JP3868394B2 - Anti-fouling sheet for tents with excellent anti-fouling properties - Google Patents
Anti-fouling sheet for tents with excellent anti-fouling properties Download PDFInfo
- Publication number
- JP3868394B2 JP3868394B2 JP2003124328A JP2003124328A JP3868394B2 JP 3868394 B2 JP3868394 B2 JP 3868394B2 JP 2003124328 A JP2003124328 A JP 2003124328A JP 2003124328 A JP2003124328 A JP 2003124328A JP 3868394 B2 JP3868394 B2 JP 3868394B2
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- JP
- Japan
- Prior art keywords
- antifouling
- plasticizer
- layer
- weight
- sheet
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 230000003669 anti-smudge Effects 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- QFFVPLLCYGOFPU-UHFFFAOYSA-N barium chromate Chemical compound [Ba+2].[O-][Cr]([O-])(=O)=O QFFVPLLCYGOFPU-UHFFFAOYSA-N 0.000 description 1
- 229940083898 barium chromate Drugs 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- AQCDIIAORKRFCD-UHFFFAOYSA-N cadmium selenide Chemical compound [Cd]=[Se] AQCDIIAORKRFCD-UHFFFAOYSA-N 0.000 description 1
- ZYCAIJWJKAGBLN-UHFFFAOYSA-N cadmium(2+);mercury(2+);disulfide Chemical compound [S-2].[S-2].[Cd+2].[Hg+2] ZYCAIJWJKAGBLN-UHFFFAOYSA-N 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- JGIATAMCQXIDNZ-UHFFFAOYSA-N calcium sulfide Chemical compound [Ca]=S JGIATAMCQXIDNZ-UHFFFAOYSA-N 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- GDMLVHQYGPXZLA-UHFFFAOYSA-N carbon monoxide;ethenyl acetate Chemical compound [O+]#[C-].CC(=O)OC=C GDMLVHQYGPXZLA-UHFFFAOYSA-N 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 229910000152 cobalt phosphate Inorganic materials 0.000 description 1
- LFYNXTOOOBFBSI-UHFFFAOYSA-K cobalt(2+) phosphate Chemical compound P(=O)([O-])([O-])[O-].[Co+2].[Co+2] LFYNXTOOOBFBSI-UHFFFAOYSA-K 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- KQCVOSSWQCNAMG-UHFFFAOYSA-L dihydroxy(dioxo)chromium hydrate Chemical compound O.O[Cr](O)(=O)=O KQCVOSSWQCNAMG-UHFFFAOYSA-L 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical class OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 description 1
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 1
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 229910021514 lead(II) hydroxide Inorganic materials 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000008029 phthalate plasticizer Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920005554 polynitrile Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- ZEGFMFQPWDMMEP-UHFFFAOYSA-N strontium;sulfide Chemical compound [S-2].[Sr+2] ZEGFMFQPWDMMEP-UHFFFAOYSA-N 0.000 description 1
- YPMOSINXXHVZIL-UHFFFAOYSA-N sulfanylideneantimony Chemical compound [Sb]=S YPMOSINXXHVZIL-UHFFFAOYSA-N 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 238000003878 thermal aging Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical class [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- UQMZPFKLYHOJDL-UHFFFAOYSA-N zinc;cadmium(2+);disulfide Chemical compound [S-2].[S-2].[Zn+2].[Cd+2] UQMZPFKLYHOJDL-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
- Y02A40/25—Greenhouse technology, e.g. cooling systems therefor
Landscapes
- Catalysts (AREA)
- Protection Of Plants (AREA)
- Greenhouses (AREA)
- Laminated Bodies (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、雨筋汚れ防止性に優れたテント用防汚性シートに関するものである。さらに詳しく述べるならば、本発明は、繊維材料からなる基布と、ポリ塩化ビニル樹脂層と、光触媒防汚層とを有し、中・大型テント、テント倉庫などの産業用資材用途として極めて有用な防汚性シートに関するものである。
【０００２】
【従来の技術】
従来、産業用資材用途のポリ塩化ビニル系樹脂被覆シートは、例えば、繊維基布の片面又は両面にポリ塩化ビニル系樹脂層が被覆されている柔軟なシートであって、中・大型テント、テント倉庫、トラック用の幌、看板用バックリットなどに広く使用されている。このようなシートは、加工性、経済性、防炎性等の点において、ポリ塩化ビニル系樹脂に固有の長所を発揮するものであるが、一方、上記の用途において、長期間屋外に曝露されるため、ポリ塩化ビニル系樹脂中に配合される安定剤等について十分な吟味がなされたものが使用された場合であっても、長年月の間に次第に樹脂が分解、劣化し、また可塑剤が表面に移行して次第に表面が粘着性を示すようになり、またその粘着性表面上に塵埃等が付着して汚染される等の重大な欠点を生じていた。
【０００３】
このような欠点を改善する方法として、ポリ塩化ビニル系樹脂層の表面に有機溶剤に溶かしたアクリル系樹脂をコーティングする方法が提案されているが、アクリル系樹脂コーティング用樹脂液の有機溶剤中にポリ塩化ビニル系樹脂層中の可塑剤が溶出移行し、及び／又は前記可塑剤がアクリル系樹脂層中に溶出移行し、やがて表面に移行するために、前記アクリル系樹脂層の防汚効果は十分ではなかった。
【０００４】
また、ポリ塩化ビニル系樹脂層の表面に光触媒層をコーティング法により形成し、それにより汚れを分解除去する方法も提案されている。例えば、ＷＯ９７−１３４（特許文献１）には光触媒層をコーティングする場合は、一般には光触媒層とポリ塩化ビニル系樹脂層の接着性を向上させ、かつポリ塩化ビニル系樹脂層を、光触媒活性作用から保護するために、これら両層の間に接着・保護層を介在させることが提案されている。しかし、この場合においても、ポリ塩化ビニル系樹脂層の可塑剤が接着・保護層を通過して光触媒層に移行するため、これが光触媒層表面の親水化及び汚れ分解作用を妨げ、防汚効果が低下してしまうという問題を生じ、特に、屋外使用時に垂直部分の雨筋汚れを十分に防止するレベルまでは至っていない。
【０００５】
また、光触媒層の光触媒作用により、ポリ塩化ビニル系樹脂層中の可塑剤が選択的に分解される場合があり、このため長年月の間に、ポリ塩化ビニル系樹脂層の風合いが次第に硬くなるという問題を生ずることがある。
【０００６】
【特許文献１】
ＷＯ９７−１３４
【０００７】
【発明が解決しようとする課題】
本発明は、優れた防汚性と耐候性とを具備しているだけでなく、長期間使用の場合でも風合いの変化が少なく、しかも防汚性において耐久性の高い雨筋汚れ防止性に優れたテント用防汚性シートを提供しようとするものである。
【０００８】
【課題を解決するための手段】
本発明の雨筋汚れ防止性に優れたテント用防汚性シート（以下本発明の防汚性シートと記す）は、繊維材料より形成された基布と、その少なくとも１面上に形成されたポリ塩化ビニル系樹脂層と、前記ポリ塩化ビニル系樹脂層の上に形成された可塑剤移行防止層と、更に前記可塑剤移行防止層の上に形成された光触媒防汚層とを有し、
前記基布は、前記繊維材料に含浸された塩化ビニル樹脂を含む下塗り層を有するものであり、
前記ポリ塩化ビニル系樹脂層が可塑剤として
（１）ポリエステル系可塑剤、トリメリット酸エステル系可塑剤、及びピロメリット酸エステル系可塑剤から選ばれた少なくとも１種からなる液状可塑剤、及び
（２）エチレン−酢酸ビニル−一酸化炭素三元共重合体及びエチレン−アクリル酸エステル−一酸化炭素三元共重合体から選ばれた少なくとも１種からなる高分子量可塑剤、
から選ばれた少なくとも１種を含み、
但し、前記液状可塑剤が単独で用いられるときにはその配合量は、ポリ塩化ビニル系樹脂１００重量部に対し、４０〜１００重量部であり、前記高分子量可塑剤が単独で用いられるときには、その配合量はポリ塩化ビニル系樹脂１００重量部に対し、５０〜１２０重量部であり、かつ、前記液状可塑剤及び高分子量可塑剤が併用されるときには、その合計配合量は、前記ポリ塩化ビニル樹脂１００重量部に対し４０〜１２０重量部であり、かつ前記可塑剤移行防止層が、フッ素含有樹脂及びアクリル系樹脂から選ばれた少なくとも１種の樹脂を主成分として含有するものであり、かつ
前記可塑剤移行防止層と、前記光触媒防汚層との間に、ポリシロキサンと、アクリルシリコーン樹脂との混合物を含む接着・保護層が形成されている、
ことを特徴とするものである。
本発明の雨筋汚れ防止性に優れたテント用防汚性シートにおいて、前記可塑剤移行防止層が、吸油量が３０〜３００ml／１００ｇの充填剤１０〜５０重量％を含有する可撓性重合体樹脂からなるものであることが好ましい。
本発明の雨筋汚れ防止性に優れたテント用防汚性シートにおいて、前記可塑剤移行防止層が、吸油量が３０〜３００ml／１００ｇの充填剤を含有する可撓性重合体樹脂層と、少なくともその上表面を被覆し、かつ前記充填剤を含有しない可撓性重合体樹脂層とからなるものであることが好ましい。
本発明の雨筋汚れ防止性に優れたテント用防汚性シートにおいて、前記光触媒防汚層が、光触媒性無機材料としてＴｉＯ2 ，ＴｉＯ3 ，ＺｎＯ，ＳｒＴｉＯ3 ，ＣｄＳ，ＧａＰ，ＩｎＰ，ＧａＡｓ，ＢａＴｉＯ3 ，Ｋ2 ＮｂＯ3 ，Ｆｅ2 Ｏ3 ，Ｔａ2 Ｏ5 ，ＷＯ3 ，ＳｎＯ2 ，Ｂｉ2 Ｏ3 ，ＮｉＯ，Ｃｕ2 Ｏ，ＳｉＣ，ＳｉＯ2 ，ＭｏＳ2 ，ＩｎＰｂ，ＲｕＯ2 、及びＣｅＯ2 から選ばれた１種以上を含むことが好ましい。
本発明の雨筋汚れ防止性に優れたテント用防汚性シートにおいて、前記光触媒防汚層が、さらにシリカゾル、モノアルキルトリアルコキシシラン、及び前記モノアルキルトリアルコキシシランの加水分解生成物から選ばれた少なくとも１種からなる結着剤を含むことが好ましい。
本発明の雨筋汚れ防止性に優れたテント用防汚性シートの前記光触媒防汚層において、光触媒性無機材料の含有量が２５〜７５重量％であることが好ましい。
本発明の雨筋汚れ防止性に優れたテント用防汚性シートにおいて、前記ポリ塩化ビニル系樹脂が、吸油量が３０〜３００ml／１００ｇの吸油性充填剤を５０重量％以下の含有量で含有することが好ましい。
本発明の雨筋汚れ防止性に優れたテント用防汚性シートにおいて、前記防汚性シートの少なくとも一部が無機系顔料によって着色されていてもよい。
【０００９】
【発明の実施の形態】
