JP5354256B2 - A wallpaper having a visible light photocatalytic function, and a method for producing the wallpaper. - Google Patents
A wallpaper having a visible light photocatalytic function, and a method for producing the wallpaper. Download PDFInfo
- Publication number
- JP5354256B2 JP5354256B2 JP2008255731A JP2008255731A JP5354256B2 JP 5354256 B2 JP5354256 B2 JP 5354256B2 JP 2008255731 A JP2008255731 A JP 2008255731A JP 2008255731 A JP2008255731 A JP 2008255731A JP 5354256 B2 JP5354256 B2 JP 5354256B2
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- JP
- Japan
- Prior art keywords
- visible light
- layer
- resin layer
- wallpaper
- foamed
- 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.)
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- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- PPSZHCXTGRHULJ-UHFFFAOYSA-N dioxazine Chemical compound O1ON=CC=C1 PPSZHCXTGRHULJ-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- MYRTYDVEIRVNKP-UHFFFAOYSA-N divinylbenzene Substances C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002168 ethanoic acid esters Chemical class 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 239000005042 ethylene-ethyl acrylate Substances 0.000 description 1
- 229920005680 ethylene-methyl methacrylate copolymer Polymers 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000009408 flooring Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 235000019239 indanthrene blue RS Nutrition 0.000 description 1
- UHOKSCJSTAHBSO-UHFFFAOYSA-N indanthrone blue Chemical compound C1=CC=C2C(=O)C3=CC=C4NC5=C6C(=O)C7=CC=CC=C7C(=O)C6=CC=C5NC4=C3C(=O)C2=C1 UHOKSCJSTAHBSO-UHFFFAOYSA-N 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- WTFXARWRTYJXII-UHFFFAOYSA-N iron(2+);iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Fe+2].[Fe+3].[Fe+3] WTFXARWRTYJXII-UHFFFAOYSA-N 0.000 description 1
- LDHBWEYLDHLIBQ-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide;hydrate Chemical compound O.[OH-].[O-2].[Fe+3] LDHBWEYLDHLIBQ-UHFFFAOYSA-M 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- PXZQEOJJUGGUIB-UHFFFAOYSA-N isoindolin-1-one Chemical compound C1=CC=C2C(=O)NCC2=C1 PXZQEOJJUGGUIB-UHFFFAOYSA-N 0.000 description 1
- GWVMLCQWXVFZCN-UHFFFAOYSA-N isoindoline Chemical compound C1=CC=C2CNCC2=C1 GWVMLCQWXVFZCN-UHFFFAOYSA-N 0.000 description 1
- CYPPCCJJKNISFK-UHFFFAOYSA-J kaolinite Chemical compound [OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[O-][Si](=O)O[Si]([O-])=O CYPPCCJJKNISFK-UHFFFAOYSA-J 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OBJNZHVOCNPSCS-UHFFFAOYSA-N naphtho[2,3-f]quinazoline Chemical compound C1=NC=C2C3=CC4=CC=CC=C4C=C3C=CC2=N1 OBJNZHVOCNPSCS-UHFFFAOYSA-N 0.000 description 1
- 229910001000 nickel titanium Inorganic materials 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
- 150000004767 nitrides Chemical class 0.000 description 1
- JVJQPDTXIALXOG-UHFFFAOYSA-N nitryl fluoride Chemical class [O-][N+](F)=O JVJQPDTXIALXOG-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- DGBWPZSGHAXYGK-UHFFFAOYSA-N perinone Chemical compound C12=NC3=CC=CC=C3N2C(=O)C2=CC=C3C4=C2C1=CC=C4C(=O)N1C2=CC=CC=C2N=C13 DGBWPZSGHAXYGK-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical compound C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical compound S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 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
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Description
本発明は、可視光領域において大気中のアルデヒド等の有機揮発性物質を分解する機能を有する、可視光型光触媒機能を有する壁紙を提供することを目的とする。 An object of this invention is to provide the wallpaper which has a function which decomposes | disassembles organic volatile substances, such as an aldehyde in air | atmosphere in visible light region, and has a visible light type photocatalytic function.
住宅内装材等においては、住宅部材から発生するホルムアルデヒド等の有機ガスによるシックハウスの問題、ペット臭、及び生活臭等の問題から揮発性有機化合物（ＶＯＣ）を分解する光触媒機能を有するに建築用内装材のニーズが高まってきている。
これまで、光触媒機能を有する建築用内装材について種々検討されてきているが、光触媒は、紫外光領域で光触媒活性を有するものが多く、このような紫外光領域のみで触媒活性を有する光触媒を住宅内装材に使用した場合には、室内の微弱な紫外光では光触媒の活性が十分に発揮されないという問題点があった。
In the case of housing interior materials, etc., the building interior has a photocatalytic function for decomposing volatile organic compounds (VOC) from problems such as sick house due to organic gas such as formaldehyde generated from housing members, pet odor, and life odor. The need for materials is increasing.
Up to now, various interior materials for buildings having a photocatalytic function have been studied. However, many photocatalysts have photocatalytic activity in the ultraviolet region, and such photocatalysts having catalytic activity only in the ultraviolet region are housed. When used as an interior material, there is a problem in that the photocatalytic activity is not sufficiently exhibited by the weak ultraviolet light in the room.
上述のようなニーズから、近年、室内での可視光にも応答する光活性機能を有する可視光型光触媒、及び該触媒薄膜が注目され、開発が進められている（特許文献１〜３）。
揮発性有機化合物の分解を考慮する場合には、壁材、天井材、床材、そして家具用等の建材に塗布することで光触媒機能を付与させることができるが、内装部材として最も大きな面積を有する壁面に機能を持たせることが有効と考えられる。
しかしながら光触媒が内装部材表面層に形成された分散剤や樹脂成分等のバインダー等の成分で覆われて固定化されている場合には、光触媒が表面十分に露出していないので光触媒機能が十分に発現しない場合がある。このような問題点を解決するために、バインダー成分を分解して光触媒材料を表面に露出させる方法も検討されている（特許文献４）。
In recent years, a visible light type photocatalyst having a photoactive function that also responds to visible light in the room and the catalyst thin film have attracted attention and have been developed (Patent Documents 1 to 3).
When considering the decomposition of volatile organic compounds, it can be applied to building materials such as wall materials, ceiling materials, flooring materials, and furniture. It is considered effective to give the wall surface a function.
However, when the photocatalyst is covered and fixed with a component such as a dispersing agent or a binder such as a resin component formed on the surface layer of the interior member, the photocatalyst function is sufficient because the surface is not sufficiently exposed. It may not develop. In order to solve such problems, a method of decomposing a binder component and exposing a photocatalytic material to the surface has been studied (Patent Document 4).
壁面内装材としては、従来から壁紙が一般的に使用されており、この壁紙の主たる材料としては、ポリ塩化ビニル系の壁紙が用いられている。
しかし従来は、ポリ塩化ビニル発泡層上に直接光触媒層を設けられているため、発泡工程において発生する発泡剤からのガス等の影響により光触媒機能が十分に発揮されないという問題があった。
本発明は、上記従来の問題点を解決して可視光領域の光照射により、大気中のアルデヒド等の揮発性有機化合物を分解する等の光触媒活性を有する壁紙を提供する。
Conventionally, wallpaper has been generally used as the wall interior material, and polyvinyl chloride-based wallpaper has been used as the main material of this wallpaper.
However, conventionally, since the photocatalyst layer is directly provided on the polyvinyl chloride foam layer, there has been a problem that the photocatalyst function is not sufficiently exhibited due to the influence of gas or the like from the foaming agent generated in the foaming process.
The present invention solves the above-mentioned conventional problems and provides a wallpaper having photocatalytic activity such as decomposing volatile organic compounds such as aldehydes in the atmosphere by light irradiation in the visible light region.
本発明は以上の事情を背景としてなされたもので、発泡オレフィン系樹脂層上に非発泡オレフィン系樹脂層を積層させて、該非発泡オレフィン系樹脂層上に可視光型光触媒と無機バインダーからなる可視光型光触媒層を形成することにより、上記課題を解決できることを見出し、本発明を完成するに至った。 The present invention has been made against the background described above. A non-foamed olefin resin layer is laminated on a foamed olefin resin layer, and a visible light photocatalyst and an inorganic binder are formed on the non-foamed olefin resin layer. It has been found that the above problems can be solved by forming the photo-type photocatalyst layer, and the present invention has been completed.
即ち、本発明は、以下の（１）ないし（６）に記載する発明を要旨とする。
（１）少なくとも発泡オレフィン系樹脂層（Ａ）に非発泡オレフィン系樹脂層（Ｂ）が積層された壁紙基材（Ｃ）に、更に非発泡オレフィン系樹脂層（Ｂ）上に可視光型光触媒層（Ｄ）が形成されていることを特徴とする、可視光型光触媒機能を有する壁紙（以下、第１の態様ということがある）。
（２）前記可視光型光触媒層（Ｄ）中の可視光型光触媒成分に酸化チタン触媒が含有されていることを特徴とする、前記（１）に記載の可視光型光触媒機能を有する壁紙。
（３）前記可視光型光触媒層（Ｄ）が可視光型光触媒と無機物バインダーから形成された層であることを特徴とする、前記（１）又は（２）に記載の可視光型光触媒機能を有する壁紙。
（４）非発泡オレフィン系樹脂層（Ｂ）と可視光型光触媒層（Ｄ）の間に絵柄模様層（Ｅ）が設けられていることを特徴とする、前記（１）ないし（３）のいずれか１に記載の可視光型光触媒機能を有する壁紙。
（５）少なくとも発泡オレフィン系樹脂層（Ａ）、非発泡オレフィン系樹脂層（Ｂ）、及び可視光型光触媒層（Ｄ）がこの順に積層された可視光型光触媒機能を有する壁紙の製造方法であって、
少なくとも前記発泡オレフィン系樹脂層（Ａ）形成用の未発泡オレフィン系樹脂層（Ａ’）に非発泡オレフィン系樹脂層が積層された壁紙基材（Ｃ’）を形成し、
次に非発泡オレフィン系樹脂層（Ｂ）上に可視光型光触媒分散液を塗布、乾燥後、
加熱により未発泡オレフィン系樹脂層（Ａ’）を発泡させて発泡オレフィン系樹脂層（Ａ）を形成することを特徴とする、
可視光型光触媒機能を有する壁紙の製造方法（以下、第２の態様ということがある）。
（６）前記加熱により未発泡オレフィン系樹脂層（Ａ’）を発泡させて発泡オレフィン系樹脂層（Ａ）を形成すると共に、塗布された可視光型光触媒分散液を乾燥させて可視光型光触媒層（Ｄ）を形成することを特徴とする、前記（５）に記載の可視光型光触媒機能を有する壁紙の製造方法。
That is, the gist of the present invention is the invention described in the following (1) to (6).
(1) A visible light photocatalyst on the wallpaper base material (C) in which the non-foamed olefin resin layer (B) is laminated on at least the foamed olefin resin layer (A) and further on the non-foamed olefin resin layer (B) A wallpaper having a visible light type photocatalytic function, wherein the layer (D) is formed (hereinafter, sometimes referred to as a first embodiment).
