JP6750348B2 - Sanitary ware with photocatalyst layer - Google Patents
Sanitary ware with photocatalyst layer Download PDFInfo
- Publication number
- JP6750348B2 JP6750348B2 JP2016133044A JP2016133044A JP6750348B2 JP 6750348 B2 JP6750348 B2 JP 6750348B2 JP 2016133044 A JP2016133044 A JP 2016133044A JP 2016133044 A JP2016133044 A JP 2016133044A JP 6750348 B2 JP6750348 B2 JP 6750348B2
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- JP
- Japan
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- sanitary ware
- mass
- layer
- photocatalyst layer
- titanium oxide
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- 239000011941 photocatalyst Substances 0.000 title claims description 64
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 40
- 239000007788 liquid Substances 0.000 claims description 36
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 34
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 31
- 239000011248 coating agent Substances 0.000 claims description 28
- 238000000576 coating method Methods 0.000 claims description 28
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 28
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 28
- -1 silicon alkoxide Chemical class 0.000 claims description 24
- 239000000377 silicon dioxide Substances 0.000 claims description 19
- 239000002243 precursor Substances 0.000 claims description 16
- 229910052726 zirconium Inorganic materials 0.000 claims description 15
- 239000010936 titanium Substances 0.000 claims description 12
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 96
- 238000010304 firing Methods 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 230000002378 acidificating effect Effects 0.000 description 12
- 230000001699 photocatalysis Effects 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 239000002585 base Substances 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 239000003513 alkali Substances 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- OVSGBKZKXUMMHS-VGKOASNMSA-L (z)-4-oxopent-2-en-2-olate;propan-2-olate;titanium(4+) Chemical compound [Ti+4].CC(C)[O-].CC(C)[O-].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O OVSGBKZKXUMMHS-VGKOASNMSA-L 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 3
- 239000013522 chelant Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 3
- 229940093858 ethyl acetoacetate Drugs 0.000 description 3
- 239000010433 feldspar Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 125000005595 acetylacetonate group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 235000014692 zinc oxide Nutrition 0.000 description 2
- NOGBEXBVDOCGDB-NRFIWDAESA-L (z)-4-ethoxy-4-oxobut-2-en-2-olate;propan-2-olate;titanium(4+) Chemical compound [Ti+4].CC(C)[O-].CC(C)[O-].CCOC(=O)\C=C(\C)[O-].CCOC(=O)\C=C(\C)[O-] NOGBEXBVDOCGDB-NRFIWDAESA-L 0.000 description 1
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 description 1
- TYKCBTYOMAUNLH-MTOQALJVSA-J (z)-4-oxopent-2-en-2-olate;titanium(4+) Chemical compound [Ti+4].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O TYKCBTYOMAUNLH-MTOQALJVSA-J 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- RCZPHVPIOWNERS-UHFFFAOYSA-N CCCO[Ti] Chemical compound CCCO[Ti] RCZPHVPIOWNERS-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 1
- ASBGGHMVAMBCOR-UHFFFAOYSA-N ethanolate;zirconium(4+) Chemical compound [Zr+4].CC[O-].CC[O-].CC[O-].CC[O-] ASBGGHMVAMBCOR-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- ZEIWWVGGEOHESL-UHFFFAOYSA-N methanol;titanium Chemical compound [Ti].OC.OC.OC.OC ZEIWWVGGEOHESL-UHFFFAOYSA-N 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 description 1
- ZGSOBQAJAUGRBK-UHFFFAOYSA-N propan-2-olate;zirconium(4+) Chemical compound [Zr+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] ZGSOBQAJAUGRBK-UHFFFAOYSA-N 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B33/00—Clay-wares
- C04B33/24—Manufacture of porcelain or white ware
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B33/00—Clay-wares
- C04B33/32—Burning methods
- C04B33/34—Burning methods combined with glazing
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/86—Glazes; Cold glazes
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/87—Ceramics
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Catalysts (AREA)
- Sanitary Device For Flush Toilet (AREA)
Description
本発明は、耐久性に優れた、光触媒層を有する衛生陶器に関し、更に詳しくは、本発明は、酸とアルカリという液性の異なる条件下での繰り返しの洗浄に対しても耐久性を備える、光触媒層を有する衛生陶器に関する。 The present invention relates to a highly durable sanitary ware having a photocatalyst layer, and more specifically, the present invention has durability against repeated washing under different liquid conditions of acid and alkali, The present invention relates to sanitary ware having a photocatalyst layer.
釉薬層を有する基材の釉薬層表面に光触媒層を設け、その光触媒の分解活性または親水活性を利用した機能性部材が種々の用途において用いられている。例えば、衛生陶器表面に光触媒表面層を形成した衛生陶器が知られている。このような衛生陶器は、その光触媒層に光、好ましくは紫外線を照射することで発揮する親水性による汚物付着抑制とともに、光触媒による分解作用によって菌の繁殖も抑制できる。これによりその清掃負荷が軽減される。 A photocatalyst layer is provided on the surface of a glaze layer of a base material having a glaze layer, and a functional member utilizing the decomposition activity or hydrophilic activity of the photocatalyst is used in various applications. For example, a sanitary ware in which a photocatalyst surface layer is formed on the surface of the sanitary ware is known. Such sanitary ware can suppress the attachment of dirt due to the hydrophilicity exhibited by irradiating the photocatalyst layer with light, preferably ultraviolet light, and also can suppress the growth of bacteria by the decomposition action of the photocatalyst. This reduces the cleaning load.
このような釉薬層表面に設けられる光触媒層として、酸化チタンと、ジルコニア化合物とを含む層が、良好な光触媒活性を維持しながら、良好な膜強度、耐水性、または耐摩耗性を有すると提案されている(特開2012−206907号公報(特許文献1)、特開2014−69098号公報(特許文献2))。 As a photocatalyst layer provided on such a glaze layer surface, a layer containing titanium oxide and a zirconia compound is proposed to have good film strength, water resistance, or abrasion resistance while maintaining good photocatalytic activity. (Japanese Patent Laid-Open No. 2012-206907 (Patent Document 1) and Japanese Patent Laid-Open No. 2014-69098 (Patent Document 2)).
