd.) 4 parts Epicote 1001 (manufactured by Ciel Corporation) 2 parts Solbetsuso #100 (manufactured by Etsuso Corporation) 40 parts After that, the glass plate was heat treated at 450°C for 20 minutes, and the remaining After removing the material by washing with water, we were able to obtain a glass plate with a beautiful pine character pattern formed on it.

Example 3 Gravure printing was sequentially performed on a base sheet made of polyethylene terephthalate film using inks having the following compositions (a), (b), (c), and (d) to prepare a transfer paper.

(a) Release agent composition Dianal BR-50 (manufactured by Mitsubishi Rayon Co., Ltd.)
10 parts Toluene 90 parts (B) Second gas diffusion preventive agent composition Glass frit OC-410 (manufactured by Okuno Pharmaceutical Co., Ltd.) 30 parts Esrex C (manufactured by Sekisui Chemical Co., Ltd.) 7 parts Methyl ethyl ketone 33 parts Methyl isobutyl ketone 30 parts (C) Part 1 Gas diffusion inhibitor composition High melting point glass frit OC-790 (manufactured by Okuno Pharmaceutical Co., Ltd.)
30 parts Almatex 762LV55A (manufactured by Mitsui Toatsu Chemical Co., Ltd.)
7 parts Yuban 20SE60 (manufactured by Mitsui Toatsu Chemical Co., Ltd.) 2 parts Epicote 1001 (manufactured by Ciel Corporation) 1 part Solbetuso 60 parts (d) Glass corrosive composition Aluminum ammonium fluoride salt (NH ₄ ) ₃ AlF ₆ 30 parts Hydrogen phosphate - Potassium KH ₂ PO ₄ 5 parts Epicote 1009 (manufactured by Ciel) 10 parts Methyl ethyl ketone 53 parts Duomin TDO (manufactured by Lion Akzo) 2 parts Tetrahydrophthalic anhydride 0.2 parts Using the above transfer paper, transfer to a glass plate under the following transfer conditions. A glass corrosive layer, a first gas diffusion prevention layer, and a second gas diffusion prevention layer were sequentially provided on a glass plate. After that, it is fired at 500℃ for 30 minutes.
As a result of removing the reaction residue by washing with water, it was possible to obtain a highly accurate scale line in the shape of a pine.

Transfer conditions Roll transfer machine Transfer temperature 200°C Transfer speed 5 cm/sec Transfer pressure 3 mm pressure Comparative Example Only the glass corrosive agent used in Example 1 was applied to the same thickness on the surface of a glass plate. Glass plates were placed at intervals of about 1 mm to cover the top, and heat treatment was performed under the same conditions as in Example 1. As a result, the glass plates placed on top were severely corroded.

Next, in Examples 1, 2, and 3 below, a glass plate was placed to cover the top in the same manner, and heat treatment was performed under each condition. As a result, in all cases, the glass plate placed on top was not corroded at all. Nakatsuta. Therefore, it can be seen that in Examples 1, 2, and 3, almost no glass corrosive gas was diffused into the atmosphere.

Claims (1)

[Scope of Claims] 1. An ink composition whose main components are a glass corrosive agent that generates glass corrosive gas when heated and an organic substance capable of forming a solid film on a necessary portion of the surface of a ceramic substrate. A corrosive agent layer is provided by using a glass corrosive agent, a gas diffusion prevention layer is provided to cover the corrosive agent layer, and then the glass corrosive agent is thermally decomposed to generate a glass corrosive gas. A method for manufacturing a ceramic product having a characteristic uneven surface. 2. The method for manufacturing a ceramic product having an uneven surface according to claim 1, wherein the gas diffusion prevention layer is made of a high melting point inorganic substance. 3. The uneven surface according to claim 1, wherein the gas diffusion prevention layer is formed by laminating a layer made of a low melting point inorganic substance on a layer made of a high melting point inorganic substance. A method for manufacturing ceramic products. 4. Having an uneven surface according to claim 1, wherein the gas diffusion prevention layer is mainly composed of a solid base and/or a nitrogen-containing resin that chemically bonds with a glass corrosive gas. Method of manufacturing ceramic products.