(2) The wallpaper having a visible light photocatalytic function according to (1), wherein the visible light photocatalyst component in the visible light photocatalyst layer (D) contains a titanium oxide catalyst.
(3) The visible light photocatalytic layer according to (1) or (2), wherein the visible light photocatalyst layer (D) is a layer formed of a visible light photocatalyst and an inorganic binder. Having wallpaper.
(4) The pattern pattern layer (E) is provided between the non-foamed olefin resin layer (B) and the visible light type photocatalyst layer (D). The wallpaper which has a visible light type photocatalyst function of any one.
(5) A wallpaper producing method having a visible light photocatalytic function in which at least a foamed olefin resin layer (A), a non-foamed olefin resin layer (B), and a visible light photocatalyst layer (D) are laminated in this order. There,
Forming at least the foamed olefin resin layer (A) unfoamed olefin resin layer for forming (A ') to the non-foamed olefinic wallpaper substrate resin layer are laminated (C'),
Next, a visible light photocatalyst dispersion is applied onto the non-foamed olefin resin layer (B), dried,
The foamed olefin-based resin layer (A) is formed by foaming the unfoamed olefin-based resin layer (A ′) by heating,
A method for producing a wallpaper having a visible light photocatalytic function (hereinafter sometimes referred to as a second embodiment).
(6) The unfoamed olefin resin layer (A ′) is foamed by the heating to form the foamed olefin resin layer (A), and the applied visible light photocatalyst dispersion is dried to form a visible light photocatalyst. The method for producing wallpaper having a visible light photocatalytic function according to (5), wherein the layer (D) is formed.
本発明の第１の態様である「可視光型光触媒機能を有する壁紙」は、可視光領域において光触媒機能を有しているので、室内中のアルデヒド等の揮発性有機化合物等を分解する等の光活性機能以外に、ペット臭の除去、更に光触媒による防汚性、抗菌性、消臭性等の機能を付与することも可能である。
又、発泡オレフィン系樹脂層（Ａ）と可視光型光触媒層（Ｄ）との間に非発泡オレフィン系樹脂層（Ｂ）があることで、未発泡オレフィン系樹脂層（Ａ'）の発泡工程で発生する発泡ガス等の揮発成分による可視光型光触媒機能の低下、具体的には、可視光型光触媒機能を発揮する酸化チタンなどの粒子への悪影響を防止できる。
本発明の第２の態様である「可視光型光触媒機能を有する壁紙の製造方法」の採用により、可視光型光触媒分散液の塗布後、可視光型光触媒層（Ｄ）の乾燥工程と未発泡オレフィン系樹脂層（Ａ'）の発泡工程を同時に行なえることで製造工程が少なくなり、コストを低減できる。又、発泡工程後に、絵柄模様層（Ｅ）や可視光型光触媒層（Ｄ）を形成した場合、発泡層の凹凸の影響により、前記層を綺麗に塗付することが難しかったが、発泡工程前に前記層を形成可能となったため綺麗に塗付することが可能となる。
可視光型光触媒分散液塗布後、可視光型光触媒層（Ｄ）形成のための乾燥と未発泡オレフィン系樹脂層（Ａ'）の発泡を同時に行なえることが可能となり、製造工程が少なくなり、コストを低減できる。
発泡後に、絵柄層や光触媒層を形成する場合、発泡層の凹凸の影響により、前記層を綺麗に塗付することが難しかったが、発泡工程前に絵柄模様層（Ｅ）を形成可能となったため綺麗に塗付可能である。
The “wallpaper having a visible light type photocatalytic function” which is the first aspect of the present invention has a photocatalytic function in the visible light region, and therefore decomposes volatile organic compounds such as aldehydes in the room. In addition to the photoactive function, it is also possible to provide functions such as removal of pet odor and antifouling, antibacterial, and deodorizing properties by a photocatalyst.
Moreover, the non-foamed olefin resin layer (A ′) is foamed by the non-foamed olefin resin layer (B) between the foamed olefin resin layer (A) and the visible light photocatalyst layer (D). Decrease in visible light photocatalytic function due to volatile components such as foaming gas generated in the above, specifically, adverse effects on particles such as titanium oxide exhibiting the visible light photocatalytic function can be prevented.
By adopting the “method for producing wallpaper having a visible light type photocatalytic function” according to the second aspect of the present invention, after applying the visible light type photocatalyst dispersion, the visible light type photocatalyst layer (D) is dried and unfoamed. Since the foaming process of the olefin resin layer (A ′) can be performed simultaneously, the number of manufacturing processes is reduced, and the cost can be reduced. In addition, when the pattern layer (E) or the visible light photocatalyst layer (D) was formed after the foaming step, it was difficult to apply the layer neatly due to the unevenness of the foam layer. Since the layer can be formed before, it can be applied neatly.
After applying the visible light photocatalyst dispersion, drying for forming the visible light photocatalyst layer (D) and foaming of the unfoamed olefin resin layer (A ′) can be performed at the same time, thereby reducing the number of manufacturing steps. Cost can be reduced.
When forming a pattern layer or photocatalyst layer after foaming, it was difficult to apply the layer neatly due to the unevenness of the foam layer, but the pattern layer (E) can be formed before the foaming step. Therefore, it can be applied neatly.
以下、本発明の可視光型光触媒機能を有する壁紙、及び該壁紙の製造方法について説明する。
本発明の「可視光型光触媒機能を有する壁紙（以下、本発明の壁紙ということがある。）」は、非発泡オレフィン系樹脂層（Ｂ）と可視光型光触媒層（Ｄ）との間に絵柄模様層（Ｅ）を形成することが可能である。また、発泡オレフィン系樹脂層（Ａ）の裏面に非発泡オレフィン系樹脂層（Ｆ）や裏打ち紙層（Ｇ）を形成、或いは非発泡オレフィン系樹脂層（Ｆ）を介して裏打ち紙層（Ｇ）を形成することができる。
Hereinafter, the wallpaper which has a visible light type photocatalyst function of this invention, and the manufacturing method of this wallpaper are demonstrated.
The “wallpaper having a visible light photocatalytic function (hereinafter sometimes referred to as the wallpaper of the present invention)” of the present invention is between the non-foamed olefin resin layer (B) and the visible light photocatalyst layer (D). It is possible to form a picture pattern layer (E). Further, the non-foamed olefin resin layer (F) and the backing paper layer (G) are formed on the back surface of the foamed olefin resin layer (A), or the backing paper layer (G ) Can be formed.
〔１〕本発明の第１の態様である「可視光型光触媒機能を有する壁紙」について
上述したように本発明の第１の態様に係る「可視光型光触媒機能を有する壁紙」は、少なくとも発泡オレフィン系樹脂層（Ａ）に非発泡オレフィン系樹脂層（Ｂ）が積層された壁紙基材（Ｃ）に、更に非発泡オレフィン系樹脂層（Ｂ）上に可視光型光触媒層（Ｄ）が形成されていることを特徴とする。
以下本発明の、少なくとも発泡オレフィン系樹脂層（Ａ）に非発泡オレフィン系樹脂層（Ｂ）が積層された壁紙基材（Ｃ）、可視光型光触媒層（Ｄ）について説明する。
[1] About the “wallpaper having a visible light type photocatalytic function” according to the first aspect of the present invention As described above, the “wallpaper having a visible light type photocatalytic function” according to the first aspect of the present invention is at least foamed. A visible light photocatalyst layer (D) is further formed on the non-foamed olefin resin layer (B) on the wallpaper base material (C) in which the non-foamed olefin resin layer (B) is laminated on the olefin resin layer (A). It is formed.
Hereinafter, the wallpaper base material (C) and the visible light photocatalyst layer (D) in which the non-foamed olefin resin layer (B) is laminated on at least the foamed olefin resin layer (A) of the present invention will be described.
（１）壁紙基材（Ｃ）
（１−１）発泡オレフィン系樹脂層（Ａ）
発泡オレフィン樹脂層（Ａ）は、発泡剤含有オレフィン樹脂層が発泡することにより形成された層である。発泡剤含有樹脂層は、化学発泡剤又は物理発泡剤の作用により発泡するもの（例えば加熱された際に発泡するもの）であれば特に制限されるものではないが、エチレン系樹脂であることが好ましい。
エチレン系樹脂としては例えば、エチレン単独重合体樹脂、エチレン−酢酸ビニル共重合体樹脂（ＥＶＡ）、エチレン−メチルアクリレート共重合体樹脂（ＥＭＡ）、エチレン−エチルアクリレート共重合体樹脂（ＥＥＡ）、炭素原子数３〜５のエチレン−アルキルアクリレート共重合体樹脂、エチレン−メチルメタクリレート共重合体樹脂（ＥＭＭＡ）、エチレン−メタクリル酸共重合体樹脂（ＥＭＡＡ）等のエチレン系共重合体樹脂、これらの樹脂の混合物等が挙げられる。これらの樹脂は、後述する電離放射線を照射することにより、容易に樹脂架橋させることでき、その照射により優れた耐スクラッチ性、耐摩耗性等、表面強度などが向上させることができる。これらの樹脂に中で、優れた耐スクラッチ性、耐摩耗性等、表面強度が優れる点で、ＥＶＡ樹脂、ＥＭＡＡ樹脂が好ましく、特にＥＭＡＡ樹脂が好ましい。
例えば、ＥＶＡ樹脂、ＥＭＡＡ樹脂、無機充填剤、顔料、熱分解型発泡剤及びセル調整剤を含む樹脂組成物を好適に用いることができる。その他にも、安定剤、滑剤等を添加剤として用いることができる。
発泡オレフィン系樹脂層（Ａ）の厚みは特に限定されるものではないが、２０〜２００μｍ程度が好ましく、５０〜１２０μｍ程度がより好ましい。
(1) Wallpaper base material (C)
(1-1) Foamed olefin resin layer (A)
The foamed olefin resin layer (A) is a layer formed by foaming the foaming agent-containing olefin resin layer. The foaming agent-containing resin layer is not particularly limited as long as it is foamed by the action of a chemical foaming agent or a physical foaming agent (for example, foamed when heated), but may be an ethylene resin. preferable.
Examples of ethylene resins include ethylene homopolymer resin, ethylene-vinyl acetate copolymer resin (EVA), ethylene-methyl acrylate copolymer resin (EMA), ethylene-ethyl acrylate copolymer resin (EEA), carbon Ethylene copolymer resins such as ethylene-alkyl acrylate copolymer resins having 3 to 5 atoms, ethylene-methyl methacrylate copolymer resin (EMMA), ethylene-methacrylic acid copolymer resin (EMAA), and the like. And the like. These resins can be easily crosslinked by irradiating ionizing radiation described later, and the surface strength such as excellent scratch resistance and abrasion resistance can be improved by the irradiation. Among these resins, EVA resin and EMAA resin are preferable, and EMAA resin is particularly preferable in terms of excellent surface strength such as excellent scratch resistance and abrasion resistance.
For example, a resin composition containing an EVA resin, an EMAA resin, an inorganic filler, a pigment, a pyrolytic foaming agent, and a cell regulator can be suitably used. In addition, stabilizers, lubricants, and the like can be used as additives.
The thickness of the foamed olefin resin layer (A) is not particularly limited, but is preferably about 20 to 200 μm, and more preferably about 50 to 120 μm.
樹脂成分としてＥＶＡ樹脂を用いる場合、ＥＶＡ樹脂中の酢酸ビニル単位（共重合比率）は特に限定されるものではないが、５〜３０重量％程度であることが好ましく、１０〜２０重量％程度がより好ましい。樹脂成分のメルトフローレート値（ＭＦＲ）は特に限定されないが、５〜７５ｇ／１０分程度が好ましく、４０〜７０ｇ／１０分程度がより好ましい。なお、本明細書においてＭＦＲは、ＪＩＳ Ｋ ７２１０（熱可塑性プラスチックの流れ試験方法）記載の試験方法により測定した値である。試験条件は、ＪＩＳ Ｋ ６７６０記載の「１９０℃、２１．１８Ｎ（２．１６ｋｇｆ）」を採用したものである。発泡樹脂層の発泡状態（例えば、発泡セルの大きさ、発泡セル密度等）は特に限定されず、発泡壁紙の種類、用途等に応じて適宜設計することができる。
また、樹脂成分として、ＥＭＡＡ樹脂を用いる場合は、ＥＭＡＡ樹脂中のメタクリル酸単位（共重合比率）は、４〜２０重量％程度であることが好ましい。樹脂成分のメルトフローレート値（ＪＩＳ Ｋ ７２１０、１９０℃、２．１６ｋｇ）は、用いる重合体の種類等によるが、通常は６０〜２００ｇ／１０分とすることが好ましい。特に、１００〜２００ｇ／１０分という高い範囲でも、良好な発泡状態を維持できるという点で有利である。
When an EVA resin is used as the resin component, the vinyl acetate unit (copolymerization ratio) in the EVA resin is not particularly limited, but is preferably about 5 to 30% by weight, and about 10 to 20% by weight. More preferred. The melt flow rate value (MFR) of the resin component is not particularly limited, but is preferably about 5 to 75 g / 10 minutes, and more preferably about 40 to 70 g / 10 minutes. In the present specification, MFR is a value measured by a test method described in JIS K 7210 (Method for testing the flow of thermoplastics). As test conditions, “190 ° C., 21.18 N (2.16 kgf)” described in JIS K 6760 is adopted. The foamed state of the foamed resin layer (for example, the size of the foamed cell, the foamed cell density, etc.) is not particularly limited, and can be appropriately designed according to the type and use of the foamed wallpaper.
Moreover, when using EMAA resin as a resin component, it is preferable that the methacrylic acid unit (copolymerization ratio) in EMAA resin is about 4 to 20 weight%. The melt flow rate value (JIS K 7210, 190 ° C., 2.16 kg) of the resin component depends on the type of polymer to be used, but is usually preferably 60 to 200 g / 10 minutes. In particular, it is advantageous in that a good foamed state can be maintained even in a high range of 100 to 200 g / 10 minutes.
本発明で使用する発泡剤は、上記した発泡剤の中でも化学発泡剤が好ましく、化学発泡剤の中でも熱分解型発泡剤が好ましい。熱分解型発泡剤としては公知の発泡剤から選択することができる。例えば、アゾジカルボンアミド（ＡＤＣＡ）、アゾビスホルムアミド等のアゾ系；オキシベンゼンスルホニルヒドラジド（ＯＢＳＨ）、パラトルエンスルホニルヒドラジド等のビドラジド系などが挙げられる。熱分解型発泡剤の配合量は、発泡剤の種類、発泡倍率等に応じて適宜設定できる。発泡倍率は、１．５倍以上、好ましくは３〜７倍程度であることから、熱分解型発泡剤の配合量は、樹脂成分１００重量部に対して、１〜２０重量部程度とすることが好ましい。また、物理発泡剤としては、熱膨張型マイクロカプセルが挙げられ、例えば、プロパン、ブタン、イソブタン、ペンタン、ヘキサン等の揮発性液体膨張剤を塩化ビニリデン−アクリロニトリル−ジビニルベンゼンコポリマー、メタアクリレート−アクリロニトリル−ジビニルベンゼンコポリマー等の熱可塑性高分子重合体殻中に内包したマイクロカプセルであって、平均直径が１〜１００μｍの範囲にあるようなものが利用可能である。 The foaming agent used in the present invention is preferably a chemical foaming agent among the above-mentioned foaming agents, and is preferably a pyrolytic foaming agent among the chemical foaming agents. The pyrolytic foaming agent can be selected from known foaming agents. For example, azo compounds such as azodicarbonamide (ADCA) and azobisformamide; and bidazides such as oxybenzenesulfonyl hydrazide (OBSH) and paratoluenesulfonyl hydrazide. The blending amount of the pyrolytic foaming agent can be appropriately set according to the type of foaming agent, the expansion ratio, and the like. Since the expansion ratio is 1.5 times or more, preferably about 3 to 7 times, the blending amount of the pyrolytic foaming agent should be about 1 to 20 parts by weight with respect to 100 parts by weight of the resin component. Is preferred. Examples of the physical foaming agent include thermal expansion type microcapsules. For example, a volatile liquid expansion agent such as propane, butane, isobutane, pentane, hexane or the like is used as a vinylidene chloride-acrylonitrile-divinylbenzene copolymer, methacrylate-acrylonitrile- A microcapsule encapsulated in a thermoplastic polymer polymer shell such as divinylbenzene copolymer having an average diameter in the range of 1 to 100 μm can be used.
発泡オレフィン系樹脂層（Ａ）中には、以下に記載する添加剤を配合することができる。
セル調整剤は、例えばステアリン酸亜鉛等の金属石鹸等を使用することができる。セル調整剤の配合量は、樹脂成分１００重量部に対して、０．３〜１０重量部程度が好ましく、１〜５重量部程度がより好ましい。
無機充填剤としては、例えば、炭酸カルシウム、水酸化アルミニウム、水酸化マグネシウム、三酸化アンチモン、ホウ酸亜鉛、モリブデン化合物等が挙げられる。該無機充填剤を含むことにより、目透き抑制効果、表面特性向上効果等が得られる。該無機充填剤の配合量は、樹脂成分１００重量部に対して０〜１００重量部程度が好ましく、２０〜７０重量部程度がより好ましい。
顔料については、例えば酸化チタン、亜鉛華、カーボンブラック、黒色酸化鉄、黄色酸化鉄、黄鉛、モリブデートオレンジ、カドミウムイエロー、ニッケルチタンイエロー、クロムチタンイエロー、酸化鉄（弁柄）、カドミウムレッド、群青、紺青、コバルトブルー、酸化クロム、コバルトグリーン、アルミニウム粉、ブロンズ粉、雲母チタン、硫化亜鉛等の無機顔料；例えば、アニリンブラック、ペリレンブラック、アゾ系（アゾレーキ、不溶性アゾ、縮合アゾ）、多環式（イソインドリノン、イソインドリン、キノフタロン、ペリノン、フラバントロン、アントラピリミジン、アントラキノン、キナクリドン、ペリレン、ジケトピロロピロール、ジブロムアンザントロン、ジオキサジン、チオインジゴ、フタロシアニン、インダントロン、ハロゲン化フタロシアニン）等の有機顔料が挙げられる。該顔料の含有量は、樹脂成分１００重量部に対して１０〜５０重量部程度が好ましく、１５〜３０重量部程度がより好ましい。発泡剤含有オレフィン系樹脂層の発泡方法としては、後記の製造方法に記載された方法等に従って実施することができる。
In the foamed olefin resin layer (A), additives described below can be blended.
As the cell adjusting agent, for example, a metal soap such as zinc stearate can be used. About 0.3 to 10 weight part is preferable with respect to 100 weight part of resin components, and, as for the compounding quantity of a cell regulator, about 1 to 5 weight part is more preferable.
Examples of the inorganic filler include calcium carbonate, aluminum hydroxide, magnesium hydroxide, antimony trioxide, zinc borate, and a molybdenum compound. By including the inorganic filler, an effect of suppressing see-through, an effect of improving surface characteristics, and the like are obtained. The blending amount of the inorganic filler is preferably about 0 to 100 parts by weight and more preferably about 20 to 70 parts by weight with respect to 100 parts by weight of the resin component.
As for the pigment, for example, titanium oxide, zinc white, carbon black, black iron oxide, yellow iron oxide, yellow lead, molybdate orange, cadmium yellow, nickel titanium yellow, chrome titanium yellow, iron oxide (valve), cadmium red, Inorganic pigments such as ultramarine, bitumen, cobalt blue, chromium oxide, cobalt green, aluminum powder, bronze powder, titanium mica, zinc sulfide; for example, aniline black, perylene black, azo (azo lake, insoluble azo, condensed azo), many Cyclic (isoindolinone, isoindoline, quinophthalone, perinone, flavantron, anthrapyrimidine, anthraquinone, quinacridone, perylene, diketopyrrolopyrrole, dibromanthanthrone, dioxazine, thioindigo, phthalocyanine, indanthrone And organic pigments halogenated phthalocyanine), or the like. About 10-50 weight part is preferable with respect to 100 weight part of resin components, and, as for content of this pigment, about 15-30 weight part is more preferable. As a foaming method of a foaming agent containing olefin resin layer, it can carry out according to the method etc. which were described in the below-mentioned manufacturing method.
（１−２）非発泡オレフィン系樹脂層（Ｂ）
非発泡オレフィン系樹脂層（Ｂ）は、主として発泡オレフィン系樹脂層（Ａ）を保護すると共に、発泡オレフィン系樹脂層（Ａ）を形成する際の発泡工程で発泡ガス等の揮発分成分による可視光型光触媒機能の低下を防止する機能を有する。非発泡オレフィン系樹脂層（Ｂ）を形成する樹脂として、発泡オレフィン系樹脂層（Ａ）に使用したのと同様のオレフィン系樹脂を使用することができる。尚、非発泡オレフィン系樹脂層（Ｂ）に使用する樹脂は、発泡オレフィン系樹脂層（Ａ）に使用する樹脂種と同一でも良く、異なるものであってもよいが、非発泡オレフィン系樹脂層（Ｂ）と発泡オレフィン系樹脂層（Ａ）との間の密着性を向上するために、同種類の樹脂もしくは樹脂組成物、また、原料モノマーと物性が近似しているものを使用することが望ましい。
(1-2) Non-foamed olefin resin layer (B)
The non-foamed olefin-based resin layer (B) mainly protects the foamed olefin-based resin layer (A) and is visible due to a volatile component such as a foaming gas in the foaming process when the foamed olefin-based resin layer (A) is formed. It has a function of preventing a decrease in the photocatalytic function. As the resin for forming the non-foamed olefin resin layer (B), the same olefin resin as that used for the foamed olefin resin layer (A) can be used. The resin used for the non-foamed olefin resin layer (B) may be the same as or different from the resin type used for the foamed olefin resin layer (A). In order to improve the adhesion between (B) and the foamed olefin-based resin layer (A), it is possible to use the same type of resin or resin composition, or a material whose physical properties are similar to those of the raw material monomer. desirable.