光触媒層の存在により清掃負荷が軽減されるとはいえ、衛生陶器は定期的に清掃され、その際に酸性またはアルカリ性の液性の洗剤を用いることが一般的であり、また、汚れを落とすためにブラシなどで摺動され、物理的な応力が加えられる。光触媒層には、このような清掃時の負荷に長期間耐え得る性能、とりわけ光触媒の活性を失わない、剥離しないなどの性能が求められる。 Although the cleaning load is reduced due to the presence of the photocatalyst layer, sanitary ware is generally cleaned at regular intervals using an acidic or alkaline liquid detergent, and to remove dirt. It is slid with a brush or the like and is subjected to physical stress. The photocatalyst layer is required to have a performance capable of withstanding such a load during cleaning for a long period of time, in particular, a property of not losing the activity of the photocatalyst and not peeling.
他方で、強固な光触媒膜を形成するため、通常500〜1000℃の高温焼成が必要であるが、このような高温下に、衛生陶器の釉薬中のアルカリイオンが拡散して、これにより光触媒活性が低下することが知られている。その対策として、基材と光触媒層との間にシリカ等を主成分としアルカリイオンの拡散を抑制する中間層を設けることが知られている(例えば、特開平10−235201号公報(特許文献3)、特開平11−228865号公報(特許文献4)、特開2001−152051号公報(特許文献5)、特開2003−277056号公報(特許文献6))。しかしながら、これら中間層はアルカリ拡散防止を主たる目的とするものであり、また本発明者らの行った実験によれば、酸化チタンと、ジルコニア化合物とを含む光触媒層の耐久性は本発明と比較して劣るものであった。 On the other hand, in order to form a strong photocatalyst film, it is usually necessary to perform high temperature baking at 500 to 1000°C, but under such high temperature, the alkali ions in the glaze of sanitary ware diffuse, which causes photocatalytic activity. Is known to decrease. As a countermeasure against this, it is known to provide an intermediate layer containing silica or the like as a main component between the base material and the photocatalyst layer to suppress the diffusion of alkali ions (for example, JP-A-10-235201 (Patent Document 3). ), JP-A-11-228865 (Patent Document 4), JP-A-2001-152051 (Patent Document 5), and JP-A-2003-277056 (Patent Document 6)). However, these intermediate layers are mainly intended to prevent alkali diffusion, and according to experiments conducted by the present inventors, the durability of the photocatalyst layer containing titanium oxide and a zirconia compound is comparable to that of the present invention. Was inferior to
光触媒層の耐久性の評価にあって、酸性の液単独に曝した後、またはアルカリ性の液単独に曝さらした後の光触媒層を試験することはこれまで一般的に行われていた。そして、酸性またはアルカリ性の液性にそれぞれ単独で曝された後にあっても良好な光触媒活性を維持しまたは剥離し難いならば、良好な耐久性を有すると評価した。しかし、今般、本発明者らが得た知見によれば、実際の使用環境において、例えば、酸性の液性の洗浄液による清掃が行われ、その後アルカリ性の液性の洗浄液による清掃が行なわれることがあり、そのような場合、従来提案されている光触媒層の耐久性が十分でないことがあった。 In evaluating the durability of a photocatalyst layer, it has been common practice to test the photocatalyst layer after exposure to an acidic liquid alone or after exposure to an alkaline liquid alone. Then, it was evaluated as having good durability if it maintained a good photocatalytic activity or was difficult to be peeled off even after being exposed to an acidic or alkaline liquid alone, respectively. However, according to the knowledge obtained by the present inventors, in an actual environment of use, for example, cleaning with an acidic liquid cleaning liquid is performed and then cleaning with an alkaline liquid cleaning liquid is performed. However, in such a case, the durability of the conventionally proposed photocatalyst layer may not be sufficient.
本発明者らは、今般、酸化チタンと酸化ジルコニウムとを含んでなる光触媒層を釉薬層上に設ける際、その間に、シリカを主成分とし、酸化チタンおよび/または酸化ジルコニウムを特定の割合で含む層を設けることで、光触媒層の耐久性を大きく向上できるとの知見を得た。とりわけ、酸とアルカリとに交互に曝されるような清掃が繰り返しなされるような状況においても優れた耐久性を示すとの知見を得た。本発明はかかる知見に基づくものである。 The present inventors, when providing a photocatalyst layer containing titanium oxide and zirconium oxide on the glaze layer, contain silica as a main component and titanium oxide and/or zirconium oxide in a specific ratio between them. It was found that the durability of the photocatalyst layer can be greatly improved by providing the layer. In particular, it has been found that excellent durability is exhibited even in a situation where cleaning is repeatedly performed by being alternately exposed to acid and alkali. The present invention is based on such findings.
従って、本発明は、耐久性に優れた光触媒層を有する衛生陶器の提供を目的としている。特に、本発明は、酸とアルカリとに交互に曝される環境にあっても、耐久性に優れた光触媒層を有する衛生陶器の提供をその目的としている。 Therefore, an object of the present invention is to provide a sanitary ware having a photocatalyst layer having excellent durability. In particular, an object of the present invention is to provide a sanitary ware having a photocatalyst layer having excellent durability even in an environment where it is alternately exposed to acid and alkali.
そして、本発明による衛生陶器は、釉薬層と、この釉薬層上に設けられた中間層と、この中間層上に設けられた光触媒層とを備えてなる衛生陶器であって、
前記光触媒層が、酸化チタンと酸化ジルコニウムとを、それぞれ95質量%〜75質量%および5〜25質量%の量で含んでなり、
前記中間層が、シリカと、酸化チタンおよび/または酸化ジルコニウムとを、それぞれ98質量%〜85質量%、および(酸化チタンと酸化ジルコニウムの両方を含む場合その合計として)2質量%〜15質量%含んでなることを特徴とするものである。
The sanitary ware according to the present invention is a sanitary ware comprising a glaze layer, an intermediate layer provided on the glaze layer, and a photocatalyst layer provided on the intermediate layer.
The photocatalyst layer comprises titanium oxide and zirconium oxide in amounts of 95% by weight to 75% by weight and 5 to 25% by weight, respectively,
The intermediate layer contains silica and titanium oxide and/or zirconium oxide in an amount of 98% by mass to 85% by mass, respectively, and (in the case of containing both titanium oxide and zirconium oxide, as a total thereof) 2% by mass to 15% by mass. It is characterized by including.
