JPWO2011108472A1 - Glaze glass, glaze, and photocatalyst member - Google Patents
Glaze glass, glaze, and photocatalyst member Download PDFInfo
- Publication number
- JPWO2011108472A1 JPWO2011108472A1 JP2012503118A JP2012503118A JPWO2011108472A1 JP WO2011108472 A1 JPWO2011108472 A1 JP WO2011108472A1 JP 2012503118 A JP2012503118 A JP 2012503118A JP 2012503118 A JP2012503118 A JP 2012503118A JP WO2011108472 A1 JPWO2011108472 A1 JP WO2011108472A1
- Authority
- JP
- Japan
- Prior art keywords
- glaze
- glass
- component
- crystal
- photocatalytic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000113 methacrylic resin Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000005304 optical glass Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- 238000002294 plasma sputter deposition Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- UKDIAJWKFXFVFG-UHFFFAOYSA-N potassium;oxido(dioxo)niobium Chemical compound [K+].[O-][Nb](=O)=O UKDIAJWKFXFVFG-UHFFFAOYSA-N 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 238000005029 sieve analysis Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000013526 supercooled liquid Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
- C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
- C03C17/007—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/14—Silica-free oxide glass compositions containing boron
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/16—Silica-free oxide glass compositions containing phosphorus
- C03C3/21—Silica-free oxide glass compositions containing phosphorus containing titanium, zirconium, vanadium, tungsten or molybdenum
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
- C03C8/08—Frit compositions, i.e. in a powdered or comminuted form containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
- C03C8/18—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing free metals
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/44—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the composition of the continuous phase
- C03C2217/45—Inorganic continuous phases
- C03C2217/452—Glass
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
- C03C2217/48—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase having a specific function
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/71—Photocatalytic coatings
Abstract
加熱によって光触媒特性を有する結晶を生成する釉薬用ガラス、釉薬、及び光触媒特性を有する釉薬層を備える部材が提供される。前記釉薬層の原料となる釉薬用ガラスは、酸化物換算組成のモル％で、ＴｉＯ２、ＷＯ３、ＺｎＯ、Ｎｂ２Ｏ５、およびＴａ２Ｏ５より選択される１種以上の成分を合計で５〜９９％、ＳｉＯ２、Ｂ２Ｏ３、Ｐ２Ｏ５、及びＧｅＯ２から選択される１種以上の成分を合計で１〜８５％含有し、加熱することで釉薬層中にＴｉＯ２結晶、ＷＯ３結晶、ＺｎＯ結晶、ＲｎＮｂＯ３、ＲｎＴａＯ３、ＲＮｂＯ３、ＲＴａＯ３、ナシコンタイプの結晶相及びこれら結晶の固溶体からなる群から選ばれるいずれか１つ以上の光触媒結晶を生成するものである。There is provided a member comprising a glaze glass that produces crystals having photocatalytic properties by heating, a glaze, and a glaze layer having photocatalytic properties. The glaze glass used as the raw material of the glaze layer is a mol% of the oxide conversion composition, and a total of one or more components selected from TiO2, WO3, ZnO, Nb2O5, and Ta2O5 is 5 to 99%, SiO2, It contains 1 to 85% in total of one or more components selected from B2O3, P2O5, and GeO2, and by heating, the TiO2 crystal, WO3 crystal, ZnO crystal, RnNbO3, RnTaO3, RNbO3, RTaO3, One or more photocatalytic crystals selected from the group consisting of NASICON type crystal phases and solid solutions of these crystals are produced.
Description
本発明は、様々な生活用品および建築用外装材等に用いられる、陶磁器製品および琺瑯製品の表面をコーティングする釉薬に係り、その釉薬の材料として好適なガラス組成物、該ガラス組成物を含有する釉薬、該釉薬でコーティングされた光触媒部材、及びその製造方法に関するものである。 The present invention relates to a glaze that coats the surface of ceramic products and glaze products used for various daily necessities and building exterior materials, and contains a glass composition suitable as a material for the glaze, and the glass composition. The present invention relates to a glaze, a photocatalytic member coated with the glaze, and a method for producing the same.
光を照射することにより触媒作用を示す物質を光触媒という。光によって励起状態になり、そのエネルギーを他に与えることができる物質は、原理的に何でも光触媒になり得るが、典型的な光触媒は半導体であり、酸化チタン（ＴｉＯ２）を始め多くの金属酸化物半導体が光触媒特性を有していることが報告されている。光触媒特性を有する半導体は、バンドギャップエネルギー以上のエネルギーの光を吸収すると電子や正孔を生成し、これらの電子や正孔により光触媒反応が起こる。光触媒反応による代表的な作用としては、酸化作用や超親水現象をあげることができる。光触媒の持つ酸化力は、汚れや汚染物質、悪臭成分などを分解・除去し、浄化する働きをするうえ、太陽光などを利用できるところから、エネルギーフリーな環境浄化技術として注目を浴びている。また光により超親水性が現れる特性は、セルフクリーニングまたは防曇機能を有する部材や、印刷方法等への応用が期待されている。A substance that exhibits a catalytic action when irradiated with light is called a photocatalyst. Any substance that can be excited by light and give other energy can in principle be a photocatalyst, but a typical photocatalyst is a semiconductor, and many metal oxides such as titanium oxide (TiO 2 ). It has been reported that physical semiconductors have photocatalytic properties. A semiconductor having photocatalytic properties generates electrons and holes when it absorbs light having energy higher than the band gap energy, and a photocatalytic reaction occurs due to these electrons and holes. Typical actions by the photocatalytic reaction include an oxidation action and a superhydrophilic phenomenon. The oxidizing power of photocatalysts is attracting attention as an energy-free environmental purification technology because it works by decomposing, removing, and purifying dirt, pollutants, and offensive odor components, as well as using sunlight. Further, the property that superhydrophilicity appears by light is expected to be applied to a member having a self-cleaning or anti-fogging function, a printing method, and the like.
前述した光触媒の酸化分解特性は光触媒と反応物の界面で起こる反応であり、光による超親水性も光触媒の表面で起こる現象であることから、光触媒は一般的に基材等の表面にコーティングされた形で利用される。このための固定化技術には様々なものがあり、光触媒を含有する塗料を塗布する方法、光触媒ゾルを塗布して焼成する方法、スパッタ法等で成膜する方法、多孔質材料の細孔部分に光触媒を充填させる方法などが挙げられる。 The oxidative decomposition characteristics of the photocatalyst described above are reactions that occur at the interface between the photocatalyst and the reactant, and the superhydrophilicity caused by light is also a phenomenon that occurs on the surface of the photocatalyst. Therefore, the photocatalyst is generally coated on the surface of a substrate or the like. It is used in the form. There are various immobilization techniques for this purpose, such as a method of applying a paint containing a photocatalyst, a method of applying and baking a photocatalyst sol, a method of forming a film by a sputtering method, etc., a pore portion of a porous material And a method of filling the photocatalyst with a photocatalyst.
このうち、基材の表面に無機チタン化合物層を形成するために用いられる塗布剤として、合成樹脂を分散相とする水性エマルジョンに高濃度の無機チタン化合物が含まれた光触媒性塗布剤が開示されている（例えば、特許文献１）。このような塗料は、常温硬化する点においては利便性が高いが、分散剤およびバインダーとして光触媒によって分解される恐れのある有機物を使っているため、塗布された光触媒層の基材との密着性および耐久性が悪いという問題がある。 Among these, as a coating agent used for forming an inorganic titanium compound layer on the surface of a substrate, a photocatalytic coating agent in which a high concentration inorganic titanium compound is contained in an aqueous emulsion having a synthetic resin as a dispersed phase is disclosed. (For example, Patent Document 1). Such a paint is convenient in terms of curing at room temperature, but uses an organic substance that may be decomposed by the photocatalyst as a dispersant and binder, so that the coated photocatalyst layer adheres to the substrate. And there is a problem of poor durability.
光触媒ゾルを用いる方法としては、超微粒子の酸化チタンを水に懸濁させる、または、アルコールと四塩化チタンや金属チタンとの反応によって得られるチタンのアルコキシドを加水分解するなどして調製したチタニアゾルを基板にコーティングした後、焼成することを特徴とする酸化チタン薄膜光触媒の製造方法が開示されている（例えば、特許文献２）。ゾルを用いる方法は、原液の作製に時間がかかる、原液の製造や塗布作業は大気中では出来ないので雰囲気制御を必要とする等の問題があり、膜自体の付着強度も十分でなく剥離しやすい。 As a method using a photocatalyst sol, titania sol prepared by suspending ultrafine titanium oxide in water or hydrolyzing titanium alkoxide obtained by reaction of alcohol with titanium tetrachloride or metal titanium is used. A method for producing a titanium oxide thin film photocatalyst characterized by firing after coating on a substrate is disclosed (for example, Patent Document 2). The method using sol has a problem that it takes time to prepare the stock solution, and the manufacturing and coating work of the stock solution cannot be performed in the air, so the atmosphere needs to be controlled, and the adhesion strength of the film itself is not sufficient. Cheap.
また、光触媒粒子から成る光触媒層を基材に密着させるために基材と光触媒層との間にバインダー層を形成し、バインダー層の軟化温度よりも高く且つ基材の軟化温度よりも低い雰囲気温度で加熱処理することにより光触媒を露出しつつ基材に密着させる方法が開示されている（例えば、特許文献３）。しかしこのような方法においては、露出する光触媒粉末の大きさが光触媒活性に大きく影響する。比表面積を大きくして光触媒活性を高めるためには、平均粒径が非常に小さい光触媒を用いる必要があるが、微粒子は表面エネルギーが高く凝集し易いので、均一に分散させることが難しく、取扱いも困難である。 In addition, a binder layer is formed between the substrate and the photocatalyst layer in order to adhere the photocatalyst layer composed of photocatalyst particles to the substrate, and the ambient temperature is higher than the softening temperature of the binder layer and lower than the softening temperature of the substrate. A method is disclosed in which the photocatalyst is adhered to the base material while being exposed to heat (for example, Patent Document 3). However, in such a method, the size of the exposed photocatalyst powder greatly affects the photocatalytic activity. In order to increase the specific surface area and increase the photocatalytic activity, it is necessary to use a photocatalyst with a very small average particle diameter. However, since the fine particles have high surface energy and are easy to aggregate, it is difficult to disperse uniformly and handle them. Have difficulty.
また、プラズマ溶射またはスパッタ法等を用いる場合には（例えば、特許文献４）、設備が大規模になり、製造コストが非常に高くなるという問題がある。 Further, when plasma spraying or sputtering is used (for example, Patent Document 4), there is a problem that the equipment becomes large and the manufacturing cost becomes very high.
一方、密着性および強度において良好な特性を期待できる光触媒の固定化方法として、釉薬を使用することが知られている。釉薬は基材の表面に焼き付けるものであるため、釉薬層そのものが光触媒活性を有していれば、その効果が半永久的に持続するという利点がある。また、釉薬層および光触媒コーティング層を複数の工程に分けて形成する必要がないので、製造工程がシンプルになる。 On the other hand, it is known to use glaze as a method for immobilizing a photocatalyst that can be expected to have good properties in adhesion and strength. Since the glaze is baked onto the surface of the base material, if the glaze layer itself has photocatalytic activity, there is an advantage that the effect is maintained semipermanently. Moreover, since it is not necessary to form the glaze layer and the photocatalyst coating layer in a plurality of steps, the manufacturing process is simplified.
また、施釉製品は一般的に光触媒機能を付与するニーズが高い。琺瑯材を含む施釉製品は主にタイル、洗面台、便器などの衛生陶器、および屋内向けの建材等に使われることが多く、これらの部材は、水分、油分による汚れ、カビなどが発生しやすい場所に利用されることが多いので、光触媒による浄化機能を有することが好ましい。 In addition, glazed products generally have a high need for providing a photocatalytic function. Glazed products containing glazed materials are often used mainly for tiles, washstands, sanitary ware such as toilets, and indoor building materials. These components are prone to moisture, oil stains, and mold. Since it is often used in places, it is preferable to have a purification function using a photocatalyst.
そこで例えば、光触媒としてアナターゼ型酸化チタン粉末と、無機質ガラス粉末（フリット）とを混合したスラリーを塗布し、焼成することによりガラス質被膜からなる釉薬層を形成した琺瑯材の開示がある（特許文献４〜６）。しかしながら、これらの技術において、大きい酸化・還元力を得るためには、釉薬に添加する光触媒としてナノオーダーの微粒子を用いる必要があった。反応物との界面における光触媒粒子のサイズが微細であるほど光触媒活性が高くなるからである。しかし、このような微粒子は、表面エネルギーが高く、凝集しようとする力が大きいので、釉薬に均一に分散させることが非常に難しい。また容易に飛散するので、あらゆる工程において取扱いおよび回収が困難であるという問題がある。 Thus, for example, there is a disclosure of a glaze material in which a glaze layer made of a glassy film is formed by applying and firing a slurry in which anatase-type titanium oxide powder and inorganic glass powder (frit) are mixed as a photocatalyst (Patent Document) 4-6). However, in these techniques, in order to obtain a large oxidizing / reducing power, it is necessary to use nano-order fine particles as a photocatalyst added to the glaze. This is because the photocatalytic activity increases as the size of the photocatalyst particles at the interface with the reactant becomes finer. However, since such fine particles have a high surface energy and a large force to aggregate, it is very difficult to uniformly disperse them in the glaze. Moreover, since it scatters easily, there exists a problem that handling and collection | recovery are difficult in every process.
また、光触媒釉薬として、アナターゼ型酸化チタンを含有し６００℃以上７００℃未満の温度で焼成可能な釉薬が開示されている（例えば、特許文献７）。しかし、この釉薬は、アナターゼ型酸化チタンの相転移を防ぐために７００℃未満という比較的低い温度範囲で焼成する必要があり、強固な釉薬層を形成するには限界があった。この光触媒釉薬を強固に固定するために高温処理をすると、その過程で光触媒の活性が悪くなってしまう。また、この釉薬の焼成後の表面は、多孔質的かつ微細な凹凸が形成されたものであり、防汚性が不十分になり易く、光沢感や透明感といった釉薬特有の質感が得られないという問題がある。 Moreover, the glaze which contains anatase type titanium oxide and can be baked at the temperature of 600 to 700 degreeC as a photocatalyst glaze is disclosed (for example, patent document 7). However, this glaze needs to be fired in a relatively low temperature range of less than 700 ° C. in order to prevent the phase transition of anatase-type titanium oxide, and there is a limit to forming a strong glaze layer. If high-temperature treatment is performed in order to firmly fix the photocatalytic glaze, the photocatalytic activity deteriorates in the process. In addition, the surface of the glaze after firing has porous and fine irregularities, and the antifouling property tends to be insufficient, and a glaze-like and transparent texture specific to the glaze cannot be obtained. There is a problem.
施釉製品に幅広く適用するためには、光触媒釉薬は、釉薬が有する本来の光沢性を失わない釉薬層を形成するものであることが好ましい。また、釉薬の透明感を出すために、光触媒釉薬による釉薬層は、透明であることが好ましい。透明であれば基材の色を損ねることなく利用できるし、光を遮らないのでランプカバー、窓材などにも適用できる。 In order to widely apply to glazed products, it is preferable that the photocatalytic glaze forms a glaze layer that does not lose the original gloss of the glaze. Moreover, in order to bring out the transparency of the glaze, the glaze layer made of the photocatalytic glaze is preferably transparent. If it is transparent, it can be used without damaging the color of the base material, and it can be applied to lamp covers, window materials, etc. because it does not block light.
これに関連して、光沢性を有する琺瑯材が開示されている（例えば、特許文献８）。この琺瑯材は、光触媒粒子と無機質ガラス粉末とを含む釉薬スラリーを基材に塗布して、前記無機質ガラス粉末の軟化温度以上で焼成することで作られる。しかし、この釉薬もアナターゼ型酸化チタンの相転移を防ぐために低い温度範囲で焼成する必要がある。また一般的に、釉薬原料に光触媒微粒子を混入して形成した釉薬層は、溶融した釉薬原料の流動が該粒子によって妨げられ、滑らかな面を形成することが困難であるという問題がある。そこで、前記特許文献２では、光沢性を損なわず釉薬層の表面から光触媒粒子を露出させるために、光触媒の粒子を５０ｎｍ以下の１次粒子が集まった凝集体にする必要があるとしている。しかし前述したように、ナノオーダーの超微粒子は生成後の回収及びその後の取扱いが非常に難しく、製造工程が複雑になる。 In relation to this, a glaze having gloss is disclosed (for example, Patent Document 8). This glaze is produced by applying a glaze slurry containing photocatalyst particles and inorganic glass powder to a base material and firing at a temperature equal to or higher than the softening temperature of the inorganic glass powder. However, this glaze also needs to be fired in a low temperature range in order to prevent the phase transition of anatase-type titanium oxide. In general, the glaze layer formed by mixing photocatalyst fine particles into the glaze raw material has a problem that the flow of the molten glaze raw material is hindered by the particles, and it is difficult to form a smooth surface. Therefore, in Patent Document 2, it is said that the photocatalyst particles need to be aggregates of primary particles of 50 nm or less in order to expose the photocatalyst particles from the surface of the glaze layer without impairing the gloss. However, as described above, nano-order ultrafine particles are very difficult to recover after production and subsequent handling, and the manufacturing process becomes complicated.
本発明はこのような事情に鑑みてなされたものであり、光触媒の微粒子を扱う必要がなく、密着性向上または強度向上のために高温焼成を行っても光触媒活性の劣化が少なく、基材との密着性に優れ、かつ簡便な工程により光触媒機能を有する釉薬層を形成することが可能な、新規な釉薬組成物を提供することをその目的とする。 The present invention has been made in view of such circumstances, it is not necessary to handle fine particles of photocatalyst, and there is little deterioration in photocatalytic activity even when high-temperature firing is performed for improving adhesion or strength, and the substrate and It is an object of the present invention to provide a novel glaze composition capable of forming a glaze layer having excellent photoadhesiveness and having a photocatalytic function by a simple process.
また、本発明は該釉薬組成物を用いて形成した釉薬層を有する部材であって、光沢性、耐久性、及び光触媒機能に優れた光触媒部材を得ることをその目的とする。さらに、取り扱いが困難な微粒子を扱う必要がなく、簡便な工程により前記光触媒部材を製造することを目的とする。 Another object of the present invention is to obtain a photocatalyst member having a glaze layer formed using the glaze composition and having excellent glossiness, durability, and photocatalytic function. It is another object of the present invention to produce the photocatalyst member by a simple process without having to handle fine particles that are difficult to handle.
本発明者らは、上記課題を解決するために、鋭意試験研究を重ねた結果、ガラスを加熱することでガラスから光触媒活性を有する結晶（以下、光触媒結晶という）を析出することが可能であることを見出した。そして基材に前記ガラスを含む釉薬を施釉することで、釉薬特有の質感および機能を損なうことなく光触媒機能を有する施釉部材が得られることを見出し、本発明を完成するに至った。具体的には、本発明は以下のようなものを提供する。 In order to solve the above-mentioned problems, the present inventors have conducted intensive test studies, and as a result, it is possible to precipitate crystals having photocatalytic activity (hereinafter referred to as photocatalytic crystals) from the glass by heating the glass. I found out. And it discovered that the glaze member which has a photocatalyst function was obtained without impairing the texture and function peculiar to a glaze by glaze the glaze containing the said glass to a base material, and came to complete this invention. Specifically, the present invention provides the following.
（１）加熱によって、光触媒特性を有する結晶を生成する、釉薬用ガラス。
（２）酸化物換算組成のモル％で、ＴｉＯ２、ＷＯ３、ＺｎＯ、Ｎｂ２Ｏ５、およびＴａ２Ｏ５より選択される１種以上の成分を合計で５〜９９％、並びに、ＳｉＯ２、Ｂ２Ｏ３、Ｐ２Ｏ５、及びＧｅＯ２から選択される１種以上の成分を合計で１〜８５％以下含有する、（１）記載の釉薬用ガラス。
（３）酸化物換算組成のモル％で、ＲＯ成分及び／またはＲｎ２Ｏ成分を０〜５０％（式中、ＲはＭｇ、Ｃａ、Ｓｒ、Ｂａから選ばれる１種以上、ＲｎはＬｉ、Ｋ、Ｎａから選ばれる１種以上とする）含有する、（１）または（２）いずれか記載の釉薬用ガラス。
（４）酸化物換算組成のモル％で、
Ａｌ２Ｏ３成分を０〜３０％、
Ｇａ２Ｏ３成分を０〜３０％、
Ｉｎ２Ｏ３成分を０〜３０％、
ＺｒＯ２成分を０〜２０％、
ＳｎＯ成分を０〜２０％、
Ｂｉ２Ｏ３成分及び／又はＴｅＯ２成分を０〜２０％、
ＭｏＯ成分を０〜３０％、
Ｌｎ２Ｏ３成分を０〜３０％（ＬｎはＹ、Ｃｅ、Ｌａ、Ｎｄ、Ｇｄ、Ｄｙ、Ｙｂから選ばれる一種以上）、
ＭｘＯｙ成分を０〜１０％（Ｍは、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、及びＮｉから選ばれる一種以上とし、ｘ及びｙはそれぞれｘ：ｙ＝２：（Ｍの価数）を満たす最小の自然数とする）
Ａｓ２Ｏ３成分及び／又はＳｂ２Ｏ３成分を０〜５％、
含有する、（１）から（３）いずれか記載の釉薬用ガラス。
（５）酸化物換算組成のガラス全物質量に対する外割り質量％で、
Ｆ、Ｃｌ、Ｂｒ、Ｓ、Ｎ、及びＣから選ばれる１種以上の非金属元素成分を０．０１〜１０％含有する、（１）から（４）いずれか記載の釉薬用ガラス。
（６）酸化物換算組成のガラス全物質量に対する外割り質量％で、
Ｃｕ、Ａｇ、Ａｕ、Ｐｄ、Ｐｔ、Ｒｕ、Ｒｅ及びＲｈから選ばれる１種以上の金属元素成分を０．００１〜５％含有する、（１）から（５）いずれか記載の釉薬用ガラス。
（７）前記（１）から（６）いずれか記載の釉薬用ガラスを結晶化させることで得られた、釉薬用結晶化ガラス。
（８）ＴｉＯ２結晶、ＷＯ３結晶、ＺｎＯ結晶、ＲｎＮｂＯ３、ＲｎＴａＯ３、ＲＮｂＯ３、ＲＴａＯ３、ナシコンタイプの結晶及びこれら結晶の固溶体からなる群から選ばれるいずれか１つ以上の結晶を含む（７）記載の釉薬用結晶化ガラス（式中、ＲはＭｇ、Ｃａ、Ｓｒ、Ｂａから選ばれる１種以上、ＲｎはＬｉ、Ｋ、Ｎａから選ばれる１種以上とする）。
（９）（１）から（８）いずれか記載の釉薬用ガラス及び／または釉薬用結晶化ガラスからなる粉粒体。
（１０）（１）から（９）いずれか記載の粉粒体を含む釉薬。
（１１）前記粉粒体を５０〜９９％、および植物の灰、石灰、珪石、長石、粘土、フリット、有機バインダーから選ばれるいずれか１つ以上を合計で１〜５０％含有する（１０）記載の釉薬。
（１２）（１０）又は（１１）いずれか記載の釉薬からなる釉薬層が形成された光触媒部材。
（１３）ガラス相および光触媒特性を有する結晶相を含有し、且つ、前記釉薬層の光沢度が６０°の入射角の測定で５以上であることを特徴とする（１２）記載の部材。
（１４）前記結晶相の平均結晶粒径が５μｍ以下である（１２）または（１３）に記載の部材。
（１５）前記釉薬層が、酸化物換算組成のモル％で、ＴｉＯ２、ＷＯ３、ＺｎＯ、Ｎｂ２Ｏ５、およびＴａ２Ｏ５より選択される１種以上の成分を合計で５〜９９％、並びに、ＳｉＯ２、Ｂ２Ｏ３、Ｐ２Ｏ５、及びＧｅＯ２から選択される１種以上の成分を合計で１〜８５％含有する、（１２）から（１４）記載の部材。
（１６）前記釉薬層が、酸化物換算組成のモル％で、ＲＯ成分及び／またはＲｎ２Ｏ成分を０〜５０％（式中、ＲはＭｇ、Ｃａ、Ｓｒ、Ｂａから選ばれる１種以上、ＲｎはＬｉ、Ｋ、Ｎａから選ばれる１種以上とする）を含有する、（１２）から（１５）いずれか記載の部材。
（１７）前記釉薬層が、酸化物換算組成のモル％で、
Ａｌ２Ｏ３成分を０〜３０％、
Ｇａ２Ｏ３成分を０〜３０％、
Ｉｎ２Ｏ３成分を０〜３０％、
ＺｒＯ２成分を０〜２０％、
ＳｎＯ成分を０〜２０％、
Ｂｉ２Ｏ３成分及び／又はＴｅＯ２成分を０〜２０％、
ＭｏＯ成分を０〜３０％、
Ｌｎ２Ｏ３成分を０〜３０％（ＬｎはＹ、Ｃｅ、Ｌａ、Ｎｄ、Ｇｄ、Ｄｙ、Ｙｂから選ばれる一種以上）、
ＭｘＯｙ成分を０〜１０％（Ｍは、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、及びＮｉから選ばれる一種以上とし、ｘ及びｙはそれぞれｘ：ｙ＝２：（Ｍの価数）を満たす最小の自然数とする）、
Ａｓ２Ｏ３成分及び／又はＳｂ２Ｏ３成分を０〜５％、
含有する、（１２）から（１６）いずれか記載の部材。
（１８）前記釉薬層が、酸化物換算組成の全物質量に対する外割り質量％で、Ｆ、Ｃｌ、Ｂｒ、Ｓ、Ｎ、及びＣから選ばれる１種以上の非金属元素成分を０．０１〜１０％含有する、（１２）から（１７）いずれか記載の部材。
（１９）前記釉薬層が、酸化物換算組成のガラス全物質量に対する外割り質量％でＣｕ、Ａｇ、Ａｕ、Ｐｄ、Ｐｔ、Ｒｕ、Ｒｅ及びＲｈから選ばれる１種以上の金属元素成分を０．００１〜５％含有する、（１２）から（１８）いずれか記載の部材。
（２０）前記釉薬層が、ＴｉＯ２結晶、ＷＯ３結晶、ＺｎＯ結晶、ＲｎＮｂＯ３、ＲｎＴａＯ３、ＲＮｂＯ３、ＲＴａＯ３、ＴｉＰ２Ｏ７、（ＴｉＯ）２Ｏ７、ＲＴｉＯ３、ナシコンタイプの結晶及びこれら結晶の固溶体からなる群から選ばれるいずれか１つ以上の結晶を含む（１２）から（１９）いずれか記載の部材（式中、ＲはＭｇ、Ｃａ、Ｓｒ、Ｂａから選ばれる１種以上、ＲｎはＬｉ、Ｋ、Ｎａから選ばれる１種以上とする）。
（２１）前記釉薬層におけるＪＩＳ Ｒ １７０３−２：２００７に基づくメチレンブルーの分解活性指数が３．０ｎｍｏｌ／Ｌ／ｍｉｎ以上である（１２）から（２０）いずれか記載の部材。
（２２）前記釉薬層における紫外領域から可視領域までの波長の光を照射した表面と水滴との接触角が３０°以下である（１２）から（２１）いずれか記載の部材。
（２３）（１２）から（２２）のいずれか一つに記載の部材を製造する方法であって、釉薬を調製する釉薬調製工程と、調製された前記釉薬を焼成前の基材の表面に施釉し釉薬層を形成する施釉工程と、前記釉薬が施釉された前記基材を焼成炉内に配し、６００℃以上、１２００℃以下の焼成温度で焼成する焼成工程と、を有する製造方法。
（２４）釉薬層の原料を配置した基材を、該原料に含まれるガラスの粘性が１×１０１０ｐｏｉｓｅ以下となるまで加熱する工程を含むことを特徴とする（２３）記載の製造方法。
（２５）前記釉薬層に対して、ドライエッチング及び／又はウェットエッチングを行うエッチング工程をさらに有する、（２３）または（２４）記載の製造方法。(1) Glaze glass that produces crystals having photocatalytic properties by heating.
(2) 5 % to 99% in total of one or more components selected from TiO 2 , WO 3 , ZnO, Nb 2 O 5 , and Ta 2 O 5 in mol% of the oxide equivalent composition, and SiO The glass for glazes according to (1), which contains 1 to 85% or less in total of one or more components selected from 2 , B 2 O 3 , P 2 O 5 , and GeO 2 .
(3) In mol% of oxide conversion composition, RO component and / or Rn 2 O component is 0 to 50% (wherein, R is one or more selected from Mg, Ca, Sr, Ba, Rn is Li, The glaze glass according to any one of (1) and (2), wherein the glass is contained in one or more selected from K and Na.
(4) mol% of oxide equivalent composition,
0 to 30% of Al 2 O 3 component,
Ga 2 O 3 component 0-30%,
0-30% of In 2 O 3 component,
0 to 20% of ZrO 2 component,
0 to 20% of SnO component,
Bi 2 O 3 component and / or TeO 2 component 0-20%
0-30% of MoO component,
0-30% of Ln 2 O 3 component (Ln is one or more selected from Y, Ce, La, Nd, Gd, Dy, Yb),
M x O y component 0 to 10% (M is at least one selected from V, Cr, Mn, Fe, Co, and Ni, and x and y are each x: y = 2: (valence of M)) The smallest natural number satisfying
0 to 5% of As 2 O 3 component and / or Sb 2 O 3 component,
The glass for glaze according to any one of (1) to (3).
(5) The externally divided mass% with respect to the total amount of glass in the oxide equivalent composition,
The glass for glaze according to any one of (1) to (4), containing 0.01 to 10% of one or more non-metallic element components selected from F, Cl, Br, S, N, and C.
(6) The externally divided mass% with respect to the total amount of glass in the oxide equivalent composition,
The glass for glaze according to any one of (1) to (5), containing 0.001 to 5% of one or more metal element components selected from Cu, Ag, Au, Pd, Pt, Ru, Re, and Rh.
(7) A crystallized glass for glaze obtained by crystallizing the glass for glaze according to any one of (1) to (6).
(8) TiO 2 crystals, WO 3 crystal, ZnO crystal, RnNbO 3, RnTaO 3, RNbO 3, RTaO 3, any one or more crystals selected from the group consisting of a solid solution of NASICON type crystals and these crystals The crystallized glass for glaze according to (7), wherein R is one or more selected from Mg, Ca, Sr, and Ba, and Rn is one or more selected from Li, K, and Na.
(9) A granular material comprising the glaze glass and / or the crystallized glass for glaze according to any one of (1) to (8).
(10) A glaze containing the granular material according to any one of (1) to (9).
(11) 50 to 99% of the granular material and 1 to 50% in total of any one or more selected from plant ash, lime, silica, feldspar, clay, frit, and organic binder (10) The glaze described.
(12) A photocatalytic member having a glaze layer formed of the glaze according to any one of (10) and (11).
(13) The member according to (12), characterized in that it contains a glass phase and a crystalline phase having photocatalytic properties, and the glossiness of the glaze layer is 5 or more as measured by an incident angle of 60 °.
(14) The member according to (12) or (13), wherein an average crystal grain size of the crystal phase is 5 μm or less.
(15) The glaze layer is a mol% of the oxide conversion composition, and a total of one or more components selected from TiO 2 , WO 3 , ZnO, Nb 2 O 5 , and Ta 2 O 5 are 5 to 99 in total. %, And a member according to (12) to (14), containing 1 to 85% in total of at least one component selected from SiO 2 , B 2 O 3 , P 2 O 5 , and GeO 2 .
