JP7151509B2 - Photocatalyst coated body - Google Patents
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- JP7151509B2 JP7151509B2 JP2019010990A JP2019010990A JP7151509B2 JP 7151509 B2 JP7151509 B2 JP 7151509B2 JP 2019010990 A JP2019010990 A JP 2019010990A JP 2019010990 A JP2019010990 A JP 2019010990A JP 7151509 B2 JP7151509 B2 JP 7151509B2
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- photocatalyst
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- coated body
- cerium oxide
- resin
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- 239000011941 photocatalyst Substances 0.000 title claims description 55
- 229920005989 resin Polymers 0.000 claims description 36
- 239000011347 resin Substances 0.000 claims description 36
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 25
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 24
- 230000000694 effects Effects 0.000 claims description 17
- 239000008199 coating composition Substances 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 11
- 230000001699 photocatalysis Effects 0.000 claims description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 8
- 239000010954 inorganic particle Substances 0.000 claims description 7
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 6
- 238000000354 decomposition reaction Methods 0.000 claims description 6
- 238000000691 measurement method Methods 0.000 claims description 6
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 6
- 239000001023 inorganic pigment Substances 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 67
- 238000012360 testing method Methods 0.000 description 29
- 239000002245 particle Substances 0.000 description 16
- 229920001296 polysiloxane Polymers 0.000 description 15
- 239000000758 substrate Substances 0.000 description 13
- 239000002585 base Substances 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 229910044991 metal oxide Inorganic materials 0.000 description 8
- 150000004706 metal oxides Chemical class 0.000 description 8
- 239000006096 absorbing agent Substances 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 230000006866 deterioration Effects 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 239000002612 dispersion medium Substances 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000010422 painting Methods 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 239000002562 thickening agent Substances 0.000 description 4
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000008119 colloidal silica Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 3
- 239000004611 light stabiliser Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 3
- 229910052912 lithium silicate Inorganic materials 0.000 description 3
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- -1 polysiloxane Polymers 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229920002050 silicone resin Polymers 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 239000004111 Potassium silicate Substances 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000003373 anti-fouling effect Effects 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 2
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 2
- 229910052913 potassium silicate Inorganic materials 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- VMRIVYANZGSGRV-UHFFFAOYSA-N 4-phenyl-2h-triazin-5-one Chemical compound OC1=CN=NN=C1C1=CC=CC=C1 VMRIVYANZGSGRV-UHFFFAOYSA-N 0.000 description 1
- 241000972756 Boronia Species 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 241000588731 Hafnia Species 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- HGAZMNJKRQFZKS-UHFFFAOYSA-N chloroethene;ethenyl acetate Chemical compound ClC=C.CC(=O)OC=C HGAZMNJKRQFZKS-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 1
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Description
本発明は、建築物等の外装用途に適した光触媒塗装体に関する。 TECHNICAL FIELD The present invention relates to a photocatalyst-coated body suitable for exterior applications such as buildings.
光触媒層を基材の上に設けるにあたり、基材との密着性や光触媒による劣化を防ぐために、中間層を設けることが行われている。例えば、特開２００１－２５９４３２号公報（特許文献１）には、光触媒による分解され難い材質であるポリシロキサンやシリコーン樹脂を中間層に用いることが記載されている。 When a photocatalyst layer is provided on a base material, an intermediate layer is provided in order to prevent deterioration due to adhesion to the base material and photocatalyst. For example, Japanese Patent Application Laid-Open No. 2001-259432 (Patent Document 1) describes the use of an intermediate layer made of polysiloxane or silicone resin, which is a material that is difficult to decompose with a photocatalyst.
一方で、上記のポリシロキサンやシリコーン樹脂は汎用性が低く高価であることや、製造工程を簡素化してコストを下げるために、中間層を省略する技術も提案されている。例えば、特開２００８－２６４７４７号公報（特許文献２）には、光触媒層中の光触媒濃度を１～２０％程度と比較的低くすることで、中間層を設けることなく有機基材に直接光触媒層を形成可能な光触媒コーティング液および塗装体が開示されている。光触媒濃度を下げれば光触媒活性は低くなるが、このような活性の低下を防ぐために特許文献２は、光触媒層を主として粒子成分とすることで、有害ガスの透過性を高め、光触媒粒子への接触機会を上げて、ガス分解性を確保している。 On the other hand, the above-mentioned polysiloxane and silicone resin have low versatility and are expensive, and in order to simplify the manufacturing process and reduce the cost, a technique of omitting the intermediate layer has been proposed. For example, Japanese Patent Application Laid-Open No. 2008-264747 (Patent Document 2) discloses that the photocatalyst concentration in the photocatalyst layer is relatively low at about 1 to 20%, so that the photocatalyst layer is directly applied to the organic substrate without providing an intermediate layer. A photocatalytic coating solution and coated body capable of forming a are disclosed. Lowering the photocatalyst concentration lowers the photocatalytic activity, but in order to prevent such a decline in activity, Patent Document 2 discloses that the photocatalyst layer is mainly made of particles to increase the permeability of harmful gases and prevent contact with the photocatalyst particles. Taking the opportunity, gas decomposability is ensured.
さらに、塗料の技術分野にあっては、塗膜の耐候性を高める、すなわち劣化防止のために、紫外線吸収剤を添加することが広く行われている。紫外線吸収剤としては、有機系および無機系の材料があり、無機系の紫外線吸収剤としては、酸化セリウムが知られている。例えば、特許文献１の段落００５２、００５３に例示がされているが、当該特許文献において酸化セリウムを実際に用いた実施例の記載はない。 Furthermore, in the technical field of paints, it is widely practiced to add an ultraviolet absorber to improve the weather resistance of the paint film, that is, to prevent deterioration. UV absorbers include organic and inorganic materials, and cerium oxide is known as an inorganic UV absorber. Examples are given in paragraphs 0052 and 0053 of Patent Document 1, for example, but there is no description of examples in which cerium oxide is actually used in the patent document.
