JP5568744B2 - Self-cleaning antifouling sheet - Google Patents
Self-cleaning antifouling sheet Download PDFInfo
- Publication number
- JP5568744B2 JP5568744B2 JP2010233353A JP2010233353A JP5568744B2 JP 5568744 B2 JP5568744 B2 JP 5568744B2 JP 2010233353 A JP2010233353 A JP 2010233353A JP 2010233353 A JP2010233353 A JP 2010233353A JP 5568744 B2 JP5568744 B2 JP 5568744B2
- Authority
- JP
- Japan
- Prior art keywords
- photocatalyst
- sheet
- resin
- synthetic resin
- sea
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 230000003373 anti-fouling effect Effects 0.000 title claims description 64
- 238000004140 cleaning Methods 0.000 title claims description 48
- 239000011941 photocatalyst Substances 0.000 claims description 209
- 239000002245 particle Substances 0.000 claims description 121
- 229920003002 synthetic resin Polymers 0.000 claims description 94
- 239000000057 synthetic resin Substances 0.000 claims description 94
- 230000001699 photocatalysis Effects 0.000 claims description 78
- 239000010410 layer Substances 0.000 claims description 72
- 239000002346 layers by function Substances 0.000 claims description 60
- 239000000835 fiber Substances 0.000 claims description 48
- 239000000463 material Substances 0.000 claims description 33
- 239000004744 fabric Substances 0.000 claims description 28
- 239000000758 substrate Substances 0.000 claims description 25
- 239000002131 composite material Substances 0.000 claims description 10
- 150000002978 peroxides Chemical class 0.000 claims description 9
- 239000011162 core material Substances 0.000 claims description 8
- 229920005989 resin Polymers 0.000 description 102
- 239000011347 resin Substances 0.000 description 102
- 239000000203 mixture Substances 0.000 description 96
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 32
- 238000000576 coating method Methods 0.000 description 32
- 238000009472 formulation Methods 0.000 description 32
- 239000011248 coating agent Substances 0.000 description 31
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 25
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 20
- 239000002335 surface treatment layer Substances 0.000 description 20
- 239000007788 liquid Substances 0.000 description 17
- -1 polyethylene Polymers 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
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- 238000000354 decomposition reaction Methods 0.000 description 13
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 12
- 229920002050 silicone resin Polymers 0.000 description 12
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- 229920006026 co-polymeric resin Polymers 0.000 description 10
- 230000003628 erosive effect Effects 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 150000001451 organic peroxides Chemical class 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 239000012528 membrane Substances 0.000 description 9
- 239000002759 woven fabric Substances 0.000 description 9
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
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- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
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- 239000004800 polyvinyl chloride Substances 0.000 description 4
- 229920000915 polyvinyl chloride Polymers 0.000 description 4
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000011246 composite particle Substances 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 229920000578 graft copolymer Polymers 0.000 description 3
- 239000002905 metal composite material Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 235000012424 soybean oil Nutrition 0.000 description 3
- 239000003549 soybean oil Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 description 2
- 235000011010 calcium phosphates Nutrition 0.000 description 2
- 239000000378 calcium silicate Substances 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- IQBJFLXHQFMQRP-UHFFFAOYSA-K calcium;zinc;phosphate Chemical compound [Ca+2].[Zn+2].[O-]P([O-])([O-])=O IQBJFLXHQFMQRP-UHFFFAOYSA-K 0.000 description 2
- 238000003421 catalytic decomposition reaction Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 description 2
- 229960001545 hydrotalcite Drugs 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
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- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
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- XXQBEVHPUKOQEO-UHFFFAOYSA-N potassium superoxide Chemical compound [K+].[K+].[O-][O-] XXQBEVHPUKOQEO-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 239000004945 silicone rubber Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 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 2
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- 229910000166 zirconium phosphate Inorganic materials 0.000 description 2
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 2
- NLBJAOHLJABDAU-UHFFFAOYSA-N (3-methylbenzoyl) 3-methylbenzenecarboperoxoate Chemical compound CC1=CC=CC(C(=O)OOC(=O)C=2C=C(C)C=CC=2)=C1 NLBJAOHLJABDAU-UHFFFAOYSA-N 0.000 description 1
- AGKBXKFWMQLFGZ-UHFFFAOYSA-N (4-methylbenzoyl) 4-methylbenzenecarboperoxoate Chemical compound C1=CC(C)=CC=C1C(=O)OOC(=O)C1=CC=C(C)C=C1 AGKBXKFWMQLFGZ-UHFFFAOYSA-N 0.000 description 1
- PEVRKKOYEFPFMN-UHFFFAOYSA-N 1,1,2,3,3,3-hexafluoroprop-1-ene;1,1,2,2-tetrafluoroethene Chemical group FC(F)=C(F)F.FC(F)=C(F)C(F)(F)F PEVRKKOYEFPFMN-UHFFFAOYSA-N 0.000 description 1
- VCRZAKVGPJFABU-UHFFFAOYSA-N 10-phenoxarsinin-10-yloxyphenoxarsinine Chemical compound C12=CC=CC=C2OC2=CC=CC=C2[As]1O[As]1C2=CC=CC=C2OC2=CC=CC=C21 VCRZAKVGPJFABU-UHFFFAOYSA-N 0.000 description 1
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- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
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- RPBWMJBZQXCSFW-UHFFFAOYSA-N 2-methylpropanoyl 2-methylpropaneperoxoate Chemical compound CC(C)C(=O)OOC(=O)C(C)C RPBWMJBZQXCSFW-UHFFFAOYSA-N 0.000 description 1
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- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
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- 238000009792 diffusion process Methods 0.000 description 1
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- 238000007598 dipping method Methods 0.000 description 1
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Landscapes
- Laminated Bodies (AREA)
- Catalysts (AREA)
Description
本発明は、自浄防汚シートに関するものである。更に詳しく述べるならば、本発明は自浄防汚と耐久性に優れ、中大型テント、テント倉庫などの膜構造建築物用部材、屋外大型看板用サインシート、店舗一体型内照看板などの産業用資材として好適に用いられる自浄防汚に優れた可撓性シートに関するものである。 The present invention relates to a self-cleaning antifouling sheet. More specifically, the present invention is excellent in self-cleaning antifouling and durability, and is suitable for industrial use such as medium and large tents, members for membrane structure buildings such as tent warehouses, outdoor large signboards, store-integrated interior lighting signs, etc. The present invention relates to a flexible sheet excellent in self-cleaning antifouling used suitably as a material.
繊維布帛を基布として、その片面以上に熱可塑性樹脂製防水層を形成してなる積層シート、いわゆるターポリンや帆布は、日除けテント、中大型テント、テント倉庫、及び建築養生シートなどの建築部材、並びにトラック用幌、看板用サインシート、及びフレキシブルコンテナーなどの産業資材シートの分野に用いられている。最近、日除けテント、中大型テント、テント倉庫などの膜構造物の恒久性用途において、その耐用年数の向上に伴う付加価値としての光触媒防汚技術が注目されるようになり、本出願人においてもこのような光触媒層付の膜材を種々提案してきた。（特許文献１〜３） A laminated sheet formed by forming a waterproof layer made of a thermoplastic resin on one side or more of a fiber cloth as a base cloth, so-called tarpaulins and canvases are building members such as sunshade tents, medium and large tents, tent warehouses, and building curing sheets, In addition, it is used in the field of industrial material sheets such as truck hoods, signboards for signboards, and flexible containers. Recently, in the permanent use of membrane structures such as sunshade tents, medium- and large-sized tents, and tent warehouses, photocatalytic antifouling technology as an added value accompanying the improvement of the service life has attracted attention. Various film materials with such a photocatalyst layer have been proposed. (Patent Documents 1 to 3)
これらの光触媒層付膜材は、膜材表面に光触媒層を設けることで汚れ成分を光触媒で分解し、この残滓を降雨洗浄しようとするものであるが、しばしば、これらの膜材では汚れの種類や付着状態によっては除去効果発現までに長いリードタイムを要していた。このようなリードタイムの短縮の方法として、光触媒層の風化による汚れ除去の提案がなされている。この方法は意図的に光触媒層表面を分解コントロールして、付着汚れごと表面層を脱落させ、常時新しい表面を露出させることで美観維持を図ろうとするものである。（特許文献４） These film materials with a photocatalyst layer are intended to decompose a dirt component with a photocatalyst by providing a photocatalyst layer on the surface of the film material and to wash this residue by rain. Depending on the adhesion state, a long lead time was required until the removal effect was manifested. As a method for shortening the lead time, there has been proposed removal of dirt by weathering the photocatalyst layer. In this method, the surface of the photocatalyst layer is intentionally decomposed and controlled, and the surface layer is dropped together with the attached dirt, so that a new surface is always exposed to maintain the aesthetic appearance. (Patent Document 4)
しかし、これらの方法では光触媒層の自己衰痩を伴うため、一定期間の使用を過ぎると急激に防汚効果が消失してしまう問題を孕んでいる。従って、防汚層の分解作用による汚れ除去効果を発揮しながら、尚且つ防汚層を保持することが出来れば、膜材の使用開始から長期間に渡たる防汚効果を持続させることが可能となる。 However, these methods involve the self-decay of the photocatalyst layer, and therefore, there is a problem that the antifouling effect disappears rapidly after a certain period of use. Therefore, it is possible to maintain the antifouling effect for a long period of time from the start of use of the membrane material if the antifouling layer can be retained while exhibiting the effect of removing the dirt due to the decomposition action of the antifouling layer. It becomes.
本発明は、光触媒機能層を附帯する膜材において、光触媒層の分解作用による汚れ除去効果を発揮しながら、光触媒層を保持し、それによって膜材の使用開始から長期間に渡たっての防汚効果を持続させることが出来る自浄防汚シートを提供しようとするものである。 The present invention provides a film material with a photocatalyst functional layer that retains the photocatalyst layer while exhibiting the effect of removing dirt due to the decomposition action of the photocatalyst layer, thereby preventing antifouling over a long period from the start of use of the film material. It is intended to provide a self-cleaning antifouling sheet that can sustain the effect.
上記課題を解決するために、シート状基材の１面以上に光触媒機能層を有する可撓性シートにおいて、光触媒機能層を、光触媒粒子含有域と光触媒粒子非含有域からなる海島微細構造（Ｉ）で形成し、この海島微細構造（Ｉ）において、海成分を、光触媒粒子を含有する合成樹脂（Ａ）から形成された光触媒粒子含有域として、島成分を、光触媒粒子を含有しない合成樹脂（Ｂ）から形成された光触媒粒子非含有域として、さらに合成樹脂（Ａ）は光触媒活性による被分解性で、かつ前記合成樹脂（Ｂ）は光触媒活性に対して難分解性とすること、さらにシート状基材と光触媒機能層との間に、光触媒粒子含有域と光触媒粒子非含有域からなる海島微細構造（ＩＩ）を形成する光触媒中間層を設けること、さらに島成分に過酸化物を含有させることなどにより、光触媒層の分解作用による汚れ除去効果を発揮しながら、光触媒層を保持し、それによって膜材の使用開始から長期間に渡たっての防汚効果を持続させることを見出して本発明を完成するに至った。 In order to solve the above problems, in a flexible sheet having a photocatalytic functional layer on one or more surfaces of a sheet-like substrate, the photocatalytic functional layer is composed of a sea-island microstructure (I In this sea-island microstructure (I), the sea component is a photocatalyst particle-containing region formed from a synthetic resin (A) containing photocatalyst particles, and the island component is a synthetic resin containing no photocatalyst particles ( As a non-photocatalyst particle-containing region formed from B), the synthetic resin (A) is further decomposable by photocatalytic activity, and the synthetic resin (B) is hardly decomposable with respect to photocatalytic activity. A photocatalyst intermediate layer that forms a sea-island microstructure (II) composed of a photocatalyst particle-containing region and a photocatalyst particle-free region is added between the substrate and the photocatalyst functional layer, and the island component contains a peroxide. The present invention finds that the photocatalyst layer is retained while exhibiting the dirt removal effect due to the decomposition action of the photocatalyst layer, thereby maintaining the antifouling effect over a long period from the start of use of the film material. It came to complete.
すなわち本発明の自浄防汚シートは、シート状基材の１面以上に光触媒機能層を有する可撓性シートであって、前記光触媒機能層が、光触媒粒子含有域と光触媒粒子非含有域からなる海島微細構造（Ｉ）を形成し、この海島微細構造（Ｉ）において、海成分が光触媒粒子を含有する合成樹脂（Ａ）から形成された前記光触媒粒子含有域であり、島成分が光触媒粒子を含有しない合成樹脂（Ｂ）によって形成された前記光触媒粒子非含有域であり、さらに前記合成樹脂（Ａ）は光触媒活性による被分解性を有し、かつ前記合成樹脂（Ｂ）は光触媒活性に対して難分解性であることが好ましい。これによって本発明の自浄防汚シートは光触媒層の分解作用による汚れ除去効果を発揮しながら、光触媒層を保持し、それによって膜材の使用開始から長期間に渡たっての防汚効果を持続させることを可能とする。 That is, the self-cleaning antifouling sheet of the present invention is a flexible sheet having a photocatalytic functional layer on one or more surfaces of a sheet-like substrate, and the photocatalytic functional layer is composed of a photocatalyst particle-containing region and a photocatalyst particle-free region. A sea-island microstructure (I) is formed, and in this sea-island microstructure (I), the sea component is the photocatalyst particle-containing region formed from the synthetic resin (A) containing the photocatalyst particles, and the island component is the photocatalyst particles. The photocatalyst particle-free region formed by the synthetic resin (B) not contained, the synthetic resin (A) has decomposability due to photocatalytic activity, and the synthetic resin (B) is free from photocatalytic activity. It is preferable that it is hardly decomposable. As a result, the self-cleaning antifouling sheet of the present invention retains the photocatalyst layer while demonstrating the dirt removing effect due to the decomposition action of the photocatalyst layer, thereby maintaining the antifouling effect over a long period from the start of use of the film material. Make it possible.
本発明の自浄防汚シートは、前記シート状基材と、前記光触媒機能層との間に、光触媒粒子含有域と光触媒粒子非含有域からなる海島微細構造（ＩＩ）を形成する光触媒中間層を有し、この海島微細構造（ＩＩ）において、島成分が光触媒粒子を含有しない合成樹脂（Ｃ）から形成された前記光触媒粒子非含有域であり、海成分が光触媒粒子を含有する合成樹脂（Ｄ）によって形成された前記光触媒粒子含有域であり、さらに前記合成樹脂（Ｃ）は光触媒活性による被分解性を有し、かつ前記合成樹脂（Ｄ）は光触媒活性に対して難分解性であることが好ましい。これによって本発明の自浄防汚シートは光触媒層の分解作用による汚れ除去効果を発揮しながら、光触媒層を保持し、それによって膜材の使用開始から長期間に渡たっての防汚効果を持続させることを可能とする。 The self-cleaning antifouling sheet of the present invention comprises a photocatalyst intermediate layer forming a sea-island microstructure (II) composed of a photocatalyst particle-containing region and a photocatalyst particle-free region between the sheet-like base material and the photocatalyst functional layer. In this sea-island microstructure (II), the island component is the photocatalyst particle-free region formed from the synthetic resin (C) containing no photocatalyst particles, and the sea component contains the synthetic resin (D And the synthetic resin (C) is decomposable due to photocatalytic activity, and the synthetic resin (D) is hardly decomposable with respect to photocatalytic activity. Is preferred. As a result, the self-cleaning antifouling sheet of the present invention retains the photocatalyst layer while demonstrating the dirt removing effect due to the decomposition action of the photocatalyst layer, thereby maintaining the antifouling effect over a long period from the start of use of the film material. Make it possible.
本発明の自浄防汚シートは、前記海島微細構造（Ｉ）の海成分が、前記合成樹脂（Ａ）に対して、さらに過酸化物を０．００１〜１質量％含有することが好ましい。これによって本発明の自浄防汚シートは、島成分の分解が加速されて使い始め段階から効果的自浄防汚効果を発揮することができる。 In the self-cleaning antifouling sheet of the present invention, the sea component of the sea-island microstructure (I) preferably further contains 0.001 to 1% by mass of peroxide with respect to the synthetic resin (A). As a result, the self-cleaning antifouling sheet of the present invention can exhibit an effective self-cleaning antifouling effect from the beginning of use since the decomposition of the island components is accelerated.
本発明の自浄防汚シートは、前記シート状基材が繊維布帛を芯材として含む繊維複合積層体であることが好ましい。これによって本発明の自浄防汚シートは、中大型テント、テント倉庫などの膜構造建築物用部材、屋外大型看板用サインシート、店舗一体型内照看板などの産業用資材に好適に用いることができる。 In the self-cleaning antifouling sheet of the present invention, the sheet-like base material is preferably a fiber composite laminate including a fiber fabric as a core material. Thus, the self-cleaning antifouling sheet of the present invention can be suitably used for industrial materials such as medium- and large-sized tents, members for membrane-structured buildings such as tent warehouses, outdoor large signboards, and store-integrated interior lighting signs. it can.
中大型テント、テント倉庫などの膜構造建築物用部材、屋外大型看板用サインシート、店舗一体型内照看板などの産業用資材に本発明の自浄防汚シートを用いることによって、
光触媒層の分解作用による汚れ除去効果を発揮しながら、光触媒層を保持し、それによって膜材の使用開始から長期間に渡たる防汚効果を持続させることができるので、上記膜構造建築物や看板の外観をメンテナンスフリーで美麗に維持することが出来る。
By using the self-cleaning antifouling sheet of the present invention for industrial materials such as medium and large tents, membrane structure building members such as tent warehouses, outdoor large signboard sign sheets, store-integrated interior lighting signs,
While exhibiting the dirt removal effect by the decomposition action of the photocatalyst layer, the photocatalyst layer can be held, thereby maintaining the antifouling effect over a long period from the start of use of the membrane material. The appearance of the signboard can be maintained beautifully without maintenance.
本発明の自浄防汚シートは、シート状基材の１面以上に光触媒機能層を有する可撓性シートであって、光触媒機能層が、光触媒粒子含有域と光触媒粒子非含有域からなる海島微細構造（Ｉ）を形成し、この海島微細構造（Ｉ）において、海成分が光触媒粒子を含有する合成樹脂（Ａ）から形成された光触媒粒子含有域であり、島成分が光触媒粒子を含有しない合成樹脂（Ｂ）によって形成された光触媒粒子非含有域であり、さらに前記合成樹脂（Ａ）は光触媒活性による被分解性を有し、かつ合成樹脂（Ｂ）は光触媒活性に対して難分解性であることが好ましい。本発明を達成するための海島微細構造（Ｉ）は、合成樹脂（Ａ）と合成樹脂（Ｂ）との非相溶ブレンドによる微分散によって形成され、光触媒粒子を含有する合成樹脂（Ａ）による組成物と光触媒粒子を含有しない合成樹脂（Ｂ）による組成物とを混合することによって得ることが出来る。 The self-cleaning antifouling sheet of the present invention is a flexible sheet having a photocatalytic functional layer on one or more surfaces of a sheet-like base material, and the photocatalytic functional layer is composed of a photocatalyst particle-containing region and a photocatalyst particle-free region. In this sea-island microstructure (I), a structure (I) is formed, the sea component is a photocatalyst particle-containing region formed from a synthetic resin (A) containing photocatalyst particles, and the island component does not contain photocatalyst particles. The photocatalyst particle-free region formed by the resin (B), the synthetic resin (A) has decomposability due to photocatalytic activity, and the synthetic resin (B) is hardly decomposable with respect to photocatalytic activity. Preferably there is. The sea-island microstructure (I) for achieving the present invention is formed by fine dispersion by an incompatible blend of the synthetic resin (A) and the synthetic resin (B), and is based on the synthetic resin (A) containing photocatalyst particles. It can be obtained by mixing the composition and the composition made of the synthetic resin (B) containing no photocatalyst particles.
本発明の自浄防汚シートに用いるシート状基材は、厚さ０．１〜０．３ｍｍの熱可塑性樹脂フィルム（例えば軟質〜半硬質塩化ビニル樹脂、ポリエチレン、ポリプロピレン、ポリエステル、ポリアミド、ポリウレタンなど）、または厚さ０．３〜１．０ｍｍの熱可塑性樹脂シート（例えば軟質〜半硬質塩化ビニル樹脂、塩化ビニル系エラストマー、ポリオレフィン系エラストマー、ポリエステル系エラストマー、ポリアミド系エラストマー、ポリウレタン系エラストマーなど）を用いることができるが、特に本発明の自浄防汚シートおいては特にシート状基材が繊維布帛を芯材として含む繊維複合積層体であることが引張強度及び寸法安定性に優れ好ましい。本発明に用いる繊維複合積層体は、繊維布帛に熱可塑性樹脂を含浸（ディッピィング）して固化させた態様、繊維布帛に熱可塑性樹脂を塗布（コーティング）して固化させた態様、繊維布帛に熱可塑性樹脂フィルムやシートを熱ラミネートまたは接着剤でラミネートした態様、及びこれらの組み合せによって得られる、厚さ０．３〜１．０ｍｍのシートが挙げられ、特に繊維布帛に熱可塑性樹脂を含浸して固化させた態様で繊維布帛両面に樹脂皮膜が形成された態様、繊維布帛に熱可塑性樹脂フィルムを熱ラミネートした態様であるものが、中大型テント、テント倉庫などの膜構造建築物用部材、及び屋外大型看板用サインシート、店舗一体型内照看板などの用途に好ましい。 The sheet-like substrate used for the self-cleaning antifouling sheet of the present invention is a thermoplastic resin film having a thickness of 0.1 to 0.3 mm (for example, soft to semi-rigid vinyl chloride resin, polyethylene, polypropylene, polyester, polyamide, polyurethane, etc.) Or a thermoplastic resin sheet having a thickness of 0.3 to 1.0 mm (for example, soft to semi-rigid vinyl chloride resin, vinyl chloride elastomer, polyolefin elastomer, polyester elastomer, polyamide elastomer, polyurethane elastomer, etc.) However, particularly in the self-cleaning antifouling sheet of the present invention, it is particularly preferable that the sheet-like substrate is a fiber composite laminate including a fiber fabric as a core material because of excellent tensile strength and dimensional stability. The fiber composite laminate used in the present invention is a mode in which a fiber cloth is impregnated (dipped) with a thermoplastic resin and solidified, a mode in which a thermoplastic resin is applied to the fiber cloth (coating) and solidified, and a fiber cloth is heated. Examples include a mode in which a plastic resin film or sheet is laminated with a thermal laminate or an adhesive, and a sheet having a thickness of 0.3 to 1.0 mm obtained by a combination thereof. In particular, a fiber fabric is impregnated with a thermoplastic resin. An embodiment in which a resin film is formed on both sides of the fiber fabric in a solidified form, a form in which a thermoplastic resin film is thermally laminated on the fiber cloth, a member for a membrane structure building such as a medium-to-large tent, a tent warehouse, and the like It is preferable for applications such as sign sheets for outdoor large signboards and store-integrated interior lighting signs.
シート状基材に用いる繊維布帛には織布、編布、不織布の何れであってもよい。織布は、平織、綾織、繻子織、模紗織など公知の織布が挙げられるが、中でも平織織布が、得られる自浄防汚シートの経緯物性バランスに優れ好ましい。織布は経糸及び緯糸で織製され、糸間間隙を均等において平行に多数配置した経糸、及び糸間間隙を均等において平行に多数配置した緯糸を含んで構成された空隙率５〜５０％の目空き織布（目安として糸条打込密度５〜３０本／ｉｎｃｈ）、または空隙率５％未満の高密度織布（目安として糸条打込密度３０〜８０本／ｉｎｃｈ）の何れであってもよい。これらの使い分けは目空き織布は熱可塑性樹脂フィルムの熱ラミネート用芯材に適し、高密度織布は熱可塑性樹脂による含浸加工、または塗布加工用芯材に適している。また繊維布帛には屋外使用の際、降雨の染み込みを防止するための公知の撥水処理、また、着炎時に自己消火性を付与するための公知の防炎処理が任意で施されていてもよい。 Any of a woven fabric, a knitted fabric, and a nonwoven fabric may be sufficient as the fiber fabric used for a sheet-like base material. Examples of the woven fabric include known woven fabrics such as plain weave, twill weave, satin weave and imitation weave. Of these, plain weave fabric is preferable because of excellent balance of the physical properties of the resulting self-cleaning antifouling sheet. The woven fabric is woven with warps and wefts, and includes a warp in which a large number of inter-gap gaps are arranged in parallel and a plurality of wefts in which a large number of inter-gap gaps are arranged in parallel. It is either a woven fabric with a void (as a guideline, a thread driving density of 5 to 30 yarns / inch) or a high-density woven fabric with a porosity of less than 5% (as a guideline, a yarn driving density of 30 to 80 yarns / inch). May be. As for the proper use of these, the open woven fabric is suitable for a core material for thermal lamination of a thermoplastic resin film, and the high-density woven fabric is suitable for a core material for impregnation processing or coating processing with a thermoplastic resin. Further, the fiber fabric may be optionally subjected to a known water repellent treatment for preventing rain from permeating and a known flameproofing treatment for imparting self-extinguishing properties when flaming. Good.
シート状基材に用いる繊維布帛を構成する繊維糸条は、モノフィラメント、マルチフィラメント、短繊維紡績糸条の態様が挙げられ、これらはケナフ繊維、コットン繊維、ポリプロピレン繊維、ポリエチレン繊維、ポリエステル繊維、ナイロン繊維、ビニロン繊維、アクリル繊維、芳香族ポリマー繊維、芳香族ヘテロ環ポリマー繊維、ガラス繊維、シリカ繊維、アルミナ繊維、炭素繊維など、及びこれらの混紡繊維が挙げられる。本発明に用いる繊維布帛は、フィラメント数３〜３００本、繊度１３８〜２２２３ｄｔｅｘ（デシテックス）、特に２７７〜１１１２ｄｔｅｘのポリエステルマルチフィラメント糸条繊維（特にＰＥＴ繊維、ＰＥＮ繊維）が好ましい。 Examples of the fiber yarn constituting the fiber fabric used for the sheet-like substrate include monofilament, multifilament, and short fiber spun yarn. These include kenaf fiber, cotton fiber, polypropylene fiber, polyethylene fiber, polyester fiber, and nylon. Examples thereof include fibers, vinylon fibers, acrylic fibers, aromatic polymer fibers, aromatic heterocyclic polymer fibers, glass fibers, silica fibers, alumina fibers, and carbon fibers, and blended fibers thereof. The fiber fabric used in the present invention is preferably a polyester multifilament yarn fiber (particularly PET fiber or PEN fiber) having 3 to 300 filaments and a fineness of 138 to 2223 dtex (decitex), particularly 277 to 1112 dtex.
