JPH10286902A - Outdoor expansion film - Google Patents
Outdoor expansion filmInfo
- Publication number
- JPH10286902A JPH10286902A JP9098733A JP9873397A JPH10286902A JP H10286902 A JPH10286902 A JP H10286902A JP 9098733 A JP9098733 A JP 9098733A JP 9873397 A JP9873397 A JP 9873397A JP H10286902 A JPH10286902 A JP H10286902A
- Authority
- JP
- Japan
- Prior art keywords
- film
- layer
- parts
- outdoor
- fine particles
- 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.)
- Granted
Links
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 27
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 27
- 239000010419 fine particle Substances 0.000 claims abstract description 14
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 14
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 12
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 230000000737 periodic effect Effects 0.000 claims abstract description 5
- 239000000178 monomer Substances 0.000 claims description 52
- -1 alkyl methacrylate Chemical compound 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 31
- 229920000578 graft copolymer Polymers 0.000 claims description 16
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 12
- 229920002554 vinyl polymer Polymers 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 238000002834 transmittance Methods 0.000 claims description 8
- 239000012964 benzotriazole Substances 0.000 claims description 7
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 5
- 229910001887 tin oxide Inorganic materials 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical group C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- 239000012965 benzophenone Substances 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 229910003437 indium oxide Inorganic materials 0.000 claims description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 description 26
- 229920005989 resin Polymers 0.000 description 17
- 239000011347 resin Substances 0.000 description 17
- 238000006116 polymerization reaction Methods 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- 239000006096 absorbing agent Substances 0.000 description 12
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- 229920000642 polymer Polymers 0.000 description 12
- 125000005250 alkyl acrylate group Chemical group 0.000 description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 7
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 239000013013 elastic material Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 description 7
- 239000005020 polyethylene terephthalate Substances 0.000 description 7
- 230000008961 swelling Effects 0.000 description 7
- 229920001971 elastomer Polymers 0.000 description 6
- 239000000806 elastomer Substances 0.000 description 6
- 230000005855 radiation Effects 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- 238000001035 drying Methods 0.000 description 5
- 238000003898 horticulture Methods 0.000 description 5
- 239000000314 lubricant Substances 0.000 description 5
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229920003002 synthetic resin Polymers 0.000 description 5
- 239000000057 synthetic resin Substances 0.000 description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- 239000002250 absorbent Substances 0.000 description 4
- 230000002745 absorbent Effects 0.000 description 4
- 238000007611 bar coating method Methods 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000010556 emulsion polymerization method Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000004800 polyvinyl chloride Substances 0.000 description 4
- 229920000915 polyvinyl chloride Polymers 0.000 description 4
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 description 3
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 3
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 3
- 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 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 125000005907 alkyl ester group Chemical group 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000003851 corona treatment Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000002612 dispersion medium Substances 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- WXHVQMGINBSVAY-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 WXHVQMGINBSVAY-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920001651 Cyanoacrylate Polymers 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- MZYMWSQPRNOQIJ-UHFFFAOYSA-K [O-]P([O-])([O-])=O.CCCCCCCCCCCCCCCCCC[Zn+].CCCCCCCCCCCCCCCCCC[Zn+].CCCCCCCCCCCCCCCCCC[Zn+] Chemical compound [O-]P([O-])([O-])=O.CCCCCCCCCCCCCCCCCC[Zn+].CCCCCCCCCCCCCCCCCC[Zn+].CCCCCCCCCCCCCCCCCC[Zn+] MZYMWSQPRNOQIJ-UHFFFAOYSA-K 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000008366 benzophenones Chemical class 0.000 description 2
- 150000001565 benzotriazoles Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 208000028659 discharge Diseases 0.000 description 2
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- 238000010559 graft polymerization reaction Methods 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 238000007602 hot air drying Methods 0.000 description 2
- XLSMFKSTNGKWQX-UHFFFAOYSA-N hydroxyacetone Chemical compound CC(=O)CO XLSMFKSTNGKWQX-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 229910001463 metal phosphate Inorganic materials 0.000 description 2
- 239000000113 methacrylic resin Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000001587 sorbitan monostearate Substances 0.000 description 2
- 235000011076 sorbitan monostearate Nutrition 0.000 description 2
- 229940035048 sorbitan monostearate Drugs 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000010345 tape casting Methods 0.000 description 2
- 230000002087 whitening effect Effects 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- CNAILFQALPMJFF-UHFFFAOYSA-N (4-benzoyl-3-hydroxyphenyl) benzoate Chemical compound C=1C=C(C(=O)C=2C=CC=CC=2)C(O)=CC=1OC(=O)C1=CC=CC=C1 CNAILFQALPMJFF-UHFFFAOYSA-N 0.000 description 1
- OMWSZDODENFLSV-UHFFFAOYSA-N (5-chloro-2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=C(Cl)C=C1C(=O)C1=CC=CC=C1 OMWSZDODENFLSV-UHFFFAOYSA-N 0.000 description 1
- VDYWHVQKENANGY-UHFFFAOYSA-N 1,3-Butyleneglycol dimethacrylate Chemical compound CC(=C)C(=O)OC(C)CCOC(=O)C(C)=C VDYWHVQKENANGY-UHFFFAOYSA-N 0.000 description 1
- XSZYESUNPWGWFQ-UHFFFAOYSA-N 1-(2-hydroperoxypropan-2-yl)-4-methylcyclohexane Chemical compound CC1CCC(C(C)(C)OO)CC1 XSZYESUNPWGWFQ-UHFFFAOYSA-N 0.000 description 1
- AKUNSTOMHUXJOZ-UHFFFAOYSA-N 1-hydroperoxybutane Chemical group CCCCOO AKUNSTOMHUXJOZ-UHFFFAOYSA-N 0.000 description 1
- SQAINHDHICKHLX-UHFFFAOYSA-N 1-naphthaldehyde Chemical compound C1=CC=C2C(C=O)=CC=CC2=C1 SQAINHDHICKHLX-UHFFFAOYSA-N 0.000 description 1
- MEZZCSHVIGVWFI-UHFFFAOYSA-N 2,2'-Dihydroxy-4-methoxybenzophenone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1O MEZZCSHVIGVWFI-UHFFFAOYSA-N 0.000 description 1
- XKNLMAXAQYNOQZ-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.CC(=C)C(O)=O.CC(=C)C(O)=O.CC(=C)C(O)=O.OCC(CO)(CO)CO XKNLMAXAQYNOQZ-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- JLZIIHMTTRXXIN-UHFFFAOYSA-N 2-(2-hydroxy-4-methoxybenzoyl)benzoic acid Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1C(O)=O JLZIIHMTTRXXIN-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JJBFVQSGPLGDNX-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)COC(=O)C(C)=C JJBFVQSGPLGDNX-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- DHMNTHVOLJVHPF-UHFFFAOYSA-N 2-(3,5-dimethyl-2-octadecoxyphenyl)-5-methylbenzotriazole Chemical compound CCCCCCCCCCCCCCCCCCOC1=C(C)C=C(C)C=C1N1N=C2C=C(C)C=CC2=N1 DHMNTHVOLJVHPF-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- LOPXIGZYSAOSOK-UHFFFAOYSA-N 2-(5,6-dichlorobenzotriazol-2-yl)-4-methylphenol Chemical compound CC1=CC=C(O)C(N2N=C3C=C(Cl)C(Cl)=CC3=N2)=C1 LOPXIGZYSAOSOK-UHFFFAOYSA-N 0.000 description 1
- LGTOWDJWJQJQAO-UHFFFAOYSA-N 2-(5-methoxybenzotriazol-2-yl)-4,6-dimethylphenol Chemical compound N1=C2C=C(OC)C=CC2=NN1C1=CC(C)=CC(C)=C1O LGTOWDJWJQJQAO-UHFFFAOYSA-N 0.000 description 1
- XTARNDCHFFABBE-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,5-dichlorophenol Chemical compound OC1=CC(Cl)=C(Cl)C=C1N1N=C2C=CC=CC2=N1 XTARNDCHFFABBE-UHFFFAOYSA-N 0.000 description 1
- ODVBRJXPJKVLCZ-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-dichlorophenol Chemical compound OC1=C(Cl)C=C(Cl)C=C1N1N=C2C=CC=CC2=N1 ODVBRJXPJKVLCZ-UHFFFAOYSA-N 0.000 description 1
- MJFOVRMNLQNDDS-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-dimethylphenol Chemical compound CC1=CC(C)=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MJFOVRMNLQNDDS-UHFFFAOYSA-N 0.000 description 1
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- 229930004008 p-menthane Natural products 0.000 description 1
- QUPCNWFFTANZPX-UHFFFAOYSA-M paramenthane hydroperoxide Chemical compound [O-]O.CC(C)C1CCC(C)CC1 QUPCNWFFTANZPX-UHFFFAOYSA-M 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
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- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
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- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical class OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
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- 235000011071 sorbitan monopalmitate Nutrition 0.000 description 1
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- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
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- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
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- 239000001993 wax Substances 0.000 description 1
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
- Y02A40/25—Greenhouse technology, e.g. cooling systems therefor
Landscapes
- Protection Of Plants (AREA)
- Greenhouses (AREA)
- Laminated Bodies (AREA)
Abstract
(57)【要約】
【課題】 透明性を有し、且つ、優れた遮熱性とその持
続力を有する屋外展張用フィルムの提供。
【解決手段】 熱可塑性樹脂フィルムの少なくとも片面
上に、周期律表３Ａ、４Ａおよび５Ａ族に属する少なく
とも１種の金属がドープされた熱線遮蔽能を有する無機
酸化物微粒子を含有する層（Ａ）を設け、更にその層上
および／またはフィルムの反対面上に、紫外線吸収剤を
含有する厚さ１〜１０μｍのアクリル系樹脂層（Ｂ）を
設けてなる屋外展張用フィルム。(57) [Summary] [Problem] To provide a film for outdoor expansion having transparency, excellent heat shielding properties and its sustainability. SOLUTION: A layer (A) containing, on at least one surface of a thermoplastic resin film, at least one metal belonging to Groups 3A, 4A and 5A of the periodic table and doped with inorganic oxide fine particles having heat ray shielding ability. And an acrylic resin layer (B) having a thickness of 1 to 10 μm containing an ultraviolet absorber on the layer and / or on the opposite surface of the film.
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、施設園芸等の被覆
に用いられる屋外展張用フィルムに関するものである。
更に詳しくは、透明性を有し、且つ、優れた遮熱性とそ
の持続力を有する屋外展張用フィルムに関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an outdoor stretching film used for covering horticulture facilities.
More specifically, the present invention relates to an outdoor stretchable film having transparency and excellent heat shielding properties and its durability.
【０００２】[0002]
【従来の技術】従来からの施設園芸において、一般的に
用いられるハウス被覆資材は、冬場の保温性向上および
光合成に必要な日射量を確保することを目的に、可視光
線を極力透過させる、例えば、ポリ塩化ビニル、ポリオ
レフィン、ポリエチレンテレフタレートなどの透明合成
樹脂フィルムが使用されている。これら従来の合成樹脂
フィルムは冬場の栽培性向上を目的としたものであり、
初夏から、盛夏を経て初秋の間は、ハウス内が高温とな
り、施設園芸は困難である。そのため、夏場を越す必要
のある多年生の花卉類の場合は、内張りまたは外張りの
カーテンとしての遮光ネットや寒冷紗を使用し、日射
（可視光線含む）を約３０〜８０％遮ることによって、
ハウス内に透過してくる日射エネルギーを低下させ、ハ
ウス内温度の上昇を抑えている。花卉類の場合は、必要
な光量が少なくても栽培が可能ではあるものの、遮光に
よる植物の徒長という問題がある。2. Description of the Related Art In conventional greenhouse horticulture, a house covering material generally used transmits visible light as much as possible for the purpose of improving heat insulation in winter and securing solar radiation necessary for photosynthesis. And transparent synthetic resin films such as polyvinyl chloride, polyolefin, and polyethylene terephthalate. These conventional synthetic resin films are intended to improve cultivation in winter.
From early summer to mid-summer to early autumn, the temperature inside the house becomes high, making facility horticulture difficult. Therefore, in the case of perennial flowers that need to go through the summer, use a shading net or a cold gauze as a lining or lining curtain to block solar radiation (including visible light) by about 30 to 80%.
It reduces the solar energy that penetrates into the house and suppresses the rise in temperature inside the house. In the case of flowers, although the cultivation is possible even with a small amount of required light, there is a problem that the plants are prostrate due to shading.
【０００３】また、夏場の高温対策としてハウス内冷房
も行われているが、ミストによる冷房は、植物が濡れる
事に起因して病害が発生しやすく、また、多湿による作
業環境の悪化、更に、日本のように高温多湿環境下で
は、その効果も不十分であるといった問題点があり、普
及していない。他方、冷凍機による冷房も、日射が降り
注ぐハウスでは、冷房効率が非常に低いので、あまり行
われていない。一方、夏場の果菜類の栽培に関しては、
作物生理上および品質上、ほとんど遮光は不可能なた
め、西南暖地において、施設園芸による夏場の果菜類の
栽培は行われておらず、東北や北海道の冷涼地において
も、夏場透明フィルムの被覆下では、ハウス内が高温と
なり、品質および作業環境が問題となっている。そこ
で、可視光線は極力透過させ、熱線（即ち、近赤外線）
を極力カットするタイプの被覆資材が求められている。[0003] Cooling in a house is also performed as a countermeasure against high temperature in summer, but cooling by mist is apt to cause diseases due to wet plants, and the working environment deteriorates due to high humidity. Under the high temperature and high humidity environment like Japan, the effect is insufficient, and it is not widely used. On the other hand, cooling by a refrigerator is not often performed in a house where sunlight is poured, since the cooling efficiency is extremely low. On the other hand, regarding the cultivation of fruits and vegetables in summer,
In terms of crop physiology and quality, almost no shading is possible.In summer and southwest, greenhouse horticulture is not cultivated by greenhouse horticulture. In this case, the temperature inside the house becomes high, and the quality and the working environment are problematic. Therefore, visible light is transmitted as much as possible and heat rays (ie, near infrared rays)
There is a demand for a type of covering material that cuts as much as possible.
【０００４】そこで、合成樹脂フィルムの表面にごく薄
い金属層を蒸着した赤外線反射材料（特公昭５９−１３
３２５号公報）、近赤外線および赤外線を反射するホロ
グラムを合成樹脂フィルムと組み合わせて使用した農業
用フィルム（特開平７−２７４７３８号公報）等が提案
されているが、太陽からの日射エネルギーは、可視光領
域で約５０％、近赤外線領域、赤外線領域で約５０％の
エネルギー量を有するので、可視光を遮断すれば、透過
してくる日射エネルギー量を容易に低減できるが、可視
光量が不足するという問題がある。よって、日射エネル
ギーの中で近赤外線領域の光を積極的に吸収または反射
（遮蔽）させることが望ましく、熱線吸収剤または熱線
反射剤を合成樹脂フィルムへ練り込むこと、あるいは塗
布することが行われている。[0004] Therefore, an infrared-reflective material having a very thin metal layer deposited on the surface of a synthetic resin film (Japanese Patent Publication No. 59-13 / 1984).
No. 325), and an agricultural film using a hologram that reflects near-infrared rays and infrared rays in combination with a synthetic resin film (Japanese Patent Laid-Open Publication No. 7-274738), etc., but solar energy from the sun is visible. Since it has an energy amount of about 50% in the light region and about 50% in the near-infrared region and the infrared region, if visible light is blocked, the amount of transmitted solar radiation can be easily reduced, but the amount of visible light is insufficient. There is a problem. Therefore, it is desirable to positively absorb or reflect (block) light in the near infrared region in the solar energy, and kneading or applying a heat ray absorbent or a heat ray reflector to a synthetic resin film is performed. ing.
【０００５】[0005]
【発明が解決しようとする課題】熱線遮蔽能を有する粒
子を練り込んだ方法として、例えば、六塩化タングステ
ン、硫化第二銅、アミニウム系の近赤外線吸収色素、金
属錯体化合物等の熱線反射剤あるいは熱線吸収剤を配合
することが、特公平４−４５５４６号公報、特公昭５８
−５６５３３号公報、特公昭６２−５４１４３号公報、
特開昭５０−５１５４９号公報、特公昭５４−２５０６
０号公報、特公平１−１１４８０１号公報、特開平２−
１７３０６号公報、特開平３−２１５５６１号公報、特
開平３−１６１６４４号公報、特開平６−７３１９７号
公報、特開平８−８１５６７号公報等により提案されて
いる。As a method of kneading particles having a heat ray shielding function, for example, a heat ray reflecting agent such as tungsten hexachloride, cupric sulfide, an aminium-based near-infrared absorbing dye, a metal complex compound or the like is used. The blending of a heat ray absorbent is disclosed in Japanese Patent Publication No. 4-45546, Japanese Patent Publication No. 58-58.
JP-A-56533, JP-B-62-54143,
JP-A-50-51549, JP-B-54-2506
0, Japanese Patent Publication No. 1-114801,
It has been proposed in Japanese Patent Application Laid-Open Nos. 17306, 3-215561, 3-161644, 6-73197, 8-81567, and the like.
【０００６】また、熱線反射剤あるいは熱線吸収剤を塗
布した方法として、酸化スズ微粒子をバインダー溶液に
分散させ、透明基材上に製膜してなる可視光線透過率が
高く、しかも熱線遮蔽性に優れる熱線遮蔽膜（特開平６
−２６２７１７号公報）、ポリエチレンテレフタレート
フィルムにアミノ化合物よりなる有機物近赤外線吸収層
および酸化スズと酸化アンチモンの固溶体よりなる無機
物近赤外線吸収層を積層した近赤外線吸収性フィルム
（特開平７−１００９９６号公報）等が提案されてい
る。しかし、熱線吸収剤または反射剤とも、屋外に曝露
すると、数年以内特に有機系の場合は１年以内に熱線遮
蔽能が低下し、夏場ハウス内の高温対策としての効果が
薄れてくる問題があった。[0006] As a method of applying a heat ray reflecting agent or a heat ray absorbing agent, tin oxide fine particles are dispersed in a binder solution, and a film is formed on a transparent substrate. Excellent heat ray shielding film
-262717), a near-infrared absorbing film in which an organic near-infrared absorbing layer made of an amino compound and an inorganic near-infrared absorbing layer made of a solid solution of tin oxide and antimony oxide are laminated on a polyethylene terephthalate film (Japanese Patent Laid-Open No. 7-100996). ) Etc. have been proposed. However, when exposed to the outdoors, both heat absorbers and reflectors have the problem that, within a few years, especially in the case of organic materials, the heat-shielding ability is reduced within one year, and the effect as a countermeasure against high temperatures in summer houses is diminished. there were.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、かかる背
景下にあって、熱線を遮蔽する屋外展張用フィルムとし
て、可視光線を透過し、且つ、熱線遮蔽性能の効果の持
続性を向上させた屋外展張用フィルムを提供すべく、鋭
意検討した。Under these circumstances, the present inventors have proposed a film for outdoor spreading which shields heat rays, transmits visible light, and improves the continuity of the effect of the heat ray shielding performance. We have studied hard to provide a film for outdoor expansion.
【０００８】しかして本発明の要旨とするところは、熱
可塑性樹脂フィルムの少なくとも片面上に、周期律表３
Ａ、４Ａおよび５Ａ族に属する少なくとも１種の金属が
ドープされた熱線遮蔽能を有する無機酸化物微粒子を含
有する層（Ａ）を設け、更にその層上および／またはフ
ィルムの反対面上に、紫外線吸収剤を含有する厚さ１〜
１０μｍのアクリル系樹脂層（Ｂ）を設けてなる屋外展
張用フィルム存する。Thus, the gist of the present invention is that at least one surface of a thermoplastic resin film has a periodic table 3
A layer (A) containing inorganic oxide fine particles having heat ray shielding ability doped with at least one metal belonging to Group A, 4A and 5A is provided, and further on the layer and / or on the opposite surface of the film, Thickness 1 containing UV absorber
There is a film for outdoor expansion provided with an acrylic resin layer (B) of 10 μm.
【０００９】[0009]
【発明の実施の形態】本発明において、熱線とは波長２
００〜２６００ｎｍの範囲の近赤外線を意味し、また、
遮蔽とは反射または吸収を意味する。以下、本発明を詳
細に説明する。本発明の屋外展張用フィルムを構成する
熱可塑性樹脂としては、一般にフィルム成形に用いられ
る樹脂であれば何れでもよい。具体的には、塩化ビニ
ル、エチレン、プロピレン、アクリル酸エステル、メタ
クリル酸エステル、フッ化エチレン等の単量体の単独ま
たはこれら相互の重合体、あるいはこれら単量体中の少
なくとも１種と他の共重合可能な単量体（例えば、酢酸
ビニル、塩化ビニリデン等）との共重合体、含フッ素樹
脂、ポリエステル、ポリアミド等もしくはこれら重合体
のブレンド物があげられる。これらの中では、耐候性、
光透過性、経済性、強度等の観点から、塩化ビニル系樹
脂（即ち、ポリ塩化ビニルおよび塩化ビニルを５０重量
％以上含むその共重合体）およびエチレン系樹脂（即
ち、ポリエチレンおよびエチレンを５０重量％以上含む
その共重合体）が好適であり、最も有利にはポリエチレ
ンテレフタレートおよびフッ素樹脂である。BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a heat ray is a wavelength 2
Means near infrared in the range of 00 to 2600 nm;
Shielding means reflection or absorption. Hereinafter, the present invention will be described in detail. The thermoplastic resin constituting the outdoor stretchable film of the present invention may be any resin that is generally used for film forming. Specifically, vinyl chloride, ethylene, propylene, acrylic acid ester, methacrylic acid ester, fluorinated ethylene and the like monomers alone or their mutual polymers, or at least one of these monomers and other Examples thereof include a copolymer with a copolymerizable monomer (for example, vinyl acetate, vinylidene chloride, etc.), a fluorine-containing resin, a polyester, a polyamide, and the like, or a blend of these polymers. Among these, weather resistance,
From the viewpoints of light transmittance, economy, strength, and the like, a vinyl chloride resin (that is, polyvinyl chloride and its copolymer containing at least 50% by weight of vinyl chloride) and an ethylene resin (that is, polyethylene and ethylene at 50% by weight) % Of the copolymer), most preferably polyethylene terephthalate and fluororesins.
【００１０】ポリエチレンテレフタレートを用いる場合
は、フィルムは未延伸のものでも二軸に延伸されたもの
でもよいが、フィルムの強度の点からいえば二軸に延伸
されたものが好ましい。二軸に延伸する場合は、縦、
横、２．０〜５．０倍延伸されたものが好ましい。延伸
倍率が２．０倍未満であると、製品の強度が充分のもの
とならないので好ましくなく、５．０倍を越えたもので
は製品の強度は充分なものとなるが、製造作業が困難と
なるので好ましくない。延伸倍率は二軸方向とも、夫々
２．５〜４．０倍の範囲が特に好ましい。二軸延伸フィ
ルムを製造する方法は特に限定されるものではなく、例
えば逐次にまたは同時に縦横二軸に延伸する等、従来知
られている、如何なる方法によるものでもよい。When polyethylene terephthalate is used, the film may be unstretched or biaxially stretched, but preferably biaxially stretched from the viewpoint of film strength. When stretching biaxially, lengthwise,
Those stretched 2.0 to 5.0 times in the horizontal direction are preferable. If the stretching ratio is less than 2.0 times, the strength of the product will not be sufficient, so that it is not preferable. If the stretching ratio exceeds 5.0 times, the strength of the product will be sufficient, but the manufacturing operation is difficult. Is not preferred. The stretching ratio is particularly preferably in the range of 2.5 to 4.0 times in both biaxial directions. The method for producing the biaxially stretched film is not particularly limited, and any conventionally known method such as stretching sequentially or simultaneously biaxially in the vertical and horizontal directions may be used.
【００１１】本発明の屋外展張用フィルムに係る熱可塑
性樹脂フィルムは、厚みが０．０１〜０．３ｍｍのもの
が好ましい。厚みが０．０１ｍｍ未満であると、製品の
強度が充分なものとならず、また、０．３ｍｍを越える
とフィルムが硬くなり、取り扱い難くなるので好ましく
ない。これら熱可塑性樹脂には、必要に応じ、通常の熱
可塑性樹脂に添加される周知の可塑剤、滑剤、熱安定
剤、有機リン酸金属塩、防曇剤、防霧剤、紫外線吸収
剤、光安定剤、着色剤、安定剤、酸化防止剤等の添加助
剤を通常量配合することができる。The thermoplastic resin film according to the outdoor stretchable film of the present invention preferably has a thickness of 0.01 to 0.3 mm. If the thickness is less than 0.01 mm, the strength of the product will not be sufficient, and if it exceeds 0.3 mm, the film will be hard and difficult to handle, which is not preferable. These thermoplastic resins include, if necessary, known plasticizers, lubricants, heat stabilizers, metal organic phosphates, anti-fog agents, anti-fog agents, ultraviolet absorbers, Additives such as stabilizers, colorants, stabilizers, and antioxidants can be added in usual amounts.
【００１２】滑剤ないし熱安定剤としては、一般的に屋
外展張用フィルムに使用される、脂肪酸系滑剤、脂肪酸
アミド系滑剤、エステル系滑剤、ポリエチレンワック
ス、流動パラフィン、有機ホスファイト化合物の如きキ
レーター、フェノール類、βージケトン化合物等があげ
られる。具体的には、特公昭６２ー５３５４３号公報第
７欄第１行〜１２行目に記載の化合物等がある。紫外線
吸収剤としては、次のようなものがあげられる。シアノ
アクリレート系紫外線吸収剤である、２−エチルヘキシ
ル−２−シアノ−３，３’−ジフェニルアクリレート、
エチル−２−シアノ−３，３’−ジフェニルアクリレー
ト等。Examples of the lubricant or heat stabilizer include chelators such as fatty acid-based lubricants, fatty acid amide-based lubricants, ester-based lubricants, polyethylene wax, liquid paraffin, and organic phosphite compounds which are generally used for films for outdoor stretching. Examples include phenols and β-diketone compounds. Specific examples include compounds described in JP-B-62-53543, column 7, lines 1 to 12. Examples of the ultraviolet absorber include the following. 2-ethylhexyl-2-cyano-3,3′-diphenyl acrylate, which is a cyanoacrylate-based ultraviolet absorber;
Ethyl-2-cyano-3,3'-diphenylacrylate and the like.
【００１３】ベンゾフェノン系紫外線吸収剤である、２
−ヒドロキシ−４−メトキシベンゾフェノン、２，４−
ジヒドロキシベンゾフェノン、２−ヒドロキシ−４−ｎ
−オクトキシベンゾフェノン、２−ヒドロキシ−４−メ
トキシ−２’−カルボキシベンゾフェノン、２，２’−
ジヒドロキシ−４，４’−ジメトキシベンゾフェノン、
２−ヒドロキシ−４−ベンゾイルオキシベンゾフェノ
ン、２，２’−ジヒドロキシ−４−メトキシベンゾフェ
ノン、２−ヒドロキシ−４−メトキシ−５−スルホンベ
ンゾフェノン、２，２’，４，４’−テトラヒドロキシ
ベンゾフェノン、２，２’−ジヒドロキシ−４，４’−
ジメトキシベンゾフェノン、２−ヒドロキシ−５−クロ
ルベンゾフェノン、ビス−（２−メトキシ−４−ヒドロ
キシ−５−ベンゾイルフェニル）メタン等。A benzophenone ultraviolet absorber, 2
-Hydroxy-4-methoxybenzophenone, 2,4-
Dihydroxybenzophenone, 2-hydroxy-4-n
-Octoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2,2'-
Dihydroxy-4,4'-dimethoxybenzophenone,
2-hydroxy-4-benzoyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfonebenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, , 2'-dihydroxy-4,4'-
Dimethoxybenzophenone, 2-hydroxy-5-chlorobenzophenone, bis- (2-methoxy-4-hydroxy-5-benzoylphenyl) methane and the like.
【００１４】ベンゾトリアゾール系紫外線吸収剤であ
る、２−（２’−ヒドロキシフェニル）ベンゾトリアゾ
ール、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−５
−メチルフェニル）−５−カルボン酸ブチルエステルベ
ンゾトリアゾール、２−（２’−ヒドロキシ−５’−メ
チルフェニル）−５，６−ジクロルベンゾトリアゾー
ル、２−（２’−ヒドロキシ−５’−メチルフェニル）
−５−エチルスルホンベンゾトリアゾール、２−（２’
−ヒドロキシ−５’−ｔ−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−５’
−ｔ−ブチルフェニル）ベンゾトリアゾール、２−
（２’−ヒドロキシ−５’−アミノフェニル）ベンゾト
リアゾール、２−（２’−ヒドロキシ−３’，５’−ジ
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’−ジメチルフェニル）−５−メト
キシベンゾトリアゾール、２−（２’−メチル−４’−
ヒドロキシフェニル）ベンゾトリアゾール、２−（２’
−ステアリルオキシ−３’，５’−ジメチルフェニル）
−５−メチルベンゾトリアゾール、２−（２’−ヒドロ
キシ−５−カルボン酸フェニル）ベンゾトリアゾールエ
チルエステル、２−（２’−ヒドロキシ−３’−メチル
−５’−ｔ−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−ｔ−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’−ｔ−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’−メトキシフェニル）ベンゾトリアゾー
ル、２−（２’−ヒドロキシ−３’，５’−ジ−ｔ−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−５’−シクロヘキシルフェニル）
ベンゾトリアゾール、２−（２’−ヒドロキシ−４’，
５’−ジメチルフェニル）−５−カルボン酸ベンゾトリ
アゾールブチルエステル、２−（２’−ヒドロキシ−
３’，５’−ジクロルフェニル）ベンゾトリアゾール、
２−（２’−ヒドロキシ−４’，５’−ジクロルフェニ
ル）ベンゾトリアゾール、２−（２’−ヒドロキシ−
３’，５’−ジメチルフェニル）−５−エチルスルホン
ベンゾトリアゾール、２−（２’−ヒドロキシ−４’−
オクトキシフェニル）ベンゾトリアゾール、２−（２’
−ヒドロキシ−５’−メトキシフェニル）−５−メチル
ベンゾトリアゾール、２−（２’−ヒドロキシ−５’−
メチルフェニル）−５−カルボン酸エステルベンゾトリ
アゾール、２−（２’−アセトキシ−５’−メチルフェ
ニル）ベンゾトリアゾール等。2- (2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5), which are benzotriazole ultraviolet absorbers
-Methylphenyl) -5-carboxylic acid butyl ester benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) -5,6-dichlorobenzotriazole, 2- (2'-hydroxy-5'-methyl Phenyl)
-5-ethylsulfonebenzotriazole, 2- (2 ′
-Hydroxy-5'-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5 '
-T-butylphenyl) benzotriazole, 2-
(2'-hydroxy-5'-aminophenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-dimethylphenyl) benzotriazole, 2- (2'-hydroxy-3', 5'-dimethyl Phenyl) -5-methoxybenzotriazole, 2- (2′-methyl-4′-
Hydroxyphenyl) benzotriazole, 2- (2 ′
-Stearyloxy-3 ', 5'-dimethylphenyl)
-5-methylbenzotriazole, 2- (2'-hydroxy-5-carboxylic acid phenyl) benzotriazole ethyl ester, 2- (2'-hydroxy-3'-methyl-5'-t-butylphenyl) benzotriazole, 2
-(2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'
-Hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-methoxyphenyl) benzotriazole, 2- (2'-hydroxy-3 ' , 5'-Di-t-butylphenyl) -5-chlorobenzotriazole, 2-
(2′-hydroxy-5′-cyclohexylphenyl)
Benzotriazole, 2- (2′-hydroxy-4 ′,
5'-dimethylphenyl) -5-carboxylic acid benzotriazole butyl ester, 2- (2'-hydroxy-
3 ', 5'-dichlorophenyl) benzotriazole,
2- (2'-hydroxy-4 ', 5'-dichlorophenyl) benzotriazole, 2- (2'-hydroxy-
3 ', 5'-dimethylphenyl) -5-ethylsulfonebenzotriazole, 2- (2'-hydroxy-4'-
Octoxyphenyl) benzotriazole, 2- (2 ′
-Hydroxy-5'-methoxyphenyl) -5-methylbenzotriazole, 2- (2'-hydroxy-5'-
Methylphenyl) -5-carboxylate benzotriazole, 2- (2′-acetoxy-5′-methylphenyl) benzotriazole and the like.
【００１５】更に、これらシアノアクリレート系、ベン
ゾフェノン系、ベンゾトリアゾール系紫外線吸収剤の数
量体、重合体があげられる。これらの紫外線吸収剤は１
種あるいは２種以上併用してもよく、その使用量は熱可
塑性樹脂１００重量部当り０．０１〜５重量部、好まし
くは０．０５〜２重量部である。Further, there may be mentioned a number and polymer of these cyanoacrylate, benzophenone and benzotriazole ultraviolet absorbers. These UV absorbers are 1
Species or two or more thereof may be used in combination, and the amount of use is 0.01 to 5 parts by weight, preferably 0.05 to 2 parts by weight, per 100 parts by weight of the thermoplastic resin.
【００１６】本発明において、層（Ａ）を構成する、周
期律表３Ａ、４Ａおよび５Ａ族に属する少なくとも１種
の金属がドープされた熱線遮蔽能を有する無機酸化物微
粒子とは、例えば、酸化インジウム、酸化スズ、酸化ゲ
ルマニウム、酸化亜鉛等の金属酸化物に、３Ａ、４Ａお
よび５Ａ族に属する金属をドープさせ導電性を付与した
ものであり、具体的には、スズがドープされた酸化イン
ジウム（ＩＴＯ）、アンチモンがドープされた酸化スズ
（ＡＴＯ）、ガリウムがドープされた酸化ゲルマニウム
等があげらる。これらは２種以上ドープさせても良い。
また、周期律表とは、短周期型、長周期型いづれの周期
律表でも良い。In the present invention, the inorganic oxide fine particles which constitute the layer (A) and which are doped with at least one metal belonging to Groups 3A, 4A and 5A of the periodic table and have a heat-ray shielding ability include, for example, oxides Metal oxides such as indium, tin oxide, germanium oxide, and zinc oxide are doped with metals belonging to groups 3A, 4A, and 5A to impart conductivity, and specifically, indium oxide doped with tin (ITO), tin oxide (ATO) doped with antimony, germanium oxide doped with gallium, and the like. These may be doped with two or more kinds.
The periodic table may be either a short-period type or a long-period type.
【００１７】これら無機酸化物微粒子の粒径は、平均粒
径が２０００ｎｍを超える粗粒物になると、表面粗度が
低下し、クレーター状のへこみや突起ができて外観不良
になるほか、表面の乱反射も著しくなり、可視光線透過
率が低下するので好ましくない。よって、無機酸化物微
粒子の平均粒径は２０００ｎｍ以下が望ましい。また、
無機酸化物微粒子の添加量は、層（Ａ）および層（Ｂ）
成形後のフィルムにおいて、可視光領域（代表して５５
５ｎｍでの透過率）の透過率が６０％以上となるように
調整すべきであるが、対象作物範囲を考慮すると、可視
光線透過率値で８０％以上となるような配合量に調整す
ることがより望ましい。As for the particle size of these inorganic oxide fine particles, if the average particle size of the fine particles exceeds 2000 nm, the surface roughness is reduced, crater-like dents and projections are formed, and the appearance becomes poor. Diffuse reflection also becomes remarkable, and the visible light transmittance decreases, which is not preferable. Therefore, the average particle size of the inorganic oxide fine particles is desirably 2000 nm or less. Also,
The addition amount of the inorganic oxide fine particles depends on the layer (A) and the layer (B).
In the film after molding, in the visible light region (typically 55
(Transmittance at 5 nm) should be adjusted so as to be 60% or more. However, considering the target crop range, the blending amount should be adjusted so that the visible light transmittance value is 80% or more. Is more desirable.
【００１８】これら無機酸化物微粒子は、１種または数
種を同時に用いてもかまわない。また、アントラキノン
誘導体や、フタロシアニン化合物、ナフタロシアニン化
合物、スクアリリウム化合物、チオ尿素化合物、イモニ
ウム系化合物、アセチレン系化合物などの有機化合物あ
るいは、クロム、コバルト、銅等の金属錯体を併用して
もさしつかえない。かかる層（Ａ）を形成するには、無
機酸化物微粒子をバインダーとともに液状分散媒中に分
散させたものを熱可塑性樹脂フィルムの表面上に、塗布
した後、強制乾燥または自然乾燥し、液状分散媒を揮散
させればよい。One or more of these inorganic oxide fine particles may be used at the same time. Further, an anthraquinone derivative, an organic compound such as a phthalocyanine compound, a naphthalocyanine compound, a squarylium compound, a thiourea compound, an immonium compound, or an acetylene compound, or a metal complex such as chromium, cobalt, or copper may be used in combination. In order to form such a layer (A), a dispersion of inorganic oxide fine particles together with a binder in a liquid dispersion medium is applied on the surface of a thermoplastic resin film, and then is forcibly dried or air-dried. What is necessary is just to volatilize a medium.
【００１９】バインダーとしては、熱可塑性樹脂を用い
ればよい。具体的には、アクリル系樹脂、塩化ビニルー
酢酸ビニル系樹脂、ポリエチレン系樹脂、塩化ビニル系
樹脂、塩化ビニリデン系樹脂、ポリウレタン系樹脂、ポ
リカーボネート系樹脂、スチロール系樹脂、酢酸ビニル
系樹脂、不飽和ポリエステル系樹脂等があげられるが、
特にアクリル系樹脂が好適である。強制乾燥する方法と
しては、熱風乾燥法、赤外線輻射法等が採用できる。ま
た、塗布する方法としては、ロールコート法、ディップ
コート法、ハケ塗り法、スプレーコート法、バーコート
法、ナイフコート法等それ自体公知のいかなる方法によ
ってもよい。As the binder, a thermoplastic resin may be used. Specifically, acrylic resin, vinyl chloride-vinyl acetate resin, polyethylene resin, vinyl chloride resin, vinylidene chloride resin, polyurethane resin, polycarbonate resin, styrene resin, vinyl acetate resin, unsaturated polyester Resin, etc.
In particular, an acrylic resin is preferable. As a method of forced drying, a hot air drying method, an infrared radiation method, or the like can be employed. The coating method may be any known method such as a roll coating method, a dip coating method, a brush coating method, a spray coating method, a bar coating method, and a knife coating method.
【００２０】フィルム表面と、層（Ａ）との接着性が充
分でない場合には、層（Ａ）を塗布する前に、フィルム
表面にプラズマ処理を施すとか、もしくはコロナ放電処
理を施すとか、適当なアンカー剤の塗布等の方法によっ
てフィルム表面を改質してもよい。本発明の屋外展張用
フィルムは、層（Ａ）を形成した面上または層（Ａ）を
形成したフィルムの反対面上に、層（Ｂ）を形成する。
すなわち、層（Ａ）がフィルム片面のみに形成された場
合、層（Ｂ）は、層（Ａ）面上または層（Ａ）を形成し
ていないフィルム表面上に、あるいは両面に形成しても
よい。層（Ａ）がフィルム両面に形成された場合、少な
くとも一面に、層（Ｂ）を形成すればよい。When the adhesion between the film surface and the layer (A) is not sufficient, the film surface may be subjected to a plasma treatment or a corona discharge treatment before the application of the layer (A). The surface of the film may be modified by a method such as applying a suitable anchor agent. In the film for outdoor stretching of the present invention, the layer (B) is formed on the surface on which the layer (A) is formed or on the surface opposite to the film on which the layer (A) is formed.
That is, when the layer (A) is formed only on one surface of the film, the layer (B) may be formed on the surface of the layer (A) or on the film surface on which the layer (A) is not formed, or on both surfaces. Good. When the layer (A) is formed on both surfaces of the film, the layer (B) may be formed on at least one surface.
【００２１】本発明において層（Ｂ）を構成するアクリ
ル系樹脂としては、幹成分としての架橋アクリル酸エス
テル系弾性体の存在下に、分岐成分としてのメタクリル
酸アルキルエステル単量体、またはメタクリル酸アルキ
ルエステルを主成分としこれと共重合可能なビニル系単
量体との混合物を重合して得られるグラフト共重合体で
あって、架橋アクリル酸エステル系弾性体を５〜８０重
量％含むものが好ましい。架橋アクリル酸エステル系単
量体とは、架橋性単量体と（メタ）アクリル酸アルキル
エステル単量体、またはこれと共重合可能なビニル系単
量体との混合物を重合して得られる重合体である。In the present invention, the acrylic resin constituting the layer (B) may be a methacrylic acid alkyl ester monomer or a methacrylic acid monomer as a branching component in the presence of a crosslinked acrylate-based elastomer as a trunk component. A graft copolymer obtained by polymerizing a mixture of an alkyl ester as a main component and a vinyl monomer copolymerizable therewith, which contains 5 to 80% by weight of a crosslinked acrylate elastic body. preferable. The crosslinked acrylate monomer is a polymer obtained by polymerizing a mixture of a crosslinkable monomer and an alkyl (meth) acrylate monomer, or a vinyl monomer copolymerizable therewith. It is united.
【００２２】架橋性単量体としては、通常多官能性化合
物として使用されているものであればよく、具体例とし
ては、エチレングリコールジメタクリレート、１，３−
ブチレングリコールジメタクリレート、１，４−ブチレ
ングリコールジメタクリレート、プロピレングリコール
ジメタクリレート、トリメチロールプロパントリメタク
リレート、テトラメチロールメタンテトラメタクリレー
ト、ジプロピレングリコールジメタクリレート、ジビニ
ルベンゼン、ジビニルアジペート、ジアリルフタレー
ト、ジアリルマレート、アリルアクリレート、アリルメ
タクリレート、トリアリルシアヌレート等があげられ、
これらは２種以上を併用してよい。The crosslinking monomer may be any one which is usually used as a polyfunctional compound. Specific examples thereof include ethylene glycol dimethacrylate, 1,3-
Butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, propylene glycol dimethacrylate, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, dipropylene glycol dimethacrylate, divinylbenzene, divinyl adipate, diallyl phthalate, diallyl maleate, Allyl acrylate, allyl methacrylate, triallyl cyanurate and the like,
These may be used in combination of two or more.
【００２３】（メタ）アクリル酸アルキルエステル単量
体とは、アクリル酸のまたはメタクリル酸のアルキルエ
ステル類であり、具体的には例えば、アクリル酸メチ
ル、アクリル酸エチル、アクリル酸−ｎ−プロピル、ア
クリル酸イソプロピル、アクリル酸−ｎ−ブチル、アク
リル酸−２−エチルヘキシル、アクリル酸デシル、メタ
クリル酸メチル、メタクリル酸エチル、メタクリル酸−
ｎ−プロピル、メタクリル酸イソプロピル、メタクリル
酸−ｎ−ブチル、メタクリル酸−２−エチルヘキシル、
メタクリル酸デシル等があげられ、一般には、アルキル
基の炭素数が１〜２０個のアクリル酸アルキルエステル
および／またはアルキル基の炭素数が１〜２０個のメタ
クリル酸アルキルエステルが使用され、これらは混合し
て使用してもよい。The alkyl (meth) acrylate monomer is an alkyl ester of acrylic acid or methacrylic acid, and specifically, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, Isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, methyl methacrylate, ethyl methacrylate, methacrylic acid
n-propyl, isopropyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate,
Examples thereof include decyl methacrylate and the like. Generally, an alkyl acrylate having 1 to 20 carbon atoms in an alkyl group and / or an alkyl methacrylate having 1 to 20 carbon atoms in an alkyl group are used. You may mix and use.
【００２４】これら（メタ）アクリル酸アルキルエステ
ル単量体と共重合可能なビニル系単量体としては、メタ
クリル酸およびメタクリル酸のアルキルエステル（アル
キル基の炭素数１〜１２）、イタコン酸のジアルキルエ
ステル（アルキル基の炭素数１〜１０）、アクリロニト
リル、メタクリロニトリル、塩化ビニル、塩化ビニリデ
ン、スチレン、核アルキル置換スチレン、α−メチルス
チレン等があげられる。これら単量体は、４０重量％以
下、好ましくは２５重量％以下とするのがよい。Examples of the vinyl monomers copolymerizable with these alkyl (meth) acrylate monomers include methacrylic acid and alkyl esters of methacrylic acid (alkyl groups having 1 to 12 carbon atoms), and dialkyl of itaconic acid. Examples thereof include esters (having 1 to 10 carbon atoms in the alkyl group), acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, styrene, alkyl-substituted styrene, α-methylstyrene, and the like. These monomers are used in an amount of 40% by weight or less, preferably 25% by weight or less.
【００２５】架橋アクリル酸エステル系弾性体は、乳化
重合法によって製造するのがよい。この際使用できる重
合開始剤は、通常の遊離基発生開始剤である。具体例を
あげると、過硫酸カリウム、過硫酸アンモニウム等の無
機過酸化物；キュメンハイドロパーオキサイド、ｐ−メ
ンタンハイドロパーオキサイド、ジターシャリーブチル
ハイドロパーオキサイド等の有機ハイドロパーオキサイ
ド、キュメンパーオキサイド等の有機過酸化物や、アゾ
ビスイソブチロニトリルのようなアゾ系の開始剤をあげ
ることができる。The crosslinked acrylic ester-based elastic material is preferably produced by an emulsion polymerization method. The polymerization initiator that can be used at this time is a usual free radical generation initiator. Specific examples include inorganic peroxides such as potassium persulfate and ammonium persulfate; organic hydroperoxides such as cumene hydroperoxide, p-menthane hydroperoxide, ditertiary butyl hydroperoxide, and organic peroxides such as cumene peroxide. Examples include peroxides and azo-based initiators such as azobisisobutyronitrile.
【００２６】更にこれらの重合開始剤に、亜硫酸ナトリ
ウム、酸性亜硫酸ナトリウム、チオ硫酸ナトリウム、ナ
トリウムホルムアルデヒドスルフォキシレート、グルコ
ース、ポリアミン、アスコルビン酸ヒドロキシアセトン
等の還元剤を組み合せた、通常のレドックス系開始剤も
使用しうる。乳化剤としては、通常の乳化重合用の界面
活性剤をあげることができる。例えば、炭素数が８〜２
０個のアルキル硫酸のナトリウム、カリウム、アンモニ
ウム塩およびラウリン酸、ステアリン酸、パルミチン酸
等の脂肪族カルボン酸のナトリウム、カリウム塩等の陰
イオン界面活性剤や、アルキルフェノール類、脂肪族ア
ルコール類およびポリプロピレンオキサイド類とエチレ
ンオキサイドとの反応生成物等の非イオン界面活性剤が
あげられる。また、場合によっては、これら界面活性剤
を２種以上併用することもできる。更に、ナフタレンホ
ルムアルデヒド縮合スルフォン酸塩等の界面活性剤を添
加することもできる。更に要すれば、アルキルアミン塩
酸塩等の陽イオン界面活性剤を使用することもできる。Further, these polymerization initiators are combined with a reducing agent such as sodium sulfite, sodium acid sulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate, glucose, polyamine, hydroxyacetone ascorbate, etc. to form a normal redox initiator. Agents may also be used. Examples of the emulsifier include ordinary surfactants for emulsion polymerization. For example, when the carbon number is 8 to 2
Zero anionic surfactants such as sodium, potassium and ammonium salts of alkyl sulfates and sodium and potassium salts of aliphatic carboxylic acids such as lauric acid, stearic acid and palmitic acid; alkylphenols, aliphatic alcohols and polypropylene Nonionic surfactants such as reaction products of oxides and ethylene oxide can be used. In some cases, two or more of these surfactants can be used in combination. Further, a surfactant such as a naphthalene formaldehyde condensed sulfonate may be added. If necessary, a cationic surfactant such as an alkylamine hydrochloride can be used.
【００２７】架橋アクリル酸エステル系弾性体を製造す
る方法としては、次の乳化重合方法があげられる。 （１）アクリル酸アルキルエステル単量体、またはアク
リル酸アルキルエステル単量体とこれと共重合可能なビ
ニル系単量体との混合物に、少量の架橋性単量体を加え
て重合する方法。 （２）（１）の方法で得た重合体エマルジョンに、更に
アクリル酸アルキルエステル単量体、またはアクリル酸
アルキルエステル単量体とこれと共重合可能なビニル系
単量体との混合物を加えて重合する方法。 （３）（２）の方法において、少量の架橋剤存在下、ア
クリル酸アルキルエステル単量体またはこれと共重合可
能なビニル系単量体の混合物を加えて重合する方法。The following emulsion polymerization method can be used as a method for producing a crosslinked acrylic ester-based elastic material. (1) A method in which a small amount of a crosslinkable monomer is added to an alkyl acrylate monomer or a mixture of an alkyl acrylate monomer and a vinyl monomer copolymerizable therewith to polymerize. (2) An alkyl acrylate monomer or a mixture of an alkyl acrylate monomer and a vinyl monomer copolymerizable therewith is further added to the polymer emulsion obtained by the method of (1). To polymerize. (3) The method of (2), wherein an alkyl acrylate monomer or a mixture of a vinyl monomer copolymerizable therewith is added and polymerized in the presence of a small amount of a crosslinking agent.
【００２８】（４）アクリル酸アルキルエステル単量
体、またはアクリル酸アルキルエステル単量体とこれと
共重合可能なビニル系単量体との混合物より乳化重合し
て未架橋重合体を製造する。次いで、この重合系に、更
に、少量の架橋性単量体の存在下、アクリル酸アルキル
エステル単量体、またはアクリル酸アルキルエステル単
量体とこれと共重合可能なビニル系単量体との混合物を
加えて重合する方法。 （５）（１）〜（４）の方法で得た重合体エマルジョン
の一種に、更にアクリル酸アルキルエステル単量体、ま
たはこれと共重合可能なビニル系単量体を加え、架橋性
単量体を加えずまたは少量加えて重合する方法。(4) An uncrosslinked polymer is produced by emulsion polymerization from an alkyl acrylate monomer or a mixture of an alkyl acrylate monomer and a vinyl monomer copolymerizable therewith. Next, in this polymerization system, further, in the presence of a small amount of a crosslinkable monomer, an alkyl acrylate monomer, or an alkyl acrylate monomer and a vinyl monomer copolymerizable therewith. A method of polymerizing by adding a mixture. (5) To one of the polymer emulsions obtained by the methods (1) to (4), an alkyl acrylate monomer or a vinyl monomer copolymerizable therewith is further added to form a crosslinkable monomer. A method of polymerizing without adding a body or adding a small amount.
【００２９】架橋アクリル酸エステル系弾性体は、前記
界面活性剤の使用量や、使用する水性媒体の量を加減す
ることによって、架橋弾性体エマルジョン粒子の平均粒
子径を調整し、０．０５〜０．３０μｍの範囲とするこ
とが好ましい。０．０５μｍ以下では、被膜として使用
されるアクリル系樹脂の機械的強度が低下し、０．３０
μｍを超えると、応力白化が著しくなり好ましくない。
更に架橋アクリル酸エステル系弾性体は、次の方法で測
定したゲル含量が８０％以上で、膨潤度が１５以下のも
のがよい。The average particle diameter of the crosslinked elastomer emulsion particles is adjusted by adjusting the amount of the surfactant and the amount of the aqueous medium to be used. Preferably, it is in the range of 0.30 μm. If the thickness is less than 0.05 μm, the mechanical strength of the acrylic resin used as the coating film is reduced,
If it exceeds μm, stress whitening becomes remarkable, which is not preferable.
Further, the crosslinked acrylate-based elastic body preferably has a gel content of 80% or more and a swelling degree of 15 or less as measured by the following method.
【００３０】ゲル含量および膨潤度は、架橋弾性体の所
定量（Ｗ0）を採取し、室温でメチルエチルケトンに４
８時間浸漬した後の膨潤した重量（Ｗ1）およびこの試
料を減圧乾燥機で乾燥した後の重量（Ｗ2）を測定し、
次式により算出することが出来る。The gel content and the degree of swelling were determined by taking a predetermined amount (W 0 ) of the crosslinked elastic material and adding it to methyl ethyl ketone at room temperature.
The swollen weight (W 1 ) after immersion for 8 hours and the weight (W 2 ) after drying the sample with a vacuum dryer were measured.
It can be calculated by the following equation.
【００３１】[0031]
【数１】ゲル含量＝（Ｗ2−Ｗ0）×１００（％） 膨潤度 ＝（Ｗ1−Ｗ2）／Ｗ0 ## EQU1 ## Gel content = (W 2 −W 0 ) × 100 (%) Swelling degree = (W 1 −W 2 ) / W 0
【００３２】ゲル含量、膨潤度は、前述の架橋性単量体
の種類および量の調整以外に、弾性体を重合する時の温
度、開始剤の種類とその使用量、弾性体を構成する単量
体の添加方法、分子量調節剤の有無等の重合諸条件によ
って影響されるので、適宜調節するのがよい。ゲル含量
が８０％に満たないときは、その弾性体から得られる被
膜形成用アクリル系樹脂は、後述する有機溶媒に完全に
溶解し、または過度に膨潤し、弾性体粒子が変形してし
まい、好ましくない。膨潤度についても、１５を超える
と応力白化しやすくなり、好ましくない。The gel content and the degree of swelling are determined by adjusting the type and amount of the above-mentioned crosslinkable monomer, the temperature at which the elastomer is polymerized, the type and amount of the initiator used, and the amount of the monomer constituting the elastomer. It is preferably adjusted as appropriate because it is affected by various polymerization conditions such as the method of adding the monomer and the presence or absence of a molecular weight regulator. When the gel content is less than 80%, the acrylic resin for forming a film obtained from the elastic body is completely dissolved in an organic solvent described later or excessively swells, and the elastic body particles are deformed. Not preferred. Regarding the degree of swelling, if it exceeds 15, stress whitening tends to occur, which is not preferable.
【００３３】上記架橋アクリル酸エステル系弾性体にグ
ラフトさせる分岐成分のメタクリル酸アルキルエステル
単量体としては、弾性体製造の際に使用される前述の中
から選んでよく、これと共重合可能なビニル系単量体も
また、弾性体製造の際に使用されると例示したものの中
から選んでよい。この場合、グラフトさせる単量体成分
から得られる重合体または共重合体自体のガラス転移温
度（Ｔｇ）が５０℃以上となるように、単量体の種類や
組合せを選ぶことが好ましい。Ｔｇが５０℃に満たない
ときは、このグラフト重合体を含むアクリル系樹脂の被
膜の耐ブロッキング性が悪くなる（ブロッキングしやす
い）ので好ましくない。The alkyl methacrylate monomer as a branching component to be grafted onto the crosslinked acrylic ester-based elastic material may be selected from the above-mentioned ones used in the production of the elastic material, and may be copolymerized with this. The vinyl monomer may also be selected from those exemplified as being used in the production of the elastic body. In this case, it is preferable to select the types and combinations of monomers so that the glass transition temperature (Tg) of the polymer or copolymer obtained from the monomer component to be grafted is 50 ° C. or higher. When the Tg is less than 50 ° C., the blocking resistance of the acrylic resin film containing the graft polymer is deteriorated (it is easy to block), which is not preferable.
【００３４】グラフト重合反応は、乳化重合法によって
遂行するのがよいが、溶液重合法によってもよい。例え
ば、乳化重合法によってグラフト重合を行う場合は、架
橋アクリル酸エステル系弾性体のエマルジョンに、グラ
フトさせる単量体を加え、必要があれば乳化剤、重合開
始剤、分子量調節剤、水等を加えて、通常の乳化重合の
条件を選んで、遂行することができる。グラフトさせる
単量体との割合は、架橋弾性体エマルジョンを重合体固
形分１００重量部に対し、通常１０重量部以上、３０重
量部以上とする。The graft polymerization reaction is preferably performed by an emulsion polymerization method, but may be performed by a solution polymerization method. For example, when graft polymerization is carried out by an emulsion polymerization method, a monomer to be grafted is added to an emulsion of a crosslinked acrylate-based elastic material, and if necessary, an emulsifier, a polymerization initiator, a molecular weight regulator, water and the like are added. Thus, ordinary emulsion polymerization conditions can be selected and carried out. The ratio of the grafted monomer to the crosslinked elastic emulsion is usually 10 parts by weight or more and 30 parts by weight or more based on 100 parts by weight of the solid content of the polymer.
【００３５】アクリル系樹脂中には、グラフト教重合体
以外に、例えば、メタクリル酸アルキルエステル単量体
または、メタクリル酸アルキルエステル単量体を主成分
としてこれと共重合可能なビニル系単量体の混合物を重
合してられるメタクリル樹脂、または、グラフト共重合
体製造の際に生成するフリーなメタクリル樹脂も含まれ
る。In the acrylic resin, besides the graft polymer, for example, an alkyl methacrylate monomer or a vinyl monomer copolymerizable with an alkyl methacrylate monomer as a main component Or a free methacrylic resin formed during the production of a graft copolymer.
【００３６】更に、アクリル系樹脂には、グラフト重合
体と相溶性があり、Ｔｇが５０℃以上で透明な硬質熱可
塑性樹脂をブレンドして、被膜形成用アクリル系樹脂と
して使用することができる。アクリル系樹脂に含まれる
架橋弾性体の割合を５〜８０重量％、好ましくは１０〜
５０重量％の範囲とするのがよい。架橋弾性体の割合が
５重量％に満たないときは、機械的強度が劣り、８０重
量％を超えるときは、これを被膜として有するフィルム
の耐ブロッキング性が悪くなり、好ましくない。Further, the acrylic resin is compatible with the graft polymer, and can be used as an acrylic resin for forming a film by blending a transparent hard thermoplastic resin having a Tg of 50 ° C. or higher. The proportion of the crosslinked elastic body contained in the acrylic resin is 5 to 80% by weight, preferably 10 to
The content is preferably in the range of 50% by weight. When the proportion of the crosslinked elastic body is less than 5% by weight, the mechanical strength is inferior, and when it exceeds 80% by weight, the film having this as a coating film has poor blocking resistance, which is not preferable.
【００３７】これらアクリル系樹脂には、紫外線吸収剤
を配合して、基体フィルムの片面に被膜を形成する。紫
外線吸収剤の種類は、従来公知の紫外線吸収剤、例えば
サリチル酸系化合物、シアノアクリレート系化合物、ベ
ンゾフェノン系化合物、ベンゾトリアゾール系化合物等
があげられる。具体的には、前述したような紫外線吸収
剤とその数量体、重合体があげられる。これらの中で、
アクリル系樹脂への溶解性、熱可塑性樹脂フィルムに塗
布して屋外展張用として使用する観点から評価すると、
ベンゾフェノン系化合物、および／またはベンゾトリア
ゾール系化合物が好ましい。An ultraviolet absorber is added to these acrylic resins to form a coating on one surface of the base film. Examples of the type of the ultraviolet absorber include conventionally known ultraviolet absorbers such as salicylic acid compounds, cyanoacrylate compounds, benzophenone compounds, and benzotriazole compounds. Specifically, there may be mentioned the above-mentioned ultraviolet absorbers, their monomers and polymers. Among these,
Solubility in acrylic resin, when evaluated from the viewpoint of being applied to a thermoplastic resin film and used for outdoor expansion,
Benzophenone compounds and / or benzotriazole compounds are preferred.
【００３８】前記アクリル系樹脂に配合される紫外線吸
収剤の量は、余り少なすぎると本発明の目的が達成され
ないし、余り多すぎるとブリード・アウトの問題があ
る。好ましい配合量は、アクリル系樹脂１００重量部に
対して、１０〜２５重量部の範囲である。アクリル系樹
脂に配合される紫外線吸収剤の量、ポリエチレンテレフ
タレートの片面に形成される被膜の厚さは、種々変更し
うるが、フィルム一定面積当りの紫外線吸収剤の量を１
５０〜１０００ｍｇ／ｍ2の範囲とすると特に好まし
い。If the amount of the ultraviolet absorber blended in the acrylic resin is too small, the object of the present invention is not achieved, and if it is too large, there is a problem of bleed out. A preferred amount is in the range of 10 to 25 parts by weight based on 100 parts by weight of the acrylic resin. The amount of the UV absorber incorporated in the acrylic resin and the thickness of the film formed on one side of the polyethylene terephthalate can be variously changed.
It is particularly preferred to be in the range of 50 to 1000 mg / m 2 .
【００３９】これら紫外線吸収剤を含有するアクリル系
樹脂の被膜の厚さは、１〜１０μｍであり、特に１〜５
μｍが好適である。１μｍ未満であると本発明の目的が
達成されないので好ましくなく、１０μｍを超えると被
膜が剥離しやすいという問題が生じ好ましくない。The thickness of the acrylic resin film containing these ultraviolet absorbers is 1 to 10 μm, especially 1 to 5 μm.
μm is preferred. If the thickness is less than 1 μm, the object of the present invention is not achieved.
【００４０】本発明の層（Ｂ）を熱可塑性樹脂フィルム
表面上に形成するには、紫外線吸収剤を含む組成物を、
液状分散媒として、例えば、メチルエチルケトンのよう
なケトン類、ベンゼン、トルエン、キシレンのような芳
香族炭化水素類、酢酸メチル、酢酸エチル等の酢酸エス
テル類などの１種または２種以上を混合した有機溶媒と
の混合物を用いて分散液として用いる。この組成物を熱
可塑性樹脂フィルムの少なくとも片面に塗布し、強制乾
燥または自然乾燥して、液状分散媒を揮散させることで
塗膜を形成することができる。In order to form the layer (B) of the present invention on the surface of the thermoplastic resin film, a composition containing an ultraviolet absorbent is used.
As a liquid dispersion medium, for example, an organic material obtained by mixing one or more kinds of ketones such as methyl ethyl ketone, aromatic hydrocarbons such as benzene, toluene and xylene, and acetates such as methyl acetate and ethyl acetate. It is used as a dispersion by using a mixture with a solvent. This composition is applied to at least one surface of a thermoplastic resin film, and is forcibly dried or air-dried to volatilize the liquid dispersion medium, thereby forming a coating film.
【００４１】強制乾燥する方法としては、熱風乾燥法、
赤外線輻射法等が採用できる。強制乾燥するときの加熱
温度は、塗布された組成物によって決定されるが、５０
〜２５０℃、好ましくは７０〜２００℃の範囲である。
塗布する方法としては、ロールコート法、ディップコー
ト法、ハケ塗り法、スプレーコート法、バーコート法、
ナイフコート法等それ自体公知のいかなる方法によって
もよい。As a method of forcibly drying, hot air drying,
An infrared radiation method or the like can be adopted. The heating temperature when forcibly drying is determined by the applied composition.
To 250 ° C, preferably 70 to 200 ° C.
As a method of applying, a roll coating method, a dip coating method, a brush coating method, a spray coating method, a bar coating method,
Any known method such as a knife coating method may be used.
【００４２】フィルム表面と、層（Ｂ）との接着性が充
分でない場合には、層（Ｂ）を塗布する前に、フィルム
表面にプラズマ処理を施すとか、もしくはコロナ放電処
理を施すとか、適当なアンカー剤の塗布等の方法によっ
てフィルム表面を改質してもよい。本発明に係る屋外展
張用フィルムを展張使用する際は、層（Ｂ）が形成され
た面をハウスあるいはトンネルの外側になるように展張
する。If the adhesion between the film surface and the layer (B) is not sufficient, the film surface may be subjected to a plasma treatment or a corona discharge treatment before the application of the layer (B). The surface of the film may be modified by a method such as applying a suitable anchor agent. When the film for outdoor stretching according to the present invention is stretched and used, the surface on which the layer (B) is formed is stretched so as to be outside the house or tunnel.
【００４３】[0043]
【発明の効果】本発明に係る屋外展張用フィルムは、透
明性に優れ、且つ、層（Ａ）と層（Ｂ）との相乗効果に
より、夏場の農業用ハウス内の遮熱効果が向上し、その
効果の持続に優れるので、屋外展張用フィルムとしての
利用価値は極めて大きい。The film for outdoor stretching according to the present invention is excellent in transparency, and the heat shielding effect in the agricultural house in summer is improved by the synergistic effect of the layer (A) and the layer (B). Since the effect is excellent, the value of the film as an outdoor stretch film is extremely large.
【実施例】以下、本発明を実施例にもとづいて詳細に説
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。 実施例１〜９、比較例１〜６DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail below with reference to embodiments, but the present invention is not limited to the following examples unless it exceeds the gist. Examples 1 to 9, Comparative Examples 1 to 6
【００４４】（１）基体フィルムの調製 （i）ポリエチレンテレフタレート（ＰＥＴ）フィルム ポリエチレンテレフタレート（ｏ−クロロフェノールを
溶媒として用い、２５℃で測定した極限粘度が０．６５
のもの）１００重量部に対し、必要に応じ表−１に示し
た紫外線吸収剤を同表に示した配合割合で配合した。各
配合物をスーパーミキサーで１０分間攪拌混合したの
ち、常法によって溶融押出し、縦方向に延伸温度６５
℃、延伸倍率３．５倍、次いで横方向に延伸温度６５
℃、延伸倍率３．５倍で逐次二軸延伸し、厚さ０．１５
ｍｍの二軸配向フィルムを製造した。このフィルムの密
度は１．３７ｇ／cm3であった。(1) Preparation of base film (i) Polyethylene terephthalate (PET) film The intrinsic viscosity of polyethylene terephthalate (o-chlorophenol) measured at 25 ° C. at 0.65 was 0.65.
) Was blended with 100 parts by weight of the ultraviolet absorbers shown in Table 1 at the mixing ratios shown in the table as needed. After blending each composition with a super mixer for 10 minutes, the mixture was melt-extruded by a conventional method, and stretched at a stretching temperature of 65 in the machine direction.
° C, a draw ratio of 3.5 times, then a draw temperature of 65 in the transverse direction.
C., successively biaxially stretched at a draw ratio of 3.5 times to a thickness of 0.15
mm biaxially oriented film was produced. The density of this film was 1.37 g / cm 3 .
【００４５】（ii）軟質塩化ビニル系樹脂（ＰＶＣ）フ
ィルム ポリ塩化ビニル（重合度＝１３００）１００重量部に対
して、ジオクチルフタレートを５０重量部、トリクレジ
ルホスフェートを５重量部、エポキシ樹脂を２重量部、
Ｂａ−Ｚｎ系液状安定剤を２重量部、Ｂａ−Ｚｎ系粉末
安定剤を１重量部、ソルビタンモノパルミテートを１.
５重量部および表−１に示した紫外線吸収剤を０.１重
量部を秤量し、これらをスーパーミキサーで１０分間攪
拌混合した後、１６５℃に加熱したロール上で混練し、
Ｌ型カレンダー装置によって、幅１００ｃｍ、厚さ０．
１５ｍｍの透明な軟質塩化ビニル系樹脂フィルムを製造
した。(Ii) Soft vinyl chloride resin (PVC) film 100 parts by weight of polyvinyl chloride (degree of polymerization = 1300), 50 parts by weight of dioctyl phthalate, 5 parts by weight of tricresyl phosphate, and epoxy resin 2 parts by weight,
2 parts by weight of the Ba-Zn liquid stabilizer, 1 part by weight of the Ba-Zn powder stabilizer, and 1 part by weight of sorbitan monopalmitate.
5 parts by weight and 0.1 part by weight of the ultraviolet absorbent shown in Table 1 were weighed, and these were stirred and mixed by a super mixer for 10 minutes, and then kneaded on a roll heated to 165 ° C.
By L-type calender, width 100 cm, thickness 0.
A 15 mm transparent soft vinyl chloride resin film was produced.
【００４６】（iii）フッ素樹脂フィルム エチレン−テトラフルオロエチレン共重合樹脂フィルム
（デュポン（株）製テフゼルＡＳ、厚み６４μｍ）の片
面上に、放電電圧１２０Ｖ、放電電流４．７Ａ、ライン
スピード５〜１５ｍ／ｍｉｎでコロナ処理を行った。(Iii) Fluororesin Film A discharge voltage of 120 V, a discharge current of 4.7 A, and a line speed of 5 to 15 m were formed on one surface of an ethylene-tetrafluoroethylene copolymer resin film (Tefzel AS, manufactured by DuPont, thickness: 64 μm). / Min was subjected to corona treatment.
【００４７】（iv）ポリオレフィン系（ＰＯ）フィルム 三層インフレーション成形装置として三層ダイに１００
ｍｍφ（（株）プラ技研製）を用い、押出機は外肉層を
３０ｍｍφ（（株）プラ技研製）２台、中間層を４０ｍ
ｍφ（（株）プラ技研製）として成形温度１６０℃、ブ
ロー比２．０、引取速度５ｍ／分にて下記配合からなる
厚さ０．１５ｍｍの積層フィルムを製造した。(Iv) Polyolefin (PO) film As a three-layer inflation molding device, 100
The extruder used was 30 mmφ (manufactured by Pla Giken Co., Ltd.) and two intermediate layers were 40 m.
As a mφ (manufactured by Pla Giken Co., Ltd.), a laminated film having a thickness of 0.15 mm having the following composition was produced at a molding temperature of 160 ° C., a blow ratio of 2.0 and a take-up speed of 5 m / min.
【００４８】 ［外層］ 原料樹脂（ＥＶＡ（ＶＡ成分５％）） １００重量部 有機リン酸金属塩（リン酸モノオクタデシル亜鉛塩） ０．５ 〃 ヒンダードアミン（ＭＡＲＫ ＬＡ−５７） ０．５ 〃 紫外線吸収剤 ０．５ 〃 ソルビタンモノステアレート ０．５ 〃[Outer layer] Raw material resin (EVA (VA component: 5%)) 100 parts by weight Metal phosphate organic phosphate (monooctadecyl zinc phosphate) 0.5 Hindered amine (MARK LA-57) 0.5 UV absorption Agent 0.5 ソ ル sorbitan monostearate 0.5 〃
【００４９】 ［内層］ 原料樹脂（ＥＶＡ（ＶＡ成分１５％）） １００重量部 有機リン酸金属塩（リン酸モノオクタデシル亜鉛塩） ０．５ 〃 ヒンダードアミン（ＭＡＲＫ ＬＡ−５７） ０．５ 〃 紫外線吸収剤 ０．５ 〃 ソルビタンモノステアレート ０．５ 〃 ハイドロタルサイト類 １５ 〃[Inner layer] Raw material resin (EVA (VA component: 15%)) 100 parts by weight Organic metal phosphate (monooctadecyl zinc phosphate) 0.5 Hindered amine (MARK LA-57) 0.5 UV absorption Agent 0.5 ソ ル sorbitan monostearate 0.5 ハ イ ド ロ hydrotalcite 15 〃
【００５０】[0050]
【表１】 表ー１中、ａは、２，４−ジヒドロキシベンゾフェノン ｂは、２−ヒドロキシ−４−ｎオクトキシベンゾフェノン ｃは、２（２’−ヒドロキシ−５’−メチルフェニル）ベンゾトリアゾール をそれぞれ表す。[Table 1] In Table 1, a represents 2,4-dihydroxybenzophenone b, 2-hydroxy-4-noctoxybenzophenone c represents 2 (2′-hydroxy-5′-methylphenyl) benzotriazole, respectively.
【００５１】（２）層（Ａ） （i）層（Ａ）組成物の調製 表−２に示した種類の熱線遮蔽能を有する無機酸化物
を、アクリル系樹脂溶液（メチルメタクリレート５０重
量部、ブチルメタクリレート３０重量部および２ーヒド
ロキシエチルメタクリレート２０重量部）（固形分濃度
１０ｗｔ％）に表−２に示した配合量（重量％で示し
た）で配合し、層（Ａ）組成物を調製した。なお、ＩＴ
Ｏは、住友大阪セメント（株）製、超微粒子ＩＴＯ、Ａ
ＴＯは、住友大阪セメント（株）製、超微粒子ＡＴＯを
用いた。(2) Layer (A) (i) Preparation of Layer (A) Composition An inorganic oxide having a heat ray shielding ability of the type shown in Table 2 was mixed with an acrylic resin solution (methyl methacrylate 50 parts by weight, 30 parts by weight of butyl methacrylate and 20 parts by weight of 2-hydroxyethyl methacrylate (solid content: 10 wt%) were blended in the amounts shown in Table 2 (indicated by weight%) to prepare the layer (A) composition. did. In addition, IT
O is manufactured by Sumitomo Osaka Cement Co., Ltd.
As the TO, ultrafine particle ATO manufactured by Sumitomo Osaka Cement Co., Ltd. was used.
【００５２】（ii）層（Ａ）の形成 （１）で得られた各フィルムの片面（フッ素フィルムの
場合は、表面処理をした面上）に、（２）-（i）で得ら
れた各組成物をバーコート法によって、乾燥後の塗布量
が固形分として６ｇ／ｍ2となるように塗布し、１３０
℃の熱風中に１分間滞留させ溶媒を飛散させた。(Ii) Formation of Layer (A) On one surface of each film obtained in (1) (in the case of a fluorine film, on the surface that has been subjected to surface treatment), (2)-(i) was obtained. Each composition was applied by a bar coating method so that the applied amount after drying was 6 g / m 2 as a solid content.
The mixture was kept in hot air of 1 ° C. for 1 minute to disperse the solvent.
【００５３】（３）層（Ｂ） （ｉ）アクリル系樹脂の調製 紫外線吸収剤を配合するためのアクリル系樹脂溶液は、
次のように調製した。(3) Layer (B) (i) Preparation of Acrylic Resin An acrylic resin solution for blending an ultraviolet absorber is:
It was prepared as follows.
【００５４】（ａ）アクリル系樹脂溶液ａ ａ−１ 架橋アクリル酸エステル系弾性体の製造 重合缶中に、脱イオン水３００重量部（以下、単に
「部」と表示するのは「重量部」を意味する。）、過硫
酸カリ０．３部、燐酸二ナトリウム１２水塩０．５部、
燐酸水素ナトリウム２水塩０．３部を仕込み、充分窒素
置換を行ったのちに、内温を７０℃に昇温した。内温を
この温度に保持し、攪拌しながら、スチレン１９．８
部、アクリル酸ブチル６９．３部、メタクリル酸アリル
０．９部、ジオクチルスルホコハク酸ナトリウム（乳化
剤）２．５部からなる混合物を、２時間を要して連続的
に添加した。(A) Preparation of Acrylic Resin Solution a a-1 Crosslinked Acrylate Elastomer 300 parts by weight of deionized water (hereinafter simply referred to as "parts" means "parts by weight") in a polymerization vessel. ), 0.3 parts of potassium persulfate, 0.5 parts of disodium phosphate dodecahydrate,
After charging 0.3 parts of sodium hydrogen phosphate dihydrate and sufficiently purging with nitrogen, the internal temperature was raised to 70 ° C. The internal temperature was maintained at this temperature, and 19.8 g of styrene was added with stirring.
, 69.3 parts of butyl acrylate, 0.9 parts of allyl methacrylate, and 2.5 parts of sodium dioctylsulfosuccinate (emulsifier) were continuously added over 2 hours.
【００５５】添加終了後直ちに、ｔ−ブチルパーオキシ
−２−エチルヘキサノエート１．０部、スチレン２．２
部、アクリル酸ブチル７．７部、アクリル酸アリル０．
１部からなる混合物を加えた。加え終わってから３０分
間経過してから、内温を９０℃に昇温し、この温度で３
時間反応を続け、架橋弾性体のエマルジョンを得た。こ
の架橋弾性体の平均粒子径は０．２ｍμであり、ゲル含
量は９７．１％、膨潤度は７．２であった。Immediately after completion of the addition, 1.0 part of t-butylperoxy-2-ethylhexanoate and 2.2 parts of styrene were used.
Parts, butyl acrylate 7.7 parts, allyl acrylate 0.
One part mixture was added. After 30 minutes from the end of the addition, the internal temperature was raised to 90 ° C.
The reaction was continued for an hour to obtain a crosslinked elastic emulsion. The average particle diameter of this crosslinked elastic body was 0.2 μm, the gel content was 97.1%, and the degree of swelling was 7.2.
【００５６】ａ−２ グラフト共重合体の製造 重合缶に、上記ａ−１で得た架橋弾性体エマルジョン４
００部を仕込み、攪拌しながら、窒素置換した後、内温
を８０℃に昇温した。内温をこの温度に保持し、攪拌し
ながら脱イオン水３．０部にナトリウムホルムアルデヒ
ドスルホキシレート０．１５部を溶解した液を添加して
からメタクリル酸メチル３０．０部、ｎ−オクチルメル
カプタン０．０３部、パラメンタンパーオキサイド（５
０％溶液）０．１５部の混合物を、３０分間を要して連
続的に添加した。添加終了後、更に３０分間重合反応を
継続し、グラフト共重合体エマルジョンを得た。なおグ
ラフトさせた単量体成分から得られる共重合体自体のガ
ラス転移温度（Ｔｇ）は１０８℃であった。得られたグ
ラフト共重合体エマルジョンは、常法に従って塩析し、
重合体を濾別し、水洗し、乾燥して、グラフト共重合体
の粉末を得た。A-2 Production of Graft Copolymer The crosslinked elastomer emulsion 4 obtained in a-1 above was placed in a polymerization vessel.
After the replacement with nitrogen and stirring, the internal temperature was raised to 80 ° C. While maintaining the internal temperature at this temperature, a solution prepared by dissolving 0.15 part of sodium formaldehyde sulfoxylate in 3.0 parts of deionized water was added with stirring, and then 30.0 parts of methyl methacrylate and n-octyl mercaptan were added. 0.03 parts, paramenthane peroxide (5
(0% solution) 0.15 parts of the mixture were added continuously over a period of 30 minutes. After completion of the addition, the polymerization reaction was continued for another 30 minutes to obtain a graft copolymer emulsion. The glass transition temperature (Tg) of the copolymer itself obtained from the grafted monomer component was 108 ° C. The obtained graft copolymer emulsion is salted out according to a conventional method,
The polymer was separated by filtration, washed with water, and dried to obtain a powder of the graft copolymer.
【００５７】ａ−３ 樹脂溶液ａの調製 上記ａ−２で得たグラフト共重合体６．５部に、メタク
リル樹脂（メタクリル酸メチル／メタクリル酸エチルが
９６／４の割合の共重合体）のビーズ１３．５部を混合
し、この混合物をメチルエチルケトン６４部とトルエン
１６部とよりなる混合溶媒中に入れて、攪拌しつつ溶解
し、固形分が２０重量％のアクリル系樹脂溶液ａを調製
した。A-3 Preparation of Resin Solution a To 6.5 parts of the graft copolymer obtained in the above a-2 was added a methacrylic resin (a copolymer having a methyl methacrylate / ethyl methacrylate ratio of 96/4). 13.5 parts of beads were mixed, and this mixture was placed in a mixed solvent consisting of 64 parts of methyl ethyl ketone and 16 parts of toluene and dissolved with stirring to prepare an acrylic resin solution a having a solid content of 20% by weight. .
【００５８】（ｂ）アクリル系樹脂溶液ｂ ｂ−１ 架橋アクリル酸エステル系弾性体の製造 重合缶中に、脱イオン水２５０部、ジオクチルスルホコ
ハク酸ナトリウム２．９部、ナトリウムホルムアルデヒ
ドスルホキシレート０．０５部を仕込み、充分窒素置換
を行った。この重合缶の内容物を攪拌しつつ、メタクリ
ル酸メチル１．６部、アクリル酸ブチル８．０部、１，
３−ブチレンジメタクリレート０．４部、メタクリル酸
アリル０．１部、キュメンハイドロパーオキサイド０．
０４部からなる混合物を仕込んだ。重合缶内温を７０℃
に昇温し、この温度で６０分間反応を継続した。続い
て、この重合缶にメタクリル酸メチル１．５部、アクリ
ル酸ブチル２２．５部、１，３−ブチレンジメタクリレ
ート１．０部、メタクリル酸アリル０．２５部およびこ
れら単量体混合物に対して０．０５重量％の量のキュメ
ンハイフォロパーオキサイドを加えた混合物を６０分を
要して添加した。得られた架橋弾性体の平均粒子径は
０．１２ｍμであり、ゲル含量は９０％、膨潤度は１０
であった。(B) Acrylic resin solution b b-1 Preparation of crosslinked acrylic ester-based elastic material In a polymerization vessel, 250 parts of deionized water, 2.9 parts of sodium dioctylsulfosuccinate, and 0.1 part of sodium formaldehyde sulfoxylate. 05 parts were charged and sufficiently replaced with nitrogen. While stirring the contents of the polymerization vessel, 1.6 parts of methyl methacrylate, 8.0 parts of butyl acrylate,
0.4 part of 3-butylene methacrylate, 0.1 part of allyl methacrylate, cumene hydroperoxide 0.1 part.
A mixture consisting of 04 parts was charged. 70 ℃ inside the polymerization can
, And the reaction was continued at this temperature for 60 minutes. Subsequently, 1.5 parts of methyl methacrylate, 22.5 parts of butyl acrylate, 1.0 part of 1,3-butylene methacrylate, 0.25 part of allyl methacrylate and a mixture of these monomers were added to the polymerization vessel. A mixture of 0.05% by weight of cumene hypoperoxide was added over 60 minutes. The average particle diameter of the obtained crosslinked elastic body is 0.12 μm, the gel content is 90%, and the swelling degree is 10%.
Met.