本発明の防汚性シートの基布に用いられる繊維材料は、天然繊維、例えば、木綿、麻など、無機繊維、例えば、ガラス繊維、カーボン繊維、金属繊維など、再生繊維、例えば、ビスコースレーヨン、キュプラなど、半合成繊維、例えば、ジ−及びトリ−アセテート繊維など、及び合成繊維、例えば、ポリアミド（ナイロン６、ナイロン６６等）繊維、ポリエステル（ポリエチレンテレフタレート等）繊維、芳香族ポリアミド繊維、アクリル繊維、ポリ塩化ビニル繊維、ポリオレフィン繊維など、から選ばれる少なくとも１種類からなるものである。
【００１０】
基布中の繊維材料は、短繊維紡績糸条、長繊維糸条、スプリットヤーン、テープヤーンなどのいずれの形状のものであってもよく、また基布は、織物、編物、不織布又はこれらの複合布のいずれであってもよい。一般には、本発明の防汚性シートに用いられる繊維はポリエステル繊維であるのが好ましく、特にこのポリエステル繊維は長繊維（フィラメント）の形状にあることが好ましく、その織組織に制限はないが、平織であることが好ましい。前記繊維材料には、それに含浸された塩化ビニル樹脂を含む下塗り層が形成され、繊維材料と下塗り層とにより基布が構成される。
【００１１】
本発明の防汚性シートにおいて、基布の少なくとも１面に形成されるポリ塩化ビニル系樹脂層は、塩化ビニル重合体、及び塩化ビニル共重合体、例えば塩化ビニル−酢酸ビニル共重合体、塩化ビニル−アクリル酸エステル共重合体、及び塩化ビニル−塩化ビニリデン共重合体などを包含するものであり、これらを単独、あるいは２種以上の混合物に、可塑剤、安定剤、充填剤、防炎剤、紫外線吸収剤などの添加剤の１種以上を混合したものを使用することができる。
【００１２】
本発明の防汚性シートに用いられるポリ塩化ビニル系樹脂層に含有される可塑剤としては、汎用のフタル酸エステル系可塑剤を使用することができる。前記フタル酸エステル系可塑剤としては、防汚性を向上させるために、特定の液状可塑剤及び／又は高分子量可塑剤が用いられ、液状可塑剤は、ポリエステル系可塑剤、トリメリット酸エステル系可塑剤及びピロメリット酸エステル系可塑剤から選ばれた少なくとも１種類からなるものであり、上記高分子量可塑剤はエチレン−酢酸ビニル−一酸化炭素三元共重合体及びエチレン−アクリル酸エステル−一酸化炭素三元共重合体から選ばれた少なくとも１種類からなるものである。
【００１３】
前記液状可塑剤として使用されるポリエステル系可塑剤は、ジカルボン酸とジオールとの縮合重合により製造されるものであって、末端基としてカルボキシル基あるいは水酸基を有するものであるが、一般には末端のカルボキシル基及び水酸基は、それぞれアルコール、カルボン酸と縮合重合している。このようなポリエステル系可塑剤は、例えばアジピン酸と、２−メチル−１，８−オクタンジオール、１，２−プロパンジオール、１，３−ブタンジオール、２−エチルヘキサノール、ｎ−オクタノール類などの少なくとも１種とをポリエステル化したものなどである。ポリエステル系可塑剤の分子量は６００以上であることが好ましく、より好ましくは１０００以上であり、より好ましくは１５００〜４０００である。分子量が小さすぎると、従来のフタル酸系可塑剤と同様に、防汚層に移行及び抽出が多くなることがある。分子量が過大になると、固体となり、配合混練の際の溶融粘度が高くなり作業性が不良になるという不都合を生ずることがある。
【００１４】
本発明に使用されるトリメリット酸エステル系可塑剤及びピロメリット酸エステル系可塑剤は、トリメリット酸と１価アルコール、及びピロメリット酸と、１価アルコールとの縮合反応によって得られるものであり、トリメリット酸エステル系可塑剤としては、トリ２−エチルヘキシルトリメリレート、トリイソデシルトリメリレートなどであり、ピロメリット酸エステル系可塑剤としては、２−エチルヘキシルピロメリレートなどである。
【００１５】
これらのポリエステル系可塑剤、トリメリット酸エステル系可塑剤及びピロメリット酸エステル系可塑剤は、低揮発性で熱老化性に優れ、油及び各種溶剤による抽出量が少なく各種樹脂への非移行性に優れ、電気絶縁性も良好である。従って、耐熱電線被覆材、ガスケット、自動車用内装材など高度の性能を要求される分野のポリ塩化ビニル系樹脂に使用されている。
一方これらの可塑剤は、汎用のフタル酸エステル系可塑剤に比較すると、可塑化効率、及び耐候性が劣りそれ自体には防汚性を向上させる機能もなく、産業資材用途、特に防汚性向上を目的とする用途には使用されてない。
【００１６】
本発明者らは、基布の少なくとも１面にポリ塩化ビニル系樹脂層を形成し、前記ポリ塩化ビニル系樹脂層には、ポリエステル系可塑剤、トリメリット酸エステル系可塑剤及びピロメリット酸エステル系可塑剤から選ばれた少なくとも１種類の液状可塑剤を、ポリ塩化ビニル系樹脂１００重量部に対し４０〜１００重量部の含有量で含有し、前記ポリ塩化ビニル系樹脂層の上に可塑剤移行防止層を形成し、更に前記可塑剤移行防止層の上に光触媒防汚層を形成することにより、防汚性が格段に向上することを見出した。
本発明の防汚性シートのポリ塩化ビニル系樹脂層に含まれる液状可塑剤の配合量は、それが単独で用いられるとき、ポリ塩化ビニル系樹脂１００重量部に対し４０〜１００重量部であり、６０〜９０重量部であることが好ましい。液状可塑剤の含有量が４０重量部未満では、風合いが硬く耐寒性も不十分であり、また得られるシートの取り扱い性が不満足になる。また、それが１００重量部を越えると、得られるポリ塩化ビニル系樹脂層の強度が低下し、摩耗や引っ掻きに対する抵抗性が不十分になり、得られるシートの実用性が不満足なものになる。
【００１７】
また、本発明のポリ塩化ビニル系樹脂層に用いられる高分子量可塑剤としては、エチレン−酢酸ビニル−一酸化炭素三元共重合体、及びエチレン−アクリル酸エステル−一酸化炭素三元共重合体から選ばれた少なくとも１種が使用される。これらの可塑剤は、塩化ビニル系樹脂の永久可塑剤として働き、従来の可塑剤に比べ格段に大きい分子量を有しているため、蒸発や抽出することがなく非移行性に優れ、その成形品はすぐれた耐久性を示し、一般の可塑剤やその他の添加剤とも相溶性がよいため、幅広い配合処方が可能であり、主に、靴、電線、レザー、床タイル、ガスケットなどの高度の性能を要求される分野に使用されているが、それ自体には防汚性を向上させる機能はなく産業資材用途において防汚性向上を目的とする用途には使用されてない。
【００１８】
本発明者らは、基布の少なくとも１面にポリ塩化ビニル系樹脂層を形成し、このポリ塩化ビニル系樹脂層には、可塑剤としてエチレン−酢酸ビニル−一酸化炭素三元共重合体、エチレン−アクリル酸エステル−一酸化炭素三元共重合から選ばれた少なくとも１種類の高分子量可塑剤を、ポリ塩化ビニル系樹脂１００重量部に対し５０〜１２０重量部の含有量で含有させ、前記ポリ塩化ビニル系樹脂層の上に可塑剤移行防止層を形成し、更に前記可塑剤移行防止層の上に光触媒防汚層を形成することにより、防汚性が格段に向上することを見出した。
【００１９】
本発明の防汚性シートにおいて、ポリ塩化ビニル系樹脂に用いられる高分子量可塑剤の配合量は、それが単独で用いられるときポリ塩化ビニル系樹脂１００重量部に対し５０〜１２０重量部であり、７０〜１１０重量部であることが好ましい。高分子量可塑剤の含有量が５０重量部未満では、得られるポリ塩化ビニル系樹脂層の風合いが硬く、耐寒性も不十分であり、また得られる防汚性シートの取り扱い性が不満足なものになる。また、それが１２０重量部を越えると、得られるポリ塩化ビニル系樹脂層の強度が低下し、摩耗及び引っ掻きに対する抵抗度が不十分になり、得られる防汚性シートは実用し得ないものになる。
【００２０】
また、本発明者らは、基布の少なくとも１面にポリ塩化ビニル系樹脂層を形成し、ポリ塩化ビニル系樹脂層には、可塑剤として、ポリエステル系可塑剤、トリメリット酸エステル系可塑剤及びピロメリット酸エステル系可塑剤から選ばれた少なくとも１種類の液状可塑剤と、エチレン−酢酸ビニル−一酸化炭素三元共重合体及びエチレン−アクリル酸エステル−一酸化炭素三元共重合から選ばれた少なくとも１種類の高分子量可塑剤とを併用する場合、その合計含有量を、ポリ塩化ビニル系樹脂１００重量部に対し４０〜１２０重量部とし、好ましくは６０〜１１０重量部とし、前記ポリ塩化ビニル系樹脂層の上に可塑剤移行防止層を形成し、更に前記可塑剤移行防止層の上に光触媒防止層を形成することにより、防汚性が格段に向上することを見出した。
【００２１】
またポリ塩化ビニル系樹脂層が、可塑剤として、前記液状可塑剤と、前記高分子量可塑剤とを併用して含有していると、カレンダーフィルムの加工性が向上し、またポリ塩化ビニル系樹脂の耐候劣化が進んだ場合でも、中間層の亀裂防止性が向上する。
【００２２】
本発明の防汚性シートのポリ塩化ビニル系樹脂層が可塑剤として液状可塑剤と高分子量可塑剤とを含むとき、これらが１：９〜９：１（重量比）の割合で使用されることが好ましく、３：７〜７：３であることがより好ましい。液状可塑剤と高分子量可塑剤との合計含有量は、ポリ塩化ビニル系樹脂１００重量部に対し４０〜１２０重量部であり、６０〜１１０重量部であることが好ましい。両可塑剤の合計含有量が４０重量部未満では、得られるポリ塩化ビニル系樹脂層の風合いが硬く耐寒性も不十分であり、得られる防汚性シートの取り扱い性が不良になる。また、それが１２０重量部を越えると、得られるポリ塩化ビニル樹脂層の強度が不十分になり摩耗及び引っ掻きに対する抵抗度が不良になり、得られる防汚性シートが実用し得ないものになる。
【００２３】
また、本発明の防汚性シートのポリ塩化ビニル系樹脂層に下記３０〜３００ml／１００ｇの吸油量を有する充填剤を含有させることにより、ポリ塩化ビニル系樹脂層内の可塑剤移行が抑制され、可塑剤の光触媒防汚層への移行防止性が更に向上することを見出した。前記ポリ塩化ビニル系樹脂層に使用される充填剤の含有量は、ポリ塩化ビニル系樹脂層の重量の５０重量％以下であることが好ましく、３０重量％以下であることが更に好ましい。充填剤の含有量が５０重量％を越えるとポリ塩化ビニル系樹脂層の機械的強さが不十分になり、隣接する層との間の接着強度も不十分になり、可塑剤移行防止層及び光触媒防汚層の脱落の原因となることがある。
【００２４】
本発明の防汚性シートの可塑剤移行防止層に使用される可撓性重合体樹脂としては、一般の、合成樹脂、例えばポリ塩化ビニル樹脂、ポリエチレン樹脂、ポリプロピレン樹脂、ポリアミド樹脂、ポリエステル樹脂、エチレン−酢酸ビニル共重合体、ポリウレタン樹脂、シリコーン樹脂、フッ素含有重合体樹脂、アクリル樹脂、および塩化ビニル−酢酸ビニル共重合体など、あるいは天然ゴム又は合成ゴム、例えば、ネオプレン、ハイパロン、ポリニトリルゴム、ＳＢＲ、ポリイソブチレンゴム、ブチルゴム、ポリブタジエンゴム、ＥＰＴ、アクリルゴム、ポリウレタンゴム、フッ素含有ゴム、シリコーンゴムなどから選ばれた少なくとも１種類の樹脂を使用する。本発明の可撓性重合体樹脂は薄膜が可撓性であれば熱可塑性樹脂、熱硬化性樹脂、エラストマーの何れをも使用でき、これらの少なくとも１種を混用して使用することもできる。また金属蒸着層又は金属薄（箔）膜層であっても良い。
【００２５】
本発明の防汚性シートの可塑剤移行防止層に使用されるフッ素含有樹脂は、ポリテトラフルオロエチレン、テトラフルオロエチレン−パーフルオロオレフィン共重合体（例えばテトラフルオロエチレン−ヘキサフルオロプロピレン共重合体）、テトラフルオロエチレン−パーフルオロアルキルビニルエーテル共重合体、テトラフルオロエチレン−パーフルオロアルキルビニルエチレン共重合体、ポリクロロトリフルオロエチレン、ポリビニリデンフルオライド、およびクロロトリフルオロエチレン−エチレン共重合などから選ばれた少なくとも１種類である。これらのフッ素含有樹脂層は、フッ素含有樹脂フィルムを積層接着するラミネート法によって形成することができる。尚、フィルムの接着性を良くするために、フィルムの両面にコロナ放電処理などを施して予め濡れ性を改良したフィルムを使用してもよい。
【００２６】
また、可塑剤移行防止層用ポリビニリデンフルオライド系樹脂は、溶剤への溶解が可能であり、溶液のコーティング法又はグラビヤ法によって形成することができるものから選ばれる。ポリビニリデンフルオライド系樹脂としては、ポリビニリデンフルオライド単一重合体の他、ビニリデンフルオライドを含有する共重合体、例えば、ビニリデンフルオライドと、それと共重合可能な単量体、例えばテトラフルオロエチレン、トリフルオロエチレン、フルオロエチレンなどから選ばれる１種類以上の単量体とを共重合させて得られる共重合体が用いられる。これらの共重合体はランダム共重合体に限定されるものではなく、グラフト共重合体であってもよい。
【００２７】
また、これらの重合体又は共重合体に、それと良好な相溶性を有する他の樹脂を加えた混合物を用いることもできる。このようなポリビニリデンフルオライド樹脂との相溶性の良好な樹脂としては、例えば、メチルメタクリレートもしくはメチルアクリレートを主体とするアクリル重合体もしくは共重合体、又はシアノエチル化エチレン−ビニルアルコール共重合体などがある。
【００２８】
本発明の防汚性シートの可塑剤移行防止層に使用されるアクリル系樹脂は、アクリル酸もしくはメタクリル酸とＣ1 〜Ｃ4 アルコールとのエステルを主構成モノマーとする重合体もしくは共重合体を主成分とする樹脂から選ばれることが好ましい。このようなアクリル酸エステル系樹脂の主構成モノマーとしては、具体的には、メチルアクリレート、メチルメタクリレート、エチルアクリレート、エチルメタクリレート、プロピルアクリレート、プロピルメタクリレート、ブチルアクリレート及びブチルメタクリレートなどがあり、特にメチルアクリレート及びメチルメタクリレートが好ましい。また、これらの主構成モノマーと共重合させるコモノマーとしては、例えば、アクリル酸もしくはメタクリル酸とＣ1 〜Ｃ12アルコールとのエステル、フッ化ビニル、フッ化ビニリデン、塩化ビニル、塩化ビニリデン、酢酸ビニル、スチレン、アクリロニトリル、メタクリロニトリル、ブタジエンなどを用いることができる。このようなアクリル系樹脂により可塑剤移行防止層を形成するためには、それに対応する処理液をコーティング法、又はグラビヤ法により塗布するか、あるいは対応樹脂のフィルムを積層接着するラミネート法などによって形成することができる。