(16) The glaze layer is a mol% of the oxide equivalent composition, and the RO component and / or the Rn 2 O component is 0 to 50% (wherein R is one or more selected from Mg, Ca, Sr, Ba) , Rn contains at least one selected from Li, K, and Na). The member according to any one of (12) to (15).
(17) The glaze layer is a mol% of the oxide equivalent composition,
0 to 30% of Al 2 O 3 component,
Ga 2 O 3 component 0-30%,
0-30% of In 2 O 3 component,
0 to 20% of ZrO 2 component,
0 to 20% of SnO component,
Bi 2 O 3 component and / or TeO 2 component 0-20%
0-30% of MoO component,
0-30% of Ln 2 O 3 component (Ln is one or more selected from Y, Ce, La, Nd, Gd, Dy, Yb),
M x O y component 0 to 10% (M is at least one selected from V, Cr, Mn, Fe, Co, and Ni, and x and y are each x: y = 2: (valence of M)) The smallest natural number that satisfies
0 to 5% of As 2 O 3 component and / or Sb 2 O 3 component,
The member according to any one of (12) to (16).
(18) The glaze layer is 0.01% by mass of one or more nonmetallic element components selected from F, Cl, Br, S, N, and C in an externally divided mass% with respect to the total amount of the oxide-converted composition. The member according to any one of (12) to (17), containing 10% to 10%.
(19) The glaze layer contains one or more metal element components selected from Cu, Ag, Au, Pd, Pt, Ru, Re, and Rh in an externally divided mass% with respect to the total amount of glass in an oxide equivalent composition. The member according to any one of (12) to (18), containing 0.001 to 5%.
(20) The glaze layer is made of TiO 2 crystal, WO 3 crystal, ZnO crystal, RnNbO 3 , RnTaO 3 , RNbO 3 , RTaO 3 , TiP 2 O 7 , (TiO) 2 O 7 , RTiO 3 , NASICON type. The member according to any one of (12) to (19), which includes any one or more crystals selected from the group consisting of crystals and solid solutions of these crystals (wherein R is selected from Mg, Ca, Sr, Ba) Or more, and Rn is at least one selected from Li, K, and Na).
(21) The member according to any one of (12) to (20), wherein the decomposition activity index of methylene blue based on JIS R 1703-2: 2007 in the glaze layer is 3.0 nmol / L / min or more.
(22) The member according to any one of (12) to (21), wherein a contact angle between a surface of the glaze layer irradiated with light having a wavelength from an ultraviolet region to a visible region and a water droplet is 30 ° or less.
(23) A method for producing a member according to any one of (12) to (22), wherein a glaze preparation step for preparing a glaze, and the prepared glaze on the surface of a substrate before firing A manufacturing method comprising: a glazing step for applying a glaze and forming a glaze layer; and a firing step in which the base material on which the glaze has been applied is placed in a firing furnace and fired at a firing temperature of 600 ° C. or more and 1200 ° C. or less.
(24) The method according to (23), comprising a step of heating the substrate on which the raw material of the glaze layer is arranged until the viscosity of the glass contained in the raw material is 1 × 10 10 poise or less.
(25) The manufacturing method according to (23) or (24), further including an etching step of performing dry etching and / or wet etching on the glaze layer.
本発明の釉薬用ガラスを含有する釉薬によれば、光触媒活性を有する結晶相を含有し、且つ十分な耐久性を有する釉薬層を備える光触媒部材を提供できる。この釉薬層は、その内部および表面に光触媒活性を持つ光触媒結晶及び／又はその固溶体が均質に存在しているため、優れた光触媒活性を有し、基材との密着性が高く十分な耐久性を有する。ここで前記結晶は釉薬層の内部にも分散されており、多少のキズや欠けが発生しても光触媒機能が劣化することはない。また、本発明による釉薬用ガラスを用いた光触媒部材は光沢性に優れており、透明性を有する釉薬層を備えることも可能であるので、従来光触媒の固定が難しく普及されなかった施釉製品群への幅広い応用が期待できる。 According to the glaze containing the glass for glaze of this invention, a photocatalyst member provided with the glaze layer which contains the crystal phase which has photocatalytic activity, and has sufficient durability can be provided. This glaze layer has a photocatalytic crystal having photocatalytic activity and / or a solid solution homogeneously in the inside and on the surface thereof, so that it has excellent photocatalytic activity, high adhesion to the substrate, and sufficient durability. Have Here, the crystals are also dispersed in the glaze layer, and the photocatalytic function does not deteriorate even if some scratches or chips occur. In addition, since the photocatalyst member using the glaze glass according to the present invention is excellent in gloss and can be provided with a glaze layer having transparency, it is difficult to fix the photocatalyst and to a glazed product group that has not been widely used in the past. A wide range of applications can be expected.
また、本発明の釉薬用ガラスを用いた光触媒部材は、原料の配合組成と熱処理温度の制御によって、ガラス相から光触媒活性を呈する結晶相が生成されるため、凝集し易く取り扱いが難しいナノサイズの光触媒の結晶材料を必ずしも用いる必要がなく、特殊な設備を必要としない。従って、優れた光触媒活性を備える部材、例えば、抗菌部材、殺菌部材、親水性部材など、種々の用途に有用な部材を、工業的規模で容易に製造することができる。また、本発明によって見出された製造方法によると、光沢性、好ましくは透明性に優れる釉薬層を形成した光触媒部材を容易に製造できる。 In addition, the photocatalyst member using the glaze glass of the present invention has a nano-size that is easy to aggregate and difficult to handle because a crystal phase exhibiting photocatalytic activity is generated from the glass phase by controlling the composition of the raw materials and the heat treatment temperature. It is not always necessary to use a photocatalytic crystal material, and no special equipment is required. Therefore, members having excellent photocatalytic activity, such as antibacterial members, sterilizing members, and hydrophilic members, can be easily produced on an industrial scale. Moreover, according to the production method found by the present invention, a photocatalytic member having a glaze layer having excellent gloss, preferably transparency, can be easily produced.
以下、本発明の実施形態を説明するが、これに本発明が限定されるものではない。 Hereinafter, although an embodiment of the present invention is described, the present invention is not limited to this.
＜釉薬用ガラス＞
釉薬とは、浸水や酸化を防ぐ、色や質感を与える、などの目的で陶磁器や琺瑯の表面を覆っている層、または前記層を形成するために表面にかける薬品のことを言う。一般的に釉薬の層はガラス質であることが多く、表面にかける際には、粉粒状の原料を水などに懸濁させた液体が用いられる。釉薬は、主に網目を構成する成分、溶融性を良くする成分、および修飾成分等を含有し、それらの役割を担う原料として、長石類、粘土類、灰類、ガラスなどが用いられている。本明細書において釉薬とは、粉粒体状の原料を混濁させた液体状のものを、釉薬層は、前記釉薬を基材に塗布し焼成すること（施釉）で形成した被覆層を意味する。<Glass glass>
The glaze refers to a layer covering the surface of ceramic or glazing for the purpose of preventing flooding or oxidation, giving a color or texture, or a chemical applied to the surface to form the layer. In general, the glaze layer is often glassy, and when applied to the surface, a liquid in which a powdery raw material is suspended in water or the like is used. Glaze mainly contains a component that constitutes a network, a component that improves meltability, a modifying component, and the like, and feldspars, clays, ashes, glass, and the like are used as raw materials that play a role thereof. . In this specification, glaze means a liquid in which powdery raw materials are turbid, and glaze layer means a coating layer formed by applying the glaze to a substrate and baking (glazing). .
釉薬の原料の中には水などの溶媒に溶けてしまい不具合を生じさせたり、鉛のように材料自体をそのまま用いるには毒性が強かったり、焼成時の反応によって欠点の原因になるようなものがある。こういった欠点を解消するために、釉薬層に含ませたい成分を事前にガラスとして作っておき、釉薬の原料として利用することができる。このような、釉薬の原料として用いられるガラスの粉を、一般的にガラスフリットという。本発明におけるガラスは、釉薬の原料として、特に釉薬層に光触媒特性を有する結晶を含有させる特殊なガラスフリットとして、好適に用いられるガラスである。 Some glaze raw materials dissolve in water or other solvents and cause problems, and like lead, the material itself is highly toxic or causes defects due to reaction during firing. There is. In order to eliminate these disadvantages, it is possible to make the components to be included in the glaze layer in advance as glass and use it as a raw material for the glaze. Such glass powder used as a raw material for glaze is generally referred to as glass frit. The glass in the present invention is a glass that is suitably used as a glaze material, particularly as a special glass frit in which a glaze layer contains crystals having photocatalytic properties.
本発明の釉薬用ガラスは、ガラス、つまり非晶質の材料であるが、加熱することで光触媒特性を有する結晶を生成する。ガラスは、結晶のような規則的原子配列を有しないが、熱エネルギーを加えるとガラスを構成する原子やイオンの動きが活発になって、再配列が起こることがある。この動きが活性化する温度は、おおよそガラス転移温度〜液相温度の範囲内であり、この比較的広い温度範囲で、ガラスは過冷却液体という熱力学的に準安定な状態になる。適度な時間この状態におかれることでガラスを構成する原子やイオンの一部は結晶への相転移（結晶の「析出」という）することができ、このようにしてガラスの一部あるいはほぼ全体から微細な結晶が析出した集合体を結晶化ガラスという。結晶化ガラスは析出した結晶が有する機能の発現に加えて、ガラス相および結晶相の両方による複合的な機能を期待することができる。 The glaze glass of the present invention is a glass, that is, an amorphous material, but generates crystals having photocatalytic properties when heated. Glass does not have a regular atomic arrangement like a crystal. However, when thermal energy is applied, movement of atoms and ions constituting the glass becomes active, and rearrangement may occur. The temperature at which this movement is activated is approximately in the range of the glass transition temperature to the liquidus temperature, and in this relatively wide temperature range, the glass becomes a thermodynamically metastable state of a supercooled liquid. By being in this state for an appropriate period of time, some of the atoms and ions that make up the glass can undergo a phase transition to the crystal (called “precipitation” of the crystal). The aggregate from which fine crystals are precipitated is called crystallized glass. The crystallized glass can be expected to have a composite function of both the glass phase and the crystal phase in addition to the expression of the function of the precipitated crystal.
本発明の釉薬用ガラスは、前述したプロセスによって、ガラス相から光触媒特性を有する結晶及び／またはその固溶体を析出することを特徴とする。ここで、固溶体とは、２種類以上の金属固体または非金属固体が互いの中に原子レベルで溶け込んで全体が均一の固相になっている状態のことをいい、混晶と言う場合もある。溶質原子の溶け込み方によって、結晶格子の隙間より小さい元素が入り込む侵入型固溶体、母相原子と入れ代わって入る置換型固溶体などがある。本明細書において光触媒結晶という言葉は固溶体を含む概念として用いられる。 The glaze glass of the present invention is characterized in that crystals having photocatalytic properties and / or a solid solution thereof are precipitated from the glass phase by the process described above. Here, the solid solution means a state in which two or more kinds of metal solids or non-metal solids are dissolved in each other at an atomic level to form a uniform solid phase as a whole, and may be called a mixed crystal. . Depending on how the solute atoms permeate, there are interstitial solid solutions in which elements smaller than the gaps in the crystal lattice enter, and substitutional solid solutions in which they replace the parent phase atoms. In this specification, the term photocatalytic crystal is used as a concept including a solid solution.
結晶化ガラスの結晶化率および結晶の大きさは、加熱条件をコントロールすることで制御することができる。ガラスの組成等にもよるが、多くの場合、加熱時間が長ければ結晶化率および結晶サイズは大きくなり、短ければ結晶化率および結晶サイズは小さくなる。本発明の釉薬用ガラスは、取扱が困難で均質に分散させにくい微細な粉末原料を扱うことなく、ガラス相の内部からナノオーダーの光触媒結晶を析出するガラスであり、光触媒機能を有する釉薬層を形成する釉薬用ガラスとして好適に用いられるものである。 The crystallization rate and crystal size of the crystallized glass can be controlled by controlling the heating conditions. Depending on the glass composition and the like, in many cases, the longer the heating time, the larger the crystallization rate and the crystal size, and the shorter the heating time, the smaller the crystallization rate and the crystal size. The glaze glass of the present invention is a glass that deposits nano-order photocatalytic crystals from the inside of the glass phase without handling fine powder raw materials that are difficult to handle and difficult to disperse uniformly, and has a glaze layer having a photocatalytic function. It is suitably used as a glaze glass to be formed.
ガラスから析出する結晶の種類は、ガラスの組成およびその含有量に依存するので、ガラスに特定の成分を含有させつつ、その他の成分のバランスを巧みに調整することで、所望の結晶をガラスから析出させることが可能になる。本発明の釉薬用ガラスが含有する各成分の組成範囲を以下に述べる。なお、本明細書中において、各成分の含有量は特に断りがない場合は、全て酸化物換算組成のガラスの全物質量に対するモル％で表示されるものとする。ここで、「酸化物換算組成」とは、本発明の構成成分の原料として使用される酸化物、複合塩、金属弗化物等が溶融時に全て分解され酸化物へ変化すると仮定した場合に、当該生成酸化物の総物質量を１００モル％として、ガラス中に含有される各成分（酸化物）の含有比で表記した組成である。 Since the type of crystals precipitated from the glass depends on the composition of the glass and its content, the desired crystals can be removed from the glass by skillfully adjusting the balance of the other components while containing specific components in the glass. It becomes possible to deposit. The composition range of each component contained in the glaze glass of the present invention is described below. In addition, in this specification, unless there is particular notice, content of each component shall be displayed by mol% with respect to the total amount of substances of the glass of an oxide conversion composition. Here, the “oxide equivalent composition” means that the oxide, composite salt, metal fluoride, etc. used as the raw material of the constituent of the present invention are all decomposed and changed into oxide when melted. This is a composition expressed by the content ratio of each component (oxide) contained in the glass, with the total amount of the generated oxide as 100 mol%.
［釉薬用ガラスの組成］
本発明の釉薬用ガラスは酸化物換算組成のモル％で、ＴｉＯ２、ＷＯ３、ＺｎＯ、Ｎｂ２Ｏ５、およびＴａ２Ｏ５より選択される１種以上の成分を合計で５〜９９％、並びに、ＳｉＯ２、Ｂ２Ｏ３、Ｐ２Ｏ５、及びＧｅＯ２から選択される１種以上の成分を合計で１〜８５％以下含有することが好ましい。[Composition of glaze glass]
In mole% of glaze glass of the present invention in terms of oxide composition, TiO 2, WO 3, ZnO , Nb 2 O 5, and one or more components selected from Ta 2 O 5 in total from 5 to 99% In addition, it is preferable to contain 1 to 85% or less in total of at least one component selected from SiO 2 , B 2 O 3 , P 2 O 5 , and GeO 2 .
ＴｉＯ２成分は、ガラスを結晶化することにより、特に紫外線領域で強い光触媒活性を示すＴｉＯ２結晶、またはＴｉ成分とＰ成分との化合物の結晶、若しくはそれらの固溶体をガラスから析出させるため、本発明の釉薬用ガラスにおいて有用な成分である。また、ＴｉＯ２成分は結晶の核形成剤の役割を果たす効果もあるので、ＴｉＯ２結晶以外の光触媒結晶の析出にも寄与する。本発明の釉薬用ガラスにおいてＴｉＯ２成分は任意成分であり、含有しなくても光触媒結晶を析出することが可能であるが、釉薬層にＴｉＯ２結晶を析出させる場合には、ＴｉＯ２成分の含有量が５％未満であると十分な結晶の析出を期待できなくなるので、酸化物換算組成の全物質量に対するＴｉＯ２成分の含有量の下限は、５％、好ましくは１５％、より好ましくは３０％、最も好ましくは４０％とする。一方、ＴｉＯ２成分の含有量が９０％を超えるとガラス化が非常に難しくなるため、その上限は、９０％、好ましくは８０％、より好ましくは７０％、最も好ましくは６０％とする。ＴｉＯ２成分は、原料として例えばＴｉＯ２等を用いて釉薬用ガラス内に導入することができる。The TiO 2 component crystallizes the glass to precipitate a TiO 2 crystal exhibiting a strong photocatalytic activity particularly in the ultraviolet region, a crystal of a compound of the Ti component and the P component, or a solid solution thereof from the glass. It is a useful component in the glaze glass of the invention. Further, since the TiO 2 component also has the effect of acting as a crystal nucleating agent, it contributes to the precipitation of photocatalytic crystals other than TiO 2 crystals. TiO 2 component in the glaze glass of the present invention is an optional component, it is possible even without containing precipitating photocatalyst crystals, when precipitating the TiO 2 crystals glaze layer, the TiO 2 component If the content is less than 5%, sufficient crystal precipitation cannot be expected. Therefore, the lower limit of the content of the TiO 2 component with respect to the total substance amount of the oxide conversion composition is 5%, preferably 15%, more preferably 30%, most preferably 40%. On the other hand, if the content of the TiO 2 component exceeds 90%, vitrification becomes very difficult. Therefore, the upper limit is 90%, preferably 80%, more preferably 70%, and most preferably 60%. TiO 2 component can be introduced into the glass glaze used as the starting material for example TiO 2 or the like.
ＷＯ３成分は、ガラスの溶融性と安定性を高める成分であり、釉薬用ガラスを加熱することにより、光触媒活性を有するＷＯ３結晶又はその固溶体としてガラスから析出するため、本発明の釉薬用ガラスにおいて有用な成分である。本発明の釉薬用ガラスにおいてＷＯ３成分は任意成分であり、含有しなくても光触媒結晶を析出することが可能であるが、釉薬層にＷＯ３結晶を析出させる場合には、ＷＯ３成分の含有量が５％未満であると十分な結晶の析出を期待できなくなるので、酸化物換算組成の全物質量に対するＷＯ３成分の含有量の下限は、５％、好ましくは１０％、より好ましくは２０％、最も好ましくは３０％とする。一方、ＷＯ３成分の含有量が９０％を超えるとガラス化が非常に難しくなるため、その上限は、９０％、好ましくは８０％、より好ましくは７０％、最も好ましくは６０％とする。ＷＯ３成分は、原料として例えばＷＯ３等を用いて釉薬用ガラス中に導入することができる。The WO 3 component is a component that enhances the meltability and stability of the glass. By heating the glaze glass, it is precipitated from the glass as a WO 3 crystal having photocatalytic activity or a solid solution thereof. Is a useful component. WO 3 component in the glaze glass of the present invention is an optional component, it is possible even without containing precipitating photocatalyst crystals, when precipitating the WO 3 crystal glaze layer of WO 3 components If the content is less than 5%, sufficient crystal precipitation cannot be expected, so the lower limit of the content of the WO 3 component with respect to the total amount of the oxide-converted composition is 5%, preferably 10%, more preferably 20%, most preferably 30%. On the other hand, since vitrification becomes very difficult when the content of the WO 3 component exceeds 90%, the upper limit is 90%, preferably 80%, more preferably 70%, and most preferably 60%. The WO 3 component can be introduced into the glaze glass using, for example, WO 3 as a raw material.
ＺｎＯ成分は、ガラスの溶融性と安定性を高める成分である。また、釉薬用ガラスを加熱することでＺｎを含む結晶としてガラス中に析出し、本発明の釉薬用ガラスを用いた釉薬層に光触媒特性をもたらす有用な成分である。また、ＺｎＯ成分はガラス転移温度を下げてＴｉＯ２結晶、またはＷＯ３結晶を生成させやすくするとともに、熱処理温度をより低く抑える働きをする。熱処理温度を抑えることで、ＴｉＯ２成分を含有する場合に光触媒活性の高いアナターゼ型ＴｉＯ２結晶から光触媒活性の低いルチル型への相転移を低減する効果も期待できる。本発明の釉薬用ガラスにおいてＺｎＯ成分は任意成分であり、含有しなくても光触媒結晶を析出することが可能であるが、釉薬層にＺｎを含む光触媒結晶を析出させる場合には、ＺｎＯ成分の含有量が５％未満であると十分な結晶の析出を期待できなくなるので、酸化物換算組成の全物質量に対するＺｎＯ成分の含有量の下限は、５％、好ましくは１０％、より好ましくは２０％、最も好ましくは３０％とする。一方、ＺｎＯ成分の含有量が９０％を超えると、ガラスの安定性が著しく悪くなり、ガラス化が非常に難しくなるため、その上限は、９０％、好ましくは８０％、より好ましくは７０％、最も好ましくは６０％とする。ＺｎＯ成分は、原料として例えばＺｎＯ、ＺｎＦ２等を用いて釉薬用ガラス中に導入することができる。A ZnO component is a component which improves the meltability and stability of glass. Moreover, it is a useful component which precipitates in the glass as a crystal | crystallization containing Zn by heating the glass for glazes, and brings a photocatalytic characteristic to the glaze layer using the glass for glazes of this invention. In addition, the ZnO component lowers the glass transition temperature to facilitate the formation of TiO 2 crystals or WO 3 crystals, and also serves to keep the heat treatment temperature lower. By suppressing the heat treatment temperature, an effect of reducing the phase transition from anatase-type TiO 2 crystal having a high photocatalytic activity to a rutile type having a low photocatalytic activity when a TiO 2 component is contained can be expected. In the glass for glazes of the present invention, the ZnO component is an optional component, and it is possible to deposit a photocatalytic crystal even if it is not contained. If the content is less than 5%, sufficient crystal precipitation cannot be expected. Therefore, the lower limit of the content of the ZnO component with respect to the total amount of the oxide-converted composition is 5%, preferably 10%, more preferably 20 %, Most preferably 30%. On the other hand, if the content of the ZnO component exceeds 90%, the stability of the glass is remarkably deteriorated and vitrification becomes very difficult. Therefore, the upper limit is 90%, preferably 80%, more preferably 70%, Most preferably 60%. ZnO component may be introduced into the glass glaze used as raw materials for example ZnO, the ZnF 2, and the like.
Ｎｂ２Ｏ５成分はガラスの溶融性と安定性を高める成分である。たま、釉薬用ガラスを加熱することでＮｂを含む結晶としてガラス中に析出したり、または、光触媒結晶の近傍に存在して特性を向上させる成分であり、本発明の釉薬用ガラスを用いた釉薬層に光触媒特性をもたらす有用な成分である。本発明の釉薬用ガラスにおいてＮｂ２Ｏ５成分は任意成分であり、含有しなくても光触媒結晶を析出することが可能であるが、釉薬層にＮｂを含む光触媒結晶を析出させる場合には、Ｎｂ２Ｏ５成分の含有量が５％未満であると十分な結晶の析出を期待できなくなるので、酸化物換算組成の全物質量に対するＮｂ２Ｏ５成分の含有量の下限は、５％、好ましくは１０％、より好ましくは２０％、最も好ましくは３０％とする。一方、Ｎｂ２Ｏ５成分の含有量が９０％を超えると、ガラスの安定性が著しく悪くなり、ガラス化が非常に難しくなるため、その上限は、９０％、好ましくは８０％、より好ましくは７０％、最も好ましくは６０％とする。Ｎｂ２Ｏ５成分は、原料として例えばＮｂ２Ｏ５等を用いて釉薬用ガラス中に導入することができる。Nb 2 O 5 component is a component for enhancing the meltability and stability of glass. Occasionally, the glaze using the glaze glass of the present invention is a component that is deposited in the glass as Nb-containing crystals by heating the glaze glass or is present in the vicinity of the photocatalytic crystal and improves the characteristics. A useful component that provides photocatalytic properties to the layer. In the glass for glazes of the present invention, the Nb 2 O 5 component is an optional component, and it is possible to deposit photocatalytic crystals even if not contained, but when depositing photocatalytic crystals containing Nb in the glaze layer, If the content of the Nb 2 O 5 component is less than 5%, sufficient crystal precipitation cannot be expected. Therefore, the lower limit of the content of the Nb 2 O 5 component with respect to the total substance amount of the oxide conversion composition is 5%, Preferably it is 10%, more preferably 20%, most preferably 30%. On the other hand, when the content of the Nb 2 O 5 component exceeds 90%, the stability of the glass is remarkably deteriorated and vitrification becomes very difficult. Therefore, the upper limit is 90%, preferably 80%, more preferably 70%, most preferably 60%. The Nb 2 O 5 component can be introduced into the glaze glass using, for example, Nb 2 O 5 as a raw material.
Ｔａ２Ｏ５成分は、ガラスの安定性を高める成分である。また、釉薬用ガラスを加熱することにより、Ｔａを含む結晶としてガラス中に析出したり、または、光触媒結晶の近傍に存在して特性を向上させる成分であり、本発明の釉薬用ガラスを用いた釉薬層に光触媒特性をもたらす有用な成分である。本発明の釉薬用ガラスにおいてＴａ２Ｏ５成分は任意成分であり、含有しなくても光触媒結晶を析出することが可能であるが、釉薬層にＴａを含む光触媒結晶を析出させる場合には、Ｔａ２Ｏ５成分の含有量が５％未満であると十分な結晶の析出を期待できなくなるので、酸化物換算組成の全物質量に対するＴａ２Ｏ５成分の含有量の下限は、５％、好ましくは１０％、より好ましくは２０％、最も好ましくは３０％とする。一方、Ｔａ２Ｏ５成分の含有量が９０％を超えると、ガラスの安定性が著しく悪くなり、ガラス化が非常に難しくなるため、その上限は、９０％、好ましくは８０％、より好ましくは７０％、最も好ましくは６０％とする。Ｔａ２Ｏ５成分は、原料として例えばＴａ２Ｏ５を用いて釉薬用ガラス中に導入することができる。The Ta 2 O 5 component is a component that increases the stability of the glass. Moreover, it is a component which precipitates in the glass as a crystal containing Ta by heating the glaze glass, or is present in the vicinity of the photocatalytic crystal to improve the characteristics, and the glaze glass of the present invention was used. It is a useful component that brings photocatalytic properties to the glaze layer. In the glass for glazes of the present invention, the Ta 2 O 5 component is an optional component, and it is possible to deposit photocatalytic crystals even if it is not contained. If the content of the Ta 2 O 5 component is less than 5%, sufficient crystal precipitation cannot be expected. Therefore, the lower limit of the content of the Ta 2 O 5 component with respect to the total amount of the oxide-converted composition is 5%. Preferably, it is 10%, more preferably 20%, and most preferably 30%. On the other hand, when the content of the Ta 2 O 5 component exceeds 90%, the stability of the glass is remarkably deteriorated and vitrification becomes very difficult. Therefore, the upper limit is 90%, preferably 80%, more preferably 70%, most preferably 60%. The Ta 2 O 5 component can be introduced into the glaze glass using, for example, Ta 2 O 5 as a raw material.
本発明の釉薬用ガラスは、ＴｉＯ２、ＷＯ３、ＺｎＯ、Ｎｂ２Ｏ５、およびＴａ２Ｏ５より選択される１種以上の成分を合計で５〜９９％の範囲で含有することが好ましい。これらの成分の合計量を５％以上含有することで、加熱によって所望の光触媒結晶が析出し易くなる。より好ましい下限は１０％、さらに好ましい下限は２０％、最も好ましい下限は３０％である。しかし、これらの成分の合計含有量が９９％を超えると、ガラス化が非常に困難になり、釉薬用ガラスとして使い難くなるため、これら成分の合量の上限は９９％、好ましくは９０％、より好ましくは８０％、最も好ましくは７０％とすることが好ましい。The glaze glass of the present invention preferably contains one or more components selected from TiO 2 , WO 3 , ZnO, Nb 2 O 5 , and Ta 2 O 5 in a total range of 5 to 99%. . By containing 5% or more of the total amount of these components, the desired photocatalytic crystal is likely to be precipitated by heating. A more preferred lower limit is 10%, a still more preferred lower limit is 20%, and a most preferred lower limit is 30%. However, if the total content of these components exceeds 99%, vitrification becomes very difficult and it becomes difficult to use as a glass for glazes, so the upper limit of the total amount of these components is 99%, preferably 90%, More preferably, it is 80%, and most preferably 70%.
なお、釉薬層における主結晶相をＴｉＯ２結晶、ＷＯ３結晶、ＺｎＯ結晶、およびそれらの固溶体とする場合は、Ｎｂ２Ｏ５成分及び／又はＴａ２Ｏ５成分の合計量は３０％以下であることが好ましい。When the main crystal phase in the glaze layer is a TiO 2 crystal, a WO 3 crystal, a ZnO crystal, or a solid solution thereof, the total amount of Nb 2 O 5 component and / or Ta 2 O 5 component is 30% or less. Preferably there is.
ＳｉＯ２成分は、ガラスの網目構造を構成し、ガラスの安定性と化学的耐久性を高める成分であるとともに、Ｓｉ４＋イオンが析出した光触媒結晶相の近傍に存在し、本発明の釉薬用ガラスを用いた釉薬層の光触媒活性向上に寄与する成分であり、任意に添加できる成分である。しかし、ＳｉＯ２成分の含有量が８５％を超えると、ガラスの溶融性が悪くなり、加熱して結晶を析出する際に所望の光触媒結晶相が析出し難くなる。従って、酸化物換算組成の釉薬用ガラス全物質量に対するＳｉＯ２成分の含有量の上限は８５％、好ましくは６５％、より好ましくは４５％、最も好ましくは３０％を上限とする。ＳｉＯ２成分は、原料として例えばＳｉＯ２、Ｋ２ＳｉＦ６、Ｎａ２ＳｉＦ６等を用いて釉薬用ガラス内に含有することができる。The SiO 2 component is a component that constitutes the network structure of the glass and improves the stability and chemical durability of the glass, and is present in the vicinity of the photocatalytic crystal phase on which Si 4+ ions are deposited. It is a component that contributes to the improvement of the photocatalytic activity of the glaze layer using, and can be optionally added. However, when the content of the SiO 2 component exceeds 85%, the meltability of the glass is deteriorated, and the desired photocatalytic crystal phase is difficult to precipitate when heating to precipitate crystals. Therefore, the upper limit of the content of the SiO 2 component with respect to the total amount of glaze glass having an oxide conversion composition is 85%, preferably 65%, more preferably 45%, and most preferably 30%. The SiO 2 component can be contained in the glaze glass using, for example, SiO 2 , K 2 SiF 6 , Na 2 SiF 6 or the like as a raw material.
Ｂ２Ｏ３成分は、ガラスの網目構造を構成し、ガラスの安定性を高める成分であり、任意に添加できる成分である。しかし、その含有量が８５％を超えると、ガラスの化学耐久性が低下し、加熱して結晶を析出する際に所望の光触媒結晶相が析出し難い傾向が強くなる。従って、Ｂ２Ｏ３成分を添加する場合、酸化物換算組成の全物質量に対するＢ２Ｏ３成分の含有量の上限は８５％、好ましくは７５％、より好ましくは６５％、最も好ましくは５５％を上限とする。Ｂ２Ｏ３成分は、原料として例えばＨ３ＢＯ３、Ｎａ２Ｂ４Ｏ７、Ｎａ２Ｂ４Ｏ７・１０Ｈ２Ｏ、ＢＰＯ４等を用いて釉薬用ガラス内に導入することができる。The B 2 O 3 component is a component that constitutes a glass network structure and improves the stability of the glass, and can be optionally added. However, if the content exceeds 85%, the chemical durability of the glass is lowered, and the tendency to hardly deposit the desired photocatalytic crystal phase when the crystals are precipitated by heating is increased. Accordingly, when adding B 2 O 3 component, B 2 O 3 is the upper limit of the content of components 85% to the total amount of substance of the oxide composition in terms of, preferably 75%, more preferably 65%, most preferably 55 % Is the upper limit. B 2 O 3 component can be introduced into the glass glaze as starting materials for example H 3 BO 3, Na 2 B 4 O 7, Na 2 B 4 O 7 · 10H 2 O, the BPO 4 and the like.
