JPH0361587B2 - - Google Patents
Info
- Publication number
- JPH0361587B2 JPH0361587B2 JP58208327A JP20832783A JPH0361587B2 JP H0361587 B2 JPH0361587 B2 JP H0361587B2 JP 58208327 A JP58208327 A JP 58208327A JP 20832783 A JP20832783 A JP 20832783A JP H0361587 B2 JPH0361587 B2 JP H0361587B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- copolymer
- hydroxy
- vinyl chloride
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- -1 alkyl vinyl ether Chemical compound 0.000 claims description 46
- 229920001577 copolymer Polymers 0.000 claims description 41
- 229920005989 resin Polymers 0.000 claims description 38
- 239000011347 resin Substances 0.000 claims description 38
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 37
- 239000000178 monomer Substances 0.000 claims description 32
- 229910052731 fluorine Inorganic materials 0.000 claims description 19
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 16
- 239000011737 fluorine Substances 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 14
- 239000004094 surface-active agent Substances 0.000 claims description 14
- 239000005056 polyisocyanate Substances 0.000 claims description 13
- 229920001228 polyisocyanate Polymers 0.000 claims description 13
- 239000011247 coating layer Substances 0.000 claims description 8
- SKYXLDSRLNRAPS-UHFFFAOYSA-N 1,2,4-trifluoro-5-methoxybenzene Chemical compound COC1=CC(F)=C(F)C=C1F SKYXLDSRLNRAPS-UHFFFAOYSA-N 0.000 claims description 5
- 239000000470 constituent Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 238000012360 testing method Methods 0.000 description 21
- 238000000576 coating method Methods 0.000 description 16
- 239000011248 coating agent Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- 238000002834 transmittance Methods 0.000 description 10
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 10
- 239000006096 absorbing agent Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 8
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 235000014113 dietary fatty acids Nutrition 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- 239000000194 fatty acid Substances 0.000 description 7
- 229930195729 fatty acid Natural products 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 229920000578 graft copolymer Polymers 0.000 description 6
- 150000002978 peroxides Chemical class 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 5
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 5
- 235000011187 glycerol Nutrition 0.000 description 5
- 239000004014 plasticizer Substances 0.000 description 5
- 229920000056 polyoxyethylene ether Polymers 0.000 description 5
- 230000005855 radiation Effects 0.000 description 5
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 4
- 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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000011088 calibration curve Methods 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 4
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 3
- CFZGXWYAUQYJEC-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-cyclohexylphenol Chemical compound C1=C(N2N=C3C=CC=CC3=N2)C(O)=CC=C1C1CCCCC1 CFZGXWYAUQYJEC-UHFFFAOYSA-N 0.000 description 3
- 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 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- IYFATESGLOUGBX-YVNJGZBMSA-N Sorbitan monopalmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O IYFATESGLOUGBX-YVNJGZBMSA-N 0.000 description 3
- 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 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 235000011071 sorbitan monopalmitate Nutrition 0.000 description 3
- 239000001570 sorbitan monopalmitate Substances 0.000 description 3
- 229940031953 sorbitan monopalmitate Drugs 0.000 description 3
- 239000001587 sorbitan monostearate Substances 0.000 description 3
- 235000011076 sorbitan monostearate Nutrition 0.000 description 3
- 229940035048 sorbitan monostearate Drugs 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-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
- 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 2
- LMFQVOYNAXDCQT-UHFFFAOYSA-N 2-(5-chlorobenzotriazol-2-yl)-4-phenylphenol Chemical compound C1=C(N2N=C3C=C(Cl)C=CC3=N2)C(O)=CC=C1C1=CC=CC=C1 LMFQVOYNAXDCQT-UHFFFAOYSA-N 0.000 description 2
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 2
- DUUKZBGYNMHUHO-UHFFFAOYSA-N 253MC0P0YV Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)COCC(O)CO DUUKZBGYNMHUHO-UHFFFAOYSA-N 0.000 description 2
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 2
- 241000156978 Erebia Species 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 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
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 238000007754 air knife coating Methods 0.000 description 2
- 150000001336 alkenes Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 150000001565 benzotriazoles Chemical class 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- WXNRYSGJLQFHBR-UHFFFAOYSA-N bis(2,4-dihydroxyphenyl)methanone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1O WXNRYSGJLQFHBR-UHFFFAOYSA-N 0.000 description 2
- SODJJEXAWOSSON-UHFFFAOYSA-N bis(2-hydroxy-4-methoxyphenyl)methanone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=C(OC)C=C1O SODJJEXAWOSSON-UHFFFAOYSA-N 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 229940105990 diglycerin Drugs 0.000 description 2
- 238000007606 doctor blade method Methods 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 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
- 239000003063 flame retardant Substances 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 2
- 238000007756 gravure coating Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- NUKZAGXMHTUAFE-UHFFFAOYSA-N methyl hexanoate Chemical compound CCCCCC(=O)OC NUKZAGXMHTUAFE-UHFFFAOYSA-N 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 239000002736 nonionic surfactant 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
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-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
- ARVUDIQYNJVQIW-UHFFFAOYSA-N (4-dodecoxy-2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC(OCCCCCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 ARVUDIQYNJVQIW-UHFFFAOYSA-N 0.000 description 1
- RXUVWJWQFPJWOV-OWOJBTEDSA-N (e)-1,2-diisocyanatoethene Chemical compound O=C=N\C=C\N=C=O RXUVWJWQFPJWOV-OWOJBTEDSA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 description 1
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N 1,4-Benzenediol Natural products OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 1
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- AYMDJPGTQFHDSA-UHFFFAOYSA-N 1-(2-ethenoxyethoxy)-2-ethoxyethane Chemical compound CCOCCOCCOC=C AYMDJPGTQFHDSA-UHFFFAOYSA-N 0.000 description 1
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 description 1
- YAOJJEJGPZRYJF-UHFFFAOYSA-N 1-ethenoxyhexane Chemical compound CCCCCCOC=C YAOJJEJGPZRYJF-UHFFFAOYSA-N 0.000 description 1
- XXCVIFJHBFNFBO-UHFFFAOYSA-N 1-ethenoxyoctane Chemical compound CCCCCCCCOC=C XXCVIFJHBFNFBO-UHFFFAOYSA-N 0.000 description 1
- DJZPZWDPYDTRPM-UHFFFAOYSA-N 1-ethenoxypentan-1-ol Chemical compound CCCCC(O)OC=C DJZPZWDPYDTRPM-UHFFFAOYSA-N 0.000 description 1
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- WZUNUACWCJJERC-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CC)(CO)CO WZUNUACWCJJERC-UHFFFAOYSA-N 0.000 description 1
- GGSRTHRSSCWGGK-UHFFFAOYSA-L 2,2-dibutyl-5-hydroxy-1,3,2-dioxastannepane-4,7-dione Chemical compound CCCC[Sn]1(CCCC)OC(=O)CC(O)C(=O)O1 GGSRTHRSSCWGGK-UHFFFAOYSA-L 0.000 description 1
- PFEFOYRSMXVNEL-UHFFFAOYSA-N 2,4,6-tritert-butylphenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 PFEFOYRSMXVNEL-UHFFFAOYSA-N 0.000 description 1
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-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
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- 239000010452 phosphate Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920005670 poly(ethylene-vinyl chloride) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical class OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 1
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N salicylic acid phenyl ester Natural products OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 235000010267 sodium hydrogen 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
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 239000000271 synthetic detergent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- GAWWVVGZMLGEIW-GNNYBVKZSA-L zinc ricinoleate Chemical compound [Zn+2].CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O.CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O GAWWVVGZMLGEIW-GNNYBVKZSA-L 0.000 description 1
- 229940100530 zinc ricinoleate Drugs 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
- Protection Of Plants (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
Description
本発明は農業用被覆材として適した塩化ビニル
系樹脂フイルムに関し、さらに詳しくは、防曇持
続性、耐汚染性、耐候性等の性能に優れ長期展張
用として好適な農業用塩化ビニル系樹脂フイルム
に関する。
植物の施設栽培用のハウスやトンネルに展張さ
れる農業用フイルムの内面には、ハウスやトンネ
ルの内外の温度差のために水滴が付着し、日光の
透過率を低下させるため、該フイルムに防曇剤
(又は流滴剤)として界面活性剤を配合すること
はよく知られていることである。配合された界面
活性剤は徐々にフイルム表面に移行してフイルム
表面のヌレを良くし、防曇性を発揮するものであ
るが、特に塩化ビニル系樹脂フイルムの場合に
は、可塑剤が含まれているために界面活性剤のフ
イルム表面への移行性が大きく界面活性剤の流亡
による損失が激しく、防曇持続性が悪いという問
題がある。
このため従来から界面活性剤を配合した防曇性
塩化ビニル系樹脂フイルムの防曇持続性を改善す
る方法がいろいろと研究されており、その1つの
方法として、かかる防曇性塩化ビニル系樹脂フイ
ルムの一面に、界面活性剤の移行を抑制する樹脂
被膜層を設けることが提案され、一部は既に実用
化されている。そのような樹脂被膜層を形成する
ための樹脂として、従来、アクリル酸エステル系
モノマー、メタアクリル酸エステル系モノマーお
よび/またはこれらと共重合可能なビニル系モノ
マーの単独又は共重合体樹脂(特公昭40−12179
号、特公昭40−21269号、特公昭46−37429号、特
公昭47−28740号、特公昭48−16292号、特公昭50
−28117号及び特公昭50−31195号公報参照);等
が知られているが、これらはいずれも農園芸用フ
イルムに望まれている諸性質、たとえば防曇持続
性、耐汚染性、耐クラツク性、耐ブロツキング
性、ベースフイルムとの密着性、ヒートシール性
さらには耐候性などの諸性質を充分満足し得る程
度に兼備しておらず、まだ改良の余地を残してい
る。
そこで、本発明者らは上記のような欠点のない
樹脂被膜層を形成するのに適した樹脂成分につい
