JP2007023207A - Flame-retardant polyamide resin composition - Google Patents
Flame-retardant polyamide resin composition Download PDFInfo
- Publication number
- JP2007023207A JP2007023207A JP2005209679A JP2005209679A JP2007023207A JP 2007023207 A JP2007023207 A JP 2007023207A JP 2005209679 A JP2005209679 A JP 2005209679A JP 2005209679 A JP2005209679 A JP 2005209679A JP 2007023207 A JP2007023207 A JP 2007023207A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- polyamide resin
- flame
- metal
- resin composition
- 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 57
- 239000003063 flame retardant Substances 0.000 title claims abstract description 49
- 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 45
- 239000011342 resin composition Substances 0.000 title claims abstract description 32
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 26
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- 239000012779 reinforcing material Substances 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 7
- 239000011575 calcium Substances 0.000 claims abstract description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 6
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 5
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 5
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 32
- 229920000877 Melamine resin Polymers 0.000 claims description 29
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 29
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 14
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 13
- 239000000194 fatty acid Substances 0.000 claims description 13
- 229930195729 fatty acid Natural products 0.000 claims description 13
- 150000004665 fatty acids Chemical class 0.000 claims description 13
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 claims description 11
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 6
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 4
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 4
- 125000006832 (C1-C10) alkylene group Chemical group 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 abstract description 16
- 239000007789 gas Substances 0.000 abstract description 11
- 238000001125 extrusion Methods 0.000 abstract description 7
- 239000012433 hydrogen halide Substances 0.000 abstract description 6
- 229910000039 hydrogen halide Inorganic materials 0.000 abstract description 6
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 abstract description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 abstract description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract 1
- 229910052749 magnesium Inorganic materials 0.000 abstract 1
- 239000011777 magnesium Substances 0.000 abstract 1
- 150000003751 zinc Chemical class 0.000 abstract 1
- 239000000047 product Substances 0.000 description 43
- 239000008188 pellet Substances 0.000 description 31
- 238000000465 moulding Methods 0.000 description 22
- 238000000034 method Methods 0.000 description 20
- 238000012360 testing method Methods 0.000 description 19
- 239000004952 Polyamide Substances 0.000 description 17
- 229920002647 polyamide Polymers 0.000 description 17
- 235000011007 phosphoric acid Nutrition 0.000 description 15
- 229920002302 Nylon 6,6 Polymers 0.000 description 13
- 238000002845 discoloration Methods 0.000 description 13
- 239000003365 glass fiber Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 239000002994 raw material Substances 0.000 description 13
- 239000000835 fiber Substances 0.000 description 12
- 238000002485 combustion reaction Methods 0.000 description 11
- 238000000691 measurement method Methods 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 229920000388 Polyphosphate Polymers 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 239000001205 polyphosphate Substances 0.000 description 9