【００２９】
また、本発明の防汚性シートの可塑剤移行防止層に使用される充填剤は、ポリ塩化ビニル系樹脂層から移行して来た可塑剤を可塑剤移行防止層内に保持し、可塑剤移行防止性を更に向上するために使用され、炭酸カルシウム、珪藻土、合成シリカ、ケイ酸カルシウム（合成、アモルファス、ゾノイライト、ウォラストナイト）、タルク、酸化マグネシウム、水酸化マグネシウム、水酸化アルミニウム、カオリンクレー、などから選ばれた少なくとも１種類の充填剤を使用することができる。可塑剤移行防止層に使用される充填剤の吸油量は、３０〜３００ml／１００ｇであることが好ましく、１００〜２００ml／１００ｇであることがより好ましい。充填剤の吸油量が３０ml／１００ｇ未満の場合は得られる可塑剤移行防止層の可塑剤を保持する効果が不十分であることがある。また、それが３００ml／１００ｇを越える場合には可塑剤移行防止層を形成する時の加工性が不十分になることがある。
【００３０】
また、本発明の可塑剤移行防止層に使用される充填剤の含有量は、可塑剤移行防止層の合計重量の１０〜５０重量％であることが好ましく、１０〜３０重量％であることがより好ましい。充填剤の含有量が１０重量％未満の場合は可塑剤を保持する効果が不十分であることがある。また、それが５０重量％を越えると可塑剤移行防止層の機械的強さが不十分になり、隣接する層との間の接着強度が低下し、光触媒防汚層の脱落の原因となることがある。
【００３１】
また、本発明者らは、可塑剤移行防止層が前記３０〜３００ml／１００ｇの吸油量を有する充填剤を含有する可撓性重合体樹脂層の少なくともその上表面に前記充填剤を含有しない追加可撓性重合体樹脂層を形成することにより、可塑剤移行防止性が更に向上することも見出した。このとき、充填剤含有可撓性重合体樹脂層中の充填剤の含有量は１０〜５０重量％であることが好ましい。
【００３２】
本発明の防汚性シートの光触媒防汚層を形成するには、可塑剤移行防止層の上に、光触媒性無機材料と必要により結着剤とを含む塗布剤を塗布すればよい。このとき、可塑剤移行防止層と光触媒防汚層との間に、ポリシロキサンとアクリルシリコーン樹脂との混合物を含む接着・保護層を形成する。また、この光触媒防汚層に圧着又は加熱圧着操作を施してもよい。光触媒防汚層は、例えば、シリカゾル１〜１０重量％と、モノアルキルトリメトキシシラン又はその加水分解生成物１〜１０重量％、及び、酸化チタンゾル１〜１０重量％を含む混合液を、前記接着・保護層上に塗布乾燥して形成することができる。モノアルキルトリメトキシシランとしては、メチルトリメトキシシラン及びメチルトリエトキシシランなどを用いることができる。シリカゾルとモノアルキルトリメトキシシラン又はその加水分解生成物との混合比率は、重量比で１００／０〜６０／４０が好ましく、９０／１０〜５０／５０であることがより好ましい。光触媒性無機材料ゾルと、前記珪素有機化合物成分の配合比率は、光触媒性無機材料／珪素有機化合物の重量比が５／９５〜７５／２５になるようにすることが好ましく、１０／９０〜６５／３５であることがより好ましい。珪素有機化合物の含有比率が９５％を越えると、得られる光触媒防汚層の光触媒活性が不十分となることがあり、またそれが２５％未満では接着・保護層への接着性が不十分となることがある。
【００３３】
光触媒防汚層中に含まれる光触媒性無機材料としては、ＴｉＯ2 ，ＴｉＯ3 ，ＺｎＯ，ＳｒＴｉＯ3 ，ＣｄＳ，ＧａＰ，ＩｎＰ，ＧａＡｓ，ＢａＴｉＯ3 ，Ｋ2 ＮｂＯ3 ，Ｆｅ2 Ｏ3 ，Ｔａ2 Ｏ5 ，ＷＯ3 ，ＳｎＯ2 ，Ｂｉ2 Ｏ3 ，ＮｉＯ，Ｃｕ2 Ｏ，ＳｉＣ，ＳｉＯ2 ，ＭｏＳ2 ，ＩｎＰｂ，ＲｕＯ2 ，ＣｅＯ2 などを例示することができ、ＴｉＯ2 ，ＴｉＯ3 はＴｉＯ3 ・ｎＨ2 Ｏの形で利用することもある。またこれらの光触媒性無機材料にＰｔ，Ｒｈ，ＲｕＯ2 ，Ｎｂ，Ｃｕ，Ｓｎ，ＮｉＯなどの金属及び金属酸化物を光触媒活性促進剤として添加してもよい。光触媒防汚層中の光触媒性無機材料の含有量は、それが多くなるほど触媒無活性が高くなるが、得られる光触媒防汚層の接着性が低下するので、光触媒防汚層の合計重量に対し、２５〜７５重量％であることが好ましく、４０〜６０重量％であることがより好ましい。また光触媒防汚層が、光触媒性無機材料を含有する場合、防汚性シートの少なくとも一部（すなわち、基布、ポリ塩化ビニル系樹脂層、可塑剤移行防止層、光触媒防汚層及び接着・保護層などの一層以上、或はその一部分）が無機系顔料により着色されていてもよく、このようにすると、光劣化による変退色が防止され、或は目立たなくなる。特に光触媒性無機材料と接触する部位は無機系顔料で着色することが好ましい。
【００３４】
本発明の防汚シートに使用できる無機系顔料としては、酸化亜鉛（亜鉛華）、酸化チタン（ルチル型、アナターゼ型）、三酸化アンチモン、酸化鉄（鉄黒、べんがら）、黄色酸化鉄、フエロシアン化鉄（紺青）、紺青と黄鉛との混合物（ジンクグリーン）、酸化鉛（鉛丹）、酸化クロム、酸化ジルコニウム、酸化コバルトと酸化アルミニウムの複合物（コバルトブルー）、酸化コバルトと酸化錫と酸化マグネシウムとの複合物（セルリアンブルー）、酸化コバルトと酸化リチウムと五酸化リンの複合物（コバルトバイオレット）、酸化コバルトと酸化亜鉛と酸化マグネシウムとの複合物（コバルトグリーン）、リン酸コバルト（コバルトバイオレット）、リン酸マンガン（マンガン紫）などの金属酸化物、硫化亜鉛と硫酸バリウムの複合物（リトポン）、硫化カルシウム、硫化ストロンチウム、硫化亜鉛、硫化亜鉛カドミウム、硫化カドミウム（カドミウムイエロー）、硫化カドミウムと硫化水銀との複合物（カドミウムマーキュリーレッド）、硫化水銀（銀朱）、硫化カドミウムとセレニウム−カドミウムの複合物（カドミウムレッド、カドミウムオレンジ、カドミウムイエロー）、硫化アンチモンと三酸化アンチモンの複合物（アンチモン朱）、などの金属硫化物、硫酸バリウム、硫酸カルシウム、硫酸鉛、塩基性硫酸鉛などの金属硫化物、炭酸バリウム、炭酸カルシウム、炭酸マグネシウム、炭酸鉛と水酸化鉛の複合物（鉛白）などの金属炭酸化物、水酸化アルミニウム（アルミナホワイト）、水酸化アルミニウムと硫酸カルシウムの複合物（サチン白）、水酸化アルミニウムと硫酸バリウムの複合物（グロスホワイト）、クロム酸水和物（ビリジアン）などの金属水酸化物、クロム酸鉛（黄鉛）、クロム酸亜鉛（亜鉛黄）、クロム酸バリウム、クロム酸鉛と酸化鉛の複合物（赤口黄鉛）、クロム酸鉛とモリブデン酸鉛と硫酸鉛との複合物（クロムバーミリオン）などのクロム酸金属塩、モリブデン酸鉛と硫酸鉛の複合物（モリブデンレッド）、紺青の黄鉛との混合物（クロムグリーン）、スピネル型（ＸＹ2 Ｏ4 ）構造酸化物：〔註、ＸＹ＝Ｃｏ−Ａｌ，Ｃｏ−Ａｌ−Ｃｒ，Ｃｏ−Ｍｇ−Ｓｎ，Ｃｏ−Ｎｉ−Ｔｉ，Ｃｏ−Ｚｎ−Ｎｉ−Ｔｉ，Ｃｏ−Ｚｎ−Ｃｒ−Ｔｉ，Ｚｎ−Ｃｒ−Ｔｉ，Ｚｎ−Ｃｒ−Ｆｅ，Ｃｏ−Ｚｎ−Ｃｒ−Ｆｅ，Ｃｏ−Ｎｉ−Ｃｒ−Ｆｅ−Ｓｉ，Ｃｏ−Ｍｎ−Ｃｒ−Ｆｅ，Ｃｕ−Ｍｎ−Ｃｒ，Ｍｎ−Ｆｅなど〕、ルチル型〔Ｔｉ（ＸＹ）Ｏ2 〕構造酸化物〔註、ＸＹ＝Ｐｂ−Ｓｂ，Ｎｉ−Ｓｂ（チタンイエロー）、Ｎｉ−Ｗ，Ｆｅ−Ｍｏ，Ｃｒ−Ｓｂなど〕、カーボンブラック、チタンブラック、アセチレンブラック、黒鉛、シリカ、ホワイトカーボン、ケイ藻土、タルク、クレー、アルミニウム粉顔料、ブロンズ粉、ニッケル粉、ステンレス粉、パール顔料などを包含し、これらは目的に応じて、１種のみで、または、２種以上を組み合わせて使用する事ができる。また、これらの無機系顔料をメラミン樹脂、ベンゾクアナミン樹脂、ユリア樹脂、フエノール樹脂、エポキシ樹脂などの熱硬化性樹脂中に配合充填したものを微粉化、粉砕した熱硬化性樹脂被覆無機顔料として使用してもよい。
【００３５】
前記無機系顔料の添加量に関しては、目的とする色相の調整に応じての任意の添加量で用いることができ、特に制限はないが、ポリ塩化ビニル系樹脂１００重量部に対し、０．１〜５０．０重量部であることが、好ましく、より好ましくは１〜３０．０重量部である。無機系顔料の添加量が、０．１重量部以下では、ポリ塩化ビニル系樹脂の着色度が低く、着色シートとして十分な隠蔽性が得られないことがある。また、それが５０．０重量部を超えると、得られるポリ塩化ビニル系樹脂の成形加工性を悪化させるだけでなく、得られる着色外層の機械的強力、及び摩耗強力が不十分になることがある。
【００３６】
前記無機系顔料をポリ塩化ビニル系樹脂に配合するには、ポリ塩化ビニル系樹脂がペースト塩化ビニル樹脂の場合は、潤性カラー又はペーストカラー（ビニルトーナーカラー）が用いられ、ストレート塩化ビニル樹脂の場合は、ドライカラー又は、マスターバッチを用いることが好ましい。
【００３７】
本発明の防汚性シートにおいて、基布用繊維材料の重量は５０〜３００ｇ／ｍ2 であることが好ましく、より好ましくは１００〜２００ｇ／ｍ2 である。基布用繊維材料には、塩化ビニル、樹脂の含浸による下塗り層が形成されていて、その塗布重量は５０〜２５０ｇ／ｍ2 であることが好ましく、より好ましくは１００〜２００ｇ／ｍ2 である。ポリ塩化ビニル系樹脂層の重量は５０〜５００ｇ／ｍ2 であることが好ましく、より好ましくは１００〜３００ｇ／ｍ2 である。可塑剤移行防止層の重量は、１〜２００ｇ／ｍ2 であることが好ましく、より好ましくは５〜１００ｇ／ｍ2 である。接着・保護層を形成する場合、その重量は０．１〜５ｇ／ｍ2 であることが好ましく、より好ましくは０．５〜３ｇ／ｍ2 である。また、光触媒防汚層の重量は０．１〜５ｇ／ｍ2 であることが好ましく、より好ましくは０．５〜３ｇ／ｍ2 である。
【００３８】
本発明者らは、繊維材料と、それに含浸された塩化ビニル樹脂を含む下塗り層を有する基布の少なくとも１面にポリ塩化ビニル系樹脂層を形成し、前記ポリ塩化ビニル系樹脂層の上に可塑剤移行防止層を形成し、その上に接着・保護層を形成し、さらにその上に光触媒防汚層を形成することにより、光触媒防汚層に対するポリ塩化ビニル系樹脂層の可塑剤の影響を抑制することができるため、光触媒防汚層の表面親水化及び汚れ分解作用を妨げることがなく、光触媒防汚層の本来の防汚効果が得られることを確認し、この防汚効果は、特定の可塑剤及び顔料を使用することにより、更に格段に向上することも確認した。また、光触媒防汚層への可塑剤の移行が抑制されるため、ポリ塩化ビニル系樹脂層の可塑剤自体が光触媒作用により分解されることもなく、長年月の間のポリ塩化ビニル系樹脂層の風合い変化も少ないことを確認した。
【００３９】
【実施例】
本発明を下記実施例により更に説明する。
下記実施例において、製品の性能評価に用いられた試験方法は下記の通りである。
（１）屋外曝露試験
試料を南向きに、傾斜角３０度、及び垂直に設置して、連続屋外曝露試験に供し、試料の防汚性及び雨筋汚れの発生状態を肉眼観察により評価した。
（イ）防汚性
傾斜角３０度の設置試料について、初期の試料を基準とし、曝露６ケ月後及び１２ケ月後の試料表面の色差ΔＥを測定し、防汚性を下記のように４段階に評価した。
垂直に設置した試料について、雨筋汚れの発生状態を目視で下記のように３段階に判定した。
（２）風合い
汎用のポリ塩化ビニル系樹脂シートを基準にして、供試試料の初期及び曝露１２ヶ月後の手持ち感を評価した。
供試シートの耐寒性を、日本工業規格ＪＩＳ Ｋ ６３２８耐寒試験に従って測定した。
（４）摩耗強さ
供試試料の摩耗強さを、日本工業規格ＪＩＳ Ｌ １０９６ Ｂ法スコット形法に従って測定した。但し、試料に荷重１kgにおいて１０００回の往復摩擦試験を施し、表面の状態を目視評価した。
【００４１】
実施例１
（１）シート基体の作製（下塗り層及びポリ塩化ビニル系樹脂層の形成）
基布として、下記組織のポリエステルフィラメント平織物を用いた。
次に、ストレート塩化ビニル樹脂を含む、下記配合２の樹脂組成物からなるフィルム（０．１６mm厚）をカレンダーで作成し、これを前記下塗り層含浸基布の両面に貼着して、片面当り２００ｇ／ｍ2 のポリ塩化ビニル系樹脂層を形成し、合計重量７６０ｇ／ｍ2 のシート基体を作製した。
【００４２】
＜配合１＞
ペースト塩化ビニル樹脂 １００重量部
ＤＯＰ（可塑剤） ７０重量部
エポキシ化大豆油 ４重量部
炭酸カルシウム １０重量部
Ｂａ−Ｚｎ系安定剤 ２重量部
無機系顔料（ＴｉＯ2 ） ５重量部
トルエン（溶剤） ２０重量部
＜配合２＞
ストレート塩化ビニル樹脂 １００重量部
アジピン酸系ポリエステル（可塑剤） ８０重量部
エポキシ化大豆油 ４重量部
炭酸カルシウム １０重量部
Ｂａ−Ｚｎ系安定剤 ２重量部
無機系顔料（ＴｉＯ2 ） ５重量部
【００４３】
（２）可塑剤移行防止層の形成
前記シート基体のポリ塩化ビニル系樹脂層の上に、アクリル樹脂として下記配合３の樹脂組成物の溶剤希釈液を、グラビヤコーターを用いて、塗布量が２５ｇ／ｍ2 になるように塗布し、１２０℃で１分間乾燥後冷却し、５ｇ／ｍ2 の可塑剤移行防止層を形成した。
＜配合３＞
アクリプレン（登録商標）ペレットＨＢＳ００１
（三菱レイヨン（株）製） ２０重量部
トルエン−ＭＥＫ（５０／５０重量比）（溶剤） ８０重量部
【００４４】
（３）光触媒防汚層の形成
前記基体シートの可塑剤移行防止層の上に、下記配合４に示された組成の接着・保護層処理液をグラビヤコーターで１５ｇ／ｍ2 の塗布量で塗布し、１００℃で１分間乾燥後冷却して、１．５ｇ／ｍ2 の接着・保護層を形成し、その上に、更に下記配合５に示された組成の光触媒防汚層形成用塗布液をグラビヤコーターで１５ｇ／ｍ2 の塗布量で塗布し、１００℃で１分間乾燥後冷却して、１．５ｇ／ｍ2 の光触媒防汚層を形成して、防汚性シートを作製した。
【００４５】
＜配合４＞接着・保護層処理液組成
シリコン含有量３ mol％のアクリルシリコン樹脂
を８重量％（固形分）含有するエタノール−酢
酸エチル（５０／５０重量比）溶液 １００重量部
ポリシロキサンとしてメチルシリケートＭＳ５１
（コルコート（株））の２０％エタノール溶液 ８重量部
シランカップリング剤としてγ−グリシドキシプ
ロピルトリメトキシシラン １重量部
＜配合５＞光触媒防汚層処理液組成
酸化チタン含有量１０重量％に相当する硝酸酸性
酸化チタンゾルを分散させた水−エタノール（
５０／５０重量比）溶液 ５０重量部
酸化珪素含有量１０重量％に相当する硝酸酸性シ
リカゾルを分散させた水−エタノール（５０／
５０重量比）溶液 ５０重量部
この防汚性シートを前記試験に供した。試験結果を表１に示す。
【００４６】
実施例２
実施例１と同様にして防汚性シートを作製した。但し、実施例１のカレンダーフィルム樹脂組成物の配合を表１に記載の配合６に変更し、実施例１と同様にして防汚性シートを作製した。この防汚性シートを前記試験に供した。試験結果を表１に示す。
【００４７】
実施例３
実施例１と同様にして防汚性シートを作製した。但し、実施例１のカレンダーフィルム樹脂組成物の配合を表１に記載の配合７に変更し、実施例１と同様にして防汚性シートを作製した。この防汚性シートを前記試験に供した。試験結果を表１に示す。
【００４８】
実施例４
実施例１と同様にして防汚性シートを作製した。但し、実施例１のカレンダーフィルム樹脂組成物の配合を表１に記載の配合８に変更し、実施例１と同様にして防汚性シートを作製した。この防汚性シートを前記試験に供した。試験結果を表１に示す。
【００４９】
実施例５
実施例１と同様にして防汚性シートを作製した。但し、実施例１のカレンダーフィルム樹脂組成物の配合を表１に記載の配合９に変更し、実施例１と同様にして防汚性シートを作製した。この防汚性シートを前記試験に供した。試験結果を表１に示す。
【００５０】
実施例６
実施例１と同様にして防汚性シートを作製した。但し、実施例１のカレンダーフィルム樹脂組成物の配合を表１に記載の配合１０に変更し、実施例１と同様にして防汚性シートを作製した。この防汚性シートを前記試験に供した。試験結果を表１に示す。
【００５１】
実施例７
実施例１と同様にして防汚性シートを作製した。但し、実施例１のカレンダーフィルム樹脂組成物の配合を表１に記載の配合１１に変更し、実施例１と同様にして防汚性シートを作製した。この防汚性シートを前記試験に供した。試験結果を表１に示す。
【００５２】
実施例８
実施例１と同様にして防汚性シートを作製した。但し、実施例１のカレンダーフィルム樹脂組成物の配合を表１に記載の配合１２に変更し、実施例１と同様にして防汚性シートを作製した。この防汚性シートを前記試験に供した。試験結果を表１に示す。
【００５３】
実施例９
実施例１と同様にして防汚性シートを作製した。但し、実施例１のカレンダーフィルム樹脂組成物の配合を表１に記載の配合１３に変更し、実施例１と同様にして防汚性シートを作製した。この防汚性シートを前記試験に供した。試験結果を表１に示す。
【００５４】
実施例１０
実施例１と同様にして防汚性シートを作製した。但し、実施例１のカレンダーフィルム樹脂組成物の配合を表１に記載の配合１４に変更し、実施例１と同様にして防汚性シートを作製した。この防汚性シートを前記試験に供した。試験結果を表１に示す。
【００５５】
【表１】
実施例１〜１０で得られたシートは、優れた防汚性を有し（ΔＥ＝２以下）、屋外曝露１２ヶ月後も雨筋は認められず、非常に優れた防汚性を示し、風合い・耐寒試験・摩耗強さも良好な結果を示し、実用に適したシートであった。
【００５７】
比較例１
実施例１と同様にして防汚性シートを作製した。但し、実施例１のカレンダーフィルム樹脂組成物の配合を表２に記載の配合１５のように、可塑剤として用いられたアジピン酸系ポリエステル可塑剤の量を３０重量部に減量し、実施例１と同様にしてシートを作製した。このシートを前記試験に供した。試験結果を表２に示す。
得られたシートは実施例１で得られたシートに比べ、風合いが硬く、耐寒性も悪く、実用に適さないシートであった。
【００５８】
比較例２
実施例３と同様にして防汚性シートを作製した。但し、実施例３のカレンダーフィルム樹脂組成物の配合を表２に記載の配合１６のように、可塑剤として用いられたピロメリット酸オクチルエステル可塑剤の量を３０重量部に減量し、実施例３と同様にしてシートを作製した。このシートを前記試験に供した。試験結果を表２に示す。
得られたシートは実施例３で得られたシートに比べ、風合いが硬く、耐寒性も悪く、実用に適さないシートであった。
【００５９】
比較例３
実施例１と同様にして防汚性シートを作製した。但し、実施例１のカレンダーフィルム樹脂組成物の配合を表２に記載の配合１７のように、可塑剤として用いられたアジピン酸系ポリエステル可塑剤の量を１２０重量部に増量し、実施例１と同様にしてシートを作製した。このシートを前記試験に供した。試験結果を表２に示す。
得られたシートは実施例１で得られたシートに比べ、雨筋汚れが若干目立ち、また摩耗強さも弱く、実用に適さないシートであった。
【００６０】
比較例４
実施例３と同様にして防汚性シートを作製した。但し、実施例３のカレンダーフィルム樹脂組成物の配合を表２に記載の配合１８のように、可塑剤として用いられたピロメリット酸オクチルエステル可塑剤の量を１２０重量部に増量し、実施例３と同様にしてシートを作製した。このシートを前記試験に供した。試験結果を表２に示す。
得られたシートは実施例１３で得られたシートに比べ、雨筋汚れが若干目立ち、また摩耗強さも弱く、実用に適さないシートであった。
【００６１】
比較例５
実施例４と同様にして防汚性シートを作製した。但し、実施例４のカレンダーフィルム樹脂組成物の配合を表２に記載の配合１９のように変更し、可塑剤として用いられたアジピン酸系ポリエステル可塑剤及びピロメリット酸オクチルエステル可塑剤の配合量を両方とも１５重量部（合計配合量３０重量部）に減量した。この防汚性シートを前記試験に供した。試験結果を表２に示す。
得られたシートは、実施例４で得られたシートに比べて、風合いが硬く、耐寒性も悪く、実用に適さないシートであった。
【００６２】
比較例６
実施例４と同様にして防汚性シートを作製した。但し、実施例４のカレンダーフィルム樹脂組成物の配合を表２に記載の配合２０のように変更し、可塑剤として用いられたアジピン酸系ポリエステル可塑剤及びピロメリット酸オクチルエステル可塑剤の配合量を両方とも６０重量部（合計配合量１２０重量部）に増量した。この防汚性シートを前記試験に供した。試験結果を表２に示す。
得られたシートは、実施例４で得られたシートに比べて、雨筋汚れが若干認められ、また摩耗強さも弱く、実用に適さないシートであった。
【００６３】
比較例７
実施例５と同様にして防汚性シートを作製した。但し、実施例５のカレンダーフィルム樹脂組成物の配合を表２に記載の配合２１のように、可塑剤として用いられたエチレン−酢酸ビニル−一酸化炭素三元共重合体（エルバロイ（登録商標）７４１三井デュポンポリケミカル（株））の量を４０重量部に減量し、実施例５と同様にしてシートを作製した。このシートを前記試験に供した。試験結果を表２に示す。
得られたシートは実施例５で得られたシートに比べ、風合いが硬く、耐寒性も悪く、実用に適さないシートであった。
【００６４】
比較例８
実施例６と同様にして防汚性シートを作製した。但し、実施例６のカレンダーフィルム樹脂組成物の配合を表２に記載の配合２２のように変更し、可塑剤として用いられたエチレン−アクリル酸エステル−一酸化炭素三元共重合体（エルバロイ（登録商標）ＨＰ４４３三井デュポンポリケミカル（株））の配合量を４０重量部に減量した。この防汚性シートを前記試験に供した。試験結果を表２に示す。
得られたシートは、実施例６で得られたシートに比べて、風合いが硬く、耐寒性も悪く、実用に適さないシートであった。
【００６５】
比較例９
実施例５と同様にして防汚性シートを作製した。但し、実施例５のカレンダーフィルム樹脂組成物の配合を表２に記載の配合２３のように、可塑剤として用いられたエチレン−酢酸ビニル−一酸化炭素三元共重合体（エルバロイ（登録商標）７４１三井デュポンポリケミカル（株））の量を１４０重量部に増量し、実施例５と同様にしてシートを作製した。このシートを前記試験に供した。試験結果を表２に示す。
得られたシートは実施例５で得られたシートに比べ、摩耗強さが弱く実用に適さないシートであった。
【００６６】
比較例１０
実施例６と同様にして防汚性シートを作製した。但し、実施例６のカレンダーフィルム樹脂組成物の配合を表２に記載の配合２４のように変更し、可塑剤として用いられたエチレン−アクリル酸エステル−一酸化炭素三元共重合体（エルバロイ（登録商標）ＨＰ４４３三井デュポンポリケミカル（株））の配合量を１４０重量部に増量した。この防汚性シートを前記試験に供した。試験結果を表２に示す。
得られたシートは、実施例６で得られたシートに比べて、摩耗強さが弱く、実用に適さないシートであった。
【００６７】
【表２】
比較例１１
実施例７と同様にして防汚性シートを作製した。但し、実施例７のカレンダーフィルム樹脂組成物の配合を表３に記載の配合２５のように変更し、可塑剤として用いられたエチレン−酢酸ビニル−一酸化炭素三元共重合体（エルバロイ（登録商標）７４１三井デュポンポリケミカル（株））及びエチレン−アクリル酸エステル−一酸化炭素三元共重合体（エルバロイ（登録商標）ＨＰ４４３三井デュポンポリケミカル（株））の配合量を両方とも２０重量部（合計配合量４０重量部）に減量した。この防汚性シートを前記試験に供した。試験結果を表３に示す。 得られたシートは、実施例７で得られたシートに比べて、風合いが硬く、耐寒性も悪く、実用に適さないシートであった。
【００６９】
比較例１２
実施例７と同様にして防汚性シートを作製した。但し、実施例７のカレンダーフィルム樹脂組成物の配合を表３に記載の配合２６のように変更し、可塑剤として用いられたエチレン−酢酸ビニル−一酸化炭素三元共重合体（エルバロイ（登録商標）７４１三井デュポンポリケミカル（株））及びエチレン−アクリル酸エステル−一酸化炭素三元共重合体（エルバロイ（登録商標）ＨＰ４４３三井デュポンポリケミカル（株））の配合量を両方とも７０重量部（合計配合量１４０重量部）に増量した。この防汚性シートを前記試験に供した。試験結果を表３に示す。
得られたシートは、実施例７で得られたシートに比べて、摩耗強さが弱く、実用に適さないシートであった。
【００７０】
比較例１３
実施例８と同様にして防汚性シートを作製した。但し、実施例８のカレンダーフィルム樹脂組成物の配合を表３に記載の配合２７のように変更し、可塑剤として用いられたアジピン酸ポリエステル可塑剤及びエチレン−酢酸ビニル−一酸化炭素三元共重合体（エルバロイ（登録商標）７４１三井デュポンポリケミカル（株））の配合量を両方とも１５重量部（合計配合量３０重量部）に減量した。この防汚性シートを前記試験に供した。試験結果を表３に示す。
得られたシートは、実施例８で得られたシートに比べて、風合いが硬く、耐寒性も悪く、実用に適さないシートであった。
【００７１】
比較例１４
実施例８と同様にして防汚性シートを作製した。但し、実施例８のカレンダーフィルム樹脂組成物の配合を表３に記載の配合２８のように変更し、可塑剤として用いられたアジピン酸ポリエステル可塑剤及びエチレン−酢酸ビニル−一酸化炭素三元共重合体（エルバロイ（登録商標）７４１三井デュポンポリケミカル（株））の配合量を両方とも７０重量部（合計配合量１４０重量部）に増量した。この防汚性シートを前記試験に供した。試験結果を表３に示す。
得られたシートは、実施例８で得られたシートに比べて、雨筋汚れが若干認められ、また摩耗強さも弱く、実用に適さないシートであった。
【００７２】
比較例１５
実施例１０と同様にして防汚性シートを作製した。但し、実施例１０のカレンダーフィルム樹脂組成物の配合を表３に記載の配合２９のように変更し、可塑剤として用いられたアジピン酸系ポリエステル可塑剤、ピロメリット酸オクチルエステル可塑剤酸ポリエステル可塑剤及びエチレン−酢酸ビニル−一酸化炭素三元共重合体（エルバロイ（登録商標）７４１三井デュポンポリケミカル（株））の配合量を両方とも１０重量部（合計配合量３０重量部）に減量した。この防汚性シートを前記試験に供した。試験結果を表３に示す。
得られたシートは、実施例１０で得られたシートに比べて、風合いが硬く、耐寒性も悪く、実用に適さないシートであった。
【００７３】
比較例１６
実施例１０と同様にして防汚性シートを作製した。但し、実施例１０のカレンダーフィルム樹脂組成物の配合を表３に記載の配合３０のように変更し、可塑剤として用いられたアジピン酸系ポリエステル可塑剤、ピロメリット酸オクチルエステル可塑剤、及びエチレン−酢酸ビニル−一酸化炭素三元共重合体（エルバロイ（登録商標）７４１、三井デュポンポリケミカル（株））の配合量をそれぞれ４０重量部、４０重量部及び５０重量部（合計配合量１３０重量部）に増量した。この防汚性シートを前記試験に供した。試験結果を表３に示す。
得られたシートは、実施例１０で得られたシートに比べて、摩耗強さが弱く、実用に適さないシートであった。
【００７４】
【表３】
【発明の効果】
本発明に係る防汚性シートは、光触媒防汚層に対するポリ塩化ビニル系樹脂層の可塑剤の影響を抑制するために、特定の可塑剤を用い、かつこれら両層の間に可塑剤移行防止層を形成した事により、光触媒防汚層は、その本来の効果が十分に発現し、優れた防汚性を示すことができるようになった。また、本発明の防汚性シートは、産業資材用途のシートとして良好な風合い及び摩耗強さを有しており、実用上極めて有用なものである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an antifouling sheet for tents that is excellent in preventing rain stains. More specifically, the present invention has a base fabric made of a fiber material, a polyvinyl chloride resin layer, and a photocatalytic antifouling layer, and is extremely useful as an industrial material application such as a medium / large tent or a tent warehouse. The present invention relates to an antifouling sheet.