て鋭意研究した結果、或る種の水酸基含有含フツ
素共重合体と有機ポリイソシアネート化合物とを
組合せたものが非常に好適であることを見い出し
本発明を完成するに至つた。
しかして、本発明によれば、界面活性剤を配合
した防曇性塩化ビニル系樹脂フイルム基材料の一
面に、
[] フルオロオレフイン、シクロヘキシルビニ
ルエーテル、アルキルビニルエーテル及びヒド
ロキシアルキルビニルエーテルの4種のモノマ
ーから誘導される構成モノマー単位を合計で共
重合体の少なくとも70モル%含有し、数平均分
子量が30000〜50000の範囲内にあり且つ水酸基
当量が0.9〜1.2の範囲内にある水酸基含有含フ
ツ素共重合体と、
[] 有機ポリイソシアネート化合物より形成さ
れた硬化被膜層を有する農業用塩化ビニル系樹
脂フイルムが提案される。
本発明に従つて界面活性剤を配合した防曇性塩
化ビニル系樹脂フイルムの一面に設けられる硬化
被覆層は水酸基含有含フツ素共重合体[]と硬
化剤としての有機ポリイソシアネート化合物
[]から形成されるものであり、水酸基含有含
フツ素共重合体[]は、下記のモノマー成分:
(a) フルオロオレフイン、
(b) シクロヘキシルビニルエーテル、
(c) アルキルビニルエーテル及び
(d) ヒドロキシアルキルビニルエーテル、
並びに必要により、
(e) 共重合可能な他のモノマー
を共重合させることにより製造される、上記(a)、
(b)、(c)及び(d)の4種の必須のモノマー成分から誘
導される構成モノマー単位を合計で共重合体の全
構成モノマー単位の少なくとも70モル%、好まし
くは80モル%以上、さらに好ましくは90モル%以
上含有するものである。
上記共重合体[]の製造に使用されるフルオ
ロオレフイン(a)は、オレフインを構成している水
素原子のうちの少なくとも1個がフツ素原子で置
換され且つ場合により残りの水素原子のうちの少
なくとも1個がフツ素原子以外のハロゲン原子で
置換されていてもよいフツ素置換オレフインであ
り、一般に炭素原子数が2〜4個、好ましくは2
〜3個の直鎖状もしくは分岐鎖状のモノオレフイ
ンが好適である。そのようなフルオロオレフイン
(a)の具体例としては、フツ化ビニル、フツ化ビニ
リデン、トリフルオロエチレン、テトラフルオロ
エチレン、ヘキサフルオロプロピレン、クロロト
リフルオロエチレン等が挙げられ、中でも、クロ
ロトリフルオロエチレン、テトラフルオロエチレ
ンのようなパーハロオレフインが有利に使用され
る。これらモノマーはそれぞれ単独で使用するこ
とができ或いは2種以上組合わせて用いてもよ
い。
またシクロヘキシルビニルエーテル(b)は、式
The present invention relates to a vinyl chloride resin film suitable as an agricultural covering material, and more specifically to an agricultural vinyl chloride resin film that is excellent in performance such as anti-fog durability, stain resistance, and weather resistance and is suitable for long-term extension. Regarding. Due to the temperature difference between the inside and outside of the greenhouse or tunnel, water droplets adhere to the inner surface of agricultural films that are spread in greenhouses and tunnels for the facility cultivation of plants, reducing the transmittance of sunlight. It is well known to incorporate surfactants as fogging agents (or droplet agents). The blended surfactant gradually migrates to the film surface to improve the wetting of the film surface and exhibit antifogging properties, but especially in the case of vinyl chloride resin films, plasticizers are not included. Therefore, there is a problem that the migration of the surfactant to the film surface is large, the loss of the surfactant due to runoff is large, and the anti-fog durability is poor. For this reason, various methods have been studied to improve the antifogging durability of antifogging vinyl chloride resin films containing surfactants. It has been proposed to provide a resin coating layer on one side of the substrate to suppress the migration of surfactants, and some of these have already been put into practical use. Conventionally, as resins for forming such resin coating layers, single or copolymer resins of acrylic acid ester monomers, methacrylic acid ester monomers, and/or vinyl monomers copolymerizable with these monomers (Tokuko Showa) have been used. 40−12179
Special Publication No. 40-21269, Special Publication No. 37429, Special Publication No. 46-37429, Special Publication No. 28740, Special Publication No. 48-16292, Special Publication No. 16292, Special Publication No. 1977
-28117 and Japanese Patent Publication No. 50-31195); all of these are known to have various properties desired for agricultural and horticultural films, such as anti-fog durability, stain resistance, and crack resistance. It does not have sufficient properties such as hardness, blocking resistance, adhesion to the base film, heat sealability, and even weather resistance, and there is still room for improvement. Therefore, as a result of intensive research into resin components suitable for forming a resin coating layer free of the above-mentioned drawbacks, the present inventors found that a certain type of hydroxyl group-containing fluorine-containing copolymer and an organic polyisocyanate compound were combined. We have found that a combination of these is very suitable and have completed the present invention. Therefore, according to the present invention, on one side of the antifogging vinyl chloride resin film base material containing a surfactant, a compound derived from four types of monomers: [] fluoroolefin, cyclohexyl vinyl ether, alkyl vinyl ether, and hydroxyalkyl vinyl ether is added. A hydroxyl group-containing fluorine-containing copolymer containing a total of at least 70 mol% of the constituent monomer units of the copolymer, having a number average molecular weight within the range of 30,000 to 50,000, and having a hydroxyl group equivalent within the range of 0.9 to 1.2. An agricultural vinyl chloride resin film having a cured film layer formed from a combination of organic polyisocyanate compounds and an organic polyisocyanate compound is proposed. The cured coating layer provided on one surface of the antifogging vinyl chloride resin film containing a surfactant according to the present invention is made of a hydroxyl group-containing fluorine-containing copolymer [] and an organic polyisocyanate compound [] as a curing agent. The hydroxyl group-containing fluorine-containing copolymer [] contains the following monomer components: (a) fluoroolefin, (b) cyclohexyl vinyl ether, (c) alkyl vinyl ether, and (d) hydroxyalkyl vinyl ether, and If necessary, (e) the above (a) produced by copolymerizing other copolymerizable monomers;
The total constituent monomer units derived from the four essential monomer components (b), (c) and (d) are at least 70 mol%, preferably 80 mol% or more of the total constituent monomer units of the copolymer, More preferably, the content is 90 mol% or more. The fluoroolefin (a) used in the production of the above copolymer [] has at least one of the hydrogen atoms constituting the olefin substituted with a fluorine atom, and in some cases, the remaining hydrogen atoms are substituted with a fluorine atom. A fluorine-substituted olefin in which at least one atom may be substituted with a halogen atom other than a fluorine atom, and generally has 2 to 4 carbon atoms, preferably 2
~3 linear or branched monoolefins are preferred. Such fluoroolefins
Specific examples of (a) include vinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, etc. Among them, chlorotrifluoroethylene, tetrafluoroethylene, etc. perhaloolefins are advantageously used. These monomers can be used alone or in combination of two or more. In addition, cyclohexyl vinyl ether (b) has the formula
【式】で示されるモノマーで
あり、アルキルビニルエーテル(c)は式
CH2=CH−O−R1
式中、R1はアルキル基を表わし、ここで該ア
ルキル基としては炭素原子数が2〜8個、特に2
〜4個の直鎖状もしくは分岐鎖状のアルキル基が
好ましい、
で示されるモノマーであり、例えば、エチルビニ
ルエエーテル、プロピルビニルエーテル、イソプ
ロピルビニルエーテル、ブチルビニルエーテル、
t−ブチルビニルエーテル、ヘキシルビニルエー
テル、n−オクチルビニルエーテル、2エチルヘ
キシルビニルエーテル等が挙げられ、これらはそ
れぞれ単独で又は2種以上組合せて使用すること
ができる。
本発明で使用する共重合体[]の製造に使用
されるヒドロキシアルキルエーテル(d)は下記式
CH2=CH−O−R2−OH
式中、R2はアルキル基を表わし、ここで該ア
ルキレン基としては炭素原子数が2〜8個、特に
2〜4個の直鎖状もしくは分岐鎖状のアルキル基
が好ましい、
で示されるモノマーであり、例えば、ヒドロキシ
エチルビニルエーテル、ヒドロキシプロピルビニ
ルエーテル、ヒドロキシイソプロピルビニルエー
テル、ヒドロキシブチルビニルエーテル、ヒドロ
キシアミルビニルエーテル、ヒドロキシヘキシル
ビニルエーテル、ヒドロキシオクチルビニルエー
テル等が包含され、これらはそれぞれ単独で又は
2種以上組合わせて使用することができる。
本発明で使用する共重合体[]は、場合によ
り、該共重合体の全構成モノマー単位の30モル%
以下、好ましくは20モル%以下、さらに好ましく
は10モル%以下の量で、上記4種の必須モノマー
成分に加えて共重合可能な他のモノマーから誘導
される構成単位をさらに含有していてもよく、そ
のような他のモノマーの例としてはメチルメタア
クリレート、エチルメタアクリレート、n−プロ
ピルメタアクリレート、n−ブチルメタアクリレ
ート、シクロヘキシルメタアクリレート、2−エ
チルヘキシルメタアクリレート、メチルアクリレ
ート、エチルアクリレート、ブチルアクリレート
等の(メタ)アクリル系モノマー;塩化ビニル、
エチレン、プロピレン、アクリロニトリル、マレ
イン酸、イタコン酸、酢酸ビニル等が包含され
る。これらのモノマーもまたそれぞれ単独で又は
2種以上組合わせて使用することができる。
以上述べたモノマー(a)〜(e)の共重合体はそれ自
体公知のラジカル重合法により、例えば特開昭57
−34107号公報に記載の方法により行なうことが
できる。しかして、該共重合は例えば、上記のモ
ノマー(a)〜(e)を所定の割合で混合し、反応媒体
(例えば、水、アルコール類、エステル類、ハロ
ゲン化炭化水素など)中で又は反応媒体を用いず
に、重合開始剤の存在下で又は電離性放射線のよ
うな活性線の照射下で行なうことができる。重合
の方式としては特に制限はなく、塊状重合、懸濁
重合、乳化重合、溶液重合等の方式を採用するこ
とができるが、特に乳化重合及び溶液重合が好都
合である。
上記の重合開始剤は重合の方法や反応媒体に応
じて適宜選択しうるが、水溶性の開始剤としては
例えば過硫酸カリウム、過酸化水素又はこれらと
亜硫酸水素ナトリウム、チオ硫酸ナトリウムのご
とき還元剤との組合せからなるレドツクス開始
剤;これに少量の鉄、第一鉄塩、硝酸銀等を共存
させた系等の無機系開始剤;或いは、ジコハク酸
パーオキサイド、ジグルタール酸パーオキサイ
ド、モノコハク酸パーオキサイドのごとき二塩基
酸過酸化物やアゾビスイソブチルアミジン二塩基
酸塩等の有機系開始剤等を使用することができ、
また非水溶性の開始剤としては例えばt−ブチル
パーオキシイソブチレート、t−ブチルパーオキ
シアセテートのごときパーオキシエステル型過酸
化物;、ジイソプロピルパーオキシジカーボネー
トのごときジアルキルパーオキシジカーボネー
ト;ベンゾイルパーオキシド、アゾビスイソブチ
ロニトリル等が用いられる。これら重合開始剤は
共重合すべきモノマーの合計重量を基準にして一
般に0.005〜5重量%、好ましくは0.05〜0.5重量
%の割合で使用することができる。
また、重合温度は重合方式等にもよるが、一般
には−30℃〜150℃の範囲内の温度が適しており、
特に水性媒体中での重合の場合には0℃〜100℃、
好ましくは10℃〜90℃の範囲の温度とすることが
できる。さらに重合反応は時に制限はないが、一
般に1〜100Kg/cm2、好ましくは2〜50Kg/cm2と
することができる。
上記共重合に供するモノマー(a)〜(e)の使用量は
得られる共重合体の物性等に応じて自由に選択す
ることができるが、本発明で用いる共重合体
[]は前述したように、水酸基当量が0.9〜1.2
の範囲内、さらに好ましくは1.0〜1.1の範囲内に
あるべきであり、従つて、ヒドロキシアルキルビ
ニルエーテル(d)はかかる範囲の水酸基当量を与え
るような量で使用される。
また、本発明で使用する共重合体[]は該共
重合体の重量を基準にして一般に15〜50重量%、
好ましくは20〜40重量%、さらに好ましくは25〜
35重量%の範囲内の含量でフツ素を含有すること
ができ、従つて、前記フツ素含有モノマーである
フルオロオレフイン(a)の使用量は得られる共重合
体のフツ素含量が上記の範囲内に入るように選ば
れる。
しかして、各モノマーの使用量の一応の目安と
して以下に示す範囲を例示することができる。The alkyl vinyl ether (c) is a monomer represented by the formula: CH 2 =CH-O-R 1 , where R 1 represents an alkyl group, and the alkyl group has 2 to 2 carbon atoms. 8, especially 2
A monomer having ~4 linear or branched alkyl groups is preferred, such as ethyl vinyl ether, propyl vinyl ether, isopropyl vinyl ether, butyl vinyl ether,
Examples include t-butyl vinyl ether, hexyl vinyl ether, n-octyl vinyl ether, and 2-ethylhexyl vinyl ether, and these can be used alone or in combination of two or more. The hydroxyalkyl ether (d) used in the production of the copolymer [] used in the present invention has the following formula: CH 2 =CH-O-R 2 -OH, where R 2 represents an alkyl group, and where The alkylene group is preferably a linear or branched alkyl group having 2 to 8 carbon atoms, particularly 2 to 4 carbon atoms, such as hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxy Isopropyl vinyl ether, hydroxybutyl vinyl ether, hydroxyamyl vinyl ether, hydroxyhexyl vinyl ether, hydroxyoctyl vinyl ether, etc. are included, and these can be used alone or in combination of two or more. The copolymer [] used in the present invention may optionally be 30 mol% of the total monomer units of the copolymer.
In addition to the above four essential monomer components, it may further contain structural units derived from other copolymerizable monomers, preferably in an amount of 20 mol% or less, more preferably 10 mol% or less. Common examples of such other monomers include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate. (meth)acrylic monomers such as vinyl chloride,
Ethylene, propylene, acrylonitrile, maleic acid, itaconic acid, vinyl acetate and the like are included. These monomers can also be used individually or in combination of two or more. The copolymers of monomers (a) to (e) described above can be produced by a radical polymerization method known per se, for example, in JP-A-57
This can be carried out by the method described in JP-A-34107. Therefore, the copolymerization can be carried out, for example, by mixing the above monomers (a) to (e) in a predetermined ratio and reacting the mixture in a reaction medium (e.g., water, alcohols, esters, halogenated hydrocarbons, etc.). It can be carried out without a medium, in the presence of a polymerization initiator or under irradiation with actinic radiation such as ionizing radiation. There is no particular restriction on the polymerization method, and methods such as bulk polymerization, suspension polymerization, emulsion polymerization, and solution polymerization can be employed, but emulsion polymerization and solution polymerization are particularly convenient. The above polymerization initiator can be selected as appropriate depending on the polymerization method and reaction medium, but water-soluble initiators include, for example, potassium persulfate, hydrogen peroxide, or these combined with a reducing agent such as sodium bisulfite or sodium thiosulfate. A redox initiator consisting of a combination with; an inorganic initiator such as a system in which a small amount of iron, ferrous salt, silver nitrate, etc. coexists; or disuccinic acid peroxide, diglutaric acid peroxide, monosuccinic acid peroxide Dibasic acid peroxides such as dibasic acid peroxides and organic initiators such as azobisisobutyramidine dibasic acid salts can be used.
Examples of water-insoluble initiators include peroxyester type peroxides such as t-butyl peroxyisobutyrate and t-butyl peroxyacetate; dialkyl peroxydicarbonates such as diisopropyl peroxydicarbonate; and benzoyl peroxydicarbonates. Peroxide, azobisisobutyronitrile, etc. are used. These polymerization initiators can generally be used in a proportion of 0.005 to 5% by weight, preferably 0.05 to 0.5% by weight, based on the total weight of the monomers to be copolymerized. In addition, the polymerization temperature depends on the polymerization method, etc., but generally a temperature within the range of -30℃ to 150℃ is suitable.
0°C to 100°C, especially for polymerization in aqueous media;
Preferably, the temperature can be in the range of 10°C to 90°C. Furthermore, the polymerization reaction can be carried out at a rate of generally 1 to 100 Kg/cm 2 , preferably 2 to 50 Kg/cm 2 , although there are no restrictions. The amount of monomers (a) to (e) used in the above copolymerization can be freely selected depending on the physical properties of the copolymer obtained, but the copolymer [ ] used in the present invention is as described above. , the hydroxyl equivalent is 0.9 to 1.2
, more preferably from 1.0 to 1.1, and the hydroxyalkyl vinyl ether (d) is therefore used in such an amount as to give a hydroxyl equivalent weight in such a range. In addition, the copolymer [] used in the present invention generally contains 15 to 50% by weight based on the weight of the copolymer.
Preferably 20 to 40% by weight, more preferably 25 to 40% by weight
Fluorine can be contained in a content within the range of 35% by weight, and therefore, the amount of fluoroolefin (a) used as the fluorine-containing monomer is such that the fluorine content of the resulting copolymer falls within the above range. chosen to enter. Therefore, the ranges shown below can be exemplified as a tentative guideline for the amount of each monomer to be used.
【表】
かくして上記モノマー(a)、(b)、(c)及び(d)から誘
導される構成モノマー単位を一般にそれぞれ30〜
70モル%、5〜30モル%、10〜40モル%及び5〜
20モル%、好ましくはそれぞれ40〜60モル%、15
〜25モル%、20〜30モル%及び5〜15モル%の割
合(ただし、これらの合計は70モル%を越えない
ものとする)で含有する水酸基含有含フツ素共重
合体[]が得られるが、該共重合体[]は
30000〜50000、好ましくは33000〜45000、さらに
好ましくは35000〜42000の範囲内の数平均分子量
を有することが重要である。数平均分子量が低す
ぎるものは、防曇持続性、ブロツキング性及び耐
汚染性等の効果が少なく、反対に数平均分子量が
50000より大きくなると、共重合体の溶解性及び
被覆可撓性が低下するので良くない。
なお、本明細書で使用する「数平均分子量」は
ゲル・パーミエシヨン・クロマトグラフイー法に
より、溶離液としてテトラヒドロフラン、カラム
充填剤としてスチレン−ジビニルベンゼン共重合
体を用い、標準ポリスチレンより求めた検量線か
ら決定した値である。
本発明で使用する共重合体[]は前述のとお
り官能基として水酸基を含有するので、有機ポリ
イソシアネート化合物[]を用いて低温で架橋
硬化させることが可能となる。しかして、本発明
において硬化剤として使用される有機ポリイソシ
アネート化合物[]としては、1分子中にイソ
シアネート基を少なくとも2個、好ましくは2〜
3個有し且つ分子量が一般に90〜400、好ましく
は120〜300程度の鎖状もしくは環状又は両者の組
合わせからなる有機化合物が包含され、具体的に
は、ヘキサメチレンジイソシアネート、2,4−
トリレンジイソシアネート、4,4−ジフエニル
メタンジイソシアネート、ジアニシジンジイソシ
アネート、m−キシリレンジイソシアネート、ト
ランスビニレンジイソシアネート、2,6−ジイ
ソシアネートメチルカプロエート、イソホロンジ
イソシアネート、トリレンジイソシアネート、ト
リデンジイソシアネート、4,4′−ジシクロヘキ
シルメタンジイソシアネート(水添加4,4′−ジ
フエニルメタンジイソシアネート)水添加2,4
−トリレンジイソシアネート、水添加m−キシリ
レンジイソシアネート等が挙げられ、中でも、ヘ
キサメチレンジイソシアネート、4,4′−ジシク
ロヘキシルメタンジイソシアネート(水添加4,
4′−ジフエニルメタンジイソシアネート)、水添
加2,4−トリレンジイソシアネート、水添加m
−キシリレンジイソシアネートが好適である。
これら有機ポリイソシアネート化合物[]の
使用量は、硬化すべき共重合体[]の種類や硬
化の程度に応じて変えることができるが、一般に
は、有機ポリイソシアネート化合物[]中のイ
ソシアネート当量と硬化すべき共重合体[]の
水酸基当量の比が、0.9〜1.2の範囲、好ましくは
1.0〜1.1の範囲内となるような量で使用すること
が望ましい。
水酸基含有含フツ素共重合体[]と有機ポリ
イソシアネート化合物[]とからなる硬化性樹
脂組成物を、本発明に従い、防曇性塩化ビニル系
樹脂フイルムの一面に被膜層として適用するに際
して、該組成物は一般に溶剤に溶解した溶液とし
て該フイルム表面にコーテイングするのが便利で
ある。しかして、該組成物を溶解するために使用
しうる溶剤としては、例えば、酢酸メチル、酢酸
エチル;メチルエチルケトン、アセトン、メチル
ブチルケトン;メタノール、エタノール、イソプ
ロパノール;テトラヒドロフラン、メチルセロソ
ルブ;ジメチルホルムアミド;ベンゼン、キシレ
ン、トルエン、ミネラルスピリツト等が挙げられ
る。
該溶液中における共重合体[]の濃度には特
に制約はないが、一般に固形分濃度としては10〜
30重量%の範囲内、また、メチルブチルケトン/
キシレン=50/50の混合溶剤中の溶液粘度として
は約10〜50c.p.s程度とすることができ、また、
該溶液には、共重合体[]と有機ポリイソシア
ネート化合物[]の架橋反応を促進するための
触媒として、例えば、ジブチルチンジラウレー
ト、ジブチルチンジクロライド、ナフテン酸銅、
ナフテン酸亜鉛、硝酸亜鉛、硝酸蒼鉛、塩化第二
スズ、スタナスオクトエート、N,N,N′,
N′−テトラメチルポリメチレンジアミン、オク
チル酸カルシウム等を触媒量(例えば共重合体
[]の重量を基準にして0.0001%〜1%、好ま
しくは0.001〜0.5%)で配合することができ、さ
らに紫外線吸収剤、抗酸化剤、分散安定剤、粘度
調節剤、レベリング剤、ゲル化防止剤、顔料、ブ
ロツキング防止剤等を添加してもよい。
このようにして調製されるコーテイング溶液
は、実質的に架橋反応が進行するより以前に、防
曇性塩化ビニル系樹脂フイルムの一面に塗布す
る。塗布はそれ自体公知の手段、例えばグラビヤ
コーテイング法、ドクターブレード法、ロールコ
ート法、リバースロール法、エヤーナイフコート
法等を用いて行なうことができ、塗布量としては
乾燥後の膜厚が一般に1〜15ミクロン、好ましく
は1〜10ミクロンとなるような量が適当である。
塗膜の乾燥硬化はそれ自体公知の方法で行なう
ことができ、乾燥は例えば熱風乾燥炉、赤外線ヒ
ーター乾燥炉等の中で一般に20℃〜150℃、好ま
しくは50℃〜130℃の温度を用いて約0.5〜約10分
程度行なうことができ、乾燥後の塗膜は硬化を完
結させるために必要に応じて20℃〜40℃の温度、
通常室温に3〜10日間保持することができる。
以上に述べた方法で界面活性剤を配合した防曇
性塩化ビニル系樹脂フイルムの一面に、水酸基含
有含フツ素共重合体[]と有機ポリイソシアネ
ート化合物[]とから形成された、耐溶剤性、
耐汚染性、耐候性等に優れた柔軟な硬化被膜層を
設けることができる。
このような硬化被膜層を適用することができる
塩化ビニル系樹脂フイルムとしては、従来から農
業用フイルムとして使用されている任意の塩化ビ
ニル系樹脂フイルムであることができる。該フイ
ルムの基材となる塩化ビニル系樹脂としては、塩
化ビニルの単独重合体のほかに、塩化ビニルと酢
酸ビニル、エチレン、プロピレン、アクリル酸エ
ステル、メタアクリル酸エステル等の単量体の少
なくとも1種の40重量%以下、好ましくは30重量
%以下の量(全単量体の重量基準)との共重合
体、及び、これら単独重合体又は共重合体に対し
て相溶性のある重合体、例えば、エチレン−酢酸
ビニル共重合体、塩化ビニル−酢酸ビニル共重合
体、エチレン−塩化ビニル共重合体、プロピレン
−塩化ビニル共重合体、エチレン−プロピレン−
塩化ビニル共重合体(なお、これらの共重合体は
グラフト共重合体をも包含するものである)等を
前記塩化ビニル単独重合体又は共重合体100重量
部に対して30重量部以下、好ましくは20重量部以
下の量でブレンドした樹脂を用いることができ
る。
これら塩化ビニル系樹脂には可塑剤を配合して
軟質塩化ビニル系樹脂として使用される。可塑剤
の配合量は塩化ビニル系樹脂100重量部に対して
30〜70重量部の範囲が好ましく、40〜60重量部の
範囲が特に好ましい。配合しうる可塑剤として
は、たとえばフタル酸ジブチル、フタル酸ジオク
チル、フタル酸ジイソデシル、フタル酸ジイソノ
ニル、アジピン酸ジオクチル、セバシン酸ジオク
チル、リン酸トリクレジル、フタル酸ブチルベン
ジル、エポキシ化大豆油、エポキシ化アマニ油、
エポキシ樹脂等が挙げられる。
上記軟質塩化ビニル系樹脂には、さらに必要に
応じて、通常の添加物、例えば、滑剤、酸化防止
剤、帯電防止剤、熱安定剤、着色剤(顔料、染
料)、難燃剤等を配合することもできる。
滑剤としては、たとえばエチレンビスステアリ
ルアミド、ブチルステアレートパラフインワツク
ス、低分子量ポリエチレン、モンタン酸ワツク
ス、ステアリン酸、ステアリルアルコール等が挙
げられ、酸化防止剤としては、たとえば2,6−
ジ−tert−ブチル−4−メチルフエノール、2,
4,6−トリ−tert−ブチルフエノール、2,
2′−メチレンビス(4−メチル−6−tert−ブチ
ルフエノール)、4,4′−チオビス−(3−メチル
−6−tert−ブチルフエノール)、フエニルα−
ナフチルアミン等が挙げられる。
また、帯電防止剤としては、たとえばポリオキ
シエチレンアルキルアミド、アルキロールアミ
ド、エタノールアミド、アルキルホスフエート、
アルキルサルフエート等を使用することができ、
熱安定剤としては、たとえばジブチルスズマレー
ト、ジブチルスズジラウレート、ステアリン酸カ
ルシウム、リシノール酸亜鉛、トリフエニルホス
フアイト等が適している。
また、配合しうる着色剤としては、フタロシア
ニンブルー、フタロシアニングリーン、酸化チタ
ン、クロモフタールレツド、シンカシアレツド等
を例示することができる。
その他、酸化アンチモン、水酸化アルミニウ
ム、ハロゲン含有リン酸エステル等の難燃剤等を
適宜配合することもできる。
さらに、本発明で使用する塩化ビニル系樹脂フ
イルムは防曇性のものであり、しかして、該フイ
ルムに防曇性を付与するために配合される界面活
性剤としては、例えばカルボン酸塩、スルホン酸
塩、硫酸エステル塩、リン酸エステル塩等のアニ
オン系界面活性剤;脂肪族アミン塩およびその第
四級アンモニウム塩、芳香族第四級アンモニウム
塩等のカチオン系界面活性剤;ベタイン、アミノ
カルボン酸塩、イミダゾリジン誘導体等の両性界
面活性剤;アルキルおよびアルキルアリルポリオ
キシエチレンエーテル、グリセリンエーテルおよ
びそのポオキシエチレンエーテル、ポリオキシエ
チレン脂肪族エステル、グリセリンエステル、ソ
ルビタンエステル、ポリグリセリンエステル、二
価アルコールエステル、シヨ糖エステル、グリセ
リンエステルのポリオキシエチレンエーテル、ソ
ルビタンエステルのポリオキシエチレンエーテ
ル、ソルビトールポリオキシエチレンエーテルの
エステル、グリセリンエステルのエーテル、ソル
ビトールポリオキシエチレンポリオキシプロピレ
ンのエステル、ソルビタンポリオキシエチレンポ
リオキシプロピレンのエステル、グリセリンポリ
オキシエチレンポリオキシプロピレンのエステル
等の非イオン系界面活性剤;フツ素系界面活性
剤;シリコン系界面活性剤等が挙げられ、これら
はそれぞれ単独で又は2種もしくはそれ以上併用
してもよく、その使用量は一般塩化ビニル樹脂
100重量部当り0.5〜3.0重量部の範囲内とするこ
とができる。界面活性剤の中では非イオン系界面
活性剤が適しており、特に次のものを例示するこ
とができる:例えばソルビタンモノステアレー
ト、ソルビタンモノパルミテート等のソルビタン
脂肪酸エステル;ジグリセリンモノパルミテー
ト、ジグリセリンモノステアレート等のジグリセ
リン脂肪酸エステル;グリセリンモノステアレー
ト等のグリセリン脂肪酸エステル;ペンタエリス
リトールモノステアレート等のペンタエリスリト
ール脂肪酸エステル;ジペンタエリスリトールモ
ノパルミテート等のジペンタエリスリトール脂肪
酸エステル;ソルビタンモノパルミテート・ハー
フアジベート、ジグリセリンモノステアレート・
ハーフグルタミン酸エステル等のソルビタン及び
ジグリセリン脂肪酸・二塩酸基酸エステル;並び
にこれらとアルキレンオキサイド例えばエチレン
オキサイド、プロピレンオキサイド等との縮合
物、例えばポリオキシエチレン(2モル)ソルビ
タンモノステアレート、ポリオキシプメピレン
(2モル)ジグリセリンモノパルミテート等;ポ
リオキシエチレンラウリルエーテル等のポリオキ
シエチレン脂肪アルコール;ポリオキシエチレン
モノステアレート等のポリオキシエチレン脂肪酸
エステル等が挙げられる。
さらに、本発明で使用する塩化ビニル系樹脂フ
イルムには、該フイルムの耐候性を改善する目的
で、或いは紫外線遮蔽性フイルムを提供する目的
で、紫外線吸収剤を配合することもできる。配合
しうる紫外線吸収剤としては、例えば以下に例示
するものが挙げられる。
ハイドロキノン系−ハイドロキノン、ハイドロ
キノンジサリチレート。
サリチル酸系−フエニルサリチレート、パラオ
クチルフエニルサリチレート、4−t−ブチルフ
エニルサリチレート、レゾルシンモノベンゾエー
ト。
ベンゾフエノン系−2−ヒドロキシ−4−メト
キシベンゾフエノン、2−ヒドロキシ−4−n−
オクトキシベンゾフエノン、2−ヒドロキシ−4
−メトキシ−2′−カルボキシベンゾフエノン、
2,4−ジヒドロキシベンゾフエノン、2,2′−
ジヒドロキシ−4,4′−ジメトキシベンゾフエノ
ン、2−ヒドロキシ−4−ベンゾイルオキシベン
ゾフエノン、2,2′−ヒドロキシ−4−メトキシ
ベンゾフエノン、2−ヒドロキシ−4−メトキシ
−5−スルホンベンゾフエノン、2,2′,4,
4′−テトラヒドロキシベンゾフエノン、2,2′−
ヒドロキシ−4,4′−ジメトキシ−5−ナトリウ
ムスルホベンゾフエノン、4−ドデシルオキシ−
2−ヒドロキシベンゾフエノン、2−ハイドロキ
シ−5−クロルベンゾフエノン
ベンゾトリアゾール系−2−(2′−ヒドロキシ
−5′−メチルフエニル)ベンゾトリアゾール、2
−(2′−ヒドロキシ−5′−メチルフエニル)−5−
ブトキシカルボニルベンゾトリアゾール、2−
(2′−ヒドロキシ−5′−メチルフエニル)−5,6
−ジクロルベンゾトリアゾール、2−(2′−ヒド
ロキシ−5′−メチルフエニル)−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′−tert−ブチルフエニル)−5−クロルベンゾ
トリアゾール、2−(2′−ヒドロキシ−5′−tertブ
チルフエニル)ベンゾトリアゾール、2−(2′−
ヒドロキシ−5′−アミルフエニル)ベンゾトリア
ゾール、2−(2′−ヒドロキシ−3′,5′−ジメチル
フエニル)ベンゾトリアゾール、2−(2′−ヒド
ロキシ−3′,5′−ジロチルフエニル)−5−メト
キシベンゾトリアゾール、2−(2′−メチル−
4′−ヒドロキシフエニル)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
エニル)−5−メチルベンゾトリアゾール、2−
(2′−ヒドロキシ−5−エトキシカルボニルフエ
ニル)ベンゾトリアゾール、2−(2′ヒドロキシ
−3′−メチル−5′−tert−ブチルフエニル)ベン
ゾトリアゾール、2−(2′−ヒドロキシ−3′,5′−
ジ−tert−ブチルフエニル)−5−クロル−ベン
ゾトリアゾール、2−(2′−ヒドロキシ−5′−メ
トキシフエニル)ベンゾトリアゾール、2−
(2′−ヒドロキシ−5′−フエニルフエニル)−5−
クロルベンゾトリアゾール、2−(2′−ヒドロキ
シ−5′−シクロヘキシルフエニル)ベンゾトリア
ゾール、2−(2′−ヒドロキシ−5−シクロヘキ
シルフエニル)ベンゾトリアゾール、2−(2′−
ヒドロキシ−5−シクロヘキシルフエニル)ベン
ゾトリアゾール、2−(2′−ヒドロキシ−4′,5′−
ジメチルフエニル)−5−ブトキシカルボニルベ
ンゾトリアゾール、2−(2′−ヒドロキシ−3′,
5′−ジクロルフエニル)ベンゾトリアゾール、2
−(2′−ヒドロキシ−4′,5′−ジクロル)ベンゾト
リアゾール、2−(2′−ヒドロキシ−3′,5′−ジメ
チルフエニル)−5−エチルスルホンベンゾトリ
アゾール、2−(2′−ハイドロキシ−5′−フエニ
ルフエニル)ベンゾトリアゾール、2−(2′−ヒ
ドロキシ−5′−メトキシフエニル)−5−メチル
ベンゾトリアゾール、2−(2′−ヒドロキシ−
5′−メチルフエニル)−5−エトキシカルボニル
ベンゾトリアゾール、2−(2′−アセトキシ−
5′−メチルフエニル)ベンゾトリアゾール、2−
(2′−ヒドロキシ−3′,5′−ジ−tert−ブチルフエ
ニル)−5−クロロベンゾトリアゾール、2−
(2′−ヒドロキシ−5′−t−ブチルフエニル)ベ
ンゾトリアゾール。
これらの紫外線吸収剤のうち、ベンゾフエノン
系及びベンゾトリアゾール系のものが好適であ
り、就中ベンゾフエノン系では、2,2′−ジヒド
ロキシ−4,4′−ジメトキシベンゾフエノン、
2,2′−ジヒドロキシ−4−メチトキベンゾフエ
ノン及び2,2′,4,4′−テトラヒドロキシベン
ゾフエノン;ベンゾトリアゾール系では2−
(2′−ヒドロキシ−5′−メチルフエニル)ベンゾ
トリアゾール、2−(2′−ヒドロキシ−5′−メチ
ルフエニル)−5,6−ジクロルベンゾトリアゾ
ール)、2−(2′−ヒドロキシ−5′−tert−ブチル
フエニル)ベンゾトリアゾール、2−(2′−ヒド
ロキシ−3′,5′−ジ−tert−ブチルフエニル)−5
−クロル−ベンゾトリアゾール、2−(2′−ヒド
ロキシ−5′−フエニルフエニル)−5−クロルベ
ンゾトリアゾール、2−(2′−ヒドロキシ−3′−
tertブチルフエニル)−5−クロロベンゾトリア
ゾール、2−(2′−ヒドロキシ−3′,5′−ジtertブ
チルフエニル)ベンゾトリアゾール及び2−
(2′−ヒドロキシ−5′−tertオクチルフエニル)ベ
ンゾトリアゾールが有効である。
特に好適な紫外線吸収剤は、式
式中、R1及びR2は同一もしくは相異なり、そ
れぞれ水素原子、低級アルキル基、殊に分岐鎖状
の低級アルキル基、又はアリール基、特にフエニ
ル基を表わし、Xは水素原子又はハロゲン原子、
特に塩素原子である、
で表わされるタイプのものである。
これら紫外線吸収剤の配合量は、その添加の目
的、紫外線吸収剤の種類、フイルムの厚さ等に応
じて広範に変えることができ、例えば、塩化ビニ
ル系樹脂フイルムの耐候性の改善のみを目的とす
る場合には、塩化ビニル系樹脂100重量部(可塑
剤を配合する前の重量基準)に対して一般に0〜
3.0重量部、好ましくは0.5〜2.5重量部の範囲とす
ることができ、他方、紫外線遮蔽性のフイルムを
目的とする場合には、遮蔽すべき紫外線の波長域
とフイルムの厚さに応じて紫外線吸収剤の配合量
を変えなければならず、例えば、少なくとも
370nm及びそれ以下、特に380nm及びそれ以下
の波長の紫外線を実質的に遮蔽する塩化ビニル系
樹脂フイルムを得るためには、紫外線吸収剤の配
合量はフイルムの厚さとの間に下記の関係式が成
立することが望まれる。
50≦A×B≦600
好ましくは
80≦A×B≦400
A≦2.5
好ましくは
0.5≦A≦2.5
上記式中、Aは該フイルムを構成する塩化ビニ
ル系樹脂100重量部に対する該フイルム中に含ま
れる該ベンゾトリアゾール誘導体の単独及び併用
使用の総重量部を表わし、Bは該フイルムの厚さ
(μ)を表わす。
上記の如き紫外線吸収剤を配合することによ
り、前述した硬化被膜層と共働的に作用して、本
発明のフイルムの耐候性を著るしく向上させるこ
とができ、例えば、本発明のフイルムは市販の普
通の農業用塩化ビニル系樹脂フイルムの約3倍も
寿命を延ばすことができる。
以上述べた組成の塩化ビニル系樹脂は通常の方
法、例えば押出法、カレンダー法、溶液流延法等
の方法でフイルム状に成形することができ、得ら
れるフイルムは一般に50〜250ミクロン、好まし
くは75〜200ミクロンの厚さを有することができ
る。
このようにして調製される適宜紫外線吸収剤を
含有する防曇性塩化ビニル系樹脂フイルムは、前
述の共重合体[]と有機ポリイソシアネート化
合物[]を含有するコーテイング溶液を塗布す
るに先立ち、硬化被覆層の接着強度を高める目的
で、適宜、該フイルムの塗布面にプライマー処理
を施してもよい。そのために使用しうるプライマ
ーとしては、例えば、アクリル系共重合体、天然
ゴムとメチルメタアクリレートのグラフト共重合
体、クロロプレンゴムとメチルメタクリレートの
グラフト共重合体、エチレン−プロピレンゴムと
塩化ビニルのグラフト共重合体、ニトリルゴムと
メチルメタクリレートのグラフト共重合体、天然
ゴムとアクリロニトリルのグラフト共重合体等を
例示することができる。プライマー処理として
は、従来のグラビヤコーテイング法、ドクターブ
レード法、ロールコート法、リバースロール法、
エヤーナイフコート法等の塗布法を挙げることが
できる。
本発明により提供される農業用塩化ビニル系樹
脂フイルムは、従来の一般農業用フイルム、アク
リル処理農業用フイルムで達し得なかつた長期展
張時の防曇性、耐汚染性及び硬化被膜の亀裂(ク
ラツク性)等が著るしく向上する。
さらに、本発明のフイルムは、従来の農業用フ
イルム及びアクリル処理農業用フイルムと比較し
て、フイルムの耐候性を向上させ且つ/又は紫外
線を遮蔽性を有する紫外線吸収剤の保持性に優
れ、特に長期展張用農業用塩化ビニル系樹脂フイ
ルムとして好適であり、その利用価値は極めて大
である。
実施例 1
塩化ビニル樹脂(菱日(株)製、SG−1400)100重
量部、ジオクチルタタレート(協和醗酵工業(株))
43重量部、エポキシ化大豆油(アデカ・アーガス
化学(株)製、アデカサイザー0−130P)3重量部、
トリクレジルホスフエート(大八化学(株)製TCP)
5重量部、バリウム−亜鉛系安定剤(アデカ・ア
ーガス化学(株)製、マークAC−153)2重量部、バ
リウムステアレート(勝田化工(株)製)0.5重量部、
亜鉛ステアレート(勝田化工(株)製)1.0重量部、
ソルビタンモノパルミテート(日本油脂(株)製、
PP−40R)0.5重量部、ソルビタン・モノ・ステ
アレート(日本油脂(株)製SP−60R)1.0重量部、
及び紫外線吸収剤(チバ・ガイギ(社)製、チヌ
ビン327)0.8重量部を均一になるまで混合し、次
いで前記混合物を常法によりカレンダーロールで
厚み0.13m/mのフイルムを作成した。
このフイルムの表面に後記の第1表実施例1に
記載した組成の含フツ素共重合体溶液(固形分濃
度15%、溶剤として酢酸エチル/メチルイソブチ
ルケトン/キシレン≒80/10/10)をアプリケー
ターを使用して塗布厚みが約2μ(乾燥後)になる
ように塗布し実施例1のフイルムを得た。
実施例2〜5及び比較例1〜3
実施例1における含フツ素共重合体溶液の代り
に後記第1表に示す組成の含フツ素共重合体溶液
を使用する以外は実施例1と全く同様にして実施
例2〜5及び比較例1〜3のフイルムを作成し
た。
参考例 1
実施例1にて作成した厚さ0.13m/mの表面処
理する前のフイルムを参考例1として使用した。
参考例 2
実施例1含フツ素共重合体液の代りにアクリル
系樹脂(メチルメタアクリレート/エチルメタア
クリレート/ブチルアクリレート≒70/20/10)
溶液を塗布する以外実施例1と全く同様にして参
考例2のフイルムを得た。
以上の如くして作製した各フイルムを以下の方
法で評価した。その結果を後記第1表にまとめて
示す。
試験方法
()防曇持続性……水100c.c.を200c.c.ビーカーに
れ、ビーカーの口をフイルムでおおい、ゴム帯
及びテープで固定密閉する。浴槽の水面高さと
ビーカーの水面高さがほぼ同等になるようにビ
ーカーを固定する。浴槽温度を4日間40℃に保
ち、1日放温のサイクルでフイルムの凝縮状態
を一定時間に評価する。
上記の防曇持続性は下記の10ランクにより評価
する。その結果を第1表に示す。この評価数値の
大きい方が防曇持続性に優れていることを意味す
る。[Table] Thus, the constituent monomer units derived from the above monomers (a), (b), (c) and (d) are generally 30 to 30, respectively.
70 mol%, 5-30 mol%, 10-40 mol% and 5-
20 mol%, preferably 40-60 mol% each, 15
A hydroxyl group-containing fluorine-containing copolymer [ ] containing a proportion of ~25 mol%, 20-30 mol%, and 5-15 mol% (however, the total of these does not exceed 70 mol%) is obtained. However, the copolymer []
It is important to have a number average molecular weight within the range of 30,000 to 50,000, preferably 33,000 to 45,000, more preferably 35,000 to 42,000. If the number average molecular weight is too low, it will have little effect on anti-fogging durability, blocking properties, stain resistance, etc.
If it exceeds 50,000, it is not good because the solubility of the copolymer and the flexibility of the coating decrease. The "number average molecular weight" used in this specification is based on a calibration curve determined from standard polystyrene by gel permeation chromatography using tetrahydrofuran as the eluent and styrene-divinylbenzene copolymer as the column packing material. This is the value determined from . Since the copolymer [] used in the present invention contains a hydroxyl group as a functional group as described above, it can be crosslinked and cured at a low temperature using an organic polyisocyanate compound []. Therefore, the organic polyisocyanate compound used as a curing agent in the present invention has at least 2 isocyanate groups in one molecule, preferably 2 to 2 isocyanate groups.
Includes organic compounds having three molecules and having a molecular weight of generally about 90 to 400, preferably about 120 to 300, and are chain or cyclic, or a combination of both, and specifically include hexamethylene diisocyanate, 2,4-
Tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, dianisidine diisocyanate, m-xylylene diisocyanate, transvinylene diisocyanate, 2,6-diisocyanate methyl caproate, isophorone diisocyanate, tolylene diisocyanate, tridene diisocyanate, 4, 4'-dicyclohexylmethane diisocyanate (water added 4,4'-diphenylmethane diisocyanate) water added 2,4
-tolylene diisocyanate, water-added m-xylylene diisocyanate, etc., among them, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate (water-added m-xylylene diisocyanate),
4'-diphenylmethane diisocyanate), water-added 2,4-tolylene diisocyanate, water-added m
-xylylene diisocyanate is preferred. The amount of these organic polyisocyanate compounds [ ] can be changed depending on the type of copolymer [ ] to be cured and the degree of curing, but in general, the amount of isocyanate equivalent in the organic polyisocyanate compound [ ] and the degree of curing are determined. The ratio of hydroxyl equivalents of the copolymer [] to be used is in the range of 0.9 to 1.2, preferably
It is desirable to use the amount within the range of 1.0 to 1.1. When applying a curable resin composition comprising a hydroxyl group-containing fluorine-containing copolymer [] and an organic polyisocyanate compound [] to one surface of an antifogging vinyl chloride resin film as a coating layer according to the present invention, The composition is generally conveniently applied to the film surface as a solution in a solvent. Solvents that can be used to dissolve the composition include, for example, methyl acetate, ethyl acetate; methyl ethyl ketone, acetone, methyl butyl ketone; methanol, ethanol, isopropanol; tetrahydrofuran, methyl cellosolve; dimethyl formamide; benzene, Examples include xylene, toluene, and mineral spirits. There are no particular restrictions on the concentration of the copolymer [ ] in the solution, but the solid content concentration is generally 10 to 10.
Within the range of 30% by weight, also methyl butyl ketone/
The solution viscosity in a mixed solvent of xylene = 50/50 can be about 10 to 50 c.ps, and
The solution contains catalysts for promoting the crosslinking reaction between the copolymer [] and the organic polyisocyanate compound [], such as dibutyltin dilaurate, dibutyltin dichloride, copper naphthenate,
Zinc naphthenate, zinc nitrate, blue lead nitrate, stannic chloride, stannous octoate, N, N, N',
N′-tetramethylpolymethylene diamine, calcium octylate, etc. can be blended in a catalytic amount (for example, 0.0001% to 1%, preferably 0.001 to 0.5% based on the weight of the copolymer []), and further Ultraviolet absorbers, antioxidants, dispersion stabilizers, viscosity modifiers, leveling agents, antigelation agents, pigments, antiblocking agents, and the like may be added. The coating solution prepared in this manner is applied to one surface of the antifogging vinyl chloride resin film before the crosslinking reaction substantially proceeds. Coating can be carried out by means known per se, such as gravure coating method, doctor blade method, roll coating method, reverse roll method, air knife coating method, etc., and the coating amount is generally such that the film thickness after drying is 1. An amount of ~15 microns, preferably 1-10 microns, is suitable. Drying and curing of the coating film can be carried out by methods known per se, and the drying is generally carried out at a temperature of 20°C to 150°C, preferably 50°C to 130°C, in a hot air drying oven, an infrared heater drying oven, etc. After drying, the coating film can be heated at a temperature of 20°C to 40°C as necessary to complete curing.
It can usually be kept at room temperature for 3 to 10 days. A solvent-resistant film formed from a hydroxyl group-containing fluorine-containing copolymer [] and an organic polyisocyanate compound [] is coated on one side of an antifogging vinyl chloride resin film blended with a surfactant by the method described above. ,
A flexible cured film layer with excellent stain resistance, weather resistance, etc. can be provided. The vinyl chloride resin film to which such a cured coating layer can be applied may be any vinyl chloride resin film conventionally used as an agricultural film. The vinyl chloride resin used as the base material of the film includes, in addition to a homopolymer of vinyl chloride, at least one of vinyl chloride and monomers such as vinyl acetate, ethylene, propylene, acrylic ester, and methacrylic ester. copolymers with up to 40%, preferably up to 30% by weight of seeds (based on the weight of total monomers), and polymers which are compatible with these homopolymers or copolymers; For example, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer, ethylene-vinyl chloride copolymer, propylene-vinyl chloride copolymer, ethylene-propylene-
A vinyl chloride copolymer (note that these copolymers also include graft copolymers) etc. is preferably 30 parts by weight or less, based on 100 parts by weight of the vinyl chloride homopolymer or copolymer. A resin blended in an amount of 20 parts by weight or less can be used. These vinyl chloride resins are mixed with plasticizers and used as soft vinyl chloride resins. The amount of plasticizer blended is based on 100 parts by weight of vinyl chloride resin.
A range of 30 to 70 parts by weight is preferred, and a range of 40 to 60 parts by weight is particularly preferred. Examples of plasticizers that can be incorporated include dibutyl phthalate, dioctyl phthalate, diisodecyl phthalate, diisononyl phthalate, dioctyl adipate, dioctyl sebacate, tricresyl phosphate, butylbenzyl phthalate, epoxidized soybean oil, and epoxidized linseed. oil,
Examples include epoxy resin. The above-mentioned soft vinyl chloride resin is further blended with usual additives such as lubricants, antioxidants, antistatic agents, heat stabilizers, colorants (pigments, dyes), flame retardants, etc., as necessary. You can also do that. Examples of lubricants include ethylene bisstearylamide, butyl stearate paraffin wax, low molecular weight polyethylene, montan acid wax, stearic acid, stearyl alcohol, and examples of antioxidants include 2,6-
di-tert-butyl-4-methylphenol, 2,
4,6-tri-tert-butylphenol, 2,
2'-methylenebis(4-methyl-6-tert-butylphenol), 4,4'-thiobis-(3-methyl-6-tert-butylphenol), phenyl α-
Examples include naphthylamine. In addition, examples of antistatic agents include polyoxyethylene alkylamides, alkylolamides, ethanolamides, alkyl phosphates,
Alkyl sulfates etc. can be used,
Suitable heat stabilizers include, for example, dibutyltin malate, dibutyltin dilaurate, calcium stearate, zinc ricinoleate, triphenyl phosphite, and the like. Further, examples of colorants that can be blended include phthalocyanine blue, phthalocyanine green, titanium oxide, chromophthal red, and syncasial red. In addition, flame retardants such as antimony oxide, aluminum hydroxide, and halogen-containing phosphate esters can also be appropriately blended. Furthermore, the vinyl chloride resin film used in the present invention has antifogging properties, and the surfactants that are added to impart antifogging properties to the film include, for example, carboxylates and sulfones. Anionic surfactants such as acid salts, sulfate ester salts, phosphate ester salts; cationic surfactants such as aliphatic amine salts and their quaternary ammonium salts, aromatic quaternary ammonium salts; betaine, aminocarboxylic Amphoteric surfactants such as acid salts and imidazolidine derivatives; alkyl and alkylaryl polyoxyethylene ethers, glycerin ethers and their polyoxyethylene ethers, polyoxyethylene aliphatic esters, glycerin esters, sorbitan esters, polyglycerin esters, dihydric Alcohol ester, sucrose ester, polyoxyethylene ether of glycerin ester, polyoxyethylene ether of sorbitan ester, ester of sorbitol polyoxyethylene ether, ether of glycerin ester, sorbitol polyoxyethylene ester of polyoxypropylene, sorbitan polyoxyethylene Examples include nonionic surfactants such as polyoxypropylene ester, glycerin polyoxyethylene polyoxypropylene ester; fluorine surfactants; silicone surfactants, and these may be used alone or in combination of two or more. More than that may be used in combination, and the amount used is general vinyl chloride resin.
It can be within the range of 0.5 to 3.0 parts by weight per 100 parts by weight. Among the surfactants, nonionic surfactants are suitable, in particular the following may be mentioned: sorbitan fatty acid esters, such as sorbitan monostearate, sorbitan monopalmitate; diglycerol monopalmitate; diglycerin fatty acid esters such as diglycerin monostearate; glycerin fatty acid esters such as glycerin monostearate; pentaerythritol fatty acid esters such as pentaerythritol monostearate; dipentaerythritol fatty acid esters such as dipentaerythritol monopalmitate; sorbitan mono Palmitate/Halfazibate, Diglycerin Monostearate/
Sorbitan and diglycerin fatty acid/dihydrochloric acid esters such as half glutamate; and condensates of these with alkylene oxides such as ethylene oxide, propylene oxide, etc., such as polyoxyethylene (2 mol) sorbitan monostearate, polyoxypume Examples include pyrene (2 mol) diglycerin monopalmitate, etc.; polyoxyethylene fatty alcohols such as polyoxyethylene lauryl ether; and polyoxyethylene fatty acid esters such as polyoxyethylene monostearate. Further, the vinyl chloride resin film used in the present invention may contain an ultraviolet absorber for the purpose of improving the weather resistance of the film or providing an ultraviolet shielding film. Examples of UV absorbers that can be blended include those listed below. Hydroquinone series - Hydroquinone, Hydroquinone disalicylate. Salicylic acid series - phenyl salicylate, para-octylphenyl salicylate, 4-t-butylphenyl salicylate, resorcin monobenzoate. Benzophenone series -2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-
Octoxybenzophenone, 2-hydroxy-4
-methoxy-2'-carboxybenzophenone,
2,4-dihydroxybenzophenone, 2,2'-
Dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-benzoyloxybenzophenone, 2,2'-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfonebenzo Phenon, 2, 2', 4,
4'-tetrahydroxybenzophenone, 2,2'-
Hydroxy-4,4'-dimethoxy-5-sodium sulfobenzophenone, 4-dodecyloxy-
2-Hydroxybenzophenone, 2-hydroxy-5-chlorobenzophenone Benzotriazole-2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2
-(2'-hydroxy-5'-methylphenyl)-5-
Butoxycarbonylbenzotriazole, 2-
(2'-hydroxy-5'-methylphenyl)-5,6
-dichlorobenzotriazole, 2-(2'-hydroxy-5'-methylphenyl)-5-ethylsulfonebenzotriazole, 2-(2'-hydroxy-5'-tert-butylphenyl)-5-chlorobenzotriazole, 2 -(2'-hydroxy-5'-tertbutylphenyl)benzotriazole, 2-(2'-
Hydroxy-5'-amylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-dimethylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-dilotylphenyl)-5- Methoxybenzotriazole, 2-(2'-methyl-
4′-hydroxyphenyl)benzotriazole,
2-(2'-stearyloxy-3',5'-dimethylphenyl)-5-methylbenzotriazole, 2-
(2'-hydroxy-5-ethoxycarbonylphenyl)benzotriazole, 2-(2'-hydroxy-3'-methyl-5'-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-3',5 ′−
di-tert-butylphenyl)-5-chloro-benzotriazole, 2-(2'-hydroxy-5'-methoxyphenyl)benzotriazole, 2-
(2'-hydroxy-5'-phenylphenyl)-5-
Chlorbenzotriazole, 2-(2'-hydroxy-5'-cyclohexylphenyl)benzotriazole, 2-(2'-hydroxy-5-cyclohexylphenyl)benzotriazole, 2-(2'-
Hydroxy-5-cyclohexylphenyl)benzotriazole, 2-(2'-hydroxy-4',5'-
dimethylphenyl)-5-butoxycarbonylbenzotriazole, 2-(2'-hydroxy-3',
5′-dichlorophenyl)benzotriazole, 2
-(2'-hydroxy-4',5'-dichloro)benzotriazole, 2-(2'-hydroxy-3',5'-dimethylphenyl)-5-ethylsulfonebenzotriazole, 2-(2'- Hydroxy-5'-phenylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methoxyphenyl)-5-methylbenzotriazole, 2-(2'-hydroxy-
5'-methylphenyl)-5-ethoxycarbonylbenzotriazole, 2-(2'-acetoxy-
5′-methylphenyl)benzotriazole, 2-
(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-
(2'-Hydroxy-5'-t-butylphenyl)benzotriazole. Among these ultraviolet absorbers, benzophenone-based and benzotriazole-based ones are preferred, and among the benzophenone-based ones, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone,
2,2'-dihydroxy-4-methytokibenzophenone and 2,2',4,4'-tetrahydroxybenzophenone; in benzotriazole series, 2-
(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)-5,6-dichlorobenzotriazole), 2-(2'-hydroxy-5'-tert -butylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5
-Chlor-benzotriazole, 2-(2'-hydroxy-5'-phenylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-
tertbutylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-ditertbutylphenyl)benzotriazole and 2-
(2'-Hydroxy-5'-tertoctylphenyl)benzotriazole is effective. Particularly suitable UV absorbers have the formula In the formula, R 1 and R 2 are the same or different and each represents a hydrogen atom, a lower alkyl group, especially a branched lower alkyl group, or an aryl group, especially a phenyl group, and X is a hydrogen atom or a halogen atom,
In particular, it is a chlorine atom, of the type represented by . The amount of these UV absorbers can be varied widely depending on the purpose of addition, the type of UV absorber, the thickness of the film, etc. For example, the purpose is only to improve the weather resistance of vinyl chloride resin films. In general, the amount is 0 to 100 parts by weight of vinyl chloride resin (based on the weight before adding a plasticizer).
3.0 parts by weight, preferably in the range of 0.5 to 2.5 parts by weight; on the other hand, if the film is intended to block ultraviolet rays, the amount of ultraviolet rays may be adjusted according to the wavelength range of ultraviolet rays to be blocked and the thickness of the film. The amount of absorbent must be varied, e.g. at least
In order to obtain a vinyl chloride resin film that substantially blocks ultraviolet rays at wavelengths of 370 nm and below, particularly 380 nm and below, the following relationship between the amount of ultraviolet absorber and the thickness of the film is established. It is hoped that this will come true. 50≦A×B≦600 Preferably 80≦A×B≦400 A≦2.5 Preferably 0.5≦A≦2.5 In the above formula, A is contained in the film based on 100 parts by weight of the vinyl chloride resin constituting the film. B represents the total weight of the benzotriazole derivatives used alone and in combination, and B represents the thickness (μ) of the film. By incorporating the above-mentioned ultraviolet absorbers, the weather resistance of the film of the present invention can be significantly improved by acting cooperatively with the above-mentioned cured film layer. For example, the film of the present invention can It can extend the lifespan by about three times that of commercially available ordinary agricultural vinyl chloride resin films. The vinyl chloride resin having the composition described above can be formed into a film by a conventional method such as an extrusion method, a calendar method, a solution casting method, etc., and the obtained film generally has a diameter of 50 to 250 microns, preferably It can have a thickness of 75-200 microns. The antifogging vinyl chloride resin film containing an appropriate ultraviolet absorber prepared in this manner is cured prior to applying a coating solution containing the above-mentioned copolymer [] and organic polyisocyanate compound []. For the purpose of increasing the adhesive strength of the coating layer, the coated surface of the film may be appropriately treated with a primer. Examples of primers that can be used for this purpose include acrylic copolymers, graft copolymers of natural rubber and methyl methacrylate, graft copolymers of chloroprene rubber and methyl methacrylate, and graft copolymers of ethylene-propylene rubber and vinyl chloride. Examples include a polymer, a graft copolymer of nitrile rubber and methyl methacrylate, and a graft copolymer of natural rubber and acrylonitrile. Primer treatments include conventional gravure coating method, doctor blade method, roll coating method, reverse roll method,
Coating methods such as air knife coating can be used. The agricultural vinyl chloride resin film provided by the present invention has anti-fogging properties and stain resistance during long-term extension, which were unattainable with conventional general agricultural films and acrylic-treated agricultural films, and cracks in the cured film. performance), etc., significantly improve. Furthermore, the film of the present invention improves the weather resistance of the film and/or has excellent retention of an ultraviolet absorber that blocks ultraviolet rays, compared to conventional agricultural films and acrylic-treated agricultural films, and particularly It is suitable as an agricultural vinyl chloride resin film for long-term extension, and its utility value is extremely high. Example 1 100 parts by weight of vinyl chloride resin (SG-1400, manufactured by Ryoichi Co., Ltd.), dioctyl tatarate (Kyowa Hakko Kogyo Co., Ltd.)
43 parts by weight, 3 parts by weight of epoxidized soybean oil (Adeka Sizer 0-130P, manufactured by Adeka Argus Chemical Co., Ltd.),
Tricresyl phosphate (TCP manufactured by Daihachi Chemical Co., Ltd.)
5 parts by weight, barium-zinc stabilizer (made by Adeka Argus Chemical Co., Ltd., mark AC-153) 2 parts by weight, barium stearate (made by Katsuta Kako Co., Ltd.) 0.5 parts by weight,
Zinc stearate (manufactured by Katsuta Kako Co., Ltd.) 1.0 parts by weight,
Sorbitan monopalmitate (manufactured by NOF Corporation,
PP-40R) 0.5 parts by weight, sorbitan mono-stearate (SP-60R manufactured by NOF Corporation) 1.0 parts by weight,
and 0.8 parts by weight of an ultraviolet absorber (Tinuvin 327, manufactured by Ciba Geigi Co., Ltd.) were mixed until uniform, and then the mixture was prepared using a calender roll in a conventional manner to form a film having a thickness of 0.13 m/m. A fluorine-containing copolymer solution (solid content concentration 15%, solvent: ethyl acetate/methyl isobutyl ketone/xylene≈80/10/10) having the composition described in Example 1 of Table 1 below was applied to the surface of this film. The film of Example 1 was obtained by applying the film using an applicator to a coating thickness of about 2 μm (after drying). Examples 2 to 5 and Comparative Examples 1 to 3 Completely the same as Example 1 except that a fluorine-containing copolymer solution having the composition shown in Table 1 below was used instead of the fluorine-containing copolymer solution in Example 1. Films of Examples 2 to 5 and Comparative Examples 1 to 3 were prepared in the same manner. Reference Example 1 The film prepared in Example 1 and having a thickness of 0.13 m/m before surface treatment was used as Reference Example 1. Reference Example 2 Example 1 Acrylic resin (methyl methacrylate/ethyl methacrylate/butyl acrylate≒70/20/10) instead of the fluorine-containing copolymer liquid
A film of Reference Example 2 was obtained in exactly the same manner as in Example 1 except that the solution was applied. Each film produced as described above was evaluated by the following method. The results are summarized in Table 1 below. Test method () Anti-fog durability...Pour 100 c.c. of water into a 200 c.c. beaker, cover the mouth of the beaker with a film, and secure and seal it with a rubber band and tape. Fix the beaker so that the water surface height in the bathtub and the water surface height in the beaker are approximately the same. The temperature of the bathtub was kept at 40℃ for 4 days, and the condensation state of the film was evaluated at fixed times in a cycle of heating for 1 day. The above anti-fog durability is evaluated using the following 10 ranks. The results are shown in Table 1. The larger the evaluation value, the better the anti-fog durability.