- 235000011176 polyphosphates Nutrition 0.000 description 9
- 229920000137 polyphosphoric acid Polymers 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 8
- 238000004898 kneading Methods 0.000 description 8
- -1 polycyclic compound Chemical class 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000004953 Aliphatic polyamide Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229920003231 aliphatic polyamide Polymers 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000012760 heat stabilizer Substances 0.000 description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000005452 bending Methods 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229920006123 polyhexamethylene isophthalamide Polymers 0.000 description 5
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 4
- 229920002292 Nylon 6 Polymers 0.000 description 4
- 239000001361 adipic acid Substances 0.000 description 4
- 235000011037 adipic acid Nutrition 0.000 description 4
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- FUSNPOOETKRESL-ZPHPHTNESA-N (z)-n-octadecyldocos-13-enamide Chemical compound CCCCCCCCCCCCCCCCCCNC(=O)CCCCCCCCCCC\C=C/CCCCCCCC FUSNPOOETKRESL-ZPHPHTNESA-N 0.000 description 3
- KSNGEYQWLMRSIR-UHFFFAOYSA-L 2-hydroxypropanoate;manganese(2+) Chemical compound [Mn+2].CC(O)C([O-])=O.CC(O)C([O-])=O KSNGEYQWLMRSIR-UHFFFAOYSA-L 0.000 description 3
- XSAOTYCWGCRGCP-UHFFFAOYSA-K aluminum;diethylphosphinate Chemical compound [Al+3].CCP([O-])(=O)CC.CCP([O-])(=O)CC.CCP([O-])(=O)CC XSAOTYCWGCRGCP-UHFFFAOYSA-K 0.000 description 3
- 239000008116 calcium stearate Substances 0.000 description 3
- 235000013539 calcium stearate Nutrition 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229940005657 pyrophosphoric acid Drugs 0.000 description 3
- 229920001897 terpolymer Polymers 0.000 description 3
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-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
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 2
- GVNWZKBFMFUVNX-UHFFFAOYSA-N Adipamide Chemical compound NC(=O)CCCCC(N)=O GVNWZKBFMFUVNX-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 239000005749 Copper compound Substances 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229920000305 Nylon 6,10 Polymers 0.000 description 2
- 229920006121 Polyxylylene adipamide Polymers 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- QVKQNISQFCPYGN-UHFFFAOYSA-K aluminum;dimethylphosphinate Chemical compound [Al+3].CP(C)([O-])=O.CP(C)([O-])=O.CP(C)([O-])=O QVKQNISQFCPYGN-UHFFFAOYSA-K 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- DONULGYRZAGJQH-UHFFFAOYSA-L calcium;dimethylphosphinate Chemical compound [Ca+2].CP(C)([O-])=O.CP(C)([O-])=O DONULGYRZAGJQH-UHFFFAOYSA-L 0.000 description 2
- BFKPORWCVZVLTQ-UHFFFAOYSA-L calcium;ethyl(methyl)phosphinate Chemical compound [Ca+2].CCP(C)([O-])=O.CCP(C)([O-])=O BFKPORWCVZVLTQ-UHFFFAOYSA-L 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 150000001880 copper compounds Chemical class 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- KTLIMPGQZDZPSB-UHFFFAOYSA-N diethylphosphinic acid Chemical compound CCP(O)(=O)CC KTLIMPGQZDZPSB-UHFFFAOYSA-N 0.000 description 2
- GOJNABIZVJCYFL-UHFFFAOYSA-N dimethylphosphinic acid Chemical compound CP(C)(O)=O GOJNABIZVJCYFL-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-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
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- SZTJCIYEOQYVED-UHFFFAOYSA-N methyl(propyl)phosphinic acid Chemical compound CCCP(C)(O)=O SZTJCIYEOQYVED-UHFFFAOYSA-N 0.000 description 2
- BCDIWLCKOCHCIH-UHFFFAOYSA-N methylphosphinic acid Chemical compound CP(O)=O BCDIWLCKOCHCIH-UHFFFAOYSA-N 0.000 description 2
- VMRGZRVLZQSNHC-ZCXUNETKSA-N n-[(z)-octadec-9-enyl]hexadecanamide Chemical compound CCCCCCCCCCCCCCCC(=O)NCCCCCCCC\C=C/CCCCCCCC VMRGZRVLZQSNHC-ZCXUNETKSA-N 0.000 description 2