本発明の自浄防汚シートにおいて光触媒機能層は、光触媒粒子含有域と光触媒粒子非含有域からなる海島微細構造（Ｉ）を形成し、この海島微細構造（Ｉ）において、海成分が光触媒粒子を含有する合成樹脂（Ａ）から形成された光触媒粒子含有域であり、島成分が光触媒粒子を含有しない合成樹脂（Ｂ）によって形成された光触媒粒子非含有域である。このような海島微細構造（Ｉ）は２種類の合成樹脂の溶融混合、または２種類の液状合成樹脂の攪拌混合物からなる合成樹脂非相溶対により形成される。光触媒機能層は０．０１〜０．２５ｍｍ、特に０．０２〜０．１ｍｍの厚さであることが好ましい。光触媒機能層の厚さが０．０１ｍｍ以下だとシートの自浄防汚の長期持続性が不十分となることがある。 In the self-cleaning antifouling sheet of the present invention, the photocatalytic functional layer forms a sea-island microstructure (I) composed of a photocatalyst particle-containing region and a photocatalyst particle-free region, and in this sea-island microstructure (I), the sea component contains photocatalyst particles. It is a photocatalyst particle-containing region formed from the synthetic resin (A) contained, and is a photocatalyst particle-free region formed by the synthetic resin (B) in which the island component does not contain photocatalyst particles. Such a sea-island microstructure (I) is formed by a melt-mixing of two types of synthetic resins, or a synthetic resin incompatible pair consisting of a stirring mixture of two types of liquid synthetic resins. It is preferable that the photocatalytic functional layer has a thickness of 0.01 to 0.25 mm, particularly 0.02 to 0.1 mm. If the thickness of the photocatalytic functional layer is 0.01 mm or less, the long-term sustainability of the sheet self-cleaning antifouling may be insufficient.
本発明において光触媒機能層は、２種類の合成樹脂の混合物からなる合成樹脂非相溶対で、非相溶であれば合成樹脂の組合せに制限はない。本発明に用いられる合成樹脂（Ａ）の例は、塩化ビニル樹脂、軟質塩化ビニル樹脂、オレフィン樹脂（ＰＥ，ＰＰなど）、オレフィン系共重合体樹脂、ウレタン樹脂、ウレタン系共重合体樹脂、酢酸ビニル樹脂、酢酸ビニル系共重合体樹脂、スチレン樹脂、スチレン系共重合体樹脂、ポリエステル樹脂（ＰＥＴ，ＰＥＮ，ＰＢＴなど）、ポリエステル系共重合体樹脂、合成樹脂（Ｂ）の例は、フッ素含有共重合体樹脂（ポリフッ化ビニリデン、ポリフッ化ビニリデン−ヘキサフルオロプロピレン共重合体、ポリフッ化ビニリデン−ヘキサフルオロプロピレン−テトラフルオロエチレン共重合体）、シリコーン樹脂、シリコーンゴム、ポリカーボネート、ポリアミド、ポリエーテル、ポリエステルアミド、ポリフェニレンスルフィド、ポリエーテルエステル、及びビニルエステル樹脂など、（Ａ）群及び（Ｂ）群とから選ばれた非相溶対である。 In the present invention, the photocatalytic functional layer is a synthetic resin incompatible pair composed of a mixture of two types of synthetic resins, and there is no limitation on the combination of synthetic resins as long as they are incompatible. Examples of the synthetic resin (A) used in the present invention are vinyl chloride resin, soft vinyl chloride resin, olefin resin (PE, PP, etc.), olefin copolymer resin, urethane resin, urethane copolymer resin, acetic acid. Examples of vinyl resins, vinyl acetate copolymer resins, styrene resins, styrene copolymer resins, polyester resins (PET, PEN, PBT, etc.), polyester copolymer resins, and synthetic resins (B) include fluorine. Copolymer resin (polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, polyvinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer), silicone resin, silicone rubber, polycarbonate, polyamide, polyether, polyester Amides, polyphenylene sulfide, polyether Glycol ester, and vinyl ester resin, a heterologous 溶対 selected from the group (A) and (B) groups.
これらの合成樹脂非相溶対は相分離性を示すもので特に海島微細構造（Ｉ）であることが好ましい。この海島微細構造（Ｉ）において海成分と島成分は種類の異なる樹脂で構成され、本発明においては海成分が光触媒粒子を含有する合成樹脂（Ａ）から形成された光触媒粒子含有域であり、島成分が光触媒粒子を含有しない合成樹脂（Ｂ）によって形成された光触媒粒子非含有域である。島成分を構成する合成樹脂（Ｂ）の比率は、海成分を構成する合成樹脂樹脂（Ａ）の体積に対して１０〜７０体積％（好ましくは２０〜５０体積％）、光触媒機能層全体に対する島成分含有率は９〜４１．１体積％（好ましくは１６．６〜３３．３体積％）である。光触媒機能層全体に対する島成分含有率が９体積％未満だと得られるシートの防汚効果が不十分となることがある。また島成分含有率が４１．１体積％を越えると、海島微細構造（Ｉ）バランスが反転となることがある。 These synthetic resin immiscible pairs exhibit phase separability and particularly preferably have a sea-island microstructure (I). In this sea-island microstructure (I), the sea component and the island component are composed of different types of resins, and in the present invention, the sea component is a photocatalyst particle-containing region formed from a synthetic resin (A) containing photocatalyst particles, The island component is a photocatalyst particle non-containing region formed by the synthetic resin (B) containing no photocatalyst particles. The ratio of the synthetic resin (B) constituting the island component is 10 to 70% by volume (preferably 20 to 50% by volume) with respect to the volume of the synthetic resin resin (A) constituting the sea component, and is based on the entire photocatalytic functional layer. The island component content is 9 to 41.1% by volume (preferably 16.6 to 33.3% by volume). If the island component content relative to the entire photocatalytic functional layer is less than 9% by volume, the antifouling effect of the resulting sheet may be insufficient. If the island component content exceeds 41.1% by volume, the sea-island microstructure (I) balance may be reversed.
上記海島微細構造（Ｉ）において、合成樹脂（Ａ）は光触媒活性による被分解性を有し、かつ合成樹脂（Ｂ）は光触媒活性に対して難分解性であること、すなわち海成分が被分解性を有し、島成分が難分解性であることが好ましい。島成分の形状は球状、歪んだ球状、碁石状、ラグビーボール状などである。島成分の平均粒径は０．０５〜２５μｍであり、特に０．５〜１０μｍが好ましい。 In the above-mentioned sea-island microstructure (I), the synthetic resin (A) has decomposability due to photocatalytic activity, and the synthetic resin (B) is hardly degradable with respect to photocatalytic activity, that is, the sea component is degradable. It is preferable that the island component is hardly decomposable. The shape of the island component is a sphere, a distorted sphere, a meteorite shape, a rugby ball shape, or the like. The average particle size of the island components is 0.05 to 25 μm, and 0.5 to 10 μm is particularly preferable.
本発明において光触媒機能層は、２種類の合成樹脂の非相溶混合物からなる海島微細構造（Ｉ）を有しており、かつ、海島微細構造（Ｉ）において海成分のみが光触媒粒子を含んでいる。海成分のみが光触媒粒子を含んでいるためには、合成樹脂非相溶対を構成する２種類の合成樹脂のうち、海成分を形成する側の合成樹脂（Ａ）に光触媒粒子を混練または攪拌により均一分散し、光触媒粒子を含有する合成樹脂（Ａ）と光触媒粒子を含有しない合成樹脂（Ｂ）との混合によって、光触媒粒子含有域と光触媒粒子非含有域からなる海島微細構造（Ｉ）を形成することができる。合成樹脂（Ａ）と合成樹脂（Ｂ）は非相溶対なので、過度の混合の場合にも合成樹脂（Ａ）に含有する光触媒粒子が合成樹脂（Ｂ）内に取り込まれることはなく、これによって本発明の自浄防汚シートに不可欠な海島微細構造（Ｉ）による光触媒機能層を得ることができる。 In the present invention, the photocatalytic functional layer has a sea-island microstructure (I) made of an incompatible mixture of two types of synthetic resins, and only the sea component in the sea-island microstructure (I) contains photocatalyst particles. Yes. Since only the sea component contains the photocatalyst particles, the photocatalyst particles are kneaded or stirred into the synthetic resin (A) on the side of forming the sea component out of the two types of synthetic resins constituting the synthetic resin incompatible couple. By mixing the synthetic resin (A) containing photocatalyst particles and the synthetic resin (B) containing no photocatalyst particles, a sea-island microstructure (I) consisting of a photocatalyst particle-containing region and a photocatalyst particle-free region is obtained. Can be formed. Since the synthetic resin (A) and the synthetic resin (B) are incompatible, the photocatalyst particles contained in the synthetic resin (A) are not taken into the synthetic resin (B) even in the case of excessive mixing. Thus, a photocatalytic functional layer having a sea-island microstructure (I) indispensable for the self-cleaning antifouling sheet of the present invention can be obtained.
海成分に含有させる光触媒粒子は、酸化チタン（ＴｉＯ２）、過酸化チタン（ペルオキソチタン酸）、酸化亜鉛（ＺｎＯ）、酸化錫（ＳｎＯ２）、チタン酸ストロンチウム（ＳｒＴｉＯ３）、酸化タングステン（ＷＯ３）、酸化ビスマス（Ｂｉ２Ｏ３）、酸化鉄（Ｆｅ２Ｏ３）、及びこれらの光触媒物質にＰｔ、Ｒｈ、ＲｕＯ２、Ｎｂ、Ｃｕ、Ｓｎ、ＮｉＯなどの金属及び金属酸化物をドーピングして光触媒活性を強化したもの、から選ばれた１種以上である。また、これらの光触媒粒子を担持する無機系多孔質微粒子などを使用することもできる。無機系多孔質微粒子とは具体的に、平均一次粒子径が０．０１〜１０μｍ、特に０．０５〜５μｍのシリカ、ゼオライト、チタンゼオライト、リン酸ジルコニウム、リン酸カルシウム、リン酸亜鉛カルシウム、ハイドロタルサイト、ヒドロキシアパタイト、シリカアルミナ、ケイ酸カルシウム、ケイ酸アルミン酸マグネシウム、ケイソウ土などで、これらの多孔質に光触媒粒子を担持する複合粒子である。本発明に用いる光触媒粒子は特に酸化チタンが好ましく、アナターゼ型、ルチル型、ブルッカイト型の何れも使用できる。また光触媒活性を有する酸化チタン粒子表面をシリカ、リン酸ジルコニウム、リン酸カルシウム、リン酸亜鉛カルシウム、ヒドロキシアパタイト、シリカアルミナ、ケイ酸カルシウム、ケイ酸アルミン酸マグネシウムなどの無機化合物で部分被覆してなる光触媒活性コントロールタイプの酸化チタン複合粒子が特に好ましい。これら光触媒粒子の含有量は海成分領域全体の体積、すなわち合成樹脂（Ａ）の体積に対して１０〜９０体積％、好ましくは２５〜６５体積％である。 The photocatalyst particles to be contained in the sea component are titanium oxide (TiO 2 ), titanium peroxide (peroxotitanic acid), zinc oxide (ZnO), tin oxide (SnO 2 ), strontium titanate (SrTiO 3 ), tungsten oxide (WO 3 ), bismuth oxide (Bi 2 O 3 ), iron oxide (Fe 2 O 3 ), and these photocatalytic materials are doped with metals and metal oxides such as Pt, Rh, RuO 2 , Nb, Cu, Sn, and NiO And at least one selected from those having enhanced photocatalytic activity. Further, inorganic porous fine particles supporting these photocatalyst particles can also be used. Specifically, the inorganic porous fine particles are silica, zeolite, titanium zeolite, zirconium phosphate, calcium phosphate, zinc calcium phosphate, hydrotalcite having an average primary particle diameter of 0.01 to 10 μm, particularly 0.05 to 5 μm. Hydroxyapatite, silica alumina, calcium silicate, magnesium silicate aluminate, diatomaceous earth, and the like, which are composite particles carrying photocatalyst particles in these porous materials. The photocatalyst particles used in the present invention are particularly preferably titanium oxide, and any of anatase type, rutile type and brookite type can be used. Photocatalytic activity obtained by partially coating the surface of titanium oxide particles having photocatalytic activity with inorganic compounds such as silica, zirconium phosphate, calcium phosphate, zinc calcium phosphate, hydroxyapatite, silica alumina, calcium silicate, and magnesium aluminate silicate. Control type titanium oxide composite particles are particularly preferred. The content of these photocatalyst particles is 10 to 90% by volume, preferably 25 to 65% by volume, based on the volume of the entire sea component region, that is, the volume of the synthetic resin (A).
また、本発明における光触媒機能層は、光触媒粒子含有域である海成分、すなわち合成樹脂（Ａ）の侵食度合をコントロールする目的で充填剤を添加することが好ましい。充填剤としては、金属酸化物、金属水酸化物、金属複合酸化物、金属複合水酸化物などが挙げられ、これらは具体的に酸化アルミニウム、酸化マグネシウム、酸化チタン、酸化亜鉛、酸化ジルコニウム、酸化アンチモン、酸化ケイ素（シリカ）などの金属酸化物、及びホウ酸亜鉛、ホウ酸アルミニウム、チタン酸カリウム、ジルコニウム−アンチモンなどの金属複合酸化物など、水酸化アルミニウム、水酸化マグネシウム、塩基性炭酸マグネシウムなどの金属水酸化物、及びドロマイト、ハイドロタルサイト、ホウ砂などの金属複合水酸化物が挙げられ、その他、硫酸バリウム、炭酸カルシウム、タルク、クレー、モンモリロナイト、ベントナイトなどが挙げられる。これら充填剤の粒子径は０．０１〜１０μｍであることが好ましい。 Moreover, it is preferable to add a filler for the purpose of controlling the erosion degree of the sea component which is a photocatalyst particle containing area, ie, a synthetic resin (A), in the photocatalyst functional layer in this invention. Examples of the filler include metal oxides, metal hydroxides, metal composite oxides, metal composite hydroxides, and the like. Specifically, these include aluminum oxide, magnesium oxide, titanium oxide, zinc oxide, zirconium oxide, and oxide. Metal oxides such as antimony and silicon oxide (silica), and metal complex oxides such as zinc borate, aluminum borate, potassium titanate and zirconium-antimony, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, etc. And metal composite hydroxides such as dolomite, hydrotalcite, and borax, and other examples include barium sulfate, calcium carbonate, talc, clay, montmorillonite, and bentonite. The particle diameter of these fillers is preferably 0.01 to 10 μm.
本発明における光触媒機能層は、光触媒粒子含有域である海成分、すなわち合成樹脂（Ａ）の侵食度合をコントロールする目的で合成樹脂（Ａ）に対して過酸化物を０．００１〜１質量％添加することが好ましい。過酸化物としては、−Ｏ−Ｏ−結合を有する有機化合物であり、加熱や分解促進剤の作用により分解して遊離ラジカルを生成するものが好ましい。この遊離ラジカルが合成樹脂（Ａ）の分子鎖を攻撃することで、光触媒活性による合成樹脂（Ａ）の分解をより早くすることができる。有機過酸化物の具体例としては、ジイソプロピルベンゼンヒドロパーオキシド、１，１，３，３−テトラメチルブチルヒドロパーオキシド、クメンヒドロパーオキシド、ｔ−ブチルヒドロパーオキシドなどのヒドロパーオキシド；ジ（２−ｔ−ブチルパーオキシイソプロピル）ベンゼン、ジクミルパーオキシド、２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ）ヘキサン、ｔ−ブチルクミルパーオキシド、ジ−ｔ−ヘキシルパーオキシド、ジ−ｔ−ブチルパーオキシド、２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ）ヘキシン−３などのジアルキルパーオキシド；ジイソブチリルパーオキシド、ジ（３，５，５−トリメチルヘキサノニル）パーオキシド、ジラウロイルパーオキシド、ジスクシニックアシッドパーオキシド、ジベンゾイルパーオキシド、ジ（３−メチルベンゾイル）パーオキシド、ベンゾイル（３−メチルベンゾイル）パーオキシド、ジ（４−メチルベンゾイル）パーオキシドなどのジアシルパーオキシド；メチルエチルケトンパーオキシド、シクロヘキサンパーオキシド、アセチルアセトンパーオキシドなどのケトンパーオキサイド；などが挙げられる。これらの有機過酸化物は２種以上を組合せて用いてもよい。また無機過酸化物として、過酸化ナトリウム、過酸化カリウム、過酸化バリウム、過炭酸ナトリウム、過炭酸カリウムおよび過炭酸バリウムなどが挙げられ、これらは２種以上を組合せて用いることもできる。 The photocatalytic functional layer in the present invention is 0.001 to 1% by mass of peroxide with respect to the synthetic resin (A) for the purpose of controlling the degree of erosion of the sea component that is the photocatalyst particle-containing region, that is, the synthetic resin (A). It is preferable to add. The peroxide is preferably an organic compound having an —O—O— bond, which decomposes by heating or the action of a decomposition accelerator to generate free radicals. By this free radical attacking the molecular chain of the synthetic resin (A), the decomposition of the synthetic resin (A) due to photocatalytic activity can be accelerated. Specific examples of the organic peroxide include hydroperoxides such as diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide; 2-t-butylperoxyisopropyl) benzene, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-hexyl peroxide , Di-tert-butyl peroxide, dialkyl peroxides such as 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3; diisobutyryl peroxide, di (3,5,5-trimethyl) Hexanonyl) peroxide, dilauroyl peroxide, disuccinic acid peroxide Diacyl peroxides such as dibenzoyl peroxide, di (3-methylbenzoyl) peroxide, benzoyl (3-methylbenzoyl) peroxide, di (4-methylbenzoyl) peroxide; methyl ethyl ketone peroxide, cyclohexane peroxide, acetylacetone peroxide Ketone peroxide; and the like. These organic peroxides may be used in combination of two or more. Examples of inorganic peroxides include sodium peroxide, potassium peroxide, barium peroxide, sodium percarbonate, potassium percarbonate, and barium percarbonate. These may be used in combination of two or more.
また、本発明の自浄防汚シートは、シート状基材と、光触媒機能層との間に、光触媒粒子含有域と光触媒粒子非含有域からなる海島微細構造（ＩＩ）を形成する厚さが、０．０１〜０．２５ｍｍ、特に０．０２〜０．１ｍｍの光触媒中間層を有していてもよい。この海島微細構造（ＩＩ）は、島成分が光触媒粒子を含有しない合成樹脂（Ｃ）から形成された前記光触媒粒子非含有域であり、海成分が光触媒粒子を含有する合成樹脂（Ｄ）によって形成された前記光触媒粒子含有域であり、さらに前記合成樹脂（Ｃ）は光触媒活性による被分解性を有し、かつ前記合成樹脂（Ｄ）は光触媒活性に対して難分解性であることが好ましい。海島微細構造（ＩＩ）において、合成樹脂（Ｃ）は海島微細構造（Ｉ）における合成樹脂（Ａ）と同一であってもよく、また合成樹脂（Ｄ）は海島微細構造（Ｉ）における合成樹脂（Ｂ）と同一であってもよい。光触媒中間層において、海島微細構造（ＩＩ）は２種類の合成樹脂の溶融混合、または２種類の液状合成樹脂の攪拌混合物からなる合成樹脂非相溶対により形成される。 Further, the self-cleaning antifouling sheet of the present invention has a thickness that forms a sea-island microstructure (II) consisting of a photocatalyst particle-containing region and a photocatalyst particle-free region between the sheet-like base material and the photocatalyst functional layer, You may have a photocatalyst intermediate | middle layer of 0.01-0.25 mm, especially 0.02-0.1 mm. This sea-island microstructure (II) is the photocatalyst particle-free region formed from the synthetic resin (C) in which the island component does not contain photocatalyst particles, and the sea component is formed by the synthetic resin (D) in which the sea component contains photocatalyst particles. Preferably, the synthetic resin (C) is decomposable due to photocatalytic activity, and the synthetic resin (D) is hardly decomposable with respect to photocatalytic activity. In the sea-island microstructure (II), the synthetic resin (C) may be the same as the synthetic resin (A) in the sea-island microstructure (I), and the synthetic resin (D) is the synthetic resin in the sea-island microstructure (I). It may be the same as (B). In the photocatalyst intermediate layer, the sea-island microstructure (II) is formed by a synthetic resin immiscible pair consisting of a melt mixture of two kinds of synthetic resins or a stirring mixture of two kinds of liquid synthetic resins.
本発明において光触媒中間層は、２種類の合成樹脂の混合物からなる合成樹脂非相溶対で、非相溶であれば合成樹脂の組合せに制限はない。本発明に用いられる合成樹脂（Ｃ）の例は、塩化ビニル樹脂、軟質塩化ビニル樹脂、オレフィン樹脂（ＰＥ，ＰＰなど）、オレフィン系共重合体樹脂、ウレタン樹脂、ウレタン系共重合体樹脂、酢酸ビニル樹脂、酢酸ビニル系共重合体樹脂、スチレン樹脂、スチレン系共重合体樹脂、ポリエステル樹脂（ＰＥＴ，ＰＥＮ，ＰＢＴなど）、ポリエステル系共重合体樹脂、合成樹脂（Ｄ）の例は、フッ素含有共重合体樹脂（アクリル−フッ化ビニリデン共重合体、シリコン−フッ化ビニリデングラフト共重合体、ウレタン−フッ化ビニリデングラフト共重合体、アクリル−ウレタン−フッ化ビニリデングラフト共重合体、フッ化ビニリデン樹脂、フッ化ビニリデン−ヘキサフルオロプロピレン共重合体、フッ化ビニリデン−テトラフルオロエチレン共重合体、フッ化ビニリデン−ヘキサフルオロプロピレン−テトラフルオロエチレン共重合体、エチレン−テトラフルオロエチレン共重合体、４フッ化エチレン・パーフルオロアルキルビニルエーテル共重合体、４フッ化エチレン・６フッ化プロピレン４フッ化エチレン、ポリクロロトリフルオロエチレン共重合体、エチレン−クロロトリフルオロエチレン共重合体）、シリコーン樹脂、シリコーンゴム、ポリカーボネート、ポリアミド、ポリエーテル、ポリエステルアミド、ポリフェニレンスルフィド、ポリエーテルエステル、及びビニルエステル樹脂など、（Ｃ）群及び（Ｄ）群とから選ばれた非相溶対である。合成樹脂（Ｃ）には分解促進剤として過酸化物を０．００１〜１質量％添加して含むことが好ましい。 In this invention, a photocatalyst intermediate | middle layer is a synthetic resin incompatible couple which consists of a mixture of two types of synthetic resins, and if it is incompatible, there will be no restriction | limiting in the combination of synthetic resins. Examples of the synthetic resin (C) used in the present invention are vinyl chloride resin, soft vinyl chloride resin, olefin resin (PE, PP, etc.), olefin copolymer resin, urethane resin, urethane copolymer resin, acetic acid. Examples of vinyl resins, vinyl acetate copolymer resins, styrene resins, styrene copolymer resins, polyester resins (PET, PEN, PBT, etc.), polyester copolymer resins, and synthetic resins (D) include fluorine Copolymer resins (acrylic-vinylidene fluoride copolymer, silicon-vinylidene fluoride graft copolymer, urethane-vinylidene fluoride graft copolymer, acrylic-urethane-vinylidene fluoride graft copolymer, vinylidene fluoride resin , Vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene Copolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer, ethylene-tetrafluoroethylene copolymer, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene / hexafluoropropylene Tetrafluoroethylene, polychlorotrifluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer), silicone resin, silicone rubber, polycarbonate, polyamide, polyether, polyesteramide, polyphenylene sulfide, polyetherester, and vinyl It is an incompatible pair selected from the group (C) and the group (D) such as an ester resin. It is preferable that 0.001-1 mass% of peroxide is added to the synthetic resin (C) as a decomposition accelerator.
光触媒中間層の海成分に含む光触媒粒子は、光触媒機能層に用いたものと同様、１）．酸化チタン、過酸化チタン、酸化亜鉛、酸化錫、チタン酸ストロンチウム、酸化タングステン、及びこれらの光触媒物質のドーピング物、２）．光触媒粒子を担持する無機系多孔質微粒子、３）．光触媒活性を有する光触媒粒子粒子表面の一部を無機化合物で被覆した光触媒複合粒子などを用いることができ、なかでも特に酸化チタン光触媒粒子が好ましい。これら光触媒粒子の含有量は海成分領域全体の体積、すなわち合成樹脂（Ｄ）の体積に対して０．５〜３０体積％、好ましくは１〜１５体積％である。 The photocatalyst particles contained in the sea component of the photocatalyst intermediate layer are the same as those used for the photocatalyst functional layer 1). Titanium oxide, titanium peroxide, zinc oxide, tin oxide, strontium titanate, tungsten oxide, and doped products of these photocatalytic substances, 2). Inorganic porous fine particles supporting photocatalyst particles, 3). Photocatalyst composite particles in which a part of the surface of the photocatalyst particles having photocatalytic activity is coated with an inorganic compound can be used, and titanium oxide photocatalyst particles are particularly preferable. Content of these photocatalyst particles is 0.5-30 volume% with respect to the volume of the whole sea component area | region, ie, the volume of a synthetic resin (D), Preferably it is 1-15 volume%.
本発明において光触媒機能層さらには光触媒中間層を、シート状基材上に設ける方法としては、例えば、有機溶剤に分散させた樹脂非相溶混合物、樹脂エマルジョン（ラテックス）非相溶混合物、樹脂ディスパージョン非相溶混合物、ポリ塩化ビニル樹脂を主体とするペーストゾル非相溶混合物、熱硬化性樹脂を主体とする非相溶混合物などを用いて、公知の塗工方法、例えばディッピング（シート状基材への両面加工）、コーティング（シート状基材への片面加工、または両面加工）などの塗工が例示できる。またシート状基材にカレンダー成型、Ｔダイス押出法により成形した、非相溶熱可塑性混合物からなる０．０１〜０．２５ｍｍ、好ましくは０．０５〜１．０ｍｍのフィルム又はシートを、接着剤を介して、あるいは熱ラミネートにより積層する方法、及びこれらの塗工と積層の組合わせが例示できる。 In the present invention, the photocatalytic functional layer and further the photocatalytic intermediate layer may be provided on the sheet-like substrate by, for example, a resin incompatible mixture dispersed in an organic solvent, a resin emulsion (latex) incompatible mixture, a resin disperser. John incompatible mixture, paste sol incompatible mixture mainly composed of polyvinyl chloride resin, incompatible mixture mainly composed of thermosetting resin, etc., using known coating methods such as dipping (sheet-like substrate) Examples include coating such as double-sided processing on a material) and coating (single-sided processing or double-sided processing on a sheet-like substrate). Also, a film or sheet of 0.01 to 0.25 mm, preferably 0.05 to 1.0 mm, made of an incompatible thermoplastic mixture, formed by calender molding or T-die extrusion method on a sheet-like substrate, is used as an adhesive. And a method of laminating via heat laminating, or a combination of these coating and laminating.
また、本発明において光触媒機能層とシート状基材の中間、または光触媒中間層とシート状基材の中間には、光触媒粒子によって分解され難く、かつ皮膜形成能を有する合成樹脂（Ｄ）群、さらには、ポリシラザン、有機シリケート化合物、有機シリケート化合物の低縮合物の加水分解物（シラノール基含有シラン化合物）などのケイ素化合物縮合体のいずれか１種以上の成分からなる、厚さが０．００５〜０．１ｍｍのバリヤー層が設けられていることが好ましい。 Further, in the present invention, in the middle of the photocatalytic functional layer and the sheet-like base material, or in the middle of the photocatalytic intermediate layer and the sheet-like base material, a synthetic resin (D) group that is hardly decomposed by the photocatalyst particles and has a film forming ability, Furthermore, the thickness is 0.005, comprising at least one component of a silicon compound condensate such as polysilazane, an organic silicate compound, or a hydrolyzate of a low condensate of an organic silicate compound (silanol group-containing silane compound). A barrier layer of ~ 0.1 mm is preferably provided.
本発明の自浄防汚シートに関して、図１及び図２の可撓性シートを一例として説明する。図１の可撓性シート（１）は、シート状基材（２）として、繊維布帛（２−１）を芯材として含む繊維複合積層体（２−３）、この繊維複合積層体（２−３）は繊維布帛（２−１）の両面全面に熱可塑性樹脂層（２−２）を積層したものである。この繊維複合積層体（２−３）の片面全面上に光触媒機能層（３）が設けられている。また、図２の可撓性シートは、シート状基材（２）として、繊維布帛（２−１）を芯材として含む繊維複合積層体（２−３）を用い、この片面全面上に光触媒中間層（４）が設けられ、さらにその表面全面に光触媒機能層（３）が形成されている。 With respect to the self-cleaning antifouling sheet of the present invention, the flexible sheet of FIGS. 1 and 2 will be described as an example. A flexible sheet (1) in FIG. 1 includes a fiber composite laminate (2-3) including a fiber fabric (2-1) as a core material as a sheet-like substrate (2), and this fiber composite laminate (2 -3) is obtained by laminating a thermoplastic resin layer (2-2) on the entire surface of both sides of the fiber fabric (2-1). The photocatalytic functional layer (3) is provided on the entire surface of one side of the fiber composite laminate (2-3). 2 uses a fiber composite laminate (2-3) containing a fiber fabric (2-1) as a core material as a sheet-like substrate (2), and a photocatalyst is formed on the entire surface of one side. An intermediate layer (4) is provided, and a photocatalytic function layer (3) is formed on the entire surface.
図３は本発明の自浄防汚シート（１）の光触媒機能層（３）の海島微細構造（Ｉ）を示すものである。光触媒機能層（３）が、光触媒粒子非含有域（３−１）と光触媒粒子含有域（３−２）からなる海島微細構造（Ｉ）を形成し、この海島微細構造（Ｉ）において、島成分（３−１−ａ）は光触媒粒子（５）を含有しない合成樹脂（Ｂ）から形成された光触媒粒子非含有域（３−１）を示し、海成分（３−２−ｂ）は光触媒粒子（５−１）を含有する合成樹脂（Ａ）によって形成された光触媒粒子含有域（３−２）を示している。図４は本発明の自浄防汚シート（１）の光触媒中間層（４）の海島微細構造（ＩＩ）を示すものである。光触媒中間層（４）が、光触媒粒子非含有域（４−１）と、光触媒粒子含有域（４−２）とからなる海島微細構造（ＩＩ）を形成し、この海島微細構造（ＩＩ）において、島成分（４−１−ａ）は光触媒粒子（５）を含有しない合成樹脂（Ｃ）から形成された光触媒粒子非含有域（４−１）を示し、海成分（４−２−ｂ）は光触媒粒子（５−２）を含有する合成樹脂（Ｄ）によって形成された光触媒粒子含有域（４−２）を示している。 FIG. 3 shows the sea-island microstructure (I) of the photocatalytic functional layer (3) of the self-cleaning antifouling sheet (1) of the present invention. The photocatalytic functional layer (3) forms a sea-island microstructure (I) composed of a photocatalyst particle-free region (3-1) and a photocatalyst particle-containing region (3-2). Component (3-1-a) represents a photocatalyst particle non-containing region (3-1) formed from a synthetic resin (B) not containing photocatalyst particles (5), and sea component (3-2-b) represents a photocatalyst. The photocatalyst particle containing area (3-2) formed by the synthetic resin (A) containing the particles (5-1) is shown. FIG. 4 shows the sea-island microstructure (II) of the photocatalytic intermediate layer (4) of the self-cleaning antifouling sheet (1) of the present invention. The photocatalyst intermediate layer (4) forms a sea-island microstructure (II) composed of a photocatalyst particle non-containing region (4-1) and a photocatalyst particle-containing region (4-2). The island component (4-1-a) indicates a photocatalyst particle non-containing region (4-1) formed from the synthetic resin (C) not containing the photocatalyst particles (5), and the sea component (4-2-2). Indicates a photocatalyst particle-containing region (4-2) formed by the synthetic resin (D) containing the photocatalyst particles (5-2).
図５は本発明の自浄防汚シートの断面図（初期の汚れ付着状態）の一例を示すものである。図６は本発明の自浄防汚シート（１）の光触媒機能層（３）の海島微細構造（Ｉ）の侵食による汚れ除去過程の概念を示すものである。海成分（３−２−ｂ）である光触媒粒子（５−１）を含有する合成樹脂（Ａ）によって形成された光触媒粒子非含有域（３−２）が、自己分解による侵食により消失し、光触媒機能層（３）の表面には、島成分（３−１−ａ）である光触媒粒子非含有の合成樹脂（Ｂ）から形成された光触媒粒子含有域（３−１）が残っていることを示している。図６では図示しないが、この島成分（３−１−ａ）である光触媒粒子含有域（３−１）も、更なる海成分（３−２−ｂ）である光触媒粒子含有域（３−２）の自己分解による侵食に伴い消失する。図７は本発明の自浄防汚シート（１）の光触媒中間（４）の海島微細構造（ＩＩ）の侵食による汚れ除去過程の概念を示図すものである。島成分（４−１−ａ）である光触媒粒子（５）を含有しない合成樹脂（Ｃ）から形成された光触媒粒子非含有域（４−１）は、海成分（４−２−ｂ）である光触媒粒子（５−２）を含有する合成樹脂（Ｄ）によって形成された光触媒粒子含有域（４−２）による接触分解による侵食により緩やかな速度で消失し、光触媒中間層（４）の表面には、海成分（４−２−ｂ）である光触媒粒子（５−２）を含有する合成樹脂（Ｄ）によって形成された光触媒粒子含有域（４−２）が残っていることを示している。図７では図示しないが、この海成分（４−２−ｂ）である光触媒粒子含有域（４−２）も、更なる島成分（４−１−ａ）である光触媒粒子非含有域（４−１）の接触分解による緩やかな速度での侵食に伴い消失する。 FIG. 5 shows an example of a cross-sectional view (initial dirt adhesion state) of the self-cleaning antifouling sheet of the present invention. FIG. 6 shows the concept of the dirt removal process by erosion of the sea-island microstructure (I) of the photocatalytic functional layer (3) of the self-cleaning antifouling sheet (1) of the present invention. The photocatalyst particle non-containing region (3-2) formed by the synthetic resin (A) containing the photocatalyst particle (5-1) which is the sea component (3-2-b) disappears due to erosion due to self-decomposition, On the surface of the photocatalyst functional layer (3), the photocatalyst particle-containing region (3-1) formed from the photocatalyst particle-free synthetic resin (B) that is the island component (3-1-a) remains. Is shown. Although not shown in FIG. 6, the photocatalyst particle containing region (3-1) which is this island component (3-1-a) is also a photocatalyst particle containing region (3-2-b) (3- Disappears with erosion due to autolysis of 2). FIG. 7 shows the concept of the dirt removal process by erosion of the sea-island microstructure (II) in the middle of the photocatalyst (4) of the self-cleaning antifouling sheet (1) of the present invention. The photocatalyst particle non-containing region (4-1) formed from the synthetic resin (C) not containing the photocatalyst particle (5) which is the island component (4-1-a) is a sea component (4-2-2-b). The surface of the photocatalyst intermediate layer (4) disappears at a moderate rate by erosion due to catalytic decomposition by the photocatalyst particle containing region (4-2) formed by the synthetic resin (D) containing a certain photocatalyst particle (5-2). Shows that the photocatalyst particle containing region (4-2) formed by the synthetic resin (D) containing the photocatalyst particle (5-2) which is the sea component (4-2b) remains. Yes. Although not shown in FIG. 7, the photocatalyst particle-containing region (4-2) which is the sea component (4-2b) is also a photocatalyst particle non-contained region (4) which is a further island component (4-1-a). It disappears with erosion at a moderate rate due to catalytic decomposition of -1).
以下、本発明について実施例を挙げて具体的に説明するが、本発明はこれらに限定されるものではない。以下の実施例および比較例において、シート状基材として繊維布帛を芯材として含む下記の繊維複合積層体を用いた。シート状基材の寸法は、たて（繊維布帛の経糸方向）４５ｃｍ×よこ（繊維布帛の緯糸方向）３０ｃｍとし、実施例及び比較例において、すべて同一のシート状基材を用いた。
〈シート状基材〉
ポリエステル（ＰＥＴ）製５５５ｄｔｅｘのマルチフィラメントを用いた平織織布（密度：タテ（経糸）２３本／インチ×ヨコ（緯糸）２３本／インチ：質量１００ｇ／ｍ２：目抜度２６％）を繊維布帛として、この繊維布帛の表面と裏面それぞれに、下記の軟質塩化ビニル樹脂配合組成物からなる厚さ０．１８ｍｍのＰＶＣフィルムを熱圧着法でブリッジ積層し、厚さ０．４４ｍｍ、質量５２８ｇ／ｍ２のシート状基材を得た。ブリッジ積層とは表面と裏面に配置したＰＶＣフィルム同士が、繊維布帛の目抜部を介して、ＰＶＣフィルムの融点以上の温度で熱融着接着させると同時に、繊維布帛とも良好に密着または接着させる熱ラミネート法である。得られたシート状基材の表面（光触媒機能層形成側）に下記表面処理層を形成した。表面処理層は、８０メッシュのグラビア塗工にて１２ｇ／ｍ２（wet）均一全面塗布し、固形分付着量３．６ｇ／ｍ２のアクリル樹脂層を形成した。この表面処理層は軟質塩化ビニル樹脂配合物の拡散移行、揮発防止の役割と、光触媒機能層との接着を補助する役割を果たすものである。
EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to these. In the following Examples and Comparative Examples, the following fiber composite laminates including a fiber fabric as a core material as a sheet-like substrate were used. The dimensions of the sheet-like substrate were warp (the warp direction of the fiber fabric) 45 cm × weft (the weft direction of the fiber fabric) 30 cm, and the same sheet-like substrate was used in all the examples and comparative examples.
<Sheet substrate>
Plain woven fabric using 555 dtex multifilament made of polyester (PET) (density: warp (warp) 23 / inch x weft (weft) 23 / inch: mass 100 g / m 2 : meshing degree 26%) As a fabric, a PVC film having a thickness of 0.18 mm made of the following composition containing a soft vinyl chloride resin is bridge-laminated by a thermocompression bonding method on each of the front and back surfaces of the fiber fabric, and the thickness is 0.44 mm and the mass is 528 g / mass. A sheet-like substrate of m 2 was obtained. Bridge lamination means that PVC films placed on the front and back surfaces are heat-sealed and bonded at a temperature equal to or higher than the melting point of the PVC film through the cutouts of the fiber fabric, and at the same time, are well adhered or bonded to the fiber fabric. Thermal lamination method. The following surface treatment layer was formed on the surface (photocatalyst functional layer forming side) of the obtained sheet-like substrate. The surface treatment layer was uniformly applied at 12 g / m 2 (wet) by 80 mesh gravure coating to form an acrylic resin layer having a solid content adhesion amount of 3.6 g / m 2 . This surface treatment layer plays the role of diffusion migration and volatilization prevention of the soft vinyl chloride resin compound and assisting adhesion with the photocatalytic functional layer.
