JPH0751457B2 - Decorative pigment composition for ceramics and method for producing decorative ceramics - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decorative pigment composition for ceramics used for decoration of ceramics and a method for producing a decorative ceramics. More specifically, the present invention relates to a smectite structure represented by a specific molecular structural formula. Related to the use of synthetic silicates, which have ultra-fine particles in water or organic solvents and exhibit remarkable viscosity. Therefore, hand-painting technique, direct printing painting technique, transfer painting technique, etc. For ceramics that can be painted by the method described above, has good adhesion to porcelain precursors such as unglazed ceramics and the ceramics themselves, and develops a desired color tone after firing that is different from the color tone before firing Manufactures decorative pigment compositions and ceramics with the base itself, the lower part of the glaze (with a sketch), the inside of the glaze (with a sink-in picture), the surface of the glaze (with a picture above), etc. The method relates.

[0002]

2. Description of the Related Art Conventional pigments for ceramics are oxides or sulfides containing an element that develops a desired color tone after firing of ceramics, and are composed of substances having a crystal structure of spinel type, zircon type, rutile type, etc. Compounded into the chemical composition, 1000 ℃
The above was synthesized by heating and reacting [[Pigment for ceramics], Atsushi Otsuka, Ceramics, 18, 1983]
(No. 5), pages 377-384].

The synthesized pigment may be used by further mixing a plurality of pigments so as to obtain a desired color tone. Also, organic additives such as methylcellulose, dextrin, acrylic resin emulsion, ethylene glycol, etc. should be added depending on the decoration technique such as hand-painting technique, direct printing painting technique (eg pad printing method), transfer painting technique, etc. Momo ["Recent Ceramics Decoration Technology", Eizo Ueda, Ceramics, 18 (1983) N
o. 5, p. 385-391].

However, in order to produce conventional ceramic pigments,
Since the synthesis is performed at a high temperature, the product sinters hard, and the crushing process is indispensable for practical use. However, in the current mechanical crushing, it is generally difficult to reduce the particle size after crushing to 1 μm or less, so the adhesion of the pigment particles to the porcelain precursor such as unglazed or the porcelain itself is poor, and contact with the fingertips, etc. There was a problem such as peeling off and contamination of the decorative pattern.

Further, due to the characteristics of the crystal structure itself which constitutes the pigment substance, when it is mixed with water or an organic solvent to form an aqueous solution or an organic solution, it has poor viscosity and is used for a transfer painting technique or a pad printing technique. In order to impart viscosity, it was essential to mix the above-mentioned organic additives.

Further, the synthetic swelling silicate having a smectite structure containing a divalent heavy metal ion, an alkali metal ion, an alkaline earth metal ion and the like has various color tones depending on the swelling property, the gel property and the kind and amount of the metal ion contained. It has been disclosed that applications such as water-based paints, pigments, cosmetics, pharmaceuticals, catalysts, etc. are being developed by utilizing such characteristics as (see JP-A-62-292615 and JP-A-6-262615).
2-297210, JP-B-63-6485, etc.).

[0007]

The object of the present invention is to develop the viscosity by simply mixing the pigment with water or an organic solvent,
Therefore, it does not require an organic additive to impart viscosity, and since it is easily dispersed into fine particles when placed in water or an organic solvent after synthesizing the pigment, there is no need for a pulverizing step into fine particles, and decoration is possible. It is a synthetic pigment composition that is highly adherent to the container to be applied, and can be painted by a technique such as hand-painting technique, direct printing painting technique, transfer painting technique, etc. Is a decorative pigment composition for pottery that produces a different desired color tone, and the base material itself, the lower part of the glaze (with a sketch), using the same.
It is intended to provide a method for producing a ceramic which is decorated on the inside of the glaze (with a sink-in picture), the surface of the glaze (with a picture on the top), and the like.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies in view of the above problems, and as a result, by utilizing the characteristics of a synthetic silicate having a smectite structure represented by a specific molecular structural formula, The inventors have found that an excellent decorative pigment for ceramics, which develops an intended color tone different from the color tone before firing, can be obtained after firing, and has reached the present invention.

