JP4666896B2 - Polypropylene resin composition - Google Patents
Polypropylene resin composition Download PDFInfo
- Publication number
- JP4666896B2 JP4666896B2 JP2003294991A JP2003294991A JP4666896B2 JP 4666896 B2 JP4666896 B2 JP 4666896B2 JP 2003294991 A JP2003294991 A JP 2003294991A JP 2003294991 A JP2003294991 A JP 2003294991A JP 4666896 B2 JP4666896 B2 JP 4666896B2
- Authority
- JP
- Japan
- Prior art keywords
- polypropylene resin
- ptfe
- weight
- flame retardant
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- -1 Polypropylene Polymers 0.000 title claims description 81
- 229920001155 polypropylene Polymers 0.000 title claims description 67
- 239000004743 Polypropylene Substances 0.000 title claims description 66
- 239000011342 resin composition Substances 0.000 title claims description 22
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 62
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 62
- 239000003063 flame retardant Substances 0.000 claims description 53
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 52
- 229920005989 resin Polymers 0.000 claims description 47
- 239000011347 resin Substances 0.000 claims description 47
- 229910019142 PO4 Inorganic materials 0.000 claims description 26
- 239000010452 phosphate Substances 0.000 claims description 26
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 25
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 25
- 238000004898 kneading Methods 0.000 claims description 16
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical group [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims description 8
- 150000004706 metal oxides Chemical class 0.000 claims description 8
- 239000011159 matrix material Substances 0.000 claims description 7
- 239000000155 melt Substances 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 53
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 24
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 24
- 239000000178 monomer Substances 0.000 description 19
- 238000006116 polymerization reaction Methods 0.000 description 19
- 239000000203 mixture Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 15
- 239000000047 product Substances 0.000 description 14
- 238000002156 mixing Methods 0.000 description 13
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 12
- 239000005977 Ethylene Substances 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229920005672 polyolefin resin Polymers 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 229920005992 thermoplastic resin Polymers 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 5
- 239000011949 solid catalyst Substances 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 229920001400 block copolymer Polymers 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 229920000388 Polyphosphate Polymers 0.000 description 3
- 229920000297 Rayon Polymers 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 3
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 239000001205 polyphosphate Substances 0.000 description 3
- 235000011176 polyphosphates Nutrition 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229920001384 propylene homopolymer Polymers 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 2
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 2
- 239000004114 Ammonium polyphosphate Substances 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 2
- 229920006361 Polyflon Polymers 0.000 description 2
- 229910003902 SiCl 4 Inorganic materials 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- NJYZCEFQAIUHSD-UHFFFAOYSA-N acetoguanamine Chemical compound CC1=NC(N)=NC(N)=N1 NJYZCEFQAIUHSD-UHFFFAOYSA-N 0.000 description 2
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 2
- 229920001276 ammonium polyphosphate Polymers 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000012968 metallocene catalyst Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- UDGSVBYJWHOHNN-UHFFFAOYSA-N n',n'-diethylethane-1,2-diamine Chemical compound CCN(CC)CCN UDGSVBYJWHOHNN-UHFFFAOYSA-N 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- XZTOTRSSGPPNTB-UHFFFAOYSA-N phosphono dihydrogen phosphate;1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N)=N1.OP(O)(=O)OP(O)(O)=O XZTOTRSSGPPNTB-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- NSMWYRLQHIXVAP-OLQVQODUSA-N (2r,5s)-2,5-dimethylpiperazine Chemical compound C[C@H]1CN[C@H](C)CN1 NSMWYRLQHIXVAP-OLQVQODUSA-N 0.000 description 1
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 1
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-UHFFFAOYSA-N 0.000 description 1
- VTPNYMSKBPZSTF-UHFFFAOYSA-N 1-ethenyl-2-ethylbenzene Chemical compound CCC1=CC=CC=C1C=C VTPNYMSKBPZSTF-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 1
- HRIJSYATNFJXHM-UHFFFAOYSA-N 2,6-diamino-1h-1,3,5-triazine-4-thione Chemical compound NC1=NC(=S)N=C(N)N1 HRIJSYATNFJXHM-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- PAOXFRSJRCGJLV-UHFFFAOYSA-N 2-[4-(2-aminoethyl)piperazin-1-yl]ethanamine Chemical compound NCCN1CCN(CCN)CC1 PAOXFRSJRCGJLV-UHFFFAOYSA-N 0.000 description 1
- RXNOYRCWKRFNIM-UHFFFAOYSA-N 2-carbonochloridoylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(Cl)=O RXNOYRCWKRFNIM-UHFFFAOYSA-N 0.000 description 1
- ISRGONDNXBCDBM-UHFFFAOYSA-N 2-chlorostyrene Chemical compound ClC1=CC=CC=C1C=C ISRGONDNXBCDBM-UHFFFAOYSA-N 0.000 description 1
- YWZIIYJZQKWCIE-UHFFFAOYSA-N 2-n-[3-[(4,6-diamino-1,3,5-triazin-2-yl)amino]propyl]-1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(NCCCNC=2N=C(N)N=C(N)N=2)=N1 YWZIIYJZQKWCIE-UHFFFAOYSA-N 0.000 description 1
- BRCJAKSIYWHLPW-UHFFFAOYSA-N 2-n-[4-[(4,6-diamino-1,3,5-triazin-2-yl)amino]butyl]-1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(NCCCCNC=2N=C(N)N=C(N)N=2)=N1 BRCJAKSIYWHLPW-UHFFFAOYSA-N 0.000 description 1
- UHRBOLIZWMDRRD-UHFFFAOYSA-N 2-n-[6-[(4,6-diamino-1,3,5-triazin-2-yl)amino]hexyl]-1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(NCCCCCCNC=2N=C(N)N=C(N)N=2)=N1 UHRBOLIZWMDRRD-UHFFFAOYSA-N 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- IEJVTQXJNCSWRG-UHFFFAOYSA-N 6-amino-1h-1,3,5-triazine-2,4-dione;2,6-diamino-1h-1,3,5-triazin-4-one Chemical compound NC1=NC(=O)N=C(N)N1.NC1=NC(=O)NC(=O)N1 IEJVTQXJNCSWRG-UHFFFAOYSA-N 0.000 description 1
- QQLZTRHXUSFZOM-UHFFFAOYSA-N 6-amino-1h-1,3,5-triazine-2,4-dithione Chemical compound NC1=NC(=S)NC(=S)N1 QQLZTRHXUSFZOM-UHFFFAOYSA-N 0.000 description 1
- BVZPBJHXLZKTKX-UHFFFAOYSA-N 6-ethoxy-1,3,5-triazine-2,4-diamine Chemical compound CCOC1=NC(N)=NC(N)=N1 BVZPBJHXLZKTKX-UHFFFAOYSA-N 0.000 description 1
- XVMFICQRQHBOOT-UHFFFAOYSA-N 6-methoxy-1,3,5-triazine-2,4-diamine Chemical compound COC1=NC(N)=NC(N)=N1 XVMFICQRQHBOOT-UHFFFAOYSA-N 0.000 description 1
- BDPPZSFVSOBOIX-UHFFFAOYSA-N 6-nonyl-1,3,5-triazine-2,4-diamine Chemical compound CCCCCCCCCC1=NC(N)=NC(N)=N1 BDPPZSFVSOBOIX-UHFFFAOYSA-N 0.000 description 1
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- ATCQNYLEZRQALQ-UHFFFAOYSA-N 6-propan-2-yloxy-1,3,5-triazine-2,4-diamine Chemical compound CC(C)OC1=NC(N)=NC(N)=N1 ATCQNYLEZRQALQ-UHFFFAOYSA-N 0.000 description 1
- KVMMIYOZBPTUQR-UHFFFAOYSA-N 6-propoxy-1,3,5-triazine-2,4-diamine Chemical compound CCCOC1=NC(N)=NC(N)=N1 KVMMIYOZBPTUQR-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- AQZGPSLYZOOYQP-UHFFFAOYSA-N Diisoamyl ether Chemical compound CC(C)CCOCCC(C)C AQZGPSLYZOOYQP-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000004716 Ethylene/acrylic acid copolymer Substances 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- CJKRXEBLWJVYJD-UHFFFAOYSA-N N,N'-diethylethylenediamine Chemical compound CCNCCNCC CJKRXEBLWJVYJD-UHFFFAOYSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-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
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- MASBWURJQFFLOO-UHFFFAOYSA-N ammeline Chemical compound NC1=NC(N)=NC(O)=N1 MASBWURJQFFLOO-UHFFFAOYSA-N 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- WXCZUWHSJWOTRV-UHFFFAOYSA-N but-1-ene;ethene Chemical compound C=C.CCC=C WXCZUWHSJWOTRV-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- CJSBUWDGPXGFGA-UHFFFAOYSA-N dimethyl-butadiene Natural products CC(C)=CC=C CJSBUWDGPXGFGA-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- WLPKFQRBARNCNR-UHFFFAOYSA-N ethene 1,3,5-triazine-2,4,6-triamine Chemical compound C=C.NC1=NC(N)=NC(N)=N1.NC1=NC(N)=NC(N)=N1 WLPKFQRBARNCNR-UHFFFAOYSA-N 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- PWSKHLMYTZNYKO-UHFFFAOYSA-N heptane-1,7-diamine Chemical compound NCCCCCCCN PWSKHLMYTZNYKO-UHFFFAOYSA-N 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229940030980 inova Drugs 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- DILRJUIACXKSQE-UHFFFAOYSA-N n',n'-dimethylethane-1,2-diamine Chemical compound CN(C)CCN DILRJUIACXKSQE-UHFFFAOYSA-N 0.000 description 1
- KVKFRMCSXWQSNT-UHFFFAOYSA-N n,n'-dimethylethane-1,2-diamine Chemical compound CNCCNC KVKFRMCSXWQSNT-UHFFFAOYSA-N 0.000 description 1
- VGIVLIHKENZQHQ-UHFFFAOYSA-N n,n,n',n'-tetramethylmethanediamine Chemical compound CN(C)CN(C)C VGIVLIHKENZQHQ-UHFFFAOYSA-N 0.000 description 1
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- SFBTTWXNCQVIEC-UHFFFAOYSA-N o-Vinylanisole Chemical compound COC1=CC=CC=C1C=C SFBTTWXNCQVIEC-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- MWFNQNPDUTULBC-UHFFFAOYSA-N phosphono dihydrogen phosphate;piperazine Chemical compound C1CNCCN1.OP(O)(=O)OP(O)(O)=O MWFNQNPDUTULBC-UHFFFAOYSA-N 0.000 description 1
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 description 1
- NQQWFVUVBGSGQN-UHFFFAOYSA-N phosphoric acid;piperazine Chemical compound OP(O)(O)=O.C1CNCCN1 NQQWFVUVBGSGQN-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 238000007613 slurry method Methods 0.000 description 1
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、ポリプロピレン樹脂組成物に関する。詳しくは、外力により凝集することなく、取り扱いが容易なテトラフルオロエチレン樹脂のマスターバッチを、リン酸塩系難燃剤と共にポリプロピレン樹脂に特定量配合してなる難燃性ポリプロピレン樹脂組成物に関する。 The present invention relates to a polypropylene resin composition. More specifically, the present invention relates to a flame retardant polypropylene resin composition obtained by blending a specific amount of a tetrafluoroethylene resin masterbatch that is easy to handle without aggregating with an external force into a polypropylene resin together with a phosphate flame retardant.
テトラフルオロエチレン樹脂（ＰＴＦＥ）は、熱可塑性樹脂に少量添加することにより、熱可塑性樹脂の難燃化における滴下防止効果が大きいことが知られている。 It is known that tetrafluoroethylene resin (PTFE) has a great effect of preventing dripping in the flame retardancy of a thermoplastic resin when added in a small amount to the thermoplastic resin.
一般に、熱可塑性樹脂にＰＴＦＥを添加する場合は、ＰＴＦＥの融点が熱可塑性樹脂の加工温度より高いためにＰＴＦＥの融点以下で混練される。ＰＴＦＥはせん断力を受けることにより容易に繊維化したり凝集しやすく、熱可塑性樹脂に混練り添加されたＰＴＦＥは、ネットワーク状に繊維化して滴下防止などの効果を発揮すると言われている。しかしながら、ＰＴＦＥのこのような繊維化や凝集のし易さは、取り扱いの上では非常に厄介であり、取り扱い性の向上技術が種々提案されている。例えば、ＰＴＦＥを予め、高級脂肪酸類の分散剤で処理する方法が提案されている（特許文献1参照）。 In general, when PTFE is added to a thermoplastic resin, the melting point of PTFE is higher than the processing temperature of the thermoplastic resin, so that the PTFE is kneaded below the melting point of PTFE. PTFE is easily fibrillated or aggregated by receiving a shearing force, and PTFE kneaded and added to a thermoplastic resin is said to be fiberized into a network and exhibit effects such as dripping prevention. However, the ease of fiberization and aggregation of PTFE is very troublesome in handling, and various techniques for improving the handling properties have been proposed. For example, a method of treating PTFE with a higher fatty acid dispersant in advance has been proposed (see Patent Document 1).
一方、従来より取り扱い性を向上させるために、ＰＴＦＥを高濃度に含有する各種の粒状組成物が検討されている（特許文献２〜５参照）。しかしながら、ポリオレフィン樹脂においては、これらの技術においてもＰＴＦＥの分散性が充分でなく、難燃性、燃焼時の滴下防止性、剛性が充分に発揮されないなどの問題があった。 On the other hand, various granular compositions containing PTFE at a high concentration have been studied in order to improve the handleability (see Patent Documents 2 to 5). However, the polyolefin resin has problems such as insufficient dispersibility of PTFE even in these technologies, flame retardancy, prevention of dripping during combustion, and insufficient rigidity.
また、ポリオレフィンの難燃性を向上させる為に、特定のリン酸塩系難燃剤とドリップ防止剤を組合わせて使用する方法が提案されている（引用文献６）。しかしながら、これらの方法でも、十分な難燃性と剛性の両者を保持した組成物は達成されていない。
本発明の目的は、上記問題に鑑みポリプロピレン樹脂の難燃特性や基本物性である剛性低下の問題点を解決することであり、ＰＴＦＥとリン酸塩系難燃剤を複合することにより、燃焼時の滴下防止性、外観等に優れた、かつ少ない難燃剤の配合量で優れた難燃性を有するリン酸塩系難燃性ポリプロピレン樹脂組成物を提供することにある。 The object of the present invention is to solve the problem of rigidity reduction, which is a flame retardant property and basic physical properties of polypropylene resin in view of the above problems, and by combining PTFE and a phosphate flame retardant, An object of the present invention is to provide a phosphate-based flame-retardant polypropylene resin composition that has excellent anti-dripping properties, appearance, and the like, and has excellent flame retardancy with a small amount of flame retardant.
本発明者らは難燃性、燃焼時の滴下防止性、剛性、外観等に優れたリン系難燃性ポリオレフィン樹脂組成物を得るべく鋭意検討した結果、ＰＴＦＥをマトリクス樹脂と溶融混練して得られる粒状のＰＴＦＥマスターバッチを特定のポリプロピレン樹脂およびリン酸塩系難燃剤と溶融混練することにより目的が達成されることを見出し、本発明を完成するに至った。 As a result of intensive investigations to obtain a phosphorus-based flame-retardant polyolefin resin composition excellent in flame retardancy, anti-dripping property, rigidity, appearance, etc., the present inventors obtained PTFE by melt-kneading with a matrix resin. It was found that the object was achieved by melt-kneading the granular PTFE master batch obtained with a specific polypropylene resin and a phosphate flame retardant, and the present invention was completed.
すなわち本発明は、ＭＦＲが０．１〜８０ｇ／１０分、アイソタクチックペンタッド分率が０．９７以上の結晶性ポリプロピレン樹脂（Ａ）及びリン酸塩系難燃剤（Ｂ）の合計量１００重量部に対して、テトラフルオロエチレン樹脂（ＰＴＦＥ）を溶融混練したマスターバッチ（Ｃ）を、ＰＴＦＥとして０．０１〜３重量部を溶融混練してなる難燃性ポリプロピレン樹脂組成物であって、該マスターバッチ（Ｃ）の樹脂マトリックスがポリプロピレン樹脂であり、かつ該結晶性ポリプロピレン樹脂（Ａ）、該リン酸塩系難燃剤（Ｂ）及び該マスターバッチ（Ｃ）の溶融混練は、該結晶性ポリプロピレン樹脂（Ａ）は溶融するが、ＰＴＦＥは溶融することなく、混練温度１７０〜２３０℃で行うことを特徴とする難燃性ポリプロピレン樹脂組成物に存する。
That is, the present invention provides a total amount of 100 of the crystalline polypropylene resin (A) and the phosphate flame retardant (B) having an MFR of 0.1 to 80 g / 10 min and an isotactic pentad fraction of 0.97 or more. A masterbatch (C) obtained by melt-kneading tetrafluoroethylene resin (PTFE) with respect to parts by weight, a flame-retardant polypropylene resin composition obtained by melt-kneading 0.01 to 3 parts by weight as PTFE , The resin matrix of the master batch (C) is a polypropylene resin, and the crystalline polypropylene resin (A), the phosphate-based flame retardant (B) and the master batch (C) are melt-kneaded to produce the crystalline The flame-retardant polypropylene resin composition is characterized in that the polypropylene resin (A) is melted, but the PTFE is not melted, and the kneading temperature is 170 to 230 ° C. It resides in.
本発明によれば、優れた機械的強度、成形性に加えて、優れた難燃性を有するポリプロピレン樹脂組成物が得られる。難燃剤として少量のＰＴＦＥマスターバッチを使用し、塩素及び臭素含有化合物を使用していないので環境負荷が小さい。 According to the present invention, a polypropylene resin composition having excellent flame resistance in addition to excellent mechanical strength and moldability can be obtained. Since a small amount of PTFE masterbatch is used as a flame retardant and no chlorine and bromine-containing compounds are used, the environmental impact is small.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
ポリプロピレン樹脂（Ａ）
本発明に用いられるポリプロピレン樹脂（Ａ）としては、結晶性プロピレン単独重合体、プロピレンを主成分とし該プロピレンとエチレンもしくは炭素数４以上のα―オレフィンとのランダム共重合体、結晶性ポリプロピレンとプロピレンエチレンのゴム状共重合体からなるいわゆるブロック共重合体、もしくはこれらの２種以上の混合物等が挙げられる。
Polypropylene resin (A)
Examples of the polypropylene resin (A) used in the present invention include a crystalline propylene homopolymer, a random copolymer of propylene as a main component and the propylene and ethylene or an α-olefin having 4 or more carbon atoms, crystalline polypropylene and propylene. Examples include so-called block copolymers made of a rubbery copolymer of ethylene, or a mixture of two or more thereof.
本発明のポリプロピレン樹脂（Ａ）のメルトフローレート（ＭＦＲ）は、０．１〜８０ｇ／１０分、好ましくは５〜６０ｇ／１０分であり、アイソタクチックペンタッド分率が０．９７以上、好ましくは０．９８以上の、高度の立体規則性を有するポリプロピレン結晶性ポリプロピレン部分を有するものである。 The melt flow rate (MFR) of the polypropylene resin (A) of the present invention is 0.1 to 80 g / 10 minutes, preferably 5 to 60 g / 10 minutes, and the isotactic pentad fraction is 0.97 or more, Preferably, it has a polypropylene crystalline polypropylene portion having a high degree of stereoregularity of 0.98 or more.
本発明でのアイソタクチックペンタッド分率（[ｍｍｍｍ]）とは、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ッド単位でのアイソタクチック分率である（Macromolecules，６巻，９２５頁（1973年）参照）。換言すれば、アイソタクチックペンタッド分率は、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、Macromolecules，８巻、６８７頁（１９７５年）に記載の方法に基づいて行った。具体的な13Ｃ−ＮＭＲスペクトルのメチル炭素領域の全吸収ピーク中のケミカルシフトは、頭−尾結合しメチル分岐の方向が同一であるプロピレン単位５連鎖の第３単位目のメチル基を２１．８ｐｐｍとして設定し、他の炭素ピークのケミカルシフトはこれを基準とし、［ｍｍｍｍ］ピークの強度分率としてアイソタクチックペンタッド単位を測定する。 The isotactic pentad fraction ([mmmm]) in the present invention is an isotactic fraction of pentad units in a polypropylene molecular chain measured by a method using 13 C-NMR (Macromolecules, 6, page 925 (1973)). In other words, the isotactic pentad fraction is a fraction of a propylene monomer unit at the center of a chain in which five propylene monomer units are continuously meso-bonded. However, peak assignment was performed based on the method described in Macromolecules, Vol. 8, page 687 (1975). The chemical shift in the total absorption peak in the methyl carbon region of a specific 13 C-NMR spectrum is as follows. The methyl group of the third unit of the 5-unit propylene unit having a head-to-tail bond and the same methyl branching direction is represented by 21. It is set as 8 ppm, and the chemical shift of the other carbon peak is based on this, and the isotactic pentad unit is measured as the intensity fraction of the [mmmm] peak.
詳しくは、下記の13Ｃ−ＮＭＲスペクトルの測定方法にしたがって測定した値である。13Ｃ−ＮＭＲスペクトルは、１０ｍｍφＮＭＲ用サンプル管の中で、ポリプロピレン試料約１００ｍｇを、２ｍｌのオルトジクロロベンゼンと０．２ｍｌのベンゼン−ｄ６の混合溶媒に溶解させ、５００ＭＨｚのＮＭＲ装置（Varian社製、Ｉｎｏｖａ５００）を用いて、共鳴周波数１２５．７ＭＨｚで13Ｃ−ＮＭＲを測定した。 Specifically, it is a value measured according to the following 13 C-NMR spectrum measurement method. The 13 C-NMR spectrum was obtained by dissolving about 100 mg of a polypropylene sample in a mixed solvent of 2 ml of orthodichlorobenzene and 0.2 ml of benzene-d6 in a sample tube for 10 mmφ NMR, and a 500 MHz NMR apparatus (manufactured by Varian, 13 C-NMR was measured at a resonance frequency of 125.7 MHz using Inova 500).
［ｍｍｍｍ］は０．９７以上、好ましくは０．９８以上である。０．９７未満では、各種難燃剤を配合した際、剛性低下を引き起こし、十分な力学物性を保つことが出来ない。 [Mmmm] is 0.97 or more, preferably 0.98 or more. If it is less than 0.97, when various flame retardants are blended, rigidity is lowered and sufficient mechanical properties cannot be maintained.
本発明のポリプロピレン樹脂（Ａ）は、上記のＭＦＲと［ｍｍｍｍ］が充足される限り、特にその製造法が限定されるものではないが、通常、チーグラー型高活性触媒、あるいはメタロセン触媒を用いて製造される。 The production method of the polypropylene resin (A) of the present invention is not particularly limited as long as the above MFR and [mmmm] are satisfied. Usually, a Ziegler type highly active catalyst or a metallocene catalyst is used. Manufactured.
チーグラー（ＺＮ）触媒としては、マグネシウム、チタン、ハロゲン、電子供与体を必須成分とする固体触媒成分と有機アルミニウム化合物を組合わせた高活性触媒が好ましい。 The Ziegler (ZN) catalyst is preferably a highly active catalyst in which a solid catalyst component containing magnesium, titanium, halogen, and an electron donor as essential components and an organoaluminum compound are combined.
メタロセン触媒としては、ジルコニウム、ハフニウム、チタンなどの遷移金属にシクロペンタジエニル骨格を有する有機化合物およびハロゲン原子などが配位したメタロセン錯体と、アルモキサン化合物、イオン交換性珪酸塩、有機アルミニウム化合物などを組み合わせた触媒が有効である。 Examples of metallocene catalysts include organic compounds having a cyclopentadienyl skeleton and transition metal such as zirconium, hafnium, titanium, and metallocene complexes in which halogen atoms are coordinated, alumoxane compounds, ion-exchange silicates, organoaluminum compounds, and the like. The combined catalyst is effective.
プロピレンと共重合させるコモノマーとしては、エチレン、ブテン−１、ペンテン−１、ヘキセン−１、４−メチル−ペンテン−１等が挙げられる。これらコモノマー成分は、０〜１５重量％、好ましくは０〜１０重量％である。これらのうち、特に好ましいものは、プロピレンとエチレン及び／又はブテン−１とのランダム共重合体である。 Examples of comonomers copolymerized with propylene include ethylene, butene-1, pentene-1, hexene-1, 4-methyl-pentene-1. These comonomer components are 0 to 15% by weight, preferably 0 to 10% by weight. Among these, a particularly preferable one is a random copolymer of propylene and ethylene and / or butene-1.
反応系中の各モノマーの量比は経時的に一定である必要はなく、各モノマーを一定の混合比で供給することも便利であるし、供給するモノマーの混合比を経時的に変化させることも可能である。また、共重合反応比を考慮してモノマーのいずれかを分割添加することもできる。 The amount ratio of each monomer in the reaction system does not need to be constant over time, it is convenient to supply each monomer at a constant mixing ratio, and the mixing ratio of the supplied monomers can be changed over time. Is also possible. Also, any of the monomers can be added in portions in consideration of the copolymerization reaction ratio.
重合様式は、触媒成分と各モノマーが効率よく接触するならば、あらゆる様式の方法を採用することができる。具体的には、不活性溶媒を用いるスラリー法、不活性溶媒を実質的に用いずプロピレンを溶媒として用いるバルク法、溶液法あるいは実質的に液体溶媒を用いず各モノマーを実質的にガス状に保つ気相法を採用することができる。 As the polymerization method, any method can be adopted as long as the catalyst component and each monomer come into efficient contact. Specifically, a slurry method using an inert solvent, a bulk method using substantially no inert solvent as a solvent, a solution method, or a solution method, or substantially using each liquid without substantially using a liquid solvent. A gas phase method can be employed.
また、連続重合、回分式重合のいずれを用いてもよい。スラリー重合の場合には、重合溶媒としてヘキサン、ヘプタン、ペンタン、シクロヘキサン、ベンゼン、トルエン等の飽和脂肪族または芳香族炭化水素の単独あるいは混合物を用いることができる。 Further, either continuous polymerization or batch polymerization may be used. In the case of slurry polymerization, a saturated aliphatic or aromatic hydrocarbon such as hexane, heptane, pentane, cyclohexane, benzene and toluene can be used alone or as a polymerization solvent.
重合条件としては重合温度が−７８〜１６０℃、好ましくは０〜１５０℃であり、そのときの分子量調節剤として補助的に水素を用いることができる。また、重合圧力は０〜９０ｋｇ／ｃｍ2・Ｇ、好ましくは０〜６０ｋｇ／ｃｍ2・Ｇ、特に好ましくは１〜５０ｋｇ／ｃｍ2・Ｇである。 As the polymerization conditions, the polymerization temperature is -78 to 160 ° C, preferably 0 to 150 ° C, and hydrogen can be supplementarily used as the molecular weight regulator at that time. The polymerization pressure is 0 to 90 kg / cm 2 · G, preferably 0 to 60 kg / cm 2 · G, particularly preferably 1 to 50 kg / cm 2 · G.
リン酸塩系難燃剤（Ｂ）
本発明に用いられるリン酸塩系難燃剤（B）としては、一般的にポリオレフィン用の難燃剤として用いられるものであれば、いずれも用いることができる。例えば、ポリリン酸アンモニウム塩、ポリリン酸メラミン塩、ポリリン酸ピペラジン塩、オルトリン酸ピペラジン塩、ピロリン酸メラミン塩、ピロリン酸ピペラジン塩、ポリリン酸メラミン塩、オルトリン酸メラミン塩、リン酸カルシウム、リン酸マグネシウム等のリン酸塩化合物または混合物などが挙げられる。
Phosphate flame retardant (B)
Any phosphate-based flame retardant (B) used in the present invention can be used as long as it is generally used as a flame retardant for polyolefins. For example, ammonium polyphosphate, melamine polyphosphate, piperazine polyphosphate, piperazine orthophosphate, melamine pyrophosphate, piperazine pyrophosphate, melamine polyphosphate, melamine orthophosphate, calcium phosphate, magnesium phosphate, etc. An acid salt compound or a mixture is mentioned.
上記例示において、メラミン、ピペラジンの代わりに、Ｎ，Ｎ，Ｎ'，Ｎ'−テトラメチルジアミノメタン、エチレンジジアミン、Ｎ，Ｎ'−ジメチルエチレンジアミン、Ｎ，Ｎ'−ジエチルエチレンジアミン、Ｎ，Ｎ−ジメチルエチレンジアミン、Ｎ，Ｎ−ジエチルエチレンジアミン、Ｎ，Ｎ，Ｎ'，Ｎ'−テトラメチルエチレンジアミン、Ｎ，Ｎ，Ｎ'，Ｎ'−ジエチルエチレンジアミン、１，２−プロパンジアミン、１，３−プロパンジアミン、テトラメチレンジアミン、ペンタメチレンジアミン、ヘキサメチレンジアミン、１，７−ジアミノへプタン、１，８−ジアミノオクタン、１，９ージアミノノナン、１，１０−ジアミノデカン、ｔｒａｎｓ−２，５−ジメチルピペラジン、１，４−ビス（２−アミノエチル）ピペラジン、１，４−ビス（３−アミノプロピル）ピペラジン、アセトグアナミン、ベンゾグアナミン、アクリルグアナミン、２，４−ジアミノ−６−ノニル−１，３，５−トリアジン、２，４−ジアミノ−６−ハイドロキシ−１，３，５−トリアジン、２−アミノ−４，６−ジハイドロキシ−１，３，５−トリアジン、２，４−ジアミノ−６−メトキシ−１，３，５−トリアジン、２，４−ジアミノ−６−エトキシ−１，３，５−トリアジン、２，４−ジアミノ−６−プロポキシ−１，３，５−トリアジン、２，４−ジアミノ−６−イソプロポキシ−１，３，５−トリアジン、２，４−ジアミノ−６−メルカプト−１，３，５−トリアジン、２−アミノ−４，６−ジメルカプト−１，３，５−トリアジン、アンメリン、ベンズグアナミン、アセトグアナミン、フタロジグアナミン、メラミンシアヌレート、ピロリン酸メラミン、ブチレンジグアナミン、ノルボルネンジグアナミン、メチレンジグアナミン、エチレンジメラミン、トリメチレンジメラミン、テトラメチレンジメラミン、ヘキサメチレンジメラミン、１，３−ヘキシレンジメランミン等を置き換えた化合物も同様に使用できる。市販品としては、旭電化社製・アデカスタブＦＰ２０００、ポリリン酸アンモニウム等が挙げられる。 In the above examples, instead of melamine and piperazine, N, N, N ′, N′-tetramethyldiaminomethane, ethylenedidiamine, N, N′-dimethylethylenediamine, N, N′-diethylethylenediamine, N, N— Dimethylethylenediamine, N, N-diethylethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-diethylethylenediamine, 1,2-propanediamine, 1,3-propanediamine , Tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, trans-2,5-dimethylpiperazine, 1 , 4-Bis (2-aminoethyl) piperazine, 1,4-bis 3-aminopropyl) piperazine, acetoguanamine, benzoguanamine, acrylic guanamine, 2,4-diamino-6-nonyl-1,3,5-triazine, 2,4-diamino-6-hydroxy-1,3,5-triazine 2-amino-4,6-dihydroxy-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino-6-ethoxy-1, 3,5-triazine, 2,4-diamino-6-propoxy-1,3,5-triazine, 2,4-diamino-6-isopropoxy-1,3,5-triazine, 2,4-diamino-6 -Mercapto-1,3,5-triazine, 2-amino-4,6-dimercapto-1,3,5-triazine, ammelin, benzguanamine, acetoguanamine, phthalodi Guanamine, melamine cyanurate, melamine pyrophosphate, butylene diguanamine, norbornene diguanamine, methylene diguanamine, ethylene dimelamine, trimethylene dimelamine, tetramethylene dimelamine, hexamethylene dimelamine, 1,3-hexylene dimeramine A compound in which etc. are replaced can be used similarly. Examples of commercially available products include Asahi Denka Co., Ltd., Adeka Stub FP2000, and ammonium polyphosphate.
本発明で使用されるリン酸塩化合物の配合量は、ポリオレフィン樹脂１００重量部に対し１０〜５０重量部、好ましくは１５〜４０重量部、さらに好ましく２２〜３０重量部である。配合量が１０重量部未満では、十分な難燃効果が得られず、５０重量部を超えて添加するとポリオレフィン樹脂の特性を低下させることとなるし、経済性につても不利となるので好ましくない。 The compounding quantity of the phosphate compound used by this invention is 10-50 weight part with respect to 100 weight part of polyolefin resin, Preferably it is 15-40 weight part, More preferably, it is 22-30 weight part. If the blending amount is less than 10 parts by weight, a sufficient flame retardant effect cannot be obtained, and if it exceeds 50 parts by weight, the properties of the polyolefin resin are deteriorated, and this is disadvantageous in terms of economic efficiency. .
テトラフルオロエチレン樹脂（ＰＴＦＥ）を溶融混練したマスターバッチ（Ｃ）
本発明に用いられるＰＴＦＥは、テトラフルオロエチレンの単独重合体又はテトラフルオロエチレンを主成分とする共重合体である。テトラフルオロエチレンと共重合するコモノマーとしては、ジフルオロエチレン、トリフルオロエチレン、ヘキサフルオロプロピレン、クロロトリフルオロエチレン、フルオロアルキルエチレン、パーフルオロアルキルビニルエーテル等の含フッ素オレフィンや、パーフルオロアルキル（メタ）アクリレート等の含フッ素アルキル（メタ）アクリレートを用いることができる。共重合成分の含量は、テトラフルオロエチレンに対して１０重量％以下であることが好ましい。
Master batch (C) in which tetrafluoroethylene resin (PTFE) is melt-kneaded
The PTFE used in the present invention is a tetrafluoroethylene homopolymer or a copolymer containing tetrafluoroethylene as a main component. Comonomers copolymerized with tetrafluoroethylene include fluorine-containing olefins such as difluoroethylene, trifluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, fluoroalkylethylene, perfluoroalkyl vinyl ether, and perfluoroalkyl (meth) acrylate. The fluorine-containing alkyl (meth) acrylate can be used. The content of the copolymer component is preferably 10% by weight or less with respect to tetrafluoroethylene.
ポリテトラフルオロエチレン粒子の水性分散液の市販原料としては、旭硝子フロロポリマー社製のフルオンＡＤ−１、ＡＤ−９３６、ダイキン工業社製のポリフロンＤ−１、Ｄ−２、三井デュポンフロロケミカル社製のテフロン３０Ｊ（テフロンは登録商標）等を代表例として挙げることができる。 Commercial raw materials for aqueous dispersions of polytetrafluoroethylene particles include Asahi Glass Fluoropolymer's Fullon AD-1, AD-936, Daikin Industries' Polyflon D-1, D-2, Mitsui DuPont Fluorochemicals Teflon 30J (Teflon is a registered trademark) can be given as a representative example.
ＰＴＦＥ粒子の水性分散液は、含フッ素界面活性剤を用いる乳化重合法によって、テトラフルオロエチレンモノマーと、要すれば適宜のコモノマーを重合することにより得られる。ＰＴＦＥ粒子の水性分散液の粒子径は０．０５〜１．０μｍが好ましい。 An aqueous dispersion of PTFE particles can be obtained by polymerizing a tetrafluoroethylene monomer and, if necessary, an appropriate comonomer by an emulsion polymerization method using a fluorine-containing surfactant. The particle size of the aqueous dispersion of PTFE particles is preferably 0.05 to 1.0 μm.
ＰＴＦＥ粒子の水性分散液は、塩化カルシウム、硫酸マグネシウム等の金属塩を溶解した熱水中に投入し、塩析、凝固した後に乾燥するか、スプレードライにより粉体化することができる。得られた粉体を、酸化防止剤、安定剤、滑剤等の成形助剤と共にポリプロピレンなどのマトリクス樹脂に配合し、溶融混練することによってＰＴＦＥマスターバッチを調整することができる。 The aqueous dispersion of PTFE particles can be poured into hot water in which a metal salt such as calcium chloride or magnesium sulfate is dissolved and dried after being salted out and solidified, or powdered by spray drying. A PTFE masterbatch can be prepared by blending the obtained powder into a matrix resin such as polypropylene together with molding aids such as an antioxidant, a stabilizer and a lubricant, and melt-kneading them.
場合によっては、ＰＴＦＥ粒子の水性分散液中で重合性ビニル化合物を重合することによって、ＰＴＦＥを変性することができる。この際に得られるＰＴＦＥ変性物は、ＰＴＦＥとビニル化合物の重合体との均一な混合物を形成しており、ポリプロピレンとの混合性を向上する上に効果的である。 In some cases, PTFE can be modified by polymerizing a polymerizable vinyl compound in an aqueous dispersion of PTFE particles. The PTFE-modified product obtained at this time forms a uniform mixture of PTFE and a polymer of a vinyl compound, and is effective in improving the mixing property with polypropylene.
上記重合性ビニル化合物としては、スチレン、α−メチルスチレン、ｐ−メチルスチレン、ｏ−メチルスチレン、ｔ−ブチルスチレン、ｏ−エチルスチレン、ｐ−クロロスチレン、ｏ−クロロスチレン、２，４−ジクロロスチレン、ｐ−メトキシスチレン、ｏ−メトキシスチレン、２，４−ジメチルスチレン等の芳香族ビニル単量体；（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ブチル、（メタ）アクリル酸−２−エチルヘキシル、（メタ）アクリル酸ドデシル、（メタ）アクリル酸トリデシル、（メタ）アクリル酸オクタデシル、（メタ）アクリル酸シクロヘキシル等の（メタ）アクリル酸エステル単量体；アクリロニトリル、メタアクリロニトリル等のシアン化ビニル単量体；無水マレイン酸等のα，β−不飽和カルボン酸；Ｎ−フェニルマレイミド、Ｎ−メチルマレイミド、Ｎ−シクロヘキシルマレイミド等のマレイミド単量体；グリシジルメタクリレート等のエポキシ基含有単量体；ビニルメチルエーテル、ビニルエチルエーテル等のビニルエーテル単量体；酢酸ビニル、酪酸ビニル等のカルボン酸ビニル単量体；エチレン、プロピレン、イソブチレン等のα−オレフィン単量体；ブタジエン、イソプレン、ジメチルブタジエン等のジエン単量体等を挙げることができる。なかでも極性基を有する（メタ）アクリルモノマーが好ましい。これらの単量体は、単独であるいは２種以上混合して用いることができる。変性ＰＴＦＥ中のＰＴＦＥ含有量は、通常１〜９０重量％の範囲から選択される。 Examples of the polymerizable vinyl compound include styrene, α-methylstyrene, p-methylstyrene, o-methylstyrene, t-butylstyrene, o-ethylstyrene, p-chlorostyrene, o-chlorostyrene, 2,4-dichloro. Aromatic vinyl monomers such as styrene, p-methoxystyrene, o-methoxystyrene, 2,4-dimethylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth ) (Meth) acrylic acid ester monomers such as 2-ethylhexyl acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, octadecyl (meth) acrylate, cyclohexyl (meth) acrylate; acrylonitrile, meta Vinyl cyanide monomers such as acrylonitrile; α, β- such as maleic anhydride Saturated carboxylic acid; maleimide monomer such as N-phenylmaleimide, N-methylmaleimide, N-cyclohexylmaleimide; epoxy group-containing monomer such as glycidyl methacrylate; vinyl ether monomer such as vinylmethylether and vinylethylether; Examples thereof include vinyl carboxylate monomers such as vinyl acetate and vinyl butyrate; α-olefin monomers such as ethylene, propylene and isobutylene; and diene monomers such as butadiene, isoprene and dimethylbutadiene. Of these, a (meth) acryl monomer having a polar group is preferred. These monomers can be used alone or in admixture of two or more. The PTFE content in the modified PTFE is usually selected from the range of 1 to 90% by weight.
アクリルモノマーで変性されたＰＴＦＥの市販品としては、三菱レイヨン社製の熱可塑性樹脂用改質剤（メタブレンＡ−３０００）などが挙げられる。 Examples of commercially available PTFE modified with an acrylic monomer include a modifier for thermoplastic resin (Methbrene A-3000) manufactured by Mitsubishi Rayon Co., Ltd.
本発明のポリプロピレン樹脂組成物は、結晶性ポリプロピレン樹脂（Ａ）とリン酸塩系難燃剤（Ｂ）の合計量１００重量部に対して、ＰＴＦＥマスターバッチ（Ｃ）を、ＰＴＦＥとして０．０１〜３重量部、好ましくは０．０２〜１．０重量部、更に好ましくは０．０５〜０．５重量部配合することが重要である。 ０．０１重量部以下では燃焼時の滴下防止効果がなく、３重量部以上では機械物性の低下や外観を悪化させるだけでなく経済的に不利である。 The polypropylene resin composition of the present invention has a PTFE master batch (C) of 0.01 to PTFE based on 100 parts by weight of the total amount of the crystalline polypropylene resin (A) and the phosphate flame retardant (B). It is important to blend 3 parts by weight, preferably 0.02 to 1.0 parts by weight, more preferably 0.05 to 0.5 parts by weight. If it is 0.01 parts by weight or less, there is no effect of preventing dripping at the time of combustion, and if it is 3 parts by weight or more, it not only deteriorates mechanical properties and deteriorates the appearance, but is also economically disadvantageous.
ＰＴＦＥは、結晶性ポリプロピレン樹脂（Ａ）との溶融混練に際し、せん断力によりフイブリル化し繊維状のネットワーク構造を採るので、溶融樹脂の溶融張力を向上させる作用がある。このフイブリルを効率よく発生、分散させるためにPTFEを特殊なアクリル樹脂で変性した物が好ましい。 Since PTFE is fibrillated by a shearing force and adopts a fibrous network structure during melt kneading with the crystalline polypropylene resin (A), it has an effect of improving the melt tension of the molten resin. In order to efficiently generate and disperse this fibril, a product obtained by modifying PTFE with a special acrylic resin is preferable.
本発明において、ＰＴＦＥは、マトリクス樹脂と共に溶融混練したマスターバッチの形態で使用される。マスターバッチとしないで、ＰＴＦＥ単独の粉状体として使用した場合は、ポリプロピレン樹脂との複合時に成形体全体に均一分散されないため、有効に滴下防止効果が発揮されない。マスターバッチは、ポリプロピレン樹脂等のマトリクス成分に、変性された、或いは変性されていないＰＴＦＥ粉状品とを適当量混合し、タンブラーミキサーやヘンシェルミキサーで混合した後、二軸押し出し機等を用いて適当な溶融条件下でペレット化することで製造される。この際要すれば、酸化防止剤、滑剤、光安定剤など各種添加剤を同時に配合することができる。 In the present invention, PTFE is used in the form of a masterbatch that is melt-kneaded with a matrix resin. When not used as a masterbatch and used as a powdery body of PTFE alone, it is not uniformly dispersed throughout the molded body when combined with the polypropylene resin, so that the dripping prevention effect is not exhibited effectively. The master batch is mixed with an appropriate amount of modified or unmodified PTFE powder in a matrix component such as polypropylene resin, mixed with a tumbler mixer or Henschel mixer, and then using a twin screw extruder or the like. Manufactured by pelletizing under suitable melting conditions. If necessary, various additives such as an antioxidant, a lubricant, and a light stabilizer can be blended at the same time.
リン酸塩系難燃剤（Ｂ）は予め結晶性ポリプロピレン樹脂（Ａ）に混合しておき、その後ＰＴＦＥマスターバッチ（Ｃ）と混合してもよい。（Ａ），（Ｂ），（Ｃ）を同時に混合してもよく、更に、各種添加剤を同時に混合してもよい。 The phosphate flame retardant (B) may be previously mixed with the crystalline polypropylene resin (A) and then mixed with the PTFE master batch (C). (A), (B), (C) may be mixed simultaneously, and various additives may be mixed simultaneously.
金属酸化物（Ｄ）
本発明に用いられる金属酸化物（Ｄ）としては、酸化亜鉛、酸化鉄、酸化アルミ、酸化モリブデン等が挙げられる。より好ましい金属酸化物としては酸化亜鉛、酸化鉄であり平均粒径が３０μｍ以下、好ましくは１０μｍ以下、更に好ましくは１μｍ以下のものが好適である。金属酸化物の平均粒子径が３０μｍより大きい場合には、ポリオレフィン樹脂に対する分散性が悪くなり、高度な難燃性を得ることが出来なくなる。
Metal oxide (D)
Examples of the metal oxide (D) used in the present invention include zinc oxide, iron oxide, aluminum oxide, and molybdenum oxide. More preferable metal oxides are zinc oxide and iron oxide, and those having an average particle size of 30 μm or less, preferably 10 μm or less, and more preferably 1 μm or less are suitable. When the average particle diameter of the metal oxide is larger than 30 μm, dispersibility with respect to the polyolefin resin is deteriorated, and high flame retardance cannot be obtained.
本発明に用いる金属酸化物を使用する場合の配合量は、ポリプロピレン樹脂（Ａ）及びリン酸塩系難燃剤（Ｂ）の合計量１００重量部に対して、０．０５〜５重量部か好ましく、さらに好ましくは０．１〜３重量部である。０．０５重量部未満では十分な添加による相乗難燃効果が得られず、５重量部を超えて添加すると経済性に不利となるので好ましくない。 The compounding amount when using the metal oxide used in the present invention is preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the total amount of the polypropylene resin (A) and the phosphate flame retardant (B). More preferably, it is 0.1 to 3 parts by weight. If it is less than 0.05 part by weight, a synergistic flame retardant effect due to sufficient addition cannot be obtained, and if it exceeds 5 parts by weight, it is disadvantageous for economic efficiency.
任意成分（Ｅ）
本発明のポリプロピレン樹脂組成物には、本発明の効果を損なわない範囲で、更に他の特性を付与するために、任意の添加剤を配合することができる。例えば、酸化防止剤、加工安定剤、紫外吸収剤、光安定剤、帯電防止剤、結晶化核剤、滑剤、金属不活性剤、着色顔料、各種無機充填剤、ガラス繊維等を添加することが出来る。また、高密度ポリエチレン（ＨＤＰＥ）、高圧法低密度ポリエチレン（ＬＤＰＥ），線状低密度ポリエチレン（ＬＬＤＰＥ）、エチレン・プロピレンゴム（ＥＰＲ）、エチレン・ブテンゴム（ＥＢＲ）、Ｃ２／Ｃ６共重合体、Ｃ２／Ｃ８共重合体、ポリスチレン、エチレン・アクリル酸共重合体、エチレン・酢酸ビニル共重合体（ＥＶＡ）、スチレン・ブタジエン共重合体水添物（ＳＥＢＳ）等の重合体を複合することも可能である。また、ポリプロピレンの無水マレイン酸変性体、エチレン・プロピレン共重合体の無水マレイン酸変性体等の極性基含有の変性ポリオレフィンを複合することも可能である。
Optional component (E)
In the polypropylene resin composition of the present invention, any additive can be blended in order to further impart other characteristics within a range not impairing the effects of the present invention. For example, antioxidants, processing stabilizers, ultraviolet absorbers, light stabilizers, antistatic agents, crystallization nucleating agents, lubricants, metal deactivators, color pigments, various inorganic fillers, glass fibers, etc. may be added. I can do it. Also, high density polyethylene (HDPE), high pressure method low density polyethylene (LDPE), linear low density polyethylene (LLDPE), ethylene propylene rubber (EPR), ethylene butene rubber (EBR), C2 / C6 copolymer, C2 / C8 copolymer, polystyrene, ethylene / acrylic acid copolymer, ethylene / vinyl acetate copolymer (EVA), styrene / butadiene copolymer hydrogenated product (SEBS), etc. can be combined. is there. It is also possible to combine a modified polyolefin containing a polar group such as a maleic anhydride-modified product of polypropylene and a maleic anhydride-modified product of ethylene / propylene copolymer.
上記任意成分のうち、各種の安定剤等は、結晶性ポリプロピレン樹脂（Ａ）１００重量部に対して、通常０〜５重量部、無機充填剤や重合体系配合剤は０〜３０重量部の範囲で使用される。 Among the above optional components, various stabilizers and the like are usually in the range of 0 to 5 parts by weight with respect to 100 parts by weight of the crystalline polypropylene resin (A), and the inorganic filler and polymer system compounding agent are in the range of 0 to 30 parts by weight. Used in.
リン酸塩系難燃性ポリプロピレン樹脂組成物の製造方法
本発明のリン酸塩系難燃性ポリプロピレン樹脂組成物を製造する方法としては、特に限定されるものではない。結晶性ポリプロピレン樹脂（Ａ）およびリン酸塩系難燃剤（Ｂ）の合計量１００重量部に対して、所定量のテトラフルオロエチレンマスターバッチ（Ｃ）を混合し、必要に応じ他の添加剤の所定量を混合する。例えば、スーパーミキサー、タンブラーミキサー等の混合装置に各成分を入れ、１〜５分間混合したのち、得られた混合物を押し出し機、加熱ロール、ニーダーなどにより混練温度１７０〜２３０℃で溶融混練しペレット化する方法を挙げることができる。その中でも２軸による押し出し機混練が生産性、難燃特性面で好ましい。
＜発明の作用＞
本発明のポリプロピレン樹脂組成物は、従来知られている難燃ポリオレフィン樹脂より優れた難燃性と耐ドリップ性を示し、かつ機械的強度に優れている。ポリプロピレン樹脂と共に各種の配合成分を溶融混練するに際し、結晶性ポリプロピレン樹脂（Ａ）は溶融するが、ＰＴＦＥ成分は溶融することなく、せん断力によりフイブリル化し繊維状のネットワーク構造を採る。これが溶融樹脂の溶融張力を向上させることとなり、ドリップ防止の効果を発現する。
Method for Producing Phosphate Flame Retardant Polypropylene Resin Composition The method for producing the phosphate flame retardant polypropylene resin composition of the present invention is not particularly limited. A predetermined amount of tetrafluoroethylene masterbatch (C) is mixed with 100 parts by weight of the total amount of the crystalline polypropylene resin (A) and the phosphate flame retardant (B), and if necessary, other additives Mix a predetermined amount. For example, each component is put into a mixing apparatus such as a super mixer and a tumbler mixer, mixed for 1 to 5 minutes, and then the obtained mixture is melt-kneaded at a kneading temperature of 170 to 230 ° C. with an extruder, a heating roll, a kneader, etc. Can be mentioned. Among them, the extruder kneading with two axes is preferable in terms of productivity and flame retardancy.
<Operation of the invention>
The polypropylene resin composition of the present invention exhibits flame retardancy and drip resistance superior to conventionally known flame retardant polyolefin resins, and is excellent in mechanical strength. When various compounding components are melt-kneaded with the polypropylene resin, the crystalline polypropylene resin (A) is melted, but the PTFE component is not melted but is fibrillated by a shearing force to take a fibrous network structure. This improves the melt tension of the molten resin and exhibits the effect of preventing drip.
以下に、本発明を更に具体的に説明するために、実施例を示すが本発明はこれによって限定されるものではない。また特に断りのない限り実施例で示される部は重量部である。 In order to describe the present invention more specifically, examples are shown below, but the present invention is not limited thereto. Unless otherwise specified, the parts shown in the examples are parts by weight.
なお、各種の物性評価は次の方法により行った。
（１）ＭＦＲ（メルトフローレート）
ＪＩＳ−Ｋ６９２１−２：１９９７付属書（２３０℃、２１．１８Ｎ荷重）に準拠した。
（２）アイソタクチックペンタッド分率 ［ｍｍｍｍ］
13Ｃ−ＮＭＲ法に従った。
（３）難燃性：
ＵＬ９４Ｖ試験（アンダーライター・ラボラトリーズコーポレイテッド）の「機器の部品用プレスチック材料の燃焼試験」に規定された垂直燃焼試験方法に準拠した。
（４）滴下性（ドリップ性）：
ＵＬ９４Ｖ試験（アンダーライター・ラボラトリーズコーポレイテッド）の「機器の部品用プレスチック材料の燃焼試験」に規定された垂直燃焼試験方法に準拠し、下記の基準で評価した。即ち、
◎ ：滴下物 なし
○ ：滴下物 あり、但し、綿を着火させない（ドリップ１）
× ：綿を着火する塊状滴下物 あり（ドリップ２）
（５）外観評価：
１２０ｍｍ×１２０ｍｍ×２ｍｍの射出成形シートでの異物を目視観察し、下記の基準で評価した。即ち、
○ ：白色異物がなかったもの
△ ：０．１ｍｍ以上の白色異物が１個〜１０個観察できたもの
× ：０．１ｍｍ以上の白色異物が１１個以上観察できたもの
（６）曲げ弾性率
ＪＩＳ−Ｋ７２０３に準拠して２３℃で測定した。成形品の寸法は９０×１０×４ｍｍを用いた。単位：ＭＰａ。
Various physical properties were evaluated by the following methods.
(1) MFR (melt flow rate)
It was based on JIS-K6921-2: 1997 appendix (230 degreeC, 21.18N load).
(2) Isotactic pentad fraction [mmmm]
The 13 C-NMR method was followed.
(3) Flame retardancy:
The vertical combustion test method stipulated in the UL94V test (Underwriters Laboratories) “Plastic material combustion test for equipment parts” was used.
(4) Dripping property (drip property):
In accordance with the vertical combustion test method defined in the “flammability test of plastic materials for equipment parts” of the UL94V test (Underwriter Laboratories Corp.), the evaluation was made according to the following criteria. That is,
◎: There is no dropped material. ○: There is a dropped material. However, cotton is not ignited (drip 1).
×: Massive dripping material that ignites cotton (Drip 2)
(5) Appearance evaluation:
The foreign matters on the 120 mm × 120 mm × 2 mm injection molded sheet were visually observed and evaluated according to the following criteria. That is,
○: No white foreign matter was observed. Δ: One to ten white foreign matters of 0.1 mm or more could be observed. X: Eleven white foreign matters of 0.1 mm or more could be observed. (6) Flexural modulus. It measured at 23 degreeC based on JIS-K7203. The dimension of the molded product was 90 × 10 × 4 mm. Unit: MPa.
＜結晶性ポリプロピレン樹脂（Ａ）の製造＞
［製造例１］・・・・・（Ａ１）の製造
（チーグラー触媒の製造）
充分に窒素置換した１０Ｌ反応器に、脱水および脱酸素したｎ−ヘプタン４０００ｍｌを導入し、次いでＭｇＣｌ2を８モル、Ｔｉ（Ｏ−ｎ−Ｃ4Ｈ9）4を１６モル導入し、９５℃で２時間反応させた。反応終了後、４０℃に温度を下げ、次いでメチルヒドロポリシロキサン（２０センチストークスのもの）を９６０ｍｌ導入し、３時間反応させた。生成した固体成分をｎ−ヘプタンで洗浄した。次いで、充分に窒素置換した１０Ｌ反応器に、上記と同様に精製したｎ−ヘプタンを１０００ｍｌ導入し、上記で合成した固体成分をＭｇ原子換算で４．８モル導入した。次いでｎ−ヘプタン５００ｍｌにＳｉＣｌ4８モルを混合して３０℃、３０分間でフラスコへ導入し、７０℃で３時間反応させた。反応終了後、ｎ−ヘプタンで洗浄した。次いでｎ−ヘプタン５００ｍｌにフタル酸クロライド０．４８モルを混合して、７０℃、３０分間でフラスコへ導入し、９０℃で１時間反応させた。反応終了後、ｎ−ヘプタンで洗浄した。次いで、ＳｉＣｌ4２００ｍｌを導入して８０℃で６時間反応させた。反応終了後、ｎ−ヘプタンで充分に洗浄し固体成分を得た。このもののチタン含量は１．３重量％であった。
<Production of crystalline polypropylene resin (A)>
[Production Example 1] ... (A1) (Production of Ziegler catalyst)
Into a 10-liter reactor sufficiently purged with nitrogen, 4000 ml of dehydrated and deoxygenated n-heptane was introduced, and then 8 moles of MgCl 2 and 16 moles of Ti (On-C 4 H 9 ) 4 were introduced. For 2 hours. After completion of the reaction, the temperature was lowered to 40 ° C., and then 960 ml of methylhydropolysiloxane (20 centistokes) was introduced and reacted for 3 hours. The resulting solid component was washed with n-heptane. Next, 1000 ml of n-heptane purified in the same manner as described above was introduced into a 10 L reactor sufficiently purged with nitrogen, and 4.8 mol of the solid component synthesized above was introduced in terms of Mg atoms. Next, 8 mol of SiCl 4 was mixed with 500 ml of n-heptane, introduced into the flask at 30 ° C. for 30 minutes, and reacted at 70 ° C. for 3 hours. After completion of the reaction, washing with n-heptane was performed. Subsequently, 0.48 mol of phthalic acid chloride was mixed with 500 ml of n-heptane, introduced into the flask at 70 ° C. for 30 minutes, and reacted at 90 ° C. for 1 hour. After completion of the reaction, washing with n-heptane was performed. Next, 200 ml of SiCl 4 was introduced and reacted at 80 ° C. for 6 hours. After completion of the reaction, it was sufficiently washed with n-heptane to obtain a solid component. The titanium content of this product was 1.3% by weight.
次いで、充分に窒素置換したフラスコに、上記と同様に精製したｎ−ヘプタンを１０００ｍｌ導入し、上記で合成した固体成分を１００グラム導入し、（ｔ−Ｃ4Ｈ9）Ｓｉ（ＣＨ3）（ＯＣＨ3）2２４ｍｌ、Ａｌ（Ｃ2Ｈ5）3３４グラムを３０℃で２時間接触させた。接触終了後、ｎ−ヘプタンで充分に洗浄し、塩化マグネシウムを主体とする固体触媒成分を得た。このもののチタン含量は１．１重量％であった。 Next, 1000 ml of n-heptane purified in the same manner as described above was introduced into a sufficiently nitrogen-substituted flask, 100 g of the solid component synthesized above was introduced, and (t-C 4 H 9 ) Si (CH 3 ) ( 24 ml of OCH 3 ) 2 and 34 grams of Al (C 2 H 5 ) 3 were contacted at 30 ° C. for 2 hours. After completion of the contact, it was thoroughly washed with n-heptane to obtain a solid catalyst component mainly composed of magnesium chloride. The titanium content of this product was 1.1% by weight.
（プロピレンブロック共重合体の製造）
上記で得た固体触媒成分及びトリエチルアルミニウムを使用し、第１重合工程として反応部容積２８０Ｌを有する流動床式気相反応器を用い重合温度８５℃、プロピレン分圧２２ｋｇ／ｃｍ2 の条件下プロピレン単独重合を連続的に行った。この時、固体触媒成分は１．２ｇ／ｈｒの速度で、またトリエチルアルミニウムを５．５ｇ／ｈｒの速度で連続的に供給した。第１重合工程より抜き出されるパウダーを２４ｋｇ／ｈｒで連続的に第２重合工程として用いる反応部容積２８０Ｌを有する流動床式気相反応器に送り、プロピレンとエチレンの共重合を連続的に行った。第２重合工程から連続的に３０ｋｇ／ｈｒのポリマーを抜き出した。各重合工程での水素濃度は１槽目Ｈ2／Ｃ３＝０．０３モル比、２槽目Ｈ2／（Ｃ２＋Ｃ３）＝０．０１モル比にコントロールすることにより分子量を制御した。ゴム状プロピレン・エチレン共重合体中のエチレン組成は第２重合工程でのプロピレンとエチレンのガス組成をプロピレン／エチレン＝１／１モル比にコントロールすることによりプロピレン・エチレンブロック共重合体（Ａ１）を得た。［ｍｍｍｍ］は０．９８、ＭＦＲは３０ｇ／１０分であった。
(Production of propylene block copolymer)
Using the solid catalyst component obtained above and triethylaluminum, propylene under the conditions of a polymerization temperature of 85 ° C. and a propylene partial pressure of 22 kg / cm 2 using a fluidized bed gas phase reactor having a reaction part volume of 280 L as the first polymerization step. Homopolymerization was performed continuously. At this time, the solid catalyst component was continuously supplied at a rate of 1.2 g / hr and triethylaluminum was continuously supplied at a rate of 5.5 g / hr. The powder extracted from the first polymerization step is continuously fed at 24 kg / hr to a fluidized bed gas phase reactor having a reaction part volume of 280 L used as the second polymerization step, and propylene and ethylene are continuously copolymerized. It was. A polymer of 30 kg / hr was continuously extracted from the second polymerization step. The molecular weight was controlled by controlling the hydrogen concentration in each polymerization step to the first tank H 2 /C3=0.03 molar ratio and the second tank H 2 /(C2+C3)=0.01 molar ratio. The ethylene composition in the rubbery propylene / ethylene copolymer is a propylene / ethylene block copolymer (A1) by controlling the propylene / ethylene gas composition in the second polymerization step to a propylene / ethylene = 1/1 molar ratio. Got. [Mmmm] was 0.98, and MFR was 30 g / 10 min.
［製造例２］・・・・・（Ａ２）の製造
（チーグラー触媒の製造）
窒素置換した５００ｍｌ内容積のガラス製三ツ口フラスコ（温度計、滴下ロート、攪拌棒付き）に、１４４ｍｌの精製ヘプタンと５８ｍｌの四塩化チタンを加えた。また、滴下ロートには１２０ｍｌのヘプタンと６６ｍｌのジエチルアルミニウムクロリドを仕込んだ。フラスコを−１０℃に冷却し、１２０ｒｐｍの攪拌のもとで３時間でジエチルアルミニウムクロリドを滴下する。さらに、−１０℃で１時間反応させたのち、系の温度を１時間でゆっくりと６５℃に昇温した。６５℃で１時間反応させたのち、デカンテーションにより上澄液を分離し、新しい精製ヘプタン２００ｍｌで５回洗浄した。つぎに、２５０ｍｌのヘプタンと９９ｍｌのジイソアミルエーテルを添加し、３５℃で１時間反応させた。反応終了後、先の四塩化チタンの還元時と同様に精製ヘプタン２００ｍｌで５回洗浄した。つぎに、１５０ｍｌのヘプタンと１１６ｍｌの四塩化チタンを加えて６５℃で２時間反応させた。反応終了後、精製ヘプタン２００ｍｌで５回洗浄した。最後に、１５０ｍｌのヘプタンとｎ‐ブタノール２．３ｍｌを加え、室温で１時間反応させ、ヘプタン２００ｍｌで３回洗浄して、固体触媒成分とした。
[Production Example 2] ... Production of (A2) (Production of Ziegler catalyst)
To a 500-ml glass three-necked flask (with a thermometer, a dropping funnel, and a stirring rod) purged with nitrogen, 144 ml of purified heptane and 58 ml of titanium tetrachloride were added. The dropping funnel was charged with 120 ml of heptane and 66 ml of diethylaluminum chloride. The flask is cooled to −10 ° C., and diethylaluminum chloride is added dropwise over 3 hours under stirring at 120 rpm. Furthermore, after reacting at -10 ° C for 1 hour, the temperature of the system was slowly raised to 65 ° C in 1 hour. After reacting at 65 ° C. for 1 hour, the supernatant was separated by decantation and washed 5 times with 200 ml of fresh purified heptane. Next, 250 ml of heptane and 99 ml of diisoamyl ether were added and reacted at 35 ° C. for 1 hour. After completion of the reaction, it was washed 5 times with 200 ml of purified heptane in the same manner as in the previous reduction of titanium tetrachloride. Next, 150 ml of heptane and 116 ml of titanium tetrachloride were added and reacted at 65 ° C. for 2 hours. After completion of the reaction, washing was performed 5 times with 200 ml of purified heptane. Finally, 150 ml of heptane and 2.3 ml of n-butanol were added, reacted at room temperature for 1 hour, washed 3 times with 200 ml of heptane to obtain a solid catalyst component.
（プロピレンの重合）
内容積２００リットルの攪拌式オートクレーブをプロピレンで充分置換した後、充分に脱水・脱酸素したｎ‐ヘプタン６３リットルを導入し、ジエチルアルミニウムモノクロライドとエチルアルミニウムジクロライドとを混合し、室温で２時間撹拌し、均質化して調製したエチルアルミニウムクロリド５０ｇおよび前記三塩化チタン組成物１０ｇを６５℃でプロピレン雰囲気下で導入した。第一段重合は、オートクレーブを７０℃に昇温した後、水素濃度を５ｖｏｌ％に調節しながらプロピレンを９ｋｇ／ｈｒの流量で導入することにより開始した。２０２分後、プロピレンの導入をやめ、さらに重合を７０℃で９０分継続させた。気相部プロピレンを０．２ｋｇ／ｃｍ2 Ｇとなるまでパージした。第二段重合は、オートクレーブを６５℃に降温した後、プロピレンを４．６ｋｇ／ｈｒ、エチレンを３ｋｇ／ｈｒで導入して６０分間実施した。
(Propylene polymerization)
After thoroughly replacing the 200-liter stirred autoclave with propylene, introduce 63 liters of fully dehydrated and deoxygenated n-heptane, mix diethylaluminum monochloride and ethylaluminum dichloride, and stir at room temperature for 2 hours. Then, 50 g of ethylaluminum chloride prepared by homogenization and 10 g of the titanium trichloride composition were introduced at 65 ° C. in a propylene atmosphere. The first stage polymerization was started by heating the autoclave to 70 ° C. and then introducing propylene at a flow rate of 9 kg / hr while adjusting the hydrogen concentration to 5 vol%. After 202 minutes, the introduction of propylene was stopped, and the polymerization was further continued at 70 ° C. for 90 minutes. Vapor phase propylene was purged to 0.2 kg / cm 2 G. The second stage polymerization was carried out for 60 minutes by lowering the temperature of the autoclave to 65 ° C., and then introducing propylene at 4.6 kg / hr and ethylene at 3 kg / hr.
このようにして得られたスラリーをロ過・乾燥して粉末状のプロピレン・エチレンブロック共重合体を得た。同共重合体の[ｍｍｍｍ]は０．９５、ＭＦＲは３０ｇ／１０分であった。 The slurry thus obtained was filtered and dried to obtain a powdery propylene / ethylene block copolymer. [Mmmm] of the copolymer was 0.95, and MFR was 30 g / 10 min.
＜リン系難燃剤＞
（Ｂ１）リン酸塩系難燃剤として、旭電化社製「アデカスタブＦＰ２０００」を使用した。当該難燃剤の物性として、融点なし（２５０℃以上で分解）、窒素含量２０〜２３重量％、リン含量１８〜２１重量％である。
（Ｂ２）リン酸エステル系難燃剤として、グレートレイク社製「レオガード１０００」融点１９０〜１９５℃を使用した。
<Phosphorus flame retardant>
(B1) “ADK STAB FP2000” manufactured by Asahi Denka Co., Ltd. was used as a phosphate flame retardant. As physical properties of the flame retardant, there is no melting point (decomposition at 250 ° C. or higher), a nitrogen content of 20 to 23% by weight, and a phosphorus content of 18 to 21% by weight.
(B2) “Leoguard 1000” melting point 190 to 195 ° C. manufactured by Great Lakes was used as a phosphate ester flame retardant.
＜ＰＴＦＥ難燃剤＞
（Ｃ１）アクリル変性ＰＴＦＥを原料としたマスターバッチ
ポリプロピレン（日本ポリケム社製、プロピレン単独重合パウダー：ＦＹ4
相当品、ＭＦＲ５ｇ／１０分、）６０重量部、アクリル変性ＰＴＦＥ（三菱レイヨン社製、メタブレンＡ３０００、ＰＴＦＥ含有量２０％）４０重量部（ＰＴＦＥとして８重量部）に、更に、安定剤として、ペンタエリスリチルーテトラキス[３−（３,５―ジーｔ−ブチルー４−ヒドロキシフェニル）プロピオネートを０．０５％、トリス（２,４−ジーｔ―ブチルフェニル）フォスファイトを０．０５％、ステアリン酸カルシウムを０．０５％、それぞれタンブラーミキサーに投入し２０分間混合した。その後、二軸押し出し機（池貝社製、４５ｍｍＤ、Ｌ／Ｄ＝３８．５）を用いて温度２００℃の条件下で溶融混練しペレット化した。
<PTFE flame retardant>
(C1) Masterbatch made of acrylic modified PTFE as raw material Polypropylene (Nippon Polychem, Propylene homopolymer powder: FY4
Equivalent product, MFR 5 g / 10 min.) 60 parts by weight, acrylic modified PTFE (Mitsubishi Rayon Co., Ltd., Metabrene A3000, PTFE content 20%) 40 parts by weight (PTFE 8 parts by weight), and stabilizer as penta Erythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate 0.05%, tris (2,4-di-t-butylphenyl) phosphite 0.05%, calcium stearate 0.05% of each was put into a tumbler mixer and mixed for 20 minutes. Then, it melt-kneaded and pelletized on the conditions of the temperature of 200 degreeC using the biaxial extruder (Ikegai company make, 45mmD, L / D = 38.5).
（Ｃ２）未変性ＰＴＦＥを原料としたマスターバッチ
ポリプロピレン（日本ポリケム社製、プロピレン単独重合パウダー：ＦＹ４相当品、ＭＦＲ５ｇ／１０分、）９０重量部、未変性ＰＴＦＥ（ダイキン社製、ポリフロンＦＡ５００、ＰＴＦＥ含有量１００％）１０重量部を使用した以外は上記（Ｃ１）と同様の条件で溶融混練しペレット化した。
(C2) Master batch polypropylene made from unmodified PTFE (produced by Nippon Polychem, propylene homopolymer powder: FY4 equivalent, MFR 5 g / 10 min), 90 parts by weight, unmodified PTFE (produced by Daikin, Polyflon FA500, PTFE) (Content 100%) Except for using 10 parts by weight, the mixture was melt-kneaded and pelletized under the same conditions as in (C1) above.
（Ｃ３）アクリル変性ＰＴＦＥ（三菱レイヨン社製、メタブレンＡ３０００）の粉状品をそのまま使用した。 (C3) A powdery product of acrylic modified PTFE (Mitsubrene A3000 manufactured by Mitsubishi Rayon Co., Ltd.) was used as it was.
＜金属酸化物＞
（Ｄ１）〜（Ｄ４）
各種の粒径を有する酸化亜鉛、酸化鉄又は酸化アルミを使用した。
<Metal oxide>
(D1) to (D4)
Zinc oxide, iron oxide or aluminum oxide having various particle sizes was used.
上記の原料について、物性・商品名などを［表１］にまとめた。 [Table 1] summarizes the physical properties and product names of the above raw materials.
＜実施例１＞
ポリプロピレン樹脂として上記で得た（Ａ１）を１００重量部、リン酸塩系難燃剤として上記（Ｂ１）を２８重量部、ＰＴＦＥマスターバッチとして上記（Ｃ１）を１．２５重量部（ＰＴＦＥとして０．１重量部）、及びその他の添加剤として、ペンタエリスリチルーテトラキス[３−（３,５―ジーｔ−ブチルー４−ヒドロキシフェニル）プロピオネート（チバ・スペシャリティ・ケミカルズ社製、酸化防止剤イルガノックス１０１０）を０．２重量部、トリス（２,４−ジーｔ―ブチルフェニル）フォスファイト（チバ・スペシャリティ・ケミカルズ社製、加工安定剤イルガフォス１６８）を０．２重量部、ステアリン酸カルシウムを０．０５重量部、それぞれヘンシェルミキサーに入れ、３分間撹拌混合した。得られた混合物を口径３０ｍｍの２軸押し出し機を使用して２００℃で溶融混練押し出し、ペレット化した。得られたペレットを８０℃で４時間乾燥したのち、型締め圧１００ｔの射出成形機を用い、成型温度２００℃、金型冷却温度４０℃の設定条件下で１．５ｍｍ厚みのＵＬ９４Ｖ用試験片を作成した。また、同条件下で１２０ｍｍ×１２０ｍｍ×２ｍｍの射出成形シートを成形し外観評価用に使用した。
<Example 1>
100 parts by weight of (A1) obtained above as a polypropylene resin, 28 parts by weight of (B1) as a phosphate-based flame retardant, 1.25 parts by weight of (C1) as a PTFE masterbatch (0.005 as PTFE). 1 part by weight), and as other additives, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (manufactured by Ciba Specialty Chemicals, Inc., antioxidant Irganox 1010) ) 0.2 parts by weight, Tris (2,4-di-t-butylphenyl) phosphite (manufactured by Ciba Specialty Chemicals, Inc., processing stabilizer Irgaphos 168), 0.2 parts by weight, and calcium stearate 0.05 Each part by weight was placed in a Henschel mixer and stirred for 3 minutes. The obtained mixture was melt-kneaded and extruded at 200 ° C. using a biaxial extruder having a diameter of 30 mm, and pelletized. The obtained pellets were dried at 80 ° C. for 4 hours, and then using an injection molding machine with a clamping pressure of 100 t, a test piece for UL94V having a thickness of 1.5 mm under the setting conditions of a molding temperature of 200 ° C. and a mold cooling temperature of 40 ° C. It was created. Further, an injection molded sheet of 120 mm × 120 mm × 2 mm was molded under the same conditions and used for appearance evaluation.
難燃性ポリプロピレン樹脂組成物の配合処方及び該組成物の難燃評価結果を表２に示した。 Table 2 shows the formulation of the flame retardant polypropylene resin composition and the results of flame retardant evaluation of the composition.
＜実施例２〜１１＞
表１に示した配合原料を使用し、表２に示した配合処方に従って、実施例１と同様にして他の添加剤も配合して、撹拌・混合及び溶融混練してペレット化した。得られたペレットから試験片を作成して実施した難燃評価結果を表２に示した。
<Examples 2 to 11>
Using the blending raw materials shown in Table 1, according to the blending recipe shown in Table 2, other additives were blended in the same manner as in Example 1, and the mixture was pelletized by stirring, mixing and melt-kneading. Table 2 shows the results of flame retardant evaluation conducted by preparing test pieces from the obtained pellets.
＜比較例１〜５＞
表１に示した配合原料を使用し、表３に示した配合処方に従って、実施例１と同様にして他の添加剤も配合して、撹拌・混合及び溶融混練してペレット化した。得られたペレットから試験片を作成して実施した難燃評価結果を表３に示した。
<Comparative Examples 1-5>
Using the blending raw materials shown in Table 1, according to the blending recipe shown in Table 3, other additives were blended in the same manner as in Example 1, and the mixture was pelletized by stirring, mixing and melt-kneading. Table 3 shows the results of flame retardant evaluation performed by preparing test pieces from the obtained pellets.
表２及び表３の比較から次のことが明らかとなった。
（１）ＰＴＦＥ系難燃剤を配合しないと優れた難燃性は達成されない（比較例１）。
（２）結晶性に劣る（［ｍｍｍｍ］＝０．９５）ポリプロピレン樹脂を原料とした場合は優れた難燃性は達成されない（比較例２）。
（３）リン酸塩系難燃剤の代わりにリン酸エステル系難燃剤を配合した場合は、優れた難燃性は達成されない（比較例３，４）。
（４）ＰＴＦＥマスターバッチ（溶融混練品）の代わりにＰＴＦＥ粉状品を配合した場合は、優れた難燃性は達成されない（比較例５，６）。
From the comparison of Table 2 and Table 3, the following became clear.
(1) Excellent flame retardancy is not achieved unless a PTFE flame retardant is blended (Comparative Example 1).
(2) Inferior in crystallinity ([mmmm] = 0.95) When a polypropylene resin is used as a raw material, excellent flame retardancy is not achieved (Comparative Example 2).
(3) When a phosphate ester flame retardant is blended in place of the phosphate flame retardant, excellent flame retardancy is not achieved (Comparative Examples 3 and 4).
(4) When a PTFE powder product is blended in place of the PTFE master batch (melt kneaded product), excellent flame retardancy is not achieved (Comparative Examples 5 and 6).
本発明によれば、ポリプロピレン樹脂の優れた機械的強度、成形性に加えて、優れた難燃性が得られるので、自動車部品、電機部品、容器包装部材、建築用部材など広範な分野で利用が可能である。 According to the present invention, in addition to the excellent mechanical strength and moldability of polypropylene resin, excellent flame retardancy can be obtained, so it can be used in a wide range of fields such as automobile parts, electrical parts, container packaging members, and building members. Is possible.
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| JP5036584B2 (en) * | 2008-02-07 | 2012-09-26 | アロン化成株式会社 | Flame retardant elastomer composition |
| JP5708973B2 (en) * | 2010-04-30 | 2015-04-30 | 三菱レイヨン株式会社 | Method for producing tablet of modifier for thermoplastic resin, thermoplastic resin composition and molded article |
| JP6171666B2 (en) | 2012-08-01 | 2017-08-02 | 住友化学株式会社 | Method for producing flame retardant thermoplastic elastomer composition |
| JP6372125B2 (en) * | 2013-03-29 | 2018-08-15 | 日本ポリプロ株式会社 | Fiber reinforced polypropylene flame retardant resin composition and molded body using the same |
| JP2015078277A (en) * | 2013-10-16 | 2015-04-23 | 日本ポリプロ株式会社 | Flame retardant resin composition |
| JP6213235B2 (en) | 2013-12-27 | 2017-10-18 | 住友化学株式会社 | Method for producing flame retardant thermoplastic elastomer composition |
| JP6663096B2 (en) | 2015-02-19 | 2020-03-11 | 住友化学株式会社 | Thermoplastic elastomer composition |
| CN105906928B (en) | 2015-02-19 | 2019-12-27 | 住友化学株式会社 | Thermoplastic elastomer composition |
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Cited By (1)
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| US11339263B2 (en) | 2015-03-16 | 2022-05-24 | Shpp Global Technologies B.V. | Fibrillated polymer compositions and methods of their manufacture |
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| JP2005060603A (en) | 2005-03-10 |
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