JP5756877B2 - Agricultural film - Google Patents
Agricultural film Download PDFInfo
- Publication number
- JP5756877B2 JP5756877B2 JP2014132538A JP2014132538A JP5756877B2 JP 5756877 B2 JP5756877 B2 JP 5756877B2 JP 2014132538 A JP2014132538 A JP 2014132538A JP 2014132538 A JP2014132538 A JP 2014132538A JP 5756877 B2 JP5756877 B2 JP 5756877B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- acid
- layer
- ultraviolet absorber
- agricultural
- 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.)
- Active
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- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 45
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 25
- 239000012964 benzotriazole Substances 0.000 claims description 25
- 238000002834 transmittance Methods 0.000 claims description 16
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 7
- 239000011787 zinc oxide Substances 0.000 claims description 4
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 3
- YATYZLYTTAAVIF-UHFFFAOYSA-N 2-(5-chlorobenzotriazol-2-yl)-4,6-bis(2-methylbutan-2-yl)phenol Chemical compound CCC(C)(C)C1=CC(C(C)(C)CC)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O YATYZLYTTAAVIF-UHFFFAOYSA-N 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 90
- -1 polyethylene Polymers 0.000 description 77
- 238000000576 coating method Methods 0.000 description 32
- 239000011248 coating agent Substances 0.000 description 30
- 239000006096 absorbing agent Substances 0.000 description 27
- 238000012360 testing method Methods 0.000 description 22
- 239000003795 chemical substances by application Substances 0.000 description 21
- 238000000034 method Methods 0.000 description 18
- 229920005989 resin Polymers 0.000 description 15
- 239000011347 resin Substances 0.000 description 15
- 239000004094 surface-active agent Substances 0.000 description 15
- 230000000694 effects Effects 0.000 description 14
- 239000002585 base Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 238000000465 moulding Methods 0.000 description 11
- 229920005672 polyolefin resin Polymers 0.000 description 11
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 10
- 229910052731 fluorine Inorganic materials 0.000 description 10
- 239000011737 fluorine Substances 0.000 description 10
- 239000004925 Acrylic resin Substances 0.000 description 9
- 229920000178 Acrylic resin Polymers 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 229920000098 polyolefin Polymers 0.000 description 9
- 239000004711 α-olefin Substances 0.000 description 9
- 235000014113 dietary fatty acids Nutrition 0.000 description 8
- 239000000194 fatty acid Substances 0.000 description 8
- 229930195729 fatty acid Natural products 0.000 description 8
- 239000010419 fine particle Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 7
- 239000005977 Ethylene Substances 0.000 description 7
- 229910052749 magnesium Inorganic materials 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- 125000003386 piperidinyl group Chemical group 0.000 description 7
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 239000007983 Tris buffer Substances 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- OCWYEMOEOGEQAN-UHFFFAOYSA-N bumetrizole Chemical compound CC(C)(C)C1=CC(C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O OCWYEMOEOGEQAN-UHFFFAOYSA-N 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 6
- 239000005038 ethylene vinyl acetate Substances 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910001868 water Inorganic materials 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 238000003851 corona treatment Methods 0.000 description 5
- 208000028659 discharge Diseases 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- UWSMKYBKUPAEJQ-UHFFFAOYSA-N 5-Chloro-2-(3,5-di-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O UWSMKYBKUPAEJQ-UHFFFAOYSA-N 0.000 description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 4
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 125000005907 alkyl ester group Chemical group 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 150000002484 inorganic compounds Chemical class 0.000 description 4
- 229910010272 inorganic material Inorganic materials 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 239000002344 surface layer Substances 0.000 description 4
- 229920005992 thermoplastic resin Polymers 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
- 241000607479 Yersinia pestis Species 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 3
- 229920001684 low density polyethylene Polymers 0.000 description 3
- 239000004702 low-density polyethylene Substances 0.000 description 3
- 239000012968 metallocene catalyst Substances 0.000 description 3
- 239000010445 mica Substances 0.000 description 3
- 229910052618 mica group Inorganic materials 0.000 description 3
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 3
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- 229920003002 synthetic resin Polymers 0.000 description 3
- 239000000057 synthetic resin Substances 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- 235000014692 zinc oxide Nutrition 0.000 description 3
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- QHZLMUACJMDIAE-UHFFFAOYSA-N 1-monopalmitoylglycerol Chemical compound CCCCCCCCCCCCCCCC(=O)OCC(O)CO QHZLMUACJMDIAE-UHFFFAOYSA-N 0.000 description 2
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- GAMRDXGPACRSMU-UHFFFAOYSA-N 1-tridecoxycarbonylbutane-1,1,2-tricarboxylic acid Chemical compound C(CCCCCCCCCCCC)OC(=O)C(C(CC)C(=O)O)(C(=O)O)C(=O)O GAMRDXGPACRSMU-UHFFFAOYSA-N 0.000 description 2
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 2
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 2
- WZUNUACWCJJERC-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CC)(CO)CO WZUNUACWCJJERC-UHFFFAOYSA-N 0.000 description 2
- ZSSVCEUEVMALRD-UHFFFAOYSA-N 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(octyloxy)phenol Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C1=NC(C=2C(=CC(C)=CC=2)C)=NC(C=2C(=CC(C)=CC=2)C)=N1 ZSSVCEUEVMALRD-UHFFFAOYSA-N 0.000 description 2
- MVRPPTGLVPEMPI-UHFFFAOYSA-N 2-cyclohexylphenol Chemical group OC1=CC=CC=C1C1CCCCC1 MVRPPTGLVPEMPI-UHFFFAOYSA-N 0.000 description 2
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical group CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 241000233866 Fungi Species 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- WOGWRXSITPCETK-UHFFFAOYSA-N [3-(2,3-dihydroxypropoxy)-2-hydroxypropyl] hexadecanoate Chemical compound CCCCCCCCCCCCCCCC(=O)OCC(O)COCC(O)CO WOGWRXSITPCETK-UHFFFAOYSA-N 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- UJMDYLWCYJJYMO-UHFFFAOYSA-N benzene-1,2,3-tricarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1C(O)=O UJMDYLWCYJJYMO-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 2
- 230000000740 bleeding effect Effects 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 239000000378 calcium silicate Substances 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- 235000012241 calcium silicate Nutrition 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- ZCGNNESZWJPBLW-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite 2-[2-(2-hydroxyphenyl)propan-2-yl]-3,4,5,6-tetra(tridecyl)phenol Chemical compound OP(O)OP(O)O.CCCCCCCCCCCCCC1=C(CCCCCCCCCCCCC)C(CCCCCCCCCCCCC)=C(O)C(C(C)(C)C=2C(=CC=CC=2)O)=C1CCCCCCCCCCCCC ZCGNNESZWJPBLW-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-MDZDMXLPSA-N elaidic acid Chemical compound CCCCCCCC\C=C\CCCCCCCC(O)=O ZQPPMHVWECSIRJ-MDZDMXLPSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 229960001545 hydrotalcite Drugs 0.000 description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
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- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- SGKKYCDALBXNCG-UHFFFAOYSA-N tris[2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenyl)sulfanyl-5-methylphenyl] phosphite Chemical compound CC(C)(C)C1=C(O)C(C)=CC(SC=2C(=CC(OP(OC=3C(=CC(SC=4C=C(C(O)=C(C)C=4)C(C)(C)C)=C(C)C=3)C(C)(C)C)OC=3C(=CC(SC=4C=C(C(O)=C(C)C=4)C(C)(C)C)=C(C)C=3)C(C)(C)C)=C(C=2)C(C)(C)C)C)=C1 SGKKYCDALBXNCG-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- 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
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- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Protection Of Plants (AREA)
- Greenhouses (AREA)
Description
本発明はフィルムやシートに加工した場合に、紫外線遮蔽性に優れつつもブリードアウト等による光線透過性及び防曇性の低下が抑制された農業用フィルムに関し、特にフィルム厚が薄い場合でも良好な耐ブリードアウト特性を示す上、長期間使用した場合でも紫外線吸収能が消失しにくい、ハウス内環境において病害菌やカビの繁殖抑制、害虫防除性及び内張資材の劣化防止性等にも優れた農業用フィルムに関するものである。 The present invention relates to an agricultural film that is excellent in ultraviolet shielding properties but has reduced light transmittance and antifogging deterioration due to bleed-out when processed into a film or sheet, and is particularly good even when the film thickness is thin. In addition to exhibiting bleed-out resistance, it is difficult to lose its ability to absorb ultraviolet rays even when used for a long period of time. It is excellent in controlling the growth of pests and fungi in the house environment, pest control and deterioration of lining materials. It relates to agricultural films.
農業用ハウスは年々大型化しており、ハウスをフィルムで覆うためのフィルム展張作業は多くの人手を要するようになってきている。その一方で、農業従事者の数は年々減少すると共に高齢化が進行しており、毎年の展張作業に人手を確保することは容易ではない状況にある。この様な状況に鑑み、ハウスに展張するフィルムは展張作業が容易で極力張り替えまでの使用期間の長いフィルム、言いかえれば、2年以上の長寿命を有し、長期間にわたり当初性能を保持できる高性能な農業用フィルムの開発が求められている。 Agricultural houses have become larger year by year, and the film expansion work for covering the houses with films has become more labor-intensive. On the other hand, the number of farmers is declining year by year and aging is progressing, and it is not easy to secure manpower for annual expansion work. In view of such a situation, the film to be spread in the house is a film that is easy to stretch and has a long use period until re-covering as much as possible, in other words, has a long life of 2 years or more and can maintain the initial performance over a long period of time. There is a need to develop high performance agricultural films.
こうした被覆資材のなかでも、ポリオレフィン系樹脂を主体とした農業用ポリオレフィン系樹脂フィルムは、密度が塩化ビニル樹脂より小さいために軽く、焼却しても有毒ガスの発生が少なく、可塑剤を添加する必要が無いために、可塑剤のブリードアウトによる硬化の問題も無く、更にインフレーション成型法により幅継ぎの為の接着加工を必要としない広幅フィルムが安価に提供できることなどから盛んに利用されるようになってきている。 Among these coating materials, agricultural polyolefin-based resin films mainly composed of polyolefin-based resins are lighter in density than vinyl chloride resins, generate little toxic gas even when incinerated, and need to add a plasticizer. Therefore, there is no problem of curing due to bleed-out of the plasticizer, and wide film that does not require adhesive processing for splicing by the inflation molding method can be provided at low cost. It is coming.
一方、以前より農業用フィルムに紫外線吸収剤を少量添加して紫外線の一部分をカットし、農業用フィルムの紫外線劣化を防止する方法が知られているが、今日、更に紫外線領域(300nm〜380nm)全般の紫外線を実質完全にカットする紫外線カットフィルムを作成し、ハウス内環境における病害菌やカビの繁殖抑制、害虫防除性をすることにより減農薬栽培を行なう試みがなされてきている。 On the other hand, a method of adding a small amount of an ultraviolet absorber to an agricultural film to cut off a part of the ultraviolet light to prevent the deterioration of the agricultural film in the ultraviolet is known, but today, the ultraviolet region (300 nm to 380 nm) is further increased. Attempts have been made to reduce pesticide cultivation by creating UV-cutting films that cut all UV rays substantially completely, and controlling the growth and control of pests and fungi in the house environment.
農業用フィルムには、長期展張タイプと、短〜中期展張タイプがあり、作物の栽培形態やハウスの構造、各地域での最適栽培方法等により、使用方法に合わせて選択されている。 Agricultural films are classified into a long-term stretch type and a short to medium-term stretch type, and are selected according to the method of use depending on the cultivation form of the crop, the structure of the house, the optimum cultivation method in each region, and the like.
全フィルム厚みが0.15mm未満である比較的薄い農業用フィルム(主に短〜中期展張で使用される)において、紫外線を完全にカットするためには、フィルム中に紫外線吸収剤を高濃度で含有する必要がある。しかし、紫外線吸収剤を高濃度添加すると、紫外線吸収剤のブリードアウトにより、フィルムの失透や防曇性の低下を招くケースがあった。 In a relatively thin agricultural film (mainly used in short to medium-term stretching) with a total film thickness of less than 0.15 mm, in order to completely cut off the ultraviolet rays, a high concentration of ultraviolet absorber is contained in the film. It is necessary to contain. However, when a high concentration of the UV absorber is added, there are cases where the UV absorber bleeds out and causes devitrification of the film and a decrease in antifogging property.
一方、ブリードアウトしないギリギリの量の紫外線吸収剤を入れた場合は、紫外線吸収剤自体の失効により、初期の紫外線カット性を長期間維持することが出来ず、問題となっていた。また、展張初期又は経時後に、実際に紫外線遮蔽効果が期待できる波長域の一部が透過してしまうフィルムが多く、その改良が期待されていた。 On the other hand, in the case where a UV absorber in an amount that does not bleed out is added, the initial UV cut ability cannot be maintained for a long time due to the expiration of the UV absorber itself, which is a problem. In addition, many films that transmit a part of the wavelength region that can actually be expected to have an ultraviolet shielding effect after the initial stage of stretching or after lapse of time have been expected to be improved.
ポリオレフィン系樹脂を主体とした農業用ポリオレフィン系樹脂フィルムなどに配合される紫外線吸収剤としては、従来はニッケル系化合物が中心であったが、近年、ベンゾフェノン型、ベンゾトリアゾール型、トリアジン型等の紫外線吸収剤が開発され、種々の用途へ展開されている。 Conventionally, nickel-based compounds have mainly been used as UV absorbers for agricultural polyolefin-based resin films mainly composed of polyolefin-based resins, but in recent years, UV light of benzophenone-type, benzotriazole-type, triazine-type, etc. Absorbents have been developed and deployed in various applications.
