JPS5849200B2 - Method for painting ceramics, etc. using primer for transfer on glaze and primer for transfer on nuclear glaze - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides an over-glaze transfer primer used when painting ceramics, etc., and a painting method that simultaneously performs glaze heating and pattern firing using the over-glaze transfer primer. It is related to.

Conventionally, in order to paint ceramics, etc., a glaze is applied to the ceramic base to form a raw glaze layer, heated at about 1000 to 1400 degrees Celsius, and then a pattern layer formed on transfer paper is transferred onto it. However, a method has been adopted in which the synthetic resin contained in the pattern layer is decomposed and volatilized by further firing at about 500 to 1000°C.

This method requires two steps: firing the raw glaze layer and firing the pattern layer, which is complicated, has poor thermal efficiency, and is economically disadvantageous.

In order to improve the above method, a primer mainly consisting of a synthetic resin emulsion, a water-soluble polymer, or a mixture thereof was applied to the surface of the raw glaze layer to improve the structural strength of the raw glaze layer, and then a primer was applied to the surface of the raw glaze layer. A method has been proposed in which the formed pattern is transferred onto the surface of the raw glaze layer and brought into close contact with the raw glaze layer, and the firing of the raw glaze layer and the pattern layer are performed at the same time. It had poor adhesiveness and poor adhesion, and it had the disadvantage of causing lifting of images, pinholes, shrinkage, etc. during pre-drying and firing, resulting in a high defect rate.

The present invention improves the above-mentioned drawbacks by adding a solvent that is compatible with a synthetic resin, which is a film-forming agent for a pattern to be transferred from a transfer paper, to an aqueous solution of a water-soluble organic polymer. The primer for glaze transfer is made by adding a polymer emulsion, and the primer is applied onto the raw glaze layer, and then the design for transfer is transferred from the transfer paper and then fired, thereby allowing the firing of the raw glaze layer and the design firing. This relates to a method of painting that simultaneously performs the following.

The present invention will be explained in detail below.

The water-soluble organic polymers used in the present invention include, for example, sodium alginate, carboxymethyl cellulose, hydroxyethyl cellulose, methoxy cellulose, polyacrylamide, polyacrylic acid and its salts, partially saponified polyacrylic ester, and polymethacrylic acid. The salts,
α, β monounsaturated acid monovinyl monomer copolymers and their salts, such as polymethacrylic acid and its salts, partially saponified polymethacrylic acid esters, maleic acid-polyisobutylene copolymers, acetic acid vinyl-itaconic acid copolymers, etc. All water-soluble organic polymers such as , polyvinyl ether, polyvinylpyrrolidone, polyvinyl alcohol, water-soluble acrylic ester copolymer, water-soluble methacrylic ester copolymer, water-soluble polyester, water-soluble polyurethane, tragacanth gum, rosin and rosin derivative salts, etc. It contains an aqueous solution of.

The above examples are not intended to limit the invention.

The above-mentioned water-soluble organic polymer provides initial adhesive strength when transferring the pattern layer, and acts as a binder to bind the glaze fine particles that make up the raw glaze layer, increasing the structural strength of the raw glaze layer during transfer. Although it improves its ability to withstand external forces, it decomposes and evaporates when fired.

The solvent used in the present invention is a solvent that is compatible with the synthetic resin that is the film forming agent for the pattern transferred from the transfer paper and that dissolves or swells the synthetic resin.

Synthetic resins such as polyacrylate, polymethacrylate, ethyl cellulose, and polyvinyl butyral are generally used as film-forming agents for patterns, so the solvent used must be compatible with these synthetic resins that are film-forming agents. You should choose something.