前記樹脂成分としては、例えばアクリル酸及びメタクリル酸の少なくとも１種のモノマーとエチレンとの組合せにより得られる共重合体を樹脂成分として好適に用いることができる。より具体的には、エチレン−メタクリル酸共重合体、エチレン−アクリル酸共重合体及びアイオノマー樹脂の少なくとも１種を用いることが望ましい。アイオノマー樹脂としては、エチレン−メタクリル酸共重合体及び／又はエチレン−アクリル酸共重合体の分子間をナトリウム、亜鉛等の金属のイオンで分子間結合した構造を有する樹脂が使用できる。このような樹脂成分を用いる場合には、特に樹脂中の水素結合等に起因する強固な層を形成することができるので、優れた耐スクラッチ性、耐摩耗性等を得ることができる。これらは、公知又は市販のものを使用することができる。 As the resin component, for example, a copolymer obtained by a combination of at least one monomer of acrylic acid and methacrylic acid and ethylene can be suitably used as the resin component. More specifically, it is desirable to use at least one of an ethylene-methacrylic acid copolymer, an ethylene-acrylic acid copolymer, and an ionomer resin. As the ionomer resin, a resin having a structure in which the molecules of ethylene-methacrylic acid copolymer and / or ethylene-acrylic acid copolymer are intermolecularly bonded with metal ions such as sodium and zinc can be used. When such a resin component is used, it is possible to form a strong layer particularly due to hydrogen bonds in the resin, so that excellent scratch resistance, abrasion resistance, and the like can be obtained. These may be known or commercially available.
前記共重合体におけるアクリル酸又はメタクリル酸の含有量は４〜１５重量％程度であることが好ましい。このような樹脂も市販品を使用することができる。前記樹脂組成物には、公知の添加剤を配合することもできる。非発泡樹脂層の厚みは限定的ではないが、１０〜５０μｍ程度が好ましく、特に１０〜２０μｍ程度がより好ましい。また、樹脂組成物中の前記樹脂成分の含有量は限定的ではないが、通常７０〜１００重量％の範囲内で適宜設定することが好ましい。
前記樹脂成分のメルトフローレート値（ＭＦＲ）は、用いる樹脂成分の種類等によるが、一般に１０ｇ／１０分以上の範囲内で適宜設定すれば良い。通常は１０〜１００ｇ／１０分、特に１０〜９５ｇ／１０分、さらに２０〜８０ｇ／１０分の範囲にあることが好ましい。このような数値範囲のものを使用することにより、より優れた耐スクラッチ性、耐摩耗性等を得ることができる。尚、メルトフローレート値（ＭＦＲ）の測定条件は、発泡オレフィン系樹脂層（Ａ）の項に記載したのと同様である。
The content of acrylic acid or methacrylic acid in the copolymer is preferably about 4 to 15% by weight. Such a resin can also use a commercial item. A known additive can also be blended in the resin composition. The thickness of the non-foamed resin layer is not limited, but is preferably about 10 to 50 μm, more preferably about 10 to 20 μm. Moreover, although content of the said resin component in a resin composition is not limited, Usually, it is preferable to set suitably in the range of 70 to 100 weight%.
Although the melt flow rate value (MFR) of the resin component depends on the type of the resin component to be used, etc., it is generally set as appropriate within a range of 10 g / 10 minutes or more. Usually, it is preferably 10 to 100 g / 10 minutes, particularly preferably 10 to 95 g / 10 minutes, and more preferably 20 to 80 g / 10 minutes. By using a material having such a numerical range, more excellent scratch resistance, wear resistance and the like can be obtained. The measurement conditions for the melt flow rate value (MFR) are the same as those described in the section of the foamed olefin resin layer (A).
（１−３）その他
本発明の壁紙基材（Ｃ）には、以下に記載する任意の層を積層することができる。
（ｉ）絵柄模様層（Ｅ）
本発明の壁紙基材（Ｃ）は、必要に応じて非発泡オレフィン系樹脂層（Ｂ）の表側面に絵柄模様層（Ｅ）を形成することができる。
絵柄模様層（Ｅ）は、壁紙に意匠性を付与する。絵柄模様層（Ｅ）の絵柄模様としては、例えば木目模様、石目模様、砂目模様、タイル貼模様、煉瓦積模様、布目模様、皮絞模様、幾何学図形、文字、記号、抽象模様等が挙げられる。該絵柄模様は、本発明の壁紙の種類に応じて選択できる。絵柄模様層（Ｅ）は、例えば、非発泡オレフィン系樹脂層（Ｂ）の表側面に絵柄模様を印刷することで形成できる。なお、絵柄模様層（Ｅ）を形成する際には、必要に応じてあらかじめプライマー層を形成しても良い。印刷手法としては、例えば、グラビア印刷、フレキソ印刷、シルクスクリーン印刷、オフセット印刷等が挙げられる。印刷インキとしては、着色剤、結着材樹脂、溶剤（又は分散媒）を含む印刷インキが使用できる。これらのインキは公知又は市販のものを使用しても良い。
(1-3) Others Any layer described below can be laminated on the wallpaper base material (C) of the present invention.
(I) Pattern pattern layer (E)
As for the wallpaper base material (C) of this invention, a design pattern layer (E) can be formed in the front side surface of a non-foaming olefin resin layer (B) as needed.
The design pattern layer (E) imparts design properties to the wallpaper. Examples of pattern patterns in the pattern pattern layer (E) include wood pattern, stone pattern, sand pattern, tiled pattern, brickwork pattern, cloth pattern, leather pattern, geometric figure, characters, symbols, abstract pattern, etc. Is mentioned. The pattern can be selected according to the type of wallpaper of the present invention. The pattern pattern layer (E) can be formed, for example, by printing a pattern pattern on the front side surface of the non-foamed olefin resin layer (B). In addition, when forming a pattern pattern layer (E), you may form a primer layer previously as needed. Examples of printing methods include gravure printing, flexographic printing, silk screen printing, and offset printing. As the printing ink, a printing ink containing a colorant, a binder resin, and a solvent (or a dispersion medium) can be used. These inks may be known or commercially available.
前記着色剤としては、例えば、前記の発泡剤含有樹脂層で使用されるような顔料を適宜使用することができる。バインダー樹脂は、例えば、アクリル系樹脂、スチレン系樹脂、ポリエステル系樹脂、ウレタン系樹脂、塩素化ポリオレフィン系樹脂、塩化ビニル−酢酸ビニル共重合体系樹脂、ポリビニルブチラール樹脂、アルキド系樹脂、石油系樹脂、ケトン樹脂、エポキシ系樹脂、メラミン系樹脂、フッ素系樹脂、シリコーン系樹脂、繊維素誘導体、ゴム系樹脂等が挙げられる。 As the colorant, for example, a pigment used in the foaming agent-containing resin layer can be appropriately used. The binder resin is, for example, an acrylic resin, a styrene resin, a polyester resin, a urethane resin, a chlorinated polyolefin resin, a vinyl chloride-vinyl acetate copolymer resin, a polyvinyl butyral resin, an alkyd resin, a petroleum resin, Examples include ketone resins, epoxy resins, melamine resins, fluorine resins, silicone resins, fiber derivatives, rubber resins, and the like.
前記溶剤（又は分散媒）としては、例えば、ヘキサン、ヘプタン、オクタン、トルエン、キシレン、エチルベンゼン、シクロヘキサン、メチルシクロヘキサン等の石油系有機溶剤；酢酸エチル、酢酸ブチル、酢酸−２−メトキシエチル、酢酸−２−エトキシエチル等のエステル系有機溶剤；メチルアルコール、エチルアルコール、ノルマルプロピルアルコール、イソプロピルアルコール、イソブチルアルコール、エチレングリコール、プロピレングリコール等のアルコール系有機溶剤；アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系有機溶剤；ジエチルエーテル、ジオキサン、テトラヒドロフラン等のエーテル系有機溶剤、；ジクロロメタン、四塩化炭素、トリクロロエチレン、テトラクロロエチレン等の塩素系有機溶剤；水などが挙げられる。絵柄模様層（Ｅ）の厚みは、絵柄模様の種類より異なるが、一般には０．１〜１０μｍ程度とすることが好ましい。 Examples of the solvent (or dispersion medium) include petroleum organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; ethyl acetate, butyl acetate, 2-methoxyethyl acetate, acetic acid- Ester organic solvents such as 2-ethoxyethyl; alcohol organic solvents such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, propylene glycol; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Ketone-based organic solvents; ether-based organic solvents such as diethyl ether, dioxane, and tetrahydrofuran; dichloromethane, carbon tetrachloride, trichloroethylene, tetrachloroethylene Chlorinated organic solvents emissions and the like; and water. The thickness of the design pattern layer (E) is different from the type of design pattern, but is generally preferably about 0.1 to 10 μm.
（ii）非発泡オレフィン系樹脂層（Ｆ）、裏打ち紙層（Ｇ）
本発明の壁紙基材（Ｃ）の裏面には、裏打ち紙層（Ｇ）を積層させることもがき、又、必要に応じて発泡オレフィン系樹脂層（Ａ）と裏打ち紙層（Ｇ）との間に接着機能を有する非発泡オレフィン系樹脂層（Ｆ）を設けることもできる。特に、本発明の裏側面に裏打ち紙層（Ｇ）を設ける場合に、発泡オレフィン系樹脂層（Ａ）と裏打ち紙層（Ｇ）との間に設けられる非発泡オレフィン系樹脂層（Ｆ）が接着剤層として形成される場合は、優れた密着性を得ることができる。非発泡オレフィン系樹脂層（Ｆ）としては、発泡オレフィン系樹脂層（Ａ）に使用したのと同様のオレフィン系樹脂を使用することができるが、例えば、エチレン−酢酸ビニル共重合体等を好適に用いることができる。非発泡オレフィン系樹脂層（Ｆ）は樹脂成分以外に公知の添加剤を含んでもよいが、樹脂成分の含有量が７０〜１００重量％となるように配合することが好ましい。
(Ii) Non-foamed olefin resin layer (F), backing paper layer (G)
A backing paper layer (G) can be laminated on the back surface of the wallpaper substrate (C) of the present invention, and if necessary, between the foamed olefin resin layer (A) and the backing paper layer (G). A non-foamed olefin-based resin layer (F) having an adhesive function can be provided. In particular, when the backing paper layer (G) is provided on the back side surface of the present invention, the non-foamed olefin resin layer (F) provided between the foamed olefin resin layer (A) and the backing paper layer (G) is provided. When formed as an adhesive layer, excellent adhesion can be obtained. As the non-foamed olefin resin layer (F), the same olefin resin as that used for the foamed olefin resin layer (A) can be used. For example, an ethylene-vinyl acetate copolymer is preferable. Can be used. The non-foamed olefin-based resin layer (F) may contain a known additive in addition to the resin component, but is preferably blended so that the content of the resin component is 70 to 100% by weight.