That is, the invention according to claim 1 of the present invention comprises the following formula (Chemical formula 3) containing an element exhibiting a desired color tone after firing.
Is a decorative pigment composition for ceramics, which has as a main component at least one selected from synthetic silicates having a smectite structure and having a color tone different from the color tone before firing. In the formula, X ⁺ is an alkali metal ion such as Na and Li, X ²⁺ is an alkaline earth metal ion such as Ca and Mg,
M ³⁺ is a trivalent metal ion such as Al and Fe, M ²⁺ is N
i, Co, Zn, Cu, Fe, Mn, Pb, Cd, etc. 2
Represents a valent metal ion. n ≧ 0.

[0010]

[Chemical 3] ^{X +} is alkali metal ion in the ^{formula, X 2+} is an alkaline earth metal ^{ion, M 3+} is a trivalent metal ^{ion, M 2+} 2
Represents a valent metal ion. n ≧ 0. In addition, ()
"," Means "and / or" .

The invention according to claim 2 of the present invention is the decorative pigment composition for ceramics according to claim 1, characterized in that the synthetic silicate is subjected to a lipophilic treatment. The lipophilic treatment is carried out by using, for example, dialkyldimethylammonium ion, monoalkyltrimethylammonium ion, trialkylmonomethylammonium ion, or quaternary ammonium ion such as alkylbenzyl quaternary ammonium ion such as alkyldimethylbenzylammonium ion. It can be performed by introducing it between layers.

The invention according to claim 3 of the present invention is characterized in that the synthetic silicate is a synthetic silicate having a smectite structure represented by the following formula (Formula 4). A decorative pigment composition for ceramics. M ²⁺ in the formula
Represents a divalent metal ion such as Ni, Co, Zn, Cu, Fe, Mn, Pb, or Cd. The values of a and b are 0 ≦ a <
3, 0 <b ≦ 3 and n ≧ 0.

[0013]

[Chemical 4] M ²⁺ in the formula represents a divalent metal ion. The values of a, b, and c are 2.5 ≦ a ≦ 3.5, 0 ≦ b <3, and 0 <c ≦ 1. In addition, "," in () indicates "and / or"
You

The invention according to claim 4 of the present invention is the decorative pigment composition for ceramics according to any one of claims 1 to 3, characterized in that an aqueous dispersion or organic solvent dispersion of the synthetic silicate is used. is there.

The invention of claim 5 of the present invention uses at least one selected from the decorative pigment composition for ceramics according to claim 1, directly on a ceramic or a ceramic precursor before decoration, or A decoration characterized in that it is painted through a glaze, and if necessary, it is glazed, and then fired in an oxidizing atmosphere and / or a reducing atmosphere to obtain a decorative ceramic having a desired color tone. It is a manufacturing method of ceramics.

According to a sixth aspect of the present invention, at least one selected from the decorative pigment composition for ceramics according to the first aspect is used as a pigment for kneading a base material to prepare a ceramics precursor, and an oxidizing atmosphere is prepared. And / or firing in a reducing atmosphere to produce a decorative ceramic having a desired color tone, or at least one of the above types selected from the decorative pigment composition for ceramics according to claim 1. Using different types and / or the same type, directly or through a glaze on the decorated ceramics or the ceramics precursors, and if necessary, after applying a glaze, an oxidizing atmosphere and / or A method for producing a decorated ceramic which comprises firing in a reducing atmosphere to obtain a decorated ceramic having a desired color tone.

The invention according to claim 7 of the present invention is characterized in that at least one selected from the decorative pigment composition for ceramics according to claim 1 is mixed in the glaze. It is a method for manufacturing a decorated ceramic according to claim 6.

The substance having a smectite structure represented by the general formula (Formula 3) used in the present invention is present in nature, but contains impurities and is not a subject of the present invention. The synthetic silicate having a smectite structure used in the present invention is represented by the general formula (Chemical Formula 3), and the raw materials are blended and prepared so as to have a desired composition, and hydrothermally heated under the condition of 100 to 35 ° C. It is obtained by carrying out the reaction. For example,
JP-B-63-6485, JP-A-62-29261
It can be obtained by synthesizing by the method described in JP-A No. 5 and JP-A No. 62-297210, but it is not limited thereto.

An excellent decorative pigment composition for ceramics, which is capable of developing a desired color tone after firing of a synthetic silicate substance having a smectite structure represented by the general formula (Formula 3) after firing. In order to achieve the above, the type and amount of the X ion and the M ion in the general formula (Formula 3) are changed to manufacture. In this case, it is also possible to produce a delicately colored pigment by using a plurality of ions for both X and M ions. It is also possible to mix and manufacture a plurality of kinds of X ions and M ions, which are manufactured separately with different kinds and amounts.

