CN116724079A - Flame-retardant polyamide resin composition and molded article thereof - Google Patents
Flame-retardant polyamide resin composition and molded article thereof Download PDFInfo
- Publication number
- CN116724079A CN116724079A CN202280009842.6A CN202280009842A CN116724079A CN 116724079 A CN116724079 A CN 116724079A CN 202280009842 A CN202280009842 A CN 202280009842A CN 116724079 A CN116724079 A CN 116724079A
- Authority
- CN
- China
- Prior art keywords
- mass
- polyamide resin
- polyamide
- parts
- flame
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920006122 polyamide resin Polymers 0.000 title claims abstract description 53
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 239000003063 flame retardant Substances 0.000 title claims abstract description 27
- 239000011342 resin composition Substances 0.000 title claims abstract description 21
- 229920005989 resin Polymers 0.000 claims abstract description 34
- 239000011347 resin Substances 0.000 claims abstract description 34
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 19
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 19
- 229920002292 Nylon 6 Polymers 0.000 claims abstract description 18
- 229920002302 Nylon 6,6 Polymers 0.000 claims abstract description 18
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 15
- 239000000194 fatty acid Substances 0.000 claims abstract description 15
- 229930195729 fatty acid Natural products 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 150000003839 salts Chemical class 0.000 claims abstract description 15
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 12
- 239000011574 phosphorus Substances 0.000 claims abstract description 12
- 239000000314 lubricant Substances 0.000 claims abstract description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 7
- 235000021355 Stearic acid Nutrition 0.000 claims description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 5
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 5
- 239000008117 stearic acid Substances 0.000 claims description 5
- 229910000859 α-Fe Inorganic materials 0.000 claims description 3
- 238000002845 discoloration Methods 0.000 abstract description 11
- 239000000203 mixture Substances 0.000 abstract description 10
- 238000002156 mixing Methods 0.000 description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- -1 poly (m-xylylene adipamide Chemical compound 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 5
- GXURZKWLMYOCDX-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.OCC(CO)(CO)CO GXURZKWLMYOCDX-UHFFFAOYSA-N 0.000 description 4
- 229920000877 Melamine resin Polymers 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 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
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 4
- SSADPHQCUURWSW-UHFFFAOYSA-N 3,9-bis(2,6-ditert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C)=CC(C(C)(C)C)=C1OP1OCC2(COP(OC=3C(=CC(C)=CC=3C(C)(C)C)C(C)(C)C)OC2)CO1 SSADPHQCUURWSW-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 229920006020 amorphous polyamide Polymers 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- ZETYUTMSJWMKNQ-UHFFFAOYSA-N n,n',n'-trimethylhexane-1,6-diamine Chemical compound CNCCCCCCN(C)C ZETYUTMSJWMKNQ-UHFFFAOYSA-N 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000001488 sodium phosphate Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 description 2
- AIBRSVLEQRWAEG-UHFFFAOYSA-N 3,9-bis(2,4-ditert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP1OCC2(COP(OC=3C(=CC(=CC=3)C(C)(C)C)C(C)(C)C)OC2)CO1 AIBRSVLEQRWAEG-UHFFFAOYSA-N 0.000 description 2
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 description 2
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 2
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 2
- 235000021314 Palmitic acid Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000000740 bleeding effect Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- VCMZIKKVYXGKCI-UHFFFAOYSA-N 1,1-bis(2,4-ditert-butyl-6-methylphenyl)-2,2-bis(hydroxymethyl)propane-1,3-diol dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)C(C)(C)C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1C)C(C)(C)C)C(C)(C)C VCMZIKKVYXGKCI-UHFFFAOYSA-N 0.000 description 1
- RGASRBUYZODJTG-UHFFFAOYSA-N 1,1-bis(2,4-ditert-butylphenyl)-2,2-bis(hydroxymethyl)propane-1,3-diol dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C RGASRBUYZODJTG-UHFFFAOYSA-N 0.000 description 1
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- YLUZWKKWWSCRSR-UHFFFAOYSA-N 3,9-bis(8-methylnonoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCC(C)C)OCC21COP(OCCCCCCCC(C)C)OC2 YLUZWKKWWSCRSR-UHFFFAOYSA-N 0.000 description 1