Ｐ２Ｏ５成分は、ガラスの網目構造を構成する成分であり、ＴｉＯ２やＷＯ３などの成分をより多く取り込ませる効果があるので、任意に添加できる成分である。また、釉薬層にＴｉＯ２結晶を析出させる場合にはＰ２Ｏ５成分を一緒に含有すると、より低い熱処理温度で結晶を析出することが可能であるため、光触媒活性の高いアナターゼ型ＴｉＯ２結晶から光触媒活性がアナターゼ型結晶よりは低いルチル型への相転移を低減することができる。しかしＰ２Ｏ５の含有量が８５％を超えると釉薬用ガラスの耐候性が低下するとともに、釉薬用ガラスを加熱して結晶を析出する際に所望の光触媒結晶相が析出し難くなる。従って、酸化物換算組成の釉薬用ガラス全物質量に対するＰ２Ｏ５成分の含有量の上限は８５％、好ましくは７５％、より好ましくは６５％、最も好ましくは６０％とする。Ｐ２Ｏ５成分は、原料として例えばＡｌ（ＰＯ３）３、Ｃａ（ＰＯ３）２、Ｂａ（ＰＯ３）２、Ｎａ（ＰＯ３）、ＢＰＯ４、Ｈ３ＰＯ４等を用いて釉薬用ガラス内に導入することができる。The P 2 O 5 component is a component that constitutes a glass network structure, and has the effect of incorporating more components such as TiO 2 and WO 3, and thus can be arbitrarily added. In addition, when TiO 2 crystals are precipitated in the glaze layer, if the P 2 O 5 component is contained together, it is possible to precipitate the crystals at a lower heat treatment temperature. Therefore, anatase TiO 2 crystals having a high photocatalytic activity. Can reduce the phase transition to rutile type, which has a lower photocatalytic activity than anatase type crystals. However, if the content of P 2 O 5 exceeds 85%, the weather resistance of the glaze glass is lowered, and a desired photocatalytic crystal phase is hardly precipitated when the glaze glass is heated to precipitate crystals. Therefore, the upper limit of the content of the P 2 O 5 component with respect to the total amount of glaze glass having an oxide conversion composition is 85%, preferably 75%, more preferably 65%, and most preferably 60%. The P 2 O 5 component is used for glaze using, for example, Al (PO 3 ) 3 , Ca (PO 3 ) 2 , Ba (PO 3 ) 2 , Na (PO 3 ), BPO 4 , H 3 PO 4, etc. as raw materials. It can be introduced into the glass.
ＧｅＯ２成分は、上記のＳｉＯ２と相似な働きを有する成分であり、本発明の釉薬用ガラスに任意に添加できる成分である。特に、ＧｅＯ２成分の含有量を６０％以下にすることで、高価なＧｅＯ２成分の使用が抑えられるため、釉薬用ガラスの材料コストを低減することができる。従って、酸化物換算組成の釉薬用ガラス全物質量に対するＧｅＯ２成分の含有量は６０％、好ましくは４０％、より好ましくは３０％、最も好ましくは２０％を上限とする。ＧｅＯ２成分は、原料として例えばＧｅＯ２等を用いて釉薬用ガラス内に含有することができる。The GeO 2 component is a component having a function similar to that of the above-mentioned SiO 2 and can be arbitrarily added to the glaze glass of the present invention. In particular, by making the content of the GeO 2 component 60% or less, the use of expensive GeO 2 component can be suppressed, so that the material cost of the glaze glass can be reduced. Therefore, the upper limit of the content of the GeO 2 component is 60%, preferably 40%, more preferably 30%, and most preferably 20% with respect to the total amount of glaze glass having an oxide conversion composition. The GeO 2 component can be contained in the glaze glass using, for example, GeO 2 as a raw material.
本発明の釉薬用ガラスは、ＳｉＯ２成分、ＧｅＯ２成分、Ｂ２Ｏ３成分、及びＰ２Ｏ５成分から選ばれる少なくとも１種以上の成分を１％以上８５％以下の範囲内で含有することが好ましい。これらの成分の合計量を１％以上８５％以下にすることで、ガラスの溶融性、安定性及び化学耐久性が向上するとともに、加熱によって所望の光触媒結晶が析出し易くなる。ＳｉＯ２成分、ＧｅＯ２成分、Ｂ２Ｏ３成分、及びＰ２Ｏ５成分から選ばれる少なくとも１種以上の成分の合量は、光触媒結晶の析出量および釉薬層としての化学的・機械的特性の両方を考慮して適宜選ぶことができるが、酸化物換算組成の全物質量に対するこれらの成分の合計量は、１％、好ましくは１５％、より好ましくは２０％、最も好ましくは２５％を下限とし、８５％、好ましくは７５％、より好ましくは７０％、最も好ましくは６５％を上限とすることが好ましい。The glass for glazes of the present invention contains at least one component selected from SiO 2 component, GeO 2 component, B 2 O 3 component, and P 2 O 5 component in the range of 1% to 85%. It is preferable. By making the total amount of these components 1% or more and 85% or less, the meltability, stability, and chemical durability of the glass are improved, and desired photocatalytic crystals are easily precipitated by heating. The total amount of at least one component selected from the SiO 2 component, the GeO 2 component, the B 2 O 3 component, and the P 2 O 5 component depends on the amount of photocatalytic crystal deposited and the chemical / mechanical characteristics of the glaze layer. However, the total amount of these components with respect to the total amount of substances in the oxide conversion composition is 1%, preferably 15%, more preferably 20%, most preferably 25%. The lower limit is 85%, preferably 75%, more preferably 70%, and most preferably 65%.
さらに、本発明の釉薬用ガラスは酸化物換算組成のモル％で、Ｒｎ２Ｏ成分及び／またはＲＯ成分を０〜５０％（式中、ＲｎはＬｉ、Ｋ、Ｎａから選ばれる１種以上、ＲはＭｇ、Ｃａ、Ｓｒ、Ｂａから選ばれる１種以上とする）含有することが好ましい。Furthermore, a mole% of the glaze glass of the present invention in terms of oxide composition, 0-50% of Rn 2 O component and / or RO component (wherein, Rn is Li, K, 1 or more selected from Na, R is preferably one or more selected from Mg, Ca, Sr, and Ba).
Ｌｉ２Ｏ成分は、ガラスの溶融性と安定性を向上させ、焼成後の釉薬層にひび割れを生じ難くする成分であり、任意に添加できる成分である。また、ガラス転移温度を下げて光触媒結晶を生成させやすくするとともに、熱処理温度をより低く抑える成分である。また、熱処理温度を抑えることで、ＴｉＯ２成分を含有する場合に光触媒活性の高いアナターゼ型ＴｉＯ２結晶から光触媒活性の低いルチル型への相転移を低減する効果も期待できる。また、他の成分と結合または固溶して光触媒活性を有する結晶を生成する場合もある。しかし、Ｌｉ２Ｏ成分の含有量が５０％を超えると、かえってガラスの安定性が悪くなり、ガラスを加熱して結晶を析出する際に所望の光触媒結晶が析出し難くなる。従って、酸化物換算組成の釉薬用ガラス全物質量に対するＬｉ２Ｏ成分の含有量は５０％、好ましくは４０％、より好ましくは３０％、最も好ましくは２５％を上限とする。Ｌｉ２Ｏ成分は、原料として例えばＬｉ２ＣＯ３、ＬｉＮＯ３、ＬｉＦ等を用いて釉薬用ガラス内に導入することができる。Li 2 O component improves the meltability and stability of glass is a component that hardly generated cracks in the glaze layer after firing, is a component that can be added optionally. In addition, it is a component that lowers the glass transition temperature to make it easier to produce photocatalytic crystals and lowers the heat treatment temperature. In addition, by suppressing the heat treatment temperature, an effect of reducing the phase transition from anatase-type TiO 2 crystal having a high photocatalytic activity to a rutile type having a low photocatalytic activity when a TiO 2 component is contained can be expected. In some cases, a crystal having photocatalytic activity is produced by binding or solid solution with other components. However, if the content of the Li 2 O component exceeds 50%, the stability of the glass is deteriorated, and the desired photocatalytic crystal is difficult to precipitate when the glass is heated to precipitate the crystal. Therefore, the upper limit of the content of the Li 2 O component is 50%, preferably 40%, more preferably 30%, and most preferably 25% with respect to the total amount of glaze glass having an oxide conversion composition. Li 2 O component may be introduced into the glass glaze, for example, using Li 2 CO 3 as a raw material, LiNO 3, LiF and the like.
Ｋ２Ｏ成分は、ガラスの溶融性と安定性を向上させ、焼成後の釉薬層にひび割れを生じ難くする成分であり、任意に添加できる成分である。また、ガラス転移温度を下げて光触媒結晶を生成させやすくするとともに、熱処理温度をより低く抑える成分である。また、熱処理温度を抑えることで、ＴｉＯ２成分を含有する場合に光触媒活性の高いアナターゼ型ＴｉＯ２結晶から光触媒活性の低いルチル型への相転移を低減する効果も期待できる。また、他の成分と結合または固溶して光触媒活性を有する結晶を生成する場合もある。しかし、Ｋ２Ｏ成分の含有量が５０％を超えると、かえってガラスの安定性が悪くなり、ガラスを加熱して結晶を析出する際に所望の光触媒結晶が析出し難くなる。従って、酸化物換算組成の釉薬用ガラス全物質量に対するＫ２Ｏ成分の含有量は５０％、好ましくは４０％、より好ましくは３０％、最も好ましくは２５％を上限とする。Ｋ２Ｏ成分は、原料として例えばＫ２ＣＯ３、ＫＮＯ３、ＫＦ、ＫＨＦ２、Ｋ２ＳｉＦ６等を用いて釉薬用ガラス内に導入することができる。K 2 O component improves the meltability and stability of glass is a component that hardly generated cracks in the glaze layer after firing, is a component that can be added optionally. In addition, it is a component that lowers the glass transition temperature to make it easier to produce photocatalytic crystals and lowers the heat treatment temperature. In addition, by suppressing the heat treatment temperature, an effect of reducing the phase transition from anatase-type TiO 2 crystal having a high photocatalytic activity to a rutile type having a low photocatalytic activity when a TiO 2 component is contained can be expected. In some cases, a crystal having photocatalytic activity is produced by binding or solid solution with other components. However, if the content of the K 2 O component exceeds 50%, the stability of the glass is deteriorated, and the desired photocatalytic crystal is difficult to precipitate when the glass is heated to precipitate the crystal. Therefore, the upper limit of the content of the K 2 O component is 50%, preferably 40%, more preferably 30%, and most preferably 25% with respect to the total amount of glaze glass having an oxide conversion composition. K 2 O component may be introduced into the glass glaze by using the raw material as for example K 2 CO 3, KNO 3, KF, KHF 2, K 2 SiF 6 and the like.
Ｎａ２Ｏ成分は、ガラスの溶融性と安定性を向上させ、焼成後の釉薬層にひび割れを生じ難くする成分であり、任意に添加できる成分である。また、ガラス転移温度を下げて光触媒結晶を生成させやすくするとともに、熱処理温度をより低く抑える成分である。また、熱処理温度を抑えることで、ＴｉＯ２成分を含有する場合に光触媒活性の高いアナターゼ型ＴｉＯ２結晶から光触媒活性の低いルチル型への相転移を低減する効果も期待できる。また、他の成分と結合または固溶して光触媒活性を有する結晶を生成する場合もある。しかし、Ｎａ２Ｏ成分の含有量が５０％を超えると、かえってガラスの安定性が悪くなり、ガラスを加熱して結晶を析出する際に所望の光触媒結晶が析出し難くなる。従って、酸化物換算組成の釉薬用ガラス全物質量に対するＮａ２Ｏ成分の含有量は５０％、好ましくは４０％、より好ましくは３０％、最も好ましくは２５％を上限とする。Ｎａ２Ｏ成分は、原料として例えばＮａ２Ｏ、Ｎａ２ＣＯ３、ＮａＮＯ３、ＮａＦ、Ｎａ２Ｓ、Ｎａ２ＳｉＦ６等を用いて釉薬用ガラス内に導入することができる。Na 2 O component improves the meltability and stability of glass is a component that hardly generated cracks in the glaze layer after firing, is a component that can be added optionally. In addition, it is a component that lowers the glass transition temperature to make it easier to produce photocatalytic crystals and lowers the heat treatment temperature. In addition, by suppressing the heat treatment temperature, an effect of reducing the phase transition from anatase-type TiO 2 crystal having a high photocatalytic activity to a rutile type having a low photocatalytic activity when a TiO 2 component is contained can be expected. In some cases, a crystal having photocatalytic activity is produced by binding or solid solution with other components. However, when the content of the Na 2 O component exceeds 50%, the stability of the glass is rather deteriorated, and when the glass is heated to precipitate crystals, it becomes difficult to deposit desired photocatalytic crystals. Therefore, the upper limit of the content of the Na 2 O component is 50%, preferably 40%, more preferably 30%, and most preferably 25% with respect to the total amount of glaze glass having an oxide conversion composition. Na 2 O component may be introduced into the glass glaze used as raw materials for example Na 2 O, Na 2 CO 3 , NaNO 3, NaF, Na 2 S, the Na 2 SiF 6 or the like.
本発明の釉薬用ガラスは、Ｒｎ２Ｏ（式中、ＲｎはＬｉ、Ｎａ、およびＫからなる群より選択される１種以上）成分から選ばれる少なくとも１種以上の成分を５０％以下含有することが好ましい。特に、Ｒｎ２Ｏ成分の合計量を５０％以下にすることで、ガラスの安定性が向上し、光触媒結晶が析出し易くなるため、釉薬用ガラスを用いた釉薬層の光触媒活性を確保することができる。従って、酸化物換算組成の全物質量に対する、Ｒｎ２Ｏ成分の合計量は５０％、好ましくは４０％、より好ましくは３０％、最も好ましくは２５％を上限とする。また、Ｒｎ２Ｏ成分を含有する場合、その効果を発現させるための含有量として、好ましくは０．１％、より好ましくは０．５％、もっとも好ましくは１％を下限とする。The glaze glass of the present invention contains 50% or less of at least one component selected from Rn 2 O (wherein Rn is one or more selected from the group consisting of Li, Na, and K). It is preferable. In particular, when the total amount of the Rn 2 O component is 50% or less, the stability of the glass is improved and the photocatalytic crystal is likely to be precipitated, so that the photocatalytic activity of the glaze layer using the glaze glass is ensured. Can do. Therefore, the total amount of the Rn 2 O component is 50%, preferably 40%, more preferably 30%, and most preferably 25% with respect to the total amount of substances in oxide equivalent composition. Further, when containing Rn 2 O component, a content to express the effect, preferably 0.1%, more preferably 0.5%, most preferably the lower limit of 1%.
ＭｇＯ成分は、ガラスの溶融性と安定性を向上させる成分であり、任意に添加できる成分である。光触媒結晶を生成させやすくするとともに、他の成分と結合または固溶して光触媒活性を有する結晶になることもある。また、ガラス転移温度を下げて熱処理温度をより低く抑える働きをするので、ＴｉＯ２成分を含有する場合に光触媒活性の高いアナターゼ型ＴｉＯ２結晶から光触媒活性の低いルチル型への相転移を低減する効果も期待できる。しかし、ＭｇＯ成分の含有量が５０％を超えると、かえって釉薬用ガラスの安定性が悪くなり、釉薬用ガラスを加熱して結晶を析出する際に所望の光触媒結晶相が析出し難くなる。従って、酸化物換算組成の全物質量に対するＭｇＯ成分の含有量は５０％、好ましくは３５％、より好ましくは２５％、最も好ましくは１５％を上限とする。ＭｇＯ成分は、原料として例えばＭｇＣＯ３、ＭｇＦ２等を用いて釉薬用ガラス内に導入することができる。The MgO component is a component that improves the meltability and stability of the glass and can be arbitrarily added. While making it easy to produce | generate a photocatalyst crystal | crystallization, it may couple | bond or solid-solve with another component and may become a crystal | crystallization which has photocatalytic activity. In addition, it functions to lower the glass transition temperature and lower the heat treatment temperature, so that when it contains a TiO 2 component, it reduces the phase transition from anatase-type TiO 2 crystal with high photocatalytic activity to a rutile type with low photocatalytic activity. The effect can also be expected. However, if the content of the MgO component exceeds 50%, the stability of the glaze glass is deteriorated, and a desired photocatalytic crystal phase is hardly precipitated when the glaze glass is heated to precipitate crystals. Therefore, the upper limit of the content of the MgO component is 50%, preferably 35%, more preferably 25%, and most preferably 15% with respect to the total amount of the oxide conversion composition. The MgO component can be introduced into the glaze glass using, for example, MgCO 3 or MgF 2 as a raw material.
ＣａＯ成分は、ガラスの溶融性と安定性を向上させる成分であり、任意に添加できる成分である。光触媒結晶を生成させやすくするとともに、他の成分と結合または固溶して光触媒活性を有する結晶を生成する場合もある。また、ガラス転移温度を下げて熱処理温度をより低く抑える働きをするので、ＴｉＯ２成分を含有する場合に光触媒活性の高いアナターゼ型ＴｉＯ２結晶から光触媒活性の低いルチル型への相転移を低減する効果も期待できる。しかし、ＣａＯ成分の含有量が５０％を超えると、かえってガラスの安定性が悪くなり、ガラスを加熱して結晶を析出する際に所望の光触媒結晶が析出し難くなる。従って、酸化物換算組成の全物質量に対するＣａＯ成分の含有量は、５０％、好ましくは３５％、より好ましくは２５％、最も好ましくは１５％を上限とする。ＣａＯ成分は、原料として例えばＣａＣＯ３、ＣａＦ２等を用いて釉薬用ガラス内に導入することができる。A CaO component is a component which improves the meltability and stability of glass, and is a component which can be added arbitrarily. In addition to facilitating the formation of photocatalytic crystals, there are cases where crystals having photocatalytic activity are produced by binding or solid solution with other components. In addition, it functions to lower the glass transition temperature and lower the heat treatment temperature, so that when it contains a TiO 2 component, it reduces the phase transition from anatase-type TiO 2 crystal with high photocatalytic activity to a rutile type with low photocatalytic activity. The effect can also be expected. However, when the content of the CaO component exceeds 50%, the stability of the glass is deteriorated, and the desired photocatalytic crystal is difficult to precipitate when the glass is heated to precipitate the crystal. Therefore, the upper limit of the CaO component content is 50%, preferably 35%, more preferably 25%, and most preferably 15% with respect to the total amount of the oxide-converted composition. CaO component can be introduced into the glass glaze used as the starting material for example CaCO 3, CaF 2 and the like.
ＳｒＯ成分は、ガラスの溶融性と安定性を向上させる成分であり、任意に添加できる成分である。光触媒結晶を生成させやすくするとともに、他の成分と結合または固溶して光触媒活性を有する結晶を生成する場合もある。また、ガラス転移温度を下げて熱処理温度をより低く抑える働きをするので、ＴｉＯ２成分を含有する場合に光触媒活性の高いアナターゼ型ＴｉＯ２結晶から光触媒活性の低いルチル型への相転移を低減する効果も期待できる。しかし、ＳｒＯ成分の含有量が５０％を超えると、かえってガラスの安定性が悪くなり、ガラスを加熱して結晶を析出する際に所望の光触媒結晶が析出し難くなる。従って、酸化物換算組成の全物質量に対するＳｒＯ成分の含有量は５０％、好ましくは３５％、より好ましくは２５％、最も好ましくは１５％を上限とする。ＳｒＯ成分は、原料として例えばＳｒ（ＮＯ３）２、ＳｒＦ２等を用いて釉薬用ガラス内に導入することができる。A SrO component is a component which improves the meltability and stability of glass, and is a component which can be added arbitrarily. In addition to facilitating the formation of photocatalytic crystals, there are cases where crystals having photocatalytic activity are produced by binding or solid solution with other components. In addition, it functions to lower the glass transition temperature and lower the heat treatment temperature, so that when it contains a TiO 2 component, it reduces the phase transition from anatase-type TiO 2 crystal with high photocatalytic activity to a rutile type with low photocatalytic activity. The effect can also be expected. However, if the content of the SrO component exceeds 50%, the stability of the glass is deteriorated, and the desired photocatalytic crystal is difficult to precipitate when the glass is heated to precipitate the crystal. Therefore, the upper limit of the SrO component content is 50%, preferably 35%, more preferably 25%, and most preferably 15% with respect to the total amount of substances in oxide equivalent composition. The SrO component can be introduced into the glaze glass using, for example, Sr (NO 3 ) 2 , SrF 2 or the like as a raw material.
ＢａＯ成分は、ガラスの溶融性と安定性を向上させる成分であり、任意に添加できる成分である。光触媒結晶を生成させやすくするとともに、他の成分と結合または固溶して光触媒活性を有する結晶を生成する場合もある。また、ガラス転移温度を下げて熱処理温度をより低く抑える働きをするので、ＴｉＯ２成分を含有する場合に光触媒活性の高いアナターゼ型ＴｉＯ２結晶から光触媒活性の低いルチル型への相転移を低減する効果も期待できる。しかし、ＢａＯ成分の含有量が５０％を超えると、かえってガラスの安定性が悪くなり、ガラスを加熱して結晶を析出する際に所望の光触媒結晶が析出し難くなる。従って、酸化物換算組成の全物質量に対するＢａＯ成分の含有量は５０％、好ましくは３５％、より好ましくは２５％、最も好ましくは１５％を上限とする。ＢａＯ成分は、原料として例えばＢａＣＯ３、Ｂａ（ＮＯ３）２、ＢａＦ２等を用いて釉薬用ガラス内に導入することができる。A BaO component is a component which improves the meltability and stability of glass, and is a component which can be added arbitrarily. In addition to facilitating the formation of photocatalytic crystals, there are cases where crystals having photocatalytic activity are produced by binding or solid solution with other components. In addition, it functions to lower the glass transition temperature and lower the heat treatment temperature, so that when it contains a TiO 2 component, it reduces the phase transition from anatase-type TiO 2 crystal with high photocatalytic activity to a rutile type with low photocatalytic activity. The effect can also be expected. However, if the content of the BaO component exceeds 50%, the stability of the glass is deteriorated, and the desired photocatalytic crystal is difficult to precipitate when the glass is heated to precipitate the crystal. Therefore, the upper limit of the content of the BaO component is 50%, preferably 35%, more preferably 25%, and most preferably 15% with respect to the total amount of substances in oxide equivalent composition. The BaO component can be introduced into the glaze glass using, for example, BaCO 3 , Ba (NO 3 ) 2 , BaF 2 or the like as a raw material.
本発明の釉薬用ガラスは、ＲＯ（式中、ＲはＭｇ、Ｃａ、ＳｒおよびＢａからなる群より選択される１種以上）成分から選ばれる少なくとも１種以上の成分を５０％以下含有することが好ましい。特に、ＲＯ成分の合計量を５０％以下にすることで、ガラスの安定性が向上し、光触媒活性を有する所望の結晶が析出し易くなるため、釉薬用ガラスを用いた釉薬層の光触媒活性を確保することができる。従って、酸化物換算組成の全物質量に対する、ＲＯ成分の合計量は５０％、好ましくは４０％、より好ましくは３０％、最も好ましくは２５％を上限とする。また、ＲＯ成分を含有する場合、その効果を発現させるための合量として、好ましくは０．１％、より好ましくは０．５％、もっとも好ましくは１％を下限とする。 The glaze glass of the present invention contains 50% or less of at least one component selected from RO (wherein R is one or more selected from the group consisting of Mg, Ca, Sr and Ba). Is preferred. In particular, when the total amount of RO components is 50% or less, the stability of the glass is improved, and desired crystals having photocatalytic activity are likely to precipitate. Therefore, the photocatalytic activity of the glaze layer using glaze glass is improved. Can be secured. Therefore, the upper limit of the total amount of the RO component is 50%, preferably 40%, more preferably 30%, and most preferably 25% with respect to the total amount of substances of the oxide conversion composition. Moreover, when it contains RO component, as a total amount for expressing the effect, Preferably it is 0.1%, More preferably, it is 0.5%, Most preferably, let 1% be a minimum.
本発明の釉薬用ガラスは、Ｒｎ２Ｏ成分及び／又はＲＯ成分から選ばれる少なくとも１種以上の成分の合量が５０％以下であることが好ましい。特に、Ｒｎ２Ｏ成分及び／又はＲＯ成分の合計量を５０％以下にすることで、ガラスの安定性が向上し、光触媒活性を有する所望の結晶が析出し易くなるため、釉薬用ガラスを用いた釉薬層の光触媒活性を確保することができる。従って、酸化物換算組成の全物質量に対する、Ｒｎ２Ｏ成分及び／又はＲＯ成分の合計量は５０％、好ましくは４０％、より好ましくは３０％、最も好ましくは２５％を上限とする。また、これらの成分を含有する場合、その効果を発現させるための合量として、１％、好ましくは３％、より好ましくは５％、もっとも好ましくは７％を下限とする。In the glaze glass of the present invention, the total amount of at least one component selected from the Rn 2 O component and / or the RO component is preferably 50% or less. In particular, when the total amount of the Rn 2 O component and / or the RO component is 50% or less, the stability of the glass is improved, and desired crystals having photocatalytic activity are easily precipitated. It is possible to ensure the photocatalytic activity of the glaze layer. Therefore, the total amount of the Rn 2 O component and / or the RO component is 50%, preferably 40%, more preferably 30%, and most preferably 25% with respect to the total amount of substances in oxide equivalent composition. Moreover, when these components are contained, the lower limit is 1%, preferably 3%, more preferably 5%, and most preferably 7% as a total amount for expressing the effect.
また、本発明の釉薬用ガラスは酸化物換算組成のモル％で、
Ａｌ２Ｏ３成分を０〜３０％、
Ｇａ２Ｏ３成分を０〜３０％、
Ｉｎ２Ｏ３成分を０〜３０％、
ＺｒＯ２成分を０〜２０％、
ＳｎＯ成分を０〜２０％、
Ｂｉ２Ｏ３成分及び／又はＴｅＯ２成分を０〜２０％、
ＭｏＯ成分を０〜３０％、
Ｌｎ２Ｏ３成分を０〜３０％（ＬｎはＹ、Ｃｅ、Ｌａ、Ｎｄ、Ｇｄ、Ｄｙ、Ｙｂから選ばれる１種以上）、
ＭｘＯｙ成分を０〜１０％（Ｍは、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、及びＮｉから選ばれる１種以上とし、
ｘ：ｙ＝２：（Ｍの価数）を満たす最小の自然数とする）
Ａｓ２Ｏ３成分及び／又はＳｂ２Ｏ３成分を０〜５％、含有することが好ましい。Moreover, the glass for glazes of this invention is the mol% of an oxide conversion composition,
0 to 30% of Al 2 O 3 component,
Ga 2 O 3 component 0-30%,
0-30% of In 2 O 3 component,
0 to 20% of ZrO 2 component,
0 to 20% of SnO component,
Bi 2 O 3 component and / or TeO 2 component 0-20%
0-30% of MoO component,
Ln 2 O 3 component 0-30% (Ln is one or more selected from Y, Ce, La, Nd, Gd, Dy, Yb),
M x O y component is 0 to 10% (M is at least one selected from V, Cr, Mn, Fe, Co, and Ni,
x: y = 2: a minimum natural number satisfying (the valence of M))
The as 2 O 3 component and / or Sb 2 O 3 ingredients 0-5%, and preferably.
Ａｌ２Ｏ３成分は、ガラスの安定性及び釉薬層の化学的耐久性を高め、釉薬用ガラスからの光触媒結晶の析出を促進し、且つＡｌ３＋イオンが光触媒の結晶相に固溶して光触媒特性の向上に寄与する成分であり、任意に添加できる成分である。しかし、その含有量が３０％を超えると、溶解温度が著しく上昇し、ガラス化し難くなる。従って、酸化物換算組成の釉薬用ガラス全物質量に対するＡｌ２Ｏ３成分の含有量は、３０％、好ましくは２０％、より好ましくは１５％、最も好ましくは１０％を上限とする。また、Ａｌ２Ｏ３成分を添加する場合、その下限は好ましくは０．１％、より好ましくは０．５％、最も好ましくは１．０％とする。Ａｌ２Ｏ３成分は、原料として例えばＡｌ２Ｏ３、Ａｌ（ＯＨ）３、ＡｌＦ３等を用いて釉薬用ガラスに導入することができる。Al 2 O 3 component enhances the stability of the glass and the chemical durability of the glaze layer, promotes the precipitation of photocatalytic crystals from the glass for glazes, and Al 3+ ions dissolve in the crystal phase of the photocatalyst to form a photocatalyst It is a component that contributes to the improvement of characteristics and can be optionally added. However, when the content exceeds 30%, the melting temperature is remarkably increased and vitrification becomes difficult. Therefore, the upper limit of the content of the Al 2 O 3 component is 30%, preferably 20%, more preferably 15%, and most preferably 10% with respect to the total amount of glaze glass having an oxide conversion composition. Further, when the Al 2 O 3 component is added, the lower limit is preferably 0.1%, more preferably 0.5%, and most preferably 1.0%. The Al 2 O 3 component can be introduced into the glaze glass using, for example, Al 2 O 3 , Al (OH) 3 , AlF 3 or the like as a raw material.
Ｇａ２Ｏ３成分は、ガラスの安定性を高め、釉薬用ガラスから光触媒結晶の析出を促進し、且つＧａ３＋イオンが光触媒の結晶相に固溶して光触媒特性の向上に寄与する成分であり、任意に添加できる成分である。しかし、その含有量が３０％を超えると、溶解温度が著しく上昇し、ガラス化し難くなる。従って、酸化物換算組成の釉薬用ガラス全物質量に対するＧａ２Ｏ３成分の含有量は、好ましくは３０％、より好ましくは２０％、最も好ましくは１０％を上限とする。Ｇａ２Ｏ３成分は、原料として例えばＧａ２Ｏ３、ＧａＦ３等を用いて釉薬用ガラスに導入することができる。The Ga 2 O 3 component is a component that enhances the stability of the glass, promotes the precipitation of photocatalytic crystals from the glaze glass, and contributes to the improvement of the photocatalytic properties by dissolving Ga 3+ ions in the crystal phase of the photocatalyst. , A component that can be optionally added. However, when the content exceeds 30%, the melting temperature is remarkably increased and vitrification becomes difficult. Therefore, the upper limit of the content of the Ga 2 O 3 component with respect to the total amount of glaze glass having an oxide conversion composition is preferably 30%, more preferably 20%, and most preferably 10%. Ga 2 O 3 component can be introduced into the glass glaze used as the raw material for instance Ga 2 O 3, GaF 3, and the like.
Ｉｎ２Ｏ３成分は、上記のＡｌ２Ｏ３及びＧａ２Ｏ３と相似な効果がある成分であり、任意に添加できる成分である。しかし、その含有量が３０％を超えると、溶解温度が著しく上昇し、ガラス化し難くなる。また、Ｉｎ２Ｏ３成分は高価なため、その含有量の上限は１０％以下にすることが好ましく、８％以下にすることがより好ましく、５％以下にすることが最も好ましい。Ｉｎ２Ｏ３成分は、原料として例えばＩｎ２Ｏ３、ＩｎＦ３等を用いて釉薬用ガラスに導入することができる。The In 2 O 3 component is a component having an effect similar to that of the above Al 2 O 3 and Ga 2 O 3 and can be arbitrarily added. However, when the content exceeds 30%, the melting temperature is remarkably increased and vitrification becomes difficult. In addition, since the In 2 O 3 component is expensive, the upper limit of its content is preferably 10% or less, more preferably 8% or less, and most preferably 5% or less. The In 2 O 3 component can be introduced into the glaze glass using, for example, In 2 O 3 or InF 3 as a raw material.
