JPH01308891A - Graze composition and method for painting with said composition - Google Patents

Abstract

PURPOSE:To prolong the pot-life of a graze, by compounding a graze with an aqueous emulsion of an anionic resin and a water-soluble pyrophosphate or tripolyphosphate. CONSTITUTION:The objective graze composition is produced by compounding (A) 100 pts.wt. of a graze with (B) 40-20 pts.wt. (in terms of solid resin component) of an aqueous emulsion of an anionic resin and (C) 0.05-5wt.% (based on the solid resin component of the component B) of a water-soluble pyrophosphate and/or tripolyphosphate. The above water-soluble polyphosphate is preferably added to a polymerization system of the aqueous emulsion of the anionic resin in emulsion polymerization and subjected to emulsion polymerization, however, it may be added to the emulsion of the anionic resin after the emulsion polymerization. When the amount of the salt exceeds 5wt.%, the water-resistance of the pattern prepared from the graze becomes unfavorably poor.

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]

To decorate ceramics, etc., a fresh glaze is applied to a ceramic base that has been baked, and then aged at around 1,000 to 1,400 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 destroyed by further firing at a temperature of about SOO to 1.400°C.

This method requires both firing of the glaze and firing of the pattern layer, and has the drawbacks of being complicated, having poor thermal efficiency, and being 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 a pattern for transfer is applied. A method was proposed in which the maturing of the glaze and the firing of the pattern layer were carried out at the same time.
Special Publication No. 60-45073). This method simplifies the heat treatment process to just one step, but since Rima-sho primer, an aqueous polymer solution containing a large amount of water, is applied to the raw glaze, there is still the risk of damaging the glaze skin.

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, by further applying the primer on the raw glaze layer, then transferring the transfer pattern from the transfer paper and firing it, the glaze aging and the pattern firing can be performed simultaneously. A method of painting 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.

We thought that by using a composition containing a water-based resin emulsion that has good adhesion to the pattern layer and is highly water resistant to the glaze, glazing and priming could 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.

Japanese Patent Publication No. 61-11903 states that mixing a glaze and an aqueous resin emulsion in an alkaline state stabilizes the mixture.
It is stated that it can prevent aggregation.

However, it is not stable over time and tends to gel easily under high temperatures such as in summer.

There is no problem if the glaze and a normal 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.

Therefore, we investigated preventing this gelation by limiting the amount of acid groups in the FM ice-water emulsion, and first developed a method based on α,β-unsaturated carboxylic acids for the ceramic base and for the glaze. Carboxyl group (-COOI() is 1.4
A composition containing an anionic resin aqueous emulsion of a copolymer containing a proportion of X 10-3 to 1.8 proposed a ceramic painting method characterized by simultaneously performing glaze heat formation and design firing by transferring a pattern for transfer or applying a layer of glaze aqueous dispersion, and then firing.
(Japanese Patent Application No. 61-243363).

This method provides a shelf-stable emulsion that can be glazed and primed in one step.

[Problem to be solved by the invention]

However, some ceramic manufacturers dilute the mixture of glaze and resin aqueous emulsion with a large amount of water to make it easier to apply the glaze composition to the base material. The adhesion of the glaze decreases, and the water resistance of the glaze becomes a problem.

In order to improve the adhesion of the glaze to the substrate, it is sufficient to increase the attack of acid groups based on α,β-unsaturated carboxylic acids in the aqueous anionic resin emulsion. However, as mentioned above, the pot life of the mixture of glaze and anionic resin emulsion is short, and the viscosity increases over time. If the proportion is increased to 10% by weight, the pot life of the mixture is only about half a day.

In the present invention, it is an object of the present invention to provide a glaze composition that has a long pot life even when the proportion of α, β-unsaturated carboxylic acid and OH group-containing unsaturated monomer in the copolymer in the emulsion is high. purpose.

[Specific means to solve the problem]

In the present invention, in order to prevent gelation of the anionic resin aqueous emulsion and glaze mixture, a mixture of the anionic resin aqueous emulsion, pyrophosphate and/or tripolyphosphate, and glaze is used.

That is, the first aspect of the present invention is a two-glaze prison component: 10011 L parts (B) component: 4 to 20 parts by weight of anionic resin aqueous emulsion resin (Q component: water-soluble pyrophosphate and/or tripolyphosphate) 0.05 to 5% by weight of the solid resin content of the salt (1) component A glaze composition is provided in which the above components IA), (B), and (Q) are blended in the above proportions.