（２）可視光型光触媒層（Ｄ）
（２−１）可視光型光触媒
可視光型光触媒層（Ｄ）に使用する可視光型光触媒としては、可視光線により光触媒作用を奏する化合物であれば特に制限なく使用可能であり、例えば可視光応答製を有する酸化チタン粒子の製造法として特開２００１−２７８６２５号公報、特開２００１−３０２２４１号公報、特開２００３−２７５６００号公報等に開示されているものを使用することができる。
また、可視光型光触媒としては、特開２００７−２６８５２３号公報に開示されているように、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のような金属元素の１種又は２種以上の酸化物、窒化物、硫化物、酸窒化物、酸硫化物、窒弗化物、酸弗化物、酸窒弗化物なども使用することができる。これらの中でもアナターゼ型又はルチル型の酸化チタンが好ましく、可視光線ないし蛍光灯の照射で触媒活性を示すものとしてアナターゼ型酸化チタンが好ましい。
(2) Visible light type photocatalyst layer (D)
(2-1) Visible light type photocatalyst The visible light type photocatalyst used in the visible light type photocatalyst layer (D) can be used without particular limitation as long as it is a compound that exhibits a photocatalytic action by visible light. As a method for producing titanium oxide particles having a product, those disclosed in JP 2001-278625 A, JP 2001-302241 A, JP 2003-275600 A, and the like can be used.
Moreover, as a visible light type photocatalyst, as disclosed in JP 2007-268523 A, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, 1 of metal elements such as Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu, Ag, Au, Zn, Cd, Ga, In, Tl, Ge, Sn, Pb, Bi, La, Ce Species or two or more oxides, nitrides, sulfides, oxynitrides, oxysulfides, nitrofluorides, oxyfluorides, oxynitrofluorides, and the like can also be used. Among these, anatase-type or rutile-type titanium oxide is preferable, and anatase-type titanium oxide is preferable as a catalyst that shows catalytic activity when irradiated with visible light or fluorescent light.
また、上記可視光型光触媒には、必要に応じて、各種添加剤を分散体として含有させることができる。このような添加剤としては、例えば、非晶質シリカ、シリカゾルのような珪素酸化物、非晶質アルミナ、アルミナゾルのようなアルミニウムの酸化物や水酸化物、ゼオライト、カオリナイトのようなアルミノ珪酸塩、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、水酸化バリウムのようなアルカリ土類金属の酸化物や水酸化物、リン酸カルシウム、モレキュラーシーブ、活性炭、ならびに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のような金属元素の水酸化物およびこれらの金属元素の非晶質酸化物などが挙げられる。これら添加物は、１種のみであってもよいし、２種以上であってもよい。
本発明における可視光型光触媒は、蛍光灯による光照射に対して光触媒活性を示すものであることが好ましい。詳しくは、波長約４３０ｎｍ〜約８３０ｎｍの光照射に対して光触媒活性を示す光触媒が好ましい。
Moreover, the visible light type photocatalyst may contain various additives as a dispersion, if necessary. Examples of such additives include amorphous silica, silicon oxide such as silica sol, amorphous alumina, aluminum oxide and hydroxide such as alumina sol, aluminosilicate such as zeolite and kaolinite. Oxides and hydroxides of alkaline earth metals such as salts, magnesium oxide, calcium oxide, strontium oxide, barium oxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, calcium phosphate, molecular sieve, activated carbon , And Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu, Ag, Au, Metal element hydroxides such as Zn, Cd, Ga, In, Tl, Ge, Sn, Pb, Bi, La, Ce Beauty and amorphous oxides of these metal elements and the like. These additives may be only one type or two or more types.
The visible light type photocatalyst in the present invention preferably exhibits photocatalytic activity with respect to light irradiation by a fluorescent lamp. Specifically, a photocatalyst exhibiting photocatalytic activity for light irradiation with a wavelength of about 430 nm to about 830 nm is preferable.
（２−２）可視光型光触媒層（Ｄ）
本発明の可視光型光触媒層（Ｄ）は、例えば、前記した可視光型光触媒と無機バインダーを溶媒に分散させた分散液を、グラビアコート、スプレーコート、ディップコート、又はハケ塗りなどの方法により壁紙基材（Ｃ）上に塗布し、その後、分散液中の溶媒を除去しうる温度で加熱する方法が挙げられるが
本発明は該方法に限定されるものではない。
無機バインダーとしては、例えば、アルコキシシラン類の縮合物、オルガノポリシロキサン、有機ポリシロキサン化合物の重縮合物、加水分解物、シリコンワニス等のシリカ化合物；リン酸亜鉛、重リン酸塩、リン酸アルミニウムなどのリン酸塩；シリカ、コロイダルシリカ、水ガラス、セメント、石灰、セッコウ、ほうろう用フリット、グラスライニング用うわぐすり、プラスターなどの無機系バインダーを挙げることができる。
(2-2) Visible light photocatalyst layer (D)
The visible light photocatalyst layer (D) of the present invention is obtained by, for example, applying a dispersion liquid in which the above visible light photocatalyst and an inorganic binder are dispersed in a solvent by a method such as gravure coating, spray coating, dip coating, or brush coating. Although the method of apply | coating on a wallpaper base material (C) and heating at the temperature which can remove the solvent in a dispersion liquid after that is mentioned, this invention is not limited to this method.
Examples of inorganic binders include, for example, condensates of alkoxysilanes, organopolysiloxanes, polycondensates of organic polysiloxane compounds, hydrolysates, silica compounds such as silicon varnish; zinc phosphate, polyphosphate, aluminum phosphate And inorganic binders such as silica, colloidal silica, water glass, cement, lime, gypsum, enamel frit, glass lining glaze, and plaster.
可視光型光触媒層（Ｄ）のバインダーに樹脂組成物を使用すると、可視光型光触媒は樹脂組成物中に分散するか、樹脂によりコートされた状態で存在するので、可視光型光触媒が十分に露出しておらず、可視光型光触媒機能が十分に発現しないおそれがある。
従って、本発明においては、可視光型光触媒のバインダーとして有機物バインダーを使用するよりは無機物バインダーを使用して、多孔質層として、可視光型光触媒を可視光型光触媒層（Ｄ）の表面に多く露出させることが望ましい。
可視光型光触媒層（Ｄ）形成の具体例としては、特開２００７−１８５５５６号公報に記載されているように、酸化チタン（ＴｉＯ２）、酸化ニオブ、及び無機バインダーを溶媒に混合した水又は有機溶媒中で混合して可視光型光触媒分散液を得ることができる。該可視光型光触媒分散液は、非発泡オレフィン系樹脂層（Ｂ）上に直接塗布しても良く、光触媒層転写フィルムを作製して転写法によって転写することも可能である。塗布する手段は、例えば、前述した通りのグラビアコート、スプレーコート、ディップコート等、各種の塗布方法を選択しうる。コート液の塗布は、一回のみならず、複数回行ってもよい。
その後、溶媒を除去しうる程度の温度で加熱乾燥して溶媒を除去する。乾燥が完了した後、３０〜６０℃程度の温度で所要時間エージングを行うこともできる。これにより、コーティングした可視光型光触媒層（Ｄ）の剥離強度を向上させることができる。
可視光型光触媒層（Ｄ）の厚さは、目的、用途等により０．０１μｍ〜１μｍ程度の範囲で任意に選択して使用することができる。
When the resin composition is used for the binder of the visible light type photocatalyst layer (D), the visible light type photocatalyst is dispersed in the resin composition or exists in a state coated with the resin. There is a possibility that the visible light photocatalytic function is not sufficiently developed because it is not exposed.
Therefore, in the present invention, an inorganic binder is used rather than an organic binder as a binder for the visible light photocatalyst, and the visible light photocatalyst is increased on the surface of the visible light photocatalyst layer (D) as a porous layer. It is desirable to expose.
As a specific example of formation of the visible light type photocatalyst layer (D), as described in JP-A No. 2007-185556, water in which titanium oxide (TiO 2 ), niobium oxide, and an inorganic binder are mixed in a solvent or A visible light photocatalyst dispersion can be obtained by mixing in an organic solvent. The visible light photocatalyst dispersion may be applied directly on the non-foamed olefin resin layer (B), or a photocatalyst layer transfer film can be produced and transferred by a transfer method. As a means for applying, for example, various application methods such as gravure coating, spray coating, and dip coating as described above can be selected. The coating liquid may be applied not only once but a plurality of times.
Thereafter, the solvent is removed by heating at a temperature at which the solvent can be removed. After drying is completed, aging can be performed for a required time at a temperature of about 30 to 60 ° C. Thereby, the peeling strength of the coated visible light type photocatalyst layer (D) can be improved.
The thickness of the visible light type photocatalyst layer (D) can be arbitrarily selected and used within a range of about 0.01 μm to 1 μm depending on the purpose and application.
〔２〕本発明の第２の態様である「可視光型光触媒機能を有する壁紙の製造方法」について
「可視光型光触媒機能を有する壁紙の製造方法」は、
少なくとも発泡オレフィン系樹脂層（Ａ）、非発泡オレフィン系樹脂層（Ｂ）、及び可視光型光触媒層（Ｄ）がこの順に積層された可視光型光触媒機能を有する壁紙の製造方法であって、
少なくとも前記発泡オレフィン系樹脂層（Ａ）形成用の未発泡オレフィン系樹脂層（Ａ’）に非発泡オレフィン系樹脂層が積層された壁紙基材（Ｃ’）を形成し、
次に非発泡オレフィン系樹脂層（Ｂ）上に可視光型光触媒分散液を塗布、乾燥後、
加熱により未発泡オレフィン系樹脂層（Ａ’）を発泡させて発泡オレフィン系樹脂層（Ａ）を形成することを特徴とする。
[2] Regarding the “method for producing wallpaper having a visible light photocatalytic function” according to the second aspect of the present invention, “the method for producing wallpaper having a visible light photocatalytic function”
A method for producing a wallpaper having a visible light photocatalytic function in which at least a foamed olefin resin layer (A), a non-foamed olefin resin layer (B), and a visible light photocatalyst layer (D) are laminated in this order,
Forming at least the foamed olefin resin layer (A) unfoamed olefin resin layer for forming (A ') to the non-foamed olefinic wallpaper substrate resin layer are laminated (C'),
Next, a visible light photocatalyst dispersion is applied onto the non-foamed olefin resin layer (B), dried,
The foamed olefin resin layer (A) is formed by foaming the unfoamed olefin resin layer (A ′) by heating.
（ｉ）壁紙基材（Ｃ）の形成
壁紙基材（Ｃ）の製造方法は特に限定されない。例えば、Ｔダイ押出し機による未発泡オレフィン系樹脂層（Ａ'）と非発泡オレフィン系樹脂層（Ｂ）との同時押出しが好適である。２つの層に対応する溶融樹脂を同時に押出すことにより２層の同時成膜が可能なマルチマニホールドタイプのＴダイを用いることができる。この場合、発泡剤含有樹脂層を形成するための樹脂組成物及び非発泡樹脂層を形成するための樹脂組成物をそれぞれ別個のシリンダー中に入れ、２種２層を同時に押出し成膜・積層すればよい。この方法では、同時押出し積層体は、紙質基材上に同時積層（成膜）する。紙質基材上に押出しと同時に積層された樹脂層は、熱溶融により接着性を有するため紙質基材と接着される。
尚、予め２種２層を同時成膜した積層体を用意して、それを紙質基材上に載せて、熱ラミネートすることにより壁紙基材（Ｃ）と接着してもよい。
これらの２種２層に使用される発泡オレフィン系樹脂層（Ａ）／非発泡オレフィン系樹脂層（Ｂ）としての好ましい組合せは、ＥＶＡ樹脂／ＥＶＡ樹脂、ＥＭＡＡ樹脂／ＥＶＡ樹脂、ＥＶＡ樹脂／ＥＭＡＡ樹脂、ＥＭＡＡ樹脂／ＥＭＡＡ樹脂が挙げられ、耐スクラッチ性、耐摩耗性等が優れる点で、ＥＭＡＡ樹脂／ＥＶＡ樹脂、ＥＶＡ樹脂／ＥＭＡＡ樹脂、ＥＭＡＡ樹脂／ＥＭＡＡ樹脂が好ましく、特にＥＭＡＡ樹脂／ＥＭＡＡ樹脂が好ましい。
(I) Formation of wallpaper base material (C) The manufacturing method of a wallpaper base material (C) is not specifically limited. For example, coextrusion of the unfoamed olefin resin layer (A ′) and the non-foamed olefin resin layer (B) by a T-die extruder is suitable. A multi-manifold type T-die capable of simultaneously forming two layers by simultaneously extruding molten resin corresponding to two layers can be used. In this case, the resin composition for forming the foaming agent-containing resin layer and the resin composition for forming the non-foamed resin layer are placed in separate cylinders, and two types and two layers are simultaneously extruded to form and laminate. That's fine. In this method, the coextruded laminate is simultaneously laminated (film formation) on a paper-based substrate. The resin layer laminated simultaneously with extrusion on the paper base is bonded to the paper base because it has adhesiveness by heat melting.
