JPS60171283A - Manufacture of ornamental ceramic - 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 The present invention relates to a method for producing decorative ceramics having a surface with a color close to gold and a golden maple luster.

Conventionally, gold-colored decorations have been applied to the surface of ceramics using an overglaze method in which leftover liquid is used and fired at a temperature of OO°C to g5θ°C, but the durability of the product surface has been poor. In recent years, with the development of sink-in gold that can be fired to a higher degree of severity (see %Kaikast, -QBRIlIg and Japanese Patent Publication No. 57-15θ6Q), a gold color with excellent wear resistance has been developed. You can now obtain decorations. However, in any of the above cases, the products are expensive because gold, which is a precious metal, is used.

As a way to achieve a color similar to gold without using gold.

A method of using phlogopite, a method of coating mica with titanium oxide (see #Kaikai51.-1'132 Otsu),
There are also methods to create a color close to gold by mixing pigments with titanium mica (see I# Kaikai Kai A-15!Og No. 1), but since mica decomposes at both temperatures, the color is developed at a high temperature. However, the wear resistance of the product is poor.

As a result of intensive research, Kiko Myoja succeeded in solving the above-mentioned problems of the conventional technology, and was able to obtain a highly durable ceramic product with a surface that has a color close to gold and a metallic luster. □It was.

An object of the present invention is to provide a method for manufacturing decorative ceramics with a surface finish having the above-mentioned properties by using titanium nitride as the main coloring component and baking at high temperatures. It is known that by forming a thin film on the surface of ceramics using ion silating method or other method and baking it, the color becomes very gold, almost ink color. However, in this case, 11. Since it has to be treated in a heated atmosphere, the % fi is huge, and it is not common. Painting is carried out by direct printing or transfer using a printing paint containing titanium nitride, and then at a high temperature, preferably about 7.000° C. or higher, more preferably about 7.000° C. to about 3.0° C. By performing glaze firing at a temperature of 0°C, it is possible to obtain a highly durable ceramic product with a surface having a color close to gold and a metallic luster.

Generally, a composition containing titanium nitride, a glass composition, and a pigment for ceramics can be used as the printing paint, and preferably titanium crabide/θ~gθ weight ratio, glass composition 10-gθ weight ratio and a suitable amount of a ceramic pigment. The printing paint can be prepared, for example, by mixing and pulverizing titanium nitride, a ceramic pigment, and a glass composition, and mixing the mixture with a vehicle to form an a14 coating.

As titanium nitride, purity is 99 or higher, particle size is 1.3t*
tn or less is preferable, and the amount used is selected in consideration of photochromicity and gloss. Paint composition for printing! Based on lyl standards,
If the lθ0 weight part is too small, the golden color will become unclear and gO
If the amount exceeds the weight it%, the gloss will be poor.

The pigment for ceramics may be of any color as long as it is a pigment for overpainting that is commonly used in the art industry, and can be used alone or as a mixture, but from the viewpoint of coloring assistance, yellowish and orange pigments are preferred. preferable.

The glass composition is added to make the paint easier to bake, and the amount to be used is selected in consideration of photochromicity and gloss. As the lθ weight decreases, it becomes difficult to see the golden light color.1. If the number is higher than that of goxtt, the gloss tends to be poor. The glass composition is preferably 5102 with a weight of 60 to 7S, /θ to θ.
203, 2-4% of CaO, 2-4% (K+N
a) MgO with 20 &'i' 4 or less.

Fine powders containing ZnO or the like having a Ωθ coefficient or less, fine powders in which at least a portion of these are covered with PbO or B2O3-containing frit and/or zirconium silicate, etc. can be used. However, the glass composition.

The composition is not limited to the above composition (it can be arbitrarily selected depending on the purpose of the present invention).

As mentioned above, the present invention does not use gold, which is a precious metal, so it is inexpensive, and it does not require a vacuum or special gas atmosphere, so the equipment is simple.
Since it is baked at a high temperature of 00°C or higher, a light color close to gold with excellent durability can be obtained.

In addition, the painting method is a known method in the painting industry,
For example, hand-painting, copper plate printing, lithograph printing, screen printing, spraying, direct printing using a rubber stamp, transfer method, etc. may be used, and as the glaze, those known in the art industry may be used.

The method of the present invention can be used to decorate ceramic products such as tableware, porcelain products, and sanitary ware.

The present invention will be explained below with reference to examples, but these are merely illustrative and do not limit Kikomei in any way. In each example, hff1l and 9 mean parts by weight and parts by weight, respectively.

Example 1 The following ingredients: Sandstone 35 feldspar 351 Limestone 201 Dolomite 5 parts Zinc white 51 No. 1? Time type mixing at θ in the hot mill 4'+'
do.

The particles had a particle size of 70 microns or less and were dried to prepare a glass composition.

