JPS5819634B2 - Manufacturing method of colored ceramic products - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to improvements in the coloring and painting process and the glazing process in a method for manufacturing ceramic products such as porcelain, lamps, earthenware, and enamel whose surfaces have been treated with a glaze.

Conventionally, colored ceramic products, especially colored patterned ceramic products, have been mainly produced by the following method.

(1) A method in which various patterns are applied to a base material, for example, an unglazed surface, a glaze layer is formed on the surface, and then the colored pattern is covered with a glaze layer by firing.

This method has the advantage that the formed colored pattern is coated and fixed with a glassy glaze layer, making the colored pattern extremely durable, but the colored pattern is usually applied by a printing method using oil-based ink. Therefore, if a water-based glaze slurry is applied on top of the glaze, the glaze slurry will be repelled by the ink, making it difficult to form a smooth glaze layer, and furthermore, there will be an incompatibility between the ink and the glaze layer during subsequent firing. There is a disadvantage that the surface of the obtained ceramic product becomes even more uneven due to its properties.

This method is usually called the underpainting method.

(2) As a method to eliminate the drawbacks of method (1) above,
A method in which a colored pattern is applied to the ceramic surface that has already been glazed and fired, and then fired to create the colored pattern on the glazed surface.

This method is called overglaze method, and it solves the drawback of (1) above and gives a product with a smooth surface, but since the colored pattern is baked on the glaze layer once fired, the color of the formed colored pattern may fade. ; It is severely inferior in fastness, and also has a serious drawback in the process of double firing.

Instead of the above-mentioned method, it is also possible to form a glaze layer on the surface of the unglazed clay, then apply a colored pattern, and then fire it, but in this method, the glaze and glaze layer are not fired, so It cannot withstand the printing pressure used to apply colored patterns, and the glaze layer is frequently damaged, making it industrially worthless.

Furthermore, some methods have been proposed to add water-soluble polymers to the glaze slurry to reinforce the glaze layer, but this method has various problems such as the need for long heat treatment, making it difficult to industrially use. It's not worth much.

This method is called the Inglaze method.

As a result of intensive research to solve the drawbacks of the conventional methods, especially the inglaze method, the inventors of the present invention have found that the above-mentioned drawbacks of the conventional methods can be solved at the same time, the surface smoothness is good, and the colored pattern does not fade. We have discovered a method for manufacturing ceramic products that does not require double firing.

That is, the present invention forms a glaze layer on the surface of a substrate using a glaze slurry made of a photocurable resin material and a glaze, irradiates the surface with light without drying the glaze layer, and then applies the glaze layer before firing. Apply any coloring or coloring pattern to the surface,
Next, a method for manufacturing a colored ceramic product characterized by integrally firing a glaze layer and a colored layer, and a glaze layer is formed on the surface of the base material using glaze slurry, and the glaze layer is photocured on the surface without drying. After applying a plastic resin paint and irradiating it with light, the surface of the glaze layer is given any coloring or colored pattern before firing, and then the glaze layer and the colored layer are fired simultaneously and integrally. This is a method for producing colored ceramic products.

The photocurable resin material used in the present invention and which characterizes the present invention itself is a known material, and is described in "Photosensitive Resin, Author: Takahiro Tsunoda, Published by Printing Society Publishing Department" and various other documents and patent publications. Disclosed.

Among such photocurable resin materials, preferred materials for the purpose of the present invention are hydrophilic materials or hydrophobic materials emulsified and dispersed in water.

Furthermore, although there are photocurable resin materials that are crosslinked by light and materials that are polymerized by light, it has been found that the latter gives more preferable results.

Preferred photocurable resin materials are monomers, oligomers, prepolymers and/or polymers having addition-polymerizable double bonds in their structure, which can be polymerized by light, especially ultraviolet irradiation, in the presence of a photosensitizer. It is an organic material that increases its molecular weight by crosslinking and forming a network.

Examples of these materials include polyester resins having addition polymerizable groups, acrylic resins, acrylic-modified epoxy resins, acrylic-modified urethane resins, alkyd resins, and the like.

In the present invention, even if the ultraviolet ray polymerizable material is an oil-soluble material, it can be used, but since glaze is usually used after being turned into a slurry with water, the ultraviolet ray polymerizable material must be hydrophilic, water-soluble, or water-soluble. Preferably, it is decentralized.

Furthermore, a non-hydrophilic or water-insoluble ultraviolet polymerizable material can be used in the present invention as a hydrophilic or water-soluble material by introducing, for example, a carboxyl group or a hydroxyl group in advance during its production.

