JP2011038060A - Precoat liquid for base layer of photocatalyst layer, wallpaper intermediate fitted with photocatalyst layer, and wallpaper fitted with photocatalyst layer - Google Patents
Precoat liquid for base layer of photocatalyst layer, wallpaper intermediate fitted with photocatalyst layer, and wallpaper fitted with photocatalyst layer Download PDFInfo
- Publication number
- JP2011038060A JP2011038060A JP2009189485A JP2009189485A JP2011038060A JP 2011038060 A JP2011038060 A JP 2011038060A JP 2009189485 A JP2009189485 A JP 2009189485A JP 2009189485 A JP2009189485 A JP 2009189485A JP 2011038060 A JP2011038060 A JP 2011038060A
- Authority
- JP
- Japan
- Prior art keywords
- photocatalyst
- layer
- wallpaper
- photocatalyst layer
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 130
- 239000007788 liquid Substances 0.000 title claims abstract description 57
- 229920005989 resin Polymers 0.000 claims abstract description 42
- 239000011347 resin Substances 0.000 claims abstract description 42
- 238000005187 foaming Methods 0.000 claims abstract description 38
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000004088 foaming agent Substances 0.000 claims abstract description 32
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 239000004927 clay Substances 0.000 claims abstract description 18
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 17
- 150000003839 salts Chemical class 0.000 claims abstract description 15
- 150000007524 organic acids Chemical class 0.000 claims abstract description 10
- 239000006185 dispersion Substances 0.000 claims description 54
- 239000002775 capsule Substances 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 abstract description 15
- 238000009835 boiling Methods 0.000 abstract description 8
- 238000009792 diffusion process Methods 0.000 abstract description 4
- 230000035939 shock Effects 0.000 abstract 1
- 230000001699 photocatalysis Effects 0.000 description 27
- 239000000243 solution Substances 0.000 description 26
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 24
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 24
- 239000000126 substance Substances 0.000 description 24
- 238000000034 method Methods 0.000 description 20
- 239000002245 particle Substances 0.000 description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- 239000002253 acid Substances 0.000 description 18
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 18
- 235000011007 phosphoric acid Nutrition 0.000 description 17
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 16
- 239000002243 precursor Substances 0.000 description 16
- 229910001930 tungsten oxide Inorganic materials 0.000 description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 14
- 238000001035 drying Methods 0.000 description 13
- 239000007787 solid Substances 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 12
- 229910052901 montmorillonite Inorganic materials 0.000 description 12
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 12
- 239000010949 copper Substances 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- -1 polysiloxane Polymers 0.000 description 9
- 239000002612 dispersion medium Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 235000006408 oxalic acid Nutrition 0.000 description 8
- 229910052763 palladium Inorganic materials 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 239000002270 dispersing agent Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000010931 gold Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 229910052697 platinum Inorganic materials 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
- 239000000654 additive Substances 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000006260 foam Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000002609 medium Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 101150003085 Pdcl gene Proteins 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 2
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000007611 bar coating method Methods 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
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- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
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- 229910052731 fluorine Inorganic materials 0.000 description 2
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- 229910002094 inorganic tetrachloropalladate Inorganic materials 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
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- 235000019837 monoammonium phosphate Nutrition 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
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- 230000015572 biosynthetic process Effects 0.000 description 1
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- 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
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- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
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- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
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- 230000001443 photoexcitation Effects 0.000 description 1
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- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
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Abstract
Description
本発明は光触媒体層の下地層用プレコート液、光触媒体層付壁紙中間体および光触媒体層付壁紙に関する。 The present invention relates to a precoat solution for a base layer of a photocatalyst layer, a wallpaper intermediate with a photocatalyst layer, and a wallpaper with a photocatalyst layer.
半導体にバンドギャップ以上のエネルギーを持つ光を照射すると、価電子帯の電子が伝導体に励起され、価電子帯に正孔が生成する。このようにして生成した正孔は強い酸化力を有し、励起した電子は強い還元力を有することから、半導体に接触した物質に酸化還元作用を及ぼす。この酸化還元作用は光触媒作用と呼ばれており、かかる光触媒作用を示し得る半導体は光触媒体と呼ばれている。このような光触媒体としては粒子状の酸化チタンや酸化タングステンなどが知られている。 When a semiconductor is irradiated with light having energy greater than or equal to the band gap, electrons in the valence band are excited by the conductor and holes are generated in the valence band. The holes generated in this manner have a strong oxidizing power, and the excited electrons have a strong reducing power, so that the material in contact with the semiconductor has a redox action. This redox action is called a photocatalytic action, and a semiconductor that can exhibit such a photocatalytic action is called a photocatalyst. As such a photocatalyst, particulate titanium oxide, tungsten oxide, or the like is known.
このような粒子状の光触媒体は、例えば悪臭の原因となる有機物を分解できることから、粒子状の光触媒体からなる光触媒体層を壁紙の表面に形成し、この光触媒体層が形成された壁紙を室内の内装に使用することにより、室内空間の悪臭防止が期待できる。このような光触媒体層は粒子状の光触媒体を分散媒中に分散させて分散液とし、これを壁紙表面に塗布することにより形成できる。 Since such a particulate photocatalyst can decompose, for example, organic substances that cause malodors, a photocatalyst layer composed of a particulate photocatalyst is formed on the surface of the wallpaper, and the wallpaper on which the photocatalyst layer is formed is formed. By using it for the interior of the room, prevention of bad odor in the indoor space can be expected. Such a photocatalyst layer can be formed by dispersing a particulate photocatalyst in a dispersion medium to form a dispersion, which is applied to the wallpaper surface.
一方、壁紙としては、一般に基材シート単独からなるものが知られているが、クッション性を持たせたり、高級感を演出したりする目的で、壁紙に発泡処理により凹凸模様を形成したものが知られている。この壁紙は、一般に基材シート上にカプセル発泡剤を含む樹脂層を形成し、そのカプセル発泡剤を発泡させる発泡処理をして、レリーフ状の凹凸模様を形成したものである[特許文献１]。カプセル発泡剤は低沸点有機溶剤を熱可塑性樹脂の中空粒子内に封入した粒子である。発泡処理は樹脂層を加熱することにより行われる。カプセル発泡剤は、加熱することにより膨張して弾力性のある発泡処理後カプセル発泡剤となる。 On the other hand, wallpaper is generally known that consists of a single base sheet, but for the purpose of giving a cushioning effect or creating a high-class feel, the wallpaper has a concavo-convex pattern formed by foaming. Are known. This wallpaper generally forms a relief-like uneven pattern by forming a resin layer containing a capsule foaming agent on a base sheet, and foaming the capsule foaming agent [Patent Document 1]. . The capsule foaming agent is a particle in which a low-boiling organic solvent is enclosed in a hollow particle of a thermoplastic resin. The foaming process is performed by heating the resin layer. The capsule foaming agent expands by heating and becomes an elastic capsule foaming agent after the foaming treatment.
このような発泡処理が施された壁紙においても最表面を光触媒体層とすることによって、悪臭防止が期待できる。このような悪臭防止効果を有し、発泡処理された壁紙を得るには、発泡処理前カプセル発泡剤を含む樹脂層の上に光触媒体層を設けた後にそのカプセル発泡剤を発泡させる方法が考えられる。 Even in the wallpaper subjected to such foaming treatment, it is possible to prevent malodor by making the outermost surface a photocatalyst layer. In order to obtain a foam-treated wallpaper having such a bad odor prevention effect, a method of foaming the capsule foaming agent after providing a photocatalyst layer on the resin layer containing the capsule foaming agent before foaming treatment is considered. It is done.
また、発泡処理前カプセル発泡剤を含む樹脂層と光触媒体層の接着性を増すために、前記樹脂層上にプレコート液を予め塗布して下地層を形成しておき、この下地層の上に光触媒体分散液を塗布して光触媒体層を形成することも考えられる。このような目的で使用されるプレコート液としてはシリコン変性樹脂、ポリシロキサン含有樹脂、又はコロイダルシリカ含有樹脂を含むものが知られている[特許文献２]。 In addition, in order to increase the adhesiveness between the resin layer containing the capsule foaming agent before foaming and the photocatalyst layer, a precoat liquid is preliminarily applied on the resin layer to form a base layer. It is also conceivable to form a photocatalyst layer by applying a photocatalyst dispersion. As a precoat liquid used for such a purpose, a liquid containing a silicon-modified resin, a polysiloxane-containing resin, or a colloidal silica-containing resin is known [Patent Document 2].
しかし、このようにして形成される従来の光触媒体層では、悪臭防止の効果が不十分であった。その原因として発泡処理時における衝撃で前記下地層が破断してしまい、その破断部分を通じて膨張したカプセル発泡剤が光触媒体層に露出し、加熱、加圧などによってカプセル発泡剤が潰れて中に含まれている低沸点有機溶剤が光触媒体層に移動し分解されることから、見かけ上、室内の悪臭成分に対する光触媒活性が低下するという問題が新たに見出された。 However, the conventional photocatalyst layer formed as described above has an insufficient effect of preventing malodor. The cause is that the underlayer breaks due to impact during foaming treatment, and the capsule foaming agent expanded through the fractured portion is exposed to the photocatalyst layer, and the capsule foaming agent is crushed by heating, pressurizing, etc. Since the low-boiling organic solvent that has been transferred moves to the photocatalyst layer and is decomposed, a problem has been found that the photocatalytic activity against the malodorous component in the room is apparently reduced.
本発明は前記問題点を解決するものであって、発泡処理のような機械的衝撃を受けても光触媒体層の下地層が破断されない機械的強度と柔軟性を有し、かつ、低沸点有機溶剤の拡散を抑制する機能を持つ、光触媒体層の下地層用プレコート液、そのプレコート液を用いて形成された光触媒体層付壁紙中間体およびその光触媒体層付壁紙中間体に発泡処理がなされた光触媒体層付壁紙を提供することを課題とする。 The present invention solves the above problems, and has a mechanical strength and flexibility that prevents the underlayer of the photocatalyst layer from being broken even when subjected to a mechanical impact such as foaming, and is a low-boiling organic material. Foaming is applied to the precoat liquid for the underlayer of the photocatalyst layer, the wallpaper intermediate with the photocatalyst layer formed using the precoat liquid, and the wallpaper intermediate with the photocatalyst layer, which has a function of suppressing the diffusion of the solvent. It is an object to provide a wallpaper with a photocatalyst layer.
本発明者は、前記課題を解決するため鋭意研究を重ねた結果、粘土化合物を含有する下地層が機械的強度と柔軟性を有し、膨張したカプセル発泡剤の露出を抑制するため、光触媒体活性の低下を抑制できることを見出し本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventor has a mechanical layer and a flexible base layer containing a clay compound, and suppresses the exposure of the expanded capsule foaming agent. The inventors have found that the decrease in activity can be suppressed and have completed the present invention.
