JPH1135342A - Polyfunctional glass and its production - Google Patents
Polyfunctional glass and its productionInfo
- Publication number
- JPH1135342A JPH1135342A JP9190294A JP19029497A JPH1135342A JP H1135342 A JPH1135342 A JP H1135342A JP 9190294 A JP9190294 A JP 9190294A JP 19029497 A JP19029497 A JP 19029497A JP H1135342 A JPH1135342 A JP H1135342A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- film
- tio
- glass
- electronegativity
- 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.)
- Pending
Links
- 239000011521 glass Substances 0.000 title claims abstract description 42
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 239000000758 substrate Substances 0.000 claims abstract description 16
- 239000005361 soda-lime glass Substances 0.000 claims abstract description 13
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 9
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 8
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 8
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 8
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 7
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 26
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 26
- 239000002184 metal Substances 0.000 claims description 23
- 238000000576 coating method Methods 0.000 claims description 22
- 239000011248 coating agent Substances 0.000 claims description 17
- 239000010419 fine particle Substances 0.000 claims description 13
- 229910052719 titanium Inorganic materials 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- -1 organic acid salt Chemical class 0.000 claims description 7
- 229910052706 scandium Inorganic materials 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 13
- 239000011941 photocatalyst Substances 0.000 abstract description 11
- 239000003513 alkali Substances 0.000 abstract description 7
- 239000000377 silicon dioxide Substances 0.000 abstract description 7
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 7
- 229910052681 coesite Inorganic materials 0.000 abstract description 4
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 4
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 4
- 229910052682 stishovite Inorganic materials 0.000 abstract description 4
- 229910052905 tridymite Inorganic materials 0.000 abstract description 4
- 239000012528 membrane Substances 0.000 abstract 3
- 229910052772 Samarium Inorganic materials 0.000 abstract 1
- 230000003993 interaction Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 77
- 239000000243 solution Substances 0.000 description 26
- 239000010936 titanium Substances 0.000 description 25
- 230000001699 photocatalysis Effects 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- 150000004703 alkoxides Chemical class 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000005357 flat glass Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 125000005595 acetylacetonate group Chemical group 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000013003 hot bending Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 2
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- DVQHRBFGRZHMSR-UHFFFAOYSA-N sodium methyl 2,2-dimethyl-4,6-dioxo-5-(N-prop-2-enoxy-C-propylcarbonimidoyl)cyclohexane-1-carboxylate Chemical compound [Na+].C=CCON=C(CCC)[C-]1C(=O)CC(C)(C)C(C(=O)OC)C1=O DVQHRBFGRZHMSR-UHFFFAOYSA-N 0.000 description 2
- 238000005496 tempering Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- RASBDVLERRNNLJ-UHFFFAOYSA-N CCCCO[Ti] Chemical compound CCCCO[Ti] RASBDVLERRNNLJ-UHFFFAOYSA-N 0.000 description 1
- 102100024462 Cyclin-dependent kinase 4 inhibitor B Human genes 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 101000980919 Homo sapiens Cyclin-dependent kinase 4 inhibitor B Proteins 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229940072049 amyl acetate Drugs 0.000 description 1
- PGMYKACGEOXYJE-UHFFFAOYSA-N anhydrous amyl acetate Natural products CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000005328 architectural glass Substances 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000005340 laminated glass Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000007777 multifunctional material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000000843 powder 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
- 238000007650 screen-printing Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 239000005341 toughened glass Substances 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3417—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials all coatings being oxide coatings
-
- 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
-
- 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
- C03C2217/47—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase consisting of a specific material
- C03C2217/475—Inorganic materials
- C03C2217/477—Titanium oxide
-
- 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
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、建築用、自動車用
等の窓材、さらには鏡等の各種の分野のガラス物品にお
いて用いられる多機能ガラスおよびその製造方法に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a multifunctional glass for use in glass materials in various fields such as window materials for buildings and automobiles, and mirrors and the like, and a method for producing the same.
【０００２】[0002]
【従来の技術】最近、防汚・消臭・抗菌・親水等のため
にガラスの表面に光触媒機能を有する被膜を形成するこ
とが行われている。例えば、特開平５ー２５３５４４号
公報に記載のアナターゼ型ＴiＯ2を主体とする光触媒微
粉末をその一部がバインダ層表面から露出するようにし
た板状部材、特開平７−２３２０８０号公報に記載の光
触媒微粒子がＴiＯ2、ＺnＯ、ＳrＴiＯ2、Ｆe2Ｏ3、Ｗ
Ｏ3、ＦeＴiＯ2、Ｂi2Ｏ3、ＳnＯ2等であり、光触媒粒
子の間隙充填粒子がＳn、Ｔi、Ａg、Ｃu、Ｚn、Ｆe、Ｐ
t、Ｃo、Ｎiの金属または酸化物である光触媒機能を有
する多機能材、特開平９−５９０４２号公報記載の光触
媒性の平均結晶粒子径が約０.１μm以下のＴiＯ2の粒子
を含有する防曇性被膜で覆われた透明基材等が知られて
いる。2. Description of the Related Art Recently, a film having a photocatalytic function has been formed on a glass surface for antifouling, deodorizing, antibacterial, hydrophilic, and the like. For example, a plate-like member which is adapted a part photocatalyst fine powder mainly comprising anatase TiO 2 described in JP-A-5 over 253,544 are exposed from the binder layer surface described in Japanese Patent Laid-Open No. 7-232080 Are fine particles of TiO 2 , ZnO, SrTiO 2 , Fe 2 O 3 , W
O 3 , FeTiO 2 , Bi 2 O 3 , SnO 2, etc., and the gap filling particles of the photocatalyst particles are Sn, Ti, Ag, Cu, Zn, Fe, P
t, Co, multifunctional material having a photocatalytic function is a metal or an oxide of Ni, average crystal grain size of the photocatalytic Hei 9-59042 JP contains about 0.1μm or less of the TiO 2 particles A transparent substrate or the like covered with an antifogging film is known.