Examples of hydrophilic or water-soluble ultraviolet polymerizable materials include glycidyl (meth)acrylate adducts of carboxyl group-containing acrylic polymers disclosed in JP-A-50-100119, and (meth)acrylic acid adducts of polyepoxy compounds. Acid addition reaction products, (meth)acrylic acid adducts of carboxyl group-containing polyesters, and products obtained by subjecting the hydroxyl groups of hydroxyl group-containing polyesters to an addition reaction with a polyhydric carboxylic acid anhydride and then adding glycidyl (meth)acrylate. Polymerizable materials containing various hydrophilic or water-soluble monomers and various photosensitizers as main components, as well as JP-A-52-47887 and JP-A-52-1
The water-dispersed photocurable resin material disclosed in Japanese Patent No. 38215 is also suitable for the purpose of the present invention.

The glaze used in the present invention is a glaze normally used for porcelain, lamps, pottery, enamel glaze, etc., and is not particularly limited.

In the present invention, in order to form a glaze layer on the surface of a substrate using a glaze slurry made of a photocurable resin material and a glaze, a glaze slurry to which a photocurable resin material is added is prepared at the time of glazing, and this is applied to the surface of the substrate. or by applying a glaze slurry to the surface of the substrate and then applying a photocurable resin material to the surface of the glaze layer.

When applying the glaze, the proportion of the photocurable resin material added to the glaze slurry is approximately 1 part by weight per 100 parts by weight of the glaze in terms of solid content.
It is suitable that it is 20 parts by weight.

Even if the photocurable resin material is contained in such a proportion, the viscosity of the glaze slurry will hardly increase because the material has a relatively low molecular weight.

After applying the glaze slurry to the base surface, the photocurable resin material applied to the glaze surface is a water-dispersible hydrophobic type or hydrophilic type liquid material. It may be a lower alcohol, acetone, methyl ethyl ketone, or other organic solvent with a concentration of 5 to 40%, and the amount applied to the glaze layer surface with a spray gun, etc. is the photocurable resin in terms of solid content per 1 m2 of the glaze layer surface. Approximately 5 to 40 ingredients? is appropriate.

In this way, after forming a glaze layer on the surface of a ceramic product with a glaze slurry made of a photocurable resin material and a glaze, the glaze layer is coated on the surface without drying, preferably about 20%
When irradiated with ultraviolet rays of 00λ to 4,600 degrees using a commonly known ultraviolet irradiation device such as a xenon lamp or mercury lamp for a very short period of time, for example, several seconds to several tens of seconds, the photocurable resin material present on the surface and inside of the glaze layer will polymerize. It crosslinks, becomes reticulated, has a high molecular weight, solidifies with the glaze, and adheres to the base material.

Therefore, the glaze layer is significantly strengthened.

In contrast to the method of the present invention, as in the prior art,
In the method of simply adding a water-soluble resin, the glaze layer must be dried in order to be reinforced with the resin, and this drying process not only takes a long time, but also causes the glaze layer to crack, break, break, peel, etc. due to evaporation of water. occurs.

In the case of the present invention, the glaze layer is strongly reinforced without substantially removing water, so the above-mentioned disadvantages do not occur at all.

Next, any coloring or coloring pattern is applied to the surface of the glaze layer formed as described above before firing using a conventionally known coloring agent for ceramic products or transfer paper, etc. At that time, printing is performed using a printing machine. Even if the glaze layer is subjected to pressure and is not fired, the glaze layer will not be deformed, collapsed, or destroyed by the force.

On the other hand, in the case of a glaze layer that is not reinforced as in the conventional method, such suppressed printing is virtually impossible.

As the colorant and transfer paper used, conventionally known ceramic colorants and transfer paper can be used as they are.

Next, the base material having the colored glaze layer formed in this way is fired as usual at a high temperature of about 700°C to 1500°C, and the glaze layer and the colored layer are fired as an integral product to form the desired product. However, at this time, the high-molecular-weight photocurable resin material in the glaze layer is completely burned out, leaving no effect on the resulting ceramic product.

The colored ceramic product produced by the method of the present invention as described above has a smooth surface, whereas the conventional method for overglazing has a colored pattern under the glaze layer, resulting in an uneven surface of the glaze layer after firing. Moreover, since the colored pattern is fired at the same time as the glaze layer, the colored pattern sufficiently penetrates into the glaze layer and is completely covered with the glassy glaze.

Therefore, conventional overpainting does not cause any color fading problems as required by law.

Furthermore, whereas the conventional overglazing method requires two firings, the method of the present invention simplifies the firing process by one step.

Furthermore, if we compare the conventional inglaze method and the improved inglaze method of the present invention, we find that in the case of the conventional method, a very long and careful drying period is required in order to obtain the reinforcing effect of the added water-soluble polymer. However, no matter how careful you are, the occurrence of a large number of defective products due to cracking, breakage, and peeling is unavoidable.However, in the case of the present invention, reinforcement of the glaze layer can be achieved in a short time of several seconds to several tens of seconds. Moreover, there is no occurrence of defective products unlike in the conventional method.

Therefore, the method of the present invention is industrially significantly superior to any conventional method.

Next, examples of the present invention will be described.

Incidentally, the word ``takashi'' in the text indicates weight percentage.