本発明の光触媒体層の下地層用プレコート液は、カプセル発泡剤を含む樹脂層の表面に光触媒体層を形成するために、あらかじめ、前記樹脂層の表面に下地層を形成するための下地層用プレコート液であって、少なくとも粘土化合物を含有することを特徴とする。
本発明の前記プレコート液は、さらに有機酸またはリン酸もしくはその塩を含有する。
In order to form a photocatalyst layer on the surface of a resin layer containing a capsule foaming agent, the precoat liquid for the base layer of the photocatalyst layer of the present invention is used to form a base layer on the surface of the resin layer in advance. The precoat liquid for use is characterized by containing at least a clay compound.
The precoat solution of the present invention further contains an organic acid, phosphoric acid or a salt thereof.
本発明の光触媒体層付壁紙中間体は、基材シートと、該基材シートの一方の面上に形成された発泡処理前カプセル発泡剤を含む樹脂層と、該樹脂層の上に形成された下地層と、該下地層の上に形成された光触媒体層とを備えたものであって、前記下地層は、前記プレコート液を前記樹脂層上に塗布して形成されたものであり、前記光触媒体層は、光触媒体分散液を前記下地層上に塗布して形成されたものであることを特徴とする。
本発明の光触媒体層付壁紙は、前記光触媒体層付壁紙中間体の発泡処理前カプセル発泡剤に対して発泡処理を施されてなることを特徴とする。
The wallpaper intermediate with a photocatalyst layer of the present invention is formed on a base sheet, a resin layer containing a pre-foaming capsule foaming agent formed on one surface of the base sheet, and the resin layer. An underlayer and a photocatalyst layer formed on the underlayer, wherein the underlayer is formed by applying the precoat liquid onto the resin layer, The photocatalyst layer is formed by applying a photocatalyst dispersion on the underlayer.
The wallpaper with a photocatalyst layer according to the present invention is characterized in that a foaming treatment is applied to the capsule foaming agent before foaming of the wallpaper intermediate with a photocatalyst layer.
本発明によれば、発泡処理前カプセル発泡剤を含む樹脂層に、粘土化合物を含有する下地層用プレコート液を塗布して下地層を形成し、次いで該下地層上に光触媒体分散液を塗布して形成することにより、発泡後における下地層の破断によるカプセル発泡剤の露出を抑制することができ、その結果、カプセル発泡剤に含まれる低沸点有機溶剤によって、光触媒体層の有する光触媒活性が低下するのを阻止することができるという効果がある。 According to the present invention, an undercoat layer precoat solution containing a clay compound is applied to a resin layer containing a capsule foaming agent before foaming treatment to form an undercoat layer, and then a photocatalyst dispersion liquid is applied onto the undercoat layer. As a result, the exposure of the capsule foaming agent due to the breakage of the base layer after foaming can be suppressed. As a result, the photocatalytic activity of the photocatalyst layer is reduced by the low boiling point organic solvent contained in the capsule foaming agent. There is an effect that it can be prevented from lowering.
（プレコート液）
本発明のプレコート液は、光触媒体層の下地層を形成するためのプレコート液であって、少なくとも粘土化合物を含有する。プレコート液は流動性のある液体状でもよいし、ゾル状やゲル状のいずれでもよい。プレコート液は塗布後、光触媒体層を形成するための下地層となる。
(Precoat liquid)
The precoat liquid of the present invention is a precoat liquid for forming an underlayer of the photocatalyst layer, and contains at least a clay compound. The precoat liquid may be in the form of a fluid liquid, or in the form of a sol or gel. The precoat liquid becomes an underlayer for forming a photocatalyst layer after coating.
（粘土化合物）
本発明において用いる粘土化合物は、少なくとも水中で分散できるものであれば特に限定されるものではなく、例えば、雲母、バーミキュライト、モンモリロナイト、バイデライト、サポナイト、ヘクトライト、スチーブンサイト、スメクタイト、カオリナイト、セリサイト、パイロフィライト、ディッカイト、タルク、ハロサイト、アタパルジャイト、セピオライト、ハイドロタルサント、及びノントロナイトが挙げられる。なお、これら粘土化合物は、単独で用いてもよいし、２種以上を併用してもよく、プレコート液中の粘土化合物の濃度は、プレコート液１００質量部あたり全粘土化合物として０．０１質量部以上、１０質量部以下である。
(Clay compound)
The clay compound used in the present invention is not particularly limited as long as it can be dispersed at least in water. For example, mica, vermiculite, montmorillonite, beidellite, saponite, hectorite, stevensite, smectite, kaolinite, sericite. Pyrophyllite, dickite, talc, halosite, attapulgite, sepiolite, hydrotalcant, and nontronite. These clay compounds may be used alone or in combination of two or more. The concentration of the clay compound in the precoat solution is 0.01 parts by mass as the total clay compound per 100 parts by mass of the precoat solution. The amount is 10 parts by mass or less.
本発明のプレコート液は、上記粘土化合物に加えて、有機酸またはリン酸もしくはその塩（以下、リン酸（塩）という）を含有することができる。有機酸やリン酸（塩）は、粘土化合物の分散剤として働くため、これによりプレコート液中での粘土化合物の分散性が向上し、プレコート液を樹脂層に塗布したときに、前記樹脂層を覆う粘土化合物からなる均一な膜を得ることができ、これにより、樹脂層中の発泡剤の光触媒体層への拡散をより効果的に抑制できる。 The precoat solution of the present invention may contain an organic acid, phosphoric acid or a salt thereof (hereinafter referred to as phosphoric acid (salt)) in addition to the clay compound. Since organic acid and phosphoric acid (salt) work as a dispersant for the clay compound, this improves the dispersibility of the clay compound in the precoat solution, and when the precoat solution is applied to the resin layer, the resin layer A uniform film made of the covering clay compound can be obtained, whereby the diffusion of the foaming agent in the resin layer to the photocatalyst layer can be more effectively suppressed.
（有機酸）
本発明のプレコート液で用いる有機酸としては、後述するプレコート液の溶媒に溶解するものであれば特に制限はなく、例えば、蓚酸、蓚酸アンモニウム、マロン酸、クエン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、マレイン酸、フマル酸、フタル酸、イソフタル酸、テレフタル酸、ポリカルボン酸アンモニウム等の、多価カルボン酸及びその塩があげられる。なお、これら有機酸は、単独で用いてもよいし、２種以上を併用してもよく、有機酸の全添加量としては、粘土化合物１００質量部あたり１質量部以上、１００質量部以下である。
(Organic acid)
The organic acid used in the precoat solution of the present invention is not particularly limited as long as it is soluble in the solvent of the precoat solution described later. For example, oxalic acid, ammonium oxalate, malonic acid, citric acid, succinic acid, glutaric acid, adipine Examples thereof include polyvalent carboxylic acids and salts thereof such as acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, and ammonium polycarboxylate. In addition, these organic acids may be used independently and may use 2 or more types together, As total addition amount of an organic acid, they are 1 mass part or more and 100 mass parts or less per 100 mass parts of clay compounds. is there.
（リン酸（塩））
本発明のプレコート液で用いるリン酸（塩）としては、例えば、リン酸、ピロリン酸、ポリリン酸もしくはこれらのアンモニウム塩、ナトリウム塩、カリウム塩等が挙げられるが、これらの中でも特に、リン酸、リン酸二水素アンモニウム、リン酸水素二アンモニウムが好ましい。なお、リン酸（塩）は、単独で用いてもよいし、２種以上を併用してもよい。これらリン酸（塩）の全添加量としては、粘土化合物１００質量部あたり１質量部以上、１００質量部以下である。
(Phosphoric acid (salt))
Examples of the phosphoric acid (salt) used in the precoat solution of the present invention include phosphoric acid, pyrophosphoric acid, polyphosphoric acid or ammonium salts, sodium salts, potassium salts and the like thereof. Among these, phosphoric acid, Ammonium dihydrogen phosphate and diammonium hydrogen phosphate are preferred. In addition, phosphoric acid (salt) may be used independently and may use 2 or more types together. The total addition amount of these phosphoric acids (salts) is 1 part by mass or more and 100 parts by mass or less per 100 parts by mass of the clay compound.
（プレコート液用の溶媒）
本発明のプレコート液の溶媒は、通常、水溶性有機溶媒、水、水と水溶性有機溶媒との混合媒体などが用いられる。水溶性有機溶媒としては、例えば、メタノール、エタノール、プロパノール、ブタノールなどの水溶性アルコール、アセトン、メチルエチルケトン等が挙げられる。なお、水溶性有機溶媒は単独で用いてもよいし、２種以上を併用してもよい。水溶性アルコールとしては通常、エタノールが使用される。
(Solvent for precoat solution)
As the solvent for the precoat solution of the present invention, a water-soluble organic solvent, water, a mixed medium of water and a water-soluble organic solvent, or the like is usually used. Examples of the water-soluble organic solvent include water-soluble alcohols such as methanol, ethanol, propanol, and butanol, acetone, and methyl ethyl ketone. In addition, a water-soluble organic solvent may be used independently and may use 2 or more types together. Usually, ethanol is used as the water-soluble alcohol.
（プレコート液の調製）
本発明のプレコート液は、前記粘土化合物を前記プレコート液用の溶媒に添加し、そこに前記有機酸もしくはリン酸（塩）を溶解した液を添加することにより得ることが出来る。これらの工程は必要に応じて撹拌しながら行ってもよいし、加熱しながら行ってもよい。
(Preparation solution preparation)
The precoat solution of the present invention can be obtained by adding the clay compound to a solvent for the precoat solution and adding a solution in which the organic acid or phosphoric acid (salt) is dissolved. These steps may be performed while stirring as necessary, or may be performed while heating.
（プレコート液の用途）
このようにして得られた本発明のプレコート液は、本発明の光触媒体層付壁紙中間体および光触媒体層付壁紙における光触媒体層の下地層を形成するために用いることができる。
(Use of precoat solution)
The precoat liquid of the present invention thus obtained can be used for forming the underlayer of the photocatalyst layer in the wallpaper intermediate with the photocatalyst layer and the wallpaper with the photocatalyst layer of the present invention.
（光触媒体層付壁紙中間体）
本発明の光触媒体層付壁紙中間体は、前記のとおり、樹脂層と、光触媒体層用の下地層と、光触媒体層とを含む。
(Wallpaper intermediate with photocatalyst layer)
As described above, the wallpaper intermediate with a photocatalyst layer of the present invention includes a resin layer, a base layer for the photocatalyst layer, and a photocatalyst layer.
（樹脂層）
樹脂層は、基材シートの一方の面上に形成され、発泡処理前カプセル発泡剤を含有したものである。
基材シートは、壁紙用の難燃紙（パルプ主体のシート、スルファミン酸グアニジン、リン酸グアニジン等の難燃剤で処理したシート）、水酸化アルミニウム紙、無機質紙等の一般紙である。
樹脂層は樹脂からなる層である。樹脂としては、エチレン−酢酸ビニル共重合体樹脂、塩化ビニル樹脂、エチレン−メタクリル酸共重合体樹脂、エチレン−メチルメタクリレート共重合体樹脂、アクリル樹脂等が挙げられる。樹脂層には、発泡処理前カプセル発泡剤が含まれている。発泡処理前カプセル発泡剤は低沸点有機溶剤を熱可塑性樹脂の中空粒子内に封入した、粒径１０〜３０μｍの微小球である。熱可塑性樹脂としては、塩化ビニリデン・アクリロニトリル共重合体、アクリロニトリル・アクリル系共重合体、ニトリル系共重合体等が使用され、低沸点有機溶剤としては、イソブタン、ブタン、ペンタン、イソペンタン、ヘキサン等が使用される。
(Resin layer)
The resin layer is formed on one surface of the base sheet and contains a capsule foaming agent before foaming.
The base sheet is a general paper such as a flame retardant paper for a wallpaper (a pulp-based sheet, a sheet treated with a flame retardant such as guanidine sulfamate or guanidine phosphate), aluminum hydroxide paper, or inorganic paper.
The resin layer is a layer made of resin. Examples of the resin include ethylene-vinyl acetate copolymer resin, vinyl chloride resin, ethylene-methacrylic acid copolymer resin, ethylene-methyl methacrylate copolymer resin, and acrylic resin. The resin layer contains a capsule foaming agent before foaming. The capsule foaming agent before foaming treatment is a microsphere having a particle size of 10 to 30 μm in which a low boiling point organic solvent is enclosed in a hollow particle of a thermoplastic resin. As the thermoplastic resin, vinylidene chloride / acrylonitrile copolymer, acrylonitrile / acrylic copolymer, nitrile copolymer, etc. are used, and as the low boiling point organic solvent, isobutane, butane, pentane, isopentane, hexane, etc. are used. used.
（下地層）
本発明における下地層は、前記樹脂層の上に本発明のプレコート液を塗布し、乾燥することにより形成される。プレコート液の塗布は、印刷法、シート形成法、スプレー吹き付け法、ディップコーティング法、スピンコーティング法、バーコート法等で行うことができる。プレコート液の塗布後の乾燥条件としては、乾燥圧力は通常、０．００８〜０．１２ＭＰａ、好ましくは０．００９〜０．１１ＭＰａであり、乾燥温度は通常、０〜１２０℃、好ましくは６０〜１００℃であり、乾燥時間は通常、１〜２０分である。下地層の厚さは、通常０．５〜１０μｍ、好ましくは１〜５μｍである。
(Underlayer)
The underlayer in the present invention is formed by applying the precoat liquid of the present invention on the resin layer and drying it. The precoat liquid can be applied by a printing method, a sheet forming method, a spray spraying method, a dip coating method, a spin coating method, a bar coating method, or the like. As drying conditions after application of the precoat liquid, the drying pressure is usually 0.008 to 0.12 MPa, preferably 0.009 to 0.11 MPa, and the drying temperature is usually 0 to 120 ° C., preferably 60 to It is 100 degreeC and drying time is 1 to 20 minutes normally. The thickness of the underlayer is usually 0.5 to 10 μm, preferably 1 to 5 μm.
（光触媒体層）
本発明における光触媒体層は、前記下地層に光触媒体分散液を塗布し、乾燥することにより形成されたものである。
(Photocatalyst layer)
The photocatalyst layer in the present invention is formed by applying a photocatalyst dispersion liquid to the underlayer and drying it.
（光触媒体分散液）
光触媒体分散液は、少なくとも粒子状の光触媒体と光触媒体分散媒とを有し、電子吸引性物質またはその前駆体を含有することが好ましく、本発明の効果を損なわない範囲で公知の各種の添加剤を含んでいてもよい。
(Photocatalyst dispersion)
The photocatalyst dispersion liquid preferably has at least a particulate photocatalyst and a photocatalyst dispersion medium, and preferably contains an electron-withdrawing substance or a precursor thereof, and various known types within a range not impairing the effects of the present invention. An additive may be included.
（光触媒体）
光触媒体とは、例えば、紫外線や可視光線の照射により光触媒作用を発現する半導体であり、具体的には、特定の結晶構造を示す金属元素と酸素、窒素、硫黄、フッ素との化合物等が挙げられる。金属元素としては、例えば、Ｔｉ、Ｚｒ、Ｈｆ、Ｖ、Ｎｂ、Ｔａ、Ｃｒ、Ｍｏ、Ｗ、Ｍｎ、Ｔｃ、Ｒｅ、Ｆｅ、Ｃｏ、Ｎｉ、Ｒｕ、Ｒｈ、Ｐｄ、Ｏｓ、Ｉｒ、Ｐｔ、Ｃｕ、Ａｇ、Ａｕ、Ｚｎ、Ｃｄ、Ｇａ、Ｉｎ、Ｔｌ、Ｇｅ、Ｓｎ、Ｐｂ、Ｂｉ、Ｌａ、Ｃｅが挙げられる。その化合物としては、これら金属の１種類または２種類以上の酸化物、窒化物、硫化物、酸窒化物、酸硫化物、窒弗化物、酸弗化物、酸窒弗化物などが挙げられる。なかでも、Ｔｉ、Ｗ、Ｎｂの酸化物が好ましく、とりわけメタチタン酸、酸化チタン、酸化タングステンなどが好ましい。なお、光触媒体は単独で用いてもよいし2種類以上を併用してもよい。
(Photocatalyst)
The photocatalyst is, for example, a semiconductor that exhibits photocatalytic action by irradiation with ultraviolet rays or visible light, and specifically includes a compound of a metal element having a specific crystal structure and oxygen, nitrogen, sulfur, fluorine, and the like. It is done. Examples of metal elements include Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, and Cu. , Ag, Au, Zn, Cd, Ga, In, Tl, Ge, Sn, Pb, Bi, La, and Ce. Examples of the compound include one or more oxides, nitrides, sulfides, oxynitrides, oxysulfides, nitrofluorides, oxyfluorides, and oxynitrofluorides of these metals. Of these, oxides of Ti, W, and Nb are preferable, and metatitanic acid, titanium oxide, tungsten oxide, and the like are particularly preferable. The photocatalyst may be used alone or in combination of two or more.
（メタチタン酸）
メタチタン酸（Ｈ２ＴｉＯ３、ＴｉＯ（ＯＨ）２、βー水酸化チタン）は、例えば硫酸チタニルの水溶液を加熱して加水分解することにより得ることが出来る。
メタチタン酸の粒子径は、特に制限されないが、光触媒作用の観点からは、平均分散粒子径で、通常２０〜１５０ｎｍ、好ましくは４０〜１００ｎｍである。前記メタチタン酸のＢＥＴ比表面積は、特に制限されないが、光触媒作用の観点からは、通常１００〜５００ｍ２／ｇ、好ましくは３００〜４００ｍ２／ｇである。
(Metatitanic acid)
Metatitanic acid (H 2 TiO 3 , TiO (OH) 2 , β-titanium hydroxide) can be obtained, for example, by heating and hydrolyzing an aqueous solution of titanyl sulfate.
The particle diameter of metatitanic acid is not particularly limited, but from the viewpoint of photocatalysis, the average dispersed particle diameter is usually 20 to 150 nm, preferably 40 to 100 nm. BET specific surface area of the metatitanic acid is not particularly limited, from the viewpoint of photocatalytic activity, usually 100 to 500 m 2 / g, preferably from 300~400m 2 / g.
（酸化チタン）
酸化チタン（ＴｉＯ２）は、例えば、(i)硫酸チタニルまたは塩化チタンの水溶液を加熱することなく、これに塩基を加えることにより沈殿物を得、この沈殿物を焼成する方法、(ii)チタンアルコキシドに水、酸性水溶液、塩基性水溶液等を加えて沈殿物を得、この沈殿物を焼成する方法、(iii)メタチタン酸を焼成する方法等によって得ることができる。これらの方法で得られる酸化チタンは、焼成する際の焼成温度や焼成時間を調整することにより、アナターゼ型、ブルッカイト型、ルチル型など所望の結晶型にすることができる。
また酸化チタンとしては、前記の他にも、特開２００１−７２４１９号公報、特開２００１−１９０９５３号公報、特開２００１−３１６１１６号公報、特開２００１−３２２８１６号公報、特開２００２−２９７４９号公報、特開２００２−９７０１９号公報、ＷＯ０１／１０５５２パンフレット、特開２００１−２１２４５７公報、特開２００２−２３９３９５号公報）、ＷＯ０３／０８０２４４パンフレット、ＷＯ０２／０５３５０１パンフレット、特開２００７−６９０９３号公報、Chemistry Letters, Vol.32, No.2, P.196-197(2003)、Chemistry Letters, Vol.32, No.4, P.364-365(2003)、Chemistry Letters, Vol.32, No.8, P.772-773(2003)、Chem. Mater., 17, P.1548-1552(2005)等に記載の酸化チタンを用いてもよい。また、特開２００１−２７８６２５号公報、特開２００１−２７８６２６号公報、特開２００１−２７８６２７号公報、特開２００１−３０２２４１号公報、特開２００１−３３５３２１号公報、特開２００１−３５４４２２号公報、特開２００２−２９７５０号公報、特開２００２−４７０１２号公報、特開２００２−６０２２１号公報、特開２００２−１９３６１８号公報、特開２００２−２４９３１９号公報などに記載の方法により得ることもできる。
酸化チタンの粒子径は、特に制限されないが、光触媒作用の観点からは、平均分散粒子径で、通常２０〜１５０ｎｍ、好ましくは４０〜１００ｎｍである。前記酸化チタンのＢＥＴ比表面積は、特に制限されないが、光触媒作用の観点からは、通常１００〜５００ｍ２／ｇ、好ましくは３００〜４００ｍ２／ｇである。
(Titanium oxide)
Titanium oxide (TiO 2 ) is obtained, for example, by (i) a method in which a precipitate is obtained by adding a base thereto without heating an aqueous solution of titanyl sulfate or titanium chloride, and (ii) titanium is fired. It can be obtained by adding water, an acidic aqueous solution, a basic aqueous solution or the like to the alkoxide to obtain a precipitate, and baking the precipitate, or (iii) a method of baking metatitanic acid. The titanium oxide obtained by these methods can be made into a desired crystal type such as anatase type, brookite type, rutile type, etc. by adjusting the baking temperature and baking time at the time of baking.
In addition to the above, as titanium oxide, JP 2001-72419 A, JP 2001-190953 A, JP 2001-316116 A, JP 2001-322816 A, and JP 2002-29749 A. Publication, JP 2002-97019, WO 01/10552 pamphlet, JP 2001-212457, JP 2002-239395), WO 03/080244 pamphlet, WO 02/053501 pamphlet, JP 2007-69093, Chemistry. Letters, Vol.32, No.2, P.196-197 (2003), Chemistry Letters, Vol.32, No.4, P.364-365 (2003), Chemistry Letters, Vol.32, No.8, P.772-773 (2003), Chem. Mater., 17, P.1548-1552 (2005), etc. may be used. JP 2001-278625 A, JP 2001-278626 A, JP 2001-278627 A, JP 2001-302241 A, JP 2001-335321 A, JP 2001-354422 A, It can also be obtained by the methods described in JP 2002-29750 A, JP 2002-47012 A, JP 2002-60221 A, JP 2002-193618 A, JP 2002-249319 A, and the like.
The particle diameter of titanium oxide is not particularly limited, but from the viewpoint of photocatalysis, the average dispersed particle diameter is usually 20 to 150 nm, preferably 40 to 100 nm. BET specific surface area of the titanium oxide is not particularly limited, from the viewpoint of photocatalytic activity, usually 100 to 500 m 2 / g, preferably from 300~400m 2 / g.
（酸化タングステン）
酸化タングステン（ＷＯ３）は、例えば、(i)タングステン酸塩の水溶液に酸を加えることにより、沈殿物としてタングステン酸を得、このタングステン酸を焼成する方法、(ii)メタタングステン酸アンモニウム、パラタングステン酸アンモニウムを加熱することにより熱分解する方法、等によって得ることができる。
酸化タングステンの粒子径は、特に制限されないが、光触媒作用の観点からは、平均分散粒子径で、通常５０〜２００ｎｍ、好ましくは８０〜１７０ｎｍである。前記酸化タングステンのＢＥＴ比表面積は、特に制限されないが、光触媒作用の観点からは、通常５〜１００ｍ２／ｇ、好ましくは２０〜５０ｍ２／ｇである。
(Tungsten oxide)
Tungsten oxide (WO 3 ) is obtained, for example, by (i) a method in which tungstic acid is obtained as a precipitate by adding an acid to an aqueous solution of tungstate, and this tungstic acid is baked; (ii) ammonium metatungstate, para It can be obtained by a method of thermally decomposing by heating ammonium tungstate.
The particle diameter of tungsten oxide is not particularly limited, but from the viewpoint of photocatalysis, the average dispersed particle diameter is usually 50 to 200 nm, preferably 80 to 170 nm. BET specific surface area of the tungsten oxide is not particularly limited, from the viewpoint of photocatalytic activity, typically 5 to 100 m 2 / g, preferably from 20 to 50 m 2 / g.
（光触媒体分散媒）
光触媒体分散液を構成する光触媒体分散媒は、前記粒子状の光触媒体が分散できれば特に制限はなく、通常、水を主成分とする水性溶媒が用いられる。具体的には、水単独であってもよいし、水と水溶性有機溶媒との混合溶媒であってもよい。水と水溶性有機溶媒との混合媒体を用いる場合には、水の含有量が５０質量％以上であることが好ましい。水溶性有機溶媒としては、例えば、メタノール、エタノール、プロパノール、ブタノールなどの水溶性アルコール、アセトン、メチルエチルケトン等が挙げられる。なお、水溶性有機溶媒は単独で用いてもよいし、２種以上を併用してもよい。
また、公知の分散剤を含有してもよい。
(Photocatalyst dispersion medium)
The photocatalyst dispersion medium constituting the photocatalyst dispersion liquid is not particularly limited as long as the particulate photocatalyst can be dispersed. Usually, an aqueous solvent containing water as a main component is used. Specifically, water alone or a mixed solvent of water and a water-soluble organic solvent may be used. When a mixed medium of water and a water-soluble organic solvent is used, the content of water is preferably 50% by mass or more. Examples of the water-soluble organic solvent include water-soluble alcohols such as methanol, ethanol, propanol, and butanol, acetone, and methyl ethyl ketone. In addition, a water-soluble organic solvent may be used independently and may use 2 or more types together.
Moreover, you may contain a well-known dispersing agent.
（分散剤）
本発明で用いる光触媒体分散液は、必要に応じて、光触媒体粒子の分散媒中での分散安定性を向上させる目的で、分散剤を用いることができる。該分散剤としては、例えば、ジカルボン酸、トリカルボン酸などのような多価カルボン酸、リン酸（塩）が挙げられる。ジカルボン酸としては、例えば蓚酸が、トリカルボン酸としては、例えばクエン酸が挙げられる。多価カルボン酸およびリン酸として遊離酸を用いてもよいし、塩を用いてもよい。塩としては、例えば、アンモニウム塩が挙げられる。かかる分散剤として、好ましくは蓚酸、蓚酸アンモニウム、リン酸二水素アンモニウムなどが挙げられる。
前記分散剤の使用量は、例えば光触媒体として酸化チタンを使用する場合、ＴｉＯ２換算の光触媒体酸化チタン１モルに対して通常、０．００１モル倍以上、好ましくは、０．０２モル倍以上であり、経済性の点で通常、０．５モル倍以下、好ましくは０．３モル倍以下である。
(Dispersant)
In the photocatalyst dispersion liquid used in the present invention, a dispersant can be used as needed for the purpose of improving the dispersion stability of the photocatalyst particles in the dispersion medium. Examples of the dispersant include polycarboxylic acids such as dicarboxylic acid and tricarboxylic acid, and phosphoric acid (salt). Examples of the dicarboxylic acid include succinic acid, and examples of the tricarboxylic acid include citric acid. A free acid may be used as the polyvalent carboxylic acid and phosphoric acid, and a salt may be used. Examples of the salt include ammonium salts. Preferred examples of the dispersant include oxalic acid, ammonium oxalate, and ammonium dihydrogen phosphate.
For example, when titanium oxide is used as the photocatalyst, the amount of the dispersant used is usually 0.001 mol times or more, preferably 0.02 mol times or more with respect to 1 mol of the photocatalyst titanium oxide in terms of TiO 2. In terms of economy, it is usually 0.5 mol times or less, preferably 0.3 mol times or less.
（電子吸引性物質またはその前駆体）
光触媒体分散液を構成する電子吸引性物質とは、光触媒体の表面に担持されて電子吸引性を発揮しうる化合物であり、光触媒体分散液を構成する電子吸引性物質の前駆体とは、光触媒体の表面で電子吸引性物質に遷移しうる化合物（例えば光照射により電子吸引性物質に還元されうる化合物）である。電子吸引性物質が光触媒体の表面に担持されて存在すると光の照射により伝導体に励起された電子と価電子帯に生成した正孔との再結合が抑制され、光触媒作用をより高めることができる。
(Electron-withdrawing substance or its precursor)
The electron-withdrawing substance constituting the photocatalyst dispersion liquid is a compound that is supported on the surface of the photocatalyst body and can exhibit electron-withdrawing properties, and the precursor of the electron-withdrawing substance constituting the photocatalyst dispersion liquid is A compound that can transition to an electron-withdrawing substance on the surface of the photocatalyst (for example, a compound that can be reduced to an electron-withdrawing substance by light irradiation). When an electron-withdrawing substance is supported on the surface of the photocatalyst, recombination of electrons excited by the conductor with light irradiation and holes generated in the valence band is suppressed, and the photocatalytic action is further enhanced. it can.
前記電子吸引性物質の前駆体を添加した場合には、添加後に光照射を行うことが好ましい。照射する光としては、光触媒体のバンドギャップ以上のエネルギーを持つ光であれば特に制限はない。光の照射を行うことにより、光励起によって生成した電子によって前駆体が還元されて電子吸引性物質となり光触媒体の表面に担持される。なお光の照射は、光触媒体分散液に対して行ってもよいが、光触媒体層の形成後に行ってもよい。より好ましくは複数の光触媒体を混合する場合は、混合前におこなうのがよい。
さらに、より効率的に電子吸引性物質を担持する目的で光の照射する前に犠牲剤としてメタノール、エタノール、蓚酸等を加えることもできる。
When the electron-withdrawing substance precursor is added, light irradiation is preferably performed after the addition. The light to be irradiated is not particularly limited as long as the light has energy higher than the band gap of the photocatalyst. By irradiating with light, the precursor is reduced by the electrons generated by photoexcitation to become an electron-withdrawing substance and is carried on the surface of the photocatalyst. In addition, although light irradiation may be performed with respect to a photocatalyst body dispersion liquid, you may perform after formation of a photocatalyst body layer. More preferably, when a plurality of photocatalysts are mixed, it is preferably performed before mixing.
In addition, methanol, ethanol, oxalic acid, or the like can be added as a sacrificial agent before light irradiation for the purpose of more efficiently supporting an electron-withdrawing substance.
前記電子吸引性物質またはその前駆体は、Ｃｕ、Ｐｔ、Ａｕ、Ｐｄ、Ａｇ、Ｆｅ、Ｎｂ、Ｒｕ、Ｉｒ、ＲｈおよびＣｏからなる群より選ばれる１種以上の金属原子を含有してなるものであることが好ましい。より好ましくは、Ｃｕ、Ｐｔ、ＡｕおよびＰｄのうちの１種以上の金属原子を含有してなるものである。例えば、前記電子吸引性物質としては、前記金属原子からなる金属、もしくは、これらの金属の酸化物や水酸化物等が挙げられ、電子吸引性物質の前駆体としては、前記金属原子からなる金属の硝酸塩、硫酸塩、ハロゲン化物、有機酸塩、炭酸塩、リン酸塩等が挙げられる。 The electron withdrawing substance or its precursor contains one or more metal atoms selected from the group consisting of Cu, Pt, Au, Pd, Ag, Fe, Nb, Ru, Ir, Rh and Co. It is preferable that More preferably, it contains one or more metal atoms of Cu, Pt, Au and Pd. For example, the electron-withdrawing substance may be a metal made of the metal atom, or an oxide or hydroxide of these metals, and the precursor of the electron-withdrawing substance may be a metal made of the metal atom. Nitrates, sulfates, halides, organic acid salts, carbonates, phosphates, and the like.