本発明者らは、今般、従来紫外線吸収剤として知られていた酸化セリウムが、それが有する紫外線吸収作用では説明できない現象として、光触媒塗装体の耐候性を向上させるとの知見を得た。本発明は係る知見に基づくものである。 The present inventors have recently found that cerium oxide, which has been conventionally known as an ultraviolet absorber, improves the weather resistance of photocatalyst-coated bodies, a phenomenon that cannot be explained by its ultraviolet absorption action. The present invention is based on such findings.
したがって、本発明は、耐候性に優れた光触媒塗装体の提供をその目的としている。 Accordingly, an object of the present invention is to provide a photocatalyst-coated article having excellent weather resistance.
そして、本発明による光触媒塗装体は、
基材と、前記基材の表面に、有機樹脂を含む第１層と、当該第１層に接して設けられた光触媒を含む第２層とを備えてなり、
前記第１層が、酸化セリウム（ＣｅＯ２）をさらに含んでなり、
前記第２層が、ＪＩＳ Ｒ １７０３－２：２０１４に規定されたメチレンブルー分解活性測定法にて定められる光触媒活性値として５ｎｍｏｌ／Ｌ／ｍｉｎ以上３０ｎｍｏｌ／Ｌ／ｍｉｎ以下を有するものである。
And the photocatalyst-coated body according to the present invention is
A base material, a first layer containing an organic resin on the surface of the base material, and a second layer containing a photocatalyst provided in contact with the first layer,
wherein the first layer further comprises cerium oxide (CeO 2 );
The second layer has a photocatalytic activity value of 5 nmol/L/min or more and 30 nmol/L/min or less as determined by the methylene blue decomposition activity measurement method specified in JIS R 1703-2:2014.
本発明による光触媒塗装体
本発明による光触媒塗装体は、基材の表面に、有機樹脂を含む第１層と、当該第１層に接して設けられた光触媒を含む第２層とを備えてなる基本構成を有し、第１層が酸化セリウム（ＣｅＯ２）をさらに含んでなり、かつ記第２層の光触媒活性が、ＪＩＳ Ｒ １７０３－２：２０１４に規定されたメチレンブルー分解活性測定法にて定められる値で５ｎｍｏｌ／Ｌ／ｍｉｎ以上３０ｎｍｏｌ／Ｌ／ｍｉｎ以下、好ましくは５ｎｍｏｌ／Ｌ／ｍｉｎ以上２３ｎｍｏｌ／Ｌ／ｍｉｎ以下と比較的高い活性を備えるものである。本発明による光触媒塗装体は、このような構成を備えることで、長期間にわたり光触媒活性を維持しながら、優れた耐候性を示す。具体的には、本発明による光触媒塗装体は、長期間にわたり、光触媒層が安定に基材に密着し、剥離したりせず、また変退色する等の劣化も生じ難いとの効果を備える。したがって、例えば、建築物等の外装用途に好ましく用いられる。
Photocatalyst-coated body according to the present invention A photocatalyst-coated body according to the present invention comprises a first layer containing an organic resin and a second layer containing a photocatalyst provided in contact with the first layer on the surface of a substrate. It has a basic configuration, the first layer further contains cerium oxide (CeO 2 ), and the photocatalytic activity of the second layer is determined by the methylene blue decomposition activity measurement method specified in JIS R 1703-2: 2014. It has a relatively high activity of 5 nmol/L/min or more and 30 nmol/L/min or less, preferably 5 nmol/L/min or more and 23 nmol/L/min or less. The photocatalyst-coated body according to the present invention exhibits excellent weather resistance while maintaining photocatalytic activity for a long period of time by providing such a configuration. Specifically, the photocatalyst-coated body according to the present invention has the effect that the photocatalyst layer stably adheres to the substrate for a long period of time, does not peel off, and is less susceptible to deterioration such as discoloration or fading. Therefore, for example, it is preferably used for exterior applications such as buildings.
本発明にあっては、酸化セリウムの存在が主にこの優れた耐候性の発現を生じさせているものと考えられる。酸化セリウムは、紫外線吸収作用を有するものとして公知であるが、本発明による優れた耐候性は、酸化セリウムが有する紫外線吸収作用では説明できない現象である。それは、紫外線吸収剤として酸化セリウムと同程度である従来公知の紫外線吸収剤によっては、本発明によるような顕著な耐候性の改善が見られなかった事実により明らかにされる。このような酸化セリウムの作用効果は、当業者にとり意外なものであったと言える。 In the present invention, the presence of cerium oxide is considered to be the main cause of the development of this excellent weather resistance. Cerium oxide is known to have an ultraviolet absorbing effect, but the excellent weather resistance of the present invention is a phenomenon that cannot be explained by the ultraviolet absorbing effect of cerium oxide. This is clarified by the fact that conventionally known UV absorbers, which are equivalent to cerium oxide as UV absorbers, do not exhibit such remarkable improvement in weather resistance as the present invention. It can be said that such effects of cerium oxide were unexpected for those skilled in the art.
基材
本発明に用いる基材は、その上に有機樹脂を含む第１層が形成可能な材料であれば無機材料、有機材料を問わず種々の材料であってよく、その形状も限定されない。材料の観点からみた基材の好ましい例としては、金属、セラミック、ガラス、プラスチック、ゴム、石、セメント、コンクリ－ト、繊維、布帛、木、紙、それらの組合せ、それらの積層体、それらの表面に少なくとも一層の被膜を有するものが挙げられる。用途の観点からみた基材の好ましい例としては、建材、建物外装、窓枠、窓ガラス、構造部材、乗物の外装及び塗装、機械装置や物品の外装、防塵カバー及び塗装、交通標識、各種表示装置、広告塔、道路用遮音壁、鉄道用遮音壁、橋梁、ガードレ－ルの外装及び塗装、トンネル内装及び塗装、碍子、太陽電池カバー、太陽熱温水器集熱カバー、ビニールハウス、車両用照明灯のカバー、屋外用照明器具、台及び上記物品表面に貼着させるためのフィルム、シート、シール等といった外装材全般が挙げられる。
Substrate The substrate used in the present invention may be any material, whether inorganic or organic, as long as the first layer containing an organic resin can be formed thereon, and its shape is not limited. Preferred examples of substrates from the viewpoint of materials include metals, ceramics, glass, plastics, rubber, stone, cement, concrete, fibers, fabrics, wood, paper, combinations thereof, laminates thereof, and laminates thereof. Examples include those having at least one layer of coating on the surface. Preferable examples of the substrate from the viewpoint of use include building materials, building exteriors, window frames, window glass, structural members, exteriors and coatings of vehicles, exteriors of machinery and articles, dustproof covers and coatings, traffic signs, and various displays. Equipment, advertising towers, sound insulation walls for roads, sound insulation walls for railways, bridges, exterior and painting of guardrails, interior and painting of tunnels, insulators, solar cell covers, solar water heater heat collection covers, vinyl houses, vehicle lighting covers , outdoor lighting fixtures, stands, and exterior materials in general such as films, sheets, seals, etc. to be adhered to the surfaces of the articles.
有機樹脂を含む第１層
本発明において、有機樹脂を含む第１層は、基材と光触媒層である第２層との間に設けられ、光触媒による基材の劣化を防止する保護層としての機能を有するものである。また、付随的に、基材表面を意匠的に修飾するものであってもよい。
First Layer Containing Organic Resin In the present invention, the first layer containing an organic resin is provided between the base material and the second layer, which is a photocatalyst layer, and serves as a protective layer for preventing deterioration of the base material due to the photocatalyst. It has a function. In addition, the surface of the base material may be additionally modified in design.
本発明において、第１層を構成する有機樹脂は、基材との密着性が確保され、それに接して光触媒層を設けることができるものである限り特に限定されないが、例えば、フッ素樹脂、シリコーン、アクリルシリコーン、酢酸ビニル、酢酸ビニルアクリル、アクリルウレタン、アクリル、エポキシ、塩化ビニル酢酸ビニル、塩化ビニリデン、ＳＢＲ、アルキド、メラミン、ポリエステル、ナイロン、ポリオレフィン、ポリカーボネート等が挙げられる。 In the present invention, the organic resin that constitutes the first layer is not particularly limited as long as it ensures adhesion to the substrate and allows a photocatalyst layer to be provided in contact therewith. Examples include fluororesin, silicone, acrylic silicone, vinyl acetate, vinyl acetate acrylic, acrylic urethane, acrylic, epoxy, vinyl chloride vinyl acetate, vinylidene chloride, SBR, alkyd, melamine, polyester, nylon, polyolefin, polycarbonate and the like.
さらに、本発明の別の態様によれば、有機樹脂は、水分散体、エマルション、ディスパージョン等の組成物の形態で基材に適用されて第１層とされてもよい。したがって、本発明において、有機樹脂を含む第１層の形成方法は特に限定されないが、有機樹脂を含む塗料またはコーティング組成物を適宜基材に塗布することで形成されてよい。また、有機樹脂を溶媒に分散せた分散体を形成し、それを基材に適用してもよい。 Further, according to another aspect of the present invention, the organic resin may be applied to the substrate as a first layer in the form of a composition such as an aqueous dispersion, emulsion, dispersion, or the like. Therefore, in the present invention, the method of forming the first layer containing the organic resin is not particularly limited, but it may be formed by appropriately applying a paint or coating composition containing the organic resin to the substrate. Alternatively, a dispersion may be formed by dispersing the organic resin in a solvent and applied to the substrate.
本発明の一つの態様によれば、第１層の有機樹脂を、必ずしも、分解され難い材質であるポリシロキサンやシリコーン樹脂などシリコーン系の樹脂で構成しなくともよいとの利点が得られる。本発明にあっては、シリコーン系の樹脂の利用を排除するものではないが、本発明の一つの態様によれば、Ｓｉを含まないか、含むとしても含有量が２重量％未満の樹脂を利用することができ、したがって、広範な樹脂の利用が可能であって汎用性の極めて高い技術である。 According to one aspect of the present invention, there is an advantage that the organic resin of the first layer does not necessarily have to be composed of a silicone-based resin such as polysiloxane or silicone resin, which is a material that is difficult to decompose. In the present invention, the use of silicone-based resins is not excluded, but according to one aspect of the present invention, a resin containing no Si or containing less than 2% by weight of Si is used. It is an extremely versatile technology that can be used and therefore can be used with a wide range of resins.
本発明において、有機樹脂を含む第１層は、酸化セリウムを含んでなる。酸化セリウムは、有機樹脂を含む第１層に添加可能である限り、その形態は特に限定されないが、好ましくは、水に分散されたゾルの形態で上記した有機樹脂の組成物に添加される。 In the present invention, the first layer containing organic resin contains cerium oxide. The form of cerium oxide is not particularly limited as long as it can be added to the first layer containing the organic resin, but it is preferably added to the organic resin composition in the form of a sol dispersed in water.
