JP2004115651A - Flame-retardant polyamide resin composition - Google Patents
Flame-retardant polyamide resin composition Download PDFInfo
- Publication number
- JP2004115651A JP2004115651A JP2002280911A JP2002280911A JP2004115651A JP 2004115651 A JP2004115651 A JP 2004115651A JP 2002280911 A JP2002280911 A JP 2002280911A JP 2002280911 A JP2002280911 A JP 2002280911A JP 2004115651 A JP2004115651 A JP 2004115651A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- polyamide resin
- flame
- parts
- poly
- 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
- 229920006122 polyamide resin Polymers 0.000 title claims abstract description 140
- 239000003063 flame retardant Substances 0.000 title claims abstract description 86
- 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 abstract description 79
- 239000011342 resin composition Substances 0.000 title claims abstract description 47
- -1 borate compound Chemical class 0.000 claims abstract description 82
- 229910052751 metal Inorganic materials 0.000 claims abstract description 47
- 239000002184 metal Substances 0.000 claims abstract description 47
- 229920001296 polysiloxane Polymers 0.000 claims description 95
- 125000003118 aryl group Chemical group 0.000 claims description 73
- 229920005989 resin Polymers 0.000 claims description 68
- 239000011347 resin Substances 0.000 claims description 68
- 150000001875 compounds Chemical class 0.000 claims description 56
- 239000004952 Polyamide Substances 0.000 claims description 43
- 229920002647 polyamide Polymers 0.000 claims description 43
- 239000012779 reinforcing material Substances 0.000 claims description 40
- 229920001955 polyphenylene ether Polymers 0.000 claims description 25
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 19
- 239000003365 glass fiber Substances 0.000 claims description 14
- 229920006123 polyhexamethylene isophthalamide Polymers 0.000 claims description 14
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 14
- 229920001577 copolymer Polymers 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 11
- FQLAJSQGBDYBAL-UHFFFAOYSA-N 3-(azepane-1-carbonyl)benzamide Chemical group NC(=O)C1=CC=CC(C(=O)N2CCCCCC2)=C1 FQLAJSQGBDYBAL-UHFFFAOYSA-N 0.000 claims description 8
- 239000004953 Aliphatic polyamide Substances 0.000 claims description 6
- 229920003231 aliphatic polyamide Polymers 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- 229920001897 terpolymer Polymers 0.000 claims description 6
- DJZKNOVUNYPPEE-UHFFFAOYSA-N tetradecane-1,4,11,14-tetracarboxamide Chemical group NC(=O)CCCC(C(N)=O)CCCCCCC(C(N)=O)CCCC(N)=O DJZKNOVUNYPPEE-UHFFFAOYSA-N 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 claims description 4
- 229920006128 poly(nonamethylene terephthalamide) Polymers 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 3
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 230000001588 bifunctional effect Effects 0.000 claims description 2
- 125000004494 ethyl ester group Chemical group 0.000 claims description 2
- 125000004492 methyl ester group Chemical group 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims 3
- PGGROMGHWHXWJL-UHFFFAOYSA-N 4-(azepane-1-carbonyl)benzamide Chemical group C1=CC(C(=O)N)=CC=C1C(=O)N1CCCCCC1 PGGROMGHWHXWJL-UHFFFAOYSA-N 0.000 claims 1
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical group O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims 1
- 239000012765 fibrous filler Substances 0.000 claims 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 9
- 239000011574 phosphorus Substances 0.000 abstract description 9
- 229910052787 antimony Inorganic materials 0.000 abstract description 7
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 4
- 150000001491 aromatic compounds Chemical class 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 42
- 238000002485 combustion reaction Methods 0.000 description 37
- 239000008188 pellet Substances 0.000 description 30
- 239000000203 mixture Substances 0.000 description 28
- 238000004519 manufacturing process Methods 0.000 description 27
- 238000000034 method Methods 0.000 description 26
- 239000002994 raw material Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000000835 fiber Substances 0.000 description 12
- 229910052736 halogen Inorganic materials 0.000 description 11
- 150000002367 halogens Chemical class 0.000 description 11
- 238000001746 injection moulding Methods 0.000 description 11
- 238000000465 moulding Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 8
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 150000002366 halogen compounds Chemical class 0.000 description 7
- 238000004898 kneading Methods 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 238000011144 upstream manufacturing Methods 0.000 description 7
- 240000008042 Zea mays Species 0.000 description 6
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 6
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 235000005822 corn Nutrition 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- 229920005992 thermoplastic resin Polymers 0.000 description 6
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 150000001463 antimony compounds Chemical class 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 230000020169 heat generation Effects 0.000 description 5
- 239000012760 heat stabilizer Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000000691 measurement method Methods 0.000 description 5
- 150000002736 metal compounds Chemical class 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 4
- 229920000877 Melamine resin Polymers 0.000 description 4
- 229920002292 Nylon 6 Polymers 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 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 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- BSWWXRFVMJHFBN-UHFFFAOYSA-N 2,4,6-tribromophenol Chemical compound OC1=C(Br)C=C(Br)C=C1Br BSWWXRFVMJHFBN-UHFFFAOYSA-N 0.000 description 3
- JHJUYGMZIWDHMO-UHFFFAOYSA-N 2,6-dibromo-4-(3,5-dibromo-4-hydroxyphenyl)sulfonylphenol Chemical compound C1=C(Br)C(O)=C(Br)C=C1S(=O)(=O)C1=CC(Br)=C(O)C(Br)=C1 JHJUYGMZIWDHMO-UHFFFAOYSA-N 0.000 description 3
- GVLZQVREHWQBJN-UHFFFAOYSA-N 3,5-dimethyl-7-oxabicyclo[2.2.1]hepta-1,3,5-triene Chemical compound CC1=C(O2)C(C)=CC2=C1 GVLZQVREHWQBJN-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 239000004734 Polyphenylene sulfide Substances 0.000 description 3
- 229920006121 Polyxylylene adipamide Polymers 0.000 description 3
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 3
- 150000001642 boronic acid derivatives Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 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 3
- 238000000605 extraction Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 150000003018 phosphorus compounds Chemical class 0.000 description 3
- 229920005668 polycarbonate resin Polymers 0.000 description 3
- 239000004431 polycarbonate resin Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920000069 polyphenylene sulfide Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- WGKLIJDVPACLGG-UHFFFAOYSA-N trizinc diborate hydrate Chemical compound O.[Zn++].[Zn++].[Zn++].[O-]B([O-])[O-].[O-]B([O-])[O-] WGKLIJDVPACLGG-UHFFFAOYSA-N 0.000 description 3
- QQOMQLYQAXGHSU-UHFFFAOYSA-N 2,3,6-Trimethylphenol Chemical compound CC1=CC=C(C)C(O)=C1C QQOMQLYQAXGHSU-UHFFFAOYSA-N 0.000 description 2
- BDFBPPCACYFGFA-UHFFFAOYSA-N 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine Chemical compound BrC1=CC(Br)=CC(Br)=C1OC1=NC(OC=2C(=CC(Br)=CC=2Br)Br)=NC(OC=2C(=CC(Br)=CC=2Br)Br)=N1 BDFBPPCACYFGFA-UHFFFAOYSA-N 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 2
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 description 2
- LIAWCKFOFPPVGF-UHFFFAOYSA-N 2-ethyladamantane Chemical compound C1C(C2)CC3CC1C(CC)C2C3 LIAWCKFOFPPVGF-UHFFFAOYSA-N 0.000 description 2
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical class O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 239000004114 Ammonium polyphosphate Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- ASMQGLCHMVWBQR-UHFFFAOYSA-N Diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(O)OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-N 0.000 description 2
- 229920000305 Nylon 6,10 Polymers 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000004695 Polyether sulfone Substances 0.000 description 2
- 239000004697 Polyetherimide Substances 0.000 description 2
- 229920000388 Polyphosphate Polymers 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 2
- 229920001276 ammonium polyphosphate Polymers 0.000 description 2
- 229910000410 antimony oxide Inorganic materials 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910021538 borax Inorganic materials 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000012433 hydrogen halide Substances 0.000 description 2
- 229910000039 hydrogen halide Inorganic materials 0.000 description 2
- 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 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 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
- 150000002989 phenols Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 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
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920006393 polyether sulfone Polymers 0.000 description 2
- 229920001601 polyetherimide Polymers 0.000 description 2
- 239000001205 polyphosphate Substances 0.000 description 2
- 235000011176 polyphosphates Nutrition 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 239000004328 sodium tetraborate Substances 0.000 description 2
- 235000010339 sodium tetraborate Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- BHYQWBKCXBXPKM-UHFFFAOYSA-N tris[3-bromo-2,2-bis(bromomethyl)propyl] phosphate Chemical compound BrCC(CBr)(CBr)COP(=O)(OCC(CBr)(CBr)CBr)OCC(CBr)(CBr)CBr BHYQWBKCXBXPKM-UHFFFAOYSA-N 0.000 description 2
- FEODVXCWZVOEIR-UHFFFAOYSA-N (2,4-ditert-butylphenyl) octyl hydrogen phosphite Chemical compound CCCCCCCCOP(O)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C FEODVXCWZVOEIR-UHFFFAOYSA-N 0.000 description 1
- NJHVXCSESBEOEB-UHFFFAOYSA-N (2,6-ditert-butyl-4-methylphenyl) dihydrogen phosphite Chemical compound CC1=CC(C(C)(C)C)=C(OP(O)O)C(C(C)(C)C)=C1 NJHVXCSESBEOEB-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は難燃性ポリアミド樹脂組成物に関する。特に、電気・電子分野のコネクター、ブレーカー、マグネットスイッチ等の部品、自動車分野の電装部品等の部品材料に好適に用いられる難燃性ポリアミド樹脂組成物に関する。とりわけ、本発明は、ポリアミド樹脂が本来有する機械的特性、電気特性を損なうことなく難燃性を向上させ、かつ塩素、臭素等のハロゲン系難燃剤、アンチモン系助難燃剤並びリン系難燃剤を含有しない難燃性ポリアミド樹脂組成物に関する。
【０００２】
【従来の技術】
従来、ポリアミド樹脂は、機械的性質、成形加工性、電気絶縁性等に優れることから、自動車部品、機械部品、電気・電子部品などの広範な分野で使用されている。しかしながら、ポリアミド樹脂は易燃性であり、安全性の問題から種々の難燃化技術が提案されてきた。そしてそれらは一般的に高い難燃化効果を持つ臭素化合物等のハロゲン系難燃剤と酸化アンチモンをポリアミド樹脂に配合する方法が取られている。
【０００３】
例えば、ポリアミド樹脂への塩素置換多環式化合物の添加（例えば、特許文献１参照。）や臭素系難燃剤、例えば、デカブロモジフェニルエーテルの添加（例えば、特許文献２参照。）、臭素化ポリスチレンの添加（例えば、特許文献３及び特許文献４参照。）、臭素化ポリフェニレンエーテルの添加（例えば、特許文献５参照。）、臭素化架橋芳香族重合体の添加（例えば、特許文献６参照。）、臭素化スチレン−無水マレイン酸重合体の添加（例えば、特許文献７参照。）等が知られている。特にこれらハロゲン系難燃剤をガラス繊維等で強化したポリアミド樹脂に配合した組成物は高度の難燃性と高い剛性から、電気・電子部品用途、特にプリント積層板に搭載されたり、接続されたりするコネクター用途に多用されてきた。しかしながら、ハロゲン系難燃剤は難燃性を向上させる一方、射出成形などの加熱加工時に、腐食性のハロゲン化水素を発生し、金型等を腐食する問題があった。また、ハロゲン系難燃剤と併用されるアンチモン化合物も難燃性を向上させる一方、電気・電子用途に必要な電気特性（耐トラッキング性）を大きく低下させる問題があった。
【０００４】
このことから、ハロゲンフリーのリン系難燃剤が注目され、数多く検討がなされてきた。例えば、リン酸メラミン、ピロリン酸メラミン、あるいはポリリン酸メラミンをガラス繊維強化ポリアミド樹脂に使用するハロゲンフリーの難燃技術（例えば、特許文献８参照。）、無機質強化ポリアミド樹脂にポリリン酸メラミンを加え、チャー化触媒及び／又はチャー形成剤を併用する難燃技術（例えば、特許文献９参照。）が提案され、１／１６インチの成形品において難燃規格ＵＬ９４Ｖ−０規格を満足することが知られている。しかし、これらの技術では、電気・電子部品のコネクター用途で特に要求される薄肉成形品でのＵＬ９４Ｖ−０規格を満足するためには、リン酸メラミン系難燃剤を多く用いる必要があり、この為、ガラス繊維強化ポリアミド樹脂組成物の機械的特性が大きく低下するばかりでなく、電気特性、とりわけ高い電圧環境下に於いて使用される電気部品に要求される耐トラッキング性を大きく低下させた。さらには成形加工時の離型性にも劣り、必ずしも電気・電子部品用の成形材料として満足されるものではなかった。
【０００５】
また、薄肉成形品での難燃規格ＵＬ９４Ｖ−０を達成する技術として、イントメッセント型難燃剤である硫酸メラミンをガラス繊維強化半芳香族ポリアミド樹脂に適用した技術（例えば、特許文献１０参照。）も開示されているが、この技術においてもポリアミド樹脂成分量に対して難燃剤を多く配合する必要があり、上記と同様の問題があった。さらには、薄肉成形品での難燃規格ＵＬ９４Ｖ−０を達成しつつ、高い耐トラッキング性を付与する技術として、無機質強化ポリアミド樹脂にリン酸メラミン複合難燃剤に加え、アルカリ土類金属塩を配合する技術（例えば、特許文献１１参照。）も提案されているが、この技術で得られた成形品は非常に脆い問題があった。更には成形加工性においても満足出来なく、また成形品を例えば６０℃、９５％ＲＨ等の高温高湿の環境下で長時間放置時、成形品表面にポリアミドオリゴマーや難燃剤が析出する、いわゆるブリードアウト現象が生じるなどの問題があり満足出来るものではなかった。
【０００６】
これらに対して、ホウ酸亜鉛化合物を難燃剤としての難燃材開発も行われている。ポリアミド樹脂、無機充填材、臭素系難燃剤、ホウ酸亜鉛、熱安定剤からなるアンチモン化合物の代替にホウ酸亜鉛化合物を使用する難燃化技術（例えば、特許文献１２参照。）が開示されている。しかし、難燃剤としてのハロゲン化合物が必須成分であり、これを使用せずに難燃性を付与することは難しい。またハロゲン化合物を使用しない技術として、ポリフェニレンエーテル樹脂、ポリカーボネート樹脂、ポリエーテルイミド樹脂、ポリエーテルスルホン樹脂、ポリフェニレンスルフィド樹脂等の少なくとも２０％が芳香族の主鎖を含むポリマー成分に、難燃剤としてフッ素化合物とホウ素化合物を使用する難燃化技術（例えば、特許文献１３参照。）、ポリジオルガノシロキサン流体を含むポリカーボネート樹脂、ポリ（エステルカーボネート）樹脂に、自由流動性粉末として混合されているポリジオルガノシロキサン流体−充填材ブレンドを含む難燃性ポリマーブレンドに、有効量の繊維状ポリテトラフルオロエチレンや有効量の無水ホウ酸亜鉛を含む難燃性ポリカーボネートの技術（例えば、特許文献１４参照。）、ポリカーボネート系樹脂及びポリエステル系樹脂からなる熱可塑性樹脂に対して、ホウ酸亜鉛及び／又はホウ酸亜鉛水和物、アルコール変性シリコーンオイルからなる難燃性熱可塑性樹脂組成物の技術（例えば、特許文献１５参照。）が開示されているが、これらの技術は主にポリカーボネート樹脂などで行われたものでポリアミド樹脂や他樹脂に適用しても充分な難燃性を発現しない場合や他の物性を低下させることがある。また、これらの技術ではガラス繊維などの強化剤を添加した場合、燃焼時にドリップが発生し、充分な難燃性を発現しない場合があった。さらに、ポリカーボネートでは、成形性、引張強度、電気特性などの物性や耐薬品性に劣り有機溶媒等に接触する恐れのある用途には使用できない場合があった。
【０００７】
【特許文献１】
特開昭４８−２９８４６号公報
【特許文献２】
特開昭４７−７１３４号公報
【特許文献３】
特開昭５１−４７０４４号公報
【特許文献４】
特開平４−１７５３７１号公報
【特許文献５】
特開昭５４−１１６０５４号公報
【特許文献６】
特開昭６３−３１７５５２号公報
【特許文献７】
特開平３−１６８２４６号公報
【特許文献８】
特表平１０−５０５８７５号公報
【特許文献９】
国際公開第９８／４５３６４号パンフレット
【特許文献１０】
特開２０００−１１９５１２号公報
【特許文献１１】
国際公開第００／０９６０６号パンフレット
【特許文献１２】
特表２００２−５０６９０５号公報
【特許文献１３】
特開平２−１８０９６９号公報
【特許文献１４】
特開平５−２０２２８０号公報
【特許文献１５】
特開平１１−３４３４００号公報
【０００８】
【発明が解決しようとする課題】
本発明の目的は、塩素、臭素等のハロゲン系難燃剤、アンチモン系難燃助剤並びにリン系難燃剤を含有せずに、ポリアミド樹脂が本来有する機械的特性、耐薬品性、良成形性、電気特性を損なうことなく難燃性を大きく向上させ、かつ燃焼時の発熱速度とドリップ発生が抑制された難燃性ポリアミド樹脂組成物を提供することにある。
【０００９】
【課題を解決するための手段】
本発明者等は、鋭意研究を重ねた結果、芳香族成分を含むポリアミド樹脂、ホウ酸金属化合物を必須成分とした際にポリアミド樹脂、ハロゲン化合物、ホウ酸金属化合物の三者を含む組成物において、問題となっていた射出成形などの加熱加工時に、腐食性のハロゲン化水素等が発生し、金型等を腐食する点を解決ができ、かつ燃焼時の発熱速度とドリップ発生が抑制された難燃性ポリアミド樹脂組成物を提供できることを見いだした。さらに、強化材、シリコーン化合物、ポリフェニレンエーテル樹脂を任意成分として組み合わせた際に、ＵＬ試験評価やコーンカロリーメーター試験での燃焼時の発熱速度の減少などの難燃性を更に向上させることができ、さらに物性の改良、流動性の向上等の更なる性質の改良が実現できることを見いだし、この知見に基づき本発明を完成するに至った。
また、本発明は、ポリアミド樹脂をホウ酸亜鉛のみを難燃剤として用いて難燃化を達成することに成功したものである。
すなわち、本発明は、（ａ）芳香族成分を含むポリアミド樹脂、及び（ｂ）ホウ酸金属化合物からなる難燃性ポリアミド樹脂組成物である。
【００１０】
本発明について、以下具体的に説明する。
本発明の（ａ）芳香族成分を含むポリアミド樹脂としては、例えば、ジカルボン酸とジアミンとの重縮合物、環状ラクタムの開環重合物、アミノカルボン酸の重縮合物などが挙げられ、具体的にはポリ（メタキシリレンアジパミド）（以下ポリアミドＭＸＤ６と略す）、ポリ（ヘキサメチレンテレフタルアミド）（以下ポリアミド６Ｔと略す）、ポリ（ヘキサメチレンイソフタルアミド）（以下ポリアミド６Ｉと略す）、ポリ（ノナメチレンテレフタルアミド）（以下ポリアミド９Ｔと略す）、ポリ（テトラメチレンイソフタルアミド）（以下ポリアミド４Ｉと略す）等の脂肪族−芳香族ポリアミド及びこれらの共重合体や混合物を挙げることができ、さらに前記の脂肪族−芳香族ポリアミドとポリ（カプロラクタム）（以下ポリアミド６と略す）、ポリ（ヘキサメチレンアジパミド）（以下ポリアミド６６と略す）、ポリ（テトラメチレンアジパミド）（以下ポリアミド４６と略す）、ポリ（ヘキサメチレンセバカミド）（以下ポリアミド６１０と略す）、ポリ（ヘキサメチレンドデカミド）（以下ポリアミド６１２と略す）、ポリ（ウンデカメチレンアジパミド）（以下ポリアミド１１６）、ポリ（ウンデカラクタム）（以下ポリアミド１１と略す）、ポリ（ドデカラクタム）（以下ポリアミド１２と略す）等の脂肪族ポリアミドとの共重合体や混合物も挙げることができる。
【００１１】
まず本発明に好ましい芳香族成分を含むポリアミドとしては、芳香族二酸であるイソフタル酸やテレフタル酸成分を含むものより重合されたポリアミドが高い難燃性を発現するので特に好ましい。例えばポリアミド６Ｔ、ポリアミド６Ｉ、ポリアミド９Ｔ、ポリアミド４Ｉ、及びこれらの共重合体や混合物が挙げられる。更に好ましくは、６６／６Ｉ共重合ポリアミド、６６／６Ｉ／６Ｔ三元共重合ポリアミド、６６／６Ｉ／６三元共重合ポリアミド、ポリアミド９Ｔ、ポリアミド６Ｉが高い難燃性と成形性を併せて満足するので好ましい。
【００１２】
具体的には、（１）ポリ（ヘキサメチレンアジパミド）単位６０〜９５重量％及びポリ（ヘキサメチレンイソフタルアミド）単位５〜４０重量％からなる共重合体；（２）ポリ（ヘキサメチレンアジパミド）単位５０〜９４重量％、ポリ（ヘキサメチレンイソフタルアミド）単位５〜４０重量％及びポリ（ヘキサメチレンアジパミド）以外の脂肪族ポリアミド単位１〜１０重量％からなる３元共重合体；（３）ポリ（ヘキサメチレンアジパミド）成分６０〜９５重量％及びポリ（ヘキサメチレンイソフタルアミド）成分５〜４０重量％を含有する混合ポリアミド；（４）ポリ（ヘキサメチレンアジパミド）成分５０〜９４重量％、ポリ（ヘキサメチレンイソフタルアミド）成分５〜４０重量％及びポリ（ヘキサメチレンアジパミド）以外の脂肪族ポリアミド成分１〜１０重量％を含有する混合ポリアミドが挙げられ、これらの芳香族成分を含むポリアミドは更に好ましい。また、上記（２）中のポリ（ヘキサメチレンアジパミド）以外の脂肪族ポリアミド単位及び（４）中のポリ（ヘキサメチレンアジパミド）以外の脂肪族ポリアミド成分としては、ポリ（カプロラクタム）即ちポリアミド６の単位及び成分などが挙げられる。
【００１３】
次に、芳香族成分を含むポリアミドとしてはジアミンであるキシリレンジアミン成分（メタキシリレンジアミンやパラキシリレンジアミンが挙げられる）を含むものより重合されたポリアミドが不燃層（又は炭化層）生成量が大きく、高い難燃性を発現するので特に好ましい。この様なものとして、具体的にはポリアミドＭＸＤ６が挙げられ、ホウ酸金属化合物と組み合わせて用いた際に燃焼時に不燃層（又は炭化層）を形成し、優れた難燃性を発現するので好ましい。
【００１４】
本発明で用いられる（ｂ）ホウ酸金属化合物は、具体的にはホウ酸亜鉛化合物、ホウ酸マグネシウム化合物、ホウ酸カルシウム化合物、ホウ酸アルミニウム化合物等が挙げられる。本発明に好ましいホウ酸金属化合物としては、燃焼時に熱源である炎から樹脂への熱を遮断すること（断熱能力）によって、樹脂の分解で燃料となるガスの発生を抑制し、難燃性を高めるのに必要な不燃層（又は炭化層）の形成効率が高く、即ち難燃性に優れるので、ｘＺｎＯ・ｙＢ２Ｏ３・ｚＨ２Ｏ（ｘ＞０、ｙ＞０、ｚ≧０）で表されるホウ酸亜鉛化合物が挙げられる。好ましくは、２ＺｎＯ・３Ｂ２Ｏ３・３．５Ｈ２Ｏ、４ＺｎＯ・Ｂ２Ｏ３・Ｈ２Ｏ、２ＺｎＯ・３Ｂ２Ｏ３で表されるホウ酸亜鉛化合物が挙げられ、更に好ましくは、燃焼時に脱水することによって水蒸気を発生し、不燃層をより発泡させ、不燃層の断熱能力を更に増大させるができ、同時に水の気化熱により燃焼系中を冷却できる、２ＺｎＯ・３Ｂ２Ｏ３・３．５Ｈ２Ｏ、４ＺｎＯ・Ｂ２Ｏ３・Ｈ２Ｏで表されるホウ酸亜鉛水和物が挙げられ、最も好ましくは、含有する水の比率が高い２ＺｎＯ・３Ｂ２Ｏ３・３．５Ｈ２Ｏが挙げられる。
【００１５】
さらには、これらのホウ酸金属化合物はシラン系カップリング剤、チタネート系カップリング剤等の表面処理剤で処理されていてもよい。また、平均粒径は、好ましくは３０μｍ以下であり、更に好ましくは、１５μｍ以下であり、特に好ましくは７μｍ以下である。
本発明に用いる（ｃ）強化材は任意成分であり、本成分が無くとも、本発明の目的は達成されるが、更なる難燃性、機械特性の向上を図る際には、本成分を添加することができる。
【００１６】
（ｃ）強化材としては、ガラス繊維、炭素繊維、チタン酸カリウム繊維、石膏繊維、黄銅繊維、ステンレス繊維、スチール繊維、セラミックス繊維、ボロンウィスカ繊維、マイカ、タルク、シリカ、炭酸カルシウム、カオリン、焼成カオリン、ウオラストナイト、ガラスビーズ、ガラスフレーク、酸化チタン等の繊維状、粒状、板状、あるいは針状の無機質強化材が挙げられる。これらの強化材は二種以上組み合わせて用いてもよい。特にガラス繊維等の繊維状強化剤が燃焼時のドリップ抑制効果が高く、また、燃焼時に生成する不燃層（又は炭化層）強化を行い、発泡した不燃層（又は炭化層）の形状を維持し、高い難燃化を実現できるので好ましく使用される。
【００１７】
また、ガラス繊維は長繊維タイプのロービング、短繊維タイプのチョップドストランド、ミルドファイバー等から選択して用いることが出来る。ガラス繊維は表面処理した物を用いるのが好ましい。とりわけ、ガラス繊維を用いると、物性、難燃性に特に優れるため特に好ましい。そのなかでもガラス繊維の平均繊維径が５〜３０μｍが好ましい。また、ガラス繊維の表面処理をしたものが優れた物性を付与するので一層好ましい。
【００１８】
強化材は配合されることによって、燃焼時に生成する不燃層（又は炭化層）の強度を一層向上させることができ、燃焼時に不燃層（又は炭化層）が破損しにくくなり、安定した断熱能力を発揮できるようになり、より大きな難燃効果が得られる。さらに、高い剛性も付与することができる。
本発明で用いられる（ｄ）シリコーン化合物は任意成分であり、本成分が無くとも、本発明の目的は達成されるが、更なる難燃性、流動性、機械特性の向上を図る際には、本成分を添加することができる
（ｄ）シリコーン化合物の構造は、以下に示す４つのシロキサン単位（Ｍ単位、Ｄ単位、Ｔ単位、Ｑ単位）の少なくともいずれかが重合してなるポリマーである。
【００１９】
１）Ｍ単位（一官能性）
【化５】
２）Ｄ単位（二官能性）
【化６】
３）Ｔ単位（三官能性）
【化７】
４）Ｑ単位（四官能性）
【化８】
（但し、Ｒは、それぞれ同一又は異なる置換基で、アルキル基、アリール基、ベンジル基、ビニル基、アリル基、アルコキシ基、ヒドロキシ基、アミノ基、メチルエステル基およびエチルエステル基から選択される。）
この内、特にＴ単位及び／又はＱ単位を含有すると分岐状構造となる。そして、本発明の（ｄ）シリコーン化合物の構造は特に規定が無く、分岐状でも直鎖状でも良く、液状でも固体状でも良い。
【００２４】
この様なものとしては、例えば以下のものが挙げられる。直鎖状のオルガノポリシロキサンとしては、ジメチルポリシロキサン、メチルフェニルポリシロキサン、ビニルメチルオルガノポリシロキサン、ビニルフェニルメチルポリシロキサン等が挙げられ、分岐状のオルガノポリシロキサンとしてはメチルポリシロキサンレジン、メチルフェニルポリシロキサンレジン、フェニルポリシロキサンレジン、ビニルメチルオルガノポリシロキサンレジン、ビニルフェニルメチルポリシロキサンレジン等が挙げられる。更に変性したオルガノポリシロキサン（レジン）として、アミノ変性オルガノポリシロキサン（レジン）、エポキシ変性オルガノポリシロキサン（レジン）、カルボキシル変性オルガノポリシロキサン（レジン）、カルビノール変性オルガノポリシロキサン（レジン）、メタクリル変性オルガノポリシロキサン（レジン）、メルカプト変性オルガノポリシロキサン（レジン）、ポリエーテル変性オルガノポリシロキサン（レジン）、メチルスチリル変性オルガノポリシロキサン（レジン）、高級アルキル変性オルガノポリシロキサン（レジン）、高級アルキル脂肪酸エステル変性オルガノポリシロキサン（レジン）、アルキルアラルキル変性オルガノポリシロキサン（レジン）、ヒドロキシル変性オルガノポリシロキサン（レジン）、アルコキシ変性オルガノポリシロキサン（レジン）、アルコール変性オルガノポリシロキサン（レジン）、フッ素変性オルガノポリシロキサン（レジン）、シラノール変性オルガノポリシロキサン（レジン）等が挙げられ、これらの有機置換基の導入位置はオルガノポリシロキサンの主鎖末端や側鎖が挙げられ、導入率は一部又は全部でも良い。
【００２５】
ポリアミド分子中には極性の高いアミド結合が存在するが、シリコーン分子中にはさほど高い極性の官能基はないために、両者の相溶性は乏しい。そのために多量にシリコーンを含む場合には、成形片に剥離などによって外観が悪化するときがあるので、このことを回避するために、使用するシリコーン化合物の主鎖末端や側鎖の一部又は全部をここに挙げたアミノ基、エポキシ基、カルボキシル基、カルビノール基、メルカプト基、高級アルキル脂肪酸エステル基、アルコキシ基、ヒドロキシル基等のような極性官能基によって変性されたシリコーンを用いことができる。
【００２６】
シリコーンは配合されることによって、燃焼時に生成する不燃層（又は炭化層）が、一層大きく膨らみ断熱能力に富んだものになり、より一層大きな難燃効果が得られる。また、良流動性や耐衝撃性も付与することができる。
これらシリコーンの有機置換基の内にビニル基を含有するものが好ましい。また、ビニル基が直接ケイ素原子に結合したシリコーン化合物が高い難燃性を発現するので特に好ましく、末端基（トリメチルシリル基やアルコキシ基等）を除くケイ素原子に結合している全有機置換基の内、ビニル基率がモル比で２％以上であるシリコーンが一層高い難燃性を発現するので、更に好ましい。理由は明らかではないが、燃焼時に反応性の高いビニル基を含有するシリコーンが不燃層を形成し易くし、その形成された不燃層を強化材が強化する両者の相乗効果によって、優れた難燃効果即ち燃焼時のドリップ抑制効果を発揮すると思われる。
【００２７】
また、シリコーン化合物の添加方法は特に限定せず、一度シリコーン化合物と芳香族成分を含むポリアミド樹脂等の樹脂を押出機等で混練させて、シリコーン化合物含有の樹脂組成物を得た後に、これとホウ酸金属化合物、強化材等とを混練させる二段法でも、一度に、シリコーン化合物、ホウ酸金属化合物、強化材、芳香族成分を含むポリアミド樹脂等の樹脂を混練する一段法でも構わず、シリコーン化合物が液状である場合は、液添ポンプなどの液添装置で、押出機中の溶融樹脂への添加でも、樹脂のペレットなどに外潤でブレンドした後に、押出機などで混練する方法などが挙げられる。この内、液添装置を用いる場合には、シリコーン化合物のタンクやシリコーン化合物の流路をヒーターなどで加熱し粘度を下げても構わない。また、固体状の時には、押出機のトップの供給口（トップフィーダー）や押出機途中の供給口（サイドフィーダー）等からの供給や樹脂のペレットなどとブレンドした後に、押出機などで混練する方法などが挙げられる。
【００２８】
本発明において用いられる（ｅ）ポリフェニレンエーテル樹脂は任意成分であり、本成分が無くとも、本発明の目的は達成されるが、更なる難燃性、機械特性の向上を図る際には、本成分を添加することができる。
（ｅ）ポリフェニレンエーテル樹脂とは、繰り返し単位構造
【００２９】
【化９】
（Ｒ１、Ｒ４は、それぞれ独立して、水素、第一級もしくは第二級の低級アルキル、フェニル、アミノアルキルまたは炭化水素オキシを表す。Ｒ２、Ｒ３は、それぞれ独立して、水素、第一級もしくは第二級の低級アルキルまたはフェニルを表す。）
からなり、還元粘度（０．５ｇ／ｄｌ、クロロホルム溶液、３０℃測定）が、０．１５ｄｌ／ｇ以上１．０ｄｌ／ｇ以下の範囲にあるホモ重合体及び／または共重合体である。さらに好ましい還元粘度は、０．２０ｄｌ／ｇ以上０．７０ｄｌ／ｇ以下の範囲、最も好ましくは０．４０ｄｌ／ｇ以上０．６０ｄｌ／ｇ以下の範囲である。また、流動性や成形性を改良するために低い還元粘度のものを併用することもでき、低い還元粘度のものとしては０．０３ｄｌ／ｇ以上０．４０ｄｌ／ｇ以下の範囲であり、好ましくは、０．０６ｄｌ／ｇ以上０．３０ｄｌ／ｇ以下の範囲である。
【００３１】
具体例としては、ポリ（２，６−ジメチル−１，４−フェニレンエーテル）、ポリ（２−メチル−６−エチル−１，４−フェニレンエーテル）、ポリ（２−メチル−６−フェニル−１，４−フェニレンエーテル）、ポリ（２，６−ジクロロ−１，４−フェニレンエーテル）等が挙げられ、さらに、２，６−ジメチルフェノールと他のフェノール類（例えば、２，３，６−トリメチルフェノールや２−メチル−６−ブチルフェノール）との共重合体のようなポリフェニレンエーテル共重合体も挙げられる。中でもポリ（２，６−ジメチル−１，４−フェニレンエーテル）、２，６−ジメチルフェノールと２，３，６−トリメチルフェノールとの共重合体が好ましく、さらにポリ（２，６−ジメチル−１，４−フェニレンエーテル）が好ましい。
【００３２】
本発明で使用するポリフェニレンエーテルの製造方法の例として、米国特許第３３０６８７４号明細書記載の第一銅塩とアミンのコンプレックスを触媒として用い、２，６−キシレノールを酸化重合する方法がある。米国特許第３３０６８７５号、同第３２５７３５７号および同第３２５７３５８号の明細書、特公昭５２−１７８８０号および特開昭５０−５１１９７号および同６３−１５２６２８号の各公報等に記載された方法もポリフェニレンエーテルの製造方法として好ましい。
【００３３】
さらに、ポリフェニレンエーテル樹脂の内、一部又は全部を無水マレイン酸などの相溶化剤で変性したものであると、ポリアミド樹脂との相溶性を高めることによって、物性や外観などが向上し好ましい。また、この際の方法は特に限定せず、一度相溶化剤とポリフェニレンエーテル樹脂等を押出機中で反応させて、変性されたポリフェニレンエーテル等を得た後に、これとポリアミド等とを混練させる二段法でも、一度に相溶化剤、ポリフェニレンエーテル樹脂、ポリアミド樹脂等を混練する一段法でも構わない。
【００３４】
本発明の好ましい態様として、成分（ａ）及び（ｂ）が必須成分であり、このニ成分により、本発明の目的は達成させることができる。そして、成分（ｃ）、（ｄ）及び（ｅ）は任意成分であり、添加することによって更なる難燃性の付与、機械特性の向上、流動性の向上等の効果が追加される。
本発明の難燃性ポリアミド樹脂組成物において、（ｂ）ホウ酸金属化合物の割合は、特に定めない。しかし、成型加工性、機械物性、難燃性をさらに一層向上させる際には（ａ）芳香族成分を含むポリアミド樹脂１００重量部に対して、０．１重量部以上２００重量部以下が好ましい。２００重量部より多いと成形加工性、機械的物性の向上が少し不十分で、０．１重量部より少ないと難燃性の向上が少し不十分である。より好ましくは１重量部以上１５０重量部以下であり、更に好ましくは２重量部以上１２０重量部以下であり、最も好ましくは、５重量部以上１００重量部以下である。
【００３５】
（ｃ）強化材は、任意成分であるが、添加する際の割合は、（ａ）芳香族成分を含むポリアミド樹脂１００重量部に対して、５重量部以上２００重量部以下が好ましい。２００重量部より多いと押出時や射出成形時に成形加工性が著しく低下し、５重量部より少ないと添加しない場合と比べて、引張強度や剛性など機械的性質の向上があまりみられない。より好ましくは１０重量部以上１８０重量部以下であり、更に好ましくは１５重量部以上１５０重量部以下である。
【００３６】
（ｄ）シリコーン化合物は、任意成分であるが、添加する際の割合は、（ａ）芳香族成分を含むポリアミド樹脂１００重量部に対して、０．０１重量部以上１００重量部以下が好ましい。１００重量部より多いと混練時に分解ガスが発生したり、成形加工時に成形金型に汚染性物質が付着したりするなどの問題が発生し、０．０１重量部より少ないと添加しない場合と比べて、難燃性の向上、流動性の向上や耐衝撃性の向上があまりみられない。より好ましくは０．０５重量部以上８０重量部以下であり、更に好ましくは０．１重量部以上６０重量部以下である。
【００３７】
（ｅ）ポリフェニレンエーテル樹脂は、任意成分であるが、添加する際の割合は、（ａ）芳香族成分を含むポリアミド樹脂１００重量部に対して、０．１重量部以上１００重量部以下が好ましい。１００重量％より多いとポリアミド樹脂がもつ成形加工性、機械的物性が低下し、０．１重量部以下だと流動性の向上はほとんど見られない。より好ましくは、１重量部以上８０重量部以下であり、更に好ましくは３重量部以上６０重量部以下である。
【００３８】
本明細書中でのハロゲン系難燃剤、アンチモン系難燃助剤、リン系難燃剤とは、ハロゲン化合物、アンチモン化合物、リン化合物の中で難燃性を高めることを目的とした化合物に該当する。しかし、本願の難燃性に影響を与えない範囲で、難燃性以外の耐熱安定性など性質を高めるため等の目的のハロゲン化合物、アンチモン化合物、リン化合物はこの表現からは外れる。
【００３９】
難燃性を高めることを目的とした化合物として、まずハロゲン化合物として、例として、塩素系難燃剤として塩素化パラフィン、塩素化ポリエチレン、ドデカクロロペンタシクロオクタデカ−７，１５−ジエン（オキシデンタルケミカル社製デクロランプラス２５＜登録商標＞）、無水ヘット酸等、臭素系難燃剤としてヘキサブロモシクロドデカン（ＨＢＣＤ）、デカブロモジフェニルオキサイド（ＤＢＤＰＯ）、オクタブロモジフェニルオキサイド、テトラブロモビスフェノールＡ（ＴＢＢＡ）、ビス（トリブロモフェノキシ）エタン、ビス（ペンタブロモフェノキシ）エタン（ＢＰＢＰＥ）、テトラブロモビスフェノールＡエポキシ樹脂（ＴＢＢＡエポキシ）、テトラブロモビスフェノールＡカーボネート（ＴＢＢＡ−ＰＣ）、エチレン（ビステトラブロモフタル）イミド（ＥＢＴＢＰＩ）、エチレンビスペンタブロモジフェニル、トリス（トリブロモフェノキシ）トリアジン（ＴＴＢＰＴＡ）、ビス（ジブロモプロピル）テトラブロモビスフェノールＡ（ＤＢＰ−ＴＢＢＡ）、ビス（ジブロモプロピル）テトラブロモビスフェノールＳ（ＤＢＰ−ＴＢＢＳ）、臭素化ポリフェニレンエーテル（ポリジプロモフェニレンエーテル等を含む）（ＢｒＰＰＥ）、臭素化ポリスチレン（ポリジブロモスチレン等を含む）（ＢｒＰＳ）、臭素化架橋芳香族重合体、臭素化エポキシ樹脂、臭素化フェノキシ樹脂、臭素化スチレン−無水マレイン酸重合体、テトラブロモビスフェノールＳ（ＴＢＢＳ）、トリス（トリブロモネオペンチル）フォスフェート（ＴＴＢＮＰＰ）、ポリブロモトリメチルフェニルインダン（ＰＢＰＩ）、トリス（ジブロモプロピル）−イソシアヌレート（ＴＤＢＰＩＣ）等、反応型難燃剤としてテトラブロモビスフェノールＡ（ＴＢＢＡ）（臭素系難燃剤にも記載）、テトラブロモフタレート、テトラブロモフタレートジオール、テトラブロモフタレートエステル、テトラブロモフタレートジソジウム、テトラクロロ無水フタル酸、テトラブロモ無水フタル酸、トリブロモフェノール（ＴＢＰ）、ジブロモフェノール、ジブロモメタクレゾール、ジブロモネオペンチルグリコール、ポリ（ペンタブロモベンジルポリアクリレート）（ＰＰＢＢＡ）、クロレント酸、無水クロレント酸、臭素化フェノール、ジブロモクレジルグリシジルエーテル、ビニルブロマイド、ジブロモスチレン、トリブロモスチレン等が挙げられる。
【００４０】
次に、アンチモン化合物としては、例として、三酸化アンチモン、四酸化アンチモン、五酸化アンチモン等の酸化アンチモン類やアンチモン酸ソーダ等が挙げられる。
三番目に、リン化合物としては、例として、赤リン系難燃剤として赤リン、リン酸エステル系難燃剤として、トリフェニルフォスフェート（ＴＰＰ）、トリクレジルフォスフェート（ＴＣＰ）、トリキシレニルフォスフェート（ＴＸＰ）、トリエチルフォスフェート、トリブチルフォスフェート（ＴＢＰ）、トリオクチルフォスフェート（ＴＯＰ）、トリス（ブトキシエチル）フォスフェート、クレジルジフェニルフォスフェート（ＣＤＰ）、キシレニルジフェニルフォスフェート、ビス（ノニルフェニル）フェニルフォスフェート（ＤＮＰ）、クレジルビス（ジ２，６−キシレニル）フォスフェート、２−エチルヘキシルジフェニルフォスフェート、レゾルシノールビス（ジフェニル）フォスフェート（ＲＤＰ）、ビスフェノールＡビス（ジフェニル）フォスフェート（ＢＰＡ−ＤＰ）、ビスフェノールＡビス（ジクレジル）フォスフェート（ＢＰＡ−ＤＣ）、レゾルシノールビス（ジ２，６−キシレニル）フォスフェート、ジエチルーＮ，Ｎ−ビス（２−ヒドロキシエチル）アミノメチルホスフォネート、ジメチルメチルフォスフォネート等、ハロゲン化リン酸エステル系難燃剤として、トリス（クロロエチル）フォスフェート、トリス（クロロプロピル）フォスフェート、トリス（ジクロロプロピル）フォスフェート、トリス（トリブロモネオペンチル）フォスフェート等、リン酸アミド系難燃剤として、トリフェニルフォスフォルアミド等、リン酸塩系難燃剤として、ポリリン酸アンモニウム（ＡＰＰ）、リン酸メラミン、リン酸グアニジン、ピロリン酸メラミン、ポリリン酸メラミン等、フォスフィン系難燃剤としては、トリフェニルフォスフィン、トリフェニルフォスフィンオキサイド、テトラキス（ヒドロキシメチル）フォスフォニウムクロライド、テトラキス（ヒドロキシメチル）サルフェイト等、フォスファゼン系難燃剤としては、プロポキシフォスファゼン、フェノキシフォスファゼン、アミノフォスファゼン、ポリ（フロロアルキルフォスファゼン）、ジプロポキシフォスファゼン等のリン化合物が挙げられる。
【００４１】
一方、本願の難燃性に影響を与えない範囲で、耐熱安定性向上や変色防止等のための化合物として一般的に用いられているもの、例えば、ハロゲンを含むものとしては、ヨウ化カリウム、臭化カルウム、塩化銅、臭化銅、ヨウ化銅等のハロゲン化合物、リン系の熱安定剤、リン酸銅、テトラキス（２，４−ジ−ｔ−ブチルフェニル）−４，４’−ビフェニレンフォスフォナイト、ビス（２，６−ジ−ｔ−ブチル−４−メチルフェニル）ペンタエリスリトール−ジ−ホスファイト、２，２−メチレンビス（４，６−ジ−ｔ−ブチルフェニル）オクチルホスファイト、トリフェニルホスファイト、トリス（２，４−ジ−ｔ−ブチルフェニル）フォスファイト、ジフェニルイソデシルフォスファイト、フェニルジイソデシルフォスファイト、４，４−ブチリデン−ビス（３−メチル−６−ｔ−ブチルフェニル−ジ−トリデシル）フォスファイト、サイクリックネオペンタンテトライルビス（オクタデシルホスファイト）、サイクリックネオペンタンテトライルビス（２，６−ジ−ｔ−ブチル−４−メチルフェニル）ホスファイト、トリス（ノニル・フェニル）ホスファイト、ジイソデシルペンタエリスリトールジフォスファイト、９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキサイド、１０−（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）−９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキサイド、１０−デシロキシ−９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン、リン酸トリメチル、次亜リン酸ナトリウム等のリン化合物等が挙げられる。
【００４２】
本発明の組成物に、難燃性を更に一層向上させるために、芳香族を含む熱可塑性樹脂を加えることができる。例えば、ポリスチレン樹脂、シンジオタクチックポリスチレン樹脂、ポリフェニレンエーテル樹脂、ポリフェニレンスルフィド樹脂、ポリアミドイミド樹脂、ポリアリルエーテルケトン樹脂、ポリエーテルエーテルケトン樹脂、ポリエーテルイミド樹脂、ポリエーテルケトン樹脂、ポリエーテルケトンケトン樹脂、ポリエーテルサルホン樹脂、ポリフタルアミド樹脂、ポリサルホン樹脂等が挙げられる。
【００４３】
更に、ポリフェニレンエーテル樹脂、ポリフェニレンスルフィド樹脂が燃焼時に生成する不燃層（又は炭化層）が多く、難燃性に優れ、そしてまた、外観に優れるので好ましい。そして特に、ポリフェニレンエーテル樹脂が最も好ましい。本発明の強化された難燃性ポリアミド樹脂組成物の製造方法は、特に限定はなく、ポリアミド樹脂、ホウ酸金属化合物、強化材（任意成分）、シリコーン化合物（任意成分）、ポリフェニレンエーテル樹脂（任意成分）を常用の単軸または２軸の押出機やニーダー等の混練機を用いて、２００〜３５０℃の温度で溶融混練する方法等であればよい。
【００４４】
本発明の難燃性ポリアミド樹脂組成物には、本発明の目的を損なわない範囲で、他の成分、例えば難燃剤、フィブリル化剤、顔料、染料等の着色剤や、熱可塑性樹脂の一般的な熱安定剤である銅系熱安定剤（例えばヨウ化銅、酢酸銅等とヨウ化カリウム、臭化カルウムとの併用）、ヒンダードフェノール系酸化劣化防止剤に代表される有機系耐熱剤、耐候性改良剤、核剤、可塑剤、帯電防止剤等の添加剤等を添加することができる。また、不燃層（又は炭化層）の発泡を促進し、断熱効果を増大し、高難燃性を発現するために、燃焼時に水蒸気、窒素、二酸化炭素等のガス成分を発生させる成分、例えば水酸化アルミニウム、水酸化マグネシウム等の水酸化金属化合物、メラミン、メレム、メロン、メラミンシアヌレート等の窒素化合物、炭酸カルシウム等の炭酸金属化合物を添加させることもできる。
本発明の組成物は、射出成形、押出成形、ブロー成形など公知の方法によってコネクター、コイルボビン、ブレーカー、電磁開閉器、ホルダー、プラグ、スイッチ等の電気、電子、自動車用途の各種成形品に成形される。
【００４５】
【発明の実施の形態】
以下の実施例により本発明をさらに詳しく説明するが、本発明はこれに限定されるものではない。
なお、実施例及び比較例に用いた原材料及び測定方法を以下に示す。
［原材料］
（ａ）芳香族成分を含むポリアミド樹脂
（ａ−１）：ポリアミドＭＸＤ６ 三菱エンジニアリングプラスチックス（株）製 商品名 レニー６００２
（ａ−２）：製造例１のポリアミド６６／６Ｉ （共重合成分のモル比 ６６：６Ｉ＝８５：１５）
【００４６】
（ｂ）ホウ酸金属化合物
（ｂ−１）：ホウ酸亜鉛（水和物）２ＺｎＯ・３Ｂ２Ｏ３・３．５Ｈ２Ｏ Ｕ．Ｓ． Ｂｏｒａｘ社製 商品名 Ｆｉｒｅｂｒａｋｅ ＺＢ
（ｂ−２）：ホウ酸亜鉛（無水物）２ＺｎＯ・３Ｂ２Ｏ３ Ｕ．Ｓ． Ｂｏｒａｘ社製 商品名 Ｆｉｒｅｂｒａｋｅ ５００
（ｃ）強化材
（ｃ−１）：ガラス繊維 日本電気硝子（株）製 商品名 ＥＣＴ０３Ｔ２７５Ｈ／ＰＬ（平均繊維径１０μｍ）
【００４７】
（ｄ）シリコーン化合物
（ｄ−１）：ビニル基含有シリコーン（２０℃において液状） 信越化学工業（株）製 商品名 Ｘ−４０−９２４３
このシリコーン化合物を重クロロホルムに溶解させ、２９Ｓｉ−ＮＭＲ及び１Ｈ−ＮＭＲ測定し、シリコーン化合物の構造解析を行い、ビニル基の有無を確認した。また、この測定で得られた積分比よりこのシリコーン化合物は末端基（トリメチルシリル基やアルコキシ基等）を除くケイ素上の全有機置換基の内、ビニル基率はモル比で１０％であった。
（ｄ−２）：製造例３のビニル基含有シリコーン化合物（２０℃において液状）
ｄ−１と同様に測定を行い、ビニル基率はモル比で８％であった。
（ｄ−３）：ジメチルシリコーンオイル（２０℃において液状） 信越化学工業（株）製 商品名 ＫＦ９６−１００
（ｄ−４）：シリコーンレジン（無溶剤メチル系ワニス）（２０℃において固体状） ＧＥ東芝シリコーン（株）製 商品名 ＹＲ３３７０
（ｅ）ポリフェニレンエーテル樹脂
（ｅ−１）：製造例２の無水マレイン酸変性ポリフェニレンエーテル
【００４８】
【製造例１】
アジピン酸とヘキサメチレンジアミンの等モル塩２．００ｋｇとイソフタル酸とヘキサメチレンジアミンの等モル塩０．３５ｋｇ、アジピン酸０．１ｋｇ、および純水２．５ｋｇを５Ｌのオートクレーブの中に仕込み良く撹拌した。充分窒素置換した後、撹拌しながら温度を室温から２２０℃まで約１時間かけて昇温した。この際、オートクレーブ内の水蒸気による自然圧で内圧はゲージ圧で１．７６ＭＰａになるが、１．７６ＭＰａ以上の圧にならないよう水を反応系外に除去しながら加熱を続けた。更に２時間後内温が２６０℃に到達した時点で加熱を止め、オートクレーブのバルブを閉止し、約８時間かけて室温まで冷却した。冷却後オートクレーブを開け、約２ｋｇのポリマーを取りだし粉砕した。得られた粉砕ポリマーを、１０Ｌのエバポレーターに入れ窒素気流下、２００℃で１０時間固相重合した。固相重合によって得られたポリアミドは、融点２４５℃、硫酸相対粘度２．３８であった。
【００４９】
【製造例２】
２，６−ジメチルフェノールを酸化重合して得られた還元粘度（０．５ｇ／ｄｌクロロホルム溶液、３０℃測定）０．５２のポリ（２，６−ジメチル−１，４−フェニレンエーテル）（以下ポリフェニレンエーテルと略記）を１００重量部と、相溶化剤として無水マレイン酸を１．０重量部とを上流側に１ヶ所（以下ｔｏｐ−Ｆと略記）と、押出機中央部並びにダイに近い下流側の２ヶ所に供給口（以下押出機中央部をｓｉｄｅ−１、ダイに近い下流側をｓｉｄｅ−２とそれぞれ略記）を有する二軸押出機（Ｗｅｒｎｅｒ＆Ｐｆｌｅｉｄｅｒｅｒ社製：ＺＳＫ−４０）のｓｉｄｅ−１とｓｉｄｅ−２は塞いだ状態にして、シリンダー設定温度３２０℃、スクリュー回転３００ｒｐｍ、吐出量２０．１５ｋｇ／ｈｒの条件下で、ポリフェニレンエーテルと無水マレイン酸をドライブレンドしたものをｔｏｐ−Ｆより供給し、溶融混練してストランド状に取り出し、ストランドバス（水槽）で冷却後、カッターで造粒し無水マレイン酸変性ポリフェニレンエーテルのペレットを得た。
【００５０】
【製造例３】
トリクロロフェニルシラン４２．３ｇ、ジクロロメチルビニルシラン４２．３ｇ、ジクロロメチルフェニルシラン３８．２ｇ、ジクロロジメチルシラン１６７．８ｇの混合液を水４５０．８ｇ、トルエン１４３ｇの混合液中にゆっくり滴下し加水分解した後、８０℃で１時間熟成した。そして、過剰量のクロロトリメチルシランを反応液に滴下し、さらに８０℃で１時間熟成した。分液ロートで水相を捨て、有機（トルエン）相を中性になるまで１０％硫酸ナトリウム水溶液で数回抽出した。
その後、蒸留装置に有機相を移して、ある程度溶媒のトルエンを除去し、最後にエバポレーターを用いて溶媒を完全に減圧留去を行い、ビニル基含有シリコーン約１８０ｇを得た。
この一連の操作を必要な量に達するまで繰り返した。
【００５１】
［測定方法］
（１）ＵＬ−９４ＶＢ
ＵＬ９４（米国Ｕｎｄｅｒ Ｗｒｉｔｅｒｓ Ｌａｂｏｒａｔｏｒｉｅｓ Ｉｎｃで定められた規格）の方法を用いて１サンプル当たりそれぞれ１０本づつ測定を行った。なお試験片は長さが１２７ｍｍ、幅が１２．７ｍｍ、厚みが１／８インチとし、射出成形機（日精工業（株）製：ＰＳ４０Ｅ）を用いて成形して得た。また厚みが１／８インチの試験片でＶ−０又はＶ−１であったサンプルについてはより厳しい条件となる厚さが１／１６インチについても射出成形機（日精工業（株）製：ＰＳ４０Ｅ）を用いて成形して得た。
ドリップには、各試料の試験中に綿着火の原因となるドリップをしたサンプル数を示した。平均時間（ｓ）には、各試料１０秒間を２回即ち計２０回接炎後の消炎時間の平均燃焼時間を示した。最大時間（ｓ）には、同じく計２０回接炎後の消炎時間の最大燃焼時間を示した。しかし、試験片が燃え尽きてしまった場合や消炎時間が長すぎて、明らかにＶ−０、Ｖ−１、Ｖ−２のいずれのも該当しない場合のサンプルについては平均時間、最大時間には値を記載しない。評価にはＵＬ９４垂直燃焼試験によって分類される難燃性のクラスを示した。分類方法の概要は以下の通り。詳細はＵＬ９４規格に準じる。
【００５２】
Ｖ−０
綿着火無し 平均燃焼時間５秒以下 最大燃焼時間１０秒以下
Ｖ−１
綿着火無し 平均燃焼時間２５秒以下 最大燃焼時間３０秒以下
Ｖ−２
綿着火有り 平均燃焼時間２５秒以下 最大燃焼時間３０秒以下
Ｖ−２ｏｕｔ
上記３項目に該当しない
【００５３】
（２）成形性
射出成形機（日精工業（株）製：ＰＳ４０Ｅ）を用いて、それぞれのサンプルの短冊試験片（３．２×１２．７×１２７ｍｍ）を成形した際に、射出成形機のペレットホッパーから成形機スクリューへの樹脂の供給効率を評価した。全く問題なくペレットがスクリュー部へ供給されるものを合格（◎）、合格よりも多少供給に問題（具体的には、ペレットがスクリューに食い込みにくい等）があり、可塑化時間が長くなるが、射出サイクルにはほとんど問題ないものをやや合格（○）、供給に問題があり、全サンプル中半分以下のサンプルで射出サイクルが遅れてしまうものをやや不合格（△）、供給にかなり問題があり、全サンプル中半分以上のサンプルで射出サイクルが遅れてしまうものを不合格（×）とした。
【００５４】
（３）ＭＤ
上記の成形性評価と同時にそれぞれのサンプル成形でのモールドデポジット（ＭＤ）の付着も目視で判断した。評価は各サンプル３０ショット成形後の金型への付着物を判断し、ＭＤが全く無いものを合格（◎）、ＭＤが少量あるがほとんど問題なしのものをやや合格（○）、ＭＤが多く少し問題になるものをやや不合格（△）、ＭＤがかなり多く問題になるものを不合格（×）とした。
【００５５】
（４）燃焼挙動（コーンカロリーメーター試験）
サンプルの燃焼の様子を調べるために、燃焼中の発熱速度の経時変化が観測できるコーンカロリーメーターを用いて、燃焼挙動を調べた。
装置は、（株）東洋精機製作所製コーンカロリーメーターＩＩＩをもちいた。
燃焼させるサンプルは、５．０ｍｍ×３２．５ｍｍ×１１４ｍｍの厚肉試験片を射出成形機（東芝機械製：ＩＳ１５０）で成形したものを切削し、５．０ｍｍ×３２．５ｍｍ×１００ｍｍの形状のサンプルを得た。このサンプルをアルミ箔を用いて測定時に上面となる３２．５ｍｍ×１００ｍｍの一面を残して、他の５面（側面及び下面）を覆った。
測定条件としては、コーンヒーターの輻射量を５０ｋＷ／ｍ２、排気流量を０．０２４ｍ３／ｓｅｃ、オリフィスタイプをラージ、サンプルの上面とコーンヒーターとの距離を２５ｍｍ、測定までサンプルを輻射熱遮断するためにシャッターとイグナイタ（試料から発生した可燃性ガスに着火させるための１０ｋＶの高電圧スパーク）を用いる設定で行った。シャッターを開け、コーンヒーターの輻射熱による加熱が始まると同時に試験開始とし、試料が加熱で分解し、その分解ガスにイグナイタで着火し、サンプルが燃焼し、燃えなくなるまで続けた。
【００５６】
評価は、単位面積あたりの発熱速度＝Ｈ．Ｒ．Ｒ．（ｋＷ／ｍ２）を燃焼の激しさの指標として行った。
最大Ｈ．Ｒ．Ｒ．は、サンプルに着火してから消えるまでの間のＨ．Ｒ．Ｒ．の最大値を示した。
平均Ｈ．Ｒ．Ｒ．は、サンプルに着火してから消えるまでの間のＨ．Ｒ．Ｒ．の平均値を示した。
不燃層の厚みは、サンプル燃焼中に形成される不燃層（又は炭化層）の厚みを測ることを目的に、試験後の燃え残ったサンプルの高さの最大値をノギスを用いて測定した。ちなみに試験前の高さは５ｍｍである。
そして、この不燃層の厚みが、厚いものほど未燃焼の樹脂（燃料）と炎（熱源）の距離が大きく、即ち断熱効果が大きくなり、燃焼の継続を抑制できるので、高い難燃性を発現できる。
不燃層の硬さは、サンプル燃焼中に形成される不燃層（又は炭化層）の強さを測ることを目的に、試験後の燃え残ったサンプルを指で突いた際の抵抗より判断した。硬いものは◎、やや硬いものは○、脆いものは×とした。
【００５７】
（５）グローワイヤー発火性試験（ＧＷＩ）
ＩＥＣ６０６９５−２−１規格の方法で、日立化成工業（株）製 グローワイヤー燃焼性試験機 ＨＡＴ−２１４の装置を用いて、燃焼性（ＧＷＦＩ）、着火性（ＧＷＩＴ）の試験項目について試験を行った。なお試験片は６５ｍｍ×９０ｍｍ×１．０ｍｍ（厚み１．０ｍｍ）とし、射出成形機（東芝機械製：ＩＳ１５０）を用いて成形して得た。
【００５８】
（６）電気特性（ＣＴＩ）
ＩＥＣ Ｐｕｂｌｉｃａｔｉｏｎ １１２規格の方法で、日立化成工業（株）製耐トラッキング試験機 ＨＡＴ−５００−３型の装置を用いて、耐トラッキング試験を行った。なお試験片は１３０ｍｍ×１３０ｍｍ×３．０ｍｍ（厚み３．０ｍｍ）とし、射出成形機（東芝機械製：ＩＳ１５０）を用いて成形して得た。
測定の概要は試験片を装置にセットし、試験片表面に二本の電極によって１００〜６００Ｖの電圧を印加し、その電極間に０．１％塩化アンモニウム水溶液を３０秒毎に滴下し、試験片がトラッキングを起こすことなく、５０滴で破壊しない最大電圧（ＣＴＩ）を測定し、その値を示した。この値が高いほど耐トラッキング性に優れる。
【００５９】
【実施例１】
芳香族成分を含むポリアミド樹脂ａ−１が１００．０重量部（７２．０重量％）、ホウ酸金属化合物ｂ−１が１１．１重量部（８．０重量％）、強化材ｃ−１が２７．８（２０．０重量％）からなるポリアミド組成物を得た。
原材料（即ち、押出機への投入速度の設定）は芳香族成分を含むポリアミド樹脂ａ−１が７２．０重量％、ホウ酸金属化合物ｂ−１が８．０重量％、強化材ｃ−１が２０．０重量％となるように用意し、上流側に１ヶ所（以下ｔｏｐ−Ｆと略記）と、押出機中央部並びにダイに近い下流側の２ヶ所に供給口（以下押出機中央部をｓｉｄｅ−１、ダイに近い下流側をｓｉｄｅ−２とそれぞれ略記）を有する二軸押出機（東芝機械製：ＴＥＭ３５）を用いてシリンダー設定温度２４０℃、スクリュー回転２００ｒｐｍ、吐出量３０ｋｇ／ｈｒの条件下で、芳香族成分を含むポリアミド樹脂ａ−１はｔｏｐ−Ｆから、ホウ酸金属化合物ｂ−１はｓｉｄｅ−１から、強化材ｃ−１はｓｉｄｅ−２から合計の吐出量が３０ｋｇ／ｈｒになるようにそれぞれ調節して供給し、溶融混練してストランド状に取り出し、ストランドバス（水槽）で冷却後、カッターで造粒しポリアミド樹脂組成物ペレットを得た。
得られたペレットを前記した測定方法にてＵＬ−９４ＶＢ、成形性、ＭＤ、燃焼挙動（コーンカロリーメーター試験）、グローワイヤー発火性試験（ＧＷＩ）、電気特性（ＣＴＩ）を調べた。その結果を表１と表２に示す。
【００６０】
【実施例２】
芳香族成分を含むポリアミド樹脂ａ−１が１００．０重量部（６４．０重量％）、ホウ酸金属化合物ｂ−１が２５．０重量部（１６．０重量％）、強化材ｃ−１が３１．３重量部（２０．０重量％）からなるポリアミド組成物を得た。
用意する原材料（即ち、押出機への投入速度の設定）を芳香族成分を含むポリアミド樹脂ａ−１が６４．０重量％、ホウ酸金属化合物ｂ−１が１６．０重量％とした以外は実施例１と同様にしてペレットを得て、ＵＬ−９４ＶＢ、成形性、ＭＤ、燃焼挙動（コーンカロリーメーター試験）、グローワイヤー発火性試験（ＧＷＩ）、電気特性（ＣＴＩ）を調べた。その結果を表１と表２に示す。
【００６１】
【製造例４】
芳香族成分を含むポリアミド樹脂ａ−１が１００．０重量部（９０．０重量％）、シリコーン化合物ｄ−１が１１．１重量部（１０．０重量％）からなる１０重量％シリコーン含有ポリアミド樹脂組成物を得た。
上流側に１ヶ所（以下ｔｏｐ−Ｆと略記）と、押出機中央部に１ヶ所に供給口（以下押出機中央部をｓｉｄｅ−１と略記）を有する二軸押出機（Ｗｅｒｎｅｒ＆Ｐｆｌｅｉｄｅｒｅｒ社製：ＺＳＫ−２５）のシリンダーの中央付近（トップフィード用ホッパーから１０ブロック中６ブロック目）に液添装置を取り付け、ｓｉｄｅ−１を塞いだものを用いて、シリンダー設定温度２４０℃、スクリュー回転３００ｒｐｍ、吐出量１０ｋｇ／ｈｒの条件下で、芳香族成分を含むポリアミド樹脂ａ−１を添加量９．０ｋｇ／ｈｒでｔｏｐ−Ｆより供給し、シリコーン化合物ｄ−１は液添装置を用いて添加量１．０ｋｇ／ｈｒでシリンダー系中に直接添加し、両者を混練してストランド状に取り出し、ストランドバス（水槽）で冷却後、カッターで造粒し１０重量％シリコーン含有ポリアミド樹脂組成物ペレットを得た。
【００６２】
【実施例３】
芳香族成分を含むポリアミド樹脂ａ−１が１００．０重量部（７０．０重量％）、ホウ酸金属化合物ｂ−１が１１．４重量部（８．０重量％）、強化材ｃ−１が２８．６重量部（２０．０重量％）、シリコーン化合物ｄ−１が２．９重量部（２．０重量％）からなるポリアミド組成物を得た。
原材料（即ち、押出機への投入速度の設定）は芳香族成分を含むポリアミド樹脂ａ−１が５２．０重量％、製造例４の１０重量％シリコーン含有ポリアミド樹脂が２０．０重量％、ホウ酸金属化合物ｂ−１が８．０重量％、強化材ｃ−１が２０．０重量％となるように用意し、上流側に１ヶ所と、押出機中央部並びにダイに近い下流側の２ヶ所に供給口を有する二軸押出機（東芝機械製：ＴＥＭ３５）を用いてシリンダー設定温度２４０℃、スクリュー回転２００ｒｐｍ、吐出量３０ｋｇ／ｈｒの条件下で、芳香族成分を含むポリアミド樹脂ａ−１と製造例４の１０重量％シリコーン含有ポリアミド樹脂はｔｏｐ−Ｆから、ホウ酸金属化合物ｂ−１はｓｉｄｅ−１から、強化材ｃ−１はｓｉｄｅ−２から合計の吐出量が３０ｋｇ／ｈｒになるようにそれぞれ調節して供給し、溶融混練してストランド状に取り出し、ストランドバス（水槽）で冷却後、カッターで造粒しポリアミド樹脂組成物ペレットを得た。
得られたペレットを前記した測定方法にてＵＬ−９４ＶＢ、成形性、ＭＤ、燃焼挙動（コーンカロリーメーター試験）、グローワイヤー発火性試験（ＧＷＩ）、電気特性（ＣＴＩ）を調べた。その結果を表１と表２に示す。
【００６３】
【実施例４】
芳香族成分を含むポリアミド樹脂ａ−１が１００．０重量部（６８．０重量％）、ホウ酸金属化合物ｂ−１が１１．８重量部（８．０重量％）、強化材ｃ−１が２９．４重量部（２０．０重量％）、シリコーン化合物ｄ−１が５．９重量部（４．０重量％）からなるポリアミド組成物を得た。
用意する原材料（即ち、押出機への投入速度の設定）を芳香族成分を含むポリアミド樹脂ａ−１が３２．０重量％、製造例４の１０重量％シリコーン含有ポリアミド樹脂が４０．０重量％とした以外は実施例３と同様にしてペレットを得て、ＵＬ−９４ＶＢ、成形性、ＭＤ、燃焼挙動（コーンカロリーメーター試験）、グローワイヤー発火性試験（ＧＷＩ）、電気特性（ＣＴＩ）を調べた。その結果を表１と表２に示す。
【００６４】
【実施例５】
芳香族成分を含むポリアミド樹脂ａ−１が１００．０重量部（６４．８重量％）、ホウ酸金属化合物ｂ−１が１２．３重量部（８．０重量％）、強化材ｃ−１が３０．９重量部（２０．０重量％）、シリコーン化合物ｄ−１が１１．１重量部（７．２重量％）からなるポリアミド組成物を得た。
用意する原材料（即ち、押出機への投入速度の設定）を芳香族成分を含むポリアミド樹脂ａ−１が０重量％、製造例４の１０重量％シリコーン含有ポリアミド樹脂が７２．０重量％とした以外は実施例３と同様にしてペレットを得て、ＵＬ−９４ＶＢ、成形性、ＭＤ、燃焼挙動（コーンカロリーメーター試験）、グローワイヤー発火性試験（ＧＷＩ）、電気特性（ＣＴＩ）を調べた。その結果を表１と表２に示す。
【００６５】
【実施例６】
芳香族成分を含むポリアミド樹脂ａ−１が１００．０重量部（６４．８重量％）、ホウ酸金属化合物ｂ−２が１２．３重量部（８．０重量％）、強化材ｃ−１が３０．９重量部（２０．０重量％）、シリコーン化合物ｄ−１が１１．１重量部（７．２重量％）からなるポリアミド組成物を得た。
用意する原材料（即ち、押出機への投入速度の設定）を芳香族成分を含むポリアミド樹脂ａ−１が０重量％、製造例４の１０重量％シリコーン含有ポリアミド樹脂が７２．０重量％、ホウ酸金属化合物ｂ−２が８．０重量％とした以外は実施例３と同様にしてペレットを得て、ＵＬ−９４ＶＢ、成形性、ＭＤ、燃焼挙動（コーンカロリーメーター試験）、グローワイヤー発火性試験（ＧＷＩ）、電気特性（ＣＴＩ）を調べた。その結果を表１と表２に示す。
【００６６】
【製造例５】
芳香族成分を含むポリアミド樹脂ａ−１が１００．０重量部（９０．０重量％）、シリコーン化合物ｄ−２が１１．１重量部（１０．０重量％）からなる１０重量％シリコーン含有ポリアミド樹脂組成物を得た。
シリコーン化合物をｄ−２にした以外は、製造例４と同様にして、１０重量％シリコーン含有ポリアミド樹脂組成物ペレットを得た。
【００６７】
【実施例７】
芳香族成分を含むポリアミド樹脂ａ−１が１００．０重量部（６４．８重量％）、ホウ酸金属化合物ｂ−１が１２．３重量部（８．０重量％）、強化材ｃ−１が３０．９重量部（２０．０重量％）、シリコーン化合物ｄ−２が１１．１重量部（７．２重量％）からなるポリアミド組成物を得た。
用意する原材料（即ち、押出機への投入速度の設定）を芳香族成分を含むポリアミド樹脂ａ−１が０重量％、製造例５の１０重量％シリコーン含有ポリアミド樹脂が７２．０重量％とした以外は実施例３と同様にしてペレットを得て、ＵＬ−９４ＶＢ、成形性、ＭＤ、燃焼挙動（コーンカロリーメーター試験）、グローワイヤー発火性試験（ＧＷＩ）、電気特性（ＣＴＩ）を調べた。その結果を表１と表２に示す。
【００６８】
【比較例１】
芳香族成分を含むポリアミド樹脂ａ−１が１００．０重量部（８０．０重量％）、強化材ｃ−１が２５．０重量部（２０．０重量％）からなるポリアミド組成物を得た。
用意する原材料（即ち、押出機への投入速度の設定）を芳香族成分を含むポリアミド樹脂ａ−１が８０．０重量％、ホウ酸金属化合物ｂ−１が０重量％とした以外は実施例１と同様にしてペレットを得て、ＵＬ−９４ＶＢ、成形性、ＭＤ、燃焼挙動（コーンカロリーメーター試験）、グローワイヤー発火性試験（ＧＷＩ）、電気特性（ＣＴＩ）を調べた。その結果を表１と表２に示す。
【００６９】
【比較例２】
芳香族成分を含むポリアミド樹脂ａ−１が１００．０重量部（９０．０重量％）、シリコーン化合物ｄ−１が１１．１重量部（１０．０重量％）からなるポリアミド組成物を得た。
製造例４の１０重量％シリコーン含有ポリアミド樹脂ペレットをそのまま利用し、ＵＬ−９４ＶＢ、成形性、ＭＤ、燃焼挙動（コーンカロリーメーター試験）を調べた。その結果を表１と表２に示す。
【００７０】
【比較例３】
芳香族成分を含むポリアミド樹脂ａ−１が１００．０重量部（７２．０重量％）、強化材ｃ−１が２７．８重量部（２０．０重量％）、シリコーン化合物ｄ−１が１１．１重量部（８．０重量％）からなるポリアミド組成物を得た。
用意する原材料（即ち、押出機への投入速度の設定）を芳香族成分を含むポリアミド樹脂ａ−１が０重量％、製造例４の１０重量％シリコーン含有ポリアミド樹脂が８０．０重量％、ホウ酸金属化合物ｂ−１が０重量％とした以外は実施例３と同様にしてペレットを得て、ＵＬ−９４ＶＢ、成形性、ＭＤ、燃焼挙動（コーンカロリーメーター試験）、グローワイヤー発火性試験（ＧＷＩ）、電気特性（ＣＴＩ）を調べた。その結果を表１と表２に示す。
【００７１】
【製造例６】
芳香族成分を含むポリアミド樹脂ａ−１が１００．０重量部（９０．０重量％）、シリコーン化合物ｄ−３が１１．１重量部（１０．０重量％）からなる１０重量％シリコーン含有ポリアミド樹脂組成物を得た。
シリコーン化合物をｄ−３にした以外は、製造例４と同様にして、１０重量％シリコーン含有ポリアミド樹脂組成物ペレットを得た。
【００７２】
【実施例８】
芳香族成分を含むポリアミド樹脂ａ−１が１００．０重量部（７０．０重量％）、ホウ酸金属化合物ｂ−１が１１．４重量部（８．０重量％）、強化材ｃ−１が２８．６（２０．０重量％）、シリコーン化合物ｄ−３が２．９重量部（２．０重量％）からなるポリアミド組成物を得た。
原材料（即ち、押出機への投入速度の設定）は芳香族成分を含むポリアミド樹脂ａ−１が５２．０重量％、製造例６の１０重量％シリコーン含有ポリアミド樹脂が２０．０重量％、ホウ酸金属化合物ｂ−１が８．０重量％、強化材ｃ−１が２０．０重量％となるように用意し、上流側に１ヶ所と、押出機中央部並びにダイに近い下流側の２ヶ所に供給口を有する二軸押出機（東芝機械製：ＴＥＭ３５）を用いてシリンダー設定温度２４０℃、スクリュー回転２００ｒｐｍ、吐出量３０ｋｇ／ｈｒの条件下で、芳香族成分を含むポリアミド樹脂ａ−１と製造例６の１０重量％シリコーン含有ポリアミド樹脂はｔｏｐ−Ｆから、ホウ酸金属化合物ｂ−１はｓｉｄｅ−１から、強化材ｃ−１はｓｉｄｅ−２から合計の吐出量が３０ｋｇ／ｈｒになるようにそれぞれ調節して供給し、溶融混練してストランド状に取り出し、ストランドバス（水槽）で冷却後、カッターで造粒しポリアミド樹脂組成物ペレットを得た。
得られたペレットを前記した測定方法にてＵＬ−９４ＶＢ、成形性、ＭＤを調べた。その結果を表３に示す。
【００７３】
【実施例９】
芳香族成分を含むポリアミド樹脂ａ−１が１００．０重量部（６８．０重量％）、ホウ酸金属化合物ｂ−１が１１．８重量部（８．０重量％）、強化材ｃ−１が２９．４重量部（２０．０重量％）、シリコーン化合物ｄ−３が５．９重量部（４．０重量％）からなるポリアミド組成物を得た。
用意する原材料（即ち、押出機への投入速度の設定）を芳香族成分を含むポリアミド樹脂ａ−１が３２．０重量％、製造例６の１０重量％シリコーン含有ポリアミド樹脂が４０．０重量％とした以外は実施例８と同様にしてペレットを得て、ＵＬ−９４ＶＢ、成形性、ＭＤを調べた。その結果を表３に示す。
【００７４】
【実施例１０】
芳香族成分を含むポリアミド樹脂ａ−１が１００．０重量部（６４．８重量％）、ホウ酸金属化合物ｂ−１が１２．３重量部（８．０重量％）、強化材ｃ−１が３０．９重量部（２０．０重量％）、シリコーン化合物ｄ−３が１１．１重量部（７．２重量％）からなるポリアミド組成物を得た。
用意する原材料（即ち、押出機への投入速度の設定）を芳香族成分を含むポリアミド樹脂ａ−１が０重量％、製造例６の１０重量％シリコーン含有ポリアミド樹脂が７２．０重量％とした以外は実施例８と同様にしてペレットを得て、ＵＬ−９４ＶＢ、成形性、ＭＤを調べた。その結果を表３に示す。
【００７５】
【実施例１１】
芳香族成分を含むポリアミド樹脂ａ−１が１００．０重量部（６４．８重量％）、ホウ酸金属化合物ｂ−１が１２．３重量部（８．０重量％）、強化材ｃ−１が３０．９重量部（２０．０重量％）、シリコーン化合物ｄ−４が１１．１重量部（７．２重量％）からなるポリアミド組成物を得た。
原材料（即ち、押出機への投入速度の設定）は芳香族成分を含むポリアミド樹脂ａ−１が６４．８重量％、ホウ酸金属化合物ｂ−１が８．０重量％、強化材ｃ−１が２０．０重量％、細かく粉砕して粉末にしたシリコーン化合物ｄ−４が７．２重量％となるように用意し、上流側に１ヶ所と、押出機中央部並びにダイに近い下流側の２ヶ所に供給口を有する二軸押出機（東芝機械製：ＴＥＭ３５）を用いてシリンダー設定温度２４０℃、スクリュー回転２００ｒｐｍ、吐出量３０ｋｇ／ｈｒの条件下で、芳香族成分を含むポリアミド樹脂ａ−１とシリコーン化合物ｄ−４はｔｏｐ−Ｆから、ホウ酸金属化合物ｂ−１はｓｉｄｅ−１から、強化材ｃ−１はｓｉｄｅ−２から合計の吐出量が３０ｋｇ／ｈｒになるようにそれぞれ調節して供給し、溶融混練してストランド状に取り出し、ストランドバス（水槽）で冷却後、カッターで造粒しポリアミド樹脂組成物ペレットを得た。
得られたペレットを前記した測定方法にてＵＬ−９４ＶＢ、成形性、ＭＤを調べた。その結果を表３に示す。
【００７６】
【比較例４】
芳香族成分を含むポリアミド樹脂ａ−１が１００．０重量部（７２．０重量％）、強化材ｃ−１が２７．８重量部（２０．０重量％）、シリコーン化合物ｄ−３が１１．１重量部（８．０重量％）からなるポリアミド組成物を得た。
用意する原材料（即ち、押出機への投入速度の設定）を芳香族成分を含むポリアミド樹脂ａ−１が０重量％、製造例６の１０重量％シリコーン含有ポリアミド樹脂が８０．０重量％、ホウ酸金属化合物ｂ−１が０重量％とした以外は実施例８と同様にしてペレットを得て、ＵＬ−９４ＶＢ、成形性、ＭＤ、燃焼挙動（コーンカロリーメーター試験）を調べた。その結果を表３に示す。
【００７７】
【実施例１２】
芳香族成分を含むポリアミド樹脂ａ−２が熱可塑性樹脂中の１００．０重量部（５０．４重量％）、ホウ酸金属化合物ｂ−１が１５．９重量部（８．０重量％）、強化材ｃ−１が３９．７重量部（２０．０重量％）、ポリフェニレンエーテル樹脂ｅ−１が４２．９重量部（２１．６重量％）からなるポリアミド組成物を得た。
原材料（即ち、押出機への投入速度の設定）は芳香族成分を含むポリアミド樹脂ａ−２が５０．４重量％、ポリフェニレンエーテル樹脂ｅ−１が２１．６重量％、ホウ酸金属化合物ｂ−１が８．０重量％、強化材ｃ−１が２０．０重量％となるように用意し、上流側に１ヶ所と、押出機中央部並びにダイに近い下流側の２ヶ所に供給口を有する二軸押出機（東芝機械製：ＴＥＭ３５）を用いてシリンダー設定温度２８０℃、スクリュー回転２００ｒｐｍ、吐出量３０ｋｇ／ｈｒの条件下で、芳香族成分を含むポリアミド樹脂ａ−１とポリフェニレンエーテル樹脂ｅ−１はｔｏｐ−Ｆから、ホウ酸金属化合物ｂ−１はｓｉｄｅ−１から、強化材ｃ−１はｓｉｄｅ−２から合計の吐出量が３０ｋｇ／ｈｒになるようにそれぞれ調節して供給し、溶融混練してストランド状に取り出し、ストランドバス（水槽）で冷却後、カッターで造粒しポリアミド樹脂組成物ペレットを得た。
得られたペレットを前記した測定方法にてＵＬ−９４ＶＢ、成形性、ＭＤを調べた。その結果を表３に示す。
【００７８】
【比較例５】
芳香族成分を含むポリアミド樹脂ａ−２が１００．０重量部（８０．０重量％）、強化材ｃ−１が２５．０重量部（２０．０重量％）からなるポリアミド組成物を得た。
用意する原材料（即ち、押出機への投入速度の設定）を芳香族成分を含むポリアミド樹脂ａ−２が８０．０重量％、ホウ酸金属化合物ｂ−１が０重量％とした以外は実施例１と同様にしてペレットを得て、ＵＬ−９４ＶＢ、成形性、ＭＤを調べた。その結果を表３に示す。
表１〜３の実施例１〜１２と比較例１〜５から分かるように、ハロゲン系難燃剤、アンチモン系難燃助剤、リン系難燃剤を含まないポリアミド樹脂組成物であって、芳香族成分を含むポリアミド樹脂に非ハロゲン、非アンチモン、非リンの難燃剤であるホウ酸金属化合物を添加することによって、ポリアミド樹脂がもつ電気特性を低下させること無く、難燃性を向上させることができ、電気特性、難燃性の両特性のバランスを持たせることができた。
結果は、ホウ酸金属化合物により難燃性は大きく向上し、また電気特性は、ホウ酸金属化合物を添加しても、高い値を維持した非常に難燃性、電気特性の両特性のバランスの取れた材料が得られた。
【００７９】
【表１】
【表２】
【表３】
【発明の効果】
本発明の組成物は、塩素、臭素等のハロゲン系難燃剤、アンチモン系助難燃剤並びリン系難燃剤を含有しない難燃性ポリアミド樹脂材料であり、ポリアミド樹脂が本来有する機械的特性、耐薬品性、良成形性、電気特性を損なうことなく、難燃性、電気特性を向上させ、金型腐食を低減でき、家電部品、電子部品、自動車部品等の用途に好適に用いることが出来る。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a flame-retardant polyamide resin composition. In particular, the present invention relates to a flame-retardant polyamide resin composition which is suitably used for components such as connectors, breakers and magnet switches in the electric and electronic fields, and electrical components in the automobile field. In particular, the present invention is intended to improve the flame retardancy without impairing the mechanical properties and electrical properties inherent in polyamide resins, and to provide halogen-based flame retardants such as chlorine and bromine, antimony-based auxiliary flame retardants and phosphorus-based flame retardants. The present invention relates to a flame-retardant polyamide resin composition containing no such resin.
[0002]
[Prior art]
BACKGROUND ART Conventionally, polyamide resins have been used in a wide range of fields such as automobile parts, machine parts, and electric / electronic parts because of their excellent mechanical properties, moldability, electrical insulation properties, and the like. However, polyamide resins are flammable, and various flame-retarding techniques have been proposed from the viewpoint of safety. And, generally, a method is employed in which a halogen-based flame retardant such as a bromine compound having a high flame-retardant effect and antimony oxide are blended into a polyamide resin.
[0003]
For example, addition of a chlorine-substituted polycyclic compound to a polyamide resin (for example, see Patent Document 1), addition of a brominated flame retardant, for example, decabromodiphenyl ether (for example, see Patent Document 2), and addition of brominated polystyrene. Addition (for example, see Patent Documents 3 and 4), addition of a brominated polyphenylene ether (for example, see Patent Document 5), addition of a brominated crosslinked aromatic polymer (for example, see Patent Document 6), Addition of a brominated styrene-maleic anhydride polymer (for example, see Patent Document 7) is known. In particular, a composition in which these halogen-based flame retardants are blended with a polyamide resin reinforced with glass fiber or the like is used for electric and electronic parts, especially for printed laminates, or connected, due to its high flame retardancy and high rigidity. It has been frequently used for connector applications. However, while the halogen-based flame retardant improves the flame retardancy, there is a problem that corrosive hydrogen halide is generated during heat processing such as injection molding and corrodes a mold and the like. Antimony compounds used in combination with halogen-based flame retardants also have the problem of improving the flame retardancy, but significantly reducing the electrical properties (tracking resistance) required for electric and electronic applications.
[0004]
For this reason, halogen-free phosphorus-based flame retardants have attracted attention and many studies have been made. For example, halogen-free flame-retardant technology using melamine phosphate, melamine pyrophosphate, or melamine polyphosphate for a glass fiber reinforced polyamide resin (for example, see Patent Document 8), adding melamine polyphosphate to an inorganic reinforced polyamide resin, A flame retardant technology using a char forming catalyst and / or a char forming agent in combination (for example, see Patent Document 9) has been proposed, and it is known that a 1/16 inch molded product satisfies the flame retardant standard UL94V-0 standard. ing. However, in these technologies, in order to satisfy the UL94V-0 standard for thin-walled molded products particularly required for connectors for electric and electronic parts, it is necessary to use a large amount of melamine phosphate-based flame retardants. In addition, not only the mechanical properties of the glass fiber reinforced polyamide resin composition, but also the electrical properties, particularly the tracking resistance required for electrical components used in a high voltage environment, are greatly reduced. Further, the mold releasability at the time of molding was inferior and was not always satisfactory as a molding material for electric / electronic parts.
[0005]
Further, as a technique for achieving the flame retardant standard UL94V-0 for thin molded products, a technique in which melamine sulfate, which is an intumescent type flame retardant, is applied to a glass fiber reinforced semi-aromatic polyamide resin (for example, see Patent Document 10). ) Is also disclosed, but also in this technique, it is necessary to mix a large amount of a flame retardant with respect to the amount of the polyamide resin component, and there is a problem similar to the above. Furthermore, as a technology for imparting high tracking resistance while achieving the flame-retardant standard UL94V-0 for thin-walled molded products, in addition to the melamine phosphate composite flame retardant in the inorganic reinforced polyamide resin, an alkaline earth metal salt is blended. (For example, refer to Patent Document 11), but a molded article obtained by this technique has a problem that it is very brittle. Further, the molding processability is not satisfactory, and when the molded product is left for a long time in a high-temperature and high-humidity environment such as 60 ° C. and 95% RH, a polyamide oligomer or a flame retardant precipitates on the surface of the molded product. It was not satisfactory due to problems such as bleed-out phenomenon.
[0006]
On the other hand, flame retardant materials using a zinc borate compound as a flame retardant have been developed. A flame retarding technique using a zinc borate compound instead of an antimony compound comprising a polyamide resin, an inorganic filler, a brominated flame retardant, zinc borate, and a heat stabilizer (for example, see Patent Document 12) is disclosed. I have. However, a halogen compound as a flame retardant is an essential component, and it is difficult to impart flame retardancy without using it. Techniques that do not use a halogen compound include a polymer component containing at least 20% of an aromatic main chain, such as a polyphenylene ether resin, a polycarbonate resin, a polyetherimide resin, a polyether sulfone resin, and a polyphenylene sulfide resin; Flame retardant technology using a compound and a boron compound (see, for example, Patent Document 13), a polycarbonate resin containing a polydiorganosiloxane fluid, a polydiorganosiloxane mixed as a free-flowing powder with a poly (ester carbonate) resin The technology of flame-retardant polycarbonate comprising an effective amount of fibrous polytetrafluoroethylene or an effective amount of anhydrous zinc borate in a flame-retardant polymer blend including a fluid-filler blend, see, for example, US Pat. system The technology of a flame-retardant thermoplastic resin composition comprising zinc borate and / or zinc borate hydrate and alcohol-modified silicone oil with respect to a thermoplastic resin composed of a fat and a polyester resin (for example, see Patent Document 15) ) Are disclosed, but these techniques are mainly performed with a polycarbonate resin or the like, and when applied to a polyamide resin or other resin, they do not exhibit sufficient flame retardancy or deteriorate other physical properties. Sometimes. Further, in these techniques, when a reinforcing agent such as glass fiber is added, dripping occurs at the time of combustion, and sufficient flame retardancy may not be exhibited. Further, polycarbonate may be inferior in physical properties such as moldability, tensile strength, and electrical properties and chemical resistance and may not be used for applications that may come into contact with an organic solvent or the like.
[0007]
[Patent Document 1]
JP-A-48-29846
[Patent Document 2]
JP-A-47-7134
[Patent Document 3]
JP-A-51-47044
[Patent Document 4]
JP-A-4-175371
[Patent Document 5]
JP-A-54-16044
[Patent Document 6]
JP-A-63-317552
[Patent Document 7]
JP-A-3-168246
[Patent Document 8]
Japanese Patent Publication No. 10-505875
[Patent Document 9]
International Publication No. 98/45364 pamphlet
[Patent Document 10]
JP 2000-119512 A
[Patent Document 11]
WO 00/09606 pamphlet
[Patent Document 12]
JP 2002-506905 A
[Patent Document 13]
JP-A-2-180969
[Patent Document 14]
JP-A-5-202280
[Patent Document 15]
JP-A-11-343400
[0008]
[Problems to be solved by the invention]
An object of the present invention is to contain a halogen-based flame retardant such as chlorine and bromine, an antimony-based flame retardant auxiliary and a phosphorus-based flame retardant, and have mechanical properties, chemical resistance, good moldability inherently possessed by a polyamide resin, An object of the present invention is to provide a flame-retardant polyamide resin composition which has greatly improved flame retardancy without impairing electrical characteristics, and suppresses heat generation rate and drip generation during combustion.
[0009]
[Means for Solving the Problems]
The present inventors have conducted intensive studies, and found that a polyamide resin containing an aromatic component, a polyamide resin containing a metal borate compound as an essential component, a halogen compound, and a metal borate compound containing three components. The problem that corrosive hydrogen halide and the like were generated at the time of heat processing such as injection molding, which had become a problem, and that corroded molds and the like could be solved, and the heat generation rate and drip generation during combustion were suppressed. It has been found that a flame-retardant polyamide resin composition can be provided. Further, when a reinforcing material, a silicone compound, and a polyphenylene ether resin are combined as optional components, it is possible to further improve flame retardancy such as a decrease in heat generation rate during combustion in a UL test evaluation or a corn calorimeter test, Furthermore, they have found that further improvements in properties, such as improvement in physical properties and flowability, can be realized, and the present invention has been completed based on this finding.
In addition, the present invention has succeeded in achieving flame retardancy by using only a zinc borate as a flame retardant.
That is, the present invention is a flame-retardant polyamide resin composition comprising (a) a polyamide resin containing an aromatic component and (b) a metal borate compound.
[0010]
The present invention will be specifically described below.
Examples of the polyamide resin (a) containing an aromatic component of the present invention include a polycondensate of a dicarboxylic acid and a diamine, a ring-opening polymer of a cyclic lactam, and a polycondensate of an aminocarboxylic acid. Include poly (meta-xylylene adipamide) (hereinafter abbreviated as polyamide MXD6), poly (hexamethylene terephthalamide) (hereinafter abbreviated as polyamide 6T), poly (hexamethylene isophthalamide) (hereinafter abbreviated as polyamide 6I), Aliphatic-aromatic polyamides such as (nonamethylene terephthalamide) (hereinafter abbreviated as polyamide 9T), poly (tetramethylene isophthalamide) (hereinafter abbreviated as polyamide 4I), and copolymers and mixtures thereof. Further, the above-mentioned aliphatic-aromatic polyamide and poly (caprolactam) (hereinafter referred to as polyamide 6) Poly (hexamethylene adipamide) (hereinafter abbreviated as polyamide 66), poly (tetramethylene adipamide) (hereinafter abbreviated as polyamide 46), poly (hexamethylene sebacamide) (hereinafter abbreviated as polyamide 610) Poly (hexamethylene dodecamide) (hereinafter abbreviated as polyamide 612), poly (undecamethylene adipamide) (hereinafter abbreviated as polyamide 116), poly (undecalactam) (hereinafter abbreviated as polyamide 11), poly (dodecalactam) (Hereinafter abbreviated as polyamide 12), and copolymers and mixtures with aliphatic polyamides.
[0011]
First, as a polyamide containing an aromatic component which is preferable for the present invention, a polyamide polymerized from a polyamide containing an aromatic diacid such as isophthalic acid or terephthalic acid component is particularly preferable because it exhibits high flame retardancy. Examples include polyamide 6T, polyamide 6I, polyamide 9T, polyamide 4I, and copolymers and mixtures thereof. More preferably, 66 / 6I copolymer polyamide, 66 / 6I / 6T terpolymer polyamide, 66 / 6I / 6 terpolymer polyamide, polyamide 9T and polyamide 6I satisfy both high flame retardancy and moldability. Is preferred.
[0012]
Specifically, (1) a copolymer composed of 60 to 95% by weight of a poly (hexamethylene adipamide) unit and 5 to 40% by weight of a poly (hexamethylene isophthalamide) unit; Terpolymer consisting of 50 to 94% by weight of a (pamide) unit, 5 to 40% by weight of a poly (hexamethylene isophthalamide) unit and 1 to 10% by weight of an aliphatic polyamide unit other than poly (hexamethylene adipamide) (3) a mixed polyamide containing 60 to 95% by weight of a poly (hexamethylene adipamide) component and 5 to 40% by weight of a poly (hexamethylene isophthalamide) component; (4) a poly (hexamethylene adipamide) component 50 to 94% by weight, 5 to 40% by weight of a poly (hexamethylene isophthalamide) component and a fat other than poly (hexamethylene adipamide) It includes mixed polyamides containing 1 to 10 wt% family polyamide component, a polyamide containing these aromatic components is more preferred. The aliphatic polyamide units other than poly (hexamethylene adipamide) in (2) and the aliphatic polyamide components other than poly (hexamethylene adipamide) in (4) include poly (caprolactam), Examples include units and components of polyamide 6.
[0013]
Next, as a polyamide containing an aromatic component, a polyamide polymerized from a polyamide containing a xylylenediamine component (e.g., meta-xylylenediamine and para-xylylenediamine), which is a diamine, is used to form an incombustible layer (or carbonized layer). Is particularly preferred because of the high flame retardancy. Specific examples of such a material include polyamide MXD6, which is preferable because when used in combination with a metal borate compound, it forms a nonflammable layer (or a carbonized layer) during combustion and exhibits excellent flame retardancy. .
[0014]
Specific examples of the (b) metal borate compound used in the present invention include a zinc borate compound, a magnesium borate compound, a calcium borate compound, and an aluminum borate compound. The preferred metal borate compound for the present invention is to cut off heat to the resin from a flame as a heat source during combustion (adiabatic ability), thereby suppressing generation of a gas serving as a fuel by decomposition of the resin and improving flame retardancy. Since the formation efficiency of the non-combustible layer (or carbonized layer) required to increase the temperature is high, that is, excellent in flame retardancy, 2 O 3 ・ ZH 2 A zinc borate compound represented by O (x> 0, y> 0, z ≧ 0) is exemplified. Preferably, 2ZnO.3B 2 O 3 ・ 3.5H 2 O, 4ZnO ・ B 2 O 3 ・ H 2 O, 2ZnO ・ 3B 2 O 3 Zinc borate compounds represented by: More preferably, by generating water vapor by dehydration during combustion, foam the non-combustible layer, further increase the heat insulating ability of the non-combustible layer, at the same time vaporization of water 2ZnO.3B that can cool the combustion system by heat 2 O 3 ・ 3.5H 2 O, 4ZnO ・ B 2 O 3 ・ H 2 And a zinc borate hydrate represented by O, and most preferably, 2ZnO · 3B having a high ratio of contained water. 2 O 3 ・ 3.5H 2 O.
[0015]
Further, these metal borate compounds may be treated with a surface treatment agent such as a silane coupling agent or a titanate coupling agent. Further, the average particle size is preferably 30 μm or less, more preferably 15 μm or less, and particularly preferably 7 μm or less.
The reinforcing material (c) used in the present invention is an optional component, and the object of the present invention can be achieved without this component. However, in order to further improve the flame retardancy and mechanical properties, this component is used. Can be added.
[0016]
(C) As the reinforcing material, glass fiber, carbon fiber, potassium titanate fiber, gypsum fiber, brass fiber, stainless steel fiber, steel fiber, ceramic fiber, boron whisker fiber, mica, talc, silica, calcium carbonate, kaolin, calcined Examples thereof include fibrous, granular, plate-like, and needle-like inorganic reinforcing materials such as kaolin, wollastonite, glass beads, glass flakes, and titanium oxide. These reinforcing materials may be used in combination of two or more. In particular, a fibrous reinforcing agent such as glass fiber has a high drip suppression effect at the time of combustion, and also strengthens the non-combustible layer (or carbonized layer) generated at the time of combustion to maintain the shape of the foamed non-combustible layer (or carbonized layer). It is preferably used because high flame retardancy can be realized.
[0017]
The glass fiber can be selected from long fiber type roving, short fiber type chopped strand, milled fiber and the like. It is preferable to use a surface-treated glass fiber. In particular, the use of glass fibers is particularly preferable because it is particularly excellent in physical properties and flame retardancy. Among them, the average fiber diameter of the glass fibers is preferably 5 to 30 μm. Further, a glass fiber surface-treated is more preferable because it imparts excellent physical properties.
[0018]
By blending the reinforcing material, the strength of the non-combustible layer (or carbonized layer) generated at the time of combustion can be further improved, and the non-combustible layer (or carbonized layer) is less likely to be damaged at the time of combustion. It is possible to exert the effect, and a greater flame retardant effect can be obtained. Further, high rigidity can be provided.
The silicone compound (d) used in the present invention is an optional component, and the object of the present invention can be achieved without this component. However, in order to further improve the flame retardancy, fluidity, and mechanical properties, , This component can be added
(D) The structure of the silicone compound is a polymer obtained by polymerizing at least one of the following four siloxane units (M unit, D unit, T unit, and Q unit).
[0019]
1) M unit (monofunctional)
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2) D unit (bifunctional)
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3) T unit (trifunctional)
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4) Q unit (tetrafunctional)
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(Provided that R is the same or different substituent and is selected from an alkyl group, an aryl group, a benzyl group, a vinyl group, an allyl group, an alkoxy group, a hydroxy group, an amino group, a methyl ester group and an ethyl ester group. )
Of these, a branched structure is obtained particularly when T units and / or Q units are contained. The structure of the silicone compound (d) of the present invention is not particularly limited, and may be branched or linear, and may be liquid or solid.
[0024]
Examples of such a device include the following. Examples of the linear organopolysiloxane include dimethylpolysiloxane, methylphenylpolysiloxane, vinylmethylorganopolysiloxane, and vinylphenylmethylpolysiloxane, and examples of the branched organopolysiloxane include methylpolysiloxane resin and methylphenyl. Examples include polysiloxane resin, phenylpolysiloxane resin, vinylmethylorganopolysiloxane resin, vinylphenylmethylpolysiloxane resin, and the like. Further modified organopolysiloxanes (resin) include amino-modified organopolysiloxane (resin), epoxy-modified organopolysiloxane (resin), carboxyl-modified organopolysiloxane (resin), carbinol-modified organopolysiloxane (resin), and methacryl-modified Organopolysiloxane (resin), mercapto-modified organopolysiloxane (resin), polyether-modified organopolysiloxane (resin), methylstyryl-modified organopolysiloxane (resin), higher alkyl-modified organopolysiloxane (resin), higher alkyl fatty acid ester Modified organopolysiloxane (resin), alkylaralkyl modified organopolysiloxane (resin), hydroxyl-modified organopolysiloxane (resin), alcohol Examples thereof include organo-modified organopolysiloxanes (resins), alcohol-modified organopolysiloxanes (resins), fluorine-modified organopolysiloxanes (resins), and silanol-modified organopolysiloxanes (resins). The terminal of the main chain or the side chain of the polysiloxane may be mentioned, and the introduction ratio may be part or all.
[0025]
Although a highly polar amide bond exists in the polyamide molecule, the compatibility between the two is poor because there is no very high polarity functional group in the silicone molecule. Therefore, when a large amount of silicone is contained, the appearance may be deteriorated due to peeling or the like of the molded piece, and in order to avoid this, a part or all of the main chain terminal or side chain of the silicone compound to be used is used. Silicones modified with polar functional groups such as amino groups, epoxy groups, carboxyl groups, carbinol groups, mercapto groups, higher alkyl fatty acid ester groups, alkoxy groups, hydroxyl groups, and the like can be used.
[0026]
By blending silicone, the non-combustible layer (or carbonized layer) generated at the time of combustion swells more and becomes more adiabatic, and a greater flame-retardant effect is obtained. In addition, good fluidity and impact resistance can be imparted.
Of these organic substituents, those containing a vinyl group are preferred. Further, a silicone compound in which a vinyl group is directly bonded to a silicon atom is particularly preferable because of exhibiting high flame retardancy, and among all organic substituents bonded to a silicon atom except for a terminal group (such as a trimethylsilyl group or an alkoxy group). Silicones having a vinyl group ratio of 2% or more in molar ratio are more preferable because they exhibit higher flame retardancy. Although the reason is not clear, silicone having a highly reactive vinyl group at the time of combustion facilitates the formation of a nonflammable layer, and the formed nonflammable layer is strengthened by a reinforcing material. It is considered that the effect, that is, the effect of suppressing dripping during combustion is exhibited.
[0027]
The method of adding the silicone compound is not particularly limited. Once a resin such as a polyamide resin containing a silicone compound and an aromatic component is kneaded with an extruder or the like, a silicone compound-containing resin composition is obtained. The two-stage method of kneading the metal borate compound, the reinforcing material, and the like, or a single-stage method of kneading a resin such as a polyamide resin containing a silicone compound, a metal borate compound, the reinforcing material, and an aromatic component at a time, When the silicone compound is in a liquid state, it can be added to the molten resin in the extruder using a liquid addition device such as a liquid addition pump, or it can be kneaded with an extruder after being blended with the resin pellets using external moisture. Is mentioned. When a liquid addition device is used, the viscosity may be reduced by heating the tank of the silicone compound or the flow path of the silicone compound with a heater or the like. In the case of a solid state, a method of kneading with an extruder or the like after supplying from a supply port (top feeder) at the top of the extruder or a supply port (side feeder) in the middle of the extruder or blending with resin pellets or the like. And the like.
[0028]
The polyphenylene ether resin (e) used in the present invention is an optional component, and the object of the present invention can be achieved without the present component. Ingredients can be added.
(E) Polyphenylene ether resin is a repeating unit structure
[0029]
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(R 1 , R 4 Each independently represents hydrogen, primary or secondary lower alkyl, phenyl, aminoalkyl or hydrocarbonoxy. R 2 , R 3 Each independently represents hydrogen, primary or secondary lower alkyl or phenyl. )
And a homopolymer and / or copolymer having a reduced viscosity (0.5 g / dl, chloroform solution, measured at 30 ° C.) in the range of 0.15 dl / g or more and 1.0 dl / g or less. More preferably, the reduced viscosity is in the range of 0.20 dl / g to 0.70 dl / g, and most preferably in the range of 0.40 dl / g to 0.60 dl / g. In addition, in order to improve fluidity and moldability, a compound having a low reduced viscosity can be used in combination, and a compound having a low reduced viscosity is in a range of 0.03 dl / g or more and 0.40 dl / g or less, preferably , 0.06 dl / g or more and 0.30 dl / g or less.
[0031]
Specific examples include poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), and poly (2-methyl-6-phenyl-1). , 4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether) and the like. Further, 2,6-dimethylphenol and other phenols (for example, 2,3,6-trimethyl) Polyphenylene ether copolymers such as copolymers with phenol and 2-methyl-6-butylphenol). Among them, poly (2,6-dimethyl-1,4-phenylene ether) and a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol are preferable, and poly (2,6-dimethyl-1) is more preferable. , 4-phenylene ether) are preferred.
[0032]
As an example of the method for producing the polyphenylene ether used in the present invention, there is a method described in U.S. Pat. No. 3,308,874, in which a complex of a cuprous salt and an amine is used as a catalyst to oxidatively polymerize 2,6-xylenol. The methods described in U.S. Pat. Nos. 3,306,875, 3,257,357 and 3,257,358, JP-B-52-17880, JP-A-50-51197, and JP-A-63-152628 are also used. It is preferable as a method for producing ether.
[0033]
Furthermore, it is preferable that a part or all of the polyphenylene ether resin is modified with a compatibilizing agent such as maleic anhydride, because the compatibility with the polyamide resin is improved, and the physical properties and appearance are improved. The method in this case is not particularly limited, and the compatibilizer and the polyphenylene ether resin or the like are once reacted in an extruder to obtain a modified polyphenylene ether or the like, and then kneaded with the polyamide or the like. A single-stage method or a single-stage method in which a compatibilizer, a polyphenylene ether resin, a polyamide resin, and the like are kneaded at a time may be used.
[0034]
In a preferred embodiment of the present invention, the components (a) and (b) are essential components, and the object of the present invention can be achieved by these two components. The components (c), (d) and (e) are optional components, and when added, effects such as further imparting flame retardancy, improving mechanical properties, and improving fluidity are added.
In the flame-retardant polyamide resin composition of the present invention, the ratio of the (b) metal borate compound is not particularly defined. However, in order to further improve moldability, mechanical properties, and flame retardancy, it is preferable that the amount is 0.1 to 200 parts by weight based on 100 parts by weight of the polyamide resin (a) containing an aromatic component. If the amount is more than 200 parts by weight, the improvement in molding processability and mechanical properties is slightly insufficient, and if it is less than 0.1 part by weight, the improvement in flame retardancy is slightly insufficient. It is more preferably 1 part by weight to 150 parts by weight, further preferably 2 parts by weight to 120 parts by weight, and most preferably 5 parts by weight to 100 parts by weight.
[0035]
(C) The reinforcing material is an optional component, but the ratio at the time of addition is preferably 5 parts by weight or more and 200 parts by weight or less based on 100 parts by weight of the polyamide resin (a) containing an aromatic component. If the amount is more than 200 parts by weight, the moldability during extrusion or injection molding is significantly reduced, and if the amount is less than 5 parts by weight, the mechanical properties such as tensile strength and rigidity are not so much improved as compared with the case where they are not added. The content is more preferably 10 parts by weight or more and 180 parts by weight or less, and still more preferably 15 parts by weight or more and 150 parts by weight or less.
[0036]
(D) The silicone compound is an optional component, but the proportion when added is preferably from 0.01 to 100 parts by weight based on 100 parts by weight of the polyamide resin (a) containing an aromatic component. If the amount is more than 100 parts by weight, decomposition gas is generated at the time of kneading, or a contaminant is attached to a molding die during molding. As a result, there is not much improvement in flame retardancy, fluidity and impact resistance. More preferably, it is 0.05 to 80 parts by weight, and still more preferably 0.1 to 60 parts by weight.
[0037]
(E) The polyphenylene ether resin is an optional component, but the proportion at the time of addition is preferably 0.1 parts by weight or more and 100 parts by weight or less based on 100 parts by weight of the polyamide resin containing the aromatic component (a). . When the amount is more than 100% by weight, the moldability and mechanical properties of the polyamide resin are reduced, and when the amount is less than 0.1 part by weight, almost no improvement in fluidity is observed. More preferably, it is 1 part by weight or more and 80 parts by weight or less, and still more preferably 3 parts by weight or more and 60 parts by weight or less.
[0038]
The halogen-based flame retardant, the antimony-based flame retardant auxiliary, and the phosphorus-based flame retardant in the present specification correspond to a compound intended to enhance flame retardancy among halogen compounds, antimony compounds, and phosphorus compounds. . However, halogen compounds, antimony compounds, and phosphorus compounds for the purpose of enhancing properties such as heat stability other than flame retardancy, which do not affect the flame retardancy of the present application, fall outside this expression.
[0039]
As a compound intended to enhance the flame retardancy, first, as a halogen compound, for example, as a chlorinated flame retardant, chlorinated paraffin, chlorinated polyethylene, dodecachloropentacyclooctadeca-7,15-diene (oxydental chemical) Hexachlorocyclododecane (HBCD), decabromodiphenyl oxide (DBDPO), octabromodiphenyl oxide, tetrabromobisphenol A (TBBA) , Bis (tribromophenoxy) ethane, bis (pentabromophenoxy) ethane (BPBPE), tetrabromobisphenol A epoxy resin (TBBA epoxy), tetrabromobisphenol A carbonate (TBBA-PC), ethylene Bistetrabromophthal) imide (EBTBPI), ethylenebispentabromodiphenyl, tris (tribromophenoxy) triazine (TTBPTA), bis (dibromopropyl) tetrabromobisphenol A (DBP-TBBA), bis (dibromopropyl) tetrabromobisphenol S (DBP-TBBS), brominated polyphenylene ether (including polydibromophenylene ether, etc.) (BrPPE), brominated polystyrene (including polydibromostyrene, etc.) (BrPS), brominated cross-linked aromatic polymer, brominated epoxy Resin, brominated phenoxy resin, brominated styrene-maleic anhydride polymer, tetrabromobisphenol S (TBBS), tris (tribromoneopentyl) phosphate (TTBNPP), polybromotri Reactive flame retardants such as butylphenylindane (PBPI), tris (dibromopropyl) -isocyanurate (TDPIC), tetrabromobisphenol A (TBBA) (also described as brominated flame retardant), tetrabromophthalate, tetrabromophthalate diol , Tetrabromophthalate ester, tetrabromophthalate disodium, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, tribromophenol (TBP), dibromophenol, dibromomethcresol, dibromoneopentyl glycol, poly (pentabromobenzylpolyacrylate) (PPBBA), chloric acid, chloric anhydride, brominated phenol, dibromocresyl glycidyl ether, vinyl bromide, dibromostyrene, tribromostyrene, etc. Is mentioned.
[0040]
Next, examples of the antimony compound include antimony oxides such as antimony trioxide, antimony tetroxide, and antimony pentoxide, and sodium antimonate.
Third, examples of the phosphorus compound include red phosphorus as a red phosphorus-based flame retardant, and triphenyl phosphate (TPP), tricresyl phosphate (TCP), and trixylenyl phosphate as phosphate-based flame retardants. Fate (TXP), triethyl phosphate, tributyl phosphate (TBP), trioctyl phosphate (TOP), tris (butoxyethyl) phosphate, cresyl diphenyl phosphate (CDP), xylenyl diphenyl phosphate, bis ( Nonylphenyl) phenyl phosphate (DNP), cresylbis (di2,6-xylenyl) phosphate, 2-ethylhexyldiphenylphosphate, resorcinol bis (diphenyl) phosphate (RDP), bisphenol A bis ( Phenyl) phosphate (BPA-DP), bisphenol A bis (dicresyl) phosphate (BPA-DC), resorcinol bis (di2,6-xyenyl) phosphate, diethyl N, N-bis (2-hydroxyethyl) amino Tris (chloroethyl) phosphate, tris (chloropropyl) phosphate, tris (dichloropropyl) phosphate, tris (tribromoneo) as halogenated phosphate ester flame retardants such as methylphosphonate and dimethylmethylphosphonate. As a phosphoric acid amide-based flame retardant such as pentyl) phosphate, etc., as triphenylphosphoramide or the like, and as a phosphate-based flame retardant, ammonium polyphosphate (APP), melamine phosphate, guanidine phosphate, melamine pyrophosphate, Examples of phosphine-based flame retardants such as melamine acid include triphenylphosphine, triphenylphosphine oxide, tetrakis (hydroxymethyl) phosphonium chloride, and tetrakis (hydroxymethyl) sulfate. Phosphorus compounds such as phazen, phenoxyphosphazene, aminophosphazene, poly (fluoroalkylphosphazene), dipropoxyphosphazene and the like.
[0041]
On the other hand, as long as it does not affect the flame retardancy of the present application, compounds that are generally used as a compound for improving heat stability or preventing discoloration, for example, those containing halogen include potassium iodide, Halogen compounds such as calcium bromide, copper chloride, copper bromide, and copper iodide, phosphorus-based heat stabilizers, copper phosphate, tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylene Phosphonite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, Triphenyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, 4,4- Butylidene-bis (3-methyl-6-t-butylphenyl-di-tridecyl) phosphite, cyclic neopentanetetraylbis (octadecylphosphite), cyclic neopentanetetraylbis (2,6-di-t -Butyl-4-methylphenyl) phosphite, tris (nonylphenyl) phosphite, diisodecylpentaerythritol diphosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- ( 3,5-di-t-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9-oxa- 10-phosphaphenanthrene, trimethyl phosphate, hypophosphorous acid Phosphorus compounds such as sodium and the like.
[0042]
In order to further improve the flame retardancy, a thermoplastic resin containing an aromatic compound can be added to the composition of the present invention. For example, polystyrene resin, syndiotactic polystyrene resin, polyphenylene ether resin, polyphenylene sulfide resin, polyamideimide resin, polyallyletherketone resin, polyetheretherketone resin, polyetherimide resin, polyetherketone resin, polyetherketoneketone resin , Polyethersulfone resin, polyphthalamide resin, polysulfone resin and the like.
[0043]
Further, polyphenylene ether resin and polyphenylene sulfide resin are preferable because they have many non-combustible layers (or carbonized layers) generated at the time of combustion, are excellent in flame retardancy, and are excellent in appearance. In particular, a polyphenylene ether resin is most preferable. The method for producing the reinforced flame-retardant polyamide resin composition of the present invention is not particularly limited, and the polyamide resin, metal borate compound, reinforcing material (optional component), silicone compound (optional component), polyphenylene ether resin (optional) Component) may be melt-kneaded at a temperature of 200 to 350 ° C. using a conventional kneader such as a single-screw or twin-screw extruder or kneader.
[0044]
In the flame-retardant polyamide resin composition of the present invention, other components, such as a flame retardant, a fibrillating agent, a coloring agent such as a pigment and a dye, and a general thermoplastic resin, as long as the object of the present invention is not impaired. Heat stabilizers such as copper heat stabilizers (for example, a combination of copper iodide and copper acetate with potassium iodide and potassium bromide), organic heat stabilizers represented by hindered phenol-based antioxidants, Additives such as a weather resistance improver, a nucleating agent, a plasticizer, and an antistatic agent can be added. Further, in order to promote foaming of the non-combustible layer (or carbonized layer), increase the heat insulating effect, and exhibit high flame retardancy, a component that generates gas components such as water vapor, nitrogen, and carbon dioxide during combustion, such as water Metal hydroxide compounds such as aluminum oxide and magnesium hydroxide, nitrogen compounds such as melamine, melem, melon and melamine cyanurate, and metal carbonate compounds such as calcium carbonate can also be added.
The composition of the present invention is formed into various molded products for electric, electronic, and automotive applications such as connectors, coil bobbins, breakers, electromagnetic switches, holders, plugs, and switches by known methods such as injection molding, extrusion molding, and blow molding. You.
[0045]
BEST MODE FOR CARRYING OUT THE INVENTION
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.
In addition, the raw materials and measuring methods used in the examples and comparative examples are shown below.
[raw materials]
(A) Polyamide resin containing aromatic component
(A-1): Polyamide MXD6 manufactured by Mitsubishi Engineering-Plastics Corporation Renee 6002
(A-2): Polyamide 66 / 6I of Production Example 1 (molar ratio of copolymer components 66: 6I = 85: 15)
[0046]
(B) Metal borate compounds
(B-1): Zinc borate (hydrate) 2ZnO · 3B 2 O 3 ・ 3.5H 2 O U. S. Borax product name Firebreak ZB
(B-2): Zinc borate (anhydride) 2ZnO · 3B 2 O 3 U. S. Borax 500 Firebreak 500
(C) Reinforcement
(C-1): Glass fiber manufactured by NEC Corporation ECT03T275H / PL (average fiber diameter 10 μm)
[0047]
(D) Silicone compound
(D-1): Vinyl group-containing silicone (liquid at 20 ° C.) Product name X-40-9243 manufactured by Shin-Etsu Chemical Co., Ltd.
This silicone compound is dissolved in deuterated chloroform, 29 Si-NMR and 1 By H-NMR measurement, the structure of the silicone compound was analyzed, and the presence or absence of a vinyl group was confirmed. From the integration ratio obtained in this measurement, the silicone compound was found to have a vinyl group ratio of 10% in terms of a molar ratio among all organic substituents on silicon except for terminal groups (such as a trimethylsilyl group and an alkoxy group).
(D-2): Vinyl group-containing silicone compound of Production Example 3 (liquid at 20 ° C.)
The measurement was carried out in the same manner as in d-1, and the vinyl group ratio was 8% in molar ratio.
(D-3): Dimethyl silicone oil (liquid at 20 ° C) KF96-100 manufactured by Shin-Etsu Chemical Co., Ltd.
(D-4): Silicone resin (solvent-free methyl varnish) (solid at 20 ° C.) Product name YR3370 manufactured by GE Toshiba Silicone Co., Ltd.
(E) Polyphenylene ether resin
(E-1): maleic anhydride-modified polyphenylene ether of Production Example 2
[0048]
[Production Example 1]
Charge 2.00 kg of equimolar salt of adipic acid and hexamethylenediamine, 0.35 kg of equimolar salt of isophthalic acid and hexamethylenediamine, 0.1 kg of adipic acid, and 2.5 kg of pure water into a 5 L autoclave and stir well. did. After sufficient nitrogen replacement, the temperature was raised from room temperature to 220 ° C. over about 1 hour with stirring. At this time, the internal pressure becomes 1.76 MPa as a gauge pressure due to the natural pressure of the steam in the autoclave, but heating was continued while removing water outside the reaction system so that the pressure did not become 1.76 MPa or more. After 2 hours, when the internal temperature reached 260 ° C., the heating was stopped, the valve of the autoclave was closed, and the mixture was cooled to room temperature over about 8 hours. After cooling, the autoclave was opened, and about 2 kg of the polymer was taken out and pulverized. The obtained ground polymer was placed in a 10 L evaporator and subjected to solid-state polymerization at 200 ° C. for 10 hours under a nitrogen stream. The polyamide obtained by the solid-state polymerization had a melting point of 245 ° C. and a sulfuric acid relative viscosity of 2.38.
[0049]
[Production Example 2]
Poly (2,6-dimethyl-1,4-phenylene ether) (hereinafter referred to as 0.52) having a reduced viscosity (0.5 g / dl chloroform solution, measured at 30 ° C.) obtained by oxidative polymerization of 2,6-dimethylphenol 100 parts by weight of polyphenylene ether), 1.0 part by weight of maleic anhydride as a compatibilizer at one location on the upstream side (hereinafter abbreviated as top-F), and at the center of the extruder and downstream near the die. Side-1 of a twin-screw extruder (ZSK-40, manufactured by Werner & Pfleiderer) having two supply ports (hereinafter, the central part of the extruder is abbreviated as side-1 and the downstream side near the die is abbreviated as side-2). And side-2 in a closed state, and under the conditions of a cylinder set temperature of 320 ° C., a screw rotation of 300 rpm, and a discharge rate of 20.15 kg / hr, polyphenylene A dry blend of polyester and maleic anhydride is supplied from top-F, melt-kneaded, taken out in strand form, cooled in a strand bath (water tank), granulated with a cutter, and pelletized with maleic anhydride-modified polyphenylene ether. Obtained.
[0050]
[Production Example 3]
A mixture of 42.3 g of trichlorophenylsilane, 42.3 g of dichloromethylvinylsilane, 38.2 g of dichloromethylphenylsilane, and 167.8 g of dichlorodimethylsilane was slowly dropped into a mixture of 450.8 g of water and 143 g of toluene to hydrolyze. Thereafter, aging was performed at 80 ° C. for 1 hour. Then, an excessive amount of chlorotrimethylsilane was dropped into the reaction solution, and the mixture was further aged at 80 ° C. for 1 hour. The aqueous phase was discarded with a separating funnel, and the organic (toluene) phase was extracted several times with a 10% aqueous sodium sulfate solution until the organic phase became neutral.
Thereafter, the organic phase was transferred to a distillation apparatus to remove toluene as a solvent to some extent, and finally, the solvent was completely distilled off under reduced pressure using an evaporator to obtain about 180 g of a vinyl group-containing silicone.
This series of operations was repeated until the required amount was reached.
[0051]
[Measuring method]
(1) UL-94VB
Using a method of UL94 (a standard defined by Under Writers Laboratories Inc in the United States), 10 samples were measured for each sample. The test piece had a length of 127 mm, a width of 12.7 mm and a thickness of 1/8 inch, and was obtained by molding using an injection molding machine (PS40E, manufactured by Nissei Kogyo Co., Ltd.). In addition, for a sample having a thickness of 1/8 inch and a specimen of V-0 or V-1, which is a more severe condition, an injection molding machine (PS40E manufactured by Nissei Kogyo Co., Ltd .; ).
The drip indicates the number of samples that drip causing cotton ignition during the test of each sample. As the average time (s), the average burning time of the quenching time after the sample was contacted twice for 10 seconds for each sample, that is, 20 times in total was shown. For the maximum time (s), the maximum combustion time of the extinction time after a total of 20 flame contacts was shown. However, the average time and the maximum time for the sample when the test piece has burned out or the quenching time is too long and none of V-0, V-1, and V-2 are clearly applicable. Is not described. The evaluation indicated the class of flame retardancy classified by the UL94 vertical burning test. The outline of the classification method is as follows. Details conform to the UL94 standard.
[0052]
V-0
No cotton ignition Average burning time 5 seconds or less Maximum burning time 10 seconds or less
V-1
No cotton ignition Average burning time 25 seconds or less Maximum burning time 30 seconds or less
V-2
With cotton ignition Average burning time 25 seconds or less Maximum burning time 30 seconds or less
V-2out
Not applicable to the above three items
[0053]
(2) Formability
When a strip test piece (3.2 × 12.7 × 127 mm) of each sample was molded using an injection molding machine (manufactured by Nissei Industry Co., Ltd .: PS40E), the molding machine was removed from the pellet hopper of the injection molding machine. The supply efficiency of the resin to the screw was evaluated. If the pellets are supplied to the screw part without any problems pass (◎), there is a problem in the supply slightly more than the pass (specifically, the pellets hardly bite into the screw, etc.), plasticization time is long, There is little problem with the injection cycle, a little pass (○), and there is a problem with the supply. If less than half of all samples delay the injection cycle, a little rejection (△), there is a problem with the supply. In addition, a sample in which the injection cycle was delayed in more than half of all the samples was judged as failed (x).
[0054]
(3) MD
At the same time as the evaluation of the moldability, the adhesion of the mold deposit (MD) in each sample molding was also visually judged. The evaluation was performed by judging the adherence to the mold after molding 30 shots of each sample. A sample having no MD was passed (◎), a sample having a small amount of MD but having little problem was passed (○), and having many MDs. Those that were a little problematic were rejected slightly (ＭＤ), and those that had a fairly large number of MDs were rejected (x).
[0055]
(4) Combustion behavior (corn calorimeter test)
In order to examine the state of combustion of the sample, the combustion behavior was examined using a cone calorimeter capable of observing the change over time in the heat generation rate during combustion.
The apparatus used was a corn calorimeter III manufactured by Toyo Seiki Seisaku-sho, Ltd.
The sample to be burned was formed by cutting a thick test piece of 5.0 mm × 32.5 mm × 114 mm with an injection molding machine (manufactured by Toshiba Machine Co., IS150) and cutting it into a 5.0 mm × 32.5 mm × 100 mm shape. A sample was obtained. This sample was covered with the other five surfaces (side surface and lower surface) using an aluminum foil except for one surface of 32.5 mm × 100 mm which was the upper surface during measurement.
As the measurement conditions, the radiation amount of the cone heater was set to 50 kW / m. 2 , The exhaust flow rate is 0.024m 3 / Sec, large orifice type, 25 mm distance between upper surface of sample and cone heater, shutter and igniter to shut off radiant heat of sample until measurement (10 kV high voltage spark to ignite combustible gas generated from sample) ). The shutter was opened, and the test was started at the same time as the heating by the radiant heat of the cone heater was started. The sample was decomposed by heating, the decomposed gas was ignited by an igniter, and the test was continued until the sample burned and stopped burning.
[0056]
The evaluation was made based on the heat generation rate per unit area = H. R. R. (KW / m 2 ) Was used as an indicator of the intensity of combustion.
Maximum H. R. R. H. between the time the sample ignited and the time it extinguished. R. R. Showed the maximum value.
Mean H. R. R. H. between the time the sample ignited and the time it extinguished. R. R. The average value was shown.
The thickness of the non-combustible layer was measured using a vernier caliper to measure the maximum height of the unburned sample after the test in order to measure the thickness of the non-combustible layer (or carbonized layer) formed during sample combustion. Incidentally, the height before the test is 5 mm.
The thicker the non-combustible layer, the greater the distance between the unburned resin (fuel) and the flame (heat source), that is, the greater the adiabatic effect, and the continuation of combustion can be suppressed. it can.
The hardness of the non-combustible layer was determined from the resistance of the unburned sample after the test when the finger was struck with a finger in order to measure the strength of the non-combustible layer (or carbonized layer) formed during sample combustion.も の: hard, ○: slightly hard, ×: brittle
[0057]
(5) Glow wire ignition test (GWI)
The test items of flammability (GWFI) and ignitability (GWIT) were tested by the method of IEC60695-2-1 standard using the device of HAT-214, a glow-wire flammability tester manufactured by Hitachi Chemical Co., Ltd. Was. The test piece was 65 mm × 90 mm × 1.0 mm (thickness: 1.0 mm), and was obtained by molding using an injection molding machine (TOSHIBA MACHINE: IS150).
[0058]
(6) Electrical characteristics (CTI)
A tracking resistance test was performed by a method of IEC Publication 112 standard using a tracking resistance tester HAT-500-3 manufactured by Hitachi Chemical Co., Ltd. The test piece had a size of 130 mm × 130 mm × 3.0 mm (thickness: 3.0 mm) and was obtained by molding using an injection molding machine (manufactured by Toshiba Machine: IS150).
The outline of the measurement is as follows. A test piece is set on the apparatus, a voltage of 100 to 600 V is applied to the test piece surface by two electrodes, and a 0.1% ammonium chloride aqueous solution is dropped between the electrodes every 30 seconds. The maximum voltage (CTI) at which the piece did not break in 50 drops without tracking and was measured and indicated. The higher this value, the better the tracking resistance.
[0059]
Embodiment 1
100.0 parts by weight (72.0% by weight) of polyamide resin a-1 containing an aromatic component, 11.1 parts by weight (8.0% by weight) of metal borate compound b-1 and reinforcing material c-1 Was 27.8 (20.0% by weight).
The raw materials (that is, the setting of the feeding rate to the extruder) were as follows: polyamide resin a-1 containing an aromatic component: 72.0% by weight; metal borate compound b-1: 8.0% by weight; 20.0% by weight, and a supply port (hereinafter referred to as an extruder central portion) is provided at one location on the upstream side (hereinafter abbreviated as top-F), and at two locations on the central portion of the extruder and on the downstream side near the die. Using a twin-screw extruder (TEM35, manufactured by Toshiba Machine Co., Ltd.) having a cylinder set temperature of 240 ° C., a screw rotation of 200 rpm, and a discharge rate of 30 kg / hr. Under the conditions, the total discharge amount of the polyamide resin a-1 containing an aromatic component from top-F, the metal borate compound b-1 from side-1 and the reinforcing material c-1 from side-2 is 30 kg /. hr Adjusted by supplying, by melt-kneading extraction in a strand shape, cooled in a strand bath (water bath) to give a granulated polyamide resin composition pellets with a cutter.
The obtained pellets were examined for UL-94VB, moldability, MD, combustion behavior (cone calorimeter test), glow wire ignition test (GWI), and electrical characteristics (CTI) by the above-described measurement methods. The results are shown in Tables 1 and 2.
[0060]
Embodiment 2
100.0 parts by weight (64.0% by weight) of polyamide resin a-1 containing an aromatic component, 25.0 parts by weight (16.0% by weight) of metal borate compound b-1, and reinforcing material c-1 Was obtained in 31.3 parts by weight (20.0% by weight).
Except that the raw materials to be prepared (that is, the setting of the feeding rate to the extruder) were 64.0% by weight of the polyamide resin a-1 containing an aromatic component and 16.0% by weight of the metal borate compound b-1. Pellets were obtained in the same manner as in Example 1, and UL-94VB, moldability, MD, combustion behavior (cone calorimeter test), glow wire ignition test (GWI), and electrical characteristics (CTI) were examined. The results are shown in Tables 1 and 2.
[0061]
[Production Example 4]
10% by weight silicone-containing polyamide comprising 100.0 parts by weight (90.0% by weight) of a polyamide resin a-1 containing an aromatic component and 11.1 parts by weight (10.0% by weight) of a silicone compound d-1 A resin composition was obtained.
A twin-screw extruder (manufactured by Werner & Pfleiderer: ZSK) having one location on the upstream side (hereinafter abbreviated as top-F) and one supply port at the central part of the extruder (hereinafter the central part of the extruder is abbreviated as side-1) -25) Attach a liquid adding device near the center of the cylinder (6th block out of 10 blocks from the top feed hopper) and block the side-1 using a cylinder set temperature of 240 ° C, screw rotation of 300 rpm, and discharge. Under the condition of an amount of 10 kg / hr, the polyamide resin a-1 containing an aromatic component was supplied from top-F at an addition amount of 9.0 kg / hr, and the addition amount of the silicone compound d-1 was 1 using a liquid addition device. 0.0kg / hr, added directly to the cylinder system, kneaded the two, taken out into strands, cooled with a strand bath (water tank), and formed with a cutter. To obtain a 10 wt% silicone-containing polyamide resin composition pellets.
[0062]
Embodiment 3
100.0 parts by weight (70.0% by weight) of polyamide resin a-1 containing an aromatic component, 11.4 parts by weight (8.0% by weight) of metal borate compound b-1 and reinforcing material c-1 Was obtained, and a polyamide composition comprising 28.6 parts by weight (20.0% by weight) and 2.9 parts by weight (2.0% by weight) of the silicone compound d-1 was obtained.
The raw materials (that is, the setting of the feeding rate to the extruder) were as follows: 52.0% by weight of the polyamide resin a-1 containing an aromatic component, 20.0% by weight of the 10% by weight silicone-containing polyamide resin of Production Example 4, An acid metal compound b-1 was prepared so as to be 8.0% by weight, and a reinforcing material c-1 was prepared so as to be 20.0% by weight. One was provided on the upstream side, and two were provided on the central part of the extruder and on the downstream side near the die. Polyamide resin a-1 containing an aromatic component under the conditions of a cylinder set temperature of 240 ° C., a screw rotation of 200 rpm, and a discharge rate of 30 kg / hr, using a twin screw extruder (manufactured by Toshiba Machine Co., Ltd .: TEM35) having supply ports at three locations. And 10% by weight silicone-containing polyamide resin of Production Example 4 from top-F, metal borate compound b-1 from side-1 and reinforcing material c-1 from side-2 to a total discharge rate of 30 kg / hr. Become Uni adjusted to supply respectively, and melt-kneaded extraction in a strand shape, cooled in a strand bath (water bath) to give a granulated polyamide resin composition pellets with a cutter.
The obtained pellets were examined for UL-94VB, moldability, MD, combustion behavior (cone calorimeter test), glow wire ignition test (GWI), and electrical characteristics (CTI) by the above-described measurement methods. The results are shown in Tables 1 and 2.
[0063]
Embodiment 4
100.0 parts by weight (68.0% by weight) of polyamide resin a-1 containing an aromatic component, 11.8 parts by weight (8.0% by weight) of metal borate compound b-1, and reinforcing material c-1 Was obtained, and a polyamide composition comprising 29.4 parts by weight (20.0% by weight) and 5.9 parts by weight (4.0% by weight) of the silicone compound d-1 was obtained.
The raw materials to be prepared (that is, the setting of the feeding rate to the extruder) were as follows: the polyamide resin a-1 containing an aromatic component was 32.0% by weight, the 10% by weight of Production Example 4 the silicone-containing polyamide resin was 40.0% by weight. A pellet was obtained in the same manner as in Example 3 except that the test was conducted, and the UL-94VB, moldability, MD, combustion behavior (cone calorimeter test), glow wire ignition test (GWI), and electrical characteristics (CTI) were examined. Was. The results are shown in Tables 1 and 2.
[0064]
Embodiment 5
100.0 parts by weight (64.8% by weight) of a polyamide resin a-1 containing an aromatic component, 12.3 parts by weight (8.0% by weight) of a metal borate compound b-1, and a reinforcing material c-1 Was obtained, and a polyamide composition comprising 30.9 parts by weight (20.0% by weight) and 11.1 parts by weight (7.2% by weight) of the silicone compound d-1 was obtained.
The raw materials to be prepared (that is, the setting of the feeding speed to the extruder) were such that the polyamide resin a-1 containing an aromatic component was 0% by weight, and the 10% by weight silicone-containing polyamide resin of Production Example 4 was 72.0% by weight. Except for the above, pellets were obtained in the same manner as in Example 3, and UL-94VB, moldability, MD, combustion behavior (cone calorimeter test), glow wire ignition test (GWI), and electrical characteristics (CTI) were examined. The results are shown in Tables 1 and 2.
[0065]
Embodiment 6
100.0 parts by weight (64.8% by weight) of polyamide resin a-1 containing an aromatic component, 12.3 parts by weight (8.0% by weight) of metal borate compound b-2, reinforcing material c-1 Was obtained, and a polyamide composition comprising 30.9 parts by weight (20.0% by weight) and 11.1 parts by weight (7.2% by weight) of the silicone compound d-1 was obtained.
The raw materials to be prepared (that is, the setting of the feeding rate to the extruder) were as follows: the polyamide resin a-1 containing an aromatic component was 0% by weight, the 10% by weight silicone-containing polyamide resin of Production Example 4 was 72.0% by weight, A pellet was obtained in the same manner as in Example 3 except that the acid metal compound b-2 was 8.0% by weight, and UL-94VB, moldability, MD, combustion behavior (cone calorimeter test), glow wire ignitability The test (GWI) and the electrical characteristics (CTI) were examined. The results are shown in Tables 1 and 2.
[0066]
[Production Example 5]
10% by weight of a polyamide containing 10% by weight (90.0% by weight) of a polyamide resin a-1 containing an aromatic component and 11.1% by weight (10.0% by weight) of a silicone compound d-2 A resin composition was obtained.
Except that the silicone compound was changed to d-2, a 10% by weight silicone-containing polyamide resin composition pellet was obtained in the same manner as in Production Example 4.
[0067]
Embodiment 7
100.0 parts by weight (64.8% by weight) of a polyamide resin a-1 containing an aromatic component, 12.3 parts by weight (8.0% by weight) of a metal borate compound b-1, and a reinforcing material c-1 Was obtained, and a polyamide composition comprising 30.9 parts by weight (20.0% by weight) and 11.1 parts by weight (7.2% by weight) of the silicone compound d-2 was obtained.
The raw materials to be prepared (that is, the setting of the feeding rate to the extruder) were such that the polyamide resin a-1 containing an aromatic component was 0% by weight, and the 10% by weight silicone-containing polyamide resin of Production Example 5 was 72.0% by weight. Except for the above, pellets were obtained in the same manner as in Example 3, and UL-94VB, moldability, MD, combustion behavior (cone calorimeter test), glow wire ignition test (GWI), and electrical characteristics (CTI) were examined. The results are shown in Tables 1 and 2.
[0068]
[Comparative Example 1]
A polyamide composition comprising 100.0 parts by weight (80.0% by weight) of a polyamide resin a-1 containing an aromatic component and 25.0 parts by weight (20.0% by weight) of a reinforcing material c-1 was obtained. .
Except that the raw materials to be prepared (that is, the setting of the feeding rate to the extruder) were 80.0% by weight of the polyamide resin a-1 containing an aromatic component and 0% by weight of the metal borate compound b-1. Pellets were obtained in the same manner as in Example 1, and UL-94VB, moldability, MD, combustion behavior (cone calorimeter test), glow wire ignition test (GWI), and electrical characteristics (CTI) were examined. The results are shown in Tables 1 and 2.
[0069]
[Comparative Example 2]
A polyamide composition comprising 100.0 parts by weight (90.0% by weight) of a polyamide resin a-1 containing an aromatic component and 11.1 parts by weight (10.0% by weight) of a silicone compound d-1 was obtained. .
Using the 10% by weight silicone-containing polyamide resin pellet of Production Example 4 as it was, UL-94VB, moldability, MD, and combustion behavior (corn calorimeter test) were examined. The results are shown in Tables 1 and 2.
[0070]
[Comparative Example 3]
100.0 parts by weight (72.0% by weight) of polyamide resin a-1 containing an aromatic component, 27.8 parts by weight (20.0% by weight) of reinforcing material c-1 and 11 of silicone compound d-1 A polyamide composition comprising 0.1 parts by weight (8.0% by weight) was obtained.
The raw materials to be prepared (that is, the setting of the feeding rate to the extruder) were as follows: the polyamide resin a-1 containing an aromatic component was 0% by weight, the 10% by weight silicone-containing polyamide resin of Production Example 4 was 80.0% by weight, A pellet was obtained in the same manner as in Example 3 except that the acid metal compound b-1 was 0% by weight, and UL-94VB, moldability, MD, combustion behavior (corn calorimeter test), glow wire ignition test ( GWI) and electrical characteristics (CTI). The results are shown in Tables 1 and 2.
[0071]
[Production Example 6]
10% by weight silicone-containing polyamide comprising 100.0 parts by weight (90.0% by weight) of polyamide resin a-1 containing an aromatic component and 11.1 parts by weight (10.0% by weight) of silicone compound d-3 A resin composition was obtained.
Pellets of 10% by weight silicone-containing polyamide resin composition were obtained in the same manner as in Production Example 4 except that the silicone compound was changed to d-3.
[0072]
Embodiment 8
100.0 parts by weight (70.0% by weight) of polyamide resin a-1 containing an aromatic component, 11.4 parts by weight (8.0% by weight) of metal borate compound b-1 and reinforcing material c-1 Was obtained, and a polyamide composition comprising 28.6 (20.0% by weight) and 2.9 parts by weight (2.0% by weight) of the silicone compound d-3 was obtained.
The raw materials (that is, the setting of the feeding rate to the extruder) were as follows: 52.0% by weight of the polyamide resin a-1 containing an aromatic component, 20.0% by weight of the 10% by weight silicone-containing polyamide resin of Production Example 6, and An acid metal compound b-1 was prepared so as to be 8.0% by weight, and a reinforcing material c-1 was prepared so as to be 20.0% by weight. One was provided on the upstream side, and two were provided on the central part of the extruder and on the downstream side near the die. Polyamide resin a-1 containing an aromatic component under the conditions of a cylinder set temperature of 240 ° C., a screw rotation of 200 rpm, and a discharge rate of 30 kg / hr, using a twin screw extruder (manufactured by Toshiba Machine Co., Ltd .: TEM35) having supply ports at three locations. And the total weight of the 10 wt% silicone-containing polyamide resin of Production Example 6 from top-F, the metal borate compound b-1 from side-1 and the reinforcing material c-1 from side-2 to 30 kg / hr. Become Uni adjusted to supply respectively, and melt-kneaded extraction in a strand shape, cooled in a strand bath (water bath) to give a granulated polyamide resin composition pellets with a cutter.
The obtained pellets were examined for UL-94VB, moldability, and MD by the above-described measurement methods. Table 3 shows the results.
[0073]
Embodiment 9
100.0 parts by weight (68.0% by weight) of polyamide resin a-1 containing an aromatic component, 11.8 parts by weight (8.0% by weight) of metal borate compound b-1, and reinforcing material c-1 Was obtained and a polyamide composition comprising 29.4 parts by weight (20.0% by weight) and 5.9 parts by weight (4.0% by weight) of the silicone compound d-3 was obtained.
The raw materials to be prepared (that is, the setting of the feeding rate to the extruder) were as follows: the polyamide resin a-1 containing an aromatic component was 32.0% by weight, and the 10% by weight silicone-containing polyamide resin in Production Example 6 was 40.0% by weight. Pellets were obtained in the same manner as in Example 8 except that UL-94VB, moldability, and MD were examined. Table 3 shows the results.
[0074]
Embodiment 10
100.0 parts by weight (64.8% by weight) of a polyamide resin a-1 containing an aromatic component, 12.3 parts by weight (8.0% by weight) of a metal borate compound b-1, and a reinforcing material c-1 Was obtained, and a polyamide composition comprising 30.9 parts by weight (20.0% by weight) and 11.1 parts by weight (7.2% by weight) of the silicone compound d-3 was obtained.
Raw materials to be prepared (that is, setting of the feeding rate to the extruder) were such that the polyamide resin a-1 containing an aromatic component was 0% by weight, and the 10% by weight silicone-containing polyamide resin of Production Example 6 was 72.0% by weight. Except for the above, pellets were obtained in the same manner as in Example 8, and UL-94VB, moldability, and MD were examined. Table 3 shows the results.
[0075]
Embodiment 11
100.0 parts by weight (64.8% by weight) of a polyamide resin a-1 containing an aromatic component, 12.3 parts by weight (8.0% by weight) of a metal borate compound b-1, and a reinforcing material c-1 Was obtained, and a polyamide composition comprising 30.9 parts by weight (20.0% by weight) and 11.1 parts by weight (7.2% by weight) of the silicone compound d-4 was obtained.
The raw materials (that is, the setting of the feeding rate to the extruder) were as follows: polyamide resin a-1 containing an aromatic component was 64.8% by weight, metal borate compound b-1 was 8.0% by weight, reinforcing material c-1 Is prepared so that the silicone compound d-4 finely pulverized into powder becomes 20.0% by weight and 7.2% by weight, and one at the upstream side and at the center of the extruder and the downstream side near the die. Using a twin-screw extruder having two supply ports (manufactured by Toshiba Machine Co., Ltd .: TEM35), under the conditions of a cylinder set temperature of 240 ° C., a screw rotation of 200 rpm, and a discharge rate of 30 kg / hr, a polyamide resin containing an aromatic component a- 1 and the silicone compound d-4 are adjusted from top-F, the metal borate compound b-1 is adjusted from side-1 and the reinforcing material c-1 is adjusted from side-2 so that the total discharge rate is 30 kg / hr. And supply Melt kneading a strand shape taken out and cooled in a strand bath (water bath) to give a granulated polyamide resin composition pellets with a cutter.
The obtained pellets were examined for UL-94VB, moldability, and MD by the above-described measurement methods. Table 3 shows the results.
[0076]
[Comparative Example 4]
100.0 parts by weight (72.0% by weight) of the polyamide resin a-1 containing an aromatic component, 27.8 parts by weight (20.0% by weight) of the reinforcing material c-1 and 11 of the silicone compound d-3 A polyamide composition comprising 0.1 parts by weight (8.0% by weight) was obtained.
The raw materials to be prepared (that is, the setting of the feeding speed to the extruder) were as follows: the polyamide resin a-1 containing an aromatic component was 0% by weight, the 10% by weight silicone-containing polyamide resin of Production Example 6 was 80.0% by weight, Pellets were obtained in the same manner as in Example 8 except that the acid metal compound b-1 was 0% by weight, and UL-94VB, moldability, MD, and combustion behavior (corn calorimeter test) were examined. Table 3 shows the results.
[0077]
Embodiment 12
100.0 parts by weight (50.4% by weight) of the polyamide resin a-2 containing an aromatic component in the thermoplastic resin, 15.9 parts by weight (8.0% by weight) of the metal borate compound b-1 in the thermoplastic resin, A polyamide composition comprising 39.7 parts by weight (20.0% by weight) of the reinforcing material c-1 and 42.9 parts by weight (21.6% by weight) of the polyphenylene ether resin e-1 was obtained.
The raw materials (that is, the setting of the feeding rate to the extruder) were as follows: the polyamide resin a-2 containing an aromatic component was 50.4% by weight, the polyphenylene ether resin e-1 was 21.6% by weight, and the metal borate compound b- 1 was 8.0% by weight and the reinforcing material c-1 was 20.0% by weight, and one supply port was provided on the upstream side, and two supply ports were provided on the central portion of the extruder and on the downstream side near the die. Using a twin screw extruder (manufactured by Toshiba Machine Co., Ltd .: TEM35) at a cylinder set temperature of 280 ° C., a screw rotation of 200 rpm, and a discharge rate of 30 kg / hr, a polyamide resin a-1 containing an aromatic component and a polyphenylene ether resin e. -1 is adjusted from top-F, metal borate compound b-1 is adjusted from side-1, and reinforcing material c-1 is adjusted from side-2 so that the total discharge rate is 30 kg / hr. Dissolution Kneading a strand shape taken out and cooled in a strand bath (water bath) to give a granulated polyamide resin composition pellets with a cutter.
The obtained pellets were examined for UL-94VB, moldability, and MD by the above-described measurement methods. Table 3 shows the results.
[0078]
[Comparative Example 5]
A polyamide composition comprising 100.0 parts by weight (80.0% by weight) of the polyamide resin a-2 containing an aromatic component and 25.0 parts by weight (20.0% by weight) of the reinforcing material c-1 was obtained. .
Except that the raw materials to be prepared (that is, the setting of the feeding rate to the extruder) were 80.0% by weight of the polyamide resin a-2 containing an aromatic component and 0% by weight of the metal borate compound b-1. Pellets were obtained in the same manner as in Example 1, and UL-94VB, moldability, and MD were examined. Table 3 shows the results.
As can be seen from Examples 1 to 12 and Comparative Examples 1 to 5 in Tables 1 to 3, a polyamide resin composition containing no halogen-based flame retardant, antimony-based flame retardant auxiliary agent, and phosphorus-based flame retardant, By adding a metal borate compound that is a non-halogen, non-antimony, and non-phosphorous flame retardant to a polyamide resin containing components, the flame retardancy can be improved without lowering the electrical characteristics of the polyamide resin. The balance between the electrical characteristics and the flame retardancy can be achieved.
As a result, the flame retardancy was greatly improved by the metal borate compound, and the electrical characteristics maintained a high value even when the metal borate compound was added. The removed material was obtained.
[0079]
[Table 1]
[Table 2]
[Table 3]
【The invention's effect】
The composition of the present invention is a flame-retardant polyamide resin material that does not contain a halogen-based flame retardant such as chlorine or bromine, an antimony-based auxiliary flame retardant, or a phosphorus-based flame retardant. Flame retardancy and electrical properties can be improved, mold corrosion can be reduced without impairing the properties, good moldability and electrical properties, and it can be suitably used for applications such as home electric parts, electronic parts and automobile parts.
Claims (20)
（１）ポリ（ヘキサメチレンアジパミド）単位６０〜９５重量％及びポリ（ヘキサメチレンイソフタルアミド）単位５〜４０重量％からなる共重合体、
（２）ポリ（ヘキサメチレンアジパミド）単位５０〜９４重量％、ポリ（ヘキサメチレンイソフタルアミド）単位５〜４０重量％及びポリ（ヘキサメチレンアジパミド）以外の脂肪族ポリアミド単位１〜１０重量％からなる３元共重合体、
（３）ポリ（ヘキサメチレンアジパミド）成分６０〜９５重量％及びポリ（ヘキサメチレンイソフタルアミド）成分５〜４０重量％を含有する混合ポリアミド、（４）ポリ（ヘキサメチレンアジパミド）成分５０〜９４重量％、ポリ（ヘキサメチレンイソフタルアミド）成分５〜４０重量％及びポリ（ヘキサメチレンアジパミド）以外の脂肪族ポリアミド成分１〜１０重量％を含有する混合ポリアミドからなる群から選ばれる少なくとも１種の重合体である請求項１〜５のいずれかに記載の難燃性ポリアミド樹脂組成物。(A) a polyamide resin containing an aromatic component,
(1) a copolymer comprising 60 to 95% by weight of a poly (hexamethylene adipamide) unit and 5 to 40% by weight of a poly (hexamethylene isophthalamide) unit;
(2) 50 to 94% by weight of a poly (hexamethylene adipamide) unit, 5 to 40% by weight of a poly (hexamethylene isophthalamide) unit and 1 to 10% by weight of an aliphatic polyamide unit other than poly (hexamethylene adipamide) % Terpolymer,
(3) a mixed polyamide containing 60 to 95% by weight of a poly (hexamethylene adipamide) component and 5 to 40% by weight of a poly (hexamethylene isophthalamide) component; (4) a poly (hexamethylene adipamide) component 50 And at least one selected from the group consisting of mixed polyamides containing 1 to 10% by weight of an aliphatic polyamide component other than poly (hexamethylene adipamide) and 5 to 40% by weight of a poly (hexamethylene isophthalamide) component. The flame-retardant polyamide resin composition according to any one of claims 1 to 5, which is one kind of polymer.
１）Ｍ単位（一官能性）
1) M unit (monofunctional)
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2006002005A (en) * | 2004-06-16 | 2006-01-05 | Asahi Kasei Chemicals Corp | Flame-retardant polyamide resin composition |
| JP2009524712A (en) * | 2006-01-26 | 2009-07-02 | ディーエスエム アイピー アセッツ ビー．ブイ． | Flame-retardant polyamide composition for molding |
| CN104031264A (en) * | 2014-06-25 | 2014-09-10 | 东莞市意普万尼龙科技股份有限公司 | Transparent copolymer nylon and preparation method thereof |
| CN113004688A (en) * | 2021-02-04 | 2021-06-22 | 张家港大塚化学有限公司 | Preparation process of high-performance polyamide composite material for halogen-free flame-retardant LED |
| WO2023116334A1 (en) * | 2021-12-20 | 2023-06-29 | 金发科技股份有限公司 | Polyester composite material, preparation method therefor and application thereof |
| CN117534915A (en) * | 2024-01-09 | 2024-02-09 | 广东电缆厂有限公司 | Halogen-free low-smoke flame-retardant cable sheath, preparation method thereof and cable comprising sheath |
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2002
- 2002-09-26 JP JP2002280911A patent/JP4209164B2/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006002005A (en) * | 2004-06-16 | 2006-01-05 | Asahi Kasei Chemicals Corp | Flame-retardant polyamide resin composition |
| JP2009524712A (en) * | 2006-01-26 | 2009-07-02 | ディーエスエム アイピー アセッツ ビー．ブイ． | Flame-retardant polyamide composition for molding |
| CN104031264A (en) * | 2014-06-25 | 2014-09-10 | 东莞市意普万尼龙科技股份有限公司 | Transparent copolymer nylon and preparation method thereof |
| CN113004688A (en) * | 2021-02-04 | 2021-06-22 | 张家港大塚化学有限公司 | Preparation process of high-performance polyamide composite material for halogen-free flame-retardant LED |
| WO2023116334A1 (en) * | 2021-12-20 | 2023-06-29 | 金发科技股份有限公司 | Polyester composite material, preparation method therefor and application thereof |
| CN117534915A (en) * | 2024-01-09 | 2024-02-09 | 广东电缆厂有限公司 | Halogen-free low-smoke flame-retardant cable sheath, preparation method thereof and cable comprising sheath |
| CN117534915B (en) * | 2024-01-09 | 2024-03-22 | 广东电缆厂有限公司 | Halogen-free low-smoke flame-retardant cable sheath, preparation method thereof and cable comprising sheath |
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