JPS5888142A - Glass etchant for high temperature use and etching of glass using said etchant - Google Patents

Abstract

PURPOSE:To provide a glass etchant for high temperature use, convenient for handling and storage, capable of forming a film decomposable at high temperature, and composed of a composition obtained by mixing an organic polymer substance with a material derived from a metal fluoride and ammonium fluoride. CONSTITUTION:A glass etchant for high temperature use and capable of forming a film decomposable at high temperature, is prepared by compounding (A) a mixture, double salt, or complex salt of a metal fluoride (fluoride of a III-group metal or transition metal; e.g. aluminum fluoride) and ammonium fluoride, e.g. (NH4)3AlF6, (B) an organic polymer substance unreactive with the component (A), and if necessary (C) additives (e.g. diluent, filler, stabilizer, flux, softening agent, etc.). When the etchant is applied to the surface of a glass article, dried to form a solid film, and thermally decomposed at about 250-550 deg.C, the glass surface is easily etched with the generated hydrogen fluoride gas.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for corroding glass, and more particularly to a corrosive agent for corroding glass by dry heating and a method for corroding glass by high-temperature heating using the corrosive agent.

Conventionally, any part of the surface of a glass product such as a glass plate or a fume container is treated with a hydrofluoric acid solution, a mixture of fluorinated hydrogen and sulfuric acid, or A so-called wet corrosion method using an ammonium fluoride solution is used. Therefore, during work, highly toxic and corrosive solutions such as hydrofluoric acid must be handled, which poses a high risk of harming the health of the workers.In addition, disposal of the waste liquid is difficult and requires enormous processing costs. It has its drawbacks.

For this reason, in recent years, this wet corrosion method has been on the decline due to pollution problems, and sandplast methods that produce rough surfaces are now being used more frequently.

In view of the current situation, the present inventor has conducted extensive research in an attempt to improve the various drawbacks of these conventional wet corrosion methods, and has found that it is possible to form a solid film containing a relatively stable and less toxic corrosive agent. It was discovered that the various drawbacks of the conventional methods can be solved by forming a solid film of the corrosive agent on the glass surface using ink and dry heating it at an appropriate temperature to corrode the glass, and based on this knowledge, As a result, the present invention was completed.

That is, the present invention has as essential components a mixture of a substance consisting of a metal fluoride and ammonium 77ide, and an organic polymeric substance that does not react with the substance, and if necessary, an extender, a filler, a stabilizer, a flux, and a softener. A solid glass corrosive agent and nuclear corrosive agent for high temperature use, characterized in that it contains at least one third substance selected from the group consisting of agents, and is capable of forming a high-temperature decomposable solid film. The present invention provides a method for corroding glass, characterized in that a film is formed on the glass surface and then heat treated at 1 to 560°C.

The present invention! This will be explained in detail. First, the first invention, a high-temperature glass corrosive agent, will be explained.

Examples of metal fluorides used in the corrosive agent include Group 8 metal fluorides and transition gold monomonides. This 8th cover metal l
Suitable E-fluorides include aluminum tulfide, cerium fluoride, indium fluoride, and scandium fluoride, and the intermediate amount is also important.

aluminum chloride.

Next #CIII transfer metal fluorides include vanadium fluoride, fluoride fluoride, manganese fluoride, iron trouside, cobalt fluoride, nifkel fluoride, fluoride steel, divinium fluoride, and niobium fluoride. , molybdenum fluoride, ibuturium fluoride, cerium fluoride, lanthanum fluoride, tanta fluoride, tungsten fluoride, antimony fluoride, bismuth fluoride, tin fluoride, lead fluoride, etc., singly or in combination, or a combination thereof. It is an oxygen-containing compound. Next, the substance consisting of a metal fluoride and ammonium fluoride is a compound, a mixture, a double salt, or an anchor ring of the above metal fluoride and ammonium fluoride, and among them, water-insoluble double salts or complex salts are suitable. .

Among these, the industrially important one is (NH4)sAI
Fa(NH4)2COF4, (NH4)2NiF4, (
NH4)2MnF4, (NH41BOrF6(NH4)
2ZrF6, (NH4)3Zr%, (liH4)3V
It is a complex salt such as F6, (NH4)3FeF6NH4BiF4.