Examples of such solvents include n-hexane, n-hebutane,
Aliphatic solvents such as n-octane, petroleum ether, gasoline, kerosene, petroleum spirit, petroleum naphtha, etc., aromatic solvents such as benzene, toluene, xylene, coal tar naphtha, solvent naphtha, tetralin, turpentine oil, pine oil, cyclohexane, methyl Cyclic hydrocarbon solvents such as cyclohexane, halogenated hydrocarbon solvents such as chloroform, carbon tetrachloride, trichloroethane, chlorobenzene, bromotoluene, fluorodichloromethane, dichloroethyl ether, methyl phenyl ether, ethylbenzyl ether, dioxane, trioxane, furfural, tetrahydrofuran, tetrahydropyran, cineole,
Ethers such as methylal, acetal solvents, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetone oil, ketone solvents such as holon, acetophenone, dibunone, probyl formate, ethyl acetate, ethyl propionate, methyl butyrate, methyl lactate, methyl benzoate , ester solvents such as dibutyl oxalate, ethylene glycol,
Methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve, cellosolve acetate, butyl cellosolve, phenyl cellosolve, ethylene glycol diacetate, ethylene chlorohydrin, methyl cellosolve,
Polyhydric alcohol solvents such as butyl carbitol, polyethylene glycol, flopylene glycol, chrycerin, alcohol solvents such as methanol, ethanol, propanol, butanol, imbutanol, amyl alcohol, fusel oil, octanol, fricidol, formic acid, acetic acid , propionic acid, butyric acid, valeric acid, trimethylacetic acid, caproic acid, ethylbutyric acid, caprylic acid, oleic acid,
Fatty acids such as lactic acid, nitrogen compounds such as nitromethane, nitrobenzene, monomethylamine, diethylamine, butylamine, aniline, o-toluidine, monoethanolamine, triethanolamine, acetamide, penzonitrine, quinoline, morpholine, carbon disulfide, triethyl phosphate, Compounds such as sulfur, phosphorus, carbonic acid such as diethyl carbonate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, butyl benzyl phthalate, ethylphthalyl ethyl glycolate, butyl phthalyl butyl glycolate, trioctyl trimetate, dioctyl azide bate, dioctyl azelate, dibutyl sebacate, methyl acetyl ricinoleate,
Dimethyl maleate, dibutyl maleate, cyoctyl maleate, propylene glycol adipate, epoxidized soybean oil, glycerol tributyrate, cellulose acetate phthalate, trimethyl phosphate, r-+
All plasticizers as high-boiling solvents are included, such as J-phthyl phosphate, triphenyl phosphate, triphenyl phosphite, trichloroethyl phosphite, etc.

The above examples are not intended to limit the invention.

If a plasticizer is used as part or all of the solvent used, there is less risk of the solvent volatilizing before firing, which reduces the possibility of odor, which is extremely desirable from a safety and health perspective, and results in exactly the same results as with other solvents. It will be done.

When a solvent is added to the aqueous solution of the water-soluble polymer used in the present invention, lower alcohols, ketones, etc. are easily dissolved in the aqueous solution of the water-soluble polymer, but the added solvent may be difficult to dissolve uniformly. Alternatively, if the solvent does not dissolve, the same result can be obtained by using these solvents as an emulsion in water.

When used as an emulsion, it is preferable to emulsify the solvent in water by adding an emulsifier to the solvent or water in a conventional manner.

When the water-soluble polymer itself acts as a protective colloid, an emulsifier may not necessarily be necessary.

Generally, all of nonionic surfactants, anionic surfactants, and cationic surfactants can be used as emulsifiers.

Examples of anionic surfactants include fatty acid salts, stearates, oleates, alkyl sulfates, alkylbenzenesulfonates, alkylnaphthalenesulfonates, diallylsulfosuccinates, alkyl phosphates, Naphthalene sulfonic acid formalin condensate, polyoxyethylene alkyl sulfate, nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkylphenol ether, polyoxyethylene fatty acid ester, nrubitan fatty acid ester, polyoxyethylene sorbicun fatty acid ester, glycerin fatty acid ester,
Examples of the oxyethylene oxypropylene block polymer and cationic surfactants include all surfactants such as alkylamine salts, quaternary ammonium salts, and polyoxyethylene alkylamines.

The above examples are not intended to limit the invention.

The above-mentioned solvent is added in an amount of 2 parts or more to 100 parts by weight (hereinafter simply referred to as "parts") of the above-mentioned aqueous solution of the water-soluble organic polymer to dissolve or emulsify it, but the purpose of the present invention can of course be achieved even outside this range.

Furthermore, if desired, a polymer emulsion may be added in order to improve the initial adhesive strength with the pattern layer to be transferred and the binding strength of the green glaze layer.

Polymer emulsions include, for example, styrene-butadiene rubber latex, acrylonitrile-butadiene rubber latex, butadiene rubber latex, imprene rubber latex, polyethylene emulsion, ethylene-vinyl acetate copolymer emulsion, polyvinyl acetate emulsion, and acrylic ester. It includes all polymer emulsions such as vinyl acetate copolymer emulsions, polyacrylic emulsions, polyvinyl chloride emulsions, and polyvinylidene chloride emulsions.

The above examples are not intended to limit the invention.

Moreover, instead of adding a polymer emulsion to a water-soluble organic polymer solution, a polymer emulsion obtained by emulsion polymerization using a water-soluble organic polymer as a protective colloid by a conventional method may be used.