定義
本発明において、「衛生陶器」とは、トイレおよび洗面所周りで用いられる陶器製品を意味し、具体的には大便器、小便器、便器のサナ、便器タンク、洗面台の洗面器、手洗い器などを意味する。また、「陶器」とは、陶磁器のうち、素地の焼き締まりがやや吸水性のある程度で、かつ表面に釉薬を施したものを意味する。
Definitions In the present invention, "sanitary ware" means pottery products used around toilets and washrooms, and specifically, urinals, urinals, toilet bowls, toilet tanks, washbasin washbasins, handwashing. Means a vessel, etc. In addition, the term “pottery” refers to a pottery that has a degree of slightly water-absorption of the base material and has a glaze on the surface.
本発明にあって、光触媒層の「耐久性」とは、光触媒層が剥離し難いこと、光触媒活性の経時的劣化が少ないことを個別にまたは総合的に表す語句として用いるが、とりわけ、酸とアルカリの液性に交互に曝されたときに、光触媒層が剥離し難く、また光触媒活性の劣化が少ないことを個別にまたは総合的に表す語句として用いる。 In the present invention, the “durability” of the photocatalyst layer is used as a phrase that individually or comprehensively represents that the photocatalyst layer is difficult to be peeled off and that deterioration of the photocatalytic activity over time is small. It is used as a phrase that individually or collectively represents that the photocatalyst layer is less likely to be peeled off and that the photocatalytic activity is less deteriorated when alternately exposed to the alkaline liquid property.
酸性とは、弱酸性から強酸性までを意味し、具体的にはpH5以下の範囲にあることを意味し、またアルカリ性とは、弱アルカリ性から強アルカリ性までを意味し、具体的にはpH8以上の範囲にあることを意味する。 Acidic means from weakly acidic to strongly acidic, specifically in the range of pH 5 or less, and alkaline means from weakly alkaline to strongly alkaline, specifically pH 8 or more. It means in the range of.
本発明による衛生陶器
本発明による衛生陶器は、基体と、その表面の釉薬層と、この釉薬層上に設けられた中間層と、この中間層上に設けられた光触媒層とを備えてなる基本構造を有する。そして、中間層と、光触媒層が後記する特定の組成で構成される。
Sanitary Ware According to the Present Invention The sanitary ware according to the present invention is basically a substrate, a glaze layer on the surface thereof, an intermediate layer provided on the glaze layer, and a photocatalyst layer provided on the intermediate layer. Have a structure. Then, the intermediate layer and the photocatalyst layer are composed of a specific composition described later.
本発明による衛生陶器は、光触媒層の耐久性に優れる。特に、酸性とアルカリ性とに交互に曝されるような環境におかれても、光触媒層は優れた耐久性を示す。上記のとおり、光触媒層の耐久性の評価にあって、酸性の液単独に曝した後、またはアルカリ性の液単独に曝した後の光触媒層を試験することはこれまで一般的に行われていた。しかしながら、酸またはアルカリ単独の評価で十分な耐久性を示す従来の光触媒層であっても、酸性とアルカリ性とに交互に曝されるような環境におかれると、予想外に短い時間で光触媒層の剥離または光触媒活性の劣化が観察された。本発明にあっては、このような、酸性とアルカリ性とに交互に曝されるような環境におかれても、改善された耐久性を示す光触媒層を備えた衛生陶器が提供される。 The sanitary ware according to the present invention has excellent durability of the photocatalyst layer. In particular, the photocatalyst layer exhibits excellent durability even in an environment where it is alternately exposed to acidity and alkalinity. As described above, in the evaluation of the durability of the photocatalyst layer, it has been general to test the photocatalyst layer after being exposed to an acidic liquid alone or after being exposed to an alkaline liquid alone. .. However, even a conventional photocatalyst layer that shows sufficient durability when evaluated by acid or alkali alone, will be unexpectedly short in a short time when exposed to an environment where it is alternately exposed to acidity and alkalinity. Peeling or deterioration of photocatalytic activity was observed. According to the present invention, there is provided a sanitary ware provided with a photocatalyst layer exhibiting improved durability even under such an environment that is alternately exposed to acidity and alkalinity.
特定の理論に拘束されることを望むものではないが、本発明による衛生陶器の光触媒層の耐久性に優れる理由は次のように考えられる。すなわち、酸化チタンと酸化ジルコニウムとを含んでなる光触媒層は、極めてわずかな水透過性を有しており、これにより衛生陶器の釉薬層表面に水が至ることがある。この水の液性が酸性およびアルカリ性と交互に代わると次のような反応が促進される。まず、酸性の水により釉薬中のカリウム、カルシウム、マグネシウム、亜鉛などの金属元素が溶出し、アルカリ性の水がこの溶出箇所に至ると、その近傍のケイ素−ケイ素結合を切断する。この繰り返しにより、釉薬層と光触媒層との間の結合が弱くなり、最悪の場合、光触媒層が剥離してしまう。本発明において中間層は、このわずかな水の浸入を阻害しながら、釉薬表面と光触媒層を強固に結合させるものであると考えられる。以上の説明はあくまで仮定であって、本発明はこれに限定されるものではない。 Although not wishing to be bound by a particular theory, the reason why the photocatalyst layer of the sanitary ware according to the present invention is excellent in durability is considered as follows. That is, the photocatalyst layer containing titanium oxide and zirconium oxide has a very slight water permeability, which may cause water to reach the glaze layer surface of the sanitary ware. When the liquid property of this water alternates between acidic and alkaline, the following reaction is promoted. First, acidic water elutes metal elements such as potassium, calcium, magnesium, and zinc in the glaze, and when alkaline water reaches this elution site, the silicon-silicon bond in the vicinity is cleaved. By repeating this, the bond between the glaze layer and the photocatalyst layer becomes weak, and in the worst case, the photocatalyst layer peels off. In the present invention, the intermediate layer is considered to firmly bond the surface of the glaze and the photocatalyst layer while hindering the slight penetration of water. The above description is merely an assumption, and the present invention is not limited to this.