【０００３】また従来、ガラス表面に各種の機能性膜を
被覆するに際し、ガラスから機能性膜へのナトリウムイ
オンの移行を防止するために、該機能性膜の下層にアン
ダーコート膜を形成する事が知られている。例えば、特
開平４−１８２３７号公報記載のＺnＯを含有した紫外
線吸収膜の下層にＳiＯ2を主成分とする金属酸化物被膜
を設けた表面処理ガラス、特開平７−３１５８８０号公
報記載のガラス板表面にＳiＯ2を主成分とする薄膜、Ｔ
iＯ2を主成分とする薄膜、ＳnＯ2を主成分とする薄膜を
順次被覆させた透明導電膜付きガラス板、特開平８−１
９００８８号公報記載のガラス基板からのアルカリ金属
イオンの拡散を防止する金属酸化物の障壁層と該障壁層
の上層の金属含有被覆からなるガラス物品等が知られて
いる。[0003] Conventionally, when coating various functional films on a glass surface, an undercoat film is formed under the functional film in order to prevent sodium ions from migrating from the glass to the functional film. It has been known. For example, surface-treated glass having a metal oxide film containing SiO 2 as a main component in the lower layer of the ultraviolet absorbing film containing ZnO of JP-A 4-18237 JP, a glass plate of JP-A 7-315880 JP On the surface, a thin film mainly composed of SiO 2 , T
iO 2 as main components a thin film, the transparent conductive film-attached glass plate is sequentially coated film on the basis of SnO 2, JP-A-8-1
No. 90088 discloses a glass article or the like comprising a metal oxide barrier layer for preventing diffusion of alkali metal ions from a glass substrate and a metal-containing coating on the barrier layer.
【０００４】[0004]
【発明が解決しようとする課題】上記従来の光触媒膜を
ガラス上に形成した多機能ガラスにおいては、該光触媒
膜をガラス表面に直接被覆する場合、高温で処理すると
ガラス中に含まれるナトリウムイオンが該光触媒膜に移
行し、光触媒膜のＴiＯ2の酸化作用を促進する電子を中
和してしまい、上述の光触媒機能が損なわれてしまう欠
点があった。In the above-mentioned conventional multifunctional glass having a photocatalytic film formed on glass, when the photocatalytic film is directly coated on the glass surface, sodium ions contained in the glass can be reduced by high-temperature treatment. photocatalyst film proceeds to, will neutralize the electrons to accelerate the oxidation of the TiO 2 photocatalyst film, the above-described photocatalytic function is a drawback that impairs.
【０００５】また、光触媒膜の下層に、アンダーコート
層としてのＳiＯ2膜を被覆した場合には光触媒膜と該Ｓ
iＯ2膜との密着性が充分でなく、耐久性評価試験で光触
媒膜が剥離してしまう欠点が生じた。When an SiO 2 film as an undercoat layer is coated under the photocatalytic film, the photocatalytic film and the S
Adhesion with the SiO 2 film was not sufficient, and the photocatalytic film peeled off in a durability evaluation test.
【０００６】[0006]
【課題を解決するための手段】本発明は、従来のかかる
課題に鑑みてなしたものであって、アンダーコート層の
組成を種々検討した結果、光触媒膜中のＴi元素と電気
陰性度が同じか或いは近似した金属元素をアンダーコー
ト膜中に含有させることにより、該金属元素と光触媒膜
中のＴiとの親和性が高まり、アンダーコート層と光触
媒膜間の密着強度が著しく向上することを見出した。SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned conventional problems, and as a result of various studies on the composition of the undercoat layer, it has been found that the Ti element in the photocatalytic film has the same electronegativity as the Ti element. It has been found that by including a metal element which is similar or similar in the undercoat film, the affinity between the metal element and Ti in the photocatalytic film is increased, and the adhesion strength between the undercoat layer and the photocatalytic film is significantly improved. Was.
【０００７】本発明は、ソーダライムガラス基板の表面
に、第１層としてＴi及びＴi元素の電気陰性度に近似し
た電気陰性度をもつ金属元素を少なくとも１種以上含む
ＳiＯ2膜を成膜し、その上に第２層としてＴiＯ2膜また
はＴiＯ2微粒子を分散したＳiＯ2膜を成膜した多機能ガ
ラスおよびその製造方法であって、アンダーコート層で
ある第１層にＴi及びＴiの電気陰性度に近似の金属元素
を含有させることにより、アンダーコート層と光触媒膜
との密着性が向上し、耐温水性、耐湿性、耐アルカリ性
などの耐久性に優れた光触媒機能を有する多機能ガラス
を容易に得ることができるものである。According to the present invention, an SiO 2 film containing at least one kind of Ti and a metal element having an electronegativity close to the electronegativity of the Ti element is formed as a first layer on the surface of a soda lime glass substrate. , a TiO 2 film or multifunction glass and a manufacturing method thereof dispersed the SiO 2 film of TiO2 particles was deposited as a second layer thereon, Ti and Ti of the electronegative first layer is an undercoat layer Incorporating a metal element that is close to the degree, the adhesion between the undercoat layer and the photocatalytic film is improved, and a multifunctional glass having a photocatalytic function with excellent durability such as warm water resistance, moisture resistance, alkali resistance, etc. It can be easily obtained.
【０００８】なお、上記の電気陰性度は、分子内の結合
に与かる原子が電子を引きつける能力を意味し、例えば
Ｔi元素の電気陰性度は「Ｊ.Ｉnorg.Ｎucl.Ｃhem.,17,2
15(1961)」によれば１.５４である。The above-mentioned electronegativity means the ability of an atom participating in a bond in a molecule to attract an electron. For example, the electronegativity of a Ti element is described in J. Inorg. Nucl. Chem., 17, 2
15 (1961) "is 1.54.
【０００９】なお、第１層中のＳiを除く金属元素の電
気陰性度は、１.３〜１.７が好ましい。また、第１層中
のＳiを除く金属元素は、Ｔi、Ｚr、Ａl、Ｖ、Ｃr、Ｍ
n、Ｚn、Ｓcであることが望ましく、各金属元素の電気
陰性度は「Ｊ.Ｉnorg.Ｎucl.Ｃhem.,17,215(1961)」」
によれば、上記のＴi元素以外は、Ｚr：１.３３、Ａl：
１.６１、Ｖ：１.６３、Ｃr：１.６６、Ｍn：１.５５、
Ｚn：１.６５、Ｓc：１.３６である。The electronegativity of the metal element other than Si in the first layer is preferably from 1.3 to 1.7. The metal elements other than Si in the first layer are Ti, Zr, Al, V, Cr, M
n, Zn, and Sc, and the electronegativity of each metal element is “J. Inorg. Nucl. Chem., 17, 215 (1961)”.
According to the above, Zr: 1.33, Al:
1.61, V: 1.63, Cr: 1.66, Mn: 1.55,
Zn: 1.65 and Sc: 1.36.
