JP2008273808A - Decorated ceramic article, method for producing the same, and ink for inkjet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a decorated ceramic article having a clear pattern and a smooth surface, and to provide an ink for inkjet ink using to the same. <P>SOLUTION: In the decorated ceramic article, a glazed layer is provided on the surface of a ceramic base material and the surface of the glazed layer is subjected to painting. The decorated ceramic article is characterized in that the surface of the grazed layer is flat, pigments used for forming the pattern exist in the grazed layer, and the concentration of the pigments is highest at the outermost surface of the grazed layer. In a method for producing the decorated ceramic article comprising applying a glaze on the surface of the ceramic base material, subjecting the surface of the applied glaze to painting by inkjet printing using an ink containing the pigments, and firing; the ink is an frit-free ink in which a frit is not incorporated, and the particle diameters of the pigments are ≤5,000 nm. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a decorated ceramic body to which a painting is applied, a method for producing the same, and an ink-jet ink used for the production.

  As a method for producing a decorated ceramic body that has been painted with a pigment, a glaze is applied to the surface of the ceramic substrate, and then the surface of the glaze layer is painted with an ink containing a pigment, and then dried. The firing technique is widely adopted.

Conventionally, the ink for inkjet used in this painting is blended with a frit (finely pulverized glass frit) (Document 1 below). This is because if the frit is not blended in the ink, the pigment does not sufficiently adhere to the undercoat layer even when baked.
JP 2001-81363 A

  When an ink containing a pigment and a frit is used for painting by an ink jet method and firing, a glass layer derived from the frit in the ink remains as if it is raised on the surface of the lower shell, and the pigment is mainly contained in this glass layer. It comes to exist. In this case, since the glass layer is sufficiently fused and integrated with the lower eyelid, the pigment is not peeled off and the pattern is robust.

  However, as described above, the portion where the ink is attached by ink jet is raised by the glass layer derived from frit, so that it is not suitable for products that require a smooth appearance or appearance. In addition, after painting, a technique is also known in which an upper glazing made of transparent glazing is applied to the glazing and then baked. In that case, the pigment is dispersed or diffused in the upper glazing, resulting in a sharp pattern. May decrease.

  In general, an ink is obtained by dispersing a pigment and a frit in water and / or an organic solvent, but there is an upper limit to the concentration of a medium (frit and pigment) that can be dispersed in a liquid medium. Therefore, when frit is blended, it is necessary to reduce the blending amount of the pigment, and as a result, the pigment concentration in the ink is lowered and the color of the pattern is lightened.

  An object of the present invention is to solve the above-mentioned conventional problems, to provide a decorative ceramic body having a clear pattern and a smooth surface, a method for producing the same, and an ink jet ink used for the production. To do.

  The decorative ceramic body according to claim 1 is a decorative ceramic body in which a cocoon layer is provided on the surface of a ceramic base material, wherein the surface of the cocoon layer is painted. The surface of the soot layer is flat, and the pigment showing the pattern is present in the soot layer, and the pigment concentration is highest in the outermost layer of the soot layer.

  The method for producing a decorated ceramic body according to claim 2 is a method of decorating ceramics, in which a glaze is applied to the surface of a ceramic substrate, and the surface of the glaze is painted by ink jet printing using an ink containing a pigment, and then fired. In the body manufacturing method, the ink is a frit-free ink containing no frit, and the particle diameter of the pigment is 5000 nm or less.

  The method for producing a decorative ceramic body according to claim 3 is characterized in that, in claim 2, the viscosity of the ink when painting is 50 cp or less and the surface tension is 60 mN / m or less. .

  The ink-jet ink according to claim 4 is a frit-free ink which does not contain a frit in an ink-jet ink containing a pigment for painting a ceramic substrate, and the pigment has a particle size of 5000 nm or less. It is characterized by being.

  The decorated ceramic body provided by the present invention has the highest pigment concentration in the outermost surface layer of wrinkles, and the pattern becomes clear. Further, since the pigment is present in the soot layer, the pattern is robust and beautiful over a long period of time. In the present invention, the surface of the soot layer is flat and the appearance is also good.