Alternatively, a laminate in which two types and two layers are simultaneously formed in advance may be prepared, placed on a paper substrate, and thermally laminated to adhere to the wallpaper substrate (C).
Preferred combinations as the foamed olefin resin layer (A) / non-foamed olefin resin layer (B) used in these two types and two layers are EVA resin / EVA resin, EMAA resin / EVA resin, EVA resin / EMAA Resin, EMAA resin / EMAA resin can be mentioned, and EMAA resin / EVA resin, EVA resin / EMAA resin, EMAA resin / EMAA resin are preferable, and EMAA resin / EMAA resin is particularly preferable in terms of excellent scratch resistance, abrasion resistance, etc. Is preferred.
更に上記に加えて非発泡オレフィン系樹脂層（Ｆ）を形成する場合は、非発泡オレフィン系樹脂層（Ｂ）、未発泡オレフィン系樹脂層（Ａ'）、及び非発泡オレフィン系樹脂層（Ｆ）がこの順に積層された３層を形成するのに、３種３層を同時に押出し成膜・積層することもできる。３層同時押出しすることにより、非発泡オレフィン系樹脂層（Ｂ）を表面特性向上に寄与する層とし、非発泡オレフィン系樹脂層（Ｆ）を密着性向上に寄与する層とすることにより、発泡壁紙の特性も向上する点で好ましい。なお３種３層に使用される非発泡オレフィン系樹脂層（Ｆ）としては、上記の２種２層に使用される発泡オレフィン系樹脂樹脂（Ａ）／非発泡オレフィン系樹脂層（Ｂ）の組合せに加えて、非発泡オレフィン系樹脂層（Ｆ）としてＥＶＡ樹脂が使用することが、密着性を向上する点で好ましい。 Furthermore, in addition to the above, when the non-foamed olefin resin layer (F) is formed, the non-foamed olefin resin layer (B), the non-foamed olefin resin layer (A ′), and the non-foamed olefin resin layer (F) 3) can be formed and laminated by simultaneously extruding three types and three layers to form three layers laminated in this order. By three-layer coextrusion, the non-foamed olefin resin layer (B) is used as a layer that contributes to improving surface characteristics, and the non-foamed olefin resin layer (F) is used as a layer that contributes to improved adhesion. This is preferable because the characteristics of the wallpaper are also improved. In addition, as a non-foaming olefin resin layer (F) used for 3 types and 3 layers, the foamed olefin resin resin (A) / non-foamed olefin resin layer (B) used for the above 2 types and 2 layers In addition to the combination, it is preferable that EVA resin is used as the non-foamed olefin-based resin layer (F) in terms of improving adhesion.
未発泡オレフィン系樹脂層（Ａ'）を形成する樹脂組成物に無機充填剤を含むときに、発泡剤含有樹脂層を押出し成形により形成する場合には、押出し成形機の押出し口（いわゆるダイス）に無機充填剤の残渣（いわゆる目やに）が発生し易く、これがシート表面の異物となり易い。そのため、未発泡オレフィン系樹脂層（Ａ'）に無機充填剤が含まれる場合には、上記非発泡オレフィン系樹脂層（Ｂ）及び非発泡オレフィン系樹脂層（Ｆ）をそれぞれ形成する樹脂組成物を、未発泡オレフィン系樹脂層（Ａ'）を形成する樹脂組成物と共に同時押出し成形することが好ましい。同時押出し成形は、例えば、マルチマニホールドタイプのＴダイを用いることにより行える。このように未発泡オレフィン系樹脂層（Ａ'）を２つの非発泡オレフィン系樹脂層によって挟み込んだ態様で同時押出し成形することにより、前記目やにの発生を抑制することができる。 When the resin composition for forming the unfoamed olefin-based resin layer (A ′) contains an inorganic filler, when the foaming agent-containing resin layer is formed by extrusion molding, the extrusion port of the extrusion molding machine (so-called die) Inorganic filler residues (so-called eyes and eyes) are likely to occur, and this tends to be a foreign matter on the sheet surface. Therefore, when the non-foamed olefin resin layer (A ′) contains an inorganic filler, the resin composition for forming the non-foamed olefin resin layer (B) and the non-foamed olefin resin layer (F), respectively. Is preferably coextruded with the resin composition forming the unfoamed olefin-based resin layer (A ′). The coextrusion molding can be performed, for example, by using a multi-manifold type T die. In this manner, the unfoamed olefin-based resin layer (A ′) is co-extruded in such a manner that the two non-foamed olefin-based resin layers are sandwiched between the two, so that the occurrence of the above-described eye corners can be suppressed.
（ii）可視光型光触媒分散液の塗布、乾燥
本発明の可視光型光触媒分散液中に存在する可視光型光触媒は、粒子状でも繊維状でもよい。粒子状の場合の平均一次粒子径通常５００ｎｍ以下、好ましくは２００ｎｍ以下、より好ましくは１８０ｎｍ以下であるのが好ましく、また、その平均二次粒子径は通常１５μｍ以下であるのが好ましい。
本発明の可視光型光触媒分散液中に占める可視光型光触媒の含有量は、用途に応じて適宜設定すればよく特に制限されないが、通常、下限は０．１重量％以上、好ましくは１重量％以上、上限は３０重量％以下になるように設定される。なお、可視光型光触媒の含有量（すなわち分散液中の粉末の量）が多くなるほど、後述する混合（特に初期混合）を効率的に行うことができる。このことを考慮して、仕込み時には可視光型光触媒の含有量が所定量よりも多くなるような設定にしておき、後工程で溶媒を添加して希釈することにより所望の含有量となるようにすることもできる。
本発明における水系溶媒は、水を主成分とし、後述するリン酸アンモニウム塩を溶解するものであればよく、例えば、水；エタノール、メタノール、２−プロパノール、ブタノール等のアルコール類と水との混合溶媒のような水性媒体；などが挙げられる。これらの中でも特に、水が好ましい。
(Ii) Application and drying of visible light photocatalyst dispersion The visible light photocatalyst present in the visible light photocatalyst dispersion of the present invention may be in the form of particles or fibers. In the case of particles, the average primary particle size is usually 500 nm or less, preferably 200 nm or less, more preferably 180 nm or less, and the average secondary particle size is preferably 15 μm or less.
The content of the visible light type photocatalyst in the visible light type photocatalyst dispersion of the present invention is not particularly limited as long as it is appropriately set depending on the application, but the lower limit is usually 0.1% by weight or more, preferably 1% by weight. % And the upper limit is set to be 30% by weight or less. Note that as the content of the visible light type photocatalyst (that is, the amount of powder in the dispersion) increases, the later-described mixing (particularly initial mixing) can be performed more efficiently. Taking this into consideration, the content of the visible light photocatalyst is set to be higher than a predetermined amount at the time of preparation, and a desired content is obtained by adding a solvent and diluting in a subsequent step. You can also
The aqueous solvent in the present invention may be any solvent that contains water as a main component and dissolves an ammonium phosphate salt described later. For example, water; a mixture of alcohols such as ethanol, methanol, 2-propanol, butanol, and water. An aqueous medium such as a solvent; and the like. Among these, water is particularly preferable.
本発明の可視光型光触媒分散液を得るに際しては、前記混合で得られた混合物に、さらに必要に応じて、粗大粒子の除去、可視光型光触媒含有量の調整（希釈等）、ｐＨ調整などの操作を施すことができる。これら操作の具体的手法としては、特に制限はなく、従来公知の方法を採用すればよい。
本発明の可視光型光触媒分散液を保管する際には、光が当たらない条件下で保管することが好ましく、例えば、暗室内に保管するか、もしくは、紫外線および可視光線の透過率が各々１０％以下の遮光性容器に入れて保管することが好ましい。
本発明の可視光型光触媒分散液を用いて塗膜を形成するに際しては、例えば、スピンコート、ディップコート、ドクターブレード、スプレーまたはハケ塗りなど従来公知の方法により分散液を塗布し、その後、分散液中の水系溶媒を除去しうる温度で加熱する等すればよい。本発明の可視光型光触媒分散液による塗膜形成は、例えば、硝子、プラスチック、金属、陶磁器、コンクリートなど、あらゆる基材に対して行なうことができる。
When obtaining the visible light photocatalyst dispersion of the present invention, the mixture obtained by the above mixing is further removed, if necessary, removal of coarse particles, adjustment of the visible light photocatalyst content (dilution, etc.), pH adjustment, etc. Can be performed. There is no restriction | limiting in particular as a specific method of these operation, What is necessary is just to employ | adopt a conventionally well-known method.
When storing the visible light type photocatalyst dispersion liquid of the present invention, it is preferable to store it under conditions where it is not exposed to light. For example, the visible light type photocatalyst dispersion liquid is stored in a dark room or has an ultraviolet and visible light transmittance of 10 each. It is preferable to store it in a light-shielding container of no more than%.
When forming a coating film using the visible light type photocatalyst dispersion liquid of the present invention, for example, the dispersion liquid is applied by a conventionally known method such as spin coating, dip coating, doctor blade, spray or brush coating, and then dispersed. What is necessary is just to heat at the temperature which can remove the aqueous solvent in a liquid. The coating film formation by the visible light type photocatalyst dispersion liquid of the present invention can be performed on any base material such as glass, plastic, metal, ceramics, concrete and the like.