- DLYLVPHSKJVGLG-UHFFFAOYSA-N 4-(cyclohexylmethyl)cyclohexane-1,1-diamine Chemical compound C1CC(N)(N)CCC1CC1CCCCC1 DLYLVPHSKJVGLG-UHFFFAOYSA-N 0.000 description 1
- IGSBHTZEJMPDSZ-UHFFFAOYSA-N 4-[(4-amino-3-methylcyclohexyl)methyl]-2-methylcyclohexan-1-amine Chemical compound C1CC(N)C(C)CC1CC1CC(C)C(N)CC1 IGSBHTZEJMPDSZ-UHFFFAOYSA-N 0.000 description 1
- ADRNSOYXKABLGT-UHFFFAOYSA-N 8-methylnonyl diphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OCCCCCCCC(C)C)OC1=CC=CC=C1 ADRNSOYXKABLGT-UHFFFAOYSA-N 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920003189 Nylon 4,6 Polymers 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 229920000572 Nylon 6/12 Polymers 0.000 description 1
- FDBMBOYIVUGUSL-UHFFFAOYSA-N OP(O)OP(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)C)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1C(C)(C)C)C)C(C)(C)C Chemical compound OP(O)OP(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)C)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1C(C)(C)C)C)C(C)(C)C FDBMBOYIVUGUSL-UHFFFAOYSA-N 0.000 description 1
- QAEPIAHUOVJOOM-UHFFFAOYSA-N OP(O)OP(O)O.C(CCCCCCCC)C1=C(C=CC=C1)C(O)(C(CO)(CO)CO)C1=C(C=CC=C1)CCCCCCCCC Chemical compound OP(O)OP(O)O.C(CCCCCCCC)C1=C(C=CC=C1)C(O)(C(CO)(CO)CO)C1=C(C=CC=C1)CCCCCCCCC QAEPIAHUOVJOOM-UHFFFAOYSA-N 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 229920006100 Vydyne® Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- FIASKJZPIYCESA-UHFFFAOYSA-L calcium;octacosanoate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O FIASKJZPIYCESA-UHFFFAOYSA-L 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920006039 crystalline polyamide Polymers 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- KEIQPMUPONZJJH-UHFFFAOYSA-N dicyclohexylmethanediamine Chemical compound C1CCCCC1C(N)(N)C1CCCCC1 KEIQPMUPONZJJH-UHFFFAOYSA-N 0.000 description 1
- SHXZLWBBEAWQJP-UHFFFAOYSA-N dihydroxyphosphanyl [2,3,5,6-tetrakis(2,4-ditert-butylphenyl)-4-phenylphenyl] hydrogen phosphite Chemical compound CC(C)(C)C1=CC(=C(C=C1)C2=C(C(=C(C(=C2C3=C(C=C(C=C3)C(C)(C)C)C(C)(C)C)OP(O)OP(O)O)C4=C(C=C(C=C4)C(C)(C)C)C(C)(C)C)C5=C(C=C(C=C5)C(C)(C)C)C(C)(C)C)C6=CC=CC=C6)C(C)(C)C SHXZLWBBEAWQJP-UHFFFAOYSA-N 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- GQYGRYMNLHLHNK-UHFFFAOYSA-N manganese(2+);diphosphite Chemical compound [Mn+2].[Mn+2].[Mn+2].[O-]P([O-])[O-].[O-]P([O-])[O-] GQYGRYMNLHLHNK-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920006139 poly(hexamethylene adipamide-co-hexamethylene terephthalamide) Polymers 0.000 description 1
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- XWKBMOUUGHARTI-UHFFFAOYSA-N tricalcium;diphosphite Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])[O-].[O-]P([O-])[O-] XWKBMOUUGHARTI-UHFFFAOYSA-N 0.000 description 1
- IVIIAEVMQHEPAY-UHFFFAOYSA-N tridodecyl phosphite Chemical compound CCCCCCCCCCCCOP(OCCCCCCCCCCCC)OCCCCCCCCCCCC IVIIAEVMQHEPAY-UHFFFAOYSA-N 0.000 description 1
- VMFOHNMEJNFJAE-UHFFFAOYSA-N trimagnesium;diphosphite Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])[O-].[O-]P([O-])[O-] VMFOHNMEJNFJAE-UHFFFAOYSA-N 0.000 description 1
- CNUJLMSKURPSHE-UHFFFAOYSA-N trioctadecyl phosphite Chemical compound CCCCCCCCCCCCCCCCCCOP(OCCCCCCCCCCCCCCCCCC)OCCCCCCCCCCCCCCCCCC CNUJLMSKURPSHE-UHFFFAOYSA-N 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
- QEDNBHNWMHJNAB-UHFFFAOYSA-N tris(8-methylnonyl) phosphite Chemical compound CC(C)CCCCCCCOP(OCCCCCCCC(C)C)OCCCCCCCC(C)C QEDNBHNWMHJNAB-UHFFFAOYSA-N 0.000 description 1
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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Abstract
The invention provides a flame-retardant polyamide resin composition which has flame retardance of UL94V-0 level in a wide thickness range, has little exudation of flame retardant, and is excellent in heat discoloration resistance, formability, buckling property of parts and the like. A flame-retardant polyamide resin composition comprising a polyamide resin (A) and melamine cyanurate (B), wherein the polyamide resin (A) and the melamine cyanurate (B) are contained in a proportion of 90 to 98 parts by mass based on 100 parts by mass of the total of the components (A) and (B); in the polyamide resin (A), the proportion of the polyamide 66 resin (A1) is 55 to 85 mass percent, and the proportion of the polyamide 6 resin (A2) is 15 to 45 mass percent; and the composition comprises (A) a phosphorus antioxidant (C) in an amount of 0.01 to 1 part by mass, (D) a hindered phenol antioxidant (D) in an amount of 0.01 to 1 part by mass, and (E) a fatty acid metal salt lubricant having 22 or less carbon atoms in an amount of 0.1 to 1 part by mass, based on 100 parts by mass of the total of the components (A) and (B).
