JP2008222962A - Inorganic pigment, its manufacturing method, ink for inkjet, decorative ceramic, and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an inorganic pigment improved in color developing property and an ink for inkjet using the same. <P>SOLUTION: The inorganic pigment, which is a compound oxide-based inorganic pigment having an average grain size of 500 nm or smaller, manufactured by mixing a raw material powder comprising two or more metal oxides, baking it, then pulverizing it, characterized in that use is made of a powder having an average grain size of 1,000 nm or smaller as the raw material powder. The ink for inkjet contains this inorganic pigment. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an inorganic pigment, a production method thereof, an ink jet ink, a decorative ceramic body, and a production method thereof. Specifically, the inorganic pigment of the present invention is composed of a composite oxide.

I. Various researches have been made on painting ceramic substrates such as tiles by an ink jet method. However, when baking high-resolution decorations by the inkjet method, “Four primary colors are difficult to obtain”, “Color development is remarkably reduced due to finer pigments”, “Low-temperature baking at 1000 ° C. or lower is necessary to improve color development. Thus, the number of firings is increased and the productivity is inferior ”, and“ expensive because a gold pigment is used for red color development ”.

II. In general, a pigment used for decorating ceramics is manufactured using a raw material of about 0.8 μm, usually 2 to 5 μm, even if the average particle size is fine. This is because when the used particle size of the pigment is about 1 μm or more, if the raw material particle size is too fine, irregular reflection on the surface increases and color development deteriorates.

III. Japanese Patent Application Laid-Open No. 2005-350327 discloses a decorative ceramic body in which a glaze layer is provided on the surface of a ceramic substrate and is painted with a red pigment, and the composition of the glaze is SiO ₂ 60- 76 mol%
Al ₂ O ₃ 4~11 mol%
K ₂ O 4~10 mol%
Na ₂ O 0.5 to 5 mol%
Li ₂ O 0~0.5 mol%
B ₂ O ₃ 0 to 2 mol%
CaO 4-10 mol%
BaO 0-6 mol%
ZnO 0-5 mol%
MgO 0-2 mol%
SrO 0 to 1 mol%
MnO ₃ 0-0.6 mol%
ZrO ₂ 0-6 mol%
Fe ₂ O ₃ 0 to 0.15 mol%
The decorative ceramic body is characterized in that the red pigment is a chromium oxide / tin oxide oxide pigment having a particle size of 500 nm or less.

  Even when this glaze layer is fired at a high temperature of 1190 ° C. or higher, the metal oxide pigment is not deteriorated.

  Even when this metal oxide pigment is finely pulverized to a particle size of 500 nm or less, the glaze layer having the above composition does not deteriorate the metal oxide pigment during firing.

  As a result, it is possible to use a glaze having a high melting point, for example, firing at 1140 to 1260 ° C., and the durability of the glaze layer is improved.

  Further, by using a finely pulverized pigment having an average particle diameter of 500 nm or less, a high-resolution picture can be drawn by inkjet.

IV. Ink-jet inks containing inorganic pigments composed of complex oxides are known (Japanese Patent Laid-Open No. 9-25589).
JP 2005-350327 A Japanese Patent Laid-Open No. 9-25589

  The present invention relates to an inorganic pigment having good color developability even when finely pulverized, a method for producing the same, an ink-jet ink using the inorganic pigment, a decorative ceramic body using the ink-jet ink, and a method for producing the same The purpose is to provide.

  The inorganic pigment according to claim 1 is a composite oxide inorganic pigment having an average particle diameter of 500 nm or less, which is produced by mixing raw material powders composed of two or more kinds of metal compounds, firing and then pulverizing. A material powder having an average particle diameter of 1000 nm or less is used.

  The inorganic pigment according to claim 2 is characterized in that, in claim 1, the raw material powder having an average particle diameter of not more than twice the average particle diameter of the inorganic pigment is used.

  The inorganic pigment according to claim 3 is characterized in that, in claim 1 or 2, the inorganic pigment has an average particle diameter of 100 to 400 nm, and the raw material powder has an average particle diameter of 80 to 800 nm.

  The method for producing an inorganic pigment according to claim 4 is a method of mixing an inorganic pigment made of a composite oxide having an average particle size of 500 nm or less by mixing and firing raw material powders made of two or more kinds of metal compounds. In the manufacturing method, the raw material powder having an average particle size of 1000 nm or less is used.

