JP2007291250A - Flame-retardant polyamide resin composition - Google Patents
Flame-retardant polyamide resin composition Download PDFInfo
- Publication number
- JP2007291250A JP2007291250A JP2006121289A JP2006121289A JP2007291250A JP 2007291250 A JP2007291250 A JP 2007291250A JP 2006121289 A JP2006121289 A JP 2006121289A JP 2006121289 A JP2006121289 A JP 2006121289A JP 2007291250 A JP2007291250 A JP 2007291250A
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- JP
- Japan
- Prior art keywords
- mass
- polyamide
- resin composition
- flame
- copolymer
- 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 59
- 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 49
- 239000003063 flame retardant Substances 0.000 title claims abstract description 49
- 239000011342 resin composition Substances 0.000 title claims abstract description 45
- 229920002647 polyamide Polymers 0.000 claims abstract description 97
- 239000004952 Polyamide Substances 0.000 claims abstract description 96
- -1 aromatic vinyl compound Chemical class 0.000 claims abstract description 47
- 229920001577 copolymer Polymers 0.000 claims abstract description 47
- 239000004793 Polystyrene Substances 0.000 claims abstract description 43
- 229920002223 polystyrene Polymers 0.000 claims abstract description 43
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 28
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 23
- 229920001400 block copolymer Polymers 0.000 claims description 37
- 239000002994 raw material Substances 0.000 claims description 20
- 150000003839 salts Chemical class 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 239000012779 reinforcing material Substances 0.000 claims description 10
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 9
- 239000000194 fatty acid Substances 0.000 claims description 9
- 229930195729 fatty acid Natural products 0.000 claims description 9
- 150000004665 fatty acids Chemical class 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 5
- 238000004898 kneading Methods 0.000 claims description 5
- 230000002787 reinforcement Effects 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 abstract description 20
- 150000008064 anhydrides Chemical class 0.000 abstract description 11
- 239000008188 pellet Substances 0.000 description 42
- 238000000034 method Methods 0.000 description 30
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 23
- 238000000465 moulding Methods 0.000 description 22
- 239000007789 gas Substances 0.000 description 19
- 230000000694 effects Effects 0.000 description 17
- 239000000203 mixture Substances 0.000 description 16
- 238000000691 measurement method Methods 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 14
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 14
- 230000007423 decrease Effects 0.000 description 13
- 238000010128 melt processing Methods 0.000 description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 230000006866 deterioration Effects 0.000 description 12
- 239000000835 fiber Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 125000003277 amino group Chemical group 0.000 description 10
- 239000003365 glass fiber Substances 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 229920002292 Nylon 6 Polymers 0.000 description 8
- 229920002302 Nylon 6,6 Polymers 0.000 description 8
- 230000006872 improvement Effects 0.000 description 8
- 230000000704 physical effect Effects 0.000 description 8
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 7
- 238000005452 bending Methods 0.000 description 7
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 7
- 229910052794 bromium Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 235000019253 formic acid Nutrition 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 238000005453 pelletization Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000001746 injection moulding Methods 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000004953 Aliphatic polyamide Substances 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 229920003231 aliphatic polyamide Polymers 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229920001897 terpolymer Polymers 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 4
- 239000000292 calcium oxide Substances 0.000 description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000004985 diamines Chemical class 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 4
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- SZHOJFHSIKHZHA-UHFFFAOYSA-N tridecanoic acid Chemical compound CCCCCCCCCCCCC(O)=O SZHOJFHSIKHZHA-UHFFFAOYSA-N 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- WUOBERCRSABHOT-UHFFFAOYSA-N diantimony Chemical compound [Sb]#[Sb] WUOBERCRSABHOT-UHFFFAOYSA-N 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000012760 heat stabilizer Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 229920006123 polyhexamethylene isophthalamide Polymers 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- AHBGXHAWSHTPOM-UHFFFAOYSA-N 1,3,2$l^{4},4$l^{4}-dioxadis***e 2,4-dioxide Chemical compound O=[Sb]O[Sb](=O)=O AHBGXHAWSHTPOM-UHFFFAOYSA-N 0.000 description 2
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 2
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- FQLAJSQGBDYBAL-UHFFFAOYSA-N 3-(azepane-1-carbonyl)benzamide Chemical group NC(=O)C1=CC=CC(C(=O)N2CCCCCC2)=C1 FQLAJSQGBDYBAL-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 239000005639 Lauric acid Substances 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 229920000305 Nylon 6,10 Polymers 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 235000021314 Palmitic acid Nutrition 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920006121 Polyxylylene adipamide Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 238000004458 analytical method Methods 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
- YZXBAPSDXZZRGB-DOFZRALJSA-N arachidonic acid Chemical compound CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O YZXBAPSDXZZRGB-DOFZRALJSA-N 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-MDZDMXLPSA-N elaidic acid Chemical compound CCCCCCCC\C=C\CCCCCCCC(O)=O ZQPPMHVWECSIRJ-MDZDMXLPSA-N 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- VXZBFBRLRNDJCS-UHFFFAOYSA-N heptacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O VXZBFBRLRNDJCS-UHFFFAOYSA-N 0.000 description 2
- KEMQGTRYUADPNZ-UHFFFAOYSA-N heptadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)=O KEMQGTRYUADPNZ-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 235000013980 iron oxide Nutrition 0.000 description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 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
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- ISYWECDDZWTKFF-UHFFFAOYSA-N nonadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCCC(O)=O ISYWECDDZWTKFF-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 description 2
- 229920006128 poly(nonamethylene terephthalamide) Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
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- 239000012046 mixed solvent Substances 0.000 description 1
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- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
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- NKBWPOSQERPBFI-UHFFFAOYSA-N octadecyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCCCC NKBWPOSQERPBFI-UHFFFAOYSA-N 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
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- 150000002900 organolithium compounds Chemical class 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
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- 231100000719 pollutant Toxicity 0.000 description 1
- 229920006115 poly(dodecamethylene terephthalamide) Polymers 0.000 description 1
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- 230000002265 prevention Effects 0.000 description 1
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
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- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
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Abstract
Description
本発明は難燃性ポリアミド樹脂組成物に関する。特に本発明は、高度な難燃性が要求される電気・電子分野のコネクター等の部品、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、とりわけ、色調に優れ、薄肉での靭性やウェルド伸度に優れた成形品を与える難燃性ポリアミド樹脂組成物に関する。 The present invention relates to a flame retardant polyamide resin composition. In particular, the present invention relates to a flame retardant polyamide resin composition suitably used for parts materials such as electrical and electronic connectors and parts for automobiles, which require a high level of flame retardancy. The present invention relates to a flame retardant polyamide resin composition that gives a molded product that is excellent in thin toughness and weld elongation.
従来、ポリアミド樹脂は、機械的強度、耐熱性などに優れることから、自動車部品、機械部品、電気・電子部品などの分野で使用されている。特に、電気・電子部品用途において、ますます難燃性に対する要求レベルが高くなり、本来ポリアミド樹脂の有する自己消火性よりもさらに高度な難燃性が要求され、この為、アンダーライターズ・ラボラトリーのＵＬ９４Ｖ−０規格に適合する難燃レベルの高度化検討が数多くなされ、そしてそれらは一般にハロゲン系難燃剤を添加する方法が取られている。 Conventionally, polyamide resins are excellent in mechanical strength, heat resistance, and the like, and are therefore used in fields such as automobile parts, mechanical parts, and electric / electronic parts. Especially in electrical and electronic parts applications, the level of demand for flame retardancy is increasing, and higher flame retardancy is required than the inherent self-extinguishing properties of polyamide resins. Many studies have been made to improve the flame retardant level conforming to the UL94V-0 standard, and generally, a method of adding a halogen-based flame retardant is taken.
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）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）、臭素化ポリスチレンの添加（例えば、特許文献３、特許文献４）、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）、臭素化架橋芳香族重合体の添加（例えば、特許文献６）、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）等が知られている。特にポリアミド樹脂の場合、臭素化ポリスチレンが好んで使われることが多く、これ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、特にブレーカーのカバー材用途やコネクター材用途等に多用されてきたが、より一層の機械特性の向上が求められている。 For example, addition of a chlorine-substituted polycyclic compound to a polyamide resin (for example, Patent Document 1), addition of a brominated flame retardant such as decabromodiphenyl ether (for example, Patent Document 2), addition of brominated polystyrene (for example, Patent Document 3, Patent Document 4), addition of brominated polyphenylene ether (for example, Patent Document 5), addition of brominated cross-linked aromatic polymer (for example, Patent Document 6), brominated styrene-maleic anhydride polymer Addition (for example, patent document 7) etc. are known. In particular, in the case of polyamide resin, brominated polystyrene is often used, and the composition blended with polyamide resin reinforced with glass fiber or the like is highly flame retardant and has high rigidity. In particular, it has been frequently used for breaker cover materials and connector materials, but there is a need for further improvement in mechanical properties.
その為、機械特性を向上させるものとして、芳香族ビニル化合物とα，β不飽和ジカルボン酸無水物の共重合体を添加する技術（例えば、特許文献８）知られているが、この技術では、難燃性発現の為に必要な難燃剤を減量することが可能な為に、難燃材の耐衝撃性を大きく向上することができる、また、共重合体によってウェルド強度が向上するので、コネクター等でのピン圧入時の割れを大きく低減することもできる。 Therefore, as a technique for improving mechanical properties, a technique for adding a copolymer of an aromatic vinyl compound and an α, β unsaturated dicarboxylic acid anhydride (for example, Patent Document 8) is known. Since the amount of flame retardant required for the development of flame retardancy can be reduced, the impact resistance of the flame retardant can be greatly improved, and the weld strength is improved by the copolymer. The crack at the time of pin press-fitting can be greatly reduced.
しかし、最近では部品の小型化、薄肉化に伴って、高い耐衝撃性やウェルド強度は低下させずに、更に薄肉での靭性やウェルド部の靭性（伸度）も高めた材料が求められている。また、薄肉のコネクター材等でもやはり薄肉での靭性やピン圧入部は射出成形時にウェルドが形成されてしまうので、ウェルド部の靭性が一層優れた材料が求められている。 Recently, however, with the downsizing and thinning of parts, there has been a demand for materials that do not reduce high impact resistance and weld strength, but also have improved toughness and thinness (elongation) at the weld. Yes. Further, even in a thin connector material or the like, since the weld is formed at the thin wall toughness and the pin press-fitting portion at the time of injection molding, a material having a further excellent weld portion toughness is demanded.
また、特に非着色用途では、溶融加工後のペレットや成形品での黄色く着色してしまうので、色調の改善も求められている。ポリアミド組成物での色調を改良する手段として、ポリアミドの末端基を調整する技術（例えば、特許文献９、特許文献１０、特許文献１１、特許文献１２）が知られている。しかし、これらの技術においては、最適の色調改善効果を発揮するポリアミド末端基の調整範囲がそれぞれ異なる、即ち、ポリアミドに添加しているものが異なる系等において、色調改善効果を発揮する最善の末端基の調節範囲は、それぞれ異なることを意味し、本発明においても色調改善に効果のある末端基の調節範囲を予測することはできない。
本発明の目的は、薄肉での難燃性、押出加工性、成型加工性、耐衝撃性、ウェルド強度、機械特性が優れており、更に高いウェルド強度や高い耐衝撃性を低下させることなく、薄肉での靭性やウェルド部の靭性（伸度）を高め、加えて色調も改善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。 The object of the present invention is excellent in flame retardancy, extrudability, molding processability, impact resistance, weld strength, mechanical properties in a thin wall, without further reducing the high weld strength and high impact resistance, An object of the present invention is to provide a flame retardant polyamide resin composition having improved thinness and toughness (elongation) at the weld, and improved color tone.
本発明者らは、上記課題を解決するため鋭意検討を重ねた結果、ポリアミドの全末端基（末端アミノ基＋末端カルボキシル基）に占める末端カルボキシル基の比率を一定範囲内にしたポリアミドを含有してなるポリアミド樹脂が、上記課題を解決できることを見出し、本発明を完成するに至った。すなわち、本発明は、（ａ）末端カルボキシル基比率が５１〜９０％の範囲にあるポリアミド、（ｂ）臭素化ポリスチレン、および（ｃ）芳香族ビニル化合物とα，β不飽和ジカルボン酸無水物の共重合体を含む組成物であって、（ｃ）共重合体は、そのα，β不飽和ジカルボン酸無水物成分が、（ａ）ポリアミド、（ｂ）臭素化ポリスチレンおよび（ｃ）共重合体の総計に対し０．０６〜０．７５質量％となるように配合されている、難燃性ポリアミド樹脂組成物に関する。 As a result of intensive studies to solve the above problems, the inventors of the present invention contain a polyamide in which the ratio of terminal carboxyl groups to all terminal groups (terminal amino groups + terminal carboxyl groups) of the polyamide is within a certain range. As a result, the present inventors have found that the above-mentioned polyamide resin can solve the above-mentioned problems and have completed the present invention. That is, the present invention relates to (a) a polyamide having a terminal carboxyl group ratio in the range of 51 to 90%, (b) brominated polystyrene, and (c) an aromatic vinyl compound and an α, β unsaturated dicarboxylic acid anhydride. A composition comprising a copolymer, wherein (c) the copolymer has an α, β-unsaturated dicarboxylic acid anhydride component comprising: (a) polyamide, (b) brominated polystyrene, and (c) copolymer It is related with the flame-retardant polyamide resin composition mix | blended so that it may become 0.06-0.75 mass% with respect to the sum total of these.
本発明によれば、薄肉での難燃性、押出加工性、成型加工性、耐衝撃性、ウェルド強度、機械特性が優れており、更に高いウェルド強度や高い耐衝撃性を低下させることなく、薄肉での靭性やウェルド部の靭性（伸度）を高め、加えて色調も改善された難燃性ポリアミド樹脂組成物を提供できる。 According to the present invention, the flame retardancy at a thin wall, extrusion processability, molding processability, impact resistance, weld strength, mechanical properties are excellent, and further, without reducing the high weld strength and high impact resistance, It is possible to provide a flame retardant polyamide resin composition having improved thinness and toughness (elongation) of a weld portion, and improved color tone.
以下、本発明の内容を詳細に説明する。 Hereinafter, the contents of the present invention will be described in detail.