〈軟質塩化ビニル樹脂組成物〉
ストレート塩化ビニル樹脂（Ｐ＝１０５０）１００質量部
ＤＯＰ（可塑剤） ３０質量部
塩素化ｎ−パラフィン（可塑剤） １０質量部
アジピン酸ポリエステル（可塑剤） ３０質量部
エポキシ化大豆油（安定剤） ４質量部
Ｂａ−Ｚｎ系複合安定剤 ２質量部
ルチル型酸化チタン（着色剤） ５質量部
有機系防カビ剤（ＯＢＰＡ） ０．２質量部
紫外線吸収剤 ０．３質量部
酸化防止剤 ０．１質量部
〈表面処理層形成用塗工液〉
商品名：ソニーボンドＳＣ−４７４：ソニーケミカル（株）：アクリル系共重合樹脂
（固形分３０質量％） １００質量部
<Soft vinyl chloride resin composition>
100 parts by mass of straight vinyl chloride resin (P = 1050)
DOP (plasticizer) 30 parts by mass
Chlorinated n-paraffin (plasticizer) 10 parts by mass
Adipic acid polyester (plasticizer) 30 parts by mass
Epoxidized soybean oil (stabilizer) 4 parts by mass
Ba-Zn composite stabilizer 2 parts by mass
Rutile type titanium oxide (colorant) 5 parts by mass
Organic antifungal agent (OBPA) 0.2 parts by mass
UV absorber 0.3 parts by mass
Antioxidant 0.1 part by mass <Coating liquid for surface treatment layer formation>
Product name: Sony Bond SC-474: Sony Chemical Corporation: Acrylic copolymer resin
(Solid content 30% by mass) 100 parts by mass
次いでこの表面処理層上に、１〜３の光触媒機能層を形成し、本発明の自浄防汚シート実施例１，３，５を得た。また、特に実施例２，４，６においては、表面処理層上に光触媒中間層１〜３を形成し、光触媒中間層上に１〜３の光触媒機能層を形成した。 Subsequently, the photocatalyst functional layers 1 to 3 were formed on the surface treatment layer to obtain the self-cleaning antifouling sheet Examples 1, 3 and 5 of the present invention. Particularly in Examples 2, 4 and 6, the photocatalyst intermediate layers 1 to 3 were formed on the surface treatment layer, and the photocatalyst functional layers 1 to 3 were formed on the photocatalyst intermediate layer.
〈防汚性の評価〉
得られたシートを１２ヶ月間屋外で南向き３０°と９０°（垂直）の設置角度で曝露し、垂直面における雨筋汚れの発生の有無と、３０°面の汚れ度合いを初期（ブランク）とのΔＥ値（ＪＩＳ Ｚ−８７２９）で評価した。色差計測はＪＵＫＩ（株）製の光学色差計（ＪＰ７２００Ｆ）を用いた。ΔＥ値が３．０を超えるものはセルフクリーニング性に劣るものと判定する。
※屋外展張は、埼玉県草加市内において１０月より開始した。
ΔＥ＝０〜１．９ ：１＝汚れがなく良好。初期の状態を維持している。
ΔＥ＝２〜２．９ ：２＝うすく汚れているが外観に支障はない。
ΔＥ＝３〜３．９ ：３＝汚れ付着、雨筋が目立つ。
ΔＥ＝４以上 ：４＝汚れと雨筋が酷く、外観的に支障がある。
<Evaluation of antifouling properties>
The obtained sheet is exposed outdoors for 12 months at the installation angles of 30 ° and 90 ° (vertical) facing south. The presence or absence of rain streak on the vertical surface and the degree of contamination on the 30 ° surface are initially (blank). And ΔE value (JIS Z-8729). For color difference measurement, an optical color difference meter (JP7200F) manufactured by JUKI Corporation was used. If the ΔE value exceeds 3.0, it is determined that the self-cleaning property is poor.
* Outdoor exhibition started in October in Soka City, Saitama Prefecture.
ΔE = 0 to 1.9: 1 = Good without contamination. The initial state is maintained.
ΔE = 2 to 2.9: 2 = slightly dirty but no problem in appearance.
ΔE = 3 to 3.9: 3 = dirt adhesion, rain stripes are conspicuous.
ΔE = 4 or more: 4 = Dirty and rain streaks are severe, and the appearance is hindered.
［実施例１］
下記配合1の塩化ビニル樹脂混合物（光触媒粒子含有）に、下記配合２のフッ化ビニリデン樹脂混合物を、塩化ビニル樹脂単体の質量に対して２０質量％加えてブレンドし、フッ化ビニリデン樹脂が均一分散した非相溶樹脂混合物１の液を得た。この非相溶樹脂混合物１の液を、シート状基材のアクリル樹脂による表面処理層上にウェットコートし、この塗膜を１８０℃の熱風ブロー乾燥させ、塗膜厚さ０．０５ｍｍの光触媒機能層１を形成した。この光触媒機能層１を顕微鏡観察すると、塩化ビニル樹脂が光触媒粒子を含有する海成分を構成しており、フッ化ビニリデン樹脂が光触媒粒子非含有の島成分を構成していた。このシートを１２ヶ月間屋外曝露して汚れ状態の観察を行った結果、ΔＥは０．９の評価１レベルであった。
[光触媒機能層１形成のための非相溶樹脂混合物１]
＜配合１＞
塩化ビニル樹脂（重合度１３００） １００質量部
Ｂａ−Ｚｎ系複合安定剤 ２質量部
光触媒酸化チタン ８質量部
（無機酸化物による表面被覆率４〜１０％範囲の部分被覆）
炭酸カルシウム（平均粒子径１μｍ） １０質量部
＜配合２＞
フッ化ビニリデン樹脂 １００質量部
メチルエチルケトン（溶剤） ４００質量部
有機過酸化物（ジクミルパーオキシド） ０．０３質量部
[Example 1]
The vinylidene fluoride resin mixture of the following formulation 1 (containing photocatalyst particles) is blended by adding 20% by mass of the vinylidene fluoride resin mixture of the following formulation 2 to the mass of the vinyl chloride resin alone, and the vinylidene fluoride resin is uniformly dispersed A liquid of the incompatible resin mixture 1 was obtained. The liquid of this incompatible resin mixture 1 is wet-coated on the surface treatment layer of the sheet-like base material made of acrylic resin, and this coating film is blown dry at 180 ° C. to form a photocatalytic function having a coating thickness of 0.05 mm. Layer 1 was formed. When this photocatalyst functional layer 1 was observed with a microscope, the vinyl chloride resin constituted a sea component containing photocatalyst particles, and the vinylidene fluoride resin constituted an island component free of photocatalyst particles. As a result of exposing this sheet outdoors for 12 months and observing the soiled state, ΔE was an evaluation 1 level of 0.9.
[Incompatible resin mixture 1 for forming photocatalytic functional layer 1]
<Formulation 1>
100 parts by mass of vinyl chloride resin (degree of polymerization 1300)
Ba-Zn composite stabilizer 2 parts by mass
8 parts by mass of photocatalytic titanium oxide
(Partial coating with surface coverage of 4 to 10% by inorganic oxide)
Calcium carbonate (average particle size 1 μm) 10 parts by mass <Formulation 2>
100 parts by mass of vinylidene fluoride resin
400 parts by mass of methyl ethyl ketone (solvent)
Organic peroxide (dicumyl peroxide) 0.03 parts by mass
［実施例２］
実施例１の処方において、光触媒機能層１とシート状基材（界面は表面処理層）との間に下記光触媒中間層１を設けた以外は実施例１と同様とし、光触媒機能層１付きシートを得た。光触媒中間層１は下記配合３のフッ化ビニリデン樹脂混合物（光触媒粒子含有）に、下記配合４の塩化ビニル樹脂混合物を、フッ化ビニリデン樹脂単体の質量に対して２０質量％加えてブレンドし、塩化ビニル樹脂が均一分散した非相溶樹脂混合物２の液を得た。この非相溶樹脂混合物２の液を、シート状基材のアクリル樹脂による表面処理層上にウェットコートし、この塗膜を１８０℃の熱風ブロー乾燥させ、塗膜厚さ０．０３ｍｍの光触媒中間層１を形成した。この光触媒中間層１を顕微鏡観察すると、塩化ビニル樹脂が光触媒粒子非含有の島成分を構成しており、フッ化ビニリデン樹脂が光触媒粒子を含有する海成分を構成していた。この光触媒中間層１上に実施例１で用いた非相溶樹脂混合物１液を、シート状基材のアクリル樹脂による表面処理層上にウェットコートし、この塗膜を１８０℃の熱風ブロー乾燥させ、塗膜厚さ０．０３ｍｍの光触媒機能層１を形成した。このシートを１２ヶ月間屋外曝露して汚れ状態の観察を行った結果、ΔＥは０．８の評価１レベルであった。
[光触媒中間層１形成のための非相溶樹脂混合物２]
＜配合３＞
フッ化ビニリデン樹脂 １００質量部
光触媒酸化チタン ８質量部
（無機酸化物による表面被覆率４〜１０％範囲の部分被覆）
メチルエチルケトン（溶剤） ４００質量部
＜配合４＞
塩化ビニル樹脂（重合度１３００） １００質量部
Ｂａ−Ｚｎ系複合安定剤 ２質量部
炭酸カルシウム（平均粒子径１μｍ） １０質量部
有機過酸化物（ジクミルパーオキシド） ０．０３質量部
[Example 2]
In the formulation of Example 1, the same as Example 1 except that the following photocatalyst intermediate layer 1 was provided between the photocatalyst functional layer 1 and the sheet-like base material (the interface was a surface treatment layer). Got. The photocatalyst intermediate layer 1 is blended by adding 20% by mass of the vinyl chloride resin mixture of the following formulation 4 to the vinylidene fluoride resin mixture (containing photocatalyst particles) of the following formulation 3 with respect to the mass of the vinylidene fluoride resin alone, A liquid of incompatible resin mixture 2 in which vinyl resin was uniformly dispersed was obtained. The liquid of this incompatible resin mixture 2 is wet-coated on the surface treatment layer of the sheet-like base material made of acrylic resin, and this coating film is blown dry with hot air at 180 ° C. to obtain a photocatalyst intermediate having a coating thickness of 0.03 mm. Layer 1 was formed. When the photocatalyst intermediate layer 1 was observed with a microscope, the vinyl chloride resin constituted an island component free of photocatalyst particles, and the vinylidene fluoride resin constituted a sea component containing photocatalyst particles. One liquid of the incompatible resin mixture used in Example 1 was wet coated on the photocatalyst intermediate layer 1 on the surface treatment layer of the acrylic resin of the sheet-like base material, and this coating film was blown dry at 180 ° C. with hot air. A photocatalytic functional layer 1 having a coating thickness of 0.03 mm was formed. As a result of exposing this sheet outdoors for 12 months and observing the soiled state, ΔE was an evaluation 1 level of 0.8.
[Incompatible resin mixture 2 for forming photocatalytic intermediate layer 1]
<Formulation 3>
100 parts by mass of vinylidene fluoride resin
8 parts by mass of photocatalytic titanium oxide
(Partial coating with surface coverage of 4 to 10% by inorganic oxide)
400 parts by mass of methyl ethyl ketone (solvent) <Formulation 4>
100 parts by mass of vinyl chloride resin (degree of polymerization 1300)
Ba-Zn composite stabilizer 2 parts by mass
10 parts by mass of calcium carbonate (average particle size 1 μm)
Organic peroxide (dicumyl peroxide) 0.03 parts by mass
［実施例３］
下記配合５の軟質塩化ビニル樹脂混合物（光触媒粒子含有）に、下記配合６のフッ化ビニリデン樹脂混合物を、塩化ビニル樹脂単体の質量に対して２０質量％加えて１８０℃で加熱溶融ブレンドし、フッ化ビニリデン樹脂が均一分散した非相溶樹脂混合物３コンパウンドを得た。この非相溶樹脂混合物３コンパウンドを、１８０℃設定のカレンダー装置で圧延し、厚さ０．０８ｍｍのフィルムを得、これを光触媒機能層２とした。このフィルムをシート状基材のアクリル樹脂による表面処理層上に１７０℃で熱ラミネート積層した。この光触媒機能層２を顕微鏡観察すると、軟質塩化ビニル樹脂が光触媒粒子を含有する海成分を構成しており、フッ化ビニリデン樹脂が光触媒粒子非含有の島成分を構成していた。このシートを１２ヶ月間屋外曝露して汚れ状態の観察を行った結果、ΔＥは１．１の評価１レベルであった。
[光触媒機能層２形成のための非相溶樹脂混合物３]
＜配合５＞
塩化ビニル樹脂（重合度１３００） １００質量部
ＤＯＰ（可塑剤） ３０質量部
アジピン酸ポリエステル（可塑剤） ３０質量部
エポキシ化大豆油（安定剤） ４質量部
Ｂａ−Ｚｎ系複合安定剤 ２質量部
光触媒酸化チタン ８質量部
（無機酸化物による表面被覆率４〜１０％範囲の部分被覆）
炭酸カルシウム（平均粒子径１μｍ） １０質量部
有機過酸化物（ジクミルパーオキシド） ０．０３質量部
＜配合６＞
フッ化ビニリデン樹脂 １００質量部
[Example 3]
Add 20% by mass of the vinylidene fluoride resin mixture of the following formulation 6 to the soft vinyl chloride resin mixture (containing photocatalyst particles) of the following formulation 5 with respect to the mass of the vinyl chloride resin alone, and heat melt blend at 180 ° C. An incompatible resin mixture 3 compound in which the vinylidene chloride resin was uniformly dispersed was obtained. This incompatible resin mixture 3 compound was rolled by a calender device set at 180 ° C. to obtain a film having a thickness of 0.08 mm. This film was heat-laminated and laminated at 170 ° C. on the surface treatment layer of the sheet-like substrate made of acrylic resin. When the photocatalytic function layer 2 was observed with a microscope, the soft vinyl chloride resin constituted a sea component containing photocatalyst particles, and the vinylidene fluoride resin constituted an island component not containing photocatalyst particles. As a result of exposing this sheet outdoors for 12 months and observing the soiled state, ΔE was an evaluation 1 level of 1.1.