The reason why such a decorative ceramic body is manufactured by the method of the present invention is presumed as follows.
(1) The pigment is fine, and the ink sprayed onto the unfired glaze layer penetrates into the unfired glaze layer. The permeated pigment is taken into the soot layer by firing.
(2) Since the ink is a frit-free ink containing no frit, the glass layer derived from the ink is not formed as raised on the surface of the ridge layer.

  When the ink has a viscosity of 50 cp or less and a surface tension of 60 mN / m or less, the ink easily penetrates into the unfired glaze layer.

  Hereinafter, the present invention will be described in more detail. In the decorated ceramic body and the method for producing the same of the present invention, examples of the decorated ceramic body include tiles, glazed bricks, tableware, sanitary ware, decorative ceramic plates, other washbasins, and toilet bowls.

  In order to produce the decorative ceramic body of the present invention, preferably, the surface of the ceramic substrate is coated with a glaze in a layered manner by a technique such as curtaining, and dried to form a printing base, Paint by inkjet. The term “flat” refers to a state in which the ridge layer is provided substantially uniformly on the substrate, and includes those in which the ceramic substrate itself has irregularities.

  The ceramic substrate 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 calcined base.

[glaze]
The glaze applied to the ceramic substrate, the composition is SiO ₂ from 60 to 76 mol%, preferably 65 to 74 mol%
Al ₂ O ₃ 4~11 mol%, preferably 5-8 mol%
TiO ₂ 0-10 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.

  This glaze has a high melting point and can favorably color 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 exceeds 10 mol%, the glaze is tinged with yellow, it is difficult to have decorative seeking. A particularly preferred range of TiO ₂ is 0.1-10 mol%, especially 2-5 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.

[Inkjet ink]
As ink-jet paint inks, red, yellow, blue and black inks containing no frit, in which finely pulverized red, yellow, blue and black pigments are dispersed by a dispersant, respectively, are used. In order to make the pigment in the ink sprayed on the unfired glaze layer easily penetrate into the glaze layer, each pigment has a particle size of 5000 nm or less, particularly 50 to 5000 nm, particularly 50 to 1000 nm, more preferably 80 to 500 nm. It is desirable to pulverize so that

  When the average particle diameter of the pigment is 1/3 or less of the average pore diameter of the unfired glaze layer, the pigment particles are sufficiently easy to penetrate into the unfired glaze layer.

A metal oxide pigment is used as the pigment. As the red metal oxide pigment, a chromium oxide-tin oxide pigment is suitable, and particularly Cr ₂ O ₃ 13 to 21 wt%.
SnO ₂ 35~55wt%
SiO ₂ 15~30wt%
CaO 16-30wt%
TiO ₂ 0-8wt%
Are preferred. The chromium oxide-tin oxide pigment is painted on the glaze having the above composition and is baked at a high temperature of about 1140 to 1260 ° C., thereby exhibiting a bright red color.

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

  Note that rutile titanium oxide, uranium oxide, zircon vanadium, zircon praseodymium, and the like can also be used.

  As the blue metal oxide pigment, cobalt oxide, copper oxide, cobalt-alumina, or the like can be used.

  As the black metal oxide pigment, a mixture of iridium oxide, iron oxide, uranium oxide, cobalt oxide, chromium oxide, manganese oxide, chromium iron oxide, and the like can be used.

  In addition, the said pigment is an example and you may use pigments other than the above.

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

  In the present invention, if necessary, a white ink containing a white pigment such as tin oxide may be used.

  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.

  This ink preferably has a viscosity of 50 cp or less, for example 2 to 50 cp, particularly 7 to 20 cp, when painting by inkjet. The surface tension is preferably 60 mN / m or less, for example, 20 to 60 mN / m, particularly 25 to 35 mN / m. Inks having such a viscosity and surface tension tend to penetrate into the unfired glaze layer.

[Printing and firing]
As the nozzle for ink jet, it is preferable to use a small diameter 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.

  The ink sprayed on the unfired glaze layer by this ink jet penetrates into the glaze layer. Since pigment particles are less likely to penetrate than liquid components, they remain at the outermost layer and have a high pigment concentration. The outermost layer means about 30% or less of the glaze layer from the outermost surface of the glaze.