電子吸引性物質の好ましい具体例としては、Ｃｕ、Ｐｔ、Ａｕ、Ｐｄの金属が挙げられる。また、電子吸引性物質の前駆体の好ましい具体例としては、Ｃｕを含む前駆体として、硝酸銅〔Ｃｕ(ＮＯ3)2〕、硫酸銅〔ＣｕＳＯ4〕、塩化銅〔ＣｕＣｌ2、ＣｕＣｌ〕、臭化銅〔ＣｕＢｒ2、ＣｕＢｒ〕、沃化銅〔ＣｕＩ〕、沃素酸銅〔ＣｕＩ2Ｏ6〕、塩化アンモニウム銅〔Ｃｕ(ＮＨ4)2Ｃｌ4〕、オキシ塩化銅〔Ｃｕ2Ｃｌ(ＯＨ)3〕、酢酸銅〔ＣＨ3ＣＯＯＣｕ、(ＣＨ3ＣＯＯ)2Ｃｕ〕、蟻酸銅〔(ＨＣＯＯ)2Ｃｕ〕、炭酸銅〔ＣｕＣＯ3）、蓚酸銅〔ＣｕＣ2Ｏ4〕、クエン酸銅〔Ｃｕ2Ｃ6Ｈ4Ｏ7〕、リン酸銅〔ＣｕＰＯ4〕が；Ｐｔを含む前駆体として、塩化白金〔ＰｔＣｌ2、ＰｔＣｌ4〕、臭化白金〔ＰｔＢｒ2、ＰｔＢｒ4〕、沃化白金〔ＰｔＩ2、ＰｔＩ4〕、塩化白金カリウム〔Ｋ2(ＰｔＣｌ4)〕、ヘキサクロロ白金酸〔Ｈ2ＰｔＣｌ6〕、亜硫酸白金〔Ｈ3Ｐｔ(ＳＯ3)2ＯＨ〕、酸化白金〔ＰｔＯ2〕、塩化テトラアンミン白金〔Ｐｔ(ＮＨ3)4Ｃｌ2〕、炭酸水素テトラアンミン白金〔Ｃ2Ｈ14Ｎ4Ｏ6Ｐｔ〕、テトラアンミン白金リン酸水素〔Ｐｔ(ＮＨ3)4ＨＰＯ4〕、水酸化テトラアンミン白金〔Ｐｔ(ＮＨ3)4(ＯＨ)2〕、硝酸テトラアンミン白金〔Ｐｔ(ＮＯ3)2(ＮＨ3)4〕、テトラアンミン白金テトラクロロ白金〔(Ｐｔ(ＮＨ3)4)(ＰｔＣｌ4)〕、ジニトロジアミン白金〔(Ｐｔ(ＮＯ2)2 (ＮＨ3)2)〕が；Ａｕを含む前駆体として、塩化金〔ＡｕＣｌ〕、臭化金〔ＡｕＢｒ〕、沃化金〔ＡｕＩ〕、水酸化金〔Ａｕ(ＯＨ)2〕、テトラクロロ金酸〔ＨＡｕＣｌ4〕、テトラクロロ金酸カリウム〔ＫＡｕＣｌ4〕、テトラブロモ金酸カリウム〔ＫＡｕＢｒ4〕、酸化金〔Ａｕ2Ｏ3〕が；Ｐｄを含む前駆体として、例えば、酢酸パラジウム〔(ＣＨ3ＣＯＯ)2Ｐｄ〕、塩化パラジウム〔ＰｄＣｌ2〕、臭化パラジウム〔ＰｄＢｒ2〕、沃化パラジウム〔ＰｄＩ2〕、水酸化パラジウム〔Ｐｄ(ＯＨ)2〕、硝酸パラジウム〔Ｐｄ(ＮＯ3)2〕、酸化パラジウム〔ＰｄＯ〕、硫酸パラジウム〔ＰｄＳＯ4〕、テトラクロロパラジウム酸カリウム〔Ｋ2(ＰｄＣｌ4)〕、テトラブロモパラジウム酸カリウム〔Ｋ2(ＰｄＢｒ4)〕、テトラアンミンパラジウム塩化物〔Ｐｄ（ＮＨ３）４Ｃｌ２〕、テトラアンミンパラジウム臭化物〔Ｐｄ（ＮＨ３）４Ｂｒ２〕、テトラアンミンパラジウム硝酸塩〔Ｐｄ（ＮＨ３）４（ＮＯ３）２〕、テトラアンミンパラジウムテトラアンミンパラジウム酸テトラアンミンパラジウム塩化物〔（Ｐｄ（ＮＨ３）４）（ＰｄＣｌ４）〕、テトラクロロパラジウム酸アンモニウム〔（ＮＨ４）２ＰｄＣｌ４〕が；それぞれ挙げられる。なお、電子吸引性物質またはその前駆体は、それぞれ単独で用いてもよいし、２種以上を併用してもよい。また、１種以上の電子吸引性物質と１種以上の前駆体とを併用してもよいことは勿論である。 Preferable specific examples of the electron-withdrawing substance include Cu, Pt, Au, and Pd metals. Moreover, as a preferable specific example of the precursor of an electron withdrawing substance, as a precursor containing Cu, copper nitrate [Cu (NO 3 ) 2 ], copper sulfate [CuSO 4 ], copper chloride [CuCl 2 , CuCl], Copper bromide [CuBr 2 , CuBr], copper iodide [CuI], copper iodate [CuI 2 O 6 ], ammonium chloride [Cu (NH 4 ) 2 Cl 4 ], copper oxychloride [Cu 2 Cl (OH) ) 3 ], copper acetate [CH 3 COOCu, (CH 3 COO) 2 Cu], copper formate [(HCOO) 2 Cu], copper carbonate [CuCO 3 ), copper oxalate [CuC 2 O 4 ], copper citrate [ Cu 2 C 6 H 4 O 7 ], copper phosphate [CuPO 4 ]; as a precursor containing Pt, platinum chloride [PtCl 2 , PtCl 4 ], platinum bromide [PtBr 2 , PtBr 4 ], platinum iodide [PtI 2, PtI 4], potassium platinum chloride [K 2 (PtCl 4)], hexa Rollo chloroplatinic acid [H 2 PtCl 6], platinum sulfite [H 3 Pt (SO 3) 2 OH ], platinum oxide [PtO 2], tetraammine platinum chloride [Pt (NH 3) 4 Cl 2], bicarbonate tetraammineplatinum [ C 2 H 14 N 4 O 6 Pt], tetraammineplatinum hydrogen phosphate [Pt (NH 3 ) 4 HPO 4 ], tetraammineplatinum platinum [Pt (NH 3 ) 4 (OH) 2 ], tetraammineplatinum nitrate [Pt ( NO 3 ) 2 (NH 3 ) 4 ], tetraammine platinum tetrachloro platinum [(Pt (NH 3 ) 4 ) (PtCl 4 )], dinitrodiamine platinum [(Pt (NO 2 ) 2 (NH 3 ) 2 )] As a precursor containing Au, gold chloride [AuCl], gold bromide [AuBr], gold iodide [AuI], gold hydroxide [Au (OH) 2 ], tetrachloroauric acid [HAuCl 4 ], tetrachloro; Potassium goldate [KAuCl 4 ], tetrabromoauric acid For example, palladium [KAHBr 4 ], gold oxide [Au 2 O 3 ]; Pd-containing precursors such as palladium acetate [(CH 3 COO) 2 Pd], palladium chloride [PdCl 2 ], palladium bromide [PdBr 2 ] ], Palladium iodide [PdI 2 ], palladium hydroxide [Pd (OH) 2 ], palladium nitrate [Pd (NO 3 ) 2 ], palladium oxide [PdO], palladium sulfate [PdSO 4 ], potassium tetrachloropalladate [K 2 (PdCl 4 )], potassium tetrabromopalladate [K 2 (PdBr 4 )], tetraammine palladium chloride [Pd (NH 3 ) 4 Cl 2 ], tetraammine palladium bromide [Pd (NH 3 ) 4 Br 2 ], tetraamminepalladium nitrate [Pd (NH 3) 4 (NO 3) 2 ], tetraammine palladium tetraamine Mi Palladium tetra ammine palladium chloride [(Pd (NH 3) 4) (PdCl 4) ], ammonium tetrachloropalladate [(NH 4) 2 PdCl 4] are; like, respectively. In addition, an electron withdrawing substance or its precursor may each be used independently, and may use 2 or more types together. Needless to say, one or more electron-withdrawing substances and one or more precursors may be used in combination.
前記電子吸引性物質またはその前駆体をも含有させる場合、金属原子換算で、光触媒体粒子の合計量１００質量部に対して、通常０．００５〜０．６質量部、好ましくは０．０１〜０．４質量部で含有する。電子吸引性物質またはその前駆体が光触媒体粒子の合計量１００質量部に対して０．００５質量部未満であると、電子吸引性物質による光触媒活性の向上効果が充分に得られないおそれがあり、一方、光触媒体粒子の合計量１００質量部に対して０．６質量部を超えると、却って光触媒作用が低下するおそれがある。 When the electron-withdrawing substance or its precursor is also contained, it is generally 0.005 to 0.6 parts by mass, preferably 0.01 to 100 parts by mass in terms of metal atoms, with respect to 100 parts by mass of the total amount of photocatalyst particles. It contains in 0.4 mass part. If the electron-withdrawing substance or its precursor is less than 0.005 parts by mass with respect to 100 parts by mass of the total amount of photocatalyst particles, the effect of improving the photocatalytic activity by the electron-withdrawing substance may not be sufficiently obtained. On the other hand, when the amount exceeds 0.6 parts by mass with respect to 100 parts by mass of the total amount of the photocatalyst particles, the photocatalytic action may be lowered.
