JPS6324620B2 - - Google Patents
Info
- Publication number
- JPS6324620B2 JPS6324620B2 JP56180549A JP18054981A JPS6324620B2 JP S6324620 B2 JPS6324620 B2 JP S6324620B2 JP 56180549 A JP56180549 A JP 56180549A JP 18054981 A JP18054981 A JP 18054981A JP S6324620 B2 JPS6324620 B2 JP S6324620B2
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- weight
- modified polymer
- ethylene
- propylene
- 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
Links
- 229920000642 polymer Polymers 0.000 claims description 81
- 239000000203 mixture Substances 0.000 claims description 69
- 229920000098 polyolefin Polymers 0.000 claims description 66
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 38
- -1 propylene-ethylene Chemical group 0.000 claims description 35
- 239000000395 magnesium oxide Substances 0.000 claims description 31
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 23
- 229920005674 ethylene-propylene random copolymer Polymers 0.000 claims description 22
- 229920001155 polypropylene Polymers 0.000 claims description 22
- 239000000945 filler Substances 0.000 claims description 20
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 19
- 229920001400 block copolymer Polymers 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 15
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 14
- 239000005977 Ethylene Substances 0.000 claims description 14
- 238000004898 kneading Methods 0.000 claims description 13
- 239000003999 initiator Substances 0.000 claims description 11
- 238000012986 modification Methods 0.000 claims description 11
- 230000004048 modification Effects 0.000 claims description 11
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 10
- 239000011630 iodine Substances 0.000 claims description 10
- 229910052740 iodine Inorganic materials 0.000 claims description 10
- 238000001179 sorption measurement Methods 0.000 claims description 8
- 239000000155 melt Substances 0.000 claims description 5
- 229920005604 random copolymer Polymers 0.000 claims description 5
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 description 33
- 229920001577 copolymer Polymers 0.000 description 20
- 229920005601 base polymer Polymers 0.000 description 10
- 230000000704 physical effect Effects 0.000 description 10
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 8
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000000178 monomer Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 150000001451 organic peroxides Chemical class 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000012779 reinforcing material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-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
- XKBHBVFIWWDGQX-UHFFFAOYSA-N 2-bromo-3,3,4,4,5,5,5-heptafluoropent-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(Br)=C XKBHBVFIWWDGQX-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-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
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000008064 anhydrides Chemical class 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
- 238000012661 block copolymerization Methods 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920005653 propylene-ethylene copolymer Polymers 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- HCXVPNKIBYLBIT-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOOC(C)(C)C HCXVPNKIBYLBIT-UHFFFAOYSA-N 0.000 description 1
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- RIPYNJLMMFGZSX-UHFFFAOYSA-N (5-benzoylperoxy-2,5-dimethylhexan-2-yl) benzenecarboperoxoate Chemical compound C=1C=CC=CC=1C(=O)OOC(C)(C)CCC(C)(C)OOC(=O)C1=CC=CC=C1 RIPYNJLMMFGZSX-UHFFFAOYSA-N 0.000 description 1
- 229920003067 (meth)acrylic acid ester copolymer Polymers 0.000 description 1
- BLKRGXCGFRXRNQ-SNAWJCMRSA-N (z)-3-carbonoperoxoyl-4,4-dimethylpent-2-enoic acid Chemical compound OC(=O)/C=C(C(C)(C)C)\C(=O)OO BLKRGXCGFRXRNQ-SNAWJCMRSA-N 0.000 description 1
- PYOLJOJPIPCRDP-UHFFFAOYSA-N 1,1,3-trimethylcyclohexane Chemical compound CC1CCCC(C)(C)C1 PYOLJOJPIPCRDP-UHFFFAOYSA-N 0.000 description 1
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 1
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- AYMDJPGTQFHDSA-UHFFFAOYSA-N 1-(2-ethenoxyethoxy)-2-ethoxyethane Chemical compound CCOCCOCCOC=C AYMDJPGTQFHDSA-UHFFFAOYSA-N 0.000 description 1
- MNUHUVIZSPCLFF-UHFFFAOYSA-N 1-methylhept-6-ene-1,2,4,5-tetracarboxylic acid Chemical compound OC(=O)C(C)C(C(O)=O)CC(C(O)=O)C(C=C)C(O)=O MNUHUVIZSPCLFF-UHFFFAOYSA-N 0.000 description 1
- HQOVXPHOJANJBR-UHFFFAOYSA-N 2,2-bis(tert-butylperoxy)butane Chemical compound CC(C)(C)OOC(C)(CC)OOC(C)(C)C HQOVXPHOJANJBR-UHFFFAOYSA-N 0.000 description 1
- HSMXZESMYQNLJP-UHFFFAOYSA-N 2,4,4-trimethylpentanenitrile Chemical compound N#CC(C)CC(C)(C)C HSMXZESMYQNLJP-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
- 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 1
- JGBAASVQPMTVHO-UHFFFAOYSA-N 2,5-dihydroperoxy-2,5-dimethylhexane Chemical compound OOC(C)(C)CCC(C)(C)OO JGBAASVQPMTVHO-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- KFGFVPMRLOQXNB-UHFFFAOYSA-N 3,5,5-trimethylhexanoyl 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOC(=O)CC(C)CC(C)(C)C KFGFVPMRLOQXNB-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
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920001875 Ebonite Polymers 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 101100208721 Mus musculus Usp5 gene Proteins 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229940117975 chromium trioxide Drugs 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-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
- 239000006185 dispersion Substances 0.000 description 1
- YMRYNEIBKUSWAJ-UHFFFAOYSA-N ditert-butyl benzene-1,3-dicarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC(C(=O)OOC(C)(C)C)=C1 YMRYNEIBKUSWAJ-UHFFFAOYSA-N 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- QQYNRBAAQFZCLF-UHFFFAOYSA-N furan-maleic anhydride adduct Chemical compound O1C2C3C(=O)OC(=O)C3C1C=C2 QQYNRBAAQFZCLF-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
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- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
