JPH0242379B2 - - Google Patents
Info
- Publication number
- JPH0242379B2 JPH0242379B2 JP58217785A JP21778583A JPH0242379B2 JP H0242379 B2 JPH0242379 B2 JP H0242379B2 JP 58217785 A JP58217785 A JP 58217785A JP 21778583 A JP21778583 A JP 21778583A JP H0242379 B2 JPH0242379 B2 JP H0242379B2
- Authority
- JP
- Japan
- Prior art keywords
- propylene
- weight
- parts
- modified
- random copolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 55
- 239000004711 α-olefin Substances 0.000 claims description 45
- 229920001155 polypropylene Polymers 0.000 claims description 40
- 229920005604 random copolymer Polymers 0.000 claims description 37
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 30
- 239000004952 Polyamide Substances 0.000 claims description 26
- 229920002647 polyamide Polymers 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 24
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 18
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 15
- 239000000178 monomer Substances 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- 150000001735 carboxylic acids Chemical class 0.000 claims description 5
- 238000000034 method Methods 0.000 description 19
- -1 polypropylene Polymers 0.000 description 15
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 14
- 239000005977 Ethylene Substances 0.000 description 14
- 239000004743 Polypropylene Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 9
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 229920001971 elastomer Polymers 0.000 description 6
- 239000005060 rubber Substances 0.000 description 6
- 229920002292 Nylon 6 Polymers 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 5
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 4
- 239000011976 maleic acid Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 101100315256 Brassica campestris PEC-2 gene Proteins 0.000 description 3
- 229920002302 Nylon 6,6 Polymers 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 150000002902 organometallic compounds Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-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
- 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 2
- CNPURSDMOWDNOQ-UHFFFAOYSA-N 4-methoxy-7h-pyrrolo[2,3-d]pyrimidin-2-amine Chemical compound COC1=NC(N)=NC2=C1C=CN2 CNPURSDMOWDNOQ-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-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
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 101001073422 Homo sapiens Pigment epithelium-derived factor Proteins 0.000 description 2
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 2
- 229920000571 Nylon 11 Polymers 0.000 description 2
- 229920000305 Nylon 6,10 Polymers 0.000 description 2
- 102100035846 Pigment epithelium-derived factor Human genes 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 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
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- NIDNOXCRFUCAKQ-UHFFFAOYSA-N bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2C(O)=O NIDNOXCRFUCAKQ-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
- 238000006243 chemical reaction Methods 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 229920000554 ionomer Polymers 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- WLQXEFXDBYHMRG-UPHRSURJSA-N (z)-4-(oxiran-2-ylmethoxy)-4-oxobut-2-enoic acid Chemical compound OC(=O)\C=C/C(=O)OCC1CO1 WLQXEFXDBYHMRG-UPHRSURJSA-N 0.000 description 1
- GWQOYRSARAWVTC-UHFFFAOYSA-N 1,4-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=C(C(C)(C)OOC(C)(C)C)C=C1 GWQOYRSARAWVTC-UHFFFAOYSA-N 0.000 description 1
- GUOSQNAUYHMCRU-UHFFFAOYSA-N 11-Aminoundecanoic acid Chemical compound NCCCCCCCCCCC(O)=O GUOSQNAUYHMCRU-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- DPQHRXRAZHNGRU-UHFFFAOYSA-N 2,4,4-trimethylhexane-1,6-diamine Chemical compound NCC(C)CC(C)(C)CCN DPQHRXRAZHNGRU-UHFFFAOYSA-N 0.000 description 1
- ODBCKCWTWALFKM-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhex-3-yne Chemical compound CC(C)(C)OOC(C)(C)C#CC(C)(C)OOC(C)(C)C ODBCKCWTWALFKM-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
- 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- XDRAKJQFCQVBMP-UHFFFAOYSA-N 2-but-2-enyl-3-methylbutanedioic acid Chemical compound CC=CCC(C(O)=O)C(C)C(O)=O XDRAKJQFCQVBMP-UHFFFAOYSA-N 0.000 description 1
- FZZMTSNZRBFGGU-UHFFFAOYSA-N 2-chloro-7-fluoroquinazolin-4-amine Chemical compound FC1=CC=C2C(N)=NC(Cl)=NC2=C1 FZZMTSNZRBFGGU-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
- KSMVBYPXNKCPAJ-UHFFFAOYSA-N 4-Methylcyclohexylamine Chemical compound CC1CCC(N)CC1 KSMVBYPXNKCPAJ-UHFFFAOYSA-N 0.000 description 1