本発明の釉薬用ガラスは、Ａｌ２Ｏ３成分、Ｇａ２Ｏ３成分、及びＩｎ２Ｏ３成分から選ばれる少なくとも１種以上の成分を３０％以下含有することが好ましい。特に、これらの成分の合計量を３０％以下にすることで、光触媒の結晶相がより析出し易くなるため、本発明の釉薬用ガラスを用いた釉薬層の光触媒特性のさらなる向上に寄与することができる。従って、酸化物換算組成の釉薬用ガラス全物質量に対するこれら成分の合計量は、好ましくは３０％、より好ましくは２０％、最も好ましくは１０％を上限とする。なお、Ａｌ２Ｏ３成分、Ｇａ２Ｏ３成分、及びＩｎ２Ｏ３成分は、いずれも含有しなくとも高い光触媒特性を有する結晶化ガラスを得ることは可能であるが、その合計量が０．１％未満であると、これら成分の効果が発現されにくい。また、これらの成分の合計量を０．１％以上にすることで、光触媒結晶の析出がさらに促進されるため、釉薬層の光触媒特性のさらなる向上に寄与することができる。従って、酸化物換算組成の釉薬用ガラス全物質量に対するこれら成分の合計量は０．１％、好ましくは０．３％、より好ましくは０．５％、最も好ましくは１％を下限とする。The glaze glass of the present invention preferably contains 30% or less of at least one component selected from Al 2 O 3 component, Ga 2 O 3 component, and In 2 O 3 component. In particular, by making the total amount of these components 30% or less, the crystal phase of the photocatalyst is more likely to be precipitated, which contributes to further improvement of the photocatalytic properties of the glaze layer using the glaze glass of the present invention. Can do. Accordingly, the total amount of these components with respect to the total amount of glaze glass having an oxide conversion composition is preferably 30%, more preferably 20%, and most preferably 10%. In addition, although it is possible to obtain crystallized glass having high photocatalytic characteristics even when none of Al 2 O 3 component, Ga 2 O 3 component, and In 2 O 3 component is contained, the total amount is 0 When the content is less than 1%, the effects of these components are hardly exhibited. Moreover, since precipitation of a photocatalyst crystal | crystallization is further accelerated | stimulated by making the total amount of these components into 0.1% or more, it can contribute to the further improvement of the photocatalytic characteristic of a glaze layer. Therefore, the total amount of these components with respect to the total amount of glaze glass having an oxide conversion composition is 0.1%, preferably 0.3%, more preferably 0.5%, and most preferably 1%.
ＺｒＯ２成分は、釉薬層の化学的耐久性を高め、光触媒結晶の析出を促進し、且つＺｒ４＋イオンが光触媒の結晶相に固溶して光触媒特性の向上に寄与する成分であり、任意に添加できる成分である。しかし、ＺｒＯ２成分の含有量が２０％を超えると、ガラス化し難くなる。従って、酸化物換算組成の釉薬用ガラス全物質量に対するＺｒＯ２成分の含有量は、好ましくは２０％、より好ましくは１５％、最も好ましくは１０％を上限とする。また、ＺｒＯ２成分を添加する場合は、好ましくは０．０１％、より好ましくは０．０２％、最も好ましくは０．０３％を下限とする。ＺｒＯ２成分は、原料として例えばＺｒＯ２、ＺｒＦ４等を用いて釉薬用ガラスに導入することができる。The ZrO 2 component is a component that enhances the chemical durability of the glaze layer, promotes the precipitation of photocatalytic crystals, and contributes to the improvement of the photocatalytic properties by dissolving Zr 4+ ions in the crystal phase of the photocatalyst. It is a component that can be added. However, when the content of the ZrO 2 component exceeds 20%, vitrification becomes difficult. Therefore, the upper limit of the content of the ZrO 2 component with respect to the total amount of glaze glass having an oxide conversion composition is preferably 20%, more preferably 15%, and most preferably 10%. In addition, when adding the ZrO 2 component, the lower limit is preferably 0.01%, more preferably 0.02%, and most preferably 0.03%. ZrO 2 component can be introduced into the glass glaze as starting materials such as ZrO 2, ZrF 4, and the like.
ＳｎＯ成分は、光触媒結晶の析出を促進し、Ｔｉ４＋又はＷ６＋の還元を抑制して光触媒の結晶相を得易くし、且つ光触媒の結晶相に固溶して光触媒特性の向上に効果がある成分であり、また、光触媒活性を高める作用のある後述のＡｇやＡｕやＰｔイオンと一緒に添加する場合は還元剤の役割を果たし、間接的に光触媒の活性の向上に寄与する成分であり、任意に添加できる成分である。しかし、これらの成分の含有量が２０％を超えると、ガラスの安定性が悪くなり、釉薬層の光触媒特性も低下し易くなる。従って、酸化物換算組成の釉薬用ガラス全物質量に対するＳｎＯ成分の含有量は２０％、好ましくは１０％、より好ましくは８％、最も好ましくは５％を上限とする。また、ＳｎＯ成分を添加する場合は、好ましくは０．０１％、より好ましくは０．０２％、最も好ましくは０．０３％を下限とする。ＳｎＯ成分は、原料として例えばＳｎＯ、ＳｎＯ２、ＳｎＯ３等を用いて釉薬用ガラスに導入することができる。The SnO component promotes the precipitation of the photocatalytic crystal, suppresses the reduction of Ti 4+ or W 6+ to make it easy to obtain the photocatalytic crystal phase, and is effective in improving the photocatalytic properties by dissolving in the photocatalytic crystal phase. It is a component, and when it is added together with Ag, Au or Pt ions, which will be described later, which has the effect of enhancing the photocatalytic activity, it serves as a reducing agent and indirectly contributes to the improvement of the photocatalytic activity. It is a component that can be optionally added. However, when the content of these components exceeds 20%, the stability of the glass is deteriorated, and the photocatalytic properties of the glaze layer are liable to be lowered. Therefore, the upper limit of the SnO component content is 20%, preferably 10%, more preferably 8%, and most preferably 5% with respect to the total amount of glaze glass having an oxide equivalent composition. Further, when the SnO component is added, the lower limit is preferably 0.01%, more preferably 0.02%, and most preferably 0.03%. SnO components can be introduced into the glass glaze used as raw materials for example SnO, a SnO 2, SnO 3 and the like.
本発明の釉薬用ガラスは、ＺｒＯ２成分及びＳｎＯ成分から選ばれる少なくとも１種以上の成分を合量で２０％以下含有することが好ましい。特に、これらの成分の合計量を２０％以下にすることで、釉薬用ガラスからなる結晶化ガラスの安定性が確保されるため、良好な釉薬層を形成することができる。従って、酸化物換算組成の釉薬用ガラス全物質量に対するこれら成分の合計量は、好ましくは２０％、より好ましくは１５％、最も好ましくは１０％を上限とする。なお、ＺｒＯ２成分及びＳｎＯ成分は、いずれも含有しなくとも高い光触媒特性を有する釉薬層を得ることは可能であるが、これらの成分の合計量を０．０１％以上にすることで、釉薬層の光触媒特性をさらに向上させることができる。従って、酸化物換算組成の釉薬用ガラス全物質量に対するこれらの合計量は、好ましくは０．０１％、より好ましくは０．０２％、最も好ましくは０．０３％を下限とする。It is preferable that the glass for glazes of the present invention contains at least one component selected from ZrO 2 component and SnO component in a total amount of 20% or less. In particular, when the total amount of these components is 20% or less, the stability of the crystallized glass made of the glaze glass is secured, so that a good glaze layer can be formed. Therefore, the total amount of these components relative to the total amount of glaze glass having an oxide conversion composition is preferably 20%, more preferably 15%, and most preferably 10%. Although it is possible to obtain a glaze layer having high photocatalytic properties even if neither ZrO 2 component nor SnO component is contained, the glaze layer can be obtained by making the total amount of these components 0.01% or more. The photocatalytic properties of the layer can be further improved. Accordingly, the total amount of these materials with respect to the total amount of glaze glass having an oxide conversion composition is preferably 0.01%, more preferably 0.02%, and most preferably 0.03%.
Ｂｉ２Ｏ３成分は、ガラスの溶融性と安定性を高める成分であり、任意に添加できる成分である。また、ガラス転移温度を下げて光触媒結晶を生成させやすくするとともに、熱処理温度をより低く抑える成分である。また、熱処理温度を抑えることで、ＴｉＯ２成分を含有する場合に光触媒活性の高いアナターゼ型ＴｉＯ２結晶から光触媒活性の低いルチル型への相転移を低減する効果も期待できる。しかし、Ｂｉ２Ｏ３成分の含有量が２０％を超えると、ガラスの安定性が悪くなり、釉薬用ガラスを加熱して結晶を析出する際に所望の光触媒結晶が析出し難くなる。従って、酸化物換算組成の釉薬用ガラス全物質量に対するＢｉ２Ｏ３成分の含有量は２０％、好ましくは１０％、より好ましくは５％、最も好ましくは３％を上限とする。特に、釉薬用ガラスの主な網目を構成する成分をＢ２Ｏ３にしつつＴｉＯ２結晶を析出させる場合、ガラスの安定性を高め所望の結晶を得るためには、Ｂｉ２Ｏ３／ＴｉＯ２の含有比が０．１２未満であることが好ましい。Ｂｉ２Ｏ３成分は、原料として例えばＢｉ２Ｏ３等を用いて釉薬用ガラスに導入することができる。Bi 2 O 3 component is a component for enhancing the meltability and stability of glass and is a component that can be added optionally. In addition, it is a component that lowers the glass transition temperature to make it easier to produce photocatalytic crystals and lowers the heat treatment temperature. In addition, by suppressing the heat treatment temperature, an effect of reducing the phase transition from anatase-type TiO 2 crystal having a high photocatalytic activity to a rutile type having a low photocatalytic activity when a TiO 2 component is contained can be expected. However, when the content of the Bi 2 O 3 component exceeds 20%, the stability of the glass is deteriorated, and when the glaze glass is heated to precipitate crystals, it becomes difficult to deposit desired photocatalytic crystals. Therefore, the upper limit of the content of the Bi 2 O 3 component is 20%, preferably 10%, more preferably 5%, and most preferably 3% with respect to the total amount of glaze glass having an oxide conversion composition. In particular, in the case where TiO 2 crystals are precipitated while B 2 O 3 is used as the component constituting the main network of the glaze glass, Bi 2 O 3 / TiO 2 is used to increase the stability of the glass and obtain the desired crystals. The content ratio of is preferably less than 0.12. Bi 2 O 3 component can be introduced into the glass glaze used as the starting material for example Bi 2 O 3 and the like.
ＴｅＯ２成分は、ガラスの溶融性と安定性を高める成分であり、任意に添加できる成分である。また、ガラス転移温度を下げて光触媒結晶を生成させやすくするとともに、熱処理温度をより低く抑える成分である。また、熱処理温度を抑えることで、ＴｉＯ２成分を含有する場合に光触媒活性の高いアナターゼ型ＴｉＯ２結晶から光触媒活性の低いルチル型への相転移を低減する効果も期待できる。しかし、ＴｅＯ２成分の含有量が２０％を超えると、ガラスの安定性が悪くなり、釉薬用ガラスを加熱して結晶を析出する際に所望の光触媒結晶が析出し難くなる。従って、酸化物換算組成の釉薬用ガラス全物質量に対するＴｅＯ２成分の含有量は２０％、好ましくは１５％、より好ましくは１０％、最も好ましくは５％を上限とする。ＴｅＯ２成分は、原料として例えばＴｅＯ２等を用いて釉薬用ガラスに導入することができる。TeO 2 component is a component which enhances the meltability and stability of glass and is a component that can be added optionally. In addition, it is a component that lowers the glass transition temperature to make it easier to produce photocatalytic crystals and lowers the heat treatment temperature. In addition, by suppressing the heat treatment temperature, an effect of reducing the phase transition from anatase-type TiO 2 crystal having a high photocatalytic activity to a rutile type having a low photocatalytic activity when a TiO 2 component is contained can be expected. However, when the content of the TeO 2 component exceeds 20%, the stability of the glass deteriorates, and when the glaze glass is heated to precipitate crystals, it becomes difficult to deposit desired photocatalytic crystals. Therefore, the upper limit of the content of TeO 2 component is 20%, preferably 15%, more preferably 10%, and most preferably 5% with respect to the total amount of glaze glass having an oxide conversion composition. TeO 2 component can be introduced into the glass glaze used as the starting material for example TeO 2 or the like.
本発明の光触媒部材に用いる釉薬用ガラスは、Ｂｉ２Ｏ３成分及びＴｅＯ２成分から選ばれる少なくとも１種以上の成分を合量で２０％以下含有することが好ましい。特に、これらの成分の合計量を２０％以下にすることで、釉薬用ガラスからなる結晶化ガラスの安定性が確保されるため、良好な釉薬層を形成することができる。従って、酸化物換算組成の釉薬用ガラス全物質量に対するこれら成分の合計量は、好ましくは２０％、より好ましくは１５％、最も好ましくは１０％を上限とする。なお、Ｂｉ２Ｏ３成分及びＴｅＯ２成分は、いずれも含有しなくとも高い光触媒特性を有する釉薬層を得ることは可能であるが、その合計量が０．１％未満であると、これら成分の効果が発現されにくい。従って、酸化物換算組成の釉薬用ガラス全物質量に対する合計量は、好ましくは０．０１％、より好ましくは０．０２％、最も好ましくは０．０３％を下限とする。It is preferable that the glass for glaze used for the photocatalyst member of the present invention contains at least one component selected from Bi 2 O 3 component and TeO 2 component in a total amount of 20% or less. In particular, when the total amount of these components is 20% or less, the stability of the crystallized glass made of the glaze glass is secured, so that a good glaze layer can be formed. Therefore, the total amount of these components relative to the total amount of glaze glass having an oxide conversion composition is preferably 20%, more preferably 15%, and most preferably 10%. In addition, although it is possible to obtain a glaze layer having high photocatalytic characteristics even if neither Bi 2 O 3 component nor TeO 2 component is contained, these components are contained when the total amount is less than 0.1%. The effect of is difficult to be expressed. Therefore, the total amount of the oxide conversion composition with respect to the total amount of glaze glass is preferably 0.01%, more preferably 0.02%, and most preferably 0.03%.
ＭｏＯ３成分は、ガラスの溶融性と安定性を高める成分であり、且つ光触媒結晶相に固溶し、又はその近傍に存在することで、光触媒特性を向上させる成分であり、任意に添加できる成分である。しかし、ＭｏＯ３成分の含有量が３０％を超えると、ガラスの安定性が著しく悪くなる。従って、酸化物換算組成の釉薬用ガラス全物質量に対するＭｏＯ３成分の含有量は、好ましくは３０％、より好ましくは２０％、最も好ましくは１０％を上限とする。ＭｏＯ３成分は、原料として例えばＭｏＯ３等を用いて釉薬用ガラス内に導入することができる。The MoO 3 component is a component that enhances the meltability and stability of the glass, and is a component that improves the photocatalytic properties by being dissolved in the photocatalytic crystal phase or in the vicinity thereof, and can be optionally added It is. However, when the content of the MoO 3 component exceeds 30%, the stability of the glass is remarkably deteriorated. Therefore, the upper limit of the content of the MoO 3 component with respect to the total amount of glaze glass having an oxide conversion composition is preferably 30%, more preferably 20%, and most preferably 10%. The MoO 3 component can be introduced into the glaze glass using, for example, MoO 3 as a raw material.
Ｌｎ２Ｏ３成分（式中、ＬｎはＹ、Ｌａ、Ｃｅ、Ｎｄ、Ｇｄ、Ｄｙ、及びＹｂからなる群より選択される１種以上とする）は、釉薬用ガラス、およびそれを用いた釉薬層の化学的耐久性を高める成分であり、且つ光触媒の結晶相に固溶し、又はその近傍に存在することで、光触媒特性を向上させる成分であり、任意に添加できる成分である。しかし、Ｌｎ２Ｏ３成分の含有量の合計が３０％を超えると、ガラスの安定性が著しく悪くなる。従って、酸化物換算組成の釉薬用ガラス全物質量に対する、Ｌｎ２Ｏ３成分の合計量は、好ましくは３０％、より好ましくは２０％、最も好ましくは１０％を上限とする。Ｌｎ２Ｏ３成分の内、特にＣｅ２Ｏ３成分が光触媒結晶を形成するイオンの還元を防ぎ、光触媒結晶の析出を促進するため、光触媒特性の向上に顕著に寄与する効果がある。Ｌｎ２Ｏ３成分は、原料として例えばＬａ２Ｏ３、Ｌａ（ＮＯ３）３・ＸＨ２Ｏ（Ｘは任意の整数）、Ｇｄ２Ｏ３、ＧｄＦ３、Ｙ２Ｏ３、ＹＦ３、ＣｅＯ２、ＣｅＦ３、Ｎｄ２Ｏ３、Ｄｙ２Ｏ３、Ｙｂ２Ｏ３等を用いて釉薬用ガラスに導入することができる。Ln 2 O 3 component (wherein Ln is at least one selected from the group consisting of Y, La, Ce, Nd, Gd, Dy, and Yb) is a glaze glass and glaze using the same It is a component that enhances the chemical durability of the layer, and is a component that improves the photocatalytic properties by being dissolved in the crystal phase of the photocatalyst or in the vicinity thereof, and can be optionally added. However, if the total content of the Ln 2 O 3 components exceeds 30%, the stability of the glass is significantly deteriorated. Accordingly, the total amount of the Ln 2 O 3 component with respect to the total amount of glaze glass having an oxide conversion composition is preferably 30%, more preferably 20%, and most preferably 10%. Among the Ln 2 O 3 components, particularly the Ce 2 O 3 component prevents the reduction of ions that form the photocatalytic crystal and promotes the precipitation of the photocatalytic crystal, and therefore has the effect of significantly contributing to the improvement of the photocatalytic properties. The Ln 2 O 3 component includes, for example, La 2 O 3 , La (NO 3 ) 3 .XH 2 O (X is an arbitrary integer), Gd 2 O 3 , GdF 3 , Y 2 O 3 , YF 3 , CeO as raw materials. 2 , CeF 3 , Nd 2 O 3 , Dy 2 O 3 , Yb 2 O 3, etc. can be used to introduce into the glaze glass.
ＭｘＯｙ成分（式中、ＭはＶ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉからなる群より選択される１種以上とし、ｘ及びｙはそれぞれｘ：ｙ＝２：Ｍの価数、を満たす最小の自然数、Ｍの価数は、Ｖは５、Ｃｒは３、Ｍｎは１、Ｆｅは３、Ｃｏは２、Ｎｉは２とする。）は光触媒の結晶相に固溶するか、又はその近傍に存在することで、光触媒特性の向上に寄与し、且つ一部の波長の可視光を吸収して釉薬層に外観色を付与する成分であり、本発明の釉薬用ガラス中の任意成分である。特に、ＭｘＯｙ成分の合計量を１０％以下にすることで、ガラスの安定性を高め、釉薬層の外観色を容易に調節することができる。従って、酸化物換算組成の釉薬用ガラス全物質量に対する、ＭｘＯｙ成分の合計量は１０％、好ましくは８％、より好ましくは５％、最も好ましくは３％を上限とする。また、これらの成分を添加する場合は、その効果を発現するために、好ましくは０．０００１％、より好ましくは０．００２％、最も好ましくは０．００５％を下限とする。ＭｘＯｙ成分は例えばＶ２Ｏ５、Ｃｒ２Ｏ３、Ｆｅ２Ｏ３などを用いて釉薬用ガラスに導入することができる。M x O y component (wherein M is one or more selected from the group consisting of V, Cr, Mn, Fe, Co, Ni, and x and y are valences of x: y = 2: M, Or the valence of M is V is 5, Cr is 3, Mn is 1, Fe is 3, Co is 2 and Ni is 2) is dissolved in the crystalline phase of the photocatalyst, Or it is a component that contributes to the improvement of photocatalytic properties by being present in the vicinity thereof, and absorbs visible light of some wavelengths to give the glaze layer an appearance color, and is optional in the glaze glass of the present invention It is an ingredient. In particular, when the total amount of M x O y components is 10% or less, the stability of the glass can be improved and the appearance color of the glaze layer can be easily adjusted. Therefore, the total amount of the M x O y component is 10%, preferably 8%, more preferably 5%, and most preferably 3% with respect to the total amount of glaze glass having an oxide conversion composition. Moreover, when adding these components, in order to express the effect, Preferably it is 0.0001%, More preferably, it is 0.002%, Most preferably, let 0.005% be a minimum. The M x O y component can be introduced into the glaze glass using, for example, V 2 O 5 , Cr 2 O 3 , Fe 2 O 3 or the like.
Ａｓ２Ｏ３成分及び／又はＳｂ２Ｏ３成分は、ガラスを清澄させ、脱泡させる成分であり、また、光触媒活性を高める作用のある後述のＡｇやＡｕやＰｔイオンと一緒に添加する場合は、還元剤の役割を果たすので、間接的に光触媒活性の向上に寄与する成分であり、任意に添加できる成分である。しかし、これらの成分の含有量が合計で５％を超えると、釉薬用ガラスの安定性が悪くなり、釉薬用ガラスを焼成して作られる釉薬層の光触媒特性も低下し易くなる。従って、酸化物換算組成の釉薬用ガラス全物質量に対するＡｓ２Ｏ３成分及び／又はＳｂ２Ｏ３成分の含有量の合計は、好ましくは５％、より好ましくは３％、最も好ましくは１％を上限とする。また、これらの成分を添加する場合は、好ましくは０．００１％、より好ましくは０．００２％、最も好ましくは０．００５％を下限とする。Ａｓ２Ｏ３成分及びＳｂ２Ｏ３成分は、原料として例えばＡｓ２Ｏ３、Ａｓ２Ｏ５、Ｓｂ２Ｏ３、Ｓｂ２Ｏ５、Ｎａ２Ｈ２Ｓｂ２Ｏ７・５Ｈ２Ｏ等を用いて釉薬用ガラスに導入することができる。As 2 O 3 component and / or Sb 2 O 3 component is a component for clarifying and defoaming glass, and when added together with Ag, Au, and Pt ions, which will be described later, and has the effect of enhancing photocatalytic activity. Since it plays the role of a reducing agent, it is a component that indirectly contributes to the improvement of the photocatalytic activity and can be optionally added. However, when the content of these components exceeds 5% in total, the stability of the glaze glass is deteriorated, and the photocatalytic properties of the glaze layer produced by firing the glaze glass tend to be lowered. Accordingly, the total content of As 2 O 3 component and / or Sb 2 O 3 component with respect to the total amount of glaze glass having an oxide conversion composition is preferably 5%, more preferably 3%, and most preferably 1%. Is the upper limit. When these components are added, the lower limit is preferably 0.001%, more preferably 0.002%, and most preferably 0.005%. As 2 O 3 component and Sb 2 O 3 component are, for example, As 2 O 3 , As 2 O 5 , Sb 2 O 3 , Sb 2 O 5 , Na 2 H 2 Sb 2 O 7 .5H 2 O and the like as raw materials. And can be introduced into glaze glass.
なお、ガラスを清澄させ、脱泡させる成分は、上記のＡｓ２Ｏ３成分及びＳｂ２Ｏ３成分に限定されるものではなく、例えばＣｅＯ２成分やＴｅＯ２成分等のような、ガラス製造の分野における公知の清澄剤や脱泡剤、或いはそれらの組み合わせを用いることができる。The components for clarifying and defoaming the glass are not limited to the above As 2 O 3 component and Sb 2 O 3 component. For example, such as CeO 2 component, TeO 2 component, etc. Known fining agents and defoaming agents in the field, or a combination thereof can be used.
さらに、本発明の釉薬用ガラスは酸化物換算組成のガラス全物質量に対する外割り質量％で、Ｆ、Ｃｌ、Ｂｒ、Ｓ、Ｎ、及びＣから選ばれる１種以上の非金属元素成分を０．０１〜１０％含有することが好ましい。 Further, the glaze glass of the present invention has an externally divided mass% with respect to the total amount of glass having an oxide equivalent composition, and contains one or more non-metallic element components selected from F, Cl, Br, S, N, and C. It is preferable to contain 0.01 to 10%.
これらの成分は、光触媒の結晶相に固溶し、又はその近傍に存在することで、光触媒特性が向上する成分であり、任意に添加できる成分である。しかし、これらの成分の含有量が合計で１０％を超えると、釉薬用ガラスの安定性が著しく悪くなり、釉薬用ガラスを焼成して作られる釉薬層の光触媒特性も低下し易くなる。従って、良好な特性を確保するために、酸化物換算組成の釉薬用ガラス全質量に対する非金属元素成分の含有量の合計は、好ましくは１０％、より好ましくは５％、最も好ましくは３％を上限とする。これらの非金属元素成分は、アルカリ金属又はアルカリ土類金属のフッ化物、塩化物、臭化物、硫化物、窒化物、炭化物等の形で釉薬用ガラス中に導入することができる。なお、本明細書における非金属元素成分の含有量は、ガラスを構成するカチオン成分全てが電荷の釣り合うだけの酸素と結合した酸化物でできていると仮定し、それら酸化物でできたガラス全体の質量を１００％として、別途抜き出して合計した非金属元素成分の質量を質量％で表したもの（酸化物基準の質量に対する外割り質量％）である。非金属元素成分の原料は特に限定されないが、Ｎ成分の原料としてＡｌＮ３、ＳｉＮ４等、Ｓ成分の原料としてＮａＳ，Ｆｅ２Ｓ３，ＣａＳ２等、Ｆ成分の原料としてＺｒＦ４、ＡｌＦ３、ＮａＦ、ＣａＦ２等、Ｃｌ成分の原料としてＮａＣｌ、ＡｇＣｌ等、Ｂｒ成分の原料としてＮａＢｒ等、Ｃ成分の原料としてＴｉＣ、ＳｉＣ又はＺｒＣ等を用いることで、釉薬用ガラス内に含有することができる。なお、これらの原料は、一体的に添加してもよいし、独立に添加してもよい。These components are components in which the photocatalytic properties are improved by being dissolved in the crystal phase of the photocatalyst or existing in the vicinity thereof, and can be arbitrarily added. However, when the content of these components exceeds 10% in total, the stability of the glaze glass is remarkably deteriorated, and the photocatalytic properties of the glaze layer produced by firing the glaze glass are also easily deteriorated. Therefore, in order to ensure good characteristics, the total content of the nonmetallic element component with respect to the total mass of the glaze glass having an oxide conversion composition is preferably 10%, more preferably 5%, and most preferably 3%. The upper limit. These nonmetallic element components can be introduced into the glaze glass in the form of fluorides, chlorides, bromides, sulfides, nitrides, carbides or the like of alkali metals or alkaline earth metals. In addition, the content of the nonmetallic element component in the present specification assumes that all the cation components constituting the glass are made of an oxide combined with oxygen that balances the charge, and the entire glass made of these oxides. The mass of the non-metallic element component extracted separately and expressed as mass% is defined as 100% (externally divided mass% with respect to the oxide-based mass). The raw material of the nonmetallic element component is not particularly limited, but AlN 3 , SiN 4 or the like as the N component raw material, NaS, Fe 2 S 3 , CaS 2 or the like as the S component raw material, ZrF 4 or AlF 3 as the F component raw material , NaF, CaF 2, etc., NaCl as a raw material for Cl component, AgCl, etc., NaBr or the like as a raw material of Br components, TiC as a raw material of component C, the use of SiC or ZrC and the like, may be contained in the glass glaze it can. In addition, these raw materials may be added integrally or may be added independently.
さらに、本発明の釉薬用ガラスは酸化物換算組成のガラス全物質量に対する外割り質量％で、Ｃｕ、Ａｇ、Ａｕ、Ｐｄ、Ｐｔ、Ｒｕ、Ｒｅ及びＲｈから選ばれる１種以上の金属元素成分を０．００１〜５％含有することが好ましい。 Furthermore, the glass for glazes of the present invention is an externally divided mass% with respect to the total amount of glass in an oxide conversion composition, and one or more metal element components selected from Cu, Ag, Au, Pd, Pt, Ru, Re, and Rh It is preferable to contain 0.001 to 5%.
これらの金属元素成分は、光触媒結晶相の近傍に存在することで、光触媒活性が向上するため、任意に添加できる。しかし、これらの金属元素成分の含有量の合計が５％を超えると釉薬用ガラスの安定性が著しく悪くなり、釉薬用ガラスを焼成して作られる釉薬層を形成しにくくなったり、その光触媒特性が低下し易くなる。従って、良好な特性を確保するために、酸化物換算組成の釉薬用ガラス全質量に対する金属元素成分の含有量の合計は、好ましくは５％、より好ましくは３％、最も好ましくは１％を上限とする。これらの金属元素成分は、原料として例えばＣｕ２Ｏ、Ａｇ２Ｏ、ＡｕＣｌ３、ＰｔＣｌ４等を用いてガラス内に導入することができる。特に、Ｃｕ及びＡｇの少なくともいずれかを含む場合は、上述の光触媒特性に加えて、光照射がなくても高い抗菌性を発現できるので、これらの少なくともいずれかを含ませることがより好ましい。なお、本明細書における金属元素成分の含有量は、酸化物基準の質量に対する外割り質量％で表したものである。Since these metal element components are present in the vicinity of the photocatalytic crystal phase, the photocatalytic activity is improved, so that they can be arbitrarily added. However, if the total content of these metal element components exceeds 5%, the stability of the glaze glass is remarkably deteriorated, and it becomes difficult to form a glaze layer made by firing the glaze glass, or its photocatalytic properties. Tends to decrease. Therefore, in order to ensure good characteristics, the total content of the metal element component with respect to the total mass of the glaze glass having an oxide conversion composition is preferably 5%, more preferably 3%, and most preferably 1%. And These metal element components can be introduced into the glass using, for example, Cu 2 O, Ag 2 O, AuCl 3 , PtCl 4 or the like as a raw material. In particular, when at least one of Cu and Ag is included, in addition to the above-described photocatalytic properties, high antibacterial properties can be expressed without light irradiation, and therefore it is more preferable to include at least one of these. In addition, content of the metal element component in this specification is represented by the externally divided | segmented mass% with respect to the mass of an oxide basis.
本発明の釉薬用ガラスには、他の成分を釉薬用ガラス、該釉薬用ガラスを用いた釉薬、および該釉薬を用いた釉薬層の特性を損なわない範囲で必要に応じ、添加することができる。但し、ＰｂＯ等の鉛化合物、Ｔｈ、Ｃｄ、Ｔｌ、Ｏｓ、Ｂｅ、Ｓｅ、Ｈｇの各成分は、近年有害な化学物資として使用を控える傾向にあり、ガラスの製造工程のみならず、加工工程、及び製品化後の処分に至るまで環境対策上の措置が必要とされる。従って、環境上の影響を重視する場合には、不可避な混入を除き、これらを実質的に含有しないことが好ましい。これにより、釉薬用ガラス、釉薬、または釉薬層に環境を汚染する物質が実質的に含まれなくなる。そのため、特別な環境対策上の措置を講じなくとも、本発明の釉薬用ガラスを製造し、加工し、及び廃棄することができる。 In the glaze glass of the present invention, other components can be added as needed as long as the characteristics of the glaze glass, the glaze using the glaze glass, and the glaze layer using the glaze are not impaired. . However, lead compounds such as PbO, and components of Th, Cd, Tl, Os, Be, Se, and Hg tend to refrain from being used as harmful chemical substances in recent years. In addition, measures for environmental measures are required until disposal after commercialization. Therefore, when importance is placed on the environmental impact, it is preferable not to substantially contain them except for inevitable mixing. Accordingly, the glass for glaze, the glaze, or the glaze layer is substantially free from substances that pollute the environment. Therefore, the glaze glass of the present invention can be produced, processed, and discarded without taking any special environmental measures.
