JP2007284279A - Decorated ceramic article, method for manufacturing the same, and ink for inkjet - Google Patents
Decorated ceramic article, method for manufacturing the same, and ink for inkjet Download PDFInfo
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- JP2007284279A JP2007284279A JP2006112253A JP2006112253A JP2007284279A JP 2007284279 A JP2007284279 A JP 2007284279A JP 2006112253 A JP2006112253 A JP 2006112253A JP 2006112253 A JP2006112253 A JP 2006112253A JP 2007284279 A JP2007284279 A JP 2007284279A
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- 239000000919 ceramic Substances 0.000 title claims abstract description 54
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 238000000034 method Methods 0.000 title description 6
- 239000000049 pigment Substances 0.000 claims abstract description 68
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 18
- 239000001054 red pigment Substances 0.000 claims abstract description 17
- 239000001052 yellow pigment Substances 0.000 claims abstract description 15
- 239000000758 substrate Substances 0.000 claims abstract description 13
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 15
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 15
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 13
- DEEQPZOJZBJNDS-UHFFFAOYSA-N [Sn+2]=O.[O-2].[Cr+3] Chemical group [Sn+2]=O.[O-2].[Cr+3] DEEQPZOJZBJNDS-UHFFFAOYSA-N 0.000 claims description 12
- 238000010422 painting Methods 0.000 claims description 11
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 9
- PPTDTVLYNDRFAJ-UHFFFAOYSA-N [O-2].[Cr+3].[Sb+]=O.[O-2].[Ti+4] Chemical group [O-2].[Cr+3].[Sb+]=O.[O-2].[Ti+4] PPTDTVLYNDRFAJ-UHFFFAOYSA-N 0.000 claims description 9
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 8
- 239000011651 chromium Substances 0.000 claims description 6
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 14
- 150000004706 metal oxides Chemical class 0.000 abstract description 14
- 238000011161 development Methods 0.000 abstract description 11
- 239000000976 ink Substances 0.000 description 29
- 238000010304 firing Methods 0.000 description 14
- 239000002585 base Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 230000004907 flux Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical class CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical group O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- SKTFKNNJBFAECB-UHFFFAOYSA-N [O-2].[Cr+3].[Sb+]=O.[O-2] Chemical compound [O-2].[Cr+3].[Sb+]=O.[O-2] SKTFKNNJBFAECB-UHFFFAOYSA-N 0.000 description 2
- -1 alkylsulfosuccinate Polymers 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 description 2
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000518 rheometry Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- FGKLYHIORJGOGA-UHFFFAOYSA-N C(C)OCCCCOOOCCCCOCC Chemical compound C(C)OCCCCOOOCCCCOCC FGKLYHIORJGOGA-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 241000047703 Nonion Species 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- WZECUPJJEIXUKY-UHFFFAOYSA-N [O-2].[O-2].[O-2].[U+6] Chemical compound [O-2].[O-2].[O-2].[U+6] WZECUPJJEIXUKY-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000010296 bead milling Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- HEQBUZNAOJCRSL-UHFFFAOYSA-N iron(ii) chromite Chemical compound [O-2].[O-2].[O-2].[Cr+3].[Fe+3] HEQBUZNAOJCRSL-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910000439 uranium oxide Inorganic materials 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
Images
Abstract
Description
本発明は加飾セラミック体、その製造方法及びインクジェット用インクに関するものであり、特に赤色系顔料及び／又は黄色系顔料を用いた絵付けが施された加飾セラミック体と、その製造方法と、この製造に用いられるインクジェット用インクに関するものである。 The present invention relates to a decorative ceramic body, a method for producing the same, and an ink jet ink, and in particular, a decorated ceramic body to which a painting using a red pigment and / or a yellow pigment is applied, and a method for producing the same. The present invention relates to an ink-jet ink used in this production.
タイル等のセラミック基材にインクジェット法によって絵付けを行うことが種々研究されている。しかしながらインクジェット法による高解像度の加飾を焼き付ける場合、「４原色が得られにくい」、「顔料を微細化するため発色が著しく低下する」、「発色を良くするために１０００℃以下低温焼き付けが必要となり、焼成回数が増え生産性に劣る」、「赤発色に金顔料を使うため高価」といった問題がある。 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 coloring ”.
特開２００５−３５０３２７号公報には、セラミック基材の表面に赤色系顔料による絵付けが施された釉薬層が形成されている加飾セラミック体において、該釉薬の組成が
ＳｉＯ２ ６０〜７６モル％
Ａｌ２Ｏ３ ４〜１１モル％
Ｋ２Ｏ ４〜１０モル％
Ｎａ２Ｏ ０．５〜５モル％
Ｌｉ２Ｏ ０〜０．５モル％
Ｂ２Ｏ３ ０〜２モル％
ＣａＯ ４〜１０モル％
ＢａＯ ０〜６モル％
ＺｎＯ ０〜５モル％
ＭｇＯ ０〜２モル％
ＳｒＯ ０〜１モル％
ＭｎＯ３ ０〜０．６モル％
ＺｒＯ２ ０〜６モル％
Ｆｅ２Ｏ３ ０〜０．１５モル％
であり、前記赤色系顔料は粒径５００ｎｍ以下の酸化クロム・酸化スズ系酸化物顔料であることを特徴とする加飾セラミック体が記載されている。
Japanese Patent Application Laid-Open No. 2005-350327 discloses a decorative ceramic body in which a glaze layer is formed on a surface of a ceramic substrate and is painted with a red pigment, and the composition of the glaze is SiO 2 60 to 76 mol. %
Al 2
K 2
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%
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.
この釉薬層は１１９０℃以上の高温で焼成される場合でも、金属酸化物顔料を劣化させることがない。 Even when this glaze layer is fired at a high temperature of 1190 ° C. or higher, the metal oxide pigment is not deteriorated.
また、この金属酸化物顔料を粒径５００ｎｍ以下に微粉砕した場合でも、上記組成の釉薬層は焼成時に金属酸化物顔料を劣化させない。 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.
この結果、釉薬として高融点のものを用いることが可能となり、例えば１１４０〜１２６０℃での焼成が可能となり、釉薬層の耐久性が向上する。 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.
また、平均粒径５００ｎｍ以下に微粉砕した顔料を用いることにより、インクジェットによって高解像度の絵柄を描画することができる。
本発明は、上記特開２００５−３５０３２７号公報の加飾セラミック体よりもさらに一段と発色性が向上した加飾セラミック体と、そのためのインクジェット用インクとを提供することを目的とする。 An object of the present invention is to provide a decorative ceramic body having further improved color developability as compared with the decorative ceramic body of JP-A-2005-350327, and an ink jet ink therefor.
本発明（請求項１）の加飾セラミック体は、セラミック基材の表面にインクジェットによる赤色系顔料による絵付けが施された釉薬層が成形されている加飾セラミック体において、釉薬組成中に酸化チタンが０．１〜１０モル％含まれ、赤色系顔料が平均粒径５００ｎｍ以下の酸化クロム−酸化錫系顔料であることを特徴とするものである。 The decorative ceramic body of the present invention (invention 1) is a decorative ceramic body in which a glaze layer is formed on the surface of a ceramic substrate and is painted with a red pigment by ink jet. Titanium is contained in an amount of 0.1 to 10 mol%, and the red pigment is a chromium oxide-tin oxide pigment having an average particle diameter of 500 nm or less.
本発明（請求項２）の加飾セラミック体は、セラミック基材の表面にインクジェットによる黄色系顔料による絵付けが施された釉薬層が成形されている加飾セラミック体において、釉薬組成中に酸化チタンが０．１〜１０モル％含まれ、黄色系顔料が平均粒径５００ｎｍ以下の酸化チタン−酸化クロム−酸化アンチモン系顔料であることを特徴とするものである。 The decorative ceramic body of the present invention (Claim 2) is a decorative ceramic body in which a glaze layer is formed on the surface of a ceramic substrate and is painted with a yellow pigment by ink jet. Titanium is contained in an amount of 0.1 to 10 mol%, and the yellow pigment is a titanium oxide-chromium oxide-antimony oxide pigment having an average particle size of 500 nm or less.
本発明（請求項３）の加飾セラミック体は、セラミック基材の表面にインクジェットによる赤色系顔料および黄色系顔料による絵付けが施された釉薬層が成形されている加飾セラミック体において、釉薬組成中に酸化チタンが０．１〜１０モル％含まれ、赤色系顔料が、平均粒径５００ｎｍ以下の酸化クロム−酸化錫系顔料であり、黄色系顔料が、平均粒径５００ｎｍ以下の酸化チタン−酸化クロム−酸化アンチモン系顔料であることを特徴とするものである。 The decorative ceramic body of the present invention (Claim 3) is a decorative ceramic body in which a glaze layer formed by painting with a red pigment and a yellow pigment by ink jet is formed on the surface of a ceramic substrate. The composition contains 0.1 to 10 mol% of titanium oxide, the red pigment is a chromium oxide-tin oxide pigment having an average particle size of 500 nm or less, and the yellow pigment is titanium oxide having an average particle size of 500 nm or less. -A chromium oxide-antimony oxide pigment.
請求項４の加飾セラミック体は、請求項１又は３において、酸化クロム−酸化錫系顔料がＣｒ２Ｏ３１３〜２１ｗｔ％、ＳｎＯ２３５〜５５ｗｔ％、ＳｉＯ２１５〜３０ｗｔ％、ＣａＯ１６〜３０ｗｔ％、ＴｉＯ２０〜８ｗｔ％を含有することを特徴とするものである。
Decorative ceramic body according to
請求項５の加飾セラミック体は、請求項２又は３において、酸化チタン−酸化クロム−酸化アンチモン系顔料がＴｉＯ２７５〜９５ｗｔ％、Ｃｒ２Ｏ３１〜５ｗｔ％、Ｓｂ２Ｏ３３〜１０ｗｔ％を含有することを特徴とするものである。
The decorated ceramic body according to claim 5 is the ceramic body according to
請求項６の加飾セラミック体は、請求項１ないし５のいずれか１項において、該釉薬の組成が
ＳｉＯ２ ６０〜７６モル％
Ａｌ２Ｏ３ ４〜１１モル％
ＴｉＯ２ ０．１〜１０モル％
Ｋ２Ｏ ４〜１０モル％
Ｎａ２Ｏ ０．５〜５モル％
Ｌｉ２Ｏ ０〜０．５モル％
Ｂ２Ｏ３ ０〜７モル％
ＣａＯ ４〜１０モル％
ＢａＯ ０〜６モル％
ＺｎＯ ０〜５モル％
ＭｇＯ ０〜２モル％
ＳｒＯ ０〜１モル％
ＭｎＯ３ ０〜０．６モル％
ＺｒＯ２ ０〜６モル％
Ｆｅ２Ｏ３ ０〜０．１５モル％
であることを特徴とするものである。
The decorative ceramic body according to
Al 2
TiO 2 0.1-10 mol%
K 2
Na 2 O 0.5 to 5 mol%
Li 2 O 0~0.5 mol%
B 2 O 3 0 to 7 mol%
CaO 4-10 mol%
BaO 0-6 mol%
ZnO 0-5 mol%
MgO 0-2 mol%
MnO 3 0-0.6 mol%
ZrO 2 0-6 mol%
Fe 2 O 3 0 to 0.15 mol%
It is characterized by being.
本発明（請求項７）のインクジェット用インクは、基材表面に釉薬層が成形されているセラミック体に絵付けするためのインクジェット用インクにおいて、酸化チタンを１〜２０ｗｔ％含有すると共に、赤色系顔料として、平均粒径５００ｎｍ以下の酸化クロム−酸化錫系顔料を含有することを特徴とするものである。 The ink-jet ink of the present invention (invention 7) is an ink-jet ink for painting on a ceramic body having a glaze layer formed on the substrate surface. The pigment contains a chromium oxide-tin oxide pigment having an average particle diameter of 500 nm or less.
本発明（請求項８）のインクジェット用インクは、基材表面に釉薬層が成形されているセラミック体に絵付けするためのインクジェット用インクにおいて、酸化チタンを１〜２０ｗｔ％含有すると共に、黄色系顔料として、平均粒径５００ｎｍ以下の酸化チタン−酸化クロム−酸化アンチモン系顔料を含有することを特徴とするものである。 The ink-jet ink of the present invention (invention 8) is an ink-jet ink for painting on a ceramic body having a glaze layer formed on the surface of a base material. The pigment contains a titanium oxide-chromium oxide-antimony oxide pigment having an average particle diameter of 500 nm or less.
本発明（請求項９）の加飾セラミック体の製造方法は、セラミック基材の上に釉掛けして未焼成の釉薬層を形成し、その上に赤色系及び／又は黄色系顔料を含むインクジェット用インクによる絵付けを施し、その後焼成して釉薬層を溶融させて加飾セラミック体を製造する方法において、該釉薬の組成が
ＳｉＯ２ ６０〜７６モル％
Ａｌ２Ｏ３ ４〜１１モル％
ＴｉＯ２ ０．１〜１０モル％
Ｋ２Ｏ ４〜１０モル％
Ｎａ２Ｏ ０．５〜５モル％
Ｌｉ２Ｏ ０〜０．５モル％
Ｂ２Ｏ３ ０〜７モル％
ＣａＯ ４〜１０モル％
ＢａＯ ０〜６モル％
ＺｎＯ ０〜５モル％
ＭｇＯ ０〜２モル％
ＳｒＯ ０〜１モル％
ＭｎＯ３ ０〜０．６モル％
ＺｒＯ２ ０〜６モル％
Ｆｅ２Ｏ３ ０〜０．１５モル％
であり、前記インクジェット用インクは請求項７及び／又は８に記載のインクジェット用インクであることを特徴とするものである。
The method for producing a decorated ceramic body according to the present invention (Claim 9) is an inkjet including a red base and / or a yellow base pigment formed on a ceramic base material to form an unfired glaze layer. In the method for producing a decorated ceramic body by painting with an ink for ink and then firing to melt the glaze layer, the composition of the glaze is SiO 2 60-76 mol%
Al 2
TiO 2 0.1-10 mol%
K 2
Na 2 O 0.5 to 5 mol%
Li 2 O 0~0.5 mol%
B 2 O 3 0 to 7 mol%
CaO 4-10 mol%
BaO 0-6 mol%
ZnO 0-5 mol%
MgO 0-2 mol%
MnO 3 0-0.6 mol%
ZrO 2 0-6 mol%
Fe 2 O 3 0 to 0.15 mol%
The ink-jet ink is the ink-jet ink according to claim 7 and / or 8.