本発明の（ａ）ポリアミドとしては、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（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やポリ（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（ドデカメチレンテレフタルアミド）（以下ポリアミド１２Ｔ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）等の芳香族成分を含むポリアミド及び上記の脂肪族ポリアミド同士や芳香族成分を含むポリアミド同士や脂肪族ポリアミド同士と芳香族成分を含むポリアミドの共重合体や混合物を挙げることができる。 Examples of the polyamide (a) of the present invention include polycondensates of dicarboxylic acids and diamines, ring-opening polymerization products of cyclic lactams, and polycondensates of aminocarboxylic acids. Specifically, poly (caprolactam) (Hereinafter abbreviated as polyamide 6), poly (hexamethylene adipamide) (hereinafter abbreviated as polyamide 66), poly (tetramethylene adipamide) (hereinafter abbreviated as polyamide 46), poly (hexamethylene sebacamide) (hereinafter referred to as polyamide 6) Abbreviated as polyamide 610), poly (hexamethylene dodecamide) (hereinafter abbreviated as polyamide 612), poly (undecamethylene adipamide) (hereinafter referred to as polyamide 116), poly (undecalactam) (hereinafter abbreviated as polyamide 11), Aliphatic polyamides such as poly (dodecalactam) (hereinafter abbreviated as polyamide 12) and poly (metaxylylene resins) Pamide) (hereinafter abbreviated as polyamide MXD6), poly (hexamethylene terephthalamide) (hereinafter abbreviated as polyamide 6T), poly (hexamethylene isophthalamide) (hereinafter abbreviated as polyamide 6I), poly (nonamethylene terephthalamide) (hereinafter polyamide) 9T), poly (dodecamethylene terephthalamide) (hereinafter abbreviated as polyamide 12T), poly (tetramethylene isophthalamide) (hereinafter abbreviated as polyamide 4I) and other polyamides containing aromatic components and the above aliphatic polyamides Mention may be made, for example, of polyamides containing an aromatic component, aliphatic polyamides and a polyamide copolymer or mixture containing an aromatic component.
（ａ）ポリアミドは、融点が高すぎると溶融加工時に難燃剤が分解してしまいガス成分が増える為に溶融加工性が低下する。また、融点が低すぎると成形品におけるＨＤＴ等の耐熱性が低下してしまう。従って、本発明に用いられる（ａ）ポリアミドは、融点が２４０℃以上２７０℃以下であることが好ましい。このような（ａ）ポリアミドとしては、例えば、ポリアミド６６、ポリアミドＭＸＤ６、６６／６Ｉ共重合ポリアミド、６６／６共重合ポリアミド、６Ｉ／６Ｔ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、６／６Ｉ／６Ｔ三元共重合ポリアミドが挙げられ、また、これらのポリアミドやポリアミド６等の低融点ポリアミドと混合され、融点が２４０℃以上で且つ２７０℃以下のポリアミド樹脂も含まれる。 (A) If the melting point of the polyamide is too high, the flame retardant decomposes during the melt processing and the gas component increases, so that the melt processability decreases. On the other hand, if the melting point is too low, the heat resistance of the molded product such as HDT is lowered. Accordingly, the polyamide (a) used in the present invention preferably has a melting point of 240 ° C. or higher and 270 ° C. or lower. Examples of the polyamide (a) include polyamide 66, polyamide MXD6, 66 / 6I copolymer polyamide, 66/6 copolymer polyamide, 6I / 6T copolymer polyamide, 66 / 6I / 6T terpolymer polyamide, 66 / 6I / 6 terpolymer polyamide, 6 / 6I / 6T terpolymer polyamide, and low melting point polyamide such as polyamide 6 and polyamide 6 are mixed. A polyamide resin at a temperature of 0 ° C. or lower is also included.
最も好ましくは、成形性、物性に優れるポリアミド６６、６６／６共重合ポリアミド、６６／６Ｉ共重合ポリアミド、６６／６Ｉ／６三元共重合ポリアミドであり、また、これらのポリアミドやポリアミド６等の低融点ポリアミドと混合され、融点が２４０℃以上で且つ２７０℃以下のポリアミド樹脂も含まれる。また、これらの中で６６／６Ｉ共重合ポリアミドについては、成形性の観点から以下のものが好ましい。（１）ポリ（ヘキサメチレンアジパミド）単位６０〜９５質量％及びポリ（ヘキサメチレンイソフタルアミド）単位５〜４０質量％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質量％、ポリ（ヘキサメチレンイソフタルアミド）単位５〜４０質量％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質量％からなる３元共重合体。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としては、ポリ（カプロラクタム）即ちポリアミド６の単位などが挙げられる。 Most preferred are polyamide 66, 66/6 copolymer polyamide, 66 / 6I copolymer polyamide, 66 / 6I / 6 terpolymer polyamide having excellent moldability and physical properties, and these polyamides and polyamide 6 A polyamide resin mixed with a low melting point polyamide and having a melting point of 240 ° C. or higher and 270 ° C. or lower is also included. Among these, the 66 / 6I copolymer polyamide is preferably the following from the viewpoint of moldability. (1) Copolymer comprising 60 to 95% by mass of poly (hexamethylene adipamide) units and 5 to 40% by mass of poly (hexamethylene isophthalamide) units; (2) Poly (hexamethylene adipamide) units 50 A terpolymer comprising ˜94% by mass, 5 to 40% by mass of poly (hexamethylene isophthalamide) units and 1 to 10% by mass of aliphatic polyamide units other than poly (hexamethylene adipamide). Examples of the aliphatic polyamide unit other than poly (hexamethylene adipamide) in the above (2) include poly (caprolactam), that is, a unit of polyamide 6.
本発明の（ａ）ポリアミドの分子量は、成形可能な範囲の物であれば良く、ＡＳＴＭ Ｄ７８９に準じて求まる相対粘度（ＲＶ）にして２０〜７０の範囲にあるポリアミドが、成形流動性が良好でかつ高度な難燃レベルを保持できるので特に好ましい。更に好ましくは３０〜６０の範囲であり、最も好ましくは３５〜５５である。相対粘度（ＲＶ）は、溶媒としては９０％ギ酸、３ｇ（ポリアミド）サンプル／３０ｍｌギ酸の濃度で、２５℃の温度条件下で行う。 The molecular weight of the polyamide (a) of the present invention is only required to be in a moldable range, and a polyamide having a relative viscosity (RV) determined in accordance with ASTM D789 in the range of 20 to 70 has good molding fluidity. And a high flame retardant level can be maintained. More preferably, it is the range of 30-60, Most preferably, it is 35-55. The relative viscosity (RV) is 90% formic acid, 3 g (polyamide) sample / 30 ml formic acid as a solvent at a temperature of 25 ° C.
本発明に用いられる（ａ）ポリアミドの末端カルボキシル基比率とは、ポリアミドの末端カルボキシル基濃度（ＣＯＯＨ）と末端アミノ基濃度（ＮＨ2）との総和に対する末端カルボキシル基濃度（いずれの濃度単位もミリ当量／ｋｇポリマーである）の割合を百分率にて表したものである。 The terminal carboxyl group ratio of (a) polyamide used in the present invention is the terminal carboxyl group concentration relative to the sum of the terminal carboxyl group concentration (COOH) and terminal amino group concentration (NH 2 ) of the polyamide (all concentration units are in millimetres). The ratio of (equivalent / kg polymer) is expressed as a percentage.
本発明の（ａ）ポリアミドは、末端カルボキシル基比率が５１〜９０％の範囲にあるポリアミドである。末端カルボキシル基比率が、５１％未満では、薄肉での靭性やウェルド部の靭性（伸度）の面での大きな向上効果が発現せず、９０％を越えるとポリアミドの重合速度が小さくなるため、ポリアミドの生産性が低下したり、成形品の外観が著しく低下してしまう。好ましくは、５５〜８９％、より好ましくは６０〜８８％、更に好ましくは、６３〜８７％、最も好ましくは、７０〜８５％である。 The polyamide (a) of the present invention is a polyamide having a terminal carboxyl group ratio in the range of 51 to 90%. If the terminal carboxyl group ratio is less than 51%, a great improvement effect in terms of toughness at a thin wall and toughness (elongation) at the weld portion will not be exhibited, and if it exceeds 90%, the polymerization rate of polyamide becomes small. The productivity of the polyamide is lowered, and the appearance of the molded product is significantly lowered. Preferably, it is 55 to 89%, more preferably 60 to 88%, still more preferably 63 to 87%, and most preferably 70 to 85%.
本発明に用いる（ａ）ポリアミドの末端カルボキシル基濃度の制御方法としては、例えば重合時にジアミンとジカルボン酸の等モル塩等のポリアミド原料に、更に、モノカルボン酸、ジカルボン酸、モノアミン、モノアミンを一種又は複数種を末端基調整剤として所定量添加（配合）することにより可能である。具体的な例としては、酢酸、プロピオン酸、酪酸、吉草酸、カプロン酸、カプリル酸、ラウリン酸、ウンデカン酸、トリデシル酸、ミリスチル酸、パルミチン酸、ステアリン酸、ピバリン酸、イソブチル酸、シクロヘキサンカルボン酸、安息香酸、トルイル酸、α−ナフタレンカルボン酸、β−ナフタレンカルボン酸、メチルナフタレンカルボン酸、フェニル酢酸フェニル酢酸等のモノカルボン酸、マロン酸、ジメチルマロン酸、コハク酸、グルタル酸、アジピン酸、２−メチルアジピン酸、トリメチルアジピン酸、ピメリン酸、２，２−ジメチルグルタル酸、３，３−ジエチルコハク酸、アゼライン酸、セバシン酸、スベリン酸、ドデカン二酸、エイコジオン酸、テレフタル酸、イソフタル酸、ナフタレンジカルボン酸、２−クロロテレフタル酸、２−メチルテレフタル酸、５−メチルイソフタル酸、５−ナトリウムスルホイソフタル酸、ヘキサヒドロテレフタル酸、ヘキサヒドロテレフタル酸、ジグリコール酸等のジカルボン酸、メチルアミン、エチルアミン、プロピルアミン、ブチルアミン、ヘキシルアミン、オクチルアミン、デシルアミン、ステアリルアミン、ジメチルアミン、ジエチルアミン、ジプロピルアミン、ジブチルアミン、シクロヘキシルアミン、ジシクロヘキシルアミン、アニリン、トルイジン、ジフェニルアミン、ナフチルアミン等のモノアミン、テトラメチレンジアミン、ヘキサメチレンジアミン、オクタメチレンジアミン、デカメチレンジアミン、ウンデカメチレンジアミン、ドデカメチレンジアミン、２−メチルペンタメチレンジアミン、ノナンメチレンジアミン、２，２，４−トリメチルヘキサメチレンジアミン、２，４，４−トリメチルヘキサメチレンジアミン、５−メチルノナメチレンジアミン、２，４−ジメチルオクタメチレンジアミン、メタキシリレンジアミン、パラキシリレンジアミン、１，３−ビス（アミノメチル）シクロヘキサン、３，８−ビス（アミノメチル）トリシクロデカン、１−アミノ−３−アミノメチル−３，５，５，−トリメチルシクロヘキサン、ビス（４−アミノシクロヘキシル）メタン、ビス（３−メチル−４−アミノシクロヘキシル）メタン、２，２−ビス（４−アミノシクロヘキシル）プロパン、ビス（アミノプロピル）ピペラジン、アミノエチルピペラジン等のジアミンが挙げられる。酢酸、アジピン酸、ヘキシルアミン、ヘキサメチレンジアミン等でポリアミドの末端基を制御するのが、製造効率的に簡便で好ましい。 (A) As a method for controlling the terminal carboxyl group concentration of the polyamide used in the present invention, for example, a monocarboxylic acid, dicarboxylic acid, monoamine, monoamine is further added to a polyamide raw material such as an equimolar salt of diamine and dicarboxylic acid at the time of polymerization. Alternatively, it is possible to add (mix) a predetermined amount as a terminal group modifier. Specific examples include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, undecanoic acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, isobutyric acid, cyclohexanecarboxylic acid , Benzoic acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, monocarboxylic acid such as methylnaphthalenecarboxylic acid, phenylacetic acid phenylacetic acid, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, 3,3-diethylsuccinic acid, azelaic acid, sebacic acid, suberic acid, dodecanedioic acid, eicodioic acid, terephthalic acid, isophthalic acid , Naphthalenedicarboxylic acid, 2-chloroterephthalate Dicarboxylic acids such as phosphoric acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, hexahydroterephthalic acid, diglycolic acid, methylamine, ethylamine, propylamine, butylamine, Hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, cyclohexylamine, dicyclohexylamine, aniline, toluidine, diphenylamine, naphthylamine and other monoamines, tetramethylenediamine, hexamethylenediamine, octamethylene Diamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2-methylpentamethylenediamine, nonanemethyle Diamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, 2,4-dimethyloctamethylenediamine, metaxylylenediamine, paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 3,8-bis (aminomethyl) tricyclodecane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis (4-aminocyclohexyl) Examples include diamines such as methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, and aminoethylpiperazine. Control of the polyamide end groups with acetic acid, adipic acid, hexylamine, hexamethylenediamine or the like is simple and preferable in terms of production efficiency.
本発明における末端カルボキシル基濃度（単位：ミリ当量／ｋｇ）及び末端アミノ基濃度（単位：ミリ当量／ｋｇ）の測定方法としては、末端カルボキシル基濃度に関しては、例えば、所定量の試料を１６０℃のベンジルアルコールに溶解して、１／１０ＮＮａＯＨのエチレングリコール溶液で、指示薬としてフェノールフタレインを使用して滴定し算出する方法が挙げられる。また末端アミノ基濃度に関しては、例えば、所定量の試料を９０％フェノール水溶液に溶解して、２５℃にて１／５０Ｎ塩酸で電位滴定し算出する方法が挙げられる。 As a method for measuring the terminal carboxyl group concentration (unit: milliequivalent / kg) and the terminal amino group concentration (unit: milliequivalent / kg) in the present invention, with respect to the terminal carboxyl group concentration, for example, a predetermined amount of sample is 160 ° C. And a method of performing titration with 1/10 N NaOH ethylene glycol solution using phenolphthalein as an indicator. As for the terminal amino group concentration, for example, a method of calculating a predetermined amount of a sample dissolved in a 90% phenol aqueous solution and titrating with 1 / 50N hydrochloric acid at 25 ° C. can be mentioned.
本発明における（ａ）ポリアミドの水分は、特に限定しないが、（ａ）ポリアミドのペレット水分率を０．１〜０．５質量％に調整して、溶融混練（コンパウンド）することが好ましい。水分率が０．１質量％未満だと押出時の溶融加工による熱による色調の変化（ｂ値が増大し黄色く変色）が大きくなり、白色から離れていく傾向がある。更に難燃剤、強化材などを含む場合には、押出時のストランドに毛羽立ちが目立ち、ストランド冷却バスの水分を持ち込み易くなり、ペレタイズした後に乾燥工程が必要になる。一方、水分率が０．５質量％を超えると、溶融混練（コンパウンド）時のフィードが安定せず、生産が安定しなかったり、加水分解によりポリアミドの分子量を低下させて機械的特性の大きな低下等を招くこともある。ペレット水分率のより好ましい範囲は、０．１２〜０．４質量％である。特に好ましいのは０．１５〜０．３質量％である。 The moisture content of the polyamide (a) in the present invention is not particularly limited, but it is preferable to adjust the pellet moisture content of the polyamide (a) to 0.1 to 0.5% by mass and melt knead (compound). If the moisture content is less than 0.1% by mass, the change in color tone due to heat (b value increases and discolors yellow) due to melt processing during extrusion tends to increase, and the color tends to move away from white. Furthermore, when a flame retardant, a reinforcing material, and the like are included, fuzz is conspicuous in the strand during extrusion, and moisture in the strand cooling bath is easily brought in, and a drying step is required after pelletizing. On the other hand, if the moisture content exceeds 0.5% by mass, the feed during melt-kneading (compounding) is not stable, the production is not stable, or the molecular weight of the polyamide is lowered by hydrolysis, resulting in a significant decrease in mechanical properties. Etc. may be invited. A more preferable range of the moisture content of the pellet is 0.12 to 0.4 mass%. Particularly preferred is 0.15 to 0.3% by mass.
ポリアミド樹脂ペレットの水分率の調整方法は、既知の方法で行うことができる。溶融重合したポリアミド樹脂を水で冷却固化してペレット化する際に通常よりも水浴への浸漬を長くする方法、ペレットを水とブレンドして撹拌する方法、ペレットに霧状の水を噴霧する方法、ペレットに水蒸気を吹きかける方法、ペレットを大気中で自然吸湿させる方法等が挙げられる。特に、ペレットに霧状の水を噴霧させる方法が、任意の水分率に簡便に調整することができ、かつ、水分の偏在も少なくできるので特に好ましい。水分率の調整はペレット化した後のなるべく早い段階で行うことが、酸素の吸着を防ぐ意味からも好ましい。 The adjustment method of the moisture content of a polyamide resin pellet can be performed by a known method. When solidifying a melt-polymerized polyamide resin with water by cooling, pelletizing it into a water bath longer than usual, blending the pellet with water and stirring, spraying atomized water onto the pellet And a method of spraying water vapor on the pellet, a method of naturally absorbing the pellet in the atmosphere, and the like. In particular, a method of spraying mist-like water on pellets is particularly preferable because it can be easily adjusted to an arbitrary moisture content and the uneven distribution of moisture can be reduced. The adjustment of the moisture content is preferably performed at the earliest stage after pelletization from the viewpoint of preventing oxygen adsorption.
（ａ）ポリアミドの水分の測定方法は、既知の方法で行うことができる。例えば、カールフィッシャー水分計を用いたＩＳＯ １５５１２（他にはＪＩＳ Ｋ７２５１に示されるＢ法（水分気化法）等）での測定が挙げられる。 (A) The method for measuring the moisture content of the polyamide can be performed by a known method. For example, measurement by ISO 15512 using a Karl Fischer moisture meter (otherwise, the B method (moisture vaporization method) shown in JIS K7251) can be mentioned.
本発明の（ｂ）臭素化ポリスチレンとしては、特に制限しないが、例えば、スチレン単量体を重合してポリスチレンを製造した後、ポリスチレンのベンゼン環を臭素化したり、臭素化スチレン単量体（ブロモポリスチレン、ジブロモスチレン、トリブロモスチレン等）を重合する方法により製造することができる。 Although it does not restrict | limit especially as (b) brominated polystyrene of this invention, For example, after polymerizing a styrene monomer and manufacturing a polystyrene, bromination of the benzene ring of polystyrene or brominated styrene monomer (bromo) Polystyrene, dibromostyrene, tribromostyrene, etc.).
（ｂ）臭素化ポリスチレン中の臭素含有量は５５〜７５質量％が好ましい。臭素含有量が５５質量％未満になると、難燃化に必要な臭素量を満足させるための臭素化ポリスチレンの配合量が増加し、一般物性、ウェルド部物性、耐熱性の低下につながりうる。また、臭素含有量が７５質量％を越えると臭素化ポリスチレンの熱安定性が低下する為に、押出や成形等の溶融加工時に熱分解を起こし易くなり、ガス発生等の原因となったり、熱による変色を受け易くなる。 (B) The bromine content in brominated polystyrene is preferably 55 to 75% by mass. When the bromine content is less than 55% by mass, the blended amount of brominated polystyrene for satisfying the bromine amount necessary for flame retardancy increases, which may lead to a decrease in general physical properties, weld part physical properties, and heat resistance. In addition, if the bromine content exceeds 75% by mass, the thermal stability of brominated polystyrene is lowered, so that thermal decomposition is likely to occur during melt processing such as extrusion and molding, which may cause gas generation, It becomes easy to receive discoloration by.
（ｂ）臭素化ポリスチレンの分子量は特に制限しないが、高い方が熱安定性の面で好ましい。さらに分子量が、数平均分子量（Ｍｎ）が５０００〜２５０００の範囲にあるものが、押出性に優れるので好ましい。数平均分子量が、５０００未満だと押出時のストランドに毛羽立ちが目立ち、ストランド冷却バスの水分を持ち込み易くなり、ペレタイズした後に乾燥工程が必要になることがある。また、ストランドが途中で切れ易くなったり、生産性が低下したりすることもある。（ｂ）臭素化ポリスチレンの数平均分子量が、２５０００を越えると溶融粘度が非常に高くなり、押出時のトルクが上昇し、吐出量（生産量）が制限を受けたり、成形時にも流動性が低下する傾向がある。より好ましくは、数平均分子量が、７０００〜２１０００の範囲にあるものであり、更に好ましくは、９０００〜１７０００の範囲にあるものである。 (B) Although the molecular weight of brominated polystyrene is not particularly limited, a higher molecular weight is preferable in terms of thermal stability. Further, those having a molecular weight in the range of a number average molecular weight (Mn) of 5,000 to 25,000 are preferable because of excellent extrudability. When the number average molecular weight is less than 5,000, the strands at the time of extrusion become conspicuous and it becomes easy to bring in moisture from the strand cooling bath, and a drying step may be required after pelletizing. In addition, the strand may be easily cut off in the middle or productivity may be reduced. (B) When the number average molecular weight of brominated polystyrene exceeds 25,000, the melt viscosity becomes very high, the torque during extrusion increases, the discharge amount (production amount) is restricted, and the fluidity is also obtained during molding. There is a tendency to decrease. More preferably, the number average molecular weight is in the range of 7000 to 21000, and still more preferably in the range of 9000 to 17000.
また、重量平均分子量（Ｍｗ）についても特に制限しないが、５００００〜１５００００の範囲にあるものが、押出性に優れるので好ましい。重量平均分子量が、５００００未満だと押出時のストランドに毛羽立ちが目立ち、ストランド冷却バスの水分を持ち込み易くなり、ペレタイズした後に乾燥工程が必要になることがある。また、ストランドも途中で切れ易くなり、生産性が低下する傾向がある。一方、重量平均分子量が、１５００００を越えると溶融粘度が非常に高くなり、押出時のトルクが上昇し、吐出量（生産量）が制限を受けたり、成形時にも流動性が低下したりすることがある。より好ましくは、重量平均分子量が、７００００〜１３０００の範囲にあるものであり、更に好ましくは、９００００〜１１００００の範囲にあるものである。 Also, the weight average molecular weight (Mw) is not particularly limited, but those in the range of 50,000 to 150,000 are preferable because of excellent extrudability. When the weight average molecular weight is less than 50000, the strands at the time of extrusion become conspicuous and it becomes easy to bring in moisture from the strand cooling bath, and a drying step may be required after pelletizing. In addition, the strands are easily cut off in the middle, and the productivity tends to decrease. On the other hand, if the weight average molecular weight exceeds 150,000, the melt viscosity becomes very high, the torque at the time of extrusion increases, the discharge amount (production amount) is restricted, and the fluidity also decreases during molding. There is. More preferably, the weight average molecular weight is in the range of 70000 to 13000, and still more preferably in the range of 90000 to 110000.
（ｂ）臭素化ポリスチレン中の不純物については、できるだけ少ない方が溶融加工時のガス化が抑えられるので好ましい。特に、エラストマー成分（例えば、変性水素化ブロック共重合体成分）を含む難燃組成物においては、塩素分や硫黄分等の不純物がエラストマーの熱時劣化を促進するため、溶融加工時のガス化量が一層大きくなる。そのため、例えば好ましいものとしては、臭素化ポリスチレンの元素分析において、塩素は元素として２０００ｐｐｍ以下、好ましくは１０００ｐｐｍ以下、更に好ましくは５００ｐｐｍ以下であり、硫黄は元素として、１００ｐｐｍ以下、より好ましくは５０ｐｐｍ以下のものが挙げられる。 (B) About the impurity in brominated polystyrene, the one where it is as small as possible is preferable since gasification at the time of melt processing is suppressed. In particular, in flame retardant compositions containing elastomer components (for example, modified hydrogenated block copolymer components), impurities such as chlorine and sulfur promote thermal degradation of the elastomer, so gasification during melt processing The amount is even greater. Therefore, for example, in the elemental analysis of brominated polystyrene, for example, chlorine is 2000 ppm or less, preferably 1000 ppm or less, more preferably 500 ppm or less as an element, and sulfur is 100 ppm or less, more preferably 50 ppm or less as an element. Things.
本発明の（ｃ）芳香族ビニル化合物とα，β不飽和ジカルボン酸無水物の共重合体に用いられる芳香族ビニル化合物としては、例えば下記の一般式で表わされる化合物が挙げられる。 Examples of the aromatic vinyl compound used in the copolymer of (c) the aromatic vinyl compound and the α, β unsaturated dicarboxylic acid anhydride of the present invention include compounds represented by the following general formula.
上式においてＲ1およびＲ2は水素又は炭素数１〜３のアルキル基であり、ｋは１〜５の整数である。具体的にはスチレン、α−メチルスチレン、p−メチルスチレン等が挙げられ、中でもスチレンが好ましい。一方、（ｃ）共重合体に用いられるα，β不飽和ジカルボン酸無水物としては、例えば下記の一般式で表わされる化合物が挙げられる。
In the above formula, R 1 and R 2 are hydrogen or an alkyl group having 1 to 3 carbon atoms, and k is an integer of 1 to 5. Specific examples include styrene, α-methyl styrene, p-methyl styrene, etc. Among them, styrene is preferable. On the other hand, examples of the α, β unsaturated dicarboxylic acid anhydride used in the copolymer (c) include compounds represented by the following general formula.
上式においてＲ3およびＲ4は水素又は炭素数１〜３のアルキル基である。具体的には無水マレイン酸、メチル無水マレイン酸等が挙げられ、中でも無水マレイン酸が好ましい。
In the above formula, R 3 and R 4 are hydrogen or an alkyl group having 1 to 3 carbon atoms. Specific examples include maleic anhydride and methyl maleic anhydride. Among them, maleic anhydride is preferable.
本発明に係る難燃性ポリアミド樹脂組成物においては、（ｃ）共重合体の芳香族ビニル化合物成分が臭素化ポリスチレンと親和し、α，β不飽和ジカルボン酸無水物成分がポリアミドと親和ないし反応することにより、ポリアミドマトリックス中に臭素化ポリスチレンが分散するのを助け、微分散せしめていると考えられる。その一方、臭素化ポリスチレン、ポリアミドを含むこの系においては、α，β不飽和ジカルボン酸無水物成分によるポリアミドの劣化を誘発し易くなってしまい、押出、成形等の溶融加工時にガスの発生等の原因になりうる。そのため、本発明に係る難燃性ポリアミド樹脂組成物においては、特にα，β不飽和ジカルボン酸無水物成分の量を調整することが重要である。α，β不飽和ジカルボン酸無水物成分の量については後述する。 In the flame retardant polyamide resin composition according to the present invention, (c) the aromatic vinyl compound component of the copolymer has an affinity with brominated polystyrene, and the α, β unsaturated dicarboxylic acid anhydride component has an affinity or reaction with the polyamide. By doing so, it is considered that brominated polystyrene is dispersed in the polyamide matrix and is finely dispersed. On the other hand, in this system containing brominated polystyrene and polyamide, it becomes easy to induce degradation of the polyamide by the α, β unsaturated dicarboxylic acid anhydride component, and gas generation is caused during melt processing such as extrusion and molding. It can be a cause. Therefore, in the flame-retardant polyamide resin composition according to the present invention, it is particularly important to adjust the amount of the α, β unsaturated dicarboxylic anhydride component. The amount of the α, β unsaturated dicarboxylic anhydride component will be described later.
（ｃ）共重合体における、芳香族ビニル化合物成分とα，β不飽和ジカルボン酸無水物成分との割合は、質量比で、５０：５０〜９９：１が好ましい。芳香族ビニル化合物成分が少なすぎるとα，β不飽和ジカルボン酸無水物によるポリアミドの劣化を誘発し易くなる。また、芳香族ビニル化合物成分が多くα，β不飽和ジカルボン酸無水物成分が少なすぎると、ポリアミドと十分に親和ないし反応させるために（ｃ）共重合体を多く配合する必要が生じ、組成物機械物性、難燃性の点で好ましくない。好ましくは（ｃ）共重合体において、α，β不飽和ジカルボン酸無水物成分が５〜２０質量％、更に好ましくは８〜１５質量％である。 (C) The ratio of the aromatic vinyl compound component and the α, β unsaturated dicarboxylic anhydride component in the copolymer is preferably 50:50 to 99: 1 in terms of mass ratio. When the amount of the aromatic vinyl compound component is too small, it becomes easy to induce deterioration of the polyamide by the α, β unsaturated dicarboxylic acid anhydride. In addition, when the aromatic vinyl compound component is large and the α, β unsaturated dicarboxylic anhydride component is too small, it is necessary to add a large amount of the copolymer (c) in order to have sufficient affinity or reaction with the polyamide. It is not preferable in terms of mechanical properties and flame retardancy. Preferably, in the copolymer (c), the α, β unsaturated dicarboxylic anhydride component is 5 to 20% by mass, more preferably 8 to 15% by mass.
本発明の（ｄ）無機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。 The inorganic reinforcing material (d) of the present invention is an optional component, and even if this component is not present, the object of the present invention can be achieved. However, when further improving flame retardancy and mechanical properties, this component is added. Can be added.
（ｄ）無機強化材としては、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、ウォラストナイト、アパタイト、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材が高い物性を発現するので好ましく使用される。 (D) Examples of inorganic reinforcing materials include 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, Examples thereof include fiber-like, granular, plate-like, or needle-like inorganic reinforcing materials such as calcined kaolin, wollastonite, apatite, glass beads, glass flakes, and titanium oxide. Two or more of these reinforcing materials may be used in combination. In particular, fibrous reinforcing materials such as glass fibers are preferably used because they exhibit high physical properties.
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、物性が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５〜２０μｍが好ましい。また、ポリアミド樹脂用にガラス繊維表面を処理したものが優れた物性を付与するので一層好ましい。 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 fiber is particularly preferable because the physical properties are particularly excellent. Among these, the average fiber diameter of the glass fiber is preferably 5 to 20 μm. Moreover, since the thing which processed the glass fiber surface for polyamide resins gave the outstanding physical property, it is still more preferable.