Next, in order to form these into ink, an organic polymer substance as a binder is mixed with them.

This organic polymer material must be one that does not react with the metal fluoride and ammonium fluoride material. Therefore, the polymeric substances that can be used are preferably water-insoluble ones, such as polyvinyl vinyl, polyvinylidene agglomerate, vinyl chloride V vinyl monoacetate copolymer resin, polystyrene, acrylic resin, methacrylic resin, etc. lIIIB
, epoxy resin, urethane resin, urea resin, phenol resin, polyacrylonitrile%A. B. 8.
Resin, melamine resin, Voliente V* fat, petroleum resin, coumaron indene 11m, terpene m ni, polyolefin, polyamide, shellac, cellulose 11
Ml. Examples include polyvinyl acetate, fluorine-containing resins, synthetic rubber, natural rubber, diene resins, vegetable fat waxes, and the like.

A wide variety of these organic polymer substances are dissolved using appropriate solvents, and then kneaded with corrosives to form inks with various viscosities depending on the usage. Further, third substances such as extenders, fillers, stabilizers, fluxes, and softeners are added as appropriate.

These extenders and fillers include insoluble silicates, poorly soluble phosphates, alkaline earth metal carbonates, lead borate, zinc borate, cobalt oxide, zinc oxide, manganese oxide, aluminum oxide, iron oxide, and Nigke u, chromium oxide, zircon oxide, molybdate, barium sulfate, silica sand, clay,
White clay, talc, graphite, car pump hooks, etc. can be used.

As the stabilizer, lead salts, metal soaps, organic acid lead salts, organic tins, amines, epoxides, etc. are used. As fluxes, silicates of alkali metals or lead, phosphates of alkali metals or alkaline earth metals, tungstates of alkali metals, molybdates, diacids, boric acid compounds, alkali metal sulfates. etc. can be used.

Furthermore, as for the softening agent, high boiling point organic compounds such as phthalic acid esters, phosphoric acid esters, adipic acid esters, etc. can be used.

The corrosive agent according to the present invention is an ink-like material having the above-mentioned structure, and when it is applied to the surface of the target glass product and dried, it can be easily formed into a solid film, and
If this is heated at a high temperature, e.g. 60°C to 550°C, the solid film will be decomposed and hydrogen fluoride gas etc. (The generated gas will contain HF%SiF, 1 [4F).
occurs, which can easily corrode the glass surface.

Next, to explain the method for corroding glass, which is the second invention of the present invention, firstly, the above-mentioned ink-like S&C corrosive agent is applied by an appropriate coating method, such as a direct printing method or a dipping method.
A solid film of corrosive agent is formed by applying a coating on the entire surface or any desired part using transfer printing, spraying or various coating methods, and then drying it.

A solid film of this corrosive agent is applied to the surface of glass products such as letters, ■
If you want to apply it partially, such as a pattern, you can use the printing method or transfer printing method described above, but you can also apply a chemical resist film to the surface of the glass product (leave the parts that should be corroded in advance), or apply a chemical resist film. , You may apply V4 corrosion agent to the entire surface.

The product, thus forming a solid film of surface IC etchant, is then heated to a high temperature, in this case from 250°C to 660°C.
The fg41i in the solid film is only heated in the range of ! The il agent causes thermal decomposition, thereby generating hydrogen fluoride gas and the like, which can corrode the glass surface.

Note that if the above heat treatment temperature is 250°C or lower, the corrosive agent is stable and hardly thermally decomposed, so no corrosion effect can be obtained;
At temperatures above 50°C, rapid thermal decomposition of the corrosive agent and rapid volatilization and escape of hydrogen 7 fluoride gas occur, reducing the corrosion effect. Therefore, in the present invention, the heat treatment temperature for corrosion is Although it depends on the type and amount of the agent, it is generally necessary to select it appropriately within the range of gsoC to 550°C.

Even if there are residues of the corrosive agent on the surface of the corroded glass after the heat treatment described above, these are an unstable layer with no binder, so they can be removed by washing with water or wiping.
oC can be removed.