[0002]
[Prior art]
Conventionally, a polyvinyl chloride resin-coated sheet for industrial materials is a flexible sheet in which a polyvinyl chloride resin layer is coated on one or both sides of a fiber base fabric, for example, a medium or large tent, tent Widely used in warehouses, truck hoods, signboard backlit, etc. Such a sheet exhibits the advantages inherent in polyvinyl chloride resin in terms of processability, economy, flame resistance, etc., but on the other hand, it is exposed to the outdoors for a long time in the above applications. Therefore, even when a stabilizer that has been thoroughly examined for stabilizers and the like blended in the polyvinyl chloride resin is used, the resin gradually decomposes and deteriorates over the years, and the plasticizer The surface gradually became sticky as the surface moved to the surface, and there were serious drawbacks such as dust and the like adhering to the surface and being contaminated.
[0003]
As a method for improving such drawbacks, a method of coating the surface of the polyvinyl chloride resin layer with an acrylic resin dissolved in an organic solvent has been proposed. However, in the organic solvent of the acrylic resin coating resin liquid, The antifouling effect of the acrylic resin layer is because the plasticizer in the polyvinyl chloride resin layer migrates and / or the plasticizer elutes and migrates into the acrylic resin layer and eventually migrates to the surface. It was not enough.
[0004]
There has also been proposed a method in which a photocatalyst layer is formed on the surface of a polyvinyl chloride resin layer by a coating method, whereby dirt is decomposed and removed. For example, in WO97-134 (Patent Document 1), when a photocatalyst layer is coated, generally the adhesion between the photocatalyst layer and the polyvinyl chloride resin layer is improved, and the polyvinyl chloride resin layer is provided with a photocatalytic activity. In order to protect from the above, it has been proposed to interpose an adhesive / protective layer between these two layers. However, even in this case, the plasticizer of the polyvinyl chloride resin layer passes through the adhesion / protection layer and moves to the photocatalyst layer. In particular, it has not reached a level that sufficiently prevents rain stripes in the vertical portion when used outdoors.
[0005]
In addition, the photocatalytic action of the photocatalyst layer may selectively decompose the plasticizer in the polyvinyl chloride resin layer, so that the texture of the polyvinyl chloride resin layer gradually becomes harder over the years. May cause problems.
[0006]
[Patent Document 1]
WO97-134
[0007]
[Problems to be solved by the invention]
The present invention not only has excellent antifouling properties and weather resistance, but also has little change in texture even when used for a long period of time, and also has excellent anti-smudge properties in antifouling properties. It is intended to provide an antifouling sheet for tents.
[0008]
[Means for Solving the Problems]
The antifouling sheet for tents (hereinafter referred to as the antifouling sheet of the present invention) excellent in rain-stain antifouling property of the present invention was formed on a base fabric formed of a fiber material and on at least one surface thereof. A polyvinyl chloride resin layer, a plasticizer migration prevention layer formed on the polyvinyl chloride resin layer, and a photocatalytic antifouling layer further formed on the plasticizer migration prevention layer,
The base fabric has an undercoat layer containing a vinyl chloride resin impregnated in the fiber material,
The polyvinyl chloride resin layer as a plasticizer
(1) A liquid plasticizer comprising at least one selected from polyester plasticizers, trimellitic acid ester plasticizers, and pyromellitic acid ester plasticizers, and
(2) a high molecular weight plasticizer comprising at least one selected from ethylene-vinyl acetate-carbon monoxide terpolymer and ethylene-acrylic acid ester-carbon monoxide terpolymer,
Including at least one selected from
However, when the liquid plasticizer is used alone, the amount is 40 to 100 parts by weight with respect to 100 parts by weight of the polyvinyl chloride resin. When the high molecular weight plasticizer is used alone, the amount is The amount is 50 to 120 parts by weight with respect to 100 parts by weight of the polyvinyl chloride resin, and when the liquid plasticizer and the high molecular weight plasticizer are used in combination, the total blending amount is 100 parts by weight of the polyvinyl chloride resin 100. 40 to 120 parts by weight with respect to parts by weight, and the plasticizer migration preventing layer contains at least one resin selected from a fluorine-containing resin and an acrylic resin as a main component, and
An adhesion / protection layer containing a mixture of polysiloxane and an acrylic silicone resin is formed between the plasticizer migration prevention layer and the photocatalyst antifouling layer.
It is characterized by this.
In the antifouling sheet for tents of the present invention, which is excellent in preventing rain streak, the plasticizer migration preventing layer contains 10 to 50% by weight of a filler having an oil absorption of 30 to 300 ml / 100 g. It is preferable that it consists of united resin.
In the antifouling sheet for tents excellent in rain streak antifouling property of the present invention, the plasticizer migration preventing layer comprises a flexible polymer resin layer containing a filler having an oil absorption of 30 to 300 ml / 100 g, It is preferably composed of a flexible polymer resin layer that covers at least the upper surface thereof and does not contain the filler.
In the antifouling sheet for tents excellent in rain streak antifouling property of the present invention, the photocatalytic antifouling layer is TiO as a photocatalytic inorganic material.2 , TiOThree , ZnO, SrTiOThree , CdS, GaP, InP, GaAs, BaTiOThree , K2 NbOThree , Fe2 OThree , Ta2 OFive , WOThree , SnO2 , Bi2 OThree , NiO, Cu2 O, SiC, SiO2 , MoS2 , InPb, RuO2 , And CeO2 It is preferable that 1 or more types selected from these are included.
In the antifouling sheet for tents excellent in rain-stain antifouling property of the present invention, the photocatalytic antifouling layer is further selected from silica sol, monoalkyltrialkoxysilane, and hydrolysis product of the monoalkyltrialkoxysilane. It is preferable that the binder contains at least one kind.
In the photocatalyst antifouling layer of the antifouling sheet for tents excellent in rain stripe antifouling property of the present invention, the content of the photocatalytic inorganic material is preferably 25 to 75% by weight.
In the antifouling sheet for tents of the present invention having excellent rain streak prevention, the polyvinyl chloride resin contains an oil-absorbing filler having an oil absorption of 30 to 300 ml / 100 g in a content of 50% by weight or less. It is preferable to do.
In the antifouling sheet for tents excellent in rain line stain preventing property of the present invention, at least a part of the antifouling sheet may be colored with an inorganic pigment.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
The fiber material used for the base fabric of the antifouling sheet of the present invention includes natural fibers such as cotton and hemp, inorganic fibers such as glass fibers, carbon fibers and metal fibers, and recycled fibers such as viscose rayon. , Cupra, semi-synthetic fibers such as di- and tri-acetate fibers, and synthetic fibers such as polyamide (nylon 6, nylon 66 etc.) fibers, polyester (polyethylene terephthalate etc.) fibers, aromatic polyamide fibers, acrylic It is composed of at least one selected from fibers, polyvinyl chloride fibers, polyolefin fibers and the like.
[0010]
The fiber material in the base fabric may be in any shape such as short fiber spun yarn, long fiber yarn, split yarn, tape yarn, etc., and the base fabric may be woven fabric, knitted fabric, non-woven fabric or these Any of composite cloth may be sufficient. In general, the fiber used in the antifouling sheet of the present invention is preferably a polyester fiber, and the polyester fiber is preferably in the form of a long fiber (filament), and the woven structure is not limited. A plain weave is preferred. An undercoat layer containing a vinyl chloride resin impregnated therein is formed on the fiber material, and a base fabric is constituted by the fiber material and the undercoat layer.
[0011]
In the antifouling sheet of the present invention, the polyvinyl chloride resin layer formed on at least one surface of the base fabric comprises a vinyl chloride polymer and a vinyl chloride copolymer, such as vinyl chloride-vinyl acetate copolymer, Including vinyl-acrylic acid ester copolymer, vinyl chloride-vinylidene chloride copolymer, etc., these alone or in a mixture of two or more, plasticizer, stabilizer, filler, flameproofing agent A mixture of one or more additives such as an ultraviolet absorber may be used.
[0012]
As the plasticizer contained in the polyvinyl chloride resin layer used in the antifouling sheet of the present invention, a general-purpose phthalate plasticizer can be used. As the phthalate ester plasticizer, a specific liquid plasticizer and / or a high molecular weight plasticizer is used in order to improve antifouling properties. The liquid plasticizer is a polyester plasticizer or trimellitic ester ester. It consists of at least one selected from a plasticizer and a pyromellitic acid ester plasticizer, and the high molecular weight plasticizer is an ethylene-vinyl acetate-carbon monoxide terpolymer and an ethylene-acrylic acid ester-1 It consists of at least one selected from carbon oxide terpolymers.
[0013]
The polyester plasticizer used as the liquid plasticizer is produced by condensation polymerization of a dicarboxylic acid and a diol and has a carboxyl group or a hydroxyl group as a terminal group. The group and the hydroxyl group are condensed with alcohol and carboxylic acid, respectively. Examples of such polyester plasticizers include adipic acid, 2-methyl-1,8-octanediol, 1,2-propanediol, 1,3-butanediol, 2-ethylhexanol, and n-octanols. At least one kind is polyesterified. The molecular weight of the polyester plasticizer is preferably 600 or more, more preferably 1000 or more, and more preferably 1500 to 4000. If the molecular weight is too small, migration and extraction may increase in the antifouling layer, as with conventional phthalic acid plasticizers. If the molecular weight is excessive, it may become a solid, resulting in an inconvenience that the melt viscosity at the time of compounding and kneading becomes high and workability becomes poor.
[0014]
The trimellitic acid ester plasticizer and pyromellitic acid ester plasticizer used in the present invention are obtained by condensation reaction of trimellitic acid and monohydric alcohol, and pyromellitic acid and monohydric alcohol. Trimellitic acid ester plasticizers include tri-2-ethylhexyl trimellrate and triisodecyl trimellrate, and pyromellitic acid ester plasticizers include 2-ethylhexyl pyromellirate.
[0015]
These polyester plasticizers, trimellitic acid ester plasticizers, and pyromellitic acid ester plasticizers have low volatility and excellent thermal aging properties, and are not easily transferred to various resins with little extraction by oil and various solvents. Excellent electrical insulation. Therefore, it is used for polyvinyl chloride resins in fields requiring high performance such as heat-resistant wire covering materials, gaskets, and automotive interior materials.
On the other hand, these plasticizers are inferior in plasticization efficiency and weather resistance as compared with general-purpose phthalate ester plasticizers, and have no function of improving antifouling properties themselves, and are used for industrial materials, particularly antifouling properties. It is not used for the purpose of improvement.
[0016]
The inventors of the present invention form a polyvinyl chloride resin layer on at least one surface of a base fabric, and the polyvinyl chloride resin layer includes a polyester plasticizer, a trimellitic acid ester plasticizer, and a pyromellitic acid ester. At least one liquid plasticizer selected from plasticizers is contained in an amount of 40 to 100 parts by weight with respect to 100 parts by weight of the polyvinylchloride resin, and the plasticizer is formed on the polyvinylchloride resin layer. It has been found that the antifouling property is remarkably improved by forming a migration preventing layer and further forming a photocatalytic antifouling layer on the plasticizer migration preventing layer.
