CN1289195C - Multifunctional material with optical catalytic function and its mfg. method - Google Patents
Multifunctional material with optical catalytic function and its mfg. method Download PDFInfo
- Publication number
- CN1289195C CN1289195C CN02122422.6A CN02122422A CN1289195C CN 1289195 C CN1289195 C CN 1289195C CN 02122422 A CN02122422 A CN 02122422A CN 1289195 C CN1289195 C CN 1289195C
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- photocatalyst
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- 239000007859 condensation product Substances 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 2
- 229940112669 cuprous oxide Drugs 0.000 description 2
- 230000000881 depressing effect Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 229960002089 ferrous chloride Drugs 0.000 description 2
- 238000009408 flooring Methods 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N mono-methylamine Natural products NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- SDLBJIZEEMKQKY-UHFFFAOYSA-M silver chlorate Chemical compound [Ag+].[O-]Cl(=O)=O SDLBJIZEEMKQKY-UHFFFAOYSA-M 0.000 description 2
- 229940045105 silver iodide Drugs 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- CVOFKRWYWCSDMA-UHFFFAOYSA-N 2-chloro-n-(2,6-diethylphenyl)-n-(methoxymethyl)acetamide;2,6-dinitro-n,n-dipropyl-4-(trifluoromethyl)aniline Chemical compound CCC1=CC=CC(CC)=C1N(COC)C(=O)CCl.CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O CVOFKRWYWCSDMA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 206010014405 Electrocution Diseases 0.000 description 1
- 239000004277 Ferrous carbonate Substances 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- ZSILVJLXKHGNPL-UHFFFAOYSA-L S(=S)(=O)([O-])[O-].[Ag+2] Chemical compound S(=S)(=O)([O-])[O-].[Ag+2] ZSILVJLXKHGNPL-UHFFFAOYSA-L 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- ITBPIKUGMIZTJR-UHFFFAOYSA-N [bis(hydroxymethyl)amino]methanol Chemical compound OCN(CO)CO ITBPIKUGMIZTJR-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
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- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
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- 238000010276 construction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 1
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 230000003467 diminishing effect Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 description 1
- 235000019268 ferrous carbonate Nutrition 0.000 description 1
- 229960004652 ferrous carbonate Drugs 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000015 iron(II) carbonate Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- BQZGVMWPHXIKEQ-UHFFFAOYSA-L iron(ii) iodide Chemical compound [Fe+2].[I-].[I-] BQZGVMWPHXIKEQ-UHFFFAOYSA-L 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 230000001795 light effect Effects 0.000 description 1
- 150000004706 metal oxides Chemical group 0.000 description 1
- CEQFOVLGLXCDCX-WUKNDPDISA-N methyl red Chemical compound C1=CC(N(C)C)=CC=C1\N=N\C1=CC=CC=C1C(O)=O CEQFOVLGLXCDCX-WUKNDPDISA-N 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-N methyl sulfate Chemical compound COS(O)(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-N 0.000 description 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910003465 moissanite Inorganic materials 0.000 description 1
- 210000003097 mucus Anatomy 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 229920003217 poly(methylsilsesquioxane) Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
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- 239000013049 sediment Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- LFAGQMCIGQNPJG-UHFFFAOYSA-N silver cyanide Chemical compound [Ag+].N#[C-] LFAGQMCIGQNPJG-UHFFFAOYSA-N 0.000 description 1
- 229940098221 silver cyanide Drugs 0.000 description 1
- YSVXTGDPTJIEIX-UHFFFAOYSA-M silver iodate Chemical compound [Ag+].[O-]I(=O)=O YSVXTGDPTJIEIX-UHFFFAOYSA-M 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
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- 238000001029 thermal curing Methods 0.000 description 1
- 238000006365 thiocyanation reaction Methods 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
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- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
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- 239000010457 zeolite Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- GTLDTDOJJJZVBW-UHFFFAOYSA-N zinc cyanide Chemical compound [Zn+2].N#[C-].N#[C-] GTLDTDOJJJZVBW-UHFFFAOYSA-N 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- ZPEJZWGMHAKWNL-UHFFFAOYSA-L zinc;oxalate Chemical compound [Zn+2].[O-]C(=O)C([O-])=O ZPEJZWGMHAKWNL-UHFFFAOYSA-L 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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Abstract
The present inventive multi-functional materials are classified into those which have a photocatalytic layer 2 with a photocatalytic function directly disposed on the surface of a base 1 and those which have a photocatalytic layer 2 with a photocatalytic function disposed on the surface of a base 1 through a binder layer 6 interposed therebetween. Photocatalytic particles of the photocatalytic layer 2 are joined together by a surface energy or solid-state sintering. The photocatalytic layer 2 may have a structure in which fine particles fill interstices defined between photocatalytic particles or a structure in which no fine particles fill interstices defined between photocatalytic particles. A metal such as Ag, Pt, or the like may be fixed or not fixed to surfaces of the photocatalytic particles.
Description
This case be China the applying date be on December 9th, 1994, Chinese patent application number be 94191730.4, denomination of invention divides an application for the application of " multifunctional material and manufacture method thereof with photo-catalysis function ".
Technical field
The present invention is about the multifunctional material and the manufacture method thereof of performance deodorization function, antibacterial functions, sterilizing function, anti-pollution function etc.
Background technology
Up to now, by irradiation ultraviolet radiation, cause absorption or the desorb of organic compounds such as odor pollutant to oxygen molecule, promote the material of its decomposition (oxidation), having known has TiO
2, V
2O
3, ZnO, WO
3Deng, the TiO of crystal formation Detitanium-ore-type particularly
2Particle is as its effect height of photochemical catalyst, so advise so far forming photocatalyst layer on the surface of wall material, ceramic tile, glass (mirror), circulation filter or sanitary ceramics etc.
Form the method for above-mentioned photocatalyst layer known have on substrate surfaces such as plastics, pottery, resin, utilize CVD method (chemical vapor deposition method), sputtering method, electron beam evaporation plating method etc., directly form by TiO
2The method of the photocatalyst layer that particle etc. constitute.
But when using CVD method, sputtering method, electron beam evaporation plating method etc., equipment scale is big, and yield rate is low, thereby the manufacturing cost height.
Form the additive method of photocatalyst layer known also have photocatalyst granular is mixing in binding agent, utilize method such as spraying process to be coated on the substrate surface, perhaps utilize the dip coating dip coated after, the method for heat-treating (spy opens flat 5-201747).
But, for making TiO
2The effect of photocatalyst granulars such as particle performance photochemical catalyst; must be to the photocatalyst granular irradiation ultraviolet radiation; and make photocatalyst granular contact decomposition object matter such as foul gas; if it is but as the spy opens flat 5-201747 that photocatalyst granular is mixing in binding agent; be applied on the base material, then many photocatalyst granulars are embedded in the adhesive layer again, and ultraviolet ray can not arrive; and can not contact foul gas etc., can't give full play to catalysis.
Form known the also having of additive method of photocatalyst layer in the real alcoxylates method that is disclosed among the flat 5-7394 of opening.This method is to be coated with alkoxytitanium on glass baseplate, and roasting is carried out at hundreds of degree (Celsius) in dry back, forms photocatalyst layer, by using this photocatalyst layer of ultraviolet ray irradiation, the organic matter in the decomposition water.
Above-mentioned burning oxo-compound method can form film at lower temperature, this be favourable a bit, as base material, can effectively utilize base material that hard glass and quartz glass etc. all are difficult to soften as raw material up to 500 ℃ the time, but for example utilizing under the situations of low-melting raw material as base material such as soda-lime glass, base material has begun to soften under film forming temperature, formed photocatalyst film is embedded in the base material, thereby light can not arrive photocatalyst layer, produces the so-called unfavorable condition that can not bring into play photo-catalysis function.
In addition, open among the flat 1-288321, the spy TiO
2Colloidal sol sprays on the fibrous material ceramic paper, heat-treats at 400-700 ℃, sprays SnO then
2Colloidal sol is heat-treated at 400-700 ℃, forms the photochemical catalyst overlay film that can improve the aldehydes oxidation Decomposition with this.
Open in the method that flat 1-288321 discloses the spy, with than TiO
2Active lower SnO
2Cover the whole surface of overlay film.And, when improving film-strength, be easy to generate crackle.That is, shown in Fig. 1 (a), contain TiO in the coating of the surface of ceramic tile 100
2If the colloidal sol of particle 101 with its heat treatment (sintering), then shown in Fig. 1 (b), cracks 102.Its reason causes the volume contraction (density raising) except changing mutually to rutile-type, also because before the sintering shown in Fig. 2 (a), TiO
2101 of particles be L at interval
o, but rutile-type behind sintering shown in Fig. 2 (b), because to the other side's bulk diffusion, intergranular interval shortens and is L
1(L
1＜L
o).So department thinks that the result cracks.
On the other hand, open the method that purifies foul smell in disclosing about the compartment among the flat 4-46609 the spy, this is a kind of decomposes or modification is included in odorant in the foul smell of air in a car compartment, purify the method for foul smell in the compartment, it is characterized in that using up and be radiated at the semiconductor solid photochemical catalyst that carrying metal on the semiconductor or metal oxide form, air in a car compartment to be clean is contacted with this photochemical catalyst, decompose by photochemical reaction or modification is included in odorant in this airborne foul smell with this.
Yet when the base material that the surface has been coated with photochemical catalyst for example is used for environment such as sewage and outer wall, because of comprising macromolecule, dust and dirt, mushroom etc. in the atmosphere or in the water, adhere to pollutant easily, owing to the different attached outstanding pollutants of kind with pollutant, the situation that exists the photochemical catalyst function to reduce.
Tackled in the past by pollutant and adhered to and the strategy of the photochemical catalyst function reduction that causes can be referring to the fair 6-7905 of spy.In the fair 6-7905 of spy, disclose about utilizing the deodorization device of photochemical catalyst, it is by the semiconductor light-catalyst layer, ultraviolet lamp that is oppositely arranged with it and heater and hair-dryer constitute, make photocatalyst layer or heater, perhaps photocatalyst layer and heater move, so that the heated in sequence photochemical catalyst is all, near being heated to 400 ℃, remove the pollution that causes by macromolecule, dust and dirt etc., make the regeneration of photocatalyst layer.
But, utilize the method for this photochemical catalyst regeneration, for the parts that use in being installed in indoor equipment, the actual difficulty that implements, thereby, be desirably in and adhere to after the pollution on the photocatalyst layer, do not remove, certainly pollution is difficult for adhering to, and perhaps more tackles the problem at its root, and makes not adhering to of pollution can reduce the photochemical catalyst function.
Among the fair 6-7906 of this external spy, disclosed the strong illumination photochemical catalyst that utilizes uitraviolet intensity, the method for removing the stench in family and the office.But, when the strong illumination of uitraviolet intensity, because of the structure difference of photochemical catalyst, the resolution ratio difference of stench.In addition, base material is a porous matter in above-mentioned example, obtains enough mechanical strengths with methods such as impregnations, but is vitrfied tightener at base material, during non-porous matter raw material such as fine and close thin pottery, can not get enough mechanical strengths.
In addition, at TiO
2In different crystal formations such as Detitanium-ore-type, brookite type and rutile-type are arranged, with regard to photolytic activity, Detitanium-ore-type is excellent, the photolytic activity of other crystal formations is not good like that.Yet, even the TiO of rutile-type
2, as support metals such as Pt, Ag and also can improve photolytic activity (" surface " magazine 1987 is reported among the Vol25), still, abundant inadequately aspect odor destruction rate, compactness and adherence.When particularly adding metal A g and AgO, because they are black, so unbecoming with building materials with pottery.
In addition, owing to utilize the titanium oxide sol of preparations such as hydro-thermal method or sulfuric acid process to form by ultra-fine grain, so cohesion easily.If polymer-coated on substrate surface, then become the reason that produces hot spot and crackle.Therefore so far in order to prevent cohesion, can take to make organic dispersing agent such as triethanolamine attached to the lip-deep method of titanium oxide sol.
But, when making organic dispersing agents such as triethanolamine attached to the lip-deep method of titanium oxide sol, the monodispersed titanium oxide sol of coating on the low base material of hear resistances such as resin base material, if fix carrying out roasting less than 300 ℃, since the active site organic dispersing agent of titanium oxide sol fixedly secured, even also insufficient evaporation, decomposition in roasting process, so the member that obtains does not so have enough photocatalysis, deodorization and antibiotic property are abundant inadequately.
In addition, open to have disclosed among the flat 5-253544 the spy anatase-type titanium oxide is mixed in the binding agent, it is coated on substrate surface, the method for heat-treating again.This method is to form adhesive layer on the surface of the tabular component of the wall, flooring or the ceiling surface that constitute the living space, spraying is based on the photochemical catalyst fine powder of anatase-type titanium oxide on the surface of this adhesive layer, and a part is exposed from adhesive layer, like this attached to the surface of this adhesive layer, then heat in the scope more than 300 ℃, below 900 ℃, after making the adhesive layer fusion, cool off, so that adhesive cures.
In the method, if more than 300 ℃, heat-treat below 900 ℃, deodorization is good, but can not get good deodorization at the low temperature below 300 ℃, thereby is difficult to additional excellent good photochemical catalysts such as deodorization on base materials such as heat labile plastics.Reason can be thought in order to be coated on photocatalyst granular on the base material equably, need earlier photochemical catalyst fine grained list to be dispersed in the suspension, added organic dispersing agent for this reason, this dispersant in insufficient decomposition below 300 ℃, gasify, left behind the active site that covers on the photocatalyst granular.
Thereby, the purpose of this invention is to provide and can give full play to the photocatalysis effect, and utilize base material to keep the photocatalyst layer multifunctional material particularly well in the mode that photocatalyst layer exposes from base material.
In addition, the objective of the invention is on fine and close base material such as glass, ceramic tile, metal, plastics, to form the photocatalyst layer that is difficult for peeling off.
In addition, the objective of the invention is at the low melting point base material, for example the soda-lime glass of cheap easy processing etc. is gone up and is formed photocatalyst layer.
In addition, the purpose of this invention is to provide a kind of like this multifunctional material, this material is difficult for adhering to pollutant, and can prevent the function reduction that pollutant causes, and has antibiotic property or deodorization, the mechanical strength excellence.
In addition, even the purpose of this invention is to provide with Detitanium-ore-type TiO
2As the photocatalyst layer of main body, the multifunctional material that peel strength is also good.
In addition, the objective of the invention is to improve with rutile TiO
2Photocatalytic activity as the photocatalyst layer of main body.
Have again, the objective of the invention is with rutile TiO
2Support Ag on the photocatalyst layer as main body, improve photocatalytic activity, make the photocatalyst layer decolouring simultaneously, make outward appearance better.
Also have, even the purpose of this invention is to provide the multifunctional material that the Low Temperature Heat Treatment of carrying out below 300 ℃ also has good photo-catalysis function.
Disclosure of an invention
The invention provides a kind of multifunctional material, contain with photo-catalysis function
Base material;
Have photo-catalysis function and the photocatalyst layer that is arranged on the described substrate surface, described photocatalyst layer contains at least one top layer that is exposed to the outside, described top layer is made up of tiny photocatalyst granular, described photocatalyst granular combines, between form the gap with predetermined porosity;
Be filled among the described gap less than the particle in described gap;
And the described particle that is filled among the gap that forms between the described photocatalyst granular has photocatalytic activity.
The method that the present invention also provides a kind of preparation to have the multifunctional material of photo-catalysis function, this material have between photocatalyst granular the photocatalyst granular that forms the gap and with particle diameter particles filled less than these gaps, described method comprises the following steps:
On the surface of base material, form a photocatalysis layer,
Metal alkoxide or organic metal salt are coated on the surface of described photocatalysis layer thereafter and
Dry then and heat coated metal alkoxide or organic metal salt, use the particles filled described gap that photocatalyst granular between form littler than described gap.
In one embodiment, described method further comprises the following steps:
On this dry material, apply the coated solution of the aqueous solution of at least a metal ion among Cu, Ag, Zn, Fe, Co, Ni, Pd and the Pt and photo-reduction to separate out and the fixing metal particle.
In one embodiment, wherein said photocatalyst granular combines.
The present invention also provides a kind of preparation to have the method for the multifunctional material of photo-catalysis function, this material has between photocatalyst granular the photocatalyst granular that forms the gap and with particle diameter particles filled less than these gaps, described photocatalyst granular is combined together, and described method comprises the following steps:
Photocatalyst granular and the described more short grained mixture form with colloidal sol, precursor or suspended substance is coated on the thermoplastic matrix, form photocatalyst layer thus, this thermoplastic matrix of its after-tack, to imbed the photocatalyst layer underclad portion in the thermoplastic matrix and to solidify this thermoplastic matrix then.
In one embodiment, described method further comprises the following steps:
Before being coated in photocatalyst granular on the thermoplastic matrix, be dispersed among the solution with dispersant with photocatalyst granular with than colloidal sol, precursor or the suspended substance of granule, this dispersant only is grouped into by a kind of one-tenth, and it is vaporized under the temperature of the heat treatment temperature that is lower than softening described thermoplastic matrix.
In one embodiment, described method further comprises the following steps;
Prepare TiO 2 sol according to hydro-thermal method or sulfuric acid process, form photocatalyst granular, tiny metallic particles is fixed on the surface of TiO 2 sol particle, then dispersant or surface conditioning agent such as surfactant are added to TiO 2 sol.
In one embodiment, described method further comprises the following steps:
Photocatalyst layer is contacted with saline solns, with and be filled in that the metal ion of particle forms insoluble, colourless or white salt among the gap between the photocatalyst granular, then with containing this solution of ultraviolet light radiation.Preferred wherein said photocatalyst granular is by TiO
2Make, the metallic particles that is filled among the gap between the photocatalyst granular is made by Ag, and described saline solns contains halide such as KI, KCl, FeCl
3Deng aqueous solution, described salt and metal ion form insoluble, colourless or white salt.
In one embodiment, described method further comprises the following steps:
With the solution that aqueous solution is coated on the photocatalyst layer that is embedded in and photo-reduction is coated of at least a metal ion among Ni, Pd and the Pt to separate out and the fixing metal particle.
Multifunctional material of the present invention is at pottery, sanitary ceramics, potteries such as glass, resin, metal, directly or by adhesive layer form the material that photocatalyst layer gets on the substrate surfaces such as timber, especially to the kind of the photocatalyst granular that constitutes photocatalyst layer, particle diameter, the gap that forms between photocatalyst granular, the porosity, the relation of adhesive layer and photocatalyst layer, fill the particle in gap between photocatalyst granular, particularly be fixed on lip-deep metallic particles of photocatalyst granular etc. and do not have specific (special) requirements, good by these photocatalysis effects of photocatalyst layer that are made as deodorization etc., the multifunctional material that antibiotic property and wearability are also good.
The simple declaration of accompanying drawing
Fig. 1 (a) is the TiO that represents in the past
2State diagram before the colloidal sol sintering (b) is state diagram behind the expression rutile-type sintering.
Fig. 2 (a) is the TiO that represents in the past
2State diagram before the particle sintering (b) is state diagram behind the expression sintering.
Fig. 3 is illustrated in the multifunctional material with photo-catalysis function of the present invention, and the photocatalyst granular that constitutes photocatalyst layer combines with potential energy and the state diagram that constitutes each other.
Fig. 4 schematically is illustrated in the identical multifunctional material, constitutes the photocatalyst granular state diagram of combination with solid-phase sintering each other of photocatalyst layer.
Fig. 5 schematically is illustrated in the identical multifunctional material, chats in the gap that intergranular forms at the photochemical catalyst that constitutes photocatalyst layer and fills short grained state diagram.
Fig. 6 schematically is illustrated in the state diagram that metallic particles is immobilized on the photocatalyst granular surface of multifunctional material shown in Figure 3.
Fig. 7 schematically is illustrated in the state diagram that metallic particles is immobilized on the photocatalyst granular surface of multifunctional material shown in Figure 4.
Fig. 8 schematically is illustrated in the state diagram that metallic particles is immobilized on the photocatalyst granular surface of multifunctional material shown in Figure 5.
Fig. 9 schematically is illustrated in the identical multifunctional material, and photocatalyst layer combines with base material by adhesive layer, the state diagram that the photocatalyst granular of formation photocatalyst layer combines with potential energy each other.
Figure 10 schematically is illustrated in the identical multifunctional material, and photocatalyst layer engages with base material by adhesive layer, the state diagram that the photocatalyst granular of formation photocatalyst layer combines with solid-phase sintering each other.
Figure 11 schematically is illustrated in the identical multifunctional material, and photocatalyst layer engages by adhesive layer, fills short grained state diagram in the gap that forms between photocatalyst granular.
Figure 12 schematically is illustrated in the state diagram that metallic particles is immobilized on the surface of photocatalyst granular of multifunctional material shown in Figure 9.
Figure 13 schematically is illustrated in the state diagram that metallic particles is immobilized on the photocatalyst granular surface of multifunctional material shown in Figure 10.
Figure 14 schematically is illustrated in the state diagram that metallic particles is immobilized on the photocatalyst granular surface of multifunctional material shown in Figure 11.
Figure 15 is the explanation manufacture method figure with multifunctional material of photo-catalysis function of the present invention.
Figure 16 (a) and (b) be TiO
2Intergranular enlarged drawing.
Figure 17 (a)-(c) is explanation TiO
2The sintering mechanism figure of particle.
Figure 18 represents the curve about the antibiotic property result of the test.
When Figure 19 is illustrated in the BLB light irradiation and advances into dry run and do not enter dry run, the result of the test comparison curves of Cu loading.
Figure 20 represents that Cu loading and Cu are coated with the relation curve of layout.
Figure 21 is the process drawing of other embodiment of expression.
Figure 22 represents the result of the test curve of antibiotic property test.
When Figure 23 is illustrated in the BLB light irradiation and advances into dry run and do not enter dry run, the result of the test comparison curves of Cu loading.
Figure 24 represents the relation curve of Cu loading and Cu coating weight.
Figure 25 represents the relation curve of Ag loading and bacterium survival rate.
The concept map of the basic distribution when Figure 26 is the section direction of observing multifunctional material with EPMA (electron beam microanalyser).
The concept map of the basic distribution when Figure 27 is the section direction of observing multifunctional material with EPMA (electron beam microanalyser)
Figure 28 represents TiO
2And SnO
2Cooperation and the relation curve of film-strength and smoothness.
Figure 29 represents the relation curve of heat treatment temperature and fineness.
Figure 30 is the activity determination method figure of explanation photocatalyst film.
Figure 31 is the activity determination method figure of explanation photocatalyst film.
Figure 32 is the activity determination method figure of explanation photocatalyst film.
Figure 33 represents that ultraviolet irradiation time and pH change heavy relation curve.
Figure 34 represents R
30Relation curve with the pH variable quantity.
Figure 35 represents the porosity and deodorization (R
30) and the relation curve of wearability.
Figure 36 represents thickness and deodorization (R
30) relation curve.
Figure 37 represents thickness and deodorization (R
30) and the relation curve of anti-stripping performance.
Figure 38 represents SnO
2Addition and deodorization (R
30) and the relation curve of wearability.
Figure 39 represents SnO
2Addition adheres to the relation curve of difficulty with pollution.
Figure 40 represents SnO
2Addition and TiO
2The relation curve of the open pore rate of laminar surface.
Figure 41 represents SnO
2Addition and TiO
2The relation curve of the open pore width of laminar surface.
Figure 42 represents SnO
2Addition and deodorization R
30(L) and the relation curve of anti-fissility.
Figure 43 represents to be coated with number of times and adheres to the relation curve of difficulty with pollution.
Figure 44 represents to be coated with the relation curve of number of times and wearability.
Figure 45 represents to be coated with number of times and TiO
2The relation curve of the open pore rate of laminar surface.
Figure 46 is the expression irradiation ultraviolet radiation, makes thermosetting resin on the photocatalyst granular preferentially decompose, gasify and makes photocatalyst granular expose aerial state diagram.
Figure 47 is and the identical figure of Figure 47 that represents other embodiment.
Figure 48 is and the identical figure of Figure 47 that represents other embodiment.
Figure 49 is illustrated in to fill short grained state diagram in the gap of photocatalyst granular.
Figure 50 is that expression utilizes rutile TiO
2The block diagram of manufacture process of multifunctional material.
Cu solution concentration and photoactive relation curve when Figure 51 represents to make Cu solution drying carry out photo-reduction.
Cu solution concentration and photoactive relation curve when Figure 52 represents not make Cu solution drying carry out photo-reduction.
Figure 53 is illustrated in rutile TiO
2On the film with Cu Cu solution concentration and the stench during as carrying metal remove rate R
30Relation curve (reduction of metal ion is carried out after making the aqueous metal salt drying).
Figure 54 represents with nogging as substrate, in rutile TiO
2On the film with Cu Cu solution concentration and the odor destruction rate R during as carrying metal
30Relation curve (reduction of metal ion is carried out after making the aqueous metal salt drying).
Figure 55 is expressed as the formation rutile TiO
2Odor destruction rate R after the sintering temperature of film and the Cu immobilization
30Relation curve.
Figure 56 represents the solution concentration of Ag and Cu and the relation curve of aberration.
Figure 57 represents the porosity and R
30And the relation curve of wearability.
Figure 58 represents the loading of copper and the relation curve of bacterium survival rate.
Figure 59 represents the relation curve of the loading of the coating weight of copper and copper.
Figure 60 represents the loading of silver and the relation curve of bacterium survival rate.
Figure 61 represents the loading of silver and the relation curve of aberration.
Figure 62 represents to utilize the effect curve of KI aqueous solution decolouring processing.
Figure 63 is illustrated in the front and back of the decolouring processing that utilizes the KI aqueous solution, and the pH of the KI aqueous solution changes and odor destruction rate R
30The relation curve that changes.
Figure 64 is the curve map of comparison antibacterial action.
Figure 65 represents the wearability curve map with respect to the tin oxide weight ratio in the film.
Figure 66 represents the photolytic activity curve map with respect to the tin oxide weight ratio in the film.
Figure 67 represents the wearability curve map with respect to the tin oxide weight ratio in the film as a comparative example.
Figure 68 represents the photolytic activity curve map with respect to the tin oxide weight ratio in the film as a comparative example.
Figure 69 represents the loading of silver and the relation curve of bacterium survival rate.
Implement best mode of the present invention
In order to describe the present invention in more detail, according to description of drawings the present invention.
Fig. 3 to Figure 14 is divided into all kinds with the multifunctional material structure with photo-catalysis function of the present invention, and the multifunctional material with photo-catalysis function of the present invention belongs to wherein a kind of structure.
In the multifunctional material shown in Figure 3, the photocatalyst layer 2 with photo-catalysis function directly is set on the surface of base material 1, this photocatalyst layer 2 be tiny photocatalyst granular 3 each other with the surface can and curved surface can wait potential energy to combine and constitute.
In the multifunctional material shown in Figure 4, the photocatalyst layer 2 with photo-catalysis function directly is set on the surface of base material 1, this photocatalyst layer 2 is with the photocatalyst granular 3 solid-phase sinterings formation that combines.
In the multifunctional material shown in Figure 5, photocatalyst layer 2 with photo-catalysis function directly is set on the surface of base material 1, the littler particle 4 in this gap of packing ratio in the gap that forms between the photocatalyst granular 3 that constitutes this photocatalyst layer 2 makes photocatalyst granular 3 tie platform mutually by this granule 4 and constitutes.
In addition, in the figure, expression be that particle 4 is filled into the structure that the internal clearance forms, but particle 4 is filled at least in the gap of top layer photocatalyst granular 3 and also can.That is, with regard to the mechanical strength of photocatalyst layer,, can think that the combination on surface is important, so can only in the photocatalyst granular gap on top layer, fill fine particle for transmission in inside decay external force.But inner at this moment photocatalyst granular is by the potential energy combination, and in order to obtain enough photocatalyst layer intensity, the average grain diameter of photocatalyst granular is 0.04 μ m preferably.
In the multifunctional material shown in Fig. 6, combine also fixedly Ag, Cu and Cu on the surface of photocatalyst granular 3 constituting the photocatalyst granular 3 that directly forms photocatalyst layer 2 on the surface of base material 1 each other with potential energy
2Electronics such as O capture particle 5.
The photocatalyst granular 3 that is formed in the photocatalyst layer 2 that directly forms on the surface of base material 1 in multifunctional material shown in Figure 7 combines with solid-phase sintering each other, fixing metallic particles such as Ag and Pt 5 also on the surface of photocatalyst granular 3.
In multifunctional material shown in Figure 8, photocatalyst layer 2 with photo-catalysis function directly is set on the surface of base material 1, the little particle 4 in this gap of packing ratio in the gap that between the photocatalyst granular 3 that constitutes this photocatalyst layer 2, forms, by this granule 4, photocatalyst granular 3 mutually combines, fixing metallic particles such as Ag and Pt 5 also on the surface of photocatalyst granular 3.
In multifunctional material shown in Figure 9, on the surface of base material 1, the photocatalyst layer 2 with photo-catalysis function is set by adhesive layer 6, this photocatalyst layer 2 is when the top layer is exposed to the outside, lower floor imbeds in the adhesive layer 6, and the tiny photocatalyst granular 3 on top layer constitutes with the potential energy combination each other.
In multifunctional material shown in Figure 10, by adhesive layer 6 photocatalyst layer 2 is set equally, on the top layer of this photocatalyst layer 2, photocatalyst granular 3 combines with solid-phase sintering each other and constitutes.
In multifunctional material shown in Figure 11, by adhesive layer 6 photocatalyst layer 2 is set on base material i, the little particle 4 in this gap of packing ratio in the gap that forms between the photocatalyst granular 3 that constitutes this photocatalyst layer 2 mutually combines by this granule 4 photocatalyst granulars 3.
In multifunctional material shown in Figure 12, on the surface of base material 1, form photocatalyst layers 2 by adhesive layer 6, the photocatalyst granular 3 that constitutes this photocatalyst layer 2 combines with potential energy each other, also fixedly Ag, Cu and Cu on the surface of photocatalyst granular 3
2Electronics such as O capture particle 5.
In multifunctional material shown in Figure 13, on the surface of base material 1, form photocatalyst layer 2 by adhesive layer 6, the photocatalyst granular 3 that constitutes this photocatalyst layer 2 combines with solid-phase sintering each other, also fixedly Ag, Cu and Cu on the surface of photocatalyst granular 3
2Electronics such as O capture particle 5.
In multifunctional material shown in Figure 14, by adhesive layer 6 photocatalyst layer 2 is set on base material 1, the little particle 4 in this gap of packing ratio in the gap that between the photocatalyst granular 3 that constitutes photocatalyst layer 2, forms, mutually combine fixing metallic particles such as Ag and Pt 5 also on the surface of photocatalyst granular 3 by this granule 4 photocatalyst granulars 3.
In above multifunctional material, as base material 1, any of potteries such as ceramic tile, sanitary ceramics, glass, resin, metal, timber or its compound etc. can.
And so-called photocatalyst granular 3 is in order to bring into play photo-catalysis functions such as antibacterial functions, deodorization function, the semiconductor grain with very big energy gap.Having the reason of antibiotic property as photocatalyst granular, though have by adding the saying of the above voltage electrocution of regulation, can think general the same with the deodorization function, is the reason that has produced active oxygen when illumination is penetrated.In order to generate active oxygen, require of semi-conductive conduction band, when representing, must be positioned at hydrogen generation current potential top, and the upper end of valence band must be positioned at oxygen generation current potential below with band model.In satisfying the semiconductor of this condition, TiO is arranged
2, SrTiO
3, ZnO, SiC, phosphatization potassium, CdS, CdSe, MoS
3Deng.As if grain refined, then the position of conduction band is moved upward in addition, so if form the fine grained of 1-10nm degree, SnO
2, WO
3, Fe
2O
3, Bi
2O
3Deng all producing active oxygen.Detitanium-ore-type TiO wherein
2Because of chemically stable, can obtain active high fine grained at an easy rate, so preferred especially.
In addition, so-called electronics captures particle, is meant when illumination generates electronics and hole to above-mentioned photochemical catalyst, captures electronics, prevents electronics and the hole particle of combination again, can list Ag, Cu, Pt, Pd, Ni, Co, Fe, Cu particularly
2O etc.
