TWI445784B - Antifouling sheet - Google Patents
Antifouling sheet Download PDFInfo
- Publication number
- TWI445784B TWI445784B TW099124723A TW99124723A TWI445784B TW I445784 B TWI445784 B TW I445784B TW 099124723 A TW099124723 A TW 099124723A TW 99124723 A TW99124723 A TW 99124723A TW I445784 B TWI445784 B TW I445784B
- Authority
- TW
- Taiwan
- Prior art keywords
- layer
- antifouling
- photocatalyst
- sheet
- self
- Prior art date
Links
- 230000003373 anti-fouling effect Effects 0.000 title claims description 225
- 239000010410 layer Substances 0.000 claims description 227
- 239000011941 photocatalyst Substances 0.000 claims description 118
- 239000002344 surface layer Substances 0.000 claims description 45
- 229920005992 thermoplastic resin Polymers 0.000 claims description 36
- 238000005336 cracking Methods 0.000 claims description 23
- 239000000758 substrate Substances 0.000 claims description 18
- 229920005989 resin Polymers 0.000 description 55
- 239000011347 resin Substances 0.000 description 55
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 23
- 238000000576 coating method Methods 0.000 description 23
- 229910052731 fluorine Inorganic materials 0.000 description 23
- 239000011737 fluorine Substances 0.000 description 23
- 239000011248 coating agent Substances 0.000 description 22
- 239000000463 material Substances 0.000 description 21
- 230000000694 effects Effects 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
- 239000002245 particle Substances 0.000 description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 15
- 239000007788 liquid Substances 0.000 description 13
- 239000012790 adhesive layer Substances 0.000 description 10
- 239000004744 fabric Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- -1 polysiloxane Polymers 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 229920000178 Acrylic resin Polymers 0.000 description 7
- 239000004925 Acrylic resin Substances 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000005033 polyvinylidene chloride Substances 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 229910052586 apatite Inorganic materials 0.000 description 4
- 229910000420 cerium oxide Inorganic materials 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 230000004927 fusion Effects 0.000 description 4
- 229910010272 inorganic material Inorganic materials 0.000 description 4
- 239000011147 inorganic material Substances 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 4
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[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 VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 239000004800 polyvinyl chloride Substances 0.000 description 4
- 229920000915 polyvinyl chloride Polymers 0.000 description 4
- 239000005871 repellent Substances 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 239000008199 coating composition Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920003002 synthetic resin Polymers 0.000 description 3
- 239000000057 synthetic resin Substances 0.000 description 3
- 239000002759 woven fabric Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004709 Chlorinated polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 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
- 238000004140 cleaning Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000002123 temporal effect Effects 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium 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
- 239000011882 ultra-fine particle Substances 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229920006370 Kynar Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- IKZZIQXKLWDPCD-UHFFFAOYSA-N but-1-en-2-ol Chemical compound CCC(O)=C IKZZIQXKLWDPCD-UHFFFAOYSA-N 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
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- 230000015556 catabolic process Effects 0.000 description 1
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- 239000003086 colorant Substances 0.000 description 1
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- 238000007334 copolymerization reaction Methods 0.000 description 1
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- 238000006731 degradation reaction Methods 0.000 description 1
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- 230000020169 heat generation Effects 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
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- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Classifications
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- B08—CLEANING
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Description
本發明係有關防污性薄片,特別是有關具有基材薄片,及形成於該基材薄片之表面上的自我崩落性防污層之防污性薄片。
具有基材薄片,及形成於該基材薄片之表面上的自我崩落性防污層之防污性薄片如,JP2005-271490A記載之物。
該防污性薄片為,基材薄片之布帛表面形成自我崩落性的防污層。該自我崩落性之防污層為,含有光觸媒,及藉由該光觸媒之氧化還原作用可分解的熱塑性樹脂。
將該類構造之防污性薄片供給倉庫屋頂及卡車車棚等室外用途時,光觸媒可藉由太陽光線等照射於防污層而接受光能量,以分解存在於其周圍之熱塑性樹脂,同時使自露出防污層表面,而發現氧化還原性即防污作用。
其他已知的防污性薄片如,JP09-078454A記載的薄片之外表面形成含有光觸媒粒子之親水性表面層的屋外用薄片。該室外用薄片可利用光觸媒效果增加薄片表面之親水性,又藉由該作用可利用雨水等洗淨污垢。
又其他已知的防污性薄片如,JP2005-042257A記載的基材最上層被覆含有光觸媒之氟樹脂層的光觸媒薄片中,氟樹脂表面具有防水性之光觸媒薄片。該薄片為,薄片表面層具有防水性而不易附著污垢,且可以光觸媒分解附著之污垢。
另外已知的防污性薄片如,JP2001-064583A記載的將必須成份為聚矽氧烷丙烯酸樹脂、光觸媒粒子及水系溶劑之光觸媒塗料組成物塗佈於基材上製膜時,膜厚方向之光觸媒粒子具有濃度梯度之物。光觸媒含量設置濃度梯度係為了防止基材界面因光觸媒而惡化。該光觸媒塗料組成物所形成的塗膜為,具有光觸媒之光觸媒能力及親水化能力可得親水性、防污性、防霧性之物。又該光觸媒塗料組成物中為了防止塗佈製膜於基材上的含有光觸媒之塗膜本身分解惡化,而使用含有持有充分耐光觸媒反應造成的分解力之鍵結力的聚矽氧烷成份之聚矽氧烷丙烯酸樹脂。
JP2005-271490A之防污性薄片雖具有優良防污性,但僅限於使防污層快速進行自我崩落。即,防污層為,如上述利用粉粒狀光觸媒分解存在於其周圍之熱塑性樹脂,而使附著污垢之防污層自我崩落,而發現維持實質上不附著污垢之乾淨表面狀態的機能。因此為了早期發現所要求的防污性,需加強分解熱塑性樹脂之能力,結果會加速進行自我崩落,而縮短防污層因崩落而消失之時間。
一般要求倉庫屋頂及卡車車棚具有10年之耐用年限,因此防污層需形成對應的厚度。但防污層太厚時不具實用性,又為了製品化進行高周波熔合及熱熔合時會產生障礙,且成本高。
曾考慮減少防污層中之光觸媒量等以削弱自我崩落性之對策。但會大幅延遲發揮所需防污性能之開始時期。更詳細而言即,特別是初期開始使用防污薄片之階段中,大部份的光觸媒係埋設於防污層內部,其表面部為不存在所需量之光觸媒的狀態。此時自我崩落性較弱,故需具備對應分解表面之熱塑性樹脂以露出所需量之光觸媒的時間,因此開始使用之初期階段係無法發現所要求的防污性能。
JP09-078454A、JP2005-042257A、JP2001-064583A之防污性薄片為,各自之薄片表面具有親水性或防水性,以得到防污效果之物。又任何防污性薄片之表面層需具備污垢脫落之構造,因此表面層需注意不會因光觸媒之分解作用而分解惡化。但此等薄片無法完全去除污垢,特別是金屬垢粉末等無法經由光觸媒分解,會於薄片之使用期間緩緩累積。
為解決該問題,因此本發明之目的為,基材薄片之表面形成自我崩落性防污層的防污性薄片中,無需形成較厚的防污層,可自開始使用初期起長期維持所要求的防污性。
為了達成該目的本發明之防污性薄片的特徵為,具有基材薄片,及形成於該基板薄片之表面上的防污層,前述防污層為,含有光觸媒,及藉由該光觸媒分解之熱塑性樹脂而具有自我崩落性,又前述防污層為,其表面部之自我崩落性比內部強之物。
又,上述之防污層係亦可特定為,其表面部藉由光觸媒分解熱塑性樹脂之速度比內部快之物。
因具有該類構造,而使防污層之表面部的自我崩落性比其內部更強,故可藉由光觸媒迅速分解熱塑性樹脂。如此可伴隨防污層的自我崩落而使附著於防污層表面之污垢及灰塵脫落,因此防污性薄片可迅速自開始使用起之初期階段發現所要求的防污效果。其後,防污層之表面部隨及崩落,其內部之不如表面部般自我崩落性不強之部份徐徐顯現在防污層之表面。因此,變得可長期持續發揮所需之防污性能。
本發明自基材薄片的表面上具有自我崩落性防污層構成的防污性薄片,無需形成較厚之防污層,可自開始使用起長期維持所要求的防污性。
圖1所示的本發明之防污性薄片的實施例為,基材薄片1之表面層合防污層3。
基材薄片1可使用樹脂薄膜;樹脂薄片;織物、編物、不織物、網物等布帛等之任意的薄片材料。又可使用層合薄片之材料。其中因本發明之防污性薄片主要係使用於室外,故希望具有屋外使用時之耐久性。該類薄片材料較佳如,具有一定素材質量之織物。
基材薄片為布帛時可為聚對苯二甲酸乙二醇酯等聚酯;聚乙烯、聚丙烯、聚乙烯醇、聚氯乙烯等聚烯烴;尼龍6、尼龍66等聚醯胺;聚對苯酞醯胺(肯普拉(登記商標))等芳香族聚醯胺等所形成之布帛,或玻璃編織物、碳纖維編織物。其中就低成本且尺寸安定性優良之觀點較佳為,聚酯所形成之布帛。基材薄片為樹脂薄膜及樹脂薄片時,也可以上述聚合物形成。
又,基材薄片較佳為布帛含浸合成樹脂之樹脂含浸物,或布帛表面設置合成樹脂層之層合物。該合成樹脂可使用聚對苯二甲酸乙二醇酯等聚酯;聚丙烯、聚氯乙烯、伸乙基乙烯醇聚合物等聚烯烴;聚胺基甲酸乙酯等。其中就優良高周波發熱性之觀點較佳為聚氯乙烯。
基材薄片之厚度較佳為50μm至10mm,更佳為200μm至3mm。
將防污層3層合於基材薄片1之表面上的加工方法如,層壓、塗佈、填塞、壓延、擠壓層合等方法等。其中就易調整防污層3之厚度的觀點較佳為塗佈法。
必要時可如圖2所示,於基材薄片1及防污層3之間設置接著劑層2。接著劑層2較佳為使用於基材薄片1及防污層3之相溶性或接著性較差時。接著劑層2所使用的接著劑可為持有充分耐候性及接合力之物無特別限定。例如,氯乙烯樹脂、聚乙烯乙酸乙烯共聚物、丙烯酸樹脂、胺基甲酸乙酯樹脂、氟系樹脂、氯化聚乙烯、乙烯乙酸乙烯共聚物或此等之混合物。其中就對後述般含有光觸媒之防污層3具有優良相溶性之觀點,接著劑較佳為以聚丙烯酸、聚甲基丙烯酸、聚丙烯酸烷酯、聚甲基丙烯酸烷酯等丙烯酸樹脂為材料之物。
其次將說明防污層3。防污層3為,含有光觸媒,及藉由光觸媒分解之熱塑性樹脂(以下可單稱為「熱塑性樹脂」)。防污層除了此等較佳為,含有氟系樹脂。即,防污層較佳為,含有光觸媒、氟系樹脂及藉由光觸媒分解之熱塑性樹脂。防污層3除了此等,可含有無機系紫外線遮蔽劑、紫外線吸收劑等。
防污層3所含的熱塑性樹脂為,藉由光觸媒之氧化還原作用分解之物,例如氯乙烯樹脂、氯乙烯乙酸乙烯共聚物、丙烯酸、胺基甲酸乙酯樹脂、氯化聚乙烯、乙烯乙酸乙烯共聚物、此等之任意的混合物等。防污層3較佳為,相對於構成該防污層3之樹脂成份100質量%,含有10質量%至100質量%之熱塑性樹脂。具有該組成時可藉由後述熱塑性樹脂的自我崩落,維持乾淨表面狀態。
防污層3除了熱塑性樹脂另含有氟系樹脂時,相對於構成該防污層3之樹脂成份100質量%,較佳為含有10質量%至50質量%之熱塑性樹脂,更佳為含有20質量%至40質量%。此時防污層3含有10質量%至50質量%之熱塑性樹脂,可得良好的自我崩落性。
防污層3中構成該防污層3之樹脂成份如上述較佳為,除了熱塑性樹脂另含有氟系樹脂。防污層3含有氟系樹脂時,起因於氟系樹脂比較不易藉由光觸媒分解,而會減緩自我崩落速度,故可長期發揮所要求的防污性能。另外起因於氟系樹脂之防水防油的特性,而於初期使用防污性薄片之階段中表面不易污染。
氟系樹脂可為,藉由光觸媒分解之速度比熱塑性樹脂慢之物,例如聚偏氯乙烯(PVDF)、至少含有2單元以上之聚偏氯乙烯(PVDF)單元的共聚物,或此等之混合物。含有2單元以上之聚偏氯乙烯(PVDF)單位的共聚物如,聚偏氯乙烯(PVDF)-四氟乙烯(PTFE)共聚物、聚偏氯乙烯(PVDF)-六氟丙烯(PHFP)共聚物、聚偏氯乙烯(PVDF)-六氟丙烯(PHFP)-四氟乙烯(PTFE)共聚物。
氟系樹脂較佳為軟質氟系樹脂(以下也稱為「氟系彈性體」)。氟系樹脂為軟質氟系樹脂時,薄片不易發生皺折或傷痕等,可具有優良處理性。
