JP4453225B2 - Agricultural vinyl chloride resin film - Google Patents
Agricultural vinyl chloride resin film Download PDFInfo
- Publication number
- JP4453225B2 JP4453225B2 JP2001176490A JP2001176490A JP4453225B2 JP 4453225 B2 JP4453225 B2 JP 4453225B2 JP 2001176490 A JP2001176490 A JP 2001176490A JP 2001176490 A JP2001176490 A JP 2001176490A JP 4453225 B2 JP4453225 B2 JP 4453225B2
- Authority
- JP
- Japan
- Prior art keywords
- vinyl chloride
- chloride resin
- weight
- resin film
- parts
- 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 - Fee Related
Links
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims description 42
- 229920005989 resin Polymers 0.000 title claims description 42
- 239000011347 resin Substances 0.000 title claims description 42
- -1 1,2-cyclohexanedicarboxylic acid diester Chemical class 0.000 claims description 48
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- 239000004014 plasticizer Substances 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 239000002216 antistatic agent Substances 0.000 claims description 9
- 239000004611 light stabiliser Substances 0.000 claims description 8
- 239000006096 absorbing agent Substances 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 239000003963 antioxidant agent Substances 0.000 claims description 6
- 239000003086 colorant Substances 0.000 claims description 6
- 239000000945 filler Substances 0.000 claims description 6
- 239000000314 lubricant Substances 0.000 claims description 6
- 239000003381 stabilizer Substances 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- 230000000087 stabilizing effect Effects 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 description 16
- 239000004094 surface-active agent Substances 0.000 description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 239000012964 benzotriazole Substances 0.000 description 10
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 9
- 235000014113 dietary fatty acids Nutrition 0.000 description 7
- 239000000194 fatty acid Substances 0.000 description 7
- 229930195729 fatty acid Natural products 0.000 description 7
- 229920001296 polysiloxane Polymers 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 6
- 239000002202 Polyethylene glycol Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 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 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 229920002545 silicone oil Polymers 0.000 description 4
- 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 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 2
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- ADRNSOYXKABLGT-UHFFFAOYSA-N 8-methylnonyl diphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OCCCCCCCC(C)C)OC1=CC=CC=C1 ADRNSOYXKABLGT-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Natural products CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920001651 Cyanoacrylate Polymers 0.000 description 2
- ARIWANIATODDMH-UHFFFAOYSA-N Lauric acid monoglyceride Natural products CCCCCCCCCCCC(=O)OCC(O)CO ARIWANIATODDMH-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 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
- 239000004305 biphenyl Substances 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-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
- GLYJVQDYLFAUFC-UHFFFAOYSA-N butyl hexadecanoate Chemical compound CCCCCCCCCCCCCCCC(=O)OCCCC GLYJVQDYLFAUFC-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- PGRHXDWITVMQBC-UHFFFAOYSA-N dehydroacetic acid Chemical compound CC(=O)C1C(=O)OC(C)=CC1=O PGRHXDWITVMQBC-UHFFFAOYSA-N 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 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
- 229940049964 oleate Drugs 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N phenyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 239000008029 phthalate plasticizer Substances 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000223 polyglycerol Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- ASRAWSBMDXVNLX-UHFFFAOYSA-N pyrazolynate Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(=O)C=1C(C)=NN(C)C=1OS(=O)(=O)C1=CC=C(C)C=C1 ASRAWSBMDXVNLX-UHFFFAOYSA-N 0.000 description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 235000014692 zinc oxide Nutrition 0.000 description 2
- YEYCMBWKTZNPDH-UHFFFAOYSA-N (2,2,6,6-tetramethylpiperidin-4-yl) benzoate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)C1=CC=CC=C1 YEYCMBWKTZNPDH-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
- VNFXPOAMRORRJJ-UHFFFAOYSA-N (4-octylphenyl) 2-hydroxybenzoate Chemical compound C1=CC(CCCCCCCC)=CC=C1OC(=O)C1=CC=CC=C1O VNFXPOAMRORRJJ-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
- 0 *C1C(*)CCCC1 Chemical compound *C1C(*)CCCC1 0.000 description 1
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-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
- OLAQBFHDYFMSAJ-UHFFFAOYSA-L 1,2-bis(7-methyloctyl)cyclohexane-1,2-dicarboxylate Chemical compound CC(C)CCCCCCC1(C([O-])=O)CCCCC1(CCCCCCC(C)C)C([O-])=O OLAQBFHDYFMSAJ-UHFFFAOYSA-L 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- RZRNAYUHWVFMIP-KTKRTIGZSA-N 1-oleoylglycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-KTKRTIGZSA-N 0.000 description 1
- 229940114072 12-hydroxystearic acid Drugs 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
- WZUNUACWCJJERC-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CC)(CO)CO WZUNUACWCJJERC-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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-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
- 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
- FXYQVUGCQHGGEX-UHFFFAOYSA-N 2-(5-chlorobenzotriazol-2-yl)-4-methyl-6-(2-methylpropyl)phenol Chemical compound CC(C)CC1=CC(C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O FXYQVUGCQHGGEX-UHFFFAOYSA-N 0.000 description 1
- PXMKSNKSDOKQGZ-UHFFFAOYSA-N 2-(5-chlorobenzotriazol-2-yl)-6-(2-methylbutan-2-yl)-4-(2-methylpropyl)phenol Chemical compound CCC(C)(C)C1=CC(CC(C)C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O PXMKSNKSDOKQGZ-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
- 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
- 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 1
- PITPRNOGWXAZAW-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-methoxyphenol Chemical compound COC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 PITPRNOGWXAZAW-UHFFFAOYSA-N 0.000 description 1
- NLWDAUDWBLSJGK-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-tert-butyl-6-methylphenol Chemical compound CC1=CC(C(C)(C)C)=CC(N2N=C3C=CC=CC3=N2)=C1O NLWDAUDWBLSJGK-UHFFFAOYSA-N 0.000 description 1
- 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 1
- ITLDHFORLZTRJI-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-5-octoxyphenol Chemical compound OC1=CC(OCCCCCCCC)=CC=C1N1N=C2C=CC=CC2=N1 ITLDHFORLZTRJI-UHFFFAOYSA-N 0.000 description 1
- FJGQBLRYBUAASW-UHFFFAOYSA-N 2-(benzotriazol-2-yl)phenol Chemical compound OC1=CC=CC=C1N1N=C2C=CC=CC2=N1 FJGQBLRYBUAASW-UHFFFAOYSA-N 0.000 description 1
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
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- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
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- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- YAFOVCNAQTZDQB-UHFFFAOYSA-N octyl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(OCCCCCCCC)OC1=CC=CC=C1 YAFOVCNAQTZDQB-UHFFFAOYSA-N 0.000 description 1
- IIGMITQLXAGZTL-UHFFFAOYSA-N octyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCCCCCCC IIGMITQLXAGZTL-UHFFFAOYSA-N 0.000 description 1
- GMMWKYSAFBYKHU-UHFFFAOYSA-N octylsulfanylbenzene Chemical compound CCCCCCCCSC1=CC=CC=C1 GMMWKYSAFBYKHU-UHFFFAOYSA-N 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229940098695 palmitic acid Drugs 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- 229940031826 phenolate Drugs 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229960000969 phenyl salicylate Drugs 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
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
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- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
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- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
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- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
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- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229940100515 sorbitan Drugs 0.000 description 1
- 229940035044 sorbitan monolaurate Drugs 0.000 description 1
- 239000001593 sorbitan monooleate Substances 0.000 description 1
- 235000011069 sorbitan monooleate Nutrition 0.000 description 1
- 229940035049 sorbitan monooleate Drugs 0.000 description 1
- 239000001570 sorbitan monopalmitate Substances 0.000 description 1
- 235000011071 sorbitan monopalmitate Nutrition 0.000 description 1
- 229940031953 sorbitan monopalmitate Drugs 0.000 description 1
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229960004274 stearic acid Drugs 0.000 description 1
- 125000003696 stearoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- YPMOSINXXHVZIL-UHFFFAOYSA-N sulfanylideneantimony Chemical compound [Sb]=S YPMOSINXXHVZIL-UHFFFAOYSA-N 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- LVEOKSIILWWVEO-UHFFFAOYSA-N tetradecyl 3-(3-oxo-3-tetradecoxypropyl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCC LVEOKSIILWWVEO-UHFFFAOYSA-N 0.000 description 1
- 235000010215 titanium dioxide Nutrition 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
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- VQOXUMQBYILCKR-UHFFFAOYSA-N tridecaene Natural products CCCCCCCCCCCC=C VQOXUMQBYILCKR-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- KOWVWXQNQNCRRS-UHFFFAOYSA-N tris(2,4-dimethylphenyl) phosphate Chemical compound CC1=CC(C)=CC=C1OP(=O)(OC=1C(=CC(C)=CC=1)C)OC1=CC=C(C)C=C1C KOWVWXQNQNCRRS-UHFFFAOYSA-N 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
- LIPMRGQQBZJCTM-UHFFFAOYSA-N tris(2-propan-2-ylphenyl) phosphate Chemical compound CC(C)C1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C(C)C)OC1=CC=CC=C1C(C)C LIPMRGQQBZJCTM-UHFFFAOYSA-N 0.000 description 1
- 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)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
【０００１】
【産業上の利用分野】
本発明は、農業用塩化ビニル系樹脂フィルムに関する。
【０００２】
【従来の技術】
農業用塩化ビニル系樹脂フィルムには、その加工性の改良及び製品に柔軟性その他の性能を付与する目的で、例えばフタル酸ジ−２−エチルヘキシル（ＤＯＰ）及びフタル酸ジイソノニル（ＤＩＮＰ）に代表されるフタル酸エステル系の塩化ビニル用可塑剤が汎用されている。
【０００３】
最近、化学物質の環境問題がクローズアップされる中で、可塑剤分野においては、フタル酸エステル系可塑剤の代替としての非フタル酸エステル系可塑剤の開発が望まれている。
【０００４】
【発明が解決しようとする課題】
本発明は、非フタル酸エステル系可塑剤を含有してなる新規有用な農業用塩化ビニル系樹脂フィルムを提供することを目的とする。
【０００５】
【課題を解決するための手段】
本発明者らは、かかる課題を解決すべく鋭意検討を行った結果、特定の構造を有する１，２−シクロヘキサンジカルボン酸ジエステルが、農業用塩化ビニル系樹脂フィルム用の非フタル酸エステル系可塑剤として有用であることを見出し、かかる知見に基づいて本発明を完成するに至った。
【０００６】
即ち、本発明に係る農業用塩化ビニル系樹脂フィルムは、塩化ビニル系樹脂と一般式（１）
で表される１，２−シクロヘキサンジカルボン酸ジエステル（以下「本エステル」という。）とを含有することを特徴とする。
【０００７】
【発明の実施の形態】
本発明に係る塩化ビニル樹脂とは、塩化ビニルの単独重合体及び塩化ビニルの共重合体であり、農業用塩化ビニル系樹脂フィルム用の樹脂成分として適用される限り、特に限定されるものではない。
【０００８】
上記共重合体の場合、例えば、エチレン、プロピレン、１−ブテン、１−ペンテン、１−ヘキセン、１−ヘプテン、１−オクテン、１−ノネン、１−デセン、１−ウンデセン、１−ドデセン、１−トリデセン、１−テトラデセン等の炭素数２〜３０のα−オレフィン類、アクリル酸及びそのエステル類、メタクリル酸及びそのエステル類、マレイン酸及びそのエステル類、酢酸ビニル、プロピオン酸ビニル、アルキルビニルエーテル等のビニル化合物、ジアリルフタレート等の多官能性モノマー及びこれらの混合物と塩化ビニルモノマー（又は塩化ビニリデンモノマー）との共重合体、エチレン−アクリル酸エチル共重合体等のエチレン−アクリル酸エステル共重合体、エチレン−メタクリル酸エステル共重合体、エチレン−酢酸ビニル共重合体（ＥＶＡ）、塩素化ポリエチレン、ブチルゴム、架橋アクリルゴム、ポリウレタン、ブタジエン−スチレン−メチルメタクリレート共重合体（ＭＢＳ）、ブタジエン−アクリロニトリル−（α−メチル）スチレン共重合体（ＡＢＳ）、スチレン−ブタジエン共重合体、ポリエチレン、ポリメチルメタクリレート及びこれらの混合物へ塩化ビニルモノマー（又は塩化ビニリデンモノマー）をグラフトしたグラフト共重合体等が挙げられる。
【０００９】
塩化ビニル系樹脂の平均重合度としては、通常７００から５０００が推奨され、好ましくは９００〜３５００、更に好ましくは１０００〜３０００である。この重合度が低すぎると耐熱性等が低下し、高すぎると成形加工性が低下する傾向がある。
【００１０】
本エステルを表す一般式（１）中において、Ｒ１又はＲ２で表される炭素数９の分岐鎖状のアルキル基としては、その分岐の位置、分岐のメチル基の数によって、例えば下記のものが挙げられる。
（１）メチル分岐を１つ有するＣ９分岐状アルキル基
２−メチルオクチル基、３−メチルオクチル基、４−メチルオクチル基、５−メチルオクチル基、６−メチルオクチル基、７−メチルオクチル基
（２）メチル分岐を２つ有するＣ９分岐状アルキル基
２，４−ジメチルヘプチル基、２，５−ジメチルヘプチル基、４，６−ジメチルヘプチル基
（３）メチル分岐を３つ有するＣ９分岐状アルキル基
３，５，５−トリメチルヘキシル基、２，５，５−トリメチルヘキシル基
【００１１】
本エステルとしては、例えば、１，２−シクロヘキサンジカルボン酸ジイソノニルエステル、１，２−シクロヘキサンジカルボン酸ジ（３，５，５−トリメチルヘキシル）エステル等が例示される。
【００１２】
本エステルの含有量は、農業用塩化ビニル系樹脂フィルム用可塑剤として適用される限り特に限定されるものではないが、塩化ビニル樹脂１００重量部に対し、３０〜７０重量部が推奨され、特に４０〜６０重量部であることが好ましい。３０重量部未満の場合には、目的とする可塑化効果が得られ難く、７０重量部を越えて配合した場合には、成形品表面へのブリードが激しくなる傾向があり、いずれの場合も好ましくない。
【００１３】
本発明に係る農業用塩化ビニル系樹脂フィルム用の可塑剤としては、本エステルと共に一般式（２）
で表される１，２−シクロヘキサンジカルボン酸ジアルキル（以下「併用エステル」という。）を併用することができる。
【００１４】
本エステルと併用エステルとを併用する場合、本エステルと併用エステルとの総量に対する本エステルの重量比としては、７０〜９７重量％が推奨され、特に８０〜９７重量％が好ましい。
【００１５】
本発明に係る農業用塩化ビニル系樹脂フィルムは、１，２−シクロヘキサンジカルボン酸ジエステルに加えて、リン酸エステル系可塑剤を、塩化ビニル系樹脂１００重量部に対し、１０重量部以下併用することが好ましい。このリン酸エステル系可塑剤としては、例えば、トリクレジルホスフェート（以下「ＴＣＰ」と略記する。）、トリキシレニルホスフェート、トリス（イソプロピルフェニル）ホスフェート、トリブチルホスフェート、トリエチルホスフェート、トリオクチルホスフェート、トリス（２−エチルヘキシル）ホスフェート、オクチルジフェニルホスフェート、クレジルジフェニルホスフェート等が例示される。
【００１６】
本発明に係る農業用塩化ビニル系樹脂フィルムは、紫外線吸収剤、光安定剤、着色剤、充填剤、酸化防止剤、帯電防止剤、防曇剤、防滴剤、滑剤、防霧剤、安定剤及び安定化助剤からなる群から選ばれる公知の添加剤を配合することができる。
【００１７】
紫外線吸収剤としては、農業用塩化ビニルフィルムに通常配合されるものであればよく、ベンゾトリアゾール系、ベンゾフェノン系、サリチル酸エステル系、シアノアクリレート系等各種の紫外線吸収剤が例示され、特にベンゾトリアゾール系紫外線吸収剤、ベンゾフェノン系紫外線吸収剤が好ましい。具体的には、以下のようなものがあげられる。又、紫外線吸収剤の配合量としては、塩化ビニル系樹脂１００重量部に対して０．０１〜２重量部が推奨される。
【００１８】
ベンゾトリアゾール系化合物としては、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−３’−メチル−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’−ｔ−アミル−５’−イソブチルフェニル）−５−クロロベンゾトリアゾール、２‐（２′‐ヒドロキシ‐３′‐イソブチル‐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‐３′‐イソブチル‐５′‐プロピルフェニル）‐５‐クロロベンゾトリアゾール、２‐（２′‐ヒドロキシ‐３′，５′‐ジ‐ｔｅｒｔ‐ブチルフェニル）ベンゾトリアゾール、２‐［２′‐ヒドロキシ‐５′‐（１，１，３，３‐テトラメチル）フェニル］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が例示される。
【００１９】
ベンゾフェノン系化合物としては、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）メタン等が例示される。商品名としては、ＳＳ−１０２（シプロ化成製）等が例示される。
【００２０】
サリチル酸エステル系化合物としては、フェニルサリシレート、４−オクチルフェニルサリシレート、４−ｔｅｒｔ−ブチルフェニルサリシレート等が例示される。
【００２１】
シアノアクリレート系化合物としては、エチル−２−シアノ−３，３’−ジフェニルアクリレート、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等が例示される。
【００２２】
これらの紫外線吸収剤は、単独又は２種以上を組み合わせて使用することができる。
【００２３】
光安定剤としては、農業用フィルムに通常配合される種々の化合物を使用することができ、例えば、ヒンダードアミン系、金属錯塩系等が挙げられ、特にヒンダードアミン系光安定剤が好ましい。又、これらの光安定剤は、単独で又は２種以上を組み合わせて使用することができ、光安定剤の配合量としては、塩化ビニル系樹脂１００重量部に対して０．０１〜２重量部が推奨される。
【００２４】
ヒンダードアミン系光安定剤としては、具体的には４−シクロヘキシノイルオキシ−２，６，６−テトラメチルピペリジン、４−ベンゾイルオキシ−２，２，６，６−テトラメチルピペリジン、４−（ｏ−クロロベンジルオキシ）−２，２，６，６−テトラメチルピペリジン、テトラキス（２，２，６，６，−テトラメチル−４−ピペリジル）−１，２，３，４−ブタンテトラカルボキシレート、テトラキス（１，２，２，６，６，−ペンタメチル−４−ピペリジル）−１，２，３，４−ブタンテトラカルボキシレート、（２，２，６，６−テトラメチル−４−ピペリジルとトリデシルの混基）−１，２，３，４−ブタンテトラカルボキシレート、（１，２，２，６，６−ペンタメチル−４−ピペリジルとトリデシルの混基）−１，２，３，４−ブタンテトラカルボキシレート等が例示される。商品名としては、アデカスタブＬＡ−５７、アデカスタブＬＡ−５２、アデカスタブＬＡ−６７、アデカスタブＬＡ−６２、アデカスタブＬＡ−６３、アデカスタブＬＡ−６８、ＭＡＲＫ ＬＡ−５７、ＭＡＲＫ ＬＡ−６２、ＭＡＲＫ ＬＡ−６３、ＭＡＲＫ ＬＡ−６７、ＭＡＲＫ ＬＡ−６８（以上、旭電化工業社製）、ＴＩＮＵＶＩＮ７６５、ＴＩＮＵＶＩＮ７４４、ＴＩＮＵＶＩＮ７７０、ＴＩＮＵＶＩＮ１４４、ＴＩＮＵＶＩＮ６２２ＬＤ（以上、チバ・ガイギー社製）等が例示される。
【００２５】
金属錯塩系としては、金属がニッケルとコバルトが好ましい。具体的には、ニッケル［２，２’−チオビス（４−ｔｅｒｔ−オクチル）フェノレート］−ｎ−ブチルアミン、ニッケルジブチルチオカーバメイト、ニッケルビス［ｏ−エチル−３，５−（ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベンジル）］ホスフェート、ニッケルビス（オクチルフェニルサルファイド）コバルトジシクロヘキシルジチオホスフェート、［１−フェニル、３−メチル、４−デカノイル、ピラゾレート（５）２］ニッケル等が例示される。
【００２６】
着色剤としては、カーボンブラック、硫化鉛、ホワイトカーボン、チタン白、リトポン、べにがら、硫化アンチモン、クロム黄、クロム緑、コバルト青、モリブデン橙、フタロシアニンブルー、フタロシアニングリーン、ハンザイエロー、アリザリンレーキ、亜鉛華、パーマネントレッド、キナクリドン等が例示される。又、これらの着色剤は単独で又は２種以上を組み合わせて使用することができる。着色剤の配合量としては、塩化ビニル系樹脂１００重量部に対し０．０１〜５重量部が推奨される。
【００２７】
充填剤としては、フィルムのベタツキを抑制するために或いは保温性を更に高めるために、例えば、シリカ、タルク、珪藻土、フェライト類、水酸化アルミニウム、硫酸カルシウム、ケイ酸カルシウム、水酸化カルシウム、水酸化マグネシウム、酸化アルミニウム、酸化マグネシウム、硫酸バリウム、カオリンクレー、マイカ、アルミナ、炭酸カルシウム、炭酸マグネシウム、アルミン酸ナトリウム、導電性酸化亜鉛、リン酸リチウム、ハイドロタルサイト類、ガラス又は炭素又は金属等の繊維及び粉末、ガラス球、グラファイト、リチウム−アルミニウム複合水酸化物塩、リチウム−マグネシウム−アルミニウム複合水酸化物塩等が用いられる。これらの充填剤は単独で用いてもよいし、２種以上を適宜組み合わせて用いてもよい。又、充填剤の配合量としては、塩化ビニル系樹脂１００重量部に対して０．０５〜２０重量部が推奨され、特に０．１〜１５重量部が好ましい。
【００２８】
酸化防止剤としては、２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェノール、テトラキス［メチレン−３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］メタン、２，２’−メチレンビス−（４−メチル−６−ｔ−ブチルフェノール）、２−ヒドロキシ−４−メトキシベンゾフェノン、等のフェノール系化合物、アルキルジスルフィド、ジラウリルチオジプロピオネート、ジミリスチルチオジプロピオネート、ベンゾチアゾール等の硫黄系化合物、トリスノニルフェニルフォスファイト、ジフェニルイソデシルフォスファイト、トリフェニルフォスファイト、トリス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）フォスファイト等のリン酸系化合物、ジアルキルジチオリン酸亜鉛、ジアリールジチオリン酸亜鉛等の有機金属系化合物等が例示される。又、これらの酸化防止剤は、単独で又は２種以上を適宜組み合わせて使用することができる。酸化防止剤の配合量としては、塩化ビニル系樹脂１００重量部に対して０．０１〜１重量部が推奨される。
【００２９】
帯電防止剤としては、アルキルサルフェート型、アルキルアリルサルフェート型、アルキルホスフェート型、アルキルアミンサルフェート型、アルキルエーテルカルボン酸型又はジアルキルスルホサクシネート型のアニオン性帯電防止剤、ポリエチレングリコール誘導体、ポリオキシエチレンソルビタンモノステアレート等のソルビタン誘導体、ポリオキシエチレンアルキルアミン及びアミド、ジエタノールアミン誘導体等のノニオン性帯電防止剤、アルキルアミドアミン型、アルキルジメチルベンジル型等の第４級アンモニウム塩、アルキルイミダゾリン型、アルキルピリジニウム型の有機酸塩又は塩酸塩等のカチオン性帯電防止剤等が例示される。又、これらの帯電防止剤は、単独で又は２種以上を適宜組み合わせて使用することができる。帯電防止剤の配合量としては、塩化ビニル系樹脂１００重量部に対して０〜５重量部が推奨される。
【００３０】
防曇剤としては、特に制限されるものではないが、多価アルコールと高級脂肪酸類とから成る多価アルコール部分エステル系化合物が好適である。このような防曇剤の具体例としては、非イオン性界面活性剤、例えば、ソルビタンモノラウレート、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、ソルビタンモノオレエート、ソルビタンモノベヘネート、ソルビタンとアルキレングリコールの縮合物と脂肪酸とのエステル等のソルビタン系界面活性剤や、グリセリンモノパルミテート、グリセリンモノステアレート、グリセリンモノラウレート、グリセリンモノオレエート、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、ポリグリセリンラウリン酸エステル、ポリグリセリンオレイン酸エステル、ポリグリセリンステアリン酸エステル等のグリセリン系界面活性剤や、ポリエチレングリコールモノステアレート、ポリエチレングリコールモノパルミテート、ポリエチレングリコールアルキルフェニルエーテル等のポリエチレングリコール系界面活性剤やその他トリメチロールプロパンモノ（又はジ又はトリ）ステアレート、トリメチロールプロパンモノ（又はジ又はトリ）オレエート等のトリメチロールプロパン系界面活性剤やペンタエリスリトールモノパルミテート、ペンタエリスリトールモノステアレート等のペンタエリスリトール系界面活性剤やそれらの異性体を含むもの等を挙げることができる。これらの防曇剤は、それぞれ単独で用いてもよいし、２種以上を適宜組み合わせて用いてもよい。防曇剤の配合量としては、塩化ビニル系樹脂１００重量部に対して０．５〜５重量部、好ましくは１〜３重量部が推奨される。又、これらの防曇剤は、防滴剤としても使用できる。
【００３１】
滑剤としては、例えば、ステアリン酸、パルミチン酸、１２−ヒドロキシステアリン酸、ベヘニン酸等の脂肪酸、ステアリン酸アミド、パルミチン酸アミド、オレイン酸アミド、エチレンビスステアリン酸アミド等の脂肪酸アミド、ステアリン酸ブチル、パルミチン酸ブチル、ステアリン酸オクチル等の脂肪酸エステルや、ポリエチレンワックス、流動パラフィン、天然パラフィン、合成パラフィン、固体状の高級アルコール、グリセリン脂肪酸エステル等が挙げられる。又、これらの滑剤は、単独で又は２種以上を組み合わせて使用することができる。滑剤の配合量としては、塩化ビニル系樹脂１００重量部に対して０．１〜５０重量部が推奨される。
【００３２】
防霧剤として、フッ素系界面活性剤又はシリコーン系界面活性剤を配合することができる。フッ素系界面活性剤としては、例えばパーフロロアルキル基又はパーフロロアルケニル基を含有する高分子、或いは低分子の界面活性剤等が挙げられ、一般に、少なくとも０．００１重量％、好ましくは少なくとも０．０１重量％の水中溶解度を有し、２５℃において水の表面張力を３５ｄｙｎ／ｃｍ以下、特に３０ｄｙｎ／ｃｍ以下に低下させる能力を有するものが推奨される。又、パーフロロアルキル基は、その炭素鎖中に酸素原子が介在してもよい。
【００３３】
市販のフッ素系界面活性剤としては、例えば、ユニダインＤＳ‐４０１、ユニダインＤＳ‐４０３、ユニダインＤＳ‐４５１（以上、ダイキン工業社製）、メガファックＦ‐１４２Ｄ、メガファックＦ‐１７７（以上、大日本インキ化学工業社製）、フロラードＦＣ‐１７０、フロラードＦＣ‐１７６、フロラードＦＣ‐４３０（以上、住友スリーエム社製）、サーフロンＳ‐１４１、サーフロンＳ‐１４５、サーフロンＳ‐３８１、サーフロンＳ‐３８２、サーフロンＳ‐３９３（以上、旭硝子社製）等が挙げられる。
【００３４】
又、シリコーン系界面活性剤としては、例えば、ポリエーテル変性シリコーンオイル、カルボキシル変性シリコーンオイル、カルビノール変性シリコーンオイル、アミノ変性シリコーンオイル等が挙げられ、一般に、少なくとも０．０１重量％、好ましくは少なくとも０．１重量％の水中溶解度を有し、２５℃において水の表面張力を３５ｄｙｎ／ｃｍ以下、特に３０ｄｙｎ／ｃｍ以下に低下させる能力を有するものが好ましい。
【００３５】
市販のシリコーン系界面活性剤としては、例えばＫＦ‐３５４（信越化学社製）、ＳＨ‐３７４６（東レ・ダウコーニング社製）、ＴＳＦ‐４４４５（東芝シリコーン社製）等が挙げられる。
【００３６】
これらの防霧剤は、フッ素系界面活性剤を単独で用いてもよいし、２種以上を適宜組み合わせて用いてもよく、又、シリコーン系界面活性剤を単独で用いてもよいし、２種以上を適宜組み合わせて用いてもよい。或いはフッ素系界面活性剤の１種以上とシリコーン系界面活性剤の１種以上とを併用してもよい。防霧剤の添加量としては、塩化ビニル系樹脂１００重量部に対して０．０１〜２重量部が推奨される。
【００３７】
安定剤としては、例えば、金属石ケン系、Ｂａ‐Ｚｎ系、Ｃａ‐Ｚｎ系、Ｃａ‐Ｚｎ‐Ｂａ系、Ｂａ‐Ｍｇ‐Ａｌ系、Ｃｄ−Ｂａ系、Ｃｄ−Ｂａ−Ｚｎ系、Ｃｄ−Ｂａ−Ｐｂ系等が挙げられる。これらの安定剤は、単独で又は２種以上を組み合わせて使用することができる。安定剤の添加量としては、塩化ビニル系樹脂１００重量部に対して０．１〜５重量部が推奨される。
【００３８】
金属石ケン系安定剤として具体的には、ステアリン酸カルシウム、ステアリン酸カドミウム、ステアリン酸バリウム、ステアリン酸アルミニウム、ステアリン酸マグネシウム等が例示される。
【００３９】
安定化助剤としては、有機ホスファイト化合物、例えばトリフェニルホスファイト、ジオクチルフェニルホスファイト、トリス（ノニルフェニル）ホスファイト、ジフェニルイソデシルホスファイト等や、β−ジケトン化合物、例えばジベンゾイルメタン、ステアロイルベンゾイルメタン、デヒドロ酢酸等や、エポキシ化合物、エポキシ樹脂、ポリオール、例えば、ソルビトール、マンニトール、ペンタエリスリトール等があげられる。これらの安定化助剤は、単独で又は２種以上を適宜組み合わせて使用することができる。安定化助剤の配合量としては、塩化ビニル系樹脂１００重量部に対して０．１〜８重量部が推奨される。
【００４０】
更に、耐久性及び防塵性を向上させるために、本発明に係る農業用塩化ビニル樹脂フィルムの片面上に、アクリル系樹脂被膜を形成することも可能である。又、長期の防曇性を持たせるため、公知のシリカゾルやアルミナゾルを含んだ防曇塗膜を形成することも可能である。
【００４１】
又、公知のべたつき防止剤、例えば、コロイド状無機化合物の水性分散液と水性オルガノポリシロキサンエマルジョンの混合液等をフィルム上に塗布することができる。
【００４２】
前記塩化ビニル系樹脂フィルムには、上記の可塑剤、紫外線吸収剤、光安定剤、着色剤、充填剤、酸化防止剤、帯電防止剤、防曇剤、防滴剤、滑剤、防霧剤、安定剤、安定化助剤の他に、必要に応じて、成形用の合成樹脂に通常配合される公知の樹脂添加物、例えば、防カビ剤、防藻剤等を配合することができる。
【００４３】
本発明に係る農業用塩化ビニル樹脂系フィルムは、塩化ビニル樹脂と共に所定の可塑剤及び樹脂改質剤を所定量配合し、通常の配合技術、例えば、リボンブレンダー、バンバリーミキサー、ヘンシェルミキサー、単軸又は二軸押出機、ロールミル等の配合機や混練機を用いて均質に配合し、これをフィルム化して得ることができる。フィルム化するには公知の方法、例えば、カレンダー法、溶融押出法、インフレーション法、溶液流延法等を採用すればよい。
【００４４】
このとき、調製されるフィルムの厚さは、農業用塩化ビニル樹脂系フィルムとして適用される限り、特に制限されるものではないが、あまり薄いと強度が不十分となり、逆に厚すぎるとフィルム化作業その他に不便をきたすので、一般には０．０３〜０．３ｍｍ、好ましくは０．０５〜０．２ｍｍの範囲が適当である。又、その外観として、透明、不透明は問わない。
【００４５】
【実施例】
次に実施例を挙げて、本発明を詳しく説明するが、本発明は実施例に限定されるものではない。フィルムの性能評価は以下の方法により行った。
【００４６】
耐寒性試験
恒温槽付フィルムインパクトテスター（東洋精機社製）を用い、−１８℃で測定した脆性破壊率で次の通り評価した。
○：５０％未満、×：５０％以上
【００４７】
耐候性試験
屋外暴露台上に１２ヶ月間暴露し、ＪＩＳ−Ｋ−６７３２に基づいて測定した引張破断強度で次の通り評価した。
○：２５ＭＰａ以上、△：２０〜２５ＭＰａ、×：２０ＭＰａ未満
【００４８】
オーブン耐熱試験
得られたフィルムを２ｃｍ角に切り取り、１８０℃に設定したオーブンに入れ、１２０分後の変色具合を目視にて次の通り評価した。
○：試料の周辺部が褐色で、中央部はやや褐色。
△：試料の周辺部が黒色で、中央部は濃い褐色。
×：試料の周辺部、中央部共に黒色。
【００４９】
ＵＶ試験
得られたフィルムをＵＶテスター（岩崎電気社製）に入れ、ライト８時間、デュー８時間、レスト８時間の合計２４時間を１サイクルとし、３サイクル後の変色具合を目視にて次の通り評価した。
○：試料の一部に斑点状の変色がある。
△：試料の全面が薄い変色。
×：試料の全面が濃い変色。
【００５０】
実施例１、実施例２、実施例３、比較例
表−１に示す各成分を配合して樹脂組成物を調製したのち、４本カレンダーにより１８０℃でフィルム化し、厚さ０．１ｍｍのポリ塩化ビニルフィルムを作成した。これらのフィルムについて、耐寒性試験、耐候性試験、オーブン耐熱性試験、ＵＶ試験を行った。得られた結果を表−１に示す。
【００５１】
【表１】
【発明の効果】
本発明に係る非フタル酸エステル系可塑剤を適用することにより、耐寒性、耐候性及び耐熱性に優れた農業用塩化ビニル系樹脂フィルムを得ることができる。[0001]
[Industrial application fields]
The present invention relates to an agricultural vinyl chloride resin film.
[0002]
[Prior art]
Agricultural vinyl chloride resin films are typified by di-2-ethylhexyl phthalate (DOP) and diisononyl phthalate (DINP) for the purpose of improving processability and imparting flexibility and other performance to products. Phthalic acid ester plasticizers for vinyl chloride are widely used.
[0003]
In recent years, environmental problems of chemical substances have been highlighted, and in the plasticizer field, development of a non-phthalate plasticizer as a substitute for a phthalate plasticizer is desired.
[0004]
[Problems to be solved by the invention]
An object of the present invention is to provide a novel and useful vinyl chloride resin film for agricultural use containing a non-phthalate ester plasticizer.
[0005]
[Means for Solving the Problems]
As a result of intensive studies to solve such problems, the present inventors have found that 1,2-cyclohexanedicarboxylic acid diester having a specific structure is a non-phthalate ester plasticizer for vinyl chloride resin films for agriculture. As a result, the present invention has been completed based on this finding.
[0006]
That is, the agricultural vinyl chloride resin film according to the present invention has a vinyl chloride resin and a general formula
1,2-cyclohexanedicarboxylic acid diester (hereinafter referred to as “the present ester”).
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The vinyl chloride resin according to the present invention is a vinyl chloride homopolymer and a vinyl chloride copolymer, and is not particularly limited as long as it is applied as a resin component for agricultural vinyl chloride resin films. .
[0008]
In the case of the copolymer, for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1 Α-olefins having 2 to 30 carbon atoms such as tridecene, 1-tetradecene, acrylic acid and its esters, methacrylic acid and its esters, maleic acid and its esters, vinyl acetate, vinyl propionate, alkyl vinyl ether, etc. Vinyl compounds, polyfunctional monomers such as diallyl phthalate, and copolymers of these and vinyl chloride monomers (or vinylidene chloride monomers), ethylene-acrylate copolymers such as ethylene-ethyl acrylate copolymers , Ethylene-methacrylate copolymer, ethylene-vinyl acetate copolymer (EVA), chlorinated polyethylene, butyl rubber, crosslinked acrylic rubber, polyurethane, butadiene-styrene-methyl methacrylate copolymer (MBS), butadiene-acrylonitrile- (α-methyl) styrene copolymer (ABS), styrene-butadiene Examples thereof include a graft copolymer obtained by grafting a vinyl chloride monomer (or vinylidene chloride monomer) onto a copolymer, polyethylene, polymethyl methacrylate, and a mixture thereof.
[0009]
The average degree of polymerization of the vinyl chloride resin is usually 700 to 5000, preferably 900 to 3500, and more preferably 1000 to 3000. If the degree of polymerization is too low, heat resistance and the like are lowered, and if it is too high, moldability tends to be lowered.
[0010]
In general formula (1) representing this ester, R 1 Or R 2 Examples of the branched-chain alkyl group having 9 carbon atoms represented by the following include the following depending on the position of the branch and the number of branched methyl groups.
(1) C9 branched alkyl group having one methyl branch
2-methyloctyl group, 3-methyloctyl group, 4-methyloctyl group, 5-methyloctyl group, 6-methyloctyl group, 7-methyloctyl group
(2) C9 branched alkyl group having two methyl branches
2,4-dimethylheptyl group, 2,5-dimethylheptyl group, 4,6-dimethylheptyl group
(3) C9 branched alkyl group having three methyl branches
3,5,5-trimethylhexyl group, 2,5,5-trimethylhexyl group
[0011]
Examples of the ester include 1,2-cyclohexanedicarboxylic acid diisononyl ester, 1,2-cyclohexanedicarboxylic acid di (3,5,5-trimethylhexyl) ester, and the like.
[0012]
The content of the ester is not particularly limited as long as it is applied as a plasticizer for agricultural vinyl chloride resin films, but 30 to 70 parts by weight is recommended with respect to 100 parts by weight of vinyl chloride resin. It is preferable that it is 40-60 weight part. If it is less than 30 parts by weight, it is difficult to obtain the desired plasticizing effect, and if it exceeds 70 parts by weight, bleeding to the surface of the molded product tends to become violent. Absent.
[0013]
As a plasticizer for agricultural vinyl chloride resin films according to the present invention, the general formula (2) together with the ester is used.
A dialkyl 1,2-cyclohexanedicarboxylate represented by the following (hereinafter referred to as “combined ester”) can be used in combination.
[0014]
When the present ester and the combined ester are used in combination, the weight ratio of the present ester to the total amount of the present ester and the combined ester is recommended to be 70 to 97% by weight, and particularly preferably 80 to 97% by weight.
[0015]
In the agricultural vinyl chloride resin film according to the present invention, in addition to 1,2-cyclohexanedicarboxylic acid diester, a phosphate plasticizer is used in combination of 10 parts by weight or less with respect to 100 parts by weight of vinyl chloride resin. Is preferred. Examples of the phosphate ester plasticizer include tricresyl phosphate (hereinafter abbreviated as “TCP”), trixylenyl phosphate, tris (isopropylphenyl) phosphate, tributyl phosphate, triethyl phosphate, trioctyl phosphate, tris Examples include (2-ethylhexyl) phosphate, octyl diphenyl phosphate, cresyl diphenyl phosphate, and the like.
[0016]
The vinyl chloride resin film for agriculture according to the present invention is composed of an ultraviolet absorber, a light stabilizer, a colorant, a filler, an antioxidant, an antistatic agent, an antifogging agent, a drip-proofing agent, a lubricant, an antifogging agent, and a stability. A known additive selected from the group consisting of an agent and a stabilizing aid can be blended.
[0017]
As the UV absorber, any UV absorber that is usually blended in agricultural vinyl chloride films may be used, and various UV absorbers such as benzotriazole, benzophenone, salicylic acid ester, and cyanoacrylate are exemplified, and in particular, benzotriazole A UV absorber and a benzophenone UV absorber are preferred. Specific examples include the following. Moreover, as a compounding quantity of a ultraviolet absorber, 0.01-2 weight part is recommended with respect to 100 weight part of vinyl chloride resin.
[0018]
Examples of the benzotriazole compounds include 2- (2′-hydroxyphenyl) benzotriazole, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5-methylphenyl)- 5-carboxylic acid butyl ester benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) -5,6-dichlorobenzotriazole, 2- (2'-hydroxy-5'-methylphenyl) -5 Ethylsulfone benzotriazole, 2- (2′-hydroxy-5′-t-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3′-methyl-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′-dimethylphenyl) -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-chloro Lobenzotriazole, 2- (2′-hydroxy-5′-methoxyphenyl) benzotriazole, 2- (2′-hydroxy-3′-t-amyl-5′-isobutylphenyl) -5-chlorobenzotriazole, 2 -(2'-Hydroxy-3'-isobutyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-isobutyl-5'-propylphenyl) -5-chlorobenzotriazole 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- [2'-hydroxy-5'-(1,1,3,3-tetramethyl) phenyl] Benzotriazole, 2- (2′-hydroxy-5′-cyclohexylphenyl) benzotriazole, 2- (2′-hydroxy-4 ′, 5′-dimethyl) Phenyl) -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-carboxylic acid ester benzotriazole, 2- (2′-acetoxy-5) '-Methylphenyl) benzotriazole and the like are exemplified.
[0019]
Examples of the benzophenone compounds include 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, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2-hydroxy-5-chlorobenzophenone, bis- (2-methoxy-4-hydroxy-5-benzoyl) Phenyl) methane etc. It is. Examples of the product name include SS-102 (manufactured by Sipro Kasei).
[0020]
Examples of salicylic acid ester compounds include phenyl salicylate, 4-octylphenyl salicylate, 4-tert-butylphenyl salicylate, and the like.
[0021]
Examples of the cyanoacrylate compound include ethyl-2-cyano-3,3′-diphenyl acrylate and 2-ethylhexyl-2-cyano-3,3′-diphenyl acrylate.
[0022]
These ultraviolet absorbers can be used alone or in combination of two or more.
[0023]
As the light stabilizer, various compounds usually blended in agricultural films can be used, and examples thereof include hindered amines and metal complex salts, and hindered amine light stabilizers are particularly preferable. These light stabilizers can be used alone or in combination of two or more. The light stabilizer is blended in an amount of 0.01 to 2 parts by weight with respect to 100 parts by weight of the vinyl chloride resin. Is recommended.
[0024]
Specific examples of the hindered amine light stabilizer include 4-cyclohexinoyloxy-2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4- (o -Chlorobenzyloxy) -2,2,6,6-tetramethylpiperidine, tetrakis (2,2,6,6, -tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, Tetrakis (1,2,2,6,6, -pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, (2,2,6,6-tetramethyl-4-piperidyl and tridecyl ) -1,2,3,4-butanetetracarboxylate, (1,2,2,6,6-pentamethyl-4-piperidyl and tridecyl mixed group) -1,2,3 - butane tetra carboxylate, and the like. Product names include ADK STAB LA-57, ADK STAB LA-52, ADK STAB LA-67, ADK STAB LA-62, ADK STAB LA-63, ADK STAB LA-68, MARK LA-57, MARK LA-62, MARK LA-63, Examples include MARK LA-67, MARK LA-68 (manufactured by Asahi Denka Kogyo Co., Ltd.), TINUVIN 765, TINUVIN 744, TINUVIN 770, TINUVIN 144, TINUVIN 622LD (manufactured by Ciba Geigy).
[0025]
As the metal complex system, the metals are preferably nickel and cobalt. Specifically, nickel [2,2′-thiobis (4-tert-octyl) phenolate] -n-butylamine, nickel dibutylthiocarbamate, nickel bis [o-ethyl-3,5- (di-tert-butyl) -4-hydroxybenzyl)] phosphate, nickel bis (octylphenylsulfide) cobalt dicyclohexyldithiophosphate, [1-phenyl, 3-methyl, 4-decanoyl, pyrazolate (5) 2] nickel and the like.
[0026]
As colorants, carbon black, lead sulfide, white carbon, titanium white, lithopone, benigara, antimony sulfide, chrome yellow, chrome green, cobalt blue, molybdenum orange, phthalocyanine blue, phthalocyanine green, Hansa yellow, alizarin lake, Examples include zinc white, permanent red, quinacridone and the like. These colorants can be used alone or in combination of two or more. The blending amount of the colorant is recommended to be 0.01 to 5 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.
[0027]
As a filler, for example, silica, talc, diatomaceous earth, ferrites, aluminum hydroxide, calcium sulfate, calcium silicate, calcium hydroxide, hydroxylated, in order to suppress stickiness of the film or to further improve the heat retention. Magnesium, aluminum oxide, magnesium oxide, barium sulfate, kaolin clay, mica, alumina, calcium carbonate, magnesium carbonate, sodium aluminate, conductive zinc oxide, lithium phosphate, hydrotalcites, glass, carbon or metal fibers And powder, glass sphere, graphite, lithium-aluminum composite hydroxide salt, lithium-magnesium-aluminum composite hydroxide salt, and the like. These fillers may be used independently and may be used in combination of 2 or more types as appropriate. Moreover, as a compounding quantity of a filler, 0.05-20 weight part is recommended with respect to 100 weight part of vinyl chloride-type resin, and 0.1-15 weight part is especially preferable.
[0028]
Antioxidants include 2,6-di-tert-butyl-4-methylphenol, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 2,2 Phenolic compounds such as' -methylenebis- (4-methyl-6-tert-butylphenol), 2-hydroxy-4-methoxybenzophenone, alkyl disulfides, dilauryl thiodipropionate, dimyristyl thiodipropionate, benzothiazole Sulfur compounds such as trisnonylphenyl phosphite, diphenylisodecyl phosphite, triphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, etc., zinc dialkyldithiophosphate, Zinc diaryldithiophosphate And organometallic compounds such as Moreover, these antioxidants can be used individually or in combination of 2 or more types as appropriate. As the blending amount of the antioxidant, 0.01 to 1 part by weight is recommended with respect to 100 parts by weight of the vinyl chloride resin.
[0029]
Antistatic agents include alkyl sulfate type, alkyl allyl sulfate type, alkyl phosphate type, alkyl amine sulfate type, alkyl ether carboxylic acid type or dialkyl sulfosuccinate type anionic antistatic agent, polyethylene glycol derivative, polyoxyethylene sorbitan Sorbitan derivatives such as monostearate, nonionic antistatic agents such as polyoxyethylene alkylamines and amides, diethanolamine derivatives, quaternary ammonium salts such as alkylamidoamine type and alkyldimethylbenzyl type, alkylimidazoline type, alkylpyridinium type Examples thereof include cationic antistatic agents such as organic acid salts or hydrochlorides. Moreover, these antistatic agents can be used individually or in combination of 2 or more types as appropriate. The blending amount of the antistatic agent is recommended to be 0 to 5 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.
[0030]
Although it does not restrict | limit especially as an antifogging agent, The polyhydric alcohol partial ester type compound which consists of a polyhydric alcohol and higher fatty acids is suitable. Specific examples of such antifogging agents include nonionic surfactants such as sorbitan monolaurate, sorbitan monostearate, sorbitan monopalmitate, sorbitan monooleate, sorbitan monobehenate, sorbitan and alkylene glycol. Sorbitan surfactants such as esters of fatty acid esters and fatty acids, glycerin monopalmitate, glycerin monostearate, glycerin monolaurate, glycerin monooleate, diglycerin monopalmitate, diglycerin monostearate, poly Glycerin surfactants such as glycerol laurate, polyglycerol oleate and polyglycerol stearate, polyethylene glycol monostearate, polyethylene glycol monopalmitate Polyethylene glycol surfactants such as polyethylene glycol alkylphenyl ethers and other trimethylolpropane surfactants such as trimethylolpropane mono (or di or tri) stearate, trimethylolpropane mono (or di or tri) oleate and penta Examples include pentaerythritol surfactants such as erythritol monopalmitate and pentaerythritol monostearate and those containing isomers thereof. These antifogging agents may be used alone or in combination of two or more. As a compounding quantity of an antifogging agent, 0.5-5 weight part with respect to 100 weight part of vinyl chloride-type resin, Preferably 1-3 weight part is recommended. These antifogging agents can also be used as drip-proofing agents.
[0031]
As the lubricant, for example, fatty acid such as stearic acid, palmitic acid, 12-hydroxystearic acid, behenic acid, stearic acid amide, palmitic acid amide, oleic acid amide, fatty acid amide such as ethylene bis stearic acid amide, butyl stearate, Examples thereof include fatty acid esters such as butyl palmitate and octyl stearate, polyethylene wax, liquid paraffin, natural paraffin, synthetic paraffin, solid higher alcohol, glycerin fatty acid ester and the like. Moreover, these lubricants can be used individually or in combination of 2 or more types. As the blending amount of the lubricant, 0.1 to 50 parts by weight is recommended with respect to 100 parts by weight of the vinyl chloride resin.
[0032]
As the anti-fogging agent, a fluorine-based surfactant or a silicone-based surfactant can be blended. Examples of the fluorine-based surfactant include a polymer containing a perfluoroalkyl group or a perfluoroalkenyl group, or a low-molecular surfactant, and is generally at least 0.001% by weight, preferably at least about 0.1%. One having a solubility in water of 01% by weight and having the ability to reduce the surface tension of water to 35 dyn / cm or less, particularly 30 dyn / cm or less at 25 ° C. is recommended. The perfluoroalkyl group may have an oxygen atom in its carbon chain.
[0033]
Examples of commercially available fluorosurfactants include Unidyne DS-401, Unidyne DS-403, Unidyne DS-451 (above, manufactured by Daikin Industries), MegaFuck F-142D, MegaFuck F-177 (above, large Nippon Ink Chemical Co., Ltd.), Fluorad FC-170, Fluorad FC-176, Fluorard FC-430 (Sumitomo 3M), Surflon S-141, Surflon S-145, Surflon S-381, Surflon S-382 And Surflon S-393 (manufactured by Asahi Glass Co., Ltd.).
[0034]
Examples of the silicone surfactant include polyether-modified silicone oil, carboxyl-modified silicone oil, carbinol-modified silicone oil, amino-modified silicone oil, and the like. Generally, at least 0.01% by weight, preferably at least Those having a solubility in water of 0.1% by weight and having the ability to reduce the surface tension of water to 25 dyn / cm or less, particularly 30 dyn / cm or less at 25 ° C. are preferred.
[0035]
Examples of commercially available silicone surfactants include KF-354 (manufactured by Shin-Etsu Chemical), SH-3746 (manufactured by Dow Corning Toray), TSF-4445 (manufactured by Toshiba Silicone), and the like.