一般に、インクジェット加飾用に微細磨した、酸化クロム−酸化錫系顔料及び酸化チタン−酸化クロム−酸化アンチモン系顔料は、加飾された釉薬面で釉薬中のアルカリなどにより分解作用を受け発色が劣化する。これに対し、本発明では、釉薬中に酸化チタンが含有されている。この酸化チタンにより、上記の顔料分解作用が抑制され、酸化クロム−酸化錫系顔料の赤の発色及び酸化チタン−酸化クロム−酸化アンチモン系顔料の黄の発色が向上する。 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. On the other hand, in the present invention, titanium oxide is contained in the glaze. The titanium oxide suppresses the above-described pigment decomposition action, and improves the red color of the chromium oxide-tin oxide pigment and the yellow color of the titanium oxide-chromium oxide-antimony oxide pigment.
特に、請求項６，９の酸化チタン含有組成の釉によると、上記の顔料分解作用が十分に抑制される。
In particular, according to the soot having a titanium oxide-containing composition according to
これは、釉薬中のアルカリ成分による顔料の分解作用のうち、アルカリ成分が顔料中の酸化チタンと反応して脱色する分解作用が、釉薬中の酸化チタンによって阻害されるためであると考えられる。 This is considered to be because, among the decomposition actions of the pigment by the alkali component in the glaze, the decomposition action in which the alkali component reacts with the titanium oxide in the pigment and decolorizes is inhibited by the titanium oxide in the glaze.
以下、本発明についてさらに詳細に説明する。本発明の加飾セラミック体及びその製造方法においては、釉薬として組成が
ＳｉＯ２ ６０〜７６モル％好ましくは６５〜７４モル％
Ａｌ２Ｏ３ ４〜１１モル％好ましくは５〜８モル％
ＴｉＯ２ ０．１〜１０モル％好ましくは２〜５モル％
Ｋ２Ｏ ４〜１０モル％好ましくは４〜９モル％
Ｎａ２Ｏ ０．５〜５モル％好ましくは０．６〜３モル％
Ｌｉ２Ｏ ０〜０．５モル％好ましくは０〜０．２モル％
Ｂ２Ｏ３ ０〜７モル％好ましくは０．０５〜１．６モル％
ＣａＯ ４〜１０モル％好ましくは４〜９モル％
ＢａＯ ０〜６モル％好ましくは０〜５モル％
ＺｎＯ ０〜５モル％好ましくは０〜４モル％
ＳｒＯ ０〜１モル％好ましくは０〜０．５モル％
ＭｇＯ ０〜２モル％好ましくは０〜１モル％
ＭｎＯ３ ０〜０．６モル％好ましくは０〜０．５モル％
ＺｒＯ２ ０〜６モル％好ましくは０〜５モル％
Ｆｅ２Ｏ３ ０〜０．１５モル％好ましくは０〜０．１モル％
であるものを用いる。
Hereinafter, the present invention will be described in more detail. In the decorative ceramic body and the method for producing the same according to the present invention, the composition as a glaze is SiO 2 60 to 76 mol%, preferably 65 to 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%
Use what is.
この釉薬は、融点が高く、しかも青、黄、黒のみならず赤色系の金属酸化物顔料に対しても良好に発色させることが見出された。 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.
この釉薬の組成特定理由は次の通りである。 The reason for specifying the composition of this glaze is as follows.
ＳｉＯ２は釉薬を焼成することにより生成するガラス中の珪酸塩のネットワークを構成する成分である。ＳｉＯ２が６０モル％未満であると、焼成されて生じた釉薬面の光沢が乏しくなり、また７６モル％超では釉薬の融点が過度に高くなる。このため、ＳｉＯ２の配合量は６０〜７６モル％好ましくは６５〜７４モル％とする。 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%.
Ａｌ２Ｏ３は、焼成されて生じた釉薬層の耐薬品性及び耐水性を高めるための成分である。Ａｌ２Ｏ３が４モル％未満であるとこの釉薬層の耐薬品性及び耐水性が低下し、１１モル％超の場合、釉薬の耐火度が過度に高くなる。従って、Ａｌ２Ｏ３は４〜１１モル％好ましくは５〜８モル％配合する。 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%.
ＴｉＯ２は、釉薬中のアルカリ成分が顔料に与える分解脱色作用を緩和する作用を有する。ＴｉＯ２が０．１モル％よりも少ないと、この脱色抑制作用が不足する。一方、ＴｉＯ２が１０モル％を超えると、釉薬が黄色を帯びるため、求める加飾がしにくくなる。特に好ましいＴｉＯ２の範囲は２〜５モル％である。 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%.