Description
Technical Field
The present invention relates to a non-halogen flame retardant polyamide resin composition. More specifically, the present invention relates to a non-halogen flame retardant polyamide resin composition having high flame retardancy and good snap-fit (snap-fit) properties, and excellent thermal discoloration resistance.
Background
Polyamide resins are used in various fields such as electric/electronic parts and automobile parts by utilizing their excellent mechanical properties, electrical properties, chemical resistance and the like. In these fields, when flame retardancy is required to be imparted to a non-reinforced and non-halogen flame retardant, melamine cyanurate is used as a flame retardant (for example, patent documents 1 and 2).
However, melamine cyanurate has poor dispersibility in polyamide resins, and when the amount of melamine cyanurate blended is increased, the mechanical properties of the polyamide resins are lowered; exudation of the polyamide resin; the thermal decomposition causes the problems that melamine and cyanuric acid are easily decomposed and sublimated, and silver lines are generated on the surface of a molded article during molding under the influence of the sublimated melamine and cyanuric acid, and the surface of a mold is easily polluted.
In recent years, various requirements for electric/electronic parts, automobile parts, etc. have become high, and flame retardancy at various thicknesses is required to be at the level of UL94V-0, and further, it is desired that the flame retardant has no bleeding, heat discoloration resistance, moldability, and further, higher levels of the parts snap-in property, etc.
Prior art literature
Patent document 1: japanese patent publication No. 58-25379
Patent document 2: japanese patent publication No. 58-35541
Disclosure of Invention
Problems to be solved by the invention
The invention provides a flame retardant polyamide resin composition. The flame retardant has flame retardancy of UL94V-0 level in a wide thickness range, and is less in exudation of the flame retardant and excellent in heat discoloration resistance, formability, buckling property of parts and the like.
Means for solving the problems
The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention.
Namely, the present invention has the following constitution.
[1] A flame-retardant polyamide resin composition comprising a polyamide resin (A) and melamine cyanurate (B), wherein the polyamide resin (A) and the melamine cyanurate (B) are contained in a proportion of 90 to 98 parts by mass based on 100 parts by mass of the total of the components (A) and (B); the composition comprises 0.01-1 part by mass of a phosphorus antioxidant (C), 0.01-1 part by mass of a hindered phenol antioxidant (D) and 0.1-1 part by mass of a fatty acid metal salt lubricant (E) having 22 or less carbon atoms, wherein the polyamide resin (A) comprises 55-85% by mass of a polyamide 66 resin (A1) and 15-45% by mass of a polyamide 6 resin (A2).
[2] The flame retardant polyamide resin composition according to [1], wherein the fatty acid metal salt lubricant (E) is a metal salt of stearic acid.
[3] A molded article comprising the flame retardant polyamide resin composition according to [1] or [2 ].
[4] The molded article according to [3], which is any one of a ferrite core cover, an SC lock (SC type oil seal), a cable tie (cable tie), and a harness protection member.
Effects of the invention
The flame retardant polyamide resin composition of the present invention has excellent heat discoloration resistance and moldability, does not significantly impair fracture strength and toughness, and has a flame retardancy of UL94V-0 level in a wide thickness range.