[0036]
These anti-fogging agents may be used alone as a fluorine-based surfactant, or may be used in an appropriate combination of two or more types, or may be used alone as a silicone-based surfactant. You may use suitably combining a seed | species or more. Or you may use together 1 or more types of a fluorine-type surfactant, and 1 or more types of a silicone type surfactant. The addition amount of the antifogging agent is recommended to be 0.01 to 2 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.
[0037]
Examples of the stabilizer include metal soap, Ba—Zn, Ca—Zn, Ca—Zn—Ba, Ba—Mg—Al, Cd—Ba, Cd—Ba—Zn, and Cd—. Ba-Pb system etc. are mentioned. These stabilizers can be used alone or in combination of two or more. The addition amount of the stabilizer is recommended to be 0.1 to 5 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.
[0038]
Specific examples of the metal soap stabilizer include calcium stearate, cadmium stearate, barium stearate, aluminum stearate, magnesium stearate and the like.
[0039]
Stabilization aids include organic phosphite compounds such as triphenyl phosphite, dioctylphenyl phosphite, tris (nonylphenyl) phosphite, diphenylisodecyl phosphite and the like, β-diketone compounds such as dibenzoylmethane, stearoyl Examples thereof include benzoylmethane, dehydroacetic acid, etc., epoxy compounds, epoxy resins, polyols such as sorbitol, mannitol, pentaerythritol and the like. These stabilizing aids can be used alone or in appropriate combination of two or more. The blending amount of the stabilizing aid is recommended to be 0.1 to 8 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.
[0040]
Furthermore, in order to improve durability and dustproofness, it is also possible to form an acrylic resin film on one side of the agricultural vinyl chloride resin film according to the present invention. Moreover, in order to give long-term antifogging property, it is also possible to form an antifogging coating film containing a known silica sol or alumina sol.
[0041]
Further, a known anti-sticking agent, for example, a mixed liquid of an aqueous dispersion of a colloidal inorganic compound and an aqueous organopolysiloxane emulsion can be applied on the film.
[0042]
In the vinyl chloride resin film, the plasticizer, ultraviolet absorber, light stabilizer, colorant, filler, antioxidant, antistatic agent, antifogging agent, dripproofing agent, lubricant, antifogging agent, In addition to the stabilizer and the stabilizing aid, a known resin additive that is usually blended in a molding synthetic resin, for example, an antifungal agent, an algaeproofing agent, or the like can be blended as necessary.
[0043]
The agricultural vinyl chloride resin film according to the present invention is blended with a predetermined amount of a plasticizer and a resin modifier together with a vinyl chloride resin, and a normal blending technique such as a ribbon blender, a Banbury mixer, a Henschel mixer, a uniaxial Or it can mix | blend homogeneously using compounding machines and kneading machines, such as a twin-screw extruder and a roll mill, and can obtain this by making into a film. In order to form a film, a known method such as a calendar method, a melt extrusion method, an inflation method, or a solution casting method may be employed.
[0044]
At this time, the thickness of the prepared film is not particularly limited as long as it is applied as an agricultural vinyl chloride resin film, but if it is too thin, the strength is insufficient, and conversely if it is too thick, it becomes a film. Since inconvenience is caused for work and the like, a range of generally 0.03 to 0.3 mm, preferably 0.05 to 0.2 mm is appropriate. In addition, the appearance may be transparent or opaque.
[0045]
【Example】
EXAMPLES Next, although an Example is given and this invention is demonstrated in detail, this invention is not limited to an Example. The film performance was evaluated by the following method.
[0046]
Cold resistance test
Using a film impact tester with a thermostatic bath (manufactured by Toyo Seiki Co., Ltd.), the brittle fracture rate measured at −18 ° C. was evaluated as follows.
○: Less than 50%, ×: 50% or more
[0047]
Weather resistance test
It exposed for 12 months on the outdoor exposure stand, and evaluated as follows with the tensile breaking strength measured based on JIS-K-6732.
○: 25 MPa or more, Δ: 20 to 25 MPa, ×: less than 20 MPa
[0048]
Oven heat test
The obtained film was cut into 2 cm squares, placed in an oven set at 180 ° C., and the color change after 120 minutes was visually evaluated as follows.
○: The periphery of the sample is brown and the center is slightly brown.
(Triangle | delta): The peripheral part of a sample is black and a center part is dark brown.
X: Both the periphery and the center of the sample are black.
[0049]
UV test
The obtained film was put into a UV tester (Iwasaki Electric Co., Ltd.), and the total 24 hours of light 8 hours, dew 8 hours, rest 8 hours was 1 cycle, and the color change after 3 cycles was visually evaluated as follows. did.
○: Spot discoloration occurs in a part of the sample.
Δ: pale discoloration of the entire surface of the sample.
X: The entire surface of the sample is darkly discolored.
[0050]
Example 1, Example 2, Example 3, Comparative Example
Each component shown in Table-1 was blended to prepare a resin composition, which was then formed into a film at 180 ° C. using a four-calendar to produce a 0.1 mm thick polyvinyl chloride film. These films were subjected to a cold resistance test, a weather resistance test, an oven heat resistance test, and a UV test. The obtained results are shown in Table 1.
[0051]
[Table 1]
【The invention's effect】
By applying the non-phthalate ester plasticizer according to the present invention, an agricultural vinyl chloride resin film excellent in cold resistance, weather resistance and heat resistance can be obtained.
Claims (4)
Priority Applications (1)
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| JP2001176490A JP4453225B2 (en) | 2001-06-12 | 2001-06-12 | Agricultural vinyl chloride resin film |
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| JP2001176490A JP4453225B2 (en) | 2001-06-12 | 2001-06-12 | Agricultural vinyl chloride resin film |
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| JP4553366B2 (en) * | 2005-03-31 | 2010-09-29 | アキレス株式会社 | Anti-sticking solution for agricultural vinyl chloride resin film |
| JP4676922B2 (en) * | 2006-05-22 | 2011-04-27 | アキレス株式会社 | Agricultural vinyl chloride resin film |
| KR101419062B1 (en) * | 2008-09-11 | 2014-07-11 | 에스케이종합화학 주식회사 | New plasticizer for polyvinylchloride resin |
| WO2010069796A2 (en) * | 2008-12-18 | 2010-06-24 | Basf Se | Insecticidal polymer composition |
| CN102905513A (en) * | 2010-05-28 | 2013-01-30 | 旭硝子株式会社 | Wavelength conversion film |
| JP5977954B2 (en) * | 2012-02-09 | 2016-08-24 | リンテック株式会社 | Semiconductor wafer processing sheet |
| CN102701980A (en) * | 2012-06-29 | 2012-10-03 | 太仓市新星轻工助剂厂 | Synthetic method of environmental-friendly plasticizer hexahydrobenzene diisononyl phthalate |
| JP6366422B2 (en) * | 2014-08-20 | 2018-08-01 | バンドー化学株式会社 | Vinyl chloride resin film |
| TW201619119A (en) * | 2014-10-09 | 2016-06-01 | 巴斯夫歐洲公司 | Plasticizer composition which comprises cycloalkyl esters of saturated dicarboxylic acids and 1,2-cyclohexane dicarboxylic esters |
| EP3990531B1 (en) * | 2019-06-26 | 2025-12-10 | Eastman Chemical Company | Cyclohexane dicarboxylate mixed ester compositions useful as plasticizers |
| PL448431A1 (en) * | 2024-04-26 | 2025-10-27 | Politechnika Poznańska | Method for obtaining polyvinyl chloride mixtures |
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