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- 229910010272 inorganic material Inorganic materials 0.000 description 1
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- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
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- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
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- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
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- 239000005022 packaging material Substances 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
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- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
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Description
本発明は、不飽和カルボン酸無水物によつてグ
ラフト変性された特定の耐衝撃性プロピレン系重
合体、またはこれと未変性オレフイン系重合体と
の混合物と充填剤とを混練してなる実用物性に優
れた強化ポリオレフイン組成物に関するものであ
る。
周知のように、ポリエチレンやポリプロピレン
などのポリオレフインは優れた物理的および化学
的性質、機械的性質、成形加工性等を有している
ことおよび安価であることと相俟つて、その用途
は多岐に亘つている。しかしながら、これらのポ
リオレフインをエンジニアリングプラスチツクと
して使用する場合には、機械的強度、寸法安定
性、耐熱性、耐寒性などが不十分であり、その使
用目的に耐えない場合が多い。このため、従来か
らポリオレフインの強化方法が重要な研究対象に
なつており、現在までに多くの提案がなされてい
る。その中で注目される有用な方法としては、ポ
リオレフインにガラス繊維などの繊維状物質また
は各種無機充填剤を加えることにより上記の物性
を改良する方法がある。しかし、この方法では充
填剤とポリオレフインとの接着性が悪く、その補
強効果が十分でない。このため、従来からポリオ
レフインを不飽和カルボン酸またはその無水物な
どでグラフト変性し、極性基を導入することによ
つて接着性を付与する方法が数多く提案されてい
る。例えば、ポリオレフインを特定量の無水マレ
イン酸および有機過酸化物の存在下に、押出機中
で特定の条件下に溶融混練することによつて得ら
れた変性ポリオレフインとガラス系補強材あるい
はこれらと未変性ポリオレフインとからなる強化
ポリオレフインの製造法（特公昭51−10265号、
特公昭51−29183号）、また無水マレインなどの不
飽和カルボン酸無水物で変性されたポリオレフイ
ンとガラス繊維あるいは無機充填剤および未変性
ポリオレフインとからなる組成物（特開昭49−
13244号、特開昭49−109432号、特開昭50−76149
号）あるいはこれらの組成物にさらに酸化マグネ
シウムなど金属酸化物等を添加した組成物（特開
昭50−10837号、特開昭52−121059号）、結晶性ポ
リオレフイン、線状無定形ゴム状弾性体およびガ
ラス繊維からなる組成物（特開昭52−8054号）ま
た結晶性プロピレン−エチレン共重合体をアクリ
ル酸やメタクリル酸で変性して得られる重合体を
未変性の結晶性ポリオレフインおよびガラス繊維
とからなる強化ポリオレフイン組成物（特開昭53
−130743号）等が知られている。
これらの変性ポリオレフインのベースとして、
例えばポリプロピレン、プロピレン−エチレンラ
ンダム共重合体、プロピレン−エチレンブロツク
共重合体などのプロピレン系重合体が一般に用い
られていることも公知である。
しかしながら、本発明者らの詳細な検討結果か
ら、前記のような優れた機械的性質、寸法安定
性、耐熱性、耐寒性等を有する強化ポリオレフイ
ン組成物を得るには、さらにベース樹脂であるプ
ロピレン系重合体の種類や変性重合体の構造およ
び物性を特定し、さらに特定の酸化マグネシウム
を添加する必要のあることがわかつた。また、変
性剤に関しても上記の特開昭53−130743号のよう
なアクリル酸やメタクリルを用いた場合には、変
性物の熱安定性が悪く、とくに250℃以上の温度
で成形加工した場合には分解発泡が激しく、実用
に供するものは得がたい。この原因はグラフト重
合に際して必然的に生成するアクリル酸やメタク
リル酸の低分子量重合体の熱分解によるものと考
えられる。
このような検討結果から、従来品よりも格段に
優れた強化ポリオレフイン組成物を得るには、変
性に用いるプロピレン系重合体の種類を選定する
ことは勿論のこと、変性剤の種類および変性樹脂
の構造と物性を特定する必要のあることが明らか
になり、本発明を完成するに至つた。
すなわち、本発明の目的は機械的強度、耐熱
性、耐寒性、寸法安定性等の実用性能において、
従来品に比べ格段に優れた強化ポリオレフイン組
成物を提供するところにある。本発明の強化ポリ
オレフイン組成物は、以下に詳述するような特性
値を有しており、車輌部品、船舶部品、航空機部
品、建築材料、電気部品、家具、事務用機器類、
包装材料その他複合材料として広く使用できる。
本発明は、プロピレン−エチレン系ブロツク共
重合体をラジカル開始剤の存在下に、不飽和カル
ボン酸無水物でグラフト変性して得られる変性重
合体(A)または該変性重合体と未変性オレフイン系
重合体との混合物(B)に、充填剤(C)およびヨード吸
着量が20mg・Ｉ／ｇ・MgO以上の酸化マグネシ
ウム(D)を加え、混練してなる強化ポリオレフイン
組成物において、
(1) 変性重合体(A)中の不飽和カルボン酸無水物の
含有量が0.001〜２重量％、また該変性重合体
と未変性オレフイン系重合体との混合物(B)中の
不飽和カルボン酸無水物の含有量が0.001重量
％以上であること、
(2) 変性重合体(A)の形態が連続相と分散相の不均
一構造からなり、連続相の主成分が結晶性プロ
ピレン系重合体、また分散相の主成分がエチレ
ン含有量20〜90重量％のエチレン−プロピレン
ランダム共重合体であり、かつ、連続相／分散
相の重量比が95／５〜55／45であること、
(3) 上記(2)の分散相の重量平均粒子径が0.5〜
10μ、とくに好ましくは１〜5μであること、
(4) グラフト変性前のプロピレン−エチレン系ブ
ロツク共重合体の連続相形成成分である結晶性
プロピレン系重合体の極限粘度が１〜５、また
分散相形成成分であるエチレン−プロピレンラ
ンダム共重合体の極限粘度が２〜10であり、か
つ、分散相形成成分の極限粘度が連続相形成成
分の極限粘度よりも大きいこと、
ことを特徴とする強化ポリオレフイン組成物に関
するものである。
本発明において、変性重合体(A)のベース重合体
として使用されるプロピレン−エチレン系ブロツ
ク共重合体は、一般にチーグラーナツタ型触媒を
用い、溶媒の存在下または不存在下にプロピレン
−エチレン系モノマーをブロツク共重合させて得
られる。具体的には、炭化水素溶媒中、液化プロ
ピレン中、あるいは気相中において、まずプロピ
レンを重合させてポリピレン部分をつくり、続い
てプロピレンとエチレンのモノマー混合物を一定
の組成あるいは組成を変えつつ共重合させること
によつて製造される。重合は回分式または連続式
によつて行なわれる。なお、このブロツク共重合
において、必要に応じてブテン−１、ペンテン−
１、４−メチルペンテン−１などのプロピレンお
よびエチレンと共重合可能な他のモノマーを共重
合させることもできる。
このようにして得られるプロピレン−エチレン
系ブロツク共重合体は、形態的には連続相形成成
分と粒子分散相形成成分とからなるものであり、
該連続相形成成分の主成分が結晶性プロピレン系
重合体、また分散相形成成分の主成分がエチレン
含有量20〜90重量％、好ましくは40〜80重量％の
エチレン−プロピレンランダム共重合体からなる
ものである。ここで、該結晶性プロピレン系重合
体／エチレンプロピレンランダム共重合体の重量
比は95／５〜55／45、好ましくは90／10〜60／40
である。これらの組成はグラフト変性後も実質的
に同一であるが、最終的には連続相と分散相の不
均一構造を形成する。ここで、プロピレン−エチ
レン系ブロツク共重合は単なる結晶性プロピレン
系重合体とエチレン−プロピレンランダム共重合
体との混合物とは異なるものである。また、該分
散相内には連続相成分である結晶性プロピレン系
重合体を２次構造として包含しうる。
上記のプロピレン−エチレン系ブロツク共重合
体の連続相形成成分である結晶性プロピレン系重
合体の極限粘度は１〜５、また分散相形成成分で
あるエチレン−プロピレンランダム共重合体の極
限粘度は２〜10の範囲であり、かつ、該分散相形
成成分であるエチレン−プロピレンランダム共重
合体の極限粘度が該連続相形成成分である結晶性
プロピレン系重合体の極限粘度よりも大きいこと
が必要である。
これらを特定することによつて、グラフト率が
高く、接着性ならびに樹脂強度の高い変性重合体
が得られる。ここで、結晶性プロピレン系重合体
部およびエチレン−プロピレンランダム共重合体
部の極限粘度が、それぞれ１および２未満では強
度が低く、一方これらの値がそれぞれ５および10
より大きくなると加工性が悪くなる。
変性重合体(A)は、上記のプロピレン−エチレン
系ブロツク共重合体をラジカル開始剤の存在下、
溶融混練法、溶液変性法、非溶媒中に重合体粉末
を分散させた不均一系変性法、該重合体の融点以
下の温度で無溶媒あるいは少量の溶媒存在下に粉
末状態で変性する方法等によつて製造することが
できる。これらのうち、高性能変性重合体を効率
よく、経済的に製造する方法として、溶融混練法
が推奨される。
グラフト変性によつて得られる変性重合体(A)中
の不飽和カルボン酸無水物の含有量は0.001〜２
重量％に限定されるが、0.01〜１重量％の範囲が
好ましい。ここで、不飽和カルボン酸無水物の含
有量が0.001重量％では接着性においてさしたる
改良効果はなく、一方２重量％よりも多くして
も、それ以上に顕著な効果はなく、また製造面で
も困難となる。また、変性重合体(A)のメルトイン
デツクスは１〜300のものが好ましく、さらに、
変性重合体(A)のメルトインデツクスおよびダイ・
スウエルの値は、両者ともにグラフト変性前のベ
ース重合体の値よりも大きいことが望ましい。こ
れらを規制することによつて、強度および接着が
ともに優れた変性重合体が得られる。なお、ベー
ス重合体のメルトインデツクスは15以下のものが
好ましい。ここで、ダイ・スウエルは主としてグ
ラフト変性に際して添加するラジカル開始剤の添
加量と温度や時間などの変性条件によつて容易に
制御しうる。このように、ダイ・スウエルを制御
して得られる変性重合体は、変性時にグラフト反
応と競合して起こる該ベース共重合体の結晶性プ
ロピレン系重合体部分の適度な分解反応による分
子量低下ならびにエチレン−プロピレンランダム
共重合体部分の適度な架橋反応によつて、レオロ
ジー的性質が改良されるため、前述のような高性
能を示すものと考えられる。
さらに、変性重合体(A)またはこれと未変性オレ
フイン系重合体との混合物(B)に、充填剤(C)および
ヨード吸着量が20mg・Ｉ／ｇ・MgO以上の酸化
マグネシウム(D)を加え、混練してなる強化ポリオ
レフインにおいて、変性重合体(A)の分散相の重量
平均粒子径は0.5〜10μ、好ましくは１〜5μの範囲
である。また、強化ポリオレフインの製造に際し
て、未変性オレフイン系重合体として変性重合体
のベース重合体やエチレン−プロピレンランダム
共重合体ゴム等が配合される場合には、それらの
粒子径も上記の範囲内とすることが望ましい。
ここで、該粒子径が0.5μ未満では衝撃強度およ
び剛性がともに低く、一方10μを超えた粗大粒子
となると衝撃強度が低下する傾向にある。この粒
子径は混練条件によつて変化するので、その条件
により制御しうる。
上記のように、変性重合体のベース重合体およ
びその変性重合体の構造および物性を特定するこ
とにより、接着性が格段に優れた変性重合体が得
られる。また、この変性重合体を用いることによ
り、衝撃強度と剛性とのバランスが高度に保持さ
れ、かつ、耐熱性、耐寒性、寸法安定性等に優れ
た高性能の強化ポリオレフインが得られる。な
お、上記の各特性値の測定法については後述す
る。
グラフト変性に際して用いられる不飽和カルボ
ン酸無水物としては、例えば、無水マレイン酸、
無水イタコン酸、無水シトラコン酸、無水ハイミ
ツク酸、ビシクロ（２，２，２）オクタ−５−エ
ン−２，３−ジカルボン酸無水物、４−メチルシ
クロヘキサ−４−エン−１，２−ジカルボン酸無
水物、１，２，３，４，５，８，９，10−オクタ
ヒドロナフタレン−２，３−ジカルボン酸無水
物、ビシクロ（２，２，１）オクタ−７−エン−
２，３，５，６−テトラカルボン酸−２，３，
５，６−ジ無水物、７−オキサビシクロ（２，
２，１）ヘプタ−５−エン−２，３−ジカルボン
酸無水物などが挙げられる。これらのうちでも、
とくに無水マレイン酸が好ましく使用される。ま
た、必要に応じてこれらの不飽和カルボン酸と共
重合しうるモノマー、例えばこれらのカルボン酸
無水物から誘導されるエステル、アミド、酸など
の誘導体、（メタ）アクリル酸、（メタ）アクリル
酸メチル、（メタ）アクリル酸エチルなどの（メ
タ）アクリル酸誘導体、酢酸ビニルなどのビニル
エステル、スチレン系モノマー、アクリロニトリ
ル系モノマー、ビニルシラン系モノマー等を用い
ることもできる。
変性重合体の製造に際して添加されるラジカル
開始剤は公知のものが使用できる。たとえば、
２，2′−アゾビスイソブチロニトリル、２，2′−
アゾビス（２，４，４−トリメチルバレロニトリ
ル）などのアゾ系化合物、メチルエチルケトンパ
ーオキサイド、シクロヘキサノンパーオキサイ
ド、３，５，５−トリメチルシクロヘキサン、
２，２−ビス（ｔ−ブチルパーオキシ）ブタン、
ｔ−ブチルハイドロパーオキサイド、クメンハイ
ドロパーオキサイド、ジイソプロピルベンゼンハ
イドロパーオキサイド、２，５−ジメチルヘキサ
ン−２，５−ジハイドロパーオキサイド、ジｔ−
ブチルパーオキサイド、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−３、ラウロイルパーオキサイド、
３，５，５−トリメチルヘキサノイルパーオキサ
イド、ベンゾイルパーオキサイド、ｔ−ブチルパ
ーアセテート、ｔ−ブチルパーオキシイソブチレ
ート、ｔ−ブチルパーオキシピバレート、ｔ−ブ
チルパオキシ−２−エチルヘキサノエート、ｔ−
ブチルパーオキシ−３，５，５−トリメチルヘキ
サノエート、ｔ−ブチルパーオキシラウレート、
ｔ−ブチルパーオキシベンゾエート、ジｔ−ブチ
ルジパーオキシイソフタレート、２，５−ジメチ
ル−２，５−ジ（ベンゾイルパーオキシ）ヘキサ
ン、ｔ−ブチルパーオキシマレイン酸、ｔ−ブチ
ルパーオキシイソプロピルカーボネート、ポリス
チレンパーオキサイドなど各種有機過酸化物が挙
げられる。これらのうち、100℃において１分以
上好ましくは５分以上の分解の半減期を有する有
機過酸化物がとくに効果的に使用される。また、
これらのラジカル開始剤は２種以上のものを混合
して用いることができる。これらのラジカル開始
剤の添加量は、グラフト反応率およびラジカル開
始剤による結晶性プロピレン系重合体の分解によ
る分子量低下ならびに変性重合体のダイ・スウエ
ルとの関係から該ベース共重合体100重量部あた
り0.001〜２重量部の範囲が好ましい。とくに好
ましい添加量は0.05〜１重量部である。
グラフト変性重合体(A)は前記のベース共重合
体、不飽和カルボン酸無水物およびラジカル開始
剤の混合物を溶融混練することによつて容易に製
造することができる。この場合、ベース共重合体
への不飽和カルボン酸無水物およびラジカル開始
剤の分散を良くするために、これらを少量の良溶
剤たとえば、アセトン、芳香族炭化水素、ハロゲ
ン化炭化水素等に溶かした溶液として添加するこ
ともできる。溶融混練は一般にスクリユー押出
機、バンバリーミキサー、ニーダー等を用いて行
なわれる。この際の混練温度は通常170〜300℃、
好ましくは190〜250℃、時間は0.5〜10分間の範
囲が適当である。また、反応雰囲気は空気中でも
よいが、窒素や二酸化炭素などの不活性ガス中が
望ましい。なお、得られた変性重合体中に含まれ
る未反応の不飽和カルボン酸無水物や低分子量の
副生物を除去するため、溶融下に真空引きした
り、溶剤抽出等を行うこともできる。
上記の方法で製造された変性重合体(A)と未変性
オレフイン系重合体との混合物(B)も本発明の強化
ポリオレフイン組成物の成分として使用できる。
ここで、未変性オレフイン系重合体としては、例
えば前記の変性重合体のベースであるプロピレン
−エチレン系共重合体、結晶性または非結晶性ポ
リプロピレン、結晶性または非結晶性エチレン−
プロピレンランダム共重合体、ポリブテン−１、
ポリ−４−メチルペンテン−１、プロピレン−ブ
テン−１共重合体、低密度または高密度ポリエチ
レン、エチレン−酢酸ビニル共重合体、エチレン
−（メタ）アクリル酸共重合体、エチレン−（メ
タ）アクリル酸部分金属塩共重合体、エチレン−
（メタ）アクリル酸−（メタ）アクリル酸エステル
共重合体、エチレン−（メタ）アクリル酸メチル
共重合体、エチレン−（メタ）アクリル酸エチル
共重合体、エチレン−グリシジル（メタ）アクリ
レート共重合体、エチレン−アミノアルキル（メ
タ）アクリレート共重合体、エチレン−ビニルア
ルコール共重合体、エチレン−スチレン共重合体
など、各種オレフインの単独重合体および共重合
体が挙げられる。また、これらのオレフイン系重
合体は２種類以上を混合して用いることができ
る。これらのオレフイン系重合体の添加量は、補
強効果の観点から、変性重合体と未変性オレフイ
ン系重合体との混合物中の不飽和カルボン酸無水
物の含有量が0.001重量％以上となるように配合
することが必要である。
本発明の強化ポリオレフイン組成物は該変性重
合体(A)またはこれと未変性オレフイン系重合体と
の混合物(B)に、充填剤(C)さらに特定の酸化マグネ
シウム(D)を配合することによつて製造されたもの
である。充填剤の好ましい添加量は該(A)または(B)
100重量部あたり一般に１〜200重量部である。充
填剤量のさらに好ましい範囲は５〜100重量部で
ある。ここで、充填剤の量が１重量部より少ない
と強化に関してさしたる効果はなく、一方200重
量部以上では逆に機械的強度が低下したり、成形
加工が困難となる傾向がある。
充填剤としては、例えばアルミニウム、鉄、ニ
ツケル、コバルト、クロム、亜鉛、チタン、錫、
銅などの金属の単体あるいはこれらの酸化物、合
金類、また、ガラス、セラミツクス、石綿、スレ
ート、石こう、石、砂、炭酸カルシウム、硫酸バ
リウム、タルク、シリカ、雲母、窒化ホウ素、ジ
ルコニア、炭素、炭化ケイ素、チタン酸カリウム
などの天然または合成無機充填剤、ならびにポリ
アミド、ポリイミド、ポリエステル、ポリフエニ
レンオキサイド、ポリアセタール樹脂、フエノー
ル樹脂、メラミン樹脂、アルキド樹脂、ウレタン
樹脂、エポキシ樹脂、ジアリールフタレート樹
脂、尿素樹脂、エボナイト、ウール、皮革、竹、
木材など各種の天然または合成高分子化合物等が
挙げられる。これらは、一般に0.01〜50μの微粉
末、あるいは粒状物、小片、フレーク、繊維状等
使用目的に応じていかなる大きさおよび形状をも
とりうる。また、これらの充填剤は２種類以上を
混合して用いることもできる。さらに、これらの
充填剤は各種の方法で表面処理したものも使用で
き、この処理充填剤の使用によつて特に強靭な強
化ポリオレフインが得られる。
また、変性重合体(A)または該変性重合体と未変
性オレフイン系重合体との混合物(B)と、充填剤(C)
とからなる強化ポリオレフイン組成物の製造に際
し、これらに特定の酸化マグネシウムを加える
と、とくに高性能の強化ポリオレフイン組成物が
得られる。また、酸化マグネシウムは、一般に受
酸剤として知られており、射出成形加工時におけ
る金属腐蝕を抑える効果もある。ここで、とくに
メジアン径が10μ以下で、かつヨード吸着量が20
mg・Ｉ／ｇ・MgO以上の酸化マグネシウムが有
効である。また、酸化マグネシウムの添加量は、
該変性重合体(A)または該変性重合体と未変性オレ
フイン系重合体との混合物(B)100重量部あたり0.1
〜10重量部の範囲が好適であり、さらに該変性重
合体に含まれる不飽和カルボン酸無水物に対し、
当モル以上添加することが望ましい。
なおこの強化ポリオレフイン組成物に必要に応
じポリブタジエンゴム、スチレン−ブタジエンブ
ロツク又はランダム共重合体、アクリロニトリル
−ブタジエン共重合体、ポリスチレン、AS樹脂、
ABS樹脂、MMA樹脂、塩化ビニル樹脂等他の
高分子化合物を添加することもできる。
本発明の強化ポリオレフイン組成物は任意の方
法すなわち、次のいくつかの方法で製造できる。
例えば、変性重合体、充填剤および特定の酸化マ
グネシウム、さらには未変性オレフイン系重合体
をドライブレンド法で混合したのち、押出機、バ
ンバリーミキサー、ニーダー、ロール等で溶融混
練する方法；あるいは上記の混合物を直接成形加
工する方法；また、あらかじめ変性重合体と未変
性オレフイン系重合体および特定の酸化マグネシ
ウムとからなる混練組成物をつくり、これと充填
剤とを混合する方法；あらかじめ変性重合体と充
填剤および特定の酸化マグネシウムとからなる混
練組成物をつくり、これと未変性オレフイン系重
合体とを混練する方法；さらには変性重合体の一
部を用い、溶液塗装法等によつて充填剤の表面を
被覆したのち、残部の変性重合体またはこれに未
変性オレフイン系重合体を加えて混練する方法な
どによつて製造できる。
本発明の強化ポリオレフイン組成物を用い、公
知の成形加工技術を適用することにより各種成形
品を製造することができる。また、本発明の強化
ポリオレフイン組成物は接着性にも優れているた
め、金属をはじめ各種無機材料および各種天然ま
たは合成高分子材料と積層体をつくることもでき
る。このようにして得られる成形品は、前述のよ
うに各種産業分野において広く使用することがで
き、その利用価値は極めて大である。
なお、本発明の強化ポリオレフイン組成物に対
し、必要に応じて酸化防止剤、熱安定剤、光安定
剤、造核剤、滑剤、可塑剤、帯電防止剤、無機ま
たは有機系着色剤、架橋剤、発泡剤、螢光剤、防
錆剤などの各種添加剤を該組成物の製造工程ある
いはその後の成形加工工程において添加すること
ができる。
以下に、本発明を実施例でもつて説明するが、
本発明はこれによつて限定されるものではない。
なお、本発明において示した各測定値はそれぞ
れ次の方法で測定して求めたものである。
(1) 変性重合体中の不飽和カルボン酸無水物含有
量
変性重合体をキシレンに溶解後、アセトンで
沈澱させて精製した試料について、アルカリ滴
定法で求めた。
(2) ベースのプロピレン−エチレン系ブロツク共
重合体中の結晶性プロピレン系重合体およびエ
チレン−プロピレンランダム共重合体の組成比
それぞれ重合過程において、前段で行なわれ
る結晶性プロピレン系重合体部（Ｐ部）の重合
量および後段で行なわれるエチレン−プロピレ
ンランダム共重合体部（EP部）の重合量を重
合における物質収支から求めた。
(3) エチレン−プロピレンランダム共重合体部
（EP部）のエチレン含有量
ベースのプロピレン−エチレンブロツク共重
合体の０−ジクロルベンゼン溶液を 13C−
NMR（日本電子製、FX−100型）にて、135
℃、積算回数2000〜3000回、パルス間隔45゜パ
ルス、10秒間隔の条件下に測定し、たとえば
G.J.Ray etal.、Makromol.10、773（1977）に
記載の方法に基づいてエチレン含有量を求め
た。この測定値および上記(2)項で求めたポリプ
ロピレン部（Ｐ部）／エチレン−プロピレンラ
ンダム共重合体（EP部）の組成比から、エチ
レン−プロピレンランダム共重合体のエチレン
含有量を算出した。
(4) ベースのプロピレン−エチレン系ブロツク共
重合体の極限粘度
ベースのプロピレン−エチレン系ブロツク共
重合体の製造においてまず、前段で行なわれる
結晶性ポリプロピレン部の極限粘度〔η〕ｐを
測定し、引続きエチレン−プロピレンランダム
共重合体部の重合を行なつて得られる最終重合
体の極限粘度〔η〕cpを測定する。ここでエチ
レン−プロピレンランダム共重合体の極限粘度
〔η〕EPは次式の関係が成立すると仮定して求め
た値である。
〔η〕EP＝１／fEP〔η〕CP−（１／fEP−１）〔η〕
P
ここで、fEPは全重合体中のエチレン−プロ
ピレンランダム共重合体の組成分率である。な
お、極限粘度はテトラリン溶液中、135℃で測
定した値で、その単位はdl／ｇである。
(5) エチレン−プロピレンランダム共重合体の重
量平均粒子径
変性重合体またはその組成物の成形品を液体
窒素で冷却し、その冷凍破断面を三酸化クロム
水溶液で処理したのち、その処理表面を二段レ
プリカ法にて電子顕微鏡写真を撮影し、次式に
より重量平均粒子径ｗを算出した。
ｗ＝Σnidi4／Σnidi3
ただし、niは直径がdiである粒子の個数分率
である。なお、写真上に現われた粒子が円形で
ない場合の粒子（たとえば楕円形）の大きさ
は、その最長径と最短形の算術平均値をもつて
１個の粒子径とした。
(6) メルトインデツクス（MI）
JIS Ｋ−7210−1977の方法に準拠し、2.16Kg
の荷重下、230℃で測定した。測定値の単位は
ｇ／10minである。
(7) ダイ・スウエル（DS）
毛細管の内径0.77mm、長さ25.55mm、入口角
度90゜、外径9.48mmのオリフイスを用い、これ
を内径9.55mmのレオメーター筒に挿入し、剪断
速度10〜100sec-1の範囲において一定速度で作
動するプランジヤーにて所定温度に加熱した重
合体を押出し、次式によつてダイ・スウエル
（DS）を求めた。本実施例では温度204℃、剪
断速度50sec-1のときのダイ・スウエルを示す。
DS＝（D1／D0）2
ただし、D0は毛細管の直径、D1は押出物の
直径である。
(8) 酸化マグネシウムのメジアン径
光透過式粉度分布測定器により、エチルアル
コールを媒体として測定した。メジアン径は、
積算粉度分布曲線の50％粒径をもつて表わされ
た値である。
(9) 酸化マグネシウムのヨード吸着量
ヨードの四塩化炭素溶液（0.1N）に試料を
入れ、密栓して30分間振とうし、５分間静置
後、上澄液のみを0.03N−ヨードカリ溶液に加
え、0.05N−チオ硫酸ナトリウムにて滴定して
求めた。
(10) ノツチ付アイゾツト衝撃強度
ASTM Ｄ−256−56に準拠し、20℃および
−30℃で測定した。
(11) 落球衝撃試験
厚さ２mmの射出成形板上に、20℃において、
重さ200ｇの鋼球を落下させ、板が破壊したと
きの鋼球の落下高さで表わした。
(12) 引張強度
ASTM Ｄ−638−60Tに準拠し、20℃で測
定した。
(13) 曲げ強度および曲げ剛性度
ASTM Ｄ−747−58T準拠し、20℃で測定
した。
(14) 熱変形温度
ASTM Ｄ−648−45Tに準拠して測定した。
(15) 寸法安定性（そり）