Detailed Description
The present invention will be specifically described below.
[ Polyamide resin (A) ]
The polyamide resin (A) in the present invention is not particularly limited as long as it is a polymer having an amide bond (-NHCO-) in the main chain. The polyamide resin (a) is preferably crystalline, and examples thereof include: crystalline polyamide resins such as polyamide 6 (PA 6), polyamide 66 (PA 66), polyamide 46 (PA 46), polyamide 11 (PA 11), polyamide 12 (PA 12), polyamide 610 (PA 610), polyamide 612 (PA 612), poly (m-xylylene adipamide) (PAMXD 6), hexamethylenediamine-terephthalic acid (PA 6T), copolymers of hexamethylenediamine-terephthalic acid and epsilon-caprolactam (PA 6T/66), trimethylhexamethylenediamine-terephthalic acid polymers (pamd-T), copolymers of m-xylylenediamine and adipic acid and isophthalic acid (pamxdi), copolymers of trimethylhexamethylenediamine and terephthalic acid and epsilon-caprolactam (pammdt/6), copolymers of diaminodicyclohexylmethane and isophthalic acid and dodecalactam, or blends of these, and the like, but are not limited thereto.
The amount (content) of the polyamide resin (A) to be mixed is 90 to 98 parts by mass based on 100 parts by mass of the total of the polyamide resin (A) and the melamine cyanurate (B). The mixing amount of the polyamide resin (A) is within this range, so that exudation of the flame retardant is suppressed and the composition can be kept high in flame retardancy. The mixing amount (content) of the polyamide resin (a) is preferably 92 to 96 parts by mass, more preferably 93 to 95 parts by mass. In the flame retardant polyamide resin composition of the present invention, the mixing amount of each component is directly defined as the content.
From the viewpoints of moldability, melt flowability, flame retardancy, and the like, a preferable embodiment of the polyamide resin (a) in the present invention is a mixture of the polyamide 66 resin (A1) and the polyamide 6 resin (A2).
The polyamide 66 resin (A1) in the present invention is a polyamide 66 resin obtained by polycondensation of adipic acid and hexamethylenediamine as raw materials. The relative viscosity of the polyamide 66 resin (A1) is preferably 2.2 to 3.5, as measured in 98% sulfuric acid at a concentration of 1% and a temperature of 25 ℃ in accordance with jis k 6810. At a relative viscosity of less than 2.2, the mechanical properties tend to be degraded; if the melt fluidity exceeds 3.5, the melt fluidity tends to be insufficient. The relative viscosity of the polyamide 66 resin (A1) is more preferably 2.3 to 3.0. In addition, the polyamide 66 resin (A1) may be mixed with polyamide 66 resins having different relative viscosities and adjusted to a preferable range of relative viscosities.
The terminal amino group concentration of the polyamide 66 resin (A1) is not particularly limited, but is preferably 50 to 90eq/ton, and more preferably 60 to 80eq/ton from the viewpoint of thermal discoloration resistance.
The mixing amount of the polyamide 66 resin (A1) is preferably 55 to 85 parts by mass based on 100 parts by mass of the polyamide resin (a). When the blending amount of the polyamide 66 resin (A1) exceeds 85 parts by mass, the hinge property (snap-fit property) is lowered; when the amount is less than 50 parts by mass, the molding processability tends to be lowered. From the viewpoint of balance between the fastening property and the molding processability, the blending amount of the polyamide 66 resin (A1) is more preferably 60 to 80 parts by mass.
The polyamide 6 resin (A2) in the present invention is a polyamide 6 resin produced by polycondensation using epsilon-caprolactam as a raw material. The relative viscosity of the polyamide 6 resin (A2) is preferably 1.5 to 4.0 in terms of a value measured in 98% sulfuric acid at a concentration of 1% and a temperature of 25℃according to JISK 6810. If the relative viscosity is less than 1.5, the mechanical properties tend to be lowered; if the melt fluidity exceeds 3.6, the melt fluidity tends to be impaired. The relative viscosity of the polyamide 6 resin (A2) is more preferably 1.8 to 3.6. In addition, the polyamide 6 resin (A2) may be mixed with polyamide 6 resins having different relative viscosities and adjusted to a preferable range of relative viscosities.
The terminal amino group concentration of the polyamide 6 resin (A2) is not particularly limited, but is preferably 50 to 90eq/ton, and more preferably 60 to 80eq/ton from the viewpoint of thermal discoloration resistance.