【表】
未満
[Table] Less than
【表】
() 防塵性試験
(1) 防塵性試験(その1)
ガラス板に60×60m/mの試験フイルムを
コーテイング被膜面を上にして両面接着テー
プで貼る。粉石鹸(洗たく用合成洗剤)でコ
ーテイング被膜面のよごれを洗浄する。ガラ
ス板を50℃の電気定温器(木屋製作所製型式
A−2)に入れ乾燥させた後、室温になるま
で冷却させる。次いで試験フイルムのコーテ
イング被膜面に、約35g/m2量のタルク(和
光純薬試薬一級)をふりかける。これを、50
℃の電気定温器に3日間入れた後、取出して
室温になるまで冷却させる。次いで、ガラス
板を約30゜に傾斜させて、如露で高さ約300
m/mから水を20/m2、約1分間かけてふ
りかける。この後、50℃の電気定温器に約1
時間入れ、フイルム表面を乾燥させた後室温
になるまで冷却させる。
次いで、20×40m/mにフイルムを切取り
積分球式濁度計(日本精密光学、型式、SEP
−Tで拡散透過率及び全透過率を測定して、
下記式によりヘーズ(濁度)を求める。
拡散透過率(%)
ヘーズ(%)=全透過率(%)×100
ヘーズの数値の小さい方が防塵性に優れて
いることを示す。
(2) 防塵性試験(その2)
間口約3m、奥行き約4m、棟高さ約1.5
m、屋根勾配約30度の木造骨組みを持つ試験
ハウスを用いる。屋根は棟方向長さ1mで屋
根勾配方向長さ1.2mの複数ケの木枠(スパ
ン)が形成されるように構成し、中央のスパ
ンにコーテイング被膜面をハウス外に向けて
展張した試験フイルムに於て測定を行なう。
ハウス底以外の全面に試験フイルムを展張し
て出入可能な試験ハスウを屋外に構築して、
屋外自然条件下における防曇防塵テストを行
なう。ハウス内部には温度調節機により35℃
に維持した温水槽を設置し、ハウス内の湿度
を常時100%に維持して、所定期間経過後、
石川式可視線日射計2台を用いて日射量値を
実測し、1台はハウス外において日射量値を
実測し、他の1台はハウス内の上記中央スパ
ンに展張した試験フイルムのほぼ中央部の真
下20cmの位置に於て日射量値を実測する。ハ
ウス外における実測値に対するハウス内の実
測値の%で示す。%値の大きいほど防曇防塵
性が優れていることを表わす。
試験は2年間実施した。
() 屋外暴露(表面クラツク試験)
間口約3m、奥行き約4m、棟高さ約1.5m、
屋根勾配約30度の木造骨組みを持つ試験ハスウ
を用いる。屋根は棟方向長さ1mで屋根勾配方
向長さ1.2mの複数ケの木枠(スパン)が形成
されるように構成し、中央のスパンにコーテイ
ング被膜面をハウス外に向けて展張した試験フ
イルムに於て測定を行なう。ハウス底以外の全
面に試験フイルムを展張して出入可能な試験ハ
スウを屋外に構築して、屋外自然条件下におけ
る暴露を行なう。
試験は、2年間実施した。
() 表面クラツク試験
展張されていたフイルムのほぼ中央において
フイルムを30cm×30cm角の大きさに切りとる。
このフイルムの中央を更に2cm×2cm角の大き
さに切りとつてコーテイングした表面を光学顕
微鏡を用いて100倍の倍率で観察する。
この観察により、フイルムコート表面層のク
ラツク度合を下記により評価する。
5級:全然クラツクが観察されない。
4級:わずかにクラツクが観察される(視野中
に10本以下)
3級:少しクラツクが 〃(〃20本以
下)
2級:相当 〃 〃(〃40本以
下)
1級:著しく 〃 〃(〃41本以
上)
() 紫外線吸収剤の保持率
(検量線の作成)
前記フイルムの作成に用いた各紫外線吸収剤
につき、紫外線吸収剤の添加量(Z重量部)を
変えたフイルムを作成し、分光光度計[島津製
作所(株)製品UV200]によつてフイルムの光線
透過率を求める(波長域270nmから450nmま
で)。
得られる光線透過率曲線について、紫外光が
40%透過する点で接線を引き、この接線が透過
率0%の線と交わる点の波長を読みとる(xn
m)、さらにフイルムの厚みをダイヤルゲージ
で測定する(yμ)。
以上の測定値から、xを縦軸とし、(yxz)を
横軸にとり、各紫外線吸収剤毎に、紫外線吸収剤
の添加量と厚みの関係曲線を描き、検量線とす
る。
(人工促進耐候性試験)
フイルムサンプルをスガ試験機製作所製のサン
シヤインウエザオメーター(W−O−M)により
スプレーサイクル18分/180分で耐候試験に付し
た。下記表−1に示す時間後にフイルムを取り出
し、分光光度計で該フイルムの光線透過率を測定
する。前記と同様にして、紫外線透過率が40%と
なる点で接線を引き、透過率が0%に外挿してそ
の波長を読み取る(Xnm)。次いでフイルムの厚
みを測定する(Yμ)。
次に前記で作成した検量線からXnmに対応す
る(yxz)値を読み取り、この値をYで除して紫
外線吸収剤の量Z重量部を求める。
紫外線吸収剤の保持率(%)=Z/z×100ま
た、第1表に使用する略号は次の意味を有する。
CTFE:クロロトリフルオロエチレン
TFE:テトラフルオロエチレン
CHrVE:シクロヘキシルビニルエーテル
EVE:エチルビニルエーテル
IBVE:イソブチルビニルエーテル
HBVE:ヒドロキシブチルビニルエーテル
HMbI:ヘキサメチレンジイソシアネート[Table] () Dust-proofing test (1) Dust-proofing test (Part 1) Attach a 60 x 60 m/m test film to a glass plate with the coating side up using double-sided adhesive tape. Clean the coating surface with powdered soap (synthetic detergent for washing). The glass plate is placed in an electric incubator (Kiya Seisakusho Model A-2) at 50°C, dried, and then cooled to room temperature. Next, approximately 35 g/m 2 of talc (Wako Pure Chemical Reagent Grade 1) is sprinkled on the coating surface of the test film. This is 50
After placing it in an electric incubator at ℃ for 3 days, it is taken out and allowed to cool to room temperature. Next, tilt the glass plate at an angle of about 30 degrees and raise it to a height of about 300 degrees.
Sprinkle water from m/m 20/m 2 for about 1 minute. After this, put it in an electric incubator at 50℃ for about 1 hour.
Allow time to dry the film surface, then cool to room temperature. Next, cut the film to 20 x 40 m/m and use an integrating sphere turbidity meter (Japan Seimitsu Optics, model: SEP).
- Measure the diffuse transmittance and total transmittance at T,
Determine haze (turbidity) using the following formula. Diffuse transmittance (%) Haze (%) = Total transmittance (%) x 100 A smaller haze value indicates better dustproof performance. (2) Dustproof test (Part 2) Width approx. 3m, depth approx. 4m, ridge height approx. 1.5
A test house with a wooden frame and a roof slope of approximately 30 degrees was used. The roof was constructed with multiple wooden frames (spans) each having a length of 1 m in the ridge direction and 1.2 m in the roof slope direction, and a test film was applied to the central span with the coating surface facing outside the house. Measurements will be made at .
A test film is spread over the entire surface of the house except the bottom, and an accessible test house is constructed outdoors.
Perform anti-fog and dust-proof tests under natural outdoor conditions. The temperature inside the house is 35 degrees Celsius with a temperature controller.
After a certain period of time, a hot water tank maintained at
The solar radiation value was actually measured using two Ishikawa-type visible-ray pyranometers, one measuring the solar radiation value outside the house, and the other measuring the solar radiation value approximately at the center of the test film spread over the above-mentioned center span inside the house. Measure the amount of solar radiation at a position 20cm directly below the area. It is expressed as a percentage of the actual value inside the house compared to the actual value outside the house. The larger the % value, the better the anti-fog and dust-proof properties. The study was conducted for two years. () Outdoor exposure (surface crack test) Width approx. 3m, depth approx. 4m, ridge height approx. 1.5m,
A test building with a wooden frame with a roof slope of approximately 30 degrees was used. The roof was constructed with multiple wooden frames (spans) each having a length of 1 m in the ridge direction and 1.2 m in the roof slope direction, and a test film was applied to the central span with the coating surface facing outside the house. Measurements will be made at . A test film is spread over the entire surface of the house except for the bottom of the house, an accessible test house is constructed outdoors, and the test film is exposed under natural outdoor conditions. The study was conducted for two years. () Surface crack test Cut the film into a 30cm x 30cm square approximately at the center of the stretched film.
The center of this film was further cut into a 2 cm x 2 cm square, and the coated surface was observed at 100x magnification using an optical microscope. Based on this observation, the degree of cracking of the film coat surface layer is evaluated as follows. Grade 5: No cracks observed at all. Grade 4: Slight cracks observed (less than 10 lines in the visual field) Grade 3: Slight cracks (less than 20 lines) Grade 2: Considerable (less than 40 lines) Grade 1: Significantly (less than 40 lines) 〃41 or more) () Retention rate of ultraviolet absorber (preparation of calibration curve) For each ultraviolet absorber used to make the above films, films were made with different amounts of added ultraviolet absorber (Z parts by weight). , the light transmittance of the film is determined using a spectrophotometer [UV200 manufactured by Shimadzu Corporation] (wavelength range from 270 nm to 450 nm). Regarding the light transmittance curve obtained, ultraviolet light
Draw a tangent at the point of 40% transmission, and read the wavelength at the point where this tangent intersects the line of 0% transmission (xn
m), and further measure the thickness of the film with a dial gauge (yμ). From the above measured values, with x as the vertical axis and (yxz) as the horizontal axis, a relationship curve between the amount of UV absorber added and the thickness is drawn for each UV absorber and used as a calibration curve. (Artificial Accelerated Weathering Test) The film sample was subjected to a weathering test using a Sunshine Weather-O-meter (W-O-M) manufactured by Suga Test Instruments Manufacturing Co., Ltd. at a spray cycle of 18 minutes/180 minutes. The film was taken out after the time shown in Table 1 below, and the light transmittance of the film was measured using a spectrophotometer. In the same manner as above, draw a tangent at the point where the ultraviolet transmittance is 40%, extrapolate it to the point where the transmittance is 0%, and read the wavelength (X nm). Next, measure the thickness of the film (Yμ). Next, the (yxz) value corresponding to Xnm is read from the calibration curve created above, and this value is divided by Y to determine the amount Z of the ultraviolet absorber in parts by weight. Retention rate (%) of ultraviolet absorber=Z/z×100 Furthermore, the abbreviations used in Table 1 have the following meanings. CTFE: Chlorotrifluoroethylene TFE: Tetrafluoroethylene CHrVE: Cyclohexyl vinyl ether EVE: Ethyl vinyl ether IBVE: Isobutyl vinyl ether HBVE: Hydroxybutyl vinyl ether HMbI: Hexamethylene diisocyanate
【表】【table】
Claims (1)
脂フイルム基材の一面に、 [] フルオロオレフイン、シクロヘキシルビニ
ルエーテル、アルキルビニルエーテル及びヒド
ロキシアルキルビニルエーテルの4種のモノマ
ーから誘導される構成モノマー単位を合計で共
重合体の少なくとも70モル%含有し、数平均分
子量が30000〜50000の範囲内にあり且つ水酸基
当量が0.9〜1.2の範囲内にある水酸基含有含フ
ツ素共重合体と、 [] 有機ポリイソシアネート化合物より形成さ
れた硬化被膜層を有する農業用塩化ビニル系樹
脂フイルム。[Scope of Claims] 1. On one surface of an antifogging vinyl chloride resin film base material containing a surfactant, [] a compound derived from four types of monomers: fluoroolefin, cyclohexyl vinyl ether, alkyl vinyl ether, and hydroxyalkyl vinyl ether. A hydroxyl group-containing fluorine-containing copolymer containing at least 70 mol% of constituent monomer units in total in the copolymer, having a number average molecular weight within the range of 30,000 to 50,000, and having a hydroxyl group equivalent within the range of 0.9 to 1.2. , [] An agricultural vinyl chloride resin film having a cured coating layer formed from an organic polyisocyanate compound.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP58208327A JPS60101043A (en) | 1983-11-08 | 1983-11-08 | Agricultural vinyl chloride group resin film |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP58208327A JPS60101043A (en) | 1983-11-08 | 1983-11-08 | Agricultural vinyl chloride group resin film |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS60101043A JPS60101043A (en) | 1985-06-05 |
JPH0361587B2 true JPH0361587B2 (en) | 1991-09-20 |
Family
ID=16554425
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP58208327A Granted JPS60101043A (en) | 1983-11-08 | 1983-11-08 | Agricultural vinyl chloride group resin film |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS60101043A (en) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6274935A (en) * | 1985-09-30 | 1987-04-06 | Asahi Glass Co Ltd | Coating composition for non-rigid vinyl chloride resin film |
JPS6431849A (en) * | 1987-07-27 | 1989-02-02 | Achilles Corp | Vinyl chloride polymer film for agricultural use |
JPH0832439B2 (en) * | 1988-10-21 | 1996-03-29 | 旭硝子株式会社 | Agricultural plastic sheet |
JPH071684A (en) * | 1993-06-17 | 1995-01-06 | Nippon Carbide Ind Co Inc | Agricultural composite covering material |
JP3587866B2 (en) * | 1993-08-18 | 2004-11-10 | アキレス株式会社 | Agricultural synthetic resin film |
US6706389B1 (en) | 1997-06-30 | 2004-03-16 | Cryovac, Inc. | Fog-resistant packaging film |
WO1999000250A1 (en) * | 1997-06-30 | 1999-01-07 | Cryovac, Inc. | Fog-resistant packaging film |
CN106029725A (en) * | 2014-02-26 | 2016-10-12 | 大金美国股份有限公司 | Fluoropolymer structures |
-
1983
- 1983-11-08 JP JP58208327A patent/JPS60101043A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS60101043A (en) | 1985-06-05 |
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