  After the pattern is printed by inkjet, it is dried and fired to obtain a decorated ceramic body. In the case of an interior tile, the firing temperature is preferably 1050 to 1260 ° C, particularly about 1100 to 1200 ° 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.

  By this firing, the ceramic base material is baked and the glaze layer is melted to become a glaze layer, and the pigment is present at the highest concentration on the outermost surface. As a result, the pattern of the decorative ceramic body is clear and the pattern is robust. Moreover, the surface of the eaves layer is smooth.

  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.

[Glue composition]
SiO ₂ 67 mol%
Al ₂ O ₃ 5.5 mol%
K ₂ O 7 mol%
Na ₂ O 1 mol%
Li ₂ O 0 mol%
B ₂ O ₃ 0 mol%
CaO 8 mol%
BaO 4 mol%
ZnO 2 mol%
MgO 0 mol%
SrO 0 mol%
MnO ₃ 0.5 mol%
ZrO ₂ 5 mol%
Fe ₂ O ₃ 0 mol%

  As the ink jet head, a piezo element type head (Konica 318WT) having a nozzle diameter of 40 μm was used, and a color image was printed with blue ink.

[Test 1]
(1) 20 parts of pigment cobalt alumina, 60 parts of water, and 20 parts of a cloud type dispersant were mixed and pulverized and mixed with a bead mill so that the average particle diameter of the pigment was 200 nm. Glycerin and water were added to this ink to produce inks having different viscosities. The concentration of cobalt alumina was adjusted to 12%.
(2) The surface tension adjusting agent dynol was added to the inks having different viscosities prepared in the above (1) to prepare 25 types of inks having different viscosities and surface tensions.
(3) This ink was used to decorate the surface of an unfired glaze layer (average grain size of 4 μm of glaze) using an inkjet head in a band shape, dried, and baked at 1150 ° C. for 60 minutes.
(4) In order to evaluate the adhesion of the decorated part of the baked ceramic, the surface change was observed when the decorated part was rubbed 100 times by hand with a commercially available sand eraser. The results are shown in Table 1.
(5) Similarly, in order to investigate the rise of the decorated part, the border between the decorated part and the undecorated part was rubbed with a fingertip to examine the feel. The results are shown in Table 2.
(6) The difference in gloss of the decorative part was examined visually. The results are shown in Table 3.
(7) From Tables 1 to 3, it can be seen that when inkjet printing is performed on the outermost surface of the ceramic, the viscosity of the ink is preferably 50 cp or less, preferably 40 cp or less, and the surface tension is preferably 60 mN / m or less.

[Test 2]
(1) 20 parts of pigment cobalt alumina, 60 parts of water, and 20 parts of a cloud type dispersant were mixed and pulverized and mixed with a bead mill so that the average particle diameter of the pigment was 150 nm and 250 nm. To this ink, glycerin as a viscosity adjusting agent and dynole as a surface tension adjusting agent were added to prepare an ink having a viscosity of 25 cp and a surface tension of 35 mN / m.
(2) The glaze having the above composition was finely polished with a pot mill while changing the polishing time, and the particle size of the glaze was changed from 100 μm to 5 μm. This glaze was glazed on unglazed ceramics to produce a printed base (glaze surface before firing). In addition, the pore size distribution on the glazed surface before firing was measured to determine the average pore size. The ink produced in (1) above was printed on this base with an inkjet head, and the adhesion, smoothness, and gloss were evaluated in the same manner as in Test 1. The results are shown in Tables 4-6.
(3) From Tables 4 to 6, it is recognized that the ink pigment particle diameter is preferably 1/3 or less of the average pore diameter of the pre-firing glaze.

[Test 3]
(1) Preparation of each color ink
20 parts of pigment cobalt alumina, 60 parts of water, and 20 parts of a cloud-type dispersant were mixed and pulverized and mixed with a bead mill so that the average particle diameter of the pigment was 150 nm. To this ink, glycerin as a viscosity adjusting agent and dynole as a surface tension adjusting agent were added to produce a blue ink having a viscosity of 25 cp, a surface tension of 35 mN / m, and a cobalt alumina concentration of 12%.