The mixing amount of the polyamide 6 resin (A2) is preferably 15 to 45 parts by mass based on 100 parts by mass of the polyamide resin (a). If the mixing amount of the polyamide 6 resin (A2) is less than 15 parts by mass, the hinge property (snap-fit property) tends to be lowered; if the amount exceeds 45 parts by mass, the molding processability tends to be lowered. From the viewpoint of balance between the fastening property and the molding processability, the blending amount of the polyamide 6 resin (A2) is more preferably 20 to 40 parts by mass.
In order to enhance the appearance of the molded article, the amorphous polyamide resin (A3) may be mixed.
Examples of the amorphous polyamide resin include polymers or copolymers or blends obtained by polycondensation of diamines such as 4,4 '-diamino-3, 3' -dimethyldicyclohexylmethane (CA), 4 '-diaminodicyclohexylmethane (PACM), m-xylylenediamine (MXD), trimethylhexamethylenediamine (TMD), isophoronediamine (IA), 4' -diaminodicyclohexylpropane (PACP), hexamethylenediamine, and lactams such as terephthalic acid, isophthalic acid, adipic acid, sebacic acid, dodecanedioic acid, and caprolactam, and dodecalactam. The blending amount of the amorphous polyamide resin (A3) is more preferably 0 to 15 parts by mass from the viewpoint of balance between the fastening property and the molding processability.
[ Melamine cyanurate (B) ]
As the melamine cyanurate (B) in the present invention, equimolar reactants of cyanuric acid and melamine are preferably mentioned. In addition, a part of the amino groups or hydroxyl groups in the melamine cyanurate may be substituted by other substituents. The melamine cyanurate can be obtained, for example, by mixing an aqueous solution of cyanuric acid with an aqueous solution of melamine, reacting the mixture under stirring at 90 to 100℃and filtering the precipitate thus formed. The solid obtained may be used as it is, but is preferably pulverized if necessary. The particle size is not particularly limited, but from the viewpoint of flame retardancy and toughness, the average particle size is preferably 0.5 to 20. Mu.m, more preferably 1 to 15. Mu.m.
The amount (content) of the melamine cyanurate (B) to be mixed is 2 to 10 parts by mass based on 100 parts by mass of the total of the polyamide resin (A) and the melamine cyanurate (B). From the viewpoint of flame retardancy, it is 2 parts by mass or more and from the viewpoints of fastening property and bleeding, it is 10 parts by mass or less. More preferably 3 to 9 parts by mass, still more preferably 4 to 8 parts by mass.
[ phosphorus antioxidant (C) ]
The phosphorus antioxidant (C) in the present invention may be an inorganic compound or an organic compound, and is not particularly limited. Preferable phosphorus compounds include: inorganic phosphates such as monosodium phosphate, disodium phosphate, trisodium phosphate, sodium phosphite, calcium phosphite, magnesium phosphite, and manganese phosphite; triphenyl phosphite, tris (octadecyl) phosphite, tridecyl phosphite, triisodecyl phosphite, trisnonylphenyl phosphite, diphenylisodecyl phosphite, diphenylalkyl phosphite, phenyldialkyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, distearyl pentaerythritol diphosphite, tris (2, 4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecyloxy pentaerythritol diphosphite, bis (2, 4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite, bis (2, 4, 6-tris (tert-butylphenyl)) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2, 4-di-tert-butylphenyl) -4,4' -biphenylyl diphosphite, 6-isooctyloxy-2, 4,8, 10-tetra-tert-butyl-12H-dibenzo [ d, g ] [1,3,2] -dioxa-2, 6-methylphenyl ] -2, 6-dimethyl-diphenyl-2, 6-dimethyl-2, 6-diphenyl-1, 6-dimethyl-diphenyl-2, mixing is performed to improve the thermal discoloration resistance.
As the phosphorus antioxidant (C), a phosphite compound is preferable. Among the phosphite compounds, compounds having a pentaerythritol diphosphite skeleton are preferable. Specifically, from the viewpoint of not reducing flame retardancy, further improving releasability, and also excellent in fastening properties, compounds having a pentaerythritol diphosphite skeleton of about 600 to 800, such as bis (2, 6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite ("ADK STAB PEP-36", molecular weight 633), bis (2, 4-di-t-butylphenyl) pentaerythritol diphosphite ("ADK STAB PEP-24G", molecular weight 604), distearyl pentaerythritol diphosphite ("ADK STAB PEP-8", molecular weight 733), and bis (nonylphenyl) pentaerythritol diphosphite ("ADK STAB PEP-4C", molecular weight 633), are particularly preferable.
