CN114075349A - 聚烯烃类农膜用改性剂、母料、聚烯烃类农膜以及层叠膜 - Google Patents
聚烯烃类农膜用改性剂、母料、聚烯烃类农膜以及层叠膜 Download PDFInfo
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- CN114075349A CN114075349A CN202110935447.8A CN202110935447A CN114075349A CN 114075349 A CN114075349 A CN 114075349A CN 202110935447 A CN202110935447 A CN 202110935447A CN 114075349 A CN114075349 A CN 114075349A
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- 239000003607 modifier Substances 0.000 title claims abstract description 59
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 46
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 24
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 16
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 15
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 14
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 14
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 13
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 13
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 12
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 12
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 11
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 9
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 9
- 239000011780 sodium chloride Substances 0.000 claims abstract description 8
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 7
- 239000001110 calcium chloride Substances 0.000 claims abstract description 7
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 7
- 239000001103 potassium chloride Substances 0.000 claims abstract description 7
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 7
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims abstract description 7
- 229910052939 potassium sulfate Inorganic materials 0.000 claims abstract description 7
- 235000011151 potassium sulphates Nutrition 0.000 claims abstract description 7
- 235000011132 calcium sulphate Nutrition 0.000 claims abstract description 6
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229910001629 magnesium chloride Inorganic materials 0.000 claims abstract description 6
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229920005672 polyolefin resin Polymers 0.000 claims description 46
- -1 fatty acid ester Chemical class 0.000 claims description 40
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 27
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 22
- 239000000194 fatty acid Substances 0.000 claims description 22
- 229930195729 fatty acid Natural products 0.000 claims description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 150000002148 esters Chemical class 0.000 claims description 15
- 239000003963 antioxidant agent Substances 0.000 claims description 14
- 150000004665 fatty acids Chemical class 0.000 claims description 14
- 229910052783 alkali metal Inorganic materials 0.000 claims description 13
- 230000003078 antioxidant effect Effects 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 229910021536 Zeolite Inorganic materials 0.000 claims description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 7
