JP3236725B2 - How to color ceramic members - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for coloring a ceramic member using a colorant solution, and more particularly to a method for coloring a ceramic member having a natural texture such as a marble pattern or an agate-like pattern.

[0002]

2. Description of the Related Art Conventionally, when a marble pattern or an agate pattern is applied to ceramics or the like, a kneading technique has generally been used. That is, kneading is performed by kneading raw materials of different colors into clay having sufficient plasticity, and laminating or kneading the plurality of types of clay irregularly with each other, molding and firing.

However, it has been attempted to apply a marble pattern or an agate pattern by a kneading technique using a ceramic member such as alumina (Al ₂ O ₃ ), particularly a high-purity ceramic material such as translucent alumina. However, there is a problem that a clay having sufficient plasticity cannot be made, and a marble pattern or an agate pattern cannot be applied.

Therefore, when a marble pattern or an agate pattern is applied to a ceramic member, an unglazed ceramic member is conventionally produced, and a resin such as rosin or balsam is dissolved in an organic solvent such as turpentine or petroleum. The varnish-like water repellent is applied to the marble pattern, and then an aqueous colorant is applied or impregnated and dried, and then the colorant is turned into an oxide by calcination, and then the ceramic member is sintered. It was colored by that. When a coloring agent is applied or impregnated to the unglazed ceramic member after applying the water repellent to the marble pattern, the water-repellent portion has a white pattern and a marble pattern as a whole. According to this method, a marble pattern or an agate-like pattern can also be applied to the ceramic member, and a pictorial or craft expression can be achieved. Moreover, there is little waste in the raw material, and there are few scatterings of the pigment powder and contamination by the pigment in management, and there are many advantages.

[0005]

However, in the method of applying or impregnating an aqueous colorant after applying the water repellent to the ceramic member, the steps of applying the water repellent and the step of applying the aqueous colorant are carried out. It is a two-step application or impregnation process, the process is complicated, and at the time of the work of applying the water repellent, it is the most important work that requires a natural texture when this work is completed Nevertheless, there is a problem that the final coloring state is difficult to understand.

According to this method, an ivory or white pattern which is the original color tone of ceramic is formed on a colored base material.

Further, without applying the above-mentioned water repellent,
When the colorant of the aqueous solution is applied directly to the unglazed ceramic member, the water-soluble liquid pigment takes a long time to dry and diffuses into the ceramic member, making the outline of the pattern unclear and delicate pattern Can not be drawn.

It is conceivable to add a colorant to the water repellent itself, but the colorant composed of a metal salt is water-soluble and not water repellent. Therefore, there was a problem that the oil-based water repellent was insoluble or immediately formed a precipitate, and did not become a colorant solution.

Further, in the method of applying or impregnating an aqueous colorant after applying a water repellent to the ceramic member, it has not been possible to color the colored substrate so as to form a colored pattern.

Also, without applying the above-mentioned water repellent,
When an aqueous colorant of two or more colors is directly applied to the unglazed ceramic member, the water-soluble liquid pigment takes a long time to dry, and the pigments soaked in the porous ceramic member diffuse in contact with each other, There is a problem in that the patterns are mixed and the outline of the pattern becomes unclear, and a delicate pattern cannot be drawn.

[0011]

SUMMARY OF THE INVENTION A method for coloring a ceramic member according to the present invention has been invented in view of the above-mentioned problems of the prior art. Alternatively, in a method of coloring a ceramic member, in which a colorant solution is applied to an unbaked ceramic member and fired, the colorant solution is made of a metal salt, a rosin and / or a balsam resin thickener, An alcohol or a solvent mainly composed of alcohol is used, and the colorant solution is applied and dried, and then a colorant composed of an aqueous solution of a metal salt is applied or impregnated and fired.

[0012]

When an alcohol is used as a solvent as in the present invention, the alcohol becomes a solvent for both a colorant composed of a metal salt and a thickener composed of rosin and / or balsam resin, and the alcohol is used as a solvent for the colorant and the thickener. A colorant solution consisting of the mixture can be made. When the colorant solution is applied to the green body or the baked ceramic member, the colorant solution is absorbed by the ceramic member, the solvent volatilizes quickly, and the colorant and thickener adhere to the green body or the baked article. Then, when a colorant in the form of an aqueous solution in which a colorant composed of a metal salt is dissolved in water is applied or impregnated, the rosin and / or balsam resin, which is a thickener, has water repellency. The coloring agent in the agent solution and the aqueous coloring agent to be applied or impregnated later are not mixed. After drying this,
When the colorant is oxidized by calcination and reacted with the ceramic member by firing, the ceramic member develops color. The thickener fixed to the ceramic member is burned and volatilized in the calcining step. Thus, the thickener does not adversely affect the color development and sintering of the ceramic member.