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 description 2
- 229920006128 poly(nonamethylene terephthalamide) Polymers 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 150000003112 potassium compounds Chemical class 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 150000003388 sodium compounds Chemical class 0.000 description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 2
- KOUDKOMXLMXFKX-UHFFFAOYSA-N sodium oxido(oxo)phosphanium hydrate Chemical compound O.[Na+].[O-][PH+]=O KOUDKOMXLMXFKX-UHFFFAOYSA-N 0.000 description 2
- YKIBJOMJPMLJTB-UHFFFAOYSA-M sodium;octacosanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O YKIBJOMJPMLJTB-UHFFFAOYSA-M 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- GTOWTBKGCUDSNY-UHFFFAOYSA-K tris[[ethyl(methyl)phosphoryl]oxy]alumane Chemical compound [Al+3].CCP(C)([O-])=O.CCP(C)([O-])=O.CCP(C)([O-])=O GTOWTBKGCUDSNY-UHFFFAOYSA-K 0.000 description 2
- 239000003039 volatile agent Substances 0.000 description 2
- MXMCTPBQIJWVBA-UHFFFAOYSA-L zinc;dimethylphosphinate Chemical compound [Zn+2].CP(C)([O-])=O.CP(C)([O-])=O MXMCTPBQIJWVBA-UHFFFAOYSA-L 0.000 description 2
- GYKKGOMJFMCRIN-UHFFFAOYSA-L zinc;ethyl(methyl)phosphinate Chemical compound [Zn+2].CCP(C)([O-])=O.CCP(C)([O-])=O GYKKGOMJFMCRIN-UHFFFAOYSA-L 0.000 description 2
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical class O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- OECUQWQIGXMPAN-UHFFFAOYSA-N 6-oxo-6-pyrrolidin-1-ylhexanamide Chemical compound NC(=O)CCCCC(=O)N1CCCC1 OECUQWQIGXMPAN-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- MTRJEAWGWLYPNB-CVBJKYQLSA-N C(CCCCCCCCCCC\C=C/CCCCCCCC)(=O)O.C(CCCCCCCCCCC\C=C/CCCCCCCC)(=O)O.C=C Chemical compound C(CCCCCCCCCCC\C=C/CCCCCCCC)(=O)O.C(CCCCCCCCCCC\C=C/CCCCCCCC)(=O)O.C=C MTRJEAWGWLYPNB-CVBJKYQLSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-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
- 229920000572 Nylon 6/12 Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- JVZQHCPKAARJDJ-UHFFFAOYSA-N [Ca].CP(O)=O Chemical compound [Ca].CP(O)=O JVZQHCPKAARJDJ-UHFFFAOYSA-N 0.000 description 1
- IHSZURPWPOXDOF-UHFFFAOYSA-N [PH2](O)=O.C(C)[Ca]CC Chemical compound [PH2](O)=O.C(C)[Ca]CC IHSZURPWPOXDOF-UHFFFAOYSA-N 0.000 description 1
- MWKGOHCHXBLCSH-UHFFFAOYSA-L [Zn+2].CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O MWKGOHCHXBLCSH-UHFFFAOYSA-L 0.000 description 1
- JSUGOWMJYAUSGT-UHFFFAOYSA-N [Zn].CP(O)=O Chemical compound [Zn].CP(O)=O JSUGOWMJYAUSGT-UHFFFAOYSA-N 0.000 description 1
- YDHWWBZFRZWVHO-UHFFFAOYSA-N [hydroxy(phosphonooxy)phosphoryl] phosphono hydrogen phosphate Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(=O)OP(O)(O)=O YDHWWBZFRZWVHO-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 1
- AZBWLPLVVUOKPE-UHFFFAOYSA-K aluminum methyl(phenyl)phosphinate Chemical compound [Al+3].CP([O-])(=O)c1ccccc1.CP([O-])(=O)c1ccccc1.CP([O-])(=O)c1ccccc1 AZBWLPLVVUOKPE-UHFFFAOYSA-K 0.000 description 1
- 229940063655 aluminum stearate Drugs 0.000 description 1
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 1
- QNNHFEIZWVGBTM-UHFFFAOYSA-K aluminum;diphenylphosphinate Chemical compound [Al+3].C=1C=CC=CC=1P(=O)([O-])C1=CC=CC=C1.C=1C=CC=CC=1P(=O)([O-])C1=CC=CC=C1.C=1C=CC=CC=1P(=O)([O-])C1=CC=CC=C1 QNNHFEIZWVGBTM-UHFFFAOYSA-K 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QFNNDGVVMCZKEY-UHFFFAOYSA-N azacyclododecan-2-one Chemical compound O=C1CCCCCCCCCCN1 QFNNDGVVMCZKEY-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- SIDITURPCILNEG-UHFFFAOYSA-L calcium;diphenylphosphinate Chemical compound [Ca+2].C=1C=CC=CC=1P(=O)([O-])C1=CC=CC=C1.C=1C=CC=CC=1P(=O)([O-])C1=CC=CC=C1 SIDITURPCILNEG-UHFFFAOYSA-L 0.000 description 1