円板の中心部にゲートを有する射出成形金型
にて、直径200mm、厚さ２mmの円板を作製した。
この円板を水平板上に置き、それを側面から見
たときの円板の外周下面と水平板との間に間〓
がある場合、その間〓の最小部をl1mm、また最
大部をl2mmとし、次式によつてそりを求めた。
そり（％）＝（l1−l2）／200×２×100
実施例 １
ベース重合体として、メルトインデツクス２、
ダイ・スウエル1.55、連続相および分散相の極限
粘度がそれぞれ1.6および5.2、連続相／分散相の
重量比が70／30および分散相のエチレン含有量が
50重量％であるプロピレン−エチレンブロツク共
重合体粉末を用いた。この共重合体100重量部、
無水マレイン酸粉末0.7重量部およびｔ−ブチル
パーオキシラウレート0.5重量部をヘンシエルミ
キサーで混合したのち、この混合物を53mmφ二軸
押出機にて、温度220℃、平均滞留時間１分間で
溶融混練し、グラフト変性重合体ペレツトを得
た。この変性重合体の無水マレイン酸含有量およ
び物性を第１表に示す。
この変性重合体15重量部、メルトインデツクス
８の結晶性ポリプロピレン55重量部、アミノシラ
ン系化合物で表面処理した直径約10μ、長さ約６
mmのガラス繊維30重量部、酸化マグネシウム（メ
ジアン径2.1μ、ヨード吸着量150mg・Ｉ／ｇ・
MgO、協和化学工業製）２重量部、イルガノツ
クス1010（チバガイギー社製）0.2重量部およびス
テアリン酸カルシウム0.05重量部をヘンシエルミ
キサーで混合したのち、90mmφ押出機にて230℃
で混練し、ガラス繊維強化ポリオレフインを得
た。この組成物を230℃で射出成形し、各種の物
性を測定した。この結果を第２表に示す。
比較例 １〜２
実施例１において、メジアン径3.2μ、ヨード吸
着量５mg・Ｉ／ｇ・MgOの酸化マグネシウムを
用いた場合、および酸化マグネシウムを用いなか
つた場合以外は、実施例１の方法を繰り返した。
この結果を第２表に示す。
実施例 ２
ベース重合体として、第１表に示す組成および
物性を有するプロピレン−エチレンブロツク共重
合体を用いた。この共重合体100重量部、無水マ
レイン酸0.3重量部およびｔ−ブチルパーオキシ
イソプロピルカーボネート0.2重量部からなる混
合物を65mmφ一軸押出機にて、220℃、平均滞留
時間２分間で溶融混練し、第１表に示す変性重合
体を得た。以下、酸化マグネシウム（メジアン径
2.7μ、ヨード吸着量30mg・Ｉ／ｇ・MgO）を用
いた以外は、実施例１の方法を繰返した。この結
果を第２表に示す。
比較例 ３〜４
実施例２において、メジアン径3.2μ、ヨード吸
着量５mg・Ｉ／ｇ・MgOの酸化マグネシウムを
用いた場合および酸化マグネシウムを用いなかつ
た場合以外は、実施例２の方法を繰り返した。こ
の結果を第２表に示す。
比較例 ５
ベース重合体として、メルトインデツクス２、
ダイ・スウエル2.36の結晶性プロピレン単独重合
体を用いた以外は、実施例１の方法を繰り返し
た。この結果を第１表および第３表に示す。
比較例 ６〜13
ベース重合体として、それぞれ第１表に示すプ
ロピレン−エチレンブロツク共重合体を用い、酸
化マグネシウムを添加しなかつた以外は、実施例
２の方法を繰り返した。この結果を第１表および
第３表に示す。
比較例 14
実施例２において、変性重合体の製造に際し
て、無水マレイン酸の添加量を0.0007重量部とし
た以外は、実施例２の方法を繰り返した。この結
果を第１表および第３表に示す。
比較例 15
実施例２で得られた変性重合体を0.3重量部お
よび結晶性ポリプロピレンを69.7重量部添加した
以外は、実施例２の方法を繰り返した。この結果
を第３表に示す。
比較例 16
メルトインデツクス１の結晶性ポリプロピレン
70重量部およびムーニー粘度40、エチレン含有量
50重量％のエチレン−プロピレンランダム共重合
体ゴム30重量部からなる組成物を変性重合体用の
ベース重合体として用いた以外は、実施例１の方
法を繰り返した。この結果を第１表および第３表
に示す。
実施例 ３
第２表に示した実施例１の配合処方物に、さら
にエチレン含有量50重量％、ムーニー粘度40のエ
チレン−プロピレン共重合体ゴム10重量部添加し
た以外は実施例１の方法を繰り返した。得られた
強化ポリオレフイン中のエチレン−プロピレン共
重合体（後で加えたエチレン−プロピレン共重合
体ゴムを含む）の重量平均粒径は3.7μであつた。
また、強化ポリオレフインのメルトインデツクス
は２、ノツチ付アイゾツト衝撃強度は20℃および
−30℃でそれぞれ15および９Kg−cm／cm2、落球衝
撃強度は17cm、引張強度870Kg／cm、曲げ強度950
Kg／cm2、曲げ剛性度53000Kg／cm2、熱変形温度150
℃、そり２％であり、実施例１に比べ、剛性はや
や低下するも、耐衝撃性および寸法安定性の良好
なものが得られた。
実施例４〜７および比較例17〜29
それぞれ、第４表に示した各種充填剤配合処方
品をバンバリーミキサーにて190℃で３分間混練
したのち、押出機を通して組成物ペレツトを得
た。この組成物を200℃で射出成形し、物性を測
定した。この結果を第３表に示す。
以上、各実施例で示したように、本発明の強化
ポリオレフインは非常に優れた物性を有している
ことがわかる。
The present invention provides practical physical properties obtained by kneading a specific impact-resistant propylene polymer graft-modified with an unsaturated carboxylic acid anhydride, or a mixture of this and an unmodified olefin polymer, and a filler. The present invention relates to a reinforced polyolefin composition with excellent properties. As is well known, polyolefins such as polyethylene and polypropylene have excellent physical and chemical properties, mechanical properties, moldability, etc., and are inexpensive, so their uses are wide-ranging. It's crossing. However, when these polyolefins are used as engineering plastics, they often have insufficient mechanical strength, dimensional stability, heat resistance, cold resistance, etc., and cannot withstand the intended use. For this reason, methods for strengthening polyolefins have been an important research subject, and many proposals have been made to date. Among the useful methods that have attracted attention, there is a method of improving the above-mentioned physical properties by adding fibrous substances such as glass fibers or various inorganic fillers to polyolefin. However, in this method, the adhesiveness between the filler and the polyolefin is poor, and the reinforcing effect thereof is not sufficient. For this reason, many methods have been proposed for imparting adhesive properties by graft-modifying polyolefins with unsaturated carboxylic acids or their anhydrides and introducing polar groups. For example, a modified polyolefin obtained by melt-kneading a polyolefin in the presence of a specific amount of maleic anhydride and an organic peroxide under specific conditions in an extruder and a glass-based reinforcing material, or a glass-based reinforcing material obtained by melt-kneading the polyolefin in the presence of a specific amount of maleic anhydride and an organic peroxide, or a glass-based reinforcing material or an unmixed material. Method for producing reinforced polyolefin consisting of modified polyolefin (Special Publication No. 10265/1989,
Japanese Patent Publication No. 51-29183), and compositions comprising polyolefins modified with unsaturated carboxylic acid anhydrides such as maleic anhydride, glass fibers or inorganic fillers, and unmodified polyolefins (Japanese Patent Publication No. 49-298)
No. 13244, JP-A-49-109432, JP-A-50-76149
) or compositions in which metal oxides such as magnesium oxide are further added to these compositions (JP-A-50-10837, JP-A-52-121059), crystalline polyolefins, linear amorphous rubber-like elastic (Japanese Patent Application Laid-Open No. 52-8054) A composition consisting of a polymer obtained by modifying a crystalline propylene-ethylene copolymer with acrylic acid or methacrylic acid, and an unmodified crystalline polyolefin and glass fiber. A reinforced polyolefin composition consisting of
-130743) etc. are known. As a base for these modified polyolefins,
It is also known that propylene-based polymers such as polypropylene, propylene-ethylene random copolymers, propylene-ethylene block copolymers, etc. are commonly used. However, from the detailed study results of the present inventors, it has been found that in order to obtain a reinforced polyolefin composition having excellent mechanical properties, dimensional stability, heat resistance, cold resistance, etc. as described above, it is necessary to further add propylene as a base resin. We identified the type of polymer and the structure and physical properties of the modified polymer, and found that it was necessary to add a specific magnesium oxide. In addition, when acrylic acid or methacrylic acid is used as a modifying agent as in JP-A No. 53-130743, the thermal stability of the modified product is poor, especially when molded at a temperature of 250°C or higher. Because of severe decomposition and foaming, it is difficult to obtain a product that can be put to practical use. The cause of this is thought to be the thermal decomposition of low molecular weight polymers of acrylic acid and methacrylic acid that are inevitably produced during graft polymerization. From these study results, in order to obtain a reinforced polyolefin composition that is significantly superior to conventional products, it is necessary to select not only the type of propylene polymer used for modification, but also the type of modifier and the modified resin. It became clear that it was necessary to specify the structure and physical properties, leading to the completion of the present invention. That is, the purpose of the present invention is to improve practical performance such as mechanical strength, heat resistance, cold resistance, and dimensional stability.
The purpose of the present invention is to provide a reinforced polyolefin composition that is significantly superior to conventional products. The reinforced polyolefin composition of the present invention has the characteristic values detailed below, and is used for vehicle parts, ship parts, aircraft parts, building materials, electrical parts, furniture, office equipment,
Can be widely used as packaging materials and other composite materials. The present invention relates to a modified polymer (A) obtained by graft-modifying a propylene-ethylene block copolymer with an unsaturated carboxylic acid anhydride in the presence of a radical initiator, or the modified polymer and an unmodified olefin-based copolymer. In a reinforced polyolefin composition obtained by adding a filler (C) and magnesium oxide (D) with an iodine adsorption amount of 20 mg I/g MgO or more to a mixture with a polymer (B) and kneading the mixture, (1) The content of unsaturated carboxylic anhydride in the modified polymer (A) is 0.001 to 2% by weight, and the unsaturated carboxylic anhydride in the mixture (B) of the modified polymer and unmodified olefin polymer. (2) The modified polymer (A) has a heterogeneous structure of a continuous phase and a dispersed phase, and the main component of the continuous phase is a crystalline propylene polymer, or (3) The main component of the dispersed phase is an ethylene-propylene random copolymer with an ethylene content of 20 to 90% by weight, and the continuous phase/dispersed phase weight ratio is 95/5 to 55/45. The weight average particle diameter of the dispersed phase in (2) above is 0.5~
(4) The intrinsic viscosity of the crystalline propylene polymer, which is a continuous phase forming component of the propylene-ethylene block copolymer before graft modification, is 1 to 5, and the intrinsic viscosity is 1 to 5. Reinforcement characterized in that the intrinsic viscosity of the ethylene-propylene random copolymer as the phase forming component is 2 to 10, and the intrinsic viscosity of the dispersed phase forming component is greater than the intrinsic viscosity of the continuous phase forming component. The present invention relates to polyolefin compositions. In the present invention, the propylene-ethylene block copolymer used as the base polymer of the modified polymer (A) is generally prepared by using a Ziegler-Natsuta type catalyst to prepare the propylene-ethylene monomer in the presence or absence of a solvent. It is obtained by block copolymerization of Specifically, propylene is first polymerized to form a polypylene moiety in a hydrocarbon solvent, liquefied propylene, or gas phase, and then a monomer mixture of propylene and ethylene is copolymerized at a constant composition or while changing the composition. Manufactured by Polymerization is carried out batchwise or continuously. In addition, in this block copolymerization, butene-1, pentene-1,
Other monomers copolymerizable with propylene and ethylene, such as 1,4-methylpentene-1, can also be copolymerized. The propylene-ethylene block copolymer thus obtained is morphologically composed of a continuous phase-forming component and a particle-dispersed phase-forming component,
The main component of the continuous phase forming component is a crystalline propylene polymer, and the main component of the dispersed phase forming component is an ethylene-propylene random copolymer having an ethylene content of 20 to 90% by weight, preferably 40 to 80% by weight. It is what it is. Here, the weight ratio of the crystalline propylene polymer/ethylene propylene random copolymer is 95/5 to 55/45, preferably 90/10 to 60/40.
It is. Although these compositions remain substantially the same after graft modification, they ultimately form a heterogeneous structure of continuous and dispersed phases. Here, the propylene-ethylene block copolymer is different from a simple mixture of a crystalline propylene polymer and an ethylene-propylene random copolymer. Further, the dispersed phase may include a crystalline propylene polymer, which is a continuous phase component, as a secondary structure. The intrinsic viscosity of the crystalline propylene polymer, which is the continuous phase forming component of the above propylene-ethylene block copolymer, is 1 to 5, and the intrinsic viscosity of the ethylene-propylene random copolymer, which is the dispersed phase forming component, is 2. -10, and the intrinsic viscosity of the ethylene-propylene random copolymer that is the dispersed phase forming component is required to be larger than the intrinsic viscosity of the crystalline propylene polymer that is the continuous phase forming component. be. By specifying these, modified polymers with a high grafting rate, adhesive properties, and resin strength can be obtained. Here, when the intrinsic viscosity of the crystalline propylene polymer part and the ethylene-propylene random copolymer part are less than 1 and 2, respectively, the strength is low; on the other hand, when these values are 5 and 10, respectively,
The larger the size, the worse the workability. The modified polymer (A) is obtained by preparing the above propylene-ethylene block copolymer in the presence of a radical initiator.
Melt-kneading method, solution modification method, heterogeneous modification method in which polymer powder is dispersed in a non-solvent, method of modifying the polymer in a powder state without a solvent or in the presence of a small amount of solvent at a temperature below the melting point of the polymer, etc. It can be manufactured by. Among these, the melt-kneading method is recommended as a method for efficiently and economically producing high-performance modified polymers. The content of unsaturated carboxylic acid anhydride in the modified polymer (A) obtained by graft modification is 0.001 to 2
Although limited to % by weight, a range of 0.01 to 1% by weight is preferred. Here, if the content of unsaturated carboxylic acid anhydride is 0.001% by weight, there is no significant improvement effect on adhesion, while if the content is more than 2% by weight, there is no more significant effect, and also in terms of manufacturing. It becomes difficult. Further, the melt index of the modified polymer (A) is preferably 1 to 300, and further,
Melt index and die index of modified polymer (A)
It is desirable that both swell values be larger than the values of the base polymer before graft modification. By controlling these, a modified polymer with excellent strength and adhesion can be obtained. The melt index of the base polymer is preferably 15 or less. Here, die swell can be easily controlled mainly by adjusting the amount of radical initiator added during graft modification and modification conditions such as temperature and time. In this way, the modified polymer obtained by controlling the die swell has molecular weight reduction due to the moderate decomposition reaction of the crystalline propylene polymer portion of the base copolymer that competes with the graft reaction during modification, and ethylene - It is thought that the rheological properties are improved by the appropriate crosslinking reaction of the propylene random copolymer moiety, resulting in the above-mentioned high performance. Furthermore, a filler (C) and magnesium oxide (D) with an iodine adsorption amount of 20 mg·I/g·MgO or more are added to the modified polymer (A) or a mixture of this and an unmodified olefin polymer (B). In addition, in the reinforced polyolefin formed by kneading, the weight average particle size of the dispersed phase of the modified polymer (A) is in the range of 0.5 to 10 μm, preferably 1 to 5 μm. In addition, when producing a reinforced polyolefin, if a base polymer of a modified polymer or ethylene-propylene random copolymer rubber is blended as an unmodified olefin polymer, the particle size of these should also be within the above range. It is desirable to do so. Here, if the particle size is less than 0.5 μm, both impact strength and rigidity are low, while if the particle size exceeds 10 μm, the impact strength tends to decrease. Since this particle size changes depending on the kneading conditions, it can be controlled depending on the conditions. As described above, by specifying the structure and physical properties of the base polymer of the modified polymer and the modified polymer, a modified polymer with significantly superior adhesive properties can be obtained. Further, by using this modified polymer, a high-performance reinforced polyolefin can be obtained which maintains a high balance between impact strength and rigidity, and has excellent heat resistance, cold resistance, dimensional stability, etc. Note that the method for measuring each of the above characteristic values will be described later. Examples of unsaturated carboxylic anhydrides used in graft modification include maleic anhydride,
Itaconic anhydride, citraconic anhydride, hymicic anhydride, bicyclo(2,2,2)oct-5-ene-2,3-dicarboxylic anhydride, 4-methylcyclohex-4-ene-1,2-dicarboxylic anhydride Acid anhydride, 1,2,3,4,5,8,9,10-octahydronaphthalene-2,3-dicarboxylic acid anhydride, bicyclo(2,2,1)oct-7-ene-
2,3,5,6-tetracarboxylic acid-2,3,
5,6-dianhydride, 7-oxabicyclo(2,
2,1) hept-5-ene-2,3-dicarboxylic anhydride and the like. Among these,
Maleic anhydride is particularly preferably used. In addition, if necessary, monomers that can be copolymerized with these unsaturated carboxylic acids, such as esters derived from these carboxylic acid anhydrides, amides, derivatives such as acids, (meth)acrylic acid, (meth)acrylic acid Methyl, (meth)acrylic acid derivatives such as ethyl (meth)acrylate, vinyl esters such as vinyl acetate, styrene monomers, acrylonitrile monomers, vinylsilane monomers, etc. can also be used. Any known radical initiator can be used as the radical initiator added during the production of the modified polymer. for example,
2,2'-azobisisobutyronitrile, 2,2'-
Azo compounds such as azobis(2,4,4-trimethylvaleronitrile), methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,5,5-trimethylcyclohexane,
2,2-bis(t-butylperoxy)butane,
t-Butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, di-t-
Butyl peroxide, 2,5-dimethyl-2,
5-di(t-butylperoxy)hexane, 2,
5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, lauroyl peroxide,
3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, t-butyl peracetate, t-butyl peroxyisobutyrate, t-butyl peroxy pivalate, t-butyl peroxy-2-ethylhexanoate, t-
Butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate,
t-Butylperoxybenzoate, di-t-butyldiperoxyisophthalate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butylperoxymaleic acid, t-butylperoxyisopropyl carbonate , various organic peroxides such as polystyrene peroxide. Among these, organic peroxides having a half-life of decomposition of 1 minute or more, preferably 5 minutes or more at 100° C. are particularly effectively used. Also,
Two or more types of these radical initiators can be used in combination. The amount of these radical initiators to be added is determined per 100 parts by weight of the base copolymer based on the graft reaction rate, molecular weight reduction due to decomposition of the crystalline propylene polymer by the radical initiator, and die swell of the modified polymer. A range of 0.001 to 2 parts by weight is preferred. A particularly preferable addition amount is 0.05 to 1 part by weight. The graft-modified polymer (A) can be easily produced by melt-kneading a mixture of the base copolymer, unsaturated carboxylic acid anhydride, and radical initiator. In this case, in order to improve the dispersion of the unsaturated carboxylic acid anhydride and radical initiator into the base copolymer, these are dissolved in a small amount of a good solvent such as acetone, aromatic hydrocarbons, halogenated hydrocarbons, etc. It can also be added as a solution. Melt kneading is generally carried out using a screw extruder, Banbury mixer, kneader, or the like. The kneading temperature at this time is usually 170-300℃,
Preferably, the temperature is 190 to 250°C and the time is suitably in the range of 0.5 to 10 minutes. The reaction atmosphere may be air, but preferably an inert gas such as nitrogen or carbon dioxide. In addition, in order to remove unreacted unsaturated carboxylic acid anhydride and low molecular weight by-products contained in the obtained modified polymer, evacuation while melting, solvent extraction, etc. may be performed. A mixture (B) of the modified polymer (A) produced by the above method and an unmodified olefin polymer can also be used as a component of the reinforced polyolefin composition of the present invention.
Examples of the unmodified olefin polymer include propylene-ethylene copolymer, which is the base of the modified polymer, crystalline or non-crystalline polypropylene, crystalline or non-crystalline ethylene-based copolymer,
Propylene random copolymer, polybutene-1,
Poly-4-methylpentene-1, propylene-butene-1 copolymer, low density or high density polyethylene, ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid Acid partial metal salt copolymer, ethylene-
(meth)acrylic acid-(meth)acrylic acid ester copolymer, ethylene-methyl(meth)acrylate copolymer, ethylene-ethyl (meth)acrylate copolymer, ethylene-glycidyl (meth)acrylate copolymer , ethylene-aminoalkyl (meth)acrylate copolymers, ethylene-vinyl alcohol copolymers, ethylene-styrene copolymers, and various other olefin homopolymers and copolymers. Moreover, two or more types of these olefin polymers can be used in combination. From the viewpoint of reinforcing effect, the amount of these olefinic polymers added is such that the content of unsaturated carboxylic acid anhydride in the mixture of modified polymer and unmodified olefinic polymer is 0.001% by weight or more. It is necessary to mix them. The reinforced polyolefin composition of the present invention is produced by blending the modified polymer (A) or a mixture thereof with an unmodified olefin polymer (B) with a filler (C) and a specific magnesium oxide (D). It was manufactured in this way. The preferred amount of filler added is (A) or (B).
Generally 1 to 200 parts by weight per 100 parts by weight. A more preferred range of filler amount is 5 to 100 parts by weight. Here, if the amount of the filler is less than 1 part by weight, there is no significant effect on reinforcement, while if it is more than 200 parts by weight, the mechanical strength tends to decrease or molding becomes difficult. Examples of fillers include aluminum, iron, nickel, cobalt, chromium, zinc, titanium, tin,
Single metals such as copper, or their oxides and alloys, as well as glass, ceramics, asbestos, slate, gypsum, stone, sand, calcium carbonate, barium sulfate, talc, silica, mica, boron nitride, zirconia, carbon, Natural or synthetic inorganic fillers such as silicon carbide, potassium titanate, as well as polyamides, polyimides, polyesters, polyphenylene oxides, polyacetal resins, phenolic resins, melamine resins, alkyd resins, urethane resins, epoxy resins, diaryl phthalate resins, urea resin, ebonite, wool, leather, bamboo,
Examples include various natural or synthetic polymer compounds such as wood. These may take any size and shape depending on the purpose of use, such as fine powder of 0.01 to 50 μm, granules, small pieces, flakes, fibers, etc. Moreover, two or more types of these fillers can also be used in combination. Furthermore, these fillers may be surface-treated by various methods, and by using such treated fillers, particularly tough reinforced polyolefins can be obtained. In addition, a modified polymer (A) or a mixture of the modified polymer and an unmodified olefin polymer (B), and a filler (C)
When a specific magnesium oxide is added to these during the production of a reinforced polyolefin composition consisting of the following, a particularly high-performance reinforced polyolefin composition can be obtained. Furthermore, magnesium oxide is generally known as an acid acceptor, and has the effect of suppressing metal corrosion during injection molding. Here, in particular, the median diameter is 10μ or less and the iodine adsorption amount is 20μ.
Magnesium oxide of mg·I/g·MgO or higher is effective. In addition, the amount of magnesium oxide added is
0.1 per 100 parts by weight of the modified polymer (A) or the mixture of the modified polymer and unmodified olefin polymer (B)
The range of ~10 parts by weight is suitable, and furthermore, based on the unsaturated carboxylic acid anhydride contained in the modified polymer,
It is desirable to add at least the equivalent molar amount. This reinforced polyolefin composition may optionally contain polybutadiene rubber, styrene-butadiene block or random copolymer, acrylonitrile-butadiene copolymer, polystyrene, AS resin,
Other polymer compounds such as ABS resin, MMA resin, vinyl chloride resin, etc. can also be added. The reinforced polyolefin composition of the present invention can be produced by any method, including the following several methods.
For example, a method in which a modified polymer, a filler, a specific magnesium oxide, and an unmodified olefin polymer are mixed by a dry blending method, and then melt-kneaded in an extruder, Banbury mixer, kneader, roll, etc.; A method in which the mixture is directly molded; Also, a method in which a kneaded composition consisting of a modified polymer, an unmodified olefin polymer, and a specific magnesium oxide is prepared in advance, and this is mixed with a filler; A method of preparing a kneaded composition consisting of a filler and a specific magnesium oxide, and kneading this with an unmodified olefin polymer; furthermore, using a part of the modified polymer, the filler is mixed by a solution coating method, etc. It can be produced by a method in which the surface of the polymer is coated, and then the remaining modified polymer or unmodified olefin polymer is added thereto and kneaded. Various molded products can be manufactured by using the reinforced polyolefin composition of the present invention and applying known molding techniques. Furthermore, since the reinforced polyolefin composition of the present invention has excellent adhesive properties, it can also be used to form laminates with various inorganic materials including metals, and various natural or synthetic polymeric materials. The molded product obtained in this manner can be widely used in various industrial fields as described above, and its utility value is extremely large. Additionally, antioxidants, heat stabilizers, light stabilizers, nucleating agents, lubricants, plasticizers, antistatic agents, inorganic or organic colorants, and crosslinking agents may be added to the reinforced polyolefin composition of the present invention, as necessary. Various additives such as foaming agents, fluorescent agents, and rust inhibitors can be added during the manufacturing process of the composition or the subsequent molding process. The present invention will be explained below with reference to Examples.
The present invention is not limited thereby. In addition, each measurement value shown in this invention was measured and calculated|required by the following method, respectively. (1) Content of unsaturated carboxylic acid anhydride in modified polymer The content of unsaturated carboxylic anhydride in modified polymer was determined by alkaline titration on a purified sample by dissolving the modified polymer in xylene and precipitating it with acetone. (2) Composition ratio of crystalline propylene polymer and ethylene-propylene random copolymer in the base propylene-ethylene block copolymer In each polymerization process, the crystalline propylene polymer portion (P The polymerization amount of the ethylene-propylene random copolymer portion (EP portion) and the polymerization amount of the ethylene-propylene random copolymer portion (EP portion) carried out in the subsequent stage were determined from the material balance in the polymerization. (3) Ethylene content of ethylene-propylene random copolymer part (EP part) A solution of the base propylene-ethylene block copolymer in 0-dichlorobenzene is 13 C-
135 by NMR (JEOL, Model FX-100)
℃, 2000 to 3000 integration times, 45° pulse interval, 10 second interval.
Ethylene content was determined based on the method described in GJ Ray et al., Makromol. 10, 773 (1977). The ethylene content of the ethylene-propylene random copolymer was calculated from this measured value and the composition ratio of polypropylene part (P part)/ethylene-propylene random copolymer (EP part) determined in section (2) above. (4) Intrinsic viscosity of the base propylene-ethylene block copolymer In the production of the base propylene-ethylene block copolymer, first measure the intrinsic viscosity [η]p of the crystalline polypropylene part carried out in the first step, Subsequently, the ethylene-propylene random copolymer portion is polymerized, and the intrinsic viscosity [η] cp of the final polymer obtained is measured. Here, the intrinsic viscosity [η] EP of the ethylene-propylene random copolymer is a value obtained on the assumption that the following relationship holds true. [η] EP = 1/f EP [η] CP − (1/f EP −1) [η]
P Here, f EP is the composition fraction of the ethylene-propylene random copolymer in the total polymer. Note that the intrinsic viscosity is a value measured in a tetralin solution at 135°C, and its unit is dl/g. (5) Weight average particle size of ethylene-propylene random copolymer A molded article of a modified polymer or its composition is cooled with liquid nitrogen, and its frozen fractured surface is treated with an aqueous chromium trioxide solution. Electron micrographs were taken using a two-stage replica method, and the weight average particle diameter w was calculated using the following formula. w=Σnidi 4 /Σnidi 3 where ni is the number fraction of particles with diameter di. In addition, when the particle appearing on the photograph is not circular, the size of the particle (for example, elliptical) is defined as the arithmetic mean value of its longest diameter and shortest diameter. (6) Melt index (MI) Based on the method of JIS K-7210-1977, 2.16Kg
Measured at 230°C under a load of The unit of measurement value is g/10min. (7) Die swell (DS) Using a capillary tube with an inner diameter of 0.77 mm, a length of 25.55 mm, an inlet angle of 90°, and an orifice with an outer diameter of 9.48 mm, this is inserted into a rheometer tube with an inner diameter of 9.55 mm, and the shear rate is 10. The polymer heated to a predetermined temperature was extruded using a plunger operating at a constant speed in the range of ~100 sec -1 , and the die swell (DS) was determined using the following equation. This example shows die swell at a temperature of 204°C and a shear rate of 50 sec -1 . DS=(D 1 /D 0 ) 2where D 0 is the diameter of the capillary tube and D 1 is the diameter of the extrudate. (8) Median diameter of magnesium oxide Measured using a light transmission type particle size distribution measuring device using ethyl alcohol as a medium. The median diameter is
This value is expressed as the 50% particle size of the integrated fineness distribution curve. (9) Amount of iodine adsorbed by magnesium oxide Place the sample in a carbon tetrachloride solution of iodine (0.1N), shake tightly for 30 minutes, let stand for 5 minutes, and then add only the supernatant to a 0.03N-iodopotassium solution. It was determined by titration with 0.05N sodium thiosulfate. (10) Notched Izo impact strength Measured at 20°C and -30°C in accordance with ASTM D-256-56. (11) Falling ball impact test At 20℃, on an injection molded plate with a thickness of 2mm,
A steel ball weighing 200g is dropped, and it is expressed as the falling height of the steel ball when the plate breaks. (12) Tensile strength Measured at 20°C in accordance with ASTM D-638-60T. (13) Bending strength and bending rigidity Measured at 20°C in accordance with ASTM D-747-58T. (14) Heat distortion temperature Measured in accordance with ASTM D-648-45T. (15) Dimensional stability (warpage) A disk with a diameter of 200 mm and a thickness of 2 mm was produced using an injection molding mold having a gate in the center of the disk.
This disk is placed on a horizontal plate, and when viewed from the side, there is a gap between the bottom surface of the outer circumference of the disk and the horizontal plate.
If there is, the minimum part of 〓 in between is set to l 1 mm, and the maximum part is set to l 2 mm, and the warpage is determined by the following formula. Warpage (%) = (l 1 − l 2 )/200×2×100 Example 1 As the base polymer, melt index 2,
The die swell is 1.55, the intrinsic viscosity of the continuous and dispersed phases is 1.6 and 5.2, respectively, the continuous phase/dispersed phase weight ratio is 70/30, and the ethylene content of the dispersed phase is
A 50% by weight propylene-ethylene block copolymer powder was used. 100 parts by weight of this copolymer,
After mixing 0.7 parts by weight of maleic anhydride powder and 0.5 parts by weight of t-butyl peroxylaurate in a Henschel mixer, this mixture was melt-kneaded in a 53 mmφ twin screw extruder at a temperature of 220°C and an average residence time of 1 minute. Graft modified polymer pellets were obtained. Table 1 shows the maleic anhydride content and physical properties of this modified polymer. 15 parts by weight of this modified polymer, 55 parts by weight of crystalline polypropylene with a melt index of 8, surface treated with an aminosilane compound, diameter of about 10μ, length of about 6
30 parts by weight of glass fiber of mm, magnesium oxide (median diameter 2.1μ, iodine adsorption amount 150mg・I/g・
After mixing 2 parts by weight of MgO (manufactured by Kyowa Chemical Industry Co., Ltd.), 0.2 parts by weight of Irganox 1010 (manufactured by Ciba Geigy) and 0.05 parts by weight of calcium stearate in a Henschel mixer, the mixture was heated to 230°C in a 90 mmφ extruder.
The mixture was kneaded to obtain glass fiber-reinforced polyolefin. This composition was injection molded at 230°C and various physical properties were measured. The results are shown in Table 2. Comparative Examples 1 to 2 In Example 1, the method of Example 1 was followed except when magnesium oxide with a median diameter of 3.2μ and an iodine adsorption amount of 5 mg・I/g・MgO was used, and when magnesium oxide was not used. repeated. The results are shown in Table 2. Example 2 A propylene-ethylene block copolymer having the composition and physical properties shown in Table 1 was used as the base polymer. A mixture consisting of 100 parts by weight of this copolymer, 0.3 parts by weight of maleic anhydride, and 0.2 parts by weight of t-butylperoxyisopropyl carbonate was melt-kneaded in a 65 mmφ single screw extruder at 220°C for an average residence time of 2 minutes. Modified polymers shown in Table 1 were obtained. Below, magnesium oxide (median diameter
The method of Example 1 was repeated, except that 2.7μ and iodine adsorption amount (30 mg·I/g·MgO) were used. The results are shown in Table 2. Comparative Examples 3 to 4 The method of Example 2 was repeated except that in Example 2, magnesium oxide with a median diameter of 3.2μ and an iodine adsorption amount of 5 mg・I/g・MgO was used, and when magnesium oxide was not used. Ta. The results are shown in Table 2. Comparative Example 5 As the base polymer, melt index 2,
The method of Example 1 was repeated except that a crystalline propylene homopolymer with a die swell of 2.36 was used. The results are shown in Tables 1 and 3. Comparative Examples 6 to 13 The method of Example 2 was repeated, except that the propylene-ethylene block copolymers shown in Table 1 were used as base polymers, and no magnesium oxide was added. The results are shown in Tables 1 and 3. Comparative Example 14 In Example 2, the method of Example 2 was repeated except that the amount of maleic anhydride added was 0.0007 parts by weight in producing the modified polymer. The results are shown in Tables 1 and 3. Comparative Example 15 The method of Example 2 was repeated, except that 0.3 parts by weight of the modified polymer obtained in Example 2 and 69.7 parts by weight of crystalline polypropylene were added. The results are shown in Table 3. Comparative Example 16 Crystalline polypropylene with melt index 1
70 parts by weight and Mooney viscosity 40, ethylene content
The procedure of Example 1 was repeated, except that a composition consisting of 30 parts by weight of 50% by weight ethylene-propylene random copolymer rubber was used as the base polymer for the modified polymer. The results are shown in Tables 1 and 3. Example 3 The method of Example 1 was followed except that 10 parts by weight of an ethylene-propylene copolymer rubber having an ethylene content of 50% by weight and a Mooney viscosity of 40 was added to the formulation of Example 1 shown in Table 2. repeated. The weight average particle size of the ethylene-propylene copolymer (including the ethylene-propylene copolymer rubber added later) in the obtained reinforced polyolefin was 3.7 microns.