Next, the following ingredients: Titanium nitride (Mitsuwa Kagaku Chikushoni, Ni, W) 63 parts Yellow pigment (Nippon Insulator, Ni, Tai) 27N The above glass composition lθ! A printing paint for ceramics was prepared by mixing and crushing with a grinder and gθ parts of screen printing medium N5V (manufactured by Noritake Co., Ltd.). A tile glazed with a mixture of 10 parts of (manufactured by industry) was fired at approximately 16θ°C for approximately 3θ hours, a floral pattern was screen printed on the glaze of the fired tile using the above paint, and then the same conditions as above were applied. Re-glazed and fired. A flower-patterned tile with a gold-like luster on a wine red background was obtained.

The following tests were conducted to examine the durability of the resulting tiles. As a comparative sample, NW gold liquid for overglaze (Japanese liquid,
0 Table) was concentrated to a size of approximately % by weight as a paint, and a wine red glaze was applied to a hard ceramic base (tile), and the glaze was fired for approximately 30 hours at /4θ°C. A book was used which was screen printed directly on the prepared substrate, dried and then fired at gSθ°C.

l Abrasion resistance test Carbine sand CG-/θ0 (RIKEN corundum co, L
To, d), add a load lθθ9fC, rub the painted part while replenishing water, and check the condition of the surface.Acid resistance test.Immerse the tile in a 104 solution of hydrochloric acid and observe the condition of the painted part (at room temperature). 3゜Alkali Resistance Test Tile is immersed in a solution of caustic potash at 6 parts℃±5℃.
Observation of the condition of the painted part by holding it at C. Result of the disease test From the results of the above comparative test, it can be seen that Suikomei's product has excellent durability.

! Ijl! Example: Ingredients below: Titanium nitride (manufactured by Mitsuwa Chemical Co., Ltd.)! 2' AI Example/described glass composition θl was mixed and crushed in a crusher, and this was mixed and crushed into 2 parts C, M, C, and melted S.
A printing paint was prepared by kneading with θ part.

Transparent glaze with chestnut brown pigment (manufactured by Nichinan Sangyo) 2.91 and black pigment (Touken from Nichinan) 3. An animal pattern was screen printed on a green base tile coated with a chocolate-colored glaze mixed with the glaze, and then the glaze was fired at about 10°C and 20°C for about 30 hours.

ll11 with a metallic luster close to gold on a chocolate background
] A tile with a storage area was obtained. The durability was equivalent to that of Example 1.

Example 3 The following components: Titanium nitride (manufactured by Mitsuwa Chemical Co., Ltd.) 2 g Yellow pigment (Nippon Insulator Co., Ltd.! I!!ri) Red pigment (Nippon Sangyo Co., Ltd.) % The glass composition Otsu θ! described in Zl Example 1 was mixed and ground using a grinder, mixed with part 7 of an oil-based vehicle [medium N3V for screen printing (manufactured by Noritake Company Limited)], and a printing paint was mixed. alI
Made by II.

A floral pattern was printed on the transfer paper using the above paint, and a cover coat was printed on top of the floral pattern to obtain a transfer paper.

A glazed tile with a transparent glaze mixed with red pigment (manufactured by Nichinan Sangyo Co., Ltd.) as a general coloring agent is fired for about 30 hours at a temperature of about 1/AO"C. The transfer paper was transferred and then fired for about 30 hours at about 1/6θ° C. A tile with a floral pattern on a wine red background with a metallic luster close to gold was obtained.

The durability was the same as that of Example 1 and was poor.

Procedural amendment 60.1-8 Manabu Shiga, Commissioner of the Japan Patent Office (Monday/Monday, Showa 1), Indication of the case, Patent Application No. 3238 of 1982, 2, Title of the invention, Process for manufacturing decorative ceramics 3, Person making the amendment Related: Name of applicant: Toto Kiki Co., Ltd. 4, Agent 5, Date of amendment order: Proprietor (1) “References” from page 2, line 19 to page 3, line 1 of the specification
...Poor abrasion resistance. ” is corrected as follows.

However, since mica decomposes at temperatures above 1200°C, it cannot be colored at high temperatures.

Claims (1)

[Claims] A titanium nitride-containing composition is applied on ill 1# porcelain glaze,
Next, a method for producing decorative ceramics having a surface exhibiting a color close to gold and gloss throughout the area, which is characterized by firing at a high temperature of 1,000° C. or higher. (2) The titanium nitride-containing composition has titanium nitride with a weight ratio of 10 to go, a glass composition with a weight ratio of lθ to gθ, and 11
The method for producing decorative ceramics according to claim 111, which contains Iden's pigment for ceramics. 13+ The method for manufacturing decorative ceramics according to claim 11 or claim 21, wherein the firing temperature is 1,00θ°C to /,330°C.