（添加剤）
光触媒体分散液を構成する添加剤としては、例えば、光触媒作用を向上させる目的で添加されるものが挙げられる。このような光触媒作用向上効果を目的とした添加剤としては、具体的には、非晶質シリカ、シリカゾル、水ガラス、アルコキシシラン、オルガノポリシロキサンなどの珪素化合物；非晶質アルミナ、アルミナゾル、水酸化アルミニウムなどのアルミニウム化合物；ゼオライト；酸化マグネシウム、酸化カルシウム、酸化ストロンチウム、酸化バリウム、水酸化マグネシウム、水酸化カルシウム、水酸化ストロンチウム、水酸化バリウムなどのアルカリ土類金属酸化物またはアルカリ土類金属水酸化物；リン酸カルシウム、モレキュラーシーブ、活性炭、有機ポリシロキサン化合物の重縮合物、リン酸塩、フッ素系ポリマー、シリコン系ポリマー、アクリル樹脂、ポリエステル樹脂、メラミン樹脂、ウレタン樹脂、アルキド樹脂；等が挙げられる。
さらに、前記添加剤としては、光触媒体分散液を基材表面に塗布した際に光触媒体（酸化チタン、酸化タングステン等）をより強固に基材の表面に保持させるためのバインダー等を用いることもできる（例えば、特開平８−６７８３５号公報、特開平９−２５４３７号公報、特開平１０−１８３０６１号公報、特開平１０−１８３０６２号公報、特開平１０−１６８３４９号公報、特開平１０−２２５６５８号公報、特開平１１−１６２０号公報、特開平１１−１６６１号公報、特開２００４−０５９６８６号公報、特開２００４−１０７３８１号公報、特開２００４−２５６５９０号公報、特開２００４−３５９９０２号公報、特開２００５−１１３０２８号公報、特開２００５−２３０６６１号公報、特開２００７−１６１８２４号公報参照）。
添加剤はそれぞれ単独で用いてもよいし、２種以上を併用してもよい。
(Additive)
As an additive which comprises a photocatalyst body dispersion liquid, what is added in order to improve a photocatalytic action is mentioned, for example. Examples of the additive for the purpose of improving the photocatalytic action include silicon compounds such as amorphous silica, silica sol, water glass, alkoxysilane, and organopolysiloxane; amorphous alumina, alumina sol, water Aluminum compounds such as aluminum oxide; zeolites; alkaline earth metal oxides such as magnesium oxide, calcium oxide, strontium oxide, barium oxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, or alkaline earth metal water Oxides; calcium phosphate, molecular sieve, activated carbon, polycondensates of organic polysiloxane compounds, phosphates, fluorine polymers, silicone polymers, acrylic resins, polyester resins, melamine resins, urethane resins, alkyd resins, etc. .
Further, as the additive, a binder for holding the photocatalyst (titanium oxide, tungsten oxide, etc.) more firmly on the surface of the substrate when the photocatalyst dispersion liquid is applied to the surface of the substrate may be used. (For example, JP-A-8-67835, JP-A-9-25437, JP-A-10-183061, JP-A-10-183062, JP-A-10-168349, JP-A-10-225658) JP-A-11-1620, JP-A-11-1661, JP-A-2004-059686, JP-A-2004-107381, JP-A-2004-256590, JP-A-2004-359902, Japanese Unexamined Patent Application Publication Nos. 2005-113028, 2005-230661, 2007-161824 Irradiation).
Each additive may be used alone or in combination of two or more.
（光触媒体分散液の調製）
光触媒体層を構成する光触媒体分散液は、前記光触媒体を前記光触媒体分散媒に添加し、分散することにより得ることができる。分散処理は、例えば、媒体撹拌式分散機を用いる通常の方法により行うことができる。光触媒体分散媒は、光触媒体に対して通常、５〜２００質量倍、好ましくは１０〜１００質量倍で含有する。
(Preparation of photocatalyst dispersion)
The photocatalyst dispersion liquid constituting the photocatalyst layer can be obtained by adding and dispersing the photocatalyst to the photocatalyst dispersion medium. The dispersion treatment can be performed, for example, by an ordinary method using a medium stirring type disperser. The photocatalyst dispersion medium is usually contained in an amount of 5 to 200 times, preferably 10 to 100 times the photocatalyst.
（光触媒体分散液の塗布および乾燥）
このようにして得られた光触媒体分散液を前記下地層上に塗布し、乾燥することにより光触媒体層付壁紙中間体が得られる。塗布は、印刷法、シート形成法、スプレー吹き付け法、ディップコーティング法、スピンコーティング法、バーコート法等で行うことができる。乾燥の条件としては、乾燥圧力は通常、０．００８〜０．１２ＭＰａ、好ましくは０．００９〜０．１１ＭＰａであり、乾燥温度は通常、０〜１２０℃、好ましくは６０〜１００℃であり、乾燥時間は通常、１〜２０分である。
(Application and drying of photocatalyst dispersion)
A photocatalyst layer-attached wallpaper intermediate is obtained by applying the photocatalyst dispersion liquid thus obtained onto the base layer and drying. The coating can be performed by a printing method, a sheet forming method, a spray spraying method, a dip coating method, a spin coating method, a bar coating method, or the like. As drying conditions, the drying pressure is usually 0.008 to 0.12 MPa, preferably 0.009 to 0.11 MPa, the drying temperature is usually 0 to 120 ° C., preferably 60 to 100 ° C., The drying time is usually 1 to 20 minutes.
（光触媒体付壁紙）
本発明の光触媒体層付壁紙は、前記壁紙中間体を構成する樹脂層内に含有される前記発泡処理前カプセル発泡剤に発泡処理を施すことによって得られる。ここで発泡処理とは、前記発泡処理前カプセル発泡剤が発泡すればどのような方法でもよいが、通常、加熱することにより発泡させる。発泡処理の条件としては、温度は通常、１００〜２５０℃、好ましくは１２０〜２００℃であり、圧力は通常、０．００８〜０．１２ＭＰａ、好ましくは０．００９〜０．１１ＭＰａであり、時間は通常、１〜３００秒である。また本発明の光触媒体層付壁紙は、必要に応じてエンボス加工を施してもよい。発泡処理後カプセル発泡剤は、上記発泡処理によって体積が膨張して粒径が３０〜２００μｍの球状になる。
このようにして得られた本発明の光触媒体層付壁紙は、発泡処理が施されているにもかかわらず、適宜光触媒体を選択することによって、蛍光灯やナトリウムランプのような可視光源からの光しか受けない屋内環境でも、光照射によって高い触媒作用を示す。したがって、この光触媒体層付壁紙を、例えば病院の天井材、タイル、ガラスなどに塗布して乾燥させると、屋内照明による光照射によって、ホルムアルデヒドやアセトアルデヒドなどの揮発性有機物、アルデヒド類、メルカプタン類、アンモニアなどの悪臭物質、窒素酸化物の濃度を低減させ、さらには黄色ブドウ球菌や大腸菌、炭疽菌、結核、コレラ菌、ジフテリア菌、破傷風菌、ペスト菌、赤痢菌、ボツリヌス菌、およびレジオネラ菌等の病原菌等や、インフルエンザウィルスやノロウィルス等のウィルスを死滅、分解、除去することができる。
(Wallpaper with photocatalyst)
The wallpaper with a photocatalyst layer of the present invention is obtained by subjecting the pre-foaming capsule foaming agent contained in the resin layer constituting the wallpaper intermediate to foaming. Here, the foaming treatment may be any method as long as the capsule foaming agent before foaming foams, but is usually foamed by heating. As conditions for the foaming treatment, the temperature is usually 100 to 250 ° C., preferably 120 to 200 ° C., the pressure is usually 0.008 to 0.12 MPa, preferably 0.009 to 0.11 MPa, and the time Is usually 1 to 300 seconds. Moreover, you may emboss the wallpaper with a photocatalyst body layer of this invention as needed. After the foaming treatment, the capsule foaming agent expands in volume by the foaming treatment and becomes spherical with a particle size of 30 to 200 μm.
The wallpaper with a photocatalyst layer of the present invention thus obtained has a foaming treatment, but by appropriately selecting a photocatalyst, it can be used from a visible light source such as a fluorescent lamp or a sodium lamp. Even in an indoor environment where only light is received, high catalytic action is exhibited by light irradiation. Therefore, when this wallpaper with a photocatalyst layer is applied to, for example, hospital ceiling materials, tiles, and glass, and dried, volatile organic substances such as formaldehyde and acetaldehyde, aldehydes, mercaptans, Reduces the concentration of malodorous substances such as ammonia and nitrogen oxides, and also Staphylococcus aureus, Escherichia coli, Bacillus anthracis, tuberculosis, Vibrio cholerae, Diphtheria, Tetanus, Plague, Shigella, Clostridium botulinum, Legionella, etc. Can kill, decompose and remove viruses such as influenza virus and norovirus.
以下、本発明を実施例によって詳細に説明するが、本発明はこれらの実施例によって限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by these Examples.
なお、実施例および比較例における各物性の測定およびその光触媒活性の評価については、以下の方法で行った。 In addition, about the measurement of each physical property in an Example and a comparative example, and the evaluation of the photocatalytic activity, it performed with the following method.
（結晶型）
Ｘ線回折装置（リガク社製「ＲＩＮＴ２０００／ＰＣ」）を用いてＸ線回折スペクトルを測定し、そのスペクトルから結晶型を決定した。
(Crystal type)
An X-ray diffraction spectrum was measured using an X-ray diffractometer (“RINT2000 / PC” manufactured by Rigaku Corporation), and a crystal type was determined from the spectrum.
（ＢＥＴ比表面積）
比表面積測定装置（湯浅アイオニクス社製「モノソーブ」）を用いて窒素吸着法により測定した。
(BET specific surface area)
It measured by the nitrogen adsorption method using the specific surface area measuring apparatus ("Monosorb" by Yuasa Ionics Co., Ltd.).
（平均分散粒子径）
サブミクロン粒度分布測定装置（コールター社製「Ｎ４Ｐｌｕｓ」）を用いて粒度分布を測定し、この装置に付属のソフトにより自動的に単分散モード解析して得られた結果を、平均分散粒子径（ｎｍ）とした。
(Average dispersed particle size)
The particle size distribution was measured using a sub-micron particle size distribution measuring device (“N4Plus” manufactured by Coulter, Inc.), and the result obtained by performing the monodisperse mode analysis automatically with the software attached to this device was used as the average dispersed particle size ( nm).
（走査型電子顕微鏡）
走査型電子顕微鏡（ＳＥＭ、Ｓ-2600Ｎ、日立製作所製）を用いて、下地層と光触媒体層とを形成した壁紙の表面を観察した。
(Scanning electron microscope)
Using a scanning electron microscope (SEM, S-2600N, manufactured by Hitachi, Ltd.), the surface of the wallpaper on which the base layer and the photocatalyst layer were formed was observed.