これら紫外線吸収剤は各々、その構造特有の吸収波長域を有しており、またその構造、分子量等により、基材樹脂との相溶性が異なる。農業用ポリオレフィン系フィルムにおいても、紫外線の吸収域を広くして、かつ紫外線吸収能の保持性を向上させる為に様々な試みがなされてきており、特に紫外線の吸収域から、ベンゾトリアゾール型紫外線吸収剤が多く使用されてきた。 Each of these ultraviolet absorbers has an absorption wavelength region specific to its structure, and its compatibility with the base resin varies depending on its structure, molecular weight, and the like. In the polyolefin film for agriculture, various attempts have been made to widen the absorption range of ultraviolet rays and improve the retention of ultraviolet absorption ability. Especially, the benzotriazole type ultraviolet absorption from the ultraviolet absorption range. Many agents have been used.
ところが、最近、ベンゾトリアゾール型紫外線吸収剤の一部(ベンゾトリアゾール骨格を有しつつ、特定の置換基を有する化合物)において、生物濃縮性及び有毒性について指摘されており、第一種特定化学物質や第一種監視化学物質に指定される等しているため、特に屋外使用での工業製品については適用が問題になってきており、このような環境への影響がある紫外線吸収剤を使用しない製品の開発が求められてきている。 Recently, however, bioconcentration and toxicity have been pointed out in some of the benzotriazole type UV absorbers (compounds having a benzotriazole skeleton and a specific substituent). In particular, it has become a problem for industrial products for outdoor use. Do not use UV absorbers that have an impact on the environment. There is a need for product development.
環境への影響に関しては、化合物の置換基の種類によって、程度が異なることが判明しているが、構造相関が取れておらず、具体的にどのような構造の紫外線吸収剤を用いた場合に、農業用フィルムとして好適に使用できるか未だはっきりしていない。 Regarding the impact on the environment, it has been found that the degree varies depending on the type of substituent of the compound, but the structural correlation is not taken, and in particular when using an ultraviolet absorber of any structure It is not yet clear whether it can be suitably used as an agricultural film.
このような中で、環境影響性を低減させたベンゾトリアゾール型紫外線吸収剤の検討が行われ、環境影響性がなく紫外線遮蔽性に優れる代替品(例えば、チバ・スペシャリティーケミカルズ社製TINUVIN326)が提案されてはいるが、このものは耐ブリードアウト性の点で劣っているため単独で使用することは困難である。また、このものと特定の紫外線吸収剤とを組み合わせて使用することが提案され、紫外線遮蔽性及び耐ブリードアウト性が良好であることが報告されている(特許文献1)。しかしながら、紫外線遮蔽性の持続や耐ブリードアウト性において更なる向上が求められている。 Under such circumstances, studies have been made on benzotriazole type ultraviolet absorbers with reduced environmental impact, and there is an alternative product that has no environmental impact and excellent ultraviolet shielding properties (for example, TINUVIN 326 manufactured by Ciba Specialty Chemicals). Although proposed, it is difficult to use alone because it is inferior in bleed-out resistance. Further, it has been proposed to use this in combination with a specific ultraviolet absorber, and it has been reported that the ultraviolet shielding property and bleed-out resistance are good (Patent Document 1). However, there is a need for further improvement in the ultraviolet shielding durability and bleed-out resistance.
従って、本発明は、紫外線遮蔽性に優れつつも耐ブリードアウト性に優れた農業用フィルム、特にフィルム厚が薄い場合でも良好な耐ブリードアウト特性を示す上、長期間使用した場合でも紫外線吸収能が消失しにくい農業用フィルムを提供することを目的とする。 Therefore, the present invention is an agricultural film having excellent ultraviolet shielding properties and excellent bleed-out resistance, and particularly exhibits excellent bleed-out resistance even when the film thickness is thin. An object of the present invention is to provide an agricultural film that does not easily disappear.
本発明者は、鋭意検討を行った結果、下記の特定の構造を有する紫外線吸収剤を使用した場合に、300nm〜380nmの紫外線を有効に遮蔽することができ、長期間使用した場合でも紫外線吸収能が消失しにくく、かつ耐ブリードアウト性にも優れた農業用フィルムを提供できることを見出し、本発明を完成した。 As a result of intensive studies, the present inventor can effectively shield ultraviolet rays of 300 nm to 380 nm when using an ultraviolet absorber having the following specific structure, and absorbs ultraviolet rays even when used for a long time. The present invention has been completed by finding that an agricultural film that is less likely to lose its ability and excellent in bleed-out resistance can be provided.
即ち、本発明は、下記式(1)又は(2)に記載のベンゾトリアゾール型紫外線吸収剤を含有することを特徴とする農業用フィルム、という構成を採用する。
(2−[5−クロロ(2H)−ベンゾトリアゾール−2−イル]−4,6−ジ(tert−ペンチル)フェノール)
(2- [5-Chloro (2H) -benzotriazol-2-yl] -4,6-di (tert-pentyl) phenol)
また、本発明において、上記の特定のベンゾトリアゾール型紫外線吸収剤に加えて下記式(3)で表されるトリアリールトリアジン型紫外線吸収剤を更に含有させることにより、長期間使用した場合における紫外線吸収能の消失を更に抑制することが可能となることに加えて、着色防止や紫外線カット持続性を高いレベルで付与することが可能となる。
本発明の農業用フィルムは、紫外線遮蔽性に優れつつもブリードアウト等による光線透過性及び防曇性の低下を抑制することができることから農業用フィルムとして好適に用いることができる。また、本発明のフィルムは、透明でも、梨地でも、半梨地でもよく、ハウス、トンネル、マルチング用、袋掛用等の農業用ポリオレフィン系フィルム(いわゆる農ポリ等)の用途に好適に使用することができる。 The agricultural film of the present invention can be suitably used as an agricultural film because it can suppress a decrease in light transmittance and antifogging property due to bleeding out and the like while being excellent in ultraviolet shielding properties. In addition, the film of the present invention may be transparent, satin, or semi-pear, and is preferably used for applications of polyolefin films for agriculture (so-called farm poly etc.) for house, tunnel, mulching, bag hanging, etc. Can do.
以下、本発明を詳細に説明する。
本発明における農業用フィルムとは公知の合成樹脂を基材樹脂として使用した農業用フィルムであり、例えば、ポリエチレン、エチレン−酢酸ビニル共重合体、メタロセン触媒を用いて合成されたエチレン−α−オレフィン共重合体、ポリプロピレンなどのポリオレフィン系樹脂、塩化ビニル系樹脂、ポリエチレンテレフタレートなどのポリエステル系樹脂、ポリメチルメタクリレート樹脂、フッ素樹脂などからなるフィルムを用いることができる。本発明においては、特にポリオレフィン系樹脂を用いた多層フィルムで好適に効果を発揮する。
本発明に係るポリオレフィン系農業用フィルムとしては、少なくとも外層、中間層、内層を有する3層以上の積層構造を有するフィルムが好適に使用できる。ここで、外層とは、ハウスなどに展張した際に外側となる層をいい、内層とは、ハウス展張時に内側となる層をいい、中間層とは、その外層と内層に挟まれた層をいう。以下、外層と内層を合わせて表面層と称する場合もある。また、本発明の効果を損なわない範囲で、内層と中間層の間、外層と中間層の間に、更に樹脂層を積層したり、外層や中間層、内層など自体を2層で構成して、4層以上の多層フィルムとする態様も、本願発明の範囲に含まれる。その場合の中間層は、外層と内層以外(表面層以外)の層ということになる。
本発明における外層/中間層/内層の、層厚み比は特に限定されないが、たとえば、1/1/1〜1/5/1、好ましくは、1/2/1から1/3/1の層比で形成される。
なお、本発明で言う、外層、中間層、内層とは、農業用フィルムとして機能する樹脂主成分に他の成分を添加した樹脂組成物から構成される層を意味する。従って、後述するように、内層の内側に防曇特性を意図して薄く塗布する塗布型防曇塗膜や、外層の外側に、別途の目的で形成する場合の他の塗膜は、内層、外層の概念からは外して考えるものとする。
ポリオレフィン系樹脂としては、α−オレフィン系の単独重合体、α−オレフィンを主成分とする異種単量体との共重合体、α−オレフィンと共役ジエンまたは非共役ジエン等の多不飽和化合物、アクリル酸、メタクリル酸、酢酸ビニル等との共重合体などがあげられ、例えば高密度、低密度または直鎖状低密度ポリエチレン、ポリプロピレン、エチレン−プロピレン共重合体、エチレン−ブテン共重合体、エチレン−4−メチル−1−ペンテン共重合体、エチレン−酢酸ビニル共重合体、エチレン−アクリル酸共重合体等が挙げられる。これらのうち、密度が0.890〜0.935の低密度ポリエチレンやエチレン−α−オレフィン共重合体および酢酸ビニル含有量が30重量%以下のエチレン−酢酸ビニル共重合体が、透明性や耐候性および価格の点から農業用フィルムとして好ましい。
また、本発明において、ポリオレフィン系樹脂の少なくとも一成分としてメタロセン触媒で共重合して得られるエチレン−α−オレフィン共重合樹脂を使用することができる。
Hereinafter, the present invention will be described in detail.
The agricultural film in the present invention is an agricultural film using a known synthetic resin as a base resin, for example, an ethylene-α-olefin synthesized using polyethylene, an ethylene-vinyl acetate copolymer, a metallocene catalyst. A film made of a copolymer, a polyolefin resin such as polypropylene, a vinyl chloride resin, a polyester resin such as polyethylene terephthalate, a polymethyl methacrylate resin, or a fluororesin can be used. In the present invention, a multilayer film using a polyolefin resin is particularly effective.
As the polyolefin agricultural film according to the present invention, a film having a laminated structure of three or more layers having at least an outer layer, an intermediate layer and an inner layer can be suitably used. Here, the outer layer means a layer that becomes the outer side when it is extended to a house, the inner layer means a layer that becomes the inner side when the house is extended, and the intermediate layer means a layer sandwiched between the outer layer and the inner layer. Say. Hereinafter, the outer layer and the inner layer may be collectively referred to as a surface layer. Further, as long as the effects of the present invention are not impaired, a resin layer may be further laminated between the inner layer and the intermediate layer, or between the outer layer and the intermediate layer, or the outer layer, the intermediate layer, the inner layer, and the like may be composed of two layers. The aspect made into a multilayer film of four or more layers is also included in the scope of the present invention. In this case, the intermediate layer is a layer other than the outer layer and the inner layer (other than the surface layer).
The layer thickness ratio of the outer layer / intermediate layer / inner layer in the present invention is not particularly limited. For example, the layer is 1/1/1 to 1/5/1, preferably 1/2/1 to 1/3/1. Formed in ratio.
In addition, the outer layer, the intermediate | middle layer, and inner layer said by this invention mean the layer comprised from the resin composition which added the other component to the resin main component which functions as an agricultural film. Therefore, as will be described later, a coating-type antifogging coating that is thinly applied on the inside of the inner layer for the purpose of antifogging properties, and other coatings that are formed on the outside of the outer layer for other purposes, The concept of the outer layer will be excluded.
Examples of polyolefin resins include α-olefin homopolymers, copolymers of different monomers mainly containing α-olefins, polyunsaturated compounds such as α-olefins and conjugated dienes or nonconjugated dienes, Examples include copolymers with acrylic acid, methacrylic acid, vinyl acetate, and the like, such as high density, low density or linear low density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene. Examples include -4-methyl-1-pentene copolymer, ethylene-vinyl acetate copolymer, and ethylene-acrylic acid copolymer. Among these, low density polyethylene having a density of 0.890 to 0.935, ethylene-α-olefin copolymer, and ethylene-vinyl acetate copolymer having a vinyl acetate content of 30% by weight or less are transparent and weather resistant. It is preferable as an agricultural film from the viewpoint of properties and price.
In the present invention, an ethylene-α-olefin copolymer resin obtained by copolymerization with a metallocene catalyst can be used as at least one component of the polyolefin resin.
これは、通常、メタロセンポリエチレンといわれているものであり、エチレンとブテン−1、ヘキセン−1、4−メチルペンテン−1、オクテンなどのα−オレフィンとの共重合体である。 This is usually referred to as metallocene polyethylene, and is a copolymer of ethylene and an α-olefin such as butene-1, hexene-1, 4-methylpentene-1, octene.
本発明のポリオレフィン系樹脂の少なくとも一成分として使用されるエチレン−α−オレフィン共重合体は、好ましくは以下の物性を示すものである。
メルトフローレート(MFR)
JIS−K7210により測定されたMFRが0.01〜10g/10分、好ましくは0.1〜5g/10分の値を示すものである。該MFRがこの範囲より大きいと成形時にフィルムが蛇行し安定しない。また、該MFRがこの範囲より小さすぎると成形時の樹脂圧力が増大し、成形機に負荷がかかるため、生産量を減少させて圧力の増大を抑制しなければならず、実用性に乏しい。
The ethylene-α-olefin copolymer used as at least one component of the polyolefin resin of the present invention preferably exhibits the following physical properties.
Melt flow rate (MFR)
The MFR measured according to JIS-K7210 is 0.01 to 10 g / 10 min, preferably 0.1 to 5 g / 10 min. If the MFR is larger than this range, the film meanders during molding and is not stable. On the other hand, if the MFR is too smaller than this range, the resin pressure at the time of molding increases and a load is applied to the molding machine. Therefore, the increase in pressure must be suppressed by reducing the production amount, which is not practical.