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000004716 Ethylene/acrylic acid copolymer Substances 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920000577 Nylon 6/66 Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- OXIKYYJDTWKERT-UHFFFAOYSA-N [4-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCC(CN)CC1 OXIKYYJDTWKERT-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229960002684 aminocaproic acid Drugs 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- TZYHIGCKINZLPD-UHFFFAOYSA-N azepan-2-one;hexane-1,6-diamine;hexanedioic acid Chemical compound NCCCCCCN.O=C1CCCCCN1.OC(=O)CCCCC(O)=O TZYHIGCKINZLPD-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 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
- 239000004927 clay Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 1
- 229920005674 ethylene-propylene random copolymer Polymers 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000000835 fiber Substances 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
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- LDHQCZJRKDOVOX-IHWYPQMZSA-N isocrotonic acid Chemical compound C\C=C/C(O)=O LDHQCZJRKDOVOX-IHWYPQMZSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 1
- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-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
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
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Landscapes
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Description
本発明は剛性、耐衝撃性、光沢、耐熱性に優れ
たプロピレン重合体組成物に関する。
結晶性ポリプロピレンは、剛性、表面光沢、耐
熱性等に優れているが、耐衝撃性に劣るという欠
点を有している。耐衝撃性を改良する方法として
は、従来よりプロピレン重合体にポリイソブチレ
ン、ポリブタジエン、非晶性のエチレン・プロピ
レン共重合体等のゴム状物質やポリエチレンを混
合する方法が広く行われている。しかしながらそ
の反面、これらの改質材は、プロピレン重合体に
比べ柔らかであり、プロピレン重合体本来の特徴
である剛性、耐熱性、表面硬度等を著しく低下さ
せるという欠点を有している。
一方、プロピレン重合体の耐熱性、剛性等を向
上させる目的でプロピレン重合体にポリアミド樹
脂を混合することが試みられているが、両者は相
溶性に極めて乏しい。そこでプロピレン重合体等
のポリオレフイン樹脂とポリアミドとの相溶性を
改良する方法として、ポリオレフイン樹脂40〜90
重量部、ポリアミド5〜50重量部及びアイオノマ
ー2〜25重量部とからなるポリマーブレンド物
(特公昭43―6529号公報)が提案されているが、
かかる組成物はポリオレフインとしてポリプロピ
レンを用いた場合、耐衝撃性に劣るという欠点を
有している。ポリオレフインとポリアミドを混合
する際に、ポリオレフインとして、酸、エステ
ル、アミド、酸無水物、エポキシド基の少なくと
も1つを導入した変性ポリオレフインを使用する
方法(特公昭45―30945号公報)あるいは結晶性
ポリプロピレンとポリアミドをブレンドする際に
無水マレイン酸変性ポリプロピレンを介在させる
方法(高分子化学29,265(1972))等が提案され
ている。しかしながこれらの方法ではポリプロピ
レンとポリアミドとの相溶性は改良されるもの
の、耐衝撃性については改良効果は充分ではなか
つた。
本発明者は、かかる現状に鑑み、結晶性ポリプ
ロピレンとポリアミドとからなる組成物の耐衝撃
性、耐油性、塗装性等を改良する目的で種々検討
を行つた結果、ポリプピレンとポリアミドに特定
のエチレン・α―オレフイン共重合体の不飽和ジ
カルボン酸またはその誘導体によるグラフト変性
物を添加することにより上記目的を達成できるこ
とを見出し、先に提案した(特願昭58―22882
号)。
しかし、上記提案に具体的に記載された組成物
では耐衝撃性は改良されるものの組成物の流動
性、光沢が幾分低下し、また耐衝撃性改良効果も
用途によつては充分とは言えないものであつた。
本発明はかかる問題点の解決を目的としたもの
であり、耐衝撃性改良剤として、特定の変性プロ
ピレン・α―オレフインランダム共重合体を用い
ることにより結晶性プロピレン重合体とポリアミ
ドとからなる組成物の耐衝撃性を著しく向上しう
ることを見出したものである。
すなわち、本願発明は、
結晶性プロピレン重合体(A)95ないし5重量部、
ポリアミド(B)5ないし95重量部、
および
(A)と(B)との合計100重量部に対して、
変性プロピレン・α―オレフイン共重合体(D)1
ないし80重量部とからなる組成物であつて、該変
性プロピレン・α―オレフイン共重合体(D)が、X
線による結晶化度0ないし30%、プロピレン含量
50ないし70モル%、3個のプロピレン連鎖でみた
ミクロアイソタクテイシテイ(MIT)が0.7以上、
および沸騰n―ヘプタン不溶分が5重量%以下の
プロピレン・α―オレフインランダム共重合体(C)
100重量部に、不飽和カルボン酸またはその誘導
体から選ばれるグラフトモノマーを0.01ないし5
重量部グラフト変性してなる変性プロピレン・α
―オレフイン共重合体であることを特徴とする、
剛性、耐衝撃性、耐水性、表面光沢、耐熱性等に
優れたプロピレン重合体組成物を提供するもので
ある。
本発明に用いるプロピレン重合体は、結晶性の
ものであり、好ましくは密度が0.89ないし
0.93g/cm3、メルトフローレート(MFR:
ASTMD1238,L)が0.01ないし50g/10minの
ものであり、プロピレンの単独重合体もしくはプ
ロピレンと20モル%以下のエチレン、1―ブテ
ン、4―メチル―1―ペンテン等のα―オレフイ
ンとのブロツクあるいはランダム共重合体であ
る。
本発明に用いる結晶性プロピレン重合体(A)とし
て一部もしくは全部が不飽和カルボン酸もしくは
その誘導体から選ばれるグラフトモノマーで通常
0.001ないし10重量%、好ましくは0.1ないし5重
量%グラフト変性されたプロピレン重合体を用い
ると更に耐衝撃性等の改質効果に優れるので好ま
しい。
本発明に用いるポリアミド(B)は、ヘキサメチレ
ンジアミン、デカメチレンジアミン、ドデカメチ
レンジアミン、2,2,4―または2,4,4―
トリメチルヘキサメチレンジアミン、1,3―ま
たは1,4―ビス(アミノメチル)シクロヘキサ
ン、ビス(p―アミノシクロヘキシルメタン)、
m―またはp―キシリレンジアミン等の脂肪族、
脂環族、芳香族等のジアミンとアジピン酸、スベ
リン酸、セバシン酸、シクロヘキサンジカルボン
酸、テレフタル酸、イソフタル酸等の脂肪族、脂
環族、芳香族等のジカルボン酸との重縮合によつ
て得られるポリアミド、ε―アミノカプロン酸、
11―アミノウンデカン酸等のアミノカルボン酸の
縮合によつて得られるポリアミド、ε―カプロラ
クタム、ω―ラウロラクタム等のラクタムから得
られるポリアミドあるいはこれらの成分からなる
共重合体ポリアミド、これらポリアミドの混合物
等が例示される。具体的にはナイロン6、ナイロ
ン66、ナイロン610、ナイロン9、ナイロン11、
ナイロン12、ナイロン6/66、ナイロン66/610、
ナイロン6/11等が挙げられる。これらの中で
は、剛性、耐熱性の良好な点でナイロン6及びナ
イロン66が好ましい。また分子量もとくに限定は
されないが、通常相対粘度ηr(JIS K6810、98%
硫酸中で測定)が1.0以上のポリアミドが用いら
れるが、中でも2.0以上のものが機械的強度が優
れる点で好ましい。
本発明に用いる変性プロピレン・α―オレフイ
ンランダム共重合体(D)は、X線による結晶化度が
0ないし30%、好ましくは0ないし20%及びプロ
ピレン含有量が50ないし70モル%、好ましくは55
ないし65モル%のプロピレン・α―オレフインラ
ンダム共重合体(C)100重量部に、不飽和カルボン
酸またはその誘導体から選ばれるグラフトモノマ
ーを0.01ないし5重量部、好ましくは0.1ないし
1.0重量部グラフト変性した共重合体である。
プロピレン・α―オレフインランダム共重合体
(C)の結晶化度が30%及びプロピレン含有量が70モ
ル%を越えるものをグラト変性した共重合体を用
いてもプロピレン重合体組成物の耐衝撃性はあま
り改良されない。
また該プロピレン・α―オレフインランダム共
重合体(C)は通常デカリン中135℃で測定した固有
粘度〔η〕が2ないし10dl/g、更には3ないし
6dl/gの範囲のものが好ましい。〔η〕が上記
範囲外の共重合体を用いた場合は、該共重合体か
ら得られた変性プロピレン・α―オレフインラン
ダム共重合体(D)と前記プロピレン重合体(A)及びポ
リアミド(B)との溶融粘度差が大きくなる傾向にあ
り、分散効果が充分とはいえず、耐衝撃性の改良
効果が充分でない。
本発明で用いられるプロピレン・α―オレフイ
ンランダム共重合体(C)は次の点で従来より公知で
あるエチレン・α―オレフイン共重合ゴムと区別
される。
(1) プロピレン系重合体に対する親和性に優れ
る。
(2) エチレン・α―オレフイン共重合体ゴムがペ
ルオキシ架橋型であるのに対し、ペルオキシ分
解型である。
(2)の点から、本発明でプロピレン・α―オレフ
インランダム共重合体(C)をグラフト変性して得た
変性プロピレン・α―オレフインランダム共重合
体(D)の〔η〕は、原料共重合体(C)のそれよりは低
くなるのに対し、エチレン・α―オレフイン共重
合体ゴムをグラフト変性して得た変性エチレン・
α―オレフイン共重合ゴムは変性時に架橋が進む
ため、原料ゴムより、〔η〕のより高い、すなわ
ちより流動性の悪い変性物となる。
この結果、本発明で用いる変性プロピレン・α
―オレフインランダム共重合体(C)は、本発明組成
物の他の成分である結晶性プロピレン重合体(A)と
の親和性が良く、かつ得られた組成物の溶融流動
性が優れ、従つて成形品の外観が優れるといつた
効果が得られる。
更にこのような点に加え、(1)の点から後述の実
施例と比較例とを対比すると明らかなように、変
性エチレン・α―オレフイン共重合ゴムを配合し
た場合よりも耐衝撃性がより改良されるという効
果が得られるものと考えられる。
また該プロピレン・α―オレフインランダム共
重合体(C)は、前記特性に加えて、3個のプロピレ
ン連鎖でみたミクロアイソタクテイシテイが(以
下MITと略す)が0.7以上、更には0.8以上及び沸
騰n―ヘプタン不溶分が5重量%以下、更には3
重量%以下のものが好ましい。ミクロアイソタク
テイシテイが0.7未満のものを用いるとエイジン
グ後、成形品表面に低分子量物質がブリードアウ
トし、べたつく現象が起こる。また沸騰n―ヘプ
タン不溶分が多いことは、プロピレンがブロツク
的に重合された成分の量が多いためであり、その
ような共重合体を用いると、耐衝撃性の改良効果
が少ない場合がある。
ミクロアイソタクテイシテイとは 13C核磁気共
鳴スペクトルによつて3個のプロピレン連鎖の部
分に着目し、3個のプロピレンがアイソタクテイ
ツクに配列している分率を定量した値である。
沸騰n―ヘプタン不溶分の定量は以下の方法に
より行う。すなわち、約1mm×1mm×1mm程度の
細片試料およびガラスビーズを円筒ガラスフイル
ター(G3)に入れ、ソツクスレー抽出器により
14時間抽出を行う。この場合リフラツクス頻度は
1回/5分程度とする。不溶分の重量%は溶解部
分、又は不溶分を秤量することによつて求める。
前記のような諸性質を有するプロピレン含有率
50ないし70モル%のプロピレン・α―オレフイン
ランダム共重合体(C)は、例えば(a)少なくともマグ
ネシウム、チタンおよびハロゲンを含有する複合
体、(b)周期律表第1族ないし第3族金属の有機金
属化合物および(c)電子供与体とから形成される触
媒を用いて、プロピレンとα―オレフインとをラ
ンダム共重合させることによつて得られる。上記
電子供与体(c)の一部又は全部は、複合体(a)の一部
又は全部に固定されていてもよく、又、使用に先
立つて有機金属化合物(b)と予備接触させていても
よい。とくに好ましいのは、電子供与体(c)の一部
が複合体(a)に固定されており、残部をそのまま重
合系に加えるかあるいは有機金属化合物(b)と予備
接触させて使用する態様である。この場合、複合
体(a)に固定された電子供与体と、重合系にそのま
ま加えて使用するかまたは(b)と予備接触させて使
用する電子供与体とは同一のものでも異なるもの
であつてもよい。
該プロピレン・α―オレフインランダム共重合
体(C)を構成するα―オレフイン成分単位として
は、炭素数2以上(但し3は除く)、とくに2な
いし18程度のα―オレフインであり、エチレン、
1―ブテン、1―ヘキセン、4―メチル―1―ペ
ンテン、1―デセンなどを例示することができ、
これらの1種まは2種以上の混合物である。該プ
ロピレン・α―オレフイン共重合体は通常プロピ
レン成分とα―オレフインとの共重合体である
が、場合によつては微量、たとえば0.5モル%以
下の範囲でジエン成分を含有していても差しつか
えない。
不飽和カルボン酸またはその誘導体としては、
アクリル酸、マレイン酸、フマール酸、テトラヒ
ドロフタル酸、イタコン酸、シトラコン酸、クロ
トン酸、イソクロトン酸、ナジツク酸
(エンド
シス―ビシクロ〔2,2,1〕ヘプト―5―エン
―2,3―ジカルボン酸)などの不飽和カルボン
酸、またはその誘導体、例えば酸ハライド、アミ
ド、イミド、無水物、エステルなどが挙げられ、
具体的には、塩化マレニル、マレイミド、無水マ
レイン酸、無水シトラコン酸、マレイン酸モノメ
チル、マレイン酸ジメチル、グリシジルマレエー
トなどが例示される。これらの中では、不飽和ジ
カルボン酸またはその酸無水物が好適であり、と
くにマレイン酸、ナジツク酸
またはこれらの酸
無水物が好適である。
該不飽和カルボン酸またはその誘導体から選ば
れるグラフトモノマーをプロピレン・α―オレフ
インランダム共重合体(C)にグラフト共重合して前
記変性プロピレン・α―オレフインランダム共重
合体(D)を製造するには、従来公知の種々の方法を
採用することができる。たとえば、プロピレン・
α―オレフインランダム共重合体(C)を溶融させグ
ラフトモノマーを添加してグラフト共重合させる
方法あるいは溶媒に溶解させグラフトモノマーを
添加してグラフト共重合させる方法がある。いず
れの場合にも、前記グラフトモノマーを効率よく
グラフト共重合させるためには、ラジカル開始剤
の存在下に反応を実施することが好ましい。グラ
フト反応は通常60ないし350℃の温度で行われる。
ラジカル開始剤の使用割合はプロピレン・α―オ
レフインランダム共重合体100重量部に対して通
常0.001ないし1重量部の範囲であるラジカル開
始剤としては有機ペルオキシド、有機ペルエステ
ル、例えばベンゾイルペルオキシド、ジクロルベ
ンゾイルペルオキシド、ジクミルペルオキシド、
ジ―tert―ブチルペルオキシド、2,5―ジメチ
ル―2,5―ジ(ペルオキシドベンゾエート)ヘ
キシン―3、1,4―ビス(tert―ブチルペルオ
キシイソプロピル)ベンゼン、ラウロイルペルオ
キシド、tert―ブチルペルアセテート、2,5―
ジメチル―2,5―ジ(tert―ブチルペルオキ
シ)ヘキシン―3、2,5―ジメチル―2,5―
ジ(tert―ブチルペルオキシ)ヘキサン、tert―
ブチルペルベンゾエート、tert―ブチルペルフエ
ニルアセテート、tert―ブチルペルイソブチレー
ト、tert―ブチルペル―sec―オクトエート、tert
―ブチルペルピバレート、クミルペルピバレート
およびtert―ブチルペルジエチルアセテート、そ
の他アゾ化合物、例えばアゾビスイソブチロニト
ル、ジメチルアゾイソブチレートがある。これら
のうちではジクミルペルオキシド、ジ―tert―ブ
チルペルオキシド、2,5―ジメチル―2,5―
ジ(tert―ブチルペルオキシ)ヘキシン―3、
2,5―ジメチル―2,5―ジ(tert―ブチルペ
ルオキシ)ヘキサン、1,4―ビス(tert―ブチ
ルペルオキシイソプロピル)ベンゼンなどのジア
ルキルペルオキシドが好ましい。
本発明のプロピレン重合体組成物は、前記プロ
ピレン重合体(A)が95ないし5重量部、好ましくは
90ないし10重量部、ポリアミド(B)が5ないし95重
量部、好ましくは10ないし90重量部及び変性プロ
ピレン・α―オレフインランダム共重合体(D)が(A)
+(B)=100重量部に対して1ないし80重量部、好
ましくは10ないし40重量部とから構成される。結
晶性プロピレン重合体(A)が5重量部未満では、プ
ロピレン重合体による防湿性、耐薬品性等での改
質効果が得られず、逆にポリアミド(B)が5重量部
未満ではポリアミドによる剛性、耐衝撃性、耐熱
性、ガスバリヤー性等の点で改質効果が得られな
い。変性プロピレン・α―オレフインランダム共
重合体(D)が1重量部未満では耐衝撃性向上効果が
得られず、80重量部を越えると剛性、耐熱性、表
面硬度等が大きく損われる。
本発明で用いる変性プロピレン・α―オレフイ
ンランダム共重合体(D)に代えて、エチレン・エチ
ルアクリレート共重合体、エチレン・アクリル酸
共重合体の金属塩(アイオノマー)、ポリエチレ
ンの無水マレイン酸グラフト変性物あるいはカル
ボキシル化1,2―ポリブタジエン等を用いて
も、耐衝撃性が低下して実用的でない。
本発明のプロピレン重合体組成物を得るには、
結晶性プロピレン重合体(A)、ポリアミド(B)及び変
性プロピレン・α―オレフインランダム共重合体
(D)とを前記範囲で種々公知の方法、例えばヘンシ
エルミキサー、Vブレンダー、リボンブレンダ
ー、タンブラーブレンダー等で混合する方法、あ
るいは混合後、一軸押出機、二軸押出機、ニーダ
ー、バンバリーミキサー等で溶融混練後、造粒あ
るいは粉砕する方法を採用すればよい。
本発明のプロピレン重合体組成物には、耐熱安
定剤、耐候安定剤、帯電防止剤、滑剤、スリツプ
剤、核剤、難燃剤、油剤、顔料あるいは染料、ガ
ラス繊維、炭素繊維、チタン酸カリウム繊維、ウ
オラストナイト、炭酸カルシウム、硫酸カルシウ
ム、タルク、ガラスフレーク、硫酸バリウム、ク
レー、カオリン、微粉末シリカ、マイカ、珪酸カ
ルシウム、水酸化アルミニウム、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、酸
化カルシウム、炭酸カルシウム、炭酸マグネシウ
ム、等の無機あるいは有機の補強材(充填剤を除
く。)を本発明の目的を損わない範囲で配合して
おいてもよい。
本発明のプロピレン重合体組成物の特徴は、プ
ロピレン重合体中へのポリアミドの分散剤とし
て、前記した特定の変性プロピレン・α―オレフ
インランダム共重合体を使用することにより、組
成物中でのポリアミドの分散を良好ならしめ、ポ
リアミドによるプロピレン重合体への改質効果を
十分に発揮させるとともに、組成物の剛性をほと
んど損うことく耐衝撃性を著しく向上せしめた点
にある。
本発明のプロピレン重合体組成物は従来公知の
ポリプロピレン/ポリアミド組成物に比べて耐衝
撃性が極めて優れ、外観も良好であるので、自動
車部品、電気器具、機械部品、工業用部品等剛
性、耐熱性とともに耐衝撃性を要求する用途に好
適である。
次に実施例を挙げて本発明を更に具体的に説明
するが、本発明はその要旨を越えない限り、これ
らの実施例に何ら制約されるものではない。
本発明の実施例で用いた測定方法は以下の通り
である。
引張特性 ASTM D 638
曲げ特性 ASTM D 790
アイゾツト衝撃強度 ASTM D 256 ノツ
チ付
熱変形温度 ASTM D 648 荷重4.6Kg/cm2
光 沢 度 ASTM D 523
<変性プロピレン・α―オレフインランダム共重
合体の製造例>
プロピレン含有率60モル%、結晶化度0%、
MIT 0.96,沸騰n―ヘプタン不溶分:0.1%、沸
騰酢酸メチル可溶分0.8%及び〔η〕=4.5dl/g、
のプロピレン・エチレンランダム共重合体100重
量部にアセトン1.0重量部とα,α′―ビス―tert―
ブチルパーオキシ―ジイソプロピルベンゼン0.01
重量部と無水マレイン酸0.3重量部とからなる混
合液をヘンシエルミキサーで滴下混合した後40mm
φ押出機で240℃で造粒することにより結晶化度
0%、MFR10g/10min、無水マレイン酸のグラ
フト量0.15重量%の無水マレイン酸グラフトプロ
ピレン・エチレンランダム共重合体(変性PEC
―1)を得た。
実施例
MFRが2.0g/10minのポリプロピレン(以下
PP―1という)72重量部、MFR16g/0min、無
水マレイン酸グラフト量3.8重量%の変性ポリプ
ロピレン(以下変性PPという)3重量部、98%
硫酸中1%溶液において25℃で測定した相対粘度
ηrが2.8のナイロン6(以下NY6―1という)25重
量部及び変性PEC―1 10重量部とをタンブラ
ーブレンダーでドライブレンド後40mmφ押出機で
240℃で造粒してペレツトを製造した。このペレ
ツトを乾燥後、260℃で射出成形して物性測定用
試験片を作製した。
結果を第1表に示す。
実施例 2〜5
PP―1,NY6―1、及び変性PEC―1の量比
を第1表の如く変える以外は実施例1と同様に行
つた。結果を第1表に示す。
比較例 1
実施例1において、変性PEC―1 10重量部
を加えない以外は実施例1と同様に行つた。結果
を第1表に示す。
The present invention relates to a propylene polymer composition having excellent rigidity, impact resistance, gloss, and heat resistance. Crystalline polypropylene has excellent rigidity, surface gloss, heat resistance, etc., but has the drawback of poor impact resistance. As a method of improving impact resistance, a method of mixing a propylene polymer with a rubber-like substance such as polyisobutylene, polybutadiene, amorphous ethylene-propylene copolymer, or polyethylene has been widely used. However, on the other hand, these modifiers have the disadvantage that they are softer than propylene polymers and significantly reduce the inherent characteristics of propylene polymers, such as rigidity, heat resistance, and surface hardness. On the other hand, attempts have been made to mix a polyamide resin with a propylene polymer for the purpose of improving the heat resistance, rigidity, etc. of the propylene polymer, but the compatibility between the two is extremely poor. Therefore, as a method to improve the compatibility between polyolefin resin such as propylene polymer and polyamide, polyolefin resin 40-90
A polymer blend consisting of 5 to 50 parts by weight of polyamide and 2 to 25 parts by weight of ionomer (Japanese Patent Publication No. 43-6529) has been proposed.
Such compositions have the disadvantage of poor impact resistance when polypropylene is used as the polyolefin. When mixing polyolefin and polyamide, a method in which a modified polyolefin into which at least one of acid, ester, amide, acid anhydride, and epoxide groups has been introduced is used as the polyolefin (Japanese Patent Publication No. 30945/1989), or crystalline polypropylene. A method of intervening maleic anhydride-modified polypropylene when blending polyamide and polyamide has been proposed (Kobunshi Kagaku 29 , 265 (1972)). However, although these methods improved the compatibility between polypropylene and polyamide, the effect of improving impact resistance was not sufficient. In view of the current situation, the inventors of the present invention have conducted various studies for the purpose of improving the impact resistance, oil resistance, paintability, etc. of compositions made of crystalline polypropylene and polyamide.・We discovered that the above object could be achieved by adding a graft-modified product of an unsaturated dicarboxylic acid or its derivative to an α-olefin copolymer, and proposed it earlier (Japanese Patent Application No. 58-22882).
issue). However, although the impact resistance of the composition specifically described in the above proposal is improved, the fluidity and gloss of the composition are somewhat reduced, and the effect of improving impact resistance may not be sufficient depending on the application. It was something I couldn't say. The present invention aims to solve such problems, and by using a specific modified propylene/α-olefin random copolymer as an impact modifier, a composition consisting of a crystalline propylene polymer and a polyamide can be obtained. It has been discovered that the impact resistance of objects can be significantly improved. That is, the present invention comprises: 95 to 5 parts by weight of the crystalline propylene polymer (A), 5 to 95 parts by weight of the polyamide (B), and 100 parts by weight of the total of (A) and (B), modified propylene.・α-olefin copolymer (D) 1
80 parts by weight of the modified propylene/α-olefin copolymer (D), wherein the modified propylene/α-olefin copolymer (D) contains
Linear crystallinity 0 to 30%, propylene content
50 to 70 mol%, microisotacticity (MIT) of 3 propylene chains is 0.7 or more,
and propylene/α-olefin random copolymer (C) with a boiling n-heptane insoluble content of 5% by weight or less
0.01 to 5 parts by weight of a graft monomer selected from unsaturated carboxylic acids or derivatives thereof
Modified propylene α obtained by graft modification by weight part
- Characterized by being an olefin copolymer,
The present invention provides a propylene polymer composition that has excellent rigidity, impact resistance, water resistance, surface gloss, heat resistance, etc. The propylene polymer used in the present invention is crystalline and preferably has a density of 0.89 to 0.89.
0.93g/cm 3 , melt flow rate (MFR:
ASTMD1238, L) is 0.01 to 50g/10min, and is a propylene homopolymer or a block of propylene and 20 mol% or less of ethylene, 1-butene, 4-methyl-1-pentene, etc. It is a random copolymer. The crystalline propylene polymer (A) used in the present invention is usually a graft monomer partially or wholly selected from unsaturated carboxylic acids or derivatives thereof.
It is preferable to use a propylene polymer graft-modified in an amount of 0.001 to 10% by weight, preferably 0.1 to 5% by weight, since the effect of improving impact resistance and the like is further improved. The polyamide (B) used in the present invention is hexamethylene diamine, decamethylene diamine, dodecamethylene diamine, 2,2,4- or 2,4,4-
Trimethylhexamethylene diamine, 1,3- or 1,4-bis(aminomethyl)cyclohexane, bis(p-aminocyclohexylmethane),
aliphatic such as m- or p-xylylene diamine;
By polycondensation of alicyclic, aromatic, etc. diamines with aliphatic, alicyclic, aromatic, etc. dicarboxylic acids such as adipic acid, suberic acid, sebacic acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, etc. The resulting polyamide, ε-aminocaproic acid,
Polyamides obtained by condensation of aminocarboxylic acids such as 11-aminoundecanoic acid, polyamides obtained from lactams such as ε-caprolactam and ω-laurolactam, copolymer polyamides consisting of these components, mixtures of these polyamides, etc. is exemplified. Specifically, nylon 6, nylon 66, nylon 610, nylon 9, nylon 11,
Nylon 12, Nylon 6/66, Nylon 66/610,
Examples include nylon 6/11. Among these, nylon 6 and nylon 66 are preferred because of their good rigidity and heat resistance. Although the molecular weight is not particularly limited, the relative viscosity ηr (JIS K6810, 98%
(measured in sulfuric acid) of 1.0 or more is used, and among them, polyamides of 2.0 or more are preferred because they have excellent mechanical strength. The modified propylene/α-olefin random copolymer (D) used in the present invention has an X-ray crystallinity of 0 to 30%, preferably 0 to 20%, and a propylene content of 50 to 70 mol%, preferably 55
0.01 to 5 parts by weight, preferably 0.1 to 5 parts by weight of a graft monomer selected from unsaturated carboxylic acids or derivatives thereof, to 100 parts by weight of propylene/α-olefin random copolymer (C) containing 0.01 to 65 mol%.
It is a copolymer that has been graft-modified by 1.0 parts by weight. Propylene/α-olefin random copolymer
Even if a copolymer obtained by graft-modifying (C) with a crystallinity of 30% and a propylene content of more than 70 mol% is used, the impact resistance of the propylene polymer composition is not significantly improved. The propylene/α-olefin random copolymer (C) usually has an intrinsic viscosity [η] of 2 to 10 dl/g, more preferably 3 to 6 dl/g, as measured in decalin at 135°C. When a copolymer with [η] outside the above range is used, the modified propylene/α-olefin random copolymer (D) obtained from the copolymer and the propylene polymer (A) and polyamide (B) ), the difference in melt viscosity tends to increase, the dispersion effect is not sufficient, and the effect of improving impact resistance is not sufficient. The propylene/α-olefin random copolymer (C) used in the present invention is distinguished from conventionally known ethylene/α-olefin copolymer rubbers in the following points. (1) Excellent affinity for propylene polymers. (2) Ethylene/α-olefin copolymer rubber is a peroxy crosslinked type, whereas it is a peroxy decomposed type. From the point of (2), [η] of the modified propylene/α-olefin random copolymer (D) obtained by graft modification of the propylene/α-olefin random copolymer (C) in the present invention is While it is lower than that of polymer (C), modified ethylene/α-olefin copolymer rubber obtained by graft modification is lower than that of polymer (C).
Since α-olefin copolymer rubber undergoes crosslinking during modification, it becomes a modified product with higher [η] than the raw rubber, that is, with lower fluidity. As a result, the modified propylene α used in the present invention
- The olefin random copolymer (C) has good affinity with the crystalline propylene polymer (A), which is another component of the composition of the present invention, and the resulting composition has excellent melt flowability, If the appearance of the molded product is excellent, other effects can be obtained. Furthermore, in addition to these points, as is clear from comparing the Examples and Comparative Examples described below from the point of (1), the impact resistance is higher than when the modified ethylene/α-olefin copolymer rubber is blended. It is thought that the effect of improvement can be obtained. In addition to the above properties, the propylene/α-olefin random copolymer (C) has a microisotacticity (hereinafter abbreviated as MIT) of three propylene chains of 0.7 or more, furthermore 0.8 or more and boiling point. The n-heptane insoluble content is 5% by weight or less, and even 3% by weight.
Preferably, it is less than % by weight. If a material with a microisotacticity of less than 0.7 is used, low molecular weight substances will bleed out on the surface of the molded product after aging, resulting in a sticky phenomenon. Furthermore, the large amount of boiling n-heptane insoluble matter is due to the large amount of propylene block-polymerized components, and if such a copolymer is used, the effect of improving impact resistance may be small. . Microisotacticity is a value determined by focusing on three propylene chains using 13 C nuclear magnetic resonance spectroscopy, and quantifying the fraction in which three propylene chains are arranged isotactically. The amount insoluble in boiling n-heptane is determined by the following method. That is, a small sample of approximately 1 mm x 1 mm x 1 mm and glass beads are placed in a cylindrical glass filter (G3) and extracted using a Soxhlet extractor.
Extract for 14 hours. In this case, the reflux frequency is approximately once/5 minutes. The weight percent of insoluble matter is determined by weighing the dissolved or insoluble matter. Propylene content with the above properties
The 50 to 70 mol% propylene/α-olefin random copolymer (C) is, for example, (a) a composite containing at least magnesium, titanium, and halogen, (b) a metal from Group 1 to Group 3 of the periodic table. It is obtained by random copolymerization of propylene and α-olefin using a catalyst formed from an organometallic compound and (c) an electron donor. Part or all of the electron donor (c) may be immobilized on part or all of the complex (a), or may be brought into preliminary contact with the organometallic compound (b) prior to use. Good too. Particularly preferred is an embodiment in which a part of the electron donor (c) is immobilized on the complex (a), and the remainder is added to the polymerization system as it is or is used after being brought into preliminary contact with the organometallic compound (b). be. In this case, the electron donor immobilized on the complex (a) and the electron donor used by directly adding it to the polymerization system or by pre-contacting it with (b) may be the same or different. It's okay. The α-olefin component unit constituting the propylene/α-olefin random copolymer (C) is an α-olefin having 2 or more carbon atoms (excluding 3 carbon atoms), particularly about 2 to 18 carbon atoms, and ethylene,
Examples include 1-butene, 1-hexene, 4-methyl-1-pentene, 1-decene, etc.
It is one kind or a mixture of two or more kinds of these. The propylene/α-olefin copolymer is usually a copolymer of a propylene component and an α-olefin, but in some cases it may contain a trace amount, for example, 0.5 mol% or less, of a diene component. can not use. As unsaturated carboxylic acids or derivatives thereof,
Acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, nadic acid (endocys-bicyclo[2,2,1]hept-5-ene-2,3-dicarboxylic acid) ), or derivatives thereof, such as acid halides, amides, imides, anhydrides, esters, etc.
Specific examples include maleyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, and glycidyl maleate. Among these, unsaturated dicarboxylic acids or their acid anhydrides are preferred, and maleic acid, nadic acid, and their acid anhydrides are particularly preferred. To produce the modified propylene/α-olefin random copolymer (D) by graft copolymerizing the graft monomer selected from the unsaturated carboxylic acid or its derivative onto the propylene/α-olefin random copolymer (C). Various conventionally known methods can be employed. For example, propylene
There is a method of melting the α-olefin random copolymer (C) and adding a graft monomer to carry out graft copolymerization, or a method of dissolving the α-olefin random copolymer (C) and adding a graft monomer to carry out graft copolymerization. In any case, in order to efficiently graft copolymerize the graft monomer, it is preferable to carry out the reaction in the presence of a radical initiator. The grafting reaction is usually carried out at a temperature of 60 to 350°C.
The proportion of the radical initiator used is usually in the range of 0.001 to 1 part by weight per 100 parts by weight of the propylene/α-olefin random copolymer. Examples of the radical initiator include organic peroxides, organic peresters, such as benzoyl peroxide, dichloride, etc. benzoyl peroxide, dicumyl peroxide,
Di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(peroxide benzoate) hexyne-3,1,4-bis(tert-butylperoxyisopropyl)benzene, lauroyl peroxide, tert-butyl peracetate, 2 ,5-
Dimethyl-2,5-di(tert-butylperoxy)hexyne-3,2,5-dimethyl-2,5-
Di(tert-butylperoxy)hexane, tert-
Butyl perbenzoate, tert-butyl perphenyl acetate, tert-butyl perisobutyrate, tert-butyl per-sec-octoate, tert
-butyl perpivalate, cumyl perpivalate and tert-butyl perdiethyl acetate, as well as other azo compounds such as azobisisobutyronitrile, dimethylazoisobutyrate. Among these, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-
di(tert-butylperoxy)hexyne-3,
Dialkyl peroxides such as 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane and 1,4-bis(tert-butylperoxyisopropyl)benzene are preferred. The propylene polymer composition of the present invention preferably contains 95 to 5 parts by weight of the propylene polymer (A).
90 to 10 parts by weight, 5 to 95 parts by weight, preferably 10 to 90 parts by weight of polyamide (B), and modified propylene/α-olefin random copolymer (D) as (A)
+(B)=1 to 80 parts by weight, preferably 10 to 40 parts by weight per 100 parts by weight. If the crystalline propylene polymer (A) is less than 5 parts by weight, the propylene polymer will not have the effect of improving moisture resistance, chemical resistance, etc., and conversely, if the polyamide (B) is less than 5 parts by weight, the polyamide will not be effective. No modification effect can be obtained in terms of rigidity, impact resistance, heat resistance, gas barrier properties, etc. If the modified propylene/α-olefin random copolymer (D) is less than 1 part by weight, no impact resistance improvement effect can be obtained, and if it exceeds 80 parts by weight, rigidity, heat resistance, surface hardness, etc. will be significantly impaired. In place of the modified propylene/α-olefin random copolymer (D) used in the present invention, ethylene/ethyl acrylate copolymer, metal salt (ionomer) of ethylene/acrylic acid copolymer, maleic anhydride graft modification of polyethylene Even if polyurethane or carboxylated 1,2-polybutadiene is used, the impact resistance decreases and it is not practical. To obtain the propylene polymer composition of the present invention,
Crystalline propylene polymer (A), polyamide (B) and modified propylene/α-olefin random copolymer
(D) and various known methods within the above range, such as a Henschel mixer, a V blender, a ribbon blender, a tumbler blender, etc., or after mixing, a single screw extruder, a twin screw extruder, a kneader, a Banbury mixer, etc. After melt-kneading, granulation or pulverization may be adopted. The propylene polymer composition of the present invention includes heat stabilizers, weather stabilizers, antistatic agents, lubricants, slip agents, nucleating agents, flame retardants, oil agents, pigments or dyes, glass fibers, carbon fibers, potassium titanate fibers. , wollastonite, calcium carbonate, calcium sulfate, talc, glass flakes, barium sulfate, clay, kaolin, finely powdered silica, mica, calcium silicate, aluminum hydroxide, magnesium hydroxide, aluminum oxide, magnesium oxide, calcium oxide, carbonate Inorganic or organic reinforcing materials (excluding fillers) such as calcium, magnesium carbonate, etc. may be added to the extent that the object of the present invention is not impaired. The propylene polymer composition of the present invention is characterized by the use of the above-mentioned specific modified propylene/α-olefin random copolymer as a dispersant for polyamide in the propylene polymer. The present invention has the advantage that the polyamide has a good dispersion, fully exhibits the effect of modifying the propylene polymer by the polyamide, and also significantly improves the impact resistance without substantially impairing the rigidity of the composition. The propylene polymer composition of the present invention has extremely superior impact resistance and good appearance compared to conventionally known polypropylene/polyamide compositions, so it can improve rigidity and heat resistance for automobile parts, electrical appliances, mechanical parts, industrial parts, etc. Suitable for applications that require both strength and impact resistance. Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples as long as the gist thereof is not exceeded. The measurement method used in the examples of the present invention is as follows. Tensile properties ASTM D 638 Bending properties ASTM D 790 Izot impact strength ASTM D 256 Notched heat deformation temperature ASTM D 648 Load 4.6 Kg/ cm2 Shine ASTM D 523 <Production example of modified propylene/α-olefin random copolymer > Propylene content 60 mol%, crystallinity 0%,
MIT 0.96, boiling n-heptane insoluble content: 0.1%, boiling methyl acetate soluble content 0.8% and [η] = 4.5 dl/g,
100 parts by weight of propylene/ethylene random copolymer, 1.0 parts by weight of acetone and α,α′-bis-tert-
Butylperoxy-diisopropylbenzene 0.01
A mixture of 0.3 parts by weight of maleic anhydride and 0.3 parts by weight of maleic anhydride was mixed dropwise with a Henschel mixer, and then 40 mm
A maleic anhydride-grafted propylene/ethylene random copolymer (modified PEC) with a crystallinity of 0%, an MFR of 10 g/10 min, and a graft amount of maleic anhydride of 0.15% by weight is produced by granulating it at 240°C with a φ extruder.
-1) was obtained. Example Polypropylene with MFR of 2.0g/10min (hereinafter
PP-1) 72 parts by weight, MFR 16g/0min, modified polypropylene with maleic anhydride grafting amount of 3.8% by weight (hereinafter referred to as modified PP) 3 parts by weight, 98%
25 parts by weight of nylon 6 (hereinafter referred to as NY6-1) with a relative viscosity ηr of 2.8 measured in a 1% solution in sulfuric acid at 25°C and 10 parts by weight of modified PEC-1 were dry blended in a tumbler blender and then mixed in a 40 mmφ extruder.
Pellets were produced by granulation at 240°C. After drying this pellet, it was injection molded at 260°C to prepare a test piece for measuring physical properties. The results are shown in Table 1. Examples 2 to 5 The same procedure as in Example 1 was carried out except that the quantitative ratios of PP-1, NY6-1, and modified PEC-1 were changed as shown in Table 1. The results are shown in Table 1. Comparative Example 1 The same procedure as in Example 1 was carried out except that 10 parts by weight of modified PEC-1 was not added. The results are shown in Table 1.
【表】
比較例 2
実施例1において変性PEC―1をPEC―1に
代える以外は実施例1と同様に行つた。結果を第
2表に示す。
<変性エチレン・α―オレフインランダム共重合
体の製造例>
エチレン含有率80モル%、結晶化度5%、
MFR1.2g/10minのエチレン・プロピレンラン
ダム共重合体(以下EPC―1という)100重量部
にアセトン1.0重量部とα,α′―ビス―tert―ブチ
ルパーオキシ―ジイソプロピルベンゼン0.02重量
部と無水マレイン酸1.0重量部とかなる混合液を
ヘンシエルミキサーで滴下混合した後40mmφ押出
機で240℃で造粒することにより結晶化度3%、
MFR0.8g/10min、無水マレイン酸のグラフト
量0.8重量%の無水マレイン酸グラフトエチレ
ン・プロピレンランダム共重合体(変性EPC―
1)を得た。
<変性プロピレン・α―オレフインランダム共重
合体の製造例>
プロピレン含有率85モル%、結晶化度35%、
〔η〕=2.9dl/gのプロピレン・エチレンランダ
ム共重合体(以下PEC―2という)100重量部に
アセトン1.0重量部とα,α′―ビス―tert―ブチル
パーオキシ―ジイソプロピルベンゼン0.01重量部
と無水マレイン酸0.4重量部とからなる混合液を
ヘンシエルミキサーで滴下混合した後40mmφ押出
機で240℃で造粒することにより結晶化度32%、
MFR22g/10min、無水マレイン酸のグラフト量
0.25重量%の無水マレイン酸グラフトプロピレ
ン・エチレンランダム共重合体(変性PEC―2)
を得た。
比較例 3
実施例1において、変性PEC―1の代りに変
性EPC―1を用いる以外は実施例1と同様に行
つた。結果を第2表に示す。
比較例 4
実施例1において、変性PEC―1の代りに変
性PEC―2を用いる以外は実施例1と同様に行
つた。結果を第2表に示す。
比較例 5
実施例1において、変性PEC―1の代りにエ
チレン・メタクリル酸共重合体(MFR12g/
10min、190℃、エチレン含有率88重量%、以下
EMAという)を用いる以外は実施例1と同様に
行つた。結果を第2表に示す。
<変性エチレン・α―オレフインランダム共重合
体の製造例>
エチレン含有率89モル%、結晶化度17%、
MFR1.5g/10minのエチレン・1―ブテンラン
ダム共重合体(以下EBCという)100重量部にア
セトン1.0重量部とα,α′―ビス―tert―ブチルパ
ーオキシ―ジイソプロピルベンゼン0.02重量部と
無水マレイン酸1.0重量部とからなる混合後をヘ
ンシエルミキサーで滴下混合した後40mmφで240
℃で造粒することにより結晶化度16%、
MFR0.7g/10min,無水マレイン酸のグラフト
量0.65重量%の無水マレイン酸グラフトエチレ
ン・1―ブテンランダム共重合体共重合体(変性
EBC)を得た。
比較例 6
実施例1において、変性PEC―1の代わりに
変性EBCを用いる以外は実施例1と同様に行つ
た。結果を第2表に示す。[Table] Comparative Example 2 The same procedure as in Example 1 was carried out except that modified PEC-1 in Example 1 was replaced with PEC-1. The results are shown in Table 2. <Production example of modified ethylene/α-olefin random copolymer> Ethylene content 80 mol%, crystallinity 5%,
100 parts by weight of ethylene-propylene random copolymer (hereinafter referred to as EPC-1) with an MFR of 1.2 g/10 min, 1.0 parts by weight of acetone, 0.02 parts by weight of α, α′-bis-tert-butylperoxy-diisopropylbenzene, and anhydrous maleic acid. A mixed solution containing 1.0 parts by weight of acid was mixed dropwise using a Henschel mixer, and then granulated at 240°C using a 40 mmφ extruder to obtain a crystallinity of 3%.
MFR0.8g/10min, maleic anhydride grafted ethylene/propylene random copolymer (modified EPC-
1) was obtained. <Production example of modified propylene/α-olefin random copolymer> Propylene content 85 mol%, crystallinity 35%,
[η]=100 parts by weight of propylene/ethylene random copolymer (hereinafter referred to as PEC-2) of 2.9 dl/g, 1.0 parts by weight of acetone and 0.01 parts by weight of α, α′-bis-tert-butylperoxy-diisopropylbenzene. A liquid mixture consisting of 0.4 parts by weight of maleic anhydride was mixed dropwise in a Henschel mixer, and then granulated at 240°C in a 40 mmφ extruder to obtain a crystallinity of 32%.
MFR22g/10min, amount of maleic anhydride grafted
0.25% by weight maleic anhydride grafted propylene/ethylene random copolymer (modified PEC-2)
I got it. Comparative Example 3 The same procedure as in Example 1 was conducted except that modified EPC-1 was used instead of modified PEC-1. The results are shown in Table 2. Comparative Example 4 The same procedure as in Example 1 was carried out except that modified PEC-2 was used instead of modified PEC-1. The results are shown in Table 2. Comparative Example 5 In Example 1, ethylene/methacrylic acid copolymer (MFR12g/
10min, 190℃, ethylene content 88% by weight or less
The same procedure as in Example 1 was carried out except that EMA) was used. The results are shown in Table 2. <Production example of modified ethylene/α-olefin random copolymer> Ethylene content 89 mol%, crystallinity 17%,
100 parts by weight of ethylene/1-butene random copolymer (hereinafter referred to as EBC) with an MFR of 1.5 g/10 min, 1.0 parts by weight of acetone, 0.02 parts by weight of α,α′-bis-tert-butylperoxy-diisopropylbenzene, and anhydrous maleic acid. After mixing with 1.0 parts by weight of acid, dropwise mix it with a Henschel mixer and then mix it with 40mmφ.
Crystallinity 16% by granulation at °C
MFR0.7g/10min, maleic anhydride grafted ethylene/1-butene random copolymer copolymer (modified
EBC) was obtained. Comparative Example 6 The same procedure as in Example 1 was carried out except that modified EBC was used instead of modified PEC-1. The results are shown in Table 2.
【表】
実施例6〜8、比較例7〜9
実施例1〜3、比較例1〜3においてPP―1
の代りにMFR7g/10minのポリプロピレン(以
下PP―2という)を用い、かつNY6―1の代わ
りにηrが2.2のナイロン6(以下NY6―2という)
を用いる以外は実施例1〜3、比較例1〜3と同
様に行つた。結果を第3表に示す。[Table] Examples 6 to 8, Comparative Examples 7 to 9 PP-1 in Examples 1 to 3 and Comparative Examples 1 to 3
Polypropylene (hereinafter referred to as PP-2) with an MFR of 7g/10min was used instead of , and nylon 6 with an ηr of 2.2 (hereinafter referred to as NY6-2) was used instead of NY6-1.
