JPS63205345A - Modified polypropylene composition - Google Patents
Modified polypropylene compositionInfo
- Publication number
- JPS63205345A JPS63205345A JP19637887A JP19637887A JPS63205345A JP S63205345 A JPS63205345 A JP S63205345A JP 19637887 A JP19637887 A JP 19637887A JP 19637887 A JP19637887 A JP 19637887A JP S63205345 A JPS63205345 A JP S63205345A
- Authority
- JP
- Japan
- Prior art keywords
- modified polypropylene
- polypropylene
- weight
- unsaturated carboxylic
- 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.)
- Granted
Links
- -1 polypropylene Polymers 0.000 title claims abstract description 116
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 101
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 100
- 239000000203 mixture Substances 0.000 title claims abstract description 55
- 229920000092 linear low density polyethylene Polymers 0.000 claims abstract description 17
- 239000004707 linear low-density polyethylene Substances 0.000 claims abstract description 17
- 150000001735 carboxylic acids Chemical class 0.000 claims description 19
- 238000002156 mixing Methods 0.000 abstract description 11
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 abstract description 10
- 150000001451 organic peroxides Chemical class 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 4
- 239000004342 Benzoyl peroxide Substances 0.000 abstract description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 abstract description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011521 glass Substances 0.000 abstract description 2
- 150000002739 metals Chemical class 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract 1
- 229920003002 synthetic resin Polymers 0.000 abstract 1
- 239000000057 synthetic resin Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 21
- 238000010438 heat treatment Methods 0.000 description 12
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 11
- 239000005038 ethylene vinyl acetate Substances 0.000 description 10
- 239000005977 Ethylene Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000004898 kneading Methods 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 229920001684 low density polyethylene Polymers 0.000 description 6
- 239000004702 low-density polyethylene Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 230000035699 permeability Effects 0.000 description 6
- 229920005604 random copolymer Polymers 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 229920005629 polypropylene homopolymer Polymers 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920002292 Nylon 6 Polymers 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 239000005026 oriented polypropylene Substances 0.000 description 3
- 238000005453 pelletization Methods 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- HBQGCOWNLUOCBU-ONEGZZNKSA-N (e)-4-(ethylamino)-4-oxobut-2-enoic acid Chemical compound CCNC(=O)\C=C\C(O)=O HBQGCOWNLUOCBU-ONEGZZNKSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 229940095259 butylated hydroxytoluene Drugs 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- BZVFXWPGZHIDSJ-AATRIKPKSA-N (e)-4-(diethylamino)-4-oxobut-2-enoic acid Chemical compound CCN(CC)C(=O)\C=C\C(O)=O BZVFXWPGZHIDSJ-AATRIKPKSA-N 0.000 description 1
- FSQQTNAZHBEJLS-OWOJBTEDSA-N (e)-4-amino-4-oxobut-2-enoic acid Chemical compound NC(=O)\C=C\C(O)=O FSQQTNAZHBEJLS-OWOJBTEDSA-N 0.000 description 1
- BSSNZUFKXJJCBG-OWOJBTEDSA-N (e)-but-2-enediamide Chemical compound NC(=O)\C=C\C(N)=O BSSNZUFKXJJCBG-OWOJBTEDSA-N 0.000 description 1
- BEWIWYDBTBVVIA-PLNGDYQASA-N (z)-4-(butylamino)-4-oxobut-2-enoic acid Chemical compound CCCCNC(=O)\C=C/C(O)=O BEWIWYDBTBVVIA-PLNGDYQASA-N 0.000 description 1
- OZMRKDKXIMXNRP-FPLPWBNLSA-N (z)-4-(dibutylamino)-4-oxobut-2-enoic acid Chemical compound CCCCN(CCCC)C(=O)\C=C/C(O)=O OZMRKDKXIMXNRP-FPLPWBNLSA-N 0.000 description 1
- BZVFXWPGZHIDSJ-WAYWQWQTSA-N (z)-4-(diethylamino)-4-oxobut-2-enoic acid Chemical compound CCN(CC)C(=O)\C=C/C(O)=O BZVFXWPGZHIDSJ-WAYWQWQTSA-N 0.000 description 1
- HBQGCOWNLUOCBU-ARJAWSKDSA-N (z)-4-(ethylamino)-4-oxobut-2-enoic acid Chemical compound CCNC(=O)\C=C/C(O)=O HBQGCOWNLUOCBU-ARJAWSKDSA-N 0.000 description 1
- BSSNZUFKXJJCBG-UPHRSURJSA-N (z)-but-2-enediamide Chemical compound NC(=O)\C=C/C(N)=O BSSNZUFKXJJCBG-UPHRSURJSA-N 0.000 description 1
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- VAPQAGMSICPBKJ-UHFFFAOYSA-N 2-nitroacridine Chemical compound C1=CC=CC2=CC3=CC([N+](=O)[O-])=CC=C3N=C21 VAPQAGMSICPBKJ-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- OIYTYGOUZOARSH-UHFFFAOYSA-N 4-methoxy-2-methylidene-4-oxobutanoic acid Chemical compound COC(=O)CC(=C)C(O)=O OIYTYGOUZOARSH-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- XLYMOEINVGRTEX-ARJAWSKDSA-N Ethyl hydrogen fumarate Chemical compound CCOC(=O)\C=C/C(O)=O XLYMOEINVGRTEX-ARJAWSKDSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- ZEFVHSWKYCYFFL-UHFFFAOYSA-N diethyl 2-methylidenebutanedioate Chemical compound CCOC(=O)CC(=C)C(=O)OCC ZEFVHSWKYCYFFL-UHFFFAOYSA-N 0.000 description 1
- LDCRTTXIJACKKU-ONEGZZNKSA-N dimethyl fumarate Chemical compound COC(=O)\C=C\C(=O)OC LDCRTTXIJACKKU-ONEGZZNKSA-N 0.000 description 1
- 229960004419 dimethyl fumarate Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229920005674 ethylene-propylene random copolymer Polymers 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- XLYMOEINVGRTEX-UHFFFAOYSA-N fumaric acid monoethyl ester Natural products CCOC(=O)C=CC(O)=O XLYMOEINVGRTEX-UHFFFAOYSA-N 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229920004889 linear high-density polyethylene Polymers 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- FSQQTNAZHBEJLS-UPHRSURJSA-N maleamic acid Chemical compound NC(=O)\C=C/C(O)=O FSQQTNAZHBEJLS-UPHRSURJSA-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
- 239000000463 material Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- LLLCSBYSPJHDJX-UHFFFAOYSA-M potassium;2-methylprop-2-enoate Chemical compound [K+].CC(=C)C([O-])=O LLLCSBYSPJHDJX-UHFFFAOYSA-M 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000007613 slurry method Methods 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
本発明は、ポリオレフィンあるいはエチレン−酢酸ビニ
ル共重合体ケン化物、ナイロン。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to saponified polyolefins or ethylene-vinyl acetate copolymers, and nylon.
ポリエステル、ガラス、金属等の極性物質との接着性が
良好で、しかも透明性に優れた変性ポリプロピレン組成
物に関する。The present invention relates to a modified polypropylene composition that has good adhesion to polar substances such as polyester, glass, and metals, and has excellent transparency.
一般にポリプロピレンは機械的性質、透明性、成形性、
衛生性等に優れているため広い分野にわたって使用され
ているが、無極性のため極性物質との接着性が悪く、こ
れを改良するため種々の改質が行われている。例えば極
性物質をブレンドしたり、極性モノマーをグラフト反応
させることが試みられているがまだ接着性は充分とは言
えない。そのため、接着性を更に改良するために、不飽
和カルボン酸類なグラフトした変性ポリプロピレンｃ以
下単に変性ポリプロピレンともいう）にエチレン−プロ
ピレン共重合体等のゴム物質や低密度ポリエチレン等を
混合して変性ポリプロピレン組成物として用いる方法が
提案されている（特公昭５４−４０１１２号、同５４−
，１１０１１ｉ号）。しかしながら、このようにして製
造された変性ポリプロピレン組成物は、ある程度の接着
性の改良効果はあるが反面透明性が著しく低下するとい
う欠点がある。In general, polypropylene has mechanical properties, transparency, moldability,
It is used in a wide range of fields due to its excellent hygiene properties, but because it is non-polar, it has poor adhesion to polar substances, and various modifications have been carried out to improve this. For example, attempts have been made to blend polar substances or to perform a graft reaction with polar monomers, but the adhesive properties are still not satisfactory. Therefore, in order to further improve the adhesion, modified polypropylene grafted with unsaturated carboxylic acids (hereinafter also simply referred to as modified polypropylene) is mixed with a rubber substance such as ethylene-propylene copolymer, low density polyethylene, etc. to create modified polypropylene. A method of using it as a composition has been proposed (Japanese Patent Publication No. 54-40112, No. 54-
, No. 11011i). However, although the modified polypropylene composition produced in this manner has the effect of improving adhesion to some extent, it has the disadvantage that transparency is significantly reduced.
そのため、上記変性ポリプロピレン組成物を接着層、或
いはコーティング層として用いた場合にも得られる積層
フィルムの透明性を著しく低下させるという問題を有す
る。Therefore, even when the modified polypropylene composition is used as an adhesive layer or a coating layer, there is a problem in that the transparency of the resulting laminated film is significantly reduced.
本発明者等は、透明性の低下が少く、しかも更に接着性
の良好な変性ポリプロピレン組成物について鋭意研究し
た。その結果、特定の低密度ポリエチレン、すなわち直
鎖状低密度ポリエチレンを変性ポリプロピレンに混合す
ることにより、所期の目的を達成できることを見い出し
本発明に到達した。The inventors of the present invention have conducted extensive research into modified polypropylene compositions that exhibit less deterioration in transparency and also have better adhesive properties. As a result, the inventors have discovered that the desired objective can be achieved by mixing a specific low-density polyethylene, that is, linear low-density polyethylene, with modified polypropylene, and have arrived at the present invention.
本発明は、不飽和カルボン酸類なグラフトしり変性ポリ
プロピレン又は該変性ポリプロピレン１００重量部に対
して最大５０００重量部の未変性ポリプロピレンを混合
したポリプロピレン混合物１００重量部に対し直鎖状低
密度ポリエチレンを５〜７０重量部を含有する変性ポリ
プロピレン組成物である。In the present invention, 5 to 5 parts by weight of linear low-density polyethylene is added to 100 parts by weight of graft-modified polypropylene of unsaturated carboxylic acids or a polypropylene mixture in which 100 parts by weight of the modified polypropylene is mixed with a maximum of 5000 parts by weight of unmodified polypropylene. This is a modified polypropylene composition containing 70 parts by weight.
本発明において使用する１つの樹脂成分は変性ポリプロ
ピレンである。該変性ポリプロピレンは任意の方法によ
り、ポリプロピレンに不飽和カルボン酸類をグラフト反
応させることにより得られた不飽和カルボン酸類なグラ
フトした変性ポリプロピレンである。また本発明に於い
ては上記変性ポリプロピレンに不飽和カルボン酸類をグ
ラフト反応させない゛ 所謂未変性のポリプロピレンを
混合したものを使用することができる。該未変性ポリプ
ロピレンの混合割合は一般に変性ポリプロピレン１００
重量部に対して５０００重量部以下、好ましくは１０〜
２０００重量部が適当である。不飽和カルボン酸をグラ
フトした変性ポリプロピレンの製造方法としてはポリプ
ロピレンと不飽和カルボン酸類とを、例えば溶融状態で
反応させる方法（例えば特公昭′４３−２７４２１号）
、溶液状態で反応させる方法（例えば特公昭４４−１５
４２２号）、スラリー状態で反応させる方法（例えば特
公昭４３−１８１４４号）、気相状態で反応させる方法
（例えば特開昭５０−７７４９３号）などがあるが、こ
れらの方法の中で押出機を用いる溶融混線法が操作上簡
便であるため好ましく用いられる。そこで溶融混練法に
よる前記ポリプロピレンの製造方法について詳述する。One resin component used in the present invention is modified polypropylene. The modified polypropylene is a modified polypropylene grafted with unsaturated carboxylic acids obtained by grafting polypropylene with unsaturated carboxylic acids by any method. Further, in the present invention, it is possible to use a mixture of the above-mentioned modified polypropylene and so-called unmodified polypropylene which is not subjected to a graft reaction with unsaturated carboxylic acids. The mixing ratio of the unmodified polypropylene is generally 100% of the modified polypropylene.
5000 parts by weight or less, preferably 10 to 10 parts by weight
2000 parts by weight is suitable. A method for producing modified polypropylene grafted with an unsaturated carboxylic acid is, for example, a method in which polypropylene and unsaturated carboxylic acids are reacted in a molten state (for example, Japanese Patent Publication No. 43-27421).
, a method of reacting in a solution state (for example, Japanese Patent Publication No. 44-15
422), a method of reacting in a slurry state (for example, Japanese Patent Publication No. 43-18144), and a method of reacting in a gas phase (for example, Japanese Patent Application Laid-open No. 77493-1983). Among these methods, extruder The melt intermixing method using is preferably used because it is easy to operate. Therefore, the method for producing the polypropylene using the melt-kneading method will be described in detail.
変性ポリプロピレンの原料とするポリプロピレン又は該
変性ポリプロピレンに混合して使用する未変性ポリプロ
ピレンはプロピレンのホモポリマーおよびコポリマーが
特に制限なく使用される。一般にはホモポリプロピレン
、プロピレン−エチレンランダム共重合体。As the polypropylene used as a raw material for the modified polypropylene or the unmodified polypropylene used as a mixture with the modified polypropylene, propylene homopolymers and copolymers can be used without particular limitation. Generally homopolypropylene, propylene-ethylene random copolymer.
プロピレン−エチレンブロック共重合体、プロピレンと
エチレン以外の他のα−オレフィンとの共重合体、およ
びこれらの混合物等が用いられる。これらのうち特にメ
ルトフローインデックスＣ以下単にＭＦＩ２ｎ略記する
）カ０．５乃至３０ｇ／１０分のホモボリブロピレンオ
ヨヒフロピレンーエチレンランダム共重合体が好ましく
用いられる。また、不飽和カルボン酸類としては、例え
ばアクリル酸。A propylene-ethylene block copolymer, a copolymer of propylene and an α-olefin other than ethylene, a mixture thereof, and the like are used. Among these, a homobolypropylene-ethylene random copolymer having a melt flow index of C or below (abbreviated simply as MFI2n) of 0.5 to 30 g/10 minutes is particularly preferably used. Further, examples of unsaturated carboxylic acids include acrylic acid.
メタクリル酸、マレイン酸、フマル酸、イタコン酸、シ
トラコン酸、またそれら酸無水物。Methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and their acid anhydrides.
エステル、アミド、イミド、金属塩等であり。These include esters, amides, imides, metal salts, etc.
例えば無水マレイン酸、無水シトラコン酸。For example, maleic anhydride, citraconic anhydride.
無水イタコン酸、アクリル酸メチル、メタクリル酸メチ
ル、アクリル酸エチル、メタクリル酸エチル、アクリル
酸ブチル、メタクリル酸ブチル、アクリル酸グリシジル
、メタクリル酸グリシジル、マレイン酸モノエチルエス
テル、マレイン酸ジエチルエステル、ツマに酸モノメチ
ルエステル、フマル酸ジメチルエステル、イタコン酸モ
ノメチルエステル、イタコン酸ジエチルエステル、アク
リルアミド。Itaconic anhydride, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, glycidyl acrylate, glycidyl methacrylate, monoethyl maleate, diethyl maleate, Tuma ni acid Monomethyl ester, dimethyl fumarate, monomethyl itaconate, diethyl itaconate, acrylamide.
メタクリルアミド、マレイン酸モノアミド。Methacrylamide, maleic acid monoamide.
マレイン酸ジアミド、マレイン酸−Ｎ−モノエチルアミ
ド、マレイン酸−Ｎ 、 Ｎ−ジエチルアミド、マレイ
ン酸−Ｎ−モノブチルアミド、マレイン酸−Ｎ、Ｎ−ジ
ブチルアミド。Maleic acid diamide, maleic acid-N-monoethylamide, maleic acid-N,N-diethylamide, maleic acid-N-monobutylamide, maleic acid-N,N-dibutylamide.
フマル酸モノアミド、フマル酸ジアミド、フマル酸−Ｎ
−モノエチルアミド、フマル酸−Ｎ、Ｎ−ジエチルアミ
ド、フマル酸−Ｎ−モノエチルアミド、フマル酸−Ｎ、
Ｎ−ジブチルアミド、マレイミｌ−′ｌＮ−プチルマレ
イミドウＮ−フェニルマレイミド、アクリル酸ナトリウ
ム、メタクリル酸ナトリウム、アクリル酸カリウム、メ
タクリル酸カリウム等を挙げることができる。これらの
うち、無水マレイン酸を用いるのが最も好ましい。かか
る不飽和カルボン酸類の使用量は特に制限されないが、
良好な不飽和カルボン酸類でグラフトされた変性ポリプ
ロピレンを得るためには。Fumaric acid monoamide, fumaric acid diamide, fumaric acid-N
-monoethylamide, fumaric acid-N, N-diethylamide, fumaric acid-N-monoethylamide, fumaric acid-N,
Examples include N-dibutylamide, maleimide, l-'lN-butylmaleimide, N-phenylmaleimide, sodium acrylate, sodium methacrylate, potassium acrylate, and potassium methacrylate. Among these, it is most preferable to use maleic anhydride. The amount of such unsaturated carboxylic acids used is not particularly limited, but
To obtain modified polypropylene grafted with good unsaturated carboxylic acids.
ポリプロピレン１００重量部に対して一般に０．０１乃
至２０重量部、好ましくは０．１乃至５重量部添加が好
ましい。It is generally preferred to add 0.01 to 20 parts by weight, preferably 0.1 to 5 parts by weight, per 100 parts by weight of polypropylene.
またポリプロピレンと不飽和カルボン酸類との反応を促
進するために有機過酸化物が用いられる。有機過酸化物
としては例えばベンゾイルパーオキサイド、ラウロイル
パーオキサイド、アゾビスイソブチロニトリル、ジクミ
ルパーオキサイド、 α、α′−ビス（ｔ−ブチルパー
オキシジイソプロビル）ベンゼン。Furthermore, organic peroxides are used to promote the reaction between polypropylene and unsaturated carboxylic acids. Examples of organic peroxides include benzoyl peroxide, lauroyl peroxide, azobisisobutyronitrile, dicumyl peroxide, and α,α'-bis(t-butylperoxydiisopropyl)benzene.
２．５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ
）ヘキサン、 ２，５−ジメチル−２，５−ジ（ｔ−ブ
チルパーオキシ）ヘキシン−６゜ジ−ｔ−ブチルパーオ
キサイド、クメンヒドロパーオキサイド、ｔ−ブチルヒ
ドロパーオキサイドなどが挙げられる。有機過酸化物の
添加量は特に制限されなりが、ポリプロピレン１００重
量部に対して通常０．００５乃至５重量部、好ましくは
０．０１乃至１重量部である。2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-6゜di-t-butylperoxide, Examples include cumene hydroperoxide and t-butyl hydroperoxide. The amount of organic peroxide added is not particularly limited, but is usually 0.005 to 5 parts by weight, preferably 0.01 to 1 part by weight, per 100 parts by weight of polypropylene.
不飽和カルボン酸類なグラフトした変性ポリプロピレン
は、上記に示したポリプロピレン、不飽和カルボン酸類
、有機過酸化物をタンブラ−、ヘンシェルミキサー等で
充分に混合し、ポリプロピレンの融点以上、一般には融
点以上２８０℃以下の温度で溶融混練してグラフト化反
応を行なわせる。溶融混練する方法は特に制限されず、
例えばスクリュー押出機、バンバリーミキサ−、ミキシ
ングロールなどを用いて行うことができるが、操作の簡
便さのためスクリュー押出機が好ましく使用される。溶
融混線の温度および時間は用いる有機過酸化物の分解温
度により変化するが。Modified polypropylene grafted with unsaturated carboxylic acids is prepared by thoroughly mixing the above-mentioned polypropylene, unsaturated carboxylic acids, and organic peroxide in a tumbler, Henschel mixer, etc., at a temperature above the melting point of polypropylene, generally above the melting point at 280°C. The grafting reaction is carried out by melt-kneading at the following temperature. The method of melting and kneading is not particularly limited,
For example, it can be carried out using a screw extruder, a Banbury mixer, a mixing roll, etc., but a screw extruder is preferably used because of its ease of operation. The temperature and time of melt crosstalk vary depending on the decomposition temperature of the organic peroxide used.
一般に１６０乃至２８０℃で０．３乃至３０分間、好ま
しくは１７０乃至２５０℃で１乃至１０分間が適当であ
る。なお、溶融混練は不活性ガス気流中で行なって本よ
い。Generally, a temperature of 160 to 280°C for 0.3 to 30 minutes, preferably a temperature of 170 to 250°C for 1 to 10 minutes is appropriate. Note that melt-kneading may be carried out in an inert gas stream.
しかして、上記のようにして製造した不飽和カルボン酸
類をグラフトした変性ポリプロピレンは、前記したよう
に不飽和カルボン酸類な所定の割合で用いても、その未
反応モノマーの残存が避けられない。したがって、所期
の目的を得るために上記の変性ポリプロピ１７ンをさら
に６０℃以上、好ましくは１００℃以上の温度で加熱処
理することが望ましい。Therefore, even if the modified polypropylene grafted with unsaturated carboxylic acids produced as described above is used in a predetermined proportion of unsaturated carboxylic acids as described above, unreacted monomers inevitably remain. Therefore, in order to obtain the desired purpose, it is desirable to further heat-treat the modified polypropylene 17 at a temperature of 60°C or higher, preferably 100°C or higher.
加熱温度が６０℃以下の場合、処理に長時間を要し実用
的でない。加熱温度の上限は特に制限されないが、変性
ポリプロピレンの融着な防止するために、該変性ポリプ
ロピレンの融点以下であることが好まし込。加熱処理手
段は従来知られている方法、例えば通気バンド型乾燥装
置、材料攪拌型乾燥装置、流動層乾燥装置、気流乾燥装
置、噴霧乾燥装置９回転乾燥装置、ドラム型乾燥装置、
減圧乾燥装置、赤外線乾燥装置、遠赤外線乾燥装置、マ
イクロ波乾燥装置などにより行うことができるが、熱風
乾燥装置が好ましく使用される。If the heating temperature is 60° C. or lower, the treatment will take a long time and is not practical. The upper limit of the heating temperature is not particularly limited, but it is preferably below the melting point of the modified polypropylene in order to prevent the modified polypropylene from melting. The heat treatment means may be a conventionally known method, such as an aeration band type dryer, a material agitation type dryer, a fluidized bed dryer, a flash dryer, a spray dryer, a nine-rotation dryer, a drum type dryer,
Although the drying can be carried out using a vacuum dryer, an infrared dryer, a far-infrared dryer, a microwave dryer, etc., a hot air dryer is preferably used.
なお、減圧下で加熱処理を行えば処理効果が一段と向上
する。Note that if the heat treatment is performed under reduced pressure, the treatment effect will be further improved.
加熱処理時間は特に制限されないが、加熱温度が低温で
、得られる変性ポリプロピレンが多量の不飽和カルボン
酸類の未反応モノマーを含有する場合は長時間を要し、
加熱温度が高温で未反応モノマーが少ない場合は短時間
でよい。一般には未反応モノマー量が０．１重量％以下
となるように加熱処理することが好ましい。The heat treatment time is not particularly limited, but it takes a long time when the heating temperature is low and the obtained modified polypropylene contains a large amount of unreacted monomers of unsaturated carboxylic acids.
If the heating temperature is high and there is little unreacted monomer, a short time may be sufficient. Generally, it is preferable to carry out the heat treatment so that the amount of unreacted monomer is 0.1% by weight or less.
本発明の変性ポリプロピレン組成物は、前記変性ポリプ
ロピレン又は該変性ポリプロピレンと未変性ポリプロピ
レンとのポリプロピレン混合物に特定量の直鎖状低密度
ポリエチレンを混合することによって得られる。不発明
に使用される直鎖状低密度ポリエチレンとは、実質的に
長鎖分岐を持たない直鎖状の低密度ポリエチレンである
。一般には、長鎖分岐数の定量的な尺度Ｇ＝［η〕ｂ／
〔η〕ｔ（〔η〕ｂは分岐ポリエチレンの極限粘度。The modified polypropylene composition of the present invention is obtained by mixing a specific amount of linear low density polyethylene with the modified polypropylene or a polypropylene mixture of the modified polypropylene and unmodified polypropylene. The linear low-density polyethylene used in the invention is linear low-density polyethylene having substantially no long chain branches. In general, a quantitative measure of the number of long chain branches G = [η]b/
[η]t ([η]b is the limiting viscosity of branched polyethylene.
〔η〕ｔは分岐ポリエチレンと同じ分子量を持つ直鎖状
ポリエチレンの極限粘度）がほぼ１であり（従来の通常
の高圧法低密度ポリエチレンのＧ値は０．１〜０ｏ６）
、短鎖分岐数が主鎖炭素原子１００個当り１〜３個、密
度０．９１０〜０．９４５ 、 ＭＦ Ｉ （ＡＳＴＭ
Ｄ１２３８．２３０℃）０．３〜３０ＩＩ／１０分の本
のが好ましく使用される。直鎖状低密度ポリエチレンの
製造法は特に制限されな−。[η]t (intrinsic viscosity of linear polyethylene with the same molecular weight as branched polyethylene) is approximately 1 (the G value of conventional high-pressure low-density polyethylene is 0.1 to 0o6).
, the number of short chain branches is 1 to 3 per 100 main chain carbon atoms, the density is 0.910 to 0.945, MF I (ASTM
D1238.230°C) 0.3 to 30 II/10 minutes is preferably used. The method for producing linear low density polyethylene is not particularly limited.
代表的な製造方法を例示すれば、７〜４５Ｋｆ／−の圧
力（高圧法低密度ポリエチレンの場合は通常２０００−
３０００１／ｃＩｉ）、７５〜１００℃の温度（高圧法
低密度ポリエチレンの場合は１２０〜２５０℃）で、ク
ロム系触媒またはチーグラー触媒を用層て、ブテン−１
，メチルペンテン−１，ヘキセン−１゜オクテン−１等
のα−オレフィンをコモノマーとしてエチ１／ンの共重
合を行う方法がある。To give an example of a typical manufacturing method, a pressure of 7 to 45 Kf/- (usually 2000 Kf/- for high-pressure low-density polyethylene)
Butene-1
, methylpentene-1, hexene-1°octene-1, and other α-olefins are used as comonomers to copolymerize ethyl 1/one.
また、重合方法としては、溶液注液相法、スラリー法液
相法、流動床気相法、攪拌床気相法等を用いることがで
きる。Further, as the polymerization method, a solution injection phase method, a slurry method, a liquid phase method, a fluidized bed vapor phase method, a stirred bed vapor phase method, etc. can be used.
変性ポリプロピレン組成物における直鎖状低密度ポリエ
チレンの配合量は、変性ポリプロピレン又はポリプロピ
レン混合物１００重量部に対して５乃至７Ｏ１ｉ量部、
好ましくは１０乃至５０重量部である。直鎖状低密度ポ
リエチレンの配合量が上記範囲未満の場合には接着性改
良効果が小さく、また、上記範囲を越えると接着性が低
下するのみでなく、透明性および機械的強度の低下が大
きく好ましくない。The amount of linear low density polyethylene in the modified polypropylene composition is 5 to 7 O1i parts per 100 parts by weight of the modified polypropylene or polypropylene mixture;
Preferably it is 10 to 50 parts by weight. If the amount of linear low-density polyethylene blended is less than the above range, the effect of improving adhesion will be small, and if it exceeds the above range, not only will the adhesion decrease, but also the transparency and mechanical strength will decrease significantly. Undesirable.
変性ポリプロピレン又はポリプロピレン混合物と直鎖状
低密度ポリエチレンの混合は、タンブラ−、ヘンシェル
ミキサー等ヲ用いて行うことができる。また、これらの
混合物を例えばスクリュー押出様、バンバリーミキサ−
、ミキシングロールなどを用いて溶融混練すると更に好
ましい。The modified polypropylene or polypropylene mixture and the linear low-density polyethylene can be mixed using a tumbler, Henschel mixer, or the like. Alternatively, these mixtures may be processed, for example, by screw extrusion or Banbury mixer.
It is more preferable to melt and knead the mixture using a mixing roll or the like.
本発明に使用する変性ポリプロピレン組成物の製造方法
として次のような態様も可能である。すなわち、溶融混
線法により製造した変性ポリプロピレン又は該変性ポリ
プロピレンと未変性ポリプロピレンとのポリプロピレン
混合物に所定量の直鎖状低密度ポリエチレンを混合し、
再度溶融混練した後加熱処理して変性ポリプロピレン組
成物を得る。あるいは、ポリプロピレン、直鎖状低密度
ポリエチレン、不飽和カルボン酸類および有機過酸化物
を混合し、溶融混練した後、必要に応じ加熱処理して変
性ポリプロピレン組成物を得ること本できる。The following embodiments are also possible as a method for producing the modified polypropylene composition used in the present invention. That is, a predetermined amount of linear low density polyethylene is mixed with a modified polypropylene produced by a melt mixing method or a polypropylene mixture of the modified polypropylene and unmodified polypropylene,
After melt-kneading again, heat treatment is performed to obtain a modified polypropylene composition. Alternatively, a modified polypropylene composition can be obtained by mixing polypropylene, linear low density polyethylene, unsaturated carboxylic acids, and organic peroxide, melt-kneading, and then subjecting the mixture to heat treatment if necessary.
以上のようにして製造された変性ポリプロピレン組成物
は、０．０１〜５重量％の不飽和カルボン酸類を含有す
ることが望ましい。不飽和カルボン酸類の含有量が０．
０１重ｆ％以下の場合は接着性改良効果が小さく、５重
量％を越えると製造コストが高くなるばかりか接着性改
良効果は飽和してくる。また、変性ポリプロピレン組成
物には、通常使用する程度の耐熱安定剤、耐候安定剤、
滑剤、帯電防止剤、核剤、充填剤、顔料、染料、難燃剤
。The modified polypropylene composition produced as described above desirably contains 0.01 to 5% by weight of unsaturated carboxylic acids. The content of unsaturated carboxylic acids is 0.
When the amount is less than 0.01% by weight, the effect of improving adhesion is small, and when it exceeds 5% by weight, not only does the manufacturing cost increase, but the effect of improving adhesion becomes saturated. In addition, the modified polypropylene composition contains heat stabilizers, weather stabilizers,
Lubricants, antistatic agents, nucleating agents, fillers, pigments, dyes, flame retardants.
ブロッキング防止剤などを含んでいてもよい。It may also contain an anti-blocking agent.
本発明の変性ポリプロピレン組成物は後述する実施例及
び比較例から明らかな如く、優れた接着性及び透明性を
有している。したがって、他のフィルムの接着層或いは
コーティング層として用層ることにより、該フィルムの
透明性を低下させることなく良好な接着状態で積層物を
得ることができる。特に、ガスバリヤ−性を有するエチ
レン−酢酸ビニル共重合体ケン化物、ポリアミド樹脂及
びポリエステル樹脂よりなるフィルムのコーティング層
として用いることにより、透明性に優れ、しかも変性ポ
リプロピレン組成物が有する耐水性及び耐油性が付与さ
れたガスバリヤ−性積層物が得られる。The modified polypropylene composition of the present invention has excellent adhesiveness and transparency, as is clear from the Examples and Comparative Examples described below. Therefore, by using it as an adhesive layer or coating layer for another film, a laminate can be obtained with good adhesion without reducing the transparency of the film. In particular, by using it as a coating layer of a film made of a saponified ethylene-vinyl acetate copolymer having gas barrier properties, polyamide resin, and polyester resin, it has excellent transparency and also has the water resistance and oil resistance that the modified polypropylene composition has. A gas barrier laminate is obtained.
以下実施例を挙げて説明するが、本発明はこれに限定さ
れるものではなり０
なお、本明細書中の諸物性の測定は以下の方法により測
定した。Examples will be described below, but the present invention is not limited thereto. In addition, the various physical properties in this specification were measured by the following methods.
ＯＭＦ 工
ＡＳＴＭ Ｄ １２３８−５２Ｔ により２３０
℃において２１６０１！の荷重により測定した。OMF Engineering ASTM D 1238-52T 230
21601 in °C! It was measured with a load of .
Ｏグラフト反応無水マレイン酸量
熱プレスにより厚さ約０．１＋ｗ（’）フィルムを成形
し、６時間アセトン抽出した後、５０℃の温度で２４時
間真空乾燥した試料につき、赤外吸収スペクトルを測定
し、１７８０薗−１の無水マレイン酸の吸収ピーク強度
からグラフト反応無水マレイン酸量な定量した。O graft reaction Maleic anhydride amount A film with a thickness of approximately 0.1+w(') was formed by heat pressing, extracted with acetone for 6 hours, and then vacuum dried at a temperature of 50°C for 24 hours.The infrared absorption spectrum was measured on the sample. Then, the amount of graft-reacted maleic anhydride was determined from the absorption peak intensity of maleic anhydride in 1780 Sono-1.
０接着強度 エチレン−酢酸ビニル共重合体ケン化物。0 adhesive strength Saponified ethylene-vinyl acetate copolymer.
ナイロンおよびポリエチレンテレフタレートとの接着は
、両者を共押出しし、冷却固化後、縦方向に幅２ｍに切
り出し、Ｔ−ばくり強度を測定した。For adhesion with nylon and polyethylene terephthalate, both were coextruded, cooled and solidified, and then cut into a width of 2 m in the longitudinal direction, and the T-break strength was measured.
Ｏ透明性 ＡＳＴＭ Ｄ １００３によって測定した。O transparency Measured according to ASTM D1003.
実施例１〜５および比較例１〜１１
ＭＦ Ｉ ＝ ０．６ ＩＩ／１０分、エチレン含量２
．０重量％のプロピレン−エチレンランダム共重合体１
００重量部、無水マレイン酸２重量部。Examples 1-5 and Comparative Examples 1-11 MF I = 0.6 II/10 min, ethylene content 2
．． 0% by weight propylene-ethylene random copolymer 1
00 parts by weight, 2 parts by weight of maleic anhydride.
２．５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ
）ヘキサン０．１２重量部、ブチル化ヒドロキシトルエ
ン０．１重量部、ステアリン酸カルシウム０．１重量部
をヘンシェルミキサーで５分間混合し、Ｌ／Ｄ＝２４の
４０１１１ＩＩφ押出機により２２０℃で溶融混練ペレ
タイズを行ない、次いで定温乾燥機により１４５℃で４
時間加熱処理を行ない無水マレイン酸をグラフトした変
性ポリプロピレンＣ以下、グラフトＰＰとも略ス）を得
た。このグラフトＰＰのＭＦＩ＝５２．７．９／１０分
であり、０．５重量％の無水マレイン酸をグラフト含有
していた。0.12 parts by weight of 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 0.1 parts by weight of butylated hydroxytoluene, and 0.1 parts by weight of calcium stearate were mixed in a Henschel mixer for 5 minutes. , melt-kneading pelletization was performed at 220°C using a 40111IIφ extruder with L/D = 24, and then pelletizing was performed at 145°C using a constant temperature dryer.
A modified polypropylene C grafted with maleic anhydride by heat treatment for a period of time was obtained. This grafted PP had an MFI of 52.7.9/10 minutes and contained 0.5% by weight of maleic anhydride.
次に、グラフトＰＰＩ ５重量部に表１に示す割合でＭ
Ｆ Ｉ ＝ ４．０１１７１０分の未変性ホモポリプロ
ピレン、比重０．９２２．Ｇ＝０．９８゜ＭＰ’ Ｉ
＝ ５．４１／１０分の直鎖状低密度ポリエチレン、比
重（Ｌ９２０ 、 （ｌ）＝０．２５ 、 ＭＦＩ ＝
４．０１１７１０分の高圧法低密度ポリエチレン、比
重０．９６０ 、 Ｇ＝１．０ 、ＭＦＩ＝５．０１／
１０分の直鎖状高密度ポリエチレン、エチレン含量７０
重量％、 ＭＦ Ｉ ＝５．３．９／１０分のエチレン
−プロピレンランダム共重合体。Next, M was added to 5 parts by weight of graft PPI in the proportion shown in Table 1.
F I =4.011710 min unmodified homopolypropylene, specific gravity 0.922. G=0.98゜MP' I
= 5.41/10 min linear low density polyethylene, specific gravity (L920, (l) = 0.25, MFI =
4.011710 minutes high pressure process low density polyethylene, specific gravity 0.960, G=1.0, MFI=5.01/
10 min linear high density polyethylene, ethylene content 70
Ethylene-propylene random copolymer with weight %, MFI = 5.3.9/10 min.
エチレン含量８０重量％、ＭＦＩ＝６．４Ｆ／１０分の
エチレン−ブテン−１ランダム共重合体を夫々混合し、
Ｌ／Ｄ＝２４の４０１ｍφ押出機により２２０℃で溶融
混線ペレタイズを行い、変性ポリプロピレン組成物を得
た。Mixing ethylene-butene-1 random copolymers with an ethylene content of 80% by weight and an MFI of 6.4 F/10 min, respectively,
Melt cross-wire pelletization was performed at 220° C. using a 401 mφ extruder with L/D=24 to obtain a modified polypropylene composition.
得られた変性ポリプロピレン組成物を７０μのフィルム
に製膜しヘイズな測定した。結果を表１に示す。また、
上記変性ポリプロビレン組酸物の使用例として、エチレ
ン−酢酸ビニル共重合体ケン化物、ナイロン６およびポ
リエチレンテレフタレートとの接着強度を表２に示す。The obtained modified polypropylene composition was formed into a 70μ film, and the haze was measured. The results are shown in Table 1. Also,
Table 2 shows the adhesive strength with saponified ethylene-vinyl acetate copolymer, nylon 6, and polyethylene terephthalate as an example of the use of the modified polypropylene composite acid.
なお、接着強度は以下のようにして求めた。即ち、変性
ポリプロピレン組成物をＬ／Ｄ＝２０の４０ｍ＋φ押出
機から２００℃で、またエチレン−酢酸ビニル共重合体
ケン化物（ＭＦＩ＝１９．５ｇ／ｌ ０分、エチレン含
量４５モル％、ケン化度９９％以上）。Note that the adhesive strength was determined as follows. That is, a modified polypropylene composition was heated at 200°C from a 40 m + φ extruder with L/D = 20, and a saponified ethylene-vinyl acetate copolymer (MFI = 19.5 g/l 0 min, ethylene content 45 mol%, saponified 99% or more).
ナイロン６およびポリエチレンテレフタレートをＬ／Ｄ
＝２４の３０ｍ＋φ押出機からそれぞれ２００℃、２５
０℃および２７０℃でそれぞれ共押出Ｔ−ダイを通して
押出し、変性ポリプロピレン組成物の厚さ０．５１ａｍ
、エチレン−酢酸ビニル共重合体ケン化物、ナイロン６
およびポリエチレンテレフタレートの厚さ０．２ｍの共
押出シートを夫々成形し、引張強度２０■／ｍｉｎでＴ
−剥離強度を測定した。L/D nylon 6 and polyethylene terephthalate
=24 from 30m+φ extruder at 200℃, 25
Extruded through a coextrusion T-die at 0°C and 270°C, respectively, the thickness of the modified polypropylene composition was 0.51 am.
, saponified ethylene-vinyl acetate copolymer, nylon 6
Coextruded sheets of 0.2 m thick and polyethylene terephthalate were molded, respectively, and the tensile strength was 20 cm/min.
- Peel strength was measured.
また、上記積層物のヘイズを測定した。結果を表２に併
せて示す。Further, the haze of the laminate was measured. The results are also shown in Table 2.
用途例 １
ＭＦ Ｉ ＝１．ＯＪｉｌ／１０分のホモポリプロピレ
ンを２９０℃に設定したＴ−ダイを装着した押出機に投
入し、厚さ１．５１のシートを得た。次いでこのシート
をロール表面温度を１５５℃に設定したロール式延伸機
で縦方向に５倍延伸し、厚さ０．３ｍの一軸延伸ポリプ
ロピレンシートを作った。次に２５０℃に設定した押出
しラミネーターに実施例３の変性ポリプロピレン組成物
を投入し、上記−軸延伸ポリプロピレンシート上に２０
μの厚さに押出しラミネートをした。更に２００℃に設
定した押出しラミネーターにより上記の積層シートの変
性ポリプロピレン組成物側の面に実施例３で用いたエチ
レン−酢酸ビニル共重合体ケン化物を８０μの厚さに押
出しラミネートして、−軸延伸ポリプロピレン／変性水
ＩＪ ７’ロピレン組成物／エチレンー酢酸ビニル共重
合体ケン化物の三層積層シートを得た。Application example 1 MF I =1. OJil/10 min homopolypropylene was charged into an extruder equipped with a T-die set at 290°C to obtain a sheet with a thickness of 1.51. Next, this sheet was stretched 5 times in the longitudinal direction using a roll-type stretching machine with a roll surface temperature set at 155° C. to produce a uniaxially stretched polypropylene sheet with a thickness of 0.3 m. Next, the modified polypropylene composition of Example 3 was charged into an extrusion laminator set at 250°C, and the modified polypropylene composition of Example 3 was placed on the axially stretched polypropylene sheet.
It was extruded and laminated to a thickness of μ. Furthermore, using an extrusion laminator set at 200°C, the saponified ethylene-vinyl acetate copolymer used in Example 3 was extruded and laminated to a thickness of 80μ on the surface of the modified polypropylene composition side of the above laminated sheet to form a -axis. A three-layer laminate sheet of oriented polypropylene/modified water IJ 7'lopylene composition/saponified ethylene-vinyl acetate copolymer was obtained.
この積層シートを空気温度１６０℃に設定しく２１）
たオーブン式延伸機で横方向に１０倍延伸し厚さ４０μ
の積層複合フィルムを得た。このフィルムの各層は剥離
不能であり、酸素透過度は７．１ ｃｃ／ｒｒ？ ・２
４ ｈｒ−ａｔｍ 、 ヘイズは１．８％であった。This laminated sheet was stretched 10 times in the transverse direction using an oven-type stretching machine set at an air temperature of 160°C (21) to a thickness of 40 μm.
A laminated composite film was obtained. Each layer of this film is non-peelable and has an oxygen permeability of 7.1 cc/rr?・2
4 hr-atm, haze was 1.8%.
用途比較例 １
用途例１において用いた変性ポリプロピレン組成物に代
り比較例６で用いたものを用いること以外は用途例１と
同様は行なった。得られたフィルムの酸素透過度は７．
３ＣＣ／−・２４ ｈｒ−ａｔｍ ＋ ヘイズは３．５
％であった。Application Comparative Example 1 The same procedure as Application Example 1 was carried out except that the modified polypropylene composition used in Application Example 1 was replaced with the one used in Comparative Example 6. The oxygen permeability of the obtained film was 7.
3CC/-・24 hr-atm + haze is 3.5
%Met.
用途例 ２
ＭＦＩ＝１．０＃／１０分のホモポリプロピレンを２９
０℃に設定したＴ−ダイを装着した押出機に投入し、厚
さ１．５ｍのシートを得た。次いでこのシートをロール
表面温度を１５５℃に設定したロール式延伸機で縦方向
に５倍延伸し、厚さ０．３ｗｍの一軸延伸ポリプロピレ
ンシートを作った。次にダイ温度２００℃に設定した二
種三層共押出しラミネーターにより上記−軸延伸ポリプ
ロピレンシート上に実施例４の変性ポリプロピレン組成
物２０μ／エチレン−酢酸ビニル共重合体ケン化物４０
μ／変性ポリプロピレン組成物２０μになるように共押
出しラミネートした。更にダイ温度２８０℃に設定した
ラミネーターにより上記積層シートの変性ポリプロピレ
ン組成物側にＭＦ Ｉ ＝８．０１／１ｏ分、エチレン
含ｉｔ ３．５ ＴＫｋ％のプロピレン−エチレンラン
タム共重合体２０μを押出しラミネートして、−軸延伸
ポリプロピレン／変性ポリプロピレン組成物／エチレン
−酢酸ビニル共重合体ケン化物／変性ポリプロピレン組
成物／プロピレン−エチレンランダム共重合体の５層積
層シートを得た。この積層シートを空気温度１６０℃に
設定したオーブン式延伸機で横方向に１０倍延伸し、厚
さ４０μの積層複合フィルムを得た。このフィルムの各
層は剥離不能であり、酸素透過度は１２ＣＣ／−・２４
ｈｒ・ａｔｍ、ヒートシール温度は１２６℃、ヘイズは
２．０％であった。Application example 2 Homopolypropylene with MFI = 1.0#/10 min 29
The mixture was put into an extruder equipped with a T-die set at 0°C to obtain a sheet with a thickness of 1.5 m. Next, this sheet was stretched 5 times in the longitudinal direction using a roll-type stretching machine with a roll surface temperature set at 155° C. to produce a uniaxially stretched polypropylene sheet with a thickness of 0.3 wm. Next, 20μ of the modified polypropylene composition of Example 4/40μ of the saponified ethylene-vinyl acetate copolymer was applied onto the above-mentioned axially stretched polypropylene sheet using a two-type, three-layer coextrusion laminator set at a die temperature of 200°C.
Coextrusion lamination was carried out so that the thickness of the modified polypropylene composition was 20μ. Further, using a laminator set at a die temperature of 280°C, 20μ of a propylene-ethylene lantum copolymer having an MF I =8.01/1o and an ethylene content of 3.5 TKk% was extruded onto the modified polypropylene composition side of the laminated sheet. Lamination was performed to obtain a five-layer laminate sheet of - axially oriented polypropylene/modified polypropylene composition/saponified ethylene-vinyl acetate copolymer/modified polypropylene composition/propylene-ethylene random copolymer. This laminated sheet was stretched 10 times in the transverse direction using an oven-type stretching machine set at an air temperature of 160° C. to obtain a laminated composite film with a thickness of 40 μm. Each layer of this film is non-peelable and has an oxygen permeability of 12CC/-24
hr.atm, heat sealing temperature was 126° C., and haze was 2.0%.
用途比較例 ２
用途例２において用すた変性ポリプロピレン組成物に代
り比較例７で用いたものを用いる以外は用途例２と同様
に行なった。得られたフィルムの酸素透過度は１３ＣＣ
／ｍ”・２４ｈｒ−ａｔｍ 、 ヒートシール温度は１
！１１℃。Comparative Application Example 2 The same procedure as Application Example 2 was carried out except that the modified polypropylene composition used in Application Example 2 was replaced with the one used in Comparative Example 7. The oxygen permeability of the obtained film was 13CC
/m”・24hr-atm, heat seal temperature is 1
! 11℃.
ヘイズは４．０％であった。Haze was 4.0%.