密度
JIS−K7112により測定された密度が0.880〜0.930g/cm3、好ましくは0.880〜0.920g/cm3の値を示すものである。該密度がこの範囲より大きいと透明性が悪化する。また、密度がこの範囲より小さいと、フィルム表面のべたつきによりブロッキングが生じ実用性に乏しくなる。
Density The density measured by JIS-K7112 is 0.880 to 0.930 g / cm3, preferably 0.880 to 0.920 g / cm3. When the density is larger than this range, the transparency is deteriorated. On the other hand, if the density is smaller than this range, blocking occurs due to stickiness of the film surface, resulting in poor practicality.
分子量分布
ゲルパーミュレーションクロマトグラフィー(GPC)によって求められる分子量分布(重量平均分子量/数平均分子量)は1.5〜3.5、好ましくは1.5〜3.0の値を示すものである。該分子量分布がこの範囲より大きいと機械的強度が低下し好ましくない。該分子量分布がこの範囲より小さいと成形時にフィルムが蛇行し安定しない。
Molecular weight distribution The molecular weight distribution (weight average molecular weight / number average molecular weight) determined by gel permeation chromatography (GPC) is 1.5 to 3.5, preferably 1.5 to 3.0. . When the molecular weight distribution is larger than this range, the mechanical strength is lowered, which is not preferable. If the molecular weight distribution is smaller than this range, the film meanders during molding and is not stable.
本発明で用いられるエチレン−酢酸ビニル共重合体樹脂は、酢酸ビニル含有量が3〜25重量%の範囲が好ましく、更に好ましくは5〜20重量%の範囲である。酢酸ビニル含有量がこの範囲より小さいと、得られるフィルムが硬くなりハウスへの展張時にシワや弛みが出来やすく、防曇性に悪影響が出るため実用性に乏しく、また、酢酸ビニル含有量がこの範囲より大きいと、樹脂の融点が低いためハウス展張時に夏場の高温下でフィルムが弛み、風でばたつきハウス構造体との擦れ等により破れが生じやすくなるため実用性に乏しい。 The ethylene-vinyl acetate copolymer resin used in the present invention preferably has a vinyl acetate content of 3 to 25% by weight, more preferably 5 to 20% by weight. If the vinyl acetate content is less than this range, the resulting film will be hard and will tend to wrinkle and sag when stretched in a house, which will have a negative effect on anti-fogging properties. If it is larger than the range, the melting point of the resin is low, so that the film loosens at high temperatures in summer during house extension, and is easily broken by wind and flapping with the house structure.
本発明における農業用フィルムは、下記式(1)又は(2)に記載のベンゾトリアゾール型紫外線吸収剤を含有することにより優れた紫外線吸収特性を得ることができる。
本発明における農業用フィルムは、上記のベンゾトリアゾール型紫外線吸収剤を使用することにより、300nm〜380nmの紫外線を実質的に完全に遮蔽することができる(実質的に完全に遮蔽:未使用の農業用フィルムの状態で300〜380nmにおいて1nmごとに測定した全光線透過率の平均値が2%未満)。 The agricultural film in the present invention can substantially completely shield ultraviolet rays of 300 nm to 380 nm by using the above-described benzotriazole type ultraviolet absorber (substantially completely shielded: unused agriculture). The average value of the total light transmittance measured every 1 nm at 300 to 380 nm in the state of the film for use is less than 2%).
本発明における農業用フィルムは、上記一般式(1)又は(2)に記載のベンゾトリアゾール型紫外線吸収剤に加えて、下記一般式(3)に記載のトリアリールトリアジン型紫外線吸収剤を含有することにより、フィルムとして良好な紫外線吸収能を付与できるばかりでなく、トリアリールトリアジン型紫外線吸収剤が有する良好な堅牢性(強い紫外線に対して耐える性能)から、着色防止や紫外線カット持続性を高いレベルで付与することが可能となる。
特に、前記式(3)におけるR1がヘキシル基であり、R2〜R5が水素原子である場合や、前記式(3)におけるR1がオクチル基であり、R2〜R5がメチル基である場合に、性能とコストのバランスが取れる為に好ましい。 In particular, when R1 in the formula (3) is a hexyl group and R2 to R5 are hydrogen atoms, or R1 in the formula (3) is an octyl group and R2 to R5 are methyl groups, It is preferable because it can balance performance and cost.
本発明における農業用フィルムは、求める効果に影響を与えない範囲で、公知の紫外線吸収剤を併用することが出来る。これらの紫外線吸収剤は、一種又は二種以上を本発明の効果を妨げない範囲で、本願に係る紫外線吸収剤に併用して用いることが出来る。また、酸化亜鉛、酸化セリウム等の金属酸化物を始めとする無機酸化物系紫外線吸収剤を併用することも出来る。 The agricultural film in this invention can use a well-known ultraviolet absorber together in the range which does not affect the calculated | required effect. These ultraviolet absorbers can be used in combination with the ultraviolet absorber according to the present application as long as they do not interfere with the effects of the present invention. Moreover, inorganic oxide type ultraviolet absorbers including metal oxides such as zinc oxide and cerium oxide can be used in combination.
他に併用可能な紫外線吸収剤としては、例えば、2,4−ジヒドロキシベンゾフェノン、2−ヒドロキシ−4−メトキシベンゾフェノン、2−ヒドロキシ−4−オクトキシベンゾフェノン、5,5’−メチレンビス(2−ヒドロキシ−4−メトキシベンゾフェノン)等の2−ヒドロキシベンゾフェノン類;2−(2’−ヒドロキシ−5’−メチルフェニル)ベンゾトリアゾール、2−(2’−ヒドロキシ−3’,5’−ジ第三ブチルフェニル)ベンゾトリアゾール、2−(2’−ヒドロキシ−3’,5’−ジ第三ブチルフェニル)−5−クロロベンゾトリアゾール、2−(2’−ヒドロキシ−3’−第三ブチル−5’−メチルフェニル)−5−クロロベンゾトリアゾール、2−(2’−ヒドロキシ−5’−第三オクチルフェニル)ベンゾトリアゾール、2−(2’−ヒドロキシ−3’.5’−ジクミルフェニル)ベンゾトリアゾール、2,2’−メチレンビス(4−第三オクチル−6−ベンゾトリアゾリル)フェノール等の2−(2’−ヒドロキシフェニル)ベンゾトリアゾール類;フェニルサリシレート、レゾルシノールモノベンゾエート、2,4−ジ第三ブチルフェニル−3’,5’−ジ第三ブチル−4’−ヒドロキシベンゾエート、2,4−ジ第三アミルフェニル−3’,5’−ジ第三ブチル−4’−ヒドロキシベンゾエート、ヘキサデシル−3,5−ジ第三ブチル−4−ヒドロキシベンゾエート等のベンゾエート類;2−エチル−2’−エトキシオキザニリド、2−エトキシ−4’−ドデシルオキザニリド等の置換オキザニリド類;エチル−α−シアノ−β,β−ジフェニルアクリレート、メチル−2−シアノ−3−メチル−3−(p−メトキシフェニル)アクリレート等のシアノアクリレート類等があげられる。 Examples of other UV absorbers that can be used in combination include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5,5′-methylenebis (2-hydroxy- 2-hydroxybenzophenones such as 4-methoxybenzophenone); 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-ditert-butylphenyl) Benzotriazole, 2- (2′-hydroxy-3 ′, 5′-ditert-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) ) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-tert-octylphenyl) benzotri 2- (2) such as sol, 2- (2′-hydroxy-3′.5′-dicumylphenyl) benzotriazole, 2,2′-methylenebis (4-tert-octyl-6-benzotriazolyl) phenol '-Hydroxyphenyl) benzotriazoles; phenyl salicylate, resorcinol monobenzoate, 2,4-ditertiarybutylphenyl-3', 5'-ditertiarybutyl-4'-hydroxybenzoate, 2,4-ditertiary Benzoates such as amylphenyl-3 ′, 5′-ditert-butyl-4′-hydroxybenzoate, hexadecyl-3,5-ditert-butyl-4-hydroxybenzoate; 2-ethyl-2′-ethoxyoxani Substituted oxanilides such as Lido, 2-ethoxy-4′-dodecyloxanilide; ethyl-α-cyano-β, β-diphenyl Acrylate, cyanoacrylate such as methyl 2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate.
本発明の農業用フィルム中の、紫外線吸収剤の含有量は、各々、全フィルム(積層フィルムの場合は各層の合計)に対し5重量%未満、好ましくは0.1〜3重量%、更に好ましくは0.2〜1.5重量%である。含有量が上記範囲未満では紫外線遮蔽効果が低く、上記範囲を超えるとコスト的に不利になる上に一般的な農業用フィルムに適応した場合、ブリードアウトによる白化等で問題がある。これらの含有量は、樹脂の種類及び紫外線吸収剤の種類の選択で決まる値となる。 The content of the ultraviolet absorber in the agricultural film of the present invention is less than 5% by weight, preferably 0.1 to 3% by weight, more preferably, based on the total film (total of each layer in the case of a laminated film). Is 0.2 to 1.5% by weight. When the content is less than the above range, the ultraviolet ray shielding effect is low. When the content exceeds the above range, the cost is disadvantageous, and when it is applied to a general agricultural film, there is a problem in whitening due to bleeding out. These contents are values determined by selection of the type of resin and the type of ultraviolet absorber.
本発明においては、一般式(1)又は(2)に記載のベンゾトリアゾール型紫外線吸収剤は、これを含有する農業用フィルムにおいて、300nm〜380nmの領域の紫外線を実質的に完全に遮蔽する量以上添加されることが好ましい。実質的に完全に遮蔽するとは、未使用の農業用フィルムの状態で、300〜380nmにおいて1nmごとに全光線透過率を測定したときに、各波長における透過率の平均値が、2%未満になるということである。更に、上記透過率の平均値が1%以下であると好ましく、紫外線遮蔽による効果を得られやすい。 In the present invention, the benzotriazole type ultraviolet absorber described in the general formula (1) or (2) is an amount that substantially completely blocks ultraviolet rays in the region of 300 nm to 380 nm in an agricultural film containing the benzotriazole type ultraviolet absorber. It is preferable to add more. The term “substantially completely shielded” means that when the total light transmittance is measured every 1 nm at 300 to 380 nm in the state of an unused agricultural film, the average value of the transmittance at each wavelength is less than 2%. That is. Furthermore, the average value of the transmittance is preferably 1% or less, and an effect of ultraviolet shielding is easily obtained.
本発明の農業用フィルムは、単層であっても多層であってもよい。本発明の農業用フィルムが多層フィルムである場合は、一般式(1)又は(2)に記載のベンゾトリアゾール型紫外線吸収剤をいずれの層に含有してもよい。また、本発明においては、一般式(3)に記載のトリアリールトリアジン型紫外線吸収剤や他の紫外線吸収剤を添加する場合は、これら紫外線吸収剤を多層フィルムのいずれの層に含有させてもよい。本発明においては、特に、特開2003−61483記載のように、中間層の単位体積当たりの樹脂組成物に対する紫外線吸収剤(2種以上の場合はそれらの合計)含有率(重量%)をX、内層中の単位体積当たりの紫外線吸収剤含有率(重量%)をY、外層中の単位体積当たりの紫外線吸収剤含有率(重量%)をZとしたとき、X>Y、かつX>Zである多層フィルムにすると、長期にわたり紫外線吸収能を保持できる効果が顕著であるため好ましい。例えば、多層フィルムの表面層以外(ハウス内層、ハウス外層以外:中間層とする)に紫外線吸収剤を添加する方法もある。
ここで、Y及びZはY=Zであっても、異なっていてもよい。また、特に好ましい態様としては、Y=Z=0である場合が挙げられる。
具体的には、中間層中の樹脂組成物に対する紫外線吸収剤含有率であるXとしては、0.1〜3.0重量%、好ましくは0.15〜2.0重量%、更に好ましくは0.2〜1.0重量%の範囲が挙げられる。YおよびZとしては、0〜2.0重量%、好ましくは0または、0.001〜0.5重量%の範囲が挙げられる。
更に本発明の好ましい態様としては、少なくとも外層、中間層、内層を有する3層以上の積層構造を有する農業用ポリオレフィン系多層フィルムであって、外層および内層(表面層)には紫外線吸収剤を配合せず、中間層に紫外線吸収剤を配合してなることを特徴とする農業用ポリオレフィン系多層フィルムが挙げられる。
The agricultural film of the present invention may be a single layer or a multilayer. When the agricultural film of the present invention is a multilayer film, the benzotriazole type ultraviolet absorber described in the general formula (1) or (2) may be contained in any layer. Moreover, in this invention, when adding the triaryl triazine type | mold ultraviolet absorber and other ultraviolet absorber as described in General formula (3), these ultraviolet absorbers may be contained in any layer of a multilayer film. Good. In the present invention, in particular, as described in JP-A No. 2003-61483, the content (% by weight) of the ultraviolet absorber (the total of two or more types) per unit volume of the intermediate layer is X X> Y and X> Z, where Y is the UV absorber content (% by weight) per unit volume in the inner layer and Z is the UV absorber content (% by weight) per unit volume in the outer layer A multilayer film is preferable because the effect of maintaining the ultraviolet absorbing ability over a long period is remarkable. For example, there is a method in which an ultraviolet absorber is added to other than the surface layer of the multilayer film (other than the house inner layer and the house outer layer: an intermediate layer).
Here, Y and Z may be Y = Z or may be different. A particularly preferred embodiment is the case where Y = Z = 0.
Specifically, X, which is the content of the ultraviolet absorber with respect to the resin composition in the intermediate layer, is 0.1 to 3.0% by weight, preferably 0.15 to 2.0% by weight, and more preferably 0. The range of 2 to 1.0% by weight is mentioned. Y and Z include 0 to 2.0% by weight, preferably 0 or 0.001 to 0.5% by weight.
Furthermore, as a preferred embodiment of the present invention, there is an agricultural polyolefin multilayer film having a laminated structure of at least three layers having at least an outer layer, an intermediate layer, and an inner layer, and an ultraviolet absorber is blended in the outer layer and the inner layer (surface layer). Without mentioning, an agricultural polyolefin-based multilayer film characterized in that an ultraviolet absorber is blended in the intermediate layer.
本発明の農業用フィルムには赤外線吸収剤(保温剤)を含有させることが出来る。特にポリオレフィン系多層フィルムには、少なくとも3層以上を有する多層フィルムの少なくとも一層にその構成成分としてSi,Al,Mg,Ca,Liから選ばれた少なくとも1つの原子を含有する無機化合物を含有させることで、良好な保温性を付与することが出来る。添加量の目安としては、フィルム全層中に換算した場合で3%程度以上含有させた場合に良好な赤外線吸収効果(保温性)を付与することが出来る。使用できる無機化合物として、例えば赤外線吸収剤(保温剤)や充填剤として公知のものを挙げることが出来る。この様な無機化合物の添加量が少ない場合、保温性を付与することが出来ず、過剰な場合、透明性を阻害する為、農業用フィルムとしての必要な性能を具備することが難しい。 The agricultural film of the present invention can contain an infrared absorber (heat retention agent). In particular, the polyolefin-based multilayer film contains an inorganic compound containing at least one atom selected from Si, Al, Mg, Ca, and Li as at least one layer of the multilayer film having at least three layers. Thus, good heat retention can be imparted. As a measure of the amount added, a good infrared absorption effect (heat retention) can be imparted when it is contained in about 3% or more in terms of the total film thickness. As an inorganic compound which can be used, a well-known thing can be mentioned, for example as an infrared absorber (heat retention agent) and a filler. When such an inorganic compound is added in a small amount, heat retention cannot be imparted, and when it is excessive, transparency is hindered, making it difficult to provide the necessary performance as an agricultural film.
赤外線吸収剤(保温剤)は、赤外線吸収能を有する無機微粒子であり、これらは一種又は二種以上で組み合わせて用いることができる。用いることの出来る無機微粒子は特に制限はないが、成分:Si,Al,Mg,Ca,Li から選ばれた少なくとも1つの原子を含有する無機化合物である。例えば、酸化マグネシウム、酸化カルシウム、酸化アルミニウム、酸化珪素、水酸化リチウム、水酸化マグネシウム、水酸化カルシウム、水酸化アルミニウム、炭酸マグネシウム、炭酸カルシウム、硫酸カルシウム、硫酸マグネシウム、硫酸アルミニウム、燐酸リチウム、燐酸カルシウム、珪酸マグネシウム、珪酸カルシウム、珪酸アルミニウム、アルミン酸カルシウム、アルミン酸マグネシウム、アルミノ珪酸ナトリウム、アルミノ珪酸カリウム、アルミノ珪酸カルシウム、カオリン、クレー、タルク、マイカ、ゼオライト、ハイドロタルサイト類化合物、リチウム・アルミニウム複合水酸化物、アルミニウム・リチウム・マグネシウム複合炭酸塩化合物、アルミニウム・リチウム・マグネシウム複合珪酸塩化合物、マグネシウム・アルミニウム・珪素複合水酸化物、マグネシウム・アルミニウム・珪素複合硫酸塩化合物、マグネシウム・アルミニウム・珪素複合炭酸塩化合物、複数種アニオンを含有する金属複合水酸化物塩等が挙げられる。これらは結晶水を脱水したものであってもよい。 The infrared absorbent (heat retention agent) is inorganic fine particles having infrared absorbing ability, and these can be used alone or in combination of two or more. The inorganic fine particles that can be used are not particularly limited, but are inorganic compounds containing at least one atom selected from the components: Si, Al, Mg, Ca, Li. For example, magnesium oxide, calcium oxide, aluminum oxide, silicon oxide, lithium hydroxide, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, magnesium carbonate, calcium carbonate, calcium sulfate, magnesium sulfate, aluminum sulfate, lithium phosphate, calcium phosphate , Magnesium silicate, calcium silicate, aluminum silicate, calcium aluminate, magnesium aluminate, sodium aluminosilicate, potassium aluminosilicate, calcium aluminosilicate, kaolin, clay, talc, mica, zeolite, hydrotalcite compound, lithium aluminum composite Hydroxides, aluminum / lithium / magnesium composite carbonate compounds, aluminum / lithium / magnesium composite silicate compounds, magnesium / aluminum Um silicon composite hydroxide, magnesium aluminum silicon composite sulfate compounds, magnesium aluminum silicon composite carbonate compound, a metal complex hydroxide salt containing more anions. These may be obtained by dehydrating crystal water.
上記赤外線吸収剤(保温剤)として用いる無機微粒子は天然物であってもよく、また合成品であってもよい。また、上記無機微粒子は、その結晶構造、結晶粒子径などに制限されることなく使用することが可能である。 The inorganic fine particles used as the infrared absorber (heat retention agent) may be natural products or synthetic products. The inorganic fine particles can be used without being limited by the crystal structure, crystal particle diameter, and the like.
また、上記赤外線吸収剤(保温剤)として用いる無機微粒子は、その表面をステアリン酸のごとき高級脂肪酸、オレイン酸アルカリ金属塩のごとき高級脂肪酸金属塩、ドデシルベンゼンスルホン酸アルカリ金属塩のごとき有機スルホン酸金属塩、高級脂肪酸アミド、高級脂肪酸エステルまたはワックスなどで被覆したものも使用できる。 The inorganic fine particles used as the infrared absorbing agent (heat retention agent) have a surface having a higher fatty acid such as stearic acid, a higher fatty acid metal salt such as an alkali metal oleate, or an organic sulfonic acid such as an alkali metal dodecylbenzenesulfonate. Those coated with metal salts, higher fatty acid amides, higher fatty acid esters or waxes can also be used.
上記赤外線吸収剤(保温剤)として用いる無機微粒子は、単独または2種以上組み合わせて使用することが出来る。その平均粒子径は好ましくは、0.05〜15μm、より好ましくは0.1〜10μmの範囲である。無機微粒子の平均粒子径が上記範囲より小さいと、樹脂中での分散性が劣りブツ(無機物の2次凝集物)が生成してフィルム外観が悪化すると共に、樹脂との混練時の粉立ちが激しくハンドリング性が劣る。逆に、無機微粒子の平均粒子径が上記範囲より大きいと、透明性で劣ったり押出し機ブレーカースクリーン部で目詰まりが生じ、生産性が悪化する。 The inorganic fine particles used as the infrared absorber (heat retention agent) can be used alone or in combination of two or more. The average particle diameter is preferably in the range of 0.05 to 15 μm, more preferably 0.1 to 10 μm. If the average particle size of the inorganic fine particles is smaller than the above range, the dispersibility in the resin is inferior, and the appearance of the film is deteriorated and the appearance of the film is deteriorated. The handling is severely inferior. On the other hand, if the average particle size of the inorganic fine particles is larger than the above range, the transparency is inferior or clogging occurs in the extruder breaker screen, and the productivity deteriorates.
上記赤外線吸収剤(保温剤)の使用量は、フィルム全層中に、3〜30重量部、より好ましくは3〜20重量部、更に好ましくは3〜15重量部である。3重量部未満では、充分に赤外線を吸収することはできず、30重量部を超える範囲では農業用フィルムとしての透明性及び機械的強度が劣る上、コスト的に不利である。 The usage-amount of the said infrared absorber (heat retention agent) is 3-30 weight part in a film whole layer, More preferably, it is 3-20 weight part, More preferably, it is 3-15 weight part. If it is less than 3 parts by weight, infrared rays cannot be absorbed sufficiently, and if it exceeds 30 parts by weight, transparency and mechanical strength as an agricultural film are inferior and disadvantageous in cost.
また、充てん剤としては、フィルムのベタツキを抑制するために、あるいは保温性をさらに高めるために、例えばシリカ、タルク、水酸化アルミニウム、ハイドロタルサイト、硫酸カルシウム、ケイ酸カルシウム、水酸化カルシウム、水酸化マグネシウム、カオリンクレー、マイカ、アルミナ、炭酸マグネシウム、アルミン酸ナトリウム、導電性酸化亜鉛、リン酸リチウムなどが用いられる。これらの充てん剤は1種用いてもよいし、2種以上を組み合わせて用いてもよい。 In addition, as a filler, for example, silica, talc, aluminum hydroxide, hydrotalcite, calcium sulfate, calcium silicate, calcium hydroxide, water, in order to suppress stickiness of the film or to further improve heat retention Magnesium oxide, kaolin clay, mica, alumina, magnesium carbonate, sodium aluminate, conductive zinc oxide, lithium phosphate and the like are used. One type of these fillers may be used, or two or more types may be used in combination.
本発明の農業用フィルム、特に農業用ポリオレフィン系多層フィルムにおいては、耐候剤としてヒンダードアミン化合物を多層フィルム中の少なくとも1層に添加することが出来る。また、このヒンダードアミン化合物は、一種又は二種以上組み合わせて用いることができる。ヒンダードアミン化合物は、もちろん全層に同じ種類を含有させてもよいが、例えば最内層と最外層(ハウス外面)にブリードアウトしにくい高分子量タイプを含有させ、その他の層には農業用として通常配合されるヒンダードアミン化合物を含有させることもできる。また、これら高分子量ヒンダードアミン化合物は、エチレンやその他モノマーとの共重合タイプ(例えばエチレン・環状アミノビニル化合物共重合体)でも構わないし、ポリエチレンを始めとするポリマーにグラフト付加させたものでも構わない。その場合、例えば同一の層にエチレン・環状アミノビニル化合物共重合体と農業用として通常配合されるヒンダードアミン系光安定剤を含有させることもできる。 In the agricultural film of the present invention, particularly an agricultural polyolefin-based multilayer film, a hindered amine compound can be added as a weathering agent to at least one layer in the multilayer film. Moreover, this hindered amine compound can be used 1 type or in combination of 2 or more types. Of course, the same type may be included in all layers of the hindered amine compound. For example, the innermost layer and the outermost layer (outer surface of the house) contain a high molecular weight type that does not bleed out, and the other layers are usually formulated for agriculture. The hindered amine compound to be used can also be contained. These high molecular weight hindered amine compounds may be copolymerized with ethylene or other monomers (for example, ethylene / cyclic aminovinyl compound copolymer), or may be grafted onto polymers such as polyethylene. In that case, for example, the same layer may contain an ethylene / cyclic aminovinyl compound copolymer and a hindered amine light stabilizer usually blended for agriculture.
使用可能な農業用として通常配合されるヒンダードアミン系光耐候剤は、公知のピペリジンン環含有ヒンダードアミン化合物を使用することが出来る。上記ピペリジン環含有ヒンダードアミン化合物のピペリジン環の数が2個未満では十分な耐候性が得られにくく、また、分子量が500未満では揮発しやすくなり、長期の耐候性を得ることが難しい可能性がある。また、上記ピペリジン環含有ヒンダードアミン化合物のピペリジン環の数は2〜50個であることが好ましく、また、分子量は750以上であることが好ましい。 A known hindered amine compound containing a piperidine ring can be used as the hindered amine light weathering agent usually blended for use in agriculture. If the number of piperidine rings in the piperidine ring-containing hindered amine compound is less than 2, sufficient weather resistance is difficult to obtain, and if the molecular weight is less than 500, volatilization is likely to occur and it may be difficult to obtain long-term weather resistance. . The number of piperidine rings in the piperidine ring-containing hindered amine compound is preferably 2 to 50, and the molecular weight is preferably 750 or more.
上記ピペリジン環含有ヒンダードアミン化合物としては、例えば、ビス(1,2,2,6,6−ペンタメチル−4−ピペリジル)−2−ブチル−2−(3,5−ジ第三ブチル−4−ヒドロキシベンジル)マロネート、テトラ(2,2,6,6−テトラメチル−4−ピペリジル)ブタンテトラカルボキシレート、テトラ(1,2,2,6,6−ペンタメチル−4−ピペリジル)ブタンテトラカルボキシレート、ビス(2,2,6,6−テトラメチル−4−ピペリジル)・ジ(トリデシル)ブタンテトラカルボキシレート、ビス(1,2,2,6,6−ペンタメチル−4−ピペリジル)・ジ(トリデシル)ブタンテトラカルボキシレート、3,9−ビス〔1,1−ジメチル−2−{トリス(2,2,6,6−テトラメチル−4−ピペリジルオキシカルボニルオキシ)ブチルカルボニルオキシ}エチル〕−2,4,8,10−テトラオキサスピロ〔5.5〕ウンデカン、3,9−ビス〔1,1−ジメチル−2−{トリス(1,2,2,6,6−ペンタメチル−4−ピペリジルオキシカルボニルオキシ)ブチルカルボニルオキシ}エチル〕−2,4,8,10−テトラオキサスピロ〔5.5〕ウンデカン、1,5,8,12−テトラキス〔4,6−ビス{N−(2,2,6,6−テトラメチル−4−ピペリジル)ブチルアミノ}−1,3,5−トリアジン−2−イル〕−1,5,8,12−テトラアザドデカン、1−(2−ヒドロキシエチル)−2,2,6,6−テトラメチル−4−ピペリジノール/コハク酸ジメチル縮合物、2−第三オクチルアミノ−4,6−ジクロロ−s−トリアジン/N,N’−ビス(2,2,6,6−テトラメチル−4−ピペリジル)ヘキサメチレンジアミン縮合物、N,N’−ビス(2,2,6,6−テトラメチル−4−ピペリジル)ヘキサメチレンジアミン/ジブロモエタン縮合物などがあげられる。使用可能な市販のヒンダードアミン系化合物を例示すれば、TINUVIN770、TINUVIN780、TINUVIN144、TINUVIN622LD、TINUVIN NOR 371FF、CHIMASSORB119FL、CHIMASSORB944(以上、チバ社製)、サノールLS−765(三共(株)製)、MARK LA−63、MARK LA−68、MARK LA−68、MARK LA−62、MARK LA−67、MARK LA−57、LA−900(以上、旭電化(株)製)、UV−3346、UV−3529、UV−3581、UV−3853(以上、サイテック社製)、ホスタビンN20、ホスタビンN24、ホスタビンN30、ホスタビン845、サンデュボアPR−31、ナイロスタッブS−EED(以上、クラリアント・ジャパン社製)、UVINUL5050H(以上、BASFジャパン社製)、XJ100H(日本ポリエチレン(株))等が挙げられる。これらのピペリジン環含有ヒンダードアミン化合物は、一種又は二種以上で用いられる。 Examples of the piperidine ring-containing hindered amine compound include bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-ditert-butyl-4-hydroxybenzyl). ) Malonate, tetra (2,2,6,6-tetramethyl-4-piperidyl) butanetetracarboxylate, tetra (1,2,2,6,6-pentamethyl-4-piperidyl) butanetetracarboxylate, bis ( 2,2,6,6-tetramethyl-4-piperidyl) .di (tridecyl) butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) .di (tridecyl) butanetetra Carboxylate, 3,9-bis [1,1-dimethyl-2- {tris (2,2,6,6-tetramethyl-4-piperidyloxy Rubonyloxy) butylcarbonyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [1,1-dimethyl-2- {tris (1,2,2) , 6,6-pentamethyl-4-piperidyloxycarbonyloxy) butylcarbonyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 1,5,8,12-tetrakis [4 , 6-Bis {N- (2,2,6,6-tetramethyl-4-piperidyl) butylamino} -1,3,5-triazin-2-yl] -1,5,8,12-tetraaza Dodecane, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / dimethyl succinate condensate, 2-tert-octylamino-4,6-dichloro-s-triazine N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine condensate, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) And hexamethylenediamine / dibromoethane condensate. Examples of commercially available hindered amine compounds that can be used are TINUVIN 770, TINUVIN 780, TINUVIN 144, TINUVIN 622LD, TINUVIN NOR 371FF, CHIMASSORB 119FL, CHIMASSORB 944 (above, manufactured by Ciba), Sanol LS-765 (Sankyo R Co., Ltd.) -63, MARK LA-68, MARK LA-68, MARK LA-62, MARK LA-67, MARK LA-57, LA-900 (manufactured by Asahi Denka Co., Ltd.), UV-3346, UV-3529, UV-3581, UV-3853 (above, manufactured by Cytec), Hostabin N20, Hostabin N24, Hostabin N30, Hostabin 845, Sanduboa PR-31, Nyrostub SE Examples thereof include ED (manufactured by Clariant Japan), UVINUL5050H (manufactured by BASF Japan), and XJ100H (Nippon Polyethylene Co., Ltd.). These piperidine ring-containing hindered amine compounds are used alone or in combination of two or more.
また、本発明の農業用フィルム中には、通常合成樹脂に使用される各種添加剤を併用することができる。それらの添加剤としては、例えば、金属の有機酸塩、塩基性有機酸塩および過塩基性有機酸塩、ハイドロタルサイト系化合物、エポキシ化合物、β−ジケトン化合物、多価アルコール、ハロゲン酸素酸塩、硫黄系、フェノール系およびホスファイト系などの酸化防止剤、熱安定剤、滑剤、帯電防止剤、着色剤、アンチブロッキング剤、防曇剤、防霧剤などがあげられる。 Moreover, in the agricultural film of this invention, the various additives normally used for a synthetic resin can be used together. Examples of these additives include metal organic acid salts, basic organic acid salts and overbased organic acid salts, hydrotalcite compounds, epoxy compounds, β-diketone compounds, polyhydric alcohols, and halogen oxyacid salts. Sulfur-based, phenol-based and phosphite-based antioxidants, heat stabilizers, lubricants, antistatic agents, colorants, antiblocking agents, antifogging agents, antifogging agents, and the like.
上記の金属の有機酸塩、塩基性有機酸塩および過塩基性有機酸塩を構成する金属種としては、Li,Na,K,Ca,Ba,Mg,Sr,Zn,Cd,Sn,Cs,Al,有機Snがあげられ、有機酸としては、カルボン酸、有機リン酸類またはフェノール類があげられ、該カルボン酸としては、例えば、酢酸、プロピオン酸、酪酸、吉草酸、カプロン酸、エナント酸、カプリル酸、ネオデカン酸、2−エチルヘキシル酸、ペラルゴン酸、カプリン酸、ウンデカン酸、ラウリン酸、トリデカン酸、ミリスチン酸、パルミチン酸、イソステアリン酸、ステアリン酸、12−ヒドロキシステアリン酸、ベヘニン酸、モンタン酸、エライジン酸、オレイン酸、リノール酸、リノレン酸、チオグリコール酸、メルカプトプロピオン酸、オクチルメルカプトプロピオン酸、安息香酸、モノクロル安息香酸、p−第三ブチル安息香酸、ジメチルヒドロキシ安息香酸、3,5−ジ第三ブチル−4−ヒドロキシ安息香酸、トルイル酸、ジメチル安息香酸、エチル安息香酸、クミン酸、n−プロピル安息香酸、アセトキシ安息香酸、サリチル酸、p−第三オクチルサリチル酸等の一価カルボン酸、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバチン酸、マレイン酸、フマール酸、シトラコン酸、メタコン酸、イタコン酸、アコニット酸、チオジプロピオン酸、フタル酸、イソフタル酸、テレフタル酸、オキシフタル酸、クロルフタル酸等の二価のカルボン酸あるいはこれらのモノエステル又はモノアマイド化合物、ブタントリカルボン酸、ブタンテトラカルボン酸、ヘミメリット酸、トリメリット酸、メロファン酸、ピロメリット酸等の三価又は四価カルボン酸のジ又はトリエステル化合物などがあげられ、また該有機リン酸類としては、モノまたはジオクチルリン酸、モノまたはジドデシルリン酸、モノまたはジオクタデシルリン酸、モノまたはジ−(ノニルフェニル)リン酸、ホスホン酸ノニルフェニルエステル、ホスホン酸ステアリルエステルなどがあげられ、また該フェノール類としては、フェノール、クレゾール、キシレノール、メチルプロピルフェノール、メチル第三オクチルフェノール、エチルフェノール、イソプロピルフェノール、第三ブチルフェノール、n−ブチルフェノール、ジイソブチルフェノール、イソアミルフェノール、ジアミルフェノール、イソヘキシルフェノール、オクチルフェノール、イソオクチルフェノール、2−エチルヘキシルフェノール、第三オクチルフェノール、ノニルフェノール、ジノニルフェノール、第三ノニルフェノール、デシルフェノール、ドデシルフェノール、オクタデシルフェノール、シクロヘキシルフェノール、フェニルフェノールフェノール、クレゾール、エチルフェノール、シクロヘキシルフェノール、ノニルフェノール、ドデシルフェノールなどがあげられる。 Examples of the metal species constituting the organic acid salt, basic organic acid salt and overbased organic acid salt of the metal include Li, Na, K, Ca, Ba, Mg, Sr, Zn, Cd, Sn, Cs, Examples of the organic acid include carboxylic acid, organic phosphoric acid, and phenol. Examples of the carboxylic acid include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, Caprylic acid, neodecanoic acid, 2-ethylhexylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, isostearic acid, stearic acid, 12-hydroxystearic acid, behenic acid, montanic acid, Elaidic acid, oleic acid, linoleic acid, linolenic acid, thioglycolic acid, mercaptopropionic acid, octyl mercapto Lopionic acid, benzoic acid, monochlorobenzoic acid, p-tert-butylbenzoic acid, dimethylhydroxybenzoic acid, 3,5-ditert-butyl-4-hydroxybenzoic acid, toluic acid, dimethylbenzoic acid, ethylbenzoic acid, cumin Acids, n-propylbenzoic acid, acetoxybenzoic acid, salicylic acid, p-tertiary octylsalicylic acid and other monovalent carboxylic acids, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid , Divalent carboxylic acids such as sebacic acid, maleic acid, fumaric acid, citraconic acid, metaconic acid, itaconic acid, aconitic acid, thiodipropionic acid, phthalic acid, isophthalic acid, terephthalic acid, oxyphthalic acid, chlorophthalic acid, etc. Monoester or monoamide compound, butanetricarboxylic acid, butane Examples thereof include di- or triester compounds of trivalent or tetravalent carboxylic acids such as tracarboxylic acid, hemimellitic acid, trimellitic acid, merophanic acid, and pyromellitic acid, and examples of the organic phosphoric acid include mono- or dioctylphosphoric acid. Acid, mono or didodecyl phosphoric acid, mono or dioctadecyl phosphoric acid, mono or di- (nonylphenyl) phosphoric acid, phosphonic acid nonylphenyl ester, phosphonic acid stearyl ester, etc., and the phenols include phenol, cresol , Xylenol, methylpropylphenol, methyl tertiary octylphenol, ethylphenol, isopropylphenol, tertiary butylphenol, n-butylphenol, diisobutylphenol, isoamylphenol, diamylphenol, isohexylphenol Enol, octylphenol, isooctylphenol, 2-ethylhexylphenol, tertiary octylphenol, nonylphenol, dinonylphenol, tertiary nonylphenol, decylphenol, dodecylphenol, octadecylphenol, cyclohexylphenol, phenylphenolphenol, cresol, ethylphenol, cyclohexylphenol, nonylphenol And dodecylphenol.
上記防曇剤については特に制限はないが、公知の種々の非イオン系界面活性剤、アニオン系界面活性剤、カチオン系界面活性剤等を始めとする、多価アルコールと高級脂肪酸類とから成る多価アルコール部分エステル系のものが好適である。このような防曇剤の具体例としては、例えば非イオン系界面活性剤、例えばソルビタンモノステアレート、ソルビタンモノミリステート、ソルビタンモノパルミテート、ソルビタンモノベヘネート、ソルビタンとアルキレングリコールの縮合物と脂肪酸とのエステルなどのソルビタン系界面活性剤やグリセリンモノパルミテート、グリセリンモノステアレート、グリセリンモノラウレート、ジグリセリンモノパルミテート、グリセリンジパルミテート、グリセリンジステアレート、ジグリセリンモノパルミテート・モノステアレート、トリグリセリンモノステアレート、トリグリセリンジステアレートあるいはこれらのアルキレンオキシド付加物等などのグリセリン系界面活性剤やポリエチレングリコールモノステアレート、ポリエチレングリコールモノパルミテート、ポリエチレングリコールアルキルフェニルエーテルなどのポリエチレングリコール系界面活性剤やその他トリメチロールプロパンモノステアレートなどのトリメチロールプロパン系界面活性剤やペンタエリスリトールモノパルミテート、ペンタエリスリトールモノステアレートなどのペンタエリスリトール系界面活性剤、アルキルフェノールのアルキレンオキシド付加物;ソルビタン/グリセリンの縮合物と脂肪酸とのエステル、ソルビタン/アルキレングリコールの縮合物と脂肪酸とのエステル;ジグリセリンジオレートナトリウムラウリルサルフェート、ドデシルベンゼンスルホン酸ナトリウム、セチルトリメチルアンモニウムクロライド、ドデシルアミン塩酸塩、ラウリン酸ラウリルアミドエチルリン酸塩、トリエチルセチルアンモニウムイオダイド、オレイルアミノジエチルアミン塩酸塩、ドデシルピリジニウム塩などやそれらの異性体を含むものなどを挙げることができる。 Although there is no restriction | limiting in particular about the said anti-fogging agent, It consists of polyhydric alcohol and higher fatty acids including well-known various nonionic surfactant, anionic surfactant, cationic surfactant, etc. A polyhydric alcohol partial ester type is preferred. Specific examples of such an antifogging agent include, for example, nonionic surfactants such as sorbitan monostearate, sorbitan monomyristate, sorbitan monopalmitate, sorbitan monobehenate, sorbitan / alkylene glycol condensate and fatty acid. Sorbitan surfactants such as esters and glycerol monopalmitate, glycerol monostearate, glycerol monolaurate, diglycerol monopalmitate, glycerol dipalmitate, glycerol distearate, diglycerol monopalmitate monostearate Glycerin surfactants such as glycerol, monoglycerate, triglycerin monostearate, triglycerin distearate or alkylene oxide adducts thereof, polyethylene glycol monostearate, polyethylene glycol Polyethylene glycol surfactants such as coal monopalmitate, polyethylene glycol alkyl phenyl ether, and other trimethylolpropane surfactants such as trimethylolpropane monostearate, and pentaerythritol monopalmitate, pentaerythritol monostearate, etc. Erythritol surfactant, alkylene oxide adduct of alkylphenol; sorbitan / glycerin condensate and fatty acid ester, sorbitan / alkylene glycol condensate and fatty acid ester; diglycerin dioleate sodium lauryl sulfate, dodecylbenzenesulfonic acid Sodium, cetyltrimethylammonium chloride, dodecylamine hydrochloride, lauric acid laurylamide ethyl phosphate It can be exemplified triethylammonium cetyl ammonium iodide, oleyl amino diethylamine hydrochloride, and those containing dodecyl pyridinium salts, etc. and their isomers.
上記防霧剤としては、例えばフッ素系界面活性剤やシリコーン系界面活性剤が挙げられ、フッ素系界面活性剤の具体例としては、通常の界面活性剤の疎水基のCに結合したHの代わりにその一部または全部をFで置換した界面活性剤で、特にパーフルオロアルキル基またはパーフルオロアルケニル基を含有する界面活性剤である。以上の各種添加剤は、それぞれ1種または2種以上を組み合わせて使用することができる。パーフルオロアルキル基を有する含フッ素化合物としては、例えば、アニオン系含フッ素界面活性剤、カチオン系含フッ素界面活性剤、両性含フッ素界面活性剤、ノニオン系含フッ素界面活性剤、含フッ素オリゴマーなどがあげられる。 Examples of the anti-fogging agent include a fluorine-based surfactant and a silicone-based surfactant. Specific examples of the fluorine-based surfactant include, instead of H bonded to C of the hydrophobic group of a normal surfactant. In addition, a surfactant having a part or all thereof substituted with F, particularly a surfactant containing a perfluoroalkyl group or a perfluoroalkenyl group. The above various additives can be used alone or in combination of two or more. Examples of the fluorine-containing compound having a perfluoroalkyl group include an anionic fluorine-containing surfactant, a cationic fluorine-containing surfactant, an amphoteric fluorine-containing surfactant, a nonionic fluorine-containing surfactant, and a fluorine-containing oligomer. can give.
上記パーフルオロアルキル基を有する含フッ素化合物の使用量は、熱可塑性樹脂100重量部に対し、好ましくは0.001〜10重量部、更に好ましくは0.01〜5重量部である。該含フッ素化合物の使用量が0.001重量部未満では防霧性効果がほとんど発揮されず、10重量部を超えても効果が飽和されるため好ましくない。 The amount of the fluorine-containing compound having a perfluoroalkyl group is preferably 0.001 to 10 parts by weight, more preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the thermoplastic resin. If the amount of the fluorine-containing compound used is less than 0.001 part by weight, the antifogging effect is hardly exhibited, and if it exceeds 10 parts by weight, the effect is saturated, which is not preferable.
上記フェノール系酸化防止剤としては、例えば、2,6−ジ第三ブチル−p−クレゾール、2,6−ジフェニル−4−オクタデシロキシフェノール、ステアリル(3,5−ジ第三ブチル−4−ヒドロキシフェニル)−プロピオネート、ジステアリル(3,5−ジ第三ブチル−4−ヒドロキシベンジル)ホスホネート、チオジエチレングリコールビス〔(3,5−ジ第三ブチル−4−ヒドロキシフェニル)プロピオネート〕、1,6−ヘキサメチレンビス〔(3,5−ジ第三ブチル−4−ヒドロキシフェニル)プロピオネート〕、1,6−ヘキサメチレンビス〔(3,5−ジ第三ブチル−4−ヒドロキシフェニル)プロピオン酸アミド〕、4,4’−チオビス(6−第三ブチル−m−クレゾール) 、2,2’−メチレンビス(4−メチル−6−第三ブチルフェノール)、2,2’−メチレンビス(4−エチル−6−第三ブチルフェノール)、ビス〔3,3−ビス(4−ヒドロキシ−3−第三ブチルフェニル)ブチリックアシッド〕グリコールエステル、4,4’−ブチリデンビス(6−第三ブチル−m−クレゾール)、2,2’−エチリデンビス(4,6−ジ第三ブチルフェノール)、2,2’−エチリデンビス(4−第二ブチル−6−第三ブチルフェノール) 、1,1,3−トリス(2−メチル−4−ヒドロキシ−5−第三ブチルフェニル)ブタン、ビス〔2−第三ブチル−4−メチル−6−(2−ヒドロキシ−3−第三ブチル−5−メチルベンジル)フェニル〕テレフタレート、1,3,5−トリス(2,6−ジメチル−3−ヒドロキシ−4−第三ブチルベンジル)イソシアヌレート、1,3,5−トリス(3,5−ジ第三ブチル−4−ヒドロキシベンジル)イソシアヌレート、1,3,5−トリス(3,5−ジ第三ブチル−4−ヒドロキシベンジル)−2,4,6−トリメチルベンゼン、1,3,5−トリス〔(3,5−ジ第三ブチル−4−ヒドロキシフェニル)プロピオニルオキシエチル〕イソシアヌレート、テトラキス〔メチレン−3−(3,5−ジ第三ブチル−4−ヒドロキシフェニル)プロピオネート〕メタン、2−第三ブチル−4−メチル−6−(2−アクリロイルオキシ−3−第三ブチル−5−メチルベンジル) フェノール、3,9−ビス〔1,1−ジメチル−2−{(3−第三ブチル−4−ヒドロキシ−5−メチルフェニル)プロピオニルオキシ}エチル〕−2,4,8,10−テトラオキサスピロ〔5. 5〕ウンデカン、トリエチレングリコールビス〔(3−第三ブチル−4−ヒドロキシ−5−メチルフェニル)プロピオネート〕、n−オクタデシル3−(3’,5’−ジ−t−ブチル−4’−ヒドロキシフェニル)プロピオネート、テトラキス[3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオニルオキシメチル]メタン等があげられる。 Examples of the phenol-based antioxidant include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-ditert-butyl-4- Hydroxyphenyl) -propionate, distearyl (3,5-ditert-butyl-4-hydroxybenzyl) phosphonate, thiodiethylene glycol bis [(3,5-ditert-butyl-4-hydroxyphenyl) propionate], 1,6 -Hexamethylene bis [(3,5-ditert-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylene bis [(3,5-ditert-butyl-4-hydroxyphenyl) propionic acid amide] 4,4′-thiobis (6-tert-butyl-m-cresol), 2,2′-methylenebis (4-methyl-6- Tributylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, 4, 4'-butylidenebis (6-tert-butyl-m-cresol), 2,2'-ethylidenebis (4,6-ditert-butylphenol), 2,2'-ethylidenebis (4-secondarybutyl-6- Tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3) -Tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) -2 , 4,6-trimethylbenzene, 1,3,5-tris [(3,5-ditert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tetrakis [methylene-3- (3,5-di Tert-butyl-4-hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, 3,9-bis [ 1,1-dimethyl-2-{(3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5. ] Undecane, triethylene glycol bis [(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], n-octadecyl 3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) ) Propionate, tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxymethyl] methane and the like.
上記硫黄系酸化防止剤としては、例えば、チオジプロピオン酸ジラウリル、ジミリスチル、ジステアリル等のジアルキルチオジプロピオネート類及びペンタエリスリトールテトラ(β−ドデシルメルカプトプロピオネート)等のポリオールのβ−アルキルメルカプトプロピオン酸エステル類があげられる。 Examples of the sulfur-based antioxidant include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl, and distearyl, and β-alkyl mercapto of polyols such as pentaerythritol tetra (β-dodecyl mercaptopropionate). And propionic acid esters.
上記ホスファイト系酸化防止剤としては、例えば、トリスノニルフェニルホスファイト、トリス(2,4−ジ第三ブチルフェニル)ホスファイト、トリス〔2−第三ブチル−4−(3−第三ブチル−4−ヒドロキシ−5−メチルフェニルチオ)−5−メチルフェニル〕ホスファイト、トリデシルホスファイト、オクチルジフェニルホスファイト、ジ(デシル)モノフェニルホスファイト、モノデシルジフェニルホスファイト、モノ(ジノニルフェニル)ビス(ノニルフェニル)ホスファイト、ジ(トリデシル)ペンタエリスリトールジホスファイト、ジステアリルペンタエリスリトールジホスファイト、ジ (ノニルフェニル)ペンタエリスリトールジホスファイト、ビス(2,4−ジ第三ブチルフェニル)ペンタエリスリトールジホスファイト、ビス(2,6−ジ第三ブチル−4−メチルフェニル)ペンタエリスリトールジホスファイト、テトラ(トリデシル)イソプロピリデンジフェノールジホスファイト、テトラ(トリデシル)イソプロピリデンジフェノールジホスファイト、テトラ(C 12-15 混合アルキル)−4,4’−n−ブチリデンビス(2−第三ブチル−5−メチルフェノール) ジホスファイト、ヘキサ(トリデシル)−1,1,3−トリス(2−メチル−4−ヒドロキシ−5−第三ブチルフェニル)ブタントリホスファイト、テトラキス(2,4−ジ第三ブチルフェニル)ビフェニレンジホスホナイト、2,2’−メチレンビス(4,6−ジ第三ブチルフェニル)( オクチル) ホスファイト、テトラキス(2,4−ジ−t−ブチルフェニル)4,4’−ビフェニレン−ジ−ホスホナイト、2,2−メチレンビス(4,6−ジ−t−ブチルフェニル)オクチルホスファイト等があげられる。 Examples of the phosphite-based antioxidant include trisnonylphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tris [2-tert-butyl-4- (3-tert-butyl- 4-hydroxy-5-methylphenylthio) -5-methylphenyl] phosphite, tridecyl phosphite, octyl diphenyl phosphite, di (decyl) monophenyl phosphite, monodecyl diphenyl phosphite, mono (dinonylphenyl) Bis (nonylphenyl) phosphite, di (tridecyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-ditertiarybutylphenyl) penta Erythritol diphosphie Bis (2,6-ditert-butyl-4-methylphenyl) pentaerythritol diphosphite, tetra (tridecyl) isopropylidenediphenol diphosphite, tetra (tridecyl) isopropylidenediphenol diphosphite, tetra (C 12-15 mixed alkyl) -4,4′-n-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (2-methyl-4-hydroxy-) 5-tert-butylphenyl) butanetriphosphite, tetrakis (2,4-ditert-butylphenyl) biphenylene diphosphonite, 2,2′-methylenebis (4,6-ditert-butylphenyl) (octyl) phosphite , Tetrakis (2,4-di-t-butylphenyl) 4,4′-biphenylene-di Phosphonites, 2,2-methylenebis (4,6-di -t- butyl phenyl) octyl phosphite, and the like.
上記着色剤としては、例えば、フタロシアニンブルー、フタロシアニングリーン、ハンザイエロー、アリザリンレーキ、酸化チタン、亜鉛華、群青、パーマネントレッド、キナクリドン、カーボンブラック等を挙げることができる。 Examples of the colorant include phthalocyanine blue, phthalocyanine green, hansa yellow, alizarin lake, titanium oxide, zinc white, ultramarine blue, permanent red, quinacridone, and carbon black.
アンチブロッキング剤としては、珪藻土、合成シリカ、タルク、マイカ、ゼオライト等が挙げられる。これらアンチブロッキング剤は単独で、または2種以上を組み合わせて用いることができ、通常0.01〜0.5重量%の範囲が好ましい。 Examples of the anti-blocking agent include diatomaceous earth, synthetic silica, talc, mica and zeolite. These anti-blocking agents can be used alone or in combination of two or more, and the range of usually 0.01 to 0.5% by weight is preferred.
本発明の農業用フィルムには、上述した成分を組合わせて含有させることができ、更に通常の熱可塑性樹脂フィルムに含有させることができる下記の任意成分を、必要に応じて含有させることができる。任意成分とは、その他安定剤、耐衝撃性改善剤、架橋剤、充填剤、発泡剤、帯電防止剤、造核剤、プレートアウト防止剤、表面処理剤、難燃剤、螢光剤、防黴剤、殺菌剤、金属不活性剤、離型剤、顔料、加工助剤などを挙げることができる。 The agricultural film of the present invention can contain the above-mentioned components in combination, and can further contain the following optional components that can be contained in a normal thermoplastic resin film, if necessary. . Optional components include other stabilizers, impact resistance improvers, cross-linking agents, fillers, foaming agents, antistatic agents, nucleating agents, plate-out preventing agents, surface treatment agents, flame retardants, fluorescent agents, anti-glare agents Agents, bactericides, metal deactivators, mold release agents, pigments, processing aids and the like.
本発明の農業用フィルムに各種添加剤を配合するには、各々必要な量を秤量し、リボンブレンダー、バンバリーミキサー、ヘンシェルミキサー、スーパーミキサー、単軸又は二軸押出機、ロールなどの配合機や混練機その他従来から知られている配合機、混合機を使用すればよい。このようにして得られた樹脂組成物をフィルム化するには、それ自体公知の方法、例えば、溶融押出し成形法(Tダイ法、インフレーション法を含む)、カレンダー加工、ロール加工、押出成型加工、ブロー成型、インフレーション成型、溶融流延法、加圧成型加工、ペースト加工、粉体成型等の方法を好適に使用することができる。 In order to blend various additives into the agricultural film of the present invention, each required amount is weighed, and blending machines such as a ribbon blender, a Banbury mixer, a Henschel mixer, a super mixer, a single or twin screw extruder, a roll, A kneader or other conventionally known blender or mixer may be used. In order to form the resin composition thus obtained into a film, a method known per se, for example, a melt extrusion molding method (including a T-die method and an inflation method), calendar processing, roll processing, extrusion molding processing, Blow molding, inflation molding, melt casting, pressure molding, paste processing, powder molding, and the like can be suitably used.
本発明の農業用フィルムの厚みについては、本発明の効果を得る目的において特に厚みの制約は無いが、フィルム厚みを上げ(紫外線吸収剤濃度を下げ)る事により、ブリードアウトによる影響を低減する事が出来る。特に、強度やコストの点で0.03以上1.0mm未満の範囲のものが好ましく、0.05以上0.75mm以下のものがより好ましく、更に0.05以上0.5mm以下のものが好ましい。この範囲未満では強度的に問題があり、この範囲を超えると厚みにより成形性が困難な上、展張も困難になる。 The thickness of the agricultural film of the present invention is not particularly limited for the purpose of obtaining the effects of the present invention, but the influence of bleed out is reduced by increasing the film thickness (decreasing the UV absorber concentration). I can do it. In particular, in terms of strength and cost, those in the range of 0.03 to 1.0 mm are preferable, those in the range of 0.05 to 0.75 mm are more preferable, and those in the range of 0.05 to 0.5 mm are more preferable. . If it is less than this range, there is a problem in strength, and if it exceeds this range, the moldability is difficult due to the thickness, and stretching is also difficult.