The blending amount of the liquid plasticizer contained in the polyvinyl chloride resin layer of the antifouling sheet of the present invention is 40 to 100 parts by weight with respect to 100 parts by weight of the polyvinyl chloride resin when it is used alone. 60 to 90 parts by weight is preferable. If the content of the liquid plasticizer is less than 40 parts by weight, the texture is hard and the cold resistance is insufficient, and the handleability of the resulting sheet becomes unsatisfactory. On the other hand, if it exceeds 100 parts by weight, the strength of the resulting polyvinyl chloride resin layer is lowered, the resistance to abrasion and scratching becomes insufficient, and the practicality of the resulting sheet becomes unsatisfactory.
[0017]
The high molecular weight plasticizer used in the polyvinyl chloride resin layer of the present invention includes ethylene-vinyl acetate-carbon monoxide terpolymer and ethylene-acrylic acid ester-carbon monoxide terpolymer. At least one selected from is used. These plasticizers work as permanent plasticizers for vinyl chloride resins and have a much higher molecular weight than conventional plasticizers, so they are excellent in non-migrating properties without evaporation or extraction, and their molded products Has excellent durability and is compatible with common plasticizers and other additives, so it can be used in a wide range of compounding formulas, mainly high performance such as shoes, electric wires, leather, floor tiles and gaskets. However, it does not have a function of improving the antifouling property itself, and is not used for the purpose of improving the antifouling property in industrial materials.
[0018]
The inventors of the present invention formed a polyvinyl chloride resin layer on at least one surface of the base fabric, and this polyvinyl chloride resin layer has an ethylene-vinyl acetate-carbon monoxide terpolymer as a plasticizer, Containing at least one high molecular weight plasticizer selected from ethylene-acrylic acid ester-carbon monoxide terpolymer with a content of 50 to 120 parts by weight per 100 parts by weight of the polyvinyl chloride resin, It was found that the antifouling property is remarkably improved by forming a plasticizer migration preventing layer on the polyvinyl chloride resin layer and further forming a photocatalyst antifouling layer on the plasticizer migration preventing layer. .
[0019]
In the antifouling sheet of the present invention, the amount of the high molecular weight plasticizer used in the polyvinyl chloride resin is 50 to 120 parts by weight with respect to 100 parts by weight of the polyvinyl chloride resin when used alone. 70 to 110 parts by weight. If the content of the high molecular weight plasticizer is less than 50 parts by weight, the resulting polyvinyl chloride resin layer has a hard texture, insufficient cold resistance, and the resulting antifouling sheet is unsatisfactory in handling. Become. Further, if it exceeds 120 parts by weight, the strength of the resulting polyvinyl chloride resin layer is lowered, the resistance to abrasion and scratching becomes insufficient, and the resulting antifouling sheet cannot be put into practical use. Become.
[0020]
In addition, the present inventors formed a polyvinyl chloride resin layer on at least one surface of the base fabric, and the polyvinyl chloride resin layer includes a polyester plasticizer and a trimellitic ester plasticizer as a plasticizer. And at least one liquid plasticizer selected from pyromellitic acid ester plasticizers, ethylene-vinyl acetate-carbon monoxide terpolymers, and ethylene-acrylic acid ester-carbon monoxide terpolymers When at least one kind of high molecular weight plasticizer is used in combination, the total content is 40 to 120 parts by weight, preferably 60 to 110 parts by weight, based on 100 parts by weight of the polyvinyl chloride resin. By forming a plasticizer migration preventing layer on the vinyl chloride resin layer and further forming a photocatalyst preventing layer on the plasticizer migration preventing layer, the antifouling property is remarkably improved. It was heading.
[0021]
Further, when the polyvinyl chloride resin layer contains the liquid plasticizer and the high molecular weight plasticizer in combination as a plasticizer, the processability of the calendar film is improved, and the polyvinyl chloride resin Even when the weather resistance of the intermediate layer progresses, the crack preventing property of the intermediate layer is improved.
[0022]
When the polyvinyl chloride resin layer of the antifouling sheet of the present invention contains a liquid plasticizer and a high molecular weight plasticizer as plasticizers, these are used in a ratio of 1: 9 to 9: 1 (weight ratio). It is preferable that the ratio is 3: 7 to 7: 3. The total content of the liquid plasticizer and the high molecular weight plasticizer is 40 to 120 parts by weight, preferably 60 to 110 parts by weight, based on 100 parts by weight of the polyvinyl chloride resin. If the total content of both plasticizers is less than 40 parts by weight, the resulting polyvinyl chloride resin layer has a hard texture and insufficient cold resistance, resulting in poor handling of the resulting antifouling sheet. On the other hand, if it exceeds 120 parts by weight, the strength of the resulting polyvinyl chloride resin layer becomes insufficient, the resistance to abrasion and scratching becomes poor, and the resulting antifouling sheet becomes impractical. .
[0023]
Moreover, by including a filler having an oil absorption of 30 to 300 ml / 100 g below in the polyvinyl chloride resin layer of the antifouling sheet of the present invention, the migration of the plasticizer in the polyvinyl chloride resin layer is suppressed. The present inventors have found that the prevention of migration of the plasticizer to the photocatalytic antifouling layer is further improved. The content of the filler used in the polyvinyl chloride resin layer is preferably 50% by weight or less, more preferably 30% by weight or less, based on the weight of the polyvinyl chloride resin layer. When the content of the filler exceeds 50% by weight, the mechanical strength of the polyvinyl chloride resin layer becomes insufficient, the adhesive strength between adjacent layers becomes insufficient, and the plasticizer migration prevention layer and This may cause the photocatalyst antifouling layer to fall off.
[0024]
As the flexible polymer resin used for the plasticizer migration prevention layer of the antifouling sheet of the present invention, a general synthetic resin such as polyvinyl chloride resin, polyethylene resin, polypropylene resin, polyamide resin, polyester resin, Ethylene-vinyl acetate copolymer, polyurethane resin, silicone resin, fluorine-containing polymer resin, acrylic resin, vinyl chloride-vinyl acetate copolymer, etc., or natural rubber or synthetic rubber such as neoprene, hyperon, polynitrile rubber At least one resin selected from SBR, polyisobutylene rubber, butyl rubber, polybutadiene rubber, EPT, acrylic rubber, polyurethane rubber, fluorine-containing rubber, silicone rubber, and the like is used. As the flexible polymer resin of the present invention, any of a thermoplastic resin, a thermosetting resin and an elastomer can be used as long as the thin film is flexible, and at least one of them can be used in combination. Moreover, a metal vapor deposition layer or a metal thin (foil) film layer may be sufficient.
[0025]
The fluorine-containing resin used for the plasticizer migration prevention layer of the antifouling sheet of the present invention is polytetrafluoroethylene, a tetrafluoroethylene-perfluoroolefin copolymer (for example, a tetrafluoroethylene-hexafluoropropylene copolymer). , Tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ethylene copolymer, polychlorotrifluoroethylene, polyvinylidene fluoride, and chlorotrifluoroethylene-ethylene copolymer. And at least one type. These fluorine-containing resin layers can be formed by a laminating method in which fluorine-containing resin films are laminated and bonded. In addition, in order to improve the adhesiveness of a film, you may use the film which performed the corona discharge process etc. on both surfaces of the film, and improved wettability previously.
[0026]
Further, the polyvinylidene fluoride resin for the plasticizer migration preventing layer is selected from those which can be dissolved in a solvent and can be formed by a solution coating method or a gravure method. As the polyvinylidene fluoride resin, in addition to a polyvinylidene fluoride single polymer, a copolymer containing vinylidene fluoride, for example, vinylidene fluoride and a monomer copolymerizable therewith, such as tetrafluoroethylene, A copolymer obtained by copolymerizing at least one monomer selected from trifluoroethylene, fluoroethylene and the like is used. These copolymers are not limited to random copolymers, and may be graft copolymers.
[0027]
Moreover, the mixture which added other resin which has favorable compatibility with it to these polymers or copolymers can also be used. Examples of such a resin having good compatibility with the polyvinylidene fluoride resin include an acrylic polymer or copolymer mainly composed of methyl methacrylate or methyl acrylate, or a cyanoethylated ethylene-vinyl alcohol copolymer. is there.
[0028]
The acrylic resin used for the plasticizer migration prevention layer of the antifouling sheet of the present invention is acrylic acid or methacrylic acid and C1 ~ CFour It is preferably selected from a polymer having an ester with alcohol as a main constituent monomer or a resin having a copolymer as a main component. Specific examples of the main constituent monomer of the acrylic ester resin include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, and butyl methacrylate, and particularly methyl acrylate. And methyl methacrylate are preferred. Examples of comonomers to be copolymerized with these main constituent monomers include acrylic acid or methacrylic acid and C1 ~ C12Esters with alcohol, vinyl fluoride, vinylidene fluoride, vinyl chloride, vinylidene chloride, vinyl acetate, styrene, acrylonitrile, methacrylonitrile, butadiene, and the like can be used. In order to form a plasticizer migration prevention layer with such an acrylic resin, a corresponding treatment solution is applied by a coating method or gravure method, or a lamination method in which a film of a corresponding resin is laminated and bonded. can do.
[0029]
Further, the filler used in the plasticizer migration preventing layer of the antifouling sheet of the present invention holds the plasticizer migrated from the polyvinyl chloride resin layer in the plasticizer migration preventing layer, and the plasticizer Used to further improve anti-migration, calcium carbonate, diatomaceous earth, synthetic silica, calcium silicate (synthetic, amorphous, zonolite, wollastonite), talc, magnesium oxide, magnesium hydroxide, aluminum hydroxide, kaolin clay At least one kind of filler selected from, etc. can be used. The oil absorption amount of the filler used in the plasticizer migration preventing layer is preferably 30 to 300 ml / 100 g, more preferably 100 to 200 ml / 100 g. When the amount of oil absorption of the filler is less than 30 ml / 100 g, the effect of retaining the plasticizer of the resulting plasticizer migration preventing layer may be insufficient. If it exceeds 300 ml / 100 g, the processability when forming the plasticizer migration preventing layer may be insufficient.
[0030]
Further, the content of the filler used in the plasticizer migration preventing layer of the present invention is preferably 10 to 50% by weight, and preferably 10 to 30% by weight of the total weight of the plasticizer migration preventing layer. More preferred. When the content of the filler is less than 10% by weight, the effect of retaining the plasticizer may be insufficient. On the other hand, if it exceeds 50% by weight, the mechanical strength of the plasticizer migration preventing layer becomes insufficient, the adhesive strength between adjacent layers is lowered, and the photocatalyst antifouling layer may fall off. There is.
[0031]
Further, the present inventors added that the plasticizer migration preventing layer does not contain the filler on at least the upper surface of the flexible polymer resin layer containing the filler having an oil absorption of 30 to 300 ml / 100 g. It has also been found that the formation of a flexible polymer resin layer further improves the plasticizer migration prevention property. At this time, it is preferable that content of the filler in a filler containing flexible polymer resin layer is 10 to 50 weight%.
[0032]
In order to form the photocatalytic antifouling layer of the antifouling sheet of the present invention, a coating agent containing a photocatalytic inorganic material and, if necessary, a binder may be applied on the plasticizer migration preventing layer. At this time, an adhesion / protection layer containing a mixture of polysiloxane and acrylic silicone resin is formed between the plasticizer migration prevention layer and the photocatalyst antifouling layer. Moreover, you may perform crimping | compression-bonding or thermocompression-bonding operation to this photocatalyst antifouling layer. The photocatalyst antifouling layer is, for example, bonded to a mixed liquid containing 1 to 10% by weight of silica sol, 1 to 10% by weight of monoalkyltrimethoxysilane or a hydrolysis product thereof, and 1 to 10% by weight of titanium oxide sol. -It can be formed by applying and drying on the protective layer. As the monoalkyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, or the like can be used. The mixing ratio of the silica sol and the monoalkyltrimethoxysilane or the hydrolysis product thereof is preferably 100/0 to 60/40, more preferably 90/10 to 50/50 by weight. The mixing ratio of the photocatalytic inorganic material sol and the silicon organic compound component is preferably such that the weight ratio of photocatalytic inorganic material / silicon organic compound is 5/95 to 75/25. / 35 is more preferable. If the content ratio of the silicon organic compound exceeds 95%, the photocatalytic activity of the resulting photocatalytic antifouling layer may be insufficient, and if it is less than 25%, the adhesion to the adhesion / protection layer is insufficient. May be.
[0033]
As the photocatalytic inorganic material contained in the photocatalytic antifouling layer, TiO2 , TiOThree , ZnO, SrTiOThree , CdS, GaP, InP, GaAs, BaTiOThree , K2 NbOThree , Fe2 OThree , Ta2 OFive , WOThree , SnO2 , Bi2 OThree , NiO, Cu2 O, SiC, SiO2 , MoS2 , InPb, RuO2 , CeO2 Etc., and TiO2 , TiOThree Is TiOThree ・ NH2 It may be used in the form of O. In addition, these photocatalytic inorganic materials include Pt, Rh, RuO.2 , Nb, Cu, Sn, NiO and other metals and metal oxides may be added as photocatalytic activity promoters. As the content of the photocatalytic antifouling layer in the photocatalyst antifouling layer increases, the catalyst inactivity increases, but the adhesion of the resulting photocatalytic antifouling layer decreases, so the total weight of the photocatalytic antifouling layer is reduced. It is preferably 25 to 75% by weight, and more preferably 40 to 60% by weight. When the photocatalyst antifouling layer contains a photocatalytic inorganic material, at least a part of the antifouling sheet (that is, a base fabric, a polyvinyl chloride resin layer, a plasticizer migration prevention layer, a photocatalyst antifouling layer, an adhesive One or more or a part of the protective layer or the like may be colored with an inorganic pigment. In this way, discoloration due to light deterioration is prevented or becomes inconspicuous. In particular, it is preferable to color an area in contact with the photocatalytic inorganic material with an inorganic pigment.