［釉薬用ガラスの製造方法］
本発明の釉薬用ガラスの製造方法は、原料を混合してその融液を得る溶融工程と、前記融液を冷却してガラス体を得る冷却工程と、を有する。[Manufacturing method of glaze glass]
The manufacturing method of the glass for glazes of this invention has the melting process which mixes a raw material, and obtains the melt, and the cooling process which cools the said melt and obtains a glass body.
（溶融工程）
溶融工程は、上述した組成になるように原料を混合し、その融液を得る工程である。より具体的には、出来上がったガラスの各成分の含有量が所定の範囲内になるように原料を秤量して均一に混合し、作製した混合物を白金坩堝、石英坩堝又はアルミナ坩堝に投入して電気炉で１２００〜１６００℃の温度範囲で１〜２４時間溶融して攪拌均質化して融液を作製する。なお、原料の溶融条件は上記温度範囲に限定されず、原料組成物の組成及び量等に応じて、適宜設定することができる。(Melting process)
The melting step is a step of obtaining the melt by mixing the raw materials so as to have the above-described composition. More specifically, the raw materials are weighed and mixed uniformly so that the content of each component of the finished glass is within a predetermined range, and the prepared mixture is put into a platinum crucible, quartz crucible or alumina crucible. Melt for 1 to 24 hours in a temperature range of 1200 to 1600 ° C. in an electric furnace, and homogenize with stirring to prepare a melt. In addition, the melting conditions of the raw material are not limited to the above temperature range, and can be appropriately set according to the composition and amount of the raw material composition.
（冷却工程）
冷却工程は、溶融工程で得られた融液を冷却してガラス化することで、ガラス体を作製する工程である。具体的には、融液を流出して適宜冷却することで、ガラス化されたガラス体を形成する。ここで、ガラス化の条件は特に限定されるものではなく、原料の組成及び量等に応じて適宜設定されてよい。また、本工程で得られるガラス体の形状は特に限定されず、板状、粒状等であってよいが、粉砕しやすい点では、粒状であることが好ましい。(Cooling process)
A cooling process is a process of producing a glass body by cooling and vitrifying the melt obtained at the melting process. Specifically, a vitrified glass body is formed by flowing out the melt and appropriately cooling it. Here, the conditions for vitrification are not particularly limited, and may be appropriately set according to the composition and amount of the raw material. Moreover, the shape of the glass body obtained by this process is not specifically limited, Although it may be plate shape, a granular form, etc., it is preferable that it is a granular form at the point which is easy to grind | pulverize.
＜釉薬用ガラスの結晶化＞
［光触媒結晶］
本発明の釉薬用ガラスは加熱によって光触媒特性を有する結晶を析出するものである。従って本発明の釉薬用ガラスを加熱してガラスが含有する成分の一部またはほぼ全部を結晶化させれば、光触媒結晶を有する結晶化ガラスになる。この結晶化ガラスは釉薬用ガラスと同じ組成を有するが、内部および表面に結晶相を有するという点で異なる。光触媒結晶の析出は、該釉薬用ガラスを含有する釉薬を施釉して焼成する過程、及び／または釉薬用ガラスを結晶化させるために熱処理する過程で起こる。以下、該過程において本発明の釉薬用ガラスから析出する結晶、即ち本発明の釉薬用ガラスを利用して形成した釉薬層に含まれる光触媒結晶について説明する。<Crystal crystallization of glaze glass>
[Photocatalytic crystal]
The glaze glass of the present invention precipitates crystals having photocatalytic properties by heating. Therefore, when the glaze glass of the present invention is heated to crystallize a part or almost all of the components contained in the glass, a crystallized glass having photocatalytic crystals is obtained. This crystallized glass has the same composition as glaze glass, but differs in that it has a crystalline phase inside and on the surface. Precipitation of the photocatalytic crystal occurs in the process of applying and glaze the glaze containing the glaze glass and / or in the process of heat treatment to crystallize the glaze glass. Hereinafter, the crystals precipitated from the glaze glass of the present invention in the process, that is, the photocatalytic crystals contained in the glaze layer formed using the glaze glass of the present invention will be described.
本発明の釉薬用ガラスは、Ｔｉ、Ｗ、Ｚｎ、Ｎｂ、Ｔａのうちいずれか１つ以上の成分を有し、熱処理することで該成分を含有する結晶を析出するものあり、含有する成分の有無と多少によって、ＴｉＯ２結晶、ＷＯ３結晶、ＺｎＯ結晶、ＲｎＮｂＯ３、ＲｎＴａＯ３、ＲＮｂＯ３、ＲＴａＯ３、ＲＴｉＯ３、ナシコンタイプの結晶及びこれら結晶の固溶体からなる群から選ばれるいずれか１つ以上の結晶を析出する（式中、ＲはＭｇ、Ｃａ、Ｓｒ、Ｂａから選ばれる１種以上、ＲｎはＬｉ、Ｋ、Ｎａから選ばれる１種以上とする。）。従って、これらの結晶は釉薬層に含まれることになる。The glass for glazes of the present invention has one or more components of Ti, W, Zn, Nb, Ta, and precipitates crystals containing the components by heat treatment. One selected from the group consisting of TiO 2 crystal, WO 3 crystal, ZnO crystal, RnNbO 3 , RnTaO 3 , RNbO 3 , RTaO 3 , RTiO 3 , NASICON type crystal, and solid solution of these crystals, depending on the presence or absence and some One or more crystals are precipitated (wherein R is one or more selected from Mg, Ca, Sr, and Ba, and Rn is one or more selected from Li, K, and Na). Therefore, these crystals are included in the glaze layer.
Ｔｉ成分を含む光触媒結晶としては、ＴｉＯ２、ＴｉＰ２Ｏ７、（ＴｉＯ）２Ｐ２Ｏ７、Ｃａ２Ｔｉ５Ｏ１２、ＣａＴｉＳｉＯ５、Ｃａ２Ｔｉ２Ｏ６、Ｔｉ（１−ｘ）ＺｒｘＯ２、（Ｃａ１−ｘＳｒｘ）２Ｔｉ５Ｏ１２、（Ｃａ１−ｘＳｒｘ）２Ｔｉ２Ｏ６、（Ｃａ１−ｘＳｒｘ）ＴｉＳｉＯ５、またはＳｒＴｉＯ２などを挙げることができ、本発明の釉薬用ガラスは加熱によりこれらのうちいずれか一つ以上を析出することが好ましい。このうち特に、光触媒活性が高く、化学的に安定で毒性もないことから、最も好適に使用されるＴｉＯ２を析出することが好ましい。ＴｉＯ２の結晶型としては、アナターゼ（Ａｎａｔａｓｅ）型、ルチル（Ｒｕｔｉｌｅ）型及びブルッカイト（Ｂｒｏｏｋｉｔｅ）型があるが、アナターゼ型およびブルッカイト型が好ましく、特に高い光触媒特性をもつアナターゼ型の酸化チタンを含有することが有利である。ＴｉＯ２の結晶構造は、Ｘ線回折法（ＸＲＤ測定法）により測定することができる。ＴｉＯ２結晶は、他の元素との固溶体の状態で存在していてもよい。なお、固溶体は光触媒活性があれば、置換型固溶体でも侵入型固溶体のいずれでもよい。Examples of the photocatalytic crystal containing the Ti component include TiO 2 , TiP 2 O 7 , (TiO) 2 P 2 O 7 , Ca 2 Ti 5 O 12 , CaTiSiO 5 , Ca 2 Ti 2 O 6 , and Ti (1-x) Zr. x O 2, (Ca 1- x Sr x) 2 Ti 5 O 12, (Ca 1-x Sr x) 2 Ti 2 O 6, (Ca 1-x Sr x) TiSiO 5 or the like SrTiO 2, Preferably, the glaze glass of the present invention precipitates any one or more of these by heating. Among these, it is particularly preferable to deposit TiO 2 that is most suitably used because it has high photocatalytic activity, is chemically stable and has no toxicity. As the crystal form of TiO 2 , there are anatase type, rutile type and brookite type, but anatase type and brookite type are preferable, and contains anatase type titanium oxide having particularly high photocatalytic properties. It is advantageous to do so. The crystal structure of TiO 2 can be measured by an X-ray diffraction method (XRD measurement method). The TiO 2 crystal may exist in a solid solution state with other elements. The solid solution may be either a substitutional solid solution or an interstitial solid solution as long as it has photocatalytic activity.
Ｗ成分を含む光触媒結晶としては、酸化タングステン又はその固溶体がある。酸化タングステンの結晶は、原料や調製方法により２〜６価の酸化物になり、ＷＯ３、ＷＯ、Ｗ２Ｏ３、Ｗ４Ｏ１１、ＷＯ２、Ｗ２Ｏ５、Ｗ３Ｏ８およびＷ５Ｏ１４が存在する。本発明の釉薬用ガラスから析出されるのは、光触媒活性を持つ限り酸化タングステンの種類は問わないが、特に強い光触媒活性を有するＷＯ３を析出することが好ましい。以下の説明では酸化タングステンの代表例としてＷＯ３を挙げて説明する。ＷＯ３結晶は、波長４８０ｎｍまでの可視光を吸収して光触媒活性を奏するため、釉薬層に可視光応答性の光触媒特性を付与する。ＷＯ３結晶は、立方晶系、正方晶系、斜方晶系、単斜晶系および三斜晶系の結晶構造を持つことが知られているが、光触媒活性を有する限り、どの結晶構造のものでもよい。ＷＯ３結晶は、他の元素との固溶体の状態で存在していてもよい。ここで、前記固溶体としては、例えばＭｏｑＷ１−ｑＯ３、ＲｎｑＴａＷ１−ｑＯ３、ＲｎｑＮｂｑＷ１−ｑＯ３、ＲｑＺｒｑＷ１−ｑＯ３（式中、ＲｎはＬｉ、Ｎａ、Ｋ、から選ばれる１種以上とし、ＲはＭｇ、Ｃａ、Ｓｒ、Ｂａから選ばれる１種以上とし、ｑは化学量論的にとり得る数を意味する）などを挙げることができる。なお、固溶体は光触媒活性があれば、置換型固溶体でも侵入型固溶体のいずれでもよい。As the photocatalytic crystal containing the W component, there is tungsten oxide or a solid solution thereof. The tungsten oxide crystal becomes a divalent to hexavalent oxide depending on the raw material and the preparation method. WO 3 , WO, W 2 O 3 , W 4 O 11 , WO 2 , W 2 O 5 , W 3 O 8 and W 5 O 14 is present. The type of tungsten oxide deposited from the glaze glass of the present invention is not limited as long as it has photocatalytic activity, but it is preferable to deposit WO 3 having particularly strong photocatalytic activity. In the following description, WO 3 will be described as a representative example of tungsten oxide. Since the WO 3 crystal absorbs visible light up to a wavelength of 480 nm and exhibits photocatalytic activity, it imparts a photocatalytic property of visible light responsiveness to the glaze layer. WO 3 crystals are known to have cubic, tetragonal, orthorhombic, monoclinic and triclinic crystal structures, but as long as they have photocatalytic activity, It may be a thing. The WO 3 crystal may exist in a solid solution state with other elements. Here, as the solid solution, for example, Mo q W 1-q O 3 , Rn q TaW 1-q O 3, Rn q Nb q W 1-q O 3, R q Zr q W 1-q O 3 ( wherein Rn is at least one selected from Li, Na, K, R is at least one selected from Mg, Ca, Sr, and Ba, and q is a stoichiometric number). Can be mentioned. The solid solution may be either a substitutional solid solution or an interstitial solid solution as long as it has photocatalytic activity.
Ｚｎを含む光触媒結晶としては、例えばＺｎＯ結晶、Ｚｎ２ＧｅＯ４結晶、Ｚｎ２ＳｉＯ４結晶、及びこれらの固溶体を挙げることができ、本発明の釉薬用ガラスはこれらのうちどの結晶を析出しても良いが、中でもバンドギャップが約３〜４ｅＶであり、特に強い光触媒活性を期待できるＺｎＯを析出することが好ましい。なお、これらの結晶は、光触媒活性があれば他の元素との固溶体の状態で存在していてもよく、固溶体は置換型固溶体でも侵入型固溶体でもよい。Examples of the photocatalytic crystal containing Zn include a ZnO crystal, a Zn 2 GeO 4 crystal, a Zn 2 SiO 4 crystal, and a solid solution thereof. The glaze glass of the present invention precipitates any of these crystals. However, it is preferable to deposit ZnO that has a band gap of about 3 to 4 eV and can be expected to have particularly strong photocatalytic activity. These crystals may exist in the form of a solid solution with other elements as long as they have photocatalytic activity, and the solid solution may be a substitutional solid solution or an interstitial solid solution.
Ｎｂを含む結晶は、高い光触媒活性を有し、本発明の釉薬用ガラスを含む釉薬層に光触媒特性をもたらす有用な結晶である。Ｎｂを含む結晶としては、ＮｂＯ結晶、Ｎｂ２Ｏ３結晶、ＮｂＯ２結晶、Ｎｂ２Ｏ５結晶、Ｎｂ２Ｏ５結晶、ＬｉＮｂＯ３結晶、ＮａＮｂＯ３結晶、ＫＮｂＯ３結晶、ＣａＮｂ２Ｏ６結晶、ＳｒＮｂ２Ｏ６結晶、ＢａＮｂ２Ｏ６結晶、ＭｇＮｂ２Ｏ６結晶、Ｓｒ２Ｎｂ２Ｏ７結晶、及びＫ２ＳｒＮｂ２Ｏ７結晶等があるが、特に強い光触媒活性を有するＲｎＮｂＯ３結晶又はＲＮｂＯ３結晶（ＲｎはＬｉ、Ｎａ、及びＫからなる群より選択される１種以上、ＲはＭｇ、Ｃａ、Ｓｒ、Ｂａからなる群より選択される１種以上である）を析出することが好ましい。一つの典型的なニオブ酸塩であるニオブ酸カリウム（ＫＮｂＯ３）結晶の結晶構造はペロブスカイト構造であり、温度により菱面体晶、斜方晶、正方晶、立方晶となることが知られているが、光触媒活性を有する限り、どの結晶格子のものでもよい。The crystal containing Nb is a useful crystal that has high photocatalytic activity and brings photocatalytic properties to the glaze layer containing the glaze glass of the present invention. The crystals containing Nb, NbO crystal, Nb 2 O 3 crystal, NbO 2 crystals, Nb 2 O 5 crystal, Nb 2 O 5 crystal, LiNbO 3 crystal, NaNbO 3 crystal, KNbO 3 crystal, CaNb 2 O 6 crystal, There are SrNb 2 O 6 crystal, BaNb 2 O 6 crystal, MgNb 2 O 6 crystal, Sr 2 Nb 2 O 7 crystal, K 2 SrNb 2 O 7 crystal, etc., but RnNbO 3 crystal or RNbO having particularly strong photocatalytic activity It is preferable to deposit three crystals (Rn is at least one selected from the group consisting of Li, Na, and K, and R is at least one selected from the group consisting of Mg, Ca, Sr, Ba). . One typical niobate salt, potassium niobate (KNbO 3 ), has a perovskite structure, and is known to be rhombohedral, orthorhombic, tetragonal, and cubic depending on temperature. However, any crystal lattice may be used as long as it has photocatalytic activity.
ＲｎＮｂＯ３結晶又はＲＮｂＯ３結晶は、他の元素との固溶体の状態で存在していてもよい。ここで、前記固溶体としては、例えばＲｎ（ＴａｑＮｂ１−ｑ）Ｏ３、ＲｎαＲβ（ＴａｑＮｂ１−ｑ）γＯδ（式中、Ｒｎ及びＲは前記と同じ意味を有し、ｑは化学量論的にとり得る数を意味し、α＋２β＋５γ＝２δの関係式からなり、γは１より大きい整数を意味する）などを挙げることができる。なお、固溶体は置換型固溶体でも侵入型固溶体でもよい。The RnNbO 3 crystal or the RNbO 3 crystal may exist in a solid solution state with other elements. Here, as the solid solution, for example, Rn (Ta q Nb 1-q ) O 3, Rn α R β (Ta q Nb 1-q) γ O δ ( wherein, Rn and R have the same meanings as defined above Q is a stoichiometric number, and is a relational expression of α + 2β + 5γ = 2δ, where γ is an integer greater than 1. The solid solution may be a substitutional solid solution or an interstitial solid solution.
Ｔａ成分を含む光触媒結晶としては、酸化タンタルの結晶、タンタル酸塩の結晶及び／又はこれらの固溶体を挙げられる。その結晶は、ＴａＯ結晶、Ｔａ２Ｏ３結晶、ＴａＯ２結晶、Ｔａ２Ｏ５結晶、ＬｉＴａＯ３結晶、ＮａＴａＯ３結晶、ＫＴａＯ３結晶、ＣａＴａ２Ｏ６結晶、ＳｒＴａ２Ｏ６結晶、ＢａＴａ２Ｏ６結晶、ＭｇＴａ２Ｏ６結晶、Ｓｒ２Ｔａ２Ｏ７結晶、及びＫ２ＳｒＴａ２Ｏ７結晶等を含むがこれらに限定されない。本発明の釉薬用ガラスは、光触媒活性を持つ結晶である限り析出結晶の種類を問わないが、Ｔａを含む結晶として、特に強い光触媒活性を有するＲｎＴａＯ３結晶又はＲＴａＯ３結晶（ＲｎはＬｉ、Ｎａ、及びＫからなる群より選択される１種以上、ＲはＭｇ、Ｃａ、Ｓｒ、Ｂａからからなる群より選択される１種以上である）を析出することが好ましい。一つの典型的なタンタル酸塩であるＫＴａＯ３結晶の結晶構造はペロブスカイト構造であり、温度により菱面体晶、斜方晶、正方晶、立方晶となることが知られているが、光触媒活性を有する限り、どの結晶格子のものでもよい。Examples of the photocatalytic crystal containing a Ta component include tantalum oxide crystals, tantalate crystals, and / or solid solutions thereof. The crystals are TaO crystal, Ta 2 O 3 crystal, TaO 2 crystal, Ta 2 O 5 crystal, LiTaO 3 crystal, NaTaO 3 crystal, KTaO 3 crystal, CaTa 2 O 6 crystal, SrTa 2 O 6 crystal, BaTa 2 O. 6 crystal, MgTa 2 O 6 crystal, Sr 2 Ta 2 O 7 crystal, K 2 SrTa 2 O 7 crystal and the like, but not limited thereto. The glass for glazes of the present invention may be any kind of precipitated crystal as long as it is a crystal having photocatalytic activity, but as a crystal containing Ta, RnTaO 3 crystal or RTaO 3 crystal (Rn is Li, Na) having particularly strong photocatalytic activity. And at least one selected from the group consisting of K, and R is preferably one or more selected from the group consisting of Mg, Ca, Sr, and Ba). The crystal structure of one typical tantalate, KTaO 3 crystal, is a perovskite structure, and is known to be rhombohedral, orthorhombic, tetragonal, or cubic depending on the temperature. Any crystal lattice may be used as long as it has.
ＲｎＴａＯ３結晶又はＲＴａＯ３結晶は、他の元素との固溶体の状態で存在していてもよい。ここで、前記固溶体としては、例えばＲｎ（ＴａｑＮｂ１−ｑ）Ｏ３、ＲｎαＲβ（ＴａｑＮｂ１−ｑ）γＯδ（式中、Ｒｎ及びＲは前記と同じ意味を有し、ｑは化学量論的にとり得る数を意味し、α＋２β＋５γ＝２δの関係式からなり、γは１より大きい整数を意味する）などを挙げることができる。なお、固溶体は置換型固溶体でも侵入型固溶体でもよい。The RnTaO 3 crystal or the RTaO 3 crystal may exist in a state of a solid solution with other elements. Here, as the solid solution, for example, Rn (Ta q Nb 1-q ) O 3, Rn α R β (Ta q Nb 1-q) γ Oδ ( wherein, Rn and R are as defined above , Q means a stoichiometric number, is composed of a relational expression of α + 2β + 5γ = 2δ, and γ means an integer larger than 1. The solid solution may be a substitutional solid solution or an interstitial solid solution.
ナシコンタイプの結晶は、ＡｍＢ２（ＸＯ４）３（式中、ＡはＬｉ、Ｎａ、Ｋ、Ｃｕ、Ｍｇ、Ｃａ、Ｓｒ、Ｂａの中から選択される一種または一種以上、ＢはＺｎ、Ａｌ、Ｆｅ、Ｔｉ、Ｓｎ、Ｚｒ、Ｖ、Ｎｂ、Ｔａの中から選択される一種または一種以上、ＸはＳｉ、Ｇｅ、Ｐ、Ｓ、Ｍｏ、Ｗの中から選択される一種または一種以上、０≦ｍ≦３）で表され、高い光触媒特性を期待できる結晶である。このうち、特にアルカリ金属チタンリン酸複合塩及び／又はアルカリ土類金属チタンリン酸複合塩の結晶を析出することが好ましい。これらは、ＴｉＯ２結晶相を同時に含有させると、より高い光触媒効果が発見できる。その中で、特にＲｎＴｉ２（ＰＯ４）３、ＲＴｉ４（ＰＯ４）６の効果が顕著であるので、析出することがより好ましい。また、これらの固溶体を用いることにより、バンドギャップエネルギーを調整することができるので、光に対する応答性を向上させることが可能である。本願におけるチタンリン酸塩複合結晶の固溶体として、例えばＬｉ１＋ｘＴｉ２−ｘＡｘ（ＰＯ４）３（０＜ｘ≦０．５、Ａは、３価の金属イオン）、Ｌｉ１＋３ｘＴｉ２（Ｐ１−ｘＳｉｘＯ４）３、ＬｉＴｉ２−ｘＡｘ（ＰＯ４）３（Ａは、４価の金属イオン）等が挙げられる。なお、これらの結晶は、光触媒活性があれば他の元素との固溶体の状態で存在していてもよく、固溶体は置換型固溶体でも侵入型固溶体でもよい。NASICON type crystals are A m B 2 (XO 4 ) 3 (wherein A is one or more selected from Li, Na, K, Cu, Mg, Ca, Sr, Ba, B is One or more selected from Zn, Al, Fe, Ti, Sn, Zr, V, Nb, Ta, X is one or more selected from Si, Ge, P, S, Mo, W As described above, the crystal is expressed by 0 ≦ m ≦ 3) and can be expected to have high photocatalytic properties. Among these, it is particularly preferable to precipitate crystals of alkali metal titanium phosphate composite salt and / or alkaline earth metal titanium phosphate composite salt. When these contain a TiO 2 crystal phase at the same time, a higher photocatalytic effect can be found. Among these, since the effects of RnTi 2 (PO 4 ) 3 and RTi 4 (PO 4 ) 6 are particularly remarkable, precipitation is more preferable. Moreover, since the band gap energy can be adjusted by using these solid solutions, it is possible to improve the response to light. As a solid solution of the titanium phosphate composite crystal in the present application, for example, Li 1 + x Ti 2-x A x (PO 4 ) 3 (0 <x ≦ 0.5, A is a trivalent metal ion), Li 1 + 3x Ti 2 (P 1-x Si x O 4 ) 3 , LiTi 2-x A x (PO 4 ) 3 (A is a tetravalent metal ion), and the like. These crystals may exist in the form of a solid solution with other elements as long as they have photocatalytic activity, and the solid solution may be a substitutional solid solution or an interstitial solid solution.
本発明の釉薬用ガラスは、加熱させることで、上記結晶相の１種以上析出することが好ましい。また本発明の釉薬層は上記結晶相の１種以上を含有することが好ましい。特に、応答波長および触媒反応（酸化分解または親水）が異なる結晶が同時に存在することで幅広い範囲の波長に対する応答性を有し、複数の光触媒活性を合わせ持つ特性を有することが可能になる。例えば、ＷＯ３結晶、ＺｎＯ結晶と組み合わせてＴｉＯ２結晶を含有すると紫外線から可視光までの幅広い範囲の波長に対する応答性を持つ光触媒活性を有することが可能になる。The glass for glazes of the present invention preferably precipitates at least one of the above crystal phases by heating. Moreover, it is preferable that the glaze layer of this invention contains 1 or more types of the said crystal phase. In particular, the presence of crystals having different response wavelengths and catalytic reactions (oxidative decomposition or hydrophilicity) at the same time makes it possible to have a response to a wide range of wavelengths and have a plurality of photocatalytic activities. For example, when a TiO 2 crystal is contained in combination with a WO 3 crystal or a ZnO crystal, it becomes possible to have photocatalytic activity having responsiveness to a wide range of wavelengths from ultraviolet to visible light.
＜釉薬用結晶化ガラス＞
本発明の釉薬用ガラスは、事前に熱処理を施し、上記結晶を含有する結晶化ガラスにしてから、釉薬用の原料に用いることもできる。ガラスから結晶を析出させる場合、該ガラスをガラス転移温度以上に加熱することが必要となるため、釉薬の焼成時に光触媒結晶を析出させる場合は、釉薬を施した部材をガラス転移温度以上で焼成しなければならない。しかし、釉薬用ガラスから所望の光触媒結晶を予め析出させておけば、釉薬焼成時における結晶化プロセスが不要になるので、ガラス転移温度に影響されることなく、焼成温度を基材の耐熱温度にあわせて自由に選べるという利点を有する。以下、本明細書において、釉薬の焼成段階以前に結晶化させた釉薬用ガラスを釉薬用結晶化ガラスと称する。<Glass crystallized glass>
The glass for glaze of this invention can also be used for the raw material for glazes, after heat-processing beforehand and making it the crystallized glass containing the said crystal | crystallization. When crystal is precipitated from glass, it is necessary to heat the glass to a temperature higher than the glass transition temperature. Therefore, when the photocatalytic crystal is precipitated at the time of firing the glaze, the member subjected to the glaze is fired at the glass transition temperature or higher. There must be. However, if the desired photocatalytic crystals are pre-deposited from the glaze glass, the crystallization process at the time of glaze firing becomes unnecessary, so that the firing temperature is set to the heat resistant temperature of the substrate without being affected by the glass transition temperature. It also has the advantage of being free to choose. Hereinafter, in this specification, the glass for glaze crystallized before the baking step of glaze is called crystallized glass for glaze.
［結晶化工程］
次に、本発明の釉薬用ガラスから所望の光触媒結晶を析出するプロセスについて、釉薬用結晶化ガラスを作成する工程を例に挙げて説明する。[Crystalling process]
Next, the process of depositing a desired photocatalytic crystal from the glaze glass of the present invention will be described by taking as an example the step of producing a glaze crystallized glass.
（第１実施形態）
本発明の釉薬用ガラスから光触媒結晶を析出する第１実施形態は、作ってある釉薬用ガラス体を結晶化温度領域に加熱することである。結晶化の条件は、組成によって適宜設定することができるが、結晶化温度が低すぎると所望の結晶相が得られないため、少なくともガラス体のガラス転移温度（Ｔｇ）より高い温度が必要となる。具体的に、結晶化温度の下限は、ガラス体のガラス転移温度（Ｔｇ）以上であり、好ましくはＴｇ＋５０℃以上であり、より好ましくはＴｇ＋１００℃以上であり、最も好ましくはＴｇ＋１５０℃以上である。他方、結晶化温度が高すぎると、所望の光触媒結晶の析出が少なくなるとともに、ＴｉＯ２結晶の析出を意図する場合アナターゼ型より活性度の低いルチルへ相転移したり、目的以外の結晶相が析出するなどして光触媒活性が減少する憂いがある。従って、結晶化温度の上限は、好ましくはガラス体のＴｇ＋６００℃以下であり、より好ましくはＴｇ＋５００℃以下であり、最も好ましくはＴｇ＋４５０℃以下である。(First embodiment)
The first embodiment for precipitating photocatalytic crystals from the glaze glass of the present invention is to heat the glaze glass body that has been made to the crystallization temperature region. The crystallization conditions can be appropriately set depending on the composition. However, if the crystallization temperature is too low, a desired crystal phase cannot be obtained, so at least a temperature higher than the glass transition temperature (Tg) of the glass body is required. . Specifically, the lower limit of the crystallization temperature is not less than the glass transition temperature (Tg) of the glass body, preferably not less than Tg + 50 ° C., more preferably not less than Tg + 100 ° C., and most preferably not less than Tg + 150 ° C. On the other hand, if the crystallization temperature is too high, the precipitation of the desired photocatalytic crystal is reduced, and when the precipitation of the TiO 2 crystal is intended, the phase transition to rutile, which is less active than the anatase type, There is concern that the photocatalytic activity will decrease due to precipitation. Therefore, the upper limit of the crystallization temperature is preferably Tg + 600 ° C. or less of the glass body, more preferably Tg + 500 ° C. or less, and most preferably Tg + 450 ° C. or less.
（第２実施形態）
本発明の釉薬用ガラスから光触媒結晶を析出する第２実施形態は、原料組成混合物を１２５０℃以上の温度に保持して少なくとも一部に液相を生じさせ、その後冷却して固化させることを特徴とする。より具体的には、所定の出発原料を均一に混合して白金又は耐火物などからなる容器に入れて、電気炉で１２５０℃以上の所定温度で加熱し保持して、溶融液を作製する。その後、溶融液を固化させて、目的の結晶を得る。ここで、溶融液が冷却する過程で結晶核の生成及び成長が起きる。この手法は、例えば所望の結晶相をリッチに析出し、且つガラス溶融液の状態が比較的不安定な場合などにおいて有効である。(Second Embodiment)
The second embodiment for precipitating the photocatalytic crystal from the glaze glass of the present invention is characterized in that the raw material composition mixture is maintained at a temperature of 1250 ° C. or higher to form a liquid phase at least partially, and then cooled and solidified. And More specifically, a predetermined starting material is uniformly mixed, put into a container made of platinum or refractory, and heated and held at a predetermined temperature of 1250 ° C. or higher in an electric furnace to prepare a melt. Thereafter, the melt is solidified to obtain a target crystal. Here, generation and growth of crystal nuclei occur in the process of cooling the melt. This technique is effective, for example, when a desired crystal phase is richly precipitated and the state of the glass melt is relatively unstable.
ここで、液相は、少なくとも１種以上の原料組成から生成されてよく、２以上の種類の化合物が加わることによる液相生成温度の低下も考慮することができる。従って、保持する温度は、混合する組成物の種類及び量により適宜変更することが好ましいが、一般に１２５０℃以上が好ましく、１３００℃以上がより好ましく、１３５０℃以上が最も好ましい。 Here, a liquid phase may be produced | generated from at least 1 or more types of raw material composition, and the fall of the liquid phase production temperature by adding 2 or more types of compounds can also be considered. Accordingly, the temperature to be maintained is preferably appropriately changed depending on the type and amount of the composition to be mixed, but is generally preferably 1250 ° C or higher, more preferably 1300 ° C or higher, and most preferably 1350 ° C or higher.