光触媒層
本発明による衛生陶器の光触媒層は、酸化チタンと酸化ジルコニウムとを、それぞれ95質量%〜75質量%および5〜25質量%の量で含んでなる。酸化チタンの含有量は、その好ましい下限は80質量%であり、その好ましい上限は90質量%である。また酸化ジルコニウムの含有量は、その好ましい下限は10質量%であり、その好ましい上限は20質量%である。
Photocatalyst Layer The photocatalyst layer of the sanitary ware according to the present invention comprises titanium oxide and zirconium oxide in the amounts of 95% by mass to 75% by mass and 5% by mass to 25% by mass, respectively. The preferable lower limit of the content of titanium oxide is 80% by mass, and the preferable upper limit thereof is 90% by mass. The preferable lower limit of the content of zirconium oxide is 10% by mass, and the preferable upper limit thereof is 20% by mass.
本発明において、酸化チタンは光触媒活性を有するものであれば特に限定されず、アナターゼ型、ルチル型のいずれであってもよいが、アナターゼ型が好ましい。 In the present invention, titanium oxide is not particularly limited as long as it has photocatalytic activity, and may be either anatase type or rutile type, but anatase type is preferable.
本発明において、光触媒層の膜厚は求められる光触媒活性、その他の緒特性を勘案して適宜決定されてよいが、50nm〜150nm程度であるのが好ましく、より好ましい上限は120nmである。 In the present invention, the thickness of the photocatalyst layer may be appropriately determined in consideration of the required photocatalytic activity and other characteristics, but it is preferably about 50 nm to 150 nm, and the more preferable upper limit is 120 nm.
中間層
本発明による衛生陶器にあって、中間層は、衛生陶器の釉薬層と、光触媒層との間に設けられてなり、シリカと、酸化チタンおよび/または酸化ジルコニウムとを含んでなる。シリカの含有量は98質量%〜85質量%の範囲であり、その好ましい上限は95質量%であり、好ましい下限は90質量%である。また、酸化チタンおよび酸化ジルコニウムの含有量は、その両方を含む場合その合計として、2質量%〜15質量%の範囲であり、その好ましい上限は10質量%であり、好ましい下限は5質量%である。
Intermediate Layer In the sanitary ware according to the present invention, the intermediate layer is provided between the glaze layer and the photocatalyst layer of the sanitary ware, and contains silica and titanium oxide and/or zirconium oxide. The content of silica is in the range of 98% by mass to 85% by mass, the preferable upper limit thereof is 95% by mass, and the preferable lower limit thereof is 90% by mass. Moreover, the content of titanium oxide and zirconium oxide is in the range of 2% by mass to 15% by mass as a total when both are contained, and the preferable upper limit is 10% by mass and the preferable lower limit is 5% by mass. is there.
本発明において、中間層の膜厚は、光触媒層の耐久性を高める範囲で適宜決定されてよいが、50nm〜150nm程度であるのが好ましく、より好ましい上限は120nmである。 In the present invention, the film thickness of the intermediate layer may be appropriately determined within a range that enhances the durability of the photocatalyst layer, but is preferably about 50 nm to 150 nm, and more preferably the upper limit is 120 nm.
衛生陶器
衛生陶器素地
本発明による衛生陶器の陶器素地は、特に限定されず、通常の衛生陶器素地であってよい。また、最表層の上記表面性状を有した釉薬層の下に、中間層となる釉薬層が設けられていてもよい。
Sanitary Ware Sanitary Ware Base The sanitary ware base of the present invention is not particularly limited and may be a normal sanitary ware base. Further, a glaze layer serving as an intermediate layer may be provided below the outermost glaze layer having the above-mentioned surface texture.
製造方法
本発明による衛生陶器は、以下のような方法により好ましく製造することができる。すなわち、まず、陶器素地を、ケイ砂、長石、粘土等を原料として調製した衛生陶器素地泥漿を、吸水性の型を利用した鋳込み成形を用いて、適宜形状に成形する。その後、乾燥させた成形体表面に、上記釉薬原料をスプレーコーティング、ディップコーティング、スピンコーティング、ロールコーティング等の一般的な方法を適宜選択して塗布する。得られた表面釉薬層の前駆層が形成された成形体を、次に焼成する。焼成温度は、陶器素地が焼結し、かつ釉薬が軟化する1,000℃以上1,300℃以下の温度が好ましい。
Manufacturing Method The sanitary ware according to the present invention can be preferably manufactured by the following method. That is, first, a pottery base is formed into an appropriate shape by using a sanitary ware base slurry prepared from silica sand, feldspar, clay, etc., by casting using a water-absorbing mold. Then, the glaze raw material is applied to the surface of the dried molded body by appropriately selecting a general method such as spray coating, dip coating, spin coating, or roll coating. The formed body on which the precursor layer of the surface glaze layer has been formed is then fired. The firing temperature is preferably 1,000° C. or higher and 1,300° C. or lower at which the ceramic body is sintered and the glaze is softened.
釉薬
本発明による衛生陶器の釉薬層を生成する釉薬は、上記した表面性状が実現できる限り、その組成は限定されない。本発明において、一般的には釉薬原料とは、珪砂、長石、石灰石等の天然鉱物粒子の混合物と定義する。また顔料とは、例えば、コバルト化合物、鉄化合物等であり、乳濁剤とは、例えば、珪酸ジルコニウム、酸化錫等である。非晶質釉薬とは、上記のような天然鉱物粒子等の混合物からなる釉薬原料を高温で溶融した後、急冷してガラス化させた釉薬をいい、例えば、フリット釉薬が好適に利用可能である。
Glaze The composition of the glaze which forms the glaze layer of the sanitary ware according to the present invention is not limited as long as the above-mentioned surface properties can be realized. In the present invention, the glaze raw material is generally defined as a mixture of natural mineral particles such as silica sand, feldspar, and limestone. The pigment is, for example, a cobalt compound, an iron compound or the like, and the emulsifying agent is, for example, zirconium silicate or tin oxide. Amorphous glaze refers to a glaze obtained by melting a glaze raw material composed of a mixture of natural mineral particles as described above at a high temperature and then rapidly cooling it into a glass, for example, a frit glaze can be preferably used. ..