The second aspect of the present invention is to glaze a metal or ceramic base with a composition containing an anionic resin emulsion, a water-soluble pyrophosphate and/or tripolyphosphate, and a glaze, and dry and solidify the anionic resin aqueous emulsion. A painting method characterized in that the glaze heating and the design firing are performed simultaneously by transferring the design for transfer by a water slide method, or by overcoating the glaze water dispersion, and then firing the design. It provides:

The main component of the raw material for ceramics is SiOx-AtzOs, and other materials such as kaolin, clay, mica, feldspar, bentonite, silica, and talc are used.These are mixed, weighed, and then finely ground with a grinder ( (pulverization process), then ground and defoamed (soil 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 (
raw material finishing process), box bound, 1,200-1.300
It is fired to a high temperature of 0.degree. C. (firing process), and then sent to glazing process 8.

The object to be glazed is not just ceramics, but may also be heat-resistant metals such as copper, aluminum, iron, etc., or stones.

(Glaze Composition) The raw glaze composition includes (a) glazes called transparent glaze, colored yu, crystal yu, lead glaze, frit glaze, pristol glaze, porcelain glaze, porcelain glaze, etc. depending on the ingredients, and (b) The anionic resin aqueous emulsion contains at least (C) a water-soluble pyrophosphate and/or tripolyphosphate.

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,
Fluxing agents such as Nact, Na2CO3, borax, soda feldspar, potassium carbonate, mica, and feldspar, ■ Emulsifying agents such as antimony oxide, bone ash, calcium phosphate, tin oxide, and zirconium oxide, ■ Cobalt oxide, cobalt carbonate, It is divided into pigment raw materials such as cupric oxide, manganese dioxide, iron chloride, and molybdenum trioxide. These are used as a mixture and can be classified as porcelain glaze, porcelain glaze, etc. in the case of bridges; if classified based on the type of flux, lead glaze, alkali glaze, lime glaze, feldspar glaze, boric acid glaze, alkali-lime glaze, etc. Glazes, etc.: Classified based on origin, place of production, and researcher's name: Bristol glaze, Rotskingham glaze, Seegel porcelain glaze, etc.; low heat glaze, medium heat variable axis, high heat glaze due to ease of melting; manufacturing method or glaze Depending on the method of application, glazes are classified into raw glazes and salt glazes; based on their distinctive properties, they are classified into glossy glazes, matte glazes, milky glazes, etc.

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

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

Anionic resin aqueous emulsions and water-soluble resin aqueous emulsions are, for example, (A) α, β-unsaturated carboxylic acid 0.1 to 10% by weight (b) acrylic acid alkyl ester (the number of carbon atoms in the alkyl group is 2 to 8 ) 30-70i total % (C) Monomer selected from methyl methacrylate, styrene, acrylonitrile 30-70i [amount % (d) N-phenylmaleimide, N-methylolacrylamide, acrylamide, methacrylamide, 2-hydroxy Add 100 parts by weight of a vinyl monomer mixture consisting of 0.5 to 10% by weight of a vinyl monomer selected from alkyl acrylates (the number of carbon atoms in the alkyl group is 2 to 4) to 0.05 parts by weight of pyrophosphate and/or tripolyphosphate. ~5
part by weight, 0.1 to 5 parts by weight of an anionic emulsifier and 0 to 5 parts by weight of a nonionic emulsifier, for example, by emulsion polymerization using a polymerization catalyst such as calcium persulfate. This emulsion has a film-forming aspect of the glaze layer,
In consideration of the hardness of the film, stains due to stickiness, etc., it is preferable to use an emulsion with a film-forming temperature of 10° C. or higher.

The carboxyl group (-CO
OH) and hydroxyl groups (-OH) improve the adhesion to metals and ceramic substrates and the dispersibility of glazes.

As the α,β-unsaturated carboxylic acid of component (a), acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic anhydride, etc. are used.

From the viewpoint of storage stability, pigment dispersibility, adhesion, and water resistance, this unsaturated monomer is used in a proportion of o, i to 10% by weight.

Component (b), acrylic acid alkyl ester, is a soft monomer that gives flexibility to the film, and includes ethyl acrylate, impropyl acrylate, n-butyl acrylate, t-butyl acrylate, n-propyl acrylate, and acrylic acid. 2-ethylhexyl acid and the like are used.