本発明において基材層に防曇性被膜を形成することができ、ポリオレフィン系樹脂を用いる場合、前記ポリオレフィン系基材の最内層に接して防曇性被膜を形成することができる。本発明における防曇塗膜としては既に公知の農業用フィルムに用いることができる防曇塗膜を適用することが出来る。好ましくは無機コロイド物質と親水性有機化合物を主成分とした防曇塗膜や無機コロイド物質とアクリル系樹脂を主成分とする防曇塗膜を用いることができる。 In the present invention, an antifogging film can be formed on the base material layer. When a polyolefin resin is used, the antifogging film can be formed in contact with the innermost layer of the polyolefin base material. As the anti-fogging coating film in the present invention, an anti-fogging coating film that can be used for an already known agricultural film can be applied. Preferably, an antifogging coating film mainly composed of an inorganic colloid material and a hydrophilic organic compound or an antifogging coating film mainly composed of an inorganic colloid material and an acrylic resin can be used.
本発明において用いることができる無機コロイド物質と親水性有機化合物を主成分とする防曇塗膜として、例えば、特公昭63−45432号、特公昭63−45717号、特公昭64−2158号、特許第3094296号等に示されている化合物を挙げることができる。 Examples of anti-fogging coatings mainly composed of an inorganic colloid material and a hydrophilic organic compound that can be used in the present invention include, for example, Japanese Patent Publication No. 63-45432, Japanese Patent Publication No. 63-45717, Japanese Patent Publication No. 64-2158, and patents. And compounds shown in No. 3094296.
また、無機コロイド物質及び/又は合成樹脂バインダー等を使用した公知の塗膜を、積層して形成することも出来る。 In addition, a known coating film using an inorganic colloid substance and / or a synthetic resin binder can be formed by laminating.
本発明においてはアクリル系樹脂及び無機質コロイドゾルを主成分とする防曇性被膜も好適に用いることができる。
アクリル系樹脂として好ましく用いられる1つの例としては、少なくとも合計60重量%のアクリル酸またはメタクリル酸のアルキルエステル類からなる単量体、またはアクリル酸またはメタクリル酸のアルキルエステル類とアルケニルベンゼン類との単量体混合物及び0〜40重量%の共重合しうるα、β−エチレン性不飽和単量体とを、通常の重合条件に従って、例えば乳化剤の存在下に、水系媒質中で乳化重合させて得られる水分散性の重合体または共重合体である疎水性アクリル系樹脂を挙げることができる。
本発明で用いるアクリル系樹脂は、疎水性アクリル系樹脂であることが好ましく、即ち、上記のようなアクリル酸又はメタクリル酸のアルキルエステル類、又は、アクリル酸又はメタクリル酸のアルキルエステル類とアルケニルベンゼン類との単量体混合物を、少なくとも計60重量%を含有すること、好ましくは80重量%以上含有することが好ましい。60重量%に満たないときは、形成被膜の耐水性が十分でないために、防曇持続性能を発揮しえないことがあり好ましくない。
本発明のアクリル系樹脂は、特に、ガラス転移温度が35〜80℃のものを用いるのが好ましい。ガラス転移温度が低すぎると無機質コロイド粒子が数次凝集して不均一な分散状態をとりやすく、高すぎる場合、透明性のある均一な被膜を得るのが困難となりやすい。
In the present invention, an antifogging film mainly composed of an acrylic resin and an inorganic colloidal sol can also be suitably used.
As one example preferably used as the acrylic resin, at least a total of 60% by weight of a monomer composed of alkyl esters of acrylic acid or methacrylic acid, or an alkyl ester of acrylic acid or methacrylic acid and an alkenylbenzene The monomer mixture and 0 to 40% by weight of copolymerizable α, β-ethylenically unsaturated monomer are subjected to emulsion polymerization in an aqueous medium in the presence of an emulsifier, for example, according to normal polymerization conditions. The hydrophobic acrylic resin which is the obtained water dispersible polymer or copolymer can be mentioned.
The acrylic resin used in the present invention is preferably a hydrophobic acrylic resin, that is, an alkyl ester of acrylic acid or methacrylic acid as described above, or an alkyl ester of acrylic acid or methacrylic acid and an alkenylbenzene. It is preferable to contain a monomer mixture with at least 60% by weight, preferably 80% by weight or more. When it is less than 60% by weight, the water resistance of the formed film is not sufficient, and therefore, the anti-fogging sustainability may not be exhibited, which is not preferable.
In particular, the acrylic resin of the present invention preferably has a glass transition temperature of 35 to 80 ° C. If the glass transition temperature is too low, the inorganic colloidal particles are agglomerated several times and tend to be in a non-uniform dispersion state. If it is too high, it is difficult to obtain a transparent uniform film.
本発明において、基材フィルムの表面に形成させる被膜の厚さは、基材フィルムの1/10以下を目安に選択するとよいが、必ずしもこの範囲に限定されるものではない。被膜の厚さが基材フィルムの1/10より大であると、基材フィルムと被膜とでは屈曲性に差があるため、被膜が基材フィルムから剥離する等の現象がおこりやすく、また、被膜に亀裂が生じて基材フィルムの強度を低下させるという現象が生起し、好ましくない。 In the present invention, the thickness of the coating film formed on the surface of the substrate film may be selected by using 1/10 or less of the substrate film as a guide, but is not necessarily limited to this range. If the thickness of the coating is larger than 1/10 of the base film, there is a difference in flexibility between the base film and the coating, so that a phenomenon such as peeling of the coating from the base film is likely to occur. The phenomenon that a crack occurs in the coating and the strength of the base film is lowered is not preferable.
また、基材フィルムと被膜組成物に由来する被膜との接着性が充分でない場合には、基材フィルムに表面処理を施しておいてもよい。本発明の積層フィルムの表面に施す処理の方法としては、コロナ放電処理、スパッタエッチング処理、ナトリウム処理、サンドブラスト処理等の方法が挙げられる。コロナ放電処理法は、針状あるいはナイフエッジ電極と対極間で放電を行わせ、その間に試料を入れて処理を行い、フィルム表面にアルデヒド、酸、アルコールパーオキサイド、ケトン、エーテル等の酸素を含む官能基を生成させる処理である。スパッタエッチング処理は、低気圧グロー放電を行っている電極間に試料を入れ、グロー放電によって生じた正イオンの衝撃によりフィルム上に多数の微細な突起を形成するものである。サンドブラスト処理は、フィルム面に微細な砂を吹きつけて、表面上に多数の微細な凹凸を形成するものである。これら表面処理の中では、塗布層との密着性、作業性、安全性、コスト等の点から、コロナ放電処理が好適である。 Moreover, when the adhesiveness of a base film and the coating derived from a coating composition is not enough, you may surface-treat to a base film. Examples of the treatment method applied to the surface of the laminated film of the present invention include corona discharge treatment, sputter etching treatment, sodium treatment, and sandblast treatment. In the corona discharge treatment method, discharge is performed between a needle-like or knife-edge electrode and a counter electrode, and a sample is placed between the electrodes, and the film surface contains oxygen such as aldehyde, acid, alcohol peroxide, ketone, ether, etc. This is a process for generating a functional group. In the sputter etching process, a sample is placed between electrodes that are performing low-pressure glow discharge, and a large number of fine protrusions are formed on the film by the impact of positive ions generated by the glow discharge. In the sandblasting process, fine sand is sprayed on the film surface to form a large number of fine irregularities on the surface. Among these surface treatments, corona discharge treatment is preferable from the viewpoints of adhesion to the coating layer, workability, safety, cost, and the like.
本発明に係る農業用フィルムを、実際に使用するにあたっては、防曇被膜の設けられた側をハウス又はトンネルの内側となるようにして展張するのがよい。 When the agricultural film according to the present invention is actually used, it is preferably stretched so that the side on which the anti-fogging coating is provided becomes the inside of the house or tunnel.
本発明において基材層にポリオレフィン系樹脂を用いる場合、前記ポリオレフィン系基材の最内層に接して防塵性塗膜を形成することができる。
本発明における防塵性塗膜としては既に公知の農業用フィルムに用いることができる防塵性塗膜を適用することが出来る。好ましくはアクリル系樹脂を主成分とした防塵性塗膜やアクリル系樹脂及びエチレン−アクリル共重合体を主成分とする防塵性塗膜を用いることができる。防塵性塗膜を塗工する場合には基材に対して、防曇性塗膜形成時と同様のコロナ処理等の前処理をすることができる。
In the present invention, when a polyolefin resin is used for the base material layer, a dustproof coating film can be formed in contact with the innermost layer of the polyolefin base material.
As the dust-proof coating film in the present invention, a dust-proof coating film that can be used for an already known agricultural film can be applied. Preferably, a dustproof coating film mainly composed of an acrylic resin or a dustproof coating film mainly composed of an acrylic resin and an ethylene-acrylic copolymer can be used. In the case of applying a dustproof coating film, the substrate can be subjected to pretreatment such as corona treatment similar to that at the time of forming the antifogging coating film.
このようにして得られた本願発明の農業用フィルムは、300nm〜380nmの紫外線を実質完全に遮蔽することができる。「実質完全に遮蔽」とは、未使用の農業用フィルムの状態で、その光線の透過率が2%未満であることを意味する。 The agricultural film of the present invention thus obtained can substantially completely shield ultraviolet rays of 300 nm to 380 nm. “Substantially completely shielded” means that the light transmittance is less than 2% in the state of an unused agricultural film.
以下、本発明を実施例、比較例に基づいてさらに詳細に説明するが、本発明はその要旨を越えない限り、以下の例に限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example and a comparative example, this invention is not limited to the following examples, unless the summary is exceeded.
(1)積層フィルムの調製
3層インフレーション成形装置として3層ダイに100mmφ((株)プラ工研製)を用い、押出機はチューブ外内層を30mmφ((株)プラ技研製)2台、中間層を40mmφ((株)プラ技研製)として、外内層押出し機温度180℃、中間層押し出し機温度170℃、ダイス温度180〜190℃、ブロー比2.0〜3.0、引取り速度3〜7m/分、厚さ0.15mm及び0.10mmにて表1〜表5に示した成分からなる3層の積層フィルムを得た。なお、これらのフィルムは、ハウス展張時にチューブの端部を切り開いて使用するため、展開した際に製膜時のチューブ外層が展張時にはハウスの内層(内面)となる。
(1) Preparation of laminated film As a three-layer inflation molding apparatus, a three-layer die using 100 mmφ (manufactured by Pla Koken Co., Ltd.), the extruder has two inner tube
〔配合〕添加量は表1〜5に記載の通りである。
HP−LDPE:高圧ラジカル法触媒で製造した分岐状ポリエチレン(MFR:1.1g/10分、密度0.920)日本ポリケム製ノバテックLD「YF30」
メタロセンPE:メタロセン触媒で製造したエチレン・αオレフィン共重合体(MFR:2g/10分、密度0.907)日本ポリケム製カーネル「KF270」
EVA(1) :エチレン・酢酸ビニル共重合体(酢酸ビニル含有量15重量%、MFR2g/10分)
キマソーブ944:チバ・スペシャルティ・ケミカルズ社製光安定剤
エチレン・環状アミノビニル共重合体:日本ポリケム(株)製「ノバテックLD・XJ100H」MFR=3g/10分(190℃、JIS−K6760)密度=0.931g/cm3(JIS−K6760)
ベンゾトリアゾール型紫外線吸収剤A:シプロ化成株式会社製SB704CL
(2−[5−クロロ(2H)−ベンゾトリアゾール−2−イル]−4,6−ジ(tert−ペンチル)フェノール)
(メチル2−[2−ヒドロキシ−5−(2,4,4−トリメチルペンタン−2−イル)フェニル]−2H−ベンゾトリアゾール−5−カルボキシレート)
2−[5−クロロ(2H)−ベンゾトリアゾール−2−イル]−4−メチル−6−(tert−ブチル)フェノール
2,4−ジ−tert−ブチル−6−(5−クロロベンゾトリアゾール−2−イル)フェノール
2−[4,6−ビス(2,4−ジメチルフェニル)−1,3,5−トリアジン−2−イル]−5−(オクチロキシ)フェノール
HP-LDPE: Branched polyethylene produced with a high-pressure radical catalyst (MFR: 1.1 g / 10 min, density 0.920) Novatec LD “YF30” manufactured by Nippon Polychem
Metallocene PE: An ethylene / α-olefin copolymer produced with a metallocene catalyst (MFR: 2 g / 10 min, density 0.907) Kernel “KF270” manufactured by Nippon Polychem
EVA (1): ethylene-vinyl acetate copolymer (vinyl acetate content 15% by weight, MFR 2 g / 10 min)
Kimasorb 944: Light stabilizer ethylene / cyclic aminovinyl copolymer manufactured by Ciba Specialty Chemicals: “Novatech LD / XJ100H” manufactured by Nippon Polychem Co., Ltd. MFR = 3 g / 10 min (190 ° C., JIS-K6760) Density = 0.931 g / cm 3 (JIS-K6760)
Benzotriazole type ultraviolet absorber A: SB704CL manufactured by Cypro Kasei Co., Ltd.
