JPS632881A - Porcelain painting method - 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 [Field of Industrial Application] The present invention relates to a painting method in which glaze aging and pattern firing are performed simultaneously.

[Prior art]

K, who paints ceramics, etc., applies a raw glaze to a ceramic base that has been fired, then matures it at about 1000 to 1400 degrees Celsius, then transfers a pattern layer formed on transfer paper onto it, and then applies SOO. A method has been adopted in which the synthetic resin contained in the pattern layer is decomposed and volatilized by firing at a temperature of about 1,000°C.

This method required two steps: firing the glaze and firing the pattern layer, which was complicated, had poor thermal efficiency, and was economically disadvantageous.

In order to improve the above method, heat treatment is performed as one step, in other words, a primer mainly composed of a synthetic resin emulsion, a water-soluble polymer, or a mixture thereof is applied to the surface of the raw glaze layer, and then the pattern for transfer is applied. A method has been proposed in which the glaze is aged and the pattern layer is fired at the same time.
Special Publication No. 60-45073). Although this method simplifies the heat treatment process to just one step, there is still the risk of damaging the glaze layer because a polymer aqueous solution containing a large amount of water, that is, a primer, is applied onto the raw glaze.

In addition, the method of painting on raw glaze before the glaze is aged has weak adhesion to the pattern. To improve this, mixing a resin binder into the raw glaze or applying a primer on the raw glaze is used, but this method has poor adhesion and adhesion to the pattern layer, causing the pattern to float and become pinned during pre-drying and firing. It had the disadvantage of causing holes, shrinkage, etc., and a high defect rate.

As a method to improve this drawback, a solvent and/or plasticizer that is compatible with the synthetic resin that is the film forming agent for the pattern to be transferred from the transfer paper is added to the aqueous solution of the water-soluble polymer, and if desired, a high Regarding the primer for transfer on glaze made by adding a molecular emulsion, the primer is further coated on the beef oil layer, and then the transfer pattern is transferred from the transfer paper and then fired, so that the glaze aging and the pattern firing are performed at the same time. A painting method was also proposed (Japanese Patent Application Laid-open No. 81316/1983).

In this method, the raw glaze (glaze) and the primer application are performed separately.

[Problem that the invention seeks to solve]

If a composition containing a resin aqueous emulsion that has good adhesion to the pattern layer and is highly water resistant is used as a glaze, glazing and priming can be completed in one step.

However, glazes contain various metal oxides such as chromium-based green, cadmium-based yellow to red, cobalt-based blue, iron-based reddish-brown, namali oxide, and glassy, so during storage. It was found that the anionic emulsion gelled or thickened, making it difficult to apply.

[Specific measures to solve the problem]

In the present invention, in order to prevent gelation of the anionic resin aqueous emulsion and glaze mixture, an amphoteric surfactant is blended with the resin aqueous emulsion.

That is, the present invention applies a glaze to a ceramic base with a composition containing an aqueous anionic resin emulsion and an amphoteric surfactant, and then transfers a pattern for paper transfer by a water slide method, or applies a glaze with water. To provide a method for painting ceramics, which is characterized in that glaze aging and pattern firing are performed simultaneously by layering dispersion, painting, and then firing.

The main ingredients for ceramics are Si02 and AL203, and kaolin, active parts, mica, feldspar, bentonite, silica, talc, etc. are mixed, weighed, and then finely ground in a grinder. (pulverization process), then the clay is kneaded and defoamed (soil kneading process).

This refined clay is molded into the desired shape using a plaster mold or on a potter's wheel, and then dried (forming process).

The surface of the dried molded product base is smoothed (
The raw material is finished (finishing process), then it is cased and fired at a high temperature of 1,200 to 1,300°C (compacting process), and then it goes to the glazing process.

(Glaze Composition) The raw glaze composition includes (a) glazes called transparent glaze, colored glaze, crystal glaze, lead glaze, frit glaze, bristol glaze, porcelain glaze, porcelain glaze, etc. depending on the ingredients, and anion. (e) an amphoteric surfactant.

Glaze The raw materials that make up the glaze can be broadly divided into ■cullet, lead oxide, iron oxide, manganese oxide, alumina, silica,
Metal oxides such as sodium oxide, magnesium oxide, calcium oxide, calcium chloride, boric acid, dolomite, N
aαbe NazCOa, borax, soda feldspar, potassium carbonate,
Fluxing agents such as mica and feldspar; ■ Emulsifying agents such as antimony oxide, bone ash, calcium phosphate, tin oxide, and zirconium oxide; ■ Cobalt oxide, cobalt carbonate, cupric oxide, manganese dioxide, iron chloride, and It is divided into raw materials for pigments such as molybdenum oxide. These are used in combination, and if classified,
In terms of product types, porcelain glazes, pottery glazes, porcelain glazes, etc.; categorized based on the type of flux, lead glazes, alkali glazes, lime glazes, feldspar glazes,
Boric acid glaze, alkali-lime glaze, etc.; Classified based on origin, place of production, and researcher's name, such as Priestl glaze, Rotzkingum glaze, and Seegel porcelain glaze; low-fired glaze, medium-fired glaze, and high-fired glaze in terms of ease of melting. Glaze: Raw glaze, depending on the manufacturing method or glazing method.
Salt glaze: Classified into glossy glazes, matte glazes, milky glazes, etc. based on their distinctive properties.