より具体的には、所定の出発原料を均一に混合して白金又は耐火物からなる容器に入れて、電気炉で１２５０℃以上の所定温度で加熱し保持して、溶液を作製する。その後、溶液の冷却速度を制御しつつ、固化させて、目的の結晶化ガラスを得る。ここで、溶液が冷却する過程で結晶核の生成及び成長が起きる。冷却する際の速度及び温度が結晶相の形成や結晶サイズに大きな影響を及ぼすので、これらを精密に制御することが重要である。 More specifically, a predetermined starting material is uniformly mixed, put into a container made of platinum or refractory, and heated and held at a predetermined temperature of 1250 ° C. or higher in an electric furnace to prepare a solution. Thereafter, the solution is solidified while controlling the cooling rate of the solution to obtain the target crystallized glass. Here, generation and growth of crystal nuclei occur in the process of cooling the solution. Since the cooling speed and temperature greatly affect the formation of crystal phases and the crystal size, it is important to control them precisely.
＜粉粒体＞
本発明の釉薬用ガラス及び／または釉薬用結晶化ガラスは、釉薬用組成物として用いるものであり、粉粒体であることが好ましい。この粉粒体の粒径や形状は、基材、形成したい釉薬層の厚みおよび表面特徴、およびその用途に応じて適宜設定できる。特に限定する必要はないが、好ましい平均粒径は、例えば０．０５μｍ〜５０００μｍの範囲内である。<Powder>
The glass for glazes and / or crystallized glass for glazes of the present invention is used as a composition for glazes, and is preferably a granular material. The particle size and shape of the granular material can be appropriately set according to the base material, the thickness and surface characteristics of the glaze layer to be formed, and the use thereof. Although not particularly limited, a preferable average particle diameter is, for example, in the range of 0.05 μm to 5000 μm.
例えば、陶磁器やタイルなどの生活用品に適用する場合、釉薬層中に均一に分散させ、基材との密着力を高めつつ、なめらかな表面に仕上げるためには、平均粒径は出来るだけ小さい方が好ましい。しかし細かい粒子は取扱いおよび釉薬中に均一に分散させることが難しいので、その下限は０．０５μｍ、好ましくは０．１μｍ、より好ましくは１μｍ、最も好ましくは１０μｍであることが好ましく、その上限は好ましくは８０μｍ、より好ましくは５０μｍ、最も好ましくは３０μｍであることが好ましい。また粉粒体の形状は出来るだけ球形に近い方が好ましい。一方、大型の琺瑯製品などに適用する場合はもっと粗いサイズでも良く、例えば、０．１〜２０００μｍの平均粒径とすることができる。さらに、用途によっては、ｍｍ単位の大きい粒径のガラス粉粒体を用いることも可能である。大きい粒から通孔を有する釉薬層を作ることにより、例えば濾過材（フィルタ）や、噴水などに用いる建材などへの応用も可能である。 For example, when applied to household goods such as ceramics and tiles, the average particle size should be as small as possible in order to achieve a smooth surface while being evenly dispersed in the glaze layer and improving adhesion to the substrate. Is preferred. However, since fine particles are difficult to handle and disperse uniformly in the glaze, the lower limit is preferably 0.05 μm, preferably 0.1 μm, more preferably 1 μm, most preferably 10 μm, and the upper limit is preferably Is preferably 80 μm, more preferably 50 μm, and most preferably 30 μm. Moreover, it is preferable that the shape of the granular material is as close to a spherical shape as possible. On the other hand, when it is applied to a large cocoon product or the like, a coarser size may be used, for example, an average particle diameter of 0.1 to 2000 μm. Furthermore, depending on the application, it is also possible to use glass particles having a large particle size in mm units. By making a glaze layer having through-holes from large grains, for example, it can be applied to filter materials, building materials used for fountains, and the like.
釉薬用ガラス及び／または釉薬用結晶化ガラス粉粒体の粒度分布が広く大きな粒子が存在すると、均一性または緻密性が得られず、材料内の構造に差が出てしまう可能性がある。そのため、粉粒体中に含まれる、平均粒径より極端に大きな粒子を少なくすることが好ましい。そこで、上記各平均粒径を有する粉粒体において、最大粒径は平均粒径の１０倍以下が好ましく、より好ましくは５倍以下、最も好ましくは３倍以下である。なお、平均粒径が大きいほど、最大粒径との差が小さいことが好ましい。 If the glass for glaze and / or the crystallized glass powder for glaze has a wide particle size distribution and there are large particles, uniformity or denseness cannot be obtained, and there is a possibility that the structure in the material will be different. For this reason, it is preferable to reduce the number of particles extremely larger than the average particle size contained in the granular material. Therefore, in the above-mentioned granular material having the average particle diameter, the maximum particle diameter is preferably 10 times or less of the average particle diameter, more preferably 5 times or less, and most preferably 3 times or less. In addition, it is preferable that the difference from the maximum particle size is smaller as the average particle size is larger.
なお、粉粒体を製造する際の釉薬用ガラス及び／または釉薬用結晶化ガラスの粉砕方法は、特に限定されないが、例えばボールミル、ジェットミル等を用いて行うことができる。また、粉砕ボールとしては粉粒体の組成等により、適宜設定することができるが、特にジルコニアボールが好ましい。ガラス体又は結晶化ガラス体、バインダー、分散材、その他添加剤を同時に投入し、粉砕と同時に混合しても構わない。 In addition, the grinding | pulverization method of the glass for glazes and / or the crystallized glass for glazes at the time of manufacturing a granular material is not specifically limited, For example, it can carry out using a ball mill, a jet mill, etc. The pulverized ball can be appropriately set depending on the composition of the powder and the like, and zirconia balls are particularly preferable. A glass body or a crystallized glass body, a binder, a dispersing material, and other additives may be added simultaneously and mixed simultaneously with pulverization.
なお、粉粒体の平均粒径は、例えばレーザー回折散乱法によって測定した時のＤ５０（累積５０％径）の値を使用できる。具体的には日機装株式会社の粒度分布測定装置ＭＩＣＲＯＴＲＡＣ（ＭＴ３３００ＥＸＩＩ）よって測定した値を用いることができる。なお、粉粒体の最小径が２０００μｍを超える場合、ＪＩＳ Ａ １２０に規定されている篩分析法で平均粒径を求めることができる。 In addition, the value of D50 (cumulative 50% diameter) when measured by the laser diffraction scattering method can be used for the average particle diameter of the granular material, for example. Specifically, a value measured by a particle size distribution measuring apparatus MICROTRAC (MT3300EXII) manufactured by Nikkiso Co., Ltd. can be used. In addition, when the minimum diameter of a granular material exceeds 2000 micrometers, an average particle diameter can be calculated | required with the sieve analysis method prescribed | regulated to JISA120.
本発明の釉薬用ガラス及び／または釉薬用結晶化ガラスからなる粉粒体は、光触媒特性を有する結晶を含有するか、あるいは、加熱されることによって粉粒体内部に前記結晶を生成させ得るものであるため、釉薬に混ぜて、若しくは当該ガラスを釉薬にして焼成するだけで、優れた光触媒活性を有する光触媒機能性素材を得ることを可能にする有用なものである。また、本発明の粉粒体は、それ自体の粒径や大きさに係らず、微細な光触媒結晶を釉薬層の中および表面から析出するので、凝集し易く取り扱いが難しいナノサイズの光触媒結晶材料を必ずしも用いる必要がなく、用途および工程に応じて粒径を自由に選べるというメリットを有する。なお、釉薬用ガラスおよび釉薬用結晶化ガラス粉粒体は、それぞれ単体で、または両方を一緒に用いても良い。 The granule comprising the glaze glass and / or glaze crystallized glass of the present invention contains a crystal having photocatalytic properties, or can be heated to produce the crystal inside the granule. Therefore, it is useful that it is possible to obtain a photocatalytic functional material having excellent photocatalytic activity simply by mixing with a glaze or baking the glass as a glaze. In addition, since the granular material of the present invention precipitates fine photocatalytic crystals from the glaze layer and from the surface regardless of the particle size or size of the powder itself, it is easy to agglomerate and is difficult to handle nano-sized photocatalytic crystal material Is not necessarily used, and has the advantage that the particle size can be freely selected according to the application and process. Note that the glaze glass and the glaze crystallized glass powder may be used alone or in combination.
＜釉薬＞
以上のようにして得られる本発明の釉薬用ガラス及び／または釉薬用結晶化ガラスからなる粉粒体は、該粉粒体のみを基材に配置、焼成して釉薬層を形成することもできるが、釉薬に通常用いる溶媒等と混合することによってスラリー状混合物（釉薬）を調製することにより、基材上への塗布が容易になる。本発明の釉薬は、釉薬用ガラス及び／または釉薬用結晶化ガラスの分粒体のみを、溶媒またはバインダーと混合したものでも良く、若しくは一般的に利用される釉薬に本発明の釉薬用ガラス粉粒体及び／または釉薬用結晶化ガラス粉粒体を加えたものでも良い。一般的に利用される釉薬に含有される成分としては、植物の灰、石灰、珪石、長石、粘土、フリット、及び有機バインダー等があり、本発明の釉薬においても、それらを適宜利用することができる。これらは釉薬としての機能と光触媒結晶を有する結晶化ガラスのバインダーとしての役割を果たすものである。また、これらの原料を用いることで釉薬の粘性、焼成温度等を微調整することができる。また、結晶化させる前の釉薬用ガラスは、ガラスが軟化して釉薬層を形成しつつ光触媒結晶を析出することができるので、バインダーとなる原料を用いることなく、それのみを直接基材に配置して焼結させることで釉薬層を形成することも可能である。<Glue>
The granular material comprising the glaze glass and / or glaze crystallized glass of the present invention obtained as described above can form a glaze layer by placing and firing only the granular material on a substrate. However, by preparing a slurry-like mixture (glaze) by mixing with a solvent or the like normally used for glazes, application on the substrate is facilitated. The glaze of the present invention may be a mixture of a glaze glass and / or a crystallized glass for glaze mixed with a solvent or a binder, or a glaze glass powder of the present invention for a commonly used glaze. What added the crystallized glass granular material for a granule and / or glaze may be used. Ingredients contained in glazes that are generally used include plant ash, lime, silica stone, feldspar, clay, frit, organic binders, and the like. In the glaze of the present invention, they can be used as appropriate. it can. These function as a glaze and serve as a binder for crystallized glass having photocatalytic crystals. Moreover, the viscosity of the glaze, the firing temperature, etc. can be finely adjusted by using these raw materials. In addition, since the glass for glaze before crystallization can precipitate the photocatalytic crystal while forming a glaze layer by softening the glass, only it is placed directly on the base material without using a raw material as a binder It is also possible to form a glaze layer by sintering.
無機バインダーとしては、特に限定されるものではないが、紫外線や可視光線を透過する性質のものが好ましく、例えば、珪酸塩系バインダー、リン酸塩系バインダー、無機コロイド系バインダー、アルミナ、シリカ、ジルコニア等の微粒子や、植物の灰、石灰、珪石、長石、粘土、フリット等を挙げることができる。 Although it does not specifically limit as an inorganic binder, The thing of the property which permeate | transmits an ultraviolet-ray or visible light is preferable, for example, a silicate type binder, a phosphate type binder, an inorganic colloid type binder, an alumina, a silica, a zirconia And fine particles such as plant ash, lime, quartzite, feldspar, clay, frit and the like.
有機バインダーとしては、例えば、プレス成形やラバープレス、押出成形、射出成形用の成形助剤として汎用されている市販のバインダーが使用できる。具体的には、例えば、アクリル樹脂、エチルセルロース、ポリビニルブチラール、メタクリル樹脂、ウレタン樹脂、ブチルメタアクリレート、ビニル系の共重合物等が挙げられる。有機バインダーを用いる場合、施釉工程の後、脱脂工程を経てこれらの成分を除去しても良い。 As the organic binder, for example, a commercially available binder widely used as a molding aid for press molding, rubber press, extrusion molding, or injection molding can be used. Specific examples include acrylic resin, ethyl cellulose, polyvinyl butyral, methacrylic resin, urethane resin, butyl methacrylate, vinyl copolymer and the like. When using an organic binder, you may remove these components through a degreasing process after a glazing process.
溶媒としては、例えば、水、メタノール、エタノール、プロパノール、ブタノール、イソプロピルアルコール（ＩＰＡ）、酢酸、ジメチルホルムアミド、アセトニトリル、アセトン、ポリビニルアルコール（ＰＶＡ）等の公知の溶媒が使用できるが、環境負荷を軽減できる点でアルコール又は水が好ましい。 As the solvent, for example, known solvents such as water, methanol, ethanol, propanol, butanol, isopropyl alcohol (IPA), acetic acid, dimethylformamide, acetonitrile, acetone, polyvinyl alcohol (PVA) can be used, but the environmental load is reduced. Alcohol or water is preferable because it can be used.
また、釉薬スラリーの均質化を図るために、適量の分散剤を併用してもよい。分散剤としては、特に限定されないが、例えば、トルエン、キシレン、ベンゼン、ヘキサン、シクロヘキサン等の炭化水素類、セロソルブ、カルビトール、テトラヒドロフラン（ＴＨＦ）、ジオキソラン等のエーテル類、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン類、酢酸メチル、酢酸エチル、酢酸−ｎ−ブチル、酢酸アミル等のエステル類等が挙げられ、これらは単独で又は２種以上を組み合わせて用いることができる。 In order to homogenize the glaze slurry, an appropriate amount of dispersant may be used in combination. The dispersant is not particularly limited, and examples thereof include hydrocarbons such as toluene, xylene, benzene, hexane, and cyclohexane, ethers such as cellosolve, carbitol, tetrahydrofuran (THF), dioxolane, acetone, methyl ethyl ketone, and methyl isobutyl ketone. And ketones such as cyclohexanone, and esters such as methyl acetate, ethyl acetate, n-butyl acetate and amyl acetate can be used, and these can be used alone or in combination of two or more.
本発明のスラリー状混合物（釉薬）には、その用途に応じて、上記成分以外に例えば硬化速度、比重を調節するための添加剤成分等を配合することができる。 In addition to the above components, for example, an additive component for adjusting the curing rate and specific gravity can be blended with the slurry-like mixture (glaze) of the present invention.
本発明の釉薬における釉薬用ガラス及び／または釉薬用結晶化ガラス粉粒体の含有量は、その用途に応じて適宜設定できる。従って、スラリー状混合物におけるガラス粉粒体の含有量は、特に限定されるものではないが、一例を挙げれば、十分な光触媒特性を発揮させる観点から、好ましくは５０質量％、より好ましくは５５質量％、最も好ましくは６０質量％を下限とし、釉薬スラリーとしての流動性と機能性を確保する観点から、好ましくは９９質量％、より好ましくは８０質量％、最も好ましくは６５質量％を上限とすることができる。 The content of the glaze glass and / or the crystallized glass powder particles for glaze in the glaze of the present invention can be appropriately set according to the use. Accordingly, the content of the glass particles in the slurry-like mixture is not particularly limited. However, for example, from the viewpoint of exerting sufficient photocatalytic properties, it is preferably 50% by mass, more preferably 55% by mass. %, Most preferably 60% by mass, and from the viewpoint of ensuring fluidity and functionality as a glaze slurry, preferably 99% by mass, more preferably 80% by mass, and most preferably 65% by mass. be able to.
さらに、本発明の釉薬は、光触媒活性をより高める目的で、結晶状態のＴｉＯ２およびＷＯ３を混合させることができる。本発明の釉薬は、結晶状態のこれら成分を混合しなくても、ガラスからＴｉＯ２、ＷＯ３などの光触媒結晶を生成することができるが、これら原料を添加することで、より多くの光触媒結晶相を有する釉薬層をより確実に製造できる。また、上記成分を適宜釉薬に導入した結果、釉薬中に含有されるＴｉＯ２および／またはＷＯ３の含有量は１０ｗｔ％、好ましくは２５ｗｔ％、より好ましくは３５ｗｔ％、最も好ましくは４０％を下限とし、９５ｗｔ％、好ましくは９０ｗｔ％、より好ましくは８５ｗｔ％、最も好ましくは８０ｗｔ％の範囲内であることが好ましい。Furthermore, the glaze of the present invention can be mixed with crystalline TiO 2 and WO 3 for the purpose of further enhancing the photocatalytic activity. The glaze of the present invention can produce photocatalytic crystals such as TiO 2 and WO 3 from glass without mixing these components in the crystalline state, but by adding these raw materials, more photocatalytic crystals A glaze layer having a phase can be more reliably produced. Further, as a result of appropriately introducing the above components into the glaze, the content of TiO 2 and / or WO 3 contained in the glaze is 10 wt%, preferably 25 wt%, more preferably 35 wt%, and most preferably 40%. And preferably within the range of 95 wt%, preferably 90 wt%, more preferably 85 wt%, and most preferably 80 wt%.
なお、釉薬の製造方法において、粉粒体の凝集体を除去する工程を有しても良い。ガラス粉粒体は、その粒径が小さくなるに従い、表面エネルギーが大きくなって凝集しやすくなる傾向がある。ガラス粉粒体が凝集していると、釉薬中での均一な分散ができず、所望の光触媒活性が得られないことがある。凝集体の除去は、例えば、釉薬を濾過することにより実施できる。釉薬の濾過は、例えば所定の目開きのメッシュなどの濾過材を用いて行うことができる。 In addition, in the manufacturing method of a glaze, you may have the process of removing the aggregate of a granular material. As the particle size of the glass particles decreases, the surface energy tends to increase and the particles tend to aggregate. If the glass particles are agglomerated, uniform dispersion in the glaze cannot be achieved, and the desired photocatalytic activity may not be obtained. The removal of the aggregate can be performed by, for example, filtering the glaze. The glaze can be filtered using a filter medium such as a mesh having a predetermined mesh.
本発明の釉薬は、釉薬用ガラスを含有する場合、即ち釉薬の焼成と結晶化を同時に行う場合には、その焼成温度が６００〜１２００℃の範囲であることが好ましい。焼成工程において、ガラスの結晶化温度領域で所定の時間保持することにより、光触媒活性を有しナノからミクロン単位までの所望のサイズを有するＴｉＯ２結晶、ＷＯ３結晶、ＺｎＯ結晶等の結晶がガラス体の内部に生成される。When the glaze of this invention contains the glass for glazes, ie, when baking and crystallization of a glaze are performed simultaneously, it is preferable that the baking temperature is the range of 600-1200 degreeC. In the firing step, a glass such as a TiO 2 crystal, a WO 3 crystal, or a ZnO crystal having photocatalytic activity and a desired size from nano to micron units is maintained by holding the glass in a crystallization temperature region for a predetermined time. Generated inside the body.
釉薬の結晶化温度領域は、例えばガラス転移温度を超える温度領域であり、ガラス転移温度より１０℃以上高い温度領域とすることが好ましく、２０℃以上高くすることがより好ましく、３０℃以上高くすることが最も好ましい。ガラス転移温度はガラス組成ごとに異なるため、ガラス転移温度に応じて結晶化温度を設定することが好ましく、特に限定しないが、目的とする結晶を析出する目安として、釉薬の焼成温度の下限は６００℃であり、より好ましくは６１０℃であり、最も好ましくは６２０℃である。他方、釉薬の焼成温度が高くなり過ぎると、目的以外の未知相が析出する傾向が強くなり、光触媒特性が消失し易くなるので、焼成温度領域の上限は１２００℃が好ましく、１１５０℃がより好ましく、１１００℃が最も好ましい。この工程では、昇温速度及び温度が結晶のサイズに大きな影響を及ぼすので、組成や熱処理温度に応じて適切に制御することが重要である。 The crystallization temperature region of the glaze is, for example, a temperature region exceeding the glass transition temperature, preferably a temperature region that is 10 ° C. or more higher than the glass transition temperature, more preferably 20 ° C. or more, and more preferably 30 ° C. or more. Most preferred. Since the glass transition temperature varies depending on the glass composition, it is preferable to set the crystallization temperature according to the glass transition temperature. Although not particularly limited, the lower limit of the firing temperature of the glaze is 600 as a guide for precipitating the target crystal. ° C, more preferably 610 ° C, and most preferably 620 ° C. On the other hand, if the calcination temperature of the glaze becomes too high, the tendency to deposit an unknown phase other than the target becomes strong, and the photocatalytic properties tend to disappear. Therefore, the upper limit of the calcination temperature region is preferably 1200 ° C, more preferably 1150 ° C. Most preferred is 1100 ° C. In this step, the rate of temperature increase and the temperature greatly affect the size of the crystal, so it is important to appropriately control according to the composition and the heat treatment temperature.
また、結晶化のための焼成時間は、熱処理温度に応じて設定することが好ましい。昇温速度を遅くすれば、熱処理温度まで加熱するだけでいい場合もあるが、目安としては高い温度の場合は短く、低い温度の場合は長く設定することが好ましい。具体的には、結晶をある程度まで成長させ、かつ十分な量の結晶を析出させ得る点で、好ましくは３分、より好ましくは２０分、最も好ましくは３０分を下限とする。一方、熱処理時間が２４時間を越えると、目的の結晶が大きく成長しすぎたり、他の結晶相が生成する等で、十分な光触媒特性が得られなくなるおそれがある。従って、熱処理時間の上限は、好ましくは２４時間、より好ましくは１９時間、最も好ましくは１８時間とする。結晶化過程は、１段階の熱処理過程を経ても良く、２段階以上の熱処理過程を経ても良い。ここで言う熱処理時間とは、設定した結晶化温度に到達後、温度が一定以上に保持されている時間の長さを指す。 The firing time for crystallization is preferably set according to the heat treatment temperature. If the rate of temperature increase is slow, it may be sufficient to heat only to the heat treatment temperature. However, as a guideline, it is preferable to set a short temperature at a high temperature and a long time at a low temperature. Specifically, the lower limit is preferably 3 minutes, more preferably 20 minutes, and most preferably 30 minutes, in that crystals can be grown to a certain extent and a sufficient amount of crystals can be precipitated. On the other hand, if the heat treatment time exceeds 24 hours, sufficient photocatalytic properties may not be obtained due to excessive growth of the target crystals or the formation of other crystal phases. Therefore, the upper limit of the heat treatment time is preferably 24 hours, more preferably 19 hours, and most preferably 18 hours. The crystallization process may go through a one-stage heat treatment process, or may go through two or more heat treatment processes. The heat treatment time here refers to the length of time during which the temperature is maintained above a certain level after reaching the set crystallization temperature.
一方、釉薬用結晶化ガラスを含有する釉薬は、すでに所望の光触媒結晶を含んでいるので、釉薬層を形成できる範囲内で適宜焼成温度および時間を選ぶことができる。 On the other hand, since the glaze containing the crystallized glass for glaze already contains the desired photocatalytic crystal, the firing temperature and time can be appropriately selected within the range in which the glaze layer can be formed.
＜光触媒部材＞
本発明の釉薬用ガラス及び／または釉薬用結晶化ガラスを含有する釉薬によれば、基材上に機械的強度および光触媒特性が優れた釉薬層を形成することができ、光触媒部材を製造できる。本発明における光触媒部材は、基材と、光触媒結晶及び／又はその固溶体を含有する釉薬層と、を備える光触媒機能性部材を意味する。また、本発明において釉薬層とは、釉薬を施釉し焼成することで形成したコーティング層を意味し、該釉薬層は、その内部および表面に釉薬ガラスを加熱することによって析出させた光触媒結晶、即ち、ＴｉＯ２結晶、ＷＯ３結晶、ＺｎＯ結晶、ＲｎＮｂＯ３、ＲｎＴａＯ３、ＲＮｂＯ３、ＲＴａＯ３、ナシコンタイプの結晶相及びこれら結晶の固溶体からなる群から選ばれるいずれか１つ以上の結晶が含まれており、光触媒機能を有する。また、釉薬層の内部および表面に前記結晶が析出しているので、仮に表面が多少削られても、光触媒活性が維持される。<Photocatalyst member>
According to the glaze containing the glaze glass and / or glaze crystallized glass of the present invention, a glaze layer having excellent mechanical strength and photocatalytic properties can be formed on the substrate, and a photocatalytic member can be produced. The photocatalytic member in the present invention means a photocatalytic functional member comprising a base material and a glaze layer containing a photocatalytic crystal and / or a solid solution thereof. Further, in the present invention, the glaze layer means a coating layer formed by glazing and baking the glaze, and the glaze layer is a photocatalytic crystal deposited by heating glaze glass inside and on the surface, that is, , TiO 2 crystals, WO 3 crystal, ZnO crystal, RnNbO 3, RnTaO 3, RNbO 3, RTaO 3, include any one or more crystals selected from the group consisting of NASICON type crystalline phase and a solid solution of these crystal And has a photocatalytic function. In addition, since the crystals are precipitated inside and on the surface of the glaze layer, the photocatalytic activity is maintained even if the surface is slightly cut.
本発明の光触媒部材に形成される釉薬層は、上記結晶相の１種以上を有し、特に、応答波長および触媒反応（酸化分解または親水）が異なる結晶が同時に存在することで幅広い範囲の波長に対する応答性を有し、複数の光触媒活性を合わせ持つ特性を有することが可能になる。例えば、ＷＯ３結晶、ＺｎＯ結晶と組み合わせてＴｉＯ２結晶を含有すると紫外線から可視光までの幅広い範囲の波長に対する応答性を持つ光触媒活性を有することが可能になる。ここで、光触媒結晶は、本発明の光触媒部材の基材上に釉薬を配置し焼成する過程、及び／又は基材上に形成したガラス質の釉薬層を結晶化する過程で析出し、釉薬層に含まれる。The glaze layer formed on the photocatalyst member of the present invention has one or more of the above crystal phases, and in particular, crystals having different response wavelengths and different catalytic reactions (oxidative decomposition or hydrophilicity) exist at the same time in a wide range of wavelengths. It is possible to have a characteristic of having a plurality of photocatalytic activities. For example, when a TiO 2 crystal is contained in combination with a WO 3 crystal or a ZnO crystal, it becomes possible to have photocatalytic activity having responsiveness to a wide range of wavelengths from ultraviolet to visible light. Here, the photocatalytic crystal is deposited in the process of arranging and baking the glaze on the base material of the photocatalytic member of the present invention and / or in the process of crystallizing the vitreous glaze layer formed on the base material. include.
なお、本発明の釉薬層の全物質量に対する酸化物換算組成は、本発明の釉薬用ガラスからなる粉粒体の組成と、この粉粒体に添加される成分の組成、およびそれらの含有比から求められるが、上述の釉薬用ガラス体を構成する各成分の組成範囲と同じ範囲内にすることが好ましい。これにより、釉薬層から所望の光触媒結晶が析出し易くなると同時に基材との密着度および釉薬層の耐久性が向上する。ここで、釉薬が釉薬用ガラス以外の成分（植物の灰、石灰、珪石、長石、粘度、有機バインダー等）を含む場合は、施釉時に用いた釉薬用ガラスの組成と必ずしも一致するものではないが、該釉薬用ガラス及び／または釉薬用結晶化ガラスからなる粉末の組成と、この粉末に添加される成分の組成、およびそれらの含有比から求められる組成においても、上記した釉薬用ガラス体を構成する各成分と同じ範囲の組成を有することが好ましい。また、原料として釉薬用ガラス及び／または釉薬用結晶化ガラス以外の添加物を含有しない場合、及び釉薬用ガラスのみを溶媒に分散させた場合、該釉薬を用いて形成した釉薬層は、釉薬用ガラスの組成と等しくなる。 In addition, the oxide conversion composition with respect to the total amount of substances of the glaze layer of the present invention is the composition of the powder and the composition of components added to the powder and the content ratio thereof. Although it is calculated | required from these, it is preferable to set it as the same range as the composition range of each component which comprises the above-mentioned glaze glass body. Thereby, the desired photocatalytic crystal is easily precipitated from the glaze layer, and at the same time, the degree of adhesion with the base material and the durability of the glaze layer are improved. Here, when the glaze contains components other than glaze glass (plant ash, lime, quartzite, feldspar, viscosity, organic binder, etc.), it does not necessarily match the composition of the glaze glass used at the time of glazing. The above-mentioned glass body for glaze is also constituted by the composition of the powder comprising the glaze glass and / or the crystallized glass for glaze, the composition of the components added to the powder, and the composition obtained from the content ratio thereof. It is preferable to have the same composition as each component. In addition, when no additives other than glaze glass and / or crystallized glass for glaze are contained as raw materials, and when only glaze glass is dispersed in a solvent, the glaze layer formed using the glaze is used for glaze It is equal to the glass composition.
光触媒部材を構成する釉薬層の基材は特に限定されないが、金属製、陶磁器製、ガラス製、セラミックス製等のものを適宜利用することができる。また、その形状も板状、ビーズ状、ファイバー状のものなど、様々なものに適用できる。また、前記釉薬層は、釉薬用ガラス及び／または釉薬用ガラスセラミックス粉粒体の形状や粒度を変えることで、凹凸形状、質感等の表面特性を変化させられるので、様々な用途に適した光触媒部材に適用できる。 Although the base material of the glaze layer which comprises a photocatalyst member is not specifically limited, The thing made from metal, ceramics, glass, ceramics, etc. can be utilized suitably. Moreover, the shape can be applied to various shapes such as a plate shape, a bead shape, and a fiber shape. In addition, the glaze layer can change the surface characteristics such as uneven shape and texture by changing the shape and particle size of the glaze glass and / or glaze glass ceramic powder, so that the photocatalyst suitable for various applications Applicable to members.
本発明の光触媒部材は、その釉薬層そのものが基材に対して優れた密着力を有するものであるが、釉薬層と基材表面との間に下塗り釉薬層などを有していても良い。 In the photocatalyst member of the present invention, the glaze layer itself has excellent adhesion to the substrate, but an undercoat glaze layer may be provided between the glaze layer and the substrate surface.
本発明の光触媒部材におけるＪＩＳ Ｒ １７０３−２：２００７に基づくメチレンブルーの分解活性指数は３．０ｎｍｏｌ／Ｌ／ｍｉｎ以上であることを特徴とする。本発明の光触媒部材の釉薬層は、紫外領域から可視領域までの波長の光によって触媒活性が発現される。ここで、本発明でいう紫外領域の波長の光は、波長が可視光線より短く軟Ｘ線よりも長い不可視光線の電磁波のことであり、その波長はおよそ１０〜４００ｎｍの範囲にある。また、本発明でいう可視領域の波長の光は、電磁波のうち、ヒトの目で見える波長の電磁波のことであり、その波長はおよそ４００ｎｍ〜７００ｎｍの範囲にある。ここで、本発明の光触媒部材の触媒活性は、日本工業規格ＪＩＳ Ｒ １７０３−２：２００７に基づいて求めた分解活性指数は、好ましくは３．０ｎｍｏｌ／Ｌ／ｍｉｎ、より好ましくは４．０ｎｍｏｌ／Ｌ／ｍｉｎ、最も好ましくは５．０ｎｍｏｌ／Ｌ／ｍｉｎを下限とする。 The methylene blue decomposition activity index based on JIS R 1703-2: 2007 in the photocatalyst member of the present invention is 3.0 nmol / L / min or more. The glaze layer of the photocatalyst member of the present invention exhibits catalytic activity by light having a wavelength from the ultraviolet region to the visible region. Here, the light having a wavelength in the ultraviolet region referred to in the present invention is an invisible electromagnetic wave having a wavelength shorter than that of visible light and longer than that of soft X-ray, and the wavelength is in the range of approximately 10 to 400 nm. In addition, the light having a wavelength in the visible region referred to in the present invention is an electromagnetic wave having a wavelength that can be seen by human eyes among electromagnetic waves, and the wavelength is in a range of about 400 nm to 700 nm. Here, the catalytic activity of the photocatalyst member of the present invention is preferably 3.0 nmol / L / min, more preferably 4.0 nmol / min as a decomposition activity index determined based on Japanese Industrial Standard JIS R 1703-2: 2007. L / min, most preferably 5.0 nmol / L / min is the lower limit.