- UUAUGMXREUNBAY-UHFFFAOYSA-L calcium;methyl(phenyl)phosphinate Chemical compound [Ca+2].CP([O-])(=O)C1=CC=CC=C1.CP([O-])(=O)C1=CC=CC=C1 UUAUGMXREUNBAY-UHFFFAOYSA-L 0.000 description 1
- VBUWHUGIXLGHTR-UHFFFAOYSA-L calcium;methyl(propyl)phosphinate Chemical compound [Ca+2].CCCP(C)([O-])=O.CCCP(C)([O-])=O VBUWHUGIXLGHTR-UHFFFAOYSA-L 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
- 239000004917 carbon fiber Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- BEQVQKJCLJBTKZ-UHFFFAOYSA-N diphenylphosphinic acid Chemical compound C=1C=CC=CC=1P(=O)(O)C1=CC=CC=C1 BEQVQKJCLJBTKZ-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- SWSBIGKFUOXRNJ-CVBJKYQLSA-N ethene;(z)-octadec-9-enamide Chemical compound C=C.CCCCCCCC\C=C/CCCCCCCC(N)=O.CCCCCCCC\C=C/CCCCCCCC(N)=O SWSBIGKFUOXRNJ-CVBJKYQLSA-N 0.000 description 1
- NXHKQBCTZHECQF-UHFFFAOYSA-N ethyl(methyl)phosphinic acid Chemical compound CCP(C)(O)=O NXHKQBCTZHECQF-UHFFFAOYSA-N 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000007706 flame test Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VKHLCNWQYFQMLQ-UHFFFAOYSA-M lithium octacosanoate Chemical compound [Li+].CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O VKHLCNWQYFQMLQ-UHFFFAOYSA-M 0.000 description 1
- HGPXWXLYXNVULB-UHFFFAOYSA-M lithium stearate Chemical compound [Li+].CCCCCCCCCCCCCCCCCC([O-])=O HGPXWXLYXNVULB-UHFFFAOYSA-M 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- ARIXXGBZIGZIKW-UHFFFAOYSA-L magnesium dioxidophosphanium Chemical compound [Mg++].[O-][PH2]=O.[O-][PH2]=O ARIXXGBZIGZIKW-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910001381 magnesium hypophosphite Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- HHYXZVYUIJDJAH-UHFFFAOYSA-L magnesium;diethylphosphinate Chemical compound [Mg+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC HHYXZVYUIJDJAH-UHFFFAOYSA-L 0.000 description 1
- MKNUZASDTKBRNE-UHFFFAOYSA-L magnesium;dimethylphosphinate Chemical compound [Mg+2].CP(C)([O-])=O.CP(C)([O-])=O MKNUZASDTKBRNE-UHFFFAOYSA-L 0.000 description 1
- SKBBZECXICKFJD-UHFFFAOYSA-L magnesium;ethyl(methyl)phosphinate Chemical compound [Mg+2].CCP(C)([O-])=O.CCP(C)([O-])=O SKBBZECXICKFJD-UHFFFAOYSA-L 0.000 description 1
- YCDWDGJOBAYTDW-UHFFFAOYSA-L magnesium;methyl(phenyl)phosphinate Chemical compound [Mg+2].CP([O-])(=O)C1=CC=CC=C1.CP([O-])(=O)C1=CC=CC=C1 YCDWDGJOBAYTDW-UHFFFAOYSA-L 0.000 description 1
- SSJHRSPSQJENCV-UHFFFAOYSA-L magnesium;methyl(propyl)phosphinate Chemical compound [Mg+2].CCCP(C)([O-])=O.CCCP(C)([O-])=O SSJHRSPSQJENCV-UHFFFAOYSA-L 0.000 description 1
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- RMJCJLHZCBFPDN-UHFFFAOYSA-N methyl(phenyl)phosphinic acid Chemical compound CP(O)(=O)C1=CC=CC=C1 RMJCJLHZCBFPDN-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- XZTOTRSSGPPNTB-UHFFFAOYSA-N phosphono dihydrogen phosphate;1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N)=N1.OP(O)(=O)OP(O)(O)=O XZTOTRSSGPPNTB-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920006027 ternary co-polymer Polymers 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- DJZKNOVUNYPPEE-UHFFFAOYSA-N tetradecane-1,4,11,14-tetracarboxamide Chemical group NC(=O)CCCC(C(N)=O)CCCCCCC(C(N)=O)CCCC(N)=O DJZKNOVUNYPPEE-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VLCLHFYFMCKBRP-UHFFFAOYSA-N tricalcium;diborate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]B([O-])[O-].[O-]B([O-])[O-] VLCLHFYFMCKBRP-UHFFFAOYSA-N 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
- NFMWFGXCDDYTEG-UHFFFAOYSA-N trimagnesium;diborate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]B([O-])[O-].[O-]B([O-])[O-] NFMWFGXCDDYTEG-UHFFFAOYSA-N 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- 229940048102 triphosphoric acid Drugs 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
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- PJEUXMXPJGWZOZ-UHFFFAOYSA-L zinc;diphenylphosphinate Chemical compound [Zn+2].C=1C=CC=CC=1P(=O)([O-])C1=CC=CC=C1.C=1C=CC=CC=1P(=O)([O-])C1=CC=CC=C1 PJEUXMXPJGWZOZ-UHFFFAOYSA-L 0.000 description 1
- WMLXDIOQDFWKAO-UHFFFAOYSA-L zinc;methyl(phenyl)phosphinate Chemical compound [Zn+2].CP([O-])(=O)C1=CC=CC=C1.CP([O-])(=O)C1=CC=CC=C1 WMLXDIOQDFWKAO-UHFFFAOYSA-L 0.000 description 1
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、電気・電子分野のコネクター、ブレーカー、マグネットスイッチ等の部品、自動車分野の電装部品等の部品材料に好適に用いられる難燃性ポリアミド樹脂組成物に関する。とりわけ、本発明は燃焼時に高いハロゲン化水素ガスの発生がなく、薄肉難燃性、電気特性、押出加工性、離型性、流動性等の成形加工性、機械特性が優れており、更に成形品の高温での付着物量が抑制された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 / electronic field connectors, breakers, magnet switches, and other parts, and automotive parts. In particular, the present invention does not generate high hydrogen halide gas at the time of combustion, and has excellent thin film flame retardancy, electrical characteristics, extrusion processability, mold release characteristics, fluidity and other molding processability and mechanical characteristics, and further molding. The present invention relates to a flame retardant polyamide resin composition in which the amount of deposits at a high temperature of the product is suppressed.
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やトリアジン系難燃剤を添加する方法が取られている。 Conventionally, polyamide resins have been used in fields such as automobile parts, mechanical parts, and electric / electronic parts because they are excellent in mechanical strength and heat resistance. 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 flame retardant or a triazine 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。特にこれらハロゲン系難燃剤をガラス繊維等で強化したポリアミド樹脂に配合した組成物は高度の難燃性と高い剛性から、 電気・電子部品用途、特にプリント積層板に搭載されたり接続されたりするコネクター用途に多用されてきた。しかしながら、ハロゲン系難燃剤は難燃性を向上させる一方、射出成形などの加熱加工時に、ハロゲン化水素を発生し、金型のＭＤ、または腐食する問題があった。また、ハロゲン系難燃剤と併用されるアンチモン化合物も難燃性を向上させる一方、電気・電子用途に必要な電気特性（耐トラッキング性）を大きく低下させる問題があった。 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, compositions containing these halogen-based flame retardants in polyamide resins reinforced with glass fibers, etc. are highly flame retardant and have high rigidity, so they can be mounted on or connected to printed laminates, especially for electrical and electronic parts. Has been used extensively in applications. However, while the halogen flame retardant improves flame retardancy, there is a problem in that hydrogen halide is generated during heat processing such as injection molding, and mold MD or corrosion occurs. In addition, the antimony compound used in combination with the halogen-based flame retardant also has a problem of greatly reducing the electrical properties (tracking resistance) necessary for electrical and electronic applications while improving the flame retardancy.
このことから、ハロゲンフリーのトリアジン系難燃剤が注目され数多く検討がなされている。例えば難燃剤としてメラミンを使用する技術（例えば、特許文献８）、シアヌル酸を使用する技術（例えば、特許文献９）、シアヌル酸メラミンを使用する技術（例えば、特許文献１０）が良く知られている。これらの技術で得られた非強化のポリアミド樹脂組成物はＵＬ９４Ｖ−０規格に適合する高度の難燃レベルを有するものの、ガラス繊維等の無機強化材で強化し剛性を高めた組成においては、難燃剤を多量に配合した場合であっても、燃焼時、綿着火現象があり、ＵＬ９４Ｖ−０規格に適合しない問題がある。 For this reason, halogen-free triazine flame retardants have attracted attention and many studies have been made. For example, a technique using melamine as a flame retardant (for example, Patent Document 8), a technique using cyanuric acid (for example, Patent Document 9), and a technique using melamine cyanurate (for example, Patent Document 10) are well known. Yes. Although the non-reinforced polyamide resin composition obtained by these techniques has a high flame retardant level conforming to the UL94V-0 standard, it is difficult to use a composition reinforced with an inorganic reinforcing material such as glass fiber to increase rigidity. Even when a large amount of a flame retardant is blended, there is a problem of cotton ignition during combustion, and there is a problem that it does not conform to the UL94V-0 standard.