Example 1 Glaze spoon gun and ultraviolet irradiation device downstream thereof (
Three 200W/1nch high pressure mercury lamps, lamp height 1
The present invention was carried out as follows using a production line for flat ceramics equipped with 5G1'IL) on a belt conveyor.

(1) Preparation of glaze containing ultraviolet polymerizable material 5i02
55 parts A1 03 12 parts 0205 parts Na2O6 parts Zn0 4 parts B2039 parts Zr0 Add 10 parts of an ultraviolet polymerizable material having the composition and a small amount of water to give a specific gravity of 1.
7 and used as a glaze for use in the present invention.

The composition of the ultraviolet polymerizable material is as follows.

Acrylic acid adduct of polyepoxy compound 100 parts 2-hydroxyethyl acrylate 50 parts Photosensitizer 5 parts Water: Isopropyl alcohol (2:1) 155 parts (2) Glazing and UV irradiation Belt conveyor speed set to 2 m/min The above-mentioned glaze slurry is sprayed from a spray gun while continuously moving the molded plate-like base material released from the molding press, and then continuously irradiated with ultraviolet rays.

(3) Colored pattern printing A flower pattern was printed on the surface of the glaze layer using a screen method using a conventionally known printing ink for ceramics.

(4) Firing The glazed and patterned flat surface as described above is transferred to a firing furnace and fired at a temperature of approximately 1200°C for 48 hours to form a colored flat plate with excellent gloss and no cracks, scratches, or peeling. I got ceramics.

When we examined the quality of the flat ceramics obtained by this method, we found that the surface of the glaze layer had no irregularities and was completely smooth, and no discoloration from the colored pattern was observed at all.

Comparative Example 1 (Conventional overglaze method) In the method of Example 1, a glaze layer containing no ultraviolet polymerizable material was formed, fired, a colored pattern was printed, and then fired, the resulting product was Color fading was observed in the colored part when rubbed strongly. Comparative Example 2 (Conventional overpainting is legal) In the method of Example 1, a colored pattern was printed on the base material,
When a glaze layer containing no ultraviolet polymerizable material was then formed and then fired, the colored parts of the obtained product were uneven and lacked smoothness.

Example 2 When the operation of Example 1 was repeated using a methacrylate photocurable resin emulsion in place of the photocurable resin material in Example 1, the same results as in Example 1 were obtained.

Example 3 The present invention was carried out as follows using a dish-shaped ceramic manufacturing line in which another spray gun was installed between the glaze spray gun and the ultraviolet irradiation device of the manufacturing line used in Example 1.

(1) Preparation of glaze Same as in Example 1, but no ultraviolet polymerizable material was added.

(2) Glazing, application of UV polymerizable material, and UV irradiation Same as Example 1, the speed of the belt conveyor was set to 2 m/m.
The above glaze slurry was sprayed while continuously moving the molded dish-shaped base material coming out of the molding press, and an ultraviolet polymerizable material having the following composition was applied to the surface of the formed glaze layer at a rate of about 100 r/7H2. The product is spray coated in an amount of 100 ml, and then irradiated with ultraviolet light.

'The composition of the ultraviolet polymerizable material used above is as follows.

Glycidyl acrylate addition reaction product of carboxyl group-containing unsaturated polyester 100 parts Triethylene glycol diacrylate 60 parts 2-hydroxyethyl acrylate 30 parts Photosensitizer 10
Part water: ethanol (2:1) 800 parts (3)
Colored Pattern Printing A pattern was printed on the surface of the glaze layer by a concave pad offset method (commonly known as an octopus printing method) using a conventionally known printing ink for ceramics.

(4) Firing The same procedure as in Example 1 was carried out to obtain colored plate-shaped ceramics with excellent gloss and no peeling, scratches, cracks, etc.

Comparative Example 3 (Conventional Inglaze Method) In the method of Example 3, when a colored pattern was printed on the glaze layer without applying an ultraviolet polymerizable material, the glaze layer could not withstand the printing pressure and the printing was almost impossible.

Example 4 In place of the photocurable resin material in Example 3, a polyester acrylate photocurable resin emulsion was used and the operations of Example 3 were repeated to obtain the same effect as in Example 3.

Claims (1)

[Claims] 1. A glaze layer is formed on the surface of a substrate using a glaze slurry made of a photocurable resin material and a glaze, and after the surface of the glaze layer is irradiated with light without drying, before firing. A method for producing a colored ceramic product, which comprises applying an arbitrary color or coloring pattern to the surface of the glaze layer, and then simultaneously and integrally firing the glaze layer and the colored layer. 2. A glaze layer is formed on the surface of the substrate using glaze slurry, a photocurable resin paint is applied to the surface of the glaze layer without drying it, and after irradiation with light, any arbitrary coating is applied to the surface of the glaze layer before firing. A method for producing a colored ceramic product, which comprises applying color or a colored pattern, and then simultaneously and integrally firing a glaze layer and a colored layer.