また、本発明の光触媒部材は、紫外領域から可視領域までの波長の光を照射した表面と水滴との接触角が３０°以下であることを特徴とする。本発明の光触媒部材の釉薬層は、光を照射した表面と水滴との接触角が３０°以下になるものである。これにより、光触媒部材の釉薬層表面が親水性を呈し、セルフクリーニング作用を有するため、水で容易に洗浄することができ、汚れに強い特徴を有する。また、汚れによる光触媒特性の低下も抑制することができる。光を照射した光触媒部材表面と水滴との接触角は、３０°以下が好ましく、２５°以下がより好ましく、２０°以下が最も好ましい。 Moreover, the photocatalyst member of the present invention is characterized in that the contact angle between the surface and water droplets irradiated with light having a wavelength from the ultraviolet region to the visible region is 30 ° or less. The glaze layer of the photocatalyst member of the present invention has a contact angle of 30 ° or less between the light-irradiated surface and water droplets. As a result, the glaze layer surface of the photocatalytic member exhibits hydrophilicity and has a self-cleaning action, so that it can be easily washed with water and has a characteristic of being resistant to dirt. Moreover, the deterioration of the photocatalytic property due to dirt can also be suppressed. The contact angle between the surface of the photocatalyst member irradiated with light and the water droplet is preferably 30 ° or less, more preferably 25 ° or less, and most preferably 20 ° or less.
本発明の釉薬用ガラスを用いて作製される光触媒部材は、紫外領域から可視領域までの波長の光が光触媒部材の釉薬層表面に照射されたときに触媒活性が発現されることにより、表面に付着した汚れ物質や細菌等が酸化又は還元反応により分解されるため、防汚用途や抗菌用途等に用いることができる。例えば、外界に曝されて有機物などの付着によって汚染される、又は菌類が浮遊し易い雰囲気などで使用する機械、装置、器具類、水質浄化等などの用途に有用であり、タイル、窓枠、建材等の用途にも好適に利用できる。また、光触媒部材の表面に親水性が奏されるため、これらの用途に用いたときに光触媒部材の表面に付着した汚れを雨滴等で容易に洗い流すことができる。 The photocatalyst member produced using the glaze glass of the present invention has a catalytic activity that is expressed on the surface when the glaze layer surface of the photocatalyst member is irradiated with light having a wavelength from the ultraviolet region to the visible region. Since the adhered dirt substances and bacteria are decomposed by oxidation or reduction reaction, they can be used for antifouling use, antibacterial use and the like. For example, it is useful for applications such as machines, devices, instruments, water purification, etc. that are exposed to the outside environment and contaminated by adhesion of organic substances, etc. It can be suitably used for applications such as building materials. In addition, since the surface of the photocatalyst member is hydrophilic, dirt attached to the surface of the photocatalyst member when used in these applications can be easily washed away with raindrops or the like.
本発明の光触媒部材は、本発明の釉薬用ガラス及び／または釉薬用結晶化ガラスを含有する釉薬を調合する釉薬調整工程と、該釉薬を基材に塗布する施釉工程と、前記施釉された基材を焼成する焼成工程と、を経て製造することができる。施釉工程は、スラリー状にした釉薬を基材に塗布する工程である。塗布の方法には、ディッピング、刷毛塗り等種々の方法が採用できる。この他、釉薬用ガラス粉粒体を用いる場合、粉粒状の原料を基材上に堆積させるだけで施釉することも可能である。焼成工程における具体的な手順は特に限定されないが、施釉後の基材に予熱を加える工程、設定温度へと徐々に昇温させる工程、設定温度に一定時間保持する工程、室温へと徐々に冷却する工程を含んでいてもよい。このときの温度および時間は、釉薬に含まれるガラスから光触媒結晶が析出する条件および、基材の耐熱性などを考慮して適宜選ぶことができる。 The photocatalyst member of the present invention includes a glaze adjusting step of preparing a glaze containing the glaze glass and / or glaze crystallized glass of the present invention, a glazing step of applying the glaze to a substrate, and the glazed base And a firing step of firing the material. A glazing process is a process of apply | coating the glaze made into the slurry form to the base material. Various methods such as dipping and brushing can be adopted as the application method. In addition, when using the glass powder for glazes, it is also possible to apply glaze only by depositing a granular raw material on a base material. The specific procedure in the firing step is not particularly limited, but the step of preheating the base material after glazing, the step of gradually raising the temperature to the set temperature, the step of maintaining the set temperature for a certain time, and gradually cooling to the room temperature The process of carrying out may be included. The temperature and time at this time can be appropriately selected in consideration of the conditions under which the photocatalytic crystal is precipitated from the glass contained in the glaze, the heat resistance of the substrate, and the like.
さらに、本発明の光触媒部材の製造方法は、釉薬用ガラスのフリット（粉末）を含む釉薬を基材上に図１（ａ）のように配置し、ガラスの粘性が１×１０１０ｐｏｉｓｅ以下となるまで加熱する工程を含むことができる。この工程によって本発明の光触媒部材の釉薬層表面は、その光沢度が６０°の入射角の測定で５以上とすることができ、外観的に美しい釉薬層を有するものとなる。光沢度は、１５以上であるとより好ましく、３５以上であると最も好ましい。Furthermore, the manufacturing method of the photocatalyst member of this invention arrange | positions the glaze containing the frit (powder) of the glass for glazes as shown in FIG. 1 (a), and the viscosity of glass is 1 * 10 < 10 > poise or less. The step of heating to the end can be included. By this step, the surface of the glaze layer of the photocatalyst member of the present invention can have a glossiness of 5 or more when measured at an incident angle of 60 °, and has a beautifully glaze layer. The glossiness is more preferably 15 or more, and most preferably 35 or more.
ガラスの粘性が１×１０１０ｐｏｉｓｅ以下となるまで加熱し、溶融した釉薬成分の粘性を低くすることで、ガラスが基材に広がり、図１（ｂ）のような均一な厚さの釉薬層が形成される。また、粘性が低くなったガラスの表面張力により、研磨工程を行わなくとも滑らかで光沢のある釉薬層を形成することができる。また、ガラスの軟化と同時に基材に釉薬層を密着させることができる。施釉する際のガラスの粘性が１×１０１０ｐｏｉｓｅを超えると釉薬層の光沢感が損なわれ易くなるので好ましくない。より光沢のある釉薬層を形成するためには、施釉時のガラスの粘性を１×１０７ｐｏｉｓｅ以下とすることがより好ましく、１×１０６ｐｏｉｓｅ以下とすることが最も好ましい。一方、基材上で溶融または軟化した釉薬ガラスの粘性が低くなりすぎた場合、安定なガラス質を維持せず、失透が生じ易くなる問題があるので、粘性の下限は好ましくは０．５ｐｏｉｓｅ、より好ましくは１ｐｏｉｓｅ、最も好ましくは２ｐｏｉｓｅとすることが好ましい。By heating the glass until the viscosity of the glass becomes 1 × 10 10 poise or less, and lowering the viscosity of the molten glaze component, the glass spreads on the base material, and the glaze layer has a uniform thickness as shown in FIG. Is formed. In addition, a smooth and glossy glaze layer can be formed without performing a polishing step due to the surface tension of the glass having low viscosity. In addition, the glaze layer can be brought into close contact with the substrate simultaneously with the softening of the glass. If the viscosity of the glass during glazing exceeds 1 × 10 10 poise, the glossiness of the glaze layer tends to be impaired, which is not preferable. In order to form a glossy glaze layer, the viscosity of the glass during glazing is more preferably 1 × 10 7 poise or less, and most preferably 1 × 10 6 poise or less. On the other hand, when the viscosity of the glaze glass melted or softened on the base material is too low, there is a problem that the glass does not maintain stable glass and devitrification is likely to occur. Therefore, the lower limit of the viscosity is preferably 0.5 poise. More preferably, it is 1 poise, and most preferably 2 poise.
基材上に釉薬層を形成するにあたって、施釉時の溶融または軟化したガラスの粘性を上記の値にするためには、予め釉薬用ガラス（又はフリット）のみの試料を用いて、加熱試験を行い、ある粘性以下になるときの温度を測定しておき、釉薬が配置された基材をこの温度まで加熱することが好ましい。 In forming the glaze layer on the base material, in order to bring the viscosity of the molten or softened glass at the time of glazing to the above value, a heating test is performed in advance using a sample of glaze glass (or frit) only. It is preferable to measure the temperature when the viscosity becomes below a certain viscosity and to heat the substrate on which the glaze is disposed to this temperature.
ガラスの粘性を測定するには以下のような方法が挙げられる。なお、ガラスの粘度の値は大まかに１４桁の大きさにわたっているので、測定は狭い範囲の粘度に対応した各種の手段によって行われている。 The following methods can be used to measure the viscosity of glass. In addition, since the value of the viscosity of glass is roughly on the order of 14 digits, the measurement is performed by various means corresponding to the viscosity in a narrow range.
溶融状態のガラスの粘性を求める方法としては、球落下法又は球引き上げ法が知られている。これらは溶融ガラス中の白金球の運動速度が、重力又は引き上げ力とストークスの法則による粘性抵抗力の釣り合いによって一定となることを利用した測定方法である。具体的な方法としては、溶融ガラス中に白金球を浸し、白金球を等速運動で引き上げる際にかかる粘性抵抗を負荷荷重として測定する。ここでＳｔｏｋｅｓの法則を用いると、白金球に働く重力や浮力などの関係を、微小の粒子が流体中を沈降する際の粘度と落下速度の関係を示した下式（１）により示すことができる。
η ＝ Ｇ × Ｗ／Ｖ ・・（１）
ここでηは粘度（ｄＰａ・ｓｅｃ）、Ｇは装置定数、Ｗは天秤の負荷荷重（ｇ）、Ｖは試料の速度（ｍｍ／ｓｅｃ）を表している。なお、１Ｐａ・ｓｅｃ＝１０ ｐｏｉｓｅである。本発明においては有限会社オプト企業製の球引上げ式高温粘度計（ＢＶＭ−１３ＬＨ）を用いて測定した。As a method for obtaining the viscosity of glass in a molten state, a ball dropping method or a ball pulling method is known. These are measurement methods using the fact that the movement speed of the platinum sphere in the molten glass becomes constant by the balance of gravity or the pulling force and the viscous resistance force according to Stokes' law. As a specific method, a platinum ball is immersed in molten glass, and the viscous resistance applied when the platinum ball is pulled up at a constant speed is measured as a load. Here, when Stokes' law is used, the relationship such as gravity and buoyancy acting on the platinum sphere can be expressed by the following equation (1) showing the relationship between the viscosity and the falling speed when fine particles settle in the fluid. it can.
η = G × W / V (1)
Here, η represents the viscosity (dPa · sec), G represents an apparatus constant, W represents the load applied to the balance (g), and V represents the speed of the sample (mm / sec). Note that 1 Pa · sec = 10 poise. In the present invention, the measurement was performed using a ball pulling type high temperature viscometer (BVM-13LH) manufactured by Opto Corporation.
次に、本発明の光触媒部材を製造する焼成工程において、結晶化前の釉薬用ガラスを用いて形成した釉薬層から図１（ｃ）のように結晶を析出させる結晶化工程について説明する。光触媒部材における光触媒結晶は、釉薬用ガラスのガラス転移温度（Ｔｇ）より１０℃以上、５００℃以下の温度範囲で析出する。以降この温度範囲を結晶化温度領域とする。光触媒部材において光触媒結晶を析出させる結晶化工程は、後述する二通りの形態で行うことができる。 Next, in the firing step for producing the photocatalyst member of the present invention, the crystallization step for precipitating crystals as shown in FIG. 1C from the glaze layer formed using the glaze glass before crystallization will be described. The photocatalytic crystal in the photocatalytic member is deposited in a temperature range of 10 ° C. or more and 500 ° C. or less from the glass transition temperature (Tg) of the glaze glass. This temperature range is hereinafter referred to as a crystallization temperature region. The crystallization step for precipitating the photocatalytic crystal in the photocatalytic member can be carried out in the following two forms.
（第１実施形態）
本発明の光触媒部材において光触媒結晶を析出させる第１実施形態は、ガラス質の釉薬層を形成した基材を結晶化温度領域に加熱することである。ここで、ガラス質の釉薬層とは、好ましくはガラスの粘性が１×１０１０ｐｏｉｓｅ以下となるまで加熱する工程を経て滑らかな釉薬の層を形成後、冷却固化させたものを意味し、未だ光触媒結晶が存在しない状態である。結晶化の条件は、釉薬層の組成によって適宜設定することができるが、結晶化温度が低すぎると所望の結晶相が得られないため、少なくとも釉薬層のガラス転移温度（Ｔｇ）より高い温度が必要となる。具体的に、結晶化温度の下限は、ガラス転移温度（Ｔｇ）より１０℃以上であり、好ましくはＴｇ＋２０℃以上であり、より好ましくはＴｇ＋３０℃以上であり、最も好ましくはＴｇ＋５０℃以上である。他方、結晶化温度が高すぎると、目的以外の結晶相が析出することで光触媒活性が減少してしまう。また、ＴｉＯ２結晶の析出を意図する場合、アナターゼ型より活性度の低いルチル型への相転移が起こり、光触媒活性が減少する憂いがある。従って、結晶化温度の上限は、好ましくは釉薬層のＴｇ＋５００℃以下であり、より好ましくはＴｇ＋４５０℃以下であり、最も好ましくはＴｇ＋４００℃以下である。また、ガラス質釉薬層のガラス転移温度（Ｔｇ）は、釉薬用ガラスのガラス転移温度と同一と見なして差し支えない。(First embodiment)
In the photocatalyst member of the present invention, the first embodiment for precipitating the photocatalytic crystal is to heat the base material on which the vitreous glaze layer is formed to the crystallization temperature region. Here, the vitreous glaze layer preferably means a layer obtained by forming a smooth glaze layer through a process of heating until the viscosity of the glass becomes 1 × 10 10 poise or less, and cooling and solidifying it. The photocatalytic crystal is not present. The crystallization conditions can be appropriately set depending on the composition of the glaze layer. However, if the crystallization temperature is too low, a desired crystal phase cannot be obtained. Therefore, at least a temperature higher than the glass transition temperature (Tg) of the glaze layer is required. Necessary. Specifically, the lower limit of the crystallization temperature is 10 ° C. or more from the glass transition temperature (Tg), preferably Tg + 20 ° C. or more, more preferably Tg + 30 ° C. or more, and most preferably Tg + 50 ° C. or more. On the other hand, if the crystallization temperature is too high, the photocatalytic activity decreases due to precipitation of a crystal phase other than the intended one. In addition, when the precipitation of TiO 2 crystals is intended, there is a concern that the phase transition to the rutile type having a lower activity than the anatase type occurs, and the photocatalytic activity decreases. Therefore, the upper limit of the crystallization temperature is preferably Tg + 500 ° C. or less of the glaze layer, more preferably Tg + 450 ° C. or less, and most preferably Tg + 400 ° C. or less. Further, the glass transition temperature (Tg) of the glassy glaze layer may be regarded as the same as the glass transition temperature of the glaze glass.
（第２実施形態）
本発明の光触媒部材において光触媒結晶を析出させる第２実施形態は、少なくとも一部に液相を有する釉薬層を冷却して固化させることを特徴とする結晶化工程を含むものである。ここで、釉薬層を形成するときにガラスの粘性が１×１０１０ｐｏｉｓｅ以下となるまで加熱する工程を経ることが好ましい。より具体的には、釉薬を配置した基材を、電気炉で１２００℃以上の所定温度で加熱し保持して、前記基材上で前記釉薬内の釉薬用ガラスを溶融させる。その後、溶融液を目的の基材上で固化させる。ここで、溶融液が冷却する過程において、結晶核の生成及び結晶の成長が起きる。冷却する際の速度及び温度が結晶相の形成や結晶サイズに大きな影響を及ぼすので、これらを精密に制御することが重要である。この手法は、例えば所望の結晶相をリッチに析出し、且つ溶融液状の釉薬層が比較的不安定な場合などにおいて有効である。(Second Embodiment)
The second embodiment for precipitating photocatalytic crystals in the photocatalytic member of the present invention includes a crystallization step characterized by cooling and solidifying the glaze layer having a liquid phase at least partially. Here, when forming the glaze layer, it is preferable to go through a heating step until the viscosity of the glass becomes 1 × 10 10 poise or less. More specifically, the base material on which the glaze is disposed is heated and held at a predetermined temperature of 1200 ° C. or higher in an electric furnace to melt the glaze glass in the glaze on the base material. Thereafter, the melt is solidified on the target substrate. Here, generation of crystal nuclei and crystal growth occur in the process of cooling the melt. Since the cooling speed and temperature greatly affect the formation of crystal phases and the crystal size, it is important to control them precisely. This technique is effective, for example, when a desired crystal phase is precipitated in a rich manner and the molten liquid glaze layer is relatively unstable.
析出する結晶の種類およびその粒径を比較的容易にコントロールできる点においては、第２実施形態よりも第１実施形態が望ましい。特に透明な釉薬層を形成した光触媒部材を得るには、比較的低い温度で結晶化することが好ましく、具体的にはＴｇ＋１０℃〜Ｔｇ＋１００℃の温度範囲で熱処理を行うことが好ましい。結晶化工程としては、まず低い温度で結晶核を形成させてそれからより高い温度でその結晶核を成長させるという二段階の熱処理であっても良いし、最初から結晶化温度まで加熱する一段階の熱処理であっても良い。二段階の熱処理は結晶径を制御し易い方法として一般的によく用いられているが、本発明の光触媒部材を製造するにあたっては、一段階の熱処理でも同様な目的を達成できるので、より製造工程を簡単にすることができる。 The first embodiment is more preferable than the second embodiment in that the kind of crystals to be precipitated and the particle size thereof can be controlled relatively easily. In particular, in order to obtain a photocatalytic member having a transparent glaze layer, it is preferable to crystallize at a relatively low temperature, and specifically, heat treatment is preferably performed in a temperature range of Tg + 10 ° C. to Tg + 100 ° C. The crystallization process may be a two-step heat treatment in which crystal nuclei are first formed at a low temperature and then the crystal nuclei are grown at a higher temperature, or a one-step heating from the beginning to the crystallization temperature. Heat treatment may be used. The two-stage heat treatment is generally used as a method for easily controlling the crystal diameter. However, in producing the photocatalyst member of the present invention, the same purpose can be achieved even with the one-stage heat treatment, so that the production process is more effective. Can be easy.
このようにして作られた光触媒部材が有する光触媒結晶は、釉薬層を形成する過程で釉薬の中から析出したものであり、釉薬に添加された状態で釉薬層に存在するものではない。この特徴によって、光触媒部材が有する釉薬層は高い光沢度を実現することができる。本発明の部材を施釉する際に一旦溶融または軟化した釉薬は、表面張力により滑らかな膜を形成し、その後の過程で微細な光触媒結晶が生成される。このようにガラス相の中から析出する結晶は、内部と同じく表面にも析出するが、釉薬層の表面特性、特に光沢性を妨げることなく存在することが可能である。 The photocatalytic crystals of the photocatalyst member thus produced are precipitated from the glaze in the process of forming the glaze layer, and are not present in the glaze layer in a state of being added to the glaze. Due to this feature, the glaze layer of the photocatalyst member can achieve high glossiness. The glaze once melted or softened when the member of the present invention is applied forms a smooth film due to surface tension, and fine photocatalytic crystals are generated in the subsequent process. As described above, crystals precipitated from the glass phase precipitate on the surface as well as inside, but can exist without interfering with the surface characteristics of the glaze layer, in particular, glossiness.
光沢度は、表面に光をあてた時の反射の程度を表す量で、測定部分での反射光の強さの比として求めることができる。具体的には株式会社堀場製作所の光沢計グロスチェッカ（ＩＧ−３３１）によって測定した値を用いることができる。 The glossiness is an amount representing the degree of reflection when light is applied to the surface, and can be obtained as a ratio of the intensity of reflected light at the measurement portion. Specifically, a value measured by a gloss meter gloss checker (IG-331) manufactured by HORIBA, Ltd. can be used.
なお、釉薬に釉薬用結晶化ガラスを用いることによって、焼成時における結晶化プロセスが不要となった場合には、前述した結晶化温度領域に影響されることなく、焼成温度を基材の耐熱温度にあわせて自由に選んでも良い。 In addition, when the crystallization process at the time of baking becomes unnecessary by using the crystallized glass for glaze as the glaze, the baking temperature is set to the heat resistant temperature of the substrate without being affected by the crystallization temperature region described above. You may choose freely according to.
本発明の光触媒部材が有する釉薬層に含有される光触媒結晶の大きさは、球近似したときの平均径が、５μｍを超えないことが好ましい。５μｍを超えると、光触媒特性が低下する恐れがある。有効な光触媒特性を引き出すため、光触媒結晶の平均径は３μｍ以下、より好ましくは１μｍ以下、最も好ましくは０．５μｍ以下であることが好ましい。本発明の光触媒部材が有する光触媒結晶は、ガラス相に含まれるイオンから析出するものであり、オングストローム（Å）単位の非常に微細なものからナノオーダー、ミクロオーダーまで、幅広い粒子径をとることが可能である。 The size of the photocatalyst crystal contained in the glaze layer of the photocatalyst member of the present invention is preferably such that the average diameter when approximated by a sphere does not exceed 5 μm. If it exceeds 5 μm, the photocatalytic properties may be deteriorated. In order to extract effective photocatalytic properties, the average diameter of the photocatalytic crystal is preferably 3 μm or less, more preferably 1 μm or less, and most preferably 0.5 μm or less. The photocatalytic crystal of the photocatalyst member of the present invention is precipitated from ions contained in the glass phase, and can have a wide particle size ranging from a very fine angstrom (Å) unit to nano-order and micro-order. Is possible.
光触媒結晶の粒径および量（結晶化率）は、熱処理条件をコントロールすることにより制御することが可能であり、ガラスの組成等にもよるが、多くの場合、加熱時間が長ければ結晶化率および結晶サイズは大きくなり、短ければ結晶化率および結晶サイズは小さくなる。本発明の光触媒部材における結晶の粒径は特に限定されないが、有効な光触媒特性を引き出すため、その下限を３ｎｍの範囲とすることが好ましく、５ｎｍとすることがより好ましく、１０ｎｍとすることが最も好ましい。特に、結晶径を可視光の波長より小さくすることで釉薬層を透明にすることができる。透明であれば、基材の色を損ねることなく利用できるし、光を遮らないので、ランプカバーや窓材などに適用できる。 The particle size and amount (crystallization rate) of the photocatalytic crystal can be controlled by controlling the heat treatment conditions, and depending on the glass composition, etc., in many cases, if the heating time is long, the crystallization rate In addition, the crystal size becomes large, and if it is short, the crystallization rate and crystal size become small. The particle size of crystals in the photocatalyst member of the present invention is not particularly limited, but in order to bring out effective photocatalytic properties, the lower limit is preferably in the range of 3 nm, more preferably 5 nm, and most preferably 10 nm. preferable. In particular, the glaze layer can be made transparent by making the crystal diameter smaller than the wavelength of visible light. If it is transparent, it can be used without damaging the color of the base material, and can be applied to lamp covers and window materials because it does not block light.
結晶粒径及びその平均値はＸＲＤの回折ピークの半値幅より、シェラー（Ｓｃｈｅｒｒｅｒ）の式より見積もることができる。回折ピークが弱かったり、重なったりする場合は、走査型電子顕微鏡（ＳＥＭ）又は透過型電子顕微鏡（ＴＥＭ）を用いて測定した結晶粒子面積から、これを円と仮定してその直径を求めて測定できる。顕微鏡を用いて平均値を算出する際には、無作為に１００個以上の結晶直径を測定することが好ましい。 The crystal grain size and the average value can be estimated from the half width of the XRD diffraction peak by the Scherrer equation. If the diffraction peaks are weak or overlap, measure the diameter of the crystal particle area measured using a scanning electron microscope (SEM) or transmission electron microscope (TEM), assuming that this is a circle. it can. When calculating an average value using a microscope, it is preferable to measure 100 or more crystal diameters at random.
焼成工程後の釉薬層は、光触媒結晶を有し、そのままの状態でも高い光触媒特性を奏することが可能であるが、この釉薬層に対してエッチング工程を行うことにより、結晶相の周りのガラス相が取り除かれ、表面に露出する結晶相の比表面積が大きくなるため、釉薬層の光触媒特性をより高めることが可能である。また、エッチング工程に用いる溶液やエッチング時間をコントロールすることにより、Ｎｂ含有結晶、Ｔａ含有結晶、ＴｉＯ２、ＺｎＯ、ＷＯ３結晶相が残る多孔質体を得ることが可能である。ここで、エッチング工程としては、ドライエッチング及び／又は溶液への浸漬が挙げられる。浸漬に使用される酸性もしくはアルカリ性の溶液は特に限定されず、例えばフッ素又は塩素を含む酸（フッ化水素酸、塩酸）であってよい。なお、このエッチング工程は、フッ化水素ガス、塩化水素ガス、フッ化水素酸、塩酸等を、釉薬層の表面に吹き付けることで行ってよい。The glaze layer after the firing step has a photocatalytic crystal and can exhibit high photocatalytic properties even in the state as it is, but by performing an etching step on this glaze layer, a glass phase around the crystal phase is obtained. Is removed and the specific surface area of the crystal phase exposed on the surface is increased, so that the photocatalytic properties of the glaze layer can be further enhanced. Further, by controlling the solution used in the etching step and the etching time, it is possible to obtain a porous body in which the Nb-containing crystal, the Ta-containing crystal, the TiO 2 , ZnO, and WO 3 crystal phases remain. Here, examples of the etching step include dry etching and / or immersion in a solution. The acidic or alkaline solution used for immersion is not particularly limited, and may be, for example, an acid (hydrofluoric acid, hydrochloric acid) containing fluorine or chlorine. This etching step may be performed by spraying hydrogen fluoride gas, hydrogen chloride gas, hydrofluoric acid, hydrochloric acid, or the like on the surface of the glaze layer.
次に、実施例によって本発明をさらに詳しく説明するが、本発明は、以下の実施例に制約されるものではない。 EXAMPLES Next, although an Example demonstrates this invention in more detail, this invention is not restrict | limited to a following example.
本発明の釉薬用ガラスの組成を表１〜３に示す。 The composition of the glaze glass of the present invention is shown in Tables 1-3.
本発明の実施例（１〜３０）の釉薬用ガラスは、いずれも各成分の原料として各々相当する酸化物、水酸化物、炭酸塩、硝酸塩、塩化物、水酸化物、メタ燐酸化合物等の通常のガラスに使用される高純度の原料を選定し、表１〜３に示した組成の割合になるように秤量して均一に混合した後、白金坩堝に投入し、ガラス組成の熔解難易度に応じて１２００〜１６５０℃の温度範囲で１〜２４時間熔解し、撹拌均質化して泡切れ等を行った後、１５００℃以下に温度を下げて撹拌均質化してから融液状のガラスを水に流し入れ、水砕してガラスを作製した。 The glass for glazes of the examples (1-30) of the present invention includes oxides, hydroxides, carbonates, nitrates, chlorides, hydroxides, metaphosphoric acid compounds and the like corresponding to the raw materials of the respective components. Select high-purity raw materials used for ordinary glass, weigh them so that they have the composition ratios shown in Tables 1 to 3, and after mixing them uniformly, put them into a platinum crucible, and make the glass composition difficult to melt. Depending on the temperature, melt in a temperature range of 1200 to 1650 ° C. for 1 to 24 hours, stir to homogenize and blow out bubbles, etc., lower the temperature to 1500 ° C. or less and homogenize with stirring, and then melt the molten glass into water. The glass was made by pouring and water granulation.
上述のようにして得られたガラスを遊星ボールミルに投入し、ＹＴＺφ１０ｍｍボールを用いて２００ｒｐｍでガラスの粉砕しやすさに応じて５分〜１００分、乾式もしくはエタノールを用いた湿式粉砕法により粉砕し、またはメノウ乳鉢とメノウ乳棒により手動で３分〜２０分粉砕し、釉薬用ガラス粉粒体とした。粒度分布を粒度分布測定装置（ＮＩＫＫＩＳＯ社製、商品名：ＭＴ３３００）により測定し、平均粒度は累積５０％が５μｍから１５μｍになるように粉砕した。 The glass obtained as described above is put into a planetary ball mill and pulverized by a dry pulverization method using a YTZφ10 mm ball at 200 rpm for 5 minutes to 100 minutes depending on the ease of pulverization of the glass or using ethanol. Alternatively, it was pulverized manually for 3 to 20 minutes with an agate mortar and an agate pestle to obtain a glass powder for glaze. The particle size distribution was measured with a particle size distribution measuring device (trade name: MT3300, manufactured by NIKKISO), and the average particle size was pulverized so that the cumulative 50% was 5 μm to 15 μm.
また、これら釉薬用ガラスを用いた粉粒体の一部を白金坩堝に投入し、９００℃で３０分熱処理を施し、釉薬用結晶化ガラス粉粒体とした。 Moreover, a part of the granular material using the glass for glaze was put into a platinum crucible and subjected to heat treatment at 900 ° C. for 30 minutes to obtain a crystallized glass granular material for glaze.
［釉薬（１）］
実施例１〜２３の釉薬用ガラス粉粒体および釉薬用結晶化ガラス粉粒体に、市販の釉薬用原料および溶媒を添加して釉薬とした。表４にその一例を示す。具体的には、平均粒径５．５μｍに粉砕した釉薬用ガラス１の粉粒体、または該粉粒体を結晶化させた釉薬用結晶化ガラス１粉粒体と、市販の釉薬原料（新日本造形株式会社製：楽焼き透明釉薬Ａ（無鉛））とを表４に示した組成の割合になるように秤量し、溶媒として精製水または１ｗｔ％のＣＭＣ水溶液を添加し、ボールミルやスターラーで均一になるように撹拌し、釉薬とした。[Glue (1)]
A glaze was prepared by adding a commercially available glaze raw material and solvent to the glaze glass granules and glaze crystallized glass granules of Examples 1 to 23. Table 4 shows an example. Specifically, a powder of glaze glass 1 pulverized to an average particle size of 5.5 μm, or a crystallized glass powder of glaze obtained by crystallizing the powder, and a commercially available glaze raw material (new Nippon Zoukei Co., Ltd .: Rakuyaki transparent glaze A (unleaded)) is weighed to the composition shown in Table 4, and purified water or 1 wt% CMC aqueous solution is added as a solvent, and uniform with a ball mill or stirrer. The mixture was stirred to form a glaze.
この釉薬をディッピングにより素焼きタイルに塗布し、表４に示す熱処理条件で焼成して釉薬層を形成した。 This glaze was applied to the unglazed tile by dipping and baked under the heat treatment conditions shown in Table 4 to form a glaze layer.
ここで、実施例（Ａ〜Ｆ）の釉薬層の析出結晶相の種類は、Ｘ線回折装置（フィリップス社製、商品名：Ｘ’Ｐｅｒｔ−ＭＰＤ）で同定した。 Here, the kind of the precipitated crystal phase of the glaze layer of Examples (A to F) was identified by an X-ray diffractometer (manufactured by Philips, trade name: X'Pert-MPD).
また、実施例の試料について、日本工業規格ＪＩＳ Ｒ １７０３−２：２００７に基づき、メチレンブルーの分解活性指数（ｎｍｏｌ／ｌ／ｍｉｎ）を求めた。また、釉薬層を形成していない素焼きタイルを比較例とした。 Moreover, about the sample of the Example, the decomposition activity index (nmol / l / min) of methylene blue was calculated | required based on Japanese Industrial Standard JISR1703-2: 2007. Moreover, the unglazed tile which has not formed the glaze layer was made into the comparative example.
