JPS5855348A - Method of coating glass product with glaze - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] This invention relates to a method for depositing glazes on glass.

Until now, whether it is the deposition of symbols or numeric inscriptions, the deposition of electrical conductors for resistive heating or radio antennas,
Whether it's a protective deposit to protect adhesives to hold accessories such as packs on 70-ton glass in automobiles, etc.

Used for fitting into car window glass - L5, 1m,
Whether as a protective precipitate to protect the agent or as a decorative precipitate, a suspension of the S agent in an oily vehicle or binder, generally based on pine oil, has been used. Ta.

Good glaze fI on glass with this binder
l ductility is achieved, no deterioration of the glaze coloration is observed, the viscosity is such that the glaze can be applied by serigraphy, and there is no need to worry about incompatibility with glass processing machines with many greased parts. do not have.

However, after depositing the glaze suspension, it is dried for a relatively long period in an oven to remove the binder and obtain a temporary coating of sufficient hardness to carry out the processing cycles of the glass article. It is necessary to. This temporary coating is converted into a final coating of glaze by heat treatment at high temperatures which vitrifies the glaze. This intermediate drying of the glaze suspension in the binder is particularly
Care must be taken when deposits are of large size. The reason for this is that under the action of this heat, the binder begins to boil, so that no foamed film is left on the glass. This is therefore a stage of drying, which takes a relatively long period of time. In addition, although the coating is hard, it is not truly hard, so the coated glass article must always be handled with care. This is because the final hardness can only be obtained after vitrification of the glaze. Therefore, time is wasted, drying equipment is expensive, and some of the glass articles break during the processing cycle or are difficult to handle.

For other public products, namely pottery and ceramics, in order to avoid sagging during the deposition of the glaze film,
That is, in order to avoid glaze loss during the deposition of a transparent finish layer on ceramic or porcelain III items, a small amount of ultraviolet # (UV ) proposed adding an organic compound that can be polymerized (% Gansho! 10-/Dakozari No. 3)
. The article is first irradiated with ultraviolet light to 111vJ in a bale coated with a glaze layer and then rapidly exposed to temperatures as high as 100°C. This irradiation of the organic compound with ultraviolet radiation avoids deterioration of the S+ drug and reduces processing time, but the article cannot be used before vitrification of the glaze.

This invention is suitable for making deposits on glass! The aim is to overcome the problems caused by the binders that have been used and in particular to obtain a harder temporary coating which avoids said intermediate drying and at the same time allows handling and use of the glass article before the final vitrification operation.

In order to achieve the above object, the present invention provides a glass article with a
Depositing a mixture of a glaze and a binder containing an organic compound capable of polymerizing under the action of radiation, especially ultraviolet light, said article 1%
exposing the mixed deposit area to radiation, then polymerizing and hardening the deposit to continue the processing cycle of the glass article, and treating the glass article at high temperatures to burn off the organic compounds during this treatment. , consisting of vitrifying the glaze.

The heat treatment of the glass article after polymerization by ultraviolet radiation naturally consists of heat treatment at a temperature at least equal to the vitrification temperature of the glaze, but which temperature is below the softening temperature of the glass.

This heat treatment can be combined as a step in the processing cycle of the glass article, particularly with concave or reheating for glass concave treatment or tempering.

The binders that can be used to apply such glazes on glass consist essentially of one or more monomers that are reactive to ultraviolet II (UV) light, that promote the degree of polymerization reaction, and that contain monomers that do not react with polymerization. 1. Quickly reactive to UV that can be expanded into molecules
The proportion of binder in the mixture consisting of a species or a mixture of one or more oligomers and a photoinitiator and deposited on glass is important and should account for at least 7 and 2 parts of the mixture.

Advantageously, the binder also contains additives, in particular surfactants and diluents, in order to ensure a good viscosity of the mixture and good castability on glass.

The binder must be such that when it burns it leaves virtually no residue on the glass. In fact, this residue, especially carbon residue, is detrimental to the good bonding of the glaze to the glass, and there is also the risk of changing the coloration of the glaze.

Among the monomers used in this invention, acrylic compounds give good results, among which the following monomers A and B are preferred: Monomer A (co-hydroxyethyl acrylate); I CH, - CH-C-0-CH, -CH,OH monomer B (
1 or a mixture of these monomers.

Oligoya unsaturated polyesters, and especially oligos represented by the formula below! - product C consisting of ortho-7-talic acid, maleic acid and buta/dio-rll, which facilitates the initiation and propagation of the polymerization reaction.

A photoinitiator is added to assist in rapid polymerization of the compound as described above. When this photoinitiator is exposed to radiation,
It decomposes into active radicals, and these radicals form compounds A and B.
and C-containing am polymerization in 11#1.

