JP4526153B2 - Photocatalyst carrying structure, process for producing the same, and composition for forming an intermediate layer - Google Patents
Photocatalyst carrying structure, process for producing the same, and composition for forming an intermediate layer Download PDFInfo
- Publication number
- JP4526153B2 JP4526153B2 JP2000108916A JP2000108916A JP4526153B2 JP 4526153 B2 JP4526153 B2 JP 4526153B2 JP 2000108916 A JP2000108916 A JP 2000108916A JP 2000108916 A JP2000108916 A JP 2000108916A JP 4526153 B2 JP4526153 B2 JP 4526153B2
- Authority
- JP
- Japan
- Prior art keywords
- photocatalyst
- silicon
- component
- resin
- sol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 239000011941 photocatalyst Substances 0.000 title claims description 120
- 239000000203 mixture Substances 0.000 title claims description 35
- 238000000034 method Methods 0.000 title claims description 30
- 230000008569 process Effects 0.000 title description 3
- 239000010410 layer Substances 0.000 claims description 140
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 51
- 229910052710 silicon Inorganic materials 0.000 claims description 51
- 239000010703 silicon Substances 0.000 claims description 51
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 50
- 229920005989 resin Polymers 0.000 claims description 47
- 239000011347 resin Substances 0.000 claims description 47
- 239000007787 solid Substances 0.000 claims description 35
- 239000011254 layer-forming composition Substances 0.000 claims description 34
- 229910044991 metal oxide Inorganic materials 0.000 claims description 29
- 150000004706 metal oxides Chemical class 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 25
- 150000004692 metal hydroxides Chemical class 0.000 claims description 25
- 150000003377 silicon compounds Chemical class 0.000 claims description 25
- 239000002245 particle Substances 0.000 claims description 23
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 22
- 238000004519 manufacturing process Methods 0.000 claims description 22
- 230000007062 hydrolysis Effects 0.000 claims description 19
- 238000006460 hydrolysis reaction Methods 0.000 claims description 19
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 18
- 238000006116 polymerization reaction Methods 0.000 claims description 17
- 239000000377 silicon dioxide Substances 0.000 claims description 17
- 235000012239 silicon dioxide Nutrition 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 239000004593 Epoxy Substances 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 239000000835 fiber Substances 0.000 claims description 10
- 239000011521 glass Substances 0.000 claims description 10
- 239000012790 adhesive layer Substances 0.000 claims description 9
- 239000011342 resin composition Substances 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 229910052758 niobium Inorganic materials 0.000 claims description 8
- 239000010955 niobium Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 7
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 230000009477 glass transition Effects 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 150000002736 metal compounds Chemical class 0.000 claims description 5
- 125000005372 silanol group Chemical group 0.000 claims description 5
- 229920002050 silicone resin Polymers 0.000 claims description 5
- 229910052715 tantalum Inorganic materials 0.000 claims description 5
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- 239000000919 ceramic Substances 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- 239000002023 wood Substances 0.000 claims description 4
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- 229920003002 synthetic resin Polymers 0.000 claims description 3
- 239000000057 synthetic resin Substances 0.000 claims description 3
- -1 polysiloxane Polymers 0.000 description 39
- 239000011248 coating agent Substances 0.000 description 37
- 238000000576 coating method Methods 0.000 description 36
- 230000001699 photocatalysis Effects 0.000 description 22
- 239000000499 gel Substances 0.000 description 21
- 239000000047 product Substances 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- 239000003822 epoxy resin Substances 0.000 description 11
- 229920000647 polyepoxide Polymers 0.000 description 11
- 239000000123 paper Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 239000008119 colloidal silica Substances 0.000 description 9
- 235000019441 ethanol Nutrition 0.000 description 9
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 8
- 239000004925 Acrylic resin Substances 0.000 description 8
- 229920000178 Acrylic resin Polymers 0.000 description 8
- 125000003700 epoxy group Chemical group 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- 238000009835 boiling Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000002430 hydrocarbons Chemical group 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- 239000004793 Polystyrene Substances 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000004568 cement Substances 0.000 description 5
- 239000011247 coating layer Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000012046 mixed solvent Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 229920002223 polystyrene Polymers 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 125000001309 chloro group Chemical group Cl* 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000011135 tin Substances 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- 229920002799 BoPET Polymers 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 101100258086 Postia placenta (strain ATCC 44394 / Madison 698-R) STS-01 gene Proteins 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- MSCPCXBFDHGTCB-UHFFFAOYSA-N butan-1-ol;ethanol;ethyl acetate Chemical compound CCO.CCCCO.CCOC(C)=O MSCPCXBFDHGTCB-UHFFFAOYSA-N 0.000 description 3
- 238000003851 corona treatment Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 239000010440 gypsum Substances 0.000 description 3
- 229910052602 gypsum Inorganic materials 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 2
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
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- 239000004640 Melamine resin Substances 0.000 description 2
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- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
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- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
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- 125000003277 amino group Chemical group 0.000 description 2
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- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
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- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
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Images
Landscapes
- Laminated Bodies (AREA)
- Surface Treatment Of Glass (AREA)
- Catalysts (AREA)
- Paints Or Removers (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、担体上に中間層を介して光触媒層を形成してなる光触媒担持構造体の製造方法及び中間層形成用樹脂組成物に関する。
【０００２】
【従来の技術】
従来から、プラスチックス板やガラス板、セラミックス板等の担体上に、二酸化チタン等の光触媒活性を有する物質が担持された光触媒層が形成されてなる光触媒担持構造体が知られている。
【０００３】
しかしながら、有機物を主体とする担体を用いる光触媒担持構造体は、光触媒を担体上に担持すると、その触媒作用により該有機物（担体）が分解されたり、劣化したりすることが報告されており、その耐久性に問題があった（例えば、大谷文章、高分子加工 ４２巻、５号、ｐ１８（１９９３）、清野学著、”酸化チタン”技法堂、ｐ１６５等参照）。
【０００４】
そこで、かかる問題を解決するために、担体上に中間層を設け、該中間層上に光触媒層を形成してなる光触媒構造体が提案されている。
【０００５】
例えば、ＷＯ９７／００１３４号公報には、光触媒層と担体との間に接着層を設けた構造を有する光触媒担持構造体において、接着層が、▲１▼シリコン含有量２〜６０重量％のシリコン変性樹脂、▲２▼コロイダルシリカを５〜４０重量含有する樹脂、又は▲３▼式（１）ＳｉＣｌn1(ＯＨ)ｎ2Ｒ1ｎ3(ＯＲ2)n4〔式中、Ｒ1は、（アミノ基、カルボキシル基又は塩素原子で置換されていてもよい）炭素数１〜８のアルキル基、Ｒ2は、炭素数１〜８のアルキル基もしくはアルコキシ基で置換された炭素数１〜８のアルキル基を表し、ｎ1は０、１又は２を表し、ｎ4は２，３又は４を表し、ｎ1＋ｎ2＋ｎ3＋ｎ4＝４である。〕で表される化合物の重縮合反応生成物であるポリシロキサンを３〜６０重量％含有する樹脂であり、光触媒層が、金属酸化物ゲルもしくは金属水酸化物ゲルを２５〜９５重量％含有する光触媒粒子複合体である光触媒担持構造体、接着層形成用光触媒コーティング剤、及び光触媒層形成用光触媒塗布液が記載されている。
【０００６】
この技術は、担体と光触媒層の間に接着層を設けた光触媒担持構造体において、担体と光触媒層との間に特定の接着層を設けることにより、下地の担体を光触媒による劣化から保護する作用と、光触媒層を担体に強固に接着させる作用を有する。
【０００７】
また、ＷＯ９８／２５７１１号公報には、基材表面に、下記(Ａ’)、（Ｂ’）、(Ｃ’)及び（Ｄ’）成分を含むアクリル変性シリコン樹脂コーティング材の硬化被膜からなる第１塗装層と、この第１塗装層の表面に形成された下記（Ｅ’）及び(Ｆ’)成分を含む機能性コーティング材の硬化被膜からなる第２塗装層とを備えた機能性塗装品、その製造方法及び用途が記載されている。
【０００８】
(Ａ')成分：
一般式Ｒ1'mＳｉＸ4-m（式中、Ｒ1’は、同一であっても異なってもよい置換もしくは非置換の炭素数１〜８の１価炭化水素基を示し、ｍは０〜３の整数、Ｘは加水分解性基をそれぞれ示す）で表される加水分解性オルガノシランを、有機溶媒、水又はそれらの混合溶媒に分散されたコロイダルシリカ中で、前記加水分解性基（Ｘ）１モル当量当たり水０．００１〜０．５モルを使用する条件で部分加水分解してなる、オルガノシランのシリカ分散オリゴマー溶液；
【０００９】
(Ｂ’)成分：
平均組成式Ｒ2’nＳｉ(ＯＨ)bＯ(4-a-b)/2（式中、Ｒ2’は同一であっても異なっていてもよい置換もしくは非置換の炭素数１〜８の炭化水素基を示し、ａ及びｂはそれぞれ２≦ａ≦２、０．００１≦ｂ≦３、ａ＋ｂ＜４の関係を満たす。）で表され、分子中にシラノール基を含有する、重量平均分子量（ポリスチレン換算）７００〜２０，０００であるポリオルガノシロキサン；
【００１０】
（Ｃ’）成分：
硬化触媒；
（Ｄ’）成分；
一般式ＣＨ2＝ＣＲ3’（ＣＯＯＲ4 ’）（式中、Ｒ3’は水素原子及び／又はメチル基であって；Ｒ4’が置換もしくは非置換の炭素数１〜９の１価炭化水素基である第１の（メタ）アクリル酸エステル、Ｒ4’がエポキシ基、グリシリル基及びこれらのうちの少なくとも一方を含む炭化水素基からなる群から選ばれる少なくとも１種の基である第２の（メタ）アクリル酸エステル、及びＲ4’がアルコキサルキル基及び／又はハロゲン化シリル基を含む炭化水素基である第３の（メタ）アクリル酸エステルとの共重合体であり、重量平均分子量（ポリスチレン換算）１０００〜５００００以下であるアクリル樹脂；
【００１１】
（Ｅ’)成分：
一般式Ｓｉ（ＯＲ5’）4で表される珪素化合物及び／又はコロイダルシリカ５〜３０，０００重量部、一般式Ｒ6’2Ｓｉ（ＯＲ5’）2で表される珪素化合物１００重量部、及び一般式Ｒ6’2Ｓｉ（ＯＲ5’）2で表される珪素化合物０〜６０重量部（式中、Ｒ5’、Ｒ6’は１価の炭化水素基を示す）との加水分解重縮合物からなり、その重量平均分子量がポリスチレン換算で８００以上になるように調整されているオルガノシロキサン；
（Ｆ’）成分：
光触媒；
【００１２】
この技術は、下地基材に対する塗膜の密着性に優れ、光触媒作用による基材及び塗膜の劣化が起こりにくく、また、塗膜表面の平滑性も高いため汚れ難く、かつ、高い光触媒作用を持つ機能性塗装品を提供するものである。
【００１３】
【発明が解決しようとする課題】
これらの光触媒担持構造体（機能性塗装品）は、いずれも担体と光触媒層との間に密着性を向上せしめる接着層を有し、担体を光触媒による分解から保護し、かつ、接着層（第１塗装層）自体も光触媒により光分解され難いものである。
【００１４】
しかしながら、（１）例えば、担体として透明ガラスや透明プラスチックス成形体を用いる場合等のように、特に透明性が要求される場合に、光触媒構造体（機能性塗装品）の表面が特有の色彩（金色等）を帯びて見える場合があること（いわゆる干渉色の問題）、（２）十分な光触媒活性を得るためには、ある程度、接着層（第１塗装層）及び光触媒層を厚く形成する必要があるが、表面にヒビが入り使用できなくなる場合があること、及び（３）室温での接着相の硬化速度が遅く、現場塗工できない、もしくはフィルムやシートなどの連続塗工可能な担体では、塗工速度を非常に低速にしないと硬化せず、ブロッキング現象を引き起こす問題があった。
【００１５】
そこで本発明は、担体と光触媒層との間に中間層を設けた光触媒担持構造体において、▲１▼担体と光触媒層との密着性に優れ、▲２▼担体及び中間層が光触媒により分解され難く、▲３▼いわゆる干渉色がなく、▲４▼表面にひび割れを起こさず、かつ、▲５▼常温ですばやく硬化しうる光触媒担持構造体の製造方法及び中間層形成用組成物を提供することを目的とする。
【００１６】
【課題を解決するための手段】
本発明者らは、上記課題を解決すべく鋭意検討した結果、担体と光触媒層との間に中間層を有する構造の光触媒担持構造体において、該中間層を特定の組成物から形成することにより、上記課題を解決することができることを見出し、本発明を完成するに至った。
【００１７】
即ち本発明は、第１に、担体表面に、少なくとも下記(Ａ)，(Ｂ)，(Ｃ)及び(Ｄ)成分を含有する中間層形成用組成物を塗布し、１０〜３５℃で、０．５〜７２時間乾燥させることによって中間層を形成する工程と、
前記中間層表面に、少なくとも下記（Ｅ），(Ｆ)及び（Ｇ）成分を含有する光触媒層形成用組成物を塗布し、１０〜４０℃で乾燥させることにより光触媒層を形成する工程とを有する光触媒担持構造体の製造方法を提供する。
【００１８】
(Ａ)成分：
アクリルシリコン樹脂又はエポキシシリコン樹脂を固形分として０．５〜２０重量％；
(Ｂ)成分：
金属酸化物ゾル及び／又は金属水酸化物のゾルを固形分として０．２５〜４重量％；
(Ｃ)成分：
テトラアルコキシシランの１種又は２種以上の部分加水分解生成物であって、その平均重合度３〜１０であり、テトラアルコキシシランモノマーの含有量が５重量％以下であるシリコン化合物を二酸化ケイ素に換算した固形分として０．２５〜２０重量％；
(Ｄ)成分；
二酸化ケイ素に換算した固形前記シリコン化合物の０．５〜３倍モル当量の水；
(Ｅ)成分：
金属酸化物ゾル及び／又は金属水酸化物のゾル；
(Ｆ)成分：
光触媒の粒子及び／又はゾル；
(Ｇ)成分：
シリコン化合物；
【００１９】
また、本発明は第２に、少なくとも前記(Ａ)，（Ｂ），（Ｃ）及び(Ｄ)成分を含む中間層形成用組成物を提供する。
【００２０】
前記第１及び第２の発明においては、前記中間層形成用組成物は、常温でシラノール基に配位することができる金属化合物をさらに含有するのが好ましい。
【００２１】
また前(Ａ)成分であるアクリルシリコン樹脂又はエポキシシリコン樹脂は、シリコン酸化物換算で５〜６０重量％のシリコンを含有する樹脂であるのが好ましく、そのガラス転移温度が２０〜５０℃の範囲の樹脂であるのがより好ましい。
【００２２】
前記（Ｂ）成分である金属酸化物ゾル及び／又は金属水酸化物ゾルは、珪素、アルミニウム、チタニウム、ジルコニウム、マグネシウム、ニオビウム、タンタラム、タングステン及びスズの中から選ばれた１種もしくは２種以上の金属の酸化物ゾル及び／又は水酸化物ゾルであるのが好ましく、その平均粒子径は４〜５０nmのゾルであるのがより好ましい。
【００２３】
前記（Ｃ）成分であるシリコン化合物は、アルコキシシランモノマーの含有量が１重量％以下の平均重合度が３〜１０であるテトラメトキシシラン及び／又はテトラエトキシシランの部分加水分解生成物であるのが好ましい。
【００２４】
前記(Ｅ)成分である金属酸化物ゾル及び／又は金属水酸化物ゾルは、その平均粒子径は４〜５０ｎｍのゾルであるのが好ましい。
【００２５】
前記（Ｆ）成分である光触媒の粒子及び／又はゾルの平均粒子径は、４〜５０nmであるのが好ましい。
【００２６】
また、前記（Ｇ）成分であるシリコン化合物は、テトラアルコキシシランモノマーの含有量が５重量％以下であり、平均重合度が３〜１０のテトラアルコキシシランの部分加水分解生成物であるのが好ましい。
【００２７】
第１の発明の光触媒担持構造体の製造方法によれば、前記第１の発明の光触媒担持構造体を簡便、かつ歩留りよく製造することができる。
【００２８】
特に、本発明の製造方法によれば、中間層を室温で硬化・形成することができるので、例えば、シート状の担体上に中間層を形成した後、該中間層付きシートを巻き取る工程において、該シートの中間層表面と該シートの裏面とが熱融着を生じ、いわゆるブロッキングと呼ばれる現象が生じることがなくなる。
【００２９】
また、担体上に中間層形成用組成物を塗工し、室温で硬化・形成するものであるので、例えば建築物壁面上に中間層形成用組成物を塗工・形成し、さらにその上に、光触媒層形成用組成物を塗工・形成することができ（いわゆる「現場塗工」と称される。）、製造コストの面で有利である。
【００３０】
本発明の製造方法により製造される光触媒担持構造体は、▲１▼担体と光触媒層との密着性に優れ、▲２▼担体及び中間層が光触媒により分解され難く、▲３▼いわゆる干渉色がなく、▲４▼表面にひび割れ等がなく、かつ、▲５▼常温で硬化する光触媒担持構造体となっている。
【００３１】
第２の発明の中間層形成用組成物は、担体上に塗工され、室温で硬化して中間層を形成する。この中間層は担体と光触媒層とを強固に密着せしめ、いわゆる層間剥離を生じることがなく、その上に光触媒層を形成しても、光干渉により光触媒層表面が金色や玉虫色に見えたりすることがない。
【００３２】
また、本発明の中間層形成用組成物は安定であり、長期間保存しても、不溶物が析出したり、粘度が増加することがない。
【００３３】
【発明の実施の形態】
次に本発明の発明の実施の形態を説明する。
本発明の光触媒構造体の製造方法により製造される光触媒構造体の断面図を図１に示す。
【００３４】
本発明の光触媒担持構造体は、担体１表面上に中間層２を介して光触媒層３が形成されてなる。
中間層２は、下記の(Ａ)，（Ｂ），（Ｃ）及び（Ｄ）成分を有する中間層形成用組成物から形成される。
【００３５】
(Ａ)成分：
アクリルシリコン樹脂又はエポキシシリコン樹脂を固形分として０．５〜２０重量％；
(Ｂ)成分：
金属酸化物ゾル及び／又は金属水酸化物のゾルを固形分として０．２５〜４重量％；
(Ｃ)成分：
テトラアルコキシシランの１種又は２種以上の部分加水分解生成物であって、その平均重合度３〜１０であり、テトラアルコキシシランモノマーの含有量が５重量％以下であるシリコン化合物を二酸化ケイ素に換算した固形分として０．２５〜２０重量％
(Ｄ)成分；
二酸化ケイ素に換算した固形前記シリコン化合物の０．５〜３倍モル当量の水
【００３６】
前記中間層形成用組成物の(Ａ)成分は、アクリルシリコン樹脂及び／又はエポキシシリコン樹脂である。これらの樹脂の中間層形成用組成物中の含有量は固形分として０．５〜２０重量％であるのが好ましい。
含有量が０．５重量％未満の場合には、塗膜の担体との密着性が低下し、一方、２０重量％を越えると、塗布液の安定性が悪くなる。
【００３７】
前記アクリルシリコン樹脂はシリコン変性アクリル樹脂であり、エポキシシリコン樹脂とはシリコン変性エポキシ樹脂をいう。アクリル樹脂あるいはエポキシ樹脂へのシリコンの導入（変性）方法としては、エステル交換反応による方法、シリコンマクロマーや反応性シリコンモノマーを用いたグラフト反応による方法、ヒドロシリル化反応による方法、ブロック共重合を用いた方法などがある。本発明ではどのような方法で作られた物でも用いることができる。
【００３８】
アクリル樹脂のモノマーとしては、例えば、アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸ブチル、アクリル酸―２−エチルヘキシル、アクリル酸メトキシエチル、アクリル酸ブトキシエチル、アクリル酸フェニル等のアクリル酸エステル類、
メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、、エタクリル酸メトキシメチル、メタクリルサンエトキシメチル、メタクリル酸フェニル、メタクリル酸ラウリル等のメタクリル酸エステル類、
アクリル酸−２−(Ｎ，Ｎ−ジメチルアミノ)エチル、メタクリル酸−２−（Ｎ，Ｎ−ジメチルアミノ）エチル、メタクリル酸−２−(Ｎ，Ｎ−ジベンジルアミノ)エチル、アクリル酸−２−（Ｎ，Ｎ−ジエチルアミノ）プロピル等のアクリル酸、又はメタクリル酸の置換アミノアルコールエステル類、
アクリルアミド、メタクリルアミド等の不飽和カルボン酸アミド類、
エチレングリコールジアクリレート、プロピレングリコールアイアクリレート、ネオペンチルグリコールジアクリレート、１，６−ヘキサンジオールジアクリレート、ジエチレングリコールジアクリレート、ジプロピレングリコールジアクリレート、エチレングリコールアクリレート、ジエチレングリコールジメタクリレート等のグリコールアクリレート及びグリコールメタクリレート類等を用いることができる。
【００３９】
また、エポキシ樹脂は、エポキシ基を有する熱硬化性樹脂である。通常、エポキシ基を有するプレポリマーを得たのち、硬化剤を添加して架橋反応により３次元網目構造の高分子を得る。
【００４０】
かかるプレポリマーとして、例えば、エピクロルヒドリン等のエポキシ基を有する化合物と、ビスフェノールＡ、ビスフェノールF、テトラブロモビスフェノールA、テトラフェニロールエタン、フェノールノボラック、o−クレゾールノボラックなどのフェノール誘導体から得られるフェノール系グリシジルエーテル型エポキシ樹脂、
【００４１】
エピクロルヒドリン等のエポキシ基を有する化合物と、ポリプロピレングリコール、水素化ビスフェノールＡ等のポリオール類から得られるアルコール系グリシジルエーテル型エポキシ樹脂、
エピクロルヒドリン等のエポキシ基を有する化合物と、ヘキサヒドロ無水フタル酸やダイマー酸等のカルボン酸から得られるグリシジルエステル型エポキシ樹脂、
エピクロルヒドリン等のエポキシ基を有する化合物と、ジアミノジフェニルメタン、イソシアヌル酸、ヒダントイン等の化合物から得られるグリシジルアミン型エポキシ樹脂、
エポキシ基を有する化合物と、ｐ−アミノフェノールやｐ−オキシ安息香酸等から得られる混合型エポキシ樹脂等が挙げられる。
【００４２】
これらアクリルシリコン樹脂あるいはエポキシシリコン樹脂のシリコンの含有量は、二酸化ケイ素換算で０．５〜６０重量％、好ましくは２〜６０重量％、より好ましくは５〜６０重量％である。シリコンの含有量が酸化物換算で０．５重量％未満の場合には、中間層と担体との密着性に乏しくなり、また、中間層が光触媒によって劣化しやすくなり、光触媒層が剥離しやすくなる。一方、６０重量％を越えると、中間層と担体との密着性に乏しくなる。
【００４３】
前記アクリルシリコン樹脂、エポキシシリコン樹脂のガラス転移温度は２０〜５０℃の範囲であるのがより好ましい。ガラス転移温度が２０℃未満の場合には、塗布液の安定性が悪くなり、一方、５０℃を越えると、塗膜の硬化に５０℃以上の温度が必要となる。
【００４４】
なお、シリコンが導入される樹脂としては、上述したアクリル樹脂やシリコン樹脂が成膜性、膜強度及び担体との密着性の点で最も優れているが、アルキッド樹脂、ウレタン樹脂、ポリエステル樹脂等の他の合成樹脂を用いることもできる。
【００４５】
前記中間層形成用組成物に含まれる(Ｂ)成分は金属酸化物ゾル及び／又は金属水酸化物のゾルである。金属酸化物ゾルもしくは金属水酸化物ゾルは、光触媒粉末を固着し、中間層と強固に接着させる効果を有する。金属酸化物ゾル又は金属水酸化物ゾルの中間層形成用組成物中の含有量は、固形分として０．２５〜４重量％が好ましい。含有量が０．２５重量％未満の場合には、膜の硬化が遅くなり、一方、４重量％を越えると、塗布液の安定性が悪くなる。
【００４６】
前記金属酸化物及び金属水酸化物の金属成分としては、珪素、アルミニウム、チタニウム、ジルコニウム、マギネシウム、ニオビウム、タンタラム、タングステン、錫等を例示することができる。また、金属成分として、珪素、アルミニウム、チタニウム、ジルコニウム、ニオビウムの中から選ばれた２種以上の金属を含有する酸化物もしくは水酸化物ゲルを使用することもできる。
【００４７】
本発明の中間層形成用組成物の(Ｃ)成分は、テトラアルコキシシランの１種又は２種以上の部分加水分解生成物であって、その平均重合度が３から１０であり、テトラアルコキシシランモノマーの含有量が５重量％以下であるシリコン化合物である。前記(Ｃ)成分の中間層形成用組成物中の含有量は、固形分として０．２５〜２０重量％であるのが好ましい。０．２５重量％未満の場合には、膜硬度が低下し、一方、２０重量％を越えると、担体との密着性が低下する。
【００４８】
前記テトラアルコキシランとしては、例えば、テトラメトキシシラン、テトラエトキシシラン、テトラプロポキシシラン、テトライソプロポキシシラン、テトラブトキシシラン等を用いることができる。これらのうち、本発明においては入手容易性、取扱性等の観点からテトラメトキシシラン及びテトラエトキシシランの使用が特に好ましい。
【００４９】
テトラアルコキシシランの部分加水分解生成物は、例えば、これらテトラアルコキシシランの所定量を水、メタノール、エタノール、酢酸エチル等の水もしくは有機溶媒に溶解し、そのまま加熱あるいは所定量の酸もしくは塩基を添加して部分的に加水分解させることにより調製することができる。通常、重合度は３〜１０が好ましく、また、未反応のテトラアルコキシシランモノマーの残存量は、好ましくは（Ｃ）成分全体の５重量％以下、より好ましくは１重量％以下である。
【００５０】
本発明の中間層形成用組成物は、（Ｄ）成分として、所定量の水を含有する。水の含有量は、前記（Ｃ）成分のシリコン化合物を二酸化ケイ素に換算したときの０．５〜３倍モル当量であるのが好ましい。水の含有量が前記（Ｃ）成分のシリコン化合物を二酸化ケイ素に換算したときの０．５倍モル未満の場合には、室温での膜の硬化速度が非常に低下し、一方、水の含有量が３倍モルを越える場合には、中間層形成用組成物の保存安定性が悪くなる。
【００５１】
また、前記中間層形成用組成物中には、塗布液の安定性の向上および硬化速度を向上させる目的で、常温でシラノール基に配位することができる金蔵化合物を含有せしめることができる。
【００５２】
かかる金属化合物としては、例えば、アルミニウムトリスアセチルアセトネート等の有機アルミニウム化合物、ホウ酸トリノルマルブチレートなどの有機ホウ素化合物等を挙げることができる。これらの化合物の中間層形成用組成物中の含有量は、前記テトラアルコキシシランオリゴマーの二酸化ケイ素換算重量比で、０．１重量％〜５重量％程度が好ましい。
【００５３】
また、前記中間層形成用組成物中には、中間層の光触媒作用による劣化を抑制する目的で、光安定剤及び／又は紫外線吸収剤等を混合することにより、耐久性を向上させることができる。使用できる光安定剤としては、ヒンダードアミン系が好ましいが、その他の物でも使用可能である。
【００５４】
紫外線吸収剤としてはトリアゾール系紫外線吸収剤等が使用できる。これらの添加量は、組成物全体に対して０．００５重量％〜１０重量％、好ましくは０．０１重量％〜５重量％である。
【００５５】
中間層を形成する方法としては、特に制限はないが、たとえば、前記中間層形成用組成物の有機溶媒溶液、有機溶媒縣濁液、水分散エマルジョン等を、担体表面に印刷法、シート形成法、スプレー吹きつけ法、ディップコーティング法、スピンコーティング法等でコートし、乾燥させる方法を用いることができる。
【００５６】
有機溶媒としては、比較的低沸点のものが好ましく、例えば、メタノール、エタノール、イソプロパノール、ブタノール等のアルコール類、酢酸エチル、酢酸ブチル等の酢酸エステル類、アセトン、メチルエチルケトン、メチルイソブチルケトン、アセチルアセトン、シクロヘキサノン等のケトン類、ペンタン、ヘキサン、ヘプタン等の脂肪族炭化水素、シクロヘキサン、メチルシクロヘキサン等の環状脂肪族炭化水素、ベンゼン、トルエン、キシレン等の芳香族炭化水素等、及びこれらの２種以上もしくはこれらと水との混合溶媒を用いることができる。
【００５７】
乾燥温度は溶媒や樹脂の種類によっても異なるが、１５０℃以下の温度が好ましい。特に本発明の中間層形成用組成物は、１０〜３５℃で、０．５〜７２時間乾燥することにより、硬化させることができるので、いわゆる現場塗工が可能となる。また、シート状の担体表面に中間層を形成し該シートを巻き取る工程において、いわゆるブロッキング（中間層表面と、シート裏面とが熱等により融着する現象）が生じることがなくなり生産性が向上するため好ましい。
【００５８】
また前記中間層の厚さは、１００nm以上であれば光触媒層を強固に接着し、耐久性の高い光触媒構造体を得ることができる。なお、グラビア印刷法等の短時間で中間層を乾燥硬化させることが必要な場合には、シリコン系硬化剤などの硬化促進剤を、中間層形成用組成物の固形分に対し、必要な硬化速度に応じて０．１〜１０重量％添加することも好ましい。
【００５９】
前記光触媒層形成用組成物は、少なくとも前記(Ｅ)成分及び(Ｆ)成分を含有してなる。前記(Ｅ)成分である金属酸化物ゾル及び金属水酸化物ゾルは、光触媒粉末を固着し、中間層と強固に接着させる効果を有する。また、この金属酸化物ゲル及び金属水酸化物ゲルは多孔質であることから、光触媒活性を高める効果もある。(Ｅ)成分の光触媒層形成用組成物中の含有量は、固形分として２５〜９５重量％が好ましい。２５重量％未満では、中間層との密着性に乏しくなり、９５重量％を越えると光触媒活性が不十分となる。
【００６０】
また、金属酸化物ゲル及び金属水酸化物ゲルの比表面積は、好ましくは１５０℃で乾燥後５０ｍ2／ｇ以上、より好ましくは１００ｍ2／ｇ以上であると、接着性は強固となり、光触媒活性も向上し、また、沸騰水中に浸漬した後でも優れた接着性を有している。
【００６１】
金属成分としては、珪素、アルミニウム、チタニム、ジルコニウム、マグネシウム、ニオビウム、タンタラム、タングステン、スズ等の金属酸化物ゲルもしくは金属水酸化物ゲルを例示することができる。
【００６２】
また、金属成分として、珪素、アルミニウム、チタニウム、ジルコニウム、ニオビウムの中から選ばれた２種以上の金属を含有する酸化物もしくは水酸化物ゲルを使用することにより、沸騰水に浸漬した後の光触媒層の付着性を高めることが可能である。
【００６３】
耐沸騰水性に優れた金属成分の好ましい組み合わせとしては、珪素−アルミニウム、珪素−チタニウム、珪素−ジルコニウム、珪素−ニオビウム、アルミニウム−チタニウム、アルミニウム−ジルコニウム、アルミニウム−ニオビウム、アルミニウム−タンタラム、チタニウム−ジルコニウム、チタニウム−ニオビウム、チタニウム−タンタラム、珪素−アルミニウム−ジルコニウム、珪素−アルミニウム−チタニウム等を挙げることができる。さらに好ましくは、珪素−アルミニウム、珪素−チタニウム、珪素−ジルコニウム、珪素−チタニウム−アルミニウム、珪素−アルミニウム−ジルコニウム等を挙げることができる。
【００６４】
これら金属酸化物ゾル及び金属水酸化物ゾルの実際の使用に当たっては、ゲルを形成するためのゾルを混合し乾燥して得られるゲルでも、共沈法等の方法で作られる複合酸化物ゲルを使用することもできる。光触媒と複合化する場合には、ゲルとなる前のゾルの状態で均一混合するか、又はゾルを調製する前の原料の段階で混合するのが好ましい。
【００６５】
ゲルを調製する方法には、金属塩を加水分解する方法、中和分解する方法、イオン交換する方法、金属アルコキシドを加水分解する方法等があるが、ゲルの中に光触媒粉末が均一に分散された状態で得られるものであれば、いずれの方法も使用可能である。ただし、ゲル中に多量の不純物が存在すると、光触媒の接着性や触媒活性に悪影響を与えるので、不純物の少ないゲルを用いるのが好ましい。
【００６６】
また、光触媒層形成用組成物中にシリコン変性樹脂あるいはシランカップリング剤を該組成物に対して１０〜５０重量％加えることによっても、高い触媒活性を維持しつつ、沸騰水中へ１５分間浸漬した後でＪＩＳ Ｋ５４００に規定された碁盤目テープ法による付着性試験で評価点数が６点以上の優れた付着性（接着性）のものを得ることができる。
【００６７】
すなわち、光触媒層形成用組成物中に添加するシリコン変性樹脂あるいはシランカップリング剤は、沸騰水中での光触媒層の接着性を高める役割を果たしている。
【００６８】
かかるシリコン変性樹脂としては、通常市販されているシリコン−アクリル系樹脂やシリコン−エポキシ系の樹脂が使用可能であり、溶剤に溶解したものでも、エマルジョンとなって水中に分散しているものでもいずれも使用可能である。
【００６９】
またシランカップリング剤としては、例えば、一般式：ＲＳｉ（Ｙ）3や(Ｒ)2Ｓｉ（Ｙ）2（式中、Ｒは有機性官能基を、Ｙは塩素原子又はアルコキシ基を表す。）で表される化合物を使用することができる。
【００７０】
前記一般式において、Ｒとしては、メチル基、エチル基、ビニル基、γ−グリシドキシプロピル基、γ−メタクリロキシプロピル基、γ−（２−アミノエチル）アミノプロピル基、γ−クロロプロピル基、γ−メルカプトプロピル基、γ−アミノプロピル基、γ−アクリロキシプロピル基等を挙げることができる。また、Ｙとしては、塩素原子のほか、メトキシ基、エトキシ基、β−メトキシエトキシ基、β−エトキシエトキシ基等の炭素数１〜５のアルコキシ基等が挙げられる。
【００７１】
（Ｆ）成分である光触媒は粉末状、ゾル状、溶液状など、光触媒層の乾燥温度で乾燥した時に、中間層と固着して光触媒活性を示す物であればいずれも使用することができる。ゾル状の光触媒を使用する場合、粒子径が２０nm以下、好ましくは１０nm以下のものを使用すると、光触媒層透明性が向上し、直線透過率が高くなるため、透明性が要求されるガラス基板やプラスチック清家遺体に塗布する場合に特に好ましい。また、下地の担体に色や模様が印刷されている場合には、下地の色や柄を損なうことなく、透明な光触媒層を形成することができる。
【００７２】
かかる光触媒としては、例えば、酸化チタン、酸化亜鉛、酸化錫、酸化ジルコニウム、酸化タングステン、酸化クロム、酸化モリブデン、酸化鉄、酸化ニッケル、酸化ルテニウム、酸化コバルト、酸化銅、酸化マンガン、酸化ゲルマニウム、酸化鉛、酸化カドミウム、酸化バナジウム、酸化ニオブ、酸化タンタル、酸化ロジウム、酸化レニウムなどの酸化物等が挙げられる。これらの中でも、酸化チタン、酸化亜鉛、酸化錫、酸化ジルコニウム、酸化タングステン、酸化鉄、酸化ニオブ、特にアナターゼ型二酸化チタンが、１００℃以下の低温で加熱硬化を行った場合でも優れた光触媒活性を示す点から好ましい。
【００７３】
また、これらに光触媒の光触媒還元作用を利用して、Ｐｔ，Ｒｈ，Ｒｕ，ＲｕＯ2，Ｎｂ，Ｃｕ，Ｓｎ，Ｎｉ，Ｆｅ，Ａｇ等の金属もしくはこれらの金属酸化物を添加したものを用いることができる。光触媒層中の光触媒の含有量は、多量なほど触媒活性が高くなるが、接着性の点から好ましくは、光触媒層形成用組成物に対して７５重量％以下である。
【００７４】
前記光触媒層形成用組成物は、(Ｇ)成分としてシリコン化合物を含有する。該シリコン化合物は光触媒形成用組成物の経時変化による粘度増加や粒子沈降が生じるのを抑制する役割を果たす。
【００７５】
かかるシリコン化合物としては、一般式：ＳｉＲ3n5(ＯＲ4)4-n5（式中、Ｒ3は（アミノ基、塩素原子又はカルボキシル基で置換されていてもよい）炭素数１〜８のアルキル基を表し、Ｒ4はアルコキシ基で置換されていてもよい炭素数１〜８のアルキル基を表し、ｎ5は０，１，２又は３のいずれかを表す。）で表されるアルコキシシラン類又はそれらの加水分解性生物の１種又は２種以上の混合物を用いることができる。
【００７６】
前記Ｒ3としては、メチル基、エチル基、ビニル基、γ−グリシドキシプロピル基、γ−メタクリロキシプロピル基、γ−（２−アミノエチル）アミノプロピル基、γ−クロロプロピル基、γ−メルカプトプロピル基、γ−アミノプロピル基、１−アクロキシプロピル基等が挙げられる。
【００７７】
また、ＯＲ4で表される基としては、メトキシ基、エトキシ基、n−プロポキシ基、i−プロポキシ基、n−ブトキシ基、β−メトキシエトキシ基、２−エチルヘキシロキシ基等を例示することができる。
【００７８】
前記一般式：ＳｉＲ3n5(ＯＲ4)4-n5で表されるシリコン化合物の具体例としては、テトラメトキシシラン、テトラエトキシシラン、メチルトリメトキシシラン、メチルトリエトキシシラン、及びこれらの加水分解物の１種又は２種以上の混合物を好ましく挙げることができる。
【００７９】
前記シリコン化合物の光触媒形成用組成物中の含有量は０．００１〜５重量％であるのが好ましい。０．００１重量％未満では、光触媒層形成用組成物の長期保存安定性が低下し、５重量％を越えると、光触媒の触媒活性の低下が著しい。また、前述したシランカップリング剤を添加する場合には、シリコン化合物の添加量を減らすことができる。
【００８０】
光触媒層形成用組成物は、少なくとも前記（Ｅ）,(Ｆ)及び(Ｇ)成分を含み、適当な溶媒に溶解ないしは縣濁させて用いられる。かかる溶媒としては、低沸点のものが好ましいが、例えば、水、メチルアルコール、エチルアルコール、イソプロピルアルコール、ブタノール等のアルコール類、アセトン、メチルエチルケトン、メチルイソブチルケトン、アセチルアセトン、シクロヘキサノン等のケトン類、酢酸エチル、酢酸ブチルなどのエステル類、ベンゼン、トルエン、キシレン等の芳香族炭化水素、ペンタン、ヘキサン、ヘプタン、シクロヘキサン等の脂肪族炭化水素等、及びこれらの２種以上の混合溶媒をもちいることができる。
【００８１】
光触媒層を中間層上に形成するには、前記中間層を形成するのと同様な方法で形成することができる。また、金属酸化物ゾルあるいは金属水酸化物ゾルの前駆体溶液の状態で光触媒を分散し、コート時に加水分解あるいは中和分解してゾル化もしくはゲル化させてもよい。
【００８２】
ゾルを使用する場合には、安定化のために、酸やアルカリの解膠剤等が添加されていてもよい。光触媒層形成時の乾燥温度としては、担体材質及び中間層中の樹脂材質によっても異なるが、１０〜４０℃の範囲が好ましい。
【００８３】
また光触媒層を形成する前に、中間層表面に易接着処理を施すことが好ましい。中間層表面に易接着処理を施すことにより、中間層と光触媒層との層間密着性が著しく高められ、中間層表面に光触媒層を形成した場合に、光触媒層表面が見る角度によって金色や玉虫色に見える、いわゆる干渉色が生じるのを効果的に防止することができる。
【００８４】
かかる易接着処理としては、例えば、中間層表面をコロナ放電処理やＵＶ−オゾン処理を施す方法が挙げられる。
【００８５】
光触媒層の厚みは厚い方が活性は高くなるが、通常１００ｎｍ〜５００ｎｍが好ましい。５００ｎｍ以上になると光触媒活性向上の効果が飽和する一方、１００nm未満の場合には光透過性に優れるものの光触媒が利用する紫外線をも投下してしまうために、高い活性が望めなくなる。
【００８６】
特に光触媒層の厚さを１００ｎｍ〜５００ｎｍとし、しかも、結晶粒子径が４０ｎｍ以下の光触媒粒子及び比表面積１００ｍ2／ｇ以上の金属酸化物ゲルもしくは金属水酸化物ゲルを用いると、光触媒層と中間層の合計の波長５５０ｎｍにおける全光線透過率を７０％以上とすることができる。
【００８７】
本発明の光触媒構造体に用いられる担体１としては、中間層２を介して光触媒層３を担持できるものであれば、その材質、形状等に制限はない。
【００８８】
かかる担体の形状としては、光触媒が担持可能であれば特に制限はないないが、例えばフィルム状、管状、繊維状、網状、板状、曲面板等が挙げられるる
【００８９】
より具体的には、例えば、ポリエチレン、ポリプロピレン等のポリオレフィン樹脂、ポリメタクリル酸メチル、ポリアクリル酸メチル、ポリメタクリル酸エチル等のアクリル樹脂、ポリ塩化ビニル、ポリスチレン、アクリロニトリル−ブタジエン−スチレン共重合体(ABS樹脂)、ポリカーボネート等の熱可塑性樹脂、フェノール樹脂、尿素樹脂、不飽和ポリエステル、ポリウレタン、エポキシ樹脂、メラミン樹脂、ジアリルフタレート樹脂等の熱硬化性樹脂、その他、ポリフッ化エチレン、珪素樹脂等の合成樹脂のフィルムや板状体、
【００９０】
各種ガラス、陶磁器、土器、ほうろう等のセラミックス板、石膏板、石膏スラグ板、珪酸カルシウム板、軽量発泡コンクリ−ト板、中空押出セメント板、パルプセメント板、石綿セメント板、木片セメント板、硝子繊維強化セメント板、鉄板、アルミニウム板、アルミニウム合金板、亜鉛メッキ鋼鈑、銅板、銅合金板、ステンレス鈑等の金属板
【００９１】
木材単板、木材合板、パーティクルボード、ＭＤＦ（中密度繊維板）等の木質板、クラフト紙、コート紙、チタン紙、リンター紙、板紙、石膏ボード紙、上質紙、薄葉紙、パラフィン紙、グラシン紙、アート紙、硫酸紙等の紙類、毛、絹、麻等の天然繊維、レーヨン、アセテート等の再生繊維、ナイロン、アクリル、ポリアミド、ポリエステル、ポリアクリロニトリル、ポリ塩化ビニル、ポリ塩化ビニリデン等の合成繊維、アラミド等の耐熱性繊維の単独あるいは混紡繊維からなる織布、不織布、編布等の繊維硝子繊維、石綿、チタン酸カリウム繊維、シリカ繊維、炭素繊維、アルミナ繊維等の複合強化遷移、フェノール樹脂、尿素樹脂、不飽和ポリエステル、ポリウレタン、エポキシ樹脂、メラミン樹脂等の樹脂を、硝子繊維、不織布、布帛、紙、その他各種繊維基材に含浸硬化させて複合化したいわゆるＦＲＰ板等が挙げられる。
【００９２】
また、その他、上記した各種素材の２種以上を接着剤あるいは熱融着等の公知の手法により積層した複合基材を用いることもできる。
【００９３】
本発明の光触媒担持構造体を少なくとも一部に有した物品としては、例えば、壁紙、壁面材、窓ガラス、サッシ、窓枠類等の建築物の内外装材、ブラインド、カーテン、カーペット、ショーケース等の各種インテリア製品、眼鏡、ガラスレンズ、フロントガラス、ドアミラー、鏡等の各種ガラス製品、照明器具、照明灯、ブラックライト、テレビ、冷蔵庫、オーディオ機器、コンピュータ、パソコン、プリンタ、ファクシミリ等の電気機器、テント、傘、テーブルクロス等の日用品、箪笥、本棚、机、テーブル等の家具類、自動車、電車、飛行機、船舶等の車両の内外装材、農業用フィルム、防草シート、育苗シート等の農園芸用シート類や食品包装材料等が挙げられる。
【００９４】
本発明の光触媒構造体を設けたプラスチックフィルムは、その防汚、抗菌、脱臭機能を活かして、光触媒を担持していない担体の裏面に、アクリル系あるいはシリコン系粘着剤を塗布したフィルムとすることで、自動車や各種輸送機器の窓ガラス、冷凍・冷蔵ショーケースや温室等の内面に貼り付けることができる。
【００９５】
そして、内部空間の微量有機物質の分解と、ガラス表面の汚染防止と破損時の飛散防止に有効な透視性の高いフィルムとすることが可能となる。
【００９６】
かかる透明性が高い担体としては、例えばポリエチレンテレフタレート、ポリカーボネート、ポリアクリル酸エステル、ポリメタクリレート、ポリエチレン、ポリプロピレン、ポリアミド、ポリイミド、ポリスチレン、ポリ塩化ビニル、ポリフッ化ビニリデン、ポリ四フッ化エチレン、フッ化エチレン−プロピレン共重合体、フッ化エチレンーエチレン共重合体、エチレン−酢酸ビニル共重合体などのフィルム状に成形加工したときに５５０ｎｍの波長の光の直線透過率が５０％以上である透明性の高い合成樹脂フィルム又はシートを挙げることができる。
【００９７】
【実施例】
次に、実施例により本発明を更に詳細に説明する。本発明は、以下の実施例に制限されることなく、本発明の主旨を逸脱しない範囲で、担体の材質や形状、中間層形成用組成物、光触媒層形成用組成物の組成物の内容、配合割合、各層の厚さ等を適宜変更することができる。
【００９８】
実施例１
酸化物換算でシリコン含有量２％のアクリルシリコン樹脂（ガラス転移温度２０℃）、重合度が３〜６のテトラメトキシシランの部分加水分解生成物であって、テトラメトキシシランモノマーの含有量が５重量％以下のオリゴマー、及びコロイダルシリカ（日産化学（株）製、商品名：ＩＰＡ−ＳＴ）を固形分重量比５０：４０：１０に混合し、エタノール−ブタノール−酢酸エチル混合溶媒で固形分濃度が１０重量％になるように希釈し、更に水をテトラメトキシシランオリゴマーの二酸化ケイ素換算モル比の２当量混合し中間層形成用組成物塗布液とした。
【００９９】
一方、光触媒ゾル（石原産業（株）製、商品名：ＳＴＳ−０１、固形分濃度３０重量％、平均粒子径７ｎｍ）、重合度が３〜６のテトラメトキシシランの部分加水分解生成物であるオリゴマー及びコロイダルシリカ（粒子径２０ｎｍ）を固形分重量比３０：１０：３５に混合し、エタノール及び水を用いて固形分３重量％になるように希釈して光触媒層形成用組成物の塗布液とした。
【０１００】
次いで、大きさ７０ｍｍ×７０ｍｍの耐侯性ＰＥＴフィルム表面に、バーコーターにより、先に調製した中間層塗布液を乾燥膜厚３μｍとなるように塗布し、室温で２時間乾燥してＰＥＴフィルム上に中間層を形成した。その後、先に調製した光触媒層形成用組成物の塗布液を同様な方法で中間層表面に塗布し（膜厚０．５μｍ）、室温で２４時間乾燥を行うことにより、透明な光触媒担持フィルムを作製した。
【０１０１】
実施例２
二酸化ケイ素換算でシリコン含有量２重量％のアクリルシリコン樹脂、重合度３〜６のテトラメトキシシランの部分加水分解生成物であって、テトラメトキシシランモノマーの含有量が５重量％以下のオリゴマー、及びコロイダルシリカ（日産化学（株）製、商品名：ＩＰＡ−ＳＴ）を固形分重量比６２：３３：５に混合し、エタノール−ブタノール−酢酸エチル混合溶媒で固形分濃度が１５重量％になるように希釈した。更に水をテトラメトキシシランオリゴマーの二酸化ケイ素換算モル比の２当量、及びアルミニウムトリスアセチルアセトネート、ホウ酸トリノルマルブチルをそれぞれテトラメトキシシランオリゴマーの二酸化ケイ素換算重量比で２重量％を混合して、中間層形成用組成物の塗布液を調製した。
【０１０２】
また、光触媒ゾル（石原産業（株）製、商品名：ＳＴＳ−０１、固形分濃度３０重量％、平均粒子径７ｎｍ）、テトラメトキシシランの部分加水分解生成物であり、重合度が３〜６であるオリゴマー及びコロイダルシリカ（平均粒子径２０ｎｍ）を固形分重量比３０：１０：３５に混合し、エタノール及び水を用いて固形分３重量％になるように希釈して光触媒層形成用組成物の塗布液を調製した。
【０１０３】
次いで、ソーダライムガラス基板にバーコーターにより、先に調製した中間層形成用組成物塗布液を乾燥膜厚が４μｍとなるように塗布し、室温で２時間乾燥して中間層を形成した。更に、該中間層上に先に調製した光触媒層形成用組成物の塗布液を同様な方法で塗布し（膜厚０．３μｍ）、２４時間乾燥を行って透明な光触媒層を有する光触媒担持ガラス基板を作製した。
【０１０４】
参考例１
酸化物換算でシリコン含有量２重量％のアクリルシリコン樹脂、重合度が３〜６であるテトラメトキシシランの部分加水分解生成物であるオリゴマー、及びコロイダルシリカ（日産化学（株）製、商品名：ＩＰＡ−ＳＴ）を固形分重量比６０：３５：５に混合し、エタノール−ブタノール−酢酸エチル混合溶媒で固形分濃度が１５重量％になるように希釈し、更に水をテトラメトキシシランオリゴマーの酸化物換算モル比の２当量混合して、中間層形成用組成物の塗布液を調製した。
【０１０５】
また、光触媒ゾル（石原産業（株）製、商品名：ＳＴＳ−０１，固形分濃度３０重量％、平均粒子径７ｎｍ）、重合度が３〜６であるテトラメトキシシランのオリゴマーである部分加水分解生成物、コロイダルシリカ（平均粒子径７ｎｍ）、ジルコニアゾル、及びアルミナゾルを固形分重量比２０：１５：４０：４：１に混合し、エタノール及び水を用いて固形分３重量％になるように希釈して光触媒層形成用組成物の塗布液とした。
【０１０６】
次いで、大きさ７０ｍｍ×７０ｍｍの耐光性ＰＥＴフィルムに、グラビア印刷機により先に調製した中間層形成用組成物の塗布液を塗工速度５０ｍ／分で膜厚２μｍになるように塗布し、６０℃で２分間連続乾燥した。その後、中間層の表面をコロナ放電処理を施し、中間層表面に先に調製した光触媒層形成用組成物の塗布液を塗工速度５０ｍ／分で膜厚が０．５μｍになるように塗布し、６０℃で２分間連続乾燥を行い、透明な光触媒担持フィルムを得た。
【０１０７】
比較例１
実施例１において中間層形成用組成物の塗布液に水を添加しない以外は実施例１と同様の組成の中間層形成用組成物の塗布液を用い、実施例１と同様にして耐光性PETフィルム表面に中間層を形成したところ、白濁した膜が得られた。この中間層表面に実施例１と同じ組成の光触媒層形成用組成物を形成して、図１に示すのと同様の層構成を有する光触媒担持フィルムを作製した。
【０１０８】
参考例２
コロナ放電処理を行わない以外は参考例１と同様にして、参考例２の光触媒担持フィルムを作製した。
【０１０９】
光触媒活性の評価
実施例１、２、比較例１、及び参考例１、２で得られた光触媒担持フィルムを７ｃｍ×７ｃｍに切り出し、容積４Ｌのパイレックス（登録商標）製ガラス容器中に設置した。この容器中に空気とアセトアルデヒドの混合ガスを、アセトアルデヒドの濃度が１００ｐｐｍになるように加えた。次いで、フィルム表面の紫外線強度が２ｍＷ／ｃｍ２ブラックライト（ＳＬ １５Ｂ−Ｂ 松下電器産業（株）製）の光を２時間照射後、容器内部のアセトアルデヒドガス濃度をガスクロマトグラフにより測定し、その減少量により光触媒活性を評価した。
【０１１０】
その結果、いずれの場合にも容器内部のアセトアルデヒドガス濃度は２０ｐｐｍ以下であり、実施例１、２、比較例１及び参考例２のいずれの光触媒担持フィルムも優れた光触媒活性を有していることがわかった。
【０１１１】
促進耐候性試験
実施例１、２、比較例１、及び参考例１、２で得られた光触媒担持フィルムをサンシャインカーボンアークウェザーメーター（スガ試験機（株）製、ＷＥＬ−ＳＵＮ−ＨＣＨ型）を使用して、促進耐候性試験を行った。
【０１１２】
その結果、実施例１及び実施例２のフィルムともに、５００時間経過後も光触媒層にひび割れは見られず、干渉色も認められなかった。また、５００時間の促進耐候試験後の光触媒層の水の接触角は、実施例１で２°、実施例２で２．４°、参考例１で１．０°であった。
【０１１３】
一方、比較例１のフィルムは、５００時間の促進耐候試験後において、光触媒層の表面にひび割れが認められ、ヘイズ率が２８であった。また、参考例２のフィルムは、５００時間の促進耐候試験後においても光触媒層表面にひび割れは認められず（ヘイズ率＝２．０）、その接触角も約２°であり親水性を維持していたが、表面に干渉色が現れた。
【０１１４】
以上の結果から、実施例１、２及び参考例１の光触媒担持構造体は、いずれも優れた光触媒機能を有し、５００時間以上の促進耐候性試験後においても何らその機能の低下が認められず、干渉色も現れなかった。
【０１１５】
中間層形成用組成物の保存安定性試験
実施例１で調製した中間層形成用組成物を室温で３月保存しても、不溶物は見られず、また粘度の上昇は認められなかった。従って、実施例１の中間層形成用組成物は保存安定性に優れていることがわかった。
【０１１６】
【発明の効果】
以上説明したように、本発明は、担体と光触媒層との間に中間層を設けた光触媒担持構造体であって、▲１▼担体と光触媒層との密着性に優れ、▲２▼担体及び中間層が光触媒により分解され難く、▲３▼いわゆる干渉色がなく、かつ、▲４▼表面にひび割れを起こさないものである。
【０１１７】
本発明の光触媒担持構造体の製造方法によれば、中間層形成用組成物を担体表面に塗布したのち、常温で乾燥させることにより中間層を形成することができる。従って、シート状の担体表面に中間層を形成した後、該シートを巻き取る工程の際に、いわゆるブロッキングが生じることがなくなる。また、いわゆる現場塗工が可能となるので、生産効率（作業効率）が大幅に向上している。
【０１１８】
また本発明の中間層形成用組成物は、長期保存安定性に優れている。
【図面の簡単な説明】
【図１】本発明の光触媒担持構造体の断面図である。
【符号の説明】
１…担体、２…中間層、３…光触媒層[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a photocatalyst-supporting structure in which a photocatalyst layer is formed on a carrier via an intermediate layer, and a resin composition for forming an intermediate layer.