- 239000010457 zeolite Substances 0.000 claims description 7
- 229920005862 polyol Polymers 0.000 claims description 6
- 239000000454 talc Substances 0.000 claims description 6
- 229910052623 talc Inorganic materials 0.000 claims description 6
- 239000005909 Kieselgur Substances 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 150000003077 polyols Chemical class 0.000 claims description 4
- 239000002344 surface layer Substances 0.000 claims description 3
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 claims description 2
- 150000008052 alkyl sulfonates Chemical class 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 239000000306 component Substances 0.000 claims 1
- 239000010410 layer Substances 0.000 description 28
- 238000000034 method Methods 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 18
- 239000003795 chemical substances by application Substances 0.000 description 16
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 229920001577 copolymer Polymers 0.000 description 14
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 10
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 7
- 239000005977 Ethylene Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000007334 copolymerization reaction Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
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- 239000005639 Lauric acid Substances 0.000 description 5
- 239000006096 absorbing agent Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 4
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- IRDCEJVOXCGYAV-UHFFFAOYSA-M lithium;2-dodecylbenzenesulfonate Chemical compound [Li+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O IRDCEJVOXCGYAV-UHFFFAOYSA-M 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 150000005846 sugar alcohols Polymers 0.000 description 4
- 229920005992 thermoplastic resin Polymers 0.000 description 4
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 3
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 3
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WYPSHFNKJPROSA-UHFFFAOYSA-N C(CCCCCCCC)OS(=O)(=O)C1=CC=CC=C1.[K] Chemical compound C(CCCCCCCC)OS(=O)(=O)C1=CC=CC=C1.[K] WYPSHFNKJPROSA-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000003484 crystal nucleating agent Substances 0.000 description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 239000012760 heat stabilizer Substances 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- 239000005001 laminate film Substances 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 3
- SVMNBAVEQLDZNO-UHFFFAOYSA-M potassium;2-hexadecylbenzenesulfonate Chemical compound [K+].CCCCCCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O SVMNBAVEQLDZNO-UHFFFAOYSA-M 0.000 description 3
- OFVHFMZXDRUDBH-UHFFFAOYSA-M potassium;2-pentadecylbenzenesulfonate Chemical compound [K+].CCCCCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O OFVHFMZXDRUDBH-UHFFFAOYSA-M 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 3
- CSUKGWJPGDWLPS-UHFFFAOYSA-M sodium;docosane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCCCCCCCCCCCS([O-])(=O)=O CSUKGWJPGDWLPS-UHFFFAOYSA-M 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- SRQKEEPVRWNRQZ-UHFFFAOYSA-N 1,4-bis(2-ethylhexoxy)-1,4-dioxobutane-2-sulfonic acid;potassium Chemical compound [K].CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC SRQKEEPVRWNRQZ-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 2
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- 235000021357 Behenic acid Nutrition 0.000 description 2
- RCAFPEURKGZHLK-UHFFFAOYSA-N C(CCCCCCCC)OS(=O)(=O)C1=CC=CC=C1.[Li] Chemical compound C(CCCCCCCC)OS(=O)(=O)C1=CC=CC=C1.[Li] RCAFPEURKGZHLK-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
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- GPQJPCZATZANPK-UHFFFAOYSA-M [Li+].C(CCCCCCCCCCCCCCCCCCCCC)S(=O)(=O)[O-] Chemical compound [Li+].C(CCCCCCCCCCCCCCCCCCCCC)S(=O)(=O)[O-] GPQJPCZATZANPK-UHFFFAOYSA-M 0.000 description 2
- 239000004840 adhesive resin Substances 0.000 description 2
- 229920006223 adhesive resin Polymers 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 229940116226 behenic acid Drugs 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 238000009820 dry lamination Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 108700039708 galantide Proteins 0.000 description 2
- CKDDRHZIAZRDBW-UHFFFAOYSA-N henicosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCC(O)=O CKDDRHZIAZRDBW-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- NTWKDFWKALPPII-UHFFFAOYSA-M lithium;octadecane-1-sulfonate Chemical compound [Li+].CCCCCCCCCCCCCCCCCCS([O-])(=O)=O NTWKDFWKALPPII-UHFFFAOYSA-M 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- KJNOTXZBZUBCRQ-UHFFFAOYSA-M potassium;docosane-1-sulfonate Chemical compound [K+].CCCCCCCCCCCCCCCCCCCCCCS([O-])(=O)=O KJNOTXZBZUBCRQ-UHFFFAOYSA-M 0.000 description 2
- RMOPTXQNTWWUKM-UHFFFAOYSA-M potassium;heptadecane-1-sulfonate Chemical compound [K+].CCCCCCCCCCCCCCCCCS([O-])(=O)=O RMOPTXQNTWWUKM-UHFFFAOYSA-M 0.000 description 2
- LNIAEVLCVIKUGU-UHFFFAOYSA-M potassium;octadecane-1-sulfonate Chemical compound [K+].CCCCCCCCCCCCCCCCCCS([O-])(=O)=O LNIAEVLCVIKUGU-UHFFFAOYSA-M 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- HEBRGEBJCIKEKX-UHFFFAOYSA-M sodium;2-hexadecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HEBRGEBJCIKEKX-UHFFFAOYSA-M 0.000 description 2
- PFIOPNYSBSJFJJ-UHFFFAOYSA-M sodium;2-octylbenzenesulfonate Chemical compound [Na+].CCCCCCCCC1=CC=CC=C1S([O-])(=O)=O PFIOPNYSBSJFJJ-UHFFFAOYSA-M 0.000 description 2
- VPNZAQYBGUPBSV-UHFFFAOYSA-M sodium;2-pentadecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O VPNZAQYBGUPBSV-UHFFFAOYSA-M 0.000 description 2
- QWSZRRAAFHGKCH-UHFFFAOYSA-M sodium;hexane-1-sulfonate Chemical compound [Na+].CCCCCCS([O-])(=O)=O QWSZRRAAFHGKCH-UHFFFAOYSA-M 0.000 description 2
- KBAFDSIZQYCDPK-UHFFFAOYSA-M sodium;octadecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCCCCCCCS([O-])(=O)=O KBAFDSIZQYCDPK-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- JYKSTGLAIMQDRA-UHFFFAOYSA-N tetraglycerol Chemical compound OCC(O)CO.OCC(O)CO.OCC(O)CO.OCC(O)CO JYKSTGLAIMQDRA-UHFFFAOYSA-N 0.000 description 2
- SZHOJFHSIKHZHA-UHFFFAOYSA-N tridecanoic acid Chemical compound CCCCCCCCCCCCC(O)=O SZHOJFHSIKHZHA-UHFFFAOYSA-N 0.000 description 2
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- WIBVOBURKHLIQM-UHFFFAOYSA-N potassium;tetradecyl benzenesulfonate Chemical compound [K].CCCCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 WIBVOBURKHLIQM-UHFFFAOYSA-N 0.000 description 1
- TYHSWAWOZSVJLP-UHFFFAOYSA-M potassium;tridecane-1-sulfonate Chemical compound [K+].CCCCCCCCCCCCCS([O-])(=O)=O TYHSWAWOZSVJLP-UHFFFAOYSA-M 0.000 description 1
- OVMORFVFEKUOLJ-UHFFFAOYSA-N potassium;tridecyl benzenesulfonate Chemical compound [K].CCCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 OVMORFVFEKUOLJ-UHFFFAOYSA-N 0.000 description 1
- XUCIBYHOOHJABG-UHFFFAOYSA-M potassium;undecane-1-sulfonate Chemical compound [K+].CCCCCCCCCCCS([O-])(=O)=O XUCIBYHOOHJABG-UHFFFAOYSA-M 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- KZOJQMWTKJDSQJ-UHFFFAOYSA-M sodium;2,3-dibutylnaphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S([O-])(=O)=O)=C(CCCC)C(CCCC)=CC2=C1 KZOJQMWTKJDSQJ-UHFFFAOYSA-M 0.000 description 1
- AIMUHNZKNFEZSN-UHFFFAOYSA-M sodium;decane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCS([O-])(=O)=O AIMUHNZKNFEZSN-UHFFFAOYSA-M 0.000 description 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
- JIBIRKJWPLYULV-UHFFFAOYSA-M sodium;heptadecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCCCCCCS([O-])(=O)=O JIBIRKJWPLYULV-UHFFFAOYSA-M 0.000 description 1
- RUYRDULZOKULPK-UHFFFAOYSA-M sodium;nonane-1-sulfonate Chemical compound [Na+].CCCCCCCCCS([O-])(=O)=O RUYRDULZOKULPK-UHFFFAOYSA-M 0.000 description 1
- HRQDCDQDOPSGBR-UHFFFAOYSA-M sodium;octane-1-sulfonate Chemical compound [Na+].CCCCCCCCS([O-])(=O)=O HRQDCDQDOPSGBR-UHFFFAOYSA-M 0.000 description 1
- PLQISZLZPSPBDP-UHFFFAOYSA-M sodium;pentadecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCCCCS([O-])(=O)=O PLQISZLZPSPBDP-UHFFFAOYSA-M 0.000 description 1
- AYFACLKQYVTXNS-UHFFFAOYSA-M sodium;tetradecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCCCS([O-])(=O)=O AYFACLKQYVTXNS-UHFFFAOYSA-M 0.000 description 1
- ORLPWCUCEDVJNN-UHFFFAOYSA-N sodium;tetradecyl benzenesulfonate Chemical compound [Na].CCCCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 ORLPWCUCEDVJNN-UHFFFAOYSA-N 0.000 description 1
- CACJZDMMUHMEBN-UHFFFAOYSA-M sodium;tridecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCCS([O-])(=O)=O CACJZDMMUHMEBN-UHFFFAOYSA-M 0.000 description 1
- DBMQUCVJHLWQHT-UHFFFAOYSA-M sodium;undecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCS([O-])(=O)=O DBMQUCVJHLWQHT-UHFFFAOYSA-M 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
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- 230000003068 static effect Effects 0.000 description 1
- AGGIJOLULBJGTQ-UHFFFAOYSA-N sulfoacetic acid Chemical compound OC(=O)CS(O)(=O)=O AGGIJOLULBJGTQ-UHFFFAOYSA-N 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229960002703 undecylenic acid Drugs 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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Abstract
提供一种聚烯烃类农膜用改性剂、母料、聚烯烃类农膜以及层叠膜。聚烯烃类农膜用改性剂含有:组分A,非离子性表面活性剂,组分B,有机磺酸盐,组分C,无机盐,以及组分D,除组分C的无机盐以外的无机物。组分C的无机盐是从硫酸钠、硫酸钾、硫酸钙、硫酸锂、氯化钠、氯化钾、氯化锂、氯化镁以及氯化钙中选择的至少一种。
Description
技术领域
本公开涉及一种聚烯烃类农膜用改性剂和分别含有所述改性剂的聚烯烃类农膜用母料、聚烯烃类农膜以及层叠膜。
背景技术
小拱棚栽培、温室栽培所使用的农膜需要耐久性、透明性、防雾性等各种性能。如日本特开2007-002105号公报以及日本特开平9-227744号公报中所公开的那样,提供了具有多种多样的特性的功能性膜。
例如,聚烯烃类膜出于上述的目的而广泛使用。但是,由于聚烯烃是疏水性的,所以仅由聚烯烃形成的膜存在诸多问题。例如,有可能引起水分导致的雾、静电导致的带电等。若农膜起雾,则太阳光的透射率降低,栽培作物的成长缓慢。为了改善这种情况,提供有含有防雾剂的各种聚烯烃类膜。例如,日本特开平10-000035号公报公开了一种由多元醇与碳原子数14~22的饱和脂肪酸的偏酯化合物构成的防雾剂。日本特开平10-001571号公报公开了在聚烯烃类树脂中添加失水山梨醇倍半硬脂酸酯等非离子类表面活性剂和烷基磺酸钠等烷基磺酸盐。在日本特开2018-193512号公报中,公开了在聚烯烃类树脂中混合特定的非离子性表面活性剂、特定的有机磺酸盐以及特定的无机盐,来实现优异的防雾性以及防带电性。
然而,这些聚烯烃类膜不能实现农膜所要求的优异的流滴性。流滴性是指使附着于膜的表面的凝结水沿着膜的表面流动的特性。若膜的流滴性低,则在栽培环境的湿度变高时,水分会在膜表面凝结而形成水滴,这些水滴滴下,附着在栽培作物上,有可能会产生不良影响。进而,也存在原油的价格高涨导致的生产成本增加等其他课题,也希望不使膜的生产性降低。
发明内容
因此,需要维持良好的透明性、生产性且能够长期持续优异的流滴性的聚烯烃类农膜。而且,也需要能够实现这样的聚烯烃类农膜的改性剂以及母料。
根据本公开的一方式,聚烯烃类农膜用改性剂含有:组分A,非离子性表面活性剂,组分B,有机磺酸盐,组分C,无机盐,以及与组分C无机盐不同的组分D无机物。组分C是从硫酸钠、硫酸钾、硫酸钙、硫酸锂、氯化钠、氯化钾、氯化锂、氯化镁以及氯化钙中选择的至少一种。
所述组分A例如是分子中具有羟基的脂肪酸酯。所述脂肪酸酯由多元醇和至少一种脂肪酸形成。脂肪酸也可以是脂肪酸衍生物。
所述组分B是从例如具有碳原子数为6~22的烷基的烷基磺酸碱金属盐、具有碳原子数为6~22的烷基的烷基芳基磺酸碱金属盐以及具有碳原子数6~22的烷基的磺基脂肪酸酯碱金属盐中选择的至少一种。
所述组分D是从例如二氧化硅、沸石、滑石以及硅藻土中选择的至少一种。
聚烯烃类农膜用改性剂在例如将从所述组分A到组分D的含有比例的合计设为100质量份的情况下,含有比例为1~75质量份的所述组分D。
聚烯烃类农膜用改性剂还可以含有组分E抗氧化剂。
聚烯烃类农膜用改性剂例如在含有组分E抗氧化剂且将从所述组分A到组分E的含有比例的合计设为100质量份的情况下,含有比例为2~70质量份的所述组分D。
根据本公开的一方式,母料含有上述任一项的聚烯烃类农膜用改性剂和聚烯烃类树脂。母料在将改性剂以及聚烯烃类树脂的含有比例的合计设为100质量份的情况下,含有比例为10~45质量份的改性剂。
根据本公开的一方式,聚烯烃类农膜含有上述任一种聚烯烃类农膜用改性剂和聚烯烃类树脂。聚烯烃类农膜在将改性剂以及聚烯烃类树脂的含有比例的合计设为100质量份的情况下,含有比例为0.1~5质量份的改性剂。
根据本公开的一方式,层叠膜具有上述的聚烯烃类农膜作为至少某一方的表层。层叠膜的层可以是2层,也可以设置中间层而成为3层以上。
根据本公开的所述方式,能够得到维持良好的透明性、生产性且能够长期持续高流滴性的聚烯烃类农膜。
具体实施方式
<聚烯烃类农膜>
本实施方式的农膜为聚烯烃类,例如能够用于小拱棚栽培、温室栽培等。聚烯烃类农膜(以下称为膜)是通过在聚烯烃类树脂中混合聚烯烃类农膜用改性剂(以下称为改性剂)并进行成型而制成的。另外,也可以制成含有聚烯烃类树脂和高浓度(比最终产物高的浓度)的改性剂的母料,并对母料与聚烯烃类树脂的混合物进行成型来制成膜。
<聚烯烃类农膜用改性剂>
改性剂含有:(A)非离子性表面活性剂;(B)有机磺酸盐;(C)特定的无机盐以及与(C)无机盐不同的(D)无机物。改性剂也可以含有(E)抗氧化剂。
<(A)组分:非离子性表面活性剂>
(A)非离子性表面活性剂能够使用以往公知的表面活性剂,其种类没有特别的限定。(A)非离子性表面活性剂即可以单独使用1种也可以并用2种以上。
(A)组分也可以是在作为表面活性剂的分子中具有羟基的脂肪酸酯。脂肪酸酯例如由(a1)多元醇和(a2)从脂肪酸以及脂肪酸衍生物中选择的至少一种形成。在分子中具有羟基的脂肪酸酯有时被称为“偏酯”。
作为(a1)多元醇,可以列举:1)乙二醇、甘油、季戊四醇、山梨糖醇、葡萄糖等多元醇,2)脱水山梨糖醇、山梨糖醇酐(sorbide)等通过山梨糖醇的脱水而得的环状醚多元醇(cyclic ether polyhydric alcohols),3)双甘油、乙二醇二甘油醚等(聚)醚四醇,4)三甘油、三羟甲基丙烷二甘油醚等(聚)醚戊醇,5)四甘油、二季戊四醇等(聚)醚己醇。(a1)多元醇例如从早期的流滴性的观点出发,优选为3~6价。
作为(a2)脂肪酸以及脂肪酸衍生物,可以列举己酸、山梨酸、庚酸、辛酸、壬酸、葵酸、十一烷酸、十一烯酸、月桂酸、十三烷酸、肉豆蔻酸、十五烷酸、棕榈酸、麦芽糖酸、硬脂酸、异硬脂酸、花生酸、二十一酸、二十二烷酸、油酸、亚油酸、亚麻酸、芥酸、12-羟基硬脂酸、蓖麻油酸等脂肪酸以及它们的衍生物。(a2)脂肪酸以及脂肪酸衍生物例如从早期的流滴性的观点出发,优选碳原子数为8~22。所谓脂肪酸衍生物,是指能够将脂肪酸的一部分的官能基用其他的官能基取代,例如能够通过与(a1)多元醇反应来形成脂肪酸酯的物质。
<(B)组分:有机磺酸盐>
(B)有机磺酸盐能够使用以往公知的,其种类没有特别的限定。(B)有机磺酸盐既可以单独使用1种,也可以并用2种以上。
(B)组分例如为从(b1)具有碳原子数6~22的烷基的烷基磺酸碱金属盐、(b2)具有碳原子数6~22的烷基的烷基芳基磺酸碱金属盐、以及(b3)具有碳原子数6~22的烷基的磺基脂肪酸酯碱金属盐中选择的至少一种。在某些实施方式中,从流滴性的持续性等观点出发,更优选(b1)具有碳原子数6~22的烷基的烷基磺酸碱金属盐。
作为(b1)具有碳原子数6~22的烷基的烷基磺酸碱金属盐,可列举:己基磺酸锂、己基磺酸钠、己基磺酸钾、辛基磺酸锂、辛基磺酸钠、辛基磺酸钾、壬基磺酸锂、壬基磺酸钠、壬基磺酸钾、葵基磺酸锂、葵基磺酸钠、葵基磺酸钾、十一烷基磺酸锂、十一烷基磺酸钠、十一烷基磺酸钾、十二烷基磺酸锂、十二烷基磺酸钠、十二烷基磺酸钾、十三烷基磺酸锂、十三烷基磺酸钠、十三烷基磺酸钾、十四烷基磺酸锂、十四烷基磺酸钠、十四烷基磺酸钾、十五烷基磺酸锂、十五烷基磺酸钠、十五烷基磺酸钾、十六烷基磺酸锂、十六烷基磺酸钠、十六烷基磺酸钾、十七烷基磺酸锂、十七烷基磺酸钠、十七烷基磺酸钾、十八烷基磺酸锂、十八烷基磺酸钠、十八烷基磺酸钾、二十二烷基磺酸锂、二十二烷基磺酸钠、二十二烷基磺酸钾等。作为(b2)具有碳原子数6~22的烷基的烷基芳基磺酸碱金属盐,可列举:己基苯磺酸锂、己基苯磺酸钠、己基苯磺酸钾、辛基苯磺酸锂、辛基苯磺酸钠、辛基苯磺酸钾、壬基苯磺酸锂、壬基苯磺酸钠、壬基苯磺酸钾、葵基苯磺酸锂、葵基苯磺酸钠、葵基苯磺酸钾、十一烷基苯磺酸锂、十一烷基苯磺酸钠、十一烷基苯磺酸钾、十二烷基苯磺酸锂、十二烷基苯磺酸钠、十二烷基苯磺酸钾、十三烷基苯磺酸锂、十三烷基苯磺酸钠、十三烷基苯磺酸钾、十四烷基苯磺酸锂、十四烷基苯磺酸钠、十四烷基苯磺酸钾、十五烷基苯磺酸锂、十五烷基苯磺酸钠、十五烷基苯磺酸钾、十六烷基苯磺酸锂、十六烷基苯磺酸钠、十六烷基苯磺酸钾、十七烷基苯磺酸锂、十七烷基苯磺酸钠、十七烷基苯磺酸钾、十八烷基苯磺酸锂、十八烷基苯磺酸钠、十八烷基苯磺酸钾、二十二烷基苯磺酸锂、二十二烷基苯磺酸钠、二十二烷基苯磺酸钾等、二丁基萘磺酸锂、二丁基萘磺酸钠等、二丁基萘磺酸钾等。作为(b3)具有碳原子数6~22的烷基的磺基脂肪酸酯碱金属盐,可列举:二乙基磺基琥铂酸钠、二丙基磺基琥铂酸钠、二辛基磺基琥铂酸钠、二辛基磺基琥铂酸钾、双十二烷基磺基琥铂酸锂、二十二烷基磺基琥铂酸锂、十二烷基磺基乙酸钠、壬基苯氧基聚乙二醇(氧乙烯单位的重复数1~10)磺基乙酸钾等。在某些实施方式中,在(B)组分为(b1)至(b3)的情况下,更优选为钠盐。
<(C)组分:无机盐>
(C)无机盐是从硫酸钠、硫酸钾、硫酸钙、硫酸锂、氯化钠、氯化钾、氯化锂、氯化镁以及氯化钙中选择的至少一种。在某些实施方式中,从流滴性、透明性等观点出发,(C)无机盐优选为硫酸钠以及/或氯化钠。
<(D)组分:无机物>
(D)组分只要是(C)组分以外的无机物即可,其种类没有特别的限定。(D)无机物既可以单独使用1种,也可以并用2种以上。
作为(D)组分的无机物,例如可列举硫酸镁、硝酸钾等无机盐、二氧化硅、硅藻土、氧化铝、氧化铁、铁素体等氧化物类无机粒子以及沸石、滑石、硅灰石、云母、粘土等硅酸盐类无机粒子。例如,膜通过吹胀成型或其他适当的方法而成型。此时,利用(D)组分,可抑制膜生产时的挤压变动,良好地保持生产性。(D)组分优选二氧化硅、沸石、滑石或硅藻土,更优选二氧化硅、沸石或滑石,进一步优选二氧化硅或沸石,最优选二氧化硅。
<(E)组分:抗氧化剂>
(E)抗氧化剂只要是以往公知的即可,其种类没有特别地限定。(E)抗氧化剂既可以单独使用1种,也可以并用2种以上。
作为(E)抗氧化剂,可列举例如3-(3,5-二叔丁基-4-羟苯基)丙酸十八烷酯、四[3-(3,5-二叔丁基-4-羟苯基)丙酸]季戊四醇酯(pentaerythritoltetrakis[3-(3,5-di-tert-butyl-4-hydrxyphenyl)propionate])等酚类抗氧化剂、双[3-(十二烷基硫基)丙酸]2,2-双[[3-(十二烷基硫基)-1-氧代丙氧基]甲基]-1,3-丙二醇等硫类抗氧化剂、三(2,4-二叔丁基苯基)亚磷酸酯等磷类抗氧化剂、2-叔丁基-6-甲基-4-{3-[(2,4,8,10-四-叔丁基二苯并[d,f][1,3,2]二氧杂磷杂庚英-6-基)氧基]丙基}苯酚(2-tert-butyl-6-methyl-4-[3-[(2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)oxy]propyl]phenol)等酚磷类抗氧化剂等。
<含有比例>
在将改性剂中的(A)~(D)组分的含有比例(量)的合计设为100质量份的情况下,(D)组分的含有比例优选为1~75质量份的比例。另外,在将(A)~(D)组分的含有比例的合计设为100质量份的情况下,(D)组分的含有比例更优选为2~60质量份,进一步优选为5~40质量份。
改性剂也可以含有(E)组分即抗氧化剂。在这种情况下,相对于(A)~(E)组分的含有比例的合计100质量份,例如从生产性的观点出发,优选(D)组分的含有比例为2~70质量份,更优选为5~40质量份。
<聚烯烃类树脂>
作为聚烯烃类树脂,可列举α烯烃的均聚物、与以α烯烃为主要组分的异种单体的共聚物。例如,可列举聚乙烯、聚丙烯、乙烯-丁烯共聚物、乙烯-4-甲基-1-戊烯共聚物、乙烯-己烯共聚物、乙烯-辛烯共聚物等乙烯-α烯烃共聚物、乙烯-醋酸乙烯酯共聚物、乙烯-丙烯酸酯共聚物、乙烯-丙烯酸甲酯共聚物、对由乙烯-醋酸乙烯酯得到的共聚物进行皂化而得的乙烯-乙烯醇共聚物、乙烯-甲基丙烯酸甲酯共聚物、乙烯-醋酸乙烯酯-甲基丙烯酸甲酯共聚物、离聚物树脂等。也能够混合使用上述二个以上的聚烯烃类树脂。
也能够根据目的使这些聚烯烃类树脂中含有添加剂。作为添加剂,可列举耐候剂、紫外线吸收剂、红外线吸收剂、防结块剂、抑雾剂、保温剂、热稳定剂、中和剂、增塑剂、润滑剂、阻燃剂、结晶核剂、颜料等功能赋予剂。
<母料(Master batch)>
聚烯烃类农膜用母料(以下称为母料)含有聚烯烃类农膜用改性剂和聚烯烃类树脂。在改性剂和聚烯烃类树脂的含有比例的合计为100质量份的情况下,改性剂的含量优选为10到45质量份。在母料中能够根据目的含有添加剂。作为添加剂,可列举耐候剂、紫外线吸收剂、红外线吸收剂、防结块剂、抗静电剂、防雾剂、抑雾剂、保温剂、热稳定剂、中和剂、增塑剂、润滑剂、阻燃剂、结晶核剂、颜料等。
母料的制造方法能够使用公知的方法。其中,例如可列举如下方法等。即,(1)第一方法,具有:工序(1a),预先制备高浓度地含有聚烯烃类树脂和(A)~(D)组分的高浓度母料,以及工序(1b),进一步将该母料与聚烯烃类树脂混合来成为规定的聚烯烃类树脂组合物;(2)第二方法,具有:工序(2a),预先将聚烯烃类树脂和(A)~(D)组分用转鼓式搅拌机(tumbler blender)、高速混合器(super mixer)、亨舍尔混合器(Henschel mixer)等混合器进行混合,以及工序(2b),将该混合物利用单轴挤出机、多轴挤出机等挤出机进行熔融混匀来进行造粒;(3)第三方法,具有:工序(3a),利用挤出机使聚烯烃类树脂成为熔融状态,工序(3b),通过侧进料或液状注入将(A)~(D)组分添加至熔融的聚烯烃类树脂,以及工序(3c),对聚烯烃类树脂与(A)~(D)组分的混合物进行熔融混匀来进行造粒;以及组合了第二方法以及第三方法的(4)第四方法。高浓度母料能够通过第二方法至第四方法中的任一种方法制造。将聚烯烃类树脂和(A)~(D)组分混合的装置以及方法能够根据(A)~(D)组分的坚硬度而从公知的装置以及方法中选择。在(A)~(D)组分为固体的情况下,优选使用侧进料器、滚筒搅拌机、高速混合器、亨舍尔混合器。在组分(A)~(D)为液体的情况下,优选使用液状注入、高速混合器或亨舍尔混合器。也能够在固体的组分溶解或扩散至液状的组分中之后,将该混合物注入聚烯烃类树脂。
<聚烯烃类树脂膜>
作为对膜进行成型的方法,能够使用公知的方法。例如,可列举空冷吹胀成型(air-cooling inflation molding)、空冷2级吹胀成型、空冷3级吹胀成型、水冷吹胀成型等吹胀成型、以及T模成型。在T模成型的情况下,作为T模,能够使用直管式、衣架式(coathanger type)以及将它们组合的装置等。膜的制造方法既可以包括将母料与聚烯烃类树脂混合的工序,也可以包括将改性剂直接添加于聚烯烃类树脂的工序。在将改性剂和聚烯烃类树脂的含有比例的合计设为100质量份的情况下,聚烯烃类树脂膜中的改性剂的含有比例优选为0.1到5质量份。膜的厚度例如为10μm~300μm,但并不限定于该厚度。
<层叠膜>
层叠膜具有2层以上的层叠,并具有含有上述改性剂的改性膜作为至少任一方的表层。层叠膜的其他层由热塑性树脂、粘接剂、增粘涂层剂(anchor coating agent)、粘接性树脂等形成。作为热塑性树脂,可列举聚烯烃类树脂、聚对苯二甲酸乙二醇酯等聚酯、尼龙6等聚酰胺、聚乙烯醇、聚苯乙烯、聚甲基丙烯酸甲酯等丙烯酸树脂等。作为热塑性树脂,也能够使用与改性膜所含有的材料相同的聚烯烃类树脂。也能够根据目的使热塑性树脂含有添加剂。作为添加剂,可列举耐候剂、紫外线吸收剂、红外线吸收剂、防结块剂、抗静电剂、防雾剂、抑雾剂、保温剂、热稳定剂、中和剂、增塑剂、润滑剂、阻燃剂、结晶核剂、颜料等。
层叠膜能够由公知的方法制造。例如,作为制造方法,可列举干式层压法、砂层压法(sand lamination method,)、挤出层压法、共挤出法等。在通过干式层压法、砂层压法、挤出层压法制造层叠膜的情况下,能够使用聚氨酯类粘接剂、有机钛类增粘涂层剂、异氰酸酯类增粘涂层剂以及粘接性树脂等公知的粘接剂。在利用共挤出法进行制造时,能够使用吹胀成型以及T模成型,既可以含有延伸工序,也可以不含。层叠膜的厚度例如为10μm~300μm,但并不限定于该厚度。
本公开的聚烯烃类树脂用改性剂含有(A)非离子性表面活性剂、(B)有机磺酸盐、(C)特定的无机盐以及(D)特定的无机物。由此,维持膜的良好的透明性以及生产性的同时,能够实现优异的流滴性。流滴性对于农膜是重要的效果。而且能够降低制膜时产生挤压变动的可能性,因此能够稳定地得到规定膜厚的膜,能够提高生产性。
【实施例】
以下,通过记载本公开的实施例,明确地示出其结构以及效果。以下的说明中涉及含有比例,“份”以及“%”分别表示质量份以及质量%。表1示出聚烯烃类农膜用改性剂的实施例的组成。
实施例1-1
将作为非离子性表面活性剂的双甘油与月桂酸的偏酯(A-1)63.20份、作为有机磺酸盐的烷基的碳原子数13~18的烷基磺酸钠(B-1)14.22份、作为无机盐的硫酸钠(C-1)1.58份、作为无机物的二氧化硅(D-1)20.50份、以及作为抗氧化剂的3-(3,5-二叔丁基-4-羟苯基)丙酸十八烷酯(E-1)0.5份均匀混合,由此得到改性剂(K-1)。
实施例1-2~1-15以及比较例1-1~1-4
与实施例1-1的改性剂(K-1)同样地,得到实施例1-2~1-15以及比较例1-1~1-4的改性剂(K-2~K-15,k-1~k-4)。改性剂的组成如表1所示。
【表1】
在表1中,“D/A+B+C+D”表示在(A)~(D)组分的含有比例的合计为100质量份的情况下的(D)无机物的含有比例(质量份)。“D/A+B+C+D+E”表示在(A)~(E)组分的含有比例的合计为100质量份的情况下的(D)无机物的含有比例(质量份)。
以下示出实施例以及比较例所使用的组分(A)~(E)。
A-1:双甘油与月桂酸的偏酯
A-2:双甘油与硬脂酸的偏酯
A-3:甘油与油酸的偏酯
A-4:脱水山梨糖醇与月桂酸的偏酯
A-5:四甘油与己酸的偏酯
A-6:乙二醇与二十二烷酸的偏酯
A-7:甘油与醋酸的偏酯
A-8:十甘油与月桂酸的偏酯
B-1:烷基的碳原子数13~18的烷基磺酸钠
B-2:十五烷基磺酸钠
B-3:己基磺酸钠
B-4:二十二烷基磺酸钠
B-5:烷基的碳原子数10~16的烷基苯磺酸钠
B-6:十二烷基苯磺酸钠
B-7:十二烷基苯磺酸锂
B-8:二辛基磺基琥铂酸钾
C-1:硫酸钠
C-2:氯化钠
C-3:氯化钾
C-4:氯化锂
C-5:氯化钙
C-6:硫酸钾
c-1:油酸钠
D-1:二氧化硅
D-2:沸石
D-3:滑石
D-4:硅藻土
实施例2-1
将作为聚烯烃类树脂的乙烯-(1-己烯)共聚物(密度:0.930g/cm3、MFR:1.0g/10分钟、乙烯共聚比例96%)(R-1)80份和实施例1-1的改性剂(K-1)20份均匀混合,得到改性剂的浓度为20%的母料(N-1)。
实施例2-2~2-15以及比较例2-1~2-4
与实施例2-1的母料(N-1)同样地,得到实施例2-2~2-15、比较例2-1~2-4的母料(N-2~N-15、n-1~n-4)。母料的组成如表2所示。
【表2】
以下示出表2中的组分(R)。
R-1:乙烯-(1-己烯)共聚物(密度:0.930g/cm3、MFR:1.0g/10分钟、乙烯共聚比例96%)
R-2:乙烯-(1-丁烯)共聚物(密度:0.920g/cm3、MFR:2.1g/10分钟、乙烯共聚比例95%)
R-3:乙烯-丙烯共聚物(密度:0.90g/cm3、MFR:7.0g/10分钟、乙烯共聚比例4%)
R-4:乙烯-醋酸乙烯酯共聚物(密度:0.936g/cm3、MFR:2.0g/10分钟、乙烯共聚比例85%)
表3示出各实施例中的膜的原料、组成以及厚度。表3的“原料”一栏示出为了制造膜而使用的聚烯烃类树脂和母料。表3的“组成”一栏示出被制造的膜中所含的聚烯烃类树脂和改性剂。
实施例3-1
将作为聚烯烃类树脂的乙烯-(1-己烯)共聚物(密度:0.930g/cm3、MFR:1.0g/10分、乙烯共聚比例96%)(R-1)90份和由实施例2-1所得到的母料(N-1)10份利用转鼓(tumbler)混合而得到混合材料。将混合材料通过T模法冷却至30℃的同时挤出而得到80μm的膜(F-1)。混合材料以及膜两者相对于聚烯烃类树脂98份含有2份改性剂。
实施例3-2~3-15以及比较例3-1~3-4
与实施例3-1的膜(F-1)同样地得到实施例3-2~3-15以及比较例3-1~3-4的膜(F-2~F-15、f-1~f-4)。膜的组成以及厚度如表3所示。
【表3】
通过以下方法,对膜(F-1~F-15、f-1~f-4)的流滴性、透明性、外观以及生产性进行试验。其结果如表4所示。
流滴性的评价
20℃的环境气体下放置一个盛满水温40℃的水的水槽。以膜位于贮存于水槽的水的正上方,相对于水平面30度倾斜的方式,将膜设置于安装于水槽的金属模具。3小时后观察水滴对膜的表面的附着,并根据以下的基准来评价早期的流滴性。同样地,10日后也观察水滴对膜的表面的附着,评价流滴性的持续性。另外,在对具有后述的A~C层的层叠膜进行试验的情况下,以A层朝向下方,也就是说位于B层以及C层的下方,相对于水平面30度倾斜的方式,将层叠膜设置在金属模具上。
流滴性的评价基准
4:无水滴附着
3:水滴的附着面积不足50%