[0034]
Examples of inorganic pigments that can be used in the antifouling sheet of the present invention include zinc oxide (zinc white), titanium oxide (rutile type, anatase type), antimony trioxide, iron oxide (iron black, red rose), yellow iron oxide, and ferrocyan. Iron oxide (bituminous), mixture of bitumen and yellow lead (zinc green), lead oxide (lead red), chromium oxide, zirconium oxide, composite of cobalt oxide and aluminum oxide (cobalt blue), cobalt oxide and tin oxide Composites of magnesium oxide (Cerulean blue), composites of cobalt oxide, lithium oxide and phosphorus pentoxide (cobalt violet), composites of cobalt oxide, zinc oxide and magnesium oxide (cobalt green), cobalt phosphate (cobalt) Violet), manganese phosphate (manganese purple) and other metal oxides, zinc sulfide and barium sulfate composites ( Topon), calcium sulfide, strontium sulfide, zinc sulfide, zinc cadmium sulfide, cadmium sulfide (cadmium yellow), cadmium sulfide and mercury sulfide composite (cadmium mercury red), mercury sulfide (silver vermilion), cadmium sulfide and selenium-cadmium Metal sulfides such as composites (cadmium red, cadmium orange, cadmium yellow), composites of antimony sulfide and antimony trioxide (antimony Zhu), metals such as barium sulfate, calcium sulfate, lead sulfate, basic lead sulfate Metal carbonates such as sulfide, barium carbonate, calcium carbonate, magnesium carbonate, lead carbonate and lead hydroxide composite (lead white), aluminum hydroxide (alumina white), aluminum hydroxide and calcium sulfate composite (satin White), aluminum hydroxide And barium sulfate composite (gloss white), chromic acid hydrate (viridian) and other metal hydroxides, lead chromate (yellow lead), zinc chromate (zinc yellow), barium chromate, lead chromate Chromium metal salts such as lead oxide composites (red lip yellow lead), lead chromate, lead molybdate and lead sulfate composites (chromium vermillion), lead molybdate and lead sulfate composites (molybdenum red) , Mixture with bitumen yellow lead (chrome green), spinel type (XY2 OFour ) Structural oxide: [註, XY = Co-Al, Co-Al-Cr, Co-Mg-Sn, Co-Ni-Ti, Co-Zn-Ni-Ti, Co-Zn-Cr-Ti, Zn- Cr-Ti, Zn-Cr-Fe, Co-Zn-Cr-Fe, Co-Ni-Cr-Fe-Si, Co-Mn-Cr-Fe, Cu-Mn-Cr, Mn-Fe, etc.], rutile type [Ti (XY) O2 ] Structural oxides [註, XY = Pb—Sb, Ni—Sb (titanium yellow), Ni—W, Fe—Mo, Cr—Sb, etc.], carbon black, titanium black, acetylene black, graphite, silica, white carbon , Diatomaceous earth, talc, clay, aluminum powder pigment, bronze powder, nickel powder, stainless steel powder, pearl pigment, etc., these are used alone or in combination of two or more depending on the purpose I can do it. In addition, these inorganic pigments are blended and filled into thermosetting resins such as melamine resin, benzoquamine resin, urea resin, phenolic resin, and epoxy resin, and used as finely pulverized and pulverized thermosetting resin-coated inorganic pigments. May be.
[0035]
The addition amount of the inorganic pigment can be used in any addition amount according to the adjustment of the target hue, and is not particularly limited, but is 0.1% with respect to 100 parts by weight of the polyvinyl chloride resin. It is preferable that it is -50.0 weight part, More preferably, it is 1-30.0 weight part. When the addition amount of the inorganic pigment is 0.1 parts by weight or less, the degree of coloring of the polyvinyl chloride resin is low, and sufficient concealing property as a colored sheet may not be obtained. Moreover, when it exceeds 50.0 parts by weight, not only the molding processability of the obtained polyvinyl chloride resin is deteriorated, but the mechanical strength and abrasion strength of the obtained colored outer layer may be insufficient. is there.
[0036]
In order to blend the inorganic pigment into the polyvinyl chloride resin, when the polyvinyl chloride resin is a paste vinyl chloride resin, a moist color or paste color (vinyl toner color) is used. In this case, it is preferable to use a dry color or a master batch.
[0037]
In the antifouling sheet of the present invention, the weight of the fiber material for the base fabric is 50 to 300 g / m.2 And more preferably 100 to 200 g / m.2 It is. An undercoat layer formed by impregnation of vinyl chloride and resin is formed on the fiber material for the base fabric, and the coating weight is 50 to 250 g / m.2 And more preferably 100 to 200 g / m.2 It is. The weight of the polyvinyl chloride resin layer is 50 to 500 g / m.2 And more preferably 100 to 300 g / m.2 It is. The weight of the plasticizer migration preventing layer is 1 to 200 g / m.2 And more preferably 5 to 100 g / m.2 It is. When forming an adhesive / protective layer, the weight is 0.1 to 5 g / m.2 And more preferably 0.5-3 g / m.2 It is. The weight of the photocatalyst antifouling layer is 0.1 to 5 g / m.2 And more preferably 0.5-3 g / m.2 It is.
[0038]
The inventors of the present invention form a polyvinyl chloride resin layer on at least one surface of a base material having a fiber material and an undercoat layer containing a vinyl chloride resin impregnated therein, and on the polyvinyl chloride resin layer. The effect of the plasticizer of the polyvinyl chloride resin layer on the photocatalytic antifouling layer is formed by forming the plasticizer migration preventing layer, forming the adhesive / protective layer thereon, and further forming the photocatalytic antifouling layer thereon. Therefore, it is confirmed that the original antifouling effect of the photocatalyst antifouling layer can be obtained without interfering with the surface hydrophilization and dirt decomposition action of the photocatalytic antifouling layer. It was also confirmed that the use of specific plasticizers and pigments further improved. In addition, since the migration of the plasticizer to the photocatalytic antifouling layer is suppressed, the plasticizer itself of the polyvinyl chloride resin layer is not decomposed by the photocatalytic action, and the polyvinyl chloride resin layer for many years. It was confirmed that there was little change in texture.
[0039]
【Example】
The invention is further illustrated by the following examples.
In the following examples, the test methods used for product performance evaluation are as follows.
(1) Outdoor exposure test
The sample was installed in the south direction at an inclination angle of 30 degrees and vertically, and was subjected to a continuous outdoor exposure test. The antifouling property of the sample and the occurrence of rain streak stain were evaluated by visual observation.
(I) Antifouling property
With respect to the installation sample with an inclination angle of 30 degrees, the color difference ΔE on the surface of the sample after 6 months and 12 months after exposure was measured using the initial sample as a reference, and the antifouling property was evaluated in four stages as follows.
About the sample installed vertically, the generation | occurrence | production state of rain streak was visually judged in three steps as follows.
(2) Texture
Based on a general-purpose polyvinyl chloride-based resin sheet, the initial feeling of the test sample and the hand feeling after 12 months of exposure were evaluated.
The cold resistance of the test sheet was measured according to the Japanese Industrial Standard JIS K 6328 cold resistance test.
(4) Wear strength
The wear strength of the test sample was measured according to the Japanese Industrial Standard JIS L 1096 B method Scott type method. However, the sample was subjected to 1000 reciprocating friction tests at a load of 1 kg, and the surface condition was visually evaluated.
[0041]
Example 1
(1) Production of sheet substrate (formation of undercoat layer and polyvinyl chloride resin layer)
A polyester filament plain fabric having the following structure was used as the base fabric.
Next, a film (0.16 mm thickness) made of a resin composition of the following formulation 2 containing a straight vinyl chloride resin was prepared with a calender, and this was adhered to both sides of the undercoat layer impregnated base fabric. 200 g / m2 A polyvinyl chloride resin layer of a total weight of 760 g / m2 A sheet substrate was prepared.
[0042]
<Formulation 1>
Paste vinyl chloride resin 100 parts by weight
70 parts by weight of DOP (plasticizer)
4 parts by weight of epoxidized soybean oil
10 parts by weight of calcium carbonate
Ba-Zn stabilizer 2 parts by weight
Inorganic pigment (TiO2 ) 5 parts by weight
20 parts by weight of toluene (solvent)
<Formulation 2>
100 parts by weight of straight vinyl chloride resin
Adipic acid-based polyester (plasticizer) 80 parts by weight
4 parts by weight of epoxidized soybean oil
10 parts by weight of calcium carbonate
Ba-Zn stabilizer 2 parts by weight
Inorganic pigment (TiO2 ) 5 parts by weight
[0043]
(2) Formation of plasticizer migration prevention layer
On the polyvinyl chloride resin layer of the sheet substrate, a solvent diluted solution of a resin composition of the following formulation 3 as an acrylic resin was applied using a gravure coater to a coating amount of 25 g / m.2 And dried at 120 ° C. for 1 minute and then cooled to 5 g / m2 A plasticizer migration prevention layer was formed.
<Formulation 3>
ACRYPLEN (registered trademark) pellet HBS001
(Mitsubishi Rayon Co., Ltd.) 20 parts by weight
Toluene-MEK (50/50 weight ratio) (solvent) 80 parts by weight
[0044]
(3) Formation of photocatalytic antifouling layer
On the plasticizer migration preventing layer of the base sheet, an adhesive / protective layer treatment liquid having the composition shown in the following formulation 4 was applied at 15 g / m with a gravure coater.2 The coating amount is 1.5 g / m after cooling at 100 ° C. for 1 minute and cooling.2 A coating solution for forming a photocatalytic antifouling layer having the composition shown in Formula 5 below was further applied at 15 g / m with a gravure coater.2 The coating amount is 1.5 g / m after cooling at 100 ° C. for 1 minute and cooling.2 A photocatalytic antifouling layer was formed to prepare an antifouling sheet.
[0045]
<Formulation 4> Adhesive / protective layer treatment solution composition
Acrylic silicone resin with a silicon content of 3 mol%
Ethanol-vinegar containing 8% by weight (solid content)
100 parts by weight of ethyl acid (50/50 weight ratio) solution
Methyl silicate MS51 as polysiloxane
(Colcoat Co., Ltd.) 20% ethanol solution 8 parts by weight
Γ-Glycidoxip as silane coupling agent
1 part by weight of propyltrimethoxysilane
<Formulation 5> photocatalyst antifouling layer treatment solution composition
Nitric acid acidity corresponding to titanium oxide content of 10% by weight
Water-ethanol (with titanium oxide sol dispersed)
50/50 weight ratio) Solution 50 parts by weight
A nitric acid acidic salt corresponding to a silicon oxide content of 10% by weight
Water-ethanol (50 /
50 parts by weight) 50 parts by weight of solution
This antifouling sheet was subjected to the test. The test results are shown in Table 1.
[0046]
Example 2
An antifouling sheet was produced in the same manner as in Example 1. However, the composition of the calendar film resin composition of Example 1 was changed to Formulation 6 shown in Table 1, and an antifouling sheet was produced in the same manner as in Example 1. This antifouling sheet was subjected to the test. The test results are shown in Table 1.
[0047]
Example 3
An antifouling sheet was produced in the same manner as in Example 1. However, the composition of the calendar film resin composition of Example 1 was changed to Formulation 7 described in Table 1, and an antifouling sheet was produced in the same manner as in Example 1. This antifouling sheet was subjected to the test. The test results are shown in Table 1.
[0048]
Example 4
An antifouling sheet was produced in the same manner as in Example 1. However, the composition of the calendar film resin composition of Example 1 was changed to Formulation 8 described in Table 1, and an antifouling sheet was produced in the same manner as in Example 1. This antifouling sheet was subjected to the test. The test results are shown in Table 1.
[0049]
Example 5
An antifouling sheet was produced in the same manner as in Example 1. However, the composition of the calendar film resin composition of Example 1 was changed to Formulation 9 shown in Table 1, and an antifouling sheet was produced in the same manner as in Example 1. This antifouling sheet was subjected to the test. The test results are shown in Table 1.
[0050]
Example 6
An antifouling sheet was produced in the same manner as in Example 1. However, the composition of the calendar film resin composition of Example 1 was changed to the composition 10 shown in Table 1, and an antifouling sheet was produced in the same manner as in Example 1. This antifouling sheet was subjected to the test. The test results are shown in Table 1.
[0051]
Example 7
An antifouling sheet was produced in the same manner as in Example 1. However, the composition of the calendar film resin composition of Example 1 was changed to the composition 11 shown in Table 1, and an antifouling sheet was produced in the same manner as in Example 1. This antifouling sheet was subjected to the test. The test results are shown in Table 1.
[0052]
Example 8
An antifouling sheet was produced in the same manner as in Example 1. However, the composition of the calendar film resin composition of Example 1 was changed to Formulation 12 shown in Table 1, and an antifouling sheet was produced in the same manner as Example 1. This antifouling sheet was subjected to the test. The test results are shown in Table 1.
[0053]
Example 9
An antifouling sheet was produced in the same manner as in Example 1. However, the composition of the calendar film resin composition of Example 1 was changed to Formulation 13 shown in Table 1, and an antifouling sheet was produced in the same manner as Example 1. This antifouling sheet was subjected to the test. The test results are shown in Table 1.
[0054]
Example 10
An antifouling sheet was produced in the same manner as in Example 1. However, the composition of the calendar film resin composition of Example 1 was changed to Formulation 14 shown in Table 1, and an antifouling sheet was produced in the same manner as Example 1. This antifouling sheet was subjected to the test. The test results are shown in Table 1.
[0055]
[Table 1]
The sheets obtained in Examples 1 to 10 have excellent antifouling properties (ΔE = 2 or less), no rain streaks are observed even after 12 months of outdoor exposure, and show very excellent antifouling properties. The texture, cold resistance test, and abrasion strength also showed good results, and the sheet was suitable for practical use.