[Incompatible resin mixture 3 for forming photocatalytic functional layer 2]
<Formulation 5>
100 parts by mass of vinyl chloride resin (degree of polymerization 1300)
DOP (plasticizer) 30 parts by mass
Adipic acid polyester (plasticizer) 30 parts by mass
Epoxidized soybean oil (stabilizer) 4 parts by mass
Ba-Zn composite stabilizer 2 parts by mass
8 parts by mass of photocatalytic titanium oxide
(Partial coating with surface coverage of 4 to 10% by inorganic oxide)
10 parts by mass of calcium carbonate (average particle size 1 μm)
Organic peroxide (dicumyl peroxide) 0.03 parts by mass <Formulation 6>
100 parts by mass of vinylidene fluoride resin
［実施例４］
実施例３の処方において、光触媒機能層２とシート状基材（界面は表面処理層）との間に下記光触媒中間層２を設けた以外は実施例３と同様とし、光触媒機能層２付きシートを得た。光触媒中間層２は下記配合７のフッ化ビニリデン樹脂混合物（光触媒粒子含有）に、下記配合８の軟質塩化ビニル樹脂混合物を、フッ化ビニリデン樹脂単体の質量に対して２０質量％加えて１８０℃で加熱溶融ブレンドし、軟質塩化ビニル樹脂が均一分散した非相溶樹脂混合物４コンパウンドを得た。この非相溶樹脂混合物４コンパウンドを、１８０℃設定のカレンダー装置で圧延し、厚さ０．０８ｍｍのフィルムを得、これを光触媒中間層２としてシート状基材のアクリル樹脂による表面処理層上に１７０℃で熱ラミネート積層した。この光触媒中間層２を顕微鏡観察すると、軟質塩化ビニル樹脂が光触媒粒子を非含有の島成分を構成しており、フッ化ビニリデン樹脂が光触媒粒子を含有する海成分を構成していた。この光触媒中間層２上に実施例３で用いた非相溶樹脂混合物３コンパウンドを１８０℃設定のカレンダー装置で圧延して得た厚さ０．０８ｍｍのフィルムを光触媒機能層２として１７０℃で熱ラミネート積層した。このシートを１２ヶ月間屋外曝露して汚れ状態の観察を行った結果、ΔＥは１．０の評価１レベルであった。
[光触媒中間層２形成のための非相溶樹脂混合物４]
＜配合７＞
フッ化ビニリデン樹脂 １００質量部
光触媒酸化チタン ８質量部
（無機酸化物による表面被覆率４〜１０％範囲の部分被覆）
＜配合８＞
塩化ビニル樹脂（重合度１３００） １００質量部
ＤＯＰ（可塑剤） ３０質量部
アジピン酸ポリエステル（可塑剤） ３０質量部
エポキシ化大豆油（安定剤） ４質量部
Ｂａ−Ｚｎ系複合安定剤 ２質量部
炭酸カルシウム（平均粒子径１μｍ） １０質量部
有機過酸化物（ジクミルパーオキシド） ０．０３質量部
[Example 4]
In the formulation of Example 3, the same as Example 3, except that the following photocatalyst intermediate layer 2 was provided between the photocatalyst functional layer 2 and the sheet-like substrate (the interface was a surface treatment layer), and the sheet with the photocatalyst functional layer 2 Got. The photocatalyst intermediate layer 2 is obtained by adding 20% by mass of a soft vinyl chloride resin mixture of the following formulation 8 to the vinylidene fluoride resin mixture (containing photocatalyst particles) of the following formulation 7 relative to the mass of the vinylidene fluoride resin alone at 180 ° C. Heat-blending blending was performed to obtain an incompatible resin mixture 4 compound in which a soft vinyl chloride resin was uniformly dispersed. This incompatible resin mixture 4 compound is rolled with a calender device set at 180 ° C. to obtain a film having a thickness of 0.08 mm, and this is used as a photocatalyst intermediate layer 2 on the surface treatment layer made of an acrylic resin of a sheet-like substrate. The laminate was heat laminated at 170 ° C. When this photocatalyst intermediate layer 2 was observed with a microscope, the soft vinyl chloride resin constituted an island component not containing photocatalyst particles, and the vinylidene fluoride resin constituted a sea component containing photocatalyst particles. A film having a thickness of 0.08 mm obtained by rolling the incompatible resin mixture 3 compound used in Example 3 on the photocatalyst intermediate layer 2 with a calender device set at 180 ° C. was heated at 170 ° C. as a photocatalyst functional layer 2. Laminated and laminated. As a result of exposing this sheet to the outdoors for 12 months and observing the soiled state, ΔE was an evaluation 1 level of 1.0.
[Incompatible resin mixture 4 for forming photocatalytic intermediate layer 2]
<Formulation 7>
100 parts by mass of vinylidene fluoride resin
8 parts by mass of photocatalytic titanium oxide
(Partial coating with surface coverage of 4 to 10% by inorganic oxide)
<Formulation 8>
100 parts by mass of vinyl chloride resin (degree of polymerization 1300)
DOP (plasticizer) 30 parts by mass
Adipic acid polyester (plasticizer) 30 parts by mass
Epoxidized soybean oil (stabilizer) 4 parts by mass
Ba-Zn composite stabilizer 2 parts by mass
10 parts by mass of calcium carbonate (average particle size 1 μm)
Organic peroxide (dicumyl peroxide) 0.03 parts by mass
［実施例５］
配合５の軟質塩化ビニル樹脂混合物（光触媒粒子含有）に、下記配合９のシリコーン樹脂混合物を、塩化ビニル樹脂単体の質量に対して２０質量％加えてブレンドし、シリコーン樹脂が均一分散した非相溶樹脂混合物５の液を得た。この非相溶樹脂混合物５の液を、シート状基材のアクリル樹脂による表面処理層上にウェットコートし、この塗膜を１８０℃の熱風ブロー乾燥させ、塗膜厚さ０．０５ｍｍの光触媒機能層３を形成した。この光触媒機能層３を顕微鏡観察すると、軟質塩化ビニル樹脂が光触媒粒子を含有する海成分を構成しており、シリコーン樹脂が光触媒粒子非含有の島成分を構成していた。このシートを１２ヶ月間屋外曝露して汚れ状態の観察を行った結果、ΔＥは１．４の評価１レベルであった。
[光触媒機能層３形成のための非相溶樹脂混合物５]
＜配合９＞
２液付加反応硬化型シリコーン樹脂 ５０質量部
（品名：シラスコンＲＴＶ４０８６Ａ
：ダウコーニングアジア社製）
２液付加反応硬化型シリコーン樹脂 ５０質量部
（品名：シラスコンＲＴＶ４０８６Ｂ
：ダウコーニングアジア社製）
メチルエチルケトン（溶剤） １００質量部
[Example 5]
Incompatibility with silicone resin uniformly dispersed in blend 5 of soft vinyl chloride resin mixture (containing photocatalyst particles) by adding 20% by mass of silicone resin mixture of formulation 9 below to the mass of vinyl chloride resin alone. A liquid of the resin mixture 5 was obtained. The liquid of this incompatible resin mixture 5 is wet-coated on the surface treatment layer of the sheet-like base material made of acrylic resin, and this coating film is blown dry at 180 ° C. to form a photocatalytic function having a coating thickness of 0.05 mm. Layer 3 was formed. When the photocatalytic functional layer 3 was observed with a microscope, the soft vinyl chloride resin constituted a sea component containing photocatalyst particles, and the silicone resin constituted an island component not containing photocatalyst particles. As a result of exposing this sheet outdoors for 12 months and observing the soiled state, ΔE was an evaluation 1 level of 1.4.
[Incompatible resin mixture 5 for forming photocatalytic functional layer 3]
<Formulation 9>
50 parts by weight of two-component addition reaction curable silicone resin
(Product name: Shirasukon RTV4086A
: Dow Corning Asia)
50 parts by weight of two-component addition reaction curable silicone resin
(Product name: Shirasukon RTV4086B
: Dow Corning Asia)
100 parts by mass of methyl ethyl ketone (solvent)
［実施例６］
実施例５の処方において、光触媒機能層３とシート状基材（界面は表面処理層）との間に下記光触媒中間層３を設けた以外は実施例５と同様とし、光触媒機能層３付きシートを得た。光触媒中間層３は下記配合１０のシリコーン樹脂混合物（光触媒粒子含有）に、配合８の軟質塩化ビニル樹脂混合物を、シリコーン樹脂単体の質量に対して２０質量％加えてブレンドし、軟質塩化ビニル樹脂が均一分散した非相溶樹脂混合物６の液を得た。この非相溶樹脂混合物６の液を、シート状基材のアクリル樹脂による表面処理層上にウェットコートし、この塗膜を１８０℃の熱風ブロー乾燥させ、塗膜厚さ０．０３ｍｍの光触媒中間層３を形成した。この光触媒中間層３を顕微鏡観察すると、軟質塩化ビニル樹脂が光触媒粒子を非含有の島成分を構成しており、シリコーン樹脂が光触媒粒子を含有する海成分を構成していた。この光触媒中間層３上に実施例５で用いた非相溶樹脂混合物５液を、シート状基材のアクリル樹脂による表面処理層上にウェットコートし、この塗膜を１８０℃の熱風ブロー乾燥させ、塗膜厚さ０．０３ｍｍの光触媒機能層３を形成した。このシートを１２ヶ月間屋外曝露して汚れ状態の観察を行った結果、ΔＥは１．４の評価１レベルであった。
[光触媒中間層３形成のための非相溶樹脂混合物６]
＜配合１０＞
２液付加反応硬化型シリコーン樹脂 ５０質量部
（品名：シラスコンＲＴＶ４０８６Ａ
：ダウコーニングアジア社製）
２液付加反応硬化型シリコーン樹脂 ５０質量部
（品名：シラスコンＲＴＶ４０８６Ｂ
：ダウコーニングアジア社製）
光触媒酸化チタン ８質量部
（無機酸化物による表面被覆率４〜１０％範囲の部分被覆）
メチルエチルケトン（溶剤） １００質量部
[Example 6]
In the formulation of Example 5, the same as Example 5 except that the following photocatalyst intermediate layer 3 was provided between the photocatalyst functional layer 3 and the sheet-like base material (the interface was a surface treatment layer). Got. The photocatalyst intermediate layer 3 was blended by adding 20% by mass of the soft vinyl chloride resin mixture of Formula 8 to the silicone resin mixture (containing photocatalyst particles) of Formula 10 below with respect to the mass of the silicone resin alone. A liquid of the incompatible resin mixture 6 uniformly dispersed was obtained. The liquid of this incompatible resin mixture 6 is wet-coated on the surface treatment layer of the sheet-like base material made of acrylic resin, and this coating film is blown dry with hot air at 180 ° C. to obtain a photocatalyst intermediate having a coating thickness of 0.03 mm. Layer 3 was formed. When the photocatalyst intermediate layer 3 was observed with a microscope, the soft vinyl chloride resin constituted an island component not containing photocatalyst particles, and the silicone resin constituted a sea component containing photocatalyst particles. On this photocatalyst intermediate layer 3, 5 liquids of the incompatible resin mixture used in Example 5 were wet-coated on the surface treatment layer of the sheet-like substrate made of acrylic resin, and this coating film was blown dry at 180 ° C. with hot air. A photocatalytic functional layer 3 having a coating thickness of 0.03 mm was formed. As a result of exposing this sheet outdoors for 12 months and observing the soiled state, ΔE was an evaluation 1 level of 1.4.