【００１０】また、第１層中のＳiを除く金属元素の含
有量は、１〜３０モル％であることが好ましい。なお、
各金属元素の最適含有率は、Ｔi：１〜１０モル％、Ｚ
r：２〜１５モル％、Ａl：５〜１２モル％、Ｖ：５〜９
モル％、Ｃr：６〜１０モル％、Ｍn：１〜９モル％、Ｚ
n：５〜１０モル％、Ｓc：１〜７モル％である。[0010] The content of the metal element excluding Si in the first layer is preferably 1 to 30 mol%. In addition,
The optimum content of each metal element is as follows: Ti: 1 to 10 mol%;
r: 2 to 15 mol%, Al: 5 to 12 mol%, V: 5 to 9
Mol%, Cr: 6 to 10 mol%, Mn: 1 to 9 mol%, Z
n: 5 to 10 mol%, Sc: 1 to 7 mol%.
【００１１】さらに、第２層がＴiＯ2微粒子含有ＳiＯ2
膜の場合のＴiＯ2微粒子の含有量は、１０〜９０重量％
であることが適する。また本発明は、ソーダライムガラ
ス基板の表面に、第１層としてＴi及びＴi元素の電気陰
性度に近似した電気陰性度を持つ金属元素の化合物を少
なくとも１種以上含むＳiＯ2溶液よりなる塗布液を被覆
し乾燥した後、ＴiＯ2前駆体またはＴiＯ2微粒子を分散
したＳiＯ2よりなる第２層用溶液を塗布し、乾燥・焼成
してなる多機能ガラスの製造方法に関する。Further, the second layer is made of SiO 2 containing TiO 2 fine particles.
The content of the TiO 2 fine particles in the case of the film is 10 to 90% by weight.
Is suitable. The present invention also provides a coating solution comprising a SiO 2 solution containing at least one compound of Ti and a metal element having an electronegativity close to the electronegativity of the Ti element as a first layer on the surface of a soda lime glass substrate. And then drying, and then applying a second layer solution composed of SiO 2 in which TiO 2 precursors or TiO 2 fine particles are dispersed, followed by drying and firing.
【００１２】第１層用塗布液は、Ｔi、Ｚr、Ａl、Ｖ、
Ｃr、Ｍn、Ｚn、Ｓcの硝酸塩、有機酸塩、アセチルアセ
トナート類、アルコキシド類を含んだアルコキシシラン
類の加水分解物のうちの少なくとも１種以上よりなるも
のが好ましい。The coating liquid for the first layer is Ti, Zr, Al, V,
It is preferable to use at least one selected from the group consisting of hydrolysates of nitrates of Cr, Mn, Zn and Sc, organic acid salts, acetylacetonates, and alkoxysilanes including alkoxides.
【００１３】さらに、第１層中のＳiを除く金属元素の
含有比率は、塗布液の固形分の１〜３０モル％であるこ
とが適する。Further, the content ratio of the metal element excluding Si in the first layer is preferably 1 to 30 mol% of the solid content of the coating solution.
【００１４】[0014]
【発明の実施の形態】ガラス表面に形成する、アンダー
コートとしての第１層、光触媒機能としての第２層より
なる多機能ガラスは次のようにして得る。DESCRIPTION OF THE PREFERRED EMBODIMENTS A multifunctional glass formed on a glass surface and having a first layer as an undercoat and a second layer as a photocatalytic function is obtained as follows.
【００１５】ソーダライムガラス基板としては、自動車
用ならびに建築用ガラス等に通常用いられている普通板
ガラス、所謂フロート板ガラスなどであり、クリアをは
じめグリ−ン、ブロンズ等各種着色ガラスや各種機能性
ガラス、強化ガラスやそれに類するガラス、合せガラス
のほか複層ガラス等、さらに平板あるいは曲げ板等各種
板ガラス製品として使用できることは言うまでもない。
また板厚としては例えば約１.０ｍｍ程度以上約１２mm
程度以下であり、建築用としては約２.０mm程度以上約
１０mm程度以下が好ましく、自動車用としては約１.５m
m程度以上約６.０mm程度以下が好ましく、より好ましく
は約２.０mm程度以上約４.０mm程度以下のガラスであ
る。The soda-lime glass substrate is a common plate glass or so-called float plate glass which is generally used for automobiles and architectural glass, etc., and various colored glass such as clear, green and bronze, and various functional glasses. Needless to say, it can be used as a tempered glass, a glass similar thereto, a laminated glass, a double-glazed glass, and various flat glass products such as a flat plate or a bent plate.
The thickness is, for example, about 1.0 mm or more and about 12 mm.
About 2.0 mm or more and about 10 mm or less for architectural use and about 1.5 m for automobile use.
The glass is preferably about m or more and about 6.0 mm or less, more preferably about 2.0 mm or more and about 4.0 mm or less.
【００１６】Ｔi元素に近似の電気陰性度を有する元素
としては、Ｚr、Ａl、Ｖ、Ｃr、Ｍn、Ｚn、Ｓc等が含ま
れる。なお、第１層中のＳiを除く金属元素は、無色透
明および耐酸性が必要な場合には、Ｔi、Ｚr、Ａlが好
ましい。Elements having an electronegativity close to that of the Ti element include Zr, Al, V, Cr, Mn, Zn, Sc and the like. The metal element other than Si in the first layer is preferably Ti, Zr or Al when colorless and transparent and acid resistance are required.
【００１７】また、第１層のＳiＯ2膜、第２層のＴiＯ2
膜あるいはＳiＯ2膜の主な原料としては、前記金属アル
コキド類であるが、具体例としては、Ｓiアルコキシド
類が、テトラエトキシシラン、テトラメトキシシラン、
モノメチルトリエトキシシラン、モノメチルトリメトキ
シシラン、ジメチルジメトキシシラン、ジメチルジエト
キシシラン、その他のテトラアルコキシシラン化合物、
その他のアルキルアルコキシシラン化合物、またＴiア
ルコキシド類は、テトライソプロポキシチタン、テトラ
ノルマルブトキシチタン、トリイソプロポキシチタンモ
ノアセチルアセトナ−ト等が使用できる。A first layer of SiO 2 film and a second layer of TiO 2
The main raw material of the film or the SiO 2 film is the above-mentioned metal alkoxides. Specific examples include Si alkoxides such as tetraethoxysilane, tetramethoxysilane,
Monomethyltriethoxysilane, monomethyltrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, other tetraalkoxysilane compounds,
As other alkylalkoxysilane compounds and Ti alkoxides, tetraisopropoxytitanium, tetranormal butoxytitanium, triisopropoxytitanium monoacetylacetonate and the like can be used.