本発明の好ましい態様によれば、好ましい釉薬組成は、例えば、長石が10wt%〜30wt%、珪砂が15wt%〜40wt%、炭酸カルシウムが10wt%〜25wt%、コランダム、タルク、ドロマイト、亜鉛華が、それぞれ10wt%以下、乳濁剤および顔料が合計15wt%以下のものである。 According to a preferred embodiment of the present invention, a preferable glaze composition is, for example, 10% by weight to 30% by weight of feldspar, 15% by weight to 40% by weight of silica sand, 10% by weight to 25% by weight of calcium carbonate, corundum, talc, dolomite and zinc white. 10 wt% or less, and the total amount of the emulsifying agent and the pigment is 15 wt% or less.
本発明による衛生陶器の製造法
本発明による衛生陶器は、衛生陶器の釉薬層上に、中間層、そして光触媒層を形成して製造される。中間層および光触媒層は、基本的に、シリカと、酸化チタンおよび/または酸化ジルコニウムと、あるいはそれらの前駆体を釉薬層上において焼成し、また酸化チタンと酸化ジルコニウムと、あるいはそれらの前駆体を中間層上において焼成することで形成される。ここで、中間層と光触媒層の形成のための焼成は、都度行われてもよく、また同時に焼成して形成してもよい。本発明の好ましい態様によれば、中間層および光触媒層は、上記成分を含むコーティング液として用意され、それを塗布し、その後焼成することにより形成される。
Method for manufacturing sanitary ware according to the present invention The sanitary ware according to the present invention is manufactured by forming the intermediate layer and the photocatalyst layer on the glaze layer of the sanitary ware. The intermediate layer and the photocatalyst layer are basically obtained by calcining silica, titanium oxide and/or zirconium oxide, or their precursors on the glaze layer, and also titanium oxide and zirconium oxide, or their precursors. It is formed by firing on the intermediate layer. Here, the firing for forming the intermediate layer and the photocatalyst layer may be performed each time, or may be performed by firing at the same time. According to a preferred embodiment of the present invention, the intermediate layer and the photocatalyst layer are prepared by preparing a coating liquid containing the above components, applying the coating liquid, and then baking the coating liquid.
本発明の一つの態様によれば、光触媒層は、酸化チタンと酸化ジルコニウムとを含むか、またその前駆体を含んでなるコーティング液を適用、好ましくは塗布して、その後に焼成することにより製造することが出来る。本発明の好ましい態様によれば、酸化チタンの前駆体および酸化ジルコニウムの前駆体として、チタンアルコキシドおよびジルコニウムアルコキシドとを含んでなるコーティング液を用い、これを焼成して光触媒層を得る。 According to one embodiment of the present invention, the photocatalyst layer is produced by applying a coating solution containing titanium oxide and zirconium oxide or a precursor thereof, preferably applying and then firing. You can do it. According to a preferred embodiment of the present invention, a coating liquid containing titanium alkoxide and zirconium alkoxide is used as a titanium oxide precursor and a zirconium oxide precursor, and the coating liquid is baked to obtain a photocatalyst layer.
本発明において、酸化チタンの前駆体としては、チタンアルコキシドおよびチタンキレートが好適に利用できる。チタンアルコキシドは、一般式:Ti(OR)4で基本的に表されるものであり、加水分解によって光触媒性酸化チタンを生じさせるものであれば限定されない。式中の(OR)の一部がアセチルアセトネート(C5H7O2)やエチルアセトアセテート(C6H9O3)で置換されていてもよい。本発明の好ましい態様によれば、チタンアルコキシドは、アルコキシド(RO−)の有機基R部分が低級(好ましくはC1−6)アルキル基であるものである。その好ましい具体例としては、テトラエトキシチタン、テトライソプロポキシチタン、テトラn−プロポキシチタン、テトラブトキシチタン、テトラメトキシチタン、チタンジイソプロポキシビス(アセチルアセトネート)、チタンジイソプロポキシビス(エチルアセトアセテート)およびそれらの混合物が挙げられる。また、チタンキレートとしては、例えばチタンテトラアセチルアセトネートが挙げられる。 In the present invention, titanium alkoxide and titanium chelate can be preferably used as the precursor of titanium oxide. The titanium alkoxide is basically represented by the general formula: Ti(OR) 4 , and is not limited as long as it produces a photocatalytic titanium oxide by hydrolysis. Part of (OR) in the formula may be substituted with acetylacetonate (C 5 H 7 O 2 ) or ethyl acetoacetate (C 6 H 9 O 3 ). According to a preferred embodiment of the present invention, titanium alkoxide (preferably C 1-6) a lower organic radical R moieties of the alkoxide (RO-) are those wherein the alkyl group. Specific preferred examples thereof include tetraethoxy titanium, tetraisopropoxy titanium, tetra n-propoxy titanium, tetrabutoxy titanium, tetramethoxy titanium, titanium diisopropoxy bis (acetylacetonate), titanium diisopropoxy bis (ethyl acetoacetate). ) And mixtures thereof. Examples of titanium chelates include titanium tetraacetylacetonate.
また、酸化ジルコニウムの前駆体としては、ジルコニウムアルコキシドおよびジルコニウムキレートが好適に利用できる。ジルコニウムアルコキシドは、一般式:Zr(OR)4で基本的に表されるものであり、加水分解によって酸化ジルコニウムを生じさせるものであれば限定されない。式中の(OR)の一部がアセチルアセトネート(C5H7O2)やエチルアセトアセテート(C6H9O3)で置換されていてもよい。本発明の好ましい態様によれば、アルコキシド(RO−)の有機基R部分がジルコニウムアルコキシドは、アルコキシド(RO−)の有機基R部分が低級(好ましくはC2−6)アルキル基であるものである。その好ましい具体例としては、ジルコニウムテトラエトキシド、ジルコニウムテトライソプロポキシド、ジルコニウムテトラブトキド、ジルコニウムトリブトキシモノアセチルアセトネート、ジルコニウムジブトキシビス(エチルアセトアセテート)、ジルコニウムモノブトキシアセチルアセトネートビス(エチルアセトアセテート)およびそれらの混合物が挙げられる。また、ルコニウムキレートとしては、例えばジルコニウムテトラアセチルアセトネートが挙げられる。 Further, zirconium alkoxide and zirconium chelate can be preferably used as the precursor of zirconium oxide. The zirconium alkoxide is basically represented by the general formula: Zr(OR) 4 , and is not limited as long as it produces zirconium oxide by hydrolysis. Part of (OR) in the formula may be substituted with acetylacetonate (C 5 H 7 O 2 ) or ethyl acetoacetate (C 6 H 9 O 3 ). According to a preferred embodiment of the present invention, the organic group R moiety of the alkoxide (RO − ) is a zirconium alkoxide, and the organic group R moiety of the alkoxide (RO − ) is a lower (preferably C 2-6 ) alkyl group. is there. Specific preferred examples thereof include zirconium tetraethoxide, zirconium tetraisopropoxide, zirconium tetrabutoxide, zirconium tributoxy monoacetylacetonate, zirconium dibutoxybis(ethylacetoacetate), zirconium monobutoxyacetylacetonate bis(ethyl). Acetoacetate) and mixtures thereof. Further, examples of the ruconium chelate include zirconium tetraacetylacetonate.