＜光触媒活性の評価（高照度）＞
測定対象の壁紙を５ｃｍ×１０ｃｍに切り出し、紫外線強度が２ｍＷ／ｃｍ２（トプコン社製紫外線強度計「ＵＶＲ−２」に同社製受光部「ＵＤ−３６」を取り付けて測定）となるようにブラックライトからの紫外線を１６時間照射して、これを光触媒活性測定用試料とした。
次に、この光触媒活性測定用試料をガスバッグ（内容積１Ｌ）の中に入れて密閉し、次いで、このガスバッグ内を真空にした後、酸素と窒素との体積比が１：４である混合ガス４６０ｍＬを封入し、さらにその中に１容量％でアセトアルデヒドを含む窒素ガスを、ガスバック内のアセトアルデヒドの濃度が２０ｐｐｍとなるように封入して、暗所で室温下１時間保持した。その後、市販の白色蛍光灯を光源とし、測定サンプル近傍での照度が６０００ルクス〔照度計「Ｔ−１０」（ミノルタ社製）で測定〕になるようにガスバッグを設置し、アセトアルデヒドの分解反応を行った。測定サンプル近傍の紫外光の強度は４０μＷ／ｃｍ２〔トプコン社製紫外線強度計「ＵＶＲ−２」に、同社製受光部「ＵＤ−３６」を取り付けて測定〕であった。蛍光灯照射後よりガスバッグ内のガスを１．５時間毎にサンプリングして、アセトアルデヒドの濃度をガスクロマトグラフ（島津製作所製「ＧＣ−１４Ａ」）にて測定し、光照射後３時間までの照射時間に対するアセトアルデヒドの濃度から一次反応速度定数を算出し、これをアセトアルデヒドの分解能とした。一次反応速度定数が大きいほど、アセトアルデヒドの分解能は大きい。
<Evaluation of photocatalytic activity (high illumination)>
Cut the wallpaper to be measured into 5cm x 10cm, and black so that the UV intensity is 2mW / cm 2 (measured by attaching the UV receiver "UD-36" to Topcon UV intensity meter "UVR-2") The sample was irradiated with ultraviolet light from a light for 16 hours and used as a sample for photocatalytic activity measurement.
Next, this photocatalytic activity measurement sample is put in a gas bag (internal volume 1 L) and sealed, and then the inside of the gas bag is evacuated, and then the volume ratio of oxygen and nitrogen is 1: 4. A mixed gas of 460 mL was sealed, and nitrogen gas containing acetaldehyde at 1% by volume was sealed therein so that the concentration of acetaldehyde in the gas bag was 20 ppm, and kept in the dark at room temperature for 1 hour. Then, using a commercially available white fluorescent lamp as a light source, a gas bag was installed so that the illuminance in the vicinity of the measurement sample was 6000 lux (measured with an illuminometer “T-10” (manufactured by Minolta)), and the decomposition reaction of acetaldehyde Went. The intensity of ultraviolet light in the vicinity of the measurement sample was 40 μW / cm 2 [measured by attaching a UV receiver “UD-36” to the UV intensity meter “UVR-2” manufactured by Topcon Corporation]. The gas in the gas bag is sampled every 1.5 hours after the fluorescent lamp is irradiated, and the concentration of acetaldehyde is measured with a gas chromatograph (“GC-14A” manufactured by Shimadzu Corporation). The first-order rate constant was calculated from the concentration of acetaldehyde with respect to time, and this was taken as the resolution of acetaldehyde. The higher the first order rate constant, the greater the resolution of acetaldehyde.
＜光触媒活性の評価（低照度）＞
測定サンプル近傍での照度を１０００ルクスに変えた他は、上記と同様に行った。このとき測定サンプル近傍の紫外光の強度は６．５μＷ／ｃｍ２〔トプコン社製紫外線強度計「ＵＶＲ−２」に、同社製受光部「ＵＤ−３６」を取り付けて測定〕であった。
<Evaluation of photocatalytic activity (low illuminance)>
The procedure was the same as above except that the illuminance in the vicinity of the measurement sample was changed to 1000 lux. At this time, the intensity of the ultraviolet light in the vicinity of the measurement sample was 6.5 μW / cm 2 [measured by attaching a UV receiver “UD-36” manufactured by the company to a UV intensity meter “UVR-2” manufactured by Topcon Corporation].
（製造例１−光触媒体分散液の調製）
イオン交換水４ｋｇに、粒子状の光触媒体である酸化タングステン（日本無機化学製）１ｋｇを加えて混合して混合物を得た。この混合物を、媒体攪拌式分散機（コトブキ技研社製「ウルトラアペックスミル ＵＡＭ−１」）を用いて下記の条件で分散処理して、酸化タングステン分散液を得た。
分散媒体：直径０．０５ｍｍのジルコニア製ビーズ１．８５ｋｇ
攪拌速度：周速１２．６ｍ／秒
流速：０．２５Ｌ／分
合計処理時間：約５０分
(Production Example 1-Preparation of photocatalyst dispersion)
To 4 kg of ion-exchanged water, 1 kg of tungsten oxide (manufactured by Nippon Inorganic Chemical), which is a particulate photocatalyst, was added and mixed to obtain a mixture. This mixture was subjected to a dispersion treatment under the following conditions using a medium stirring type disperser (“Ultra Apex Mill UAM-1” manufactured by Kotobuki Giken Co., Ltd.) to obtain a tungsten oxide dispersion.
Dispersion medium: 1.85 kg of zirconia beads having a diameter of 0.05 mm
Stirring speed: peripheral speed 12.6 m / sec Flow rate: 0.25 L / min Total processing time: about 50 minutes
得られた酸化タングステン分散液における酸化タングステンの平均分散粒子径は１１８ｎｍであった。また、この分散液の一部を真空乾燥して固形分を得たところ、得られた固形分のＢＥＴ比表面積は４０ｍ２／ｇであった。なお、分散処理の前の混合物についても同様に真空乾燥して固形分を得、分散処理前の混合物の固形分と分散処理後の分散液の固形分について、Ｘ線回折スペクトルをそれぞれ測定して比較したところ、どちらも結晶型はＷＯ3であり、分散処理による結晶型の変化は見られなかった。この時点で、得られた分散液を２０℃で３時間保管したところ、保管中に固液分離は見られなかった。 The average dispersion particle diameter of tungsten oxide in the obtained tungsten oxide dispersion was 118 nm. Moreover, when a part of this dispersion was vacuum-dried to obtain a solid content, the BET specific surface area of the obtained solid content was 40 m 2 / g. Similarly, the mixture before the dispersion treatment is also vacuum-dried to obtain a solid content, and X-ray diffraction spectra are respectively measured for the solid content of the mixture before the dispersion treatment and the solid content of the dispersion after the dispersion treatment. As a result of comparison, the crystal form of both was WO 3 , and no change in crystal form due to dispersion treatment was observed. At this time, when the obtained dispersion was stored at 20 ° C. for 3 hours, no solid-liquid separation was observed during storage.
この酸化タングステン分散液に、ヘキサクロロ白金酸（Ｈ２ＰｔＣｌ６）の水溶液を、ヘキサクロロ白金酸が白金原子換算で酸化タングステンの使用量１００質量部に対して０．１２質量部となるように加え、さらに、メタノールを、その濃度が全溶媒の６．２５質量％となるように加えて、ヘキサクロロ白金酸を含有した酸化タングステン分散液を得た。この分散液１００質量部中に含まれる固形分（酸化タングステンの量）は１１．４質量部（固形分濃度１１．４質量％）であった。 To this tungsten oxide dispersion, an aqueous solution of hexachloroplatinic acid (H 2 PtCl 6 ) was added so that hexachloroplatinic acid was 0.12 parts by mass with respect to 100 parts by mass of tungsten oxide in terms of platinum atoms, Furthermore, methanol was added so that the density | concentration might be 6.25 mass% of all the solvents, and the tungsten oxide dispersion liquid containing hexachloroplatinic acid was obtained. The solid content (amount of tungsten oxide) contained in 100 parts by mass of this dispersion was 11.4 parts by mass (solid content concentration 11.4% by mass).
次いで、上記ヘキサクロロ白金酸を含有した酸化タングステン分散液４８０ｇを１Ｌビーカーに移し、攪拌しながら、高圧水銀灯（ウシオ電機製、高圧水銀灯：「ＵＭ−１０２」、高圧水銀ランプ点灯装置：「ＵＭ−１０３Ｂ−Ｂ」）にて光照射（紫外線照射）を３時間行うことにより、分散液中のヘキサクロロ白金酸を白金に還元して、白金担持酸化タングステン分散液を得た。この光照射後の光触媒体分散液のｐＨは２．４であった。この時点で、得られた分散液を２０℃で３時間保管したところ、保管中に固液分離は見られなかった。 Next, 480 g of the above tungsten oxide dispersion containing hexachloroplatinic acid was transferred to a 1 L beaker and stirred, while being stirred. -B ") was subjected to light irradiation (ultraviolet irradiation) for 3 hours, whereby hexachloroplatinic acid in the dispersion was reduced to platinum to obtain a platinum-supported tungsten oxide dispersion. The pH of the photocatalyst dispersion after the light irradiation was 2.4. At this time, when the obtained dispersion was stored at 20 ° C. for 3 hours, no solid-liquid separation was observed during storage.
（実施例１）
＜プレコート液の調製＞
モンモリロナイト（商品名：クニピアＦ、クニミネ工業製）１２ｇを水３８８ｇに添加し、ホモジナイザーを用いて回転数１０，０００ｒｐｍで１時間分散処理を施した。得られたモンモリロナイト分散液（固形分濃度３質量％）６ｇに水３ｇを添加した。その後この液１．６ｇにエタノール０．４ｇを添加して、プレコート液を得た。該プレコート液のｐHは９．３であった。
Example 1
<Preparation of precoat solution>
12 g of montmorillonite (trade name: Kunipia F, manufactured by Kunimine Kogyo Co., Ltd.) was added to 388 g of water, and dispersion treatment was performed for 1 hour at a rotation speed of 10,000 rpm using a homogenizer. 3 g of water was added to 6 g of the obtained montmorillonite dispersion (solid content concentration 3 mass%). Thereafter, 0.4 g of ethanol was added to 1.6 g of this liquid to obtain a precoat liquid. The precoat solution had a pH of 9.3.
（光触媒体層付壁紙の作成）
エチレン−酢酸ビニル共重合体からなり、カプセル発泡剤を含有した樹脂層（７ｃｍ×１５ｃｍ）に、得られたプレコート液をバーコーター（２０番）で塗布し、７０℃で１５分間乾燥した。この工程を同一壁紙に５回行った後、更にその上に光触媒体分散液を同様にバーコーター（６番）で塗布して７０℃で１５分間乾燥した。その後１８０℃で１．５分間乾燥することにより発泡処理して、光触媒体層付壁紙を作成した。この壁紙の表面のＳＥＭ写真を図１に示す。図１から明らかなように発泡球の露出は見られなかった。また、この壁紙の光触媒活性を測定したところ、アセトアルデヒドの一次反応速度定数は高照度では０．２３８ｈ-1で、低照度はで０．０１６０ｈ-1であった。
(Create wallpaper with photocatalyst layer)
The resulting precoat solution was applied to a resin layer (7 cm × 15 cm) made of an ethylene-vinyl acetate copolymer and containing a capsule foaming agent with a bar coater (No. 20), and dried at 70 ° C. for 15 minutes. After carrying out this process five times on the same wallpaper, a photocatalyst dispersion was similarly applied thereon with a bar coater (No. 6) and dried at 70 ° C. for 15 minutes. Thereafter, it was dried at 180 ° C. for 1.5 minutes to be foamed to prepare a wallpaper with a photocatalyst layer. A SEM photograph of the surface of this wallpaper is shown in FIG. As is clear from FIG. 1, no exposure of the foamed spheres was observed. The measured photocatalytic activity of this picture, first-order reaction rate constant of acetaldehyde in 0.238H -1 at high illuminance, low illuminance was in 0.0160h -1.