  The method for producing an inorganic pigment according to claim 5 is characterized in that, in claim 2, the raw material powder having an average particle size not more than twice the average particle size of the inorganic pigment is used.

  The method for producing an inorganic pigment according to claim 6 is the method according to claim 4 or 5, wherein the inorganic pigment has an average particle diameter of 100 to 400 nm and the raw material powder has an average particle diameter of 80 to 800 nm. It is.

  The ink-jet ink according to claim 7 is an ink-jet ink for painting on a ceramic body having a glaze layer formed on the surface of the substrate, containing the inorganic pigment according to any one of claims 1 to 3. It is characterized by doing.

  The method for producing a decorated ceramic body according to claim 8 is applied to a ceramic base material to form an unfired glaze layer, on which a painting with an inkjet ink containing an inorganic pigment is applied, and then fired. In the method for producing a decorated ceramic body by melting the glaze layer, the ink-jet ink is the ink-jet ink according to claim 7.

  In the present invention, the average particle diameter is a value measured by a dynamic light scattering method.

  The inorganic pigment of the present invention is obtained by firing a fine raw material powder having an average particle size of 1000 nm or less and pulverizing it to an average particle size of 500 nm or less.

  The present inventor has found that the color developability of the inorganic pigment is improved by using a fine powder having an average particle size of 1000 nm or less as the raw material powder. The reason is presumed to be as follows (1) and (2).

  (1) Sintered particles produced by sintering raw material powder particles in the firing process are not homogeneous composite oxides as a whole. The existence ratio of the complex oxide is high near the interface and the particle surface, and the existence ratio of the complex oxide decreases as the distance from the interface and the surface increases.

  (2) When the sintered particles are pulverized, if the sintered particles are cracked at a site away from the interface, a surface with a small proportion of the composite oxide is exposed.

  The inorganic pigment of the present invention has good color developability even when finely pulverized, and is suitable for ink jet ink. By using this ink-jet ink, a decorated ceramic body having a fine decorative surface can be produced.

  Hereinafter, the present invention will be described in more detail.

  The inorganic pigment of the present invention is produced by mixing, firing, and pulverizing raw material powder of a metal compound.

  As the metal compound, metal salts such as metal carbonates and metal nitrates as well as metal oxides and metal hydroxides can be used.

  Metals include sodium, potassium, calcium, barium, strontium, tin (tin), silicon, titanium, chromium, iron, cobalt, manganese, zirconium, vanadium, nickel, copper, zinc, molybdenum, cadmium, antimony, dungsten, gold , Lead, bismuth, lanthanum, europium, dysprosium, praseodymium and other alkali metals, alkaline earth metals, transition metals, rare earths and the like. These two combinations and blending ratios are selected from those that develop color upon firing.

  Specific examples of the complex oxide include the following.

As the composite metal oxide pigment for red, a chromium oxide-tin oxide pigment is suitable, and particularly Cr ₂ O ₃ 1-5 wt%.
SnO ₂ 35~55wt%
SiO ₂ 15~30wt%
CaO 16-30wt%
Are preferred. This chromium oxide-tin oxide pigment is painted on the glaze and baked at a high temperature of about 1140 to 1260 ° C., thereby giving a bright red color.

As the yellow composite metal oxide pigment, a chromium oxide-antimony oxide pigment is suitable, and particularly Cr ₂ O _{3 1 to 5} wt%.
Sb ₂ O ₃ 3-10 wt%
SiO ₂ 0~10wt%
TiO ₂ 75-95 wt%
Are preferred.

As the complex oxide pigment for yellow, zirconium oxide and praseodymium oxide are also suitable. For example, ZrO ₂ 50 to 70 wt%
Pr ₆ O ₁₁ 2~15wt%
SiO ₂ 25~35wt%
Is preferred.

Examples of black inorganic pigments include iron oxide-chromium oxide-cobalt oxide-manganese oxide-based pigments such as Fe ₂ O ₃ 0-80 wt%.
Cr ₂ O ₃ 0-30 wt%
CoO 0-50wt%
Mn ₂ O ₃ 0-50 wt%
NiO 0-30wt%
Are preferred.