(C) Ingredient methyl methacrylate, Ac IJ O nide I
Styrene or styrene is a compound that gives toughness to the film, and some of these may be replaced with ethyl methacrylate, isopropyl methacrylate, or impdel methacrylate.

Component (d) (D -C0NHz group, vinyl monomer having a methylol group, hydroxyl group-containing unsaturated monomer) is used to impart adhesion to unglazed ceramics, metals, and stones.

The emulsion resin has a particle size of 0.05 to 1 micron, and an emulsion resin having a concentration of 20 to 55% by weight is usually used.

The stability of anionic resin aqueous emulsions usually decreases due to the mixing of cations and ions, but in the invention of the previous application (Japanese Patent Application No. 61-147582), the stability of anionic resin aqueous emulsions is improved by mixing with cationic emulsifiers, which are cations and ions. In order to improve
Although this objective has been achieved by incorporating large amounts of nonionic emulsifiers or amphoteric active agents, the type and amount of nonionic or amphoteric emulsifiers and the mixing procedure are limited.

Water-soluble polyphosphate In the present invention, in order to enable direct mixing without using cationic ions as an additive stabilizer, and to prevent viscosity increase and gelation when mixed with anionic resin aqueous emulsion with glaze, Therefore, a water-soluble pyrophosphate and/or tripolyphosphate is blended at a ratio of 0.05 to 5 parts by weight per 100 parts by weight of the solid content of the resin in the emulsion. It is preferable to add this water-soluble boron IJ phosphate to the polymerization system during emulsion polymerization of the anionic resin aqueous emulsion, but it is preferable to add it to the anionic resin emulsion obtained by emulsion polymerization. You can.

As such water-soluble pyrophosphate salts and tripolyphosphate salts, sodium salts, potassium salts, ammonium salts, etc. of pyrophosphoric acid and tripolyphosphoric acid can be used.

The amount of these salts added to the emulsion resin is 0.05
~5% respect. If it exceeds 5% by weight, the pattern will have poor water resistance.

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, protects the glaze surface by preventing movement of the product after glazing, preventing damage to the glaze surface during work, and preventing falling off, and improves adhesion to the pattern layer.

The prepared raw glaze is prepared by adding water and a dispersant to 100 parts by weight of the glaze, mixing in a ball mill, and adding 4 parts by weight of the anionic resin aqueous emulsion.
~20 weight parts (resin solid content), water-soluble polyphosphate 0.05 to 5 weight parts of the solid content of the emulsion resin! -%, and if necessary, add an antifoaming agent and mix.

The moisture content of the raw glaze is preferably 25 to 65% by weight.

Glazing The glaze on fired ceramic bases and metals is done 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 applying Ni, the glaze 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 coating a water-soluble polymer on the surface of the paper, printing a pattern on top of it using ink made of synthetic resin and pigment, forming a pattern layer, and then providing a reinforcing layer of synthetic resin on top of that. So, add the above transfer paper to water! ! When soaked, the water-soluble polymer dissolves and the pattern layer is peeled off from the paper along with the reinforcing layer.
This is transferred onto the surface of the above raw glaze layer. This method is generally called the slide method, and at this time, the pattern layer is transferred to 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 shaft 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 decorative transfer paper.

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 brimer can be omitted, 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, 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.

Embodiments Hereinafter, the present invention will be explained in more detail with reference to Examples. In addition, parts and percentages in the examples are based on weight unless otherwise specified.

Example 1 Temperature regulator, anchor stirrer, reflux condenser, supply container,
The following raw materials were charged into a reaction vessel equipped with a thermometer and a 9-element inlet tube.

water 2
00 parts of sulfuric acid half ester of p-nonylphenol reacted with 20 moles of ethylene oxide) 35% aqueous solution of IJum salt (anionic emulsifier) 5 parts of p-nonylphenol (nonionic emulsifier) reacted with 25 moles of ethylene oxide 20 parts of 20% solution.

Next, after purging the inside of the reaction vessel with nitrogen gas, 10% of the following feed (2) was added, and the mixture was heated to 90°C.

Supplies ■ Water 200
35% aqueous solution of the above anionic emulsifier 25 parts acrylic acid 8 parts methyl methacrylate 195 parts n-budel acrylate
189 part act “No 7th part”
Part 8.