（iii）未発泡オレフィン系樹脂層（Ａ’）の発泡
必要に応じて裏打ち紙層（Ｇ）上に未発泡オレフィン系樹脂層（Ａ’）／非発泡オレフィン系樹脂層（Ｂ）／可視光型光触媒層（Ｄ）、又は非発泡オレフィン系樹脂層（Ｆ）／未発泡オレフィン系樹脂層（Ａ’）／非発泡オレフィン系樹脂層（Ｂ）／可視光型光触媒層（Ｄ）をこの順に積層後、未発泡オレフィン樹脂層（Ａ’）を加熱することにより発泡オレフィン系樹脂層（Ａ）を形成する。加熱条件は、熱分解型発泡剤の分解により発泡オレフィン系樹脂層（Ａ）が形成される条件ならば限定されない。加熱温度は２１０〜２４０℃程度が好ましく、加熱時間は２０〜８０秒程度が好ましい。
前記加熱処理の前に、電子線照射を行ってもよい。電子線照射より樹脂成分を架橋できるため、壁紙の表面強度、発泡程度等を制御することができる。電子線のエネルギーは、１５０〜２５０ｋＶ程度が好ましい。照射量は、１〜７Ｍｒａｄ程度が好ましい。電子線源としては、公知の電子線照射装置が使用できる。なお、架橋は、化学架橋剤（架橋剤又は架橋助剤ともいう。）を用いて実施することもできる。
(Iii) Foaming of the unfoamed olefin-based resin layer (A ′) If necessary, the unfoamed olefin-based resin layer (A ′) / non-foamed olefin-based resin layer (B) / visible light on the backing paper layer (G) Type photocatalyst layer (D) , or non-foamed olefin resin layer (F) / unfoamed olefin resin layer (A ′) / non-foamed olefin resin layer (B) / visible light photocatalyst layer (D) in this order After the lamination, the foamed olefin resin layer (A) is formed by heating the unfoamed olefin resin layer (A ′). The heating conditions are not limited as long as the foamed olefin resin layer (A) is formed by the decomposition of the pyrolytic foaming agent. The heating temperature is preferably about 210 to 240 ° C., and the heating time is preferably about 20 to 80 seconds.
Electron beam irradiation may be performed before the heat treatment. Since the resin component can be cross-linked by electron beam irradiation, the surface strength of the wallpaper, the degree of foaming, and the like can be controlled. The energy of the electron beam is preferably about 150 to 250 kV. The irradiation amount is preferably about 1 to 7 Mrad. A known electron beam irradiation apparatus can be used as the electron beam source. Crosslinking can also be performed using a chemical crosslinking agent (also referred to as a crosslinking agent or a crosslinking aid).
電子線照射を行う場合には、前記組成物中に架橋剤を含有してもよい。架橋剤としては、電子線照射による架橋を促進するものであればよい。例えば、ネオペンチルグリコールジメタクリレート、トリメチロールプロパントリメタクリレート等の多官能性モノマー、オリゴマーなどが挙げられる。架橋剤は、樹脂成分１００重量部に対して０〜１０重量部程度とすることが好ましく、特に１〜４重量部とすることがより好ましい。 In the case of performing electron beam irradiation, the composition may contain a crosslinking agent. Any crosslinking agent that promotes crosslinking by electron beam irradiation may be used. Examples thereof include polyfunctional monomers such as neopentyl glycol dimethacrylate and trimethylolpropane trimethacrylate, oligomers, and the like. The crosslinking agent is preferably about 0 to 10 parts by weight, more preferably 1 to 4 parts by weight, based on 100 parts by weight of the resin component.
本発明の第２の態様である「可視光型光触媒機能を有する壁紙の製造方法」の採用により、可視光型光触媒分散液の塗布後、可視光型光触媒層（Ｄ）を形成するための乾燥工程と未発泡オレフィン系樹脂層（Ａ'）の発泡を同時に行なえることで製造工程が少なくなり、コストを低減できる。又、前記発泡後に、絵柄模様層（Ｅ）や可視光型光触媒層（Ｄ）を形成した場合、発泡オレフィン系樹脂層（Ａ）の凹凸の影響により、前記層を綺麗に塗付することが難しかったが、発泡前に前記層を形成可能となったため綺麗に塗付することが可能となる。 Drying for forming a visible light type photocatalyst layer (D) after application of a visible light type photocatalyst dispersion by employing the “method for producing a wallpaper having a visible light type photocatalytic function” according to the second aspect of the present invention. By simultaneously foaming the process and the unfoamed olefin-based resin layer (A ′), the number of manufacturing processes is reduced, and the cost can be reduced. In addition, when the pattern layer (E) or the visible light photocatalyst layer (D) is formed after the foaming, the layer can be neatly applied due to the unevenness of the foamed olefin resin layer (A). Although it was difficult, since the layer can be formed before foaming, it can be applied neatly.
以下、実施例を挙げて本発明を具体的に説明する。尚、本発明は以下に記載する方法になんら限定されるものではない。
[実施例１]
（１）可視光型光触媒機能を有する壁紙の作製
以下の（ｉ）から（iii）に記載する工程により、図１（Ａ）に示す可視光型光触媒機能を有する壁紙を作製した。
（ｉ）壁紙基材の作製
公知のＴダイ押出機を用いて、いずれもエチレン−酢酸ビニル共重合体を使用して、非発泡オレフィン系樹脂層形成樹脂組成物／未発泡オレフィン系樹脂層形成樹脂組成物／非発泡オレフィン系樹脂層樹脂組成物の順に、各層の厚みが１５μｍ／１００μｍ／１０μｍになるように製膜して３層から成る積層体Ａを得た。このとき、非発泡オレフィン系樹脂層のシリンダー温度は１６０℃とし、未発泡オレフィン系樹脂層のシリンダー温度は１２０℃とし、いずれもダイス温度は１２０℃とした。
非発泡オレフィン系樹脂層と、未発泡オレフィン系樹脂層に用いた樹脂と樹脂組成物は以下の通りである。
（ａ）非発泡オレフィン系樹脂：エチレン−酢酸ビニル系共重合体：住友化学（株）製、商品名：スミテートＣＶ５０５３：１００質量部
（ｂ）未発泡オレフィン系層樹脂組成物：エチレン−酢酸ビニル系共重合体（住友化学（株）製、商品名：スミテートＣＶ５０５３）：１００質量部
・発泡剤（永和化成製、商品名：ＡＤＣＡ＃３）：４質量部
・炭酸カルシウム（白石工業製、商品名：ホワイトンＨ）：３０質量部
・二酸化チタン（顔料）（デュポン製、商品名：タイピュアＲ−１０８）：２０質量部
・光安定材（（株）ADEKA製、商品名：ＯＦ−１０１）：１質量部
・架橋剤（ＪＳＲ（株）製、商品名：オブスターＪＶＡ−７０２）：１質量部
Hereinafter, the present invention will be specifically described with reference to examples. The present invention is not limited to the method described below.
[Example 1]
(1) Production of wallpaper having visible light type photocatalytic function A wallpaper having a visible light type photocatalytic function shown in FIG. 1 (A) was produced by the steps described in (i) to (iii) below.
(I) Production of wallpaper base material Using a known T-die extruder, both use an ethylene-vinyl acetate copolymer to form a non-foamed olefin resin layer-forming resin composition / unfoamed olefin resin layer. In order of the resin composition / non-foamed olefin resin layer resin composition, a film was formed such that the thickness of each layer was 15 μm / 100 μm / 10 μm to obtain a laminate A composed of three layers. At this time, the cylinder temperature of the non-foamed olefin resin layer was 160 ° C., the cylinder temperature of the unfoamed olefin resin layer was 120 ° C., and the die temperature was 120 ° C. in all cases.
The resin and resin composition used for the non-foamed olefin resin layer and the non-foamed olefin resin layer are as follows.
(A) Non-foamed olefin resin: ethylene-vinyl acetate copolymer: manufactured by Sumitomo Chemical Co., Ltd., trade name: Smitate CV5053: 100 parts by mass (b) Unfoamed olefin-based layer resin composition: ethylene-vinyl acetate -Based copolymer (manufactured by Sumitomo Chemical Co., Ltd., trade name: Smitate CV5053): 100 parts by mass Foaming agent (manufactured by Eiwa Kasei, trade name: ADCA # 3): 4 parts by mass Name: Whiteon H): 30 parts by mass Titanium dioxide (pigment) (manufactured by DuPont, trade name: Taipure R-108): 20 parts by mass Light stabilizer (made by ADEKA, trade name: OF-101) : 1 part by mass ・ Crosslinking agent (manufactured by JSR Corporation, trade name: Obstar JVA-702): 1 part by mass
（ii）壁紙基材に裏打ち紙層の積層
次に、前記積層体Ａの非発泡層樹脂（１０μｍ）面に裏打ち紙層（米秤量６０ｇ／ｍ２ 興人（株）製、ＷＫ−ＦＫＫＤ）を積層して積層体Ｂを得た。
その後、該積層体Ａの表面強度の向上を図る目的で、積層体Ｂに対して２００ｋＶ、５Ｍｒａｄにて電子線照射を行なった。
（iii）非発泡オレフィン系樹脂層（１５μｍ）上に、プライマー層、絵柄模様層、及び可視光型光触媒層の形成
次いで、グラビア印刷により、積層体Ｂの非発泡オレフィン系樹脂層（１５μｍ）の表面にＥＶＡ系水性エマルジョンを２ｇ／ｍ２塗布して、乾燥させ、プライマー層を形成し、積層体Ｃを得た。
積層体Ｃのプライマー層上に水性インキ（大日精化工業（株）製、商品名：ハイドリック）を用いて布目模様（絵柄模様層）を印刷し、更にその上に可視光型光触媒コーティング液（住友化学（株）製、酸化チタン光触媒コーティング剤（無機バインダー入））を乾燥後の重量が１ｇ／ｍ２となるように塗工して積層体Ｄを得た。
その後、該積層体Ｄを加熱発熱炉内で、２３０℃で発泡剤が含有されている未発泡オレフィン系樹脂層を発泡させ、次に発泡層の表側にエンボス加工を施して、布目模様パターンを賦型し、図１（Ａ）に示す壁紙を得た。
(Ii) Lamination of backing paper layer on wallpaper substrate Next, the backing paper layer (rice weighed 60 g / m 2 manufactured by Kojin Co., Ltd., WK-FKKD) on the non-foamed layer resin (10 μm) surface of the laminate A To obtain a laminate B.
Thereafter, for the purpose of improving the surface strength of the laminate A, the laminate B was irradiated with an electron beam at 200 kV and 5 Mrad.
(Iii) Formation of a primer layer, a pattern layer, and a visible light photocatalyst layer on the non-foamed olefin resin layer (15 μm) Subsequently, the non-foamed olefin resin layer (15 μm) of the laminate B is obtained by gravure printing. A 2 g / m 2 EVA aqueous emulsion was applied to the surface and dried to form a primer layer, whereby a laminate C was obtained.
A texture pattern (pattern pattern layer) is printed on the primer layer of the laminate C using water-based ink (manufactured by Dainichi Seika Kogyo Co., Ltd., trade name: Hydrick), and a visible light type photocatalytic coating solution is further formed thereon. (The Sumitomo Chemical Co., Ltd. product, the titanium oxide photocatalyst coating agent (inorganic binder containing)) was apply | coated so that the weight after drying might be 1 g / m < 2 >, and the laminated body D was obtained.
Thereafter, the laminate D is foamed with an unfoamed olefin-based resin layer containing a foaming agent at 230 ° C. in a heating exothermic furnace, and then embossed on the front side of the foamed layer to form a textured pattern. Molding was performed to obtain the wallpaper shown in FIG.