（実施例２）
モンモリロナイト（商品名：クニピアＦ、クニミネ工業製）１２ｇを水３８８ｇに添加し、ホモジナイザーを用いて回転数１０，０００ｒｐｍで１時間分散処理を施した。得られたモンモリロナイト分散液（固形分濃度３質量％）６ｇに、蓚酸水溶液（蓚酸二水和物として固形分濃度５質量％）０．７２ｇと水２．２８ｇを添加した。その後この液１．６ｇにエタノール０．４ｇを添加して、プレコート液を得た。プレコート液のｐHは２．４であった。モンモリロナイト１００質量部に対する蓚酸の含有量は１４．３質量部であった。
(Example 2)
12 g of montmorillonite (trade name: Kunipia F, manufactured by Kunimine Kogyo Co., Ltd.) was added to 388 g of water, and dispersion treatment was performed for 1 hour at a rotation speed of 10,000 rpm using a homogenizer. To 6 g of the obtained montmorillonite dispersion (solid content concentration 3 mass%), 0.72 g of an aqueous oxalic acid solution (solid content concentration 5 mass% as oxalic acid dihydrate) and 2.28 g of water were added. Thereafter, 0.4 g of ethanol was added to 1.6 g of this liquid to obtain a precoat liquid. The precoat solution had a pH of 2.4. The content of oxalic acid with respect to 100 parts by mass of montmorillonite was 14.3 parts by mass.
実施例１と同様にして、得られたプレコート液を樹脂層に塗布、乾燥して下地層を形成し、この下地層の上に製造例１で得られた光触媒体分散液を塗布して光触媒体層を形成し、その後に発泡処理することにより光触媒体層付壁紙を作成した。この壁紙の表面のＳＥＭ写真を図２に示す。図２から明らかなように発泡球の露出は見られなかった。また、この壁紙の光触媒活性を測定したところ、アセトアルデヒドの一次反応速度定数は高照度では１．４２ｈ-1で、低照度はで０．２７５ｈ-1であった。 In the same manner as in Example 1, the obtained precoat liquid was applied to a resin layer and dried to form an underlayer, and the photocatalyst dispersion liquid obtained in Production Example 1 was applied onto the underlayer to form a photocatalyst. A body layer was formed, followed by foaming treatment to prepare a wallpaper with a photocatalyst layer. An SEM photograph of the surface of this wallpaper is shown in FIG. As is apparent from FIG. 2, the exposure of the foam sphere was not observed. The measured photocatalytic activity of this picture, first-order reaction rate constant of acetaldehyde in 1.42H -1 at high illuminance, low illuminance was in 0.275h -1.
（実施例３）
モンモリロナイト（商品名：クニピアＦ、クニミネ工業製）１２ｇを水３８８ｇに添加し、ホモジナイザーを用いて回転数１０，０００ｒｐｍで１時間分散処理を施した。得られたモンモリロナイト分散液（固形分濃度３質量％）６ｇに、蓚酸水溶液（蓚酸二水和物として固形分濃度５質量％）０．７２ｇと水２．２８ｇを添加した。その後この液１．６ｇにエタノール０．４ｇを添加し、さらに１０％アンモニア水０．０３６ｇを添加してプレコート液を得た。プレコート液のｐHは５．１であった。モンモリロナイト１００質量部に対する蓚酸の含有量は１４．３質量部であった。
(Example 3)
12 g of montmorillonite (trade name: Kunipia F, manufactured by Kunimine Kogyo Co., Ltd.) was added to 388 g of water, and dispersion treatment was performed for 1 hour at a rotation speed of 10,000 rpm using a homogenizer. To 6 g of the obtained montmorillonite dispersion (solid content concentration 3 mass%), 0.72 g of an aqueous oxalic acid solution (solid content concentration 5 mass% as oxalic acid dihydrate) and 2.28 g of water were added. Thereafter, 0.4 g of ethanol was added to 1.6 g of this liquid, and 0.036 g of 10% aqueous ammonia was further added to obtain a precoat liquid. The precoat solution had a pH of 5.1. The content of oxalic acid with respect to 100 parts by mass of montmorillonite was 14.3 parts by mass.
実施例１と同様にして、得られたプレコート液を樹脂層に塗布、乾燥して下地層を形成し、この下地層の上に製造例１で得られた光触媒体分散液を塗布して光触媒体層を形成し、その後に発泡処理することにより光触媒体層付壁紙を作成した。この壁紙の表面のＳＥＭ写真を図３に示す。図３から明らかなように発泡球の露出は見られなかった。また、この壁紙の光触媒活性を測定したところ、アセトアルデヒドの一次反応速度定数は高照度では１．３７ｈ-1で、低照度はで０．２４２ｈ-1であった。 In the same manner as in Example 1, the obtained precoat liquid was applied to a resin layer and dried to form an underlayer, and the photocatalyst dispersion liquid obtained in Production Example 1 was applied onto the underlayer to form a photocatalyst. A body layer was formed, followed by foaming treatment to prepare a wallpaper with a photocatalyst layer. An SEM photograph of the surface of this wallpaper is shown in FIG. As is apparent from FIG. 3, the exposure of the foam spheres was not observed. The measured photocatalytic activity of this picture, first-order reaction rate constant of acetaldehyde in 1.37H -1 at high illuminance, low illuminance was in 0.242h -1.
（実施例４）
モンモリロナイト（商品名：クニピアＦ、クニミネ工業製）１２ｇを水３８８ｇに添加し、ホモジナイザーを用いて回転数１０，０００ｒｐｍで１時間分散処理を施した。得られたモンモリロナイト分散液（固形分濃度３質量％）６ｇに、リン酸（Ｈ３ＰＯ４）０．０５９ｇと水２．９４ｇを添加した。その後この液１．６ｇにエタノール０．４ｇを添加してプレコート液を得た。プレコート液のｐHは２．１であった。モンモリロナイト１００質量部に対するリン酸の含有量は３２．８質量部であった。
Example 4
12 g of montmorillonite (trade name: Kunipia F, manufactured by Kunimine Kogyo Co., Ltd.) was added to 388 g of water, and dispersion treatment was performed for 1 hour at a rotation speed of 10,000 rpm using a homogenizer. To 6 g of the obtained montmorillonite dispersion (solid content concentration: 3 mass%), 0.059 g of phosphoric acid (H3PO4) and 2.94 g of water were added. Thereafter, 0.4 g of ethanol was added to 1.6 g of this liquid to obtain a precoat liquid. The precoat solution had a pH of 2.1. The content of phosphoric acid with respect to 100 parts by mass of montmorillonite was 32.8 parts by mass.
実施例１と同様にして、得られたプレコート液を樹脂層に塗布、乾燥して下地層を形成し、この下地層の上に製造例１で得られた光触媒体分散液を塗布して光触媒体層を形成し、その後に発泡処理することにより光触媒体層付壁紙を作成した。この壁紙の表面のＳＥＭ写真を図４に示す。図４から明らかなように発泡球の露出は見られなかった。また、この壁紙の光触媒活性を測定したところ、アセトアルデヒドの一次反応速度定数は高照度では１．０２ｈ-1で、低照度はで０．０８７４ｈ-1であった。 In the same manner as in Example 1, the obtained precoat liquid was applied to a resin layer and dried to form an underlayer, and the photocatalyst dispersion liquid obtained in Production Example 1 was applied onto the underlayer to form a photocatalyst. A body layer was formed, followed by foaming treatment to prepare a wallpaper with a photocatalyst layer. A SEM photograph of the surface of this wallpaper is shown in FIG. As is apparent from FIG. 4, no exposure of the foam spheres was observed. The measured photocatalytic activity of this picture, first-order reaction rate constant of acetaldehyde in 1.02H -1 at high illuminance, low illuminance was in 0.0874h -1.
（比較例１）
プレコート液をエチレン−酢酸ビニル共重合体からなる壁紙（７ｃｍ×１５ｃｍ）に、塗布せずに、樹脂層に製造例１で得られた光触媒体分散液を塗布、乾燥して光触媒体層を形成し、その後に発泡処理することにより壁紙を作成した。この壁紙の表面のＳＥＭ写真を図５に示す。図５から明らかなように発泡球の露出が見られた。また、この壁紙の光触媒活性を測定したところ、アセトアルデヒドの一次反応速度定数は高照度では０．００６０２ｈ-1で、低照度はで０．００２４０ｈ-1であった。
(Comparative Example 1)
Apply the photocatalyst dispersion liquid obtained in Production Example 1 to the resin layer without applying the precoat liquid to wallpaper (7 cm x 15 cm) made of ethylene-vinyl acetate copolymer, and form a photocatalyst layer by drying. Then, wallpaper was created by foaming. An SEM photograph of the surface of this wallpaper is shown in FIG. As is apparent from FIG. 5, the exposure of the foamed spheres was observed. The measured photocatalytic activity of this picture, first-order reaction rate constant of acetaldehyde in 0.00602H -1 at high illuminance, low illuminance was in 0.00240h -1.
以上の実施例、比較例の評価結果をまとめて表１に示す。
図１〜４では、図５と比較して壁紙に含まれる発泡処理後カプセル発泡剤の露出を抑制しており、発泡処理後カプセル発泡剤に含まれる低沸点有機溶剤の光触媒体層への拡散を遮断していることがわかった。さらに実施例１と実施例２〜４を比較すると、蓚酸やリン酸を添加したプレコート液では、発泡剤の拡散をより抑制でき、低照度でも高い光触媒活性を示した。 1-4, the exposure of the foaming agent after foaming treatment contained in the wallpaper is suppressed as compared with FIG. 5, and the low boiling point organic solvent contained in the capsule foaming agent after foaming treatment diffuses into the photocatalyst layer. It turns out that it is blocking. Furthermore, when Example 1 and Examples 2-4 were compared, in the precoat liquid which added oxalic acid or phosphoric acid, the spreading | diffusion of a foaming agent could be suppressed more and the high photocatalytic activity was shown even at low illumination intensity.
Claims (4)
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| JP2012187786A (en) * | 2011-03-10 | 2012-10-04 | Nitto Denko Corp | Photocatalyst sheet |
| JP2020157289A (en) * | 2019-03-19 | 2020-10-01 | 株式会社東芝 | Photocatalysis product |
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