酸化セリウムの第１層への添加量は、その添加の効果が奏される限り特に限定されないが、例えば、樹脂固形分に対して０．３重量％～１０重量％の範囲で添加されることが好ましく、より好ましくは０．３重量％～３重量％の範囲で添加される。 The amount of cerium oxide to be added to the first layer is not particularly limited as long as the effect of the addition is exhibited. is preferred, and more preferably in the range of 0.3 wt% to 3 wt%.
本発明の一つの態様によれば、第１層は無機顔料、無機粒子を含むことが出来る。無機顔料は体質顔料として、または着色顔料として添加される。また、無機粒子は、凹凸表面形成するため、あるいは光沢制御のため、あるいは充填剤として添加され、例えば珪砂を用いることができる。 According to one aspect of the invention, the first layer can contain inorganic pigments, inorganic particles. Inorganic pigments are added as extender pigments or as color pigments. Inorganic particles are added to form an uneven surface, to control gloss, or as a filler, and silica sand, for example, can be used.
本発明において第１層の膜厚は特に限定されるものでは無いが、好ましくは１μｍ～２００μｍ、より好ましくは５μｍ～１００μｍである。 Although the film thickness of the first layer is not particularly limited in the present invention, it is preferably 1 μm to 200 μm, more preferably 5 μm to 100 μm.
本発明において第１層の形成方法は、基材に安定した層を形成可能である限り特に限定されないが、例えば、有機樹脂と酸化セリウムを含むコーティング組成物を用意し、これを基材に適用して固化、乾燥させることにより形成されてよい。コーティング組成物の適用方法として、適宜選択されてよく、例えば、ローラー、スプレー、ロールコーター、フローコーター、ディップコート、流し塗り、スクリーン印刷、電着、蒸着等の方法を利用できる。 In the present invention, the method for forming the first layer is not particularly limited as long as a stable layer can be formed on the base material. For example, a coating composition containing an organic resin and cerium oxide is prepared and applied to the base material. may be formed by solidifying and drying. A method for applying the coating composition may be selected as appropriate, and for example, methods such as roller, spray, roll coater, flow coater, dip coat, flow coating, screen printing, electrodeposition, and vapor deposition can be used.
光触媒を含む第２層
本発明において、第２層は光触媒層であって、既に公知の光触媒層であってよいが、その活性は、ＪＩＳ Ｒ １７０３－２：２０１４に規定されたメチレンブルー分解活性測定法にて定められる値で５ｎｍｏｌ／Ｌ／ｍｉｎ以上であると十分な活性を有し、実用的な防汚性を有し、１０ｎｍｏｌ／Ｌ／ｍｉｎ以上であるとさらに高い防汚性を備えるものである。
Second Layer Containing Photocatalyst In the present invention, the second layer is a photocatalyst layer, which may be a known photocatalyst layer. If it is 5 nmol/L/min or more, which is the value specified by law, it has sufficient activity and has practical antifouling properties, and if it is 10 nmol/L/min or more, it has even higher antifouling properties. is.
本発明において、第２層を構成する光触媒は、光触媒として使用可能なものであれば限定されないが、酸化チタンが好ましく用いられる。本発明において、酸化チタンは粉末状、ゾル状、溶液状など様々な形態で入手可能であるが、光触媒活性を示すものであれば、いずれの形態でも使用可能である。本発明の好ましい態様によれば、光触媒粒子が１０ｎｍ以上１００ｎｍ以下の平均粒径を有するのが好ましく、より好ましくは１０ｎｍ以上６０ｎｍ以下である。この範囲内であると、耐候性、有害ガス分解性、および所望の各種被膜特性（紫外線吸収性、透明性、膜強度等）が効率良く発揮される。また、ゾル状で市販されている光触媒を用い、粒子径を３０ｎｍ以下、好ましくは２０ｎｍ以下にすることによって、透明性が良好な光触媒層を得ることが可能である。 In the present invention, the photocatalyst constituting the second layer is not limited as long as it can be used as a photocatalyst, but titanium oxide is preferably used. In the present invention, titanium oxide is available in various forms such as powder, sol, and solution, and any form can be used as long as it exhibits photocatalytic activity. According to a preferred embodiment of the present invention, the photocatalyst particles preferably have an average particle size of 10 nm or more and 100 nm or less, more preferably 10 nm or more and 60 nm or less. Within this range, weather resistance, decomposability of harmful gases, and various desired film properties (ultraviolet absorption, transparency, film strength, etc.) are efficiently exhibited. Moreover, a photocatalyst layer with good transparency can be obtained by using a commercially available sol photocatalyst and adjusting the particle size to 30 nm or less, preferably 20 nm or less.
本発明において、光触媒の粒径は、走査型電子顕微鏡により２０万倍の視野に入る任意の１００個の粒子の長さを測定した個数平均値として算出される。粒子の形状としては真球が最も好ましいが、略円形や楕円形でも好ましく、その場合の粒子の長さは（（長径＋短径）／２）として略算出される。 In the present invention, the particle size of the photocatalyst is calculated as the number average value obtained by measuring the length of arbitrary 100 particles entering a 200,000-fold field of view with a scanning electron microscope. As for the shape of the particles, a true sphere is most preferable, but a substantially circular or elliptical shape is also preferable.