実施例６及び用途例３
ＭＦ Ｉ ＝０．６１７１０分、エチレン含量２．５重
量％のプロピレン−エチレンランダム共重合体９０重量
部、実施例１〜５で用いた直鎖状低密度ポリエチレン１
０重量部、無水７１ツイン酸０．３重量部、ベンゾイル
パーオキサイド０．１重量部、ブチル化ヒドロキシトル
エン０．１重量部、ステアリン酸カルシウムＱ、１３ｉ
量部ヲヘンシエルミキサーで５分間混合し、Ｌ／Ｄ＝２
４の４０霞φ押出機により２２０℃で溶融混線を行ない
、定温乾燥機により１４０℃で３時間加熱処理した。こ
の変性ポリプロピレン組成物は０．２１重量％の無水マ
レイン酸がグラフトしており、そのＭＦＩは８−５Ｊｉ
＋／１０分であった。一方、ＭＦ Ｉ ＝ １０ｇ７１
０分のホモポリプロピレンを２９０℃に設定したＴダイ
を装着した押出機により厚さ１．５ｍ＋のシートを作っ
た。次いでこのシートをロール表面温度を１５５℃に設
定したロール式延伸機で縦方向に５倍延伸し、厚さ０．
３■の一軸延伸ポリプロピレンシートヲ作った。Example 6 and Application Example 3 MF I =0.61710 min, 90 parts by weight of propylene-ethylene random copolymer with ethylene content of 2.5% by weight, linear low density polyethylene 1 used in Examples 1 to 5
0 parts by weight, 0.3 parts by weight of 71 twin acid anhydride, 0.1 parts by weight of benzoyl peroxide, 0.1 parts by weight of butylated hydroxytoluene, calcium stearate Q, 13i
Mix for 5 minutes with a volumetric mixer, L/D = 2
Melt blending was carried out at 220° C. using a 40 haze diameter extruder in No. 4, and heat treatment was performed at 140° C. for 3 hours using a constant temperature dryer. This modified polypropylene composition is grafted with 0.21% by weight of maleic anhydride, and its MFI is 8-5Ji.
+/10 minutes. On the other hand, MF I = 10g71
A sheet with a thickness of 1.5 m+ was made using an extruder equipped with a T-die set at 290° C. from homopolypropylene of 0.0 min. Next, this sheet was stretched 5 times in the longitudinal direction using a roll-type stretching machine with a roll surface temperature set at 155°C to a thickness of 0.
A 3-inch uniaxially stretched polypropylene sheet was made.
次にダイ温度を２００℃に設定した二種三層共押出しラ
ミネーターによりとの一軸延伸ポリプロピレンシート上
に上記の変性ポリプロピレン組成物２０μ／エチレン−
酢酸ビニル共重合体ケン化物４０μ／変性ポリプロピレ
ン組成物２０μになるように共押出ラミネートし、変性
ポリプロピレン組成物／エチレン−酢酸ビニル共重合体
ケン化物／変性ポリプロピレン組成物／−軸延伸ポリプ
ロピレンの４層シートを得た。この積層シートを空気温
度１４５℃に設定したオーブン式延伸機で横方向に１０
倍延伸し、厚さ３８μの積層複合フィルムを得た。この
フィルムの各層は剥離不能であり、酸素透過度は１３Ｃ
Ｃ／−・２４ｈｒ″ａｔｍＩ ヒートシール温度は１３
２℃。Next, the above modified polypropylene composition (20μ/ethylene-
Co-extrusion lamination was carried out so that saponified vinyl acetate copolymer 40μ/modified polypropylene composition 20μ, resulting in four layers of modified polypropylene composition/saponified ethylene-vinyl acetate copolymer/modified polypropylene composition/-axially oriented polypropylene. Got a sheet. This laminated sheet was stretched horizontally for 10
This was stretched twice to obtain a laminated composite film with a thickness of 38 μm. Each layer of this film is non-peelable and has an oxygen permeability of 13C
C/-・24hr"atmI heat seal temperature is 13
2℃.
ヘイズは２．５％であった。Haze was 2.5%.
用途比較例 ３
実施例乙において用すた直鎖状低密度ポリエチレンの代
りに比較例４〜８で用すた高圧法低密度ポリエチレンを
用いる以外は実施例６と同様に行なった。得られたフィ
ルムの酸素透過度は１４ ＣＣ／ｍ” ・２４ ｈｒ
−ａｔｍ 、ヒートシール温度は１３５℃、ヘイズは５
．２％であった。Comparative Application Example 3 The same procedure as in Example 6 was carried out except that the high-pressure low-density polyethylene used in Comparative Examples 4 to 8 was used instead of the linear low-density polyethylene used in Example B. The oxygen permeability of the obtained film was 14 CC/m”・24 hr
-atm, heat seal temperature is 135℃, haze is 5
．． It was 2%.
Claims (1)
ピレン又は該変性ポリプロピレン１００重量部に対して
最大５０００重量部の未変性ポリプロピレンを混合した
ポリプロピレン混合物１００重量部に対して直鎖状低密
度ポリエチレン５〜７０重量部を含有する変性ポリプロ
ピレン組成物。(1) Modified polypropylene grafted with unsaturated carboxylic acids or a polypropylene mixture in which 100 parts by weight of the modified polypropylene is mixed with a maximum of 5000 parts by weight of unmodified polypropylene. 5 to 70 parts by weight of linear low density polyethylene A modified polypropylene composition containing parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19637887A JPS63205345A (en) | 1987-08-07 | 1987-08-07 | Modified polypropylene composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19637887A JPS63205345A (en) | 1987-08-07 | 1987-08-07 | Modified polypropylene composition |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18701381A Division JPS5889642A (en) | 1981-11-24 | 1981-11-24 | Modified polypropylene composition and laminates using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63205345A true JPS63205345A (en) | 1988-08-24 |
| JPH0432107B2 JPH0432107B2 (en) | 1992-05-28 |
Family
ID=16356872
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19637887A Granted JPS63205345A (en) | 1987-08-07 | 1987-08-07 | Modified polypropylene composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63205345A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1712604A1 (en) * | 2004-02-03 | 2006-10-18 | Asahi Glass Company, Limited | Adhesive composition and glass plate with molding made of thermoplastic elastomer |
| WO2012115195A1 (en) * | 2011-02-25 | 2012-08-30 | 三菱化学株式会社 | Resin composition and laminated body |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52123473A (en) * | 1976-04-09 | 1977-10-17 | Mitsui Petrochem Ind Ltd | Multiply laminate structure |
-
1987
- 1987-08-07 JP JP19637887A patent/JPS63205345A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52123473A (en) * | 1976-04-09 | 1977-10-17 | Mitsui Petrochem Ind Ltd | Multiply laminate structure |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1712604A1 (en) * | 2004-02-03 | 2006-10-18 | Asahi Glass Company, Limited | Adhesive composition and glass plate with molding made of thermoplastic elastomer |
| EP1712604A4 (en) * | 2004-02-03 | 2008-07-30 | Asahi Glass Co Ltd | Adhesive composition and glass plate with molding made of thermoplastic elastomer |
| WO2012115195A1 (en) * | 2011-02-25 | 2012-08-30 | 三菱化学株式会社 | Resin composition and laminated body |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0432107B2 (en) | 1992-05-28 |
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