本発明の（ｅ）変性水素化ブロック共重合体は任意成分であり、本成分が無くとも、本発明の目的は達成されるが、更なる機械特性（特に耐衝撃性等）の向上を図る際には、本成分を添加することができる。その一方、押出が難しい臭素化ポリスチレン、ポリアミド、芳香族ビニル化合物とα，β不飽和ジカルボン酸無水物の共重合体を含むこの系においては、さらに当成分が含まれることによって、一層ポリアミドや変性水素化ブロック共重合体の劣化を誘発し易くなってしまい、押出、成形等の溶融加工時にガスの発生等の原因になりうる。そのため、本成分についても、成分や変性率、分子量、そして特に添加量に注意が必要である。 The (e) modified hydrogenated block copolymer of the present invention is an optional component, and even without this component, the object of the present invention can be achieved, but further improvement of mechanical properties (especially impact resistance, etc.) is aimed at. In this case, this component can be added. On the other hand, in this system containing a copolymer of brominated polystyrene, polyamide, aromatic vinyl compound and α, β unsaturated dicarboxylic acid anhydride, which is difficult to extrude, the addition of this component further increases polyamide and modification. It becomes easy to induce deterioration of the hydrogenated block copolymer, which may cause gas generation during melt processing such as extrusion and molding. Therefore, it is necessary to pay attention to the component, the modification rate, the molecular weight, and particularly the addition amount of this component.
本発明の（ｅ）変性水素化ブロック共重合体としては、例えば、芳香族ビニル化合物と共役ジエン化合物の水素化物とからなる水素化ブロック共重合体が挙げられる。これは、ビニル芳香族化合物重合体ブロックＡとオレフィン系化合物重合体Ｂからなる水素化ブロック共重合体を不飽和カルボン酸又はその誘導体で変性した物であって、該水素化ブロック共重合体はビニル芳香族化合物重合体ブロックと共役ジエン系化合物重合体ブロックとより成るブロック共重合体の共役ジエン部分を選択的に水素化することによって得られる物である。 Examples of the (e) modified hydrogenated block copolymer of the present invention include a hydrogenated block copolymer comprising an aromatic vinyl compound and a conjugated diene compound hydride. This is a product obtained by modifying a hydrogenated block copolymer comprising a vinyl aromatic compound polymer block A and an olefinic compound polymer B with an unsaturated carboxylic acid or a derivative thereof, and the hydrogenated block copolymer is This is a product obtained by selectively hydrogenating the conjugated diene portion of a block copolymer comprising a vinyl aromatic compound polymer block and a conjugated diene compound polymer block.
上記のビニル芳香族化合物重合体ブロックと共役ジエン系化合物重合体ブロックより成るブロック共重合体は、ビニル芳香族化合物重合体ブロック（Ｘ）と（Ｘ’）および共役ジエン系化合物重合体ブロック（Ｙ）（ただし、ＸとＸ’は同じであっても異なっていても良い。）より成るブロック共重合体で（ＸＹ）n、Ｘ−Ｙ−Ｘ’、Ｘ−（Ｙ−Ｘ−Ｙ）n−Ｘ、Ｘ−（Ｙ−Ｘ）n−Ｙ（式中ｎは１乃至１０の整数である。）で表される線状ブロック共重合体、あるいは一般式［（Ｙ−Ｘ）n］m+2−Ｚ、［（Ｘ−Ｙ）n］m+2−Ｚ、［（Ｙ−Ｘ）n−Ｙ］m+2−Ｚ、［（Ｘ−Ｙ）n−Ｘ］m+2−Ｚ（式中ｍは１乃至４の整数であり、Ｚは例えば四塩化ケイ素、四塩化スズなどのカップリング剤の残基又は、多官能有機リチウム化合物等の開始剤の残基を示す。）で表されるラジアルブロック共重合体が挙げられる。 The block copolymer comprising the above vinyl aromatic compound polymer block and the conjugated diene compound polymer block includes vinyl aromatic compound polymer blocks (X) and (X ′) and a conjugated diene compound polymer block (Y ) (Wherein X and X ′ may be the same or different.) (XY) n , XYX ′, X- (YXY) n A linear block copolymer represented by —X, X— (Y—X) n —Y (where n is an integer of 1 to 10), or a general formula [(Y—X) n ] m +2 −Z, [(XY) n ] m + 2 −Z, [(Y−X) n −Y] m + 2 −Z, [(X−Y) n −X] m + 2 −Z (In the formula, m is an integer of 1 to 4, and Z is a residue of a coupling agent such as silicon tetrachloride or tin tetrachloride or an initiator such as a polyfunctional organolithium compound. Radial block copolymer represented by a group.) Can be mentioned.
ここで用いられるビニル芳香族化合物として代表的な化合物には、例えばスチレン、α−メチルスチレン、ビニルキシレン、エチルビニルキシレン、ビニルナフタリンおよびこれらの混合物が挙げられ、また共役ジエン系化合物としては、例えばブタジエン、イソプレン、１，３−ペンタジエン又は２，３−ジメチルブタジエンおよびこれらの混合物が挙げられる。好ましくは、ビニル芳香族化合物としてはスチレン、共役ジエン系化合物としてはブタジエンである。 Typical examples of the vinyl aromatic compound used here include styrene, α-methylstyrene, vinyl xylene, ethyl vinyl xylene, vinyl naphthalene, and mixtures thereof, and examples of the conjugated diene compound include Examples include butadiene, isoprene, 1,3-pentadiene or 2,3-dimethylbutadiene and mixtures thereof. Preferably, the vinyl aromatic compound is styrene, and the conjugated diene compound is butadiene.
これらのブロック共重合体の末端ブロックは、同じであっても異なっていてもよい。これらのブロック共重合体の数平均分子量は１００００〜８０００００、好ましくは２００００〜５０００００である。また、ブロック共重合体中のビニル芳香族化合物の含有量は１０〜７０質量％が好ましく、より好ましくは１５〜５５質量％である。特に好ましくは１８〜４５質量％である。 The end blocks of these block copolymers may be the same or different. The number average molecular weight of these block copolymers is 10,000 to 800,000, preferably 20000 to 500,000. Moreover, 10-70 mass% is preferable, and, as for content of the vinyl aromatic compound in a block copolymer, More preferably, it is 15-55 mass%. Most preferably, it is 18-45 mass%.
本発明の（ｅ）変性水素化ブロック共重合体に用いる水素化ブロック共重合体は前記のブロック共重合体の共役ジエン系化合物重合体ブロックを選択的に水素化することによって得られる物であり、例えば、特公昭４２−８７０４号公報記載の方法で、つまり、ｎ−ヘキサンとシクロヘキサンの混合溶媒中でナフテン酸コバルトとトリエチルアルミニウムを触媒として水素を添加することにより、ビニル芳香族化合物ブロックの芳香族二重結合の２０％を越えない部分および共役ジエン化合物重合体の脂肪族二重結合の少なくとも８０％が水素添加されている水素化ブロック共重合体が合成される。 The hydrogenated block copolymer used in the (e) modified hydrogenated block copolymer of the present invention is obtained by selectively hydrogenating the conjugated diene compound polymer block of the block copolymer. For example, in the method described in JP-B-42-8704, that is, by adding hydrogen in a mixed solvent of n-hexane and cyclohexane using cobalt naphthenate and triethylaluminum as a catalyst, the aromaticity of the vinyl aromatic compound block A hydrogenated block copolymer is synthesized in which no more than 20% of the group double bonds and at least 80% of the aliphatic double bonds of the conjugated diene compound polymer are hydrogenated.
本発明で言うブロックＢの不飽和度とは、水素化ブロック共重合体のブロックＢに含まれる炭素−炭素二重結合の割合を意味する。これは、核磁気共鳴スペクトル（ＮＭＲ）、赤外線吸収スペクトル（ＩＲ）等の機器分析、ヨード滴定法等の化学分析により測定される。これらの水素化ブロック共重合体は一種のみならず二種以上を混合して用いることもできる。 The degree of unsaturation in block B referred to in the present invention means the proportion of carbon-carbon double bonds contained in block B of the hydrogenated block copolymer. This is measured by instrumental analysis such as nuclear magnetic resonance spectrum (NMR) and infrared absorption spectrum (IR), and chemical analysis such as iodometric titration. These hydrogenated block copolymers can be used alone or in combination of two or more.
本発明で用いられる（ｅ）変性水素化ブロック共重合体は、前記水素化ブロック共重合体に不飽和カルボン酸又はその誘導体を付加させることにより得ることができる。水素化ブロック共重合体に付加させる不飽和カルボン酸又はその誘導体の例としては、マレイン酸、フマル酸、イタコン酸、アクリル酸、クロトン酸、シス−４−シクロヘキセン−１，２−ジカルボン酸及びその無水物、エンド−シス−ビシクロ［２，２，１］−５−ヘプテン−２，３−ジカルボン酸及びその無水物、マレインイミド等が挙げられるが、これらのなかでは無水マレイン酸が特に好ましい。この変性水素化ブロック共重合体は、例えば水素化ブロック共重合体に不飽和カルボン酸又はその誘導体を溶液状態または溶融状態において、ラジカル開始剤を使用あるいは使用せずに付加せしめることによって得られる。変性共重合体の製造方法については特に限定しないが、得られた変性ブロック共重合体がゲル等の好ましくない成分を含んだり、その溶融粘度が著しく増大して加工性が悪化したりする製造方法は好ましくない。好ましい方法としては、押出機中で、ラジカル開始剤存在下で、水素化ブロック共重合体と不飽和カルボン酸またはその誘導体と反応させる方法がある。 The (e) modified hydrogenated block copolymer used in the present invention can be obtained by adding an unsaturated carboxylic acid or a derivative thereof to the hydrogenated block copolymer. Examples of the unsaturated carboxylic acid or derivative thereof to be added to the hydrogenated block copolymer include maleic acid, fumaric acid, itaconic acid, acrylic acid, crotonic acid, cis-4-cyclohexene-1,2-dicarboxylic acid and its Anhydride, endo-cis-bicyclo [2,2,1] -5-heptene-2,3-dicarboxylic acid and its anhydride, maleimide and the like can be mentioned, among which maleic anhydride is particularly preferable. This modified hydrogenated block copolymer can be obtained, for example, by adding an unsaturated carboxylic acid or a derivative thereof to a hydrogenated block copolymer in a solution state or a molten state with or without using a radical initiator. The method for producing the modified copolymer is not particularly limited, but the obtained modified block copolymer contains an undesirable component such as a gel, or its melt viscosity is remarkably increased to deteriorate the processability. Is not preferred. As a preferred method, there is a method of reacting a hydrogenated block copolymer with an unsaturated carboxylic acid or a derivative thereof in an extruder in the presence of a radical initiator.
（ｅ）変性水素化ブロック共重合体の変性量は、未変性の水素化ブロック共重合体１００質量部当たり０．０５〜３質量部であることが必要であり、好ましくは０．１５〜１．８質量部である。変性量が０．０５質量部未満では、変性共重合体としての効果が小さく、ポリアミドとの相溶性が低くなり、特に組成物にしたときの機械的特性の改良効果が小さく、成形品の折れ、割れ防止の改良効果が小さくなる。また変性量が３質量部を越えると溶融加工時の粘度が大きく上昇し、押出時にはトルクの上昇、成形時には成形性の低下及び成形品外観の悪化に繋がる。 (E) The amount of modification of the modified hydrogenated block copolymer must be 0.05 to 3 parts by mass, preferably 0.15 to 1 part per 100 parts by mass of the unmodified hydrogenated block copolymer. 8 parts by mass. If the modification amount is less than 0.05 parts by mass, the effect as a modified copolymer is small, the compatibility with polyamide is low, and the effect of improving the mechanical properties especially when the composition is made is small. The improvement effect of crack prevention is reduced. On the other hand, when the amount of modification exceeds 3 parts by mass, the viscosity at the time of melt processing is greatly increased, leading to an increase in torque at the time of extrusion, a decrease in moldability at the time of molding, and a deterioration of the appearance of the molded product.
本発明の（ｆ）高級脂肪酸金属塩は任意成分であり、本成分が無くとも、本発明の目的は達成されるが、押出が難しい臭素化ポリスチレン、ポリアミド、芳香族ビニル化合物とα，β不飽和ジカルボン酸無水物の共重合体を含む系やさらに変性水素化ブロック共重合体を添加した系においては、押出性等の溶融加工性に向上が見られる当成分を添加することができる。 The (f) higher fatty acid metal salt of the present invention is an optional component, and even without this component, the object of the present invention can be achieved, but brominated polystyrene, polyamide, aromatic vinyl compound and α, β non-extruding difficult to extrude. In a system including a copolymer of a saturated dicarboxylic acid anhydride or a system in which a modified hydrogenated block copolymer is further added, this component which can be improved in melt processability such as extrudability can be added.
本発明の（ｆ）高級脂肪酸金属塩としては、特に限定されないが、すぐれた溶融加工性を示し、難燃性の低下させないためには、例えば炭素数で１０から３２であるカルボン酸の金属塩である。具体的にはカプリン酸、ウラデシル酸、ラウリン酸、トリデシル酸、ミリスチン酸、ペンタデシル酸、パルミチン酸、ヘプタデシル酸、ステアリン酸、ノナデカン酸、アラキン酸、ベヘン酸、リグノセリン酸、セロチン酸、ヘプタコサン酸、モンタン酸、メリシン酸、ラクセル酸、ウンデシレン酸、オレイン酸、エライジン酸、セトレイン酸、エルカ酸、ブラシジン酸、ソルビル酸、リノール酸、リノレン酸、アラキドン酸、ステアロール酸、２−ヘキサデセン酸、７−ヘキサデセン酸、９−ヘキサデセン酸、ガドレイン酸、ガドエライジン酸、１１−エイコセン酸等のリチウム塩、ナトリウム塩、マグネシウム塩、カルシウム塩、亜鉛塩、アルミニウム塩等を挙げることができる。添加する際は、これら高級脂肪酸金属塩を１種類で用いてもよいし、２種類以上組み合わせて用いても良い。 The (f) higher fatty acid metal salt of the present invention is not particularly limited, but a metal salt of a carboxylic acid having, for example, 10 to 32 carbon atoms in order to exhibit excellent melt processability and not to reduce flame retardancy. It is. Specifically, capric acid, uradecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montan Acid, melissic acid, laccelic acid, undecylenic acid, oleic acid, elaidic acid, celetic acid, erucic acid, brassic acid, sorbic acid, linoleic acid, linolenic acid, arachidonic acid, stearolic acid, 2-hexadecenoic acid, 7-hexadecene Examples include lithium salts such as acid, 9-hexadecenoic acid, gadoleic acid, gadoelaidic acid, and 11-eicosenoic acid, sodium salts, magnesium salts, calcium salts, zinc salts, aluminum salts, and the like. When added, these higher fatty acid metal salts may be used alone or in combination of two or more.