  20 parts of chromium tin pigment, 60 parts of water, and 20 parts of an anionic dispersant were mixed and pulverized and mixed with a bead mill so that the average particle diameter of the pigment was 150 nm. To this ink, glycerin as a viscosity adjusting agent and dynole as a surface tension adjusting agent were added to prepare a red ink having a viscosity of 25 cp, a surface tension of 35 mN / m, and a chromium tin pigment concentration of 12%.

  20 parts of titanium chrome antimony pigment, 60 parts of water, and 20 parts of an anionic dispersant were mixed and pulverized and mixed with a bead mill so that the average particle diameter of the pigment was 150 nm. To this ink, glycerin as a viscosity adjusting agent and dynole as a surface tension adjusting agent were added to prepare a yellow ink having a viscosity of 25 cp, a surface tension of 35 mN / m, and a titanium chromium antimony concentration of 12%.

  20 parts of chromium iron pigment, 60 parts of water and 20 parts of an anionic dispersant were mixed and pulverized and mixed with a bead mill so that the average particle size of the pigment was 150 nm. To this ink, glycerin as a viscosity adjusting agent and dynole as a surface tension adjusting agent were added to prepare a black ink having a viscosity of 25 cp, a surface tension of 35 mN / m, and a chromium iron pigment concentration of 12%.

(2) Preparation of each color ink decoration sample
This blue ink is decorated in a band shape on the surface of an unfired glaze layer (average particle size of 4 μm of glaze) using an inkjet head, dried, and then baked at 1150 ° C. for 60 minutes to obtain a blue ink decorated sample. Produced.

  Similarly, for the red ink, yellow ink and black ink, an ink jet head is used to decorate the surface of the unfired glaze layer (average grain size of the glaze 4 μm) in a strip shape, and after drying, at 1150 ° C. for 60 minutes. It baked and produced the red ink decoration sample, the yellow ink decoration sample, and the black ink decoration sample.

  Each of the above decorative samples was cut with a diamond cutter in the tile thickness direction, then immersed in distilled water and subjected to ultrasonic cleaning for 5 minutes. Then, the cut surface of the decorative sample was grind | polished using the 2000th alumina particle as an abrasive | polishing agent. Next, the decorative sample was fixed with an embedding resin, and carbon was deposited on the cut surface.

(3) EPMA surface analysis and reflection electron composition imaging
Each of the above four types of decorative samples was set in an EPMA apparatus (“JXA-8800RL” manufactured by JEOL), and the element was analyzed by EPMA on the cut surface under the following analysis conditions. A reflected electron composition image of the cut surface was taken.

Acceleration voltage: 15 kV
Irradiation current: 50 nA
Analysis area: 500 μm square Measurement time: 80 ms
Number of pixels: 250 × 250
Pixel size: 2μm square

  The elements subjected to surface analysis are as follows. In parentheses are the types of spectral crystals used for elemental analysis.

Blue ink decorative sample: Co (LiFH)
Red ink decoration sample: Sn (PETH)
Yellow ink decorative sample: Ti (PETJ)
Black ink decorative sample: Fe (LiFH)

  The results are shown in FIGS. FIG. 1 shows the result of the blue ink decoration sample, FIG. 2 shows the result of the red ink decoration sample, FIG. 3 shows the result of the yellow ink decoration sample, and FIG. 4 shows the result of the black ink decoration sample.

(4) EPMA surface analysis and backscattered electron composition image (enlarged observation)
About the above-mentioned red ink decoration sample, yellow ink decoration sample, and black ink decoration sample (except for the blue ink decoration sample), the surface vicinity of the glaze layer was analyzed in more detail.

  That is, except for the vicinity of the surface of the glaze layer of the above three types of decorative samples, the analysis region was reduced to 100 μm square, the pixel size was reduced to 0.4 μm square, and the types of elements to be analyzed were increased as follows. EPMA surface analysis was performed in the same manner as in FIGS. In addition, a reflected electron composition image was taken for the analysis surface. Specifically, the analysis conditions and the elements subjected to surface analysis are as follows. In parentheses are the types of spectral crystals used for elemental analysis.