As photoinitiators, mention may be made of the ethyl ethers of benzoin in alkali as shown below: in particular the ethyl ethers of benzoin:
It decomposes under the action of radiation as follows: Et. Made by Rohm, mixture of monomers and oligomers] Plex CP16X) 44ri J, 0 [Made by Rohm, mixture of monomers and oligomers] Darocur
C1ba-o*igy), photoinitiator] A dangerous mixture from the following composition (depending on the polymerization ratio) gives satisfactory results: Flew &tL-g, Q at Part P
lex 4473.0 - 〇 M'Da
rocur 6g6 powder glaze m
1oofl& Other mixtures of the following composition also give satisfactory results: PleX 649,3. θ de O
Part DarOeur 3 Parts Powdered Glaze Ya ttosIS The powdered glaze is thus represented, for example, by the above-mentioned formula. One of the compounds is mixed with a binder.

In all these cases, the proportion of binder in the mixture deposited on the glass is important in order to have optical hardness and is greater than or equal to t/q of the mixture, preferably t/J~-. .

The glaze selected in this invention is at a temperature compatible with glass.
That is, it is one that can be vitrified at a temperature below the softening temperature of glass. Thus, it has a relatively low proportion of silica, advantageously per gold ring a/! Contains r-JO weight- of silica.

The mixture can be applied at ambient temperature onto a glass substrate by serigraphic techniques. Very tightly bonded deposits, for example with a thickness of 0,0,0, ymm, are obtained without any problems.

The thickness of the film is, for example, approximately 0.00000000000000000000000000000000000000000000000000000000000000000000 3000. /mm.

The thus coated glass is exposed to ultraviolet light for a very short period of time, for example on the order of seconds, e.g. to the light of a high pressure mercury vapor lamp with a power of 11 go quarts per length or more. Advantageously, the mercury vapor lamp emitting ultraviolet light is arranged above the glass, but likewise below the glass. This period allows the organic binder to polymerize and the glaze and polymerized resin, which we call the intermediate, to form a dry, hard, non-scratchy, and thus coated glass article that characterizes its processing cycle. A coating is obtained which is sufficient to obtain a coating of sufficient hardness because it can be carried out without special precautions and without degrading the coating. The glaze used is a colorant, such as Cu, Oe Cr!, which imparts a black color. Colorants such as O, or CuCr, O, may be included.

Glass sheets provided with such a coating can be handled by hand, transported on rollers with the coating side in contact with the rollers if necessary, and can be stacked, although with the disadvantage that the glass sheets slide over each other. , which means that there is no damage to the coating.

After completing all necessary processing operations and metallization cycles, the glass article must be subjected to a heat treatment during which the organic binder is burnt off at about 110° C., leaving only the glaze on the glass. The heat treatment is then continued to vitrify the glaze, which vitrification is carried out at temperatures below 400°C, e.g.
Occurs at SO℃. This necessary heat treatment can be combined with a step in the processing of the glass article, e.g. concaveization of the glass (curvature hardening operation or reheating for concaveization). If a deposit is made on the glass pane for making the glass part, for example on the shoulder edge of the window pane for a later applied tone layer, for example on the body side of a car. If the glaze is deposited in the form of a cloud in the organic binder, the glaze can be deposited in the form of a cloud after cutting out the glass plate and processing the end a of the glass plate. after which the glass sheet can be processed without any special precautions.The glass sheet thus treated is combined with other glass sheets and transported on rollers. The glass pane, combined with other glass panes, is placed on a tetrahedral frame and placed in a concave furnace. It is during this reheating and glazing process that the binder is burnt off and vitrification occurs.

Thus on the shoulder ll1lS of one external surface of the glass plate,
It is possible to obtain a laminated windshield fully coated with a glaze that can be used to remove glue* and scraps for mounting the windshield.

Since the binder does not contain *g*, there is no need to stencil clean the heptography, and it is generally not necessary to clean all parts that come into contact with the binder after each processing operation.

Claims (1)

Claims: l depositing on a glass article a mixture of #1 layered glaze in an organic binder that polymerizes under the action of radiation, in particular ultraviolet light, said glass article and at least the glaze mixture depositing thereon; exposing the area to radiation to obtain a hard coating and continuing to process the glass article, subjecting the glass article to sufficient heat treatment to burn off the organic binder and vitrify the glaze;
A method of coating a glass article with a glaze, characterized by: The binder consists essentially of one or more UV-polymerizable monomers, one or more UV-polymerizable oligomers and a photoinitiator, and in a mixture with the glaze, t $ 4. The method according to claim 3, wherein the 1j=r mer is an unsaturated polyester consisting of orthophthalic acid, maleic acid and butanediol-/4I. 4 (The method according to claim 1 or 3, in which the photo-H initiator is an alkyl ether of Be/Ci/). A patent in which the glaze is subjected to vitrification at a temperature of 600°C or lower, particularly 330°C or lower. The method according to any one of claims 1 to 3. 4. The method according to claim 3, wherein the glaze contains tS% to 30 To of silica. 7. Combustion decentering of organic binder and glaze The heat treatment for vitrification is carried out in combination with other treatments of the glass article, and in the above-mentioned treatments, the high temperatures required for the tetrahedralization treatment and reheating treatment for the tetrahedralization or tempering of the glass article are carried out. The method according to any one of claims 1 to 6, wherein the method is performed by: