JPH0463098B2 - - Google Patents
Info
- Publication number
- JPH0463098B2 JPH0463098B2 JP61292583A JP29258386A JPH0463098B2 JP H0463098 B2 JPH0463098 B2 JP H0463098B2 JP 61292583 A JP61292583 A JP 61292583A JP 29258386 A JP29258386 A JP 29258386A JP H0463098 B2 JPH0463098 B2 JP H0463098B2
- Authority
- JP
- Japan
- Prior art keywords
- component
- propylene
- resin composition
- ethylene
- weight
- 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
- 239000011342 resin composition Substances 0.000 claims description 31
- -1 polypropylene Polymers 0.000 claims description 23
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 21
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 21
- 229920001155 polypropylene Polymers 0.000 claims description 19
- 239000004743 Polypropylene Substances 0.000 claims description 16
- 239000002667 nucleating agent Substances 0.000 claims description 15
- 230000009477 glass transition Effects 0.000 claims description 9
- 229920005604 random copolymer Polymers 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 description 21
- 239000000203 mixture Substances 0.000 description 19
- 229920001577 copolymer Polymers 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 11
- 230000007423 decrease Effects 0.000 description 10
- 230000000704 physical effect Effects 0.000 description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
- 239000005977 Ethylene Substances 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 150000002978 peroxides Chemical class 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical group 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 229920005674 ethylene-propylene random copolymer Polymers 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 150000001451 organic peroxides Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- UBRWPVTUQDJKCC-UHFFFAOYSA-N 1,3-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC(C(C)(C)OOC(C)(C)C)=C1 UBRWPVTUQDJKCC-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- DDEWZZFCOPRPHZ-UHFFFAOYSA-N 2,4-ditert-butyl-3-[(2,6-ditert-butyl-3-hydroxyphenyl)methyl]phenol Chemical compound CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1CC1=C(C(C)(C)C)C=CC(O)=C1C(C)(C)C DDEWZZFCOPRPHZ-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
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 101100208721 Mus musculus Usp5 gene Proteins 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000002216 antistatic agent Substances 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
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical class OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-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
- 239000003086 colorant Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 229940087101 dibenzylidene sorbitol Drugs 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920001384 propylene homopolymer Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- FMZUHGYZWYNSOA-VVBFYGJXSA-N (1r)-1-[(4r,4ar,8as)-2,6-diphenyl-4,4a,8,8a-tetrahydro-[1,3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol Chemical compound C([C@@H]1OC(O[C@@H]([C@@H]1O1)[C@H](O)CO)C=2C=CC=CC=2)OC1C1=CC=CC=C1 FMZUHGYZWYNSOA-VVBFYGJXSA-N 0.000 description 1
- HGTUJZTUQFXBIH-UHFFFAOYSA-N (2,3-dimethyl-3-phenylbutan-2-yl)benzene Chemical group C=1C=CC=CC=1C(C)(C)C(C)(C)C1=CC=CC=C1 HGTUJZTUQFXBIH-UHFFFAOYSA-N 0.000 description 1
- NOBYOEQUFMGXBP-UHFFFAOYSA-N (4-tert-butylcyclohexyl) (4-tert-butylcyclohexyl)oxycarbonyloxy carbonate Chemical compound C1CC(C(C)(C)C)CCC1OC(=O)OOC(=O)OC1CCC(C(C)(C)C)CC1 NOBYOEQUFMGXBP-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 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
- 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
- 239000005711 Benzoic acid Substances 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
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- JWKNCJFGBOQAQL-UHFFFAOYSA-N butyl dodecaneperoxoate Chemical compound CCCCCCCCCCCC(=O)OOCCCC JWKNCJFGBOQAQL-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical compound [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- GUPPESBEIQALOS-UHFFFAOYSA-L calcium tartrate Chemical compound [Ca+2].[O-]C(=O)C(O)C(O)C([O-])=O GUPPESBEIQALOS-UHFFFAOYSA-L 0.000 description 1
- 235000011035 calcium tartrate Nutrition 0.000 description 1
- 239000001427 calcium tartrate Substances 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000000470 constituent 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
- XJOBOFWTZOKMOH-UHFFFAOYSA-N decanoyl decaneperoxoate Chemical compound CCCCCCCCCC(=O)OOC(=O)CCCCCCCCC XJOBOFWTZOKMOH-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- MFGZXPGKKJMZIY-UHFFFAOYSA-N ethyl 5-amino-1-(4-sulfamoylphenyl)pyrazole-4-carboxylate Chemical compound NC1=C(C(=O)OCC)C=NN1C1=CC=C(S(N)(=O)=O)C=C1 MFGZXPGKKJMZIY-UHFFFAOYSA-N 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000314 lubricant 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
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 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
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229920005653 propylene-ethylene copolymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- MLWIKSZBPROIGS-UHFFFAOYSA-M sodium;bis(4-butylphenyl) phosphate Chemical compound [Na+].C1=CC(CCCC)=CC=C1OP([O-])(=O)OC1=CC=C(CCCC)C=C1 MLWIKSZBPROIGS-UHFFFAOYSA-M 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229940070710 valerate Drugs 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
〔産業上の利用分野〕
本発明は、耐衝撃性（特に耐面衝撃性）、剛性、
などの機械的特性が優れ、家電、自動車などの分
野の成形用材料として好適なプロピレン樹脂組成
物に関する。
〔従来の技術〕
従来より、結晶性ポリプロピレン成分とエチレ
ン−プロピレンランダム共重合体成分との組成物
は、通常、ピロピレンの多段重合の後段にエチレ
ンモノマーを導入して製造されて（特開昭56−
55416号公報）、いわゆるプロピレンブロツク共重
合体と称して市販されている。
この組成物は、耐衝撃性、剛性などに優れた樹
脂として、大型雑貨をはじめ自動車、家電分野等
の各産業分野で広く用いられているが、近年にな
り、さらにその用途が拡大し、また製品の軽量化
又はコストダウンの要求により、成形品の薄肉化
及び大型化が進んだ結果、要求特性が益々高度化
してきた。
すなわち、高い流動性及び高い剛性を保持しつ
つ、耐衝撃性を一層向上させた品質が要望される
ようになつてきている。
特に、この樹脂組成物においては、アイゾツト
衝撃性だけでなく、耐面衝撃性も同時に優れてい
ることが要望されている。
しかし、従来のプロピレン樹脂組成物は、耐衝
撃性に、特に薄肉化したときの耐面衝撃性が十分
でなく、また、剛性、流動性、加工性などの物性
が悪いという欠点があつた。
また、これらの欠点を改良するために、高分子
量の該プロピレン樹脂組成物を過酸化物の存在下
で熱分解処理して、機械的物性を保ちながら流動
性を改善するしようとする試みも行なわれている
（特公昭58−7665号公報）か、この方法で得られ
たプロピレン樹脂組成物は、流動性は十分改善さ
れているものの、特に耐面衝撃性と剛性との物性
バランスが悪いという欠点があつた。
先に、本発明者らは組成物を構成するポリプロ
ピレンとエチレン−プロピレン共重合体の極限粘
度の比及びガラス転移温度を特定化して、高流動
性、かつ高い剛性と高い耐面衝撃性に優れたプロ
ピレン樹脂組成物を得ることに成功したが、この
プロピレン樹脂組成物もまだ剛性の点で不十分で
あつた。
〔発明が解決しようとする問題点〕
本発明は、耐面衝撃性などの耐衝撃性に著しく
優れ、かつ剛性、流動性にも優れた結晶性ポリプ
ロピレンとエチレン−プロピレン共重合体からな
る組成物を提供しようとするものである。
〔問題点を解決するための手段〕
本発明者らは、該プロピレン樹脂組成物の上記
物性を改善するため、種々検討を行つた結果、本
発明者らが、先に開発した樹脂組成物に特定量の
造核剤を配合することにより、さらに、物性が改
善されることを見出し本発明をなすに至つた。
すなわち、本発明のプロピレン樹脂組成物は、
(A)結晶性ポリプロピレン成分と(B)エチレン−プロ
ピレンランダム共重合体成分並びに(C)造核剤成分
を含有するプロピレン樹脂組成物であつて、(A)成
分と(B)成分との重量比が55：45ないし95：５、(A)
成分の極限粘度〔η〕pp及び(B)成分の極限粘度
〔η〕epの比〔η〕ep／〔η〕ppが0.5〜2.0であ
り、(B)成分のガラス転移温度が−30℃以下、(C)成
分の含有量が(A)成分と(B)成分の合計量100重量部
当たり0.005〜１重量部であることを特徴とする
プロピレン樹脂組成物である。
本発明の組成物において、(A)成分の含有量が95
の重量比を越えるとアイゾツト衝撃性や耐面衝撃
性などの耐衝撃性が低下し、該重量比が55未満で
あると剛性が低下する。また、極限粘度の比が
2.0を越えると耐面衝撃性が低下し、0.5未満であ
ると耐面衝撃性が低下するとともに、剛性も低下
する。
本発明の樹脂組成物に用いる(A)成分は、プロピ
レンを立体規則性触媒等を用いて重合することに
よつて得られるプロピレン単独重合体もしくは、
重合体中に２重量％以下のエチレン単位もしく
は、他のオレフイン単位を含有する実質的なプロ
ピレン単独重合体である。
(A)成分中のエチレン単位等の含有量を２重量％
よりも多いプロピレン−エチレン共重合体を用い
た場合には、得られる組成物の剛性が著しく低下
してしまうのが不適当である。
本発明の樹脂組成物に用いる(B)成分としては、
エチレンとプロピレンあるいはこれらと少量の他
のオレフインとを立体規則性触媒等を用いて重合
することによつて得られるエチレン単位が20〜80
重量％を含有するエチレン−プロピレンランダム
共重合体又は共重合体中に他のオレフイン単位を
少量含有するいわゆる実質的なエチレン−プロピ
レンランダム共重合体であり、共重合の際にでき
る少量のエチレン単独重合体を含んでいるものも
使用できる。
これらの(A)成分と(B)成分とは、それぞれ別々に
製造することができるが、通常は、二段重合法の
後段の重合槽の中で、前段での生成した(A)成分の
存在下で(B)成分の共重合反応を行うことにより直
接重合槽から組成物として得ることができる。
この(A)成分と(B)成分との割合は、別々に製造さ
れた(A)成分と(B)成分とを所定の割合で配合した
り、又は多段重合法において、その各段階の原料
モノマー組成、仕込み量や重合条件を選択して調
整することができる。
本発明の(A)成分と(B)成分の合成の際、これらの
高分子連鎖中に少量共重合し得るモノマーとして
は、例えば、１−ブテン、１−ペンテン、１−ヘ
キセン、１−ヘプテン、イソブテン、４−メチル
−１−ペンテン等のα−モノオレフインを挙げる
ことができる。
本発明においては、(B)成分であるエチレン−プ
ロピレン共重合体のガラス転移温度は−30℃以下
であることが必要であり、これ以上の転移温度に
なると耐面衝撃強度が低下する。
本発明の樹脂組成物中の、(A)成分の極限粘度
〔η〕ppと(B)成分の極限粘度〔η〕epとの比
〔η〕pp／〔η〕epは0.5〜２、好ましくは、0.7
〜1.7であることが必要であり、２以上になると
耐面衝撃強度が低下し、0.5以下になると耐面衝
撃強度だけでなく剛性も共に低下する。
本発明の樹脂組成物の(A)成分と(B)成分の極限粘
度は各成分毎に、135℃デカリン中で測定して得
たものである。
しかし、本発明の樹脂組成物中の(B)成分が、２
段重合で(A)成分の存在下の重合により製造したも
のであるときは、プロピレンの単独重合が行なわ
れる１段目の重合反応器の出口で採取したポリプ
ロピレンの極限粘度を測定して、これ(A)成分の極
限粘度〔η〕ppとして、(B)成分の極限粘度〔η〕
epは次の式によつて算出したものを、本発明
では、便宜上に使用する。
〔η〕ep＝（１／Ｍ）〔η〕ｃ
−（１／Ｍ−１）〔η〕pp
式中の〔η〕ｃは後段の重合槽から混合状態で
得られる樹脂、すなわち(A)成分と(B)成分の総合的
な極限粘度である。また、Ｍは(B)成分の重量分率
であり、樹脂の総量から前段の重合体の重量分率
を引いて求められる。
式は(A)成分と(B)成分の各々の極限粘度とそれ
を混合した組成物全体の極限粘度との間に次式が
成立するとして導かれたものである。
〔η〕ｃ＝Ｍ〔η〕ep＋（１−Ｍ）〔η〕pp
本発明の樹脂組成物は、その剛性をさらに向上
させるために、(A)成分である結晶性ポリプロピレ
ンのアイソタクチツクペンタツド分率［IP］が、
式
［IP］≧−1.02〔η〕pp＋96.0
（ただし、〔η〕ppは前記と同様の意味である。）
を満足するものであることがより好ましい。
ここでアイスタクチツクペンタツド分率とは
A.ザンベリー（Zambelli）らによつてマクロモ
レキユル（Macromolecules）．第６巻、925
（1973）に発表された方法、すなわち13C−NMR
を使用する方法で測定されるポリプロピレン分子
鎖中のペンタツド単位でのアイソタクチツク分率
である。換言すれば、アイソタクチツクベンタツ
ド分率はプロピレンモノマー単位が５個連続して
メソ結合した連鎖の中心にあるプロピレンモノマ
ー単位の分率である。ただし、ピークの帰属に関
しては、マクロモレキユル（Macromolecules）
第８巻、687（1975）に記載の上記文献の訂正版に
基づいて行つた。具体的には、13C−NMRスペク
トルのメチル炭素領域の全吸収ピーク中の
mmmmピークの強度分率としてアイソタクチツ
クペンタツド単位を測定する。
前記(A)成分と(B)成分との極限粘度及びその比、
及び前記ガラス転移温度は触媒の種類、各段階に
おける重合温度などの重合条件、重合の際に使用
する水素ガスなどの分子量調節剤の使用量を適宜
選択することにより調整することができ、一方、
前記アイソタクチツクペンタツド分率〔IP〕は、
重合触媒の種類、予備重合処理モノマーの選択及
び重合温度等の重合条件を調整することができ
る。
本発明の樹脂組成物に用いる造核剤としつて、
有機系核剤及び無機系核剤を使用することができ
る。
このうち有機系核剤としては、例えば、アルキ
ル基を芳香環に置換した安息香酸またはその誘導
体の金属塩（ｐ−ｔ−ブチルベンゾエートのアル
ミニウム塩など）、ジベンジリデンソルビトール
及びその誘導体（１，３，２，４−ジベンジリデ
ンソルビトール、１，３，２，４−ジ（ｐ−メチ
ルベンジリデン）ソルビトール、１，３，２，４
−ジ（ｐ−クロルベンジリデン）ソルビトール、
１，３，２，４−ジ（ｐ−メトキシベンジリデ
ン）ソルビトールなど）、リン酸ビス（４−ｔ−
ブチルフエニル）ナトリウム、メチレンビス
（２，４−ジ−ｔ−ブチルフエノール）アシツド
ホスフエートナトリウム塩、シユウ酸カルシウ
ム、ステアリン酸マグネシウム、サリチル酸亜
鉛、酒石酸カルシウム等の有機酸塩が挙げられ
る。
また、前記無機系核剤としては、例えば、タル
ク、クレー、マイカ、モンモリロナイト、ベント
ナイト等の粘土類、ケイ酸カルシウム、ケイ酸マ
グネシウム、硫酸カルシウム、硫酸バリウム、炭
酸カルシウム、炭酸マグネシウム等の無機塩、ア
ルミナ、酸化チタン、酸化鉄、酸化マグネシウ
ム、酸化亜鉛等の金属酸化物等が挙げられる。
前記各種の造核剤の中でも、有機系核剤として
フオスフエート系造核剤が特に好ましい。
これらの核剤の配合量は、本発明の樹脂組成物
の(A)成分と(B)成分の合計量100重量部に対して、
0.005〜１重量部、特に0.01〜0.5重量部である。
この核剤の配合量が0.005重量部よりも少ない
とポリプロピレン樹脂成形体の剛性、耐熱性及び
硬度などの向上がなく、また、その配合量を１重
量部より多くしてもポリプロピレン樹脂成形体の
剛性などがそれ以上向上しない。
なお、この組成物においては、この発明の目的
を阻害しない範囲内で他の添加剤を含有していて
も良い。
そのような添加剤として、例えば、帯電防止
剤、着色剤、難燃剤、酸化防止剤、紫外線吸収
剤、可塑剤、熱安定剤等の各種添加物が挙げられ
る。
本発明の樹脂組成物にさらに0.005〜0.3重量部
の有機過酸化物を加えて混練加熱することによ
り、より優れたプロピレン重合体組成物を得るこ
とができる。この際、組成物の各構成高分子は分
解されて低分子量になり、高流動性の樹脂組成物
を与える。
なお、その際に分子量分布の指標を示すPI値
を４以下とすると、優れた面衝撃性を有する組成
物が得られるので有利である。
ここにPI値とは、分子量分布の指標となるも
ので、ケミカルエンジニアリング第２回世界会議
〔2ed World Congress of Chemical
Engineering〕P333（1981）に記載された方法に
より求められるものである。
すなわち、溶融粘弾性測定において、貯蔵弾性
率と損失弾性率の交点の弾性率をGc（ダイン／
cm2）とすると
PI＝106／Gc
で表される。
また、この場合においては、溶融粘弾性の測定
はジヤーナル オブ アプライド ポリマー サ
イエンス（J.Appl.Poly.Sci.）第30巻3751〜3765
（1985）に準じて行い、その際、温度170℃、歪み
20％コーンプレート径25mm、コーン角度0.1radの
測定条件で実施した。
このような過酸化物による分解処理により(A)成
分の極限粘度と(B)成分の極限粘度との比は分解処
理前より１に近付く。
このような観点から、本発明の樹脂組成物の(A)
成分と(B)成分の極限粘度比が前記の範囲から外れ
る樹脂組成物の適当な条件下で、過酸化物等で分
解すれば、本発明の範囲の樹脂組成物にすること
ができる。このような方法も本発明の樹脂組成物
の製造方法として有利である。
本発明の樹脂組成物に用いることのできる有機
過酸化物としては、例えば、メチルエチルケトン
パーオキシド、メチルイソブチルケトンパーオキ
シド等のケトンパーオキシド、ｎ−ブチル−４，
４−ビス（ｔ−ブチルパーオキシ）バレレイト等
のパーオキシケタール、クメンヒドロパーオキシ
ド、ジイソプロピルベンゼンヒドロパーオキシド
等のヒドロパーオキシド、１，３−ビス（ｔ−ブ
チルパーオキシイソプロピル）ベンゼン、ジクミ
ルパーオキシド等のジアルキルパーオキシド、ベ
ンゾイルパーオキシド、デカノイルパーオキシド
等のジアシルパーオキシド、ビス−（４−ｔ−ブ
チルシクロヘキシル）パーオキシジカーボネート
等のパーカーボネート、ｔ−ブチルパーオキシア
セテート、ｔ−ブチルパーオキシラウレート等の
パーオキシエステルなどが挙げられる。
また、本発明の樹脂組成物の過酸化物による熱
処理は、通常この共重合体の溶融温度以上、分解
温度未満において、該共重合体に上述の有機過酸
化物を適量加え、一軸押出機、二軸混練機、ニー
ダー、バンバリーミキサー、ロール等で溶融混練
することにより行う。
なお、上述のようにして得られたプロピレン重
合体組成物の粉末等を用いて成形品を製造する
際、必要に応じて適量の熱安定剤、酸化防止剤、
紫外線吸収剤、アンチブロツキング剤、帯電防止
剤、中和剤、滑剤、造核剤、着色剤、顔料その他
の添加剤及び無機充填剤などを配合することがで
きる。また、耐衝撃制向上等の目的でエチレンプ
ロピレンゴム、ポリエチレン、エチレン−プロピ
レン共重合体を配合することもできる。
［発明の効果］
このようにして得られた本発明の樹脂組成物及
びその製品は、優れた耐衝撃性、特に優れた耐面
衝撃性を有するとともに、剛性にも優れ、かつ流
動性が高く、成形にも優れたポリプロピレン組成
物である。
［実施例］
本発明を実施例により、さらに詳細に説明す
る。
製造例［プロピレン重合体の製造］
内容積10の撹はん機付きオートクレーブに乾
燥したｎ−ヘキサン５を投入し、ジエチルアル
ミニウムクロリド1.0ｇと三塩化チタン0.3ｇを加
えた。
第１段階の重合反応は、液相温度を60℃に維持
し、生成するポリプロピレンが所定の極限粘度に
なるように計量された水素を連続的に添加し、反
応圧力を９Kg／cm2に維持しながらプロピレンを連
続的に供給し、90分撹はんしながら重合を行つ
た。しかる後、未反応プロピレンを除去し、液相
温度を57℃まで下げた。
次に２段階の重合反応は、温度を57℃に維持し
ながら、所定のガラス転移温度Tg及び極限粘度
比になるようにプロピレン−エチレン混合物及び
計量された水素を供給し、60分間重合を行つた。
次いで、未反応ガスを除去し、重合生成物に、
ｎ−ブタノール50℃で１時間撹はんして触媒分解
を行つた。その後、分離工程、洗浄工程、乾燥工
程を経て白色粉末状ポリマーを得た。得られたポ
リマーについて測定した物性を各表に示す。
実施例１〜５及び比較例１〜５
製造例の方法により各実施例毎に製造されたプ
ロピレン重合体に所定量の造核剤及び必要に応じ
て所定量の１，３−ビス（ｔ−ブチルパーオキシ
イソプロピル）ベンゼンを加え、均一に混合し
て、温度220℃にて押出機で溶融混練して改質ポ
リプロピレン樹脂組成物のペレツトを得た。この
ペレツトを射出成形機で試験片を作成し、その物
性を調べた。結果を第１表に示す。
実施例及び比較例において使用した表中の造核
剤の符号は次のとおりである。
イ； リン酸ビス（４−ブチルフエニル）ナトリ
ウム
ロ； ｐ−ｔ−ブチルベンゾエートのアルミニウ
ム塩
ハ； メチレンビス（２，４−ジ−ｔ−ブチルフ
エノール）アシツドホスフエート
[Industrial Field of Application] The present invention provides impact resistance (particularly surface impact resistance), rigidity,
This invention relates to a propylene resin composition that has excellent mechanical properties such as, and is suitable as a molding material in fields such as home appliances and automobiles. [Prior Art] Conventionally, a composition of a crystalline polypropylene component and an ethylene-propylene random copolymer component has been usually produced by introducing an ethylene monomer after the multi-stage polymerization of propylene (Japanese Patent Laid-Open No. 56 −
55416) and is commercially available as a so-called propylene block copolymer. This composition is widely used as a resin with excellent impact resistance and rigidity in various industrial fields such as large miscellaneous goods, automobiles, and home appliances, but in recent years, its uses have expanded further. Due to demands for lighter products or lower costs, molded products have become thinner and larger, and as a result, the required properties have become increasingly sophisticated. That is, there is a growing demand for quality products that maintain high fluidity and high rigidity while further improving impact resistance. In particular, this resin composition is required to have excellent surface impact resistance as well as isot impact resistance. However, conventional propylene resin compositions have the disadvantages of insufficient impact resistance, particularly surface impact resistance when thinned, and poor physical properties such as rigidity, fluidity, and processability. In order to improve these drawbacks, attempts have also been made to thermally decompose the high molecular weight propylene resin composition in the presence of peroxide to improve fluidity while maintaining mechanical properties. (Japanese Patent Publication No. 58-7665), the propylene resin composition obtained by this method is said to have a poor balance of physical properties, especially between surface impact resistance and rigidity, although the fluidity has been sufficiently improved. There were flaws. First, the present inventors specified the intrinsic viscosity ratio and glass transition temperature of the polypropylene and ethylene-propylene copolymer that make up the composition, and created a composition with excellent fluidity, high rigidity, and high surface impact resistance. However, this propylene resin composition was still insufficient in terms of rigidity. [Problems to be Solved by the Invention] The present invention provides a composition comprising crystalline polypropylene and ethylene-propylene copolymer, which has outstanding impact resistance such as surface impact resistance, and also has excellent rigidity and fluidity. This is what we are trying to provide. [Means for Solving the Problems] The present inventors conducted various studies in order to improve the above-mentioned physical properties of the propylene resin composition, and as a result, the present inventors found that the previously developed resin composition The present inventors have discovered that the physical properties can be further improved by incorporating a specific amount of a nucleating agent, leading to the present invention. That is, the propylene resin composition of the present invention is
A propylene resin composition containing (A) a crystalline polypropylene component, (B) an ethylene-propylene random copolymer component, and (C) a nucleating agent component, the weight of components (A) and (B) Ratio is 55:45 to 95:5, (A)
The ratio of the intrinsic viscosity [η]pp of the component and the intrinsic viscosity [η]ep of the component (B) [η]ep/[η]pp is 0.5 to 2.0, and the glass transition temperature of the component (B) is -30°C The following is a propylene resin composition characterized in that the content of component (C) is 0.005 to 1 part by weight per 100 parts by weight of the total amount of components (A) and (B). In the composition of the present invention, the content of component (A) is 95
When the weight ratio exceeds 55, impact resistance such as isot impact resistance and surface impact resistance decreases, and when the weight ratio is less than 55, rigidity decreases. Also, the ratio of the limiting viscosity is
If it exceeds 2.0, the surface impact resistance will decrease, and if it is less than 0.5, the surface impact resistance will decrease and the rigidity will also decrease. Component (A) used in the resin composition of the present invention is a propylene homopolymer obtained by polymerizing propylene using a stereoregular catalyst, or
It is essentially a propylene homopolymer containing 2% by weight or less of ethylene units or other olefin units. (A) The content of ethylene units, etc. in the component is 2% by weight.
If a larger amount of propylene-ethylene copolymer is used, the stiffness of the resulting composition will be unsuitably reduced. As the component (B) used in the resin composition of the present invention,
20 to 80 ethylene units obtained by polymerizing ethylene and propylene or a small amount of other olefins using a stereoregular catalyst, etc.
It is a so-called substantial ethylene-propylene random copolymer containing a small amount of other olefin units in the copolymer, and a small amount of ethylene alone produced during copolymerization. Those containing polymers can also be used. These (A) and (B) components can be produced separately, but usually, the (A) component produced in the previous stage is mixed in the latter stage polymerization tank of the two-stage polymerization method. A composition can be obtained directly from the polymerization tank by carrying out a copolymerization reaction of component (B) in the presence of the component (B). The ratio of component (A) and component (B) can be determined by blending separately manufactured components (A) and (B) in a predetermined ratio, or by combining the raw materials for each step in a multi-stage polymerization method. The monomer composition, amount charged, and polymerization conditions can be selected and adjusted. During the synthesis of components (A) and (B) of the present invention, examples of monomers that can be copolymerized in small amounts in these polymer chains include 1-butene, 1-pentene, 1-hexene, and 1-heptene. , isobutene, and 4-methyl-1-pentene. In the present invention, it is necessary that the glass transition temperature of the ethylene-propylene copolymer as component (B) is -30°C or lower, and if the transition temperature is higher than this, the surface impact strength decreases. In the resin composition of the present invention, the ratio [η]pp/[η]ep of the intrinsic viscosity [η]pp of component (A) to the intrinsic viscosity [η]ep of component (B) is 0.5 to 2, preferably is 0.7
~1.7; if it is 2 or more, the surface impact strength decreases; if it is 0.5 or less, not only the surface impact strength but also the rigidity decreases. The intrinsic viscosity of component (A) and component (B) of the resin composition of the present invention was obtained by measuring each component in decalin at 135°C. However, the component (B) in the resin composition of the present invention is 2
If the polypropylene is produced by stage polymerization in the presence of component (A), measure the intrinsic viscosity of the polypropylene sampled at the outlet of the first stage polymerization reactor where propylene homopolymerization is carried out. Intrinsic viscosity of component (A) [η] pp, limiting viscosity of component (B) [η]
In the present invention, ep is calculated by the following formula and is used for convenience. [η] ep = (1/M) [η] c - (1/M-1) [η] pp In the formula, [η] c is the resin obtained in a mixed state from the subsequent polymerization tank, that is, (A) This is the overall intrinsic viscosity of the components and (B) component. Furthermore, M is the weight fraction of component (B), which is determined by subtracting the weight fraction of the preceding polymer from the total amount of resin. The formula was derived on the assumption that the following formula holds between the intrinsic viscosity of each of component (A) and component (B) and the intrinsic viscosity of the entire composition in which they are mixed. [η]c=M[η]ep+(1-M)[η]pp In order to further improve the rigidity of the resin composition of the present invention, the crystalline polypropylene component (A) is Tsudo fraction [IP] is
It is more preferable that it satisfies the formula [IP]≧−1.02[η]pp+96.0 (wherein, [η]pp has the same meaning as above). What is the ice-tack pentad fraction here?
Macromolecules by A. Zambelli et al. Volume 6, 925
(1973), namely 13 C-NMR.
It is the isotactic fraction in pentad units in a polypropylene molecular chain measured by a method using In other words, the isotactic bend fraction is the fraction of the propylene monomer unit at the center of a chain of five consecutive meso-bonded propylene monomer units. However, regarding peak assignment, Macromolecules
This was carried out based on the revised version of the above document described in Vol. 8, 687 (1975). Specifically, in the total absorption peak in the methyl carbon region of the 13C -NMR spectrum,
Isotactic pentad units are measured as the intensity fraction of the mmmm peak. the intrinsic viscosity of the component (A) and component (B) and the ratio thereof;
And the glass transition temperature can be adjusted by appropriately selecting the type of catalyst, polymerization conditions such as polymerization temperature at each stage, and the amount of molecular weight regulator such as hydrogen gas used during polymerization.
The isotactic pentad fraction [IP] is
Polymerization conditions such as the type of polymerization catalyst, selection of prepolymerization monomers, and polymerization temperature can be adjusted. As a nucleating agent used in the resin composition of the present invention,
Organic and inorganic nucleating agents can be used. Examples of organic nucleating agents include metal salts of benzoic acid or derivatives thereof (such as aluminum salts of pt-butylbenzoate), dibenzylidene sorbitol and derivatives thereof (1,3 , 2,4-dibenzylidene sorbitol, 1,3,2,4-di(p-methylbenzylidene) sorbitol, 1,3,2,4
-di(p-chlorobenzylidene)sorbitol,
1,3,2,4-di(p-methoxybenzylidene)sorbitol, etc.), bis(4-t-
butylphenyl) sodium, methylenebis(2,4-di-t-butylphenol) acid phosphate sodium salt, calcium oxalate, magnesium stearate, zinc salicylate, calcium tartrate, and other organic acid salts. Examples of the inorganic nucleating agent include clays such as talc, clay, mica, montmorillonite, and bentonite; inorganic salts such as calcium silicate, magnesium silicate, calcium sulfate, barium sulfate, calcium carbonate, and magnesium carbonate; Examples include metal oxides such as alumina, titanium oxide, iron oxide, magnesium oxide, and zinc oxide. Among the various nucleating agents described above, phosphonate-based nucleating agents are particularly preferred as organic nucleating agents. The blending amount of these nucleating agents is based on 100 parts by weight of the total amount of components (A) and (B) of the resin composition of the present invention.
0.005 to 1 part by weight, especially 0.01 to 0.5 part by weight. If the amount of this nucleating agent is less than 0.005 part by weight, there will be no improvement in the rigidity, heat resistance, hardness, etc. of the polypropylene resin molded product, and even if the amount is more than 1 part by weight, the polypropylene resin molded product will not improve. Rigidity etc. will not improve any further. Note that this composition may contain other additives within a range that does not impede the object of the invention. Examples of such additives include various additives such as antistatic agents, colorants, flame retardants, antioxidants, ultraviolet absorbers, plasticizers, and heat stabilizers. By further adding 0.005 to 0.3 parts by weight of an organic peroxide to the resin composition of the present invention and kneading and heating, a more excellent propylene polymer composition can be obtained. At this time, each constituent polymer of the composition is decomposed to have a low molecular weight, giving a highly fluid resin composition. In this case, it is advantageous to set the PI value, which is an index of molecular weight distribution, to 4 or less because a composition having excellent surface impact properties can be obtained. Here, the PI value is an index of molecular weight distribution,
Engineering] P333 (1981). In other words, in melt viscoelasticity measurement, the elastic modulus at the intersection of the storage modulus and the loss modulus is expressed as Gc (dyne/
cm 2 ), it is expressed as PI=10 6 /Gc. In addition, in this case, the measurement of melt viscoelasticity is carried out in the Journal of Applied Polymer Science (J.Appl.Poly.Sci.) Vol. 30, 3751-3765.
(1985), at a temperature of 170°C and strain
The measurement was carried out under the conditions of a 20% cone plate diameter of 25 mm and a cone angle of 0.1 rad. By such decomposition treatment with peroxide, the ratio of the limiting viscosity of component (A) to the intrinsic viscosity of component (B) becomes closer to 1 than before the decomposition treatment. From this point of view, (A) of the resin composition of the present invention
A resin composition within the scope of the present invention can be obtained by decomposing a resin composition with a peroxide or the like under appropriate conditions in which the intrinsic viscosity ratio of the component and component (B) is outside the above range. Such a method is also advantageous as a method for producing the resin composition of the present invention. Examples of organic peroxides that can be used in the resin composition of the present invention include ketone peroxides such as methyl ethyl ketone peroxide and methyl isobutyl ketone peroxide, n-butyl-4,
Peroxyketals such as 4-bis(t-butylperoxy)valerate, hydroperoxides such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, 1,3-bis(t-butylperoxyisopropyl)benzene, dicumyl Dialkyl peroxides such as peroxide, diacyl peroxides such as benzoyl peroxide and decanoyl peroxide, percarbonates such as bis-(4-t-butylcyclohexyl) peroxydicarbonate, t-butyl peroxyacetate, t- Examples include peroxy esters such as butyl peroxylaurate. Further, the heat treatment of the resin composition of the present invention with a peroxide is usually carried out by adding an appropriate amount of the above-mentioned organic peroxide to the copolymer at a temperature higher than the melting temperature of the copolymer and lower than the decomposition temperature, and using a uniaxial extruder. This is carried out by melt-kneading using a twin-screw kneader, kneader, Banbury mixer, roll, etc. In addition, when manufacturing a molded article using the powder of the propylene polymer composition obtained as described above, an appropriate amount of a heat stabilizer, an antioxidant,
Ultraviolet absorbers, anti-blocking agents, antistatic agents, neutralizing agents, lubricants, nucleating agents, coloring agents, pigments and other additives, and inorganic fillers can be blended. Furthermore, ethylene propylene rubber, polyethylene, or ethylene-propylene copolymer may be blended for the purpose of improving impact resistance. [Effects of the Invention] The resin composition of the present invention and its products thus obtained have excellent impact resistance, particularly excellent surface impact resistance, as well as excellent rigidity and high fluidity. It is a polypropylene composition that is also excellent in molding. [Example] The present invention will be explained in more detail with reference to Examples. Production Example [Production of Propylene Polymer] Dry n-hexane 5 was charged into an autoclave with an internal volume of 10 and equipped with a stirrer, and 1.0 g of diethylaluminium chloride and 0.3 g of titanium trichloride were added. In the first stage polymerization reaction, the liquidus temperature is maintained at 60℃, hydrogen is continuously added in a measured amount so that the polypropylene produced has a predetermined intrinsic viscosity, and the reaction pressure is maintained at 9Kg/cm 2 . While stirring, propylene was continuously supplied, and polymerization was carried out with stirring for 90 minutes. Thereafter, unreacted propylene was removed and the liquid phase temperature was lowered to 57°C. Next, in the two-stage polymerization reaction, while maintaining the temperature at 57°C, a propylene-ethylene mixture and a metered amount of hydrogen were supplied to achieve a predetermined glass transition temperature Tg and intrinsic viscosity ratio, and polymerization was carried out for 60 minutes. Ivy. Then, unreacted gas is removed and the polymerization product is
Catalytic decomposition was carried out by stirring n-butanol at 50°C for 1 hour. Thereafter, a white powdery polymer was obtained through a separation process, a washing process, and a drying process. The physical properties measured for the obtained polymers are shown in each table. Examples 1 to 5 and Comparative Examples 1 to 5 A predetermined amount of a nucleating agent and, if necessary, a predetermined amount of 1,3-bis(t- Butylperoxyisopropyl)benzene was added, mixed uniformly, and melt-kneaded in an extruder at a temperature of 220°C to obtain pellets of a modified polypropylene resin composition. Test pieces were made from the pellets using an injection molding machine, and their physical properties were investigated. The results are shown in Table 1. The codes of the nucleating agents in the table used in Examples and Comparative Examples are as follows. A; Sodium bis(4-butylphenyl) phosphate B; Aluminum salt of pt-butylbenzoate C; Methylene bis(2,4-di-t-butylphenol) acid phosphate
【表】
比較例 ６〜10
エチレン−プロピレン共重合体のガラス転移温
度が−30℃以下、ポリプロピレンとエチレン−プ
ロピレン共重合体との極限粘度比〔η〕ep／
〔η〕ppが2.0よりも大又は0.5未満になるように
重合条件を調整して得たポリマーを用い、実施例
１〜５と同様にして作成した試験片について物性
を調べその結果を第２表に示す。
この表から明らかなように、実施例１〜５と対
応する組成のポリマーを用いた試験片であつて
も、極限粘度比が0.5〜0.2の範囲外の場合は、落
錘衝撃値が著しく低下するととともに曲げ弾性率
も全般的に低下している。[Table] Comparative Examples 6 to 10 The glass transition temperature of the ethylene-propylene copolymer is -30°C or lower, the intrinsic viscosity ratio of polypropylene and the ethylene-propylene copolymer [η] ep/
[η] Using polymers obtained by adjusting polymerization conditions so that pp is greater than 2.0 or less than 0.5, the physical properties of test pieces prepared in the same manner as in Examples 1 to 5 were examined and the results were used in the second Shown in the table. As is clear from this table, even for test pieces using polymers with compositions corresponding to Examples 1 to 5, when the intrinsic viscosity ratio is outside the range of 0.5 to 0.2, the falling weight impact value decreases significantly. At the same time, the flexural modulus generally decreases.
【表】
比較例 11〜15
エチレン−プロピレン共重合体のガラス転移温
度が−30℃よりも高く、ポリプロピレンとエチレ
ン−プロピレン共重合体との極限粘度比〔η〕
ep／〔η〕ppが0.5〜2.0の範囲になるように重合
条件を調整して得たポリマーを用い、実施例１〜
５と同様にして作成した試験片について物性を調
べその結果を第３表に示す。
この表から明らかなように、実施例１〜５と対
応する組成のポリマーを用いた試験片であつて
も、ガラス転移温度が−30℃よりも高いエチレン
−プロピレン共重合体の場合は、落錘衝撃値が著
しく低下している。[Table] Comparative Examples 11 to 15 The glass transition temperature of the ethylene-propylene copolymer is higher than -30°C, and the intrinsic viscosity ratio of polypropylene and ethylene-propylene copolymer [η]
Using polymers obtained by adjusting polymerization conditions so that ep/[η]pp was in the range of 0.5 to 2.0, Examples 1 to
The physical properties of the test pieces prepared in the same manner as in 5 were investigated and the results are shown in Table 3. As is clear from this table, even with test specimens using polymers with compositions corresponding to Examples 1 to 5, ethylene-propylene copolymers with glass transition temperatures higher than -30°C tend to fail. The weight impact value has decreased significantly.
Claims (1)
プロピレンランダム共重合体成分並びに(C)造核剤
成分を含有するプロピレン樹脂組成物であつて、
(A)成分と(B)成分との重量比が55：45ないし95：
５、(A)成分の極限粘度〔η〕pp及び(B)成分の極
限粘度〔η〕epの比〔η〕ep／〔η〕ppが0.5〜
2.0であり、(B)成分のガラス転移温度が−30℃以
下、(C)成分の含有量が(A)成分と(B)成分の合計量
100重量部当たり0.005〜１重量部であることとを
特徴とするプロピレン樹脂組成物。[Claims] 1. (A) Crystalline polypropylene component and (B) Ethylene-
A propylene resin composition containing a propylene random copolymer component and (C) a nucleating agent component,
The weight ratio of component (A) to component (B) is 55:45 to 95:
5. The ratio of the intrinsic viscosity [η]pp of component (A) and the limiting viscosity [η]ep of component (B) [η]ep/[η]pp is 0.5 to
2.0, the glass transition temperature of component (B) is -30℃ or lower, and the content of component (C) is the total amount of components (A) and (B).
A propylene resin composition characterized in that the amount is 0.005 to 1 part by weight per 100 parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29258386A JPS63146953A (en) | 1986-12-10 | 1986-12-10 | Propylene resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29258386A JPS63146953A (en) | 1986-12-10 | 1986-12-10 | Propylene resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63146953A JPS63146953A (en) | 1988-06-18 |
| JPH0463098B2 true JPH0463098B2 (en) | 1992-10-08 |
Family
ID=17783654
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29258386A Granted JPS63146953A (en) | 1986-12-10 | 1986-12-10 | Propylene resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63146953A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2091289T5 (en) † | 1990-05-14 | 2008-11-01 | UNION CARBIDE CHEMICALS & PLASTICS TECHNOLOGY CORPORATION | POLYMER COMPOSITIONS. |
| KR100977665B1 (en) * | 2009-12-18 | 2010-08-24 | 에스케이에너지 주식회사 | Ethylene-propylene block copolymer-based polypropylene resin composition having high impact strength, surface properties and flowability |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4961278A (en) * | 1972-09-26 | 1974-06-13 | ||
| JPS55139447A (en) * | 1979-04-06 | 1980-10-31 | Chisso Corp | Modification of propylene-ethylene block copolymer |
| JPS5884838A (en) * | 1981-11-17 | 1983-05-21 | Mitsui Petrochem Ind Ltd | Manufacture of polypropylene composition |
| JPS58134714A (en) * | 1982-02-03 | 1983-08-11 | Sumitomo Chem Co Ltd | Manufacture of polypropylene drawn film |
| JPS5941311A (en) * | 1982-09-02 | 1984-03-07 | Mitsui Toatsu Chem Inc | Propylene-ethylene copolymer and its preparation |
| JPS61159437A (en) * | 1985-01-05 | 1986-07-19 | Showa Denko Kk | Propylene polymer mixture |
-
1986
- 1986-12-10 JP JP29258386A patent/JPS63146953A/en active Granted
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4961278A (en) * | 1972-09-26 | 1974-06-13 | ||
| JPS55139447A (en) * | 1979-04-06 | 1980-10-31 | Chisso Corp | Modification of propylene-ethylene block copolymer |
| JPS5884838A (en) * | 1981-11-17 | 1983-05-21 | Mitsui Petrochem Ind Ltd | Manufacture of polypropylene composition |
| JPS58134714A (en) * | 1982-02-03 | 1983-08-11 | Sumitomo Chem Co Ltd | Manufacture of polypropylene drawn film |
| JPS5941311A (en) * | 1982-09-02 | 1984-03-07 | Mitsui Toatsu Chem Inc | Propylene-ethylene copolymer and its preparation |
| JPS61159437A (en) * | 1985-01-05 | 1986-07-19 | Showa Denko Kk | Propylene polymer mixture |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63146953A (en) | 1988-06-18 |
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