本発明組成物には、難燃助剤として金属酸化物を添加することができる。特に高度な難燃性、たとえば厚さ０．８ｍｍにおいて米国のＵＬ９４規制のＶ−０規格に合格するためには難燃助剤が必要である。しかし、一方ではこれら難燃助剤は、臭素化ポリスチレンと同じく、或いはより大きくウェルド部強度や引張強度を低下させる。従って、難燃助剤の量は必要最少限にとどめるべきである。このような金属酸化物としては、例えば、三酸化二アンチモン、四酸化二アンチモン、五酸化二アンチモン、アンチモン酸ナトリウム等の酸化アンチモン類、一酸化スズ、二酸化スズ等の酸化スズ、酸化第二鉄、γ酸化鉄等の酸化鉄類、酸化亜鉛、ホウ酸亜鉛、酸化カルシウム，酸化銅，酸化チタン，酸化アルミニウム等が挙げられる。これら難燃助剤は、一種単独又は二種以上組み合わせて用いることができる。なかでも難燃性効果の点から、三酸化二アンチモン、四酸化二アンチモン、五酸化二アンチモン等の酸化アンチモン類やホウ酸亜鉛が好ましく、三酸化二アンチモンが最も好ましい。さらに難燃効果を上げるためには難燃助剤としては、平均粒径が０．０１〜１０μｍであることが好ましい。 A metal oxide can be added to the composition of the present invention as a flame retardant aid. In order to pass the V-0 standard of US UL94 regulation in especially high flame retardance, for example in thickness 0.8mm, a flame retardant adjuvant is required. However, on the other hand, these flame retardant aids lower the weld strength and tensile strength in the same way as brominated polystyrene or more. Therefore, the amount of flame retardant aid should be kept to a minimum. Examples of such metal oxides include antimony trioxide, antimony tetroxide, antimony pentoxide, and antimony oxide such as sodium antimonate, tin oxide such as tin monoxide and tin dioxide, and ferric oxide. And iron oxides such as γ iron oxide, zinc oxide, zinc borate, calcium oxide, copper oxide, titanium oxide, and aluminum oxide. These flame retardant aids can be used singly or in combination of two or more. Of these, antimony oxides such as diantimony trioxide, diantimony tetroxide, and diantimony pentoxide, and zinc borate are preferred from the viewpoint of flame retardancy, and diantimony trioxide is most preferred. In order to further increase the flame retardant effect, the flame retardant aid preferably has an average particle size of 0.01 to 10 μm.
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、成形加工時の発生ガス量をより低減する目的や金型腐食性をより低減する目的の為に、金属化合物、具体的には金属酸化物、金属水酸化物や金属炭酸塩、中でも好ましくはアルカリ土類金属の酸化物、水酸化物や炭酸塩を添加することができる。 In the flame-retardant polyamide resin composition of the present invention, a metal is used for the purpose of further reducing the amount of gas generated at the time of molding and reducing the corrosiveness of the mold as long as the object of the present invention is not impaired. A compound, specifically, a metal oxide, a metal hydroxide or a metal carbonate, particularly an alkaline earth metal oxide, hydroxide or carbonate can be preferably added.
アルカリ土類金属酸化物としては、酸化ベリリウム、酸化マグネシウム、酸化カルシウム、酸化ストロンチウム、酸化バリウム、酸化ラジウム等が挙げられる。特に、酸化カルシウム、酸化マグネシウムがガス発生の抑制効果が大きく好ましい。アルカリ土類金属水酸化物としては、水酸化ベリリウム、水酸化マグネシウム、水酸化カルシウム、水酸化ストロンチウム、水酸化バリウム、水酸化ラジウム等が挙げられる。特に水酸化カルシウム、水酸化マグネシウムがガス発生の抑制効果が大きく好ましい。アルカリ土類金属炭酸塩としては、炭酸マグネシウム、炭酸カルシウム、炭酸バリウム等のアルカリ土類金属炭酸塩が挙げられる。特に炭酸カルシウム、炭酸マグネシウムがガス発生の抑制効果が大きく好ましい。これらの金属化合物の中でも、酸化カルシウムが、少量の添加でガス発生抑制効果が特に大きく、物性の低下、成形性の悪化現象もないので特に好ましい。 Examples of the alkaline earth metal oxide include beryllium oxide, magnesium oxide, calcium oxide, strontium oxide, barium oxide, and radium oxide. In particular, calcium oxide and magnesium oxide are preferable because they have a large effect of suppressing gas generation. Examples of the alkaline earth metal hydroxide include beryllium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, radium hydroxide and the like. In particular, calcium hydroxide and magnesium hydroxide are preferable because they have a large effect of suppressing gas generation. Examples of the alkaline earth metal carbonate include alkaline earth metal carbonates such as magnesium carbonate, calcium carbonate, and barium carbonate. In particular, calcium carbonate and magnesium carbonate are preferred because they have a large effect of suppressing gas generation. Among these metal compounds, calcium oxide is particularly preferable because it has a particularly large effect of suppressing gas generation when added in a small amount and does not cause deterioration of physical properties or deterioration of moldability.
これらの金属化合物の粒径は特に限定はないが、物性低下を招かない為には１００μｍ以下であることが好ましい。 The particle size of these metal compounds is not particularly limited, but is preferably 100 μm or less so as not to cause deterioration of physical properties.
本発明に係る難燃性ポリアミド樹脂組成物は、（ｃ）共重合体が、そのα，β不飽和ジカルボン酸無水物成分が（ａ）ポリアミド、（ｂ）臭素化ポリスチレン、および（ｃ）共重合体の総計に対し０．０６〜０．７５質量％となるように配合されている組成物である。本発明の難燃性ポリアミド樹脂組成物においては、（ｃ）共重合体の芳香族ビニル化合物成分が（ｂ）臭素化ポリスチレンと親和し、α，β不飽和ジカルボン酸無水物成分が（ａ）ポリアミドと親和ないし反応することにより、ポリアミドマトリックス中に臭素化ポリスチレンが分散するのを助け、微分散せしめていると考えられる。一方、（ｂ）臭素化ポリスチレン、（ａ）ポリアミドを含むこの系においては、α，β不飽和ジカルボン酸無水物成分によるポリアミドの劣化を誘発し易くなってしまい、押出、成形等の溶融加工時にガスの発生等の原因になりうる。これらを考慮すると、本発明の難燃性ポリアミド樹脂組成物においては、（ｃ）共重合体全体の量よりも（ａ）ポリアミド、（ｂ）臭素化ポリスチレンおよび（ｃ）共重合体の総計に対するα，β不飽和ジカルボン酸無水物成分の量（割合）を最適な範囲とすることが、より重要である。より具体的には、上記のα，β不飽和ジカルボン酸無水物成分が（ａ）ポリアミド、（ｂ）臭素化ポリスチレンおよび（ｃ）共重合体の総計に対し０．０６質量％未満の場合は、難燃性が大きく低下してしまう。これは、臭素化ポリスチレンの微分散が十分でない為と考えられる。さらにウェルド部の強度が低くなってしまうという問題もある。一方、α，β不飽和ジカルボン酸無水物成分が（ａ）ポリアミド、（ｂ）臭素化ポリスチレンおよび（ｃ）共重合体の総計に対し０．７５質量％を越えると、α，β不飽和ジカルボン酸無水物成分によるポリアミドの劣化を誘発し易くなってしまう。さらに押出時のストランドに毛羽立ちが目立ち、ストランド冷却バスの水分を持ち込み易くなり、ペレタイズした後に乾燥工程が必要になってしまう。さらに加えて、ストランドも途中で切れ易くなり、生産性が低下してしまう。以上より、本発明に係る難燃性折アミド樹脂組成物において（ｃ）共重合体は、そのα，β不飽和ジカルボン酸無水物成分が（ａ）ポリアミド、（ｂ）臭素化ポリスチレンおよび（ｃ）共重合体の総計に対し０．０６〜０．７５質量％となるように配合され、より好ましくは、０．１〜０．６質量％、更に好ましくは、０．２〜０．５質量％である。 The flame retardant polyamide resin composition according to the present invention comprises (c) a copolymer in which the α, β unsaturated dicarboxylic acid anhydride component is (a) polyamide, (b) brominated polystyrene, and (c) copolymer. It is a composition blended so as to be 0.06 to 0.75% by mass with respect to the total amount of the polymer. In the flame retardant polyamide resin composition of the present invention, (c) the aromatic vinyl compound component of the copolymer has an affinity for (b) brominated polystyrene, and the α, β unsaturated dicarboxylic acid anhydride component is (a). It is considered that the affinity or reaction with the polyamide helps to disperse the brominated polystyrene in the polyamide matrix and makes it finely dispersed. On the other hand, in this system containing (b) brominated polystyrene and (a) polyamide, it is easy to induce degradation of the polyamide by the α, β unsaturated dicarboxylic anhydride component, and at the time of melt processing such as extrusion and molding. It may cause gas generation. Considering these, in the flame-retardant polyamide resin composition of the present invention, the total amount of (a) polyamide, (b) brominated polystyrene, and (c) copolymer is more than the amount of (c) total copolymer. It is more important that the amount (ratio) of the α, β unsaturated dicarboxylic anhydride component is in the optimum range. More specifically, when the α, β unsaturated dicarboxylic acid anhydride component is less than 0.06% by mass with respect to the total of (a) polyamide, (b) brominated polystyrene and (c) copolymer, The flame retardancy is greatly reduced. This is probably because the fine dispersion of brominated polystyrene is not sufficient. Furthermore, there is a problem that the strength of the weld portion is lowered. On the other hand, when the α, β unsaturated dicarboxylic acid anhydride component exceeds 0.75 mass% with respect to the total of (a) polyamide, (b) brominated polystyrene and (c) copolymer, α, β unsaturated dicarboxylic acid It becomes easy to induce the deterioration of the polyamide by the acid anhydride component. Furthermore, fluff is conspicuous in the strand at the time of extrusion, it becomes easy to bring in moisture from the strand cooling bath, and a drying step is required after pelletizing. In addition, the strands are easily cut off in the middle, and the productivity is lowered. From the above, in the flame-retardant folded amide resin composition according to the present invention, the (c) copolymer has an α, β-unsaturated dicarboxylic acid anhydride component of (a) polyamide, (b) brominated polystyrene, and (c ) It is blended so as to be 0.06 to 0.75% by mass, more preferably 0.1 to 0.6% by mass, and still more preferably 0.2 to 0.5% by mass with respect to the total copolymer. %.
上記以外に配合量の制限は特にないが、好ましい範囲を以下に挙げる。ここでは、（ａ）末端カルボキシル基比率が５１〜９０％の範囲にあるポリアミドを１００質量部とした場合の各成分の配合量として記載する。 Other than the above, there is no particular limitation on the blending amount, but preferred ranges are listed below. Here, (a) It describes as a compounding quantity of each component at the time of setting the polyamide which has a terminal carboxyl group ratio in the range of 51-90% as 100 mass parts.
（ｂ）臭素化ポリスチレンの質量割合は、３０〜６０質量部の範囲である。３０質量部未満の場合には、難燃効果が充分でなく、６０質量部を越える場合には、溶融混練時に分解ガスが発生したり、成形加工時に流動性が低下したり、成形金型に汚染性物質が多く付着するなどの問題が生じることがある。又、機械的物性の著しい低下や、成形品外観の悪化の原因ともなりうる。より好ましくは、３５〜５５質量部、更に好ましくは、４０〜５０質量部である。 (B) The mass ratio of brominated polystyrene is the range of 30-60 mass parts. When the amount is less than 30 parts by mass, the flame retardant effect is not sufficient. When the amount exceeds 60 parts by mass, decomposition gas is generated during melt-kneading, fluidity is reduced during molding, Problems such as adhesion of many pollutants may occur. Further, it may cause a significant decrease in mechanical properties and a deterioration of the appearance of the molded product. More preferably, it is 35-55 mass parts, More preferably, it is 40-50 mass parts.
（ｃ）芳香族ビニル化合物とα，β不飽和ジカルボン酸無水物の共重合体の質量割合は、０．５〜１５質量部の範囲である。０．５質量部未満の場合は、相溶化によるポリアミド中での臭素化ポリスチレンの微分散が十分でない為だと考えられるが、難燃性が大きく低下してしまうことがある。さらにウェルド部の強度が低くなる傾向がある。一方、１５質量部を越える場合には、ポリアミドがもつ強度等の特性が失われやすくなり、ポリアミドの劣化を誘発し易くなってしまう。さらに押出時のストランドに毛羽立ちが目立ち、ストランド冷却バスの水分を持ち込み易くなり、ペレタイズした後に乾燥工程が必要になったり、ストランドが途中で切れ易くなり、生産性が低下してしまうこともある。より好ましくは、１〜１０質量部、更に好ましくは、２〜５質量部である。 (C) The mass ratio of the copolymer of an aromatic vinyl compound and an α, β unsaturated dicarboxylic acid anhydride is in the range of 0.5 to 15 parts by mass. In the case of less than 0.5 part by mass, it is considered that the fine dispersion of brominated polystyrene in the polyamide due to compatibilization is not sufficient, but flame retardancy may be greatly reduced. Furthermore, the strength of the weld portion tends to be low. On the other hand, when the amount exceeds 15 parts by mass, properties such as strength of the polyamide tend to be lost, and deterioration of the polyamide is easily induced. Furthermore, the strands at the time of extrusion are conspicuous and it becomes easy to bring in moisture from the strand cooling bath, and a drying process is required after pelletizing, or the strands are easily cut off in the middle, resulting in a decrease in productivity. More preferably, it is 1-10 mass parts, More preferably, it is 2-5 mass parts.
（ｄ）無機強化材は、任意成分であり、添加する際の質量割合は０〜２４０質量部、好ましくは１５〜２４０質量部の範囲である。１５質量部未満の場合には、強度、難燃性において一層の大きな向上を得難く、２４０質量部を越える場合には、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するなどの問題が生じることがある。又、機械的物性の著しい低下や、成形品外観の悪化の原因ともなりやすい。より好ましくは、２５〜１６０質量部、更に好ましくは、３８〜１１０質量部である。 (D) An inorganic reinforcement is an arbitrary component, and the mass ratio at the time of adding is 0-240 mass parts, Preferably it is the range of 15-240 mass parts. When the amount is less than 15 parts by mass, it is difficult to obtain a further great improvement in strength and flame retardancy. When the amount exceeds 240 parts by mass, decomposition gas is generated during kneading or the mold is contaminated during molding. Problems such as adhesion of substances may occur. Moreover, it is likely to cause a significant decrease in mechanical properties and a deterioration of the appearance of the molded product. More preferably, it is 25-160 mass parts, More preferably, it is 38-110 mass parts.
（ｅ）変性水素化ブロック共重合体は、任意成分であるが、更なる機械特性（特に耐衝撃性等）の向上を図る際には、本成分を添加することが非常に有効である。その一方、押出が難しい臭素化ポリスチレン、ポリアミド、芳香族ビニル化合物とα，β不飽和ジカルボン酸無水物の共重合体を含むこの系においては、さらに当成分が含まれることによって、一層ポリアミドや変性水素化ブロック共重合体の劣化を誘発し易くなってしまい、押出、成形等の溶融加工時にガスの発生等の原因になりうる。そのため、本成分については、特に添加量に注意が重要である。 (E) The modified hydrogenated block copolymer is an optional component, but it is very effective to add this component when further improving mechanical properties (especially impact resistance and the like). On the other hand, in this system containing a copolymer of brominated polystyrene, polyamide, aromatic vinyl compound and α, β unsaturated dicarboxylic acid anhydride, which is difficult to extrude, the addition of this component further increases polyamide and modification. It becomes easy to induce deterioration of the hydrogenated block copolymer, which may cause gas generation during melt processing such as extrusion and molding. Therefore, it is important to pay attention to the amount of this component added.