Ｋ２Ｏ及びＮａ２Ｏはいずれもフラックス作用を有するものである。Ｋ２Ｏが４モル％未満であると、またＮａ２Ｏが０．５モル％未満であると、釉薬の融点が過度に高くなる。また、Ｋ２Ｏが１０モル％超、Ｎａ２Ｏが９モル％超であると、溶融している釉薬（ガラス）が金属酸化物顔料を溶解させて顔料の発色を阻害するため、Ｋ２Ｏの配合量は４〜１０モル％好ましくは４〜９モル％とし、Ｎａ２Ｏの配合量は０．５〜５モル％好ましくは０．６〜３モル％とする。
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,
Ｌｉ２Ｏもフラックス作用があるので、添加してもよいが、発色阻害作用が強いので、０．５モル％以下好ましくは０．２モル％以下とする。 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.
Ｂ２Ｏ３もフラックス作用があるので、添加してもよいが、過剰に添加すると、金属酸化物顔料を溶解させて顔料の発色を阻害するため、７モル％以下、好ましくは０．０５〜１．６モル％とする。 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及びＢａＯは、適量配合された場合に釉薬の融点を低下させる作用があり、ＣａＯは４〜１０モル％好ましくは４〜９モル％配合され、ＢａＯは０〜６モル％好ましくは０〜５モル％配合される。ＣａＯ及びＢａＯの配合量が上記範囲を外れると、釉薬の融点が高くなる。 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. Mol% is blended. When the compounding amount of CaO and BaO is out of the above range, the melting point of the glaze increases.
ＺｎＯ、ＭｇＯ及びＳｒＯは、いずれも少量添加された場合にはフラックス作用を有するので配合してもよいが、ＺｎＯの配合量が５モル％超、ＭｇＯの配合量が２モル％超、ＳｒＯの配合量が１モル％超であると金属酸化物顔料の発色を阻害するので、ＺｎＯは０〜５モル％好ましくは０〜４モル％とし、ＳｒＯは０〜１モル％好ましくは０〜０．５モル％とし、ＭｇＯは０〜２モル％好ましくは０〜１モル％とする。 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%.
ＭｎＯ３は、微量配合することにより焼成後の釉薬表面に光沢を与えるため配合してもよいが、０．６モル％超になると金属酸化物顔料の発色を阻害するので、０．６モル％以下好ましくは０．５モル％以下とする。 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.
ＺｒＯ２は、少量配合した場合には、焼成後の釉薬に乳白を生じさせ、これにより顔料の発色を彩やかなものとする作用を発揮するが、５モル％超配合すると、釉薬の耐火度（融点）が高くなり、また焼成された釉薬にピンホール状の欠陥が生じ易くなるので、５モル％以下好ましくは４モル％以下とする。 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, but when blended in excess of 5 mol%, the fire resistance of the glaze 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.
なお、ＳｎＯも、ＺｒＯ２と同様の理由により、５モル％以下、特に４モル％以下配合してもよい。 Incidentally, SnO also, for the same reason as the ZrO 2, 5 mol% or less, may be added, especially 4 mol% or less.
Ｆｅ２Ｏ３は、釉薬自体を黄色ないし褐色にするため、０．１５モル％以下、好ましくは０．１モル％以下とする。 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.
本発明の加飾セラミック体を製造するには、好ましくは、セラミック基材の表面に上記組成の釉薬を幕掛け等の手法により層状に均一厚さに塗着させ、乾燥させて印刷下地を形成した後、インクジェットにより絵付けを行う。施釉した後に顔料を施すことによってレオロジー調整後でも高濃度に顔料を含む釉薬を得ることができ、絵付け後彩やかな発色を得ることが可能である。なお、インクジェットノズルから滴下するためには、釉薬をある一定の粘度にしなければならないが、釉薬と顔料を混ぜて用いると、その粘度にするためかなり薄めなくてはならず、顔料濃度が低くなる。 In order to produce the decorated ceramic body of the present invention, preferably, the glaze of the above composition is applied to the surface of the ceramic base material in a layered manner by a technique such as curtaining and dried to form a printing base. After that, painting is performed by inkjet. By applying the pigment after glazing, a glaze containing the pigment at a high concentration can be obtained even after rheology adjustment, and it is possible to obtain a colorful color after painting. 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. .
これに対し、釉薬と顔料を別々にしておく場合には、最小限薄めるだけでよく、釉薬の顔料濃度を高くすることができる。 On the other hand, when the glaze and the pigment are kept separate, it is only necessary to make the thinning minimum, and the pigment concentration of the glaze can be increased.
セラミック基材は、焼成されていない生素地であってもよく、仮焼されたものであってもよいが、内装用タイルの場合、生素地であることが望ましい。 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.
