JPH0220595B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a painting method in which glaze heating and pattern firing are performed simultaneously. [Prior art] To decorate ceramics, etc., a raw glaze is applied to a ceramic base that has been fired, and then heated at about 1000 to 1400 degrees Celsius, and then a pattern layer formed on transfer paper is placed on top of it. Transfer it, then bake it at about 500-1000℃,
A method has been used to decompose and volatilize the synthetic resin contained in the pattern layer. This method requires two steps: firing the glaze and firing the pattern layer, which is complicated, has poor thermal efficiency, and is economically disadvantageous. In order to improve the above method, heat treatment is performed as one step, in other words, after applying a primer mainly made of synthetic resin emulsion, water-soluble polymer, or a mixture thereof to the surface of the raw glaze layer, the pattern for transfer is then applied. A method was proposed in which the heating of the glaze and the firing of the pattern layer were carried out at the same time.
No. 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 heating the glaze 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 applied on the raw glaze layer, and then the transfer pattern is transferred from the transfer paper and then fired, whereby the glaze heating and the pattern firing are performed. A method of painting at the same time 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. [Problems to be solved by the invention] If a composition is used in which 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. Conceivable. However, glazes contain various metal oxides such as chromium-based green, cadmium-based yellow to red, cobalt-based blue, iron-based red cutlet, namari oxide, and glass, so during storage. It has been found that anionic emulsions gel or thicken, making application difficult. [Specific Means for Solving the Problem] In the present invention, the concentration of carboxyl groups in the aqueous anionic resin emulsion is set to a specific amount in order to prevent gelation of the aqueous anionic resin emulsion and the glaze mixture. That is, the present invention provides a ceramic base containing a carboxyl group based on an α,β-unsaturated carboxylic acid in a copolymer obtained as a glaze in a proportion of 1.4 × 10 ^-3 to 1.8 × 10 ^-2 mol. Glaze is applied with a composition containing an aqueous anionic resin emulsion, and then a pattern is transferred by a water slide method, or a water-dispersed glaze is overcoated and painted, and then fired to heat the glaze and design the pattern. The present invention provides a method for painting ceramics characterized by performing firing and firing at the same time. The main ingredients for ceramics are SiO ₂ and Al ₂ O ₃ , and kaolin, clay, mica, feldspar, bentonite, silica, talc, etc. are used, and after being mixed and weighed, they are crushed in a crusher. It is crushed finely (grinding process), then kneaded into clay and defoamed (clay mixing 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 (green base finishing process), and the molded product base is cassetted.
It is fired to a high temperature of 1300℃ (sealing process), and then goes to the glazing process. (Glaze composition) Raw glaze compositions include (a) transparent glaze, colored glaze, crystalline glaze and lead glaze, fritted glaze, bristol glaze,
It contains at least a glaze called ceramic glaze, porcelain glaze, etc., and (b) an anionic resin aqueous emulsion. Glaze The raw materials that make up glaze can be roughly divided into:
Calcut, lead oxide, iron oxide, manganese oxide, alumina, silica, sodium oxide, magnesium oxide, metal oxides such as calcium oxide, calcium chloride, boric acid, dolomite, NaCl, Na ₂ CO ₃ , borax, soda feldspar, potassium carbonate , a fluxing agent such as mica and feldspar, and an emulsifying agent such as antimony oxide, bone ash, calcium phosphate, tin oxide, and zirconium oxide,
It is classified into raw materials for pigments such as cobalt oxide, cobalt carbonate, cupric oxide, manganese dioxide, iron chloride, and molybdenum trioxide. These are used as a mixture and can be categorized into ceramic glazes, porcelain glazes, etc.; categorized based on the type of flux, such as lead glazes, alkali glazes, lime glazes, feldspar glazes, boric acid glazes, alkali-lime glazes, etc. ; Classified based on origin, place of production, and researcher's name, such as Bristol glaze, Rotskingham glaze, and Seegel porcelain glaze; Based on ease of melting, low-fired glaze, medium-fired glaze, and high-fired glaze; manufacturing method or glazing method; From the method, raw glaze,
Salt glaze: Classified into light-selective glazes, pine glazes, emulsion glazes, etc. based on their distinctive properties. For example, the ingredients of SK13 porcelain glaze are as follows. Feldspar 73.57% by weight Magnesite 5.35% by weight Limestone 0.87% by weight Kaolin 5.68% by weight Quartz 14.53% by weight In addition, dispersants, thickeners for viscosity adjustment, and water-soluble substances may be added to the glaze dispersion. good. Anionic resin aqueous emulsion The resin aqueous emulsion contains, for example, (a) α,β-unsaturated carboxylic acid 0.1 to 1.3% by weight (b) acrylic acid alkyl ester (the number of carbon atoms in the alkyl group is 2 to 8) 40 to 55% by weight (c) Monomers selected from methyl methacrylate, styrene and acrylonitrile 30-55% by weight (d) N-phenylmaleimide, N-methylol acrylamide, acrylamide, methacrylamide, 2-hydroxyalkyl acrylate (alkyl 100 parts by weight of a vinyl monomer mixture consisting of 1 to 10 wt. It is obtained by emulsion polymerization using a polymerization catalyst such as calcium persulfate in the presence of calcium persulfate. This emulsion has a film-forming temperature of 30°C or less in terms of film formation of the glaze layer, film hardness,
The film forming temperature was set at 10°C in consideration of dirt caused by stickiness.