[0002]
[Prior art]
Conventionally, a photocatalyst carrying structure in which a photocatalyst layer carrying a substance having photocatalytic activity such as titanium dioxide is formed on a carrier such as a plastics plate, a glass plate, or a ceramic plate is known.
[0003]
However, it has been reported that a photocatalyst-supporting structure using a support mainly composed of organic matter decomposes or deteriorates due to its catalytic action when the photocatalyst is supported on the support. There was a problem in durability (see, for example, Otani writing, polymer processing 42, No. 5, p18 (1993), Manabu Seino, “Titanium oxide” technique hall, p165, etc.).
[0004]
Therefore, in order to solve such a problem, a photocatalyst structure in which an intermediate layer is provided on a carrier and a photocatalyst layer is formed on the intermediate layer has been proposed.
[0005]
For example, in WO97 / 00134, in a photocatalyst carrying structure having a structure in which an adhesive layer is provided between a photocatalyst layer and a carrier, the adhesive layer has (1) silicon modification with a silicon content of 2 to 60% by weight. Resin, (2) Resin containing 5-40 weight of colloidal silica, or (3) Formula (1) SiCln1(OH) n2R1nThree(OR2) nFour[In the formula, R1Is an alkyl group having 1 to 8 carbon atoms (which may be substituted with an amino group, a carboxyl group or a chlorine atom), R2Represents an alkyl group having 1 to 8 carbon atoms substituted with an alkyl group having 1 to 8 carbon atoms or an alkoxy group, and n1Represents 0, 1 or 2, nFourRepresents 2, 3 or 4 and n1+ N2+ NThree+ NFour= 4. ] A resin containing 3 to 60% by weight of polysiloxane which is a polycondensation reaction product of the compound represented by formula (1), and the photocatalyst layer contains 25 to 95% by weight of metal oxide gel or metal hydroxide gel. A photocatalyst carrying structure which is a photocatalyst particle composite, a photocatalyst coating agent for forming an adhesive layer, and a photocatalyst coating liquid for forming a photocatalyst layer are described.
[0006]
This technology protects the underlying carrier from deterioration due to the photocatalyst by providing a specific adhesive layer between the carrier and the photocatalyst layer in the photocatalyst carrying structure in which the adhesive layer is provided between the carrier and the photocatalyst layer. And having a function of firmly bonding the photocatalyst layer to the carrier.
[0007]
WO98 / 25711 discloses a cured film of an acrylic-modified silicone resin coating material containing the following components (A ′), (B ′), (C ′) and (D ′) on the surface of a base material. Functional coating product comprising one coating layer and a second coating layer comprising a cured coating of a functional coating material containing the following components (E ′) and (F ′) formed on the surface of the first coating layer The manufacturing method and use thereof are described.
[0008]
(A ') component:
General formula R1'mSiX4-m(Wherein R1'Represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms which may be the same or different, m represents an integer of 0 to 3, and X represents a hydrolyzable group). In the colloidal silica in which the hydrolyzable organosilane represented is dispersed in an organic solvent, water or a mixed solvent thereof, 0.001 to 0.5 mol of water per 1 mol equivalent of the hydrolyzable group (X) is added. A silica-dispersed oligomer solution of organosilane obtained by partial hydrolysis under the conditions used;
[0009]
(B ′) component:
Average composition formula R2’nSi (OH)bO(4-ab) / 2(Wherein R2'Represents a substituted or unsubstituted hydrocarbon group having 1 to 8 carbon atoms which may be the same or different, and a and b are 2 ≦ a ≦ 2, 0.001 ≦ b ≦ 3 and a + b <, respectively. 4 relationship is satisfied. And a polyorganosiloxane having a weight average molecular weight (in terms of polystyrene) of 700 to 20,000, containing a silanol group in the molecule;
[0010]
(C ′) component:
Curing catalyst;
Component (D ′);
General formula CH2= CRThree’(COORFour ') (Wherein RThree'Is a hydrogen atom and / or a methyl group;FourA first (meth) acrylic ester, wherein R is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 9 carbon atoms, RFourA second (meth) acrylic acid ester, wherein 'is at least one group selected from the group consisting of an epoxy group, a glycyl group, and a hydrocarbon group containing at least one of these, and RFourIs a copolymer with a third (meth) acrylic acid ester which is a hydrocarbon group containing an alkoxylalkyl group and / or a halogenated silyl group, and an acrylic resin having a weight average molecular weight (polystyrene conversion) of 1000 to 50000 or less ;
[0011]
(E ') component:
General formula Si (ORFive’)Four5 to 30,000 parts by weight of a silicon compound and / or colloidal silica represented by the general formula R6’2Si (ORFive’)2100 parts by weight of a silicon compound represented by the general formula R6’2Si (ORFive’)20 to 60 parts by weight of a silicon compound represented by the formula:Five', R6'Represents a monovalent hydrocarbon group) and is adjusted so that its weight average molecular weight is 800 or more in terms of polystyrene;
(F ′) component:
photocatalyst;
[0012]
This technology is excellent in adhesion of the coating film to the base substrate, hardly causes deterioration of the substrate and the coating film due to photocatalytic action, and also has a high smoothness of the coating film surface so that it is difficult to get dirty and has high photocatalytic action. It provides functional paint products.
[0013]
[Problems to be solved by the invention]
Each of these photocatalyst-supported structures (functionally coated products) has an adhesive layer that improves adhesion between the carrier and the photocatalyst layer, protects the carrier from decomposition by the photocatalyst, and also has an adhesive layer (first layer). 1 coating layer) itself is difficult to be photodegraded by the photocatalyst.
[0014]
However, (1) the surface of the photocatalyst structure (functionally coated product) has a unique color when transparency is required, such as when transparent glass or a transparent plastics molded body is used as a carrier. (Gold color etc.) may appear (so-called interference color problem), (2) In order to obtain sufficient photocatalytic activity, the adhesive layer (first coating layer) and the photocatalyst layer are formed to a certain extent thick. It is necessary, but the surface may crack and become unusable, and (3) The curing speed of the adhesive phase at room temperature is slow, so it cannot be applied on-site or can be applied continuously such as film or sheet Then, unless the coating speed is made very low, there is a problem in that it does not cure and causes a blocking phenomenon.
[0015]
Therefore, the present invention provides a photocatalyst-supporting structure in which an intermediate layer is provided between the carrier and the photocatalyst layer. (1) Excellent adhesion between the carrier and the photocatalyst layer. (2) The carrier and the intermediate layer are decomposed by the photocatalyst. It is difficult to provide (3) a so-called interference color, (4) no cracking on the surface, and (5) a method for producing a photocatalyst-supporting structure that can be quickly cured at room temperature, and an intermediate layer forming composition. With the goal.
[0016]
[Means for Solving the Problems]
As a result of intensive studies to solve the above-mentioned problems, the present inventors have formed a photocatalyst-supporting structure having an intermediate layer between the support and the photocatalyst layer by forming the intermediate layer from a specific composition. The present inventors have found that the above problems can be solved, and have completed the present invention.
[0017]
That is, in the present invention, first, an intermediate layer forming composition containing at least the following components (A), (B), (C) and (D) is applied to the surface of a carrier, Forming an intermediate layer by drying for 0.5 to 72 hours;
Applying a photocatalyst layer-forming composition containing at least the following components (E), (F) and (G) to the surface of the intermediate layer and drying at 10 to 40 ° C. to form a photocatalyst layer: A method for producing a photocatalyst-supporting structure is provided.
[0018]
Component (A):
0.5-20% by weight of acrylic silicon resin or epoxy silicon resin as solid content;
(B) component:
0.25 to 4% by weight of metal oxide sol and / or metal hydroxide sol as solid content;
Component (C):
Silicon dioxide is a silicon compound having one or more partial hydrolysis products of tetraalkoxysilane having an average polymerization degree of 3 to 10 and a tetraalkoxysilane monomer content of 5% by weight or less. 0.25 to 20% by weight as a converted solid content;
Component (D);
0.5 to 3 times the molar equivalent of water of the solid silicon compound in terms of silicon dioxide;
(E) component:
Metal oxide sol and / or metal hydroxide sol;
(F) component:
Photocatalytic particles and / or sols;
(G) component:
Silicon compounds;
[0019]
The present invention also secondly provides an intermediate layer forming composition containing at least the components (A), (B), (C) and (D).
[0020]
In the first and second inventions, the intermediate layer forming composition preferably further contains a metal compound capable of coordinating with a silanol group at room temperature.
[0021]
The acrylic resin or epoxy silicon resin as the component (A) is preferably a resin containing 5 to 60% by weight of silicon in terms of silicon oxide, and its glass transition temperature is in the range of 20 to 50 ° C. It is more preferable that the resin.
[0022]
The metal oxide sol and / or metal hydroxide sol as the component (B) is one or more selected from silicon, aluminum, titanium, zirconium, magnesium, niobium, tantalum, tungsten and tin. The metal oxide sol and / or hydroxide sol are preferable, and the average particle diameter is more preferably 4 to 50 nm.
[0023]
The silicon compound as the component (C) is a partial hydrolysis product of tetramethoxysilane and / or tetraethoxysilane having an alkoxysilane monomer content of 1% by weight or less and an average degree of polymerization of 3 to 10. Is preferred.
[0024]
The metal oxide sol and / or metal hydroxide sol as the component (E) is preferably a sol having an average particle size of 4 to 50 nm.
[0025]
The average particle diameter of the photocatalyst particles and / or sol as the component (F) is preferably 4 to 50 nm.
[0026]
The silicon compound as the component (G) is preferably a partial hydrolysis product of tetraalkoxysilane having a tetraalkoxysilane monomer content of 5% by weight or less and an average degree of polymerization of 3 to 10. .
[0027]
According to the method for producing a photocatalyst carrying structure of the first invention, the photocatalyst carrying structure of the first invention can be produced simply and with good yield.
[0028]
In particular, according to the production method of the present invention, the intermediate layer can be cured and formed at room temperature. For example, after forming the intermediate layer on a sheet-like carrier, the step of winding the sheet with the intermediate layer is performed. In addition, the surface of the intermediate layer of the sheet and the back surface of the sheet cause heat fusion, so that a phenomenon called so-called blocking does not occur.
[0029]
In addition, since the intermediate layer-forming composition is applied onto the carrier and cured / formed at room temperature, for example, the intermediate layer-forming composition is applied / formed onto a building wall surface, and further on The composition for forming a photocatalyst layer can be applied and formed (referred to as “on-site coating”), which is advantageous in terms of production cost.
[0030]
The photocatalyst carrying structure produced by the production method of the present invention is excellent in (1) adhesion between the carrier and the photocatalyst layer, (2) the carrier and the intermediate layer are hardly decomposed by the photocatalyst, and (3) so-called interference color is present. (4) The photocatalyst-supporting structure is free from cracks on the surface and (5) is cured at room temperature.
[0031]
The intermediate layer forming composition of the second invention is coated on a carrier and cured at room temperature to form an intermediate layer. This intermediate layer firmly adheres the carrier and the photocatalyst layer, so-called delamination does not occur, and even if a photocatalyst layer is formed thereon, the surface of the photocatalyst layer may appear golden or iridescent due to light interference There is no.
[0032]
In addition, the composition for forming an intermediate layer of the present invention is stable and does not precipitate insolubles or increase in viscosity even when stored for a long period of time.
[0033]
DETAILED DESCRIPTION OF THE INVENTION
Next, embodiments of the present invention will be described.
A cross-sectional view of a photocatalyst structure produced by the method for producing a photocatalyst structure of the present invention is shown in FIG.
[0034]
The photocatalyst carrying structure of the present invention comprises a photocatalyst layer 3 formed on the surface of a carrier 1 via an intermediate layer 2.
The intermediate layer 2 is formed from an intermediate layer forming composition having the following components (A), (B), (C) and (D).
[0035]
Component (A):
0.5-20% by weight of acrylic silicon resin or epoxy silicon resin as solid content;
(B) component:
0.25 to 4% by weight of metal oxide sol and / or metal hydroxide sol as solid content;
Component (C):
Silicon dioxide is a silicon compound having one or more partial hydrolysis products of tetraalkoxysilane having an average polymerization degree of 3 to 10 and a tetraalkoxysilane monomer content of 5% by weight or less. 0.25 to 20% by weight as a converted solid content
Component (D);
0.5 to 3 times the molar equivalent of water of the solid silicon compound in terms of silicon dioxide
[0036]
The component (A) of the intermediate layer forming composition is an acrylic silicon resin and / or an epoxy silicon resin. The content of these resins in the intermediate layer forming composition is preferably 0.5 to 20% by weight as a solid content.
When the content is less than 0.5% by weight, the adhesion of the coating film to the carrier is lowered. On the other hand, when the content exceeds 20% by weight, the stability of the coating solution is deteriorated.
[0037]
The acrylic silicon resin is a silicon-modified acrylic resin, and the epoxy silicon resin is a silicon-modified epoxy resin. As a method for introducing (modifying) silicon into an acrylic resin or epoxy resin, a method using an ester exchange reaction, a method using a graft reaction using a silicon macromer or a reactive silicon monomer, a method using a hydrosilylation reaction, or block copolymerization was used. There are methods. In the present invention, an object made by any method can be used.
[0038]
Examples of the acrylic resin monomer include acrylic esters such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, -2-ethylhexyl acrylate, methoxyethyl acrylate, butoxyethyl acrylate, and phenyl acrylate. Kind,
Methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, methoxymethyl ethacrylate, methacrylsan ethoxymethyl, phenyl methacrylate, lauryl methacrylate,
Acrylic acid-2- (N, N-dimethylamino) ethyl, methacrylic acid-2- (N, N-dimethylamino) ethyl, methacrylic acid-2- (N, N-dibenzylamino) ethyl, acrylic acid-2 -Substituted amino alcohol esters of acrylic acid or methacrylic acid such as (N, N-diethylamino) propyl,
Unsaturated carboxylic acid amides such as acrylamide and methacrylamide;
Glycol acrylates and glycol methacrylates such as ethylene glycol diacrylate, propylene glycol eye acrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, dipropylene glycol diacrylate, ethylene glycol acrylate, diethylene glycol dimethacrylate Etc. can be used.
[0039]
The epoxy resin is a thermosetting resin having an epoxy group. Usually, after obtaining a prepolymer having an epoxy group, a curing agent is added and a polymer having a three-dimensional network structure is obtained by a crosslinking reaction.
[0040]
As such a prepolymer, for example, a phenolic glycidyl obtained from a compound having an epoxy group such as epichlorohydrin and a phenol derivative such as bisphenol A, bisphenol F, tetrabromobisphenol A, tetraphenylolethane, phenol novolac, o-cresol novolac, etc. Ether type epoxy resin,
[0041]
An alcohol-based glycidyl ether type epoxy resin obtained from a compound having an epoxy group such as epichlorohydrin and a polyol such as polypropylene glycol or hydrogenated bisphenol A;
A glycidyl ester type epoxy resin obtained from a compound having an epoxy group such as epichlorohydrin and a carboxylic acid such as hexahydrophthalic anhydride or dimer acid,
A glycidylamine type epoxy resin obtained from a compound having an epoxy group such as epichlorohydrin and a compound such as diaminodiphenylmethane, isocyanuric acid, hydantoin,
Examples thereof include a mixed epoxy resin obtained from a compound having an epoxy group, p-aminophenol, p-oxybenzoic acid and the like.
[0042]
The silicon content of these acrylic silicon resins or epoxy silicon resins is 0.5 to 60% by weight in terms of silicon dioxide, preferably 2 to 60% by weight, more preferably 5 to 60% by weight. When the silicon content is less than 0.5% by weight in terms of oxide, the adhesion between the intermediate layer and the carrier is poor, and the intermediate layer is easily deteriorated by the photocatalyst, and the photocatalytic layer is easily peeled off. Become. On the other hand, when it exceeds 60% by weight, the adhesion between the intermediate layer and the carrier becomes poor.
[0043]
The glass transition temperature of the acrylic silicone resin and epoxy silicone resin is more preferably in the range of 20 to 50 ° C. When the glass transition temperature is less than 20 ° C., the stability of the coating solution is deteriorated. On the other hand, when it exceeds 50 ° C., a temperature of 50 ° C. or more is required for curing the coating film.
[0044]
In addition, as the resin into which silicon is introduced, the above-described acrylic resin and silicon resin are most excellent in terms of film formability, film strength, and adhesion to a carrier, but alkyd resin, urethane resin, polyester resin, etc. Other synthetic resins can also be used.
[0045]
The component (B) contained in the intermediate layer forming composition is a metal oxide sol and / or a metal hydroxide sol. The metal oxide sol or metal hydroxide sol has an effect of fixing the photocatalyst powder and firmly bonding it to the intermediate layer. The content of the metal oxide sol or metal hydroxide sol in the intermediate layer forming composition is preferably 0.25 to 4% by weight as the solid content. When the content is less than 0.25% by weight, the curing of the film is delayed. On the other hand, when the content exceeds 4% by weight, the stability of the coating solution is deteriorated.
[0046]
Examples of the metal component of the metal oxide and metal hydroxide include silicon, aluminum, titanium, zirconium, magnesium, niobium, tantalum, tungsten, and tin. As the metal component, an oxide or hydroxide gel containing two or more metals selected from silicon, aluminum, titanium, zirconium, and niobium can be used.
[0047]
Component (C) of the composition for forming an intermediate layer of the present invention is one or two or more partial hydrolysis products of tetraalkoxysilane, the average degree of polymerization of which is 3 to 10, and tetraalkoxysilane A silicon compound having a monomer content of 5% by weight or less. The content of the component (C) in the composition for forming an intermediate layer is preferably 0.25 to 20% by weight as a solid content. When the amount is less than 0.25% by weight, the film hardness is lowered. On the other hand, when the amount exceeds 20% by weight, the adhesion to the carrier is lowered.
[0048]
Examples of the tetraalkoxy lane include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, and tetrabutoxysilane. Of these, the use of tetramethoxysilane and tetraethoxysilane is particularly preferred in the present invention from the viewpoints of availability, handling, and the like.
[0049]
For example, a partial hydrolysis product of tetraalkoxysilane can be obtained by dissolving a predetermined amount of these tetraalkoxysilanes in water, water such as methanol, ethanol, ethyl acetate or an organic solvent, and heating or adding a predetermined amount of acid or base. And can be prepared by partial hydrolysis. Usually, the degree of polymerization is preferably 3 to 10, and the remaining amount of the unreacted tetraalkoxysilane monomer is preferably 5% by weight or less, more preferably 1% by weight or less of the total component (C).
[0050]
The intermediate layer forming composition of the present invention contains a predetermined amount of water as the component (D). The water content is preferably 0.5 to 3 times the molar equivalent when the silicon compound of component (C) is converted to silicon dioxide. When the water content is less than 0.5 mol when the silicon compound of the component (C) is converted to silicon dioxide, the curing rate of the film at room temperature is greatly reduced, while the water content is When the amount exceeds 3 times mole, the storage stability of the intermediate layer forming composition is deteriorated.
[0051]
Further, the intermediate layer forming composition may contain a metal compound capable of coordinating with a silanol group at room temperature for the purpose of improving the stability of the coating solution and improving the curing rate.
[0052]
Examples of such metal compounds include organoaluminum compounds such as aluminum trisacetylacetonate, organoboron compounds such as trinormal butyrate borate, and the like. The content of these compounds in the composition for forming an intermediate layer is preferably about 0.1% by weight to 5% by weight in terms of the silicon dioxide equivalent weight ratio of the tetraalkoxysilane oligomer.
[0053]
Further, in the composition for forming an intermediate layer, durability can be improved by mixing a light stabilizer and / or an ultraviolet absorber for the purpose of suppressing deterioration due to the photocatalytic action of the intermediate layer. . The light stabilizer that can be used is preferably a hindered amine system, but other substances can also be used.
[0054]
As the ultraviolet absorber, a triazole ultraviolet absorber or the like can be used. These addition amounts are 0.005 weight%-10 weight% with respect to the whole composition, Preferably they are 0.01 weight%-5 weight%.
[0055]
The method for forming the intermediate layer is not particularly limited. For example, an organic solvent solution, an organic solvent suspension, an aqueous dispersion emulsion, or the like of the composition for forming an intermediate layer is printed on the surface of the carrier, or a sheet forming method. A method of coating by a spraying method, a dip coating method, a spin coating method, and the like, and drying can be used.
[0056]
As the organic solvent, those having a relatively low boiling point are preferable. For example, alcohols such as methanol, ethanol, isopropanol and butanol, acetates such as ethyl acetate and butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone and cyclohexanone. Such as ketones, aliphatic hydrocarbons such as pentane, hexane and heptane, cyclic aliphatic hydrocarbons such as cyclohexane and methylcyclohexane, aromatic hydrocarbons such as benzene, toluene and xylene, and two or more of these or these A mixed solvent of water and water can be used.
[0057]
The drying temperature varies depending on the type of solvent and resin, but a temperature of 150 ° C. or lower is preferable. In particular, the composition for forming an intermediate layer of the present invention comprises:By drying at 10-35 ° C. for 0.5-72 hours,Since it can be cured, so-called on-site coating becomes possible. In addition, in the process of forming an intermediate layer on the surface of a sheet-like carrier and winding the sheet, so-called blocking (a phenomenon in which the intermediate layer surface and the back surface of the sheet are fused by heat) does not occur and productivity is improved. Therefore, it is preferable.
[0058]
In addition, if the thickness of the intermediate layer is 100 nm or more, the photocatalyst layer can be firmly adhered to obtain a highly durable photocatalyst structure. In addition, when it is necessary to dry and cure the intermediate layer in a short time such as a gravure printing method, a curing accelerator such as a silicon-based curing agent is required for the solid content of the intermediate layer forming composition. It is also preferable to add 0.1 to 10% by weight depending on the speed.
[0059]
The photocatalyst layer forming composition contains at least the component (E) and the component (F). The metal oxide sol and metal hydroxide sol, which are the component (E), have the effect of fixing the photocatalyst powder and firmly bonding it to the intermediate layer. Moreover, since this metal oxide gel and metal hydroxide gel are porous, they also have an effect of enhancing photocatalytic activity. The content of the component (E) in the composition for forming a photocatalyst layer is preferably 25 to 95% by weight as a solid content. If it is less than 25% by weight, the adhesion to the intermediate layer is poor, and if it exceeds 95% by weight, the photocatalytic activity becomes insufficient.
[0060]
The specific surface area of the metal oxide gel and metal hydroxide gel is preferably 50 m after drying at 150 ° C.2/ G or more, more preferably 100 m2When it is / g or more, the adhesiveness becomes strong, the photocatalytic activity is improved, and it has excellent adhesiveness even after being immersed in boiling water.
[0061]
Examples of the metal component include metal oxide gels or metal hydroxide gels such as silicon, aluminum, titanium, zirconium, magnesium, niobium, tantalum, tungsten, and tin.
[0062]
Moreover, the photocatalyst after being immersed in boiling water by using an oxide or hydroxide gel containing two or more metals selected from silicon, aluminum, titanium, zirconium, and niobium as the metal component It is possible to increase the adhesion of the layer.
[0063]
Preferred combinations of metal components having excellent boiling water resistance include silicon-aluminum, silicon-titanium, silicon-zirconium, silicon-niobium, aluminum-titanium, aluminum-zirconium, aluminum-niobium, aluminum-tantalum, titanium-zirconium, Examples thereof include titanium-niobium, titanium-tantalum, silicon-aluminum-zirconium, silicon-aluminum-titanium, and the like. More preferably, silicon-aluminum, silicon-titanium, silicon-zirconium, silicon-titanium-aluminum, silicon-aluminum-zirconium, and the like can be given.
[0064]
In actual use of these metal oxide sols and metal hydroxide sols, a gel obtained by mixing and drying a sol for forming a gel may be a composite oxide gel produced by a method such as a coprecipitation method. It can also be used. When combining with a photocatalyst, it is preferable to mix uniformly in the state of the sol before becoming a gel, or to mix at the raw material stage before preparing the sol.
[0065]
Methods for preparing the gel include a method of hydrolyzing a metal salt, a method of neutralizing and decomposing, a method of ion exchange, a method of hydrolyzing a metal alkoxide, etc., but the photocatalytic powder is uniformly dispersed in the gel. Any method can be used as long as it can be obtained in the same state. However, if a large amount of impurities are present in the gel, it adversely affects the adhesion and catalytic activity of the photocatalyst, so it is preferable to use a gel with few impurities.
[0066]
Further, by adding 10 to 50% by weight of a silicon-modified resin or a silane coupling agent to the composition for forming a photocatalyst layer, the composition was immersed in boiling water for 15 minutes while maintaining high catalytic activity. Later, an excellent adhesion (adhesiveness) having an evaluation score of 6 or more can be obtained by an adhesion test by a cross-cut tape method defined in JIS K5400.
[0067]
That is, the silicon-modified resin or silane coupling agent added to the photocatalyst layer forming composition plays a role of enhancing the adhesiveness of the photocatalyst layer in boiling water.
[0068]
As the silicon-modified resin, a commercially available silicon-acrylic resin or silicon-epoxy resin can be used, either dissolved in a solvent or dispersed in water as an emulsion. Can also be used.
[0069]
Examples of the silane coupling agent include a general formula: RSi (Y)ThreeYa (R)2Si (Y)2A compound represented by the formula (wherein R represents an organic functional group, and Y represents a chlorine atom or an alkoxy group) can be used.
[0070]
In the above general formula, R is methyl group, ethyl group, vinyl group, γ-glycidoxypropyl group, γ-methacryloxypropyl group, γ- (2-aminoethyl) aminopropyl group, γ-chloropropyl group. , Γ-mercaptopropyl group, γ-aminopropyl group, γ-acryloxypropyl group and the like. Examples of Y include a chlorine atom, an alkoxy group having 1 to 5 carbon atoms such as a methoxy group, an ethoxy group, a β-methoxyethoxy group, and a β-ethoxyethoxy group.
[0071]
As the photocatalyst as the component (F), any powder, sol, solution, or the like can be used as long as it is fixed to the intermediate layer and exhibits photocatalytic activity when dried at the drying temperature of the photocatalyst layer. When a sol-like photocatalyst is used, if a particle size of 20 nm or less, preferably 10 nm or less is used, the photocatalyst layer transparency is improved and the linear transmittance is increased. It is particularly preferable when applied to a plastic body. Further, when a color or pattern is printed on the base carrier, a transparent photocatalytic layer can be formed without impairing the base color or pattern.
[0072]
Examples of such photocatalysts include titanium oxide, zinc oxide, tin oxide, zirconium oxide, tungsten oxide, chromium oxide, molybdenum oxide, iron oxide, nickel oxide, ruthenium oxide, cobalt oxide, copper oxide, manganese oxide, germanium oxide, and oxide. Examples thereof include oxides such as lead, cadmium oxide, vanadium oxide, niobium oxide, tantalum oxide, rhodium oxide, and rhenium oxide. Among these, titanium oxide, zinc oxide, tin oxide, zirconium oxide, tungsten oxide, iron oxide, niobium oxide, especially anatase-type titanium dioxide, have excellent photocatalytic activity even when heat-cured at a low temperature of 100 ° C. or less. It is preferable from the point shown.
[0073]
Further, by utilizing the photocatalytic reduction action of the photocatalyst for these, Pt, Rh, Ru, RuO2, Nb, Cu, Sn, Ni, Fe, Ag, or other metals or those added with these metal oxides can be used. The higher the content of the photocatalyst in the photocatalyst layer, the higher the catalytic activity. However, from the viewpoint of adhesiveness, the content is preferably 75% by weight or less based on the composition for forming the photocatalyst layer.
[0074]
The photocatalyst layer forming composition contains a silicon compound as the component (G). The silicon compound plays a role of suppressing an increase in viscosity and particle sedimentation due to a change over time of the photocatalyst forming composition.
[0075]
As such a silicon compound, a general formula: SiRThreenFive(ORFour) 4-nFive(Wherein RThreeRepresents an alkyl group having 1 to 8 carbon atoms (which may be substituted with an amino group, a chlorine atom or a carboxyl group), and RFourRepresents an alkyl group having 1 to 8 carbon atoms which may be substituted with an alkoxy group, and nFiveRepresents any of 0, 1, 2, or 3. Or a mixture of two or more of these hydrolyzable organisms.
[0076]
RThreeAs, methyl group, ethyl group, vinyl group, γ-glycidoxypropyl group, γ-methacryloxypropyl group, γ- (2-aminoethyl) aminopropyl group, γ-chloropropyl group, γ-mercaptopropyl group , Γ-aminopropyl group, 1-acryloxypropyl group and the like.
[0077]
ORFourExamples of the group represented by the formula include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, β-methoxyethoxy group, 2-ethylhexyloxy group and the like.
[0078]
General formula: SiRThreenFive(ORFour) 4-nFiveAs specific examples of the silicon compound represented by the formula, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, and one or a mixture of two or more of these hydrolysates are preferably mentioned. it can.
[0079]
The content of the silicon compound in the photocatalyst forming composition is preferably 0.001 to 5% by weight. If it is less than 0.001% by weight, the long-term storage stability of the composition for forming a photocatalyst layer is lowered, and if it exceeds 5% by weight, the catalytic activity of the photocatalyst is remarkably lowered. Moreover, when adding the silane coupling agent mentioned above, the addition amount of a silicon compound can be reduced.
[0080]
The composition for forming a photocatalyst layer contains at least the components (E), (F) and (G), and is used by dissolving or suspending in an appropriate solvent. As such a solvent, those having a low boiling point are preferable. For example, water, alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol and butanol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone and cyclohexanone, ethyl acetate Esters such as butyl acetate, aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as pentane, hexane, heptane and cyclohexane, and a mixture of two or more of these can be used. .
[0081]
In order to form the photocatalyst layer on the intermediate layer, it can be formed by the same method as that for forming the intermediate layer. Alternatively, the photocatalyst may be dispersed in the state of a metal oxide sol or metal hydroxide sol precursor solution, and may be hydrolyzed or neutralized and decomposed into a sol or gel during coating.
[0082]
When a sol is used, an acid or alkaline peptizer may be added for stabilization. The drying temperature when forming the photocatalyst layer varies depending on the carrier material and the resin material in the intermediate layer,10-40 ° CA range is preferred.
[0083]
Moreover, before forming a photocatalyst layer, it is preferable to perform an easily bonding process on the intermediate | middle layer surface. By applying an easy adhesion treatment to the surface of the intermediate layer, the interlayer adhesion between the intermediate layer and the photocatalyst layer is remarkably enhanced, and when the photocatalyst layer is formed on the surface of the intermediate layer, the surface of the photocatalyst layer becomes golden or iridescent depending on the angle viewed. It is possible to effectively prevent the appearance of so-called interference color.
[0084]
Examples of such easy adhesion treatment include a method of subjecting the intermediate layer surface to corona discharge treatment or UV-ozone treatment.
[0085]
The thicker the photocatalyst layer, the higher the activity, but usually 100 nm to 500 nm is preferable. When the thickness is 500 nm or more, the effect of improving the photocatalytic activity is saturated. On the other hand, when it is less than 100 nm, although the light transmittance is excellent, ultraviolet light used by the photocatalyst is also dropped, so that high activity cannot be expected.
[0086]
In particular, the thickness of the photocatalyst layer is set to 100 nm to 500 nm, and the photocatalyst particle having a crystal particle diameter of 40 nm or less and a specific surface area of 100 m.2When a metal oxide gel or metal hydroxide gel of / g or more is used, the total light transmittance at a total wavelength of 550 nm of the photocatalyst layer and the intermediate layer can be made 70% or more.
[0087]
The carrier 1 used in the photocatalyst structure of the present invention is not limited in its material, shape, etc. as long as it can carry the photocatalyst layer 3 via the intermediate layer 2.
[0088]
The shape of the carrier is not particularly limited as long as the photocatalyst can be supported, and examples thereof include a film shape, a tubular shape, a fiber shape, a net shape, a plate shape, and a curved plate.
[0089]
More specifically, for example, polyolefin resins such as polyethylene and polypropylene, acrylic resins such as polymethyl methacrylate, polymethyl acrylate, and polyethyl methacrylate, polyvinyl chloride, polystyrene, acrylonitrile-butadiene-styrene copolymer ( ABS resin), thermoplastic resins such as polycarbonate, phenolic resin, urea resin, unsaturated polyester, polyurethane, epoxy resin, melamine resin, thermosetting resin such as diallyl phthalate resin, etc., synthesis of polyfluorinated ethylene, silicon resin, etc. Resin films and plates,
[0090]
Ceramic plates such as glass, ceramics, earthenware, enamel, gypsum plates, gypsum slag plates, calcium silicate plates, lightweight foamed concrete plates, hollow extruded cement plates, pulp cement plates, asbestos cement plates, wood chip cement plates, glass fibers Metal plate such as reinforced cement plate, iron plate, aluminum plate, aluminum alloy plate, galvanized steel plate, copper plate, copper alloy plate, stainless steel plate
[0091]
Wood veneer, wood plywood, particle board, MDF (medium density fiber board), etc., kraft paper, coated paper, titanium paper, linter paper, paperboard, gypsum board paper, fine paper, thin paper, paraffin paper, glassine paper Paper such as art paper and sulfuric acid paper, natural fibers such as hair, silk and hemp, recycled fibers such as rayon and acetate, synthesis of nylon, acrylic, polyamide, polyester, polyacrylonitrile, polyvinyl chloride, polyvinylidene chloride, etc. Fiber, fiber glass fiber such as woven fabric, non-woven fabric, knitted fabric made of heat-resistant fiber such as aramid alone or mixed fiber, composite reinforcement transition such as asbestos, potassium titanate fiber, silica fiber, carbon fiber, alumina fiber, phenol Resins such as resin, urea resin, unsaturated polyester, polyurethane, epoxy resin, melamine resin, glass fiber, nonwoven fabric, cloth Paper, so-called FRP plate such complexed impregnated cured in other various fibrous substrates and the like.
[0092]
In addition, it is also possible to use a composite base material in which two or more of the various materials described above are laminated by a known method such as an adhesive or heat fusion.
[0093]
Examples of the article having the photocatalyst carrying structure of the present invention at least in part include interior and exterior materials for buildings such as wallpaper, wall materials, window glass, sashes, and window frames, blinds, curtains, carpets, and showcases. Various interior products such as glasses, glass lenses, windshields, door mirrors, various glass products such as mirrors, lighting equipment, lighting lamps, black lights, televisions, refrigerators, audio equipment, computers, personal computers, printers, facsimiles, and other electrical equipment Daily goods such as tents, umbrellas, tablecloths, furniture such as bags, bookshelves, desks, tables, etc., interior and exterior materials for vehicles such as automobiles, trains, airplanes, ships, etc., agricultural films, herbicidal sheets, seedling sheets, etc. Agricultural and horticultural sheets, food packaging materials and the like can be mentioned.
[0094]
The plastic film provided with the photocatalyst structure of the present invention should be a film in which an acrylic or silicon adhesive is applied to the back surface of a carrier not supporting a photocatalyst, utilizing its antifouling, antibacterial, and deodorizing functions. Thus, it can be attached to the inner surface of a window glass, a freezer / refrigerated showcase, a greenhouse or the like of an automobile or various transportation equipment.
[0095]
And it becomes possible to set it as a highly transparent film effective in decomposition | disassembly of the trace amount organic substance of internal space, prevention of the contamination of the glass surface, and scattering prevention at the time of a failure | damage.
[0096]
Examples of such highly transparent carriers include polyethylene terephthalate, polycarbonate, polyacrylic acid ester, polymethacrylate, polyethylene, polypropylene, polyamide, polyimide, polystyrene, polyvinyl chloride, polyvinylidene fluoride, polytetrafluoroethylene, and ethylene fluoride. -Transparency in which the linear transmittance of light having a wavelength of 550 nm is 50% or more when formed into a film such as a propylene copolymer, a fluorinated ethylene-ethylene copolymer, or an ethylene-vinyl acetate copolymer A high synthetic resin film or sheet can be mentioned.
[0097]
【Example】
Next, the present invention will be described in more detail with reference to examples. The present invention is not limited to the following examples, and within the scope not departing from the gist of the present invention, the material and shape of the carrier, the composition for forming an intermediate layer, the content of the composition for forming a photocatalyst layer, The mixing ratio, the thickness of each layer, and the like can be changed as appropriate.
[0098]
Example 1
An acrylic silicon resin (glass transition temperature 20 ° C.) having a silicon content of 2% in terms of oxide, a partial hydrolysis product of tetramethoxysilane having a polymerization degree of 3 to 6, and having a tetramethoxysilane monomer content of 5 Oligomer and colloidal silica (manufactured by Nissan Chemical Co., Ltd., trade name: IPA-ST) are mixed at a solid weight ratio of 50:40:10, and the solid content concentration is mixed with an ethanol-butanol-ethyl acetate mixed solvent. Was diluted to 10 wt%, and water was further mixed in an amount equivalent to 2 equivalents of tetramethoxysilane oligomer in terms of silicon dioxide molar ratio to obtain an intermediate layer forming composition coating solution.
[0099]
On the other hand, a photocatalytic sol (trade name: STS-01, manufactured by Ishihara Sangyo Co., Ltd., solid content concentration: 30% by weight, average particle diameter: 7 nm), a partial hydrolysis product of tetramethoxysilane having a polymerization degree of 3-6. Oligomer and colloidal silica (particle diameter 20 nm) are mixed at a solid content weight ratio of 30:10:35, diluted with ethanol and water to a solid content of 3% by weight, and a coating solution for the composition for forming a photocatalyst layer. It was.
[0100]
Next, the intermediate layer coating solution prepared above was applied to the surface of a weather-resistant PET film having a size of 70 mm × 70 mm with a bar coater so as to have a dry film thickness of 3 μm, and dried at room temperature for 2 hours on the PET film. An intermediate layer was formed. Then, the coating liquid of the composition for photocatalyst layer formation prepared previously is apply | coated to the intermediate | middle layer surface by the same method (film thickness of 0.5 micrometer), and a transparent photocatalyst carrying film is obtained by drying at room temperature for 24 hours. Produced.
[0101]
Example 2
An acrylic silicon resin having a silicon content of 2% by weight in terms of silicon dioxide, a partial hydrolysis product of tetramethoxysilane having a polymerization degree of 3 to 6, and an oligomer having a tetramethoxysilane monomer content of 5% by weight or less, and Colloidal silica (manufactured by Nissan Chemical Co., Ltd., trade name: IPA-ST) is mixed at a solid content weight ratio of 62: 33: 5 so that the solid content concentration becomes 15% by weight with an ethanol-butanol-ethyl acetate mixed solvent. Dilute to Furthermore, 2 equivalents of silicon dioxide equivalent molar ratio of tetramethoxysilane oligomer and 2% by weight of aluminum trisacetylacetonate and trinormalbutyl borate were mixed with each of tetramethoxysilane oligomer in terms of silicon dioxide equivalent weight, A coating solution for the intermediate layer forming composition was prepared.
[0102]
Further, it is a photocatalytic sol (manufactured by Ishihara Sangyo Co., Ltd., trade name: STS-01, solid content concentration 30% by weight, average particle diameter 7 nm), a partial hydrolysis product of tetramethoxysilane, and a polymerization degree of 3-6. A composition for forming a photocatalyst layer is prepared by mixing an oligomer and colloidal silica (average particle diameter 20 nm) at a solid content weight ratio of 30:10:35 and diluting to 3% by weight with ethanol and water. A coating solution was prepared.
[0103]
Next, the intermediate layer forming composition coating solution prepared above was applied to a soda lime glass substrate with a bar coater so that the dry film thickness was 4 μm, and dried at room temperature for 2 hours to form an intermediate layer. Further, the photocatalyst-supporting glass having a transparent photocatalyst layer is prepared by applying the photocatalyst layer-forming composition coating liquid prepared on the intermediate layer in the same manner (film thickness: 0.3 μm) and drying for 24 hours. A substrate was produced.
[0104]
Reference example 1
An acrylic silicon resin having a silicon content of 2% by weight in terms of oxide, an oligomer that is a partial hydrolysis product of tetramethoxysilane having a polymerization degree of 3 to 6, and colloidal silica (manufactured by Nissan Chemical Co., Ltd., trade name: IPA-ST) is mixed at a solid content weight ratio of 60: 35: 5, diluted with an ethanol-butanol-ethyl acetate mixed solvent to a solid content concentration of 15% by weight, and water is further oxidized to the tetramethoxysilane oligomer. A coating solution of the composition for forming an intermediate layer was prepared by mixing 2 equivalents of the molar ratio in terms of product.