添加する際の質量割合は０〜１５質量部、好ましくは０．５〜１５質量部の範囲である。０．５質量部未満の場合には、機械的特性（特に耐衝撃性）の改良効果が比較的小さく、１５質量部を越える場合には、溶融加工時の粘度が大きく上昇し、押出時にはトルクの上昇、成形時には成形性の低下及び成形品外観の悪化に繋がってしまうことがある。また、難燃性の向上効果が阻害され易くなり、更にポリアミドがもつ強度等の特性が失われてしまう。より好ましくは、１〜１０質量部、更に好ましくは、２〜６質量部である。 The mass ratio at the time of addition is 0-15 mass parts, Preferably it is the range of 0.5-15 mass parts. If it is less than 0.5 parts by mass, the effect of improving the mechanical properties (especially impact resistance) is relatively small. If it exceeds 15 parts by mass, the viscosity during melt processing increases greatly, and torque during extrusion In the rise and molding, the moldability may be lowered and the appearance of the molded product may be deteriorated. In addition, the effect of improving flame retardancy is likely to be hindered, and the properties such as strength of polyamide are lost. More preferably, it is 1-10 mass parts, More preferably, it is 2-6 mass parts.
（ｆ）高級脂肪酸金属塩は、任意成分であり、添加する際の質量割合は０〜２質量部、好ましくは０．１〜２質量部の範囲である。０．１質量部未満の場合には、更なる溶融加工性、機械特性の向上効果が比較的小さく、２質量部を越える場合には、押出性等の溶融加工性にある程度以上の向上効果が見られず、また、難燃性が低下してしまうこともある。より好ましくは、０．１５〜１．５質量部、更に好ましくは０．２〜１質量部である。 (F) The higher fatty acid metal salt is an optional component, and the mass ratio when added is 0 to 2 parts by mass, preferably 0.1 to 2 parts by mass. When the amount is less than 0.1 parts by mass, the effect of further improving melt processability and mechanical properties is relatively small. When the amount exceeds 2 parts by mass, the melt processability such as extrudability is improved to some extent. It is not seen, and flame retardancy may be reduced. More preferably, it is 0.15-1.5 mass part, More preferably, it is 0.2-1 mass part.
難燃助剤としての金属酸化物は、任意成分であるが、添加する際の質量割合は１〜２０質量部の範囲である。１質量部未満では、更なる難燃性の向上効果が小さく、２０質量部を越える場合には、溶融加工時の粘度が大きく上昇することがあり、押出時にはトルクの上昇、成形時には成形性の低下及び成形品外観の悪化に繋がってしまう。また、ポリアミドがもつ靭性や改良された耐衝撃性等の特性が失われる傾向がある。より好ましくは、２〜１５質量部、さらに好ましくは４〜１０質量部である。 The metal oxide as the flame retardant aid is an optional component, but the mass ratio when added is in the range of 1 to 20 parts by mass. If the amount is less than 1 part by mass, the effect of further improving flame retardancy is small. If the amount exceeds 20 parts by mass, the viscosity at the time of melt processing may greatly increase, the torque increases during extrusion, and the moldability during molding. This leads to a decrease and deterioration of the appearance of the molded product. In addition, properties such as toughness and improved impact resistance of polyamide tend to be lost. More preferably, it is 2-15 mass parts, More preferably, it is 4-10 mass parts.
成形加工時の発生ガス量を低減したり、金型腐食性を低減する目的の金属化合物は、任意成分であるが、添加する際の質量割合は、０．０１〜５質量部の範囲である。０．０１質量部未満の場合には、添加無しの系との差がほとんどなく、５質量部を超える場合には、量的な改良効果が認められないばかりか、機械的物性低下や成形流動性の低下を招いてしまう。より好ましくは、０．０５〜２質量部、更に好ましくは、０．１〜１質量部である。 The metal compound for the purpose of reducing the amount of gas generated during the molding process or reducing the mold corrosiveness is an optional component, but the mass ratio when added is in the range of 0.01 to 5 parts by mass. . When the amount is less than 0.01 parts by mass, there is almost no difference from the system without addition, and when the amount exceeds 5 parts by mass, not only a quantitative improvement effect is observed, but also mechanical properties decrease and molding flow. It will cause a decline in sex. More preferably, it is 0.05-2 mass parts, More preferably, it is 0.1-1 mass part.
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、例えば他の難燃剤、他のエラストマー、フィブリル化剤、顔料、染料等の着色剤（着色マスターバッチ含む）や、ポリアミド樹脂の一般的な熱安定剤である銅系熱安定剤、ヒンダードフェノール系やヒンダードアミン系化合物酸化劣化防止剤に代表される有機系熱安定剤、耐候性改良剤、核剤、可塑剤、帯電防止剤、流動性改良剤、他の充填剤、補強剤、展着剤、他のポリマー等を任意の段階で添加することができる。 In the flame-retardant polyamide resin composition of the present invention, other components, for example, other flame retardants, other elastomers, fibrillating agents, pigments, dyes, and the like are included within the range not impairing the object of the present invention. Master batches), copper heat stabilizers that are general heat stabilizers for polyamide resins, organic heat stabilizers typified by hindered phenols and hindered amine compounds oxidative degradation inhibitors, weather resistance improvers, Nucleating agents, plasticizers, antistatic agents, fluidity improvers, other fillers, reinforcing agents, spreading agents, other polymers and the like can be added at any stage.
本発明の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、臭素化ポリスチレン、芳香族ビニル化合物とα，β不飽和ジカルボン酸無水物の共重合体、無機強化材（任意成分）、変性水素化ブロック共重合体（任意成分）、高級脂肪酸金属塩（任意成分）、金属酸化物（任意成分）を常用の単軸又は２軸の押出機やニーダー等の混練機を用いて、樹脂の融点等に応じて、２００〜３５０℃の温度で溶融混練することが一般的であるが、機械特性を維持するために、ポリアミド、臭素化ポリスチレン、芳香族ビニル化合物とα，β不飽和ジカルボン酸無水物の共重合体、変性水素化ブロック共重合体（任意成分）、高級脂肪酸金属塩（任意成分）、金属酸化物（任意成分）を添加した後に、無機強化材（任意成分）を添加し混練するのが好ましい。また、無機充填剤の添加方法は、サイドフィード方式が良い。さもないとこれらの表面処理剤がα，β不飽和ジカルボン酸無水物と反応し好ましくない結果となる場合がある。そのため、予めα，β不飽和ジカルボン酸無水物とポリアミドをよく親和ないし反応させる為に、この両者をよく混練させることが重要である。 The method for producing the flame retardant polyamide resin composition of the present invention is not particularly limited, and is a polyamide, brominated polystyrene, a copolymer of an aromatic vinyl compound and an α, β unsaturated dicarboxylic acid anhydride, an inorganic reinforcing material (optional) Component), modified hydrogenated block copolymer (optional component), higher fatty acid metal salt (optional component), metal oxide (optional component) using a kneader such as a conventional single or twin screw extruder or kneader. Depending on the melting point of the resin, it is generally melt-kneaded at a temperature of 200 to 350 ° C. In order to maintain the mechanical properties, polyamide, brominated polystyrene, aromatic vinyl compound and α, β After adding unsaturated dicarboxylic acid anhydride copolymer, modified hydrogenated block copolymer (optional component), higher fatty acid metal salt (optional component), metal oxide (optional component), inorganic reinforcing material (optional component) ) Preferably kneaded. Moreover, the side feed system is good for the addition method of an inorganic filler. Otherwise, these surface treatment agents may react with α, β unsaturated dicarboxylic acid anhydrides, leading to undesirable results. Therefore, in order to make the α, β unsaturated dicarboxylic acid anhydride and the polyamide have a good affinity or reaction in advance, it is important to knead both of them well.
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。また、この組成物の成形品が持つ特性は、特に電気・電子用途部品に適している。特に、高い難燃性、高い耐衝撃性、高いウェルド強度に加えて高い強度や靭性を付与したものが望まれる材料（例えば、ブレーカーの内部や外部のカバー材）に適している。 The composition of the present invention is molded into various molded products for electrical, electronic and automotive applications such as connectors, coil bobbins, breakers, electromagnetic switches, holders, plugs, switches, etc. by known methods such as injection molding, extrusion molding, blow molding. The Further, the properties of the molded product of this composition are particularly suitable for parts for electric and electronic applications. In particular, it is suitable for a material (for example, a cover material inside or outside a breaker) that is desired to have high strength and toughness in addition to high flame resistance, high impact resistance, and high weld strength.
次に、実施例及び比較例によって本発明を更に詳細に説明するが、本発明はこの実施例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］
EXAMPLES Next, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to this Example.
In addition, the raw material and the measuring method which were used for the Example and the comparative example are shown below.
[raw materials]
（ａ）末端カルボキシル基比率が５１〜９０％の範囲にあるポリアミド
４０Ｌのオートクレーヴを用いて、以下の末端基濃度のポリアミドを重合した。添加する末端基調整剤の種類や量により末端基を調整、溶融重合したポリアミドを下部ノズルからストランド状に取り出し、水で冷却固化してペレット化する際に、水浴への浸漬の長さを調整して、水分率が調整されたポリアミドペレットを得た。
（ａ−１）ポリアミド１ ギ酸相対粘度（ＲＶ）＝４２．４、水分率＝０．１５質量％
末端カルボキシル基＝１０９．２ミリ当量／ｋｇ（８３％）、末端アミノ基比率＝２２．０ミリ当量／ｋｇ（１７％）
（ａ−２）ポリアミド２ ギ酸相対粘度（ＲＶ）＝４３．０、水分率＝０．１５質量％
末端カルボキシル基＝８４．１ミリ当量／ｋｇ（６４％）、末端アミノ基比率＝４６．５ミリ当量／ｋｇ（３６％）
（ａ−３）ポリアミド３ 水分率＝０．０５質量％に調整した。それ以外はポリアミド１と同様。
（ａ−４）ポリアミド４ ギ酸相対粘度（ＲＶ）＝４３．５、水分率＝０．１５質量％
末端カルボキシル基＝５９．１ミリ当量／ｋｇ（４６％）、末端アミノ基比率＝７０．４ミリ当量／ｋｇ（５４％）
(A) Polyamide having a terminal carboxyl group ratio in the range of 51 to 90% Polyamide having the following terminal group concentration was polymerized using a 40 L autoclave. The end group is adjusted according to the type and amount of the end group adjusting agent to be added, and the melt-polymerized polyamide is taken out from the lower nozzle in a strand form, cooled and solidified with water, and pelletized by adjusting the length of immersion in the water bath. As a result, polyamide pellets having a controlled moisture content were obtained.
(A-1) Polyamide 1 Formic acid relative viscosity (RV) = 42.4, moisture content = 0.15 mass%
Terminal carboxyl group = 109.2 meq / kg (83%), terminal amino group ratio = 22.0 meq / kg (17%)
(A-2) Polyamide 2 Formic acid relative viscosity (RV) = 43.0, moisture content = 0.15 mass%
Terminal carboxyl group = 84.1 milliequivalent / kg (64%), terminal amino group ratio = 46.5 milliequivalent / kg (36%)
(A-3) Polyamide 3 The water content was adjusted to 0.05% by mass. Other than that is the same as polyamide 1.
(A-4) Polyamide 4 Formic acid relative viscosity (RV) = 43.5, moisture content = 0.15 mass%
Terminal carboxyl group = 59.1 meq / kg (46%), terminal amino group ratio = 70.4 meq / kg (54%)
（ｂ）臭素化ポリスチレン
（ｂ−１）ＡＬＢＥＭＡＲＬＥ ＣＯＲＰＯＲＡＴＩＯＮ製 商品名 ＳＡＹＴＥＸ ＨＰ−７０１０Ｇ （元素分析より 臭素含有率：６３質量％、塩素含有率：１７０ｐｐｍ。ＧＰＣより数平均分子量（Ｍｎ）：１１０００、重量平均分子量（Ｍｗ）：１０１０００）
（ｂ−２）ＡＬＢＥＭＡＲＬＥ ＣＯＲＰＯＲＡＴＩＯＮ製 商品名 ＰＹＲＯ−ＣＨＥＫ ６８ＰＢＣ （元素分析より 臭素含有率：６２質量％、塩素含有率：５０００ｐｐｍ。ＧＰＣより数平均分子量（Ｍｎ）：１５０００、重量平均分子量（Ｍｗ）：９９０００）
（ｂ−３）ＡＬＢＥＭＡＲＬＥ ＣＯＲＰＯＲＡＴＩＯＮ製 商品名 ＳＡＹＴＥＸ ＨＰ−３０１０Ｇ （元素分析より 臭素含有率：６３質量％、塩素含有率：１００ｐｐｍ。ＧＰＣより数平均分子量（Ｍｎ）：２６００、重量平均分子量（Ｍｗ）：４０００）
(B) Brominated polystyrene (b-1) Product name SAYTEX HP-7010G (from elemental analysis Bromine content: 63 mass%, chlorine content: 170 ppm, number average molecular weight (Mn): 11000, weight from GPC Average molecular weight (Mw): 101000)
(B-2) Product name PYRO-CHEK 68PBC manufactured by ALBEMALLE CORPORATION (from elemental analysis bromine content: 62% by mass, chlorine content: 5000 ppm. From GPC, number average molecular weight (Mn): 15000, weight average molecular weight (Mw): 99000)
(B-3) Albemarle Corporation product name SAYTEX HP-3010G (from elemental analysis bromine content: 63 mass%, chlorine content: 100 ppm. From GPC, number average molecular weight (Mn): 2600, weight average molecular weight (Mw): 4000)
（ｃ）芳香族ビニル化合物とα，β不飽和ジカルボン酸無水物の共重合体
（ｃ−１）スチレンと無水マレイン酸の共重合体 ＮＯＶＡ Ｃｅｍｉｃａｌｓ Ｉｎｃ．製 商品名 ＤＹＬＡＲＫ ３３２（スチレン８５質量％、無水マレイン酸１５質量％の共重合体）
(C) Copolymer of aromatic vinyl compound and α, β unsaturated dicarboxylic acid anhydride (c-1) Copolymer of styrene and maleic anhydride NOVA Chemicals Inc. Product name DYLARK 332 (a copolymer of 85% by weight of styrene and 15% by weight of maleic anhydride)
（ｄ）無機強化材
（ｄ−１）ガラス繊維（ＧＦ） 旭ファイバーグラス（株）製 商品名 ０３ＪＡ４１６（平均繊維径１０μｍ）
(D) Inorganic reinforcing material (d-1) Glass fiber (GF) Asahi Fiber Glass Co., Ltd. Product name 03JA416 (average fiber diameter 10 μm)
（ｅ）変性水素化ブロック共重合体
（ｅ−１）無水マレイン酸変性された水素化スチレン−ブタジエン共重合体 旭化成ケミカルズ（株）製 商品名 タフテックＭ１９４３
(E) Modified hydrogenated block copolymer (e-1) Maleic anhydride-modified hydrogenated styrene-butadiene copolymer Product name TUFTEC M1943 manufactured by Asahi Kasei Chemicals Corporation
（ｆ）高級脂肪酸金属塩
（ｆ−１）ステアリン酸カルシウム 和光純薬工業（株）製 商品名 ステアリン酸カルシウム
（金属塩ではないが、）（ｆ−２）ステアリン酸ステアレート 和光純薬工業（株）製 商品名 ステアリン酸ステアリル
（難燃助剤）三酸化二アンチモン 第一エフ・アール（株）製 商品名 三酸化アンチモン
［測定方法］
(F) Higher fatty acid metal salt (f-1) Calcium stearate manufactured by Wako Pure Chemical Industries, Ltd. Trade name Calcium stearate (although not a metal salt) (f-2) Stearate stearate Wako Pure Chemical Industries, Ltd. Product name Stearyl stearate (Flame retardant aid) Antimony trioxide Daiichi F.R. Co., Ltd. Product name Antimony trioxide [measuring method]
（１）ポリアミド末端基濃度
（ｉ）末端カルボキシル基濃度の測定
末端カルボキシル基濃度は、ポリアミド樹脂を１７０±５℃のベンジルアルコールに溶解し、０．１ＮＮａＯＨのエチレングリコール溶液で滴定して測定し、フェノールフタレインの変色から当量点を求め、次式で算出した。
末端カルボキシル基濃度＝Ｆ×Ａ×１００／Ｓ（ミリ当量／ｋｇ）
Ｆ（−）：０．１ＮＮａＯＨのエチレングリコール溶液のファクター
Ａ（ｍｌ）：０．１ＮＮａＯＨのエチレングリコール溶液の滴定量
Ｓ（ｇ）：ポリアミド量
（ｉｉ）末端アミノ基濃度の測定
末端アミノ基濃度は、ポリアミド樹脂をフェノールに溶解し、０．０２Ｎ塩酸で滴定して測定し、滴定曲線の変曲点から当量点を求め、次式で算出した。
末端アミノ基濃度＝Ｆ×（Ａ−Ｂ）×０．０２／（Ｓ／１０００）（ミリ当量／ｋｇ）
Ｆ（−）：０．０２Ｎ塩酸のファクター
Ａ（ｍｌ）：０．０２Ｎ塩酸の滴定量
Ｂ（ｍｌ）：フェノールの当量点量
Ｓ（ｇ）：ポリアミド樹脂量
(1) Polyamide terminal group concentration (i) Measurement of terminal carboxyl group concentration The terminal carboxyl group concentration was measured by dissolving a polyamide resin in benzyl alcohol at 170 ± 5 ° C. and titrating with 0.1 N NaOH ethylene glycol solution. The equivalence point was calculated from the discoloration of phenolphthalein and calculated by the following formula.