防污層3含有氟系樹脂時,相對於構成該防污層3之樹脂成份100質量%,可含有超過0質量%且90質量%以下之氟系樹脂,較佳為含有50質量%至90質量%,更佳為含有60質量%至80質量%。氟系樹脂之含有率為90質量%以下時,不會妨礙防污層3自我崩落。
又,就減緩防污層3之自我崩落速度的觀點,防污層3中構成防污層3之樹脂成份除了熱塑性樹脂,相對於構成防污層3之樹脂成份100質量%可含有超過0質量%且90質量%以下之藉由光觸媒分解之速度比熱塑性樹脂慢,氟系樹脂以外之難分解性樹脂。該類樹脂如,丙烯酸聚矽氧烷系共聚物、胺基甲酸乙酯聚矽氧烷系共聚物等聚矽氧烷樹脂;藉由光觸媒不易分解的加工或改性之熱塑性樹脂或熱硬化性樹脂等。
構成防污層3之樹脂成份係指,熱塑性樹脂及必要時添加之氟系樹脂及/或難分解性樹脂合計。
光觸媒係指,照射紫外線時其表面會發生氧化力,藉由其氧化還原作用可分解有機物之材料。該類光觸媒較佳為,含有1種以上TiO2
、ZnO、SrTiO3
、CdS、InP、CaAs、BaTiO3
、KNbO3
、Fe2
O3
、Ta3
O5
、WO3
、SnO2
、Bi2
O3
、NiO、Cu2
O、SiC、MoS2
、InPb、RuO2
、CeO2
中所選出的材料之物。但無特別限制,可為相對於熱塑性樹脂可發現氧化還原作用之物。光觸媒於防污層3中較佳以粒徑10nm至10μm,更佳以粒徑10nm至5μm之粉粒體形態存在。防污層3可含有能充分分解熱塑性樹脂之光觸媒,其平均含量相對於構成防污層3之樹脂成份100質量份較佳為,光觸媒之固體成份換算下0.01質量份至15質量份,更佳為光觸媒之固體成份換算下0.01質量份至10質量份。光觸媒可以凝聚2個以上粒子存在。光觸媒之含量可因應其粒徑及分解作用之強度為上述範圍以外之含量。例如,光觸媒係使用粒徑較小之光觸媒,或分解作用較強之光觸媒時,可減少光觸媒含量,又光觸媒係使用粒徑較大之光觸媒,或分解作用較弱之光觸媒時,可增加光觸媒含量。本發明如後述般係沿著防污層3之厚度方向改變光觸媒含量。
光觸媒較佳為,上述光觸媒材料及金屬或金屬氧化物等無機材料之混合物;或上述光觸媒材料被覆金屬或金屬氧化物等無機材料之物。其中較佳為,二氧化鈦及二氧化矽之混合物、二氧化鈦被覆二氧化矽之被覆物、二氧化鈦及磷酸鈣(以下也稱為磷灰石)之混合物或二氧化鈦被覆磷酸鈣之被覆物。光觸媒為上述光觸媒材料及金屬或金屬氧化物等無機材料之混合物;或上述光觸媒材料被覆金屬或金屬氧化物等無機材料之被覆物時,可適度抑制因光觸媒之氧化還原作用的分解作用。
光觸媒如,昭和電工公司販售的「求彼達(商品名)」之經特殊表面處理的光觸媒,詳細上較佳為氧化鈦之微粒子表面被覆磷灰石之物。該製品可稱為光觸媒用磷灰石複合氧化鈦微粒末,因氧化鈦之表面形成磷灰石層,故防污層3具有不易分解熱塑性樹脂之效果。
防污層3所含有的無機系紫外線遮蔽劑可為,既使接受紫外線也不會發現光觸媒作用的紫外線無法通過之物,無特別限定。其中如粒徑0.1nm至50nm之氧化鈦、氧化鋅、氧化鈰等附載於球狀矽微粒子之物。以附載於球狀矽微粒子之物為佳的理由為,此等無機系紫外線遮蔽劑可藉由上述粒徑範圍之超微粒子化提升其效果。又,此等超微粒子材料因具有較高的表面活性,故會因其觸媒作用而導致其他添加成份變質。
藉由使用無機系紫外線遮蔽劑,可得紫外線不會過度到達防污層3內部之光觸媒的構造。因此可防止非自本發明計劃的防污層3之表面側,而得自內部全體分解熱塑性樹脂。使用無機系紫外線遮蔽劑也可防止基材薄片1因紫外線而光變質而減弱其強度。
防污層3含有無機系紫外線遮蔽劑時,其含量相對於構成防污層之樹脂組成物100質量份較佳為0.2質量份至5質量份。
防污層3可含有的紫外線吸收劑如,苯并三唑系、水楊酸系、二苯甲酮系等有機系紫外線吸收劑等。藉由紫外線吸收劑,可防止因紫外線而光變質而減弱其強度。防污層3含有紫外線吸收劑時,其含量相對於構成防污層之樹脂成份100質量份較佳為0.05質量份至5質量份。
防污層3可另含有光安定劑、著色劑等添加劑。
下面將說明本發明之防污性薄片的防污效果。本發明之防污性薄片為,接受太陽光之表面部藉由光觸媒分解熱塑性樹脂,而緩緩崩落其表面部構成防污層3之成份。因此可露出不附著污垢之乾淨表面,以維持該不附著污垢之乾淨表面狀態。
詳細而言,該防污性薄片使用於室外時,防污層3所含的粉粒體狀光觸媒接受光能量後,會分解存在於其周圍的熱塑性樹脂。如此可使光觸媒露出防污層3之表層,發現藉由特定氧化還原作用分解油脂等有機系之污垢的防污作用。但既使發現該類利用光觸媒之防污作用,仍無法藉由光觸媒分解矽及金屬鏽等無機系的污垢而殘存於其周圍。因此防污層3之表面會緩緩附著污垢。但該附著污垢之防污層3會如上述般藉由光觸媒緩緩分解熱塑性樹脂,而使構成防污層3之成份中未分解殘存的成份會自防污層3之表面崩落。故防污層3即防污性薄片之表面可長期維持實質上不附著污垢之乾淨狀態。