The synthetic silicate thus obtained is used as it is as a decorative pigment composition for ceramics, and is mixed with the base material itself or with the glaze itself to produce a decorated ceramics. You can The synthetic silicate after synthesis is generally obtained by hydrothermal synthesis, and since it becomes an agglomerate of primary particles when dried, it is necessary to pulverize it in actual use, but it is easy to perform with ordinary pulverization. It becomes an agglomerate of primary particles having a particle size of about 100 μm or less, and when added to water or an organic solvent, it is easily dispersed as ultrafine particles having a particle size of about 1 μm or less, mainly having a diameter of 100 to 500 nm and a thickness of 10 to 50 nm. The solution becomes thixotropic in viscosity. Further, the ones obtained by substituting the interlayer ions with a quaternary ammonium ion or the like and subjected to a lipophilic treatment become likewise ultrafine particles when dissolved in an organic solvent,
The solution becomes thixotropic in viscosity. In the present invention, when the decorative pigment composition for ceramics in the state of an aqueous solution or an organic solution containing the synthetic silicate is used, it is painted by various techniques such as a hand-painting technique, a direct printing painting technique, a transfer painting technique and the like. As a result, it is possible to easily manufacture a ceramic that is decorated on the lower part of the glaze (with a sketch), the inside of the glaze (with a sink-in picture), the surface of the glaze (with a picture above), etc.

It is also easy to make the color of the ceramics decorated with the decorative pigment composition for ceramics of the present invention into a dull artistic color. Using the decorative pigment composition for ceramics of the present invention, the reason why the above-mentioned artistic color is easily obtained is that the material of the base material, the type of glaze (simple lime glaze, lime magnesia glaze, lime zinc glaze, It is not possible to determine because the state varies depending on lime glaze such as lime barium glaze, feldspar glaze, magnesia glaze, zinc glaze, barium glaze, etc., firing conditions (oxidation, reduction or a combination thereof), but color development after firing It is considered that this is due to the diffusion of the elements that form the synthetic silicate and the elements that form the synthetic silicate in the state of ions or colloids in the glaze.

In addition, 1 of the structure limiting the general formula (Formula 3)
The substance having a hectorite type smectite structure represented by the general formula (Formula 4) is, for example, Ni, Co, Zn, Cu, Fe, Mn, Pb, C as M ion in the formula.
It is possible to obtain at least one divalent metal ion selected from divalent metal ions such as d, and to obtain a substance having various chemical compositions including other divalent metal ions such as Mg. It can be preferably used as a decorative pigment composition for ceramics. The same applies to the case where the interlayer ions are replaced with a quaternary ammonium salt or the like and subjected to a lipophilic treatment.

[0023]

In order to use the synthesized substance having a smectite structure as a pigment for decorating ceramics, it is possible to fix a metal element exhibiting a desired color tone after firing in the crystal structure. Although the color tone differs depending on the material of the base material, the type of glaze, the firing conditions, etc., for example, in the case of the type of decorative pigment composition for ceramics containing Co, blue color develops when fired in a reducing atmosphere, and similarly the type of composition containing Cu. Then, when baked in a reducing atmosphere, green or red color is produced depending on the type of glaze. When the synthetic silicate is mixed with water or an organic solvent, the solution becomes remarkably viscous. Therefore, even when the pigment is used in a paste state, it is not necessary to add an organic additive for imparting viscosity. The synthetic silicate after synthesis is obtained as an agglomerate in which primary particles are agglomerated, but when added to water or an organic solvent, it becomes easily dispersed as almost primary particles having a particle diameter of about 1 μm or less, and thus it is a conventional pigment for ceramics. The grinding step to fine particles as in manufacturing is unnecessary. In addition, since they are fine particles, they are highly adherent to a container to be decorated. Therefore, it is possible to paint by a technique such as a hand-painting technique, a direct printing painting technique, or a transfer painting technique. It is possible to manufacture ceramics with the base itself, the lower part of the glaze (with a sketch), the inside of the glaze (with a sink-in picture), the surface of the glaze (with a picture above), etc. When the decorative pigment composition for ceramics of the present invention is used, it is possible to easily obtain a dull, artistic coloration. It is thought to be due to diffusion in the state of ions and colloids.