【００１８】さらに、第１層に添加する金属元素は、上
記と同様にＴi、Ｚr、Ａl、Ｖ、Ｃr、Ｍn、Ｚn、Ｓc等
の金属アルコキシド類、アセチルアセトナート類、硝酸
塩、有機酸塩のうちの少なくとも１種を用いることがで
き、上記第１層のＳiＯ2の原料であるアルコキシシラン
類の加水分解物と混合して用いる。Further, the metal elements added to the first layer include metal alkoxides such as Ti, Zr, Al, V, Cr, Mn, Zn and Sc, acetylacetonates, nitrates and organic acid salts in the same manner as described above. At least one of them can be used, and is used by mixing with a hydrolyzate of alkoxysilanes, which is a raw material of SiO 2 for the first layer.
【００１９】また、希釈溶媒としては、アルコ−ル系溶
媒が好ましく、具体例としては、メタノ−ル、エタノ−
ル、エタノ−ル、プロパノ−ル、ブタノ−ル、エチレン
グリコ−ル、ヘキシレングリコ−ル、さらには酢酸エチ
ル、酢酸ブチル、酢酸アミルなどのエステル類、さらに
はメチルセロソルブ、エチルセロソルブ、ブチルセロソ
ルブなどのセロソルブ類及びこれらを混合した溶媒、さ
らには増粘剤としてポリエチレングリコ−ル（平均分子
量２００）、ポリプロピレングリコ−ル（平均分子量４
００）等を加えても良いし、レベリング剤としてジメチ
ルシリコーンなどのメチルシリコーン類やフッ素系レベ
リング剤を適量加えても良い。本来溶液中に含まれるア
ルコ−ル系やセロソルブ系のもの単独または混合物を、
該溶液の蒸発速度や被膜粘度を勘案して選択すればよ
い。The diluting solvent is preferably an alcoholic solvent, and specific examples thereof include methanol and ethanol.
, Ethanol, propanol, butanol, ethylene glycol, hexylene glycol, and esters such as ethyl acetate, butyl acetate, and amyl acetate; further, methyl cellosolve, ethyl cellosolve, butyl cellosolve, and the like. Cellosolves and their mixed solvents, as well as polyethylene glycol (average molecular weight 200) and polypropylene glycol (average molecular weight 4
00) or the like, or an appropriate amount of a methyl silicone such as dimethyl silicone or a fluorine-based leveling agent as a leveling agent. Alcohols or cellosolves, which are originally contained in the solution, alone or as a mixture,
The solution may be selected in consideration of the evaporation rate of the solution and the viscosity of the film.
【００２０】さらに、第１層中の塗布液において、Ｓi
を除く金属元素含有比率が塗布液の全固形分量に対し、
１乃至３０モル％を少なくとも含むものであることとし
たのは、３０モル％以上であれば、第１層のアンダーコ
ート膜のＮaイオンのパッシベーション効果が低減する
ことにより光活性が著しく低下し、１モル％以下では光
触媒膜の密着性が低下してしまう。Further, in the coating solution in the first layer, Si
Metal element content ratio except for the total solid content of the coating solution,
The reason for containing at least 1 to 30 mol% is that if it is 30 mol% or more, the passivation effect of Na ions in the undercoat film of the first layer is reduced, so that the photoactivity is remarkably reduced and 1 mol % Or less, the adhesion of the photocatalyst film is reduced.
【００２１】第２層がＴiＯ2微粒子含有ＳiＯ2膜の場
合、それに添加するＴiＯ2微粒子の含有量は、１０〜９
０重量％が好ましい。また、塗布法としては、特に限定
されるものではないが、生産性などの面からは例えばス
ピンコート法あるいはディップコ−ト法、またリバ−ス
コ−ト法、フレキソ印刷法、その他のロールコート法で
あり、さらにはノズルコ−ト法、スプレーコ−ト法、ス
クリーン印刷法などが適宜採用し得るものである。これ
ら塗布法で塗布成膜する際の塗布液中の固形分濃度とし
ては約１〜３０重量％程度で、塗布液粘度としては１〜
１００cP 程度が好ましい。[0021] If the second layer of TiO 2 fine particles containing SiO 2 film, the content of TiO 2 fine particles to be added thereto, 10-9
0% by weight is preferred. The coating method is not particularly limited, but from the viewpoint of productivity and the like, for example, a spin coating method or a dip coating method, a reverse coating method, a flexographic printing method, and other roll coating methods. Further, a nozzle coating method, a spray coating method, a screen printing method, and the like can be appropriately employed. The solid content concentration in the coating liquid when forming a coating film by these coating methods is about 1 to 30% by weight, and the coating liquid viscosity is 1 to 30% by weight.
About 100 cP is preferable.
【００２２】またさらに、第１層及び第２層の塗布後の
乾燥処理としては、乾燥温度が常温〜３００℃程度で乾
燥時間が０.５ 〜６０分間程度が好ましく、より好まし
くは前記乾燥温度が１００〜２５０℃程度で乾燥時間が
1〜３０分間程度である。また、第２層の乾燥後の焼成
処理としては、焼成温度が４００ 〜７００ ℃程度で焼
成時間が１〜３０分間程度が好ましく、さらに前記ガラ
スの熱強化または／および熱曲げ加工時に同時に行うこ
とがよく、前記ガラスの熱強化または／および熱曲げ加
工は、温度が５５０ 〜７００ ℃程度で時間が０.５ 〜
１０分間程度行うことがより好ましい。Further, the drying treatment after the application of the first layer and the second layer is preferably performed at a drying temperature of about room temperature to about 300 ° C. and a drying time of about 0.5 to 60 minutes, more preferably the aforementioned drying temperature. But the drying time is about 100-250 ° C
It is about 1 to 30 minutes. The baking treatment after the drying of the second layer is preferably performed at a baking temperature of about 400 to 700 ° C. and a baking time of about 1 to 30 minutes, and is performed simultaneously with the heat strengthening and / or hot bending of the glass. Preferably, the heat strengthening and / or hot bending of the glass is performed at a temperature of about 550 to 700 ° C. for a time of 0.5 to 500 ° C.
More preferably, it is performed for about 10 minutes.
【００２３】第１層の膜厚は、約５０〜２００nm 程度
であり、５０nm未満であれば、ガラス基板からのＮaイ
オンの影響で第２層の光触媒機能が低下し、２００nm
を超えると経済的にも無駄であり、クラックの発現の要
因となるためである。さらに好ましくは約８０〜１６０
nm 程度である。The thickness of the first layer is about 50 to 200 nm. If the thickness is less than 50 nm, the photocatalytic function of the second layer is reduced by the influence of Na ions from the glass substrate.
It is because it is economically useless if it exceeds the number, and it becomes a factor of the appearance of cracks. More preferably, about 80 to 160
nm.
【００２４】第２層の膜厚は、ＴiＯ2の含有量にもよる
が、約５０〜７００nm程度が好ましい。なお、５０nm以
下では充分な光活性が得られず、７００nm以上では光活
性の向上は得られず、膜強度は低下する。The thickness of the second layer is preferably about 50 to 700 nm, though it depends on the content of TiO 2 . If the thickness is 50 nm or less, sufficient photoactivity cannot be obtained, and if it is 700 nm or more, no improvement in photoactivity can be obtained, and the film strength decreases.
【００２５】第２層の光触媒膜の下層に、Ｔi元素の電
気陰性度に近似した金属元素を含有するＳiＯ2膜を第１
層として設けることにより、ソーダライムガラス基板か
らのナトリウムイオンの膜中への移行を防止し、光触媒
機能を十分に発揮させるとともに、第１層と第２層の膜
間の密着強度が強固になり、耐温水性、耐湿性、耐アル
カリ性、耐温塩水性等の耐久性を向上させ、厳しい環境
での長期使用に耐え、より確実でかつ安定した品質の多
機能ガラスとなる。An SiO 2 film containing a metal element having a similarity to the electronegativity of the Ti element is formed under the second photocatalytic film as the first layer.
By providing the layer, sodium ions from the soda lime glass substrate are prevented from migrating into the film, and the photocatalytic function is sufficiently exhibited, and the adhesion strength between the first and second layers is strengthened. It improves durability such as warm water resistance, moisture resistance, alkali resistance, and salt water resistance, withstands long-term use in harsh environments, and becomes a more reliable and stable quality multifunctional glass.
【００２６】[0026]
【実施例】以下、実施例により本発明を具体的に説明す
る。但し本発明はこれらの実施例に限定されるものでは
ない。The present invention will be described below in detail with reference to examples. However, the present invention is not limited to these examples.
【００２７】[0027]
【実施例１】ゾルゲル溶液ＭＴＳ-ＴＩ-２０(Ｓｉ／Ｔ
ｉ＝７５／２５、固形分濃度２０重量％、大八化学工業
製)１０ｇ,ゾルゲル溶液ＭＴＳ-２(Ｓｉ：１００％、固
形分濃度２０重量％、大八化学工業製）８０ｇを、希釈
溶剤としての酢酸イソブチル(３)-ｎ-ブタノール(１)混
合溶媒で１０倍に希釈し、第１層用の塗布液とした。こ
れをスピンコーターにより１５cm□の厚さ３.５mｍのソ
ーダライムガラス基板上に２cc滴下し成膜した後、２５
０℃で３０分乾燥後、室温までに冷却し、膜厚１００nm
のＴiＯ2−ＳiＯ2膜を得た。次に、この第１層の膜が形
成されたガラスサンプルをディップ法によりチタンアル
コキシドの部分加水分解物溶液：アトロンＮＴi-５００
（日本曹達製）で塗布したのち、２００℃で１５分間乾
燥後、５００℃で焼成することで膜厚１００nmの第２層
としてのＴiＯ2よりなる光触媒膜を成膜した。Embodiment 1 Sol-gel solution MTS-TI-20 (Si / T
i = 75/25, solid content concentration 20% by weight, Daihachi Chemical Industry Co., Ltd.) 10 g, sol-gel solution MTS-2 (Si: 100%, solid content concentration 20% by weight, Daihachi Chemical Industry Co., Ltd.) 80 g, diluted solvent Was diluted 10-fold with a mixed solvent of isobutyl acetate (3) -n-butanol (1) to obtain a coating solution for the first layer. This was dropped by 2 cc on a 3.5 cm thick soda lime glass substrate of 15 cm square by a spin coater to form a film.
After drying at 0 ° C. for 30 minutes, it is cooled to room temperature, and the film thickness is 100 nm.
Of TiO 2 —SiO 2 film was obtained. Next, the glass sample on which the film of the first layer was formed was subjected to a dipping method to obtain a partial hydrolyzate solution of titanium alkoxide: Atron NTi-500.
(Nippon Soda Co., Ltd.), dried at 200 ° C. for 15 minutes, and baked at 500 ° C. to form a 100 nm-thick photocatalytic film of TiO 2 as a second layer.
【００２８】[0028]
【実施例２】ゾルゲル溶液ＣＧ-ＴＩ-１０(Ｓｉ／Ｔｉ
＝９０／１０、固形分濃度２０重量％、大八化学工業
製)を酢酸イソブチル(３)−ｎ−ブタノール(１)混合溶
媒で１０倍に希釈したものを第１層用の塗布液とした。
これをリバースコーターにより厚さ３.５mmのソーダラ
イムガラス基板上に成膜した後、２００℃で１５分乾燥
後、室温までに冷却し、第１層の膜厚１５０nmのＴiＯ2
ーＳiＯ2膜を得た。次に、この第１層の膜が形成された
ガラスサンプルをディップ法によりチタンアルコキシド
の部分加水分解物溶液：ＤＴ００２(日本曹達製）で塗
布したのち、２００℃で１５分乾燥、５００℃で焼成す
ることで膜厚１２０nmの第２層のＴiＯ2膜を成膜した。Embodiment 2 Sol-gel solution CG-TI-10 (Si / Ti
= 90/10, solid content concentration 20% by weight, manufactured by Daihachi Chemical Industry Co., Ltd.) diluted 10-fold with a mixed solvent of isobutyl acetate (3) -n-butanol (1) was used as a coating solution for the first layer. .
This was formed on a soda lime glass substrate having a thickness of 3.5 mm by a reverse coater, dried at 200 ° C. for 15 minutes, cooled to room temperature, and then the first layer of TiO 2 having a thickness of 150 nm was formed.