The mixing amount (content) of the phosphorus antioxidant (C) is 0.01 to 1 part by mass based on 100 parts by mass of the total of the polyamide resin (A) and the melamine cyanurate (B). The mixing amount of the phosphorus antioxidant (C) is within this range, whereby discoloration during extrusion processing is suppressed, and secondary oxidative deterioration due to the induction of free radicals derived from phosphorus can be prevented. The mixing amount of the phosphorus antioxidant (C) is preferably 0.1 to 0.5 parts by mass.
[ hindered phenol antioxidant (D) ]
Examples of the hindered phenol-based antioxidant (D) in the present invention include: n, N ' -hexamethylenebis-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionamide, ethylene glycol bis (3, 3-bis- (4 ' -hydroxy-3 ' -tert-butylphenyl) butyrate), 2,1' -thioethylbis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 4' -butylidenebis (3-methyl-6-tert-butylphenol), triethylene glycol-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ("SON GNOX2450", molecular weight 633) and the like, and a mixture of two or more of these may be used.
The amount (content) of the hindered phenol antioxidant (D) to be mixed is 0.01 to 1 part by mass based on 100 parts by mass of the total of the polyamide resin (A) and the melamine cyanurate (B). The mixing amount of the phosphorus antioxidant (D) is within this range, so that the oxidative deterioration with time can be prevented with an appropriate prescribed amount corresponding to the coordination bond of the polyamide composition. The mixing amount of the hindered phenol antioxidant (D) is preferably 0.1 to 0.5 parts by mass.
[ fatty acid Metal salt Lubricants (E) having 22 or less carbon atoms ]
The fatty acid metal salt lubricant (E) having 22 or less carbon atoms in the present invention includes: metal salts of fatty acids such as stearic acid, palmitic acid and behenic acid. By using the fatty acid metal salt lubricant having 22 or less carbon atoms, not only the releasability is improved, but also the initial temperature of the combustion gas from the fatty acid during combustion and the initial temperature of the non-combustible gas generated during decomposition of melamine cyanurate are close to each other, so that ignition of the combustible gas can be prevented, and thus the flame retardancy tends to be further exhibited satisfactorily.
The metal salt of an aliphatic carboxylic acid having 18 or less carbon atoms is more preferable, and the alkali metal or alkaline earth metal salt of stearic acid, palmitic acid or the like is more preferable from the viewpoint of releasability and flame retardancy. Examples of the alkali metal or alkaline earth metal include: lithium, sodium, magnesium, calcium salts, and the like. In particular, since the initial temperature of the formation of the combustible gas derived from the fatty acid and the non-combustible gas generated in the decomposition of melamine cyanurate at the time of combustion of the alkali metal or alkaline earth metal salt of stearic acid is the same, the deterioration of flame retardancy due to the addition does not occur, and the releasability can be improved, which is most preferable.
The mixing amount (content) of the fatty acid metal salt lubricant (E) is 0.1 to 1 part by mass based on 100 parts by mass of the total of the polyamide resin (A) and the melamine cyanurate (B). If the amount exceeds 1 part by mass, the flame retardancy may be lowered. The mixing amount of the fatty acid metal salt lubricant (E) is preferably 0.2 to 0.8 parts by mass.
[ other Components ]
In addition to the above-mentioned components (a), (B), (C), (D) and (E), other components, for example, colorants such as pigments and dyes, heat stabilizers, weather resistance improvers, nucleating agents, plasticizers, mold release agents, additives such as antistatic agents, other resin polymers and the like may be added to the flame-retardant polyamide resin composition of the present invention within a range that does not impair the object of the present invention. In the flame retardant polyamide resin composition of the present invention, the total of the components (a), (B), (C), (D) and (E) is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more.
The molded parts which are suitably obtained by using the flame-retardant polyamide resin composition of the present invention are molded parts used for, in particular, connectors, bobbins (coil bobbins), circuit breakers (breakers), electromagnetic switches, holders (holders), plugs, sockets, switches, cases, covers, etc. in the fields of electric/electronic parts, automobile parts, etc., more specifically, molded parts requiring thermal discoloration resistance, fastening properties, such as ferrite core covers, SC locks, ties, electric wiring protection members, etc.