Example 1 Water in a 1 liter beaker 4
Put 00 ml, and add No. 3 water glass (SiO ₂ 28
%, Na ₂ O 9%, molar ratio 3.22) 86 g,
While stirring, 16.2 g of 95% sulfuric acid is added at once to obtain a silicic acid solution. Next, to 100 ml of water, nickel chloride hexahydrate (NiCl ₂ .6H ₂ O) special grade reagent (purity 9
9%) 65.6 g are dissolved and added to a silicic acid solution to prepare a homogeneous mixed solution, which is added dropwise to 360 ml of 2N sodium hydroxide solution with stirring for 5 minutes. Immediately after the reaction homogeneous composite precipitate obtained was filtered and washed thoroughly with water, 20 ml of water and lithium hydroxide hydrate [Li
(OH) .H ₂ O] (1.45 g) was added to form a slurry, which was transferred to an autoclave. 15.9 kg
/ Cm ² and react at 200 ° C. for 3 hours. After cooling, the reaction product was taken out and dried at 80 ° C. to obtain a Ni-containing synthetic smectite represented by the formula (Formula 5). To 1 part of the above synthetic smectite, 50 parts of water and 0.02 part of sodium acrylate as a dispersant were added, and sufficiently mixed and dispersed with a stirrer to obtain a decorative pigment composition for ceramics of the present invention in an aqueous solution state. . Put this aqueous solution in a writing brush, 900 ° C
An arbitrary pattern was drawn on a 10 cm square tile type unglazed plate that was calcined in, and dried at room temperature. In addition, Amakusa Senjo clay, which is commonly used in the Western Kyushu region, was used for the production of unglazed plates. Upon drying, the synthetic smectite firmly adhered to the surface of the unglazed surface, and the surface was not scraped off by rubbing the surface with a finger.

[0025]

[Chemical 5]

On the other hand, limestone 14.6%, Indian feldspar 2
A raw material mixture consisting of 2.2%, feldspar 32.0% with respect to the state, New Zealand kaolin 14.1%, and silica 17.1% was crushed with a pot mill and K ₂ O 0.13, Na ₂ O.
20, CaO 0.67, Al ₂ O ₃ 0.6, SiO ₂
A lime glaze having a composition of 4.9 was prepared. The glaze is applied to the dried bisque plate, and the temperature is 1300 ° C (SK10),
Firing was performed in a reducing atmosphere (CO concentration of about 3%). As a result, a porcelain tile board having a brown pattern on the surface and having a defocused decoration was obtained.

Example 2 Water in a 1 liter beaker 4
Put 00 ml, and add No. 3 water glass (SiO ₂ 28
%, Na ₂ O 9%, molar ratio 3.22) 86 g,
While stirring, 16.2 g of 95% sulfuric acid is added at once to obtain a silicic acid solution. Next, in 100 ml of water, cobalt chloride hexahydrate (CoCl ₂ .6H ₂ O) special grade reagent (purity 9
9%) 65.6 g are dissolved and added to a silicic acid solution to prepare a homogeneous mixed solution, which is added dropwise to 360 ml of 2N sodium hydroxide solution with stirring for 5 minutes. Immediately after the reaction homogeneous composite precipitate obtained was filtered and washed thoroughly with water, 20 ml of water and lithium hydroxide hydrate [Li
(OH) .H ₂ O] (1.45 g) was added to form a slurry, which was transferred to an autoclave. 15.9 kg
/ Cm ² and react at 200 ° C. for 3 hours. After cooling, the reaction product was taken out and dried at 80 ° C. to obtain a Co-containing synthetic smectite represented by the formula (Formula 6).

[0028]

[Chemical 6]

A mixture of an acrylic resin and toluene with respect to 1 part of an organic-inorganic composite obtained by lipophilicizing a synthetic smectite containing Co represented by the formula (Formula 6) with dimethyldioctadecyl ammonium chloride. By adding 1 part of a commercially available dispersion medium consisting of the above, and thoroughly mixing and dispersing with a three-roller, a decorative pigment composition for ceramics of the present invention of a mixture in a paste state was obtained. An arbitrary pattern was printed on the same biscuit plate as in Example 1 by the screen printing technique using this paste as a printing ink. Separately, an arbitrary pattern is printed on a paper containing dextrin, and an overcoat is applied to produce a transfer paper,
This transfer paper was attached to the same biscuit plate as in Example 1.
The bisque plate was calcined again at 900 ° C. to burn off organic substances such as paper. The same glaze as in Example 1 was applied to these biscuit plates, and the temperature was reduced to 1300 ° C. (SK10), reducing atmosphere (C
Firing was performed at an O concentration of about 3%). As a result, a porcelain tile board having an arbitrary pattern of blue on the surface was obtained.