-An SiO 2 film was obtained. Next, the glass sample on which the film of the first layer is formed is applied with a partial hydrolyzate solution of titanium alkoxide: DT002 (manufactured by Nippon Soda) by a dipping method, dried at 200 ° C. for 15 minutes, and baked at 500 ° C. As a result, a second-layer TiO 2 film having a thickness of 120 nm was formed.
【００２９】[0029]
【実施例３】ゾルゲル溶液ＣＧ-Ｚｒ-１０(Ｓｉ／Ｚｒ
＝９０／１０、固形分濃度２０重量％、大八化学工業
製)をエタノール(２)-ブチルセロソルブ（１)混合溶媒
で１５倍に希釈したものを第１層用の塗布液とした。こ
れをスピンコーターにより厚さ３.５mmのソーダライム
ガラス基板上に成膜した後、２００℃で１５分乾燥後、
室温までに冷却し、第１層の膜厚１２０nmのＺrＯ2ーＳ
iＯ2膜を得た。次に、この膜上にチタニア微粒子含有シ
リカバインダー液：ＳＴ-Ｋ０３(石原テクノ）をスプレ
ーにより塗布して２００℃で１５分乾燥、５００℃で焼
成することにより、第２層の膜厚１６０nmのＴiＯ2微粒
子含有ＳiＯ2膜を得た。Embodiment 3 Sol-gel solution CG-Zr-10 (Si / Zr
= 90/10, solid content concentration 20% by weight, manufactured by Daihachi Chemical Industry Co., Ltd.) diluted 15-fold with a mixed solvent of ethanol (2) -butyl cellosolve (1) was used as a coating solution for the first layer. This was formed on a 3.5 mm thick soda lime glass substrate by a spin coater, dried at 200 ° C. for 15 minutes,
After cooling to room temperature, the first layer of ZrO 2 -S having a thickness of 120 nm is formed.
An SiO 2 film was obtained. Next, a titania fine particle-containing silica binder solution: ST-K03 (Ishihara Techno) is applied on this film by spraying, dried at 200 ° C. for 15 minutes, and baked at 500 ° C. to form a second layer having a thickness of 160 nm. A SiO 2 film containing TiO 2 fine particles was obtained.
【００３０】[0030]
【実施例４】ゾルゲル溶液ＣＧ-１９(ＳiＯ2濃度１０重
量％、大八化学工業製）５０ｇに５.１ｇのＡｌジイソ
プロポキシアセチルアセトナートを溶解しているエタノ
ール(３)ｎ-ブタノール混合溶液で１０倍に希釈したも
のを第１層用の塗布液として用いた。これをスピンコー
ターにより厚さ３.５ｍｍのソーダライムガラス基板上
に塗布したのち、２００℃で１５分乾燥後室温までに冷
却し、膜厚１６０nmのＡl2Ｏ3ーＳiＯ2の第１層膜を得
た。その膜上にチタニア微粒子含有シリカバインダー
液：タイノックＣＡ-６２(多木化学)をスプレーにより
塗布し、２００℃で１５分乾燥後５００℃で焼成し、膜
厚１５０nmのＴiＯ2微粒子含有ＳiＯ2膜を得た。Example 4 Ethanol (3) n-butanol mixed solution in which 5.1 g of Al diisopropoxyacetylacetonate is dissolved in 50 g of a sol-gel solution CG-19 (10% by weight of SiO2, manufactured by Daihachi Chemical Industry) The solution diluted 10-fold was used as the coating solution for the first layer. This was applied on a 3.5 mm thick soda lime glass substrate by a spin coater, dried at 200 ° C. for 15 minutes, cooled to room temperature, and formed into a 160 nm thick Al 2 O 3 —SiO 2 first layer film. I got A silica binder solution containing titania fine particles: TINOC CA-62 (Taki Kagaku) is applied on the film by spraying, dried at 200 ° C. for 15 minutes, and baked at 500 ° C. to form a 150 nm thick SiO 2 film containing TiO 2 fine particles. I got
【００３１】[0031]
【比較例１】シリカのゾルゲル溶液コルコートＮ-１０
３Ｘ(太陽物産、固形分濃度：６重量％)を用い、浸漬法
により成膜し、厚膜１５０nmのＳiＯ2単独の第１層膜を
得た。これを実施例１と同様のアトロンＮＴi-５００
（日本曹達)を用いて浸漬法により、膜厚１００nmの第
２層のＴiＯ2膜を成膜した。なお、乾燥、焼成温度は実
施例１と同様の条件で行った。[Comparative Example 1] Silcoat solution of silica Colcoat N-10
Using 3X (Taiyo Bussan, solid content concentration: 6% by weight), a film was formed by an immersion method to obtain a 150 nm thick first layer film of SiO 2 alone. This was replaced with the same Atron NTi-500 as in Example 1.
A second layer of TiO 2 film having a thickness of 100 nm was formed by dipping using (Nippon Soda). The drying and firing temperatures were the same as in Example 1.
【００３２】得られた光触媒膜付き多機能ガラスの評価
を下記のように行った。 〔光活性試験〕１重量％オレイン酸アセトン溶液を用い
て光触媒膜表面にオレイン酸を均一に付着させ人工的に
汚れを形成した。これにブラックライトＦ１５Ｔ８ＢＬ
Ｂ(三共電気)で０.５mW/cm2(３６５nm)の紫外線を２時
間照射した。照射前後の水の接触角変化で光活性を評価
した。 〔耐温水性試験〕６０℃の温水に１０日間浸漬して外
観、膜強度（温水中でガーゼ布で強く擦り膜剥離の有無
を調べる)の変化を評価した。 〔耐湿性試験〕５０℃相対湿度９８％の蒸気中に３０日
間放置して外観、膜強度の変化を評価した。 〔耐酸性試験〕０.１％塩酸中に室温下で４８時間浸漬
して外観、膜強度の変化を評価した。 〔耐アルカリ性試験〕２０％炭酸ソーダ水溶液中に室温
下で４８時間浸漬して外観、膜強度の変化を評価した。 〔耐温塩水性試験〕６０℃の３％食塩水に室温下で４８
時間浸漬して外観、膜強度の変化を評価した。The obtained multifunctional glass with a photocatalytic film was evaluated as follows. [Photoactivity test] Using a 1% by weight acetone solution of oleic acid, oleic acid was uniformly adhered to the surface of the photocatalyst film to artificially form stains. Black Light F15T8BL
B (Sankyo Denki) was irradiated with 0.5 mW / cm 2 (365 nm) of ultraviolet light for 2 hours. The photoactivity was evaluated by the change in the contact angle of water before and after irradiation. [Water resistance test] The film was immersed in warm water at 60 ° C. for 10 days to evaluate changes in appearance and film strength (examination of film peeling by rubbing strongly with a gauze cloth in warm water). [Moisture resistance test] The composition was allowed to stand in steam at 50 ° C and a relative humidity of 98% for 30 days to evaluate changes in appearance and film strength. [Acid resistance test] The specimen was immersed in 0.1% hydrochloric acid at room temperature for 48 hours to evaluate changes in appearance and film strength. [Alkali Resistance Test] The film was immersed in a 20% aqueous sodium carbonate solution at room temperature for 48 hours to evaluate changes in appearance and film strength. [Warm salt water test] 48% in 3% saline solution at 60 ° C at room temperature.