Additionally, 10% of a solution of 2.5 parts of potassium persulfate and 2 parts of sodium pyrophosphate in 85 parts of water (Feed ■)
% into the container, the remaining feed ■ and 40% of the feed were fed into the container over 3.5 hours, and after the feeding was completed, the feed was kept at the same temperature for 2 hours and the feed ■ was polymerized to obtain an anionic resin aqueous emulsion.

70 parts by weight of water was added to 100 parts by weight of a commercially available lead glaze, and the mixture was ground and mixed in a ball mill (approx. 58% solids, pH 9.3).

Add t of the anionic resin aqueous emulsion (solid content 50 weight, pH 6.0) to 100 parts by weight of this dispersed glaze liquid.
Oil (Okibe blended and made raw glaze.

The viscosity change of this raw glaze during storage in an atmosphere of 50°C was as follows.

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

Comparative Example 1 Emulsion polymerization was carried out in the same manner as in Example 1 except that sodium pyrophosphate was not used, and the resulting aqueous resin emulsion was blended with K and a dispersed glaze liquid in the same manner as in Example 1 to obtain a raw glaze.

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

However, when the raw glaze was stored at 50°C, gelation occurred, making it unusable.

Example 2 Emulsion polymerization was carried out in the same manner as in Example 1, using the same monomer composition ratio, and the resulting aqueous resin emulsion was blended with a dispersed glaze liquid in the same manner as in Example 1 to obtain a raw glaze.

The viscosity change of this raw glaze during storage in an atmosphere of 50°C was as follows.

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

Examples 3 to 10, Comparative Examples 2 to 4 Anionic resin aqueous emulsions were obtained in the same manner as in Example 1, except that the composition of the vinyl monomer and the water-soluble boron IJ phosphate were changed as shown in Table 1. Ta.

Thereafter, painting was carried out in the same manner as in Example 1. Table 1 shows the results.
Shown below.

Example 11 A good pattern was obtained for the pond in the same manner as in Example 1, using a copper plate with a wall thickness of 2 Ifll instead of the ceramic clay plate.

(Margins below) Table 1 (Continued) (Notes in Table 1) *Freeze raw M (glaze + Emma A. John) at -5℃,
After keeping at that temperature for 2 hours, when the temperature was returned to 20° C., those that returned to their original state were considered good, and those that remained solidified were evaluated as not returning.

Example 12 Painting was carried out in the same manner as in Example 1, except that frit glaze was used instead of lead glaze. The pattern I obtained had good water resistance.

Further, the glaze composition did not show significant thickening even after 30 days and had good storage stability.

Patent applicant Mitsubishi Yuka Verdate Co., Ltd. Agent
Patent Attorney Masahisa Hase Agent Patent Attorney Takaya Yamamoto

Claims (1)

[Claims] 1) Component (A): 100 parts by weight of glaze Component (B): 4 to 20 parts by weight of anionic resin aqueous emulsion resin (solid content) Component (C): Water-soluble pyrophosphate and /or 0.05 to 5% by weight of resin solid content of tripolyphosphate (2) component A glaze composition in which the above components (A), (B) and (C) are blended in the above ratio. 2) Glaze a metal or ceramic base with a composition containing an anionic resin emulsion, a water-soluble pyrophosphate and/or tripolyphosphate, and a glaze, dry and solidify the anionic resin aqueous emulsion, and then apply water. A painting method characterized in that glaze aging and pattern firing are performed simultaneously by transferring a pattern for transfer by a slide method or applying a layer of glaze aqueous dispersion, followed by firing. 3) The copolymer of the anionic resin aqueous emulsion consists of (a) 0.1 to 10% by weight of α,β-unsaturated carboxylic acid (b) acrylic acid alkyl ester (the number of carbon atoms in the alkyl group is 2 to 8) 30-70% by weight (c) 30-70% by weight of a monomer selected from methyl methacrylate, styrene, acrylonitrile (d) N-phenylmaleimide, N-methylolacrylamide, acrylamide, methacrylamide, 2-hydroxyalkyl acrylate (The number of carbon atoms in the alkyl group is 2 to 4) 100 parts by weight of a vinyl monomer mixture consisting of 0.5 to 10% by weight of a vinyl monomer selected from 3. The painting method according to claim 2, wherein the copolymer is obtained by emulsion polymerization in the presence of 0.1 to 5 parts by weight of an anionic emulsifier and 0 to 5 parts by weight of a nonionic emulsifier.