(Example 3) 5 parts of water and 0.02 part of sodium acrylate as a dispersant were added to 1 part of the synthetic smectite containing Co represented by the formula (Formula 6), and three rollers were sufficient. By mixing and dispersing in 10 ⁵
The decorative pigment composition for ceramics of the present invention in a paste state having a remarkable viscosity of about 10 ⁶ centipoise was obtained. This paste is used as an ink for printing by the technique of pad printing,
Printing was performed on the unglazed base material of Amakusa Sengaku porcelain, which had a general dish shape with a diameter of about 20 cm and was calcined at 900 ° C. The synthetic smectite adhered firmly to the surface of the unglazed green body by drying at room temperature, and peeling did not occur by rubbing the surface with a finger normally. The same glaze as in Example 1 was applied to this unglazed body, and firing was performed in a reducing atmosphere (CO concentration of about 3%) at 1300 ° C (SK10). As a result, a porcelain tile having an arbitrary pattern of blue on the surface was obtained.

(Embodiment 4) In the same manner as in Embodiment 1, M ²⁺
A synthetic smectite in which the ions were changed to copper, iron, and manganese was prepared, an arbitrary pattern was printed on the biscuit plate in the same manner as in Example 3, the same glaze as in Example 1 was applied, and the color tone before firing was set to 1
The color tone after firing in an oxidizing atmosphere at 300 ° C. (No. SK10) and the color tone after firing in a reducing atmosphere (CO concentration of about 3%) were examined. In each case, a porcelain tile board with an arbitrary pattern having the following color tone with a blurred surface was obtained.

M ²⁺ ion Color before firing Color after firing (1300 ° C.) (Crystal structure) Redox cobalt (Smectite structure) Blue Blue Nickel green (〃) Brown Brown Copper light green (〃) Dark green Dark green (Red) ) (Note 1) Iron Brown (〃) Yellow Light Blue Manganese Yellow (〃) Brown Brown

(Note 1); As a glaze, Fukushima feldspar 42.7
%, Limestone 23.0%, calcined talc 6.6%, kaolin 7.7%, and silica stone 20.0% were crushed with a pot mill and KNaO0.20, CaO0.65, M
An earth ash glaze (lime magnesia glaze) having a composition of gO 0.15, Al ₂ O ₃ 0.30, and SiO ₂ 2.5 was used.

(Embodiment 5) The tile type unglazed plate used in Embodiment 1 is coated with the glaze used in Embodiment 1, and the temperature is 1300 ° C. (SK
No. 10) was fired in a reducing atmosphere (CO concentration of about 3%) to obtain an undecorated porcelain tile. On the glazed surface of this tile, a transfer paper prepared by using the decorative pigment composition for ceramics of the present invention of Example 2 was pasted, and after the transfer paper was dried, it was heated at 1280 ° C. (SK9) in a reducing atmosphere (CO concentration). Approximately 3%). As a result, a porcelain tile plate having a blue pattern on the surface and having a defocused decoration was obtained.

Example 6 The tile smear plate used in Example 1 was applied with the synthetic smectite used in Example 1 mixed with the glaze used in Example 1. After drying, 13
00 ° C (SK10), reducing atmosphere (CO concentration approx. 3%)
Was fired at. As a result, a porcelain tile plate with a brown surface was applied.

(Example 7) Amakusa Sengaku porcelain used in Example 1 was blended with the synthetic smectite used in Example 1 as a base material, and a bowl-shaped product was dried, and then 9
Calcination is performed at 00 ° C, then 1300 ° C (SK10
No.) and firing in a reducing atmosphere (CO concentration of about 3%).
As a result, a brown decorative brown bowl was obtained.

[0037]

INDUSTRIAL APPLICABILITY As described above, the decorative pigment composition for ceramics of the present invention uses, as a pigment material, synthetic smectite capable of synthesizing types having various coloring metal elements. Therefore, it has the effect of creating diversity as a pigment. Further, since it is possible to contain the color-forming metal element in an arbitrary ratio or to mix and use two or more kinds of synthetic smectites containing different metal elements, it is possible to synthesize a pigment having an intermediate color tone. .