The above emulsions are preferred. By the way, acrylic acid, methacrylic acid, itaconic acid, etc. are examples of α,β-unsaturated carboxylic acids (including their anhydrides) that improve adhesion to ceramic bases, but the ones considered in the present invention are As a result, since the amount of carboxylic acid greatly affects miscibility and storage stability, the total amount of carboxyl groups based on α,β-unsaturated carboxylic acids in the copolymer should be 1.4 × 10 ^-3 ~ Make it 1.8×10 ^-2 mol. Component (b), acrylic acid alkyl ester, is a soft monomer that gives the film transparency, and includes ethyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, n-propyl acrylate, and acrylic acid. 2-ethylhexyl and the like are used. Component (c), methyl methacrylate, acrylonitrile, or styrene, is a hard monomer that imparts toughness to the film, and some of these may be replaced with ethyl methacrylate, isopropyl methacrylate, or isobutyl methacrylate. Component (d), a vinyl monomer having an -OH group, _two -CONH groups, and a methylol group, is used to impart adhesion to unglazed ceramics. The particle size of the emulsion resin is 0.05 to 1 micron, and emulsion resin concentrations of 20 to 55% by weight are usually used. The stability of anionic resin aqueous emulsion usually decreases due to the mixing of cations and ions, but the invention of the previous application (Japanese Patent Application No. 147582/1983) improves the stability of mixing with a cationic emulsifier, which is a cation and ion. Therefore, the objective was achieved by blending a large amount of a nonionic emulsifier or an amphoteric active agent, but the type and amount of the nonionic or amphoteric emulsifier and the mixing procedure are limited. The present invention describes a method for directly mixing cations and ions without using their added stabilizers.
As a result of repeated studies, this objective can be achieved by limiting the -COOH (carboxylic acid group) content in the copolymer. Furthermore, depending on the type of unsaturated acid, carboxyl groups are said to be mainly distributed inside the copolymer particles in the emulsion or on the surface of the particles, and although there are differences in miscibility stability upon addition depending on the amount, heating is accelerated. As a result, it was confirmed that gelation occurred.
In addition, in a previous report (Japanese Patent Application No. 147582/1982), there was an effect of using a nonionic emulsifier in combination, but the amount of nonionic emulsifier used in a normal anionic emulsion is 1/1/2 of this amount.
Since it is about 10, its effect can be ignored, and there is no need to add an amphoteric emulsifier in the present invention. This aqueous anionic resin emulsion needs to have a total amount of carboxyl groups in the copolymer of 1.8×10 ⁻² mol or less in order to prevent gelation when mixed with a glaze. By the way, depending on the type of acid, it is natural that it will be distributed on the surface or inside the particles, but if the amount exceeds approximately 1.9 x 10 ^-2 mol of carboxylic acid, no gelation will occur when the cationic emulsifier is mixed. In a 50° C. acceleration test, it was found that the composition thickened and gelled, rendering it unusable. In addition, the carboxyl group was set to 1.4 x 10 ^-3 mol or more (0.1 mol% in terms of acrylic acid) in consideration of the balance of adhesion of the film to unglazed ceramics, mechanical stability, viscosity stability during acceleration, etc. It is. This emulsion prevents the emulsion resin from collapsing 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. Improving the strength of the glaze layer with a film,
To protect the glaze surface by preventing movement of the product after glazing, to prevent damage to the glaze surface during work, to prevent falling off, and to improve adhesion to the pattern layer. There is no problem if the glaze and ordinary anionic resin emulsion are simply mixed and used immediately. However, in factories, the entire amount of glaze solution is not used up, and it is often used 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. In the present invention, an aqueous anionic resin emulsion having a specified amount of carboxylic acid groups is used in order to prevent thickening of the glaze and anionic resin emulsion mixture. Preparation To prepare the raw glaze, add water and a dispersant to 100 parts by weight of the glaze, mix in a ball mill, add anionic resin aqueous emulsion at a ratio of 4 to 20 parts by weight (resin solid content), and extinguish as necessary. Add foaming agent and mix. The moisture content of the raw glaze is preferably 45 to 65% by weight. Glazing Glaze is applied to the fired ceramic base by methods such as spraying, dipping, and pouring, and a raw glaze layer is formed on the base. The raw glaze is made water resistant by the resin emulsion, so the raw glaze layer does not melt when painting using water for transfer. After glazing, pre-dry at 150-200℃ 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. Transfer paper with pictures is made by applying a water-soluble polymer to the surface of the paper, printing a pattern on it using ink made of synthetic resin and pigment, forming a pattern layer, and then adding a reinforcing layer of synthetic resin on top of that. When the transfer paper is immersed in water, the water-soluble polymer is dissolved and 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 while retaining a large amount of water, 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.