In addition, above-mentioned adhesive layer 6 is made of for example ardent hope materials such as glaze, unorganic glass, thermoplastic resin, slicken solder.Constitute adhesive layer with thermoplastic like this, can utilize easy and inexpensive method such as spraying process photochemical catalyst to be coated on the adhesive layer at normal temperature, and only need heat-treat, just can make base material 1, adhesive layer 6 and photocatalyst layer 2 combination securely, be favourable on manufacturing cost.
In addition, the multifunctional material with photo-catalysis function of the present invention will be layered in by the photocatalyst layer that photocatalyst granular is formed to imbed in the adhesive layer on the laminar adhesive layer that thermoplastic forms or with its part and constitute.So laminar multifunctional material is attached to after original ceramic tile, sanitary ceramics, building materials etc. go up, if heating, after this just can on original ceramic tile etc., adds functions such as deodorization, soil resistance, antibiotic property, fungus resistance.
Because it is big that specific area becomes, improve photocatalytic activity, be preferably below the 0.3 μ m so constitute the average grain diameter of the photocatalyst granular 3 of above-mentioned photocatalyst layer 2.
The thickness of above-mentioned photocatalyst layer 2 is 0.1 μ m-0.9 μ m preferably.Below 0.1 μ m, photocatalyst granular is imbedded in the adhesive layer 6 partly, produces the part that can not bring into play catalytic activity on the multifunctional material surface, causes being detained bacterium on this part, so especially antibiotic property worsens.If surpass 0.9 μ m, then the deviation of thickness becomes big, adheres on sample and pollutes difficult drop-off when polluting.Comprise the most surperficial till the part of imbedding the glaze lower floor from photocatalyst film at the thickness of this so-called photocatalyst layer, specifically, carry out EPMA elementary analyses such as (electron beam microanalysers), the principal component element value that constitutes the glaze layer increases, obtain from this value substantially the topmost of certain part measure with this to the most surperficial distance.
In addition, utilize the method for the thickness that changes photocatalyst layer 2 also can obtain special effect.Promptly, if make thickness is more than the 0.2 μ m, 0.4 below the μ m, utilize the interference of light effect on the photocatalyst layer film thickness direction, can add the iridescent colors style, in addition, if think only to form in appearance the background color of base material, style or their combination, then except producing above-mentioned interference of light agency part, with the photocatalyst layer thickness make more than the 0.1 μ m, below the 0.2 μ m or more than the 0.4 μ m, also can below the 1 μ m.Such method can be used for broad range such as ceramic tile, commode, bathtub, Device for relieving nature, sink, galley dresser.
Under the situation that only photocatalyst granular 3 mutually combines, only utilize mutual potential energy of photocatalyst granular (absorption) or sintering.But when utilizing the mutual agglomeration of photocatalyst granular, must carry out sintering in quite high temperature, on the other hand, under the situation of utilizing absorption, if do not make the specific area of photocatalyst granular quite big, and if do not make fillibility good, then associativity is not enough, the active site adsorption section that only consumes photocatalyst granular grades, and the multifunctional material for manufacturing has abundant catalytic activity and wearability is restricted on method.
In addition, in order to strengthen the combination of photocatalyst granular 3, if use the particle bigger than the gap of photocatalyst granular 3, not only can not get enough adhesions, and partly cover the photocatalyst granular that exposes on the multifunctional material surface, on the multifunctional material surface, produce the part that to bring into play catalytic activity, on this part, be detained bacterium, so antibiotic property significantly worsens.
In addition, the gap between said here photocatalyst granular is meant the neck down portions between the photocatalyst granular 3,3 shown in Figure 16 (a), and shown in Figure 16 (b), the pore between the photocatalyst granular 3,3.Therefore, the said here gap than photocatalyst granular more the granule 4 of small particle diameter be meant the little particle in gap than big either party in the neck down portions between photocatalyst granular, the pore between photocatalyst granular.The method that photocatalyst granular is mutually combined has the such especially effectively means of Figure 16 (b).
The granule 4 that is filled in the gap of photocatalyst granular 3 does not limit material basically, but can be the good material of absorption affinity.The material extremely weak with adsorption capacity can not reach the purpose that photocatalyst granular is mutually combined to each other.The probability that hides the active site on photocatalyst granular surface during in addition, with the extremely strong material of adsorption capacity rather than insert in the gap increases.From this point, as the particle material in the gap that is filled in photocatalyst granular, it is desirable to metal or oxides such as Sn, Ti, Ag, Cu, Zn, Fe, Pt, Co, Pd, Ni, the zeolite that uses as carrier, active carbon, clay etc. are unfavorable so far.In above-mentioned metal or oxide, on this aspect of adsorption capacity with appropriateness, it is desirable to tin oxide, metal such as Ag, Cu or oxide are except that making photocatalyst granular mutually combines to each other in addition, also have antibiotic property, deodorization alone, so utilizing on the purposes of this function, be desirable on the function of special fill-in light catalytic action when not having illumination to penetrate.Promptly can use above-mentioned metallic particles 5 as the granule 4 in the gap that is filled in above-mentioned photocatalyst granular 3.
Moreover the average grain diameter that is filled in the particle 4 in the gap of above-mentioned photocatalyst granular 3 is below 4/5 of average grain diameter of photocatalyst granular 3 preferably.
Fill the particle 4 in the gap of photocatalyst granular 3, adopt existing manufacture method not only on photocatalyst granular gap to each other, adhering to a certain degree still arranged on photocatalyst granular.And fill the grain diameter in gap if surpass photocatalyst granular average grain diameter 4/5, then attached to the probability on photocatalyst granular surface than the probability height of inserting in the photocatalyst granular gap, so photocatalyst granular 3 bond strength reduction to each other.If it is bigger than photocatalyst granular to fill the particle in gap, just equal partly to have covered photocatalyst granular, on the multifunctional material surface, produce and to bring into play the part of catalytic activity, because on this part, be detained bacterium, so there is the particularly remarkable possibility that worsens of antibiotic property.
In addition, the average grain diameter that is filled in the particle 4 in the gap of above-mentioned photocatalyst granular 3 preferably below the 0.01 μ m, makes specific area increase like this, and can obtain the absorption affinity of appropriateness.
Moreover, be filled in particle 4 in above-mentioned photocatalyst granular 3 gaps with respect to the total amount of photocatalyst granular 3 and filler particles 4, in molar ratio meter preferably more than 10%, below 60%.Do not take place photocatalyst granular to each other the temperature province of sintering heat-treat, when making photocatalyst layer be fixed on the base material by adhesive layer, if the grain amount in landfill gap is very few, then photocatalyst granular combination securely to each other, on the other hand, if the amount of the particle in landfill gap is too much, the grain amount that then hides photocatalyst granular increases, on the multifunctional material surface, produce the part that to bring into play catalytic activity, because on this part, be detained bacterium, so particularly antibiotic property significantly worsens, thereby above-mentioned scope is desirable.
In addition, be filled in the material of the particle 4 in above-mentioned photocatalyst granular 3 gaps as formation, select vapour pressure than the high material of material vapour pressure that constitutes photocatalyst granular, it is desirable to, make the necking section of particle aggregation between photocatalyst granular that is filled in the above-mentioned photocatalyst granular gap.Can reach photocatalyst granular more firm combination to each other like this, in order to improve the peel strength of photocatalyst layer, not only fill method but also sintering method can.In addition, the particle 4 in landfill gap is if select the high material of this class vapour pressure, even then as sintering aid, also can reduce sintering temperature.
The material that this class vapour pressure is high has tin oxide, bismuth oxide, zinc oxide etc., but from security consideration tin oxide preferably.
In addition, comprise the bed thickness preferably more than the 0.1 μ m that is filled in the particle 4 in above-mentioned photocatalyst granular 3 gaps.This layer thickness is less than 0.1 μ m, photocatalyst granular (with utilizing manufacture method and filling up the particle in gap) part is imbedded in the adhesive layer 6, on the multifunctional material surface, form the part that to bring into play catalytic activity, on this part, can be detained bacterium, so especially antibiotic property significantly worsens.Here, the bed thickness that what is called comprises the particle 4 that is filled in the photocatalyst granular gap is to comprise from the most surperficial to the underclad portion of imbedding adhesive layer the thickness that convex-concave separately is average.
Figure 15 illustrates an example with multifunctional material manufacture method of photo-catalysis function of the present invention, in the present invention, at first shown in Figure 15 (a), is ready to base material 1, shown in this figure (b), forms adhesive layer 6 on the surface of base material 1.The adhesive layer 6 selected softening temperature materials lower than the softening temperature of base material 1.If enumerate an example, when base material 1 is ceramic tile, hollow glass material or ware, can utilize to former state glaze layer or printed layers as adhesive layer 6.
Then, shown in this figure (c), on adhesive layer 6, form by TiO
2The photocatalyst layer 2 that photocatalyst granulars such as particle constitute.At this moment, to keep, also can be loaded on the adhesive layer 6 in photocatalyst layer 2 roasting afterwards from adhesive layer 6 adeciduate adhesions.
Perhaps, before forming adhesive layer 6 on the surface of base material 1, shown in this figure (b '), also can on adhesive layer 6, be pre-formed photocatalyst layer 2, this adhesive layer 6 is positioned on the matrix material 1.
After this, in surpassing 20 ℃, scope below 320 ℃, carry out heat treated at softening temperature height and the atmosphere temperature lower than the softening temperature of base material 1 than adhesive layer 6, as this figure (d) or Fig. 9 to as shown in Figure 14, in the photocatalyst layer 2, lower floor's part of above-mentioned adhesive layer side is deposited on the adhesive layer of fusion, because adhesive layer solidifies, so this part is embedded in the adhesive layer, is firmly held.In addition, in the photocatalyst layer 2, the sintering that the photocatalyst granular 3 on the top layer that formation contacts with outside atmosphere utilizes mutual potential energy, molecular separating force and produces by burning till is shown in Figure 16 (a), a part combines, and other parts are separated shown in Figure 16 (b).That is, expose to the outside in fact on the surface of photocatalyst granular in the top layer.
Here, the heat treated temperature improved secondaryly surpass 20 ℃, scope below 320 ℃ than adhesive layer 6 softening temperatures are high, if less than 20 ℃, the softening spended time of wanting of binding agent then, nor can finish the maintenance of photocatalyst granular 3a fully, on the other hand, if surpass 320 ℃, then because the rapid fusion generation of adhesive layer photocatalyst granular imbedding in adhesive layer produces male and fomale(M﹠F), and fragment and pore take place, so wish more than 40 ℃, below 300 ℃.
Moreover the proportion of supposing photocatalyst granular 3 is δ t, and the proportion of adhesive layer 6 is δ b, then will form 0≤δ t-δ b≤3.0, preferably the relation of 0.5≤δ t-δ b≤2.0.If the difference in specific gravity of photocatalyst granular and adhesive layer is too little, then when making the adhesive layer fusion, photocatalyst granular translational speed of vertical direction in adhesive layer is slack-off, photocatalyst granular is peeled off easily after roasting, if the difference in specific gravity of photocatalyst granular and adhesive layer is excessive, then photocatalyst granular increases in the translational speed of vertical direction, most of photocatalyst granular occurs and imbed phenomenon in the adhesive layer, if produce this phenomenon partly, just be detained bacterium thereon, reduce antibiotic property.
Moreover as the application mode of this method, even under the situation that must make δ t-δ b＞3.0, the 2nd adhesive layer that also can make 0≤δ t-δ b≤3.0 is between adhesive layer and photocatalyst granular.
In addition, δ t-δ b＜0 o'clock,, the identical effect with increase difference in specific gravity δ t-δ b is arranged then if when heat treated, pressurize.Therefore, handle by HIP, hot-pressing processing can obtain and 0≤δ t-δ b≤3.0 o'clock identical effects.
In addition, constitute the gap of the photocatalyst granular of exposed portions serve in the adhesive layer 6, concrete as shown in Figure 16 (a), the necking section of photocatalyst granular 3b, perhaps shown in Figure 16 (b) between the photocatalyst granular 3, in order to make the mutual combination of photocatalyst granular, can fill the little particle 4 in this gap of size ratio (metal such as Sn, Ti, Ag, Cu, Zn, Fe, Pt, Co, Pd, Ni or oxide etc.).
In addition, as other manufacture methods with multifunctional material of photo-catalysis function of the present invention, can also on base materials 1 such as pottery, resin or metal, form the adhesive layer 6 that thermoplastic is formed, then, the mixture that coating forms with colloidal sol or precursor state mixed light catalyst granules 3 and the little particle 4 of particle diameter on this adhesive layer 6, form photocatalyst layer 2, after this, above-mentioned adhesive layer 6 is softened, lower floor's part of photocatalyst layer 2 is imbedded in the adhesive layer 6, be cured subsequently.
According to this method, not only easy, also because coating with colloidal sol or precursor state mix platform in advance landfill form photocatalyst layer to the particle 4 in gap and the mixture of photocatalyst granular 3.So controlling photocatalyst granular 3 and landfill to very convenient aspect the mixing ratio of the particle 4 in gap.
In addition, as other manufacture methods with multifunctional material of photo-catalysis function of the present invention, can also be on the laminar adhesive layer 6 that thermoplastic is formed, photocatalyst granular 3 and little particle 4 mixtures of particle diameter that coating mixes with colloidal sol or precursor state, form photocatalyst layer 2, the laminar adhesive layer 6 that forms this photocatalyst layer 2 is downloaded to or sticks on the base materials such as pottery, resin or metal, then, make above-mentioned adhesive layer softening, the part of photocatalyst layer lower floor is embedded in the binding agent, then is cured.
Have again, as other manufacture methods with multifunctional material of catalysis of the present invention, also can be at pottery, form the adhesive layer 6 that thermoplastic is formed on the base material such as resin or metal 1, then, on this adhesive layer 6, form the photocatalyst layer of forming by photocatalyst granular 32, after this, above-mentioned adhesive layer 6 is softened, the part of photocatalyst layer 2 lower floors is embedded in the adhesive layer, adhesive layer is solidified, on photocatalyst layer, be coated with the solution that contains above-mentioned small size particle again, above-mentioned small size particle 4 be fixed on the photocatalyst granular through heat treatment.
When the particle of this method in the landfill gap is oxide, be easy to implement, and when making the photocatalyst layer of porous matter, the particle in landfill gap adhered in a large number.
Also have, other manufacture methods that have the multifunctional material of photo-catalysis function as the present invention, also can on the laminar adhesive layer of forming by thermoplastic 6, form the photocatalyst layer of forming by photocatalyst granular 32, then will form the laminar adhesive layer mounting of this photocatalyst layer or stick on pottery, on the base material such as resin or metal 1, after this, above-mentioned adhesive layer 6 is softened, the part of photocatalyst layer 2 lower floors is embedded in the adhesive layer 6, adhesive layer is solidified, on photocatalyst layer, be coated with the solution that contains metallic particles 4 again, the particle of above-mentioned small particle diameter be fixed on the photocatalyst granular 3 through heat treatment.
In addition, as other manufacture methods with multifunctional material of photo-catalysis function of the present invention, also can be at pottery, form the adhesive layer of forming by thermoplastic 6 on the base material such as resin or metal 1, then on this adhesive layer 6, form the photocatalyst layer of forming by photocatalyst granular 32, after this, make above-mentioned adhesive layer softening, the part of photocatalyst layer lower floor is embedded in the adhesive layer, follow the cured binders layer, on photocatalyst layer, be coated with the ion solution that contains little metallic particles 4 again, irradiation contains ultraviolet light then, makes metal ion reduction and is fixed on the photocatalyst granular.
The particle of this method in the landfill gap is easy to implement when being metal, and can carry out the fixing of metal with utmost point short time (several minutes).In addition, the lamp that is used for ultraviolet ray irradiation can be any of ultraviolet lamp, BLB lamp, xenon lamp, mercury vapor lamp, fluorescent lamp.
Have again, as other manufacture methods with multifunctional material of photo-catalysis function of the present invention, also can on the laminar adhesive layer of forming by thermoplastic, form the photocatalyst layer of forming by photocatalyst granular, then will form laminar adhesive layer 6 mountings of photocatalyst layer or stick on pottery, on the base material such as resin or metal 1, after this, above-mentioned adhesive layer 6 is softened, the part of photocatalyst layer lower floor is embedded in the adhesive layer 6, adhesive layer 6 is solidified, on photocatalyst layer 2, be coated with the ion solution that contains above-mentioned small particle diameter metallic particles 4 again, irradiation comprises ultraviolet light then, the reducing metal ion is fixed on the photocatalyst granular.
Also have, as other manufacture methods with multifunctional material of photo-catalysis function of the present invention, also can be at pottery, form the adhesive layer of forming by thermoplastic 6 on the base material such as resin or metal 1, then on this adhesive layer 6, form the photocatalyst layer of forming by photocatalyst granular 32, coating contains the ion solution of above-mentioned small particle diameter metallic particles 4 on this photocatalyst layer 2, after this irradiation comprises ultraviolet light, make metal ion reduction and be fixed on the photocatalyst granular 3, above-mentioned adhesive layer 6 is softened, the part of photocatalyst layer lower floor is embedded in the adhesive layer, subsequently the cured binders layer.
According to this method,, can boost productivity because heat-treatment process is once finished.
Have again, as other manufacture methods with multifunctional material of photo-catalysis function of the present invention, also can on the laminar adhesive layer of forming by thermoplastic 6, form the photocatalyst layer of forming by photocatalyst granular 32, coating contains the ion solution of small particle diameter metallic particles 4 on this photocatalyst layer 2, after this irradiation comprises ultraviolet light, make metal ion reduction and be fixed on the photocatalyst granular 3, to form the laminar adhesive layer mounting of photocatalyst layer 2 again or stick on pottery, on the base material such as resin or metal 1, after this, above-mentioned adhesive layer 6 is softened, the part of photocatalyst layer 2 lower floors is embedded in the adhesive layer, then the cured binders layer.
Here, can ZnO as above-mentioned photocatalyst granular, with Ag or Ag
2O is as the metallic particles 4 of filling in the gap of this photocatalyst granular.Ag or Ag
2The O particle is not only strengthened the mutual combination of light-catalyst ZnO particle, and strengthens the photocatalysis effect of ZnO, and itself also has antibiotic, odor-resistant result.Owing to select ZnO,, can utilize background color, style or their combination of base material to obtain windfall effect in addition so can eliminate cause by the Ag ion painted as photochemical catalyst.
In addition, also can be between the metal ion in filling the gap of above-mentioned photocatalyst granular, the solution that contains the salt that forms insoluble colourless or white salt is contacted with photocatalyst layer, after this shine and comprise ultraviolet light.
Like this, even do not make up ZnO and Ag or Ag
2O also can eliminate produced by the particle in landfill gap painted, can utilize base material background color, style or their combination to improve unexpected effect.
In addition, with TiO
2As photocatalyst granular, also can with more than 800 ℃, below 1000 as the heat treatment temperature that is used for softening adhesive layer 6.More than 800 ℃ the time, at TiO
2So the necking section that particle produces owing to the initial stage of generation sintering each other is although TiO
2Particle bond strength to each other improves, but if surpass 1000 ℃, then shifts to the sintering process in mid-term, follows TiO
2Solid-phase sintering, the volume of photocatalyst layer significantly shrinks, thereby is easy to generate crackle.
In addition, with TiO
2As above-mentioned photocatalyst granular, with Ag as the particle 4 of in the gap of this photocatalyst granular, filling, also can KI, KCl, FCl
3Deng halide solution as contain and this Ag ion between form the solution of the salt of insoluble colourless or white salt.Ag and alkali halide between form insoluble colourless or white salt such as AgI, AgCl, so be expected to improve the effect of utilizing base material background color, style or their combination.
In addition, last process as coating photocatalyst particle process on the adhesive layer is equipped with under the situation of dispersion process, be used for to become in the dispersant of the colloidal sol of photocatalyst granular or this dispersion process that precursor is dispersed in solution, preferably only use the composition that gasifies under than the low temperature of the heat treatment temperature of softening adhesive layer.
In prior art, less than 320 ℃ the time, do not have deodorization, this be because in dispersion process attached to TiO
2The insufficient gasification of the dispersant of particle surface, the evaporation and left behind, cause TiO
2It is the most surperficial that particle surface fully is not exposed to base material, can not reach photo-catalysis function fully.Moreover as the dispersant that low temperature gasifies down, preferred molecular weight is organic dispersing agent, the phosphoric acid series dispersant below 10,000.
Enumerate specific embodiment below.
On 150 tetragonal Ceramic Tiles substrate surfaces, form by SiO with spraying process
2-Al
2O
3-Na/K
2The adhesive layer that the O frit is formed is after the drying, with the TiO of spraying process coating 15%
2The colloidal sol aqueous solution, the TiO of formation thickness 0.8 μ m
2Layer, then, in roller hearth furnace, add thermal bake-out stacked adhesive layer and TiO
2The base material (atmosphere temperature is different with different instances) of layer, cooling curing obtains multifunctional material then.
Here, so-called TiO
2The colloidal sol aqueous solution for example is TiCl to be hydrolyzed obtain the Detitanium-ore-type TiO of crystal grain footpath 0.007-0.2 μ m degree in autoclave under the hydrothermal condition of 100-200 ℃ of scope
2, with this TiO
2In alkaline aqueous solutions such as acidic aqueous solutions such as nitric acid, hydrochloric acid or ammonia, carry out the dispersion of a few percent to percent tens with collosol state, in order to improve dispersiveness, can the scope below 0.5% add surface conditioning agents such as organic base, pentaerythrite, trihydroxymethyl propane such as triethanolamine and trihydroxy methyl amine.In addition, TiO
2The image that the particle diameter of colloidal sol utilizes SEM (ESEM) to observe is handled, and the crystallization particle diameter is from the integral breadth calculating of powder x-ray diffraction.
In addition, though coating process carries out with spraying process, estimate dip coating, revolve tumbling barrel process and also obtain same result.
The multifunctional material of gained carries out the evaluation of antibiotic property and wearability.
About antibiotic property, test is to the bactericidal effect of Escherichia coli (Escherichia coli W3110 bacterial strain).On in advance with the surface of the multifunctional material of 70% ethanol sterilization, drip bacterium liquid 0.15ml (1-5 * 10
4CFU), (10 * 10cm) go up and substrate surface is adjacent to as sample to be placed on glass plate.After white lamps (3500 Lux) irradiation 30 minutes, the sample that shone with the sterile gauze wiping and at the bacterium liquid of the sample that covers the optical condition maintenance is recovered in the 10ml physiological saline, obtains the survival rate of bacterium, as evaluation index.
About wearability, use the slip abrasion of plastic eraser, relatively the variation of outward appearance is estimated.
Follow binding agent SiO when in following table 1, having represented base material for Ceramic Tiles
2-Al
2O
3-Na/K
2The variation of O frit sintering temperature, the variation of antibiotic property, wearability.
(table 1)
Base material=Ceramic Tiles, binding agent=SiO
2-Al
2O
3-Na/K
2The O frit
Photochemical catalyst=TiO
2
| No. | 1 | 2 | 3 | 4 | 5 |
| Sintering temperature (℃) with softening temperature poor (℃) the |
700 20 ++ △ | 780 100 +++ ○ | 880 200 +++ ◎ | 980 300 - ◎ | 1000 320 - ◎ |
The colibacillary survival rate of +++: is below 10%
++: colibacillary survival rate is more than 10% below 30%
+: colibacillary survival rate is more than 30% below 70%
-: colibacillary survival rate is more than 70%
◎: back and forth do not change for 40 times
Zero: the slip at 10-40 time has scratch, photocatalyst layer (TiO
2Film) peels off
△: the slip at 5-10 time has scratch, photocatalyst layer (TiO
2Film) peels off
*: in the slip below 5 times scratch is arranged, photocatalyst layer (TiO
2Film) peels off
Here, the SiO that uses as adhesive layer
2-Al
2O
3-Na/K
2The proportion of O frit is 2.4, and the thickness during coating is 200 μ m, and softening temperature is 680 ℃.In addition, in table 1, resulting TiO
2In, No.1-3 is a Detitanium-ore-type, proportion is 3.9, and No.4, the 5th, rutile-type, proportion are 4.2.
In table 1, the No.1 sintering temperature is only higher 20 ℃ than the softening temperature of adhesive layer, for the viscosity of insufficient reduction adhesive layer, constitutes the undermost Detitanium-ore-type TiO of photocatalysis layer
2Particle is insufficient to be embedded in the binding agent, therefore 5-10 slip scratch is arranged in abrasion test, peels off.This may be interpreted as for antibiotic property, and what photocatalytic activity was good is Detitanium-ore-type, and more than 300 ℃, TiO
2The TG-DTA observed result of colloidal sol show organic principle decompose substantially, gasify, attached to TiO
2The gasification of dispersants such as lip-deep surface conditioning agent, but sintering temperature is than this temperature high treatment temperature, i.e. 700 ℃ of formation far away ++ excellent value.
The No.3-5 sintering temperature is the situation more than 800 ℃, below 1000 ℃, but durability is all fine, even the sliding test more than 40 times does not change yet.Its reason can think to follow the TiO on surface
2The initial stage roasting of particle forms the event in necking section.In addition, when 1100 ℃ are handled, behind the cooling curing from the TiO on the multifunctional material surface that roller hearth furnace takes out
2Crack on the layer.From TiO
2The TMA of sample measures and judges, can think that this is to follow TiO
2The remarkable contraction of particle volume is by mid-term, sintering caused.
No.4,5 antibiotic property inequality, all be-.Can think two reasons are wherein arranged.First TiO
2Particle is transformed into rutile-type mutually, and another is the softening temperature more than 300 ℃ that sintering temperature is higher than adhesive layer, and the viscosity of adhesive layer became low, constitutes the TiO of photocatalyst layer
2Particle is embedded in the adhesive layer.Here can not only think TiO
2Particle is transformed into the reason of rutile-type mutually.This is because no doubt rutile TiO
2Also be inferior to Detitanium-ore-type TiO
2, but photocatalysis also has certain activity.For example on porous matter aluminum oxide base material, directly spray TiO
2Colloidal sol, after 950 ℃ of roastings, the material antibiotic property that cooling curing forms is+.Therefore it is higher more than 300 ℃ than the softening temperature of adhesive layer to may be interpreted as sintering temperature, and the viscosity of adhesive layer became low, constitutes the TiO of photocatalyst layer
2Particle is embedded in the adhesive layer, also is one of reason.
In addition, utilize Ti and Si (principal component of the binding agent) elementary analysis of the EPMA etc. of sample section direction, observe the mixed layer of Ti and Si, confirm photocatalyst granular TiO
2Buried underground.
Above embodiment 1 is TiO at photochemical catalyst at least promptly
2, adhesive layer is SiO
2-Al
2O
3-Na/K
2During the O frit, confirmed the following fact.
(1) is higher than adhesive layer softening temperature more than 20 ℃ at sintering temperature, is no more than when making multifunctional material under 300 ℃ the condition, can make all good multifunctional material of antibiotic property and wearability.Its reason can think that in the said temperature scope viscosity of binding agent is adjusted to and makes TiO
2Can moderately be embedded in the value in the adhesive layer.
(2) in the multifunctional material that has confirmed to make with (1), TiO
2Particle is embedded in the binding agent.
(3) be more than 800 ℃, below 1000 ℃ the time at sintering temperature, wearability is fabulous, sliding test does not change more than 40 times yet.Can think and follow TiO
2Intergranular necking section forms and produces firm combination.
On the surface of the aluminum oxide base material 100 * 100 * 5 (aluminium oxide purity 96%), form SiO with spraying process
2-Al
2O
3The adhesive layer that-PbO frit is formed is after the drying, with the TiO of spraying process coating 15%
2The colloidal sol aqueous solution (with embodiment 1), the TiO of formation thickness 0.8 μ m
2Layer, then, in roller hearth furnace with add with the different and different atmosphere temperature of example thermal bake-out stacked adhesive layer and TiO
2The base material of layer, cooling curing obtains multifunctional material then.
In following table 2, when having listed base material and being aluminium oxide, along with binding agent SiO
2-Al
2O
3The variation of sintering temperature during-PbO frit, the variation of antibiotic property, wearability.
(table 2)
Base material=alumina plate (100 * 100 * 5),
Binding agent=SiO
2-Al
2O
3-PbO frit
Photochemical catalyst=TiO
2
| No | 6 | 7 | 8 | 9 | 10 |
| Sintering temperature (℃) with softening temperature poor (℃) the antibiotic property wearability | 560 20 ++ △ | 580 40 +++ ○ | 740 200 +++ ○ | 840 300 ++ ◎ | 860 320 + ◎ |
At this, as the SiO of binding agent use
2-Al
2O
3The softening temperature of-PbO glass is 540 ℃, and proportion is 3.8, and thickness is 150 μ m when being coated with into.In addition, resulting TiO
2Crystal formation be Detitanium-ore-type.
In the abrasion test of table 2, No.6 abrades with lower slider at 10 times, peel off, even but No.7,8 does not have scratch in the slip more than 10 times yet, has again, even No.9 obtains also not having abrasive this good result in the slip more than 40 times.
In No.9,10,, the slip more than 40 times can not think because sintering temperature is more than 800 ℃, at TiO even also abrading this
2Generate constriction between particle, TiO
2The mutual cause of combination securely of particle.
In No.6, the slip below 10 times has scratch, peels off, and this can think that the viscosity of binding agent is not very low because sintering temperature is only high 20 ℃ than binding agent softening temperature, constitutes the undermost Detitanium-ore-type TiO of photocatalyst layer
2Particle is not embedded in the cause in the adhesive layer fully.
In contrast, even in No.7, also not scratch of slip more than 8 10 times, this can think because do not reach the temperature that constriction generates temperature, but the difference of sintering temperature and binding agent softening temperature adjust to make binding agent viscosity with TiO
2Moderately be embedded in the numerical value in the adhesive layer.
On the other hand, in the test of the antibiotic property of table 2, No.6-9 obtains +++or ++ good result, but No.10 be+.This can think because sintering temperature is higher 320 ℃ than binding agent softening temperature, and the viscosity of binding agent is low excessively, constitutes the TiO of photocatalyst layer
2Particle is embedded in the cause in the adhesive layer.
With SiO
2-Al
2O
3The fusion in mould of-BaO frit behind the cooling curing, is processed, and makes 100 * 100 * 1 glass flake, is coated with 15% TiO thereon with spraying process
2The colloidal sol aqueous solution (with embodiment 1), the TiO of formation thickness 0.8 μ m
2Layer.After this, glass flake is placed on the aluminum oxide base material (100 * 100 * 5), so that different atmosphere temperatures adds thermal bake-out with example is different, cooling curing obtains multifunctional material then in silicon carbide rod furnace.
Table 3 expression is along with the variation of the sintering temperature of multifunctional material, the variation of antibiotic property, wearability.
(table 3)
Base material=alumina plate (100 * 100 * 5),
Binding agent=SiO
2-Al
2O
3-BaO frit
Photochemical catalyst=TiO
2
| No. | 11 | 12 | 13 | 14 |
| Sintering temperature (℃) with softening temperature poor (℃) the antibiotic property wearability | 640 20 ++ × | 740 120 +++ ○ | 840 220 +++ ◎ | 940 320 - ◎ |
Here, the SiO that uses as binding agent
2-Al
2O
3The softening temperature of-BaO frit is 620 ℃, and proportion is 2.8, the TiO on the multifunctional material
2Crystal formation, No.11-13 is a Detitanium-ore-type, N0.14 is a rutile-type.
In the abrasion test of table 3, No.11 has scratch in the slip below 10 times, peel off, even but No.12 does not have scratch in the slip more than 10 times yet, has again, even No.13,14 obtains also not having abrasive good result in the slip more than 40 times.
Even No.13,14 can think because sintering temperature is more than 800 ℃, at TiO in the slip more than 40 times also not scratch
2Form constriction between particle, TiO
2The mutual cause of combination securely of particle.
No.11 abrades in the slip below 10 times, peels off, can think that the viscosity of binding agent is not fully low because sintering temperature is only higher 20 ℃ than binding agent softening temperature, constitutes the undermost Detitanium-ore-type TiO of photocatalyst layer
2Particle can not be embedded in the adhesive layer fully.
In contrast, No.12 is in the slip more than 10 times also not scratch, can though think not reach the sintering temperature that constriction generates temperature, but the difference of sintering temperature and binding agent softening temperature be adjusted to the viscosity that makes binding agent can be moderately with TiO
2Be embedded in the numerical value in the adhesive layer.
On the other hand, in the test of the antibiotic property of table 3, No.11-13 obtains +++or ++ good result, but No.14 be-.Can think that this is caused by two aspect reasons: TiO
2Be rutile-type, and sintering temperature is higher 320 ℃ than binding agent softening temperature, the viscosity of binding agent is low excessively, constitutes the TiO of photocatalyst layer
2Particle is embedded in the adhesive layer.
Can confirm from above, be used in and be coated with TiO on the binding agent in advance
2Particle sticks on then and carries out the method that roasting obtains multifunctional material on the base material, also obtains and be coated with binding agent on base material, is coated with TiO then
2Particle obtains the identical effect of method of multifunctional material.
100 * 100 * 5 be acrylic resins of painting binding agent on the surface of the base material that constitutes of resin by polyimides, be coated with 15%TiO with spraying process then
2The colloidal sol aqueous solution, the TiO of formation thickness 0.8 μ m
2Layer, then in the nickel filament stove 150 ℃ of roastings stacked adhesive layer and TiO
2The base material of layer.
Expression is with the variation of the sintering temperature of above-mentioned multifunctional material, the variation of antibiotic property, wearability in following table 4.
(table 4)
Base material=polyimide resin, binding agent=acrylic resin
Photochemical catalyst=TiO
2, 150 ℃ of sintering temperatures
| No. | 15 | 16 |
| The antibiotic property wearability | - ○ | ++ ○ |
In addition, in table 4,15%TiO
2The method of adjustment of the colloidal sol aqueous solution changes as following.
No.15: the 15%TiO that former state uses embodiment 1 to use
2The colloidal sol aqueous solution.
In 110-150 ℃ of hydrolysis, with nitric acid product is adjusted to pH then is 0.8 to the No.16:TiCl aqueous solution in autoclave, disperses not using under the surface modifier, then uses the material of having removed condensation product.Spraying is to carry out immediately after removing condensation product.
Here, TiO
2Proportion be 3.9, crystal formation is a Detitanium-ore-type, the proportion of acrylic resin is 0.9, the temperature that forms corresponding to the viscosity of glass softening point is 70 ℃.
About wearability, under NO.15,16 condition, do not abrade even slide more than 10 times yet.Can think this is to make TiO because the difference range of sintering temperature and binding agent softening temperature can be adjusted to the viscosity of binding agent
2Can moderately be embedded in the value in the adhesive layer.
On the other hand, about antibiotic property test, find No.15 be-, but No.16 obtains ++ good result, even and below 30 ℃, also can make multifunctional material with antibiotic property.In DTA-TG, with the TiO of No.15
2Colloidal sol has the composition in 200-350 ℃ of decomposition, evaporation, but does not see with No.16, covers TiO so have or not
2Organic principle just become the reason of this difference.
In addition, Detitanium-ore-type TiO
2With the difference in specific gravity of acrylic resin be 3, but confirmed under this degree difference condition, constitute the TiO of photocatalyst layer
2Particle is not embedded in the adhesive layer, has good antibacterial property yet.
On 100 * 100 * 5 aluminum oxide base material surface, form the adhesive layer that constitutes with the different frit of each example etc. by proportion with spraying process after, drying is coated with 15%TiO with spraying process then
2The colloidal sol aqueous solution, the TiO of formation thickness 0.8 μ m
2Layer, then, in roller hearth furnace with 750 ℃ of atmosphere temperatures, with stacked adhesive layer and TiO
2The base material of layer adds thermal bake-out, and cooling curing obtains multifunctional material then.
The above-mentioned multifunctional material of expression is with the variation of sintering temperature, the variation of antibiotic property, wearability in following table 5.
(table 5)
Base material=alumina plate (100 * 100 * 5), photochemical catalyst=TiO
2
| No. | 17 | 18 | 19 | 20 |
| The kind of binding agent | SiO 2-Al 2O 3-PbO | SiO 2-Al 2O 3-PbO | ||
| Binding agent proportion TiO 2Proportion frit softening temperature (℃) sintering temperature (℃) | 5.3 3.9 480 750 | 3.8 3.9 540 750 | 2.8 3.9 620 750 | 2.4 3.9 680 750 |
| The antibiotic property wearability | ++ × | +++ ○ | +++ ○ | +++ ○ |
About antibiotic property test, No.17-20 obtains +++good result.In each sample, sintering temperature is higher more than 30 ℃ than softening agent softening temperature, can think below 300 ℃ that the difference range of sintering temperature and binding agent softening temperature is transferred to the viscosity of binding agent and is made TiO
2Moderately be embedded in the numerical value in the adhesive layer.
About wearability, No.17 has scratch in the slip below 5 times, peels off, even but No.18-20 does not have scratch in the slip more than 10 times yet.
Its reason can think that the proportion of binding agent compares TiO because No.17 is different with other
2Ratio great, constitute photocatalyst layer orlop Detitanium-ore-type TiO
2Particle is not embedded in the adhesive layer.
Therefore, TiO
2All influence the wearability of multifunctional material with the proportion of binding agent, if the proportion of binding agent is greater than TiO
2Proportion, wearability variation then.
On 150 tetragonal Ceramic Tiles substrate surfaces, form by SiO
2-Al
2O
3The adhesive layer that-BaO frit (620 ℃ of softening temperatures) is formed mixes, stirs TiO with the spraying process coating thereon
2Colloidal sol and SnO
2The aqueous solution that colloidal sol forms carries out roasting at 750 ℃ then, and cooling curing obtains multifunctional material.
In addition, TiO
2Collosol concentration is 4-6% (weight), uses NH
3The aqueous solution is adjusted to 11 with pH, TiO
2The crystal grain of particle directly is 0.01 μ m, SnO
2The crystal grain of particle directly is 0.0035 μ m.
In the multifunctional material that is made into like this, with respect to TiO
2And SnO
2Add up to quantitative change SnO
2Amount (mol ratio) is carried out antibiotic property and abrasion test, and it the results are shown in the following table 6.
(table 6)
Base material=Ceramic Tiles, binding agent=SiO
2-Al
2O
3-BaO frit
Photochemical catalyst=TiO
2, gap particle=SnO
2(0.0035 μ m)
| No. | 21 | 22 | 23 | 24 | 25 |
| SnO
2Amount (mol%) | 0 +++ ○ | 10 +++ ◎ | 20 +++ ◎ | 60 ++ ◎ | 100 - ◎ |
About abrasion test, with SnO
2Amount increase and improve owing to add more than 10%,, do not change even all not have to abrade 40 times sliding test yet.
About antibiotic property test,, when not adding be equally if become to the scope 20% or more +++, as if to 60%, just be limited to ++.If on this, increase again, then hide the TiO of substrate surface
2The probability of particle uprises, the antibiotic property deterioration, become 100%-.
Therefore, press the mol ratio, if make SnO
2Addition be TiO
2And SnO
2More than 10%, below 60% of total amount, preferably more than 10%, below 20%, then can provide antibiotic property and wearability all good multifunctional material.
Here, wearability is with SnO
2Amount to increase and improve be because mechanism shown below: because under the high temperature more than 600 ℃, SnO
2Vapour pressure is higher than TiO
2So, before sintering, TiO
2The interval of particle 3b is Lo shown in Figure 17 (a), but at TiO
2Particle 3 has that vapour pressure uprises on the surface of positive camber, has the surface of negative cruvature, i.e. two TiO
2The surface vapor pressure step-down of the necking section that particle 3b joins.Its result is shown in Figure 17 (b), and vapour pressure compares TiO
2High SnO
2Enter the necking section, condensing shown in Figure 17 (c), carry out sintering according to gasification-condensing mechanism.
And, if carry out sintering according to gasification-condensing mechanism, the TiO behind the sintering then
2The interval L of particle
2Generally equal the preceding interval Lo of sintering, so do not crack.
Make TiO by binding agent like this
2Stratum granulosum remains in the composite component that forms on the substrate surface, is exposing the most surperficial TiO
2Fill SnO in the gap of particle
2If particle carrying out roasting more than 600 ℃, does not then crack, because can make TiO
2The combination of intergranular necking section is so improved wearability.
Comparative example 7
Identical with embodiment 6, form by SiO on the surface of 150 square Ceramic Tiles base materials
2-Al
2O
3The adhesive layer that-BaO frit (620 ℃ of softening temperatures) is formed, the TiO that mixes and stir with the spraying process coating thereon
2Colloidal sol and SnO
2The aqueous solution that colloidal sol forms carries out roasting at 750 ℃ then, obtains multifunctional material behind the cooling curing.
In addition, TiO
2Collosol concentration is 4-6% (weight), uses NH
3The aqueous solution is adjusted to pH11, and the crystal grain of particle footpath and embodiment 6 are identical to be 0.01 μ m, but uses SnO
2The size of microcrystal of particle is 0.008 μ m and big slightly particle.
The multifunctional material that is made into is like this carried out antibiotic property test and abrasion test, in the result who compares with embodiment 6 shown in the following table 7.
(table 7)
Base material=Ceramic Tiles, binding agent=SiO
2-Al
2O
3-BaO frit
Photochemical catalyst=TiO
2, gap particle=SnO
2750 ℃ of (0.0080 μ m), heat treatments
| No. | 26 | 27 | 28 | 29 | 30 |
| SnO
2Amount (mol%) | 0 +++ ○ | 10 +++ ○ | 20 +++ ○ | 60 ++ ◎ | 100 - ◎ |
The SnO of 0.008 μ m as a result
2The raising effect of the wearability of particle is than the SnO that uses 0.0035 μ m
2A little less than during particle, to TiO
2And SnO
2If the mol of total amount, even do not abrade 40 times sliding test, does not change more than 60% than about yet yet.
About the antibiotic property test, with the SnO that uses 0.0035 μ m
2The situation of particle is identical, if become to the scope 20% or more, when not adding is equally +++, as if becoming below 60%, just be limited to ++.If on this, increase again, hide the TiO of substrate surface
2The probability of particle uprises, the antibiotic property deterioration, become 100%-.
Therefore, using 0.01 μ m TiO
2Under the situation of particle, add the SnO of 0.008 μ m
2Particle is difficult to obtain antibiotic property and all good multifunctional material of wearability.Its reason can be thought because with SnO
2Grain diameter becomes big vapour pressure and diminishes, at the remaining SnO that do not gasify
2When particle is 0.008 μ m, because and TiO
2SnO is compared in intergranular gap
2Particle is big, so SnO
2Particle does not enter in the gap, arrives TiO certainly
2Probability on the particle uprises, this and the remaining SnO that do not gasify
2SnO when particle is 0.0035 μ m
2Be present in TiO
2In the intergranular gap, the situation that can improve bond strength is relative.
From above, answer landfill TiO
2The SnO in the gap of particle
2The size of particle is TiO relatively
2The particle footpath it is desirable to below 4/5.
Embodiment 8
On 150 tetragonal Ceramic Tiles substrate surfaces, form by SiO
2-Al
2O
3The adhesive layer that-BaO frit (620 ℃ of softening temperatures) is formed is coated with TiO with spraying process thereon
2Behind the colloidal sol aqueous solution, carry out roasting, on the composite component of cooling curing, be coated with SnO with spraying process at 750 ℃
2Behind the colloidal sol aqueous solution, heat-treat, obtain multifunctional material at 110 ℃.This moment is at TiO
2Use the solution identical in the colloidal sol aqueous solution, at SnO with embodiment 6
2Use 0.0035 μ m person in the colloidal sol.
The multifunctional material of making is like this carried out antibiotic property test and abrasion test, the results are shown in the following table 8.
(table 8)
Base material=Ceramic Tiles, binding agent=SiO
2-Al
2O
3-BaO frit
Photochemical catalyst=TiO
2,
Gap particle=SnO
2750 ℃/110 ℃ of (0.0035 μ m), heat treatments
| No. | 31 | 32 | 33 | 34 | 35 |
| SnO
2Amount (mol%) | 0 +++ ○ | 10 +++ ○ | 20 +++ ◎ | 60 ++ ◎ | 100 - ◎ |
About abrasion test, with SnO
2Amount increase and improve more than (mol than),, do not change owing to add 20% even in 40 sliding tests, do not produce scratch yet yet.
About the antibiotic property test,, when adding be equally with nothing if become to the scope more than 20% +++, if become, just be limited to 60% ++.If on this, increase again, then hide substrate surface TiO
2It is big that the probability of particle becomes, the antibiotic property deterioration, became at 100% o'clock-.
In this test, because SnO
2Colloidal sol is heat-treated at 110 ℃ low temperature, so the sintering that caused by the gasification shown in the embodiment 6-condensing mechanism does not take place.Although wearability improves, this is considered to because size ratio TiO
2Particle is little, and promptly specific area is big, the SnO that absorption affinity is good
2Particle landfill TiO
2TiO is strengthened with this in the gap of particle
2The cause of the combination that particle is mutual.
On 150 tetragonal Ceramic Tiles substrate surfaces, form by SiO
2-Al
2O
3The adhesive layer that-BaO frit (620 ℃ of softening temperatures) is formed is coated with TiO with spraying process thereon
2Behind the colloidal sol aqueous solution, carry out roasting at 750 ℃, the coating copper acetate aqueous solution on the composite component that cooling curing forms, drying, irradiation comprises ultraviolet light then, and the reduction copper ion is fixed on the photocatalyst layer simultaneously, obtains multifunctional material.At this, irradiation light uses mercury vapor lamp.
About this is fixed on Cu granular size average out to 0.004 μ m on the photocatalyst layer.
The multifunctional material of making is like this carried out antibiotic property test and abrasion test, the results are shown in the table 9.
(table 9)
Base material=Ceramic Tiles, binding agent=SiO
2-Al
2O
3-BaO frit
Photochemical catalyst=TiO
2,
Gap particle=Cu (0.004 μ m), 750 ℃/photo-reduction of heat treatment
| No. | 36 | 37 | 38 | 39 | 40 |
| Cu amount (mol%) | 0 +++ ○ | 10 +++ ○ | 20 +++ ◎ | 60 +++ ◎ | 100 +++ ◎ |
About abrasion test, improve with the increase of Cu amount, owing to add more than 20% (the mol ratio),, do not change even in 40 times sliding test, do not abrade yet yet.
About the antibiotic property test,, when adding be equally with nothing as if becoming to the scope more than 20% +++, because Cu itself has antibacterial activity, so do not see the antibiotic properties deterioration that causes because of adding in a large number.
But the addition of general Cu after a little while, because of TiO
2The photocatalysis that stratum granulosum produces is dominant, and at the addition of Cu for a long time, also permission thinks that the effect that is produced by Cu is dominant.Under the situation of only looking to the Cu effect, because Cu slow stripping when using in liquid, so can think and compare with the situation of no photochemical catalyst, the life-span is short.In addition, if the interpolation quantitative change of Cu is many, this departmental cost also uprises.Therefore, think that setting Cu too much measures also meaningless.
According to present embodiment, confirmed not only as SnO
2Such oxide, and the metal as Cu can both become landfill TiO
2The particle in the gap of stratum granulosum.
On 150 tetragonal Ceramic Tiles substrate surfaces, form by SiO
2-Al
2O
3The adhesive layer that-BaO frit (620 ℃ of softening temperatures) is formed is coated with TiO with spraying process thereon
2Behind the colloidal sol aqueous solution, carry out roasting at 950 ℃, the coating copper acetate aqueous solution on the composite component that cooling curing forms, irradiation comprises ultraviolet light then, and the reduction copper ion is fixed on the photocatalyst layer simultaneously, obtains multifunctional material.
This moment, irradiation light used the BLB lamp, shone several minutes.TiO
2Be phase-changed into rutile-type through heat treatment process from Detitanium-ore-type.TiO when spraying
2Thickness be adjusted to 0.4 μ m.
The multifunctional material of making is like this carried out antibiotic property test and abrasion test.About abrasion test,, also show good result in this humidity province even do not add.Even add Cu, in 40 sliding tests, do not abrade equally with there being when interpolation yet, do not change yet.
About the antibiotic property test, be shown among Figure 18.There not being when interpolation, because TiO
2Be rutile-type, be bad+.Add Cu therein, antibiotic property increases.And during the BLB light irradiation, be exactly when not having irradiation, not only if the Cu loading is 0.7 μ g/cm
2More than, then antibacterial activity becomes ++, if the Cu loading is 1.2 μ g/cm
2More than, then antibacterial activity becomes +++.
From above, in order to provide antibiotic property and wearability all good multifunctional material, the loading of Cu can be 0.7 μ g/cm
2More than, better can be 1.2 μ g/cm
2More than.
Behind the coating copper acetate aqueous solution, before the BLB light irradiation, if enter dry run, then the leap of Cu loading improves.Be shown among Figure 19 about this relation.Can think that this is because carrying out drying, the concentration of metal ions height when then carrying out photo-reduction.
In addition, when making coating weight optimum, the Cu loading becomes maximum (Figure 20, Figure 20 are that Cu concentration is the example of the copper acetate of 1% (weight)), in the situation of Figure 20, is 0.7 μ g/cm in order to make the Cu loading
2More than, coating weight can be 0.2mg/cm
2More than, 2.7mg/cm
2Below, be 1.2 μ g/cm in order to make the Cu loading
2More than, the Cu coating weight can be 0.3mg/cm
2More than, 2.4mg/cm
2Below.
Embodiment 11
On 150 tetragonal Ceramic Tiles substrate surfaces, form by SiO
2-Al
2O
3The adhesive layer that-BaO frit (680 ℃ of softening temperatures) is formed is coated with TiO with spraying process thereon
2Behind the colloidal sol aqueous solution, carry out roasting at 950 ℃, be coated with silver nitrate aqueous solution on the composite component that cooling curing forms, carry out drying, irradiation comprises ultraviolet light then, and the reduction silver ion is fixed on the photocatalyst layer simultaneously, obtains multifunctional material.
Irradiation light uses the BLB lamp, shines several minutes.TiO in addition
2Be transformed into rutile-type through heat treatment mutually from Detitanium-ore-type.TiO when spraying
2Thickness be adjusted to 0.4 μ m.
The multifunctional material of making is like this carried out antibiotic property test and abrasion test.About wearability,, also show good result in this humidity province even do not add.Even add Ag, the same yet not scratch in 40 times sliding test when not adding does not change yet.
Be shown among Figure 70 about antibiotic property.When not adding because TiO
2Be rutile-type, thus be bad+.If add Ag therein, antibiotic property just increases.And not only when the BLB light irradiation, exactly when not shining, if the Ag loading becomes 0.05 μ g/cm
2More than, then antibacterial activity also becomes ++, if the Ag loading becomes 0.1 μ g/cm
2More than, then antibacterial activity becomes +++.
Therefore, in order to provide antibiotic property and wearability all good multifunctional material, the Ag loading can be 0.05 μ g/cm
2More than, better can be 0.1 μ g/cm
2More than.
But, Ag loading more than, painted from the dark brown black that becomes, degraded appearance.But the Ag loading becomes 1 μ g/cm
2Below, just not painted.
From above, the Ag loading can be 0.05 μ g/cm
2More than, 1 μ g/cm
2More than, be more preferably 0.1 μ g/cm
2More than, 1 μ g/cm
2Below.
On 150 tetragonal Ceramic Tiles substrate surfaces, form by SiO
2-Al
2O
3The adhesive layer that-BaO frit (680 ℃ of softening temperatures) is formed is coated with TiO with spraying process thereon
2Behind the colloidal sol aqueous solution, carry out roasting at 950 ℃, be coated with silver nitrate aqueous solution on the composite component that cooling curing forms, carry out drying, irradiation after this comprises ultraviolet light, and the reduction silver ion is fixed on the photocatalyst layer simultaneously, obtains multifunctional material.
Irradiation light uses the BLB lamp at this moment, shines several minutes.TiO in addition
2Be transformed into rutile-type through heat treatment mutually from Detitanium-ore-type.
The multifunctional material of making is like this changed TiO
2Thickness, carry out test of abrasion test, antibiotic property and stain resistance test.
About abrasion test, all show good result at 2 μ m of test in interior scope, even yet not scratch in 40 times sliding test does not change yet.
About antibiotic property test, be 0.1 μ m when above at thickness, become ++, when 0.2 μ m is above, become +++.Therefore, TiO
2Thickness can be more than the 0.1 μ m, better can be more than the 0.2 μ m.
Embodiment 13
On 150 tetragonal Ceramic Tiles substrate surfaces, form by SiO
2-Al
2O
3The adhesive layer that-BaO frit (620 ℃ of softening temperatures) is formed is thereon with spraying process coating solder(ing)acid or TiO
2The colloidal sol aqueous solution, carry out drying after, the coating silver nitrate aqueous solution, irradiation comprises ultraviolet light then, the reduction silver ion is fixed on the photocatalyst layer simultaneously, after this more than 900 ℃, carries out roasting below 1000 ℃, obtains multifunctional material behind the cooling curing.
This moment, irradiation light used the BLB lamp, shone several minutes.TiO in addition
2Be transformed into rutile-type through heat treatment mutually from Detitanium-ore-type.And the fixing Ag in surface becomes white with heat treatment from tea black, so can think become silver oxide in roasting.But adhering to of Ag fixing finished discretely, makes discovery from observation and almost do not see growing up of Ag particle before and after roasting.
The multifunctional material of making is like this carried out antibiotic property test and abrasion test.
About abrasion test, do not show good result even be not added on this humidity province yet.Even add Ag, the same when not adding, yet not scratch does not change yet in 40 times sliding test yet.
About the antibiotic property test, be shown among Figure 70, when not adding, because of TiO
2Be rutile-type, thus be bad+.If add Ag, antibiotic property increases therein.
Embodiment 14
On 150 tetragonal Ceramic Tiles substrate surfaces, form by SiO
2-Al
2O
3The adhesive layer that-BaO frit (620 ℃ of softening temperatures) is formed is coated with TiO with spraying process thereon
2Behind the colloidal sol aqueous solution,, carry out roasting below 1000 ℃ more than 900 ℃, on the composite component that cooling curing forms, the coating silver nitrate aqueous solution, irradiation comprises ultraviolet light then, the reduction silver ion is fixed on the photocatalyst layer simultaneously, more thereon with 0.1cc/cm
2The KI aqueous solution of ratio coating 0.1mol/L, with ultraviolet ray irradiation about 5 seconds, obtain multifunctional material again.This moment, the loading of Ag was 2 μ g/cm
2
Because with 0.1cc/cm
2The KI aqueous solution of ratio coating 0.1mol/L, irradiation ultraviolet radiation is about 5 seconds again, the multifunctional material of the former black of tea before this decolours white, improves in appearance.
On 150 tetragonal Ceramic Tiles substrate surfaces, form by SiO
2-Al
2O
3The adhesive layer that-BaO frit (620 ℃ of softening temperatures) is formed is coated with TiO with spraying process thereon
2Behind the colloidal sol aqueous solution, carry out roasting, cooling curing at 820 ℃, the multifunctional material of gained is tilted to place, and irradiation comprises ultraviolet light in the multifunctional material top, and the bathing pool water at public outdoor bathing place is picked up from the limit in the multifunctional material cocycle, drip continuously, observe the variation of bathing pool water.For more same device, also on the base material that photocatalyst layer is not set, drip.Observe to find at the bathing pool water that drips on the above-mentioned multifunctional material and the bathing pool water that on the base material that photocatalyst layer is not set, drips relatively, on muddy situation, do not have special difference, but on sewer water stink, have difference in addition after 14 days.The bathing pool water that drips on the base material that photocatalyst layer is not set has great sewer water smelly, and on base material, observe the mucus and the organogenous sediment of mud shape, in contrast, the bathing pool water that drips on above-mentioned multifunctional material is not all seen those situations.By above simulated test, can think that this multifunctional material can be used as the artificial waterfall of water endless form such as park, department store and the shop stone of fountain.
By above explanation as can be known, be the adhesive layer fixed photocatalyst particle of forming by the material lower than base material softening temperature, especially to make the photocatalyst granular that constitutes the photocatalyst layer skin section not imbed in the adhesive layer, expose outside state so photocatalyst granular is in its surface in fact, can bring into play the photocatalysis effect fully.In addition, constitute the particle of photocatalyst layer lower floor in the photocatalyst granular,,, be difficult to occur peeling off etc. so improve the confining force of photocatalyst layer significantly because its part is embedded in the adhesive layer.
Figure 21 represents the process drawing of other embodiment, and in this embodiment, base material 1 uses thermoplastics such as unorganic glass and thermoplastic resin, directly forms photocatalyst layer 2 on the surface of this thermoplastic matrix 1.
Just shown in Figure 21 (a), be ready to thermoplastic matrix 1, then shown in Figure 21 (b), form by TiO on the surface of thermoplastic matrix 1
2The photocatalyst layer 2 that photocatalyst granulars such as particle are formed.After this, shown in Figure 21 (c), through heat treatment, the lower floor of the above-mentioned thermoplastic matrix side among the photocatalyst layer 2 is deposited on the thermoplastic matrix, imbeds in the thermoplastic matrix through solidifying, and keeps securely.In addition, the photocatalyst granular 3 that constitutes the top layer that contacts with air among the photocatalyst layer 2 utilizes potential energy, mutual molecular separating force or sintering to combine.
About optimum condition of present embodiment etc., though same as the previously described embodiments, following narration is about specific embodiment.
Embodiment 16
At 150 tetragonal SiO
2-Al
2O
3-Na/K
2On the surface of the glass baseplate that O forms, be coated with 15%TiO with spraying process
2The colloidal sol aqueous solution, the TiO of formation thickness 0.8 μ m
2Layer, then, with stacked TiO
2The glass baseplate of layer is put into the good ceramic die of release property, adds thermal bake-out with the atmosphere temperature different with different examples in roller hearth furnace, and cooling curing obtains multifunctional glass then.
Here, so-called TiO
2The colloidal sol aqueous solution makes by following mode: with for example TiCl
4In autoclave, under the hydrothermal condition of 100-200 ℃ of scope, be hydrolyzed, obtain the Detitanium-ore-type TiO of crystal grain footpath 0.007-0.2 μ m degree
2, with this TiO
2It is tens of to be dispersed into a few percent to percent with collosol state in alkaline aqueous solutions such as acidic aqueous solutions such as nitric acid, hydrochloric acid or ammonia; In order to improve dispersiveness, add organic base, pentaerythrite, trihydroxymethyl propanes etc. such as surface conditioning agent triethanolamine and trihydroxy methyl amine with the scope below 0.5% and obtain TiO
2The colloidal sol aqueous solution.In addition, TiO
2The image that the particle diameter of colloidal sol utilizes SEM to observe is handled and is obtained, and the crystal grain footpath calculates from the integral breadth of powder x-ray diffraction.
In addition, though coating process carry out with spraying process, expection with dip coating, revolve tumbling barrel process and also can obtain same result.
The multifunctional glass of gained is carried out the evaluation of antibiotic property and wearability.
About antibiotic property, test is to the bactericidal effect of Escherichia coli (Escherichia coli W3110 bacterial strain).In advance with the most surperficial 0.15ml bacterium liquid (1-5 * 10 of dripping of the multifunctional glass of 70% ethanol sterilization
4CFU), (10 * 10cm) go up and base material is the most surperficial is adjacent to as sample to be placed on glass plate.,, be recovered in the 10ml physiological saline after 30 minutes with white lamps (3500 lux) irradiation, obtain the survival rate of bacterium, as evaluation index with the wiping of sterilization cotton yarn sample that shone and the bacterium liquid that covers the sample that keeps under the optical condition.
About wearability, use the plastic eraser abrasion of sliding, the comparison appearance change is estimated.
Expression is used by SiO in following table 10
2-Al
2O
3-Na/K
2The glass baseplate that O forms, with the variation of its sintering temperature, the variation of antibiotic property, wearability.
(table 10)
Base material=SiO
2-Al
2O
3-Na/K
2O glass
Photochemical catalyst=TiO
2
| No. | 1 | 2 | 3 | 4 | 5 |
| Sintering temperature (℃) with softening temperature poor (℃) the | 700 20 ++ △ | 780 100 +++ ○ | 880 200 +++ ◎ | 980 300 - ◎ | 1000 320 - ◎ |
The colibacillary survival rate of +++: is below 10%
++: colibacillary survival rate is more than 10% below 30%
+: colibacillary survival rate is more than 30% below 70%
-: colibacillary survival rate is more than 70%
◎: to 40 reciprocal no changes
Zero: the slip at 10-40 time has scratch, photocatalyst layer (TiO
2Film) peels off
△: the slip at 5-10 time has scratch, photocatalyst layer (TiO
2Film) peels off
*: in the slip below 5 times scratch is arranged, photocatalyst layer (TiO
2Film) peels off
Here, SiO
2-Al
2O
3-Na/K
2The proportion of the glass baseplate that O forms is 2.4, and softening temperature is 680 ℃.In addition, in table 10, resulting TiO
2, No.1-3 is a Detitanium-ore-type, proportion is 3.9, and No.4, the 5th, rutile-type, proportion are 4.2.
In table 10, the sintering temperature of No.1 is only higher 20 ℃ than the softening temperature of glass baseplate, owing to can not make the viscosity of glass baseplate fully low, constitutes the undermost Detitanium-ore-type TiO of photocatalyst layer
2Particle is insufficient to be embedded in the glass baseplate, therefore in abrasion test, 5-10 slip scratch is arranged, and peels off.In addition, also owing to be the good Detitanium-ore-type of photocatalytic activity; And more than 300 ℃ the time to TiO
2The TG-DTA of colloidal sol observe find organic principle decompose basically, gasify, attached to TiO
2Dispersants such as lip-deep surface conditioning agent gasification, but sintering temperature is 700 ℃, is than the high considerable heat treatment temperature of this temperature, so antibiotic property becomes ++ excellent value.
Though the sintering temperature of No.3-5 is more than 800 ℃, below 1000 ℃, though wearability in the sliding test more than 40 times, also no change all.Be extremely good.Its reason can think to follow the TiO on surface
2The initial stage roasting of particle produces the necking section.In addition, when handling for 1100 ℃, the TiO on the multifunctional glass surface of from roller hearth furnace, taking out behind the cooling curing
2Crack on the layer.This is from TiO
2The TMA of sample measures and judges, can think to follow TiO
2The sintering in mid-term of the remarkable volume contraction of particle causes.
No.4,5 antibiotic property all be-, be poor.Can think that this has two reasons: one of them is TiO
2Particle is transformed into rutile-type mutually, and another is that sintering temperature is higher 300 ℃ than glass baseplate softening temperature, and the viscosity of glass baseplate is low excessively, constitutes the TiO of photocatalyst layer
2Particle is embedded in the glass baseplate.Can not only consider TiO at this
2Particle is transformed into this reason of rutile-type mutually.Even this is because in rutile TiO
2In, also be inferior to Detitanium-ore-type, but also have photocatalytic activity to a certain degree.For example on porous matter aluminum oxide base material, directly spray TiO
2Colloidal sol, after 950 ℃ of roastings, the antibiotic property of the material that cooling curing forms is+.Therefore it is higher 300 ℃ than the softening temperature of glass baseplate to may be interpreted as sintering temperature, and the viscosity of glass baseplate is low excessively, forms the TiO that constitutes photocatalyst layer
2Particle is embedded in the glass baseplate, and this is another reason.
In addition,, observe the layer that Ti and Si are mixed in, confirmation photocatalyst granular TiO by Ti and Si (principal component of the glass baseplate) elementary analysis of the EPMA on the sample cross-wise direction etc.
2Buried underground.
Above embodiment 16 is TiO at photochemical catalyst at least promptly
2, glass baseplate is by SiO
2-Al
2O
3-Na/K
2When O forms, confirmed the following fact.
(1) when sintering temperature is made multifunctional glass than glass baseplate softening temperature under high 20 ℃, the not high condition more than 300 ℃, can make all good multifunctional glass of antibiotic property, wearability.Its reason can think that in the said temperature scope viscosity of glass baseplate is adjusted to and made TiO
2Moderately be embedded in the numerical value in the glass baseplate.
(2) in the multifunctional glass of in (1), making, confirmed TiO
2Particle buries in the glass baseplate.
(3) be more than 800 ℃, below 1000 ℃ the time at sintering temperature, even wearability is extremely good in the sliding test more than 40 times also no changes all.Can think with TiO
2Intergranular necking section forms, and produces firm combination and causes.
Embodiment 17
By SiO
2-Al
2O
3On 100 * 100 * 5 the glass baseplate surface that-PbO forms, with the TiO of spraying process coating 15%
2The colloidal sol aqueous solution (identical with embodiment 16) forms the O.8 TiO of μ m of thickness
2Layer, then, with stacked TiO
2The glass baseplate of layer is put into the good ceramic die of release property, adds thermal bake-out with the atmosphere temperature different with different examples in roller hearth furnace, and cooling curing obtains multifunctional glass then.
In following table 11, SiO is used in expression
2-Al
2O
3During glass baseplate that-PbO forms, change the variation of antibiotic property, wearability with sintering temperature.
(table 11)
Base material=SiO
2-Al
2O
3-PbO glass
Photochemical catalyst=TiO
2
| No. | 6 | 7 | 8 | 9 | 10 |
| Sintering temperature (℃) with softening temperature poor (℃) the antibiotic property wearability | 560 20 ++ △ | 580 40 +++ ○ | 740 200 +++ ○ | 840 300 ++ ◎ | 860 320 + ◎ |
Here, SiO
2-Al
2O
3The softening temperature of the glass baseplate that-PbO forms is 540 ℃, and proportion is 3.8, the TiO of gained
2Crystal formation be Detitanium-ore-type.
In the abrasion test of table 11, No.6 just has scratch in the slip below 10 times, peels off, even but No.7,8 does not have scratch in the slip more than 10 times yet, have again, even No.9,10 obtains also not having abrasive this good result in the slip more than 40 times.
Even in the slip more than 40 times also not scratch, can think, thereby at TiO because sintering temperature is more than 800 ℃ at No.9,10
2Form constriction between particle, make TiO
2The mutual cause of combination securely of particle.
In the slip below 10 times scratch is just arranged at No.6, peel off, can think to make the viscosity of glass baseplate enough low, constitute the Detitanium-ore-type TiO of photocatalyst layer because sintering temperature is only higher 20 ℃ than the softening temperature of glass baseplate
2Particle is not embedded in the cause in the glass baseplate fully.
In contrast, even do not abrade in the slip more than 10 times, can, can make TiO but the difference of sintering temperature and glass baseplate softening temperature is adjusted to the viscosity that makes glass baseplate though think not reach the temperature that forms constriction at No.7,8 yet
2Moderately be embedded in the numerical value in the glass baseplate.
On the other hand, in the test of the antibiotic property of table 11, No.6-9 obtains +++or ++ good result, but No.10 become+.Can think that this is that the viscosity of glass baseplate is low excessively because sintering temperature is higher 320 ℃ than the softening temperature of glass baseplate, constitutes the TiO of photocatalyst layer
2Particle is embedded in the glass baseplate.
Embodiment 18
At SiO
2-Al
2O
3On 100 * 100 * 5 the glass baseplate surface that-BaO forms, with the TiO of spraying process coating 15%
2The colloidal sol aqueous solution (identical) with embodiment 1, the TiO of formation thickness 0.8 μ m
2Layer.Then, with stacked TiO
2The glass baseplate of layer is put into the good ceramic die of release property, adds thermal bake-out with the atmosphere temperature different with different examples in the nickel filament stove, and cooling curing obtains multifunctional glass then.
Shown in the following table 12 with the variation of the sintering temperature of above-mentioned multifunctional glass, the variation of antibiotic property, wearability.
(table 12)
Base material=SiO
2-Al
2O
3-BaO glass
Photochemical catalyst=TiO
2
| No. | 11 | 12 | 13 | 14 |
| Sintering temperature (℃) with softening temperature poor (℃) the antibiotic property wearability | 640 20 ++ × | 740 120 +++ ○ | 840 220 +++ ◎ | 940 320 - ◎ |
Here, SiO
2-Al
2O
3The softening temperature of the glass baseplate that-BaO forms is 620 ℃, and proportion is 2.8, the TiO on the multifunctional glass
2Crystal formation, No.11-13 is a Detitanium-ore-type, No.14 is a rutile-type.
In the abrasion test of table 12, No.11 just has scratch in the slip below 5 times, peel off, even but No.12 does not have scratch in the slip more than 10 times yet, has again, even No.13,14 obtains also not having abrasive this good result in the slip more than 40 times.
Even No.13,14 can think because sintering temperature is more than 800 ℃, at TiO in the slip more than 40 times also not scratch
2Form constriction between particle, TiO
2The mutual cause of combination securely of particle.
No.11 just has scratch in the slip below 10 times, peels off, can think that the viscosity of glass baseplate is not enough low because sintering temperature is only higher 20 ℃ than the softening temperature of glass baseplate, constitutes the undermost Detitanium-ore-type TiO of photocatalyst layer
2Particle is not embedded in the cause in the glass baseplate fully.
In contrast, even No.12 is in the slip more than 10 times also not scratch, can though think can make TiO because do not reach the temperature that the necking section forms but the difference of sintering temperature and glass baseplate softening temperature is adjusted to the viscosity that makes glass baseplate
2Particle moderately is embedded in the numerical value in the glass baseplate.
On the other hand, in the test of the antibiotic property of table 12, No.11-13 obtains +++or ++ good result, but No.14 become-.This can think owing to two reasons: one is TiO
2Be rutile-type, it is high 320 ℃ that another is that sintering temperature is finished than the softening temperature of glass baseplate, and the viscosity of glass baseplate is low excessively, constitutes the TiO of photocatalyst layer
2Particle is embedded in the glass baseplate.
Embodiment 19
On different 100 * 100 * 5 the glass baseplate surface of proportion, with the TiO of spraying process coating 15% with different examples
2The colloidal sol aqueous solution, the TiO of formation thickness 0.8 μ m
2Layer, then, with stacked TiO
2Glass baseplate put into the good ceramic die of release property, in roller hearth furnace, with 750 ℃, add thermal bake-out as atmosphere temperature, cooling curing obtains multifunctional glass then.
Shown in the following table 13 with the variation of the glass baseplate proportion of above-mentioned multifunctional glass, the variation of antibiotic property, wearability.
(table 13)
Photochemical catalyst=TiO
2
| No. | 15 | 16 | 17 | 18 |
| The glass baseplate kind | SiO 2-Al 2O 3-PbO | SiO 2-Al 2O 3-PbO | ||
| Glass baseplate proportion TiO 2Proportion glass baseplate softening temperature (℃) sintering temperature (℃) | 5.3 3.9 480 750 | 3.8 3.9 540 750 | 2.8 3.9 620 750 | 2.4 3.9 680 750 |
| The antibiotic property wearability | ++ × | +++ ○ | +++ ○ | +++ ○ |
About antibiotic property test, No.15-18 obtains +++good result.Can think that all than the high scope more than 30 ℃, below 300 ℃ of softening temperature of glass baseplate, the poor scope of sintering temperature and glass baseplate softening temperature is adjusted to the viscosity that makes glass baseplate can make TiO to sintering temperature because in each
2Moderately be embedded in the numerical value in the glass baseplate.
About wearability, No.15 just has scratch in the slip below 5 times, peels off, even No.16-18 is in the slip more than 10 times also not scratch.
Its reason can think that the proportion of glass baseplate compares TiO because No.15 is different with other
2Than great, constitute the undermost Detitanium-ore-type TiO of photocatalyst layer
2Particle does not have abundant geography to be located in the glass baseplate
Thereby clear, TiO
2Also influence the wearability of multifunctional glass with the proportion of glass baseplate, the proportion of glass baseplate is greater than TiO
2Proportion, just worsen wearability.
At 150 tetragonal SiO
2-Al
2O
3-BaO forms on the glass baseplate of (620 ℃ of softening temperatures) formation, is coated with TiO with spraying process
2Colloidal sol and SnO
2Colloidal sol mixes and stirs the aqueous solution that forms, and carries out roasting at 750 ℃ then, and cooling curing obtains multifunctional glass.
TiO
2Collosol concentration is 4-6% (weight), uses NH
3The aqueous solution is adjusted to pH11, TiO
2The size of microcrystal of particle is 0.01 μ m, SnO
2The size of microcrystal of particle is 0.0035 μ m.
For the multifunctional glass of making like this, change with respect to TiO
2And SnO
2The various SnO of sum
2Amount (mol ratio) is carried out antibiotic property and abrasion test, and it the results are shown in the following table 14.
(table 14)
Base material=SiO
2-Al
2O
3-BaO glass
Photochemical catalyst=TiO
2, gap particle=SnO
2(0.0035 μ m)
| No. | 19 | 20 | 21 | 22 | 23 |
| SnO
2Amount (mol%) | 0 +++ ○ | 10 +++ ◎ | 20 +++ ◎ | 60 ++ ◎ | 100 - ◎ |
About abrasion test, with SnO
2Amount increase and improve owing to add more than 10%, even yet not scratch in 40 times sliding test does not change yet.
About the antibiotic property test,, when then adding be equally with nothing as if the scope that becomes to 20% +++, if become, then be limited to 60% ++.If increase again thereon, then the TiO of covering glass substrate surface
2The probability of particle uprises, and antibiotic property is inferior, to 100% become-.
Therefore, press SnO
2Addition is with respect to TiO
2And SnO
2The mol ratio of total amount be more than 10%, below 60%, preferably more than 10%, can provide antibiotic property, wearability all good multifunctional glass below 20%.
Here wearability is with SnO
2Amount increase and improve, the mechanism illustrated by Figure 17 causes.
Like this, make TiO by glass baseplate
2Stratum granulosum remains in the lip-deep composite component of glass baseplate, is exposing the most surperficial TiO
2In the particle if fill SnO
2Particle carrying out roasting more than 600 ℃, does not then crack, because can make TiO
2The combination of intergranular necking section is so improve wearability.
Comparative example 21
Identical with embodiment 20, at 150 tetragonal SiO
2-Al
2O
3-BaO forms on the glass baseplate surface of (620 ℃ of softening temperatures) formation, is coated with TiO with spraying process
2Colloidal sol and SnO
2Colloidal sol mixes and stirs the aqueous solution that forms, and carries out roasting at 750 ℃ then, and cooling curing obtains multifunctional glass.
TiO
2Collosol concentration is 4-6% (weight), uses NH
3The aqueous solution is adjusted to pH11, and the size of microcrystal of particle is identical with embodiment 5, is 0.01 μ m, but SnO
2The size of microcrystal of particle uses 0.008 μ m and big slightly particle diameter.
The multifunctional glass of making is like this carried out antibiotic property and abrasion test, with the results are shown in the following table 15 that embodiment 5 compares.
(table 15)
Base material=SiO
2-Al
2O
3-BaO glass
Photochemical catalyst=TiO
2, gap particle=SnO
2750 ℃ of (0.0080 μ m), heat treatments
| No. | 24 | 25 | 26 | 27 | 28 |
| SnO
2Amount (mol%) | 0 +++ ○ | 10 +++ ○ | 20 +++ ○ | 60 ++ ◎ | 100 - ◎ |
Consequently, the SnO of 0.008 μ m
2The effect that the particle wearability improves is than the SnO that uses 0.0035 μ m
2A little less than during particle, with respect to TiO
2Particle and SnO
2The mol of the total amount of particle, does not change even do not abrade in 40 times sliding test than being 60% when above gradually yet yet.
About the antibiotic property test, with the SnO that uses 0.0035 μ m
2The situation of particle is identical, if become the scope to 20%, when then adding with nothing is equally +++, if become below 60%, be limited to ++.If increase again thereon, then the TiO of covering glass substrate surface
2It is big that the probability of particle becomes, and the antibiotic property deterioration becomes one to 100%.
Thereby, at the TiO that uses 0.01 μ m
2Under the occasion of particle, add the SnO of 0.008 μ m
2Particle is difficult to obtain antibiotic property and all good multifunctional glass of wearability.Its reason can think because SnO
2The vapour pressure of particle becomes with particle diameter and diminishes greatly, and the remaining SnO that do not gasify
2When particle is 0.0035 μ m, be present in TiO
2In the intergranular gap, can improve bond strength, in contrast, SnO
2When particle is 0.008 μ m and TiO
2The gap of particle is compared, SnO
2Particle is big, so Sn
2The O particle does not enter in the gap, arrives TiO naturally
2Probability on the particle becomes big cause.
Find out from above, should landfill TiO
2The SnO in particle gap
2The size of particle it is desirable to respect to TiO
2Particle diameter is below 4/5.
Embodiment 22
At 150 tetragonal SiO
2-Al
2O
3-BaO forms on the glass baseplate surface of (620 ℃ of softening temperatures) formation, is coated with TiO with spraying process
2The colloidal sol aqueous solution carries out roasting at 750 ℃ then, is coated with SnO with spraying process on the composite component that cooling curing forms
2Behind the colloidal sol aqueous solution, heat-treat, obtain multifunctional glass at 110 ℃.At this moment, TiO
2The colloidal sol aqueous solution uses and embodiment 5 identical persons, SnO
2Colloidal sol uses 0.0035 μ m person.
The multifunctional glass of so making is carried out antibiotic property and abrasion test, and it the results are shown in the following table 16.
(table 16)
Base material=SiO
2-Al
2O
3-BaO glass
Photochemical catalyst=TiO
2,
Gap particle=SnO
2750 ℃/110 ℃ of (0.0035 μ m), heat treatments
| No. | 29 | 30 | 31 | 32 | 33 |
| SnO
2Amount (mol%) | 0 +++ ○ | 10 +++ ○ | 20 +++ ◎ | 60 ++ ◎ | 100 - ◎ |
About abrasion test, with SnO
2Amount increase and improve owing to add 20% more than (mol than), even yet not scratch in 40 sliding tests does not change yet.
About the antibiotic property test,, when then adding be equally with nothing as if the scope that becomes to 20% +++, if become, then be limited to 60% ++.If increase again thereon, then the TiO of covering glass substrate surface
2It is big that the probability of particle becomes, the antibiotic property deterioration, to 100% become-.
In this test, because SnO
2Colloidal sol is heat-treated at 110 ℃ low temperature, so the sintering that caused by the gasification shown in the embodiment 5-condensing mechanism does not take place.Although wearability improves, can think that this is because size ratio TiO
2Particle is little, and promptly specific area becomes big, the SnO that sorptive force is good
2Particle landfill TiO
2The gap of particle, thereby strengthen TiO
2The cause of the combination that particle is mutual.
Embodiment 23
At 150 tetragonal SiO
2-Al
2O
3-BaO forms on the glass baseplate of (620 ℃ of softening temperatures) formation, is coated with TiO with spraying process
2The colloidal sol aqueous solution carries out roasting at 750 ℃ then, and on the composite component that cooling curing forms, the coating copper acetate aqueous solution carries out drying, and irradiation after this comprises ultraviolet light, and the reduction copper ion is fixed on the photocatalyst layer simultaneously, obtains multifunctional glass.Use mercury vapor lamp at this irradiation light.
At this, the Cu granular size that is fixed on the photocatalyst layer is about average 0.004 μ m.
The multifunctional glass of so making is carried out the results are shown in the following table 17 of antibiotic property and abrasion test.
(table 17)
Base material=SiO
2-Al
2O
3-BaO glass
Photochemical catalyst=TiO
2,
Gap particle=SnO
2(0.004 μ m), 750 ℃/photo-reduction of heat treatment
| No. | 34 | 35 | 36 | 37 | 38 |
| Cu amount (mol%) | 0 +++ ○ | 10 +++ ○ | 20 +++ ◎ | 60 +++ ◎ | 100 +++ ◎ |
About wearability, improve with the increase of Cu amount, owing to add more than 20% (the mol ratio),, do not change even in 40 times sliding test, do not abrade yet yet.
About the antibiotic property test,, when then adding be equally with nothing if become to the scope more than 20% +++, because Cu itself has antibacterial activity, so see that adding the antibiotic property that causes because of volume worsens.
But probably can think Cu addition after a little while, by TiO
2Stratum granulosum and the photocatalysis that produces is dominant, the addition of Cu are that the effect that produced by Cu is dominant for a long time.When the situation of the effect of only expecting Cu, can think that because Cu slow stripping when in liquid, using so think and compare with the situation of no photochemical catalyst, the life-span lacks.In addition, if the addition of Cu for a long time, the cost of this part is also high.Therefore, it is also meaningless to think that the Cu amount was set on volume ground.
Confirm by this embodiment, not only as SnO
2Such oxide, and the metal as Cu also can become landfill TiO
2The particle in the gap of stratum granulosum.
Embodiment 24
Tetragonal 150 by SiO
2-Al
2O
3-BaO forms on the glass baseplate surface of (620 ℃ of softening temperatures) formation, is coated with TiO with spraying process
2The colloidal sol aqueous solution carries out roasting at 950 ℃ then, the coating copper acetate aqueous solution on the composite component that cooling curing forms, and irradiation after this comprises ultraviolet light, and the reduction copper ion is fixed on the photocatalyst layer simultaneously, obtains multifunctional glass.
This moment, irradiation light used the BLB lamp, shone several minutes.TiO
2Be phase-changed into rutile-type through heat treatment from Detitanium-ore-type.TiO
2Thickness in spraying, adjust to 0.4 μ m.
The multifunctional glass of so making is carried out antibiotic property and abrasion test.About abrasion test,, also show good result in this humidity province even do not add.Even add Cu, identical when also adding with nothing, even yet not scratch in 40 times sliding test does not change yet.
Test is shown among Figure 22 about antibiotic property.When not adding, because TiO
2Be rutile-type, thus be the difference+.If add Cu, then improve antibiotic property therein.And not only during the BLB light irradiation, and when not shining, the loading of Cu is if become 0.7 μ g/cm
2More than, then antibacterial activity becomes ++, if the Cu loading becomes 1.2 μ g/cm
2, then antibacterial activity becomes +++.
From as can be seen above, in order to provide antibiotic property and wearability all good multifunctional glass, the Cu loading can be 0.7 μ g/cm
2, better can be 1.2 μ g/cm
2
But,, then improve the Cu loading by leaps and bounds if behind the coating copper acetate aqueous solution, before the BLB light irradiation, enter dry run.Tie up among Figure 23 about this pass and to represent.Can think that this is because the concentration of metal ions height when carrying out drying during photo-reduction.
In addition, when making the Cu coating weight optimum, the Cu loading becomes maximum (Figure 24 is the example of the copper acetate of Cu concentration 1% (weight)), in Figure 24, is 0.7 μ g/cm in order to make the Cu loading
2More than, can make coating weight is 0.2mg/cm
2More than, 2.7mg/cm
2Below, be 1.2 μ g/cm in order to make the Cu loading
2More than, can make coating weight is 0.3mg/cm
2More than, 2.4mg/cm
2Below.
At 150 tetragonal SiO
2-Al
2O
3-BaO forms on the glass baseplate surface of (680 ℃ of softening temperatures) formation, is coated with TiO with spraying process
2The colloidal sol aqueous solution carries out roasting at 950 ℃ then, is coated with silver nitrate aqueous solution on the composite component that cooling curing forms, and carries out drying, and the back irradiation comprises ultraviolet light, and the reduction silver ion is fixed on the photocatalyst layer simultaneously, obtains multifunctional glass.
At this moment, irradiation light uses the BLB lamp, shines several minutes.TiO in addition
2Be transformed into rutile-type through heat treatment mutually from Detitanium-ore-type.TiO
2Thickness is adjusted to 0.4 μ m in spraying.
The multifunctional glass of so making is carried out antibiotic property and abrasion test.About wearability,, also obtain good result in this humidity province even do not add.Even add Ag, also identical when not adding, even yet not scratch in 40 times sliding test does not change yet.
Test is shown among Figure 25 about antibiotic property.When not adding because TiO
2Be rutile-type, thus be the difference+.If add Ag, then improve antibiotic property thereon.And not only when the BLB light irradiation, and when not shining, if the Ag loading is 0.05 μ g/cm
2More than, then antibacterial activity becomes ++, if the Ag loading is 0.1 μ g/cm
2, then antibiotic property becomes +++.
Therefore in order to provide antibiotic property and wearability all good multifunctional glass, the Ag loading can be 0.05 μ g/cm
2More than, better can be 0.1 μ g/cm
2More than.
But, if the Ag loading is many, then from the dark brown black that is coloured to, deterioration in appearance.If yet Ag loading 1 μ g/cm
2Below, then not painted.
Find out that from above the Ag loading can be 0.05 μ g/cm
2More than, 1 μ g/cm
2Below, better can be 0.1 μ g/cm
2More than, 1 μ g/cm
2Below.
Embodiment 26
Tetragonal 150 by SiO
2-Al
2O
3-BaO forms on the glass baseplate surface of (680 ℃ of softening temperatures) formation, is coated with TiO with spraying process
2The colloidal sol aqueous solution carries out roasting at 950 ℃ then, is coated with silver nitrate aqueous solution on the composite component that cooling curing forms, and carries out drying, and irradiation after this comprises ultraviolet light, and the reduction silver ion is fixed on the photocatalyst layer simultaneously, obtains multifunctional glass.
At this moment, irradiation light uses the BLB lamp, shines several minutes.In addition, TiO
2Be phase-changed into rutile-type through heat treatment from Detitanium-ore-type.
The multifunctional glass of so making is changed TiO
2Thickness, carry out test of abrasion test, antibiotic property and stain resistance test.
About abrasion test, the test thickness be 2 μ m with interior scope in, all show good result, even yet not scratch in 40 times sliding test does not change yet.
About antibiotic property test, be that 0.1 μ m becomes when above at thickness ++, more than 0.2 μ m, become +++.So TiO
2Thickness can be more than the 0.1 μ m, better can be more than the 0.2 μ m.
From above explanation as can be known, because photocatalyst granular is fixed on the thermoplastic matrix, especially to make the photocatalyst granular of the skin section that constitutes photocatalyst layer not imbed in the thermoplastic matrix, so photocatalyst granular forms its surface in fact and is exposed to outside state, can bring into play the photocatalysis effect fully.In addition, be embedded in the thermoplastic matrix because constitute the part of the particle of photocatalyst layer lower floor among the photocatalyst granular, so improve the confining force of photochemical catalyst significantly, difficult generation is peeled off etc.
Basic distribution concept map when Figure 26 and Figure 27 are the section direction of observing multifunctional material with EPMA (electron beam microanalyser).As these figure show, from the surface that contacts with air, then be the roughly certain zone (a-quadrant) of concentration that constitutes photocatalyst layer 2 compositions, the composition that after this constitutes photocatalyst layer reduces.The composition that constitutes amorphous layer (adhesive layer) in addition is not that not also seldom entering inner concentration does not more increase more on the surface.And when reaching certain thickness, constituent concentration is certain (B zone) roughly.The a-quadrant is defined as photocatalyst layer here, the B zone definitions is an amorphous layer, and the C zone definitions in the middle of it is the intermediate layer.But Figure 26 is concept map for convenience of explanation after all, in fact as shown in figure 27, in the certain part of the concentration that illustrates, supervenes the change of concentration because of the reason on the manufacture process in Figure 26 more.In this case as shown in figure 27, the border of the concentration minimum of a value in the zone (A ' zone, B ' zone) that reaches corresponding certain zone part being regarded as A ' zone and C ' zone, B ' zone and C ' zone respectively.
Here, the thickness of so-called photocatalyst layer is the thickness in a-quadrant or A ' zone, and the thickness in so-called intermediate layer is the thickness in C zone or C ' zone.
The thickness in intermediate layer can change by translational speed and the mobile possible time of control photocatalyst granular in softening amorphous layer.Difference in specific gravity, sintering temperature, atmosphere pressures of utilizing photocatalyst granular and amorphous layer etc. can be controlled translational speed.In addition, can change the mobile possible time by changing the retention time of amorphous material under softening temperature.
If make the thickness in this intermediate layer become more than 1/3 of photochemical catalyst layer thickness, then more can increase adherence.
Describe below about specific embodiment.
Embodiment 27
On the tetragonal alumina substrate of 10cm, form SiO with spraying process
2-Al
2O
3-Na/K
2The amorphous layer of O system behind the drying and roasting, is coated with the TiO of 0.01 μ m with spraying process
2The colloidal sol aqueous solution, with its 850 ℃, change the retention time and carry out roasting, form the Detitanium-ore-type TiO of 0.2 μ m, 0.5 μ m, 1 μ m
2Film.Then, at this Detitanium-ore-type TiO
2With the spraying process coating copper acetate aqueous solution, after this carry out photo-reduction (light source is 20 watts of BLB lamps, and the distance from light source to sample is 10cm, irradiation time 30 seconds) on the film, obtain sample.About the sample of gained, utilize the section elementary analysis (Ti, Si) of EPMA, measure thickness, estimate antibiotic property and wearability.
About the antibiotic property evaluation, test with Escherichia coli (Escherichia coli W3110 bacterial strain)., be placed on the glass plate (100 * 100) with the most surperficial bacterium liquid 0.15ml (1-50000CPU) that drips of the multifunctional component of 70% ethanol sterilization in advance, make it to be adjacent to, as sample with base material is the most surperficial.After 30 minutes, the sample bacterium liquid with the sterile gauze wiping was shone is recovered in the 10ml physiological saline, obtains the bacteria live rate, as evaluation index with white lamps (35 luxs) irradiation.Identical about metewand with the situation of above-mentioned table 1.
The results are summarized in the table 18.About antibiotic property all be +++.
Wearability, ◎ or zero represents good result.Especially the ratio of intermediate layer thickness and photochemical catalyst layer thickness is that the sample more than 1/3 all is ◎.
(table 18)
| TiO2 thickness (μ m) | Middle bed thickness (μ m) | Retention time (hour) | Middle bed thickness/TiO2 thickness | | Anti-fissility | |
| 1 1 1 0.5 0.5 0.2 0.2 | 0.42 0.33 0.30 0.17 0.13 0.08 0.05 | 16 2 1 2 1 2 1 | 0.42 0.33 0.30 0.34 0.26 0.40 0.25 | +++ +++ +++ +++ +++ +++ +++ | ◎ ◎ ○ ◎ ○ ◎ ○ | |
| 1 | 0 | 0 | +++ | △ |
Comparative example 28
On the tetragonal alumina substrate of 10cm, with the TiO of spraying process coating average grain diameter 0.01 μ m
2The ammonia dispersion liquid of colloidal sol carries out roasting with it at 850 ℃, forms the Detitanium-ore-type TiO of thickness 1 μ m
2Film.Then, at this Detitanium-ore-type TiO
2On the film,, carry out photo-reduction (light source is 20 watts of BLB lamps, and the distance from light source to sample is 10cm, shines 30 seconds) then, obtain sample with the spraying process coating copper acetate aqueous solution.Sample to gained is estimated antibiotic property and wearability.
Its result is good about antibiotic property +++, but wearability is △, sufficient inadequately.
By above explanation as can be seen, photocatalyst layer remains on the substrate surface, the photocatalyst layer top section will come out contiguously with air making by amorphous layer, and photocatalyst layer has in the multifunctional material of the photo-catalysis function that particle mutually combines to each other, amorphous layer and photocatalyst layer will have the intermediate layer that changes both sides' constituent concentration between them continuously, can increase the adherence of photocatalyst film and base material whereby, improve anti-fissility.Make again above-mentioned intermediate layer thickness be the photochemical catalyst layer thickness more can increase adherence more than 1/3.
Narration forms the situation of photocatalyst layer 2 about utilizing sintering below.Fig. 1 (a) is the TiO that represents in the past
2State diagram before the particle sintering (b) is state diagram behind the expression sintering, and shown in Fig. 1 (a), coating contains TiO on the surface of base material 1
2The colloidal sol of particle 3.If the raising film-strength it is heat-treated (sintering), then shown in Fig. 1 (b), be easy to generate crackle 2a.
Its reason can think and be except the transformation mutually to rutile-type causes volume contraction (density become big), also TiO before sintering
2101 of particles be L at interval
o, but be rutile-type behind the sintering, owing to shorten into L to the intergranular interval of the other side's bulk diffusion
1(L
1＜L
o), the result cracks.
Therefore, make SnO
2Condensing at TiO through sinter bonded
2The necking section of particle 3 makes the necking section thick, and strengthens TiO
2The combination that particle 3 is mutual, the result improves film-strength.
In order to form above such photocatalyst layer 2, with SnO
2Colloidal sol is at TiO
2Mix in the colloidal sol and stir, be coated on the substrate 1, heat-treat (sintering) in the temperature range of regulation.
In addition, TiO
2Collosol concentration is about 4-6% (weight), uses NH
3Solution is adjusted to pH11, TiO
2Average 1 particle diameter of particle is 0.01 μ m (10nm), SnO
2Collosol concentration is about 10% (weight), uses NH
3Solution is adjusted to pH11, SnO
2Average 1 particle diameter of particle is 0.0035 μ m.Average 1 particle diameter here is the wide crystallite dimension of obtaining of half value (1 particle) by the diffracted ray of XRD (X-ray diffraction).
Here, because SnO
2Vapour pressure be higher than TiO
2So, TiO before sintering
2The interval of particle 3 is L shown in Figure 17 (a)
o, but surface vapor pressure height with positive camber of titan oxide particles 3, the surface with negative cruvature i.e. the surface vapor pressure step-down of the necking section that joins of 2 titan oxide particles 3.The result is shown in Figure 17 (b), and vapour pressure is higher than the SnO of titanium oxide
2Enter the necking section, shown in Figure 17 (c), take place condensingly, carry out sintering according to gasification-condensing mechanism.
And, if carry out sintering according to gasification-condensing mechanism, the TiO behind the sintering then
2The interval L of particle
2Approximate the preceding interval L of sintering
o, therefore do not crack.
As mentioned above, before and after sintering, make TiO
2The interval of particle does not change in fact, and will make the photolytic activity (R that films as photochemical catalyst
30) be more than 50%, as shown in figure 28, must make SnO
2To TiO
2Ratio (internal ratio) be more than the 20-70%.
Moreover match ratio represents to be included in the weight ratio of the solid constituent in the colloidal sol separately.In addition, photoactive evaluation is carried out with the decomposition of methyl mercaptan, with the clearance (R of illumination after 30 minutes
30) as index.In detail, in the glass container of 11L, be configured in from the distance of light source (BLB fluorescent lamp, 4W) 8cm last with forming the 150 square ceramic tiles that photochemical catalyst films, methyl mercaptan gas is injected in the container with 3-5ppm, after confirmation does not have absorption when dark, light fluorescent lamp, over time with gas Chromatographic Determination concentration.
Here, R
30=(X
o-X
30)/X
o* 100%
X wherein
o=initial stage concentration [ppm] X
30Concentration after=30 minutes [ppm]
In addition, the sliding friction of plastic eraser is used in the evaluation of film-strength, and relatively appearance change is estimated.About metewand ◎, zero, △, * identical with above-mentioned (table 1).
In addition, Figure 29 is the curve map of expression heat treatment temperature and photolytic activity relation, at TiO
2When adding organic stabilizer in the colloidal sol, though reduce photolytic activity, heat treatment temperature all is 300-850 ℃.This be because heat treatment temperature be difficult to below 300 ℃ to produce active, if surpass 850 ℃, TiO then
2Structure be phase-changed into rutile-type from Detitanium-ore-type.
Find out from above explanation, coating contains the colloidal sol that titan oxide particles and vapour pressure are higher than the material of titanium oxide on ceramic tile etc., temperature roasting in regulation, forming by filming with this by the sintering of gasification-condensing mechanism, so the interval of titan oxide particles equates generally before and after sintering, be difficult for producing cracking.In addition, because the condensing SnO in the necking section between titan oxide particles
2Deng, so the peel strength of filming uprises.
Particularly, make SnO
2Deng addition (with TiO
2Internal ratio) reach 20-70%, can satisfy film-strength and photoactive requirement, in addition, more than 300 ℃, the scope below 850 ℃ is heat-treated, and can access enough photolytic activities.
But, use gas Chromatographic Determination R
30, determinator cost height, and a table apparatus can only measure a sample, and efficient is poor.
In addition, though known at TiO
2On support metal such as Pt and improve photolytic activity, but in the photocatalyst film of this spline structure, because because which kind of degree the influence of the gas absorption that metal produces is so be difficult for the clean photolytic activity of judgement.
Moreover, with ceramic tile as wall, in case after the construction, the activity of the photocatalyst film that can not form from the teeth outwards with gas chromatograph for determination.
In addition, as photolytic activity evaluation method without gas chromatograph, though also can consider to detect method because of the postradiation survival rate of light of photochemical catalyst effect killing bacteria, but more bother than operation on gas chromatograph, and in the photocatalyst film of carrying metal, because the antibacterial activity of metal itself is killing bacteria also, so be difficult for judging clean photolytic activity.Therefore, also can use the activity determination method of photocatalyst film as described below.
The TiO that the 1st kind of method forms on substrate surface
2On the photocatalyst film surface for main body, the potassium halide aqueous solution such as KI or potassium chloride that drip then, shine the ultraviolet ray of preset time to the potassium halide aqueous solution that drips.Judge the active big or small of photocatalyst film from the pH of the pre-irradiation potassium halide aqueous solution and the difference of postradiation pH.
The TiO that the 2nd kind of method forms on substrate surface
2On the photocatalyst film surface for main body, drip and in the potassium halide aqueous solution such as KI or potassium chloride, add the mixed liquor of pH indicator, then, the mixed liquor that drips is shone the ultraviolet ray of preset time, because the change color of mixed liquor, thereby can judge the active big or small of photocatalyst film.
The TiO that the 3rd kind of method forms on substrate surface
2Bonding determination of activity film on the photocatalyst film surface for main body to this determination of activity film irradiation ultraviolet ray of preset time, because the change color of determination of activity film, thereby can be judged the active size of photocatalyst film at this state.
Figure 30 illustrates the 1st kind and the 2nd kind of activity determination method, forms with TiO on substrate 1 surface
2Be the photocatalyst layer 2 of main body, can use such photocatalyst film activity determination method.
The TiO that the 1st kind of method forms on substrate surface
2On the photocatalyst film surface for main body, the potassium halide aqueous solution such as KI or potassium chloride drip, then, to the potassium halide aqueous solution that the drips irradiation ultraviolet ray of preset time, judge the active size of photocatalyst film from the difference of the pH of the pre-irradiation potassium halide aqueous solution and postradiation pH.
The 2nd kind of method, the TiO that forms on substrate surface
2On the photocatalyst film surface for main body, drip and in the potassium halide aqueous solution such as KI or potassium chloride, add the mixed liquor of pH indicator, then the mixed liquor that drips is shone the ultraviolet ray of preset time, because the change color of mixed liquor, thereby can judge the active big or small of photocatalyst film.
The TiO that the 3rd kind of method forms on substrate surface
2Bonding determination of activity film on the photocatalyst film surface for main body to this determination of activity film irradiation ultraviolet ray of preset time, because the change color of determination of activity film, thereby can be judged the active size of photocatalyst film at this state.
Figure 30 illustrates the activity determination method of the 1st kind and the 2nd kind, forms with TiO on substrate 1 surface
2Photocatalyst layer 2 for main body, in order to detect at this photocatalyst layer 2 whether photolytic activity is arranged, the potassium halide aqueous solution 30 such as KI or potassium chloride drip on the surface of photocatalyst layer 2, then, to the ultraviolet ray of 40 irradiation preset times of the potassium halide aqueous solution that drips 30 usefulness ultraviolet lamps, judge the active size of photocatalyst layer 2 from the difference of the pH of the pre-irradiation potassium halide aqueous solution and postradiation pH.
Figure 33 represents the relation of ultraviolet irradiation time and pH variable quantity, and the concentration of the potassium halide aqueous solution 30 is 0.1mol/L, and ultraviolet lamp uses the BLB fluorescent lamp of 20W, and photocatalyst layer 2 is 20cm with the distance of ultraviolet lamp 40, and irradiation time is 60 minutes.
Can see that from this figure no matter be loaded, the rutile-type of Detitanium-ore-type, metal, in the photocatalyst layer 2, ultraviolet irradiation time reaches 30 minutes, the pH of the potassium halide aqueous solution 30 uprises.
Like this, because the pH of the ultraviolet ray irradiation potassium halide aqueous solution 30 uprises, be because carry out following oxidation reaction and reduction reaction simultaneously, produce OH by reduction reaction
-(hydroxide ion).
Oxidation reaction:
Reduction reaction:
Therefore, because ultraviolet irradiation if the pH of the potassium halide aqueous solution 30 uprises, we can say that then this photocatalyst layer 2 has photolytic activity.
Figure 34 represents R
30Relation curve with the pH variable quantity.In the drawings, R
30Be the ratio (%) of shining the gas (methyl mercaptan etc.) that reduced in back 30 minutes in ultraviolet ray, know R from this figure
30With the pH variable quantity dependency relation of direct ratio is arranged.The variable quantity that is pH becomes the index that photolytic activity has or not.
In above-mentioned the 1st kind of method, the variable quantity of pH is measured sheet with pH measuring instrument or pH and is carried out, but in the 2nd kind of method, the mixed liquor that adds the pH indicator in the potassium halide aqueous solution 30 is dropped on photocatalyst layer 2 surfaces, then, to the mixed liquor that the drips irradiation ultraviolet ray of preset time, because the mixed liquor change color, thereby can judge the active size of photocatalyst layer 2.
As the pH indicator, because the pH of the potassium halide aqueous solution 30 ultraviolet pre-irradiations is about 4.5, ultraviolet postradiation pH is 5.5-6.5, so methyl red is suitable.
In addition, in above-mentioned the 1st kind and the 2nd kind of method, the potassium halide aqueous solution 30 that on photocatalyst layer 2 surfaces, drips or in the potassium halide aqueous solution 30, add the mixed liquor of pH indicator, the diffusion of dripping is panoramic on each substrate, can not guarantee that certain liquid is thick, response area is different with each substrate.
The method of eliminating this point is the method shown in Figure 31, in the method, after the potassium halide aqueous solution 30 grades of dripping on the surface of photocatalyst layer 2, pushes down the potassium halide aqueous solution 30 with transparent panels such as glass plate 60, when forming certain thickness, prevents drying.
In addition, the potassium halide aqueous solution 30 liquid such as grade be the surface with substrate 1 be level be condition, so be difficult to judge the activity of the photocatalyst film that on vertical planes such as the wall of having set up and ceiling, forms.
The method of eliminating this point is the method shown in Figure 32, in the method, bonding determination of activity film 70 on the surface of the photocatalyst layer 2 that forms on substrate 1 surface, at this state to these determination of activity film 70 irradiation ultraviolet radiations, because the change color of determination of activity film 70, thereby can judge the active big or small of photocatalyst layer 2.
Here, the determination of activity film be on organic binder bond with adding the mixed liquor drying of the potassium halide aqueous solution such as KI or potassium chloride and pH indicator, form the film shape and obtain.
Then, investigate the porosity of photocatalyst layer 2.Here, the so-called porosity is called the open pore rate, and the porosity is more than 10%, below 40%, preferably more than 10%, below 30%.
In the case, the crystallization particle diameter of photocatalyst granular can be below the 0.1 μ m, preferably below the 0.04 μ m1.Because the crystallization particle diameter is more little, the reaction effective area of per unit volume is big more, so the thickness of photocatalyst layer can be about 0.1 μ m.In addition, make the mutual solid-phase sintering of photocatalyst granular, form neck down portions, under the situation that layer intensity is improved, crystal grain directly increases to more than the 0.1 μ m with this, because the reaction effective area of per unit volume reduces, institute is preferably more than 0.6 so that thickness is more than the 0.5 μ m.
In addition, between the photocatalyst granular that constitutes the photocatalyst layer that forms on the substrate surface, can add below the crystallization particle diameter 0.01 μ m particle that best 0.008 μ m is following.Utilize to add such particle, particles filled rate and surface smoothing can be improved in the gap between can the landfill photocatalyst granular, can improve the film-strength to shear stress thus.Because the surface smoothing raising can make to pollute to be difficult for adhering to.Though cause this moment the porosity to reduce, the pore of being buried underground directly is below the crystallization particle diameter 0.01 μ m here, the size that the following particle of best 0.008 μ m enters, it is big comparing with the size (number ) of gas, so do not influence deodorization.
Here, below the crystallization particle diameter 0.01 μ m, the kind of the particle that best 0.008 μ m is following, basically any kind can, still, except that the gap of landfill photocatalyst granular, also have the danger that covers part surface, so do not damage the TiO of photocatalytic activity
2, SnO
2, ZnO, SrTiO
3, Fe
2O
3, Bi
2O
3, WO
3On oxide semiconductor or Ag, Cu etc. metal is desirable.In addition, below the crystallization particle diameter 0.01 μ m, which kind of method can basically for the adding method of the particle that best 0.008 μ m is following.For example, can utilize hydrothermal treatment consists etc. to generate such ultra-fine grain, utilize suitable dispersion liquid to be dispersed into colloidal sol, this colloidal sol is coated on the photocatalyst layer, heat-treat in that the low temperature that particle grows up does not take place, make the organic dispersing agent evaporation with spraying process.In addition, also can on photocatalyst layer, be coated with alcoxide and organic metal salt, heat-treat, evaporation diluent, organic principle etc.
In addition, also can fix the metallic particles littler than the hole diameter of the photocatalyst layer that forms on the substrate surface.By the fixing metal particle, utilize electronics to capture effect, compare during with independent photocatalyst layer, improved photocatalytic activity, it is better that deodorization becomes.
Here, the kind of metallic particles can if can capture any material of the material of electronics.For example can enumerate Cu, Ag, Pt etc.
The average grain diameter of metallic particles must be less than the average pore footpath of photochemical catalyst laminar surface.And if the average pore of photochemical catalyst laminar surface is more than 10% with the porosity directly, the sample electron microscope observation below 40% because diameter general with photocatalyst granular about equally, so require directly littler than photocatalyst granular.It is desirable to, can be little compared with the photocatalyst granular footpath of beginning raw material.The general following raw material of 0.05 μ m that uses of the initiation material of photocatalyst layer is so can be the following person of 0.05 μ m.
Below enumerate the specific embodiment of the relevant porosity.
Embodiment 28
On the tetragonal ceramic tile substrate of 15cm, use spraying process, change coating weight coating crystallization particle diameter 0.01 μ m TiO
2The ammonia dispergation type suspension of colloidal sol more than 700 ℃, with its roasting, forms photocatalyst layer below 900 ℃, and resulting test portion is estimated Detitanium-ore-type TiO
2The crystallization particle diameter of particle, the open pore rate of laminar surface, deodorization, wearability and anti-fissility.
The evaluation of deodorization is by measuring R
30(L) estimate.So-called R
30(L) be the postradiation clearance of light, specifically, in 11 liters glass container, form the face of the photocatalyst film of test portion in the last configuration of the distance of distance light source (BLB fluorescent lamp, 4W) 8cm, the initial stage concentration that makes methyl mercaptan gas is that 3ppm is injected in the container, measures the change in concentration of irradiation in the time of 30 minutes and obtains.
The sliding friction of plastic eraser is used in the wearability evaluation, and relatively the variation of outward appearance is estimated, and evaluation index is same as described above, expression in following.
◎: 40 times are not back and forth changed
Zero: in the slip more than 10 times, below 40 times scratch is arranged, photocatalyst layer (TiO
2Film) peels off
△: in the slip more than 5 times, below 10 times scratch is arranged, photocatalyst layer (TiO
2Film) peels off
*: in the slip below 5 times scratch is arranged, photocatalyst layer (TiO
2Film) peels off.
The test of anti-fissility is the test harsher than the condition of abrasion test, and what replace that plastic eraser uses bigger shearing force adds sand rubber (L1ON TYPEWRITERERASER 502).Concrete evaluation method is the test portion surface to be wiped 20 times with the power of equalization with the sand rubber, contains relatively with visual and standard specimen that the state of wound carries out.Metewand is expressed as follows.
◎: do not change fully
Zero: use up plus-minus and confirm to change slightly
△: confirm slight variations
*: a glance just can be confirmed to change
The results are shown among Figure 35-Figure 37.
Porosity when Figure 35 represents that the thickness of photocatalyst film is made 0.8 μ m and the relation of deodorization and wearability.Deodorization increases with the increase of the porosity, surpasses 50% at 10% o'clock, reaches more than 80% at 30% o'clock.On the contrary, wearability to 30% is ◎, but is zero 40%, if surpass this be △ or *.Can find out that from the above fact in order to make the member that deodorization and wearability have both, the porosity that must make photocatalyst film is more than 10%, below 40%, preferably more than 10%, below 30%.
When Figure 36 represents to constitute the porosity and is the photocatalyst granular crystallization change of size of photocatalyst film of 20-30%, the relation of deodorization and thickness.The crystallization particle diameter is that 0.1 μ m sees R
30(L) with the relation of thickness, if attenuation, then deodorization reduction.But, below 0.04 μ m, can't see the relation with thickness, even thickness 0.1 μ m also shows good deodorization.From the above fact as can be known, the size of microcrystal that makes photocatalyst granular is below the 0.1 μ m, below the best 0.04 μ m, then can makes the photocatalyst film filming also can accomplish to guarantee good deodorization to thickness 0.1 μ m degree.
When Figure 37 represents to constitute the photocatalyst granular crystallization particle diameter of photocatalyst film that the porosity is 20-30% and bonding state and all changes, the relation of deodorization and anti-fissility and thickness.The required value of mechanical strength is if rise to anti-fissility test level, the sample that does not then have the necking section be △ or *.In addition, in order to form mechanical sufficient constriction combination with the mutual solid-phase sintering of photocatalyst granular, it is not enough that photocatalyst granular is grown up to 0.04 μ m, need grow up to 0.1 μ m degree.But if photocatalyst granular is grown up to 0.1 μ m degree, then deodorization is relevant with thickness, and film is thick more, increases deodorization more, specifically, when thickness 0.5 μ m, R
30(L) surpass 50%, when 0.6 μ m, reach more than 80%.Can find out from above result, make the mutual solid-phase sintering of photocatalyst granular, between particle, form the necking section, make particle grow up to the crystallization particle diameter be more than the 0.1 μ m, then can improve film strength fully.In the case, increasing to more than the 0.1 μ m by making the crystallization particle diameter, because reduced the reaction effective area of per unit volume, is more than the 0.5 μ m so must make thickness, preferably more than the 0.6 μ m.
Embodiment 29
On the tetragonal ceramic tile substrate of 15cm, with the TiO of spraying process coating crystallization particle diameter 0.01 μ m
2The ammonia dispergation type suspension of colloidal sol 750 ℃ of roastings, forms photocatalyst film.The TiO in this stage
2The porosity of film is 45%, TiO
2The crystallization particle diameter of particle is 0.02 μ m.Be coated with the different SnO of crystallization particle diameter more thereon with spraying process respectively
2Colloidal sol 110 ℃ of dryings, obtains sample.Sample to gained carries out deodorization, wearability evaluation.
The results are shown among Figure 38.About deodorization, SnO
2The crystallization particle diameter of colloidal sol changes to 0.01 μ m from 0.0035 μ m almost not to be changed, and shows good result.In contrast, the effect of wearability when interpolation 30% (weight) is above is with SnO
2The crystallization particle diameter of colloidal sol and different.That is, in the situation of the particle below adding 0.008 μ m, improve to ◎ or zero, but do not see additive effect at 0.01 μ m.
From above result as can be known, by adding between photocatalyst granular below the crystallization particle diameter 0.01 μ m, the following particle of best 0.008 μ m improves wearability.
On the tetragonal ceramic tile substrate of 15cm, be TiO with spraying process, variation coating weight coating crystallization particle diameter 0.01 μ m
2The ammonia dispergation type suspension of colloidal sol 850 ℃ of roastings, forms the photocatalyst film of thickness 0.2 μ m.Then on this photocatalyst film,, after this carry out photo-reduction (light source 20W BLB lamp, the distance from light source to sample is 10cm, irradiation time 10 seconds), obtain sample with the rubbing method coating copper acetate aqueous solution.The copper amount that support this moment is 2 μ g/cm
2, its particle diameter is number nm-10nm.The crystallization particle diameter of photocatalyst granular is 0.1 μ m in addition.Sample to gained is estimated deodorization, wearability.
As a result, R
30(L) be 80%, wearability is ◎.Thereby compare with Figure 36, owing to support copper, so R
30(L) rise to 89% by leaps and bounds from 18%.
Can find out from above explanation, be more than 10%, below 40% by forming the porosity at substrate surface, best photocatalyst film more than 10%, below 30%, the member that can provide deodorization and wearability to have both.
Then, narration is about the embodiment of the little particle in this gap of packing ratio in the gap that forms on photocatalyst layer.Between said in the present embodiment gap is meant from intergranular gap and the recess of necking section.
In addition, though if photocatalyst layer is fine and close in film-strength, be difficult for polluting that to adhere to be good, but uprise because form the temperature of photocatalyst layer usually, limited the material of base material, so if according in subsequent handling with particles filled hope in the gap, then to add the porosity of preceding photocatalyst layer can be more than 10% to the gap particle.In addition, the film of the porosity more than 10% has good deodorization, so by regulating loading, can provide anti-method, the excellent multifunctional material of deodorization both.
Particle littler than the gap that is filled in the gap preferably is made up of the raw material of inorganic crystalloid, the preferred TiO that can come to have by oneself photocatalytic activity
2, SnO
2, ZnO, SrTiO
3, Fe
2O
3, Bi
2O
3, WO
3Deng oxide semiconductor.
The size of the particle that ratio gap is little basically can be littler than the mean value in the pore footpath that generates.The particle that reduces and reduce attached to the particle surface that photo-catalysis function is arranged by the gap improves surface smoothing and blemish minimizing, seeking to pollute in the raising that is difficult for adhering to film-strength, can be following, the following granule of 0.008 μ m preferably of 0.01 μ m particularly.But, at TiO
2Film is a Detitanium-ore-type, is fixed on the occasion on the base material heat-treating below 850 ℃, uses electron microscope observation, from average pore footpath and TiO
2The particle footpath is seen about equally, compares TiO
2The particle footpath is little just passable.The TiO that photocatalytic activity is arranged
2The initiation material of film uses the following raw material of 0.05 μ m usually, so can be the following raw material of 0.05 μ m.
Here, the apparent porosity that filler particles forms in the gap has a layer of photo-catalysis function accomplishes below 20%, can make that pollution is more difficult adheres to.The Breadth Maximum of more wishing its open pore is below the 0.04 μ m.
Here, the so-called porosity is the open pore rate of substrate surface, and the Breadth Maximum of so-called open pore is exactly to constitute in the particle with photo-catalysis function of substrate surface, and two adjacency are intergranular apart from maximum (mean value+3 * standard deviation).
In addition, if utilization is about 10% layer at the particles filled porosity at the layer that has photo-catalysis function before the above-mentioned gap, though then the porosity reduces to below 10%, but at this hole diameter of being buried underground is the size that the particle below the crystallization particle diameter 0.01 μ m enters, it is big comparing with the size (number ) of gas, so do not influence deodorization, can be TiO more than 10% with the ready-made porosity
2Film keeps equal deodorization characteristic.
In addition, the layer with formed photo-catalysis function mainly is the photocatalyst granular of crystallization, and dirt does not adhere to the firm attachment form of glass attachment formula like this, even the while incrustation scale adheres to also wipes with comparalive ease.In addition, when water circulation use, the effect that is difficult for producing algae is arranged.
Here, the photocatalyst granular of so-called crystalloid is the photocatalyst granular that will peel from member when carrying out powder x-ray diffraction under 50KV, 300mA condition, at the maximum peak of crystallization (for example at TiO
2In the particle, Detitanium-ore-type 2 θ=25.3 °, rutile-type 2 θ=27.4 °) in the degree that detects crystallization turn to photocatalyst granular.
As the method for filler particles in above-mentioned gap, use alcoxylates, organic metal salt, sulfate etc., utilize coating, drying, heat treatment to carry out.For example, the process of using metal alkoxides is with the most surperficial at photocatalyst layer of metal alkoxides and suitable diluent and mixed in hydrochloric acid solution coat then, carries out the dry heat processing then.Here so-called diluent it is desirable to alcohols such as ethanol, propyl alcohol, methyl alcohol, but is not limited to these.Can be not moisture as far as possible.If moisture, then promote the hydrolysis of metal alkoxides explosively, become the reason that crackle produces.In addition, adding hydrochloric acid is because prevented cracking when drying and during heat treatment.The rubbing method of metal alkoxides normally carries out with curtain coating.But also be not limited to this.Showering is preferably in the dry air to be carried out.If coating in common air (atmosphere), then because airborne moisture promotes hydrolysis, it is difficult that the control of thickness becomes.Can be coated with 1 time, also can be coated with for several times.This fillibility by the preceding photocatalyst layer of coating decides.After this placed several minutes in dry air, the gap that just can form photocatalyst layer is by the particles filled film that forms.
At this, if with filler particles make in advance be coated with filler particles before the identical raw material of layer, then coefficient of thermal expansion is also identical, because can form the good film of mechanical strength, is desirable.
As concrete example, the example that uses alkoxytitanium is illustrated again.Alkoxytitanium is being coated on the photochemical catalyst laminar surface again, is carrying out in the dry heat treated process, alkoxytitanium coating weight each time is converted into TiO
2Be 10 μ g/cm
2More than, 100 μ g/cm
2Below.If amount is very few, then must increase the coating number of times, so efficient is low, on the contrary, if amount is too much, then the thickness of coating is blocked up each time, thereby cracks when drying and during heat treatment.
In above-mentioned dry heat processing procedure, heat treatment temperature is more than 400 ℃, below 800 ℃, and below 400 ℃, amorphous TiO
2The non-crystallizable Detitanium-ore-type TiO that changes into
2, at 800 ℃ rapid particle takes place and grows up, so photolytic activity reduces.
In addition, make with respect to the alkoxytitanium in the coating fluid, hydrochloric acid content is more than 1% (weight), below 10% (weight).Below 1% (weight), crackle prevent that effect is not enough, if surpass 10% (weight), then, a large amount of moisture is arranged because hydrochloric acid is generally 36% aqueous solution, so too promote hydrolysis, thereby form crackle.The amount of hydrochloric acid for a long time, diluent also can be many.Because diluent suppresses hydrolysis.Its ratio is hydrochloric acid (dewatering exceptionally): diluent can be 1: 100-1: about 1000.
Moreover, form layer with photo-catalysis function, on the little particle in this gap of packing ratio forms in the gap that forms on this laminar surface layer, at least a metal among fixation of C u, Ag, Zn, Fe, Co, Ni, Pd, the Pt again.Owing to make such structure, above-mentioned metal occupies the high position of adsorptivity in the layer with photo-catalysis function in advance, and the alkali metal in the dust and dirt composition, calcium etc. are not lost photocatalytic activity attached to this position yet.Therefore, be difficult to damage the antibacterial action that produces by photochemical catalyst, also can prevent to adhere to the pollution that produces because of mushroom.In addition, as above-mentioned metal, if use Ag, Cu, Zn, then because these metals itself have antibiotic property, so can more effectively prevent adhering to of mushroom.Also utilize the electronics of these metals to capture the photolytic activity that effect improves photocatalyst layer again.
The be fixed size of metal greatly to the degree at the sorptive high position that occupies photocatalyst layer in advance, and may diminish to the highly active degree of keeping.From this viewpoint, preferably count the nm-10nm degree.
Here,, can utilize photoreduction met hod, heat treating process, sputtering method, chemical vapor deposition method etc., still, never need large-scale equipment, fairly simple method and can firmly fix and see the preferred light reducing process as the method for fixing above-mentioned metal.The process of photo-reduction is the aqueous solution that coating contains at least a metal ion among Ag, Cu, Zn, Fe, Co, Ni, Pd, the Pt, and irradiation contains ultraviolet light then.In the aqueous solution of at least a metal ion in containing Ag, Cu, Zn, Fe, Co, Ni, Pd, Pt, can enumerate copper acetate, silver nitrate, copper carbonate, copper sulphate, stannous chloride, cupric oxide, chloroplatinate, palladium bichloride, nickel chloride, zinc nitrate, cobalt chloride, frerrous chloride, iron chloride etc.The available basically above-mentioned any method of the coating process of these slaines, but spraying process or dip coating are comparatively easy.Both compare, and are few from the solution amount of using, and can be coated with equably, control thickness easily, and can see that spraying process is even more ideal in non-cohesive on demand aspect overleaf.When irradiation contained the light source of ultraviolet, so long as it is just passable to shine the light source that contains ultraviolet, specifically, any in ultraviolet lamp, BLB lamp, xenon lamp, mercury vapor lamp, the fluorescent lamp could.The method that irradiation contains ultraviolet it is desirable to make light vertically to shine and arranges sample on the shadow surface, because exposure rate the best like this.Preferred about 10 seconds to 10 minutes of irradiation time.Irradiation time is too short, above-mentioned metal is deficiently attached to the sorptive high position of photocatalyst layer, thereby adhere to alkali metal in the dust and dirt composition, calcium etc., become the reason of forfeiture photocatalytic activity, overlong time, above-mentioned metal too adheres to, and light is difficult to fully arrive photocatalyst layer, thereby reduces photocatalytic activity.Sample is apart from the preferred 1cm-30cm of the distance of light source.Distance is too short, light can not with roughly uniformly illumination shine whole sample face, be easy to generate the deviation of adhering to of above-mentioned metal, distance is long, the illumination and the square distance of light diminish inversely proportionally, are difficult to make metal to adhere to securely.
Enumerate the specific embodiment of the little particle in this gap of packing ratio in the gap that on photocatalyst layer, forms below.
Embodiment 31
On the tetragonal ceramic tile substrate of 15cm, with the TiO of spraying process coating crystallization particle diameter 0.01 μ m
2The ammonia dispergation type suspension of colloidal sol 750 ℃ of roastings, forms Detitanium-ore-type TiO
2Film.The TiO in this stage
2The film porosity is 45%, TiO
2The crystallization particle diameter of particle is 0.02 μ m.Then thereon respectively with the different SnO of spraying process coating crystallization particle diameter
2Colloidal sol 110 ℃ of dryings, obtains sample.The sample of gained is carried out the evaluation of the difficulty that deodorization, wearability, pollution adhere to.
Deodorization is by measuring R
30(L) estimate.
Use plastic eraser to carry out sliding friction about wearability, relatively the variation of outward appearance is estimated.Evaluation index is as shown in following.
◎: to 40 reciprocal no changes
Zero: in the slip more than 10 times, below 40 times scratch is arranged, TiO
2Layer is peeled off
△: in the slip more than 5 times, below 10 times scratch is arranged, TiO
2Layer is peeled off
*: in the slip below 5 times scratch is arranged, TiO
2Layer is peeled off.
Adhere to the evaluation of difficulty about pollution, on substrate surface,, estimate with the pollution condition of wiping behind the line with ethanol after the drying with the thick magic ink setting-out of black.Evaluation index is shown.
◎: complete obiteration vestige.
Zero: remaining trace slightly.
△: residual celadon vestige.
*: residual black vestige.
The results are shown among Figure 39-Figure 46.
Figure 39 represents with respect to SnO
2Addition pollutes the difficulty of adhering to.SnO in the figure
2Addition is with respect to TiO
2And SnO
2The weight and the SnO of amount
2Weight ratio is represented.Add the SnO more than 30%
2The time, pollute difficulty degree of adhering to and rapidly rise.Its reason is interpreted as following 3 points.The firstth, because the SnO of interpolation more than 30%
2So the porosity reduces to (Figure 40) below 20%.The secondth, owing to add SnO
2, the big pore in pore footpath reduces.Figure 41 represents with respect to SnO
2The Breadth Maximum of the open pore of addition, SnO
2Addition 30% when above, become 0.04 quite little μ m.The 3rd is owing to add SnO
2Surface smoothness improves, and is also influential.
Figure 42 represents with respect to SnO
2The deodorization of addition and wearability.
About deodorization, even SnO
2The crystallization particle diameter of colloidal sol changes to 0.01 μ m from 0.0035 μ m also to be changed hardly, shows good result.In addition, SnO
2Amount 50% when following, R
30Show the good result more than 80%.The SnO that compares Figure 39
2During the concerning of the addition and the porosity as can be known, SnO
2Addition more than 40%, 50% when following, though the porosity is below 10%, form good deodorization.The porosity under the result of this tendency and the particle situation of not adding the landfill gap is different with relation (Figure 35) result of deodorization.It is as follows that its reason can be thought.Though the porosity in the case reduces to below 10%, but compare the pore of also residual 0.02 μ m degree with Figure 41, and it is big that the crystallization particle diameter 0.0035 μ m of the particle in landfill gap compares with the size of gas (number ), so under this condition that particle is not grown up, the path that does not produce gas is by the such phenomenon of locking.
About wearability, at SnO
2Addition is that 30% effect when above is because of SnO
2The crystallization particle diameter of colloidal sol and different.To ◎ or zero raising, but do not see additive effect when promptly adding the following particle of 0.008 μ m at 0.01 μ m.
By this experiment as can be known:
(1) on base material, forms TiO
2Film, in the gap that this film surface generated if add the little particle (SnO of ratio gap
2Colloidal sol), then pollution is difficult to adhere to.
(2) SnO
2Addition with respect to TiO
2And SnO
2Gross weight is if more than 30% (weight), and then pollution is difficult for adhering to, and also improves wearability.
(3) SnO
2Addition with respect to TiO
2And SnO
2Gross weight then can be kept deodorization if below 50% (weight) in the same old way well.
(4) if make the porosity below 20%, the Breadth Maximum of open pore is below 0.04 μ m, and then pollution is difficult for adhering to.
Embodiment 32
Lose at the urinal operator to be provided with on the sideway stance of light and form Detitanium-ore-type TiO
2Material, carry out the site test in two weeks, and do not form common Detitanium-ore-type TiO
2The material of film compares, and both adhere to jointly and result from the dirt of yellow of mushroom and calculus such as kidney, bladder as a result.But, with dirt wiping on the grate of common closet do not come off opposite, at sideway stance with forming Detitanium-ore-type TiO
2During the material of film, if wiping, then the yellow of dirt almost significantly disappears.
Owing to unglazed irradiation, its result is interpreted as not having Detitanium-ore-type TiO at the grate sideway stance
2The photocatalysis effect of film is not equal to formed the crystalloid Detitanium-ore-type TiO that dirt is difficult to firm attachment from the teeth outwards
2Film.
Embodiment 33
On the surface of the tetragonal Ceramic Tiles of 15cm, be coated with SiO
2-Al
2O
3-Na/K
2The O frit is then in its surface with spraying process coating crystallization particle diameter 0.01 μ m TiO
2The ammonia dispergation type suspension of colloidal sol carries out roasting in 2 hours at 750 ℃, according to TiO
2The thickness of film is made three kinds of 0.2 μ m, 0.4 μ m, 0.8 μ m.The TiO in this stage
2The porosity of film is 45%, TiO
2The crystallization particle diameter of particle is 0.02 μ m.On the said sample of cooling, as carrier gas, be coated with the mixed liquor of purity titanium tetraethoxide, 36% hydrochloric acid and the ethanol of 10: 1: 400 (weight ratio) again with dry air with curtain coating, dry then.Coating weight is pressed TiO
2Count 40-50 μ g/cm
2After this carry out roasting in 10 minutes at 500 ℃.Carry out the alkoxytitanium coating process 1-5 time.Adhere to the difficulty evaluation to what the sample of gained carried out deodorization, antibiotic property, wearability, pollution.
About antibiotic property, test with Escherichia coli (Escherichia coli W3110 bacterial strain).With 0.15ml (1-50000CFU) the bacterium liquid that drips on the multifunctional material of 70% ethanol sterilization the most surperficial, be placed on that glass plate (100 * 100) is gone up and base material is the most surperficial is adjacent in advance, make sample.After white lamps (3500 lux) irradiation 30 minutes, shone the bacterium liquid of sample with the sterile gauze wiping, be recovered in the physiological saline, obtain the bacteria live rate, so the pass evaluation index +++, ++ ,+,-same as described above.
Under above-mentioned any condition, deodorization R
30(L) all be more than 80%, antibiotic property all is +++.
About dirt adhere to difficulty (Figure 44) and wearability (Figure 45), depend on alkoxytitanium coating number of times and TiO
2Thickness.Alkoxytitanium coating often, then pollute adhere to difficulty and wearability improves.In addition, TiO
2Thickness thin more can be few more alkoxytitanium coating number of times improve pollute adhere to difficulty and wearability.One of its reason can be thought by being coated with the TiO that alkoxytitanium forms
2The porosity of laminar surface reduces.In Figure 46, represent TiO
2The porosity of laminar surface and alkoxytitanium coating number of times and TiO
2The relation of thickness.The coating number of times of alkoxytitanium is many more, TiO
2The porosity of laminar surface reduces more, and TiO
2Thickness is thin more, with identical alkoxytitanium coating number of times, TiO
2The porosity of laminar surface reduces more, this relation and alkoxytitanium coating number of times and TiO
2The relation of adhering to difficulty and wearability of thickness and pollution is corresponding well.Particularly, identical with the situation of embodiment 31 in adhering to aspect the difficulty of polluting, be all to be ◎ below 30% at the porosity.
Embodiment 34
On the tetragonal ceramic brick surface of 15cm, be coated with SiO
2-Al
2O
3-Na/K
2The O frit, then in its surface, with the TiO of spraying process coating crystallization particle diameter 0.01 μ m
2The ammonia dispergation type suspension of colloidal sol carries out roasting in 2 hours, the TiO in this stage at 750 ℃
2The thickness of film is 0.4 μ m, and the porosity is 45%, TiO
2The crystallization particle diameter of particle is 0.02 μ m.On chilled said sample, use curtain coating, be coated with the purity titanium tetraethoxide of 10: 1: 400 (weight ratio) and the mixed liquor of 36% hydrochloric acid and ethanol with dry air again as carrier gas, dry then.Coating weight is according to TiO
2Meter is 40-50 μ g/cm
2Then 500 ℃ of roastings 10 minutes.Repeat the alkoxytitanium coating process three times.After this on this sample, be coated with the silver nitrate aqueous solution of 1% (weight) again, carry out photo-reduction (light source is the BLB lamp of 20W, and the distance from light source to sample is 10cm, irradiation time 30 seconds), obtain sample.Here, the silver amount that is supported on specimen surface is 0.7 μ g/cm
2, the particle diameter of silver is average 40nm degree.To the sample mensuration antibiotic property of gained and the antibiotic property after long-term the use.
About the antibiotic property after the long-term use, test as described below.At first clean the surface of gained sample well, carry out drying at 50 ℃ with ethanol etc.Then will inject the beaker of sterilization, sample will be impregnated into wherein, place one month at the bath water that gather at public its outdoor bathing place.Take out sample then, after cleaning with ethanol etc., with the surface sterilizing of 70% ethanol with multifunctional material.Then, the bacterium drops of 0.15ml (1-50000CFU) Escherichia coli (Escherichiacoli W3110 bacterial strain) on said sample the most surperficial, is placed it on the glass plate (100 * 100), be adjacent to base material is the most surperficial, as sample.
After white lamps (3500 lux) irradiation 30 minutes, shone the bacterium liquid of sample with the sterile gauze wiping, be recovered in the 10ml physiological saline, obtain the survival rate of bacterium, as evaluation index.Evaluation index is identical with the antibacterial tests of embodiment 3.
In order more also the sample that uses among the embodiment 33 to be tested.
The result is for the antibiotic property at initial stage, the sample of Zhi Zuoing in the present embodiment, and the sample of making in embodiment 33 is +++, but between but creates a difference aspect the antibiotic property after 1 month.Be the sample antibiotic property of making among the embodiment 33 worsen for+, and that the sample that present embodiment is made showed with the initial stage is indeclinable +++value.This can be interpreted as silver and occupy TiO
2The position that the adsorptivity of laminar surface is high is adhered to so in use prevent dust and dirt etc. at the high position of adsorptivity.
By above explanation as can be known, form layer with photo-catalysis function at substrate surface, because the little particle in this gap of packing ratio in the gap that this laminar surface generates, so it is little to be present in the number of gaps and the size ratio photocatalyst film in the past on surface, and because surface smoothing is good, so also improve film-strength when keeping deodorization, and can make the macromolecule that constitutes dirt composition, dust and dirt, mushroom etc. be difficult for adhering to.
Low-melting raw material such as narration soda-lime glass etc. situation about using below as base material.That is, when on the low melting point substrate surface, forming photocatalyst film, when this catalyst film formation temperature, base material has begun to soften, formed photocatalyst film is embedded in the base material, so light do not reach photocatalyst layer, and generation can not be brought into play the unfavorable condition of photo-catalysis function.
Therefore, in such occasion, by than SiO
2Layer waits the high layer of base material fusing point, and photocatalyst granular is fixed on the base material.Specific embodiment is described below.
Embodiment 35
Before being coated with titanium oxide on the soda-lime glass, at soda-lime glass surface coating silica.
Carry out silica-coating with following method to the tetragonal soda-lime glass of 10cm.At first, with 6: 2: 6: 86 (weight ratios) are mixed tetraethoxysilane, 36% hydrochloric acid, pure water and ethanol.This moment is because generate heat, so place about 1 hour.With the air-flow coating it is coated on the soda-lime glass.
Then, preparation coating solution.With 1: 9 (weight ratio) purity titanium tetraethoxide and ethanol are mixed into solution, add 36% hydrochloric acid of 10% (weight) again, make coating solution with respect to purity titanium tetraethoxide.Here, the amount of 36% hydrochloric acid that is added can be more than 1% (weight) with respect to purity titanium tetraethoxide, below 30% (weight), preferably 5% (weight) above, below 20% (weight).By adding an amount of hydrochloric acid, prevent to crack in drying that can be afterwards, the roasting process.The amount that is to say hydrochloric acid is very few, can not reach the effect that prevents crackle fully, and the amount of hydrochloric acid is too much, because the water yield that is included in the hydrochloric acid reagent increases, quickens the hydrolysis of purity titanium tetraethoxide, is difficult to form filming of homogeneous.
Then, in dry air with curtain coating with this solution coat on the soda-lime glass substrate surface.Here, so-called dry air does not mean that complete moisture free air, is meant the air that lacks than common air moisture.This moment, then because airborne moisture quickens the hydrolysis of purity titanium tetraethoxide, once the amount of filming was too much, is easy to generate crackle in drying afterwards, the roasting process if be coated with in not implementing the dry common air of handling.In addition, because hydrolysis is quickened, be difficult to the control amount of filming.In order to prevent crackle, a loading that it is desirable to titanium oxide is 100 μ g/cm
2Below.A loading of current titanium oxide is 45 μ g/cm
2
Then, in dry air, carry out 1-10 minute dry the processing, form oxidation titanium film.Obtain titanium oxide with process so far according to following principle.Here, initiation material is the purity titanium tetraethoxide (even using other alkoxytitanium also to produce identical effect on principle) of one of alkoxytitanium.Based on purity titanium tetraethoxide, when showering and the reaction that is hydrolyzed of the water in the dry air, generate titanium hydroxide.And then dehydration condensation takes place when drying, on base material, generate the amorphous titanium oxide.The titan oxide particles that generate this moment is about 3-150nm, is highly purified.Therefore this titanium oxide is compared with the titanium oxide that obtains with other manufacture methods, and low sintering characteristics are arranged.
The composite component that obtains in order to last method carries out roasting at 300-500 ℃ again, obtains multifunctional material.If desired, repeat process, titanium oxide is coated with thick from purity titanium tetraethoxide to roasting.
The sample that so obtains is carried out the evaluation of deodorization, wearability and antibiotic property.It the results are shown in the table 19.
(table 19)
| Sintering temperature (℃) | Wearability | R 30(L) | R 30(D) | Antibiotic property (L) | Antibiotic property (D) |
| 300 400 500 | ◎ ◎ ◎ | 0％ 60％ 60％ | 0％ 0％ 3％ | - + + | - - - |
About deodorization, sample is arranged on methyl mercaptan initial stage concentration adjustment to 2ppm, in the cylindrical vessel of diameter 26cm * high 21cm, with the BLB fluorescent lamp of 4W, penetrate 30 minutes from distance sample 8cm illumination after, measure the clearance (R of methyl mercaptan
30And measure and to cover the methyl mercaptan clearance (R of light situation after following 30 minutes (L)),
30(D)), estimate.
About wearability, use plastic eraser to carry out sliding friction, relatively appearance change is estimated.Evaluation index ◎, zero, the △ of this moment, * same as described above.
About antibiotic property, test with Escherichia coli (Escherichia coli W3110 bacterial strain)., be placed on the glass plate (100 * 100) with 0.15ml (1-50000CFU) the bacterium liquid that drips on the multifunctional material of 70% ethanol sterilization the most surperficial in advance, be adjacent to base material is the most surperficial, as sample.After white lamps (5200 lux) irradiation 30 minutes, shone sample and, be recovered in the 10ml physiological saline with the sterile gauze wiping covering the bacterium liquid of the sample that keeps under the optical condition, obtain the survival rate of bacterium, as evaluation index.Evaluation index +++, ++ ,+,-same as described above.
300 ℃ of sintering temperatures, the good result of demonstration ◎ in sliding test, but R
30(L) be 0%.Can think that this causes owing to not changing into Detitanium-ore-type from the amorphous crystalline titanium dioxide.
Can confirm that sliding test also shows the good result of ◎ under 400 ℃ of Detitanium-ore-type with compound experiment by X ray, but R
30(L) also bring up to 60% degree.And antibiotic property also is+.In addition, even at 500 ℃, sliding test shows the good result of ◎ too, but R
30(L) also bring up to 60% degree.
When temperature is increased,, can not make multifunctional material in the soda-lime glass generation distortion of 550 ℃ of base materials.
Embodiment 36
In order further to improve the photocatalysis characteristic of embodiment 35 gained samples, carrying metal particle.Photochemical catalyst also carries out reduction reaction in oxidation reaction.If do not carry out reduction reaction, consume electrons not, particle is charged, and oxidation reaction can not be carried out.Can think that this is R in embodiment 1
30(L) be limited to 60% reason.In order to prevent this situation, carrying metal particle on titan oxide particles is escaped electronics, can prevent charged.
Carry out supporting of metallic particles with following method.With the metal salt solution showering on photochemical catalyst, with 20cm distance, with 20W BLB fluorescent lamp 1 minute.In metal salt solution, use 1% (weight) ethanolic solution of copper acetate when supporting copper, use 1% (weight) ethanol/water=1/1 mixed liquor of silver nitrate when supporting silver.After the irradiation, clean, dry.Do not use aqueous metal salt at this.And using the solution that contains ethanol, this just makes metal salt solution good to the wetability of sample.
The sample that so obtains is carried out the evaluation of deodorization, wearability, antibiotic property.It the results are shown in the table 20.In addition, only use the sample that obtains at 500 ℃ of sintering temperatures.
(table 20)
| Sintering temperature (℃) | Wearability | R 30(L) | R 30(D) | Antibiotic property (L) | Antibiotic property (D) |
| 500 | ◎ | 98％ | 98％ | +++ | ++ |
Sliding test shows the good result of ◎.And R
30(L) rise to 98% by leaps and bounds.Antibiotic property also is +++.
Comparative example 37
Except that in embodiment 35, not implementing the silica-coating other identical carrying out.Promptly on the tetragonal soda-lime glass of 10cm, carry out the titanium oxide coating.It the results are shown in the table 21.
(table 21)
| Sintering temperature (℃) | Wearability | R 30(L) | R 30(D) | Antibiotic property (L) | Antibiotic property (D) |
| 300 400 500 | ◎ ◎ ◎ | 0％ 0％ 0％ | 0％ 0％ 0％ | - - - | - - - |
Can find out that from table 21 under 300 ℃, 400 ℃, 500 ℃ situations, sliding test all shows the good result of ◎, but R
30(L) even repeating purity titanium tetraethoxide films to the process of roasting 10 times, also be 0%, and antibiotic property all be-.
In the time of 300 ℃, R
30(L) inferior, can think that this is because titanium oxide does not change into Detitanium-ore-type from the amorphous crystalline titanium dioxide.
On the other hand, under 400 ℃, 500 ℃ situations, change into Detitanium-ore-type, R can not be described according to above-mentioned reason from the amorphous crystalline titanium dioxide
30(L) inferior.Can think that its reason is because because the soda-lime glass of base material is softening, oxidation titanium film is embedded in the glass.
From above explanation as can be known, even more low-melting base material, utilize and photocatalyst layer between have the high-melting-point layer, also can make the multifunctional material of deodorization, antibiotic property.
The embodiment that is suitable for keeping the photocatalysis effect on the surfaces such as plastics of poor heat resistance is described below.
Base material is not limited to plastics, pottery, pottery, glass or its compound etc. of poor heat resistance, and which kind of all can basically.
Which kind of shape of the shape of base material can, it both can be the simple shape of plate objects such as sphere, cylinder, cylindric thing and ceramic tile, wall material, flooring board or the like, can be again to constitute complicated shapes such as sanitary ceramics, commode, bathtub, sink, toilet seat sheet, and substrate surface can be porous matter, also can be compactness.
The kind of binding agent can be thermoplastics such as unorganic glass matter, thermoplastic resin, slicken solder, also can be thermosets such as fluororesin, silicone resin, silicones.But, from process afterwards, need irradiation to comprise ultraviolet light, preferred light corrosion resistant material.In addition, only under the heat treated situation below 300 ℃, high especially from the application's serviceability, it is desirable to thermoplastic is the material that can soften below 300 ℃, and the Thermocurable material is the material that can solidify below 300 ℃.As the material that satisfies these conditions, it is the nature of glass, slicken solder, acrylic resin etc. that thermoplastic can be enumerated boric acid, and thermosets can be enumerated fluororesin, silicone resin, silicones etc.
As the method that these adhesive layers is coated on the base material, when using thermoplastic, spraying process, rolling method, dip coating etc. are arranged, can use any method wherein, also can use additive method in addition.Binding agent when in addition, the composition of binding agent not necessarily must be finished with member is formed consistent.For example when binding agent is made up of unorganic glass matter, its coating thing can be the suspension of unorganic glass matter compositions such as granular, frit shape, bulk, powder, also can be to contain the mixture that constitutes metal ingredient salt.When binding agent is resin, both can use the resin solution of this composition, can be again additive method in addition.
Can be before coating photocatalyst particle on the adhesive layer, the dry adhesive layer that has been coated with, evaporation water grades.The method that the drying means of this moment has the room temperature utilized to place, the method that heats with base material etc.
In addition, also can be before coating photocatalyst particle on the adhesive layer, the adhesive layer that binding agent is formed and softening heat treatment has been coated with that, adhesive layer low at the softening temperature than base material becomes member when finishing.According to the method, ratio adhesive layer in advance is level and smooth when forming photocatalyst granular on adhesive layer, so even the photocatalyst granular of coating is a spot of, also can bring into play effect of sufficient.
When using thermosetting material, binding agent is mixed, is coated on method on the base material with curing agent, for example according to will in heat-curing resin, adding diluent, then add curing agent and the mixed liquor that obtains is coated on the method on the substrate surface.
Wish that the tackifying value is more than 105 pools, below 1075 pools.Form after the above high viscosity value of 105 pools, the coating photocatalyst particle, may form with the state that not exclusively buries in adhesive layer with this photocatalyst granular and to bury underground, in addition owing to form below 1075 pools, so the undermost at least part of photocatalyst granular layer is embedded in the adhesive layer.
The method of the above-mentioned photocatalyst granular of coating on the adhesive layer surface, basically according to initiation material being implemented after the suitable treatments and the method that is coated on the adhesive layer of material carry out.
As initiation material,, also can use the microparticle suspending liquid of other photochemical catalyst composition though wish it is the collosol suspension liquid of photochemical catalyst constituent.No matter under which kind of situation, film in order to form uniformly, add surface conditioning agents such as dispersant, be necessary so that the photochemical catalyst constituent in the suspension does not produce aggegation.As the coating on adhesive layer, though spraying process, rolling method, dip coating etc. are arranged, can use wherein any method, also can use additive method in addition.
Photochemical catalyst course adhesive layer imbed thickness, imbed more than 1/4 of photochemical catalyst bed thickness, with the bond strength of base material on be gratifying.Here so-called photochemical catalyst layer thickness, utilize the composition elementary analysis of the photocatalyst granular of the section direction that EPMA etc. measures to obtain according to formation, top section and the inlet part roughly certain by the composition amount of element that constitutes photocatalyst granular constitute, and inlet part begins to become between certain degree of depth in the degree of depth to the composition amount of element that constitutes binding agent that the composition amount of element that constitutes photocatalyst granular begins to reduce.
Attached to the surface conditioning agent on the photochemical catalyst mainly is to be made of the composition that adds for the initiation material colloidal sol of dispersed light catalyst granules.Can enumerate pentaerythrite, trihydroxymethyl propane, triethanolamine, trimethanolamine, silicones, alkylchlorosilane etc. particularly.
As containing 1.7mW/cm
2The light source of the following wavelength light of above 390nm can be enumerated BLB fluorescent lamp, ultraviolet lamp, bactericidal lamp, xenon lamp, mercury vapor lamp etc.
Must be to contain 1.7mW/cm
2The reason of the following wavelength light of above 390nm is for dispersant compositions such as silicones have to a certain degree light corrosion resistance, if the uitraviolet intensity of this degree does not then decompose.At this moment, ultraviolet wavelength is short more, and the decomposition of dispersant is fast more, but because the kind difference of binding agent, possibility of binder decomposed is arranged also, and human body also is harmful to.Therefore, can be more than the 250nm.In addition, reach 3mW/cm to illumination
2During degree, increase decomposition rate with illumination and accelerate, even but illumination is increased to 3mW/cm
2More than, also less help decomposition rate to improve, so 3mW/cm
2Below be enough.
Above process schematically is illustrated among Figure 47.On base material 1, the part by adhesive layer 6 photocatalyst layers 2 lower floors is embedded in the adhesive layer 6.6a is the layer that is made of the surface conditioning agent that suppresses photocatalytic activity etc.UV represents to contain 1.7mW/cm
2The light of the following wavelength light of above 390nm.
About form the layer of mainly being made up of photocatalyst granular 3 and thermosetting resin 6 on substrate surface, similarly irradiation ultraviolet radiation exposes photocatalyst layer, describes with this below.(with reference to Figure 48) also uses thermosetting resin that photocatalyst granular 3 is securely fixed on the base material in the method, and irradiation contains 1.7mW/cm
2The light of the following wavelength light of above 390nm, divide the generation light-catalyzed reaction with this illumination part on the photocatalyst granular surface, make the thermosetting resin that is in surface conditioning agent and light source direction preferentially decompose, gasify, make photocatalyst granular to expose in air, therefore can obtain sufficient photocatalytic activity.
In addition, about mainly by photocatalyst granular and thermosetting resin forms layer form method, for example, in the photocatalyst sol suspension that fully disperses, add thermosetting resin, diluent, curing agent successively and obtain mixed liquor, this mixed liquor is coated on the substrate surface, heat-treats and form.
Here, the crystallization particle diameter of the colloidal sol in the photocatalyst sol suspension can be below the 0.05 μ m, is more preferably below the 0.01 μ m.This is that photocatalytic activity is high more because the crystallization particle diameter is more little.And wish that the colloidal sol in the photocatalyst sol suspension carries out single dispersion as far as possible.Dispersiveness is good more, can form uniform coating more.
Thermosetting resin preferably has the light corrosion resistance to the light of white light and common fluorescent lamp intensity as used herein.This is because excellent durability is arranged in use.On this meaning, silicone resin, fluororesin are desirable especially.
Diluent is used to reduce the viscosity of the mixed liquor of being made up of photocatalyst sol and thermosetting resin, makes on substrate surface easily this mixed liquor of coating and adds.But diluent so long as can reach the solvent of this purpose, can use basically as used herein.For example, can make water, ethanol, propyl alcohol etc.
To the method for base material coating mixed liquor, though spraying process, rolling method, dip coating are also arranged, revolve tumbling barrel process etc., both can use any method wherein, can be again additive method in addition.
Heat-treatment furnace generally uses electric furnace, gas burner, vacuum drying oven, plus-pressure furnace etc., but is not limited thereto.
Also can be by thermoset resin layer or light-cured resin layer (intermediate layer: C) on substrate surface, form the layer of mainly forming (with reference to Figure 49) by photocatalyst granular and thermosetting resin.
According to this method, even have concavo-convexly etc. on the base material, utilize thermoset resin layer or light-cured resin layer, before the coating photocatalyst layer in the intermediate configurations of base material and photocatalyst layer, because form the face of dead smooth, so can form uniform photocatalyst layer easily.In addition, utilization is at the thermoset resin layer or the light-cured resin layer of the intermediate configurations of base material and photocatalyst layer, form fully and the combining of base material, even so on substrate surface, have concavo-convex, can unfertile land form forms by photocatalyst granular and thermosetting resin layer in, photocatalyst granular is concentrated near the substrate surface, thereby can contain 1.7mW/cm with the irradiation that shorter time is finished subsequent process
2The light irradiation process of the following wavelength light of above 390nm.In addition, because the layer that photocatalyst granular above existing and thermosetting resin are formed, even when subsequent process and use, decompose, gasify, there is the ultraviolet ray of abundant intensity can not arrive thermoset resin layer or light-cured resin layer, so can at random select about the thermosetting resin of this part in intermediate configurations.For example cheap epoxy resin can be selected, also pigmentary resin can be used in order to keep pattern for cost degradation.
Here, formation method at the thermoset resin layer of the intermediate configurations of base material and photocatalyst layer has, for example will in thermosetting resin, add diluent, add curing agent subsequently and on the mixed liquor substrates coated surface that obtains, utilize heat treatment or placement to be cured and to form.When the layer of the intermediate configurations of photochemical catalyst is the light-cured resin layer, contain ultraviolet light replacement heat treatment in addition with irradiation.At this,, on substrate surface, be coated with this mixed liquor easily, add diluent in order to reduce the viscosity of mixed liquor.Therefore, diluent so long as can reach the solvent of this purpose, basically can as used herein.For example can make water, ethanol, propyl alcohol etc.
Have again, shown in Figure 50 (a) and (b), according to the method described above, the particle that preferred packing ratio this gap is little in the gap that forms on the photocatalyst layer that exposes on substrate surface (gap particle: 4), can further improve wearability to borrow.
The granular size that ratio gap is little can be little just more passable than hole diameter that generates or concavo-convex mean value basically, the amount of the particle that ratio gap is little, and hope is to add surperficial open pore rate to become degree below 20%.Be difficult to adhere to because pollute like this.
Enumerate specific embodiment below.
Embodiment 38
On the tetragonal aluminum oxide base material of 10cm surface, be coated in the titanium oxide sol (is that dispersant carries out dispersion treatment and gets with amine) of average grain diameter 0.01 μ m and add the mixed liquor that adds silicone resin, diluent and curing agent successively in 10% (weight) and obtain successively, 150 ℃ of roastings, obtain duplicate.This sample is shone various light sources with the stipulated time, obtain sample.Deodorization R when the sample evaluation illumination of gained is penetrated
30(L).
Deodorization R when here, illumination is penetrated
30(L) be meant in 11 liters glass container and the sample face be configured in (BLB fluorescent lamp, the 4W) distance of 8cm are that 3ppm injects methyl mercaptan in the container with initial stage concentration, 30 minutes postradiation change rate of concentration of light apart from light source.
The results are shown in the table 22.
(table 22)
| Light source | Uitraviolet intensity (W/cm 2) | Irradiation time (day) | R 30(L)(％) |
| No BLB BLB ultraviolet lamp ultraviolet lamp | - 0.3 1.69 2.0 3.0 | - 7 5 3 1 | 30 32 52 74 82 |
Uitraviolet intensity is at 1.69mW/cm as a result
2Above deodorization surpasses 50%, at 2mW/cm
2When above, deodorization R
30(L) be to surpass 70% good result.Here, uitraviolet intensity is 1.69mW/cm
2Below why show good result, may be interpreted as illumination part distribution third contact of a total solar or lunar eclipse catalytic reaction on the photocatalyst granular surface, the thermosetting resin that is in surface conditioning agent and light source direction preferentially decomposes, gasifies, and makes photocatalyst granular expose aerial cause.
Embodiment 39
On the tetragonal aluminum oxide base material of 10cm surface, be coated in the silicone resin solution that adds diluent and curing agent and form, in drying at room temperature after about 6 hours, coating is added silicone resin, diluent and the curing agent of 10% (weight) and the mixed liquor that obtains successively in the titanium oxide sol of average grain diameter 0.01 μ m (be with amine dispersant carry out dispersion treatment obtain), 150 ℃ of roastings, obtain duplicate.This sample is shone various light sources with the stipulated time, obtain sample.Deodorization R when the sample evaluation illumination of gained is penetrated
30(L).
The results are shown in the table 23.
(table 23)
| Light source | Uitraviolet intensity (W/cm 2) | Irradiation time (day) | R 30(L)(％) |
| No BLB BLB ultraviolet lamp ultraviolet lamp | - 0.3 1.69 2.0 3.0 | - 7 5 3 1 | 34 38 61 82 84 |
Uitraviolet intensity is at 1.69mW/cm as a result
2More than, deodorization surpasses 60%, at 2mW/cm
2When above, deodorization R
30(L) be to surpass 80% good result.Here, uitraviolet intensity is at 1.69mW/cm
2Below why show good result, may be interpreted as illumination part distribution third contact of a total solar or lunar eclipse catalytic reaction on the photocatalyst granular surface, can make whereby attached to the surface conditioning agent on the photoirradiated surface in the photocatalyst granular surface that can not gasify, decompose with heat treatment and preferentially decompose, gasify, the result makes photocatalyst granular expose aerial cause.
On the tetragonal aluminum oxide base material of 10cm surface, the solution that diluent and curing agent form is added in coating in silicone resin, in drying at room temperature after about 6 hours, coating is added silicone resin, diluent and the curing agent of 10% (weight) and the mixed liquor that obtains successively in the titanium oxide sol of average grain diameter 0.01 μ m (be with amine dispersant carry out dispersion treatment and get), carry out roasting at 150 ℃.Particle gap in the component surface in this stage on average is about 0.1-0.2 μ m.Then, uitraviolet intensity is 2mW/cm
2Light (ultraviolet lamp) irradiation after 3 days, confirm R
30(L) surpass 80%, coating is the titanium oxide sol of 0.0035 μ m average grain diameter of 70% (weight) with respect to titanium oxide on the surface then, 110 ℃ of dryings, just obtains sample.In this sample, also show R
30(L) be 81% good result.Carry out sliding test with plastic eraser in addition, do not add the sample of tin oxide, in the slip below 5 times scratch is just arranged, titanium oxide is peeled off, even but the sample that adds tin oxide slides more than 10 times also less than changing.From above confirmation, utilize the little granules of stannic oxide in this gap of packing ratio in the gap that on component surface, forms, can improve wearability.
Can find out from the above description,, also can provide the member of good photocatalytic activity even under the situation of handling the layer be formed with photocatalysis below 300 ℃.
Secondly, though with utilize the ultraviolet ray irradiation to cause to expose purpose identical, with different means, also can provide the method for the multifunctional material of abundant photocatalysis even be described below carrying out roasting below 300 ℃.
This method is to add before the surface conditioning agents such as dispersant, surfactant in the titanium oxide sol with preparations such as hydro-thermal method or sulfuric acid process, and metal particle is fixed on the titanium oxide sol surface.
Here so-called metal particle is meant under the situation about being supported on the titanium oxide, to the titanium oxide irradiates light, can catch the metal particle of electronics when generating electronics and hole, specifically refers to Ag, Cu, Pt, Pd, Ni, Fe, Co etc.
Photoreduction met hod is easy in the method for fixing metal particulate on the titanium oxide sol surface.At this used titanium oxide sol, it is desirable to the preparation of hydro-thermal method or sulfuric acid process, but be not limited thereto.Here so-called sulfuric acid process is the platform established law of the titanium oxide that carries out with program shown below.
At first make anatase and sulfuric acid reaction, make Ti, Fe etc. become water miscible sulfate, the water extraction, the preparation principal component is the sulfate liquor of Ti, Fe.Then remove SiO
2Etc. insoluble suspension.Be cooled to 10-15 ℃ then, separate out ferric sulfate, and separate and remove.Then make the sulfuric acid oxidation titanium hydrolysis in the solution, generation contains titanium hydroxide.The titanium hydroxide that contains of gained uses autoclave equal pressure device, carries out hydrothermal treatment consists in high-temperature high pressure water (generally depressing at the saturated vapor below 200 more than 110 ℃), and crystallization obtains titanium oxide sol.
In addition, so-called hydro-thermal method is to use autoclave equal pressure device, at high-temperature high pressure water (generally depressing) hydrothermal treatment consists is carried out in titanium sources such as titanium tetrachloride, titanium sulfate, hydrolysis takes place and obtain the method for titanium oxide sol at the saturated vapor below 200 ℃ more than 110 ℃.
Method shown below specifies the method for photoreduction met hod to titanium oxide sol surface fixing metal particulate of utilizing.
At first, make the titanium oxide suspension that utilizes hydro-thermal method or sulfuric acid process to make become acidity or alkalescence.The isoelectric point of titanium oxide is pH6.5, so because neutral aggegation easily.Preferably use ammonia in order to be adjusted to alkalescence in addition.Securely attached on the titanium oxide, these metals such as preemption have the titanium oxide active site to alkali metal such as Na, K easily, then reduce photocatalytic activity, meanwhile hinder on the active sites attached to titanium oxide such as Ag, Cu, Pt, Pd, Ni, Fe, Co.
Then titanium oxide sol suspension and the roughly the same metal salt solution of pH are mixed into titanium oxide sol suspension, and irradiation contains ultraviolet light metal is fixed.Make superfluous precipitated metal if necessary, from solution, remove.Here so-called metal salt solution, be meant when being supported on the titanium oxide, when making illumination penetrate titanium oxide to produce electronics and hole, by containing the slaine that to catch electronics and the solution of solvent composition, more particularly, be meant the salt that contains Ag, Cu, Pt, Pd, Ni, Fe, Co etc. and the solution of solvent composition.As the salt that contains Ag, Cu, Pt, Pd, Ni, Fe, Co etc., can enumerate silver nitrate, copper acetate, copper carbonate, copper sulphate, stannous chloride, copper chloride, chloroplatinate, palladium bichloride, nickel chloride, cobalt chloride, frerrous chloride, iron chloride etc.In addition, solvent can make water, ethanol, propyl alcohol etc., still also can use the solvent with the titanium oxide sol suspension identical type that should form.In solvent, add pH as required and adjust agent.Adjust agent as pH, can use nitric acid, sulfuric acid, hydrochloric acid etc. to sour side.Adjust agent as pH in addition and use ammonia to the alkali side.
Shine and contain the ultraviolet light time, note point shown below.At first so long as light source irradiation to contain ultraviolet light just passable.Can enumerate ultraviolet lamp, BLB lamp, xenon lamp, mercury vapor lamp, fluorescent lamp etc. particularly.The method that irradiation contains ultraviolet light is also no problem basically, but quadrature is penetrated at first from container.Because there is not container to absorb ultraviolet ray.The distance of its secondary light source and container can be that number cm-counts the 10cm degree.If near excessively, owing to having, the heat of sending from light source makes the danger that becomes dry above the solution, if far away excessively, then illumination reduces.Irradiation time is different because of illumination intensity of light source, and the irradiation several seconds, metal was just securely attached on the photocatalyst granular when the tens of seconds left and right sides.
Then on substrate surface, form by coating and support the titanium oxide sol of above-mentioned metal and heat-treat and the film that forms, thereby form multifunctional material with photocatalysis.
Heat treatment normally utilizes the hydrothermal treatment consists of roasting or use autoclave etc. in the atmosphere that uses electric furnace and gas burner etc., but is not limited thereto.
Titan oxide particles average grain diameter in the oxidation titanium film that is obtained by such method is preferably below the 1 μ m.When being used in this above particle diameter, because specific area reduces, so photocatalytic activity reduces.
In addition, on substrate surface, form the colloidal sol of coating claim 1 and heat-treat the film that forms, make member like this with photocatalysis by binding agent.Owing to utilize binding agent, can improve caking property with base material.
Its concrete grammar is with thermoplastic adhesive or different with thermosetting adhesive because of binding agent.Much less each form of implementation that illustrates below also can use additive method as satisfying above-mentioned formation.Here as thermoplastic adhesive, can enumerate unorganic glass matter, slicken solders etc. such as thermoplastic adhesive, glaze such as acrylic resin particularly.As thermosetting adhesive, can enumerate fluororesin, epoxy resin, silicone resin etc. in addition.
When using thermoplastic adhesive, the member of photocatalysis is arranged with order manufacturing shown below.Coating thermoplastic binding agent on substrate surface at first.Then coating has thereon supported the titanium oxide sol of metallic particles, heat-treats.Heat treatment is low at the heat resisting temperature than base material, and the temperature higher than the softening point of thermoplastic adhesive carried out.Bury in the adhesive layer by heat-treat, make a titanium oxide layer lower floor part that has supported metallic particles in such temperature, can make base material and the thin film of titanium oxide combination securely that has supported metallic particles thus.