For example, the components of SKI 3 porcelain glaze are as follows.

Feldspar 73.57% by weight Magnesite 5.35% Limestone 0.87% by weight Kaolin 5.68% by weight Quartz 14.53% by weight In addition, the glaze dispersion contains dispersants and thickeners for adjusting viscosity. Agents or water-soluble substances may be added.

Anionic Resin Aqueous Emulsion Resin aqueous emulsion is obtained by emulsion polymerization of vinyl monomers in the presence of anionic surfactants such as sodium dodecylbenzenesulfonate and sulfuric acid half ester of p-nonylphenol, and calcium persulfate. It is something.

As a vinyl monomer, n-propyl methacrylate (Tg
81°C), styrene (100°C), Acrylic acid nitrile (100°C), methyl methacrylate (105°C), methacrylic acid (130°C), itaconic acid (130°C), acrylamide (153°C), acrylic acid 2 -ethylhexyl (Tg-as℃), n-butyl acrylate (-54
), acrylic acid , vinyl acetate (30℃),
t-Butyl acrylate (45°C), 2-hydroxyethyl methacrylate (55°C), ethyl methacrylate (65°C)
°C), isobutyl methacrylate (67 °C), vinyl chloride (79 °C), vinylidene chloride (-18 °C), ethylene, etc. are used alone or as a mixture of two or more (numbers in parentheses indicate these vinyl monomers). (the glass transition temperature of a homopolymer of the same polymer).

The type and amount of these monomers to be used are determined by considering the usage temperature of the resulting emulsion and using the glass transition point of the resulting resin as a guide.

In the present invention, it is preferable to use an emulsion in which the film forming temperature is 30° C. or lower from the viewpoint of forming a film in the glaze layer, and the film forming temperature is 10° C. or higher in consideration of film hardness, stickiness, stains, etc.

Although it is possible to use a film-forming agent in combination to lower the apparent film temperature, do not use it because the added film-forming agent will volatilize during pre-drying after glazing, making it more likely to cause defects such as foaming. It is better.

The emulsion resin has a particle size of 0-OS to 1 micron, and an emulsion resin having a concentration of 20 to 55% by weight is usually used. Further, antifoaming agents, dispersants, thickeners, antifreeze agents, etc. may be added.

This emulsion prevents deterioration of the glaze layer by adjusting the viscosity of the glaze composition and improving the water resistance of the glaze layer when transferring to the glaze layer using transfer paper using the water slide method and when painting with glaze. This improves the strength of the glaze layer, prevents movement of the product after glazing, prevents the glaze surface from being scratched during work, prevents it from falling off, and improves adhesion to the pattern layer.

There is no problem if the amphoteric surfactant glaze and anionic resin emulsion are simply mixed and used immediately. However, in the factory, the entire amount of glaze solution is not used up, and it is often done for summer use at a later date, adjusted in advance, or not used suddenly. These liquid mixtures are stored in factories or outdoors and are affected by sunlight and heat, but at this time the viscosity of the liquid mixture increases and phenomena such as gelation are observed, making it impossible to apply the glaze properly.

The amphoteric surfactant of the present invention is blended with the glaze for the purpose of preventing thickening of the anionic resin emulsion mixture. As the amphoteric surfactant, for example, those in the table below can be used.

(Margin below) Table 1 Nonionic surfactants have little effect in preventing thickening. In cationic systems, gelation of the resin emulsion occurs immediately upon addition.

The prepared raw glaze is prepared by (a) adding water and a dispersant to 100 parts by weight of the glaze and mixing in a ball mill; Blend the surfactant at a ratio of 0.4 to 10 parts by weight, add an antifoaming agent if necessary, and mix.The water content of the raw glaze is 4.
It is preferably 5 to 65% by weight.

Glazing The glaze is applied to the fired ceramic base by spraying, dipping, pouring, etc., and a raw glaze layer is formed on the base.

Since the raw glaze is made water resistant by the resin emulsion, the raw glaze layer will not dissolve when painting using water for transfer.

After glazing, it is pre-dried at 150-200°C to remove moisture in the raw glaze. Note that it may be lower, but it will require more time. However, it is necessary that the temperature is higher than the film forming temperature of the emulsion.

Painted transfer paper is made by applying a water-soluble polymer to the surface of the paper, printing a paper pattern on top of it using ink made from a synthetic resin and pigment, and then forming a pattern layer, which is then coated with a reinforcing layer of synthetic resin. When the transfer paper is immersed in water, the water-soluble polymer is dissolved, the pattern layer is peeled off from the paper together with the reinforcing layer, and this is transferred onto the surface of the raw glaze layer. This method is generally called the slide method, and at this time, the pattern layer is transferred onto the surface of the raw glaze layer with a large amount of moisture attached, but since it has water resistance due to the synthetic resin emulsion component, it is certain that the raw glaze layer will not collapse. is prevented. This also applies when applying the overglaze directly without using transfer paper.