[0057]
Comparative Example 1
An antifouling sheet was produced in the same manner as in Example 1. However, the amount of the adipic acid-based polyester plasticizer used as a plasticizer was reduced to 30 parts by weight as in Formulation 15 shown in Table 2 in the formulation of the calendar film resin composition of Example 1, and Example 1 A sheet was prepared in the same manner as described above. This sheet was subjected to the test. The test results are shown in Table 2.
The obtained sheet was harder than the sheet obtained in Example 1 and had poor cold resistance, and was not suitable for practical use.
[0058]
Comparative Example 2
An antifouling sheet was produced in the same manner as in Example 3. However, the composition of the calender film resin composition of Example 3 was reduced to 30 parts by weight of the pyromellitic acid octyl ester plasticizer used as a plasticizer as shown in Formulation 16 shown in Table 2. In the same manner as in No. 3, a sheet was produced. This sheet was subjected to the test. The test results are shown in Table 2.
The obtained sheet was harder in texture and cold resistant than the sheet obtained in Example 3, and was not suitable for practical use.
[0059]
Comparative Example 3
An antifouling sheet was produced in the same manner as in Example 1. However, the amount of the adipic acid-based polyester plasticizer used as a plasticizer was increased to 120 parts by weight as in Formulation 17 shown in Table 2 in the formulation of the calendar film resin composition of Example 1, and Example 1 A sheet was prepared in the same manner as described above. This sheet was subjected to the test. The test results are shown in Table 2.
Compared with the sheet obtained in Example 1, the obtained sheet was slightly unnoticeable with rain streak stains and weak in abrasion strength, and was not suitable for practical use.
[0060]
Comparative Example 4
An antifouling sheet was produced in the same manner as in Example 3. However, the composition of the calender film resin composition of Example 3 was increased to 120 parts by weight of the pyromellitic acid octyl ester plasticizer used as a plasticizer as shown in Formulation 18 in Table 2. In the same manner as in No. 3, a sheet was produced. This sheet was subjected to the test. The test results are shown in Table 2.
Compared with the sheet obtained in Example 13, the obtained sheet was slightly unnoticeable with rain streak stains and weak in abrasion strength, and was not suitable for practical use.
[0061]
Comparative Example 5
An antifouling sheet was produced in the same manner as in Example 4. However, the amount of the adipic acid-based polyester plasticizer and pyromellitic acid octyl ester plasticizer used as plasticizers was changed as shown in Formulation 19 in Table 2 by changing the composition of the calendar film resin composition of Example 4 Both were reduced to 15 parts by weight (total amount 30 parts by weight). This antifouling sheet was subjected to the test. The test results are shown in Table 2.
The obtained sheet was not suitable for practical use because it had a harder texture and a lower cold resistance than the sheet obtained in Example 4.
[0062]
Comparative Example 6
An antifouling sheet was produced in the same manner as in Example 4. However, the amount of the adipic acid-based polyester plasticizer and pyromellitic acid octyl ester plasticizer used as plasticizers was changed as shown in the formulation 20 of Table 2 by changing the composition of the calendar film resin composition of Example 4 Both were increased to 60 parts by weight (total blending amount 120 parts by weight). This antifouling sheet was subjected to the test. The test results are shown in Table 2.
The obtained sheet was slightly unsuitable for practical use because it had some rain streak stains and a low abrasion strength compared to the sheet obtained in Example 4.
[0063]
Comparative Example 7
An antifouling sheet was produced in the same manner as in Example 5. However, the blend of the calender film resin composition of Example 5 was an ethylene-vinyl acetate-carbon monoxide terpolymer (Elvalloy (registered trademark)) used as a plasticizer as in the blend 21 shown in Table 2. 741 Mitsui DuPont Polychemical Co., Ltd.) was reduced to 40 parts by weight, and a sheet was produced in the same manner as in Example 5. This sheet was subjected to the test. The test results are shown in Table 2.
The obtained sheet was harder in texture and cold resistant than the sheet obtained in Example 5, and was not suitable for practical use.
[0064]
Comparative Example 8
An antifouling sheet was produced in the same manner as in Example 6. However, the blending of the calender film resin composition of Example 6 was changed as blending 22 shown in Table 2, and an ethylene-acrylic acid ester-carbon monoxide terpolymer (Elvalloy) used as a plasticizer was used. (Registered trademark) HP443 Mitsui DuPont Polychemical Co., Ltd.) was reduced to 40 parts by weight. This antifouling sheet was subjected to the test. The test results are shown in Table 2.
The obtained sheet was not suitable for practical use because it had a harder texture and a lower cold resistance than the sheet obtained in Example 6.
[0065]
Comparative Example 9
An antifouling sheet was produced in the same manner as in Example 5. However, the blend of the calender film resin composition of Example 5 was an ethylene-vinyl acetate-carbon monoxide terpolymer (Elvalloy (registered trademark)) used as a plasticizer as shown in Formulation 23 of Table 2. 741 Mitsui DuPont Polychemical Co., Ltd.) was increased to 140 parts by weight, and a sheet was produced in the same manner as in Example 5. This sheet was subjected to the test. The test results are shown in Table 2.
The obtained sheet was not suitable for practical use because its abrasion strength was weaker than that of the sheet obtained in Example 5.
[0066]
Comparative Example 10
An antifouling sheet was produced in the same manner as in Example 6. However, the blending of the calender film resin composition of Example 6 was changed as blending 24 shown in Table 2, and an ethylene-acrylic acid ester-carbon monoxide terpolymer (Elvalloy) used as a plasticizer was used. (Registered trademark) HP443 Mitsui DuPont Polychemical Co., Ltd.) was added to 140 parts by weight. This antifouling sheet was subjected to the test. The test results are shown in Table 2.
The obtained sheet was less suitable for practical use because its abrasion strength was weaker than that of the sheet obtained in Example 6.
[0067]
[Table 2]
Comparative Example 11
An antifouling sheet was produced in the same manner as in Example 7. However, the blend of the calender film resin composition of Example 7 was changed as blend 25 shown in Table 3, and an ethylene-vinyl acetate-carbon monoxide terpolymer (Elvalloy (registered) was used as a plasticizer. Trademark) 741 Mitsui DuPont Polychemical Co., Ltd.) and ethylene-acrylic acid ester-carbon monoxide terpolymer (Elvalloy (registered trademark) HP443 Mitsui DuPont Polychemical Co., Ltd.) The total weight was reduced to 40 parts by weight. This antifouling sheet was subjected to the test. The test results are shown in Table 3. The obtained sheet was not suitable for practical use because it had a harder texture and a lower cold resistance than the sheet obtained in Example 7.
[0069]
Comparative Example 12
An antifouling sheet was produced in the same manner as in Example 7. However, the composition of the calender film resin composition of Example 7 was changed to the composition 26 shown in Table 3, and an ethylene-vinyl acetate-carbon monoxide terpolymer (Elvalloy (registered) was used as a plasticizer. (Trademark) 741 Mitsui DuPont Polychemical Co., Ltd.) and ethylene-acrylic acid ester-carbon monoxide terpolymer (Elvalloy (registered trademark) HP443 Mitsui DuPont Polychemical Co., Ltd.). The total amount was increased to 140 parts by weight. This antifouling sheet was subjected to the test. The test results are shown in Table 3.
The obtained sheet was a sheet not suitable for practical use because its abrasion strength was weaker than that of the sheet obtained in Example 7.
[0070]
Comparative Example 13
An antifouling sheet was produced in the same manner as in Example 8. However, the blending of the calender film resin composition of Example 8 was changed as blending 27 shown in Table 3, and adipic acid polyester plasticizer and ethylene-vinyl acetate-carbon monoxide ternary used as plasticizers The blending amounts of the polymers (Elvalloy (registered trademark) 741 Mitsui DuPont Polychemical Co., Ltd.) were both reduced to 15 parts by weight (total blending amount: 30 parts by weight). This antifouling sheet was subjected to the test. The test results are shown in Table 3.
The obtained sheet was not suitable for practical use because it had a harder texture and a lower cold resistance than the sheet obtained in Example 8.
[0071]
Comparative Example 14
An antifouling sheet was produced in the same manner as in Example 8. However, the blending of the calender film resin composition of Example 8 was changed as blending 28 shown in Table 3, and adipic acid polyester plasticizer and ethylene-vinyl acetate-carbon monoxide ternary used as plasticizers. Both blending amounts of the polymer (Elvalloy (registered trademark) 741 Mitsui DuPont Polychemical Co., Ltd.) were increased to 70 parts by weight (total blending amount: 140 parts by weight). This antifouling sheet was subjected to the test. The test results are shown in Table 3.
The obtained sheet was a sheet unsuitable for practical use because it showed some rain streak stains and a low abrasion strength as compared with the sheet obtained in Example 8.
[0072]
Comparative Example 15
An antifouling sheet was produced in the same manner as in Example 10. However, the blending of the calender film resin composition of Example 10 was changed as blending 29 shown in Table 3, and the adipic acid polyester plasticizer and pyromellitic acid octyl ester plasticizer acid polyester plastic used as plasticizers were used. The amount of the compounding agent and ethylene-vinyl acetate-carbon monoxide terpolymer (ELVALOY (registered trademark) 741 Mitsui DuPont Polychemical Co., Ltd.) was reduced to 10 parts by weight (total amount of 30 parts by weight). . This antifouling sheet was subjected to the test. The test results are shown in Table 3.
The obtained sheet was not suitable for practical use because it had a harder texture and a lower cold resistance than the sheet obtained in Example 10.
[0073]
Comparative Example 16
An antifouling sheet was produced in the same manner as in Example 10. However, the blending of the calender film resin composition of Example 10 was changed as blending 30 described in Table 3, and adipic acid polyester plasticizer, pyromellitic acid octyl ester plasticizer, and ethylene used as plasticizers -Compounding amounts of vinyl acetate-carbon monoxide terpolymer (Elvalloy (registered trademark) 741, Mitsui DuPont Polychemical Co., Ltd.) were 40 parts by weight, 40 parts by weight and 50 parts by weight, respectively (total blending amount 130 weights) Part). This antifouling sheet was subjected to the test. The test results are shown in Table 3.
The obtained sheet had a low abrasion strength as compared with the sheet obtained in Example 10, and was not suitable for practical use.
[0074]
[Table 3]
【The invention's effect】
The antifouling sheet according to the present invention uses a specific plasticizer in order to suppress the influence of the plasticizer of the polyvinyl chloride resin layer on the photocatalytic antifouling layer, and prevents plasticizer migration between these two layers. By forming the layer, the photocatalyst antifouling layer has fully exhibited its original effect and can exhibit excellent antifouling properties. Further, the antifouling sheet of the present invention has a good texture and abrasion strength as a sheet for industrial materials, and is extremely useful in practice.
Claims (8)
前記基布は、前記繊維材料に含浸された塩化ビニル樹脂を含む下塗り層を有するものであり、
前記ポリ塩化ビニル系樹脂層は、可塑剤として、
（１）ポリエステル系可塑剤、トリメリット酸エステル系可塑剤、及びピロメリット酸エステル系可塑剤から選ばれた少なくとも１種からなる液状可塑剤、及び
（２）エチレン−酢酸ビニル−一酸化炭素三元共重合体及びエチレン−アクリル酸エステル−一酸化炭素三元共重合体から選ばれた少なくとも１種からなる高分子量可塑剤、
から選ばれた少なくとも１種を含むものであり、
但し、前記液状可塑剤が単独で用いられるときには、その配合量は、ポリ塩化ビニル系樹脂１００重量部に対し、４０〜１００重量部であり、前記高分子量可塑剤が単独で用いられるときには、その配合量はポリ塩化ビニル系樹脂１００重量部に対し、５０〜１２０重量部であり、かつ、前記液状可塑剤及び高分子量可塑剤が併用されるときには、その合計配合量は、前記ポリ塩化ビニル樹脂１００重量部に対し４０〜１２０重量部であり、
前記可塑剤移行防止層が、フッ素含有樹脂及びアクリル系樹脂から選ばれた少なくとも１種の樹脂を主成分として含有するものであり、かつ
前記可塑剤移行防止層と、前記光触媒防汚層との間に、ポリシロキサンと、アクリルシリコーン樹脂との混合物を含む接着・保護層が形成されている、
ことを特徴とする雨筋汚れ防止性に優れたテント用防汚性シート。A base fabric made of a fiber material, a polyvinyl chloride resin layer formed on at least one surface thereof, a plasticizer migration preventing layer formed on the polyvinyl chloride resin layer, and the plasticizer A photocatalytic antifouling layer formed on the migration preventing layer;
The base fabric has an undercoat layer containing a vinyl chloride resin impregnated in the fiber material,
The polyvinyl chloride resin layer is a plasticizer,
(1) a liquid plasticizer comprising at least one selected from polyester plasticizers, trimellitic acid ester plasticizers, and pyromellitic acid ester plasticizers, and (2) ethylene-vinyl acetate-carbon monoxide A high molecular weight plasticizer comprising at least one selected from an original copolymer and an ethylene-acrylic acid ester-carbon monoxide terpolymer;
At least one selected from a Dressings containing,
However, when the liquid plasticizer is used alone, the blending amount is 40 to 100 parts by weight with respect to 100 parts by weight of the polyvinyl chloride resin, and when the high molecular weight plasticizer is used alone, The blending amount is 50 to 120 parts by weight with respect to 100 parts by weight of the polyvinyl chloride resin, and when the liquid plasticizer and the high molecular weight plasticizer are used in combination, the total blending amount is the polyvinyl chloride resin. 40 to 120 parts by weight with respect to 100 parts by weight,
The plasticizer migration prevention layer contains at least one resin selected from a fluorine-containing resin and an acrylic resin as a main component ; and
An adhesion / protection layer containing a mixture of polysiloxane and an acrylic silicone resin is formed between the plasticizer migration prevention layer and the photocatalyst antifouling layer.
An antifouling sheet for tents with excellent rain streak prevention .
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