After immersion for a time, changes in appearance and film strength were evaluated.
【００３３】実施例及び比較例における性能評価結果を
表ー１に示す。光活性試験においては、実施例及び比較
例ともに、紫外線照射前の水の接触角が２２〜２４°で
あったものが、照射後３〜５°に大幅に小さくなた。こ
れらの結果から、実施例及び比較例ともに第２層にＴi
Ｏ2を有する光触媒層を成膜しているため、いずれも良
好な光触媒としての光活性機能を有していることが確認
できる。Table 1 shows the performance evaluation results in the examples and comparative examples. In the photoactivity test, the contact angle of water before irradiation with ultraviolet light was 22 to 24 ° in both the examples and comparative examples, but was significantly reduced to 3 to 5 ° after irradiation. From these results, Ti was added to the second layer in both the example and the comparative example.
Since the photocatalyst layer containing O 2 is formed, it can be confirmed that each has a photoactive function as a good photocatalyst.
【００３４】耐温水性試験について、実施例１〜４は１
０日間経過後も外観、膜強度、光活性に変化がなかっ
た。比較例１については、２日目に第２層膜が剥離し
た。耐湿性試験については、実施例１〜４は３０日間経
過後も変化は認められないのに対し、比較例１は１２日
目に第２層膜が剥離した。Regarding the hot water resistance test, Examples 1 to 4
Even after 0 days, there was no change in appearance, film strength, and photoactivity. In Comparative Example 1, the second layer film was peeled off on the second day. Regarding the moisture resistance test, in Examples 1 to 4, no change was observed even after elapse of 30 days, whereas in Comparative Example 1, the second layer film was peeled off on the 12th day.
【００３５】耐酸性試験については、実施例および比較
例ともに変化は認められなかった。耐アルカリ性試験に
ついては、実施例１〜４は４８時間経過後、全く変化は
なかった。一方、比較例１は１１時間後に第２層膜が剥
離した。In the acid resistance test, no change was observed in both the examples and comparative examples. Regarding the alkali resistance test, Examples 1 to 4 showed no change after 48 hours. On the other hand, in Comparative Example 1, the second layer film was peeled off after 11 hours.
【００３６】耐温塩水性試験については、実施例では変
化は認められなかった。なお、表-１において、（○印)
は試験後の変化がなく良好な結果が得られたことを示
し、（×印)は試験中に膜の剥離を生じたものを示す。Regarding the warm salt water resistance test, no change was observed in the examples. In addition, in Table-1, (○ mark)
Indicates that a good result was obtained without any change after the test, and (x) indicates that the film was peeled off during the test.
【００３７】以上の評価結果に示すように、本発明の実
施例１〜４は比較例１に比べ、耐温水性、耐湿性、耐ア
ルカリ性、耐温塩水性において極めて優れ、第１層膜と
第２層膜の膜間の密着強度が極めて大きく強固であるこ
とが判る。As shown in the above evaluation results, Examples 1 to 4 of the present invention are extremely excellent in hot water resistance, moisture resistance, alkali resistance and hot salt water resistance as compared with Comparative Example 1, and the first layer film It can be seen that the adhesion strength between the second layer films is extremely large and strong.
【００３８】[0038]
【表１】 [Table 1]
【００３９】[0039]
【発明の効果】光触媒膜の下層に、Ｔi元素の電気陰性
度に近似した金属元素を少なくとも１種以上含有するＳ
iＯ2膜を設けることにより、ソーダライムガラス基板か
ら光触媒膜へのナトリウムイオンの移行を防止し、光触
媒機能を十分に発揮させるとともに、第１層に添加した
金属元素が第２層である光触媒膜のＴi元素と相互作用
を起こすことにより、第１層と第２層の層間の密着強度
が強固になり、耐温水性、耐湿性、耐アルカリ性、耐温
塩水性等の耐久性を長期に持続し、厳しい環境下におい
て確実でかつ安定した品質の多機能ガラスが得られ、建
築用、車両用、鏡等のその他の各種ガラス物品に広く用
いることができる。According to the present invention, an S layer containing at least one metal element close to the electronegativity of the Ti element in the lower layer of the photocatalytic film.
By providing the SiO 2 film, the transfer of sodium ions from the soda lime glass substrate to the photocatalytic film is prevented, the photocatalytic function is sufficiently exhibited, and the metal element added to the first layer is the photocatalytic film as the second layer. Interacts with the Ti element to strengthen the adhesion strength between the first and second layers and maintain durability over a long period of time, such as warm water resistance, moisture resistance, alkali resistance, and warm salt water resistance. In addition, a reliable and stable quality multifunctional glass can be obtained under severe environment, and can be widely used for various other glass articles such as architectural, vehicular, mirror and the like.
Claims (7)
としてＴi及びＴi元素の電気陰性度に近似した電気陰性
度を持つ金属元素を少なくとも１種以上含むＳiＯ2膜を
成膜し、その上に第２層としてＴiＯ2膜またはＴiＯ2微
粒子を分散したＳiＯ2膜を成膜した多機能ガラス。To 1. A soda-lime glass surface of the substrate, a metal element having an electronegativity that approximate electronegativity of Ti and Ti element as a first layer and a SiO 2 film containing at least one or more kinds, their Multifunctional glass having a TiO 2 film or a SiO 2 film in which TiO 2 fine particles are dispersed as a second layer formed thereon.
ある請求項１記載の多機能ガラス。2. The multifunctional glass according to claim 1, wherein the metal element has an electronegativity of 1.3 to 1.7.
r、Ａl、Ｖ、Ｃr、Ｍn、Ｚn、Ｓcである請求項１記載の
多機能ガラス。3. The metal element other than Si in the first layer is Ti, Z
The multifunctional glass according to claim 1, wherein the glass is r, Al, V, Cr, Mn, Zn, or Sc.