As an inorganic pigment for blue made of a complex oxide, cobalt-alumina inorganic pigment such as CoO 40 to 45 wt%
Al ₂ O ₃ 60~55wt%
ZnO 0-30wt%
Are preferred.

  The average particle diameter of the raw material powder is 1000 nm or less, preferably 100 to 1000 nm, particularly preferably 100 to 500 nm, and more preferably 200 to 400 nm.

  When the average particle diameter of the raw material powder exceeds the above range, the color developability of the composite oxide after pulverization is lowered. When the average particle diameter of the raw material powder is smaller than the above range, the pulverization cost becomes excessively high.

  The two or more raw material powders are sufficiently pulverized and mixed using a medium stirring mill such as a ball mill, a sand mill, or a bead mill, and then fired.

  Although a calcination temperature changes with raw material powders, it is selected from the range of about 800-1400 degreeC. The firing time is preferably selected from about 2 to 72 hours. The firing temperature and time are preferably selected so that the sintered product after firing is sufficiently colored and is easily pulverized.

  The sintered product is preferably pulverized to an inorganic pigment by a pulverizer such as a medium stirring mill to an average particle size of 500 nm or less, preferably 100 to 500 nm, particularly preferably 100 to 400 nm, more preferably 100 to 300 nm. The reason why the upper limit of the average particle diameter of the inorganic pigment is set to 500 nm is that it is used for precise decoration such as ink-jet ink. If the average particle size of the inorganic pigment is smaller than the above range, the pulverization cost becomes excessive and the color developability also decreases.

  As the ink-jet ink, red, yellow, blue and black inks are used in which finely pulverized red, yellow, blue and black pigments are dispersed by a dispersant.

  As the dispersant, any one of an anion, a cation, a nonion and an amphoteric surfactant can be appropriately selected and used. For example, it is desirable to use polycarboxylate, acrylate, dodecylbenzenesulfonate, alkylsulfosuccinate, polyoxyethylene alkyl ether and the like.

  In addition to ink, various water-soluble organic solvents such as polyhydric alcohols such as glycerin and polyethylene glycol, ethanols such as methanol and ethanol, ethers of ethoxybutoxy ether, and various interfaces such as dodecylbenzene sulfonate, as necessary. Activators are added to adjust rheology such as wettability, viscosity, and surface tension.

  In the present invention, 1 to 20 wt%, particularly 10 to 20 wt% of titanium oxide may be added to the inkjet ink. Thereby, the decoloring effect which the pigment in an ink receives in a baking process can be suppressed.

  In the inkjet ink of the present invention, a pigment other than the complex oxide may be used as a part of the inorganic pigment.

  In this invention, you may decorate using white ink containing white pigments, such as a tin oxide, as needed.

  In order to produce the decorated ceramic body of the present invention, the surface of the ceramic substrate is painted by ink jetting, and then the glaze is applied in a layered manner to a uniform thickness by a technique such as curtaining. In addition, in order to drop from the inkjet nozzle, the glaze must have a certain viscosity, but when the glaze and the pigment are mixed and used, the viscosity must be reduced considerably to obtain that viscosity, resulting in a low pigment concentration. .

  On the other hand, when the glaze and the pigment are kept separate, it is only necessary to thin the glaze to the minimum, and the pigment concentration of the glaze can be increased.

  The ceramic base material may be a green base that has not been fired or may be calcined, but in the case of an interior tile, it is preferably a green base.

  Next, a preferred example of the glaze applied to the surface of the ceramic substrate will be described.

In general, chromium oxide-tin oxide pigments and titanium oxide-chromium oxide-antimony oxide pigments that have been finely polished for ink-jet decoration are colored on the decorated glaze surface by being decomposed by alkali in the glaze. to degrade. Therefore, in the present invention, titanium glaze is contained in the glaze, and the pigment decomposition action is suppressed in the titanium oxide, and the red coloring of the chromium oxide-tin oxide pigment and the yellow color of the titanium oxide-chromium oxide-antimony oxide pigment are performed. In order to improve the color development, the composition as a glaze is SiO ₂ 60-76 mol%, preferably 65-74 mol%
Al ₂ O ₃ 4~11 mol%, preferably 5-8 mol%
TiO ₂ 0.1-10 mol%, preferably 2-5 mol%
K ₂ O 4 to 10 mol%, preferably 4-9 mol%
Na ₂ O 0.5 to 5 mol%, preferably 0.6 to 3 mol%
Li ₂ O 0-0.5 mol%, preferably 0-0.2 mol%
B ₂ O ₃ 0-7 mol%, preferably 0.05-1.6 mol%
CaO 4-10 mol%, preferably 4-9 mol%
BaO 0-6 mol%, preferably 0-5 mol%
ZnO 0-5 mol%, preferably 0-4 mol%
SrO 0-1 mol%, preferably 0-0.5 mol%
MgO 0-2 mol%, preferably 0-1 mol%
MnO ₃ 0-0.6 mol%, preferably 0-0.5 mol%
ZrO ₂ 0-6 mol%, preferably 0-5 mol%
Fe ₂ O ₃ 0-0.15 mol%, preferably 0-0.1 mol%
Is preferably used.