[Incompatible resin mixture 6 for forming photocatalytic intermediate layer 3]
<Formulation 10>
50 parts by weight of two-component addition reaction curable silicone resin
(Product name: Shirasukon RTV4086A
: Dow Corning Asia)
50 parts by weight of two-component addition reaction curable silicone resin
(Product name: Shirasukon RTV4086B
: Dow Corning Asia)
8 parts by mass of photocatalytic titanium oxide
(Partial coating with surface coverage of 4 to 10% by inorganic oxide)
100 parts by mass of methyl ethyl ketone (solvent)
［実施例７］
下記配合１１のポリウレタン樹脂混合物（光触媒粒子含有）に、配合1のフッ化ビニリデン樹脂混合物を、ポリウレタン樹脂単体の質量に対して２０質量％加えてブレンドし、フッ化ビニリデン樹脂が均一分散した非相溶樹脂混合物７の液を得た。この非相溶樹脂混合物７の液を、シート状基材のアクリル樹脂による表面処理層上にウェットコートし、この塗膜を１８０℃の熱風ブロー乾燥させ、塗膜厚さ０．０５ｍｍの光触媒機能層４を形成した。この光触媒機能層４を顕微鏡観察すると、ポリウレタン樹脂が光触媒粒子を含有する海成分を構成しており、フッ化ビニリデン樹脂が光触媒粒子非含有の島成分を構成していた。このシートを１２ヶ月間屋外曝露して汚れ状態の観察を行った結果、ΔＥは１．０の評価１レベルであった。
[光触媒機能層４形成のための非相溶樹脂混合物７]
＜配合１１＞
ポリウレタン樹脂（エステル系） １００質量部
光触媒酸化チタン ８質量部
（無機酸化物による表面被覆率４〜１０％範囲の部分被覆）
炭酸カルシウム（平均粒子径１μｍ） １０質量部
有機過酸化物（ジクミルパーオキシド） ０．０３質量部
[Example 7]
A non-phase in which a vinylidene fluoride resin mixture of Formulation 1 is added to a polyurethane resin mixture of Formulation 11 (containing photocatalyst particles) below in an amount of 20% by mass based on the mass of the polyurethane resin alone, and the vinylidene fluoride resin is uniformly dispersed. A solution of the molten resin mixture 7 was obtained. The liquid of this incompatible resin mixture 7 is wet-coated on the surface-treated layer of the sheet-like base material made of acrylic resin, and this coating film is blown dry at 180 ° C. to form a photocatalytic function having a coating thickness of 0.05 mm. Layer 4 was formed. When this photocatalyst functional layer 4 was observed with a microscope, the polyurethane resin constituted a sea component containing photocatalyst particles, and the vinylidene fluoride resin constituted an island component not containing photocatalyst particles. As a result of exposing this sheet to the outdoors for 12 months and observing the soiled state, ΔE was an evaluation 1 level of 1.0.
[Incompatible resin mixture 7 for forming photocatalytic functional layer 4]
<Formulation 11>
100 parts by mass of polyurethane resin (ester)
8 parts by mass of photocatalytic titanium oxide
(Partial coating with surface coverage of 4 to 10% by inorganic oxide)
10 parts by mass of calcium carbonate (average particle size 1 μm)
Organic peroxide (dicumyl peroxide) 0.03 parts by mass
［実施例８］
実施例７の処方において、光触媒機能層４とシート状基材（界面は表面処理層）との間に下記光触媒中間層４を設けた以外は実施例７と同様とし、光触媒機能層４付きシートを得た。光触媒中間層４は配合７のフッ化ビニリデン樹脂混合物（光触媒粒子含有）に、配合１１のポリウレタン樹脂混合物を、フッ化ビニリデン樹脂単体の質量に対して２０質量％加えてブレンドし、ポリウレタン樹脂が均一分散した非相溶樹脂混合物８の液を得た。この非相溶樹脂混合物８の液を、シート状基材のアクリル樹脂による表面処理層上にウェットコートし、この塗膜を１８０℃の熱風ブロー乾燥させ、塗膜厚さ０．０３ｍｍの光触媒中間層４を形成した。この光触媒中間層４を顕微鏡観察すると、ポリウレタン樹脂が光触媒粒子を非含有の島成分を構成しており、フッ化ビニリデン樹脂が光触媒粒子を含有する海成分を構成していた。この光触媒中間層４上に実施例７で用いた非相溶樹脂混合物７液を、シート状基材のアクリル樹脂による表面処理層上にウェットコートし、この塗膜を１８０℃の熱風ブロー乾燥させ、塗膜厚さ０．０３ｍｍの光触媒機能層４を形成した。このシートを１２ヶ月間屋外曝露して汚れ状態の観察を行った結果、ΔＥは０．９の評価１レベルであった。
[Example 8]
In the formulation of Example 7, a sheet with the photocatalyst functional layer 4 is the same as Example 7 except that the following photocatalyst intermediate layer 4 is provided between the photocatalyst functional layer 4 and the sheet-like base material (the interface is a surface treatment layer). Got. The photocatalyst intermediate layer 4 is blended by adding 20% by mass of the polyurethane resin mixture of Formulation 11 to the vinylidene fluoride resin mixture (containing photocatalyst particles) of Formulation 7 with respect to the mass of the vinylidene fluoride resin alone, and the polyurethane resin is uniform. A liquid of dispersed incompatible resin mixture 8 was obtained. The liquid of this incompatible resin mixture 8 is wet-coated on the surface treatment layer of the sheet-like base material made of acrylic resin, and this coating film is blown dry with hot air at 180 ° C. to obtain a photocatalyst intermediate having a coating thickness of 0.03 mm. Layer 4 was formed. When the photocatalyst intermediate layer 4 was observed with a microscope, the polyurethane resin constituted an island component not containing photocatalyst particles, and the vinylidene fluoride resin constituted a sea component containing photocatalyst particles. On this photocatalyst intermediate layer 4, the incompatible resin mixture 7 liquid used in Example 7 was wet-coated on the surface treatment layer of the sheet-like base material made of acrylic resin, and this coating film was blown dry at 180 ° C. with hot air. A photocatalytic functional layer 4 having a coating thickness of 0.03 mm was formed. As a result of exposing this sheet outdoors for 12 months and observing the soiled state, ΔE was an evaluation 1 level of 0.9.
実施例１〜８のシートは、１年間の屋外曝露試験の結果、いずれもΔＥ＝０〜１．９の範囲内であり、防汚シートとして充分な自浄防汚効果を有するものであった。特に光触媒機能層の海成分中に有機過酸化物（ジクミルパーオキシド）を０．００１〜１質量％含有することで海成分の分解速度が加速され、使用開始から３ヶ月目でのΔＥは０〜１．９の自浄性を示していた。光触媒機能層の海成分中に有機過酸化物（ジクミルパーオキシド）を含有しない場合、ΔＥは０〜１．９の範囲内となるまでに４ヶ月を必要とした。これより光触媒機能層の海成分中に有機過酸化物を用いることで、１ヶ月早い段階で自浄性が得られるので美観維持に効果的である。また実施例１〜８のシートはいずれも高周波溶着性を有し、大型テント構造物施工用に適したものであった。
As a result of the outdoor exposure test for one year, the sheets of Examples 1 to 8 were all in the range of ΔE = 0 to 1.9, and had sufficient self-cleaning antifouling effects as antifouling sheets. In particular, by containing 0.001 to 1% by mass of organic peroxide (dicumyl peroxide) in the sea component of the photocatalytic functional layer, the decomposition rate of the sea component is accelerated, and ΔE at the third month from the start of use is It showed a self-cleaning property of 0-1.9. When no organic peroxide (dicumyl peroxide) was contained in the sea component of the photocatalytic functional layer, 4 months were required until ΔE was in the range of 0 to 1.9. By using an organic peroxide in the sea component of the photocatalytic functional layer, self-cleaning can be obtained at an early stage of one month, which is effective for maintaining aesthetics. The sheets of Examples 1 to 8 all had high frequency weldability and were suitable for large tent structure construction.
［比較例１］
実施例１において、配合１の塩化ビニル樹脂混合物から光触媒粒子を省略した以外は実施例１と同様にしてシートを得た。得られたシートを１年間屋外暴露して防汚性評価を行った結果、ΔＥは３．６の評価３レベルであった。
[Comparative Example 1]
In Example 1, a sheet was obtained in the same manner as in Example 1 except that the photocatalyst particles were omitted from the vinyl chloride resin mixture of Formulation 1. The obtained sheet was exposed outdoors for 1 year to evaluate the antifouling property. As a result, ΔE was 3.6, which was an evaluation 3 level.
［比較例２］
実施例１において、配合２のフッ化ビニリデン樹脂混合物の併用を省略した以外は実施例１と同様にしてシートを得た。得られたシートを１年間屋外暴露して防汚性評価を行った結果、約９ヶ月経過より光触媒機能層が脱落して消失し、下地のアクリル樹脂層が露出することによって汚れの蓄積が目立ち始めた。ΔＥは３．３の評価３レベルであった。
[Comparative Example 2]
In Example 1, a sheet was obtained in the same manner as in Example 1 except that the combined use of the vinylidene fluoride resin mixture of Formulation 2 was omitted. The resulting sheet was exposed outdoors for 1 year and evaluated for antifouling. As a result, the photocatalyst functional layer dropped out and disappeared after about 9 months, and the accumulation of dirt was conspicuous when the underlying acrylic resin layer was exposed. I started. ΔE was the evaluation 3 level of 3.3.
［比較例３］
実施例３において、配合５の塩化ビニル樹脂混合物から光触媒粒子を省略した以外は実施例３と同様にしてシートを得た。得られたシートを１年間屋外暴露して防汚性評価を行った結果、ΔＥは４．２の評価４レベルであった。
[Comparative Example 3]
In Example 3, a sheet was obtained in the same manner as in Example 3 except that the photocatalyst particles were omitted from the vinyl chloride resin mixture of Formulation 5. The obtained sheet was exposed outdoors for 1 year to evaluate the antifouling property. As a result, ΔE was 4.2, which was an evaluation 4 level.
［比較例４］
実施例３において、配合６のフッ化ビニリデン樹脂混合物の併用を省略した以外は実施例３と同様にしてシートを得た。得られたシートを１年間屋外暴露して防汚性評価を行った結果、可塑剤のブリードによる汚れ付着の蓄積が酷く、光触媒機能層が効果的に作用せずにΔＥは７．８の評価４レベルであった。
[Comparative Example 4]
In Example 3, a sheet was obtained in the same manner as in Example 3 except that the combined use of the vinylidene fluoride resin mixture of Formulation 6 was omitted. The resulting sheet was exposed outdoors for 1 year and evaluated for antifouling. As a result, accumulation of dirt due to bleed of plasticizer was severe, and the photocatalytic functional layer did not act effectively, and ΔE was 7.8. There were 4 levels.
比較例１〜４のシートは、１年間の屋外曝露試験の結果、いずれもΔＥ＝２を越えており、防汚シートとして充分な自浄防汚効果が得られないものであった。 As a result of the outdoor exposure test for one year, the sheets of Comparative Examples 1 to 4 all exceeded ΔE = 2, and a sufficient self-cleaning antifouling effect was not obtained as an antifouling sheet.
本発明の自浄防汚シートを、中大型テント、テント倉庫などの膜構造建築物用部材、屋外大型看板用サインシート、店舗一体型内照看板などの産業用資材に用いることによって、光触媒層の分解作用による汚れ除去効果を発揮しながら、光触媒層を保持し、それによって膜材の使用開始から長期間に渡たる防汚効果を持続させることができるので、上記膜構造建築物や看板の外観をメンテナンスフリーで美麗に維持することを可能とする。 By using the self-cleaning antifouling sheet of the present invention for industrial materials such as medium and large tents, membrane structure building members such as tent warehouses, outdoor large signboards, store-integrated interior lighting signs, etc. While maintaining the photocatalyst layer while exhibiting the dirt removal effect due to the decomposition action, it can maintain the antifouling effect for a long time from the start of use of the membrane material, so the appearance of the above membrane structure buildings and signs It is possible to maintain beautifully without maintenance.
１：自浄防汚シート
２：シート状基材
２−１：繊維布帛
２−２：熱可塑性樹脂層
２−３：繊維複合積層体
３：光触媒機能層：海島微細構造（Ｉ）
３−１：光触媒粒子非含有域：合成樹脂（Ｂ）による
３−２：光触媒粒子含有域：合成樹脂（Ａ）による
３−１−ａ：島成分
３−２−ｂ：海成分
４：光触媒中間層：海島微細構造（ＩＩ）
４−１：光触媒粒子非含有域：合成樹脂（Ｃ）による
４−２：光触媒粒子含有域：合成樹脂（Ｄ）による
４−１−ａ：島成分
４−２−ｂ：海成分
５：光触媒粒子
５−１：光触媒粒子（海島微細構造（Ｉ）に含む）
５−２：光触媒粒子（海島微細構造（ＩＩ）に含む）
６：汚れ（初期付着状態）
1: Self-cleaning antifouling sheet 2: Sheet-like substrate 2-1: Fiber fabric 2-2: Thermoplastic resin layer 2-3: Fiber composite laminate 3: Photocatalyst functional layer: Sea-island microstructure (I)
3-1: Photocatalyst particle non-contained area: According to synthetic resin (B) 3-2: Photocatalyst particle-containing area: According to synthetic resin (A) 3-1-a: Island component 3-2-b: Sea component 4: Photocatalyst Intermediate layer: sea-island microstructure (II)
4-1: Photocatalyst particle-free area: According to synthetic resin (C) 4-2: Photocatalyst particle-containing area: According to synthetic resin (D) 4-1-a: Island component 4-2b: Sea component 5: Photocatalyst Particle 5-1: Photocatalyst particles (included in the sea-island microstructure (I))
5-2: Photocatalyst particles (included in the sea-island microstructure (II))
6: Dirt (initial adhesion state)
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