インクジェット用の絵の具インクとしては、微粉砕された赤、黄、青及び黒の各顔料をそれぞれ分散剤によって分散させた赤、黄、青及び黒のインクを用いる。インクジェットにより鮮明な像を印刷するために、各顔料は、粒径が５００ｎｍ以下特に１００〜４００ｎｍとなるように微粉砕されることが望ましい。 As ink-jet paint inks, red, yellow, blue and black inks are used in which finely pulverized red, yellow, blue and black pigments are dispersed by a dispersant. In order to print a clear image by inkjet, it is desirable that each pigment is finely pulverized so that the particle diameter is 500 nm or less, particularly 100 to 400 nm.
分散剤としては、アニオン、カチオン、ノニオン及び両性の界面活性剤いずれかを適宜選択して使用できる。例えばポリカルボン酸塩、アクリル酸塩、ドデシルベンゼンスルホン酸塩、アルキルスルホコハク酸塩、ポリオキシエチレンアルキルエーテルなどを用いることが望ましい。インクには、その他、必要に応じ、グリセリン、ポリエチレングリコールなど多価アルコール類、メタノール、エタノールなどエタノール類、エトキシブトキシエーテルのエーテル類などの各種水溶性有機溶媒、ドデシルベンゼンスルホン酸塩などの各種界面活性剤などを添加し、湿潤性、粘性、表面張力などのレオロジーを調整する。 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.
顔料としては、金属酸化物系顔料を用いる。赤色用の金属酸化物系顔料としては、酸化クロム−酸化スズ系顔料が好適であり、特に
Ｃｒ２Ｏ３ １３〜２１ｗｔ％
ＳｎＯ２ ３５〜５５ｗｔ％
ＳｉＯ２ １５〜３０ｗｔ％
ＣａＯ １６〜３０ｗｔ％
ＴｉＯ２ ０〜８ｗｔ％
であるものが好適である。この酸化クロム−酸化スズ系顔料は、上記組成の釉薬上に塗着されて約１１４０〜１２６０℃程度の高温で焼成されることにより、彩やかな赤色を呈する。
A metal oxide pigment is used as the pigment. As the metal oxide pigment for red, 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. This 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. to give a bright red color.
黄色用金属酸化物顔料としては、酸化クロム−酸化アンチモン系顔料が好適であり、特に
Ｃｒ２Ｏ３ １〜５ｗｔ％
Ｓｂ２Ｏ３ ３〜１０ｗｔ％
ＳｉＯ２ ０〜１０ｗｔ％
ＴｉＯ２ ７５〜９５ｗｔ％
であるものが好適である。
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.
青色用金属酸化物顔料としては、酸化コバルト、酸化銅、コバルト・アルミナなどを用いることができる。 As the blue metal oxide pigment, cobalt oxide, copper oxide, cobalt-alumina, or the like can be used.
黒色用金属酸化物顔料としては、酸化イリジウム、酸化鉄、酸化ウラニウム、酸化コバルト、酸化クロム、酸化マンガン、クロム鉄酸化物などの混合物を用いることができる。 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.
なお、上記顔料は一例であり、上記以外の顔料を用いてもよい。 In addition, the said pigment is an example and you may use pigments other than the above.
本発明では、このインクに酸化チタンを１〜２０ｗｔ％特に１０〜２０ｗｔ％添加してもよい。これにより、インク中の顔料が焼成工程において受ける脱色作用をさらに抑制することができる。 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 | action which the pigment in ink receives in a baking process can further be suppressed.
本発明では、必要に応じ、酸化スズ等の白色顔料を含む白色用インクを用いてもよい。 In the present invention, if necessary, a white ink containing a white pigment such as tin oxide may be used.
インク用のノズルとしては、ノズル径が８０μｍ以下特に５０μｍ以下、例えば３０〜５０μｍ以下の細径ノズルを用いるのが好ましく、これにより極めて繊細な像をインクジェット印刷することができる。 As the nozzle for ink, 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 ink-jet printed.
インクジェット等により絵柄を印刷した後、乾燥し、焼成して加飾セラミック体とする。内装用タイルの場合、焼成温度は１１４０〜１２６０℃特に１１５０〜１２５０℃程度が好適である。焼成にはローラーハースキルン、トンネル窯などを用いる。ローラーハースキルンの場合、炉の入口から出口までの炉内滞留時間は２０〜１００分特に２０〜６０分程度が好適である。 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.
以下、実施例及び比較例について説明する。 Hereinafter, examples and comparative examples will be described.