Terminal carboxyl group concentration = F × A × 100 / S (milli equivalent / kg)
F (-): Factor of 0.1N NaOH in ethylene glycol solution A (ml): Titration of 0.1 N NaOH in ethylene glycol solution S (g): Polyamide amount (ii) Measurement of terminal amino group concentration Terminal amino group concentration is The polyamide resin was dissolved in phenol, and titrated with 0.02N hydrochloric acid. The equivalence point was determined from the inflection point of the titration curve, and calculated by the following formula.
Terminal amino group concentration = F × (AB) × 0.02 / (S / 1000) (milli equivalent / kg)
F (-): Factor of 0.02N hydrochloric acid A (ml): Titration of 0.02N hydrochloric acid B (ml): Equivalent point of phenol S (g): Amount of polyamide resin
（２）水分率
ポリアミドペレットをＩＳＯ １５５１２に準拠した方法でカールフィッシャー水分計を用いて水分率を測定した。
(2) Moisture content The moisture content of the polyamide pellets was measured using a Karl Fischer moisture meter by a method based on ISO 15512.
（３）相対粘度
相対粘度（ＲＶ）は、溶媒としては９０％ギ酸、３ｇ（ポリアミド）サンプル／３０ｍｌギ酸の濃度で、２５℃の温度条件下で行い、詳細はＡＳＴＭ Ｄ７８９に準拠した方法で測定した。
(3) Relative Viscosity Relative viscosity (RV) is 90% formic acid, 3g (polyamide) sample / 30ml formic acid as a solvent at a temperature of 25 ° C. The details are measured by a method according to ASTM D789. did.
（４）押出性
組成物を作製するに当たり、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３００ｒｐｍ、吐出量５０ｋｇ／ｈｒの条件下で行ったが、この条件で溶融混練して、ストランド状に取り出した際、そのストランドの表面を目視で観察し、毛羽立ちなく滑らかであるものを（◎）、毛羽立ちはほとんどないが多少滑らかさが小さいものを（○）、多少毛羽立ちがあるがほとんど問題のないものを（△）、毛羽立ちしてしまい、ペレタイズ後のペレットを手で触った際に手に水分が付着するほど水を持ち込んだものを（×）とした。
同時に、押出機の紡口から出てきたストランド状の溶融樹脂から発生する分解ガス（白い煙、臭気）についても評価を行った。ほとんどガスの発生のないものを（◎）、多少ガスの発生が見られるものを（○）、ガスの発生が見られるがストランドが切れないものを（△）、ガスの発生が見られ、ストランド切れが頻発し、生産性が低下したものを（×）とした。
(4) Extrudability In producing the composition, a twin-screw extruder (manufactured by Toshiba Machine: TEM35) was used under conditions of a cylinder set temperature of 280 ° C., a screw rotation of 300 rpm, and a discharge rate of 50 kg / hr. When melt-kneaded under conditions and taken out in the form of a strand, the surface of the strand is visually observed. (◎) indicates that the surface is smooth without fluffing (◎); The ones that are slightly fuzzy but have almost no problem (△), and the ones that fuzzed and brought water to the hand when the pelletized pellets were touched by hand were marked with (×). .
At the same time, evaluation was also made on the cracked gas (white smoke, odor) generated from the strand-like molten resin coming out from the spinning nozzle of the extruder. Those with almost no gas generation (◎), those with some gas generation (◯), those with gas generation but no strand break (△), gas generation was seen, strand The case where cutting frequently occurred and the productivity was lowered was designated as (x).
（５）難燃性（ＵＬ−９４ＶＢ）
ＵＬ９４（米国Ｕｎｄｅｒ Ｗｒｉｔｅｒｓ Ｌａｂｏｒａｔｏｒｉｅｓ Ｉｎｃで定められた規格）の方法を用いて測定を行った。なお試験片（長さ１２７ｍｍ、幅１２．７ｍｍ、厚みは１／３２インチ）は射出成形機（日精工業（株）製：ＰＳ４０Ｅ）を用いて成形して得た。
難燃等級には、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。その他詳細はＵＬ９４規格に準じる。
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
規格外
上記３項目に該当しないものや試験片を保持するクランプまで燃え上がってしまった場合
(5) Flame retardancy (UL-94VB)
Measurements were made using the method of UL94 (standard established by Under Writers Laboratories Inc., USA). A test piece (length 127 mm, width 12.7 mm, thickness 1/32 inch) was obtained by molding using an injection molding machine (manufactured by Nissei Kogyo Co., Ltd .: PS40E).
In the flame retardancy class, the flame retardance class classified by UL94 vertical flame test is shown. The outline of the classification method is as follows. Other details conform to the UL94 standard.
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
There is cotton ignition. Average burning time 25 seconds or less Maximum burning time 30 seconds or less Non-standard If the flame burns up to a clamp that holds the test piece and does not correspond to the above three items
（６）色調
溶融混練後のペレット、並びに下記（７）耐衝撃性試験で成形した成形片を日本電色工業（株）製の色差計ＮＤ−３００Ａで測定し、ｂ値で判定した。ｂ値は、−（負）で絶対値が大きいほど、色調は白くて良好であり、＋（正）で絶対値が大きいほど、黄色く着色が起こっており、色調としては好ましくないことを示す。
(6) Color tone The pellets after melt-kneading and the molded piece molded in the following (7) impact resistance test were measured with a color difference meter ND-300A manufactured by Nippon Denshoku Industries Co., Ltd., and judged by the b value. As the b value is-(negative) and the absolute value is larger, the color tone is whiter and better, and as the absolute value is + (positive) and the absolute value is larger, yellow coloration occurs and the color tone is not preferable.
（７）耐衝撃性
ＡＳＴＭ Ｄ２５６に準拠した方法で、射出成形機（日精工業（株）製：ＰＳ４０Ｅ）を用いて、成形した後、切削し、ノッチを入れた試験片でＩｚｏｄ衝撃試験を実施し、Ｉｚｏｄ衝撃値を求めた。
(7) Impact resistance After molding using an injection molding machine (manufactured by Nissei Kogyo Co., Ltd .: PS40E) in accordance with ASTM D256, the Izod impact test was carried out using a test piece with a notch. The Izod impact value was determined.
（８）薄肉特性（流動直角方向曲げ試験）
射出成形機（東芝機械製：ＩＳ１５０Ｅ）を用いて、１３０ｍｍ×１３０ｍｍ×厚み１ｍｍの平板を成形した。この平板から流動直角方向に１３ｍｍ×１３０ｍｍ×厚み１ｍｍの矩形試験片を切り出し（但し、流動方向にみて流動末端側とゲート側の両端は避けた）を支点間距離２５ｍｍ、曲げ速度５ｍｍ／ｍｉｎにした以外は、ＡＳＴＭ Ｄ７９０に準拠した方法で曲げ試験を実施し、曲げ強度を求めた。またその際、曲げ破壊が起こった変位量（ｍｍ）を曲げ撓みとし、その値も求めた。
(8) Thin wall characteristics (flow direction bending test)
A 130 mm × 130 mm × thickness 1 mm flat plate was molded using an injection molding machine (Toshiba Machine: IS150E). A rectangular test piece of 13 mm × 130 mm × 1 mm thickness is cut out from this flat plate in the direction perpendicular to the flow (however, the flow end side and the gate side are avoided in the flow direction) at a fulcrum distance of 25 mm and a bending speed of 5 mm / min. Except for the above, a bending test was carried out by a method based on ASTM D790, and the bending strength was obtained. At that time, the amount of displacement (mm) at which bending fracture occurred was defined as bending deflection, and the value was also obtained.
（９）ウェルド強度
長さ１２７ｍｍ、幅１２．７ｍｍ、厚み０．８ｍｍの形状の長さ方向の両端から、溶融樹脂が流れ込み、長さ方向の中央部にウェルドが形成されるような金型を取り付けた、射出成形機（日精工業（株）製：ＰＳ４０Ｅ）で成形を行い、試験片を得た。この成形した試験片をチャック間距離５０ｍｍ、引張速度５０ｍｍ／ｍｉｎにした以外は、ＡＳＴＭ Ｄ６３８に準拠した方法で引張試験を実施し、引張強度、引張伸度を求めた。
＜実施例及び比較例＞
表１に示す組成物を得た。
(9) Weld strength A mold in which molten resin flows from both ends in the length direction of a length of 127 mm, a width of 12.7 mm, and a thickness of 0.8 mm, and a weld is formed at the center in the length direction. Molding was performed with the attached injection molding machine (manufactured by Nissei Kogyo Co., Ltd .: PS40E) to obtain a test piece. A tensile test was carried out by a method based on ASTM D638, except that the molded test piece was set to a distance between chucks of 50 mm and a tensile speed of 50 mm / min, and tensile strength and tensile elongation were obtained.
<Examples and Comparative Examples>
The composition shown in Table 1 was obtained.
〔実施例１〕
原材料はａ−１が１００．０質量部、ｂ−１が４５．０質量部、難燃助剤が７．０質量部、ｃ−１が４．０質量部、ｄ−１が７０．０質量部、ｅ−１が４．０質量部、ｆ−１が０．５質量部となるように用意し、押出機の上流側（トップの位置）に１ヶ所（以下ｔｏｐ−Ｆと略記）と、押出機のダイに近い下流側に供給口（以下ｓｉｄｅ−Ｆと略記）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２８０℃、スクリュー回転３００ｒｐｍ、吐出量５０ｋｇ／ｈｒ、ベント真空度−４０ｃｍＨｇの条件下で、ｂ成分とｄ成分を除く成分を予めブレンドしたもの重量式フィーダー１を用いてｔｏｐ−Ｆから、ｂ成分は２つ目の重量式フィーダー２を用いて同じくｔｏｐ−Ｆから、ｄ成分は３つ目の重量式フィーダー３を用いてｓｉｄｅ−Ｆから合計の吐出量が５０ｋｇ／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。また、ストランドのストランドバスへの浸漬長を調節して、ペレット水分が、０．０４〜０．０６質量％の範囲になるようにした。その際に、押出性の評価を行った。
また、得られたペレットを前記した測定方法にて、難燃性、色調、耐衝撃性、薄肉特性、ウェルド特性を調べた。その結果を表１に示す。
[Example 1]
The raw materials are 100.0 parts by mass for a-1, 45.0 parts by mass for b-1, 7.0 parts by mass for flame retardant aid, 4.0 parts by mass for c-1, and 70.0 for d-1. 1 part (hereinafter abbreviated as top-F) on the upstream side (top position) of the extruder is prepared so that the mass part, e-1 is 4.0 parts by mass, and f-1 is 0.5 parts by mass. And a twin-screw extruder (manufactured by Toshiba Machine: TEM35) having a supply port (hereinafter abbreviated as side-F) on the downstream side near the die of the extruder, a cylinder set temperature of 280 ° C., a screw rotation of 300 rpm, and a discharge amount of 50 kg. / Hr, vent vacuum degree −40 cmHg, pre-blended components except component b and component d from top-F using weight-type feeder 1, b component is second weight-type feeder 2 Also from top-F, d component is the third weight type feeder Are adjusted and supplied from side-F so that the total discharge amount becomes 50 kg / hr, melt-kneaded, taken out into a strand, cooled in a strand bath (water tank), granulated with a cutter, and polyamide Resin composition pellets were obtained. Moreover, the immersion length to the strand bath of a strand was adjusted so that the pellet moisture might be in the range of 0.04 to 0.06% by mass. At that time, the extrudability was evaluated.
The obtained pellets were examined for flame retardancy, color tone, impact resistance, thin-wall characteristics, and weld characteristics by the above-described measurement methods. The results are shown in Table 1.
〔実施例２〕
原材料のａ−１をａ−２に変更した。それ以外は、実施例１と同様に溶融混練して、ポリアミド樹脂組成物ペレットを得た。その際に、押出性の評価を行った。
また、得られたペレットを前記した測定方法にて、難燃性、色調、耐衝撃性、薄肉特性、ウェルド特性を調べた。その結果を表１に示す。
[Example 2]
The raw material a-1 was changed to a-2. Other than that was melt-kneaded in the same manner as in Example 1 to obtain polyamide resin composition pellets. At that time, the extrudability was evaluated.