  It has been found that this glaze has a high melting point, and can color well not only blue, yellow and black but also red metal oxide pigments.

  The reason for specifying the composition of this glaze is as follows.

SiO ₂ is a component constituting a silicate network in glass produced by firing glaze. When the SiO ₂ content is less than 60 mol%, the gloss of the glaze surface produced by firing becomes poor, and when it exceeds 76 mol%, the melting point of the glaze becomes excessively high. Therefore, the amount of SiO ₂ is set to 60 to 76 mol%, preferably 65 to 74 mol%.

Al ₂ O ₃ is a component for increasing the chemical resistance and water resistance of the glaze layer produced by firing. If Al ₂ O ₃ is less than 4 mol%, the chemical resistance and water resistance of the glaze layer are lowered, and if it exceeds 11 mol%, the fire resistance of the glaze becomes excessively high. Accordingly, _Al 2 _{O 3} is 4 to 11 mol% preferably formulated 5-8 mol%.

TiO ₂ has an action of alleviating the decomposition and decoloring action that the alkali component in the glaze gives to the pigment. When TiO ₂ is less than 0.1 mol%, this decoloration suppressing action is insufficient. On the other hand, when the TiO ₂ is more than 10 mol%, the glaze is tinged with yellow, it is difficult to have decorative seeking. A particularly preferable range of TiO ₂ is 2 to 5 mol%.

Both K ₂ O and Na ₂ O have a flux action. When K ₂ O is less than 4 mol% and Na ₂ O is less than 0.5 mol%, the melting point of the glaze becomes excessively high. Further, K 2 _O is 10 mol percent, the Na 2 _O is 9 mole percent, since the glaze has melted (glass) to inhibit color development of the pigment by dissolving the metal oxide pigments, K ₂ the amount of O is set to 4 to 10 mol%, preferably 4-9 mol%, the amount of Na ₂ O is 0.5 to 5 mol%, preferably 0.6 to 3 mol%.

Li ₂ O also has a flux action and may be added. However, since it has a strong color development inhibiting action, it is 0.5 mol% or less, preferably 0.2 mol% or less.

Since B ₂ O ₃ also has a flux action, it may be added. However, if excessively added, the metal oxide pigment is dissolved and the color development of the pigment is inhibited, so 7 mol% or less, preferably 0.05 to 1.6 mol%.

  CaO and BaO have the effect of lowering the melting point of the glaze when blended in proper amounts. CaO is blended in an amount of 4-10 mol%, preferably 4-9 mol%, and BaO is 0-6 mol%, preferably 0-5. It is blended in mol%. When the compounding amount of CaO and BaO is out of the above range, the melting point of the glaze increases.

  ZnO, MgO and SrO all have a flux action when added in small amounts, and may be blended. However, the blending amount of ZnO exceeds 5 mol%, the blending amount of MgO exceeds 2 mol%, SrO If the blending amount is more than 1 mol%, the color development of the metal oxide pigment is inhibited, so that ZnO is 0 to 5 mol%, preferably 0 to 4 mol%, and SrO is 0 to 1 mol%, preferably 0 to 0.00. 5 mol%, MgO is 0 to 2 mol%, preferably 0 to 1 mol%.

MnO ₃ may be blended in order to give gloss to the glaze surface after firing by blending in a small amount, but if it exceeds 0.6 mol%, it inhibits color development of the metal oxide pigment, so 0.6 mol% The amount is preferably 0.5 mol% or less.