本発明において第２層は、安定かつＪＩＳ Ｒ １７０３－２：２０１４に規定されたメチレンブルー分解活性測定法にて定められる値で５ｎｍｏｌ／Ｌ／ｍｉｎ以上３０ｎｍｏｌ／Ｌ／ｍｉｎ以下の活性の光触媒層が形成可能である限り特に限定されないが、例えば、光触媒を含むコーティング組成物を用意し、第１層の上に適用して、固化、乾燥させることにより形成されてよい。コーティング組成物の適用方法として、適宜選択されてよく、例えば、ローラー、スプレー、ロールコーター、フローコーター、ディップコート、流し塗り、スクリーン印刷、電着、蒸着等の方法を利用できる。 In the present invention, the second layer is a photocatalyst layer that is stable and active at a value determined by the methylene blue decomposition activity measurement method specified in JIS R 1703-2:2014 of 5 nmol / L / min or more and 30 nmol / L / min or less. Although it is not particularly limited as long as it can be formed, for example, it may be formed by preparing a coating composition containing a photocatalyst, applying it on the first layer, solidifying it, and drying it. A method for applying the coating composition may be selected as appropriate, and for example, methods such as roller, spray, roll coater, flow coater, dip coat, flow coating, screen printing, electrodeposition, and vapor deposition can be used.
第２層の膜厚は特に限定されるものでは無いが好ましくは０．１μｍ～３μｍ、より好ましくは０．５μｍ～１．５μｍである。 Although the film thickness of the second layer is not particularly limited, it is preferably 0.1 μm to 3 μm, more preferably 0.5 μm to 1.5 μm.
本発明の好ましい態様によれば、第２層は無機粒子を含む。無機粒子としては、シリカ、アルミナ、ジルコニア、セリア、イットリア、ボロニア、マグネシア、カルシア、フェライト、無定型チタニア、ハフニア等の単一酸化物に加え、チタン酸バリウム、ケイ酸カルシウム等の複合酸化物が使用可能であり、シリカ粒子が好適に利用できる。これら無機酸化物は、水を分散媒とした水性コロイド、またはエチルアルコール、イソプロピルアルコールまたはエチレングリコールなどの親水性溶媒にコロイド状に分散させたオルガノゾルの形態が好ましく、特に、コロイダルシリカの利用が好ましい。無機粒子の粒径は、水性コロイドまたはオルガノゾルの形態とされたときの平均粒径が１０ｎｍ以上４０ｎｍ未満であれば好ましく、より好ましくは１０ｎｍ以上３０ｎｍ以下である。 According to a preferred embodiment of the invention, the second layer contains inorganic particles. Inorganic particles include single oxides such as silica, alumina, zirconia, ceria, yttria, boronia, magnesia, calcia, ferrite, amorphous titania, and hafnia, as well as complex oxides such as barium titanate and calcium silicate. can be used, and silica particles can be preferably used. These inorganic oxides are preferably in the form of aqueous colloids using water as a dispersion medium, or organosols in which they are colloidally dispersed in a hydrophilic solvent such as ethyl alcohol, isopropyl alcohol or ethylene glycol, and the use of colloidal silica is particularly preferred. . The particle size of the inorganic particles is preferably 10 nm or more and less than 40 nm, more preferably 10 nm or more and 30 nm or less, when the inorganic particles are in the form of aqueous colloid or organosol.
ここで、平均粒径は、走査型電子顕微鏡により２０万倍の視野に入る任意の１００個の粒子の長さを測定した個数平均値として算出される。粒子の形状としては真球が最も好ましいが、略円形や楕円形でも好ましく、その場合の粒子の長さは（（長径＋短径）／２）として略算出される。 Here, the average particle diameter is calculated as a number average value obtained by measuring the length of arbitrary 100 particles entering a 200,000-fold field of view with a scanning electron microscope. As for the shape of the particles, a true sphere is most preferable, but a substantially circular or elliptical shape is also preferable.
また、水溶性無機非晶質物質を含むことができ、その例としては、アルカリ珪酸塩、アルカリホウ珪酸塩、アルカリジルコン酸塩、およびアルカリリン酸塩等のリン酸金属塩からなる群から選択される一種以上を含んでなるものが挙げられる。これらの物質は水の存在により容易に化学吸着水層を形成し、高度かつ長期的にわたって親水性を呈すことができる。これらの中でもアルカリ珪酸塩が好ましく、より好ましくは、珪酸ナトリウム、珪酸カリウム、珪酸リチウム、珪酸アンモニウムの少なくとも１つ以上が挙げられる。一般に接着性は珪酸ナトリウム、珪酸カリウムの順に強く、耐水性は珪酸アンモニウム、珪酸リチウムの順に強いと考えられるが、被膜性、膜硬度、耐水性等を考慮すると珪酸リチウムを含むのがより好ましい。 It may also contain water-soluble inorganic amorphous materials, examples of which are selected from the group consisting of metal phosphates such as alkali silicates, alkali borosilicates, alkali zirconates, and alkali phosphates. and those containing one or more of the These substances can easily form a chemisorbed water layer in the presence of water and can exhibit high hydrophilicity over a long period of time. Among these, alkali silicates are preferred, and at least one of sodium silicate, potassium silicate, lithium silicate and ammonium silicate is more preferred. In general, sodium silicate and potassium silicate have the highest adhesiveness, and ammonium silicate and lithium silicate have the highest water resistance. Considering film properties, film hardness, water resistance, etc., lithium silicate is more preferable.
また、その他の無機バインダーを含んでもよく、例えば、加水分解性シリコーン等が挙げられる。加水分解性シリコーンとは、アルコキシ基を有するオルガノシロキサンおよび／またはその部分加水分解縮合物の総称である。加水分解性シリコーンとしては、４官能シリコーン化合物がよく使用され、例えば、エチルシリケート４０（オリゴマー、Ｒがエチル基）、エチルシリケート４８（オリゴマー、Ｒがエチル基）メチルシリケート５１（オリゴマー、Ｒがメチル基）（いずれもコルコート社製）の形で市販されている。 In addition, other inorganic binders may be included, such as hydrolyzable silicone. Hydrolyzable silicone is a general term for organosiloxanes having alkoxy groups and/or partial hydrolysis condensates thereof. As the hydrolyzable silicone, tetrafunctional silicone compounds are often used. base) (both manufactured by Colcoat).