The reinforced polyolefin has a melt index of 2, a notched isot impact strength of 15 and 9 Kg-cm/cm 2 at 20°C and -30°C, respectively, a falling ball impact strength of 17 cm, a tensile strength of 870 Kg/cm, and a bending strength of 950.
Kg/cm 2 , bending rigidity 53000Kg/cm 2 , heat distortion temperature 150
℃ and warpage of 2%, and although the rigidity was slightly lower than that of Example 1, a product with good impact resistance and dimensional stability was obtained. Examples 4 to 7 and Comparative Examples 17 to 29 Each of the various filler-containing formulations shown in Table 4 was kneaded in a Banbury mixer at 190°C for 3 minutes, and then passed through an extruder to obtain composition pellets. This composition was injection molded at 200°C and its physical properties were measured. The results are shown in Table 3. As shown in the examples above, it can be seen that the reinforced polyolefin of the present invention has very excellent physical properties.
【表】【table】
【表】【table】
【表】【table】
【表】【table】
Claims (1)
ラジカル開始剤の存在下に、不飽和カルボン酸無
水物でグラフト変性して得られる変性重合体(A)ま
たは該変性重合体と未変性オレフイン系重合体と
の混合物(B)に、充填剤(C)およびヨード吸着量が20
mg・Ｉ／ｇ・MgO以上の酸化マグネシウム(D)を
加え、混練してなる強化ポリオレフイン組成物に
おいて、 (1) 変性重合体(A)中の不飽和カルボン酸無水物の
含有量が0.001〜２重量％、また該変性重合体
と未変性オレフイン系重合体との混合物(B)中の
不飽和カルボン酸無水物の含有量が0.001重量
％以上であること、 (2) 変性重合体(A)の形態が連続相と分散相の不均
一構造からなり、連続相の主成分が結晶性プロ
ピレン系重合体、また分散相の主成分がエチレ
ン含有量20〜90重量％のエチレン−プロピレン
ランダム共重合体であり、かつ、連続相／分散
相の重量比が95／５〜55／45であること、 (3) 上記(2)の分散相の重量平均粒子径が0.5〜10μ
であること、 (4) グラフト変性前のプロピレン−エチレン系ブ
ロツク共重合体の連続相形成成分である結晶性
プロピレン系重合体の極限粘度が１〜５、また
分散相形成成分であるエチレン−プロピレンラ
ンダム共重合体の極限粘度が２〜10であり、か
つ、分散相形成成分の極限粘度が連続相形成成
分の極限粘度よりも大きいこと、 を特徴とする強化ポリオレフイン組成物。 ２ 変性重合体(A)のメルトインデツクスおよびダ
イ・スウエルの値が、両者ともにグラフト変性前
のプロピレン−エチレン系ブロツク共重合体の値
よりも大きいことを特徴とする特許請求の範囲第
１項記載の強化ポリオレフイン組成物。 ３ 変性重合体(A)の連続相／分散相の重量比が
90／10〜60／40である特許請求の範囲第１項記載
の強化ポリオレフイン組成物。 ４ 変性重合体(A)の分散相の主成分がエチレン含
有量40〜80重量％のエチレン−プロピレンランダ
ム共重合体である特許請求の範囲第１項記載の強
化ポリオレフイン組成物。 ５ 変性重合体(A)のメルトインデツクスが１〜
300である特許請求の範囲第１項記載の強化ポリ
オレフイン組成物。 ６ 充填剤(C)の量が、変性重合体(A)または該変性
重合体と未変性オレフイン系重合体との混合物(B)
100重量部に対して、１〜200重量部である特許請
求の範囲第１項記載の強化ポリオレフイン組成
物。 ７ 酸化マグネシウム(D)のメジアン径が10μ以下
で、かつ、その添加量が変性重合体(A)または該変
性重合体と未変性ポリオレフインとの混合物(B)
100重量部あたり0.1〜10重量部である特許請求の
範囲第１項記載の強化ポリオレフイン組成物。[Scope of Claims] 1. A modified polymer (A) obtained by graft-modifying a propylene-ethylene block copolymer with an unsaturated carboxylic acid anhydride in the presence of a radical initiator, or the modified polymer and an unsaturated polymer. The filler (C) and the iodine adsorption amount are 20% in the mixture (B) with the modified olefin polymer.
In a reinforced polyolefin composition obtained by adding and kneading magnesium oxide (D) in an amount of mg·I/g·MgO or more, (1) the content of unsaturated carboxylic acid anhydride in the modified polymer (A) is 0.001 to 2% by weight, and the content of unsaturated carboxylic acid anhydride in the mixture (B) of the modified polymer and unmodified olefinic polymer is 0.001% by weight or more; (2) modified polymer (A); ) has a heterogeneous structure of a continuous phase and a dispersed phase, the main component of the continuous phase is a crystalline propylene polymer, and the main component of the dispersed phase is an ethylene-propylene random copolymer with an ethylene content of 20 to 90% by weight. It is a polymer, and the weight ratio of continuous phase/dispersed phase is 95/5 to 55/45; (3) The weight average particle diameter of the dispersed phase in (2) above is 0.5 to 10μ.
(4) The intrinsic viscosity of the crystalline propylene polymer which is a continuous phase forming component of the propylene-ethylene block copolymer before graft modification is 1 to 5, and the ethylene-propylene which is a dispersed phase forming component is A reinforced polyolefin composition characterized in that the random copolymer has an intrinsic viscosity of 2 to 10, and the intrinsic viscosity of the dispersed phase forming component is greater than the intrinsic viscosity of the continuous phase forming component. 2. Claim 1, characterized in that the melt index and die swell values of the modified polymer (A) are both larger than the values of the propylene-ethylene block copolymer before graft modification. Reinforced polyolefin compositions as described. 3 The weight ratio of continuous phase/dispersed phase of modified polymer (A) is
The reinforced polyolefin composition according to claim 1, which has a ratio of 90/10 to 60/40. 4. The reinforced polyolefin composition according to claim 1, wherein the main component of the dispersed phase of the modified polymer (A) is an ethylene-propylene random copolymer having an ethylene content of 40 to 80% by weight. 5 Melt index of modified polymer (A) is 1~
300. The reinforced polyolefin composition of claim 1, wherein the composition is 6 The amount of filler (C) is the modified polymer (A) or a mixture of the modified polymer and an unmodified olefin polymer (B)
The reinforced polyolefin composition according to claim 1, wherein the amount is 1 to 200 parts by weight per 100 parts by weight. 7 The median diameter of magnesium oxide (D) is 10μ or less, and the amount added is a modified polymer (A) or a mixture of the modified polymer and unmodified polyolefin (B)
The reinforced polyolefin composition according to claim 1, wherein the amount is 0.1 to 10 parts by weight per 100 parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56180549A JPS5883043A (en) | 1981-11-10 | 1981-11-10 | Reinforced polyolefin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56180549A JPS5883043A (en) | 1981-11-10 | 1981-11-10 | Reinforced polyolefin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5883043A JPS5883043A (en) | 1983-05-18 |
| JPS6324620B2 true JPS6324620B2 (en) | 1988-05-21 |
Family
ID=16085215
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56180549A Granted JPS5883043A (en) | 1981-11-10 | 1981-11-10 | Reinforced polyolefin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5883043A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59179551A (en) * | 1983-03-29 | 1984-10-12 | Ube Ind Ltd | Adhesive polyolefin composition and laminatings therefrom |
| JPS61197650A (en) * | 1985-02-27 | 1986-09-01 | Chisso Corp | Polypropylene resin composition |
| JPS62146945A (en) * | 1985-12-19 | 1987-06-30 | Chisso Corp | Polypropylene resin composition |
| JPS62146946A (en) * | 1985-12-19 | 1987-06-30 | Chisso Corp | Polypropylene composition |
| JPH0253846A (en) * | 1988-08-18 | 1990-02-22 | Fujikura Ltd | Resin composition |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4998484A (en) * | 1973-01-11 | 1974-09-18 | ||
| JPS5010837A (en) * | 1973-06-04 | 1975-02-04 | ||
| JPS5148195A (en) * | 1974-10-23 | 1976-04-24 | Hitachi Ltd | KONEKUTA |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5148195B2 (en) * | 1972-02-02 | 1976-12-18 |
-
1981
- 1981-11-10 JP JP56180549A patent/JPS5883043A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4998484A (en) * | 1973-01-11 | 1974-09-18 | ||
| JPS5010837A (en) * | 1973-06-04 | 1975-02-04 | ||
| JPS5148195A (en) * | 1974-10-23 | 1976-04-24 | Hitachi Ltd | KONEKUTA |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5883043A (en) | 1983-05-18 |
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