The obtained pellets were examined for flame retardancy, color tone, impact resistance, thin-wall characteristics, and weld characteristics by the above-described measurement methods. The results are shown in Table 1.
〔比較例１〕
原材料のａ−１をａ−４に変更した。それ以外は、実施例１と同様に溶融混練して、ポリアミド樹脂組成物ペレットを得た。その際に、押出性の評価を行った。
また、得られたペレットを前記した測定方法にて、難燃性、色調、耐衝撃性、薄肉特性、ウェルド特性を調べた。その結果を表１に示す。
比較例１に比較すると、色調、直角曲げ撓み、ウェルド引張伸度等の点で、実施例のほうが優れていた。
[Comparative Example 1]
The raw material a-1 was changed to a-4. Other than that was melt-kneaded in the same manner as in Example 1 to obtain polyamide resin composition pellets. At that time, the extrudability was evaluated.
The obtained pellets were examined for flame retardancy, color tone, impact resistance, thin-wall characteristics, and weld characteristics by the above-described measurement methods. The results are shown in Table 1.
Compared to Comparative Example 1, the example was superior in terms of color tone, right-angle bending deflection, weld tensile elongation, and the like.
〔比較例２〕
原材料のｃ−１の量を０質量部（即ち、添加しない）に変更した。それ以外は、実施例１と同様に溶融混練して、ポリアミド樹脂組成物ペレットを得た。その際に、押出性の評価を行った。
また、得られたペレットを前記した測定方法にて、難燃性が非常に低下した為に、ウェルド特性の評価を行ったが、それ以上の評価は行わなかった。その結果を表１に示す。
[Comparative Example 2]
The amount of c-1 in the raw material was changed to 0 parts by mass (that is, not added). Other than that was melt-kneaded in the same manner as in Example 1 to obtain polyamide resin composition pellets. At that time, the extrudability was evaluated.
Moreover, since the flame retardance of the obtained pellets was greatly reduced by the measurement method described above, the weld characteristics were evaluated, but no further evaluation was performed. The results are shown in Table 1.
〔実施例３〕
原材料のｃ−１の量を１．５質量部に変更した。それ以外は、実施例１と同様に溶融混練して、ポリアミド樹脂組成物を得た。その際に押出性の評価を行った。
また得られたペレットを前記した測定方法にて、難燃性、色調、耐衝撃性、ウェルド特性を調べた。その結果を表１に示す。
Example 3
The amount of c-1 in the raw material was changed to 1.5 parts by mass. Other than that was melt-kneaded like Example 1, and obtained the polyamide resin composition. At that time, the extrudability was evaluated.
The obtained pellets were examined for flame retardancy, color tone, impact resistance, and weld characteristics by the measurement method described above. The results are shown in Table 1.
〔実施例４〕
原材料のｃ−１の量を３．０質量部に変更した。それ以外は、実施例１と同様に溶融混練して、ポリアミド樹脂組成物を得た。その際に押出性の評価を行った。
また得られたペレットを前記した測定方法にて、難燃性、色調、耐衝撃性、薄肉特性、ウェルド特性を調べた。その結果を表１に示す。
Example 4
The amount of raw material c-1 was changed to 3.0 parts by mass. Other than that was melt-kneaded like Example 1, and obtained the polyamide resin composition. At that time, the extrudability was evaluated.
Further, the obtained pellets were examined for flame retardancy, color tone, impact resistance, thin wall characteristics, and weld characteristics by the above-described measurement methods. The results are shown in Table 1.
〔実施例５〕
原材料のｃ−１の量を５．５質量部に変更した。それ以外は、実施例１と同様に溶融混練して、ポリアミド樹脂組成物を得た。その際に押出性の評価を行った。
また得られたペレットを前記した測定方法にて、難燃性、色調、耐衝撃性、ウェルド特性を調べた。その結果を表１に示す。
Example 5
The amount of raw material c-1 was changed to 5.5 parts by mass. Other than that was melt-kneaded like Example 1, and obtained the polyamide resin composition. At that time, the extrudability was evaluated.
The obtained pellets were examined for flame retardancy, color tone, impact resistance, and weld characteristics by the measurement method described above. The results are shown in Table 1.
〔比較例３〕
原材料のｃ−１の量を１０質量部に変更した。それ以外は、実施例１と同様に溶融混練して、ポリアミド樹脂組成物ペレットを得た。その際に、押出性の評価を行ったが、押出性が非常に悪く、生産性が低かった為に、それ以上の評価は行わなかった。その結果を表１に示す。
[Comparative Example 3]
The amount of c-1 in the raw material was changed to 10 parts by mass. Other than that was melt-kneaded in the same manner as in Example 1 to obtain polyamide resin composition pellets. At that time, the extrudability was evaluated, but since the extrudability was very poor and the productivity was low, no further evaluation was performed. The results are shown in Table 1.
〔実施例６〕
原材料のａ−１をａ−３に変更した。それ以外は、実施例１と同様に溶融混練して、ポリアミド樹脂組成物ペレットを得た。その際に、押出性の評価を行った。
また、得られたペレットを前記した測定方法にて、難燃性、色調、耐衝撃性、薄肉特性、ウェルド特性を調べた。その結果を表１に示す。
Example 6
The raw material a-1 was changed to a-3. Other than that was melt-kneaded in the same manner as in Example 1 to obtain polyamide resin composition pellets. At that time, the extrudability was evaluated.
The obtained pellets were examined for flame retardancy, color tone, impact resistance, thin-wall characteristics, and weld characteristics by the above-described measurement methods. The results are shown in Table 1.
〔実施例７〕
原材料のｅ−１の量を０質量部（即ち、添加しない）に変更した。それ以外は、実施例１と同様に溶融混練して、ポリアミド樹脂組成物ペレットを得た。その際に、押出性の評価を行った。
また、得られたペレットを前記した測定方法にて、難燃性、色調、耐衝撃性、薄肉特性、ウェルド特性を調べた。その結果を表１に示す。
Example 7
The amount of raw material e-1 was changed to 0 parts by mass (that is, not added). Other than that was melt-kneaded in the same manner as in Example 1 to obtain polyamide resin composition pellets. At that time, the extrudability was evaluated.
The obtained pellets were examined for flame retardancy, color tone, impact resistance, thin-wall characteristics, and weld characteristics by the above-described measurement methods. The results are shown in Table 1.
〔実施例８〕
原材料のｂ−１をｂ−２に変更した。それ以外は、実施例１と同様に溶融混練して、ポリアミド樹脂組成物ペレットを得た。その際に、押出性の評価を行った。
また、得られたペレットを前記した測定方法にて、難燃性、色調、耐衝撃性、薄肉特性、ウェルド特性を調べた。その結果を表１に示す。
Example 8
The raw material b-1 was changed to b-2. Other than that was melt-kneaded in the same manner as in Example 1 to obtain polyamide resin composition pellets. At that time, the extrudability was evaluated.
The obtained pellets were examined for flame retardancy, color tone, impact resistance, thin-wall characteristics, and weld characteristics by the above-described measurement methods. The results are shown in Table 1.
〔実施例９〕
原材料のｂ−１をｂ−３に変更した。それ以外は、実施例１と同様に溶融混練して、ポリアミド樹脂組成物ペレットを得た。その際に、押出性の評価を行った。
また、得られたペレットを前記した測定方法にて、難燃性、色調、耐衝撃性、薄肉特性、ウェルド特性を調べた。その結果を表１に示す。
Example 9
The raw material b-1 was changed to b-3. Other than that was melt-kneaded in the same manner as in Example 1 to obtain polyamide resin composition pellets. At that time, the extrudability was evaluated.
The obtained pellets were examined for flame retardancy, color tone, impact resistance, thin-wall characteristics, and weld characteristics by the above-described measurement methods. The results are shown in Table 1.
〔実施例１０〕
原材料のｆ−１の量を０質量部（即ち、添加しない）に変更した。それ以外は、実施例１と同様に溶融混練して、ポリアミド樹脂組成物ペレットを得た。その際に、押出性の評価を行った。
また、得られたペレットを前記した測定方法にて、難燃性、色調、耐衝撃性、薄肉特性、ウェルド特性を調べた。その結果を表１に示す。
Example 10
The amount of raw material f-1 was changed to 0 parts by mass (that is, not added). Other than that was melt-kneaded in the same manner as in Example 1 to obtain polyamide resin composition pellets. At that time, the extrudability was evaluated.
The obtained pellets were examined for flame retardancy, color tone, impact resistance, thin-wall characteristics, and weld characteristics by the above-described measurement methods. The results are shown in Table 1.
〔実施例１１〕
原材料のｆ−１をｆ−２に変更した。それ以外は、実施例１と同様に溶融混練して、ポリアミド樹脂組成物ペレットを得た。その際に、押出性の評価を行った。
また、得られたペレットを前記した測定方法にて、難燃性、色調、耐衝撃性、薄肉特性、ウェルド特性を調べた。その結果を表１に示す。
Example 11
The raw material f-1 was changed to f-2. Other than that was melt-kneaded in the same manner as in Example 1 to obtain polyamide resin composition pellets. At that time, the extrudability was evaluated.
The obtained pellets were examined for flame retardancy, color tone, impact resistance, thin-wall characteristics, and weld characteristics by the above-described measurement methods. The results are shown in Table 1.
〔実施例１２〕
原材料のｄ−１の量を５３質量部に変更した。それ以外は、実施例１と同様に溶融混練して、ポリアミド樹脂組成物ペレットを得た。その際に、押出性の評価を行った。
また、得られたペレットを前記した測定方法にて、難燃性、色調、耐衝撃性、薄肉特性、ウェルド特性を調べた。その結果を表１に示す。
Example 12
The amount of d-1 in the raw material was changed to 53 parts by mass. Other than that was melt-kneaded in the same manner as in Example 1 to obtain polyamide resin composition pellets. At that time, the extrudability was evaluated.
The obtained pellets were examined for flame retardancy, color tone, impact resistance, thin-wall characteristics, and weld characteristics by the above-described measurement methods. The results are shown in Table 1.
〔実施例１３〕
原材料のｄ−１の量を４０質量部に変更した。それ以外は、実施例１と同様に溶融混練して、ポリアミド樹脂組成物ペレットを得た。その際に、押出性の評価を行った。
また、得られたペレットを前記した測定方法にて、難燃性、色調、耐衝撃性、薄肉特性、ウェルド特性を調べた。その結果を表１に示す。
Example 13
The amount of raw material d-1 was changed to 40 parts by mass. Other than that was melt-kneaded in the same manner as in Example 1 to obtain polyamide resin composition pellets. At that time, the extrudability was evaluated.
The obtained pellets were examined for flame retardancy, color tone, impact resistance, thin-wall characteristics, and weld characteristics by the above-described measurement methods. The results are shown in Table 1.
本発明は、薄肉での難燃性、押出加工性、成型加工性、耐衝撃性、ウェルド強度、機械特性が優れており、更に高いウェルド強度や高い耐衝撃性を低下させることなく、薄肉での靭性やウェルド部の靭性（伸度）を高め、加えて色調も改善された難燃性ポリアミド樹脂組成物を提供できるため、高い難燃性、高い耐衝撃性、高いウェルド強度に加えて高い薄肉での靭性や高いウェルド部の靭性（伸度）を付与したものや色調の改良が望まれる用途分野において非常に有用である。例えば、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、スイッチ等電気・電子部品、自動車用途が挙げられる。 The present invention is excellent in flame retardancy, extrusion processability, molding processability, impact resistance, weld strength, and mechanical properties in a thin wall, and it is thin without reducing high weld strength and high impact resistance. High flame retardancy, high impact resistance, high weld strength, high flame retardant polyamide resin composition with improved toughness and weld toughness (elongation) and improved color tone It is very useful in applications where thin toughness or high weld toughness (elongation) is imparted or where color tone improvement is desired. For example, electrical / electronic parts such as connectors, coil bobbins, breakers, electromagnetic switches, holders, plugs and switches, and automotive applications can be mentioned.
Claims (10)
（ｂ）臭素化ポリスチレン、および
（ｃ）芳香族ビニル化合物とα，β不飽和ジカルボン酸無水物の共重合体を含み、
（ｃ）共重合体は、そのα，β不飽和ジカルボン酸無水物成分が、（ａ）ポリアミド、（ｂ）臭素化ポリスチレン、および（ｃ）共重合体の総計に対し０．０６〜０．７５質量％となるように配合されている、難燃性ポリアミド樹脂組成物。 (A) a polyamide having a terminal carboxyl group ratio in the range of 51 to 90%;
(B) brominated polystyrene, and (c) a copolymer of an aromatic vinyl compound and an α, β unsaturated dicarboxylic acid anhydride,
The (c) copolymer has an α, β-unsaturated dicarboxylic acid anhydride component of 0.06 to 0.000 relative to the total of (a) polyamide, (b) brominated polystyrene, and (c) copolymer. A flame retardant polyamide resin composition, blended so as to be 75% by mass.
（ｂ）臭素化ポリスチレン３０〜６０質量部、および
（ｃ）芳香族ビニル化合物とα，β不飽和ジカルボン酸無水物の共重合体０．５〜１５質量部を含み、
（ｃ）共重合体は、そのα，β不飽和ジカルボン酸無水物成分が、（ａ）ポリアミド、（ｂ）臭素化ポリスチレン、および（ｃ）共重合体の総計に対し０．０６〜０．７５質量％となるように配合されている、難燃性ポリアミド樹脂組成物。 (A) 100 parts by mass of polyamide having a terminal carboxyl group ratio in the range of 51 to 90%;
(B) 30 to 60 parts by mass of brominated polystyrene, and (c) 0.5 to 15 parts by mass of a copolymer of an aromatic vinyl compound and an α, β unsaturated dicarboxylic acid anhydride,
The (c) copolymer has an α, β-unsaturated dicarboxylic acid anhydride component of 0.06 to 0.000 relative to the total of (a) polyamide, (b) brominated polystyrene, and (c) copolymer. A flame retardant polyamide resin composition, blended so as to be 75% by mass.
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| JP2012525482A (en) * | 2009-05-01 | 2012-10-22 | アルベマール・コーポレーシヨン | Pelletized low molecular weight brominated aromatic polymer composition |
| US8487024B2 (en) | 2008-03-12 | 2013-07-16 | Asahi Kasei Chemicals Corporation | Polyamide, polyamide composition, and method for producing polyamide |
| US9023975B2 (en) | 2009-09-11 | 2015-05-05 | Asahi Kasei Chemicals Corporation | Polyamide and polyamide composition |
| US9090739B2 (en) | 2011-03-15 | 2015-07-28 | Asahi Kasei Chemicals Corporation | Polyamide and polyamide composition |
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| WO2020040191A1 (en) | 2018-08-24 | 2020-02-27 | 株式会社クラレ | Polyamide composition and molded product composed of said polyamide composition |
| US11970612B2 (en) | 2018-08-24 | 2024-04-30 | Kuraray Co., Ltd. | Polyamide composition and molded product composed of said polyamide composition |
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