The method for producing the flame-retardant polyamide resin composition of the present invention is not particularly limited, and a general single-screw extruder, a twin-screw extruder, a pressure kneader, or the like can be used as the kneading apparatus, but a twin-screw extruder is particularly preferred in the present invention. As an embodiment, the above-mentioned (a), (B), (C), (D), (E), and pigment according to the use, etc. are mixed and fed into a twin-screw extruder. By uniformly kneading in a twin-screw extruder, a polyamide resin composition having high toughness and excellent flame retardancy can be obtained. The kneading temperature in the twin-screw extruder is preferably 220 to 300℃and the kneading time is preferably about 2 to 15 minutes.
Examples
Hereinafter, the present invention will be described in further detail by way of examples, but the present invention is not limited to these examples.
The following materials were used for each component.
Polyamide resin (A)
A1-1: polyamide 66 (RV=2.8) Vydyne 21Z (manufactured by Assnd Co., ltd.) with a melting point of 265 DEG C
A1-2: polyamide 66 (RV=2.4) EPR24 (manufactured by Shanghai Seama plastics technology Co., ltd.) with melting point 265 DEG C
A2-1: polyamide 6 (RV=2.0) M2000 (manufactured by MEIDA Co., ltd.) with a melting point of 225 DEG C
A2-2: polyamide 6 (RV=3.6) ZISAMIDE TP6603 (manufactured by Seisakusho Co., ltd.) with a melting point of 225 DEG C
Melamine cyanurate (B)
B: MC6000 (manufactured by Nissan chemical Co., ltd.)
Phosphorus antioxidant (C)
C: ADK STAB PEP-36 (manufactured by ADEKA Co., ltd.)
Hindered phenol antioxidant (D)
D: SONGNOX2450 (manufactured by SONGWON International Japan Co., ltd.)
Fatty acid metal salt lubricant (E)
E1: magnesium stearate n.p. -1500S (manufactured by light south chemical industry co., ltd.)
Other mold release agents:
e2: calcium montanate CS-8-CP (manufactured by Nito chemical industry Co., ltd.)
E3: fatty acid ester Licolab WE-40 (manufactured by Clariant Japan Co., ltd.)
Examples 1 to 12 and comparative examples 1 to 7
Evaluation samples were produced as follows: the respective raw materials were weighed in the mixing ratio shown in Table 1, and mixed by a tumbler (screw), and then fed into a twin-screw extruder. The set temperature of the twin-screw extruder is 250-300 ℃, and the mixing time is 5-10 minutes. The resulting pellets were molded into various evaluation samples by an injection molding machine. The barrel temperature of the injection molding machine was set at 250 to 280℃and the mold temperature was set at 80 ℃.
Various evaluation methods are shown below. The evaluation results are shown in Table 1.
1. Relative viscosity [ RV ] of Polyamide resin (98% sulfuric acid solution method)
The relative viscosity was measured at a concentration of 1g/dl of the polyamide resin in 98 mass% sulfuric acid solution at 25℃using an Ubbelohde viscometer.
2. Melting Point of Polyamide resin
The melting point was determined by measuring the temperature at a heating rate of 20℃per minute using a differential scanning calorimeter (Seiko Instruments EXSTAR 6000, inc.) and using the peak top temperature of the endothermic peak as the melting point.
3. Snap-fit (tensile strength, tensile elongation): the tensile strength (tensile strength) and the tensile elongation (tensile breaking strain) were determined based on IS 0527.
4. Combustibility: measured according to UL94, vertical burn test. V-0 represents the highest flame retardance.
5. Exudation: the 100mm X100 mm molded article having a thickness of 2mm was left to stand in a constant temperature and humidity tank set at a temperature of 80℃and a temperature of 95% RH for 96 hours, and the operation was repeated at least 2 times or more, and then the temperature was returned to room temperature, and the presence or absence of precipitate on the surface was visually confirmed under a solid microscope.
6. Thermochromic: the color difference (. DELTA.E) between the particles after 8 hours of standing in the oven at 120℃and the particles before treatment was calculated.
7. Formability: the mold was molded at the molding temperature using a mold equipped with a mold release force measuring device, and the mold release force from the 31 st injection to the 35 th injection was measured to obtain the mold release resistance.