なお、以下の実施例及び比較例においては陶石、粘土等を主原料とした内装用タイルの生素地成形体上に幕掛け法により表１に示す下地用釉薬を掛け、乾燥後、インクジェットにより絵付けし、乾燥させた後、ローラーハースキルンにて焼成して１辺が２００ｍｍの内装用タイルを製造した。 In the following examples and comparative examples, the base glaze shown in Table 1 is applied by the curtain method on the green raw material of the interior tile mainly made of ceramic stone, clay, etc., and after drying, by inkjet After painting and drying, an interior tile having a side of 200 mm was manufactured by firing with a roller hearth kiln.
インクジェットヘッドとしては、ノズル径４０μｍ、ピエゾ素子方式のヘッド（コニカ３１８ＷＴ）を使用し、赤、黄の各色のインクによりカラー画像を印刷した。 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 red and yellow inks.
赤、黄インクとしては、各色の顔料（粉体）を購入し、水に分散させて調製したものを用いた。赤顔料としては日研（株）のＳｎ−Ｓｉ−Ｃａ−Ｃｒ−Ｔｉ系酸化物顔料ＴＧ１００６−１、黄顔料としては日研（株）のＴｉ−Ｃｒ−Ｓｂ系酸化物顔料Ｇ４５を採用した。これらの赤、黄顔料粉体１０重量部に対し分散剤１〜４重量部、水３５〜５５重量部、その他に乾燥防止剤３２〜５２重量部、表面張力調整のため界面活性剤を添加したものをビーズミルにて細磨及び分散させて水系分散物とした。各水系分散物中の顔料の平均粒径（Ｄ５０）は、赤：１５５ｎｍ、黄：１５０ｎｍである。 As red and yellow inks, pigments (powder) of each color were purchased and prepared by dispersing in water. Niken Co., Ltd. Sn-Si-Ca-Cr-Ti oxide pigment TG1006-1 was used as the red pigment, and Niken Co. Ti-Cr-Sb oxide pigment G45 was used as the yellow pigment. . 1 to 4 parts by weight of a dispersant, 35 to 55 parts by weight of water, and 32 to 52 parts by weight of a drying inhibitor and a surfactant for adjusting the surface tension were added to 10 parts by weight of these red and yellow pigment powders. The product was finely ground and dispersed in a bead mill to obtain an aqueous dispersion. The average particle diameter (D 50 ) of the pigment in each aqueous dispersion is red: 155 nm, yellow: 150 nm.
なお、ビーズミル細磨後、粘性、表面張力をインクジェットヘッド仕様に合わせた。 After bead milling, the viscosity and surface tension were adjusted to the inkjet head specifications.
焼成条件は、１１５６℃×２６分とした。 The firing conditions were 1156 ° C. × 26 minutes.
Ｎｏ．１〜４の釉薬組成（モル％）を表１に示し、各色の発色状況の測定結果（Ｌ＊，ａ＊，ｂ＊）を表２〜４及び図１〜３に示す。 No. The glaze composition (mol%) of 1-4 is shown in Table 1, and the measurement result (L * , a * , b * ) of the coloring condition of each color is shown in Tables 2-4 and FIGS.
なお、釉薬はＬｉ２Ｏ、ＢａＯ、ＳｒＯ、Ｍ０Ｏ３、ＳｎＯ２を実質的に含有しない。 Incidentally, the glaze does not contain Li 2 O, BaO, SrO, and M 0 O 3, SnO 2 substantially.
次に、インクへのＴｉＯ２添加試験の比較例、実施例を表５に示す。釉薬組成は比較例１の組成を用い、焼成条件は１１５６℃×２６分とした。各色の発色状況の測定結果（Ｌ＊，ａ＊，ｂ＊）を表６，７及び図４，５に示す。 Next, Table 5 shows comparative examples and examples of the TiO 2 addition test to the ink. The glaze composition was the same as that of Comparative Example 1, and the firing conditions were 1156 ° C. × 26 minutes. The measurement results (L * , a * , b * ) of the color development status of each color are shown in Tables 6 and 7 and FIGS.
表１〜４、図１〜３より次の事項が認められる。即ち、酸化チタンを添加することにより赤、黄色の発色が向上する。また、赤と黄色の混合であるオレンジについても発色が向上する。 The following matters are recognized from Tables 1-4 and FIGS. That is, the addition of titanium oxide improves red and yellow color development. Color development is also improved for orange, which is a mixture of red and yellow.
表５〜７、図４，５より次の事項が認められる。即ち、インクに酸化チタンを添加することにより赤、黄の発色が向上する。 The following matters are recognized from Tables 5 to 7 and FIGS. That is, the coloration of red and yellow is improved by adding titanium oxide to the ink.
Claims (9)
釉薬組成中に酸化チタンが０．１〜１０モル％含まれ、
赤色系顔料が平均粒径５００ｎｍ以下の酸化クロム−酸化錫系顔料であることを特徴とする加飾セラミック体。 In the decorated ceramic body in which the glaze layer is painted on the surface of the ceramic substrate with a red pigment by inkjet,
0.1-10 mol% of titanium oxide is contained in the glaze composition,
A decorative ceramic body, wherein the red pigment is a chromium oxide-tin oxide pigment having an average particle size of 500 nm or less.