The anionic synthetic resin emulsion of the present invention may also be used as a pigment-reinforcing synthetic resin for transfer paper for decoration.

After glaze painting, if necessary, we draw lines or add patterns to make the ceramic finished beautifully.
Second firing (glaze firing) at a temperature of ℃.

At this time, the resin and surfactant in the emulsion are decomposed and volatilized, completing the painting.

〔effect〕

According to the method of the present invention, the step of treating the raw glaze layer with a primer can be omitted, there is no need to worry about chipping of the raw glaze due to applying a water-based composition directly on the raw glaze, which has low water resistance, and - By firing the glaze, the maturation of the glaze and the firing of the design are performed at the same time, improving thermal efficiency and streamlining the process.

Furthermore, the glaze mixture can be stored for a long period of time, making it economical.

Example 1 To 100 parts by weight of a commercially available lead glaze, 70 parts by weight of water and 0.5 parts by weight of a dispersant 1 Nopco 44C" (trade name of San Nobuco Co., Ltd.) were added, and the mixture was ground and mixed in a ball mill (solids approx. 58%, p
)(9,3). To 100 parts by weight of this dispersed glaze solution, methyl methacrylate (47%), acrylic, 1ln-butyl (
so%) Acrylic acid (3%) copolymer anion water pourable emulsion (solid content 50%, I)E(9,3)1
0 parts by weight and 160 parts by weight of Lion ■'s amphoteric surfactant "Enadicol CNS" (trade name) were blended to prepare a raw glaze.

The viscosity change of this raw glaze when stored in an atmosphere of 40°C is as follows.

1. Spray the raw glaze that has been prepared for one day on the surface of a ceramic clay plate that has been baked at 200°C, pre-dry it at 150°C, and then transfer it onto the surface of the raw glaze layer. The printed pattern layer was transferred using the water slide method, and the plate with this pattern was
The pattern after the second firing (glaze firing) at 250°C was a good pattern with clear outlines and no glaze collapse or pinholes.

Example 2 As an anionic resin emulsion to be added to the raw glaze, an acrylic regular au emulsion from Mitsubishi Yuka Verdice ■, 1 Acronal YJ-2730D'' (product name:
The solid content was 47%, the pH was 9.0, and the film forming temperature was 33°C.

10 parts of Acronal YJ-2730D and 1.5 parts of aminoethylimidacillin organic acid salt (Libomin COH1 manufactured by Lion) were mixed with 100 parts by weight of the glaze dispersion of Example 1, and the thickener Colafral VL (trade name, BASF
(manufactured by) Nite viscosity is so.

A raw glaze was obtained by adjusting to cps.

The change in viscosity of this raw glaze during storage is shown below.

Thereafter, painting was carried out in the same manner as in Example 1 using the raw glaze.

The resulting pattern was as good as that of Example 1.

Example 3 An ethylene/vinyl acetate copolymer latex (trade name: Sumikaflex 900, Sumitomo Chemical's Bi-Ethylene Vinegar) was used as an anionic resin emulsion to be added to the raw glaze.
Painting was carried out in the same manner as in Example 1, except that acrylic copolymer (acrylic copolymer) was used, and a good pattern was obtained.

Comparative Example 1 Painting was carried out in the same manner as in Example 1 except that the amphoteric surfactant was not added to the raw glaze, and a good pattern was obtained.

However, when the raw glaze was stored at 40°C, gelation occurred and it became unusable.

Comparative Example 2 4 parts of carboxy methyl cellulose was added to 57 parts of commercially available lead glaze.
% aqueous solution and 40 parts of water were mixed in a ball mill to prepare a raw glaze.

Immediately, painting was carried out in the same manner as in Example 1 using the raw glaze.

The resulting pattern had some deterioration in the glaze, and some curling was observed in the pattern.

Example 4 70 parts by weight of water and 1.0 parts by weight of the dispersant Nobuko 44 C were added to 100 parts of a commercially available Bristol glaze and mixed in a ball mill. Next, 10 parts of the anionic resin aqueous emulsion (solid content 50%, pH 93) used in Example 1 and 1.5 parts of N-stearyl-β-aminopropionic acid Na salt as an alanine-type amphoteric surfactant were mixed. , mix, and reduce the viscosity to 4 with the thickener Latecol D (Mitsubishi Yuka Bardatesier).
0 Q cps raw glaze (solid promise 57%, pH 9.4)
was prepared.

Thereafter, decoration was carried out in the same manner as in Example 1, and a good pattern was obtained.

Claims (1)

[Claims] 1) Glaze a ceramic base with a composition containing an anionic resin aqueous emulsion and an amphoteric surfactant as a glaze,
The aqueous anionic resin emulsion is dried and solidified, and then the pattern for transfer is transferred by the water slide method, or the aqueous glaze dispersion is layered and painted, and then fired, thereby simultaneously aging the glaze and firing the design. A method of painting ceramics characterized by: 2) The blending ratio of anionic resin aqueous emulsion and amphoteric surfactant is 1:0.05 to 0.25 (solid weight ratio)
The painting method according to claim 1, characterized in that: