JPH01278546A - Flame-retardant polypropylene resin composition - Google Patents
Flame-retardant polypropylene resin compositionInfo
- Publication number
- JPH01278546A JPH01278546A JP63109537A JP10953788A JPH01278546A JP H01278546 A JPH01278546 A JP H01278546A JP 63109537 A JP63109537 A JP 63109537A JP 10953788 A JP10953788 A JP 10953788A JP H01278546 A JPH01278546 A JP H01278546A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- group
- polypropylene resin
- formulas
- flame
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- -1 polypropylene Polymers 0.000 title claims description 44
- 239000004743 Polypropylene Substances 0.000 title claims description 35
- 229920001155 polypropylene Polymers 0.000 title claims description 35
- 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 title claims description 19
- 239000003063 flame retardant Substances 0.000 title claims description 19
- 239000011342 resin composition Substances 0.000 title claims description 14
- 239000000203 mixture Substances 0.000 claims abstract description 27
- 229920005989 resin Polymers 0.000 claims abstract description 27
- 239000011347 resin Substances 0.000 claims abstract description 27
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004114 Ammonium polyphosphate Substances 0.000 claims abstract description 13
- 229920001276 ammonium polyphosphate Polymers 0.000 claims abstract description 13
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims abstract description 13
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 12
- 125000003118 aryl group Chemical group 0.000 claims abstract description 12
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 12
- 238000004132 cross linking Methods 0.000 claims abstract description 9
- 229920003051 synthetic elastomer Polymers 0.000 claims description 15
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 14
- 239000005977 Ethylene Substances 0.000 claims description 14
- 229920013716 polyethylene resin Polymers 0.000 claims description 14
- 150000001408 amides Chemical class 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 10
- 239000005061 synthetic rubber Substances 0.000 claims description 9
- 239000000806 elastomer Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 6
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 claims description 5
- 125000000587 piperidin-1-yl group Chemical group [H]C1([H])N(*)C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 claims description 5
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical class C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 claims description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims 1
- 229920001384 propylene homopolymer Polymers 0.000 claims 1
- 239000002341 toxic gas Substances 0.000 abstract description 6
- 239000007789 gas Substances 0.000 abstract description 5
- 150000000182 1,3,5-triazines Chemical class 0.000 abstract description 4
- 150000003918 triazines Chemical class 0.000 abstract 1
- 238000002156 mixing Methods 0.000 description 16
- 238000012360 testing method Methods 0.000 description 14
- 239000000047 product Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 238000002485 combustion reaction Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 239000008188 pellet Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000012442 inert solvent Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- JZNDMMGBXUYFNQ-UHFFFAOYSA-N tris(dodecylsulfanyl)phosphane Chemical compound CCCCCCCCCCCCSP(SCCCCCCCCCCCC)SCCCCCCCCCCCC JZNDMMGBXUYFNQ-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 229920005676 ethylene-propylene block copolymer Polymers 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000007706 flame test Methods 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 150000002484 inorganic compounds Chemical class 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 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
- 239000006227 byproduct Substances 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- DZCCLNYLUGNUKQ-UHFFFAOYSA-N n-(4-nitrosophenyl)hydroxylamine Chemical compound ONC1=CC=C(N=O)C=C1 DZCCLNYLUGNUKQ-UHFFFAOYSA-N 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- GUSFEBGYPWJUSS-UHFFFAOYSA-N pentaazanium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O GUSFEBGYPWJUSS-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LGXAANYJEHLUEM-UHFFFAOYSA-N 1,2,3-tri(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC(C(C)C)=C1C(C)C LGXAANYJEHLUEM-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 description 1
- RJGWCYRVKPVEED-UHFFFAOYSA-N 10,10-diphenyldecylsulfanyl-bis(sulfanyl)phosphane Chemical compound C=1C=CC=CC=1C(CCCCCCCCCSP(S)S)C1=CC=CC=C1 RJGWCYRVKPVEED-UHFFFAOYSA-N 0.000 description 1
- FCMUPMSEVHVOSE-UHFFFAOYSA-N 2,3-bis(ethenyl)pyridine Chemical compound C=CC1=CC=CN=C1C=C FCMUPMSEVHVOSE-UHFFFAOYSA-N 0.000 description 1
- MUEJUOUFUTUSED-UHFFFAOYSA-N 2,4-dichloro-6-piperidin-1-yl-1,3,5-triazine Chemical compound ClC1=NC(Cl)=NC(N2CCCCC2)=N1 MUEJUOUFUTUSED-UHFFFAOYSA-N 0.000 description 1
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 1
- FEXBEKLLSUWSIM-UHFFFAOYSA-N 2-Butyl-4-methylphenol Chemical compound CCCCC1=CC(C)=CC=C1O FEXBEKLLSUWSIM-UHFFFAOYSA-N 0.000 description 1
- UQAMDAUJTXFNAD-UHFFFAOYSA-N 4-(4,6-dichloro-1,3,5-triazin-2-yl)morpholine Chemical compound ClC1=NC(Cl)=NC(N2CCOCC2)=N1 UQAMDAUJTXFNAD-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
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 description 1
- 239000004386 Erythritol Substances 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- JESBRDPKBQBMRC-UHFFFAOYSA-N OP(O)OP(O)O.C(CCCCCCC)C(S)(C(CS)(CO)CO)CCCCCCCC Chemical compound OP(O)OP(O)O.C(CCCCCCC)C(S)(C(CS)(CO)CO)CCCCCCCC JESBRDPKBQBMRC-UHFFFAOYSA-N 0.000 description 1
- LXVRNQSQTAMKHU-UHFFFAOYSA-N OP(O)OP(O)O.C(CCCCCCCCCCC)C(S)(C(CS)(CO)CO)CCCCCCCCCCCC Chemical compound OP(O)OP(O)O.C(CCCCCCCCCCC)C(S)(C(CS)(CO)CO)CCCCCCCCCCCC LXVRNQSQTAMKHU-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- QLENWSVUXFFPHT-UHFFFAOYSA-N bis(sulfanyl)-tridecylsulfanylphosphane Chemical compound CCCCCCCCCCCCCSP(S)S QLENWSVUXFFPHT-UHFFFAOYSA-N 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 description 1
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 1
- 229940009714 erythritol Drugs 0.000 description 1
- 235000019414 erythritol Nutrition 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- CGNKSELPNJJTSM-UHFFFAOYSA-N phenylphosphonous acid Chemical compound OP(O)C1=CC=CC=C1 CGNKSELPNJJTSM-UHFFFAOYSA-N 0.000 description 1
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoramidic acid Chemical compound NP(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- SVUVNJONFSNDKX-UHFFFAOYSA-N tris(cyclohexylsulfanyl)phosphane Chemical compound C1CCCCC1SP(SC1CCCCC1)SC1CCCCC1 SVUVNJONFSNDKX-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
Abstract
Description
【発明の詳細な説明】
(産業上の利用分野)
本発明は難燃性ポリプロピレン樹脂組成物に関する。さ
らに詳しくはポリプロピレン樹脂を主成分とし、腐食性
のガスや有毒性のガスの発生がなく、成形加工性の低下
や成形品としたときに該成形品の機械的強度の低下も少
なく、高度の難燃性能を有する成形品が得られる難燃性
ポリプロピレン樹脂組成物に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a flame-retardant polypropylene resin composition. More specifically, it is mainly composed of polypropylene resin, does not generate corrosive or toxic gases, has little deterioration in molding processability or mechanical strength of the molded product, and has a high degree of The present invention relates to a flame-retardant polypropylene resin composition from which a molded article having flame-retardant properties can be obtained.
従来よシ、ポリプロピレン樹脂は、加工性、耐薬品性、
耐候性、電気的特性および機械的強度の良さから家庭用
電気製品の分!i!fを始めとして、建築物、室内装飾
品、自動車部品など各種の分野に多用されている。Conventionally, polypropylene resin has excellent processability, chemical resistance,
Minutes for household electrical products due to its weather resistance, electrical properties, and mechanical strength! i! It is widely used in various fields including f, buildings, interior decoration, and automobile parts.
(従来の技術)
本来ポリプロピレン樹脂は、燃焼しやすい樹脂であるが
、使用される用途の拡大にともないポリプロピレン樹脂
も難燃材料としての性能が要求され、しかも年々要求さ
れる性能が厳しくなってきている。これらの要求に応え
るために種々の難燃性ポリプロピレン樹脂組成物が提案
されている。(Prior art) Polypropylene resin is originally a resin that easily burns, but as the applications for which it is used expand, polypropylene resin is also required to have performance as a flame retardant material, and the performance requirements are becoming stricter year by year. There is. Various flame-retardant polypropylene resin compositions have been proposed to meet these demands.
例えば特開昭53−92855号公報、特開昭4ノ
54−29350号公報、特開昭54−7765号公報
、特開昭56−26954号公報、特開昭57−874
62号公報、特開昭60−110738号公報などに開
示されているように含水無機化合物(例えば水酸化マグ
ネシウム、水酸化アルミニウム、硫酸バリウム、酸化マ
グネシウム、アンチモン酸化物、ハイドロタルサイトな
ど)をポリプロピレン樹脂に添加した組成物、例えば特
公昭55−30739号公報に開示されているようにメ
ルトインデックス、0.01〜20のポリエチレンおよ
びデカブロモ・ジフェニルエーテル(マたはドテカクロ
ロドデ力ヒドロメタノジベンゾシクロオクテン)および
粉末状のタルク、カオリナイト、セリサイト、シリカ、
ケイ藻土から選ばれた1以上の無機質充填剤をポリプロ
ピレン樹脂に添加した組成物、特開昭59−14705
0号公報に開示されているように、燐酸アンモニウム(
もしくは燐酸アミド゛)および]、、、 3.5− )
リアジン誘導体のオリゴマー(もしくけポリマー)をポ
リプロピレン樹脂に添加した組成物などが提案されてい
る。For example, JP-A-53-92855, JP-A-4-54-29350, JP-A-54-7765, JP-A-56-26954, JP-A-57-874.
As disclosed in Japanese Patent Publication No. 62 and Japanese Patent Application Laid-open No. 110738/1984, hydrous inorganic compounds (for example, magnesium hydroxide, aluminum hydroxide, barium sulfate, magnesium oxide, antimony oxide, hydrotalcite, etc.) are added to polypropylene. Compositions added to the resin, such as polyethylene with a melt index of 0.01 to 20 and decabromo diphenyl ether (or dotecachlorododehydromethanodibenzocyclooctene) and powder as disclosed in Japanese Patent Publication No. 55-30739. talc, kaolinite, sericite, silica,
Composition in which one or more inorganic fillers selected from diatomaceous earth are added to polypropylene resin, JP-A-59-14705
As disclosed in Publication No. 0, ammonium phosphate (
or phosphoric acid amide) and],,, 3.5-)
Compositions in which riazine derivative oligomers (moshikke polymers) are added to polypropylene resin have been proposed.
しかしながら、含水無機化合物をポリプロピレン樹脂に
添加した組成物、例えば水酸化マグネシウムを添加した
組成物では高度の難燃性を賦与させるためには、多量の
該含水無機化合物を添加する必要があシ、その結果、該
組成物は成形加工性の低下や成形品としたときの該成形
品の機械的強度の低下をもたらす。However, in a composition in which a hydrous inorganic compound is added to a polypropylene resin, for example, a composition in which magnesium hydroxide is added, it is necessary to add a large amount of the hydrous inorganic compound in order to impart a high degree of flame retardance. As a result, the composition causes a decrease in moldability and a decrease in the mechanical strength of the molded article.
また、ハロゲン系化合物を添加した組成物は成形加工性
の低下や成形品としたときの該成形品の機械的強度の低
下は比較的少なく、高度の難燃性を有する成形品が得ら
れるが加工時や燃焼時に、腐食性のカスや有毒性のガス
が発生するといった欠点がある。In addition, compositions containing halogen compounds have relatively little reduction in molding processability or mechanical strength of molded products, and molded products with a high degree of flame retardancy can be obtained. Disadvantages include the generation of corrosive scum and toxic gases during processing and combustion.
捷だ、特開昭59−147050号公報に開示されてい
る難燃性ポリプロピレン樹脂組成物は成形加工性の低下
や成形品としたときの該成形品の機械的強度の低下は比
較的少なく、加工時や燃焼時に、腐食性のガスや有毒性
のガスが発生することも少ない。However, the flame-retardant polypropylene resin composition disclosed in JP-A No. 59-147050 has relatively little reduction in molding processability or mechanical strength of the molded product. Corrosive and toxic gases are rarely generated during processing or combustion.
しかしながら、該組成物はULサブジェクト94(アン
ターライター・ラボラトリーズインコーポレーション)
の1−機器の部品用プラスチック材料の燃焼試験」の垂
直燃焼試験に準拠した試験(以下UL94燃焼試験とい
う。)では燃焼性のランクが1/8インチ肉厚でv−O
となるが、更に高度の難燃性が要求される5■試験では
、液滴の滴下および溶断による燃焼片の落下(以下、こ
れらの滴下物および落下物をドリップといい、ドリップ
を起こす性質をドリップ性という。)が生じるため、高
度の難燃性である1/8インチ肉厚で5Vの難燃性を達
成することが難しい。捷だ、該組成物に通常ポリプロピ
レンの衝撃強度の改善に用いられるエチレン系合成ゴム
もしくはエラストマーを添加してもアイゾツト衝撃強度
などの衝撃性の改善効果がほとんどみられない。However, the composition is UL Subject 94 (Unterliter Laboratories, Inc.)
In a test based on the vertical combustion test (hereinafter referred to as UL94 combustion test) of 1-Flammation test of plastic materials for equipment parts, the flammability rank was V-O with a wall thickness of 1/8 inch.
However, in the 5■ test, which requires an even higher degree of flame retardancy, the dripping of liquid droplets and the falling of burning pieces due to melting (hereinafter, these drippings and falling objects are referred to as drips, and the properties that cause drips are Because of this, it is difficult to achieve a flame retardancy of 5V with a 1/8 inch wall thickness, which is a high degree of flame retardancy. Unfortunately, even if ethylene-based synthetic rubber or elastomer, which is usually used to improve the impact strength of polypropylene, is added to the composition, there is almost no effect of improving impact properties such as Izot impact strength.
(発明が解決しようとする課題)
本発明者らは、高度の難燃性すなわちUL94燃焼試験
で1/8インチ肉厚で5Vの難燃性を有し、加工時や燃
焼時に腐食性のガスや有毒性のガスを発生させず、しか
も成形扉]二性の低下や成形品としたときの該成形品の
機械的強度の低下が少なく優れた耐衝撃性を有する成形
品が得られる難燃性ポリプロピレン樹脂組成物を得るべ
く鋭意研究した。その結果、ポリプロピレン樹脂にポリ
エチレン樹脂もしくはポリエチレン樹脂とエチレン系合
成ゴムもしくはエラストマー、ポリ燐酸アンモニウムも
しくはポリ燐酸アミド、下り己一般式〔I〕で表わされ
る構造を有する1、、3.5− トIJアジン誘導体、
〔式中、Xはモルホリノ基もしくはピペリジノ基、Yは
ピペラジンの2価の基、nは2〜50の整数である。〕
架橋助剤および一般式〔II〕、〔川〕、〔■〕 およ
び(V)で表わされるもののなかから選ばれたチオホス
ファイトの1以上の特定量を配合した組成物が上述の課
題を解決することができることをみいだし、この知見に
基づき本発明を完成した。(Problem to be Solved by the Invention) The present inventors have discovered that the present inventors have a high degree of flame retardancy, that is, a flame retardance of 5V at 1/8 inch wall thickness in the UL94 combustion test, and that they do not contain corrosive gases during processing or combustion. A molded door that does not emit gas or toxic gas] A flame retardant that allows molded products with excellent impact resistance to be obtained with less deterioration in properties and mechanical strength of the molded product when made into a molded product. We conducted extensive research in order to obtain a polypropylene resin composition. As a result, polypropylene resin, polyethylene resin, polyethylene resin, ethylene synthetic rubber or elastomer, ammonium polyphosphate or polyphosphoric acid amide, and a 1,,3,5-toIJ azine having a structure represented by the general formula [I]. Derivative, [wherein X is a morpholino group or a piperidino group, Y is a divalent group of piperazine, and n is an integer of 2 to 50. ] A composition containing a crosslinking auxiliary agent and a specific amount of one or more thiophosphites selected from those represented by the general formulas [II], [Kawa], [■] and (V) solves the above-mentioned problems. We have found that the problem can be solved, and based on this knowledge, we have completed the present invention.
CH−CH2SP (SRI)2
奪
CH3
〔式中、RIは炭素数6個以上のアルキル基もしくはシ
クロアルキル基もしくはアリール基を表わす。CH-CH2SP (SRI)2 CH3 [wherein, RI represents an alkyl group having 6 or more carbon atoms, a cycloalkyl group, or an aryl group.
R2は一8R′2マたは−R:であり、R8は−SR/
sまたは−R二であり、−R′2、− R’3は炭素数
6個以上の同種または異種のアルキル基もしくはシクロ
アルキル基もしくはアリール基を表わす。R2 is -8R'2ma or -R:, and R8 is -SR/
s or -R2, and -R'2 and -R'3 represent the same or different alkyl groups, cycloalkyl groups, or aryl groups having 6 or more carbon atoms.
Xは−(CH2)−、−(CH2)−〇−(CH2)−
もしくはn n
mS−R。X is -(CH2)-, -(CH2)-〇-(CH2)-
Or n n
mS-R.
ここでn、m、lは2〜6の同数または異数の整数を表
わす。〕
以上の記述から明らかなように、本発明の目的は上述の
課題を解決した高度の難燃性を有する成形品が得られる
難燃性ポリプロピレン樹脂組成物を提供することである
。Here, n, m, and l represent the same or different integers from 2 to 6. ] As is clear from the above description, an object of the present invention is to provide a flame-retardant polypropylene resin composition from which a molded article having a high degree of flame retardancy can be obtained, which solves the above-mentioned problems.
(課題を解決するだめの手段) 本発明は下記の構成を有する。(Failure to solve the problem) The present invention has the following configuration.
(1)下記(A)から(F)までの合計を100重量%
とじて、
(A) ポリエチレン樹脂 5〜30重量%
(B) ポリ燐酸アンモニウムまたはポリ燐酸アミド
12〜25重量係
(C)下記一般式〔I〕で表わされる構造を有する1゜
3.5−トIJアジン誘導体 5〜10重量%〔式中
、Xはモルホリノ基もしくはピペリジノ基、Yはピペラ
ジンの2価の基、nは2〜5゜の整数である。〕
(D+ 架橋助剤 1〜15重量%(El
下記一般式[[)、Cu1l)、CIV)および〔■
〕で表わされるもののなかから選ばれたチオホスファイ
ト 0.05〜5重量係冒。(1) The total of the following (A) to (F) is 100% by weight.
(A) Polyethylene resin 5-30% by weight
(B) Ammonium polyphosphate or polyphosphoric acid amide 12 to 25% by weight (C) 1°3.5-IJ azine derivative having a structure represented by the following general formula [I] 5 to 10% by weight [in the formula, X is a morpholino group or a piperidino group, Y is a divalent group of piperazine, and n is an integer of 2 to 5°. ] (D+ Crosslinking aid 1-15% by weight (El
The following general formula [[), Cu1l), CIV) and [■
] Thiophosphite selected from those represented by 0.05 to 5% by weight.
CHCH25P(SRI)2
〔式中、R8は炭素数6個以上のアルキル基もしくはシ
クロアルキル基もしくはアリール基を表わす。R2は−
S R’tまたは−R;であシ、R3はSR:または−
R1であシ、−R′2、−R曳は炭素数6個以上の同種
または異種のアルキル基もしくはシクロアルキル基もし
くはアリール基を表わす。Xは=(CH2)−1(CH
2) O(CH2)−n n
mS RI
される。ここでn、m、lは2〜6の同数または異数の
整数を表わす。〕
(F) 残りポリプロピレン樹脂
である難燃性ポリプロピレン樹脂組成物。CHCH25P(SRI)2 [wherein R8 represents an alkyl group, a cycloalkyl group, or an aryl group having 6 or more carbon atoms. R2 is-
SR't or -R; R3 is SR: or -
R1, -R'2, and -R represent the same or different alkyl groups, cycloalkyl groups, or aryl groups having 6 or more carbon atoms. X is =(CH2)-1(CH
2) O(CH2)-n n
mSRI is performed. Here, n, m, and l represent the same or different integers from 2 to 6. ] (F) A flame-retardant polypropylene resin composition, which is the remaining polypropylene resin.
(2) 下記(A)までの合計を100重量%として
、
囚 ポリエチレン樹脂 5〜30重量%(■3
) ポリ燐酸アンモニアまたはポリ燐酸アミド12〜
25重量係
(C)下記一般式〔I〕で表わされる構造を有する1゜
3.5−トIJアジン誘導体 5〜10重量%Y
〔式中、Xはモルホリノ基もしくはピペリジノ基、Yは
ピペラジンの2価の基、nは2〜5゜の整数である。〕
CD+架橋助剤 1〜15重量%(E)
下記一般式〔H〕、〔■〕、〔■〕および〔V〕 で表
わされる物のなかから選ばれたチオホスファイト
0.05〜5重量%CHCH2−3P (
5RI)2
晶3
〔式中、R1は炭素数6個以上のアルキル基もしくはシ
クロアルキル基もしくはアリール基を表わす。R2は−
SR′2−または−R;であり、R3は一3R二または
−R1であり、−R′2、−R;は炭素数6個以上の同
種または異種のアルキル基もしくけシクロアルキル基も
しくはアリール基を表わす。Xは−(CJ(2)−1−
(CH2) −0−(CHt) −n
n m5−R。(2) Taking the total of (A) below as 100% by weight, polyethylene resin 5-30% by weight (■3
) Ammonia polyphosphate or polyphosphoric acid amide 12~
25 weight ratio (C) 1゜3.5-toIJ azine derivative having a structure represented by the following general formula [I] 5 to 10% by weight Y [wherein, X is a morpholino group or a piperidino group, and Y is a piperazine group] A divalent group, n is an integer of 2 to 5°. ] CD + crosslinking aid 1-15% by weight (E)
Thiophosphite selected from those represented by the following general formulas [H], [■], [■] and [V]
0.05-5% by weight CHCH2-3P (
5RI)2 Crystal 3 [In the formula, R1 represents an alkyl group, a cycloalkyl group, or an aryl group having 6 or more carbon atoms. R2 is-
SR'2- or -R; R3 is -R2 or -R1; -R'2, -R; is the same or different alkyl group having 6 or more carbon atoms, a cycloalkyl group, or an aryl group; represents a group. X is -(CJ(2)-1-
(CH2) -0-(CHt) -n
nm5-R.
れる。ここで1〕、m、Aは2〜6の同数または異数の
整数を表わす。〕
(G) エチレン系合成ゴムもしくはエラストマー5
〜30i量係
(F) 残りポリプロピレン樹脂
である難燃性ポリプロピレン樹脂組成物。It will be done. 1], m, and A represent the same or different integers from 2 to 6. ] (G) Ethylene-based synthetic rubber or elastomer 5
~30i amount factor (F) A flame-retardant polypropylene resin composition with the remaining polypropylene resin.
以上含有する結晶性共重合体であって、プロピレンとエ
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、ヘプテン−1、オクテン−1、
デセン−1のなかから選ばれた1以上との結晶性共重合
体もしくはこれらの2以上の混合物をあげることができ
る。特に結晶性エチレン−プロピレンブロック共重合体
が好ましい。A crystalline copolymer containing the above, comprising propylene and ethylene, butene-1, pentene-1, hexene-1,4
-methylpentene-1, heptene-1, octene-1,
A crystalline copolymer with one or more selected from decene-1 or a mixture of two or more of these can be mentioned. Particularly preferred is a crystalline ethylene-propylene block copolymer.
本発明で用いるポリエチレン樹脂は高密度ポリエチレン
、中密度ポリエチレン、低密度ポリエチレンの何れでも
使用可能であるが、成形物の剛性の低下を防ぐためには
高密度ポリエチレンを使用することが好ましい。The polyethylene resin used in the present invention can be high density polyethylene, medium density polyethylene, or low density polyethylene, but it is preferable to use high density polyethylene in order to prevent a decrease in the rigidity of the molded product.
該ポリエチレン樹脂の配合割合は組成物に対して5〜3
0重量%、好ましくは7〜20重N′%、特に好ましく
は10〜20重量%である。該配合割合が5重量%未満
ではUL94燃焼試験でl/8インチ肉厚で5Vの難燃
性を達成することができす、オた30重量%を超えると
、また1/8インチ肉厚で5Vの難燃性を達成すること
ができなくなるので好ましくない。The blending ratio of the polyethylene resin is 5 to 3 to the composition.
0% by weight, preferably 7-20% by weight, particularly preferably 10-20% by weight. If the blending ratio is less than 5% by weight, a flame retardance of 5V can be achieved with a 1/8 inch wall thickness in the UL94 flame test, and if it exceeds 30% by weight, a flame retardance of 5V can be achieved with a 1/8 inch wall thickness. This is not preferable because it becomes impossible to achieve flame retardancy of 5V.
本発明で用いるエチレン系合成ゴムもしくはエラストマ
ーとしては、例えばエチレン−プロピレンゴム、エチ1
/ンープロビし/ンージエンゴム、エチレン−1−ブテ
ンゴム、エチレン−酢酸ビニル共重合体、ポリオレフィ
ン系熱可塑性エラストマー等をいう。なかでもエチレン
−プロピレンゴム、エチレンープロビレンージエンゴム
ヲ使用するのhへ゛衝撃強度改善の点から好ましい。Examples of the ethylene-based synthetic rubber or elastomer used in the present invention include ethylene-propylene rubber, ethylene-propylene rubber,
/N-Provinyl/N-diene rubber, ethylene-1-butene rubber, ethylene-vinyl acetate copolymer, polyolefin thermoplastic elastomer, etc. Among these, ethylene-propylene rubber and ethylene-propylene diene rubber are preferably used from the viewpoint of improving impact strength.
該エチレン系合成ゴム孔しくζdエラストマーの配合割
合は組成物に対して5〜30重量%、好ましくは7〜2
0重量%、特に好丑しくは10〜20重量%である。該
配合割合が5重量%未満では衝撃強度の改善効果が乏し
く、丑た30重量%を超えるとポリプロピレン本来の良
好な機械強度や耐熱性が失われてくるので好捷しくない
。The blending ratio of the ethylene synthetic rubber porous ζd elastomer is 5 to 30% by weight, preferably 7 to 2% by weight based on the composition.
0% by weight, particularly preferably 10-20% by weight. If the blending ratio is less than 5% by weight, the effect of improving impact strength is poor, and if it exceeds 30% by weight, the good mechanical strength and heat resistance inherent to polypropylene are lost, which is not desirable.
本発明で用いるポリ燐酸アンモニウムまたはポリ燐酸ア
ミドは通常市販品をその寸ま用いればよく、該市販品と
しては例えばポリ燐酸アンモニウムとしてはスミセーフ
P(商品名、住人化学工業■製)、ポリ燐酸アミドとし
てはスミセーフPM(商品名、住人化学工業■製)をあ
げることができる。As the ammonium polyphosphate or polyphosphoric acid amide used in the present invention, it is sufficient to use a commercially available product in its exact size. Examples of the commercially available ammonium polyphosphate include Sumisaf P (trade name, manufactured by Sumitomo Kagaku Kogyo ■), polyphosphoric acid amide, etc. An example of this is Sumisaf PM (trade name, manufactured by Sumima Kagaku Kogyo ■).
該ポリ燐酸アンモニウムまたはポリ燐酸アミドの配合割
合は組成物に対して12〜25重量%である。該配合割
合が12重量%未満ではUL94燃焼試験で1/8イン
チ肉厚で5■の難燃性を達成する組成物が得られず、ま
た25重量%を超えて配合してもそれ以上の難燃性の向
上効果が得られないのみならず、該ポリ燐酸アンモニウ
ムまたはポリ燐酸アミドに起因して吸湿性が増大するの
で好ましくない。The blending ratio of the ammonium polyphosphate or polyphosphoric acid amide is 12 to 25% by weight based on the composition. If the blending ratio is less than 12% by weight, it will not be possible to obtain a composition that achieves a flame retardancy of 5■ with a wall thickness of 1/8 inch in the UL94 flame test, and if the blending ratio exceeds 25% by weight, it will not be possible to obtain a composition that achieves a flame retardancy of 5. Not only is the effect of improving flame retardancy not obtained, but also the hygroscopicity increases due to the ammonium polyphosphate or polyphosphoric acid amide, which is not preferable.
本発明で用いる1、 3.5−トリアジン誘導体として
は、2−ビペラジニレンー4−モルホリノ−1゜3.5
−トリアジンのオリゴマーもしくはポリマー、2−ピペ
ラジエレン−4−ピペリジノ−1,、3,5−トリアジ
ンのオリコマ−もしくはポリマーを例示することができ
る。The 1,3,5-triazine derivative used in the present invention includes 2-biperazinylene-4-morpholino-1°3.5
Examples include oligomers or polymers of -triazine, and oligomers or polymers of 2-piperadiene-4-piperidino-1,3,5-triazine.
該1.,3.5− ト1)アジン誘導体の配合割合は組
成物に対して5〜10重量係である。談配合割合が5重
量%未満では高度の難燃性であるUL94燃焼試験の1
/8インチ肉厚で5vの難燃性が達成できず、また10
M量%を超えて配合してもそれ以上の難燃性の向上効果
が得られない。また、該1.3.5−トリアジン誘導体
の1樵である上述の2−ビペラジニレンー4−モルホリ
ノ−1,3,5−トリアジンのオリゴマーもしくはポリ
マーは、例えば次の方法によって得ることができる。す
々わち、等モルの2,6−シハロー4−モルホリノ−1
,3,5−トリアジン(例えば2,6−ジクロロ−4−
モルホリノ−1,3,5−トリアジンもしくは2,6−
ジプロモー4−モルホリノ−1,3,5−1−リアジン
)とピペラジンとを有機もしくは無機塩基(例えばトリ
エチルアミン、トリブチルアミン、水酸化ナトリウム、
水酸化カリウム、炭酸ナトリウムなど)の存在下にキシ
レンなどの不活性溶媒中で加熱下好ましくは該不活性溶
媒の沸点下で反応させ、反応終了後、該反応混合物を涙
過して副生物の塩を分離、除去し、沸騰水で洗浄して乾
燥することによって得ることができる。Part 1. , 3.5-1) The blending ratio of the azine derivative is 5 to 10% by weight relative to the composition. If the blending ratio is less than 5% by weight, it is highly flame retardant.
/8 inch wall thickness cannot achieve 5V flame retardancy, and 10
Even if it is blended in an amount exceeding M%, no further flame retardant improvement effect can be obtained. Further, the above-mentioned oligomer or polymer of 2-biperazinylene-4-morpholino-1,3,5-triazine, which is one of the 1,3,5-triazine derivatives, can be obtained, for example, by the following method. That is, equimolar amounts of 2,6-cyhalo4-morpholino-1
,3,5-triazine (e.g. 2,6-dichloro-4-
Morpholino-1,3,5-triazine or 2,6-
dipromo-4-morpholino-1,3,5-1-riazine) and piperazine with an organic or inorganic base (e.g. triethylamine, tributylamine, sodium hydroxide,
The reaction is carried out in an inert solvent such as xylene under heating, preferably at the boiling point of the inert solvent, in the presence of potassium hydroxide, sodium carbonate, etc.), and after the completion of the reaction, the reaction mixture is filtered to remove by-products. It can be obtained by separating and removing the salt, washing with boiling water and drying.
また、上述の2−ピペラジエレン−4−ピペリジノ−1
,3,5−1−リアジンのオリゴマーもしくはポリマー
も、例えば次の方法によって得ることができる。すなわ
ち、等モルの2.6−シハロー4−ピペリジノ−1,3
,5−トリアジン(例えば2,6−ジクロロ−4−ピペ
リジノ−1,3,5−トリアジンもしくは2,6−ジプ
ロモー4−ピペリジノ−1,3゜5−トリアジン)とピ
ペラジンとを有機もしくは無機塩基(例えばトリエチル
アミン、トリブチルアミン、水酸化ナトリウム、水酸化
カリウム、炭酸ナトリウムなど)の存在下にトリイソプ
ロピルベンゼンのような不活性溶媒を用いて加熱下好ま
しくは該不活性溶媒の沸点下に反応させ、反応終了後、
該反応混合物を濾過して副生物の塩を分離、除去したの
ち、沸騰水で洗浄して乾燥することによって得ることが
できる。In addition, the above-mentioned 2-piperadiene-4-piperidino-1
, 3,5-1-riazine oligomers or polymers can also be obtained, for example, by the following method. That is, equimolar 2,6-cyhalo4-piperidino-1,3
, 5-triazine (e.g. 2,6-dichloro-4-piperidino-1,3,5-triazine or 2,6-dipromo-4-piperidino-1,3°5-triazine) and piperazine are combined with an organic or inorganic base ( For example, the reaction is carried out using an inert solvent such as triisopropylbenzene in the presence of triethylamine, tributylamine, sodium hydroxide, potassium hydroxide, sodium carbonate, etc. under heating, preferably below the boiling point of the inert solvent. After the end,
It can be obtained by filtering the reaction mixture to separate and remove by-product salts, washing with boiling water, and drying.
本発明で用いられる架橋助剤としては、多官能性モノマ
ー、オキシムニトロン化合物、マレイミド化合物などを
あげることができる。具体例としては、例えばトリアリ
ルイソシアヌレート、(ジ)エチレングリコールジ(メ
タ)アクリレート、l・リメチロールプロパントリアク
リレート、トリメチロールプロパントリメタクリレート
、)・リスチロールエチレントリアクリレート、ペンタ
エリスリトールトリアクリレート、ペンタエリスリト−
ルテトラアクリレ−1・、ジビニルベンゼン、ジアリル
フタレート、ジビニルピリジン、キノンジオキシム、ベ
ンゾキノンジオキシム、p−二トロソ7 エンール、N
、N’−m−フェニレンビスマレイミドなどをあげるこ
とができるが、好適にはトリメヂロールプロパントリ(
メタ)アクリレートやペンタエリリスドールトリアクリ
レートなどの多官能性(メタ)アクリル酸エステルであ
る。Examples of the crosslinking aid used in the present invention include polyfunctional monomers, oxime nitrone compounds, maleimide compounds, and the like. Specific examples include triallyl isocyanurate, (di)ethylene glycol di(meth)acrylate, l-rimethylolpropane triacrylate, trimethylolpropane trimethacrylate, )-ristyrolethylene triacrylate, pentaerythritol triacrylate, pentaerythritol triacrylate, and pentaerythritol triacrylate. Erythritol
Lutetraacryle-1, divinylbenzene, diallylphthalate, divinylpyridine, quinonedioxime, benzoquinonedioxime, p-nitroso7enol, N
, N'-m-phenylene bismaleimide, etc., but preferably trimedylolpropane tri(
Polyfunctional (meth)acrylic acid esters such as meth)acrylate and pentaeryrisdole triacrylate.
該架橋助剤の配合割合は1〜15重量係、より好ましく
は1〜7重量係である。1重量%未満の場合には、燃焼
時のドリップ防止効果がほとんどなく、また15重量%
を超えて添加してもかまわ々いが、ドリップ防止効果の
それ以上の向上がなくなるので意味がない。The blending ratio of the crosslinking aid is 1 to 15% by weight, more preferably 1 to 7% by weight. If it is less than 1% by weight, there is almost no drip prevention effect during combustion, and if it is less than 15% by weight,
Although it is possible to add more than 20% of the total amount, there is no point in adding more than 100% of the total amount, since there will be no further improvement in the anti-drip effect.
本発明で用いられる前述の一般式(ID、〔m)、CI
V)および〔v〕で表わされるチオホスファイトとじて
は、トリラウリルトリチオホスファイト、トリデシルト
リチオホスファイト、トリベンジルトリチオホスファイ
ト、トリシクロヘキシルトリチオホスファイト、トリ(
2−エチルヘキシル)トリチオポスファイト、トリナフ
チルトリチオホスファイト、ジフェニルデシルトリチオ
ホスファイト、ジフェニルラウリルトリチオポスファイ
ト、テトララウリル−4−オキサブチレン−1,7−テ
トラチオホスフアイト、テトラキス(メルカプトラウリ
ル)−1,6−ジメルカブトヘキシレンジポスフアイト
、ペンタキス(メルカプトラウリル)ビス(1,6−ヘ
キジレンージメルカブト)トリチオホスファイト、テ1
−ラキス(メルカプトラウリル)−2,9−ジメルカプ
ト−パラ−メチレンジホスファイト、ビス(メルカプト
ラウリル)−1,6−ジメルカプトヘキシレン−ビス(
ベンゼンホスホナイト)、テトラキス(メルカプトラウ
リル)−2,9−ジメルカプト−パラ−メチレンジホス
ファイト、ジオクチルジチオペンタエリスリトールジホ
スファイト、ジラウリルジチオペンタエリスリトールジ
ホスファイト、フェニルラウリルジチオペンタエリスリ
トールジホスファイトおよびこれらの2以上の混合物を
あげることができる。The aforementioned general formula (ID, [m) used in the present invention, CI
The thiophosphites represented by V) and [v] include trilauryltrithiophosphite, tridecyltrithiophosphite, tribenzyltrithiophosphite, tricyclohexyltrithiophosphite, tri(
2-ethylhexyl) trithioposphite, trinaphthyl trithiophosphite, diphenyldecyl trithiophosphite, diphenyl lauryl trithioposphite, tetralauryl-4-oxabutylene-1,7-tetrathiophosphite, tetrakis(mercaptrauryl) -1,6-dimercabutohexylene diposphite, pentakis(mercaptrauryl)bis(1,6-hexylene-dimerkabut)trithiophosphite, Te1
-Rakis(mercaptrauryl)-2,9-dimercapto-para-methylene diphosphite, bis(mercaptrauryl)-1,6-dimercaptohexylene-bis(
benzenephosphonite), tetrakis(mercaptrauryl)-2,9-dimercapto-para-methylene diphosphite, dioctyl dithiopentaerythritol diphosphite, dilauryl dithiopentaerythritol diphosphite, phenyllauryl dithiopentaerythritol diphosphite, and A mixture of two or more of these can be mentioned.
該チオホスファイトの配合割合は0.05〜5重量係、
より好ましくけ01〜2重量係である。配合割合が00
5重量重量溝では、ドリップ防止効果が乏しく、また5
重量%を超えて添加してもドリップ防止効果の向上がな
くなるので意味がない。The blending ratio of the thiophosphite is 0.05 to 5% by weight,
More preferably, the weight ratio is 01 to 2. Mixing ratio is 00
5 weight groove has poor drip prevention effect;
Even if it is added in excess of this amount by weight, there is no point in improving the anti-drip effect.
本発明の組成物にあたっては、通常ポリプロピレン樹脂
に添加される各種の添加剤例えば酸化防止剤、帯電防止
剤、滑剤、顔料を併用することができる。In the composition of the present invention, various additives that are usually added to polypropylene resins, such as antioxidants, antistatic agents, lubricants, and pigments, can be used in combination.
本発明の難燃性ポリプロピレン樹脂組成物は、例えば次
のような方法によって製造することができる。The flame-retardant polypropylene resin composition of the present invention can be produced, for example, by the following method.
すなわち、ポリプロピレン樹脂に上述のポリエチレン樹
脂あるいけポリエチレン樹脂とエチレン系合成ゴムもし
くはエラストマー、ポリ燐酸アンモニウムまたはポリ燐
酸アミド、一般式〔I〕で表わされる構造を有する1、
3.5−トIJアジン誘導体、架橋助剤および一般式(
II)、C11l)、〔■〕および〔v〕で表わされる
もののなかから選ばれたチオホスファイトならびに上述
の各種添加剤の所定量を撹拌混合装置、例えばヘンセル
ミキサー(商品名)、スーパーミキサー、タンブラ−ミ
キサーに入れ、1〜10分間撹拌混合したのち、得られ
た混合物を、ロール、押出機などによシ溶融混練温度1
70〜220℃で溶融混練し、ベレット化することによ
って得ることができる。That is, polypropylene resin, the above-mentioned polyethylene resin, polyethylene resin, ethylene-based synthetic rubber or elastomer, ammonium polyphosphate or polyphosphoric acid amide, 1 having a structure represented by the general formula [I],
3.5-IJ azine derivative, crosslinking aid and general formula (
II), C11l), [■], and [v], as well as a predetermined amount of the above-mentioned various additives, are stirred and mixed using a mixing device such as a Hensel mixer (trade name) or a super mixer. , put in a tumbler mixer, stirred and mixed for 1 to 10 minutes, and then melt-kneaded the resulting mixture using a roll, extruder, etc. at a melt-kneading temperature of 1.
It can be obtained by melt-kneading at 70 to 220°C and forming pellets.
(実施例)
以下、実施例および比較例を用いて本発明を具体的に説
明するが、本発明はこれに限定されるものではない。実
施例、比較例において用いた評価方法は次の方法によっ
た。(Examples) Hereinafter, the present invention will be specifically explained using Examples and Comparative Examples, but the present invention is not limited thereto. The evaluation method used in Examples and Comparative Examples was as follows.
1)!M燃性
ULサブジェクト94(アンダーライター・ラボラトリ
ーズインコーポレーション)の[機器部品用プラスチッ
ク材料の燃焼試験−1の5V燃焼試験のA法に準拠。試
験片の肉厚1/8インチ。1)! Conforms to method A of 5V combustion test of [Flammability test of plastic materials for equipment parts-1] of M Flammability UL Subject 94 (Underwriter Laboratories Inc.). The wall thickness of the specimen is 1/8 inch.
2)曲げ弾性率 、JIS K 7203に準拠。2) Flexural modulus , based on JIS K 7203.
3)アイゾツト衝撃強度 JIS K 7110に準拠。3) Izotsu impact strength Compliant with JIS K 7110.
実施例1、比較例1〜2
ポリプロピレン樹脂として、エチレン含有量85重量係
、メルトフローレート(温度230℃、荷重2.16
kgを加えたときの10分間の溶融樹脂の吐出量)20
g710分の結晶性エチレン−プロピレンブロック共重
合体51重量係、成分(A)であるポリエチレン樹脂ど
してメルトインデクス(温度190℃、荷重2.1.6
kgを加えたときの10分間の溶融樹脂の吐出量)
6.5 g/ 1.0分のエチレン単独重合体(チッソ
ポリエチ(商標)M6801チッソ■製)15M量係1
成分(Blであるポリ燐酸アンモニウム(スミセーフP
(商標)住人化学工業■製)21重重量%成分子clで
ある1、3゜5−トリアジン誘導体として2−ピペラジ
エレン−4−モルホリノ−1,3,5−トリアジンのポ
リマー(n=11、分子量的2770)8重量%、成分
(D)である架橋助剤として、トリメチロールプロパン
トリアクリレート3重量%、成分(Elであるチオホス
ファイトとして、トリラウリルトリチオホスファイl−
0,5重量%、その他者種添加剤として2.6−ジーt
−ブチル−p−クレゾール0.15重量%、ジ−ミリス
チル−β2β−チオジプロピオネート0.2重量%およ
びステアリン酸カルシウム0.1重量%をヘンセルミキ
サー(商品名)に入れ、3分間撹拌混合した。得られた
混合物を口径45闘の押出機で溶融混線温度200℃で
溶融混線押出し、ペレット化した。Example 1, Comparative Examples 1 to 2 As a polypropylene resin, ethylene content was 85% by weight, melt flow rate (temperature 230°C, load 2.16%).
Discharge amount of molten resin in 10 minutes when adding kg) 20
g 710 min crystalline ethylene-propylene block copolymer 51 weight ratio, polyethylene resin as component (A) melt index (temperature 190°C, load 2.1.6
(amount of molten resin discharged in 10 minutes when adding kg)
6.5 g/1.0 min ethylene homopolymer (Chisso Polyethylene (trademark) M6801 made by Chisso ■) 15M weight factor 1
Ingredients (Ammonium polyphosphate (Sumisafe P)
(Trademark) manufactured by Sumima Kagaku Kogyo ■) 21% by weight of a polymer of 2-piperadiene-4-morpholino-1,3,5-triazine (n = 11, molecular weight 2770) 8% by weight, 3% by weight of trimethylolpropane triacrylate as a crosslinking agent (D), trilauryl trithiophosphite l- as a thiophosphite (El),
0.5% by weight, 2.6-Gt as other additives
- Put 0.15% by weight of butyl-p-cresol, 0.2% by weight of di-myristyl-β2β-thiodipropionate and 0.1% by weight of calcium stearate into a Hensel mixer (trade name), and mix with stirring for 3 minutes. did. The obtained mixture was melt-cross-extruded using an extruder with a diameter of 45 mm at a melt-mixing temperature of 200° C. and pelletized.
また、比較例1.2として、比較例1は成分穴であるポ
リエチレン樹脂を配合せず、比較例2は成分(D)およ
び(E)であるトリメチロールプロパントリアクリレー
トとトリラウリルトリチオホスファイトを配合しない以
外は実施例1に準拠した配合割合で各配合成分をヘンセ
ルミキサー(商品名)に入れ、実施例]に準拠して撹拌
混合、溶融混線押出し、ペレット化した。In addition, as Comparative Example 1.2, Comparative Example 1 does not contain polyethylene resin, which is the component hole, and Comparative Example 2 contains trimethylolpropane triacrylate and trilauryl trithiophosphite, which are components (D) and (E). The ingredients were put into a Hensel mixer (trade name) in the proportions as in Example 1, except that they were not blended, and mixed by stirring, melt-cross-extruded, and pelletized in accordance with Example.
実施例、比較例で得られたベレットを100’Cの温度
で3時間乾燥したのち、該ベレットを用いてシリンター
の最高温度を220°Cに設定した射出成形機で難燃性
、曲げ弾性率、アイゾツト衝撃強度測定用の所定の試験
片をそれぞれ成形した。After drying the pellets obtained in Examples and Comparative Examples at a temperature of 100°C for 3 hours, the pellets were tested for flame retardancy and flexural modulus using an injection molding machine with the maximum temperature of the cylinder set at 220°C. , and predetermined test pieces for Izod impact strength measurement were molded.
該試験片を用いて難燃性、曲げ弾性率、アイゾツト衝撃
強度の測定を行った。その結果を@1表に示した。Using this test piece, flame retardancy, flexural modulus, and Izod impact strength were measured. The results are shown in Table @1.
実施例2〜5、比較例3〜4
ポリプロピレン樹脂、ポリエチレン樹脂、トリメチロー
ルプロパントリアクリレートおよびトリラウリルトリチ
オホスファイトを第1表に記載の配合割合に変化させた
以外は実施例1に準拠して各配合成分をヘンセルミキサ
ー(商品名)に入れ、実施例1に準拠して撹拌混合、溶
融混練押出し、ペレット化した。Examples 2 to 5, Comparative Examples 3 to 4 Based on Example 1 except that the blending ratios of polypropylene resin, polyethylene resin, trimethylolpropane triacrylate, and trilauryltrithiophosphite were changed as shown in Table 1. Each of the ingredients was put into a Hensel mixer (trade name), mixed by stirring, melt-kneaded and extruded, and pelletized in accordance with Example 1.
実施各側、比較各側で得られたベレットを用いて実施例
1に準拠して難燃性評価用試験片を調製し難燃性を評価
した。その結果を第1表に示した。A test piece for flame retardancy evaluation was prepared according to Example 1 using the pellets obtained in each of the implementation and comparison sides, and the flame retardance was evaluated. The results are shown in Table 1.
実施例6
成分(C)である1、3.5−トリアジン誘導体として
2−ビペラジニレンー4−ピペリジノ−1,3,5−ト
リアジンのポリマー(n=11.分子量的2800)を
用いる以外は実施例1に準拠して各配合成分をヘンセル
ミキサー(商品名)に入れ、実施例1に準拠して撹拌混
合、溶融混線押出し、ペレット化為
した。得られたベレットを用いて実施例1に準拠して難
燃性評価用試験片をpi製し難燃性を評価した。その結
果を第1表に示した。Example 6 Example 1 except that a polymer of 2-biperazinylene-4-piperidino-1,3,5-triazine (n=11, molecular weight 2800) was used as the 1,3,5-triazine derivative serving as component (C). Each compounded component was put into a Hensel mixer (trade name) according to Example 1, and mixed by stirring, melt cross-wire extruded, and pelletized according to Example 1. Using the obtained pellets, a test piece for flame retardancy evaluation was prepared using pi in accordance with Example 1, and flame retardancy was evaluated. The results are shown in Table 1.
実施例7〜怪、比較例5〜13
成分(F)であるポリプロピレン樹脂として、エチレン
含有量8.5重量%、メルトフローレート20.971
0分の結晶性エチレン−プロピレンブロック共重合体、
成分穴であるポリエチレン樹脂としてメルトインデクス
6.5.9/10分のエチレン単独重合体(チッソポリ
エチ(商標)M680、チッソ■製)、成分(G)であ
るエチレン系合成ゴムもL<はエラストマーとしてエチ
レン−プロピレンゴム(JSREP(商標)02P、日
本合成ゴム■製)、成分CD+であるトリメチロールプ
ロパントリアクリレートおよび成分(E)であるトリラ
ウリルトリチオポスファイトを第2表に記載の配合割合
で添加し、さらに成分(13)であるポリ燐酸アンモニ
ウム(スミセーフP(商標)住人化学工業■製)21重
量%、成分子c)である1、3.5− トI)アジン誘
導体として2−ビペラジニレンー4−モルホリノ−1,
,3,5−トリアジンのポリマー (n=11、分子量
的2770)Sffi量%および各種添加剤として2.
6−ジーt−ブチル−p−クレゾール、0.15重ta
%、ジ−ミリスチル−β、β−チオジブロピオネー1−
0.2重量%およびステアリン酸カルシウム0.1重量
%をヘンセルミキサー (商品名)に入れ、3分間撹拌
混合した。得られた混合物を口径45iiの押出機で溶
融混練温度200’Cで溶融混練押出し、ペレット化し
た。Examples 7 to 13, Comparative Examples 5 to 13 The polypropylene resin as component (F) had an ethylene content of 8.5% by weight and a melt flow rate of 20.971.
0 minute crystalline ethylene-propylene block copolymer,
The polyethylene resin that is the component hole is an ethylene homopolymer with a melt index of 6.5.9/10 (Chisso Polyethylene (trademark) M680, manufactured by Chisso ■), and the ethylene synthetic rubber that is the component (G) is also an elastomer. ethylene-propylene rubber (JSREP (trademark) 02P, manufactured by Japan Synthetic Rubber ■), trimethylolpropane triacrylate as component CD+, and trilauryltrithioposphite as component (E) in the blending ratios listed in Table 2. In addition, 21% by weight of ammonium polyphosphate (Sumisafe P (trademark) manufactured by Sumitomo Chemical Co., Ltd.) as component (13), 1,3.5- as component c), and 2- as an azine derivative biperazinylene-4-morpholino-1,
, 3,5-triazine polymer (n=11, molecular weight 2770) as Sffi amount % and various additives.
6-di-t-butyl-p-cresol, 0.15 ta
%, di-myristyl-β, β-thiodibropione 1-
0.2% by weight and 0.1% by weight of calcium stearate were placed in a Hensel mixer (trade name) and stirred and mixed for 3 minutes. The resulting mixture was melt-kneaded and extruded using an extruder with a diameter of 45ii at a melt-kneading temperature of 200'C to form pellets.
実施各側、比較各側で得られたベレットを100°Cの
温度で3時間乾燥したのち、該ベレットを用いてシリン
ダーの最高温度を220°Cに設定した射出成形機で難
燃性、アイゾツト衝撃強度測定用の所定の試験片をそれ
ぞれ成形した。該試験片を用いて難燃性、アイゾツト衝
撃強度の測定を行った。その結果を第2表に示した。After drying the pellets obtained on each experimental side and each comparative side at a temperature of 100°C for 3 hours, the pellets were used to mold flame retardant and Izotsu resin in an injection molding machine with the maximum temperature of the cylinder set at 220°C. Predetermined test pieces for impact strength measurements were each molded. Flame retardancy and Izod impact strength were measured using the test piece. The results are shown in Table 2.
(発明の効果)
本発明の組成物は高度の難燃性、すなわちUL94燃焼
試験で1/8インチ肉厚で5Vの難燃性を有し、加工時
や燃焼時に腐食性のガスや有毒性のガスの発生もなく、
しかも成形加工性の低下や成形品としたときの該成形品
の機械的強度の低下も少なく優れた耐衝撃性を有する成
形品が得られる難燃性ポリプロピレン樹脂組成物である
。従って建築物、室内装飾品、家庭用電気製品の部品、
自動車用部品などの製造に好適に用いることができる。(Effects of the Invention) The composition of the present invention has a high degree of flame retardancy, that is, a flame retardance of 5V at 1/8 inch wall thickness in the UL94 flame test, and is free from corrosive gases and toxic gases during processing and combustion. There is no generation of gas,
Moreover, it is a flame-retardant polypropylene resin composition that can produce molded products with excellent impact resistance, with little deterioration in molding processability or mechanical strength of the molded products. Therefore parts of buildings, interior decoration, household appliances,
It can be suitably used for manufacturing automobile parts and the like.
以上that's all
Claims (3)
として、 (A)ポリエチレン樹脂5〜30重量% (B)ポリ燐酸アンモニウムまたはポリ燐酸アミド12
〜25重量% (C)下記一般式〔 I 〕で表わされる構造を有する1
,3,5−トリアジン誘導体5〜10重量% ▲数式、化学式、表等があります▼〔 I 〕 〔式中、Xはモルホリノ基もしくはピペリジノ基、Yは
ピペラジンの2価の基、nは2〜50の整数である。〕 (D)架橋助剤1〜15重量% (E)下記一般式〔II〕、〔III〕、〔IV〕および〔V
〕で表わされるもののなかから選ばれたチオホスファイ
ト0.05〜5重量% ▲数式、化学式、表等があります▼〔III〕 ▲数式、化学式、表等があります▼〔IV〕 ▲数式、化学式、表等があります▼〔V〕 〔式中、R_1は炭素数6個以上のアルキル基もしくは
シクロアルキル基もしくはアリール基を表わす。R_2
は−SR′_2または−R′_2であり、R_3は−S
R′_3または−R′_3であり、−R′_2、−R′
_3は炭素数6個以上の同種または異種のアルキル基も
しくはシクロアルキル基もしくはアリール基を表わす。 Xは−(CH_2)_n、−(CH_2)_n−O−(
CH_2)_m−もしくは▲数式、化学式、表等があり
ます▼で表わされ る。ここでn、m、lは2〜6の同数または異数の整数
を表わす。〕 (F)残りポリプロピレン樹脂 である難燃性ポリプロピレン樹脂組成物。(1) The total of the following (A) to (F) is 100% by weight.
(A) 5 to 30% by weight of polyethylene resin (B) Ammonium polyphosphate or polyphosphoric acid amide 12
~25% by weight (C) 1 having the structure represented by the following general formula [I]
, 3,5-triazine derivative 5-10% by weight ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ [I] [In the formula, X is a morpholino group or piperidino group, Y is a divalent group of piperazine, and n is 2- It is an integer of 50. ] (D) 1 to 15% by weight of crosslinking aid (E) The following general formulas [II], [III], [IV] and [V
0.05 to 5% by weight of thiophosphite selected from those represented by , tables, etc. ▼ [V] [In the formula, R_1 represents an alkyl group, a cycloalkyl group, or an aryl group having 6 or more carbon atoms. R_2
is -SR'_2 or -R'_2, and R_3 is -S
R'_3 or -R'_3, -R'_2, -R'
_3 represents the same or different alkyl group, cycloalkyl group, or aryl group having 6 or more carbon atoms. X is -(CH_2)_n, -(CH_2)_n-O-(
It is represented by CH_2)_m- or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. Here, n, m, and l represent the same or different integers from 2 to 6. ] (F) A flame-retardant polypropylene resin composition, which is the remaining polypropylene resin.
として、 (A)ポリエチレン樹脂5〜30重量% (B)ポリ燐酸アンモニウムまたはポリ燐酸アミド12
〜25重量% (C)下記一般式〔 I 〕で表わされる構造を有する1
,3,5−トリアジン誘導体5〜10重量% ▲数式、化学式、表等があります▼〔 I 〕 〔式中、Xはモルホリノ基もしくはピぺリジノ基、Yは
ピペラジンの2価の基、nは2〜50の整数である。〕 (D)架橋助剤1〜15重量% (E)下記一般式〔II〕、〔III〕、〔IV〕および〔V
〕で表わされるもののなかから選ばれたチオホスファイ
ト0.05〜5重量% ▲数式、化学式、表等があります▼〔II〕▲数式、化学
式、表等があります▼〔III〕 ▲数式、化学式、表等があります▼〔IV〕 ▲数式、化学式、表等があります▼〔V〕 〔式中、R_1は炭素数6個以上のアルキル基もしくは
シクロアルキル基もしくはアリール基を表わす。R_2
は−SR′_2または−R′_2であり、R_3は−S
R′_3または−R′_3であり、−R′_2、−R′
_3は炭素数6個以上の同種または異種のアルキル基も
しくはシクロアルキル基もしくはアリール基を表わす。 Xは−(CH_2)_n−、−(CH_2)_n−O−
(CH_2)_m−もしくは▲数式、化学式、表等があ
ります▼で表わ される。ここでn、m、lは2〜6の同数または異数の
整数を表わす。〕 (G)エチレン系合成ゴムもしくはエラストマー5〜3
0重量% (F)残りポリプロピレン樹脂 である難燃性ポリプロピレン樹脂組成物。(2) The total of the following (A) to (G) is 100% by weight.
(A) 5 to 30% by weight of polyethylene resin (B) Ammonium polyphosphate or polyphosphoric acid amide 12
~25% by weight (C) 1 having the structure represented by the following general formula [I]
, 3,5-triazine derivative 5-10% by weight ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ [I] [In the formula, X is a morpholino group or piperidino group, Y is a divalent group of piperazine, and n is It is an integer from 2 to 50. ] (D) 1 to 15% by weight of crosslinking aid (E) The following general formulas [II], [III], [IV] and [V
0.05 to 5% by weight of thiophosphite selected from those represented by , tables, etc. ▼ [IV] ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ [V] [In the formula, R_1 represents an alkyl group, a cycloalkyl group, or an aryl group having 6 or more carbon atoms. R_2
is -SR'_2 or -R'_2, and R_3 is -S
R'_3 or -R'_3, -R'_2, -R'
_3 represents the same or different alkyl group, cycloalkyl group, or aryl group having 6 or more carbon atoms. X is -(CH_2)_n-, -(CH_2)_n-O-
It is represented by (CH_2)_m- or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. Here, n, m, and l represent the same or different integers from 2 to 6. ] (G) Ethylene-based synthetic rubber or elastomer 5-3
0% by weight (F) Flame-retardant polypropylene resin composition, which is the remaining polypropylene resin.
独重合体、プロピレン成分を70重量%以上含有する結
晶性共重合体であつて、プロピレンとエチレン、ブテン
−1、ペンテン−1、ヘキセン−1、4−メチルペンテ
ン−1、ヘプテン−1、オクテン−1、デセン−1のな
かから選ばれた1以上との結晶性共重合体もしくはこれ
らの2以上の混合物を用いる請求項1もしくは請求項2
記載の難燃性ポリプロピレン樹脂組成物。(3) The polypropylene resin is a crystalline propylene homopolymer or a crystalline copolymer containing 70% by weight or more of a propylene component, which includes propylene and ethylene, butene-1, pentene-1, hexene-1, 4- Claim 1 or Claim 2 wherein a crystalline copolymer with one or more selected from methylpentene-1, heptene-1, octene-1, and decene-1 or a mixture of two or more of these is used.
The flame retardant polypropylene resin composition described.
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP10953788A JPH0662818B2 (en) | 1988-05-02 | 1988-05-02 | Flame-retardant polypropylene resin composition |
CA000587950A CA1307069C (en) | 1988-01-29 | 1989-01-11 | Flame-retardant polypropylene resin composition |
US07/298,951 US4966931A (en) | 1988-01-29 | 1989-01-19 | Flame-retardant polypropylene resin composition |
DE89101198T DE68909255T2 (en) | 1988-01-29 | 1989-01-24 | Fire retardant polypropylene composition. |
EP89101198A EP0326082B1 (en) | 1988-01-29 | 1989-01-24 | Flame-retardant polypropylene resin composition |
KR1019890000866A KR970005900B1 (en) | 1988-01-29 | 1989-01-27 | Flame-retardant polypropylene resin composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP10953788A JPH0662818B2 (en) | 1988-05-02 | 1988-05-02 | Flame-retardant polypropylene resin composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH01278546A true JPH01278546A (en) | 1989-11-08 |
JPH0662818B2 JPH0662818B2 (en) | 1994-08-17 |
Family
ID=14512763
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP10953788A Expired - Fee Related JPH0662818B2 (en) | 1988-01-29 | 1988-05-02 | Flame-retardant polypropylene resin composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0662818B2 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH04139241A (en) * | 1990-09-28 | 1992-05-13 | Chisso Corp | Production of ammonium polyphosphate-containing bleed-free olefin-based polymer composition |
JPH05331322A (en) * | 1990-10-11 | 1993-12-14 | Chisso Corp | Flame-retardant composition of thermoplastic olefin elastomer |
WO2006070042A1 (en) * | 2004-12-24 | 2006-07-06 | Gasca Miramon Judit Maria | Artwork restoration composition and method |
-
1988
- 1988-05-02 JP JP10953788A patent/JPH0662818B2/en not_active Expired - Fee Related
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH04139241A (en) * | 1990-09-28 | 1992-05-13 | Chisso Corp | Production of ammonium polyphosphate-containing bleed-free olefin-based polymer composition |
JPH05331322A (en) * | 1990-10-11 | 1993-12-14 | Chisso Corp | Flame-retardant composition of thermoplastic olefin elastomer |
WO2006070042A1 (en) * | 2004-12-24 | 2006-07-06 | Gasca Miramon Judit Maria | Artwork restoration composition and method |
ES2258914A1 (en) * | 2004-12-24 | 2006-09-01 | Maria Angeles Solis Parra | Artwork restoration composition and method |
Also Published As
Publication number | Publication date |
---|---|
JPH0662818B2 (en) | 1994-08-17 |
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