(2- [5-Chloro (2H) -benzotriazol-2-yl] -4,6-di (tert-pentyl) phenol)
(Methyl 2- [2-hydroxy-5- (2,4,4-trimethylpentan-2-yl) phenyl] -2H-benzotriazole-5-carboxylate)
2- [5-Chloro (2H) -benzotriazol-2-yl] -4-methyl-6- (tert-butyl) phenol
2,4-Di-tert-butyl-6- (5-chlorobenzotriazol-2-yl) phenol
2- [4,6-Bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol
(2)フィルムの表面処理
得られたチューブ状フィルムの外層表面を、放電電圧120V、放電電流4.7A、ラインスピード10m/minでコロナ放電処理を行い、JIS−K6768による「濡れ指数」を測定し、その値を確認した。
(2) Surface treatment of film The outer layer surface of the obtained tubular film was subjected to corona discharge treatment at a discharge voltage of 120 V, a discharge current of 4.7 A, and a line speed of 10 m / min, and the “wetting index” according to JIS-K6768 was measured. The value was confirmed.
(3)防曇性塗膜の形成(防曇塗膜塗布タイプ)
防曇剤組成物配合は以下の配合とした。
無機質コロイドゾル(コロイダルシリカ) 4.0
熱可塑性樹脂(サンモールSW−131) 3.0
架橋剤(T.A.Z.M) 0.1
分散媒(水/エタノール=3/1) 93
(注)無機質コロイドゾルの配合量は、無機質粒子量で示し熱可塑性樹脂の配合量は重合体固形分量で示す。
コロイダルシリカ:日産化学社製スノーテックス30、平均粒子径15nm
サンモールSW−131:三洋化成社製アクリルエマルジョン
T.A.Z.M:相互薬工社製アジリジン系化合物
(2)で表面処理した基体フィルムの表面に、上記の防曇剤組成物を#5バーコーターを用いて各々塗布した。塗布したフィルムを80℃のオーブン中に1分間保持して、液状分散媒を揮発させ防曇性塗膜を形成した。得られた各フィルムの塗膜の厚みは約1μmであった。
(3) Formation of anti-fogging coating film (anti-fogging coating type)
The antifogging agent composition was blended as follows.
Inorganic colloidal sol (colloidal silica) 4.0
Thermoplastic resin (Sanmor SW-131) 3.0
Cross-linking agent (TAZM) 0.1
Dispersion medium (water / ethanol = 3/1) 93
(Note) The amount of inorganic colloidal sol is indicated by the amount of inorganic particles, and the amount of thermoplastic resin is indicated by the solid content of the polymer.
Colloidal silica:
Sunmole SW-131: acrylic emulsion T.E. A. Z. M: The above antifogging composition was applied to the surface of a base film surface-treated with an aziridine compound (2) manufactured by Mutual Yakuhin Co., Ltd. using a # 5 bar coater. The applied film was kept in an oven at 80 ° C. for 1 minute to volatilize the liquid dispersion medium to form an antifogging coating film. The thickness of the coating film of each obtained film was about 1 μm.
今回、防曇性塗膜を設けたタイプを用いて試験を行ったが、防曇剤を練り混んだタイプでも同様の効果が得られる。また、今回用いた樹脂、添加剤以外の組み合わせ、又は今回と異なるフィルム厚みでも、その要旨を変えない限り、同様の効果が得られる。今回用いた各々のサンプルについて以下のような評価を行った。実施例及び比較例における各評価の測定方法を以下に示す。 Although the test was conducted using a type provided with an antifogging coating film this time, the same effect can be obtained with a type in which an antifogging agent is mixed. Moreover, the same effect is acquired even if it is a combination other than the resin used this time, an additive, or film thickness different from this time, unless the summary is changed. Each sample used this time was evaluated as follows. The measuring method of each evaluation in an Example and a comparative example is shown below.
(1)全光線透過率
3層インフレーション成形により得られた積層フィルム(ハウス内層側表面に防曇性塗膜を形成(塗工)後)を分光光度計(日立製作所製、U3500型)により測定し、各波長におけるその値を示した。 全光線透過率は、初期及び耐堅牢性試験後の試料について行った。耐堅牢性試験は次の条件で行った。
(a)60℃、湿度70%の条件下、295〜780nmの波長分布の光を80mW/cm2の照射強度で5時間
(b)30℃、98%(シャワーによる水噴霧あり)の条件下、照射無しで1時間のサイクルで、各記載の時間、負荷試験を実施した
(1) Total light transmittance Measured with a spectrophotometer (U3500, manufactured by Hitachi, Ltd.), a laminated film (after forming (coating) an antifogging coating on the inner layer side surface) obtained by three-layer inflation molding The values at each wavelength are shown. The total light transmittance was performed on the sample after the initial stage and the fastness test. The fastness test was conducted under the following conditions.
(A) Conditions of 60 ° C. and
(2)全光線透過率の透過率平均値
(1)の方法で測定した1nmごとの透過率を平均して算出した。
(2) Average transmittance of total light transmittance The transmittance for every 1 nm measured by the method of (1) was calculated by averaging.
(3)UVカット性
(2)の方法で算出した初期の透過率を下記の基準で分類した。
○・・300〜380nmにおける透過率平均値(%)が2%未満
×・・300〜380nmにおける透過率平均値(%)が2%以上
(3) UV cut property The initial transmittance calculated by the method of (2) was classified according to the following criteria.
○ ・ Transmittance average value (%) at 300 to 380 nm is less than 2% × · Transmittance average value (%) at 300 to 380 nm is 2% or more
(4)耐ブリードアウト性
3層インフレーション成形により得られた積層フィルム(ハウス内層側表面に防曇性塗膜を形成(塗工)後)について、フィルム製膜後3ヶ月後の試料について噴出し性を目視により評価し、その差異を下記の基準で分類した。
○・・フィルムの表面に粉状の噴出しが認められない。
×・・フィルムの表面の粉状の噴出しが認められる。
(4) Bleed-out resistance About a laminated film (after forming (coating) an anti-fogging coating on the inner layer side surface) obtained by three-layer inflation molding, a sample ejected three months after film formation The properties were evaluated visually, and the differences were classified according to the following criteria.
○ ・ ・ No powdery eruption is observed on the film surface.
× ·· A powdery eruption on the surface of the film is observed.
(5)耐候性試験後の物性
耐候性試験機(The Q−PANEL COMPANY製)にフィルム試料を暴露した。耐候性試験開始から1050時間経過後に試料を取り出しフィルムの縦方向(樹脂流れ方向)の破断点強度を引張り試験(JIS−K6732準拠)により測定した。
(5) Physical properties after weather resistance test Film samples were exposed to a weather resistance tester (manufactured by The Q-PANEL COMPANY). A sample was taken out after 1050 hours from the start of the weather resistance test, and the breaking strength in the longitudinal direction (resin flow direction) of the film was measured by a tensile test (based on JIS-K6732).
〔実施例1、2及び比較例1〕
本願に係るベンゾトリアゾール型紫外線吸収剤を含有する総フィルム厚み150μmの三層フィルムを、表1及び2に記載した配合により作製し、前記方法により紫外線カット性能、耐ブリードアウト性及び耐候性試験後の物性の評価を行った。その結果を表2に示す。ここで、比較例1は、環境影響性がなく紫外線遮蔽性に優れるとされるベンゾトリアゾール型紫外線吸収剤(TINUVIN326)を配合した三層フィルムである。また、これらフィルムの耐堅牢性試験後(140時間後)の光線透過特性を図1に示す。
[Examples 1 and 2 and Comparative Example 1]
A three-layer film having a total film thickness of 150 μm containing the benzotriazole-type ultraviolet absorber according to the present application was prepared by the formulation described in Tables 1 and 2, and after the UV cut performance, bleed-out resistance and weather resistance tests by the above methods. The physical properties of were evaluated. The results are shown in Table 2. Here, Comparative Example 1 is a three-layer film in which a benzotriazole type ultraviolet absorber (TINUVIN 326), which has no environmental impact and is excellent in ultraviolet shielding properties, is blended. In addition, the light transmission characteristics of these films after a fastness test (after 140 hours) are shown in FIG.
表2及び図1から、実施例1及び2は初期の紫外線カット性能、耐ブリードアウト性及び耐候性試験後の物性に優れ、また、耐堅牢性試験後の紫外線カット性能については比較例1よりも優れていることが示される。
〔実施例3,4及び比較例2〕
本願に係るベンゾトリアゾール型紫外線吸収剤を含有する総フィルム厚み100μmの三層フィルムを、表3及び4に記載した配合により作製し、前記方法により紫外線カット性能及び耐ブリードアウト性の評価を行った。その結果を表4に示す。ここで、比較例2は、環境影響性がなく紫外線遮蔽性に優れるとされるベンゾトリアゾール型紫外線吸収剤(TINUVIN326)を配合した三層フィルムである。これらフィルムの耐堅牢性試験後(66時間後)の光線透過特性を図2に示す。
[Examples 3 and 4 and Comparative Example 2]
A three-layer film having a total film thickness of 100 μm containing the benzotriazole type ultraviolet absorber according to the present application was prepared by the formulation described in Tables 3 and 4, and the ultraviolet cut performance and bleed-out resistance were evaluated by the above methods. . The results are shown in Table 4. Here, Comparative Example 2 is a three-layer film in which a benzotriazole type ultraviolet absorber (TINUVIN 326), which has no environmental impact and is excellent in ultraviolet shielding properties, is blended. The light transmission characteristics of these films after the fastness test (after 66 hours) are shown in FIG.
表4及び図2から、実施例3及び4は初期の紫外線カット性能及び耐ブリードアウト性に優れ、耐堅牢性試験後の紫外線カット性能についても比較例2よりも優れていることが示される。
表2及び表4で示した結果から、本発明の特定のベンゾトリアゾール型紫外線吸収剤は、単独で使用しても、TINUVIN326を使用した場合に対して耐ブリードアウト性に優れ、耐堅牢性試験後の紫外線カット性にも優れることが示される。 From the results shown in Table 2 and Table 4, the specific benzotriazole type ultraviolet absorber of the present invention is excellent in bleed-out resistance when compared with the case where TINUVIN 326 is used, and the robustness test. It is shown that it is excellent also in the later ultraviolet ray cut-off property.
〔実施例5、6及び比較例4,5〕
本願に係るベンゾトリアゾール型紫外線吸収剤とトリアリールトリアジン型紫外線吸収剤を含有する総フィルム厚み150μmの三層フィルムを、表1及び5に記載した配合により作製し、前記方法により紫外線カット性能、耐ブリードアウト性及び耐候性試験後の物性の評価を行った。その結果を表5に示す。ここで、比較例3として、TINUVIN326と環境影響性のある従来型のベンゾトリアゾール型紫外線吸収剤(TINUVIN327)の組合わせとトリアリールトリアジン型紫外線吸収剤を配合した三層フィルムを用いた。これらフィルムの負荷試験後(330時間後)の光線透過特性を図3に示す。
[Examples 5 and 6 and Comparative Examples 4 and 5]
A three-layer film having a total film thickness of 150 μm containing a benzotriazole type ultraviolet absorber and a triaryltriazine type ultraviolet absorber according to the present application was prepared according to the formulation described in Tables 1 and 5, and the ultraviolet ray cutting performance, The physical properties after the bleed-out property and the weather resistance test were evaluated. The results are shown in Table 5. Here, as Comparative Example 3, a three-layer film in which a combination of TINUVIN 326 and a conventional benzotriazole type ultraviolet absorber (TINUVIN 327) having an environmental impact and a triaryltriazine type ultraviolet absorber were blended was used. The light transmission characteristics after a load test (after 330 hours) of these films are shown in FIG.
表5及び図3から、実施例5及び6は初期の紫外線カット性能、耐ブリードアウト性及び耐候性試験後の物性に優れることが示される。また、比較例3は、紫外線吸収剤としての特性を具備するが環境影響性のあるTINUVIN327を使用するものであり、耐ブリードアウト性が良好であるが、本発明に係る実施例4及び5は、耐堅牢性試験後の紫外線カット性能において比較例3より優れていることが示される。
以上の結果から明らかなように、本願に係る特定のベンゾトリアゾール型紫外線吸収剤を配合したフィルムは、総フィルム厚みが150μmの場合、及び従来は紫外線遮蔽性とブリードアウト性の両立が困難とされてきた総フィルム厚みが100μmの場合についても初期及び負荷試験後で優れた紫外線吸収特性を有することが示された。また、本願に係るベンゾトリアゾール型紫外線吸収剤とトリアリールトリアジン型紫外線吸収剤を配合した場合には、耐堅牢性試験後の紫外線遮蔽性を更に向上できることが示された。 As is clear from the above results, it is difficult for the film containing the specific benzotriazole type ultraviolet absorber according to the present application to have both the ultraviolet shielding property and the bleed out property when the total film thickness is 150 μm. Even when the total film thickness was 100 μm, it was shown that the film had excellent ultraviolet absorption characteristics at the initial stage and after the load test. Further, it was shown that when the benzotriazole type ultraviolet absorber according to the present application and the triaryltriazine type ultraviolet absorber are blended, the ultraviolet shielding property after the fastness resistance test can be further improved.
Claims (4)
(2−[5−クロロ(2H)−ベンゾトリアゾール−2−イル]−4,6−ジ(tert−ペンチル)フェノール)
(式中、Rは直鎖又は分岐C1〜C8アルキル基である。) An agricultural film comprising a benzotriazole type ultraviolet absorber according to the following formula (1) or (2), wherein the content of the ultraviolet absorber is 3% by weight or less based on the total film.
(2- [5-Chloro (2H) -benzotriazol-2-yl] -4,6-di (tert-pentyl) phenol)
(In the formula, R is a linear or branched C1-C8 alkyl group.)
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