【００５９】ｂ−２ グラフト共重合体の製造 上記ｂ−１で得た架橋弾性体エマルジョンを含む重合缶
に、イオン水３部にナトリウムホルムアルデヒドスルホ
キシレート０．０１部を溶解した液を添加してから、メ
タクリル酸メチル５部、アクリル酸ブチル５部、アクリ
ル酸アリル０．１部およびこれら単量体に対して０．０
３重量％の量のキュメンハイドロパーオキサイドを加え
た混合物を３０分要して、連続的に添加した。添加終了
後、更に３０分間重合反応を継続した。B-2 Production of Graft Copolymer A solution prepared by dissolving 0.01 part of sodium formaldehyde sulfoxylate in 3 parts of ionic water was added to a polymerization vessel containing the crosslinked elastic emulsion obtained in b-1 above. Then, 5 parts of methyl methacrylate, 5 parts of butyl acrylate, 0.1 part of allyl acrylate and 0.0
The mixture to which 3% by weight of cumene hydroperoxide was added was added continuously over 30 minutes. After completion of the addition, the polymerization reaction was continued for another 30 minutes.
【００６０】この重合缶に、イオン水３部にナトリウム
ホルムアルデヒドスルホキシレート０．０５部を溶解し
た液を添加してから８０℃に昇温し、メタクリル酸メチ
ル５２．２５部、アクリル酸ブチル２．７５部、パラメ
ンタンハイドロパーオキサイド（５０％溶液）０．１３
部よりなる混合物を、３０分間を要して添加した。添加
終了後、更に８０℃で３０分間重合反応を継続し、グラ
フト共重合体エマルジョンを得た。なお最外層にグラフ
トさせた単量体成分から得られる共重合体自体のガラス
転移温度（Ｔｇ）は１０３℃であった。得られたグラフ
ト共重合体エマルジョンは、常法に従って塩析し、重合
体を濾別し、水洗し、乾燥して、グラフト共重合体の粉
末を得た。A solution prepared by dissolving 0.05 part of sodium formaldehyde sulfoxylate in 3 parts of ionic water was added to the polymerization vessel, and the temperature was raised to 80 ° C. to obtain 52.25 parts of methyl methacrylate and 2 parts of butyl acrylate. .75 parts, paramenthane hydroperoxide (50% solution) 0.13
Parts of the mixture were added over 30 minutes. After the completion of the addition, the polymerization reaction was further continued at 80 ° C. for 30 minutes to obtain a graft copolymer emulsion. The glass transition temperature (Tg) of the copolymer itself obtained from the monomer component grafted on the outermost layer was 103 ° C. The obtained graft copolymer emulsion was salted out according to a conventional method, and the polymer was separated by filtration, washed with water, and dried to obtain a graft copolymer powder.
【００６１】ｂ−３ 樹脂溶液ｂの調製 上記ｂ−２で得たグラフト共重合体２０部をメチルエチ
ルケトン６４部とトルエン１６部とよりなる混合溶媒中
に入れて攪拌し、固形分が２０重量％のアクリル系樹脂
溶液ｂを調製した。B-3 Preparation of Resin Solution b 20 parts of the graft copolymer obtained in b-2 above was placed in a mixed solvent consisting of 64 parts of methyl ethyl ketone and 16 parts of toluene, and stirred to obtain a solid content of 20% by weight. Was prepared.
【００６２】（ii）層（Ｂ）組成物の調整 上記（i）に記載の方法に従って調製したアクリル系樹
脂溶液に、表−２に示した種類の紫外線吸収剤を、同表
に記載した割合（樹脂固形分に対する割合（重量％）を
意味する。）を添加した。 （iii）層（Ｂ）の形成 （２）で得られたフィルムの層（Ａ）を形成した面上
に、（３）−（ii）で得られた各種組成物をバーコート
法によって塗布し、１４０℃の熱風中に１分間滞留させ
溶媒を飛散させた。(Ii) Preparation of Layer (B) Composition Into the acrylic resin solution prepared according to the method described in the above (i), an ultraviolet absorber of the type shown in Table 2 was added in the proportion shown in the table. (Meaning a ratio (% by weight) to the resin solid content) was added. (Iii) Formation of Layer (B) On the surface of the film obtained in (2) on which layer (A) is formed, various compositions obtained in (3)-(ii) are applied by a bar coating method. At a temperature of 140 ° C. for 1 minute to disperse the solvent.
【００６３】[0063]
【表２】 [Table 2]
【００６４】表−２中の注（＊１）は以下のものを表
す。 Ｘ：２−（２'−ヒドロキシ−５'−ｔーブチルフェニ
ル）ベンゾトリアゾール Ｙ：２−（２'−ヒドロキシ−３'，５'−ジｔーブチル
フェニル）−５−クロロベンゾトリアゾール Ｚ：２，４−ジヒドロキシベンゾフェノンThe note (* 1) in Table 2 indicates the following. X: 2- (2'-hydroxy-5'-tert-butylphenyl) benzotriazole Y: 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole Z: 2,4- Dihydroxybenzophenone
【００６５】（４）評価 得られた各フィルムと耐候試験後（５０００ｈ後）のフ
ィルムについて次に記載した方法で各種の性質を評価
し、結果を表−３に示した。 （ｉ）耐候試験 紫外線ロングライフ・フェードメーター（スガ試験機
（株）製ＦＡＬ−５型）にてサンシャインカーボンアー
ク光源を使用し、耐候試験を行った。 （ii）可視光線透過率 自記分光光度計（日立３３０型）を用い、６０φ積分球
を使用し、５５５ｎｍでの全光線透過率を測定した。 （iii）熱線遮断率 自記分光光度計（日立３３０型）を用い、６０φ積分球
を使用し、２００〜２６００ｎｍでの全光線透過率を測
定し、かつ、太陽からの日射エネルギーの波長依存性デ
ータを合わせ、基材によって遮断される日射エネルギー
と基材がなく直接受ける日射エネルギーとの比で示し
た。(4) Evaluation Various properties of each of the obtained films and the film after the weathering test (after 5000 hours) were evaluated by the methods described below, and the results are shown in Table 3. (I) Weather resistance test A weather resistance test was performed using a sunshine carbon arc light source with an ultraviolet long life fade meter (FAL-5 type manufactured by Suga Test Instruments Co., Ltd.). (Ii) Visible light transmittance Total light transmittance at 555 nm was measured using a self-recording spectrophotometer (Hitachi 330 type) using a 60φ integrating sphere. (Iii) Heat-ray cutoff ratio Using a self-recording spectrophotometer (Hitachi 330 type), using a 60φ integrating sphere, measure the total light transmittance at 200 to 2600 nm, and obtain the wavelength dependence data of solar radiation energy from the sun. And the ratio of the solar energy blocked by the substrate to the solar energy directly received without the substrate.
【００６６】（iv）熱線遮蔽効果持続性 耐候試験後の熱線遮蔽効果を初期のそれと比較し、以下
の基準により評価した。 ５点：ほぼ初期の効果を持続 ４点：やや効果が劣るが、栽培性は良好 ３点：やや効果が劣り、栽培性にもやや影響が生じる ２点：僅かに熱線遮蔽効果は残っているが、夏場の栽培
性に効果無し １点：ほぼ効果が消滅(Iv) Persistence of heat ray shielding effect The heat ray shielding effect after the weathering test was compared with that at the initial stage and evaluated according to the following criteria. 5 points: Maintains almost the initial effect. 4 points: Slightly inferior effect, but good cultivation. 3 points: Slightly inferior effect, slightly affects cultivation. 2: Slight heat ray shielding effect remains. But no effect on summer cultivation 1 point: almost no effect
【００６７】[0067]
【表３】 [Table 3]
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｂ３２Ｂ 27/18 Ｂ３２Ｂ 27/18 Ｚ ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification code FI B32B 27/18 B32B 27/18 Z
Claims (6)
上に、周期律表３Ａ、４Ａおよび５Ａ族に属する少なく
とも１種の金属がドープされた熱線遮蔽能を有する無機
酸化物微粒子を含有する層（Ａ）を設け、更にその層上
および／またはフィルムの反対面上に、紫外線吸収剤を
含有する厚さ１〜１０μｍのアクリル系樹脂層（Ｂ）を
設けてなる屋外展張用フィルム。1. A layer (A) containing at least one surface of a thermoplastic resin film containing at least one metal belonging to Groups 3A, 4A and 5A of the periodic table and doped with an inorganic oxide having a heat ray shielding ability. ), And an acrylic resin layer (B) having a thickness of 1 to 10 μm and containing an ultraviolet absorber is further provided on the layer and / or on the opposite side of the film.
００ｎｍの無機酸化物微粒子と、そのバインダーとして
熱可塑性樹脂とを用いたものである、請求項１記載の屋
外展張用フィルム。2. The layer (A) having an average particle diameter of 5 to 20
2. The film for outdoor stretching according to claim 1, wherein the film comprises 00 nm inorganic oxide fine particles and a thermoplastic resin as a binder thereof.
以上である請求項１または２記載の屋外展張用フィル
ム。3. The linear light transmittance at 555 nm is 80%.
The film for outdoor stretching according to claim 1 or 2, which is the above.
モンがドープされた酸化スズ微粒子またはスズがドープ
された酸化インジウム微粒子である、請求項１ないし３
のいずれかの項に記載の屋外展張用フィルム。4. The inorganic oxide fine particles of the layer (A) are tin oxide fine particles doped with antimony or fine particles of indium oxide doped with tin.
The film for outdoor expansion according to any one of the above items.
物および／またはベンゾトリアゾール系化合物であり、
その量がフィルム１ｍ2あたり１５０〜１０００ｍｇの
範囲である請求項１ないし４のいずれかの項に記載の屋
外展張用フィルム。5. The ultraviolet absorber is a benzophenone-based compound and / or a benzotriazole-based compound,
Outdoor stretched film according to any one of the paragraphs to the amount of claims 1 ranges 150~1000mg per film 1 m 2 4.
しての架橋アクリル酸エステル系弾性体の存在下に、分
岐成分としてのメタクリル酸アルキルエステル単量体、
またはメタクリル酸アルキルエステルを主成分としこれ
と共重合可能なビニル系単量体との混合物を重合して得
られるグラフト共重合体である請求項１ないし５のいず
れかの項に記載の屋外展張用フィルム。6. An acrylic resin of the layer (B), wherein an alkyl methacrylate monomer as a branching component is formed in the presence of a crosslinked acrylate-based elastic body as a trunk component;
6. The outdoor stretch according to claim 1, wherein the graft is a graft copolymer obtained by polymerizing a mixture of a vinyl monomer which is mainly composed of an alkyl methacrylate and is copolymerizable therewith. For film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09873397A JP3787948B2 (en) | 1997-04-16 | 1997-04-16 | Film for outdoor extension |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09873397A JP3787948B2 (en) | 1997-04-16 | 1997-04-16 | Film for outdoor extension |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10286902A true JPH10286902A (en) | 1998-10-27 |
| JP3787948B2 JP3787948B2 (en) | 2006-06-21 |
Family
ID=14227723
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP09873397A Expired - Fee Related JP3787948B2 (en) | 1997-04-16 | 1997-04-16 | Film for outdoor extension |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3787948B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010089441A (en) * | 2008-10-10 | 2010-04-22 | Toli Corp | Heat barrier sheet |
| JP2015177781A (en) * | 2013-10-09 | 2015-10-08 | パナソニックＩｐマネジメント株式会社 | greenhouse |
| WO2024162180A1 (en) * | 2023-02-02 | 2024-08-08 | Ａｇｃ株式会社 | Heat-ray blocking film and agricultural greenhouse |
-
1997
- 1997-04-16 JP JP09873397A patent/JP3787948B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010089441A (en) * | 2008-10-10 | 2010-04-22 | Toli Corp | Heat barrier sheet |
| JP2015177781A (en) * | 2013-10-09 | 2015-10-08 | パナソニックＩｐマネジメント株式会社 | greenhouse |
| WO2024162180A1 (en) * | 2023-02-02 | 2024-08-08 | Ａｇｃ株式会社 | Heat-ray blocking film and agricultural greenhouse |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3787948B2 (en) | 2006-06-21 |
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