本発明において、第２層およびコーティング組成物における光触媒粒子の含有量は、光触媒粒子、無機酸化物粒子の合計量１００質量部に対して、一般的に１質量部以上５０質量部未満であるが、光触媒活性や外観、耐久性等の性能を考慮して適宜選択することができる。 In the present invention, the content of the photocatalyst particles in the second layer and the coating composition is generally 1 part by mass or more and less than 50 parts by mass with respect to the total amount of 100 parts by mass of the photocatalyst particles and the inorganic oxide particles. , photocatalytic activity, appearance, durability, and other performances can be taken into account and selected as appropriate.
本発明をさらに以下の実施例により説明するが、本発明はこれら実施例に限定されるものではない。 The invention is further illustrated by the following examples, but the invention is not limited to these examples.
材料
光触媒塗装体の調製のために、以下の材料を用意した。
第１層用コーティング組成物のための材料として以下のものを用意した。
（１）樹脂
樹脂１ ケイ素含有量が、シリコーン変性樹脂の固形分に対して２質量％未満のシリコーン変性アクリル樹脂
樹脂２ ケイ素含有量が、シリコーン変性樹脂の固形分に対して約３０質量％のシリコーン変性アクリル樹脂
樹脂３ シリコーン成分を含まないアクリル樹脂
（２）金属酸化物
下記の種々の酸化物の水性ゾルまたは粉体を用いた。
１．酸化セリウムCeO2
２．酸化セリウム以外の金属酸化物
２－１．紫外線の中波長から長波長の波長域に吸収が見られる金属酸化物
酸化鉄Fe2O3
酸化マンガンMnO2
酸化ニオブNb2O5
２－２．ランタノイド系金属酸化物
酸化ランタンLa2O3
酸化ネオジムNd2O3
２－３．一般的な金属酸化物
酸化アルミニウムAl2O3
酸化ジルコニウムZrO2
（３）分散媒：イオン交換水
（４）顔料：
鉄・マンガン複合酸化物（大日精化社製、商品名：MF-5533 Black）（樹脂１、２に使用）
酸化チタン（大日精化社製、商品名：MF-5765 White）（樹脂３に使用）
（５）紫外線吸収剤：ヒドロキシフェニルトリアジン系紫外線吸収剤（ＵＶＡ）
（６）造膜助剤：テキサノール（ＫＨネオケム社製、商品名：キョーワノールＭ）
（７）増粘剤：
増粘剤１：ヘクトライト
増粘剤２：アルカリ膨潤型粘性調整剤
（８）硬化剤：加水分解性シリコーン化合物（樹脂２に使用）
（９）光安定剤：ヒンダートアミン系光安定剤
Materials The following materials were prepared for the preparation of the photocatalyst-coated body.
The following materials were prepared for the coating composition for the first layer.
(1) Resin Resin 1 Silicone-modified acrylic resin having a silicon content of less than 2% by mass relative to the solid content of the silicone-modified resin Resin 2 Silicon content having a silicon content of approximately 30% by mass relative to the solid content of the silicone-modified resin Silicone-modified acrylic resin Resin 3 Acrylic resin containing no silicone component (2) Metal oxides Aqueous sols or powders of the following various oxides were used.
1. Cerium Oxide CeO2
2. Metal oxides other than cerium oxide 2-1. A metal oxide that exhibits absorption in the middle to long wavelength range of ultraviolet rays Iron oxide Fe2O3
manganese oxide MnO2
Niobium Oxide Nb2O5
2-2. Lanthanide metal oxide Lanthanum oxide La2O3
Neodymium Oxide Nd2O3
2-3. Common Metal Oxide Aluminum Oxide Al2O3
Zirconium oxide ZrO2
(3) dispersion medium: deionized water (4) pigment:
Iron-manganese composite oxide (manufactured by Dainichiseika Co., Ltd., trade name: MF-5533 Black) (used for resins 1 and 2)
Titanium oxide (manufactured by Dainichiseika Co., Ltd., trade name: MF-5765 White) (used for resin 3)
(5) UV absorber: hydroxyphenyltriazine-based UV absorber (UVA)
(6) film-forming aid: Texanol (manufactured by KH Neochem, trade name: Kyowanol M)
(7) Thickener:
Thickener 1: Hectorite Thickener 2: Alkali-swelling viscosity modifier (8) Curing agent: Hydrolyzable silicone compound (used for Resin 2)
(9) light stabilizer: hindered amine light stabilizer
第２層用コーティング組成物のための材料として以下のものを用意した。
（１）光触媒
酸化チタン水分散体（アナターゼ型、粒径：レーザ回折・散乱法（ＪＩＳ Ｚ ８８２５：２０１３）によりＸ９０＝７２．５ｎｍ、塩基性）
（２）バインダー
水分散型コロイダルシリカ（日産化学工業社製、商品名：スノーテックスＳ、固形分含有率 ３０％）
（３）分散媒：イオン交換水
（４）添加剤：ポリエーテル変性シリコーン系界面活性剤
The following materials were prepared for the coating composition for the second layer.