より具体的には、以下のような手順でメチレンブルーの分解活性指数を求めた。０．０２０ｍＭのメチレンブルー水溶液（以下、吸着液とする）と０．０１０ｍＭのメチレンブルー水溶液（以下、試験液とする）を調製した。そして、光触媒特性が認められた実施例の試料の表面と、石英管（内径１０ｍｍ、高さ３０ｍｍ）の一方の開口と、を高真空用シリコーングリース（東レ・ダウコーニング株式会社製）で固定し、石英管の他方の開口から吸着液を注入して試験セルを吸着液で満たした。その後、石英管の他方の開口と吸着液の液面とをカバーガラス（松浪ガラス工業株式会社製、商品名：白縁磨フロストＮｏ．１）で覆い、光が当たらないようにしながら、１２〜２４時間にわたって吸着液を試料に十分に吸着させた。吸着後の吸着液について、分光光度計（日本分光株式会社製、型番：Ｖ−６５０）を用いて波長６６４ｎｍの光に対する吸光度を測定し、この吸着液の吸光度が試験液について同様に測定された吸光度よりも大きくなった時点で、吸着を完了させた。このとき、試験液について測定された吸光度（Ａｂｓ（０））とメチレンブルー濃度（ｃ（０）＝１０［μｍｏｌ／Ｌ］）の値から、下式（１）を用いて換算係数Ｋ［μｍｏｌ／Ｌ］を求めた。
Ｋ＝ｃ（０）／Ａｂｓ（０） ・・（１）
次いで、カバーガラスを取り外して石英管内の液を試験液に入れ替えた後、石英管の他方の開口と吸着液の液面とをカバーガラスで再度覆い、１．０ｍＷ／ｃｍ２の紫外線を照射した。そして、紫外線を６０分、１２０分及び１８０分間にわたり照射した後における波長６６４ｎｍの光に対する吸光度を測定した。
紫外光の照射を開始してｔ分後に測定された吸光度Ａｂｓ（ｔ）の値から下式（２）を用いて、紫外光の照射を開始してｔ分後のメチレンブルー試験液の濃度Ｃ（ｔ）［μｍｏｌ／Ｌ］を求めた。ここで、Ｋは上述の換算係数である。
Ｃ（ｔ）＝Ｋ×Ａｂｓ（ｔ） ・・（２）
そして、上述により求められたＣ（ｔ）を縦軸にとり、紫外線の照射時間ｔ［ｍｉｎ］を横軸にとってプロットを作成した。このとき、プロットから得られる直線の傾きａ［μｍｏｌ／Ｌ／ｍｉｎ］を最小二乗法によって求め、下式（３）を用いて分解活性指数Ｒ［ｎｍｏｌ／Ｌ／ｍｉｎ］を求めた。
Ｒ＝｜ａ｜×１０００ ・・（３）More specifically, the decomposition activity index of methylene blue was determined by the following procedure. A 0.020 mM methylene blue aqueous solution (hereinafter referred to as an adsorption solution) and a 0.010 mM methylene blue aqueous solution (hereinafter referred to as a test solution) were prepared. Then, the surface of the sample of the example in which the photocatalytic characteristics were recognized and one opening of the quartz tube (inner diameter 10 mm, height 30 mm) were fixed with high vacuum silicone grease (manufactured by Dow Corning Toray). The adsorbing liquid was injected from the other opening of the quartz tube to fill the test cell with the adsorbing liquid. Thereafter, the other opening of the quartz tube and the liquid surface of the adsorbing liquid are covered with a cover glass (manufactured by Matsunami Glass Industry Co., Ltd., trade name: white edge polished frost No. 1), and the light is not exposed to the glass. The adsorbed liquid was sufficiently adsorbed to the sample over 24 hours. About the adsorption liquid after adsorption | suction, the light absorbency with respect to the light of wavelength 664nm was measured using the spectrophotometer (The JASCO Corporation make, model number: V-650), and the light absorbency of this adsorption liquid was similarly measured about the test liquid. Adsorption was completed when the absorbance was greater. At this time, from the values of absorbance (Abs (0)) and methylene blue concentration (c (0) = 10 [μmol / L]) measured for the test solution, the conversion coefficient K [μmol / L].
K = c (0) / Abs (0) (1)
Next, after removing the cover glass and replacing the liquid in the quartz tube with the test solution, the other opening of the quartz tube and the liquid surface of the adsorbing liquid were covered again with the cover glass and irradiated with ultraviolet rays of 1.0 mW / cm 2 . . And the light absorbency with respect to the light of wavelength 664nm after irradiating an ultraviolet-ray for 60 minutes, 120 minutes, and 180 minutes was measured.
Using the following formula (2) from the value of absorbance Abs (t) measured t minutes after the start of ultraviolet light irradiation, the concentration C (methylene blue test solution concentration t (t minutes after the start of ultraviolet light irradiation) t) [μmol / L] was determined. Here, K is the conversion factor described above.
C (t) = K × Abs (t) (2)
A plot was created with C (t) determined as described above on the vertical axis and the irradiation time t [min] of ultraviolet rays on the horizontal axis. At this time, the slope a [μmol / L / min] of the straight line obtained from the plot was determined by the least square method, and the decomposition activity index R [nmol / L / min] was determined using the following equation (3).
R = | a | × 1000 (3)
また、実施例Ｅに記載された組成によって形成された釉薬層について、ＨＦ濃度が４６％（質量百分率）のフッ酸溶液（和光純薬工業株式会社製）に３分間浸漬させ、エッチング工程を行った。エッチング工程後における分解活性指数（ｎｍｏｌ／ｌ／ｍｉｎ）を求め、図４に示した。 Further, the glaze layer formed with the composition described in Example E was immersed in a hydrofluoric acid solution (manufactured by Wako Pure Chemical Industries, Ltd.) having an HF concentration of 46% (mass percentage) for 3 minutes to perform an etching process. It was. The decomposition activity index (nmol / l / min) after the etching step was determined and shown in FIG.
表５に表されるように、実施例（Ａ〜Ｆ）の光触媒担持部材析出結晶相には、いずれも光触媒活性の高いアナターゼ型のＴｉＯ２結晶が含まれていた。このことは、図２示した実施例（Ｂ）の光触媒担持部材についてのＸＲＤパターンにおいて、入射角２θ＝２５．３°付近をはじめ、「○」で表される入射角にピークが生じていることからも明らかである。As shown in Table 5, the photocatalyst-supporting member precipitated crystal phases of Examples (A to F) all contained anatase-type TiO 2 crystals having high photocatalytic activity. This is because, in the XRD pattern for the photocatalyst carrying member of Example (B) shown in FIG. It is clear from that.
これらのうち、実施例（Ａ〜Ｆ）の釉薬層の光触媒特性について分解活性指数（ｎｍｏｌ／ｌ／ｍｉｎ）を求めたところ、表４および図３に示すように、分解活性指数が１５．０ｎｍｏｌ／ｌ／ｍｉｎ以上、より具体的には１６．９ｎｍｏｌ／ｌ／ｍｉｎ以上であった。一方、釉薬層を形成していない素焼きタイルの分解活性指数はほぼ０であった。 Among these, when the decomposition activity index (nmol / l / min) was determined for the photocatalytic properties of the glaze layers of Examples (A to F), as shown in Table 4 and FIG. 3, the decomposition activity index was 15.0 nmol. / L / min or more, more specifically 16.9 nmol / l / min or more. On the other hand, the decomposition activity index of the unglazed tile without the glaze layer was almost zero.
エッチング工程を行った後の実施例（Ｅ）の釉薬層は、図４に示すように、エッチング工程前の分解活性指数に比べて高くなっていた。具体的にはその値が１７．４ｎｍｏｌ／ｌ／ｍｉｎから２４．３ｎｍｏｌ／ｌ／ｍｉｎに上昇した。そのため、本発明の実施例の釉薬層は、エッチング工程を行うことで分解活性指数が高められるため、より高い光触媒特性を得ることが可能であることが明らかになった。 As shown in FIG. 4, the glaze layer of Example (E) after the etching process was higher than the decomposition activity index before the etching process. Specifically, the value increased from 17.4 nmol / l / min to 24.3 nmol / l / min. Therefore, it became clear that the glaze layer of the Example of this invention can obtain a higher photocatalytic characteristic, since a decomposition activity index | exponent is raised by performing an etching process.
［釉薬（２）］
実施例１、７、１５〜１６、２０、２２〜３０のガラス粉粒体に水を添加して釉薬とした。具体的には釉薬用ガラス粉粒体１００ｇに精製水５０ｇを添加し、ボールミルやスターラーで均一になるように撹拌し、釉薬とした。[Glue (2)]
Water was added to the glass granules of Examples 1, 7, 15-16, 20, 22-30 to form glazes. Specifically, 50 g of purified water was added to 100 g of glass powder for glaze, and stirred with a ball mill or stirrer to make a glaze.
この釉薬を素焼きタイル上に配置し、８０℃の炉で３〜１５分加熱保持して乾燥させた後、１２００℃〜１３００℃の温度範囲で５〜２０分加熱し、徐冷して素焼きタイル上にガラス質からなる釉薬層を形成した。 This glaze is placed on an unglazed tile, heated and dried in an oven at 80 ° C. for 3 to 15 minutes, heated in a temperature range of 1200 ° C. to 1300 ° C. for 5 to 20 minutes, and gradually cooled to unglazed tile. A glaze layer made of glass was formed on top.
以上のようにして得られた、ガラス層を形成したタイルを、電気炉で６００〜１０００℃で１時間保持する熱処理を行った。その後電気炉から取り出し、室温にて徐冷し、光触媒部材とした。 The tile formed with the glass layer formed as described above was subjected to heat treatment for 1 hour at 600 to 1000 ° C. in an electric furnace. Thereafter, it was taken out from the electric furnace and slowly cooled at room temperature to obtain a photocatalyst member.
熱処理後の光触媒部材の釉薬層について、結晶相の種類をＸ線回折装置（フィリップス社製、商品名：Ｘ’Ｐｅｒｔ−ＭＰＤ）で同定した。また、ＸＲＤの回折ピークの半値幅より、シェラー（Ｓｃｈｅｒｒｅｒ）の式；Ｄ＝０．９λ／（βｃｏｓθ）に基づいて各結晶のサイズを見積った。ここで、Ｄは、結晶の大きさ、λはＸ線の波長、θはブラッグ角（回折角２θの半分）である。その結果を、表５に示す。本発明の光触媒部材の釉薬層には高い光触媒活性を有するＴｉＯ２結晶、ＷＯ３結晶、ＮａＮｂＯ３結晶、ナシコン型結晶（Ｍｇ０．５Ｔｉ２（ＰＯ４）３、ＮａＴｉ２（ＰＯ４）３）、ＺｎＯ結晶等が析出しており、主結晶相のサイズが５μｍ以下、より具体的には０．１μｍ以下であることが判明した。About the glaze layer of the photocatalyst member after heat processing, the kind of crystal phase was identified with the X-ray-diffraction apparatus (The Philips company make, brand name: X'Pert-MPD). The size of each crystal was estimated from the half width of the XRD diffraction peak based on the Scherrer equation; D = 0.9λ / (βcosθ). Here, D is the crystal size, λ is the X-ray wavelength, and θ is the Bragg angle (half the diffraction angle 2θ). The results are shown in Table 5. TiO 2 crystal having a high photocatalytic activity in the glaze layer of the photocatalytic member of the present invention, WO 3 crystal, NaNbO 3 crystal, Nasicon-type crystal (Mg 0.5 Ti 2 (PO 4 ) 3, NaTi 2 (PO 4) 3 ), ZnO crystals and the like are precipitated, and it has been found that the size of the main crystal phase is 5 μm or less, more specifically 0.1 μm or less.
図５に実施例（２６）に記載された組成によって作製された光触媒部材についてのＸＲＤパターンを示す。アナターゼ型は、入射角２θ＝２５．３付近をはじめ、「○」で表される入射角にピークが生じていること、ルチル型は、入射角２θ＝２７．４付近をはじめ、「▲」で表される入射角にピークが生じていることから明らかに確認できる。 FIG. 5 shows an XRD pattern for the photocatalytic member produced by the composition described in Example (26). The anatase type has a peak at an incident angle represented by “◯”, including an incident angle of 2θ = 25.3, and the rutile type has an “▲” at an incident angle of 2θ = 27.4. It can be clearly confirmed from the fact that a peak occurs at the incident angle represented by.
また、図６に実施例（２０）に記載された組成によって作製された光触媒部材についてのＸＲＤパターンを示す。ＮａＮｂＯ３結晶は、入射角２θ＝３２．５付近をはじめ、「□」で表される入射角にピークが生じていることから明らかに確認できる。Moreover, the XRD pattern about the photocatalyst member produced by the composition described in Example (20) in FIG. 6 is shown. The NaNbO 3 crystal can be clearly confirmed from the fact that a peak occurs at an incident angle represented by “□” including an incident angle near 2θ = 32.5.
また、図７に実施例（３０）に記載された組成によって作製された光触媒部材についてのＸＲＤパターンを示す。Ｍｇ０．５Ｔｉ２（ＰＯ４）３結晶は、入射角２θ＝２４．３付近をはじめ、「◇」で表される入射角にピークが生じていることから明らかに確認できる。Moreover, the XRD pattern about the photocatalyst member produced by the composition described in Example (30) in FIG. 7 is shown. The Mg 0.5 Ti 2 (PO 4 ) 3 crystal can be clearly confirmed from the fact that a peak occurs at the incident angle represented by “◇”, including the vicinity of the incident angle 2θ = 24.3.
また、実施例（２３、２４、２５）に記載された組成によって作製された光触媒部材について、上述した日本工業規格ＪＩＳ Ｒ １７０３−２：２００７に基づき、メチレンブルーの分解活性指数（ｎｍｏｌ／Ｌ／ｍｉｎ）を求めた。その結果を図８に示す。また、釉薬層を形成していない素焼きタイルを比較例とした。その結果、図８に表されるように、分解活性指数が５ｎ ｍｏｌ／Ｌ／ｍｉｎ以上、より具体的には５．５ ｎ ｍｏｌ／Ｌ／ｍｉｎ以上であった。一方、釉薬層を形成していない素焼きタイルの分解活性指数は１．１ ｎ ｍｏｌ／Ｌ／ｍｉｎであった。 Moreover, about the photocatalyst member produced by the composition described in the Example (23, 24, 25), based on the above-mentioned Japanese Industrial Standard JIS R 1703-2: 2007, the decomposition activity index of methylene blue (nmol / L / min) ) The result is shown in FIG. Moreover, the unglazed tile which has not formed the glaze layer was made into the comparative example. As a result, as shown in FIG. 8, the decomposition activity index was 5 nmol / L / min or more, more specifically 5.5 nmol / L / min or more. On the other hand, the decomposition activity index of the unglazed tile in which no glaze layer was formed was 1.1 nmol / L / min.
また、実施例（２３、３０）に記載された組成によって作製された光触媒部材について、ＨＦ濃度が４．６％（質量百分率）のフッ酸溶液（和光純薬工業株式会社製）に１０秒間浸漬させ、エッチング工程を行った。実施例２３のエッチング工程前後における分解活性指数（ｎ ｍｏｌ／Ｌ／ｍｉｎ）、および実施例３０のエッチング工程後における分解活性指数（ｎ ｍｏｌ／Ｌ／ｍｉｎ）を求め、図９に示した。 Moreover, about the photocatalyst member produced by the composition described in Example (23,30), it immersed for 10 second in the hydrofluoric acid solution (made by Wako Pure Chemical Industries Ltd.) whose HF density | concentration is 4.6% (mass percentage). And an etching process was performed. The decomposition activity index (n mol / L / min) before and after the etching process of Example 23 and the decomposition activity index (n mol / L / min) after the etching process of Example 30 were determined and shown in FIG.
エッチング工程を行った光触媒部材は図９に表されるように、高い分解活性指数を有していた。また、実施例２３に表されるように、エッチング後は、エッチング工程前に比べて分解活性指数が高くなっていた。具体的にはその値が５．５ ｎ ｍｏｌ／Ｌ／ｍｉｎから７．８ ｎ ｍｏｌ／Ｌ／ｍｉｎに上昇した。そのため、本発明の光触媒部材は、エッチング工程を行うことで分解活性指数を高められ、より高い光触媒特性を得ることが可能であることが明らかになった。 As shown in FIG. 9, the photocatalyst member subjected to the etching process had a high decomposition activity index. Moreover, as represented in Example 23, the decomposition activity index was higher after etching than before the etching step. Specifically, the value increased from 5.5 nmol / L / min to 7.8 nmol / L / min. Therefore, it became clear that the photocatalytic member of the present invention can increase the decomposition activity index by performing the etching process, and can obtain higher photocatalytic properties.
また、実施例（２４）に記載された組成を有する釉薬用ガラスによって作製された光触媒部材について、光触媒ガラスの親水性についてθ／２法によりサンプル表面と水滴との接触角を測定することにより評価した。すなわち、紫外線照射前および照射後のガラスの表面にそれぞれ水を滴下し、ガラスの表面から水滴の頂点までの高さｈと、水滴の試験片に接している面の半径ｒと、を協和界面科学社製の接触角計（ＤＭ５０１）を用いて測定し、θ＝２ｔａｎ−１（ｈ／ｒ）の関係式より、水との接触角θを求めた。なお、紫外線照射は、水銀ランプを用い、照度１０ｍＷ／ｃｍ２、照射時間０〜４時間で行った。比較例として、組成が３０ＳｉＯ２−２０Ｂ２Ｏ３−２０Ａｌ２Ｏ３−２０Ｇｄ２Ｏ３−１０Ｌａ２Ｏ３である光学ガラスを用いた。Moreover, about the photocatalyst member produced with the glass for glazes having the composition described in Example (24), the hydrophilicity of the photocatalyst glass was evaluated by measuring the contact angle between the sample surface and water droplets by the θ / 2 method. did. That is, water is dropped on the surface of the glass before and after the ultraviolet irradiation, and the height h from the glass surface to the top of the water droplet and the radius r of the surface in contact with the test piece of the water droplet are determined as the Kyowa interface. It measured using the contact angle meter (DM501) by a scientific company, and contact angle (theta) with water was calculated | required from the relational expression of (theta) = 2tan < -1 > (h / r). The ultraviolet irradiation was performed using a mercury lamp at an illuminance of 10 mW / cm 2 and an irradiation time of 0 to 4 hours. As a comparative example, the composition was of the optical glass is 30SiO 2 -20B 2 O 3 -20Al 2 O 3 -20Gd 2 O 3 -10La 2 O 3.
以上のように親水性を評価したところ、図１０に示すように、２〜３時間の紫外線の照射によって水との接触角が３０°以下となることが確認された。一方、比較例のガラスは、紫外線照射を続けても、水との接触角に有意な変化は認められなかった。これにより、本発明の実施例の光触媒部材は、高い親水性を有することが明らかになった。 When the hydrophilicity was evaluated as described above, it was confirmed that the contact angle with water was 30 ° or less by irradiation with ultraviolet rays for 2 to 3 hours, as shown in FIG. On the other hand, the glass of the comparative example showed no significant change in the contact angle with water even when the ultraviolet irradiation was continued. Thereby, it became clear that the photocatalyst member of the Example of this invention has high hydrophilicity.
また、実施例（２０）に記載された組成によって作製された光触媒部材について、ＨＦ濃度が４．６％（質量百分率）のフッ酸溶液（和光純薬工業株式会社製）に１０秒間浸漬させ、エッチング工程を行った後、１０ｍＷ／ｃｍ２の照度で親水性を評価し、図１１に示した。Moreover, about the photocatalyst member produced by the composition described in Example (20), it was immersed for 10 second in the hydrofluoric acid solution (made by Wako Pure Chemical Industries Ltd.) whose HF concentration is 4.6% (mass percentage), After performing the etching process, the hydrophilicity was evaluated at an illuminance of 10 mW / cm 2 and shown in FIG.
エッチング工程を行った光触媒部材は図１１に表されるように、エッチング工程前に比べて親水性が高くなっていた。具体的には接触角が紫外線を３０分照射した時点で３０°を下回った。そのため、本発明の光触媒部材は、エッチング工程を行うことで親水性を高められるため、より高い光触媒特性を得ることが可能であることが明らかになった。 As shown in FIG. 11, the photocatalyst member subjected to the etching step had higher hydrophilicity than before the etching step. Specifically, the contact angle was less than 30 ° when irradiated with ultraviolet rays for 30 minutes. Therefore, the photocatalyst member of the present invention can be improved in hydrophilicity by performing the etching step, and thus it has been clarified that higher photocatalytic properties can be obtained.
また、実施例（３０）に記載された組成によって作製された光触媒部材について、ＨＦ濃度が４．６％（質量百分率）のフッ酸溶液（和光純薬工業株式会社製）に１０秒間浸漬させ、エッチング工程を行った後、１ｍＷ／ｃｍ２の照度で親水性を評価し、図１２に示した。Moreover, about the photocatalyst member produced by the composition described in Example (30), it was immersed in the hydrofluoric acid solution (made by Wako Pure Chemical Industries Ltd.) whose HF concentration is 4.6% (mass percentage) for 10 seconds, After performing the etching step, the hydrophilicity was evaluated at an illuminance of 1 mW / cm 2 and shown in FIG.
また、実施例（１、７、１５〜１６、２０、２２〜３０）に記載された組成の釉薬用ガラスによって作製された光触媒部材について、光沢度が６０°の入射角の測定を行った。光沢度は、表面に光をあてた時の反射の程度を表す量で、測定部分での反射光の強さの比として求めることができる。具体的には株式会社堀場製作所の光沢計グロスチェッカ（ＩＧ−３３１）によって測定した。比較例として市販の釉薬付きのタイルを測定した。 Moreover, about the photocatalyst member produced with the glass for glazes of the composition described in the Example (1, 7, 15-16, 20, 22-30), the incident angle whose glossiness is 60 degrees was measured. The glossiness is an amount representing the degree of reflection when light is applied to the surface, and can be obtained as a ratio of the intensity of reflected light at the measurement portion. Specifically, it was measured with a gloss meter gloss checker (IG-331) manufactured by HORIBA, Ltd. As a comparative example, a commercially available tile with glaze was measured.
図１３に測定結果を示す。それぞれ６０以上の光沢を有していた。より具体的には６４以上の光沢を有していた。比較とした市販のタイルの光沢が６１であるため、本発明の光触媒部材は市販のタイルと同等の高い光沢を有していることが確認された。 FIG. 13 shows the measurement results. Each had a gloss of 60 or more. More specifically, it had a gloss of 64 or more. Since the gloss of the commercial tile used as a comparison was 61, it was confirmed that the photocatalyst member of the present invention had a high gloss equivalent to that of the commercial tile.
また、実施例（２３）に記載された組成によって作製された光触媒部材について、ＨＦ濃度が４．６％（質量百分率）のフッ酸溶液（和光純薬工業株式会社製）に１０秒間浸漬させ、エッチング工程を行った。エッチング工程を行った後、光沢度を評価し、図１４に示した。 Moreover, about the photocatalyst member produced by the composition described in Example (23), it was immersed in the hydrofluoric acid solution (made by Wako Pure Chemical Industries Ltd.) whose HF concentration is 4.6% (mass percentage) for 10 seconds, An etching process was performed. After the etching process, the glossiness was evaluated and is shown in FIG.
エッチング工程を行った光触媒部材は図１４に表されるように、エッチング工程前に比べて光沢度に有意な変化は認められなかった。具体的にはエッチング工程前後においてどちらも６０°の光沢度において１７５以上の光沢度を有していた。そのため、本発明の光触媒部材は、エッチング工程を行うことで分解活性指数等の光触媒としての性能を向上させても、光沢度が低下することはないことが明らかになった。 As shown in FIG. 14, the photocatalyst member subjected to the etching process did not have a significant change in the glossiness compared to before the etching process. Specifically, both had a glossiness of 175 or more at a glossiness of 60 ° before and after the etching process. Therefore, it has been clarified that the photocatalyst member of the present invention does not lower the glossiness even when the performance as a photocatalyst such as a decomposition activity index is improved by performing an etching process.
以上のとおり、本発明の実施例の釉薬用ガラス及び／又は釉薬用結晶化ガラスを用いた釉薬層は、光触媒の結晶が容易に析出し、しかも高い酸化分解能力と親水性を有することが可能であり、優れた光触媒部材を提供することが確認された。 As described above, the glaze layer using the glaze glass and / or glaze crystallized glass according to the embodiment of the present invention can easily precipitate photocatalyst crystals, and can have high oxidative decomposition ability and hydrophilicity. Thus, it was confirmed that an excellent photocatalytic member was provided.
以上、本発明を例示の目的で詳細に説明したが、本実施例はあくまで例示の目的のみであって、本発明の思想及び範囲を逸脱することなく多くの改変を当業者により成し得ることが理解されよう。本国際出願は、２０１０年３月１日に出願された日本国特許出願２０１０−０４４３９７号、２０１０年５月１８日に出願された日本国特許出願２０１０−１１４３９５号、及び２０１０年７月８日に出願された日本国特許出願２０１０−１５５５７５号に基づく優先権を主張するものであり、その全内容をここに援用する。 Although the present invention has been described in detail for the purpose of illustration, this embodiment is only for the purpose of illustration, and many modifications can be made by those skilled in the art without departing from the spirit and scope of the present invention. Will be understood. This international application includes Japanese Patent Application 2010-044397 filed on March 1, 2010, Japanese Patent Application 2010-114395 filed on May 18, 2010, and July 8, 2010. Claiming priority based on Japanese Patent Application No. 2010-155575 filed in Japan, the entire contents of which are incorporated herein by reference.
（ａ） 基材上に釉薬（釉薬（２））を配置した状態
（ｂ） 基材上に溶融形成されたガラス質の釉薬層
（ｃ） ガラス質の釉薬層に光触媒結晶を析出した状態
１０ 釉薬用ガラス
２０ 釉薬塗布層
２１ ガラス質の釉薬層
２２ 結晶化後の釉薬層
３０ 基材
４０ 光触媒結晶(A) State in which glaze (glaze (2)) is arranged on the substrate (b) Glassy glaze layer melt-formed on the substrate (c) State in which photocatalytic crystals are deposited on the glassy glaze layer 10 Glaze glass 20 Glaze coating layer 21 Glassy glaze layer 22 Glazed glaze layer 30 Base material 40 Photocatalytic crystal
Claims (25)
Ａｌ２Ｏ３成分を０〜３０％、
Ｇａ２Ｏ３成分を０〜３０％、
Ｉｎ２Ｏ３成分を０〜３０％、
ＺｒＯ２成分を０〜２０％、
ＳｎＯ成分を０〜２０％、
Ｂｉ２Ｏ３成分及び／又はＴｅＯ２成分を０〜２０％、
ＭｏＯ成分を０〜３０％、
Ｌｎ２Ｏ３成分を０〜３０％（ＬｎはＹ、Ｃｅ、Ｌａ、Ｎｄ、Ｇｄ、Ｄｙ、Ｙｂから選ばれる一種以上）、
ＭｘＯｙ成分を０〜１０％（Ｍは、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、及びＮｉから選ばれる一種以上とし、ｘ及びｙはそれぞれｘ：ｙ＝２：（Ｍの価数）を満たす最小の自然数とする）
Ａｓ２Ｏ３成分及び／又はＳｂ２Ｏ３成分を０〜５％、
含有する、請求項１から３いずれか記載の釉薬用ガラス。In mol% of oxide equivalent composition,
0 to 30% of Al 2 O 3 component,
Ga 2 O 3 component 0-30%,
0-30% of In 2 O 3 component,
0 to 20% of ZrO 2 component,
0 to 20% of SnO component,
Bi 2 O 3 component and / or TeO 2 component 0-20%
0-30% of MoO component,
0-30% of Ln 2 O 3 component (Ln is one or more selected from Y, Ce, La, Nd, Gd, Dy, Yb),
M x O y component 0 to 10% (M is at least one selected from V, Cr, Mn, Fe, Co, and Ni, and x and y are each x: y = 2: (valence of M)) The smallest natural number satisfying
0 to 5% of As 2 O 3 component and / or Sb 2 O 3 component,
The glass for glazes in any one of Claim 1 to 3 to contain.
Ｆ、Ｃｌ、Ｂｒ、Ｓ、Ｎ、及びＣから選ばれる１種以上の非金属元素成分を０．０１〜１０％含有する、請求項１から４いずれか記載の釉薬用ガラス。In the externally divided mass% with respect to the total amount of glass of oxide equivalent composition,
The glass for glazes in any one of Claim 1 to 4 containing 0.01 to 10% of 1 or more types of nonmetallic element components chosen from F, Cl, Br, S, N, and C.
Ｃｕ、Ａｇ、Ａｕ、Ｐｄ、Ｐｔ、Ｒｕ、Ｒｅ及びＲｈから選ばれる１種以上の金属元素成分を０．００１〜５％含有する、請求項１から５いずれか記載の釉薬用ガラス。In the externally divided mass% with respect to the total amount of glass of oxide equivalent composition,
The glass for glaze according to any one of claims 1 to 5, comprising 0.001 to 5% of one or more metal element components selected from Cu, Ag, Au, Pd, Pt, Ru, Re, and Rh.
Ａｌ２Ｏ３成分を０〜３０％、
Ｇａ２Ｏ３成分を０〜３０％、
Ｉｎ２Ｏ３成分を０〜３０％、
ＺｒＯ２成分を０〜２０％、
ＳｎＯ成分を０〜２０％、
Ｂｉ２Ｏ３成分及び／又はＴｅＯ２成分を０〜２０％、
ＭｏＯ成分を０〜３０％、
Ｌｎ２Ｏ３成分を０〜３０％（ＬｎはＹ、Ｃｅ、Ｌａ、Ｎｄ、Ｇｄ、Ｄｙ、Ｙｂから選ばれる一種以上）、
ＭｘＯｙ成分を０〜１０％（Ｍは、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、及びＮｉから選ばれる一種以上とし、ｘ及びｙはそれぞれｘ：ｙ＝２：（Ｍの価数）を満たす最小の自然数とする）、
Ａｓ２Ｏ３成分及び／又はＳｂ２Ｏ３成分を０〜５％、
含有する、請求項１２から１６いずれか記載の部材。The glaze layer is a mol% of the oxide equivalent composition,
0 to 30% of Al 2 O 3 component,
Ga 2 O 3 component 0-30%,
0-30% of In 2 O 3 component,
0 to 20% of ZrO 2 component,
0 to 20% of SnO component,
Bi 2 O 3 component and / or TeO 2 component 0-20%
0-30% of MoO component,
0-30% of Ln 2 O 3 component (Ln is one or more selected from Y, Ce, La, Nd, Gd, Dy, Yb),
M x O y component 0 to 10% (M is at least one selected from V, Cr, Mn, Fe, Co, and Ni, and x and y are each x: y = 2: (valence of M)) The smallest natural number that satisfies
0 to 5% of As 2 O 3 component and / or Sb 2 O 3 component,
The member according to any one of claims 12 to 16, which is contained.
Priority Applications (1)
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| JP2012503118A JP5820799B2 (en) | 2010-03-01 | 2011-02-25 | Glaze glass, glaze, and photocatalyst member |
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| JP2010155575 | 2010-07-08 | ||
| JP2010155575 | 2010-07-08 | ||
| PCT/JP2011/054387 WO2011108472A1 (en) | 2010-03-01 | 2011-02-25 | Glass for glaze, glaze, and photocatalyst member |
| JP2012503118A JP5820799B2 (en) | 2010-03-01 | 2011-02-25 | Glaze glass, glaze, and photocatalyst member |
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| JP5820799B2 (en) | 2015-11-24 |
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