Acceleration voltage: 15 kV
Irradiation current: 50 nA
Analysis area: 100 μm square Measurement time: 80 ms
Number of pixels: 250 × 250
Pixel size: 0.4 μm square Red ink decoration sample: Sn (PETH), Cr (PETJ)
Yellow ink decorative sample: Ti (PETJ), Sb (PETH), Cr (PETJ)
Black ink decorative sample: Fe (LiFH), Mn (PETJ), Co (LiF)

  The results are shown in FIGS. FIG. 5 shows the result of the red ink decorated sample, FIG. 6 shows the result of the yellow ink decorated sample, and FIG. 7 shows the result of the black ink decorated sample.

(5) Summary of results As is clear from FIGS. 1 to 7, the surface of the glaze layer was a flat surface, and the surface was not uneven.

  Moreover, as is apparent from FIGS. 1 to 7, each element contained in the pigment was present at a high concentration on the surface side of the glaze layer. Thus, when each element in the pigment is present at a high concentration on the surface side of the glaze layer, it is possible to apply a clear pattern with a small amount of pigment.

  In particular, as shown in FIG. 1, the Co element contained in the pigment of the blue ink was present at a very high concentration in a region very close to the surface from the surface of the glaze layer to about 30 μm. Further, as shown in FIGS. 4 and 7, Co, Fe, and Mn elements contained in the pigment of the black ink were present at a very high concentration in a region close to the surface from the surface of the glaze layer to about 50 μm.

(A) is a reflected-electron image of the cut surface of a blue ink decoration sample, (b) is drawing which shows the EPMA surface analysis result of Co element about the area | region of (a). (A) is a reflected electron image of the cut surface of a red ink decoration sample, (b) is drawing which shows the EPMA surface analysis result of Sn element about the area | region of (a). (A) is a reflected-electron image of the cut surface of a yellow ink decoration sample, (b) is drawing which shows the EPMA surface analysis result of Ti element about the area | region of (a). (A) is a reflected-electron image of the cut surface of a black ink decoration sample, (b) is drawing which shows the EPMA surface analysis result of Fe element about the area | region of (a). (A) is a backscattered electron image in the vicinity of the surface of the cut surface in FIG. 2, (b) is a drawing showing an EPMA surface analysis result of Sn element in the region (a), and (c) is in the region (a). It is drawing which shows the EPMA surface analysis result of Cr element. (A) is a reflected electron image near the surface of the cut surface of FIG. 3, (b) is a drawing showing the results of EPMA surface analysis of Ti element for the region (a), (c) is for the region (a). Drawing which shows the EPMA surface analysis result of Sb element, (d) is a figure which shows the EPMA surface analysis result of Cr element about the area | region of (a). 4A is a reflected electron image near the surface of the cut surface in FIG. 4, FIG. 4B is a drawing showing an EPMA surface analysis result of Fe element in the region (a), and FIG. Drawing which shows the EPMA surface analysis result of Mn element, (d) is a figure which shows the EPMA surface analysis result of Co element about the area | region of (a).

Claims (4)

A decorative ceramic body provided with a cocoon layer on the surface of a ceramic substrate, wherein the surface of the cocoon layer is painted,
The surface of the soot layer is flat;
The decorative ceramic body, wherein the pigment showing the pattern is present in the cocoon layer and the concentration of the pigment is highest in the outermost layer of the cocoon layer. In a method for producing a decorated ceramic body in which a glaze is applied to the surface of a ceramic substrate, and the ink is printed by ink jet printing using an ink containing a pigment on the surface of the glaze, the ink is mixed with frit. Not frit-free ink,
A method for producing a decorated ceramic body, wherein the pigment has a particle size of 5000 nm or less.   3. The method for producing a decorated ceramic body according to claim 2, wherein the viscosity of the ink when painting is 50 cp or less and the surface tension is 60 mN / m or less. In an inkjet ink containing a pigment for painting on a ceramic substrate,
It is a frit-free ink that does not contain frit,
An ink-jet ink, wherein the pigment has a particle size of 5000 nm or less.

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