は、１〜３０モル％である請求項３項記載の多機能ガラ
ス。4. The multifunctional glass according to claim 3, wherein the content of the metal element excluding Si in the first layer is 1 to 30 mol%.
の場合、該ＴiＯ2微粒子の含有量は、１０〜９０重量％
である請求項１記載の多機能ガラス。5. When the second layer is a SiO 2 film in which TiO 2 fine particles are dispersed, the content of the TiO 2 fine particles is 10 to 90% by weight.
The multifunctional glass according to claim 1, wherein
としてＴi及びＴi元素の電気陰性度に近似した電気陰性
度をもつ金属元素の化合物を少なくとも１種以上含むＳ
iＯ2溶液よりなる塗布液を被覆した後、ＴiＯ2前駆体ま
たはＴiＯ2微粒子を分散したＳiＯ2よりなる第２層用溶
液を塗布し、乾燥・焼成してなる多機能ガラスの製造方
法。6. An S-layer containing, as a first layer, at least one compound of Ti and a metal element having an electronegativity close to the electronegativity of the Ti element on the surface of the soda-lime glass substrate.
After coating the iO 2 solution consisting of the coating solution, a second layer solution consisting of SiO 2 containing dispersed TiO 2 precursor or TiO 2 particles coated, method for producing multifunctional glass obtained by drying and baking.
Ｃr、Ｍn、Ｚn、Ｓc元素の硝酸塩、有機酸塩、アセチル
アセトナート化合物、アルコキシド化合物を含んだアル
コキシシラン化合物の加水分解物のうちの少なくとも１
種以上よりなる請求項６記載の多機能ガラスの製造方
法。7. The coating solution for the first layer comprises Ti, Zr, Al, V,
At least one of a hydrolyzate of an alkoxysilane compound including a nitrate, an organic acid salt, an acetylacetonate compound, and an alkoxide compound of Cr, Mn, Zn, and Sc elements.
The method for producing a multifunctional glass according to claim 6, comprising at least one kind.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9190294A JPH1135342A (en) | 1997-07-15 | 1997-07-15 | Polyfunctional glass and its production |
| DE19831610A DE19831610A1 (en) | 1997-07-15 | 1998-07-14 | Photocatalytic glass article and process for its manufacture |
| GB9815371A GB2327428B (en) | 1997-07-15 | 1998-07-15 | Photocatalytic glass article and method for producing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9190294A JPH1135342A (en) | 1997-07-15 | 1997-07-15 | Polyfunctional glass and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH1135342A true JPH1135342A (en) | 1999-02-09 |
Family
ID=16255782
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9190294A Pending JPH1135342A (en) | 1997-07-15 | 1997-07-15 | Polyfunctional glass and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH1135342A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6582839B1 (en) | 1999-09-02 | 2003-06-24 | Central Glass Company, Limited | Article with photocatalytic film |
| CN102975416A (en) * | 2012-12-05 | 2013-03-20 | 中山市创科科研技术服务有限公司 | Energy-saving door/window base material with high oxidation resistance |
| JP2013119511A (en) * | 2011-12-08 | 2013-06-17 | Panasonic Corp | Coated member |
| KR20170114338A (en) * | 2016-04-04 | 2017-10-16 | 주식회사 케이씨씨 | Coating glass for preventing stain |
| US11925332B2 (en) | 2018-12-28 | 2024-03-12 | Auris Health, Inc. | Percutaneous sheath for robotic medical systems and methods |
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| JPH0781977A (en) * | 1993-07-29 | 1995-03-28 | Central Glass Co Ltd | Anti-reflection coating and production thereof |
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| JPH0971437A (en) * | 1995-09-05 | 1997-03-18 | Nippon Soda Co Ltd | Window glass |
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| JPH10231146A (en) * | 1996-12-18 | 1998-09-02 | Nippon Ita Glass Techno Res Kk | Antifogging and antifouling glass article |
| JPH119994A (en) * | 1996-05-31 | 1999-01-19 | Toshiba Lighting & Technol Corp | Photocatalyst and light source |
| JPH11511109A (en) * | 1995-08-18 | 1999-09-28 | ヘラー、アダム | Self-cleaning glass and method for producing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03208837A (en) * | 1990-01-08 | 1991-09-12 | Central Glass Co Ltd | Single heat insulating glass sheet and its colored glass |
| JPH0632635A (en) * | 1992-07-16 | 1994-02-08 | Central Glass Co Ltd | Heat shielding glass having low reflecting characteristic of electrical radiation |
| JPH0781977A (en) * | 1993-07-29 | 1995-03-28 | Central Glass Co Ltd | Anti-reflection coating and production thereof |
| WO1996029375A1 (en) * | 1995-03-20 | 1996-09-26 | Toto Ltd. | Method of photocatalytically making the surface of base material ultrahydrophilic, base material having ultrahydrophilic and photocatalytic surface, and process for producing said material |
| JPH11511109A (en) * | 1995-08-18 | 1999-09-28 | ヘラー、アダム | Self-cleaning glass and method for producing the same |
| JPH0971437A (en) * | 1995-09-05 | 1997-03-18 | Nippon Soda Co Ltd | Window glass |
| JPH0972761A (en) * | 1995-09-05 | 1997-03-18 | Nippon Soda Co Ltd | Cover glass for instrument |
| JPH119994A (en) * | 1996-05-31 | 1999-01-19 | Toshiba Lighting & Technol Corp | Photocatalyst and light source |
| JPH10231146A (en) * | 1996-12-18 | 1998-09-02 | Nippon Ita Glass Techno Res Kk | Antifogging and antifouling glass article |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6582839B1 (en) | 1999-09-02 | 2003-06-24 | Central Glass Company, Limited | Article with photocatalytic film |
| JP2013119511A (en) * | 2011-12-08 | 2013-06-17 | Panasonic Corp | Coated member |
| CN102975416A (en) * | 2012-12-05 | 2013-03-20 | 中山市创科科研技术服务有限公司 | Energy-saving door/window base material with high oxidation resistance |
| KR20170114338A (en) * | 2016-04-04 | 2017-10-16 | 주식회사 케이씨씨 | Coating glass for preventing stain |
| US11925332B2 (en) | 2018-12-28 | 2024-03-12 | Auris Health, Inc. | Percutaneous sheath for robotic medical systems and methods |
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