When ZrO ₂ is blended in a small amount, it produces milky white in the glaze after firing, thereby demonstrating the effect of making the color of the pigment colorful. Since (melting point) becomes high and pinhole-like defects are likely to occur in the fired glaze, it is set to 5 mol% or less, preferably 4 mol% or less.

Incidentally, SnO also, for the same reason as the ZrO _2, 5 mol% or less, may be added, especially 4 mol% or less.

Fe ₂ O ₃ is made 0.15 mol% or less, preferably 0.1 mol% or less in order to make the glaze itself yellow or brown.

  As a nozzle for performing printing with the ink for ink jet, it is preferable to use a fine nozzle having a nozzle diameter of 80 μm or less, particularly 50 μm or less, for example, 30 to 50 μm or less, whereby an extremely delicate image can be inkjet printed. .

  After the pattern is printed by inkjet or the like, it is dried and fired to obtain a decorated ceramic body. In the case of an interior tile, the firing temperature is preferably about 1140 to 1260 ° C, particularly about 1150 to 1250 ° C. A roller hearth kiln or a tunnel kiln is used for firing. In the case of the roller hearth kiln, the residence time in the furnace from the entrance to the exit of the furnace is preferably about 20 to 100 minutes, particularly about 20 to 60 minutes.

  Hereinafter, examples and comparative examples will be described.

  In the following examples and comparative examples, a base glaze having the following composition is hung on a green body of an interior tile mainly made of porcelain stone, clay, etc. by a curtain method, dried, and then painted by inkjet. After applying and drying, an interior tile having a side of 200 mm was manufactured by firing with a roller hearth kiln.

SiO ₂ 68.90 mol%
ZrO ₂ 3.38 mol%
Al ₂ O ₃ 5.66 mol%
Br ₂ O ₃ 4.92 mol%
K ₂ O 3.84 mol%
Na ₂ O 1.76 mol%
CaO 7.08 mol%
ZnO 2.31 mol%
MgO 0.51 mol%
Fe ₂ O ₃ 0.02 mol%
TiO ₂ 1.64 mol%
As the ink jet head, a piezo element type head (Konica 318WT) having a nozzle diameter of 40 μm was used.

The average particle size was measured using a measuring device based on the dynamic light scattering method of Nikkiso Co., Ltd. Nanotrack 250. The solvent at the time of measurement was water, and the viscosity was 0.001 Pa · sec.
[Example 1 and Comparative Example 1]
The raw material of the pink pigment, 47 parts of tin oxide, 25 parts of lime, 25 parts of silica, and 3 parts of chromium oxide were finely polished to an average particle size of 3 μm with a ball mill. A part of this was fractionated and further polished to an average particle size of 0.2 μm with a medium stirring mill. These were dried and fired at 1250 ° C. for 18 hours using the same kiln to obtain a so-called chrome tin pink pigment.

  This pigment is finely polished with a medium stirring mill to a mean particle size of 0.5, 0.4, 0.3, 0.15, or 0.1 μm together with a dispersant, etc., and the viscosity is carefully adjusted so that the pigment concentration does not change. After adjusting the surface tension, the surface coated with the above glaze was printed with an inkjet head and baked at 1150 ° C. for 30 minutes.

  Table 1 and FIG. 1 show the colorimetric data obtained by the colorimeter for the decorative surface.

As shown in Table 1 and FIG. 1, pigments with a fine raw material particle size are slightly inferior in color at a coarse particle size at the initial stage of fine polishing, but even if the pulverization proceeds and becomes finer, the color development is less likely to proceed. When the raw material particle size is coarse, the color development suddenly decreases at a particle size of 0.5 μm or less.
[Example 2 and Comparative Example 2]
The test was also conducted with the same test yellow pigment as described above.

  85 parts of titanium oxide, 4 parts of chromium oxide and 4 parts of antimony oxide as raw materials were finely polished to an average particle size of 3 μm by a ball mill. A part of this was collected and further polished to a mean particle size of 0.25 μm with a medium stirring mill. These were dried and then fired at 1000 ° C. for 14 hours using the same kiln to obtain a so-called titanium chrome yellow pigment.

  Be careful not to change the pigment concentration by finely polishing this pigment with a dispersing agent to an average particle size of 0.6, 0.5, 0.4, 0.3, 0.2, 0.1 μm with a medium stirring mill. Then, after adjusting the viscosity and the surface tension, the surface coated with the glaze was discharged and printed by an inkjet head, and baked at 1150 ° C. for 30 minutes.