防污層3中藉由光觸媒分解熱塑性樹脂,而使其他成份崩落之過程中,防污層3可一持性形成洞穴形狀或多孔質形狀。
下面將說明防污層3之詳細構造。本發明中,防污層3係以,其表面部一方之自我崩落性比內部強之條件構成。
例如如圖3所示,防污層3係自含有表面層5及內側層4的2層以上之層構成,又表面層5之光觸媒含有率高於內側層4,故表面層5一方之自我崩落性比內側層4強。此時表面層5係指,構成防污層3之層中,離基材薄片1最遠之層,內側層4係指,構成防污層3之層中,比表面層5更靠近基材薄片1之層。防污層3為3層以上時,係以複數層構成內側層4。但就易進行製造步驟之觀點,防污層3較佳以表面層5及內側層4之雙層構成。
防污層3係2層以上之層構成時,表面層5之光觸媒含有率與內側層4之光觸媒含有率的比值較佳為1500:1至5:3,更佳為20:1至3:1。該光觸媒含有率係指,相對於形成表面層5及側面層4之樹脂成份的光觸媒含有率。各層中光觸媒之含有比率為上述範圍時,可使初期的優良自我崩落性及長期自我崩落持續性反應。
此時表面層5之光觸媒含量相對於構成表面層5之樹脂成份100質量份較佳為,光觸媒之固體成份換算下5質量份至15質量份。表面層5之光觸媒含量相對於樹脂成份100質量份為5質量份以上時,初期可得優良自我崩落性,又表面層5之光觸媒含量相對於樹脂成份100質量份為15質量份以下時,可減少過剩的光觸媒,以低成本得到本發明之效果。
內側層4之光觸媒含量相對於構成內側層4之樹脂成份100質量份較佳為,光觸媒之固體成份換算下0.01質量份至3質量份。內側層4之光觸媒含量相對於樹脂成份100質量份為0.01質量份以上時,可良好分解熱塑性樹脂,內側層之光觸媒含量相對於樹脂成份100質量份為3質量份以下時,崩落速度不會太快,可長時間維持本發明之效果。
防污層3為3層以上時,內側層4可以,位於最靠近基材薄片1之最深層,及表面層與最深層之間的1或2以上之中間層構成。中間層之光觸媒含有率無特別限定,但較佳為表面層之光觸媒含有率以下,最深層之光觸媒含有率較佳為中間層之光觸媒含有率以下。由此構成時可長時間維持本發明之效果。又,內側層係最深層及中間層構成時,上述內側層中光觸媒之含有率及含量可自,視內側層為單層而求取。
防污層3係以2層以上之層構成時,表面層5之厚度與內側層4之厚度的比值較佳為1:1至1:30,更佳為5:8至1:15。各層中光觸媒之含有比率為上述範圍時,可初期的優良自我崩落性及長期自我崩落持續性兩立。
此時表面層5之厚度較佳為1μm至5μm。表面層5之厚度為1μm以上時,可得充分的初期自我崩落性,表面層5之厚度為5μm以下時,可低價製造。
相對地內側層4之厚度較佳為5μm至55μm。內側層4之厚度為5μm以上時,可得長期的自我崩落持續性,內側層4之厚度為55μm以下時,可低價製造該內側層5。
防污層3為3層以上時,構成內側層4之各層的厚度無特別限定。但中間層之厚度較佳為表面層5之厚度以上,最深層之厚度較佳為中間層之厚度以上。由此構成時可長期均勻發揮本發明之效果。又,內側層係最深層及中間層構成時,上述內側層之厚度係合計最深層及中間層而求取。
本發明因係以2層以上之層構成防污層3,故可形成較薄的自我崩落速度較快之表面層5,及形成較厚的自我崩落速度較慢之內側層4,而發揮特別優良之效果。其因為,發現自我崩落性所需時間較長之內側層4的表面,配置可早期發現自我崩落性之較薄層的表面層5,因此至內側層4發現自我崩落性為止,可藉由表面層5較強的自我崩落作用,維持不附著污垢之乾淨表面。又因所構成的表面層5較薄,故表面層5自我崩落之狀態下,部分的光能量可通過表面層5到達內側層4,而使存在於內側層4中之光觸媒接受光能量,而預先積存某程度的光能量,因此當內側層4露出表面時,易發現快速的自我崩落作用。
又,防污層3係單層形成時,可藉由調整其表面部一方之光觸媒含有率比內部高的方法,得到相同構造。
又,使防污層3之表面部分含有氧化鈦等活性較強的光觸媒,其內部含有氧化鋅等活性比表面部弱之光觸媒時,可得相同構造。此時表面部之活性較強的光觸媒含有率,比內部活性較弱之光觸媒含有率高時,可進一步提高使表面部一方之自我崩落性比內部強的傾向。
又,防污層3之表面部使用易藉由光觸媒分解之熱塑性樹脂,其內部使用較不易分解之樹脂時,可得相同構造。此時併用其他構造,可進一步提高使表面部一方之自我崩落性比內部強的傾向。
又可使用其他方法。即,可使本發明之防污層3為,表面部一方之自我崩落性比內部強之構造下,可任意使用能得到該構造之方法。例如可利用使沿著防污層3之厚度方向單純減少自我崩落性般的特性變化,或其他任意的特性變化,設定其自我崩落性。
由此構成之防污層3的厚度較佳為6μm至60μm,更佳為6μm至30μm。具有該範圍之厚度時,可迎合防污性薄片的彎度或曲折。防污層3使用氟系樹脂時,氟系樹脂為氟系彈性體可得不易產生皺折及傷痕等問題之優點。