The present invention does not have the corrosive properties of conventional fuvic acid when forming an ink having the above structure, so there is almost no danger to workers, and the corrosion mechanism is based on the heating of the solid film. Since the process is based on dry corrosion, there is no need for conventional waste liquid treatment, and if necessary, the need for distributing all books can be completely eliminated by simply removing the hydrogen fluoride gas generated during heat treatment. be. When a suitable high-temperature glass corrosive agent is selected to form a solid film on the glass and then thermally decomposed, the maximum glass corrosive effect can be obtained with a small amount of fluorine compound.

In addition, this corrosive is stable at temperatures below 200°C, so it is not only convenient to handle and store, but when applied to various printing machines and printing methods, it hardly damages the printing plates. It can be applied to various printing methods such as gravure printing, letterpress printing, offset printing, flexo printing, screen printing, etc. Therefore, patterning and shading of corroded areas can be easily obtained, blurred designs and continuous Gradation patterns and the like also appear and are of great industrial value.

Next, examples of the present invention will be described. Note that the Examples are merely illustrative and do not necessarily limit the corrosive agent and the corrosive method of the present invention.

Example 1 The substances listed in the table below were mixed at the compounding ratios shown, placed in a paint shaker, and kneaded for about 1 hour to obtain an ink-like high-temperature corrosion agent.

Example 2 In place of each substance shown in the table of Example 1, the substances shown in the table below were mixed at the compounding ratio shown, put into a homogenizer, and kneaded for about 2 hours to form an ink. A caustic agent was obtained.

Example 8! ! In the same manner as in Example 8, the materials shown in the table below were placed in a homogenizer and kneaded for about 2 hours to obtain an ink-formed high-temperature glass corrosive agent.

Example No. The ink-formed corrosive agent prepared in Example 1 was printed in a polka dot pattern on the outer periphery l11i of a glass cup by screen printing method, and this was air-dried to obtain about 50 μm.
A glass pot with a polka dot pattern formed with a corrosive solid film with a thickness of A glass tip on which an opaque polka dot pattern was formed was obtained.

Example 5 The ink-formed corrosive agent prepared in Example 2.

Tree 111 is printed on a 26μ polyester film in advance using a gravure printing machine! On the surface of the release layer of a base film provided with a release layer made of a 60% butyral resin, partially scattered floral patterns are printed and dried to form a fixed film with a thickness of 10 μm. part to ν(
A transfer material was prepared by applying and drying a solution dissolved in 30 parts of solvent to form a heat-sensitive adhesive layer.

Next, using the transfer material, the corrosive agent on the transfer material was transferred onto the surface of a glass plate with a thickness of 6 cm using a heated row M type transfer machine,
After that, this was placed in the center of the firing furnace and heated at 450°C for 80 minutes, and the residue on the surface was removed by washing with water.
A glass plate with matte floral patterns scattered on its surface was obtained.

patent applicant Nissha Printing Co., Ltd.

Claims (1)

[Scope of Claims] The essential components are a mixture of metal fluoride, ammonium fufluoride, and an organic polymer substance that does not react with the substance, and optionally an extender, a filler, a stabilizer, and a flux. ,
A high-temperature glass corrosive agent, characterized in that it contains at least one third substance selected from the group consisting of softeners, and forms a solid film that is decomposable at high temperatures. 2. The high 1 compound according to claim 1, wherein the substance consisting of a metal fluoride and ammonium fluoride is a composite or complex salt of ammonium heptabutide and ammonium fugide.
Glass caustic agent. 2. The high-temperature gaff corrosive according to claim 1, wherein the substance consisting of an 8-metal heptadide and ammonium fluoride is a composite or complex salt of a transition metal fluoride and ammonium fuginate. 4. A mixture of metal fluorides, ammonium fufluoride, and organic polymeric substances that do not react with the substances as essential components, and as necessary, extenders, fillers, and stabilizers. A solid film of a high-temperature glass corrosive agent containing at least one third substance selected from the group consisting of fluxing agents and softeners is formed on the glass surface, and then heated at 860°C to 56°C.
A method for corroding glass, characterized by heat treatment at 0'ct. 5 Metal fluorides and ammonium fluoride and more! The method for corroding glass according to claim 4J, wherein the substance is a composite or complex salt of aluminum fluoride and ammonium fugide. 6. The method for corroding glass according to claim 1, wherein the substance consisting of a metal fluoride and ammonium fluoride is a composite or complex salt of a transition metal fluoride and ammonium fluoride.