  Table 2 and FIG. 2 show the colorimetric data obtained by the colorimeter for the decorative surface.

[Example 3 and Comparative Example 3]
As a zircon pigment that is generally excellent in coloration stability, a test was conducted on zircon praseo yellow.

  Zirconium oxide 64%, praseodymium oxide 6% and silica 30% were mixed and finely ground to an average particle size of 4 μm using a ball mill. A part of this was fractionated and further polished to a mean particle size of 0.3 μm with a medium stirring mill. These were dried and then fired at 1000 ° C. for 12 hours using the same kiln to obtain a so-called zircon praseo yellow pigment.

  Be careful not to change the pigment concentration by finely polishing this pigment with a dispersing agent to an average particle size of 0.6, 0.5, 0.4, 0.3, 0.2, 0.1 μm with a medium stirring mill. Then, after adjusting the viscosity and surface tension, the ink-jet head was used for ejection printing on the surface coated with the glaze disclosed in JP-A-2005-350327, and baked at 1150 ° C. for 30 minutes.

  Table 3 and FIG. 3 show the colorimetric data obtained by the colorimeter for the decorative surface.

[Example 4 and Comparative Example 4]
As a general black pigment, a chromium iron pigment was tested.

  Iron oxide 25%, chromium oxide 25%, cobalt oxide 25% and manganese oxide 25% were mixed and finely polished to an average particle size of 6 μm using a ball mill. A part of this was fractionated and further polished to an average particle size of 0.2 μm with a medium stirring mill. These were dried and fired at 1300 ° C. for 16 hours using the same kiln to obtain a so-called chromium iron pigment.

  Be careful not to change the pigment concentration by finely polishing this pigment with a dispersing agent to an average particle size of 0.6, 0.5, 0.4, 0.3, 0.2, 0.1 μm with a medium stirring mill. Then, after adjusting the viscosity and surface tension, the ink-jet head was used for ejection printing on the surface coated with the glaze disclosed in JP-A-2005-350327, and baked at 1150 ° C. for 30 minutes.

  Table 4 and FIG. 4 show the colorimetric data obtained by the colorimeter for the decorative surface.

  According to the present invention from Tables 1 to 4 and Figs. It was clearly recognized that the decrease in color development can be suppressed.

It is a graph which shows the result of an Example and a comparative example. It is a graph which shows the result of an Example and a comparative example. It is a graph which shows the result of an Example and a comparative example. It is a graph which shows the result of an Example and a comparative example.

Claims (8)

In the composite oxide inorganic pigment having an average particle size of 500 nm or less, which is produced by mixing and firing raw material powders composed of two or more kinds of metal compounds, and then crushing,
An inorganic pigment having an average particle diameter of 1000 nm or less as the raw material powder.   2. The inorganic pigment according to claim 1, wherein the raw material powder has an average particle size of not more than twice the average particle size of the inorganic pigment.   The inorganic pigment according to claim 1 or 2, wherein the inorganic pigment has an average particle size of 80 to 400 nm and the raw material powder has an average particle size of 80 to 800 nm. In a method for producing an inorganic pigment made of a composite oxide having an average particle size of 500 nm or less, by mixing raw material powders made of two or more kinds of metal compounds, firing and then pulverizing,
A method for producing an inorganic pigment, wherein the raw material powder has an average particle size of 1000 nm or less.   3. The method for producing an inorganic pigment according to claim 2, wherein the raw material powder has an average particle size of not more than twice the average particle size of the inorganic pigment.   6. The method for producing an inorganic pigment according to claim 4, wherein the inorganic pigment has an average particle diameter of 80 to 400 nm and the raw material powder has an average particle diameter of 80 to 800 nm. Ink-jet ink for painting on a ceramic body in which a glaze layer is formed on the surface of the substrate,
An ink-jet ink comprising the inorganic pigment according to any one of claims 1 to 3. An unfired glaze layer is formed on a ceramic substrate, painted with ink-jet ink containing an inorganic pigment, and then fired to melt the glaze layer to form a decorative ceramic body. In the manufacturing method,
The method for producing a decorated ceramic body, wherein the ink-jet ink is the ink-jet ink according to claim 7.

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