Examples 1 to 12 have tensile strength equivalent to that of the typical polyamide 6 or 66 resins, and have tensile elongation of 5% or more, and even if they exceed the tensile yield point, they are not broken and do not undergo severe embrittlement, so that it is expected to have good fastening properties. Of the flame retardancy at thicknesses of 0.4, 0.8, 1.6, and 3.0mm, examples 1 to 12 also achieved UL94V-0 evaluation, indicating high flame retardancy at a wide range of thicknesses. In the thermochromatic properties, it was also found that the ΔE after 8 hours at 120℃in examples 1 to 12 was 20 or less, and the discoloration in the hot environment was suppressed. In the evaluation of moldability, the resistance value at the time of demolding of the molded article was 1MPa or less, and even if continuous molding was performed, the molded article was formed into a composition having a low possibility of causing deformation and blocking during demolding.
On the other hand, although comparative examples 1 to 7 partially satisfy the characteristics, comparative example 1 was evaluated as UL 94V-2 in terms of flame retardancy at thicknesses of 0.4, 0.8, 1.6, and 3.0mm, and the flame retardancy was greatly lowered, so that it was not preferable. The tensile strength of comparative example 2 was 3%, and embrittlement could not be suppressed, which was not preferable. Comparative example 3 was not preferable because the tensile strength was 3% except that the flame retardancy at thicknesses of 0.4, 0.8, 1.6 and 3.0mm was evaluated as UL 94V-2, and it was difficult to say that the flame retardancy and the snap-fit property were both sufficient. The flame retardancy of comparative examples 4, 5 and 7 was evaluated as UL 94V-2 at thicknesses of 0.8, 1.6 and 3.0mm, and it was difficult to say that the flame retardancy was high at a wide range of thicknesses, so that it was not preferable. In addition, comparative example 7, in which the mold release resistance as an index of moldability exceeded 1MPa, was not satisfactory in terms of moldability. Finally, comparative example 6 was not preferable because it was difficult to say that the flame retardancy at a thickness of 0.8, 1.6 and 3.0mm was evaluated as UL 94V-2, and the tensile strength was 3%.
Industrial applicability
The flame retardant polyamide resin composition of the present invention has a wide range of product thicknesses and is suitable for molded products having a hinge portion. The molded article obtained has high flame retardancy over a wide range of product thicknesses and is excellent in fastening properties, and therefore can be preferably used for electric/electronic parts, automobile parts, and the like, which are expected to have both high flame retardancy and fastening properties.
Claims (4)
1. A flame retardant polyamide resin composition comprising a polyamide resin (A) and a melamine cyanurate (B), wherein the polyamide resin (A) comprises, relative to 100 parts by mass of the total of the components (A) and (B), 90 to 98 parts by mass of the polyamide resin (A), 2 to 10 parts by mass of the melamine cyanurate (B), 0.01 to 1 part by mass of a phosphorus antioxidant (C), 0.01 to 1 part by mass of a hindered phenol antioxidant (D) and 0.1 to 1 part by mass of a fatty acid metal salt lubricant (E) having 22 or less carbon atoms, and the polyamide resin (A) comprises 55 to 85% by mass of the polyamide 66 resin (A1) and 15 to 45% by mass of the polyamide 6 resin (A2).
2. The flame retardant polyamide resin composition according to claim 1, wherein said fatty acid metal salt lubricant (E) is a metal salt of stearic acid.
3. A molded article comprising the flame retardant polyamide resin composition according to claim 1 or 2.
4. The molded article according to claim 3, which is any one of a ferrite core cover, an SC lock, a tie, and a harness protection member.
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| PCT/JP2022/001087 WO2022158383A1 (en) | 2021-01-22 | 2022-01-14 | Flame-retardant polyamide resin composition and molded article comprising same |
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| JPS62195043A (en) * | 1986-02-21 | 1987-08-27 | Mitsubishi Chem Ind Ltd | Flame-retardant polyamide resin composition |
| CN108795037B (en) * | 2018-06-21 | 2020-11-17 | 广东聚石化学股份有限公司 | Ultraviolet-resistant halogen-free flame-retardant nylon composition for fasteners and preparation method thereof |
| WO2021044880A1 (en) * | 2019-09-02 | 2021-03-11 | 東洋紡株式会社 | Flame-retardant polyamide resin composition and molded article comprising same |
-
2022
- 2022-01-14 WO PCT/JP2022/001087 patent/WO2022158383A1/en active Application Filing
- 2022-01-14 CN CN202280009842.6A patent/CN116724079A/en active Pending
- 2022-01-14 JP JP2022576644A patent/JPWO2022158383A1/ja active Pending
- 2022-01-17 TW TW111101800A patent/TW202237744A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| TW202237744A (en) | 2022-10-01 |
| WO2022158383A1 (en) | 2022-07-28 |
| JPWO2022158383A1 (en) | 2022-07-28 |
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