[0105]
In addition, photocatalyst sol (Ishihara Sangyo Co., Ltd., trade name: STS-01, solid content concentration 30 wt%, average particle diameter 7 nm), partial hydrolysis which is an oligomer of tetramethoxysilane having a polymerization degree of 3-6 The product, colloidal silica (average particle size 7 nm), zirconia sol, and alumina sol are mixed at a solid content weight ratio of 20: 15: 40: 4: 1 so that the solid content is 3% by weight using ethanol and water. It diluted and used as the coating liquid of the composition for photocatalyst layer formation.
[0106]
Subsequently, the coating solution of the intermediate layer forming composition previously prepared by a gravure printing machine was applied to a light-resistant PET film having a size of 70 mm × 70 mm so that the film thickness was 2 μm at a coating speed of 50 m / min. Continuous drying at 2 ° C. for 2 minutes. Thereafter, the surface of the intermediate layer is subjected to corona discharge treatment, and the coating solution of the photocatalyst layer forming composition prepared earlier is applied to the intermediate layer surface so that the film thickness becomes 0.5 μm at a coating speed of 50 m / min. The film was continuously dried at 60 ° C. for 2 minutes to obtain a transparent photocatalyst carrying film.
[0107]
Comparative Example 1
A light-resistant PET was prepared in the same manner as in Example 1 except that water was not added to the coating solution for the intermediate layer forming composition in Example 1, except that the coating solution for the intermediate layer forming composition having the same composition as in Example 1 was used. When an intermediate layer was formed on the film surface, a cloudy film was obtained. A photocatalyst layer-forming composition having the same composition as in Example 1 was formed on the surface of the intermediate layer to produce a photocatalyst-supporting film having the same layer structure as shown in FIG.
[0108]
Reference example 2
Other than not performing corona discharge treatmentReference example 1LikeReference example 2A photocatalyst-supporting film was prepared.
[0109]
Evaluation of photocatalytic activity
Examples 1 and 2, Comparative Example 1, and Reference Examples 1 and 2The photocatalyst-supporting film obtained in the above was cut into 7 cm × 7 cm and placed in a 4 L volume Pyrex (registered trademark) glass container. A mixed gas of air and acetaldehyde was added to the container so that the concentration of acetaldehyde was 100 ppm. Next, the UV intensity of the film surface is 2 mW / cm2After irradiation with black light (SL 15B-B, manufactured by Matsushita Electric Industrial Co., Ltd.) for 2 hours, the acetaldehyde gas concentration inside the container was measured by a gas chromatograph, and the photocatalytic activity was evaluated based on the amount of decrease.
[0110]
As a result, in any case, the concentration of acetaldehyde gas inside the container is 20 ppm or less,Examples 1 and 2, Comparative Example 1 and Reference Example 2It was found that any of the photocatalyst-supporting films had excellent photocatalytic activity.
[0111]
Accelerated weathering test
Examples 1 and 2, Comparative Example 1, and Reference Examples 1 and 2Using the sunshine carbon arc weather meter (Suga Test Instruments Co., Ltd. product, WEL-SUN-HCH type), the accelerated weather resistance test was conducted on the photocatalyst-supported film obtained in (1).
[0112]
As a result, in both the films of Example 1 and Example 2, no cracks were observed in the photocatalyst layer after 500 hours, and no interference color was observed. The water contact angle of the photocatalyst layer after the 500-hour accelerated weathering test was 2 ° in Example 1, 2.4 ° in Example 2,Reference example 1The angle was 1.0 °.
[0113]
On the other hand, in the film of Comparative Example 1, cracks were observed on the surface of the photocatalyst layer after the accelerated weathering test for 500 hours, and the haze ratio was 28. Also,Reference example 2In the film of FIG. 1, no cracks were observed on the surface of the photocatalyst layer even after the accelerated weathering test for 500 hours (haze ratio = 2.0), and the contact angle was about 2 ° and the hydrophilicity was maintained. The interference color appeared.
[0114]
From the above results,Examples 1 and 2 and Reference Example 1Each of the photocatalyst-supporting structures has an excellent photocatalytic function and is 500 hours or more.ofAccelerated resistanceWeatherEven after the sex test, no decrease in the function was observed, and no interference color appeared.
[0115]
Storage stability test of intermediate layer forming composition
Even when the composition for forming an intermediate layer prepared in Example 1 was stored at room temperature for 3 months, no insoluble matter was observed and no increase in viscosity was observed. Therefore, it was found that the intermediate layer forming composition of Example 1 was excellent in storage stability.
[0116]
【The invention's effect】
As described above, the present invention is a photocatalyst-supporting structure in which an intermediate layer is provided between a carrier and a photocatalyst layer, and (1) excellent adhesion between the carrier and the photocatalyst layer. The intermediate layer is difficult to be decomposed by the photocatalyst, (3) there is no so-called interference color, and (4) the surface does not crack.
[0117]
According to the method for producing a photocatalyst-supporting structure of the present invention, the intermediate layer can be formed by applying the intermediate layer-forming composition to the surface of the carrier and then drying it at room temperature. Therefore, after forming the intermediate layer on the surface of the sheet-like carrier, so-called blocking does not occur in the step of winding the sheet. In addition, since so-called on-site coating is possible, production efficiency (working efficiency) is greatly improved.
[0118]
Moreover, the composition for intermediate layer formation of this invention is excellent in long-term storage stability.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view of a photocatalyst carrying structure of the present invention.
[Explanation of symbols]
1 ... support, 2 ... intermediate layer, 3 ... photocatalyst layer
Claims (19)
（Ａ）成分：アクリルシリコン樹脂又はエポキシシリコン樹脂を固形分として０．５〜２０重量％；
（Ｂ）成分：金属酸化物ゾル及び／又は金属水酸化物のゾルを固形分として０．２５〜４重量％；
（Ｃ）成分：テトラアルコキシシランの１種又は２種以上の部分加水分解生成物であって、その平均重合度３〜１０であり、テトラアルコキシシランモノマーの含有量が５重量％以下であるシリコン化合物を二酸化ケイ素に換算した固形分として０．２５〜２０重量％；
（Ｄ）成分；二酸化ケイ素に換算した固形前記シリコン化合物の０．５〜３倍モル当量の水；
（Ｅ）成分：金属酸化物ゾル及び／又は金属水酸化物ゾル；（Ｆ）成分：光触媒の粒子及び／又はゾル；
（Ｇ）成分：シリコン化合物；An intermediate layer forming composition containing at least the following components (A), (B), (C) and (D) is applied to the surface of the carrier and dried at 10 to 35 ° C. for 0.5 to 72 hours. Applying the composition for forming a photocatalyst layer containing at least the following components (E), (F) and (G) on the surface of the intermediate layer and drying at 10 to 40 ° C. And a step of forming a photocatalyst layer by a method for producing a photocatalyst-supporting structure.
Component (A): 0.5-20% by weight of acrylic silicon resin or epoxy silicon resin as a solid content;
Component (B): 0.25 to 4% by weight of metal oxide sol and / or metal hydroxide sol as solid content;
Component (C): Silicon that is one or more partial hydrolysis products of tetraalkoxysilane, having an average degree of polymerization of 3 to 10, and a tetraalkoxysilane monomer content of 5% by weight or less 0.25 to 20% by weight as a solid content of the compound converted to silicon dioxide;
Component (D): 0.5 to 3 times the molar equivalent of water of the solid silicon compound converted to silicon dioxide;
(E) component: metal oxide sol and / or metal hydroxide sol; (F) component: photocatalyst particles and / or sol;
(G) component: silicon compound;
（Ａ）成分：アクリルシリコン樹脂又はエポキシシリコン樹脂を固形分として０．５〜２０重量％；
（Ｂ）成分：金属酸化物ゾル及び／又は金属水酸化物のゾルを固形分として０．２５〜４重量％；
（Ｃ）成分：テトラアルコキシシランの１種又は２種以上の部分加水分解生成物であって、その平均重合度３〜１０であり、テトラアルコキシシランモノマーの含有量が５重量％以下であるシリコン化合物を二酸化ケイ素に換算した固形分として０．２５〜２０重量％；
（Ｄ）成分：二酸化ケイ素に換算した固形前記シリコン化合物の０．５〜３倍モル当量の水；The resin composition for intermediate | middle layer formation of the photocatalyst support structure formed by forming a photocatalyst layer through an intermediate | middle layer on a support | carrier containing the following (A), (B), (C) and (D) component .
Component (A): 0.5-20% by weight of acrylic silicon resin or epoxy silicon resin as a solid content;
Component (B): 0.25 to 4% by weight of metal oxide sol and / or metal hydroxide sol as solid content;
Component (C): Silicon that is one or more partial hydrolysis products of tetraalkoxysilane, having an average degree of polymerization of 3 to 10, and a tetraalkoxysilane monomer content of 5% by weight or less 0.25 to 20% by weight as a solid content of the compound converted to silicon dioxide;
(D) component: 0.5-3 times molar equivalent of water of the solid silicon compound converted to silicon dioxide;
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| JP2004067947A (en) * | 2002-08-08 | 2004-03-04 | Nippon Soda Co Ltd | Coating liquid for forming photocatalytic layer and photocatalyst carrying structure |
| JP4660766B2 (en) * | 2006-02-22 | 2011-03-30 | 独立行政法人物質・材料研究機構 | Visible light responsive complex oxide photocatalyst |
| BRPI0717926B1 (en) * | 2006-11-09 | 2021-11-30 | Akzo Nobel Chemicals International B.V. | METHOD OF PRODUCING AN AQUEOUS DISPERSION OF PIGMENT FREE OF AN ORGANIC BINDER, AQUEOUS DISPERSION OF PIGMENT FREE OF AN ORGANIC BINDER, AND USE OF A DISPERSION |
| JP2008126153A (en) * | 2006-11-21 | 2008-06-05 | Matsushita Electric Works Ltd | Antifouling coated article |
| WO2008081589A1 (en) * | 2006-12-28 | 2008-07-10 | Nippon Soda Co., Ltd. | Photocatalyst-supporting structure |
| US7919425B2 (en) | 2008-03-26 | 2011-04-05 | Toto Ltd. | Photocatalyst-coated body and photocatalytic coating liquid for the same |
| JP5192187B2 (en) * | 2007-06-12 | 2013-05-08 | 東邦チタニウム株式会社 | Composition for forming adhesive layer for photocatalyst film, adhesive layer for photocatalyst film, method for forming adhesive layer for photocatalyst film, and photocatalyst structure |
| JP5122925B2 (en) * | 2007-11-30 | 2013-01-16 | ケイミュー株式会社 | Painted body |
| JP5063436B2 (en) * | 2008-03-27 | 2012-10-31 | 株式会社きもと | Photocatalyst sheet, primer composition for photocatalyst |
| JP5170752B2 (en) * | 2008-04-25 | 2013-03-27 | 国立大学法人静岡大学 | Photocatalyst, photocatalytic functional member, and method for producing hydrogen |
| JP2010005610A (en) * | 2008-05-27 | 2010-01-14 | Toto Ltd | Article coated with photocatalyst |
| US7846866B2 (en) | 2008-09-09 | 2010-12-07 | Guardian Industries Corp. | Porous titanium dioxide coatings and methods of forming porous titanium dioxide coatings having improved photocatalytic activity |
| US8647652B2 (en) | 2008-09-09 | 2014-02-11 | Guardian Industries Corp. | Stable silver colloids and silica-coated silver colloids, and methods of preparing stable silver colloids and silica-coated silver colloids |
| CN102159317B (en) * | 2008-09-16 | 2014-04-16 | 株式会社东芝 | Hydrophilic films and components and structures using same |
| US20100112359A1 (en) * | 2008-11-03 | 2010-05-06 | Sharma Pramod K | Titanium dioxide coatings having barrier layers and methods of forming titanium dioxide coatings having barrier layers |
| US8545899B2 (en) | 2008-11-03 | 2013-10-01 | Guardian Industries Corp. | Titanium dioxide coatings having roughened surfaces and methods of forming titanium dioxide coatings having roughened surfaces |
| CN104759297B (en) * | 2010-07-29 | 2018-02-23 | Toto株式会社 | Object with photo-catalyst coating and photocatalyst coating liquid |
| JP2012086104A (en) * | 2010-10-15 | 2012-05-10 | Asahi Kasei Chemicals Corp | Photocatalyst composition |
| JP5884271B2 (en) * | 2011-02-09 | 2016-03-15 | 大日本印刷株式会社 | Wallpaper with visible light photocatalytic function |
| KR101700075B1 (en) * | 2011-11-25 | 2017-01-26 | 닛뽕소다 가부시키가이샤 | Photocatalyst-supporting structure |
| JP2017145355A (en) * | 2016-02-19 | 2017-08-24 | 大日本塗料株式会社 | Two-liquid aqueous undercoating composition, coated body, and method for producing the same |
| CN117255744A (en) * | 2021-06-25 | 2023-12-19 | 日本制铁株式会社 | Coated metal plate |
| CN116159596B (en) * | 2023-02-24 | 2024-05-14 | 无锡威孚环保催化剂有限公司 | Forming method of corrugated base material |
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| JPH09310039A (en) * | 1996-05-21 | 1997-12-02 | Nippon Soda Co Ltd | Photocatalyst coating agent |
| JPH1067543A (en) * | 1996-06-18 | 1998-03-10 | Toto Ltd | Photocatalytic hydrophilic parts material |
| JP3702927B2 (en) * | 1997-08-04 | 2005-10-05 | 株式会社ブリヂストン | Computer display |
| JPH1191030A (en) * | 1997-09-25 | 1999-04-06 | Toto Ltd | Hydrophilic member with photocatalystic property |
| JPH11267518A (en) * | 1997-11-07 | 1999-10-05 | Nippon Soda Co Ltd | Photocatalyst-supporting thermoplastic resin molding |
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