Synthetic smectite is obtained as an agglomerate of primary particles, but since it is easily dispersed as primary particles in water or an organic solvent, the pulverization step into fine particles after synthesis is unnecessary, and the cost required for pulverization is reduced. it can. Further, when mixed with other materials, since they are fine particles, they can be mixed uniformly, and defects such as color unevenness are less likely to occur in the decorated pattern.
Further, when decorated on unglazed or the like, particles can be firmly adhered to the surface of the unglazed, and defects such as peeling of pigment and contamination are less likely to occur, and handling on the production line becomes easy. When synthetic smectite is dispersed in water or organic solvent,
It has the property of expressing remarkable viscosity. Therefore, it is possible to paint with a technique such as a hand-painting technique, a direct printing painting technique, or a transfer painting technique. It is possible to manufacture porcelain decorated with the base material itself, the lower part of the glaze (with a sketch), the inside of the glaze (with a sink-in picture), the surface of the glaze (with a picture above). For example, when the decoration is performed by using a printing technique, the auxiliary agent for imparting the viscosity, which has been conventionally added, is unnecessary, and the preparation work for adjusting the printing ink is simple and easy. Further, since the auxiliary agent is not added, the effect of diluting the auxiliary agent with respect to the pigment is eliminated, the content of the pigment particles is relatively increased, the concentration of the metal element is increased, and strong color development is obtained.

Conventionally, when an organic auxiliary agent for imparting viscosity is added, it has been impossible to store printing ink for a long period of time due to decay, deterioration, drying and solidification, etc. However, synthetic smectite is an inorganic material, so it is putrefactive. Since it does not deteriorate and can be reused by adding water or an organic solvent even after being dried and solidified, it can be stably used even after being stored for a long period of time. By using the decorative pigment composition for ceramics of the present invention, it is possible to easily obtain a mellow, artistic color.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Toshikazu Fujisaki 1-2-7 Hayatominami, Hoei-shi, Niigata Prefecture (72) Inventor Hiroshi Saiki 2074-2 Otakubo, Urawa-shi, Saitama Examiner Masahiro Hiratsuka

Claims (7)

[Claims] 1. At least a synthetic silicate having a smectite structure represented by the following formula (Formula 1) containing an element exhibiting a desired color tone after firing and having a tone different from the tone before firing. A decorative pigment composition for ceramics, which comprises one kind as a main component. [Chemical 1] ^{X +} is alkali metal ion in the ^{formula, X 2+} is an alkaline earth metal ^{ion, M 3+} is a trivalent metal ^{ion, M 2+} 2
Represents a valent metal ion. n ≧ 0. In addition, "," in () shows "and / or" . 2. The decorative pigment composition for ceramics according to claim 1, wherein the synthetic silicate has been subjected to a lipophilic treatment. 3. The decorative pigment composition for ceramics according to claim 1, wherein the synthetic silicate is a synthetic silicate having a smectite structure represented by the following formula (Formula 2). [Chemical 2] M ²⁺ in the formula represents a divalent metal ion. The values of a, b, and c are 2.5 ≦ a ≦ 3.5, 0 ≦ b <3, and 0 <c ≦ 1. In addition, "," in () shows "and / or" . 4. The decorative pigment composition for ceramics according to claim 1, wherein an aqueous dispersion or an organic solvent dispersion of the synthetic silicate is used. 5. Using at least one selected from the decorative pigment composition for ceramics according to claim 1, the ceramics or ceramic precursor before decoration is painted directly or through a glaze, A method for producing a decorative ceramics, characterized in that the decorative ceramics having a desired color tone is obtained by, if necessary, glazeing it and then firing it in an oxidizing atmosphere and / or a reducing atmosphere. 6. A ceramics precursor is prepared by using at least one selected from the decorative pigment composition for ceramics according to claim 1 as a pigment for kneading a base material, and is burned in an oxidizing atmosphere and / or a reducing atmosphere. To produce a decorative ceramic having a desired color tone, or at least 1 selected from the decorative pigment composition for ceramics according to claim 1.
Using a different type and / or the same type from the above types of types, painting on the decorated ceramics or the ceramics precursor directly or via glaze, and after glazing on them as necessary, A method for producing a decorated ceramic, which comprises firing in an oxidizing atmosphere and / or a reducing atmosphere to obtain a decorated ceramic having a desired color tone. 7. The decorative ceramics according to claim 5 or 6, characterized in that at least one kind selected from the decorative pigment composition for ceramics according to claim 1 is mixed in the glaze. Manufacturing method.