本発明において中間層は、シリカおよび酸化チタンおよび/または酸化ジルコニウムを含むか、またその前駆体を含んでなるコーティング液を適用、好ましくは塗布して、その後に焼成することにより製造することが出来る。本発明の好ましい態様によれば、シリカ前駆体としては、メチルシリケート、エチルシリケートなどのアルキルシリケート、それらの重合体が挙げられる。また、酸化チタンの前駆体および酸化ジルコニウムの前駆体としては、光触媒について例示したものを好ましく用いることが出来る。 In the present invention, the intermediate layer can be produced by applying, preferably applying, a coating liquid containing silica and titanium oxide and/or zirconium oxide, or a precursor thereof, and then firing. .. According to a preferred embodiment of the present invention, examples of the silica precursor include alkyl silicates such as methyl silicate and ethyl silicate, and polymers thereof. As the titanium oxide precursor and the zirconium oxide precursor, those exemplified for the photocatalyst can be preferably used.
また、コーティング液の溶媒としては、エタノール、イソプロパノール、ノルマルブタノールなどのアルコール類、メチルセロソルブ、ブチルセロソルブなどのセロソルブ類、トルエン、キシレンなどの芳香族炭化水素類、や酢酸エチル、酢酸ブチルなどのエステル類が挙げられるが、チタンアルコキシドおよびジルコニウムアルコキシドが溶解する溶媒であれば特に限定されない。 As a solvent for the coating liquid, alcohols such as ethanol, isopropanol, and normal butanol, cellosolves such as methyl cellosolve and butyl cellosolve, aromatic hydrocarbons such as toluene and xylene, and esters such as ethyl acetate and butyl acetate. However, it is not particularly limited as long as it is a solvent in which titanium alkoxide and zirconium alkoxide are dissolved.
コーティング液には、上記成分に加え、例えば、塗布層の均一性を上げるためにレベリング剤などの界面活性剤を添加することができる。 In addition to the above components, for example, a surfactant such as a leveling agent can be added to the coating liquid in order to improve the uniformity of the coating layer.
コーティング液の衛生陶器への適用は、好ましくは、刷毛塗り、ローラー、スプレー、ロールコーター、フローコーター、ディップコート、流し塗り、スクリーン印刷等、一般に広く行われている方法により行われてよい。 The application of the coating liquid to sanitary ware may preferably be carried out by a commonly used method such as brush coating, roller, spray, roll coater, flow coater, dip coating, flow coating, screen printing and the like.
上記中間層および光触媒層を形成するためのコーティング液が適用された衛生陶器は、焼成工程に付される。焼成は、中間層、その後光触媒層と行われてもよいが、本発明の好ましい態様によれば、同時に焼成される。焼成条件は適宜決定されてよいが、例えば、700〜900℃の温度で、5時間程度行われればよく、好ましくは750〜850℃の温度で、0.5〜3時間程度である。 The sanitary ware to which the coating liquid for forming the intermediate layer and the photocatalyst layer is applied is subjected to a firing process. Firing may be performed with the intermediate layer and then with the photocatalyst layer, but according to a preferred embodiment of the present invention, firing is performed simultaneously. The firing conditions may be appropriately determined, but for example, it may be carried out at a temperature of 700 to 900° C. for about 5 hours, preferably at a temperature of 750 to 850° C. for about 0.5 to 3 hours.
以上より明らかなように、本発明の好ましい態様によれば、本発明による衛生陶器の製造方法が提供される。この方法は、衛生陶器の釉薬層上に、シリコンアルコキシドまたはその加水分解物およびチタンアルコキシドおよび/またはジルコニウムアルコキシドとを混合したコーティング液を塗布し、さらにその酸化チタンの前駆体および酸化ジルコニウムの前駆体を含むコーティング液を塗布し、その後、750〜850℃の温度で焼成する工程を含んでなることを特徴とする。 As is clear from the above, according to a preferred aspect of the present invention, there is provided a method for manufacturing a sanitary ware according to the present invention. In this method, a coating liquid in which a silicon alkoxide or a hydrolyzate thereof and a titanium alkoxide and/or a zirconium alkoxide are mixed is applied onto a glaze layer of sanitary ware, and the titanium oxide precursor and the zirconium oxide precursor are applied. Is applied, and then firing is carried out at a temperature of 750 to 850° C.
本発明を以下の例に基づいて具体的に説明するが、本発明はこれらの例に限定されるものではない。 The present invention will be specifically described based on the following examples, but the present invention is not limited to these examples.