(1) Photocatalyst Titanium oxide aqueous dispersion (anatase type, particle size: X90 = 72.5 nm by laser diffraction/scattering method (JIS Z 8825: 2013), basic)
(2) Binder Water-dispersed colloidal silica (manufactured by Nissan Chemical Industries, trade name: Snowtex S, solid content 30%)
(3) Dispersion medium: deionized water (4) Additive: polyether-modified silicone surfactant
第１層用コーティング組成物の調製
表１に記載の組成となるよう、（１）樹脂と、（２）金属酸化物と、（３）分散媒と、（４）～（９）の種々添加剤とを適宜混合して、第１層用コーティング組成物を調製した。ここで、表１における金属酸化物の濃度は、樹脂固形分に対する固形分濃度の割合を意味する。その他の添加剤の濃度は、塗料中の有効成分の濃度を意味する。また、増粘剤２は最後に添加し、粘度が５００～１０００ｍＰａ・sになる量とした（約０．５～３．０質量％）。粘度は、塗料温度２５℃、Ｂ型粘度計Ｍ３ローター６０ｒｐｍにて測定した。
第２層用コーティング組成物の調製
表２に記載の組成となるよう、（１）酸化チタン水分散体と、（２）水分散型コロイダルシリカと、（３）分散媒：イオン交換水と、（４）添加剤：ポリエーテル変性シリコーン系界面活性剤とを混合して、光触媒コーティング液を得た。光触媒コーティング液中の光触媒およびバインダーの合計の固形分濃度は５．５質量％とした。ここで、固形分濃度とは、コーティング液を１０５～１１０℃で乾燥し恒量となったときの質量％を意味する。
基材の作製
アルミ板にエポキシ系シーラーを塗装し、常温乾燥させシーラー塗装体を得た。さらに、シーラー塗装体にアクリル系白色エナメルを塗装し、十分に乾燥させ基材を得た。
Fabrication of Base Material An aluminum plate was coated with an epoxy sealer and dried at room temperature to obtain a sealer-coated body. Furthermore, acrylic white enamel was applied to the sealer-coated body and dried sufficiently to obtain a base material.
光触媒塗装体試験体の作製
上で得た基材を板温度６０℃に加熱し、その表面に第１層用コーティング組成物を、１５０±５０ｇ／ｍ２の塗布量でエアスプレーにて塗装し、８０℃で５分間乾燥して、第１層を基材上に形成した。
The base material obtained in the preparation of the photocatalyst-coated body test body was heated to a plate temperature of 60°C, and the coating composition for the first layer was applied to the surface thereof with an air spray at a coating amount of 150 ± 50 g / m 2 . and dried at 80° C. for 5 minutes to form a first layer on the substrate.
次に、第１層を塗装した基材を板温度６０℃に加熱し、第２層用コーティング組成物を、１０±２．５ｇ／ｍ２の塗布量でエアスプレーにて塗装し、自然乾燥させて、第２層を形成した。こうして得た光触媒塗装体を試験体とした。 Next, the substrate coated with the first layer is heated to a plate temperature of 60°C, and the coating composition for the second layer is applied with an air spray in an amount of 10 ± 2.5 g/m 2 and dried naturally. to form a second layer. The photocatalyst-coated body thus obtained was used as a test body.
光触媒塗装体の評価試験
上で得た光触媒塗装体を、以下の方法により評価した。
（１）光触媒活性評価試験
メチレンブルー分解活性測定法（ＪＩＳ Ｒ １７０３－２：２０１４）に準拠して評価した。
（２）耐候性評価試験
（２－１）粘着テープ試験法（ＪＩＳ Ｚ ０２３７：２００９を参考に次の１～６の手順で評価をした ）
１．試験体作製：塗装後、２３±１℃、５０±５%ＲＨで２４時間以上放置し、メタリングウェザーメーター（東洋精機社製）にて照射と降雨のサイクルを繰り返し、積算エネルギー１６２ＭＪ／ｍ２前後の試験体を評価した。
２．試験雰囲気：２３±１℃、５０±５％ＲＨで以下の３および４の工程を実施した。
３．テープの圧着：２ｋｇゴムローラーを１０±０．５ｍｍ／ｓｅｃの速度で合計２往復
４．剥離速度：テープを１８０°で折り返し５．０±０．２ｍｍ／ｓｅｃで運転
５．測定値：テープ変位量の初めの３０ｍｍを無視し、その後の２０ｍｍの応力測定値を平均する
６．テープ密着率維持率の計算：メタリングウェザーメーター試験後の測定値が、試験前の測定値の何％であるかを計算する。なお、本評価試験によるテープ密着率維持率８０％以上が、実用上、好ましい値である。
（２－２）光沢保持率
ＪＩＳ Ｚ８７４１により、光沢度計（ＶＧ２０００ 日本電色工業製）にて６０°の光沢値を測定し、メタリングウェザーメーター試験後の測定値が、試験前の測定値の何％であるかを計算した。
試験体作製：塗装後、２３±１℃、５０±５％ＲＨで２４時間以上放置し、メタリングウェザーメーター（東洋精機社製）にて照射と降雨のサイクルを繰り返し、積算エネルギー９０ＭＪ／ｍ２前後の試験体を評価した。
The photocatalyst-coated body obtained in the evaluation test of the photocatalyst-coated body was evaluated by the following methods.
(1) Photocatalytic Activity Evaluation Test Evaluation was made in accordance with the methylene blue decomposition activity measurement method (JIS R 1703-2:2014).
(2) Weather resistance evaluation test (2-1) Adhesive tape test method (evaluated according to the following procedures 1 to 6 with reference to JIS Z 0237: 2009)
1. Test sample preparation: After painting, leave at 23±1° C., 50±5% RH for 24 hours or more, repeat the cycle of irradiation and rainfall with a metering weather meter (manufactured by Toyo Seiki Co., Ltd.), accumulated energy 162 MJ / m 2 The test specimens before and after were evaluated.