（２）可視光型光触媒機能を有する壁紙の評価
（ｉ）紫外光照射によるアセトアルデヒドの分解試験
前記壁紙試験片（５ｃｍ×１０ｃｍ）を、内容量５リットル（Ｌ）のテドラーバック内に挿入し、５Ｌの合成空気〔（窒素：酸素）容積比：４／１、ＲＨ５０％〕をテドラーバック内に送り込み、ブラックライト２ｍＷ／ｃｍ２で１６時間初期化処理をした。
その後、テドラーバック内のアセトアルデヒド濃度が２０ｐｐｍとなるように１体積％のアセトアルデヒド０．９４ｍｌをテドラーバック内に送り込み、ブラックライト１ｍＷ／ｃｍ２を照射して、アセトアルデヒドの分解試験を実施した。テドラーバック内のアセトアルデヒド濃度の経時変化はガスクロマトグラフィーにより測定した。測定結果を図２に示す。
（ii）可視光照射によるアセトアルデヒドの分解試験
上記壁紙試験片（５ｃｍ×１０ｃｍ）を内容量５リットル（Ｌ）のテドラーバック内に挿入し、４６９ミリリットル（ｍＬ）の合成空気〔（窒素：酸素）容積比：４／１、ＲＨ５０％〕を送り込み、ブラックライト２ｍＷ／ｃｍ２で３２時間初期化処理を施した。
その後、テドラーバック内のアセトアルデヒド濃度が２０ｐｐｍとなるように１体積％のアセトアルデヒド０．９４ｍｌをテドラーバック内に送り込み、蛍光灯６０００ｌｘを照射して、アセトアルデヒドの分解試験を実施した。テドラーバック内のアセトアルデヒド濃度の経時変化はガスクロマトグラフィーにより測定した。測定結果を図３に示す。
（iii）考察
実施例１で作製した壁紙は、ブラックライト、及び蛍光灯のいずれにおいても光活性を有していることが確認された。
(2) Evaluation of wallpaper having visible light type photocatalytic function (i) Decomposition test of acetaldehyde by ultraviolet light irradiation The wall paper test piece (5 cm × 10 cm) was inserted into a Tedlar bag having an internal volume of 5 liters (L). The synthetic air [(nitrogen: oxygen) volume ratio: 4/1, RH 50%] was fed into the Tedlar bag and initialized with black light of 2 mW / cm 2 for 16 hours.
Thereafter, 0.94 ml of 1% by volume of acetaldehyde was fed into the Tedlar bag so that the concentration of acetaldehyde in the Tedlar bag was 20 ppm, and 1 mW / cm 2 of black light was irradiated to conduct the acetaldehyde decomposition test. The time-dependent change of the acetaldehyde concentration in the Tedlar bag was measured by gas chromatography. The measurement results are shown in FIG.
(Ii) Decomposition test of acetaldehyde by irradiation with visible light The above-mentioned wall paper test piece (5 cm × 10 cm) was inserted into a 5 liter (L) Tedlar bag, and 469 ml (mL) of synthetic air [(nitrogen: oxygen) volume Ratio: 4/1, RH 50%], and an initialization process was performed with black light of 2 mW / cm 2 for 32 hours.
Thereafter, 0.94 ml of 1% by volume of acetaldehyde was fed into the Tedlar bag so that the concentration of acetaldehyde in the Tedlar bag was 20 ppm, and a fluorescent lamp 6000 lx was irradiated to conduct an acetaldehyde decomposition test. The time-dependent change of the acetaldehyde concentration in the Tedlar bag was measured by gas chromatography. The measurement results are shown in FIG.
(Iii) Discussion It was confirmed that the wallpaper produced in Example 1 has photoactivity both in the black light and the fluorescent lamp.
[比較例１]
（１）壁紙の作製
（ｉ）壁紙基材の作製
基材として壁紙用裏打紙（興人（株）製、商品名：ＷＫ−ＦＫＫＤ、米秤量６０ｇ／ｍ２）上に、コンマコーター法を用い、下記組成の発泡樹脂組成物を１００μｍの厚みとなるように積層壁紙基材を得た。
・塩化ビニル樹脂（東ソー（株）製、商品名：Ｒ-７２０）：１００重量部
・二酸化チタン（顔料 デュポン製、商品名：タイピュアＲ−１０８）：１７重量部
・炭酸カルシウム：白石工業製、商品名：ホワイトンＨ）：１００重量部
・可塑剤（三建加工製、ＤＯＰ）：５５重量部
・発泡剤（永和化成製、商品名：ＡＤＣＡ＃３）：４重量部
・光安定材（（株）ADEKA製、商品名：ＯＦ−１０１）：１重量部
・セル調整剤（共同薬品製、商品名：ＫＦ-１１０Ａ-６）：１重量部
[Comparative Example 1]
(1) Preparation of wallpaper (i) Preparation of wallpaper substrate A comma coater method is used on a backing paper for wallpaper (made by Kojin Co., Ltd., trade name: WK-FKKD, rice weighing 60 g / m 2 ) as a substrate. Using the foamed resin composition having the following composition, a laminated wallpaper base material was obtained so as to have a thickness of 100 μm.
-Vinyl chloride resin (manufactured by Tosoh Corporation, trade name: R-720): 100 parts by weight-Titanium dioxide (manufactured by DuPont, trade name: Taipure R-108): 17 parts by weight
・ Calcium carbonate: manufactured by Shiroishi Kogyo Co., Ltd., trade name: Whiten H): 100 parts by weight ・ Plasticizer (manufactured by Sanken Processing Co., Ltd., DOP): 55 parts by
（ii）絵柄模様層、触媒層の形成
前記壁紙基材上に水性インキ（大日精化工業（株）製、商品名：ハイドリック）を用いて、布目模様（絵柄模様層）を印刷した。
次に、上記絵柄層の上に可視光型光触媒コーティング液（住友化学（株）製、酸化チタン光触媒コーティング剤（無機バインダー入））を乾燥後の重量が１ｇ／ｍ２となるように塗工して積層体を得た。該積層体を加熱発泡炉を用いて２３０℃で発泡させて発泡樹脂層を形成した後、発泡体の表側にエンボス加工を施して、布目パターンを賦型して、図１（Ｂ）に示す壁紙を得た。
（２）壁紙の評価
実施例１に記載したと同様に、ブラックライト、及び蛍光灯によるアセトアルデヒドの分解試験を実施した。結果を図２、３に示す。
比較例１で作製した壁紙は、ブラックライト、及び蛍光灯のいずれにおいてもアセトアルデヒドの分解は殆ど観察されず、光活性を有していなかった。
(Ii) Formation of pattern pattern layer and catalyst layer A texture pattern (pattern pattern layer) was printed on the wallpaper base material using water-based ink (manufactured by Dainichi Seika Kogyo Co., Ltd., trade name: Hydrick).
Next, a visible light photocatalyst coating solution (manufactured by Sumitomo Chemical Co., Ltd., titanium oxide photocatalyst coating agent (with inorganic binder)) is applied onto the pattern layer so that the weight after drying is 1 g / m 2. To obtain a laminate. The laminate is foamed at 230 ° C. using a heating foaming furnace to form a foamed resin layer, then embossed on the front side of the foam, and a texture pattern is formed, as shown in FIG. 1 (B). Got a wallpaper.
(2) Evaluation of wallpaper In the same manner as described in Example 1, a decomposition test of acetaldehyde with a black light and a fluorescent lamp was performed. The results are shown in FIGS.
The wallpaper produced in Comparative Example 1 showed almost no degradation of acetaldehyde in both the black light and the fluorescent lamp, and had no photoactivity.
[比較例２]
（１）壁紙の作製
前記実施例１に記載の壁紙において、絵柄模様層の上に、可視光型光触媒コーティング液の代わりに、水系アクリルコート液（日信化学工業（株）製、商品名：ビニブラン）を乾燥後の塗布重量が１ｇ／ｍ２となるように塗工し、乾燥して、図１（Ｃ）に示す壁紙を得た。
（２）壁紙の評価
実施例１に記載したと同様に、ブラックライト、及び蛍光灯によるアセトアルデヒドの解試験を実施した。結果を表１と図２、３に示す。
比較例２で作製した壁紙は、ブラックライト、及び蛍光灯のいずれにおいてもアセトアルデヒドの分解は殆ど観察されず、光活性を有していなかった。
[Comparative Example 2]
(1) Production of wallpaper In the wallpaper described in Example 1, an aqueous acrylic coating solution (manufactured by Nissin Chemical Industry Co., Ltd., trade name) on the pattern layer instead of the visible light type photocatalytic coating solution. Viniblanc) was applied so that the coating weight after drying was 1 g / m 2 and dried to obtain the wallpaper shown in FIG.
(2) Evaluation of wallpaper In the same manner as described in Example 1, an acetaldehyde solution test was performed using a black light and a fluorescent lamp. The results are shown in Table 1 and FIGS.
The wallpaper produced in Comparative Example 2 showed almost no degradation of acetaldehyde in both the black light and the fluorescent lamp, and had no photoactivity.
１０ 壁紙
１１ 発泡オレフィン系樹脂層（Ａ）
１２ 非発泡オレフィン系樹脂層（Ｂ）
１３ 可視光型光触媒層（Ｄ）
１４ 絵柄模様相（Ｅ）
１５ 裏打ち紙層（Ｇ）
１６ 非発泡オレフィン系樹脂層（Ｆ）
２０ 比較例１で形成した壁紙
２１ 塩化ビニル樹脂発泡層
３０ 比較例２で形成した壁紙
３１ アクリルコート層
10
12 Non-foamed olefin resin layer (B)
13 Visible light photocatalyst layer (D)
14 Pattern (E)
15 Backing paper layer (G)
16 Non-foamed olefin resin layer (F)
20
Claims (6)
少なくとも前記発泡オレフィン系樹脂層（Ａ）形成用の未発泡オレフィン系樹脂層（Ａ’）に非発泡オレフィン系樹脂層が積層された壁紙基材（Ｃ’）を形成し、
次に非発泡オレフィン系樹脂層（Ｂ）上に可視光型光触媒分散液を塗布、乾燥後、
加熱により未発泡オレフィン系樹脂層（Ａ’）を発泡させて発泡オレフィン系樹脂層（Ａ）を形成することを特徴とする、
可視光型光触媒機能を有する壁紙の製造方法。 A method for producing a wallpaper having a visible light photocatalytic function in which at least a foamed olefin resin layer (A), a non-foamed olefin resin layer (B), and a visible light photocatalyst layer (D) are laminated in this order,
Forming at least the foamed olefin resin layer (A) unfoamed olefin resin layer for forming (A ') to the non-foamed olefinic wallpaper substrate resin layer are laminated (C'),
Next, a visible light photocatalyst dispersion is applied onto the non-foamed olefin resin layer (B), dried,
The foamed olefin-based resin layer (A) is formed by foaming the unfoamed olefin-based resin layer (A ′) by heating,
A method for producing a wallpaper having a visible light photocatalytic function.
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| JP5884271B2 (en) * | 2011-02-09 | 2016-03-15 | 大日本印刷株式会社 | Wallpaper with visible light photocatalytic function |
| JP5732957B2 (en) * | 2011-03-25 | 2015-06-10 | 大日本印刷株式会社 | Photocatalytic foam wallpaper |
| JP2012211402A (en) * | 2011-03-30 | 2012-11-01 | Dainippon Printing Co Ltd | Method for producing anti-allergic wallpaper |
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