中間層形成のためのコーティング液の調製
シリカアルコキシド(アルコキシシラン加水分解液、コルコート株式会社製)と、チタンアルコキシド(チタンジイソプロポキシビス(アセチルアセトネート)、NDH−510C、日本曹達株式会社製)またはジルコニウムアルコキシド(化合物名:ジルコニウムトリブトキシモノアセチルアセトネート 商品名:オルガチックスZC−540、マツモトファインケミカル株式会社製)とを、焼成後の固形分の重量比が下記の表に記載される割合となるように混合した。次いで、この混合物を、2-プロパノール(80%)とメチルセロソルブ(20%)の混合溶媒で、焼成後の固形分が0.5%になるように希釈し、希釈液を攪拌機で混合した。得られた混合液を1時間以上放置して、これを中間層形成のためのコーティング液とした。
Preparation of coating liquid for forming intermediate layer Silica alkoxide (alkoxysilane hydrolysis liquid, manufactured by Colcoat Co., Ltd.) and titanium alkoxide (titanium diisopropoxybis(acetylacetonate), NDH-510C, manufactured by Nippon Soda Co., Ltd.) Alternatively, zirconium alkoxide (compound name: zirconium tributoxy monoacetylacetonate, trade name: Organix ZC-540, manufactured by Matsumoto Fine Chemical Co., Ltd.), and the weight ratio of the solid content after firing and the proportions described in the table below Mixed so that Next, this mixture was diluted with a mixed solvent of 2-propanol (80%) and methyl cellosolve (20%) so that the solid content after firing was 0.5%, and the diluted solution was mixed with a stirrer. The obtained mixed liquid was left standing for 1 hour or more, and this was used as a coating liquid for forming an intermediate layer.
光触媒層形成のためのコーティング液の調製
チタンアルコキシド(化合物名:チタンジイソプロポキシビス(アセチルアセトネート)商品名:NDH−510C、日本曹達株式会社製)と、ジルコニウムアルコキシド(化合物名:ジルコニウムトリブトキシモノアセチルアセトネート 商品名:オルガチックスZC−540、マツモトファインケミカル株式会社製)とを、焼成後の酸化チタン/酸化ジルコニウムの固形分の重量比が下記の表に記載される割合となるように混合した。次いで、この混合物を、2-プロパノール(80%)とメチルセロソルブ(20%)の混合溶媒で、焼成後の固形分が0.5%になるように希釈し、希釈液を攪拌機で混合した。得られた混合液を1時間以上放置して、これをコーティング液とした。
Preparation of coating liquid for forming photocatalyst layer Titanium alkoxide (Compound name: titanium diisopropoxybis(acetylacetonate) Trade name: NDH-510C, manufactured by Nippon Soda Co., Ltd.) and zirconium alkoxide (Compound name: zirconium tributoxy). Monoacetylacetonate (trade name: Organix ZC-540, manufactured by Matsumoto Fine Chemical Co., Ltd.) is mixed so that the weight ratio of titanium oxide/zirconium oxide solid content after firing is the ratio described in the following table. did. Next, this mixture was diluted with a mixed solvent of 2-propanol (80%) and methyl cellosolve (20%) so that the solid content after firing was 0.5%, and the diluted solution was mixed with a stirrer. The obtained mixed liquid was left standing for 1 hour or more, and this was used as a coating liquid.
陶器タイルの作成
陶器原料を鋳込み成形して素地を得て、この素地の表面にハンドスプレーガン(F100 明治機械製作所株式会社製)を使用して釉薬を塗布した。続いて、徐々に昇温および降温しながら最高温度1180℃に設定されたトンネル窯を24時間通過させて焼成して、陶器タイルを得た。なお、釉薬は、以下の範囲の組成のものを用いた。
釉薬組成
SiO2 55〜80重量%
Al2O3 5〜13重量%
Fe2O3 0.1〜0.4重量%
MgO 0.8〜3重量%
CaO 8〜17重量%
ZnO 3〜8重量%
K2O 1〜4重量%
Na2O 0.5〜2.5重量%
ZrO 0.1〜15重量%
顔料 0.01〜5重量%
Preparation of pottery tile A pottery raw material was cast and molded to obtain a base material, and a glaze was applied to the surface of the base material using a hand spray gun (F100 manufactured by Meiji Machine Mfg. Co., Ltd.). Subsequently, while gradually raising and lowering the temperature, it was passed through a tunnel kiln set to a maximum temperature of 1180° C. for 24 hours and fired to obtain a ceramic tile. The glaze used had a composition within the following range.
Glaze composition
SiO 2 55-80% by weight
Al 2 O 3 5 to 13% by weight
Fe 2 O 3 0.1-0.4 wt%
MgO 0.8-3% by weight
CaO 8-17% by weight
ZnO 3-8 wt%
K 2 O 1-4% by weight
Na 2 O 0.5-2.5 wt%
ZrO 0.1-15% by weight
Pigment 0.01-5% by weight
中間層の形成
上で得られた陶器タイル表面に、ハンドスプレーガン(F100 明治機械製作所株式会社製)を用いて、上で得た中間層形成用コーティング液を、焼成後の膜厚が50nmになるように塗布量を制御して塗布した。
Using a hand spray gun (F100, manufactured by Meiji Kikai Seisakusho Co., Ltd.), the coating liquid for forming an intermediate layer obtained above was applied to the surface of the ceramic tile obtained in the formation of the intermediate layer to a film thickness of 50 nm after firing. The coating amount was controlled so as to achieve the above.
光触媒層の形成および焼成
上で得られた中間層形成用コーティング液を塗布した陶器タイル表面に、ハンドスプレーガン(F100 明治機械製作所株式会社製)を用いて、上で得た光触媒層形成用コーティング液を焼成後の膜厚が50nmになるように塗布量を制御してコーティングした。
Formation of a photocatalyst layer and firing A photocatalyst layer-forming coating obtained above using a hand spray gun (F100 manufactured by Meiji Kikai Seisakusho Co., Ltd.) on the surface of a ceramic tile coated with the coating liquid for forming an intermediate layer obtained above Coating was performed by controlling the coating amount so that the film thickness after baking the liquid would be 50 nm.
次いで、徐々に昇温および降温しながら最高温度800℃に設定された高温電気炉(FUH732DA ADVANTEC株式会社製)で24時間かけて焼成して、光触媒コーティングタイルを得た。 Then, while gradually raising and lowering the temperature, it was fired for 24 hours in a high temperature electric furnace (manufactured by FUH732DA ADVANTEC Co., Ltd.) set to a maximum temperature of 800° C. to obtain a photocatalyst coated tile.
光触媒活性
光触媒コーティングタイルの光触媒活性を、JIS R1703−2に準じたメチレンブルー分解指数で評価した。その結果を以下の基準で評価した。
分解指数が7以上:○
5以上7未満:△
分解指数が5未満:×
その結果は以下の表に示されるとおりであった。
Photocatalytic activity The photocatalytic activity of the photocatalytic coating tile was evaluated by the methylene blue decomposition index according to JIS R1703-2. The results were evaluated according to the following criteria.