In addition, when using thermosetting adhesive, the member of photocatalysis is arranged with order manufacturing shown below.At first in thermosetting adhesive, add diluent successively, curing agent is made mixed liquor, and it is coated on the base material, utilizes method such as heat treatment to solidify.Then be coated with thereon and in the titanium oxide sol that has supported metallic particles, add the mixed liquor that thermal curing agents resin, diluent, curing agent are made successively, utilize method such as heat treatment to solidify.
Have, instead thermosetting adhesive equally also can utilize the photo-curable binding agent again.
Like this, in the titanium oxide sol that utilizes methods such as hydro-thermal method or sulfuric acid process to make, before adding surface conditioning agents such as dispersant, surfactant, metallic particles such as Ag, Cu, Pt, Pd, Ni, Fe, Co are fixed on TiO
2On the colloidal sol surface, use metallic particles such as Ag, Cu, Pt, Pd, Ni, Fe, the Co active site of capping oxidation titanium colloidal sol in advance with this, even add surface conditioning agents such as dispersant, surfactant in the process afterwards, these materials are adsorbed on the active site of titanium oxide sol, not loss of activity.Therefore utilize the interaction energy of surface conditioning agents such as dispersant, surfactant stably to disperse photocatalyst sol, on substrate surface, can form the film of homogeneous, even meanwhile carry out roasting, also can prevent on the active site of the photocatalyst granular layer that forms on the plug material surfaces, SURFACTANT ADSORPTION such as dispersant, surfactant ground and the photocatalysis that causes reduces at the low temperature below 300 ℃.Utilize the metallic particles such as Ag, Cu, Pt, Pd, Ni, Fe, Co of the active site occupy titanium oxide sol to catch the effect of electronics simultaneously, improve photocatalytic activity.
Enumerate specific embodiment below.
Embodiment 41
In the cold water bath, in titanium tetrachloride, add water and obtain liquid material, in autoclave, resulting liquid material is carried out hydrothermal treatment consists, obtain anatase-type titanium oxide colloidal sol in 140 ℃.The anatase-type titanium oxide colloidal sol of gained is dispersed in the nitric acid.The pH of this dispersion liquid is 0.8.Add in this dispersion liquid with nitric acid and adjust roughly 0.8 3-5% (weight) copper sulfate solution of pH, quadrature is penetrated and is contained ultraviolet light from container.This moment, light source used the BLB lamp of 4W, shone 15 minutes from the distance of the about 10cm of solution.In this solution, add the dispersant of forming by organic acetate, make the colloidal sol stabilisation.This colloidal sol is coated on the tetragonal tile substrate of 15cm, heat-treats, obtain sample at 150 ℃.Deodorization R when illumination is penetrated to gained sample mensuration
30(L) and antibiotic property.
Deodorization R when illumination is penetrated
30Be meant in 11 liters glass container that (L) (in methyl mercaptan gas injection container, its initial stage concentration is 3ppm for BLB fluorescent lamp, 4W) the distance configuration sample of 8cm, and the change rate of concentration after 30 minutes is penetrated in illumination at the distance light source.
In addition, about antibiotic property, test with Escherichia coli (Escherichia coli W3110 bacterial strain)., be positioned on the glass plate (100 * 100) with 0.15ml (10000-50000CFU) the bacterium liquid that drips on the said sample of 70% ethanol sterilization the most surperficial in advance, it is the most surperficial to make it to be adjacent to base material, as sample.After 30 minutes, the bacterium liquid of the sample that the wiping of usefulness sterile gauze was shone is recovered in the 10ml physiological saline, obtains the survival rate of bacterium, as evaluation index with white lamps (3500 lux) irradiation.Evaluation criterion +++, ++ ,+,-same as described above.
R as a result
30(L) show 85% good result, antibiotic property shows +++good result.
Comparative example 42
In the cold water bath, in titanium tetrachloride, add water and obtain liquid material, in autoclave, carry out hydrothermal treatment consists in 140 ℃ of liquid material to gained, obtain anatase-type titanium oxide colloidal sol with this.The anatase-type titanium oxide colloidal sol of gained is dispersed in the nitric acid.The pH of this dispersion liquid is 0.8.In this solution, add the dispersant of forming by organic acetate, make the colloidal sol stabilisation, this colloidal sol is coated on the tetragonal tile substrate of 15cm, heat-treat, obtain sample, the deodorization R when the sample mensuration illumination of gained is penetrated at 150 ℃
30(L) and antibiotic property.
R as a result
30(L) be 5%, antibiotic property is-, all not enough.
Embodiment 43
In the cold water bath, in titanium tetrachloride, add water and obtain liquid material, in autoclave, carry out hydrothermal treatment consists in 140 ℃ of liquid material to gained, obtain anatase-type titanium oxide colloidal sol thus.The anatase-type titanium oxide colloidal sol of gained is dispersed in the nitric acid.The pH of this dispersion liquid is 0.8.Add in this solution with nitric acid and adjust the copper sulfate solution that pH is roughly 0.8 3-5% (weight), quadrature is penetrated and is contained ultraviolet light from container.At this moment, light source uses the BLB lamp of 4W, from penetrating 15 minutes apart from illumination of the about 10cm of distance solution.In this solution, add the dispersant of forming by organic acetate, make the colloidal sol stabilisation.Then, the mixed liquor of diluent propyl alcohol and curing agent formation is added in coating successively in silicone resin on the tetragonal aluminum oxide base material of 10cm surface, on 100 ℃ of dried members, be coated on the molten of method for preparing and add 20% (weight successively in, with respect to the titanium oxide amount) silicone resin, propyl alcohol and curing agent and the mixed liquor made, carry out roasting at 150 ℃, obtain sample.Deodorization R when the sample mensuration illumination of gained is penetrated
30(L) estimate.
R as a result
30(L) good result of demonstration 80%.
Comparative example 44
In the cold water bath.In titanium tetrachloride, add water and obtain liquid material, in autoclave, carry out hydrothermal treatment consists, obtain anatase-type titanium oxide colloidal sol thus in 140 ℃ of liquid material to gained.The anatase-type titanium oxide colloidal sol of gained is dispersed in the nitric acid.The pH of this dispersion liquid is 0.8.In this solution, add the dispersant of forming by organic acetate, make the colloidal sol stabilisation, then the mixed liquor that diluent propyl alcohol and curing agent are made is added in coating in advance successively in silicone resin on the tetragonal aluminum oxide base material of 10cm surface, add 20% (weight successively on 100 ℃ of dry members of crossing, being coated on the colloidal sol of method for preparing, with respect to the titanium oxide amount) silicone resin, propyl alcohol and curing agent and the mixed liquor made, 150 ℃ of roastings, obtain sample, the deodorization R when the sample mensuration illumination of gained is penetrated
30(L).R as a result
30(L) be 22%, abundant inadequately.
From above explanation as can be known, in the titanium oxide sol that methods such as utilizing hydro-thermal method or sulfuric acid process is prepared into, before adding surface conditioning agents such as dispersant, surfactant, by metallic particles such as Ag, Cu, Pt, Pd, Ni, Fe, Co are fixed on the titanium oxide sol surface, even carry out roasting at the low temperature below 300 ℃, also can on the base material of thermolability, for example on plastic material, provide member with abundant photocatalysis.
Above embodiment mainly describes about Detitanium-ore-type TiO
2, below describe about rutile TiO
2
Figure 51 is that expression utilizes rutile TiO
2The block diagram of multifunctional material manufacture process, the present invention at first forms rutile TiO on substrate surfaces such as ceramic tile
2Film.As rutile TiO
2The formation method of film as raw material, is used TiO
2The sulfate of colloidal sol, alkoxytitanium, Ti, the chloride solution of Ti etc. are coated on the substrate, heat-treat then.
Using TiO
2During colloidal sol, because TiO
2Isopotential point is 6.5, is roughly neutral, so use the aqueous solution that disperses with acid or alkali, is coated on the substrate equably easily.When the substrate of this moment was metal, from the corrosion resistance viewpoint, the alkali dispersion liquid was desirable.As acid, can enumerate sulfuric acid, hydrochloric acid, acetate, phosphoric acid, organic acid etc.Under the situation of alkali, can enumerate the hydroxide of ammonia, alkali metal containing etc., after heat treatment, do not generate metal pollutant, ammonia is desirable especially.Moreover, in these dispersion liquids, can add the dispersant of organic acid, phosphoric acid system, surface conditioning agent, surfactant again.In addition, if particle diameter is little, then the initial stage sintering can obtain the good photocatalyst film of peel strength at low temperatures in more low temperature generation, so TiO
2The average grain diameter of colloidal sol can be below the 0.05 μ m, preferably below the 0.01 μ m.
As the method that is applied to substrate, with above-mentioned raw materials spraying, dip-coating, roller coat, rotation are coated with, CVD, electron beam evaporation plating, sputter etc. compare, wishing does not need special equipment, can form stable filming.
Heat treatment can utilize roasting in the atmosphere that uses electric furnace and gas burner or use the hydrothermal treatment consists of autoclave.
On the other hand, prepare Cu, Ag, Fe, Co, Pt, Ni, Pd, Cu in advance
2At least a solution among the O (the metal ion aqueous solution), with this solution coat in rutile TiO
2On the film.At this, during the coating metal saline solution, the back side that aqueous metal salt is not transferred to substrate gets final product.Solution in metal salt solution can utilize water, ethanol etc.Making under the situation of water, as protective oxidizing agent, it also is effective adding alcohol, unsaturated hydrocarbons etc.Have again, with ethanolic solution as solution, for example reason that produces at the rust that does not become metal base and rate of drying fast aspect, compare with other solvents such as ether, acetone, methyl alcohol, be harmless, this point is desirable.
Then, in order to improve the efficient that supports above-mentioned aqueous metal salt, in room temperature～110 ℃ drying, slaine irradiation is contained light below the 390nm, the reducing metal ion is separated out this metal and is fixed on rutile TiO
2On the film.At this, the lamp that is used to shine can use ultraviolet lamp, BLB lamp (near ultraviolet ray) lamp, xenon lamp, mercury vapor lamp, fluorescent lamp etc.In irradiation this moment,, light vertically is radiated on the shadow surface gets final product in order to improve exposure rate.
Enumerate specific embodiment below
Embodiment 45
On the tetragonal alumina substrate of 10cm, with the TiO of spraying process coating average grain diameter 0.01 μ m
2The ammonia dispersion liquid of colloidal sol 900 ℃ of roastings, forms rutile TiO
2Film.Then, in this rutile TiO
2On the film, with the spraying process coating copper acetate aqueous solution, after this carry out photo-reduction (light source is a 20W BLB lamp, from light source to sample apart from 10cm, irradiation time 10 seconds), obtain sample.Sample to gained is estimated photolytic activity A (L).
Photolytic activity A (L) expression makes and gets gas concentration is Y-axis, when the reaction time is X-axis the response curve near linear time slope absolute value.Concentration when even being located at time t is Xt, then
Xt=X
o10
-A (L) t(1) therefore, contain ultraviolet light and passed through by on the photocatalyst film of penetrating, certain decomposition gas is obtained in the minimizing of the decomposition gas concentration during by observation elapsed time t.In this experiment, use is the methyl mercaptan of odor pollutant in decomposition gas, in methyl mercaptan initial stage concentration is adjusted into the cylindrical vessel of 2ppm, diameter 26cm * high 21cm, sample is set, the BLB fluorescent lamp that makes 4W is apart from sample 8cm, the time of the methylsulfuric acid concentration during by the observation irradiates light changes, and obtains decomposition gas.
Gained the results are shown among Figure 52 and Figure 53.Figure 52 and Figure 53 are the Cu concentration of expression in the solution and the curve of photolytic activity A (L) relation, wherein, Figure 52 represents to make the situation of carrying out photo-reduction after the copper acetate aqueous solution drying of atomizing, and Figure 53 represents not carry out the situation that the copper acetate aqueous solution of drying regime carries out photo-reduction with the atomizing former state.
Carry out in the situation of photo-reduction at the copper acetate aqueous solution that does not carry out drying regime with the atomizing former state of Figure 53, even the Cu concentration in the solution is increased to 0.1% (weight) from 0.001% (weight), A (L) also is 3 * 10
-5Degree does not change, and reaches capacity.
In contrast, carrying out in the situation of photo-reduction after the copper acetate aqueous solution drying of the atomizing that makes Figure 52, during 0.001% (weight), is 2 * 10
-5Degree is the value of roughly the same degree with not carrying out that dry situation compares, but if increase to 0.1% (weight), then observes to reach 1 * 10
-2Degree, A (L) improves by leaps and bounds.
Embodiment 46
Carry out in the same manner with embodiment 45, on ground furring tile and wall ceramic tile, form rutile TiO
2Film is utilizing photo-reduction that Cu (coating of the copper acetate aqueous solution, dry back) is fixed on this rutile TiO
2Under the situation on the film, solution metal constituent concentration and odor destruction rate R
30The testing result of relation be shown among Figure 54, Figure 55.
Can know by these figure, after drying, utilize photo-reduction to handle, if the solution metal constituent concentration greatly to a certain degree, even base material is a ceramic tile, also can be removed odor pollutant.
Embodiment 47
On the tetragonal ceramic tile substrate of 15cm, with the TiO of spraying process coating average grain diameter 0.01 μ m
2The ammonia dispersion liquid of colloidal sol in the different temperatures roasting, forms rutile TiO
2Film.Then in this rutile TiO
2On the film, with the spraying process coating copper acetate aqueous solution, after this carry out photo-reduction (light source is the BLB lamp of 20W, from light source to sample apart from 10cm, irradiation time 10 seconds), obtain sample.Sample to gained is estimated deodorization R
30
Gained the results are shown among Figure 56.R when 900 ℃ (open pore rate 10%)
30Value is better than the sample of the only rutile-type of carrying metal not.In addition, if make temperature rise to 1000 ℃ (open pore rates 30%), the R of the sample of carrying metal not then
30Value significantly reduces, and also observes some reduction even add the sample of Cu.Therefore, compare during with 900 ℃, two reasons are arranged 1000 ℃ of deodorization reductions.One is to follow the open pore rate to reduce the rutile TiO of the photochemical catalyst that can contact with decomposition gas
2Film size reduces.Can think to become the not main cause of the deodorization reduction of carrying metal sample.Another reason is, follows the open pore rate to reduce, and the area that utilizes photoreduction met hod precipitating metal particle to exist also reduces.Because it is big that the mean free path in electronics moves becomes.
The relation of Ag, Cu concentration and aberration in the solution when in addition, expression is filmed in Figure 57.As known in the figure, Cu compares with Ag, change in aberration and brightness which aspect all little, painted not obvious.In addition, this painted difference is utilized the analysis of ESCA (being used for chemico-analytic electronics line optical spectroscopy) etc. with regard to Cu, detect 0 valency and the 1 valency material of Cu, so can think that this is the influence that is difficult for 1 valency composition of colour developing.
Embodiment 48
On the tetragonal ceramic tile substrate of 15cm, with the TiO of spraying process coating average grain diameter 0.01 μ m
2The ammonia dispersion liquid of colloidal sol in the different temperatures roasting, forms rutile TiO
2Film.Then, with spraying process silver nitrate aqueous solution is coated on this rutile TiO
2On the film, after this carry out photo-reduction (light source is the BLB lamp of 20W, from light source to sample apart from 10cm, irradiation time 10 seconds), obtain sample.In the sample about gained, rutile TiO
2The evaluation result of the porosity of film and deodorization and wearability is shown among Figure 58.
The porosity shows good deodorization 10% when above, 40% when following, wearability is reached more than 0.
About wearability, use the sliding friction of plastic eraser, relatively appearance change is estimated.Evaluation index is expressed as follows.
◎: relative 40 no changes repeatedly
Zero: in the slip below 40 times more than 10 times scratch is arranged, oxidation titanium film is peeled off
△: in the slip below 10 times more than 5 times scratch is arranged, oxidation titanium film is peeled off
*: in the slip below 5 times scratch is arranged, oxidation titanium film is peeled off.
Embodiment 49
On the tetragonal alumina substrate of the 10cm that is pre-formed the glaze layer, the TiO of spraying process coating average grain diameter 0.01 μ m is arranged
2The ammonia dispersion liquid of colloidal sol in roasting below 1000 ℃ more than 850 ℃, forms rutile TiO
2Film.Then, in this rutile TiO
2Be coated with silver nitrate aqueous solution with spraying process on the film, carry out then photo-reduction (light source is the BLB lamp of 20W, from light source to sample apart from 10cm, irradiation time 10 seconds), obtain sample.
The gained sample is carried out antibiotic property, wearability, anti-fissility, stain resistance, acid resistance, alkali resistance, silver-colored coloring evaluation.
About antibiotic property, test with Escherichia coli (Escherichia coli W3110 bacterial strain)., be positioned on the glass plate (100 * 100) with the most surperficial 0.15ml bacterium liquid that drips of the multifunctional material of 70% ethanol sterilization in advance, be adjacent to base material is the most surperficial, as sample.After white lamps (3500 lux) irradiation 30 minutes, the sample that shone with the sterile gauze wiping and at the bacterium liquid that covers maintenance sample under the optical condition is recovered in the 10ml physiological saline, obtains the survival rate of bacterium, as evaluation index.About evaluation index +++, ++ ,+,-same as described above.
Anti-fissility test is the test harsher than abrasion test condition, uses the sand rubber (LION TYPEWR ITER ERASER 502) that adds of bigger shear strength to replace plastic eraser.Concrete evaluation method is with the power of sand rubber with equalization, on specimen surface, wipes 20 times, and the visual scratch state of comparing with standard specimen, metewand is expressed as follows.
◎: do not change fully
Zero: use up the plus-minus mode and confirm to change a little
△: confirm variation a little
*: a glance is just confirmed to change
So-called stain resistance test is the test of adhering to difficulty about dirt.Concrete evaluation method is to make dirt with 0.5% aqueous solution of methylene blue at specimen surface, and dry after washing has or not dirt with visualization.Metewand is expressed as follows.
◎: eliminate dirt fully
Zero:, have a spot of residual though do not see the color of dirt
△: residual light dirt look
*: obvious residual soil look
About acid resistance, after the 10%HCl aqueous solution floods 120 hours, with the rutile TiO that supports Ag on the visualization substrate surface
2The ANOMALOUS VARIATIONS of thin layer is estimated with this.Metewand is expressed as follows.
◎: no change
Zero: the utmost point is variable color a little
△: variable color a little
*: obviously variable color
About alkali resistance, dipping is 120 hours in the 5%NaOH aqueous solution, with the rutile TiO that supports Ag on the visualization substrate surface
2The ANOMALOUS VARIATIONS of thin layer is estimated with this, and metewand is expressed as follows.
◎: no change
Zero: the utmost point is variable color a little
△: variable color a little
*: obviously also variable color
About silver-colored coloring, by carrying out visually relatively estimating with the sample that does not add Ag.Metewand is expressed as follows.
◎: not painted
Zero: the utmost point is painted a little
△: painted a little
*: dark brown coloured part is arranged
More than 7 evaluation results be summarised in the table 24.In addition, thickness, sintering temperature are shown in Table 25 the influence of antibiotic property.
(table 24)
The relation of photocatalyst film thickness and all characteristics
| Thickness (μ m) | Antibiotic property (L) | Wearability | Anti-fissility | Stain resistance | Acid resistance | Alkali resistance | The Ag coloring |
| 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 | +++ +++ +++ +++ +++ +++ +++ +++ +++ +++ | ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ | ◎ ◎ ◎ ◎ ○ ○ ○ ○ ○ × | ◎ ◎ ◎ ◎ ○ ○ ○ ○ ○ × | ◎ ◎ ◎ ◎ ○ ○ ○ ○ ○ ○ | ◎ ◎ ◎ ◎ ○ ○ ○ ○ ○ ○ | ◎ ◎ ◎ ◎ ○ ○ ○ ○ ○ × |
| There is not scratch (0.4) | △ |
(table 25)
Thickness, sintering temperature are to the influence of the antibiotic property of photocatalyst film
About antibiotic property, be more than the 0.1 μ m, in the following scope of 1 μ m at the thickness of the photocatalyst film that present embodiment is made, if make sintering temperature all suitable, then show +++good result.But, shown in table 24 like that, if thickness is thinned to below the 0.2 μ m, the antibiotic property of the sample of 980 ℃ of high-temperature roastings is ++.See the tendency that antibiotic property reduces.Can think that this is that photocatalyst film is embedded in the cause in the scratch layer partly because because glaze layer softening.In addition, though Ag itself also has antibacterial activity, the interdependent tendency of the sintering temperature of this antibiotic property, the antibacterial activity of the composite component of making according to the application's method also shows the rutile TiO beyond the antibacterial action with Ag
2Film characteristics relevant (because Ag supports after roasting as described above).
Can think in addition and in all samples, follow the glaze layer to soften, generation photocatalyst film to a certain degree is to the sinking of glaze layer, but present embodiment confirms, if make sintering temperature suitable, can make the above photocatalyst film of at least 0.1 μ m remain on the top layer of glaze layer.
About wearability, the thickness of the photocatalyst film of making in the present embodiment all shows the good result of ◎ more than 0.1 μ m, in the following scope of 1 μ m.This result is that △ is different with the sample of not making by glaze with identical manufacture method, centre in order to compare, and shows extremely good result.Can think that this is because the middle glaze of getting involved, because glaze softening, the part of photocatalyst film lower floor is buried in the glaze layer when roasting.
In contrast, for anti-fissility test, 0.1 μ m is above, 0.4 μ m is ◎ when following, and 0.4 μ m is above, 0.9 μ m when being zero, 1 μ m when following is *, the thickness of observing with photocatalyst film increases, and the tendency of variation occurs.Can think that this is because owing to increase the cause that is not easy to peel off to the ratio of burying thickness and thickness underground of glaze layer.Unusual person in abrasion test is poor in anti-disbonded test in addition, and this is to be caused by varying in size of shearing force.
About stain resistance, the photocatalyst film thickness more than 0.1 μ m, 0.4 μ m is ◎ when following, 0.4 μ m is above, 0.9 μ m when being zero, 1 μ m when following is *, observe increase with the photocatalyst film thickness, the tendency of variation appears.
About acid resistance, the photocatalyst film thickness of making in the present embodiment is in the scope that 0.1 μ m is above, 1 μ m is following, all shows good result.But more than 0.4 μ m, 1 μ m is zero when following, more than 0.1 μ m, 0.4 μ m is ◎ when following, the thin person of thickness shows gratifying value.
About alkali resistance, the photocatalyst film thickness of making in the present embodiment is in the scope that 0.1 μ m is above, 1 μ m is following, all shows good result.But more than 0.4 μ m, 1 μ m is zero when following, more than 0.1 μ m, 0.4 μ m is ◎ when following, the thin person of thickness shows gratifying value.About the Ag coloring, the photocatalyst film thickness is that 0.1 μ m is above, 0.4 μ m is ◎ when following, 0.4 μ m is above, 0.9 μ m when being zero, 1 μ m when following is *, observe increase with the photocatalyst film thickness, the tendency of variation appears.This tendency is consistent with stain resistance.
By above 7 tests as can be known, the thickness of photocatalyst film is more than the 0.1 μ m, below the 0.9 μ m, preferably more than the 0.1 μ m, below the 0.4 μ m.See in addition by the glaze layer photocatalyst film is fixed on the base material, improve wearability.
In addition, utilize thickness also to change the feature of design.Promptly, utilize the interference effect of visible light and photocatalyst film, produce the striped style of iridescent colors, give special in appearance impression more than the 0.2 μ m, below the 0.4 μ m.On the contrary, below the 0.2 μ m and more than the 0.4 μ m, below the 0.9 μ m, do not produce the striped style of above-mentioned iridescent colors.Can utilize to former state the color of base material or the color that constitutes by glaze, style or with its in conjunction with relevant outward appearance.
On the tetragonal ceramic tile substrate of 15cm, with the TiO of spraying process coating average grain diameter 0.01 μ m
2The ammonia dispersion liquid of colloidal sol 900 ℃ of roastings, forms the rutile TiO of thick 0.8 μ m
2Film.Then, on this ceramic tile surface, change the coating weight of the copper acetate aqueous solution (solution concentration 0.2% (weight), 0.5% (weight), 1% (weight)), with the spraying process coating copper acetate aqueous solution, after this (light source is the BLB lamp of 20W to carry out photo-reduction, from light source to sample apart from 10cm, irradiation time 10 seconds), obtain sample.The gained sample is estimated antibiotic property.Reclaim postradiation residual water solution, calculate the Cu loading from initial copper amount and the difference that reclaims the copper amount.
(L) and the bacteria live rate relation of (D) when dark when Cu loading shown in Figure 59 and illumination are penetrated.The road is following true as known in the figure.
First utilizes that Cu's support the raising antibiotic property.Secondly (L) when dark (D) supporting under the situation of lacking Cu the antibiotic property height when illumination was penetrated.This is because when illumination is penetrated (L), because Cu supports, recovers photoactive rutile TiO
2The photocatalysis of film is worked.From this figure as can be known, add 0.12 μ g/cm
2More than be ++, adding 0.3 μ g/cm
2Above to +++improve.
Self also has antibacterial action known Cu, increases the loading of copper when therefore dark, can find that antibiotic property improves.At this moment, loading is 0.7 μ g/cm
2When above be ++, loading is 1.2 μ g/cm
2The time, be increased to +++.
Therefore, according to ++ the level evaluation is 0.12 μ g/cm
2More than, 0.7 μ g/cm
2Below, according to ++ the evaluation of+level is 0.3 μ g/cm
2More than, 1.2 μ g/cm
2Following Cu loading, (L) has good antibacterial property when illumination is penetrated, and can think by Cu and rutile TiO
2Film combinations and the special-effect that produces are because rutile TiO
2Film exists.The Cu loading can lack.Like this, the Cu loading can reduce, and is critical nature when this composite component uses around the water especially, and the purposes in copper can the environment of stripping in water also can suppress stripping quantity when for example using on the groove face in commode and sanitary ceramics etc.
In addition, under the situation of Cu, with Cu
2The form of O also obtains same effect.This is because the surface when photo-reduction detects 1 valency Cu by ESCA, though Cu
2Partly become Cu
+, but observe the effect that photolytic activity recovers.
On the other hand, by making the Cu loading at 0.7 μ g/cm
2More than, 1.2 μ g/cm preferably
2More than, no matter have or not illumination to penetrate, can both obtain good antibacterial property.
In addition, Figure 60 be the Cu concentration in the solution when being 1% (weight) the Cu coating weight and the relation of Cu loading, find out that by this figure even increase the coating weight of Cu merely, the loading of Cu does not increase yet, for the loading that makes copper is 0.7 μ g/cm
2More than, the coating weight that can make Cu is 0.2mg/cm
2More than, 2.7mg/cm
2Below, for the loading that makes Cu is 1.2 μ g/cm
2More than, the coating weight that can make Cu is 0.3mg/cm
2More than, 2.4mg/cm
2Below.
Embodiment 51
On the tetragonal ceramic tile substrate of 15cm, with the TiO of spraying process coating average grain diameter 0.01 μ m
2The ammonia dispersion liquid of colloidal sol 900 ℃ of roastings, forms the rutile TiO of thick 0.8 μ m
2Film.Then, on this ceramic tile surface, change silver nitrate aqueous solution (solution concentration 0.2% (weight), 0.5% (weight), 1% (weight)) coating weight, be coated with this solution with spraying process, after this (light source is the BLB lamp of 20W to carry out photo-reduction, from light source to sample apart from 10cm, irradiation time 10 seconds), obtain sample.Sample to gained is estimated antibiotic property.Reclaim postradiation residual water solution, calculate the Ag loading from initial silver amount and the silver-colored difference of measuring of recovery.
(L) and the relation of the bacteria live rate of (D) when dark when Figure 61 represents that Ag loading and illumination are penetrated.Can know the following fact by this figure.
At first the situation with Cu is different, when illumination is penetrated (L) and when dark the bacteria live rate curve of (D) overlap.Having under the situation of Ag, this does not produce the effect different with the situation that Cu is arranged, not equal to the antibacterial activity of Ag is much larger than Cu, just tell on considerably less loading, thus can think that illumination is penetrated the time (L) and when dark the difference of the necessary loading of (D) be included in result in the experimental error scope.
In addition, as known in the figure, the loading by making Ag is at 0.05 μ g/cm
2More than, 0.1 μ g/cm preferably
2More than, no matter have or not illumination to penetrate, can both obtain good antibacterial property.
In addition, Figure 62 is the aberration relation of loading with the sample that does not support silver of expression silver, if the loading of silver surpasses 1 μ g/cm
2, it is big that aberration just sharply becomes, and surpasses 2.General aberration is more than 2, and the difference of look just significantly.If adhere to silver, just from the dark brown black that becomes, so ugly in appearance, undesirable.Therefore, it is desirable to Difference Control below 2, for this reason, the loading of silver is accomplished 1 μ g/cm
2Get final product.Have again, measure aberration with beam splitting type colour difference meter (Tokyo electricity look (strain) is made).
But, in the above-described embodiments, the chemical combination ability of being carried out covering such as some molecular substance and dust for the active site of doing one's utmost to prevent photochemical catalyst by surface conditioning agent and causing reduces or makes activation recovering, the active site that covers the particulate with photocatalytic activity with metal particles such as silver, copper, platinum, palladium, gold, nickel, iron, cobalt, zinc has been described, but because such metal is a non-ferrous metal, so if a large amount of coating, on substrate surface, just have patterns such as solid colour, the color of infringement base material, style.
Therefore, the discoloration method of not only keeping high photocatalytic activity but also not damaging patterns such as base material color, style is described below.
As fundamental method, by in process with fixing metal particulate on the particle of photocatalytic activity, make the above-mentioned metallic particles and the aqueous solution or gas react, form on metal particle surface at least these two processes of process of colourless or white salt, the catalyst of manufacturing containing metal particulate.
The order that above-mentioned two processes are carried out is different, but carries out wherefrom all can.Promptly, can have be fixed with the non-ferrous metal particulate on the particle of photocatalytic activity after, the above-mentioned metal particle and the aqueous solution or gas are reacted, at least form colourless or white salt on the metal particle surface, the non-ferrous metal particulate and the aqueous solution or gas are reacted, at least after the metal particle surface forms colourless or white salt, be fixed on the particle of photocatalytic activity.
In addition; also can be with particle that photocatalytic activity arranged with after the non-ferrous metal particulate mixes; be fixed on the base material, in the case, for example; order is carried out following process; that is, be mixed with the process of the particle and the non-ferrous metal particulate of photocatalytic activity, the process of the above-mentioned mixed liquor of coating on base material; carry out roasting and make said mixture be fixed on process on the base material, react, form on the metal particle surface at least the process of colourless or white salt with gas.
Moreover, carry out roasting make said mixture be fixed on the process of substrate surface and with gas reaction, form process colourless or white salt on metal particle surface at least and can carry out simultaneously.
So-called non-ferrous metal particulate is meant that silver, copper, platinum, palladium, gold, nickel, zirconium, cobalt, zinc plasma tendency are little, and self is the easy metal particle of reduction also.
Utilizing reactant aqueous solution to form colourless or during white salt, when perhaps using the catalyst of containing metal particulate in liquid, formed colourless or white salt can be slightly solubility or insoluble.
Be fixed on when using on the base material at catalyst, can in advance the particle that photocatalytic activity is arranged be fixed on the base material, make the catalyst of containing metal particulate then the containing metal particulate, also can make the catalyst of containing metal particulate after, be fixed on the base material.
Under situation by the catalyst of making the containing metal particulate in advance fixedly having the particle of photocatalytic activity on the base material, can be undertaken by following order, promptly on base material, form the process of stratum granulosum with photocatalytic activity, be fixed with the process of non-ferrous metal particulate thereon, above-mentioned non-ferrous metal particulate covering formed the process of colourless or white salt.
Be coated with the non-ferrous metal particulate and form the process of colourless or white salt, for example to react with above-mentioned non-ferrous metal particulate, at least can form the method that the solution of colourless or white salt contacts with metal particle carries out on the surface of metal particle, perhaps to react with above-mentioned non-ferrous metal particulate, the method that contacts with metal particle at the surperficial reacting gas that can form colourless or white salt of metal particle is carried out at least.
White or colourless salt in the salt of above-mentioned non-ferrous metal particulate it is desirable to slightly solubility or insoluble salt.Therefore salt can be on the surface of metal particle, formed easily at least with reactant aqueous solution, and use can be stablized having under the environment of water.