2. Test atmosphere: The following steps 3 and 4 were performed at 23±1° C. and 50±5% RH.
3. Pressing of tape: A total of 2 reciprocations of a 2 kg rubber roller at a speed of 10±0.5 mm/sec4. Peeling speed: 5.0±0.2 mm/sec for tape folding at 180°5. Measurements: Ignore the first 30 mm of tape displacement and average the subsequent 20 mm stress measurements6. Calculation of tape adhesion rate maintenance rate: Calculate the percentage of the measured value after the metering weather meter test to the measured value before the test. Incidentally, a tape adhesion rate maintenance rate of 80% or more according to this evaluation test is a practically preferable value.
(2-2) Gloss retention rate According to JIS Z8741, the gloss value at 60 ° is measured with a gloss meter (VG2000 manufactured by Nippon Denshoku Industries), and the measured value after the metering weather meter test is the measured value before the test. We calculated what percentage of
Test specimen preparation: After painting, leave at 23 ± 1 ° C., 50 ± 5% RH for 24 hours or more, repeat the cycle of irradiation and rainfall with a metering weather meter (manufactured by Toyo Seiki Co., Ltd.), accumulated energy 90 MJ / m 2 The test specimens before and after were evaluated.
評価結果
試験１
下記表３の第１層および第２層の組み合わせの塗装体を調製し、これらを試験体として上記耐候性評価試験を行った。その結果は、表３に示されるとおりであった。
test 1
Coated bodies having combinations of the first layer and the second layer shown in Table 3 below were prepared, and the above weather resistance evaluation tests were conducted using these as test bodies. The results were as shown in Table 3.
表３の結果は、Ｓｉ含有量が小さな（２重量％未満）の樹脂であっても、酸化セリウムを含有させることにより、Ｓｉ含有量が比較的大きな（約３０重量％）樹脂と同等の耐候性を得ることが出来ることを示している。 The results in Table 3 show that even with a resin with a small Si content (less than 2% by weight), by including cerium oxide, the weather resistance is equivalent to that of a resin with a relatively large Si content (about 30% by weight). It shows that you can get sexuality.
試験２
下記表４の第１層および第２層の組み合わせの塗装体を調製し、これらを試験体として上記光触媒活性評価試験および耐候性評価試験を行った。その結果は、表４に示されるとおりであった。
Coated bodies of combinations of the first layer and the second layer shown in Table 4 below were prepared, and the above photocatalytic activity evaluation test and weather resistance evaluation test were performed using these as test specimens. The results were as shown in Table 4.
表４の結果は、酸化セリウムの添加が、それを添加していない塗装体との対比において、耐候性の低下を有効に防いでいることを明確に示している。 The results in Table 4 clearly show that the addition of cerium oxide effectively prevents deterioration of the weather resistance in comparison with the coated body to which it is not added.
試験３
下記表５の第１層および第２層の組み合わせの塗装体を調製し、これらを試験体として上記耐候性評価試験を行った。その結果は、表５に示されるとおりであった。
Coated bodies having combinations of the first layer and the second layer shown in Table 5 below were prepared, and the above weather resistance evaluation tests were conducted using these as test bodies. The results were as shown in Table 5.
表５の結果は、種々の金属酸化物にあっても、酸化セリウムのみが耐候性を顕著に向上させるものであることを示している。 The results in Table 5 show that among various metal oxides, only cerium oxide significantly improves the weather resistance.
試験４
下記表６の第１層および第２層の組み合わせの塗装体を調製し、これらを試験体として上記耐候性評価試験を行った。その結果は、表６に示されるとおりであった。
Coated bodies having combinations of the first layer and the second layer shown in Table 6 below were prepared, and the above weather resistance evaluation tests were conducted using these as test bodies. The results were as shown in Table 6.
表６の結果は、紫外線吸収剤や光安定剤を添加した場合でも、耐候性を向上させる作用を備えるものは酸化セリウムのみであることを示している。本試験において紫外線吸収剤の添加量は、酸化セリウムの紫外線吸収能と同等以上になる量としている。よって、酸化セリウムの耐候性を向上させた作用は、それが有する紫外線吸収効果によるものではないことが示唆される。
The results in Table 6 show that only cerium oxide has the effect of improving weather resistance even when an ultraviolet absorber or light stabilizer is added. In this test, the amount of the ultraviolet absorber to be added is set to be equal to or greater than the ultraviolet absorbability of cerium oxide. Therefore, it is suggested that the effect of improving the weather resistance of cerium oxide is not due to its ultraviolet absorption effect.
Claims (7)
前記第１層が、酸化セリウム（ＣｅＯ２）をさらに含んでなり、
前記第２層が、ＪＩＳ Ｒ １７０３－２：２０１４に規定されたメチレンブルー分解活性測定法にて定められる光触媒活性値として５ｎｍｏｌ／Ｌ／ｍｉｎ以上３０ｎｍｏｌ／Ｌ／ｍｉｎ以下を有するものである、光触媒塗装体。 A base material, a first layer containing an organic resin on the surface of the base material, and a second layer containing a photocatalyst provided in contact with the first layer,
wherein the first layer further comprises cerium oxide (CeO 2 );
A photocatalyst coating in which the second layer has a photocatalytic activity value of 5 nmol/L/min or more and 30 nmol/L/min or less as determined by the methylene blue decomposition activity measurement method specified in JIS R 1703-2:2014. body.
A coating composition for producing a photocatalyst-coated body according to any one of claims 1 to 6, comprising an organic resin and cerium oxide.
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| JP2004001400A (en) | 2002-04-05 | 2004-01-08 | Murakami Corp | Composite material |
| JP2005021825A (en) | 2003-07-03 | 2005-01-27 | Tadashi Inoue | Photocatalyst composition containing inorganic antibacterial agent |
| JP2006116461A (en) | 2004-10-22 | 2006-05-11 | Jsr Corp | Laminate having visible light photocatalyst layer and visible light photocatalyst coating film |
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