Decomposition index is 7 or more: ○
5 or more and less than 7: △
Decomposition index less than 5: ×
The results are shown in the table below.
酸性アルカリ性耐久性試験
酸性水(pH3.5)とアルカリ水(pH9.5)を2分間隔で交互に10秒間流出する試験装置を用意し、この装置の流水下に光触媒コーティングタイルを設置した。このとき、酸性水とアルカリ水とを双方適用して、これを1サイクルとした。
Acid/Alkali Durability Test A test apparatus was prepared in which acidic water (pH 3.5) and alkaline water (pH 9.5) were alternately flown out at 2 minute intervals for 10 seconds, and a photocatalyst-coated tile was installed under running water of this apparatus. At this time, both acidic water and alkaline water were applied to make one cycle.
所定サイクル経過後、JISK5600−5−6に基づきテープ剥離試験を実施した。その結果を以下の基準で評価した。
14000サイクルで剥離なし:◎
10000サイクルを越え14000サイクルまで剥離が発生:○
6000サイクルを越え10000サイクルまで剥離が発生:△
6000サイクルまで剥離が発生:×
その結果は以下の表に示されるとおりであった。
After a lapse of a predetermined cycle, a tape peeling test was carried out based on JISK5600-5-6. The results were evaluated according to the following criteria.
No peeling in 14000 cycles: ◎
Peeling occurred over 10,000 cycles and up to 14,000 cycles: ○
Peeling occurred over 6000 cycles and up to 10,000 cycles: △
Peeling occurred up to 6000 cycles: ×
The results are shown in the table below.
耐摺動性試験
ラビングテスター(太平理化工業株式会社製)を使用して、光触媒コーティングタイルの耐摺動性試験を実施した。ウレタンスポンジ(スコッチブライト(SS−72K 住友3M株式会社製))を2.24cm角に切断したものを、両面テープを用いて不織布の部分が摺動面に当たるようにヘッドに接着したあと、蒸留水で濡らした。次いで、250gの錘を載せて(荷重条件:5kPa)所定回数摺動し、表面のキズの有無を目視で確認した。ウレタンスポンジは1000回摺動ごとに新しいものと取り替えた。結果を以下の基準で評価した。
20000回の摺動後に視認できるキズなし:◎
10000回を越え20000回までの摺動で視認できるキズあり:○
2000回を越え10000回までの摺動で視認できるキズあり:△
2000回までの摺動で視認できるキズあり:×
その結果は以下の表に示されるとおりであった。
Sliding resistance test A rubbing tester (manufactured by Taihei Rika Kogyo Co., Ltd.) was used to perform a sliding resistance test of the photocatalyst-coated tile. Urethane sponge (Scotch Bright (SS-72K, manufactured by Sumitomo 3M Co., Ltd.)) was cut into 2.24 cm square pieces and bonded to the head using a double-sided tape so that the non-woven fabric part hits the sliding surface, and then distilled water. I got wet with. Then, a weight of 250 g was placed (loading condition: 5 kPa) and slid a predetermined number of times, and the presence or absence of scratches on the surface was visually confirmed. The urethane sponge was replaced with a new one after every 1000 slides. The results were evaluated according to the following criteria.
No visible scratches after sliding 20000 times: ◎
There are scratches that can be visually recognized after sliding 10,000 times to 20,000 times: ○
There are scratches visible after sliding 2000 times to 10,000 times: △
There are scratches visible when sliding up to 2000 times: ×
The results are shown in the table below.
なお、表中数値は質量%またはそれを基準とする値である。 The numerical values in the table are mass% or values based on it.
Claims (9)
前記光触媒層が、酸化チタンと酸化ジルコニウムとを、それぞれ95質量%〜75質量%および5〜25質量%の量で含んでなり、
前記中間層が、シリカと、酸化チタンおよび/または酸化ジルコニウムとを、それぞれ98質量%〜85質量%、および(酸化チタンと酸化ジルコニウムの両方を含む場合その合計として)2質量%〜15質量%含んでなる
ことを特徴とする、衛生陶器。 A sanitary ware comprising a glaze layer, an intermediate layer provided on the glaze layer, and a photocatalyst layer provided on the intermediate layer.
The photocatalyst layer comprises titanium oxide and zirconium oxide in amounts of 95% by weight to 75% by weight and 5 to 25% by weight, respectively,
The intermediate layer contains silica and titanium oxide and/or zirconium oxide in an amount of 98% by mass to 85% by mass, respectively, and (in the case of containing both titanium oxide and zirconium oxide, as a total thereof) 2% by mass to 15% by mass. Sanitary ware characterized by comprising.
衛生陶器の釉薬層上に、シリコンアルコキシドまたはその加水分解物およびチタンアルコキシドおよび/またはジルコニウムアルコキシドとを混合したコーティング液を塗布し、
さらにその酸化チタンの前駆体および酸化ジルコニウムの前駆体を含むコーティング液を塗布し、
その後、750〜850℃の温度で焼成する工程を含んでなることを特徴とする、衛生陶器の製造方法。 A method for manufacturing a sanitary ware according to any one of claims 1 to 8,
On the glaze layer of sanitary ware, apply a coating liquid in which silicon alkoxide or its hydrolyzate and titanium alkoxide and/or zirconium alkoxide are mixed,
Furthermore, a coating liquid containing the titanium oxide precursor and the zirconium oxide precursor is applied,
Then, the manufacturing method of the sanitary ware characterized by including the process of baking at the temperature of 750-850 degreeC.
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
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KR1020160093349A KR101865598B1 (en) | 2015-09-15 | 2016-07-22 | Sanitary ware having photocatalyst layer |
CN201610809150.6A CN106518169B (en) | 2015-09-15 | 2016-09-07 | Sanitary earthenware with photocatalyst layer |
TW105129149A TWI650247B (en) | 2015-09-15 | 2016-09-08 | Sanitary pottery with photocatalyst layer |
US15/263,902 US10010865B2 (en) | 2015-09-15 | 2016-09-13 | Sanitary ware having photocatalyst layer |
EP16188446.5A EP3144288B1 (en) | 2015-09-15 | 2016-09-13 | Sanitary ware having photocatalyst layer |
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