Furthermore, the aqueous anionic resin emulsion of the present invention may be used as a synthetic resin for reinforcing the application material of transfer paper for decoration. Glaze After painting, if necessary, lines are drawn or patterns are added to make the ceramic beautiful.
Second firing (glaze firing) at a temperature of ~1400℃. At this time, the resin and surfactant in the emulsion are decomposed and volatilized, completing the painting. [Effects] According to the method of the present invention, the step of treating the raw glaze layer with a primer can be omitted, and there is no need to worry about chipping of the raw glaze due to applying a water-based composition directly onto the raw glaze, which has low water resistance. Because the glaze is heated and the pattern is fired at the same time in one firing,
Thermal efficiency is improved and the process is streamlined. Furthermore, the glaze mixture can be stored for a long period of time, making it economical. Embodiments Hereinafter, the present invention will be explained in more detail with reference to Examples. Note that parts and percentages in the examples are based on weight unless otherwise specified. Production Example of Emulsion 1 The following raw materials were charged into a reaction vessel equipped with a temperature controller, an anchor stirrer, a reflux condenser, a supply container, a thermometer, and a nitrogen introduction tube. 200 parts water 5 parts 35% aqueous sodium salt of the sulfuric acid half ester of p-nonylphenol (anionic emulsifier) reacted with 20 moles ethylene oxide 20 parts p-nonylphenol (nonionic emulsifier) reacted with 25 moles ethylene oxide % solution 20 parts. Next, after purging the inside of the reaction vessel with nitrogen gas, 10% of the following feed was added, and the mixture was heated to 90%
heated to ℃. Feed Water 200 parts 35% aqueous solution of the above anionic emulsifier 25 parts Methyl methacrylate 195 parts n-butyl acrylate 189 parts Acrylic acid 8 parts Acrylamide 8 parts. Furthermore, after charging 10% of 2.5 parts of potassium persulfate dissolved in 85 parts of water (feed) into the container, all remaining feed and 40% of the feed
Supplied into the container over 3.5 hours, and after supplying, 2
The feed was polymerized keeping at the same temperature for a period of time to obtain an anionic resin aqueous emulsion. Examples 2 to 12 Anionic resin aqueous emulsions were obtained in the same manner as in Example 1, except that the composition of the vinyl monomer was changed as shown in Table 1.

【table】

Claims (1)

[Claims] 1 A carboxyl group (-COOH) based on an α,β-unsaturated carboxylic acid is added to the glaze on a ceramic base.
Glaze with a composition containing an anionic resin aqueous emulsion of a copolymer containing 1.4 x 10 ^-3 to 1.8 x 10 ^-2 mol, dry and solidify the anionic resin aqueous emulsion, and then apply a water slide method. A method for painting ceramics characterized by performing heating of the glaze and firing of the pattern at the same time by transferring a pattern for transfer or applying an aqueous glaze dispersion for painting, followed by firing. 2 α,β-unsaturated carboxylic acid is acrylic acid,
The painting method according to claim 1, characterized in that the compound is selected from methacrylic acid and itaconic acid. 3 The copolymer of the anionic resin aqueous emulsion contains (a) α,β-unsaturated carboxylic acid 0.1 to 1.3% by weight (b) Acrylic acid alkyl ester (the number of carbon atoms in the alkyl group is 2 to 8) 40 to 55% by weight % (c) Monomer selected from methyl methacrylate, styrene, acrylonitrile 30-55% by weight (d) N-phenylmaleimide, N-methylolagrilamide, acrylamide, methacrylamide, 2-hydroxyalkyl acrylate ( Add 100 parts by weight of a vinyl monomer mixture consisting of 1 to 10% by weight of a vinyl monomer whose alkyl group has 2 to 4 carbon atoms to 0.1 to 5 parts by weight of an anionic emulsifier and 0 to 5 parts by weight of a nonionic emulsifier. The painting method according to claim 1, which is a copolymer obtained by emulsion polymerization in the presence of.