本發明之防污性薄片為,開始使用之初期階段中光觸媒係少數露出於防污層3之表層。但當使用期間表層部之光觸媒接受光能量時,會分解其周圍的熱塑性樹脂,而使自露出於表層。此時被分解之熱塑性樹脂會連同附著的污垢崩落,例如藉由降雨時之雨水等而流失。如此使光觸媒露出於表層,可充分發現特有的氧化還原作用即特有的防污作用。防污層3為,其表面部一方之自我崩落性比內部強。故表面部可早期藉由光觸媒分解熱塑性樹脂,而快速發現例如比利用上述氟系樹脂之防污效果更優良的特有防污作用,即藉由附著污垢之防污層3的表面崩落而維持乾淨表面之機能。
防污層3之表面部如上述般因自我崩落性強,而在較短之期間內崩落。且,其後較其自我崩落性為弱之部份變得露出,因此可長期持續所需之防污性。
即本發明可加強防污層3之表面部的自我崩落性,而早期發現利用防污層3之表面崩落維持乾淨表面的機能,且防污層3之內部的自我崩落性比較弱,但可發揮所要求之程度下,可防止因過度自我崩落而使防污層早期消失,因此對應該防污性薄片之製品壽命的期間內可持續所要求的防污性。
又,防污層3整體之自我崩落性較弱時,可發現長期的防污性。但此時開始發現利用防污層3之表面崩落以維持乾淨表面之機能為止,例如需數年般長時間,故無實用性。
圖1至圖3所示的防污性薄片為,基材薄片1之表面上層合防污層3之物,因此易使用熱熔合裝置接合複數防污性薄片,或防污性薄片及其他材料,或2片以上之防污性薄片的端部同士。
重疊接合防污性薄片之端部同士時,預先於基材薄片1之背面(配置防污層3之表面的相反側之面)設置接著劑層,或其中一方防污性薄片之防污層3上重疊接合另一方防污性薄片之基材薄片1時,於兩者間配置接著劑層之情形下,既使防污層3與基材薄片1之相溶性較低,也易接合。接著劑層可同樣使用上述層合基材薄片1及防污層3而一體化用之接著劑。
圖4為,基材薄片1之表背雙面設有接著劑層2及6,且防污層3係由表面層5及內側層4雙層構成時之剖面構造圖。
下面各實施例及比較例中,防污層、表面層及內側層之厚度的測定方法,以及光觸媒及無機紫外線吸收劑等之粒徑的測定方法如下所述。
使用KEYENCE公司製數據微示器VHX-900,將試料剖面擴大為250倍至2500倍進行測定。
使用島津製作所公司製雷射衍射粒度分佈測定裝置SALD-2100測定質量平均粒徑。
所使用的基材薄片為,自聚酯纖維形成之織物中含浸聚氯乙烯而得的薄片。
準備氟系樹脂之聚偏氟乙烯(PVDF)-四氟乙烯(PTFE)共聚物(ARKEMA公司製,商品名:kynar)70質量%,及熱塑性樹脂用之丙烯酸樹脂(三菱人造絲公司製,商品名:艾庫里)30質量%所形成之樹脂成份。
其次相對於該2成份所形成的樹脂成份100質量份,添加光觸媒用之粉粒體狀的粒徑約150nm之二氧化鈦及二氧化矽的混合物(昭和電工公司製,商品名:求彼達)1質量份、紫外線遮蔽劑用之氧化鋅1質量份,及紫外線吸收劑用之苯并三唑系紫外線吸收劑(吉巴日本公司製,商品名:吉奴敏326)1質量份。
將添加光觸媒、紫外線遮蔽劑及紫外線吸收劑之樹脂成份溶解或分散於溶劑用之甲基乙基酮中,使全溶質:溶劑之質量比為2:8,製作塗佈液1。
與塗佈液1相比,除了使光觸媒量相對於樹脂成份100質量份為7質量份外,其他同塗佈液1之製作步驟,製作塗佈液2。
與塗佈液1相比,除了使光觸媒量相對於樹脂成份100質量份為10質量份外,其他同塗佈液1之製作步驟,製作塗佈液3。
使用刮刀塗佈機將接著劑用之丙烯酸系樹脂塗佈於基材薄片之雙面上,使乾燥厚為2μm,形成接著劑層。其次使用塗佈輥將上述塗佈液1塗佈於一方接著劑層上,使乾燥厚10μm,形成防污層之內側層。接著使用塗佈輥將塗佈液2塗佈於內側層上,使乾燥厚為3μm,形成防污層之表面層。由此而得防污性薄片。該防污性薄片為,防污層中表面層一方之自我崩壞性比內側層強。
使用刮刀塗佈機將接著劑用之丙烯酸系樹脂塗佈於基材薄片之表面上,使乾燥厚為2μm,形成接著劑層。其次使用塗佈輥將塗佈液3塗佈於接著劑層上,使乾燥厚為13μm,得基材薄片之表面形成防污層的防污性薄片。該比較例1之防污性薄片中防污層為單層,且如後述般光觸媒係均勻分散於防污層,故防污層之內部及表面部的自我崩壞性同等。
與比較例1相比,除了將塗佈液3變更為塗佈液1外,其他同比較例1得比較例2之薄片。該比較例2之薄片同比較例1之薄片,其中防污層為單層,如後述般光觸媒係均勻分散於防污層,故防污層之內部及表面部的自我崩壞性同等。
將實施例、比較例1、比較例2之防污性薄片供給下述試驗。試驗條件如下所述。
將試料以試料之防污層朝南,且對地面之傾斜角為45℃之條件設置於暴露於太陽光下之室外。每一定期間後使用KEYENCE公司製數據微示器VHX-900,將試料剖面擴大為250倍至2500倍後觀察測定防污層之厚度。膜厚保持率係以下述算出。