[0013]

Embodiments of the present invention will be described below in detail. In the method for coloring a ceramic member according to the present invention, a colorant solution is applied to an unbaked ceramic member.

The unglazed ceramic member is formed as follows. That is, for example, high-purity alumina 100
To the parts, 0.5 to 1 part of a dispersant, 2 to 5 parts of a binder, and 25 to 30 parts of pure water are added, and mixed by a ball mill, followed by vacuum degassing, and a formed product is formed by, for example, a casting method. .
Next, after drying the formed product, 5 g
Slowly raise the temperature to around 00 ° C and heat at 900 to 1000 ° C. Thereby, an unglazed product of a porous ceramic member is formed.

Next, a colorant solution is applied to the unglazed ceramic member. The colorant solution used in the present invention comprises a colorant, a water-repellent thickener, and a solvent.

As a coloring agent, chromium nitrate (Cr (N
_{O 3) 2 · 9H 2 O} ), cobalt nitrate (Co (NO _{3) 2} ·
6H ₂ O), nickel nitrate _{(Ni (NO 3) 2 ·} 6H
₂ O), manganese nitrate (Mn (NO ₃ ) ₂ .nH ₂ O) (n
= 4-6), copper acetate ((CH ₃ COO) ₂ .Cu.H
A metal salt such as ₂ O) is used. Chromium nitrate is pink ~
Red to deep red, cobalt nitrate develops light blue to dark blue, nickel nitrate develops gray to blue when fired in a vacuum furnace, yellow green to dark green when fired in a gas furnace, and manganese nitrate vacuum The color is pink when fired in a furnace, orange when fired in a gas furnace, and copper acetate is colored brown when fired in a vacuum furnace and dark brown when fired in a gas furnace.

Examples of the water repellent thickener include pine resin and balsam resin. This thickener is desirably contained at least 5% by weight based on the colorant solution in order to make the colorant solution viscous, and 10% by weight in order to draw a clear pattern without bleeding. It is preferable to add the above. On the other hand, when this thickener exceeds 20% by weight,
The colorant solution sticks strongly and is not practical. Therefore, the content of the thickener in the colorant solution is 5 to 20% by weight.
Is desirable. The thickener may be rosin alone, balsam resin alone, or both rosin and balsam resin. Also,
This thickener is added so that when a water-soluble colorant is applied to the surface of the unbaked ceramic member, the colorant is instantaneously absorbed and diffused by the porous ceramic member. In addition, the dried colorant exhibits water repellency due to the thickener. Further, this thickener may be dissolved in advance with a solvent such as turpentine oil or petroleum. In particular, when a pattern or the like is drawn with a brush, the usability, such as the degree of sliding of the brush, is improved.

Examples of the solvent include methyl alcohol and ethyl alcohol. The methyl alcohol or ethyl alcohol dissolves in both water and oil, and becomes a solvent for both the colorant composed of the above-mentioned metal salt and the thickener composed of rosin or balsam resin.

Such a colorant solution is applied to the surface of the unglazed ceramic member. When applying to the surface of a ceramic member, pinch a sponge, cloth, sponge, etc. with tweezers, apply a colorant solution instead of a brush, and apply while applying a tone while continuously tapping the surface of the ceramic member. .

The above-mentioned colorant solution can be used as a coloring agent for underlaying, thereby expanding the possibility of a decoration technique.

After the colorant solution is applied to the green body or the unbaked ceramic member and dried, the colorant in the form of an aqueous solution is then applied or impregnated. This coloring agent is the same as the above-mentioned metal salt, and is a solution dissolved in pure water.

Since the colorant in the previously applied colorant solution becomes water-repellent when dried, it does not dissolve or mix with the aqueous colorant to be applied later.

After the water-repellent colorant solution and the water-soluble formed form are applied in this manner, they are dried, calcined at about 1000 ° C., and fired at a temperature of 1650 ° C. or more.