2:水滴的附着面积为50%以上且不足80%
1:水滴的附着面积为80%以上
透明性的评价
将膜在20℃且相对湿度65%的条件下调湿24小时。之后,使用雾度计(日本电色工业公司制造的商品名(NDH-5000)),根据以JISK7136:2000为基准的方法测定雾度值。根据以下的基准来评价膜的透明性。
透明性的评价基准
3(优):雾度值不足10%
2(良):雾度值为10%以上且不足20%
1(不良):雾度值为20%以上
外观的评价
将膜在20℃且相对湿度65%的条件下调湿24小时后,目视观察膜。根据以下的基准来评价膜的外观。
外观的评价基准
3(优):在膜上观察不到(因分散不良而产生的无机物的)块
2(良):在膜上观察到轻微的块
1(不良):在膜上观察到大量的块
生产性的评价
在制膜时,目视观察膜的制膜稳定性,根据以下的基准评价生产性。
生产性的评价基准
4(优):从制膜开始5小时以上,在制作膜上未见挤压变动,得到均匀膜厚的膜。
3(良):从制膜开始2小时以上且不足5小时,没有在制作膜上看到挤压变动,得到均匀膜厚的膜。
2(及格):从制膜开始30分钟以上且不足2小时,没有在制作膜上看到挤压变动,但无法得到均匀膜厚的膜。
1(不良):从制膜开始不足30分钟就在制作膜上看到挤压变动,无法得到均匀膜厚的膜。
【表4】
实施例3-1至3-15具有优异的流滴性、透明性、外观以及生产性。另一方面,比较例3-1的(C)无机盐不是硫酸钠、硫酸钾、硫酸钙、硫酸锂、氯化钠、氯化钾、氯化锂、氯化镁以及氯化钙中的任一种,因此流滴性的持续性差。比较例3-2不含(A)非离子性表面活性剂,因此流滴性差。比较例3-3不含(B)有机磺酸盐,因此流滴性的持续性差。比较例3-4不含(D)无机物,因此生产性差。
表5示出各实施例以及各比较例中的层叠膜的组成以及膜厚。层叠膜具有含有改性剂的膜即A层和不含改性剂的聚烯烃类树脂即B层和C层。A层的“原料”一栏示出制造膜时所使用的聚烯烃类树脂和母料的种类和量。A层的“组成”一栏示出A层所含的聚烯烃类树脂和改性剂的组成。表5还示出各层的厚度之比与层叠膜的膜厚。
实施例4-1
将作为聚烯烃类树脂的乙烯-(1-己烯)共聚物(密度:0.930g/cm3、MFR:1.0g/10分钟、乙烯共聚比例96%)(R-1)90份和母料(N-1)10份混合而得到混合材料。混合材料相对于聚烯烃类树脂98份含有2份改性剂。将混合材料用作单侧的外层(表层1:A层)的原料。将乙烯-(1-己烯)共聚物(R-1)用作中间层(B层)的原料以及另一方的外层(表层2:C层)的原料。将A~C层利用T模法冷却至30℃同时进行共挤出,得到厚度100μm的3层结构的层叠膜(M-1)。A层:B层:C层的膜厚之比为1:8:1。
实施例4-2~4-15以及比较例4-1~4-4
与实施例4-1的层叠膜(M-1)同样地得到实施例4-2~4-15以及比较例4-1~4-4的层叠膜(M-2~M-15、m-1~m-4)。层叠膜的组成以及膜厚如表5所示。
【表5】
根据上述的方法对层叠膜(M-1~M-15、m-1~m-4)的流滴性、透明性、外观以及生产性进行试验。表6表示层叠膜的试验结果。
【表6】
实施例4-1至4-15具有优异的流滴性、透明性、外观以及生产性。另一方面,比较例4-1的(C)无机盐不是硫酸钠、硫酸钾、硫酸钙、硫酸锂、氯化钠、氯化钾、氯化锂、氯化镁以及氯化钙中任一种,因此流滴性的持续性差。比较例4-2不含(A)非离子性表面活性剂,因此流滴性差。比较例4-3不含(B)有机磺酸盐,因此流滴性的持续性差。比较例4-4不含(D)无机物,因此生产性差。
Claims (10)
1.一种聚烯烃类农膜用改性剂,其特征在于,含有:
组分A,非离子性表面活性剂,
组分B,有机磺酸盐,
组分C,从硫酸钠、硫酸钾、硫酸钙、硫酸锂、氯化钠、氯化钾、氯化锂、氯化镁以及氯化钙中选择的至少一种无机盐,以及
组分D,除组分C的无机盐以外的无机物。
2.根据权利要求1所述的聚烯烃类农膜用改性剂,其特征在于,
所述组分A是分子中具有至少一个羟基的脂肪酸酯,
所述脂肪酸酯由多元醇与至少一个脂肪酸以及/或至少一个脂肪酸衍生物形成。
3.根据权利要求1或2所述的聚烯烃类农膜用改性剂,其特征在于,
所述组分B是从具有碳原子数6~22的烷基的烷基磺酸碱金属盐、具有碳原子数6~22的烷基的烷基芳基磺酸碱金属盐以及具有碳原子数6~22的烷基的磺基脂肪酸酯碱金属盐中选择的至少一种。
4.根据权利要求1~3中任一项所述的聚烯烃类农膜用改性剂,其特征在于,
所述组分D是从二氧化硅、沸石、滑石以及硅藻土中选择的至少一种。
5.根据权利要求1~4中任一项所述的聚烯烃类农膜用改性剂,其特征在于,
在所述组分A、所述组分B、所述组分C以及所述组分D的总量为100质量份的情况下,所述组分D的量为1~75质量份。
6.根据权利要求1~5中任一项所述的聚烯烃类农膜用改性剂,其特征在于,
还含有组分E抗氧化剂。
7.根据权利要求6所述的聚烯烃类农膜用改性剂,其特征在于,
在所述组分A、所述组分B、所述组分C、所述组分D以及所述组分E的总量为100质量份的情况下,所述组分D的量为2~70质量份。
8.一种聚烯烃类农膜用母料,其特征在于,
含有权利要求1~7中任一项所述的聚烯烃类农膜用改性剂和聚烯烃类树脂,
在所述改性剂以及所述聚烯烃类树脂的总量为100质量份的情况下,所述改性剂的量为10~45质量份。
9.一种聚烯烃类农膜,其特征在于,
含有权利要求1~7中任一项所述的聚烯烃类农膜用改性剂和聚烯烃类树脂,
在所述改性剂以及所述聚烯烃类树脂的总量为100质量份的情况下,所述改性剂的量为0.1~5质量份。
10.一种层叠膜,其特征在于,
作为其表层的至少一方,具有权利要求9所述的聚烯烃类农膜。
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US20130287985A1 (en) * | 2011-01-11 | 2013-10-31 | Mehmet Demirors | Antioxidant compounds for polyolefin resins |
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CN1628967A (zh) * | 2003-12-19 | 2005-06-22 | 竹本油脂株式会社 | 包装用薄膜 |
CN102029762A (zh) * | 2009-10-06 | 2011-04-27 | C.I.化成株式会社 | 农业用聚烯烃类多层薄膜及其制造方法 |
US20130287985A1 (en) * | 2011-01-11 | 2013-10-31 | Mehmet Demirors | Antioxidant compounds for polyolefin resins |
CN110621734A (zh) * | 2017-05-22 | 2019-12-27 | 竹本油脂株式会社 | 聚烯烃系树脂用改性剂、聚烯烃系树脂组合物、改性聚烯烃系树脂膜和层积膜 |
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