When adding a solvent to a polymer emulsion containing a water-soluble organic polymer as a protective colloid, the solvent is directly added to the polymer emulsion and dissolved or emulsified and dispersed by stirring, or the solvent and/or plasticizer is added to the surfactant in advance. and/or adding an emulsion emulsified in the presence of a protective colloid, any method may be used.

The primer for transfer onto the glaze is prepared in this way, and the following steps are taken to carry out painting using the above primer.

First, glaze is applied to the ceramic base to give the raw glaze layer its shape.

The glaze referred to in the present invention includes all glazes such as lead yew, frit yew, bristol yew, and porcelain yew.

General methods such as dipping, pouring, and spraying are used for glazing.

After glazing and preliminary drying, the primer described above is applied to the surface of the raw glaze layer.

Application methods include general methods such as brushing, spraying, and dipping.

After applying the above primer, paste the transfer pattern from the transfer paper while it is still wet.

Although the purpose of the present invention can be easily achieved using any transfer method, the water slide method is one of the most preferred methods because it causes fewer defects and has good workability.

In the water slide transfer method, a water-soluble organic polymer is applied to the surface of the base paper, a pattern is printed on top of it using ink containing a mixture of pigments and synthetic resin, and a pattern layer is formed, and a synthetic resin is applied on top of the pattern. This paper uses a transfer paper provided with a reinforcing layer, and when the transfer paper is immersed in water, the water-soluble organic polymer dissolves and the pattern layer is peeled off from the paper along with the reinforcing layer. The primer is transferred to the surface of the applied raw glaze layer before it dries.

At this time, the pattern layer is transferred to the surface of the primer-treated raw glaze layer with a certain amount of moisture attached, but the primer is mainly added to the water-soluble organic polymer or water-soluble organic polymer aqueous solution in the undried state. The polymer emulsion component imparts appropriate tackiness, that is, initial adhesion, to the surface of the raw glaze layer for transfer work of the pattern layer, and furthermore, due to the residual solvent in the primer, the synthetic resin that is the film forming agent of the pattern layer is Because it partially dissolves or swells due to the residual solvent, it blends well with the surface of the raw glaze layer, resulting in good adhesion.Furthermore, volatile components such as water and solvent contained in the raw glaze layer and primer are partially dissolved or swelled. It becomes possible to easily volatilize through the pattern layer, and it is possible to reliably prevent pinholes, floating, shrinkage, and deterioration of the pattern layer.

After transferring the pattern layer onto the raw glaze layer, it is usually 1000 to 140
Calcinate at a temperature of 0°C.

The raw glaze layer is thermally formed by the above firing, and at the same time, the water-soluble polymer in the primer, the plasticizer, the polymer substance in the polymer emulsion, and the resin that is the film form or agent for the pattern layer are decomposed and volatilized. Painting will be done.

Thus, in the present invention, maturation of the glaze and firing of the pattern can be performed simultaneously in one firing, thereby improving thermal efficiency and streamlining the process.

Examples of the present invention will be described below.

Example 1 Primer prescription for overglaze transfer Partially saponified polyvinyl alcohol 10 parts water
60 parts petyl cellosolve
30 partsProduction method Add water to polyvinyl alcohol and dissolve completely while heating and stirring.

This was cooled and putyl cellosolve was added to obtain a primer.

Example 2 Primer formulation for on-glaze transfer Methyl cellulose 1 part (2%, 2
00C, 4000cps) Water 49 parts Dibutyl fucrate 35 parts Oleic acid
3-part triethanolamine
2 part SBR emulsion
10 parts Production method Methyl cellulose was dissolved in cold water, dibutyl phthalate mixed with oleic acid was added to this aqueous solution with strong stirring, and triethanolamine was further added to prepare an emulsion.

Next, SBR emulsion was added to this to obtain a primer.

Example 3 On-glaze transfer primer formulation Vinyl acetate-maleic acid copolymer 10 parts water
60 parts polyoxyethylene lauryl 5 parts ether (HLB 1 5) petroleum naphtha.

5 Sound Production Method Vinyl acetate-maleic acid copolymer was dissolved in water, polyoxyethylene lauryl ether and petroleum naphtha were added thereto, and the mixture was emulsified using a homogenizer to obtain a primer.