White or colourless salt in the above-mentioned non-ferrous metal particulate salt for example can be enumerated silver chlorate, silver bromide, silver iodide, silver oxalate, silver thiosulfate, silver cyanide, thiocyanation silver, stannous chloride, cuprous bromide, cuprous cyanide, cuprous rhodanide, cuprous oxide, trbasic zinc phosphate, zinc oxalate, zinc cyanide, cyaniding palladium, zinc sulphide, zinc carbonate, ferrous carbonate, zinc oxide etc.Can form the solution of above-mentioned salt, for example under the situation of silver chlorate, can enumerate Klorvess Liquid, sodium chloride solution, ammonium chloride solution, solution of ferrous chloride etc., under the situation of silver iodide, can enumerate liquor kalii iodide, IodineSodium Solution, iron iodide solution, aquae hydrogenii dioxidi, Ozone Water etc., but be not limited to these, all can be extensive use of if contain the anionic soluble-salt solution of various salt.
In addition, if can form the anion element that the reacting gas of above-mentioned salt also contains various salt, then also can be extensive use of.If for example above-mentioned salt is oxides such as zinc oxide, cuprous oxide, then by in air, in the oxygen, heat in the water vapour, perhaps with O
3Deng oxidant reaction, can make the metallic surface oxidation, can form oxide skin(coating) on the surface.
Enumerate specific embodiment below
Embodiment 52
On the tetragonal tile substrate of 15cm surface, the titanium oxide sol of coating average grain diameter 0.01 μ m then, is heat-treated at 900 ℃, forms the Titanium Dioxide Rutile Top grade film.The sample that forms till this stage is sample 1 as a comparison.
After this, be coated with silver nitrate aqueous solution, as light source irradiation 10 minutes, silver be fixed on the Titanium Dioxide Rutile Top grade film with the BLB lamp of 20W with spraying process.This moment, the loading of silver was 1.2 μ g/cm
2, present dark brown.With the sample that till this stage, forms sample 2 as a comparison.
After this, with 0.1cc/cm
2Ratio the potassium iodide aqueous solution of 0.1mol/L is coated on the duplicate 2, make its reaction.Specimen surface changes to yellow-white as a result, and whitening.Can think because form the iodate silver layer.With this sample as embodiment sample 1.
These samples are estimated aberration, photolytic activity, deodorization and antibiotic property.
Measure aberration with beam splitting type colour difference meter (Tokyo electricity look (strain) is made).At this moment, standard specimen sample 1 as a comparison.The results are shown among Figure 63.Duplicate 2 aberration are 3.5 as a result, and in contrast, owing to handle with potassium iodide aqueous solution, embodiment sample 1 aberration reduces to 1, show the bag degree and reduce.
About photolytic activity, with Δ pH test evaluation.The results are shown among Figure 64 of photolytic activity and deodorization.By the comparison of duplicate 1 and 2, owing to support silver, the photolytic activity of duplicate 2 recovers, Δ pH and R
30(L) all show good result.In addition, embodiment sample 1 and duplicate 2 are more known, Δ pH and R
30(L) all be the value of roughly the same degree, even if utilize decolouring to handle, photolytic activity does not change yet, and can keep good characteristic.
About antibiotic property, test in addition with Escherichia coli (Escherichia coli W3110 bacterial strain).In advance with the most surperficial 0.15ml (2 * 10 that drips of the sample of 70% ethanol sterilization
4CFU) bacterium liquid is positioned on the glass plate (100 * 100), is adjacent to base material is the most surperficial, as sample., be recovered in the 10ml physiological saline with the sample (L) of white lamps (3500 lux) irradiation preset time with covering the bacterium liquid that optical condition keeps sample (D) with the sterile gauze wiping, detect the existence bacterial population, estimate.
The results are shown among Figure 65 of relevant antibiotic property.Duplicate 1 is not because support silver, so can't see the antibacterial effect of (D) when dark.In contrast, embodiment sample 1 although the surface that utilizes decolouring to handle silver is varied to compound, is also seen the antibacterial effect of (D) when dark.(L) observes stronger antibacterial effect when illumination is penetrated in addition, not only observes the antibacterial effect of silver, and observes the photocatalytic activity recovery effects of Titanium Dioxide Rutile Top grade film.
Embodiment 53
Behind coating glaze on the tetragonal sanitary ceramics shaping of the 15cm base, 1100-1200 ℃ of roasting, be coated with the anatase-type titanium oxide colloidal sol of average grain diameter 0.01 μ m then, 900-1000 ℃ of roasting, fixing Titanium Dioxide Rutile Top grade film on sanitary ceramics shaping base base material.
After this, be coated with silver nitrate aqueous solution thereon, irradiation ultraviolet radiation is separated out on thin film of titanium oxide silver.Be coated with ferrous chloride aqueous solution more thereon, irradiation ultraviolet radiation decolours, and aberration reduces to 0.3 from 3.Antibiotic property all contacts 30 minutes when dark with sample when illumination is penetrated in addition, and the bacterium that confirms to live only is below 10% of original bacterium number, shows good result.
Embodiment 54
Behind coating glaze on the tetragonal sanitary ceramics shaping of the 15cm base, 1100-1200 ℃ of roasting, be coated with the anatase-type titanium oxide colloidal sol of average grain diameter 0.01 μ m then, carry out roasting, fixing Titanium Dioxide Rutile Top grade film on sanitary ceramics shaping base base material at 900-1000 ℃.
After this, be coated with silver nitrate aqueous solution thereon, irradiation ultraviolet radiation makes silver on thin film of titanium oxide.Again sample was placed about 2 hours in having the drier of ozone generator (ozone concentration 10ppm), decoloured, confirm that the bacterium of existence only is below 10% of original bacterium number, show good result.
Embodiment 55
Behind coating glaze on the tetragonal sanitary ceramics shaping of the 15cm base, 1100-1200 ℃ of roasting, coating is dispersed in the anatase-type titanium oxide colloidal sol of the average grain diameter 0.01 μ m in the aqueous solution of nitric acid and the mixture of silver nitrate aqueous solution thereon again, carry out roasting then, fixing thin film of titanium oxide on sanitary ceramics is shaped bad base material.This moment is dark brown as if then presenting in roasting below 700 ℃, but then decolours in roasting more than 700 ℃.May be interpreted as because the composition in silver surface and the atmosphere reacts.In addition to 850 ℃ of roastings, fixedly the sample of anatase-type titanium oxide film is measured antibiotic property on sanitary ceramics shaping base base material, contact 3 hours with sample jointly when dark when illumination is penetrated, the confirmation bacterium that survives only is below 10% of original bacterium number, shows good result.
Embodiment 56
Behind coating glaze on the tetragonal sanitary ceramics shaping of the 15cm base, 1100-1200 ℃ of roasting, be coated with the anatase-type titanium oxide colloidal sol of average grain diameter 0.01 μ m more thereon, 900-1000 ℃ of roasting, fixing Titanium Dioxide Rutile Top grade film on sanitary ceramics is shaped bad base material.
Then, be coated with silver nitrate aqueous solution thereon, irradiation ultraviolet radiation is separated out on thin film of titanium oxide silver.Be coated with aquae hydrogenii dioxidi more thereon, make its decolouring.Antibiotic property all contact 3 hours when dark with sample when illumination is penetrated in addition, and the bacterium that confirms to survive only is below 10% of original bacterium number, shows good result.
Then, describe about rutile TiO
2Particle and tin oxide mix, and are seeking to improve photocatalyst film compactness and close-burning while the problem that raising is active.
The formation method of photocatalyst film can be utilized any of following two kinds of methods.
A kind of is to be pre-mixed TiO
2Colloidal sol and tin oxide sol are coated on the method for carrying out roasting on the substrate surface.
TiO
2Being blended in the alkaline aqueous solution of colloidal sol and tin oxide sol carried out.The both shows fine dispersion is because see it is the alkali side from electrochemistry.As alkaline aqueous solution, can enumerate the hydroxide of ammonia, alkali metal containing or alkaline-earth metal, but after heat treatment, not produce metal pollutant, ammonia is desirable especially.Moreover, in these dispersion liquids, also can further add organic system, phosphoric acid is dispersant, surface conditioning agent, surfactant.
As rubbing method, have the method that above-mentioned mixed liquor spraying, dip-coating, roller coat, rotation are coated with, formation such as CVD, electron beam evaporation plating, sputter is filmed, but can be wherein any method, also can be additive method in addition.But spraying, dip-coating, roller coat are compared with CVD, electron beam evaporation plating, sputter etc., and having does not need special equipment, can form the advantage of filming at an easy rate.
After the coating, can before roasting, make the film drying.Drying can be carried out about room temperature-100 ℃.
Roasting is carried out under the temperature conditions that fully generates rutile.This temperature is more than 830 ℃ when coexisting with tin oxide under normal pressure.
Unnecessary formation TiO
2Solid solution with tin oxide.In order to form TiO
2Need at high temperature to keep for a long time with the solid solution of tin oxide, so the production efficiency step-down.
Another method is to form rutile TiO
2Behind the film, add tin oxide sol thereon, carry out the method for roasting.
This method at first is coated with the initiation material that contains Ti on base material.Here use TiO as initiation material
2The sulfate of colloidal sol, alkoxytitanium, Ti, the chloride solution of Ti etc.Using TiO
2The occasion of colloidal sol, TiO
2Isoelectric point be pH6.5, substantially neutral, so the aqueous solution that uses acid or alkali to disperse is coated on the base material, be easy to be coated with equably.When this moment, base material was metal, from the corrosion resistance viewpoint, the alkali dispersion liquid was desirable.Under situations such as ware, ceramic tile, pottery, can use acid, any class dispersion liquid of alkali.Can enumerate nitric acid, sulfuric acid, hydrochloric acid, acetate, phosphoric acid, organic acid etc. as acid.As alkaline aqueous solution, can enumerate the hydroxide of ammonia, alkali metal containing or alkaline-earth metal, but not generate the viewpoint of metal pollutant after the heat treatment, ammonia is desirable especially.Moreover, all right dispersant, surface conditioning agent, the surfactant that further adds organic system, phosphoric acid system in these dispersion liquids.In addition, initiation material TiO
2The average grain diameter of colloidal sol can be below the 0.05 μ m, preferably below the 0.01 μ m.If particle diameter is little, then produce the initial stage sintering, so can generate the good photocatalyst film of peel strength at low temperature at low temperature more.The method that the useful spraying of method, dip-coating, roller coat, the rotation that is applied to base material is coated with, CVD, electron beam evaporation plating, sputter etc. film these dispersion liquids can be any method wherein, also can be additive method in addition.But spraying, dip-coating, roller coat are compared with CVD, electron beam evaporation plating, sputter etc., and having does not need special equipment, can form the advantage of filming at an easy rate.After the coating, can before roasting, carry out drying.Drying can be carried out about room temperature-100 ℃.
Then with the composite component roasting that is coated with.Roasting is carried out in the temperature that generates rutile.This temperature is more than 900 ℃ under normal pressure.
After this being coated with on the composite component of cooling curing becomes the initiation material in Sn source again, and carries out roasting.As the initiation material that becomes the Sn source tin oxide sol etc. is arranged.In tin oxide sol, can use alkaline aqueous solution.Because tin oxide sol sees that from electrochemistry the alkali side is stable.Can enumerate the hydroxide of ammonia, alkali metal containing or alkaline-earth metal as alkaline aqueous solution, but not generate the viewpoint of metal pollutant after the heat treatment, ammonia is desirable especially.Moreover, in these dispersion liquids, also can further add dispersant, surface conditioning agent, the surfactant of organic system, phosphoric acid.Be applied to the method for base material, useful spraying, dip-coating, roller coat, rotation are coated with, CVD, electron beam evaporation plating, sputter etc. form the method for filming with these dispersion liquids coatings, can be any methods wherein, also can be additive methods in addition.But spraying, dip-coating, roller coat are compared with CVD, electron beam evaporation plating, sputter etc., and having does not need special equipment, can form the advantage of filming at an easy rate.After the coating, can before roasting, carry out drying.Dry about room temperature-100 ℃, carry out to good.Sintering temperature can be the temperature that evaporates the organic additive composition from tin oxide.This temperature is more than 300 ℃ under normal pressure.In addition, unnecessary formation TiO
2Solid solution with tin oxide.In order to form TiO
2Need at high temperature to keep long-time with the solid solution of tin oxide, thereby the production efficiency step-down.
In addition, form by rutile TiO at substrate surface
2The film of forming with the mixture of tin oxide below the crystallization particle diameter 0.01 μ m, can be again fixation of C u, Ag, Pt, Fe, Co, Ni, Pd, Cu thereon
2At least a metal among the O.
These metals have the seizure electronic action, utilize this point to improve by rutile TiO
2The photocatalytic activity of the film of forming with the mixture of tin oxide below the crystallization particle diameter 0.01 μ m.
Especially Cu, Ag itself have antibacterial activity, can give the dark activity of relevant antibiotic property, so even not only shine the antibacterial activity that also may keep to a certain degree.Fixation of C u, Ag, Pt, Fe, Co, Ni, Pd, Cu
2At least a metal among the O.Method, be at least a aqueous metal salt of coating in these metals, utilize photoreduction met hod or heat treating process to fix then.
In the aqueous metal salt, dissolving gets final product metal as cation basically.Can enumerate copper acetate, silver nitrate, copper carbonate, copper sulphate, stannous chloride, copper chloride, chloroplatinic acid, palladium bichloride, nickel chloride, cobalt chloride, frerrous chloride, iron chloride etc. particularly.
The rubbing method of aqueous metal salt has spraying process or dip coating etc., but since can accomplish few, the even coating of use amount, easily control thickness, can non-cohesively on demand wait overleaf, spraying process is better.
Under the situation of photoreduction met hod, irradiation thereafter contains ultraviolet light, makes metal ion reduction, by rutile TiO
2Fixation of C u, Ag, Pt, Fe, Co, Ni, Pd, Cu on the film of forming with the mixture of tin oxide below the crystallization particle diameter 0.01 μ m
2At least a metal among the O.
Irradiation contains the light source of ultraviolet, can be to shine the light source that contains ultraviolet, can be any of ultraviolet lamp, BLB lamp, xenon lamp, mercury vapor lamp, fluorescent lamp etc. particularly.Irradiation contains the method for ultraviolet, it is desirable to, and makes light vertically contact shadow surface and disposes sample like that.Because illumination efficiency the best.Distance from light source to sample is that 1cm-30cm is desirable.Distance is too short, can not be on whole sample face with the illumination irradiates light of approximate equality, adhering to of above-mentioned metal species is easy to generate deviation, and distance is long, because the illumination of illuminated light is inversely proportional the diminishing of quadratic power with distance, so be difficult to make metal species to be adhered to securely.
When heat treating process,, be heated to enough temperature and carry out immobilization thereafter for the set metal.This temperature is preferably more than 100 ℃.But for example when the so-called high temperature more than 800 ℃ is handled,, perhaps do not lose the metal of antibiotic property because so burning in the case, is not lost electronics seizure effect even be defined as oxidation yet.Promptly should be defined in Ag, Cu.Under Ag, Cu situation, even do not catch effect or antibiotic property, so manufacture method shown below also can because also do not lose electronics in high-temperature roasting.Promptly be pre-mixed TiO
2Colloidal sol and tin oxide sol are coated on the substrate surface, then the method for carrying out roasting behind the coating metal saline solution.If according to the method, then can once finish roasting process, the effect that productivity ratio improves, manufacturing cost reduces is arranged.
Below enumerate specific embodiment
Embodiment 55
In being adjusted to the ammonia spirit of pH11, add the TiO of the crystallization particle diameter 0.01 μ m of 4-6% (weight)
2Colloidal sol is made suspending liquid A.In other container, in being adjusted to the ammonia spirit of pH11, add the tin oxide sol of the crystallization particle diameter 0.0035 μ m of 10% (weight), make suspension B.Behind given ratio mixing suspension A and suspension B, be coated on the tetragonal tile substrate of the 15cm surface with spraying process, dry back obtains sample 850 ℃ of roastings 2 hours.TiO in the gained sample
2Crystal type is a rutile-type.Measure lattice paprmeter with powder x-ray diffraction in addition, do not see that tin oxide is solidly soluted into TiO
2In the lattice.Sample to gained is estimated photolytic activity and wearability.
About photolytic activity, dripping potassium iodide aqueous solution on the specimen surface, then the potassium iodide aqueous solution irradiation ultraviolet ray in 30 minutes to dripping utilizes the potassium iodide aqueous solution pH of pre-irradiation and the difference of postradiation potassium iodide aqueous solution pH to estimate.Promptly according to this method, if the photolytic activity of specimen surface improves, redox reaction then shown below is easier carries out, so postradiation pH is than the pH height of pre-irradiation.
Oxidation reaction:
Reduction reaction:
In addition, wearability is carried out sliding friction with plastic eraser, and relatively the variation of outward appearance is estimated.About evaluation index ◎, zero, △, * same as described above.
Expression changes with respect to the wearability of the tin oxide weight ratio in the film in Figure 66.No matter have or not tin oxide, wearability all shows good result, is ◎ or zero.Can think to produce sintering because handle at 850 ℃ so-called high temperature, the particle in the film combines each other securely.
Especially, tin oxide surpasses at 30% o'clock, is ◎.This is because initiation material TiO
2The size ratio of colloidal sol (crystallization particle diameter 0.01 μ m) and tin oxide (crystallization particle diameter 0.0035 μ m) is more than 2, particulate oxide tin particles landfill TiO
2Fillibility is improved in the gap of particle, and film is more fine and close.
Expression is with respect to the photoactive variation of tin oxide weight ratio in the film among Figure 67.For relatively, also be illustrated in the rutile TiO that shows good antibiotic property and deodorization simultaneously
2On support the sample of Cu (at R
30Be 60%) Δ pH and show the Detitanium-ore-type TiO of very good antibiotic property and deodorization
2Sample is (at R
30Be 97%) Δ pH.Add the rutile TiO of tin oxide
2Δ pH be unable to catch up with Detitanium-ore-type TiO
2, the interpolation weight ratio of tin oxide is above below 10%, 80% or more than 20%, below 70%, in rutile TiO
2On support the sample of Cu Δ pH show bigger value, good photolytic activity is arranged.
Also do not improve photocatalytic activity even add the above tin oxide of average grain diameter 0.01 μ m, this is that granules of stannic oxide is not enough to generate the energy gap of active oxygen because move inadequately on the conductive strips position that is caused by the tin oxide micronize.In addition, if be no more than 10%, then do not produce enough photolytic activities, this is that amount by granules of stannic oxide is than causing inadequately.On the other hand, a little less than 80% above effect, this is because the tin oxide in the photocatalyst layer uprises in abutting connection with the probability that exists, thereby the frequency that particle is grown up more than average grain diameter 0.01 μ m when inferring heat treatment uprises.
Comparative example 56
In being adjusted to the ammonia spirit of pH11, add the TiO of the crystallization particle diameter 0.01 μ m of 4-6% (weight)
2Colloidal sol.Make suspending liquid A.In other container, in being adjusted to the ammonia spirit of pH11, add the tin oxide sol of the crystallization particle diameter 0.01 μ m of 10% (weight), make suspension B.Behind given ratio mixing suspension A and suspension B, be coated on the tetragonal tile substrate of the 15cm surface with spraying process, roasting in 2 hours is carried out at 850 ℃ in dry back, obtains sample.TiO in the gained sample
2Crystal type be rutile-type.Measure TiO with powder x-ray diffraction
2Lattice paprmeter does not see that tin oxide is to TiO
2Solid solution in the lattice.This sample is estimated photolytic activity and wearability.
Expression changes with respect to the wearability of the tin oxide weight ratio in the film in Figure 68.No matter have or not tin oxide, wearability all shows good result, is zero.Can think that the particle in the film is combination securely to each other owing to the so-called high temperature at 850 ℃ produces sintering.But, but make addition increase can not improve wearability more specifically with tin oxide.Can think that this is because the TiO of initiation material
2The size ratio of colloidal sol (crystallization particle diameter 0.01 μ m) and tin oxide sol (crystallization particle diameter 0.01 μ m) about equally.
Expression changes with respect to the photolytic activity of the tin oxide weight ratio in the film in Figure 69.For relatively, also be illustrated in the rutile TiO that shows good antibiotic property and deodorization simultaneously
2On support Cu sample Δ pH and show the very Detitanium-ore-type TiO of good antibacterial property and deodorization
2The Δ pH of sample.Add the rutile TiO of tin oxide
2Δ pH, both be nothing like Detitanium-ore-type TiO specifically
2The Δ pH of sample also can not show a candle in rutile TiO
2On support the Δ pH of the sample of Cu.
Embodiment 57
In being adjusted to the ammonia spirit of pH11, add the TiO of the crystallization particle diameter 0.01 μ m of 4-6% (weight)
2Colloidal sol is made suspending liquid A.In other container, in the ammonia spirit that is adjusted to pH 11, add the tin oxide sol of the crystallization particle diameter 0.0035 μ m of 10% (weight), make suspension B.Behind given ratio mixing suspension A and suspension B, be coated on the 15cm square tile substrate surface with spraying process, roasting in 2 hours is carried out at 850 ℃ in dry back, obtains composite component.TiO in the gained composite component
2Crystal type is a rutile-type.And the weight ratio of the tin oxide in the film is 60%.In addition, measure TiO with powder x-ray diffraction
2Lattice paprmeter, do not see that tin oxide is to TiO
2Solid solution in the lattice.After being coated with the copper acetate aqueous solution of 5% (weight) again with spraying process on this composite component, carry out drying, carry out then photo-reduction (light source is the BLB lamp of 20W, from light source to sample apart from 10cm, irradiation time 1 minute), obtain sample.The gained sample is estimated deodorization R
30
Here utilize test shown below to obtain R
30Use methyl mercaptan in decomposition gas, sample is arranged on methylsulfuric acid initial stage concentration and adjusts to 2ppm, in the cylindrical vessel of diameter 26cm * high 21cm.The BLB fluorescent lamp that makes 4W is apart from sample 8cm, and illumination was penetrated 30 minutes, calculates the concentration slip of methyl mercaptan, the deodorization R when obtaining illumination and penetrating
30(L).In addition, calculate irradiates light not, the concentration slip of the methyl mercaptan during through 30 minutes, obtain the deodorization R when dark
30(D).The results are shown in the table 26.For relatively, the sample of making in embodiment 55 and comparative example 56 (weight ratio of tin oxide is 60%) is tested simultaneously.Can know and to find out, effect shown below is arranged owing to add Cu by table 26.
(table 26)
| Sample | R 30(L) | R 30(D) |
| | 82 | 0 |
| | 97 | 92 |
| Comparative example | 32 | 0 |
(SnO
2Weight ratio all be 60%)
Can find out from table 26, compare R with the sample of embodiment 53
30(L) some raising is arranged.Can think that this catches effect by the electronics that utilizes Cu and causes.In addition, compare R with embodiment 53 with comparative example 54
30(D) significantly improve.The catalytic effect that this dark active raising may be interpreted as by copper causes.
As seen from the above description, on substrate surface, form in the member of photocatalyst film, by TiO at photocatalyst film
2The sintering temperature that becomes to be divided into rutile-type is handled, and can keep sufficient compactness and TiO
2Film-strength.At this moment, remove rutile TiO
2In addition, if the following tin oxide of crystallization particle diameter 0.01 μ m is arranged, then can improve the photocatalytic activity of photocatalyst film.
At least a metal among fixation of C u, Ag, Pt, Fe, Co, Ni, the Pd on photocatalyst film utilizes electronics seizure effect again, can further improve photocatalytic activity.
Industrial applicibility
As mentioned above, of the present invention have antibiotic property, soil resistance, deodorization and a decomposing N OxEtc. the multifunctional material of the photo-catalysis function of harmful substance, the sanitary ceramics such as the stone material that be applicable to wall material, ceramic tile, glass, mirror, uses as the shop stone of the artificial waterfall of circulation filter such as water-cycling mode and water spray or closet, commode, prevent equipment, residential equipment machine, antimycotic equipment, viral infection resisting equipment etc. in the hospital that the bacterium inside-hospital infection such as MRSA uses.
Claims (12)
1. the multifunctional material with photo-catalysis function contains base material;
Have photo-catalysis function and the photocatalyst layer that is arranged on the described substrate surface, described photocatalyst layer contains at least one top layer that is exposed to the outside, described top layer is made up of tiny photocatalyst granular, described photocatalyst granular combines, between form the gap with predetermined porosity;
Be filled among the described gap less than the particle in described gap;
And the described particle that is filled among the gap that forms between the described photocatalyst granular has photocatalytic activity.
2. method for preparing the multifunctional material with photo-catalysis function, this material have the photocatalyst granular that forms the gap between photocatalyst granular and with particle diameter particles filled less than these gaps, described method comprises the following steps:
On the surface of base material, form a photocatalysis layer,
Metal alkoxide or organic metal salt are coated on the surface of described photocatalysis layer thereafter and
Dry then and heat coated metal alkoxide or organic metal salt, use the particles filled described gap that photocatalyst granular between form littler than described gap.
3. the method for preparing multifunctional material of claim 2, it further comprises the following steps:
On this dry material, apply the coated solution of the aqueous solution of at least a metal ion among Cu, Ag, Zn, Fe, Co, Ni, Pd and the Pt and photo-reduction to separate out and the fixing metal particle.
4. the method for claim 2, wherein said photocatalyst granular combines.
5. method for preparing multifunctional material with photo-catalysis function, this material has between photocatalyst granular the photocatalyst granular that forms the gap and with particle diameter particles filled less than these gaps, described photocatalyst granular is combined together, and described method comprises the following steps:
Photocatalyst granular and the described more short grained mixture form with colloidal sol, precursor or suspended substance is coated on the thermoplastic matrix, form photocatalyst layer thus, this thermoplastic matrix of its after-tack, to imbed the photocatalyst layer underclad portion in the thermoplastic matrix and to solidify this thermoplastic matrix then.
6. the method for claim 5, it further comprises the following steps:
Before being coated in photocatalyst granular on the thermoplastic matrix, be dispersed among the solution with dispersant with photocatalyst granular with than colloidal sol, precursor or the suspended substance of granule, this dispersant only is grouped into by a kind of one-tenth, and it is vaporized under the temperature of the heat treatment temperature that is lower than softening described thermoplastic matrix.
7. the method for claim 5, it further comprises the following steps:
Prepare TiO 2 sol according to hydro-thermal method or sulfuric acid process, form photocatalyst granular, tiny metallic particles is fixed on the surface of TiO 2 sol particle, then dispersant or surface conditioning agent are added to TiO 2 sol.
8. the method for claim 7, surface conditioning agent wherein is a surfactant.
9. the method for claim 5, it further comprises the following steps:
Photocatalyst layer is contacted with saline solns, with and be filled in that the metal ion of particle forms insoluble, colourless or white salt among the gap between the photocatalyst granular, then with containing this solution of ultraviolet light radiation.
10. the method for claim 9, wherein said photocatalyst granular is by TiO
2Make, the metallic particles that is filled among the gap between the photocatalyst granular is made by Ag, and described saline solns contains halid aqueous solution, and described salt and metal ion form insoluble, colourless or white salt.
11. the method for claim 10, halide wherein are KI, KCl or FeCl
3
12. the method for claim 5, it further comprises the following steps:
With the solution that aqueous solution is coated on the photocatalyst layer that is embedded in and photo-reduction is coated of at least a metal ion among Ni, Pd and the Pt to separate out and the fixing metal particle.
Applications Claiming Priority (35)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5310165A JPH07155598A (en) | 1993-12-10 | 1993-12-10 | Photocatalyst coating film and its formation |
| JP310165/1993 | 1993-12-10 | ||
| JP310165/93 | 1993-12-10 | ||
| JP313061/1993 | 1993-12-14 | ||
| JP313062/1993 | 1993-12-14 | ||
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| JP5348073A JPH07191011A (en) | 1993-12-24 | 1993-12-24 | Method and film for measuring activity of thin photocatalyst film |
| JP348073/93 | 1993-12-24 | ||
| JP348073/1993 | 1993-12-24 | ||
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| JP143473/1994 | 1994-06-24 | ||
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| JP254242/94 | 1994-09-22 | ||
| JP254242/1994 | 1994-09-22 | ||
| JP25424294A JP3309591B2 (en) | 1993-12-28 | 1994-09-22 | Multifunctional material with photocatalytic function |
| JP271912/94 | 1994-09-29 | ||
| JP271912/1994 | 1994-09-29 | ||
| JP27191294 | 1994-09-29 | ||
| JP274165/94 | 1994-09-30 | ||
| JP6274165A JPH08103488A (en) | 1994-09-30 | 1994-09-30 | Multifunctional material having photocatalyst function |
| JP274165/1994 | 1994-09-30 | ||
| JP28238294A JP3225761B2 (en) | 1994-10-11 | 1994-10-11 | Multifunctional material with photocatalytic function |
| JP282382/94 | 1994-10-11 | ||
| JP282382/1994 | 1994-10-11 | ||
| JP297760/1994 | 1994-10-24 | ||
| JP29776094A JP3246235B2 (en) | 1994-10-24 | 1994-10-24 | Multifunctional material having photocatalytic function and method for producing the same |
| JP307173/1994 | 1994-11-04 | ||
| JP6271499A JPH08131524A (en) | 1994-11-04 | 1994-11-04 | Multi-functional material having photocatalytic function and manufacture thereof |
| JP271499/1994 | 1994-11-04 | ||
| JP311398/1994 | 1994-11-09 | ||
| JP313967/1994 | 1994-11-11 | ||
| JP310896/1994 | 1994-12-14 |
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| CN94191730A Division CN1102445C (en) | 1993-12-10 | 1994-12-09 | Multi-functional material having photo-catalytic function and production method therefor |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB2005100729417A Division CN100378038C (en) | 1993-12-10 | 1994-12-09 | Multi-functional material with photocatalytic functions and method of manufacturing same |
| CN200610101461.3A Division CN1899696A (en) | 1993-12-10 | 1994-12-09 | Multi-functional material with photocatalytic functions and method of manufacturing same |
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| CN1443605A CN1443605A (en) | 2003-09-24 |
| CN1289195C true CN1289195C (en) | 2006-12-13 |
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| CN02122422.6A Expired - Lifetime CN1289195C (en) | 1993-12-10 | 1994-12-09 | Multifunctional material with optical catalytic function and its mfg. method |
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Correction item: Priority Correct: Increase1994-10-24 JP 297760/94|1994-11-4 JP 271499/94|1994-11-4 JP 307173/94|1994-11-9 JP 311398/94|1994-11-11 JP 313967/94|1994-12-14 JP 310896/94 False: Lack of 6 entries Number: 50 Page: 949 Volume: 22 |
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Correction item: Priority Correct: Increase1994-10-24 JP 297760/94|1994-11-4 JP 271499/94|1994-11-4 JP 307173/94|1994-11-9 JP 311398/94|1994-11-11 JP 313967/94|1994-12-14 JP 310896/94 False: Lack of 6 entries Number: 50 Page: The title page Volume: 22 |
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Free format text: CORRECT: PRIORITY; FROM: LACK OF 6 TO: ADD ^1994-10-24 JP 297760/94^1994-11-4 JP 271499/94^1994-11-4 JP 307173/94^1994-11-9 JP 311398/94^1994-11-11 JP 313967/94^1994-12-14 JP 310896/94 |
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Free format text: CORRECT: PRIORITY; FROM: LACK OF 6 TO: ADD ^1994-10-24 JP 297760/94^1994-11-4 JP 271499/94^1994-11-4 JP 307173/94^1994-11-9 JP 311398/94^1994-11-11 JP 313967/94^1994-12-14 JP 310896/94 |
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Owner name: TOTO CO., LTD. Free format text: FORMER NAME OR ADDRESS: TOTO LTD. |
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Address after: Kitakyushu, Fukuoka, Japan Patentee after: TOTO Ltd. Address before: Fukuoka Prefecture Patentee before: Toto Ltd. |
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Application publication date: 20030924 Assignee: Love and Tao (Guangdong) Ceramics Co., Ltd. Assignor: TOTO Ltd. Contract record no.: 2012990000754 Denomination of invention: Multi-functional material with photocatalytic functions and method of manufacturing same Granted publication date: 20061213 License type: Common License Record date: 20121015 |
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