一方、イントメッセント型難燃剤であるリン酸メラミン、ピロリン酸メラミンあるいはポリリン酸メラミンをガラス繊維強化ポリアミド樹脂に使用するハロゲンフリーの難燃技術（例えば、特許文献１１）、無機質強化ポリアミド樹脂にポリリン酸メラミンに加えチャー化触媒及び／又はチャー形成剤を併用する難燃技術（例えば、特許文献１２）が公開されている。これらの技術で得られたガラス繊維強化のポリアミド樹脂組成物は、１／３２ｉｎｃｈの薄肉成形品においても難燃規格ＵＬ９４Ｖ−０規格を満足するが、そのためには難燃剤を多く用いる必要があるため、ポリアミド樹脂が持つ優れた機械特性（特に曲げ撓み等の靭性）や電気特性（耐トラッキング性）を大きく低下させてしまう。そのため、高い靭性や高い電気特性が必要となる一部の電気・電子部品用の成形材料として十分に満足されるものではなかった。また、押出加工性、成型加工性、流動性、離型性も十分で
はなかった。
On the other hand, halogen-free flame retardant technology (for example, Patent Document 11) using melamine phosphate, melamine pyrophosphate or melamine polyphosphate, which is an intumescent flame retardant, as a glass fiber reinforced polyamide resin, polyphosphoric acid as an inorganic reinforced polyamide resin. A flame retardant technique (for example, Patent Document 12) using a charification catalyst and / or a char-forming agent in addition to melamine acid is disclosed. The glass fiber reinforced polyamide resin composition obtained by these techniques satisfies the flame retardancy standard UL94V-0 even in 1/32 inch thin-walled molded products, but for that purpose, it is necessary to use a large amount of flame retardant. The excellent mechanical properties (particularly toughness such as bending deflection) and electrical properties (tracking resistance) of the polyamide resin are greatly reduced. Therefore, it has not been fully satisfied as a molding material for some electrical / electronic components that require high toughness and high electrical characteristics. Further, the extrusion processability, molding processability, fluidity, and releasability were not sufficient.
さらには、ホスフィン酸塩と（メラミンとリン酸の反応物）を組み合わせた難燃剤コンビネーション技術（例えば、特許文献１３、特許文献１４）が提案され、１／１６ｉｎｃｈの成形品において難燃規格ＵＬ９４Ｖ−０規格を満足することが知られている。この技術では、二種以上の難燃剤による相乗効果のために、難燃剤を減量することが可能になり、機械特性（特に曲げ撓み等の靭性）、電気特性（耐トラッキング性）の改良ができる。しかし、成形時の流動性や離型性等の改良には効果があまりない。さらに、成形品の高温での付着物の量が多いという点で満足できるものではなかった。尚、ここでいう成形品の高温での付着物とは、成形品が高温、例えば１２０℃下に長時間さらされると、該成形品から揮発物が発生し、これが冷却面と接触すると析出して白く曇った表面を形成する現象で、例えば、内部が高温で、外部の透明筐体が外気にさらされているような電気・電子用途に使用する場合には、内部の部品から揮発物が発生し、透明筐体の内部に析出物が着くので、見た目の点で満足できなかった。 Furthermore, a flame retardant combination technique (for example, Patent Document 13 and Patent Document 14) in which a phosphinic acid salt and a reaction product of melamine and phosphoric acid are combined is proposed, and a flame retardant standard UL94V- It is known to satisfy the 0 standard. With this technology, due to the synergistic effect of two or more flame retardants, it is possible to reduce the amount of the flame retardant and improve mechanical properties (particularly toughness such as bending deflection) and electrical properties (tracking resistance). . However, it is not very effective in improving fluidity and mold release during molding. Furthermore, it was not satisfactory in that the amount of deposits at a high temperature of the molded product was large. Incidentally, the high-temperature deposit on the molded product referred to here means that when the molded product is exposed to a high temperature, for example, 120 ° C. for a long time, volatiles are generated from the molded product, and this deposits when it contacts the cooling surface. A phenomenon that forms a white and cloudy surface.For example, when used in electrical / electronic applications where the internal temperature is high and the external transparent housing is exposed to the outside air, volatiles are generated from the internal components. It occurred and deposits were deposited inside the transparent casing, which was not satisfactory in terms of appearance.