[0024] - Example 1 chromium nitrate nonahydrate _{(Cr (NO 3) 2 ·} 9H 2 O) 30
g was dissolved in ethyl alcohol to make a total of 100 ml. 10 g of pine resin was dissolved therein to obtain a transparent varnish-like colorant solution having a deep green color. The colorant solution was adhered to a sponge piece on a high-purity fine-powder alumina molded body which had been unbaked at 900 ° C., and the pattern was drawn while pinching and tapping the sponge piece. A clear pattern could be drawn with little bleeding. After drying, 6 g of manganese nitrate (Mn (NO ₃ ) ₂ .nH ₂ O) (n = 4 to 6) is dissolved in pure water to make a light pink transparent aqueous color solution having a total volume of 100 ml. To perform impregnation coloring. Natural drying was carried out all day and night and calcined at 1100 ° C. in an electric furnace.
This was sintered at 1750 ° C. in a vacuum furnace to obtain an alumina ceramic having a red marble pattern on a light pink background.
Further, this was fired again at 1650 ° C. in a gas furnace to obtain an alumina ceramic having a delicate red marble pattern on an orange background.

Example 2 Cobalt nitrate hexahydrate (Co (NO ₃ ) ₂ .6H ₂ O) 2
0 g was dissolved in methyl alcohol to make a total of 100 ml. 13 g of pine resin was dissolved therein to obtain a transparent varnish-like colorant solution having a light red color. A pattern was drawn on this uncolored baked product in the same manner as in Example 5 using the same coloring agent solution. After drying, nickel nitrate hexahydrate (Ni (NO ₃ ) ₂
(6H ₂ O) was dissolved in pure water, and impregnation coloring was performed using a transparent aqueous colorant having a pale green color with a total volume of 100 ml. Drying and calcination were performed in the same manner as in Example 5. This was sintered in a vacuum furnace at 1700 ° C. to obtain an alumina ceramic member having gray and black agate patterns. Further, this was fired again at 1600 ° C. in a gas furnace to obtain an alumina ceramic member having a delicate blue agate pattern on a green background.

[0026] - Example 3 chromium nitrate nonahydrate _{(Cr (NO 3) 2 ·} 9H 2 O) 15
g was dissolved in ethyl alcohol to make a total of 50 ml. 10 g of Koppai Babalsum was dissolved in 50 ml of turpentine oil while warming. These were mixed to obtain a clear varnish-like colorant solution exhibiting a deep green color. A pattern was drawn on this uncolored baked product in the same manner as in Example 5 using the same coloring agent solution. After drying, nickel nitrate hexahydrate (Ni
(NO ₃₎ the ₂ · 6H ₂ O) 4g was dissolved in pure water, the entire
Impregnation coloring was performed using a clear aqueous colorant having a pale green color of 00 ml. Drying and calcination were performed in the same manner as in Example 5. This was sintered in a vacuum furnace at 1750 ° C. to obtain an alumina ceramic having a gray-red marble pattern on a gray background. This was further fired at 1650 ° C. in a gas furnace to obtain an alumina ceramic having a red-brown marble pattern on a yellow-green background.

[0027]

As described above, according to the method for coloring a ceramic member according to the present invention, a colorant comprising a metal salt and a thickening agent comprising a rosin and / or a balsam resin are applied to the formed or unglazed ceramic member. After applying and drying a coloring agent solution composed of a coloring agent and a solvent composed mainly of alcohol or a solvent mainly composed of alcohol, a colorant in the form of an aqueous solution in which a coloring agent composed of a metal salt is dissolved in water is applied or impregnated and fired. As a result, the color when baked is the same as when the colorant solution is applied, and it is possible to easily perform coloring with a natural texture and easily color with a colored pattern on a colored substrate Can be done.

Claims (1)

(57) [Claims] 1. A method for coloring a ceramic member, in which a colorant solution is applied to a green body or an unbaked ceramic member and fired, wherein the colorant solution comprises a colorant comprising a metal salt, a rosin and / or a balsam resin. A thickener comprising, and a solvent composed mainly of alcohol or alcohol, and applying and drying this colorant solution, followed by applying or impregnating a colorant composed of an aqueous solution of a metal salt and firing. A method for coloring a ceramic member.