The same procedure as in Examples 1 to 3 and Comparative Examples 1 to 3 was performed except that . The results are shown in Table 3.
【表】【table】
Claims (1)
部、 ポリアミド(B)5ないし95重量部、 および (A)と(B)との合計100重量部に対して、 変性プロピレン・α―オレフイン共重合体(D)1
ないし80重量部とからなる組成物であつて、該変
性プロピレン・α―オレフイン共重合体(D)が、X
線による結晶化度0ないし30%、プロピレン含量
50ないし70モル%、3個のプロピレン連鎖でみた
ミクロアイソタクテイシテイ(MIT)が0.7以上、
および沸騰n―ヘプタン不溶分が5重量%以下の
プロピレン・α―オレフインランダム共重合体(C)
100重量部に、不飽和カルボン酸またはその誘導
体から選ばれるグラフトモノマーを0.01ないし5
重量部グラフト変性してなる変性プロピレン・α
―オレフイン共重合体であることを特徴とするプ
ロピレン重合体組成物。[Scope of Claims] 1. 95 to 5 parts by weight of crystalline propylene polymer (A), 5 to 95 parts by weight of polyamide (B), and 100 parts by weight of (A) and (B) in total, modified. Propylene/α-olefin copolymer (D) 1
80 parts by weight of the modified propylene/α-olefin copolymer (D), wherein the modified propylene/α-olefin copolymer (D) contains
Linear crystallinity 0 to 30%, propylene content
50 to 70 mol%, microisotacticity (MIT) of 3 propylene chains is 0.7 or more,
and propylene/α-olefin random copolymer (C) with a boiling n-heptane insoluble content of 5% by weight or less
0.01 to 5 parts by weight of a graft monomer selected from unsaturated carboxylic acids or derivatives thereof
Modified propylene α obtained by graft modification by weight part
- A propylene polymer composition characterized by being an olefin copolymer.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP21778583A JPS60110740A (en) | 1983-11-21 | 1983-11-21 | Propylene polymer composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP21778583A JPS60110740A (en) | 1983-11-21 | 1983-11-21 | Propylene polymer composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS60110740A JPS60110740A (en) | 1985-06-17 |
JPH0242379B2 true JPH0242379B2 (en) | 1990-09-21 |
Family
ID=16709686
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP21778583A Granted JPS60110740A (en) | 1983-11-21 | 1983-11-21 | Propylene polymer composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS60110740A (en) |
Families Citing this family (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62158739A (en) * | 1986-01-07 | 1987-07-14 | Tonen Sekiyukagaku Kk | Polypropylene composition |
JPS62158740A (en) * | 1986-01-07 | 1987-07-14 | Tonen Sekiyukagaku Kk | Production of thermoplastic resin composition |
JPS62241941A (en) * | 1986-04-14 | 1987-10-22 | Tonen Sekiyukagaku Kk | Thermoplastic resin composition |
JPS62241938A (en) * | 1986-04-14 | 1987-10-22 | Tonen Sekiyukagaku Kk | Production of thermoplastic resin composition |
US4962148A (en) * | 1987-09-09 | 1990-10-09 | Nippon Petrochemicals Co., Ltd | Thermoplastic resin composition and method for preparing the same |
JPS6487652A (en) * | 1987-09-29 | 1989-03-31 | Toyota Motor Corp | Impact-resistant polypropylene resin composition |
FR2697465A1 (en) * | 1992-10-30 | 1994-05-06 | Atochem Elf Sa | Laminates based on polyamide / polyolefin alloys and coextrusion binders, objects obtained therefrom, coating methods therewith. |
JP3300442B2 (en) * | 1992-12-28 | 2002-07-08 | 三井化学株式会社 | Method for improving impact resistance of thermoplastic resin molded article and composition therefor |
JP2602162B2 (en) * | 1993-02-24 | 1997-04-23 | 三ツ星ベルト株式会社 | Polyamide resin composition |
JPH0732356A (en) * | 1993-07-19 | 1995-02-03 | Mitsuboshi Belting Ltd | Equipment and method for kneading rubber |
EP0683210B1 (en) * | 1994-05-20 | 1999-08-25 | Ube Industries, Ltd. | Resin composite containing polyamide matrix and polyolefin grains dispersed therein |
JP2766875B2 (en) | 1995-04-10 | 1998-06-18 | 日本ピラー工業株式会社 | Shaft sealing system device |
DE19653590C2 (en) * | 1996-12-20 | 1998-10-15 | Benecke Kaliko Ag | High-frequency weldable polymer mixture |
ES2407851T3 (en) * | 2008-03-27 | 2013-06-14 | Mitsui Chemicals, Inc. | Resin composition and use thereof |
FR3016167B1 (en) * | 2014-01-03 | 2017-05-19 | Arkema France | POLYPROPYLENE THERMOPLASTIC COMPOSITION AND POLYAMIDE GRAFTED POLYOLEFIN |
EP4339242A1 (en) * | 2021-05-10 | 2024-03-20 | Mitsubishi Chemical Corporation | Polymer composition and molded article thereof |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5536279A (en) * | 1978-09-08 | 1980-03-13 | Mitsubishi Chem Ind Ltd | Production of polyamide resin composition |
JPS58219276A (en) * | 1982-06-14 | 1983-12-20 | Taisei Polymer Kk | Resin composition for secondary backing of carpet |
JPS59126461A (en) * | 1983-01-11 | 1984-07-21 | Mitsui Petrochem Ind Ltd | Polyamide composition |
JPS59129258A (en) * | 1983-01-17 | 1984-07-25 | Mitsui Petrochem Ind Ltd | Polyamide composition |
JPS59149940A (en) * | 1983-02-16 | 1984-08-28 | Mitsui Petrochem Ind Ltd | Propylene polymer composition |
JPS6047062A (en) * | 1983-08-25 | 1985-03-14 | Mitsubishi Chem Ind Ltd | Polyamide resin composition |
JPS6076548A (en) * | 1983-10-03 | 1985-05-01 | Mitsui Petrochem Ind Ltd | Polypropylene composition containing incorporated inorganic filler |
-
1983
- 1983-11-21 JP JP21778583A patent/JPS60110740A/en active Granted
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5536279A (en) * | 1978-09-08 | 1980-03-13 | Mitsubishi Chem Ind Ltd | Production of polyamide resin composition |
JPS58219276A (en) * | 1982-06-14 | 1983-12-20 | Taisei Polymer Kk | Resin composition for secondary backing of carpet |
JPS59126461A (en) * | 1983-01-11 | 1984-07-21 | Mitsui Petrochem Ind Ltd | Polyamide composition |
JPS59129258A (en) * | 1983-01-17 | 1984-07-25 | Mitsui Petrochem Ind Ltd | Polyamide composition |
JPS59149940A (en) * | 1983-02-16 | 1984-08-28 | Mitsui Petrochem Ind Ltd | Propylene polymer composition |
JPS6047062A (en) * | 1983-08-25 | 1985-03-14 | Mitsubishi Chem Ind Ltd | Polyamide resin composition |
JPS6076548A (en) * | 1983-10-03 | 1985-05-01 | Mitsui Petrochem Ind Ltd | Polypropylene composition containing incorporated inorganic filler |
Also Published As
Publication number | Publication date |
---|---|
JPS60110740A (en) | 1985-06-17 |
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