Example 4 On-glaze transfer primer formulation Vinyl acetate 20.0 parts Butyl acrylate 15.0 parts Partially saponified polyvinyl alcohol 2.5 parts Sodium polyoxyethylene alkyl ester sulfate 4.5 parts Potassium persulfate 0.1 part water
58, Part o Production method: Charge water, polyvinyl alcohol, sodium polyoxyethylene alkyl ether sulfate, and potassium persulfate into a reactor, and drop vinyl acetate and butyl acrylate at 80°C while stirring to emulsion polymerize to form an emulsion. To this emulsion were added 200 parts of water and 100 parts of mineral spirit, and the mixture was stirred and mixed to obtain a primer for transfer on glaze.

Example 5 Primer prescription Partially saponified polyvinyl alcohol 15 parts water
83 parts petyl cellosol
1.8 parts Production method Polyvinyl alcohol was dissolved in water, and butyl cellosolve was added thereto to obtain a primer.

Comparative example Primer prescription Partially saponified polyvinyl alcohol 15 parts water
85 parts Production method Polyvinyl alcohol was dissolved in water to obtain a primer.

The primers prepared in Examples 1 to 5 and Comparative Examples were applied at a rate of 150j;lr/,2 onto the raw glaze layer glazed on the ceramic base, and then the pattern layer was transferred using the water slide method.
It was fired at 200-1300°C.

A polymethacrylic ester-based film-forming agent was used for the pattern.

Baking Results From the above results, the pattern condition was poor in the comparative example, but based on the present invention, a small amount of solvent (an aqueous solution of a water-soluble organic polymer or a polymer emulsion with a water-soluble organic polymer as a protective colloid) was used. (2 parts or less of solvent per 100 parts of aqueous liquid)
In Example 4 where the addition was made, the pattern condition was improved, especially 2
It was found that when more than 1 part was added (Examples 1 to 3), very good results could be obtained.

Claims (1)

[Scope of Claims] 1. A primer for over-glaze transfer, which is prepared by adding to an aqueous solution of a water-soluble organic polymer a solvent that is compatible with a synthetic resin that is a film-forming agent for a pattern to be transferred from a transfer paper. 2 An aqueous solution of a water-soluble organic polymer is added with a solvent that is compatible with a synthetic resin that is a film-forming agent for a pattern to be transferred from a transfer paper, and part or all of the solvent is a plasticizer. A primer for overglaze transfer. 3. A primer for over-glaze transfer, which is made by adding a polymer emulsion and a solvent that is compatible with a synthetic resin, which is a film-forming agent for the pattern to be transferred from transfer paper, to an aqueous solution of a water-soluble organic polymer. 4 A polymer emulsion and a solvent that is compatible with a synthetic resin that is a film-forming agent for a pattern to be transferred from a transfer paper are added to an aqueous solution of a water-soluble organic polymer, and a part of the solvent or a polymer emulsion is added. A primer for overglaze transfer that is entirely made of plasticizer. 5 A primer for glaze transfer, which is made by adding a solvent compatible with a synthetic resin, which is a film-forming agent for the pattern to be transferred from the transfer paper, to an aqueous solution of a water-soluble organic polymer is glazed onto a base material such as ceramics. A painting method in which the raw glaze layer is fired and the design is fired at the same time by coating the raw glaze layer, then transferring a transfer pattern from transfer paper, and then firing. 6 A solvent is added to an aqueous solution of a water-soluble organic polymer, and a solvent that is compatible with a synthetic resin that is a film forming agent for a pattern to be transferred from a transfer paper is added, and part or all of the solvent is a plasticizer. A certain glaze transfer primer is applied onto the raw glaze layer formed on the base material such as ceramics, and then the design is transferred from the transfer paper to create a decoration, and then the raw glaze layer is fired. A painting method that involves simultaneously firing the pattern and firing. 7. A primer for glaze transfer, which is made by adding a polymer emulsion and a solvent that is compatible with a synthetic resin, which is a film forming agent for the pattern to be transferred from the transfer paper, to an aqueous solution of a water-soluble organic polymer is applied to ceramics, etc. A painting method in which the raw glaze layer and the design are simultaneously fired by applying the glaze onto the raw glaze layer formed on the base material, then painting by transferring the transfer design from the transfer paper, and then firing the raw glaze layer. 8 A polymer emulsion and a solvent that is compatible with a synthetic resin that is a film-forming agent for a pattern to be transferred from transfer paper are added to an aqueous solution of a water-soluble organic polymer, and a part of the solvent or a polymer emulsion is added. A primer for glaze transfer, which is made entirely of plasticizer, is applied to the glaze layer of the base material such as ceramics, and then the transfer pattern is transferred from the transfer paper to create a painting, and then fired. A painting method in which the raw glaze layer and the pattern are fired at the same time.