=一定期間後試料中防污層之厚度/試驗開始後試料中防污層之厚度×100
使用黑光以一定時間將波長310至400nm、照射強度1mW/cm2
之紫外線,照射於試料表面全體。又使用密那爾公司製紫外線強度計UM36調整紫外線照射強度。將水滴滴落於照射一定時間之紫外線後的試料上,再使用協和界面科學公司製接觸角測定裝置DCA-WZ測定30秒後試料與水滴之接觸角。
自實施例、比較例1、比較例2之防污性薄片切取各試料,以液體氮冷卻試料後,以剃刀切斷試料。其次對切斷後之試料剖面進行碳蒸鍍,再使用電場放出型掃描型電子顯微鏡(JSM-7600F(日本電子公司製)),將試料剖面擴大為2000倍後以鈦進行元素製圖測定。
實施例之防污薄片自初期起防污性良好,水滴接觸角如圖5所示,試驗期間為一定的70至80度。因此確認實施例之防污薄片不為,已知薄片般其表面會藉由光觸媒之親水化作用而親水化而降低接觸角以發現自淨作用之物,又不為,使其表面為防水性而增加對水之接觸角之發現自淨作用之物。防污層之厚度如圖6所示,試驗開始後經過4年仍可保持初期厚度之約60%。但開始使用後,防污層會因自我崩落而發現防污作用。又,自元素製圖測定之結果可確認,實施例之防污性薄片中存在於表面層一方之鈦元素比內側層多。又起因於既使基材薄片之背面也設置接著劑層的構造,重合2枚防污性薄片之端部同士進行高周波熔合時可良好接合。
比較例1之防污薄片同實施例,初期具有良好防污性。但如圖6所示,試驗開始後經過2年時防污層會完全分解消失。又自元素製圖測定之結果可確認,比較例1之防污薄片中防污層之內部及表面部存在同程度的鈦元素。
比較例2之防污薄片如圖6所示,經過4年時防污層之厚度保持初期厚度為70%。但試驗開始後1年內膜厚保持率為100%,無法發現藉由防污層之自我表面崩落維持乾淨表面之機能,因此初期無法得到充分防污性。又自元素製圖測定之結果可確認,比較例2之防污薄片中防污層之內部及表面部存在同程度的鈦元素。
本發明之防污性薄片因自初期起可長期具有藉由表面之自我崩落維持乾淨表面之機能(自動改裝機能),故適用於展開薄片使用之用途。因此本發明之防污性薄片例如可使用於卡車車棚、雨遮棚、帳篷倉庫用膜材料、中大型長篷用膜材料、天花板材料、看板用膜材料等。
1...基材薄片
2...接著劑層
3...防污層
4...內側層
5...表面層
6...接著劑層
圖1為,本發明之防污性薄片的實施例之中樞部剖面圖。
圖2為,本發明之防污性薄片的另一實施例之中樞部剖面圖。
圖3為,本發明之防污性薄片的又一實施例之中樞部剖面圖。
圖4為,本發明之防污性薄片的又一實施例之中樞部剖面圖。
圖5為,附著於防污層表面之水滴表面具有站立角度時的接觸角之經時變化圖。
圖6為,防污性薄片中防污層之膜厚保持的經時變化圖。
Claims (4)
- 一種防污性薄片,其特徵為,具有基材薄片,及形成於該基材薄片之表面上的防污層,前述防污層為,含有光觸媒,及藉由該光觸媒分解之熱塑性樹脂而具有自我崩落性,又前述防污層為,具有包含內側層,及自我崩落性比內側層強之表面層的2層以上之層。
- 如申請專利範圍第1項之防污性薄片,其中表面層之光觸媒含有率與內側層之光觸媒含有率的比為1500:1至5:3。
- 如申請專利範圍第1項之防污性薄片,其中表面層之厚度與內側層之厚度的比為1:1至1:30。
- 如申請專利範圍第1項之防污性薄片,其中表面層之厚度為1μm至5μm。
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US20120015165A1 (en) | 2012-01-19 |
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JP4531120B1 (ja) | 2010-08-25 |
SA110310592B1 (ar) | 2014-12-31 |
KR101472872B1 (ko) | 2014-12-15 |
JPWO2011013176A1 (ja) | 2013-01-07 |
KR20120037368A (ko) | 2012-04-19 |
EP2460655A4 (en) | 2013-01-16 |
CN102414022A (zh) | 2012-04-11 |
CN102414022B (zh) | 2015-11-25 |
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ES2524368T3 (es) | 2014-12-05 |
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