釉薬組成中に酸化チタンが０．１〜１０モル％含まれ、
黄色系顔料が平均粒径５００ｎｍ以下の酸化チタン−酸化クロム−酸化アンチモン系顔料であることを特徴とする加飾セラミック体。 In the decorated ceramic body in which the glaze layer is painted on the surface of the ceramic substrate with a yellow pigment by inkjet,
0.1-10 mol% of titanium oxide is contained in the glaze composition,
A decorative ceramic body, wherein the yellow pigment is a titanium oxide-chromium oxide-antimony oxide pigment having an average particle diameter of 500 nm or less.
釉薬組成中に酸化チタンが０．１〜１０モル％含まれ、
赤色系顔料が、平均粒径５００ｎｍ以下の酸化クロム−酸化錫系顔料であり、
黄色系顔料が、平均粒径５００ｎｍ以下の酸化チタン−酸化クロム−酸化アンチモン系顔料であることを特徴とする加飾セラミック体。 In the decorative ceramic body in which a glaze layer is formed on the surface of the ceramic substrate with a red pigment and a yellow pigment by inkjet,
0.1-10 mol% of titanium oxide is contained in the glaze composition,
The red pigment is a chromium oxide-tin oxide pigment having an average particle size of 500 nm or less,
A decorative ceramic body, wherein the yellow pigment is a titanium oxide-chromium oxide-antimony oxide pigment having an average particle diameter of 500 nm or less.
ＳｉＯ２ ６０〜７６モル％
Ａｌ２Ｏ３ ４〜１１モル％
ＴｉＯ２ ０．１〜１０モル％
Ｋ２Ｏ ４〜１０モル％
Ｎａ２Ｏ ０．５〜５モル％
Ｌｉ２Ｏ ０〜０．５モル％
Ｂ２Ｏ３ ０〜７モル％
ＣａＯ ４〜１０モル％
ＢａＯ ０〜６モル％
ＺｎＯ ０〜５モル％
ＭｇＯ ０〜２モル％
ＳｒＯ ０〜１モル％
ＭｎＯ３ ０〜０．６モル％
ＺｒＯ２ ０〜６モル％
Ｆｅ２Ｏ３ ０〜０．１５モル％
であることを特徴とする加飾セラミック体。 In any one of claims 1 to 5, the composition of the glaze is SiO 2 60 to 76 mol%
Al 2 O 3 4~11 mol%
TiO 2 0.1-10 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 7 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%
A decorated ceramic body characterized by being.
酸化チタンを１〜２０ｗｔ％含有すると共に、赤色系顔料として、平均粒径５００ｎｍ以下の酸化クロム−酸化錫系顔料を含有することを特徴とするインクジェット用インク。 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 1 to 20 wt% of titanium oxide and a chromium oxide-tin oxide pigment having an average particle size of 500 nm or less as a red pigment.
酸化チタンを１〜２０ｗｔ％含有すると共に、黄色系顔料として、平均粒径５００ｎｍ以下の酸化チタン−酸化クロム−酸化アンチモン系顔料を含有することを特徴とするインクジェット用インク。 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 1 to 20 wt% of titanium oxide and containing, as a yellow pigment, a titanium oxide-chromium oxide-antimony oxide pigment having an average particle size of 500 nm or less.
該釉薬の組成が
ＳｉＯ２ ６０〜７６モル％
Ａｌ２Ｏ３ ４〜１１モル％
ＴｉＯ２ ０．１〜１０モル％
Ｋ２Ｏ ４〜１０モル％
Ｎａ２Ｏ ０．５〜５モル％
Ｌｉ２Ｏ ０〜０．５モル％
Ｂ２Ｏ３ ０〜７モル％
ＣａＯ ４〜１０モル％
ＢａＯ ０〜６モル％
ＺｎＯ ０〜５モル％
ＭｇＯ ０〜２モル％
ＳｒＯ ０〜１モル％
ＭｎＯ３ ０〜０．６モル％
ＺｒＯ２ ０〜６モル％
Ｆｅ２Ｏ３ ０〜０．１５モル％
であり、前記インクジェット用インクは請求項７及び／又は８に記載のインクジェット用インクであることを特徴とする加飾セラミック体の製造方法。 An unfired glaze layer is formed on a ceramic substrate, painted on it with ink-jet ink containing red and / or yellow pigment, and then fired to melt the glaze layer. In the method of manufacturing a decorative ceramic body,
The composition of the glaze is SiO 2 60-76 mole%
Al 2 O 3 4~11 mol%
TiO 2 0.1-10 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 7 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 method for producing a decorated ceramic body, wherein the ink-jet ink is the ink-jet ink according to claim 7 and / or 8.
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