本発明の目的は、燃焼時にハロゲン化水素ガスの発生がなく、薄肉難燃性、電気特性、押出加工性、離型性、流動性等の成形加工性、機械特性が優れており、更に成形品の高温での付着物量が抑制された難燃性ポリアミド樹脂組成物を提供することにある。 The purpose of the present invention is that hydrogen halide gas is not generated during combustion, and has excellent thin film flame retardancy, electrical properties, extrusion processability, mold release properties, fluidity, and other molding processability and mechanical properties. An object of the present invention is to provide a flame retardant polyamide resin composition in which the amount of deposits at a high temperature of the product is suppressed.
本発明者は、上記課題を解決するため鋭意検討を重ねた結果、ポリアミド樹脂、ホスフィン酸塩、メラミンとリン酸とから形成される付加物、金属化合物とから形成される付加物の系に、炭素−炭素不飽和結合を含む脂肪酸アミドを適用した際に、前記目的を達成しうることを見いだし、この知見に基づき本発明を完成するに至った。即ち、本発明は以下のとおりである。
本発明の第１は、（ａ）ポリアミド樹脂２４〜８０重量％、（ｂ）強化材０〜６０重量％、（ｃ）以下の式（Ｉ）で表されるホスフィン酸塩及び／又は以下の式（ＩＩ）で表されるジホスフィン酸塩１〜３０重量％、（ｄ）メラミンとリン酸とから形成される付加物１〜３０重量％、（ｅ）金属酸化物、金属水酸化物、炭酸金属塩、ホウ酸金属塩から選択される１種以上の金属化合物０．１〜１０重量％、（ｆ）（ｂ）〜（ｅ）成分以外の金属化合物が、０．００１〜０．０５重量％の各成分からなり、合計が１００重量％になる難燃性ポリアミド樹脂組成物、
As a result of intensive studies in order to solve the above problems, the present inventor has obtained a polyamide resin, a phosphinate, an adduct formed from melamine and phosphoric acid, an adduct formed from a metal compound, It has been found that the above object can be achieved when a fatty acid amide containing a carbon-carbon unsaturated bond is applied, and the present invention has been completed based on this finding. That is, the present invention is as follows.
The first of the present invention is (a) polyamide resin 24 to 80% by weight, (b) reinforcing material 0 to 60% by weight, (c) phosphinic acid salt represented by the following formula (I) and / or 1 to 30% by weight of a diphosphinate represented by the formula (II), (d) 1 to 30% by weight of an adduct formed from melamine and phosphoric acid, (e) a metal oxide, a metal hydroxide, carbonic acid 0.1 to 10% by weight of one or more metal compounds selected from metal salts and metal salts of boric acid, and metal compounds other than the components (f) (b) to (e) are 0.001 to 0.05% by weight. % Flame retardant polyamide resin composition comprising a total of 100% by weight,
本発明の第２は、さらに、（ｇ）炭素−炭素不飽和結合を含む脂肪酸アミド０．０１〜１重量％を含むことを特徴とする請求項１に記載の難燃性ポリアミド樹脂組成物、
本発明の第３は、本発明の第１又は２に記載の難燃性ポリアミド樹脂組成物からなる成形品、
本発明の第４は、本発明の第１又は２に記載の難燃性ポリアミド樹脂組成物から成形された電気・電子用途部品である。
The second of the present invention further comprises (g) 0.01 to 1% by weight of a fatty acid amide containing a carbon-carbon unsaturated bond,
3rd of this invention is a molded article which consists of a flame-retardant polyamide resin composition as described in 1 or 2 of this invention,
A fourth aspect of the present invention is an electric / electronic application part molded from the flame retardant polyamide resin composition according to the first or second aspect of the present invention.
本発明によれば、燃焼時にハロゲン化水素ガスの発生がなく、薄肉難燃性、電気特性、押出加工性、離型性、流動性等の成形加工性、機械特性が優れており、更に成形品の高温での付着物量が抑制された難燃性ポリアミド樹脂組成物を提供できる。 According to the present invention, there is no generation of hydrogen halide gas at the time of combustion, and thin film flame retardancy, electrical properties, extrusion processability, mold release properties, fluidity and other molding processability and mechanical properties are excellent, and molding The flame-retardant polyamide resin composition in which the amount of deposits at a high temperature of the product is suppressed can be provided.
以下、本発明の内容を詳細に説明する。
本発明の（ａ）ポリアミド樹脂としては、例えば、ジカルボン酸とジアミンとの重縮合物、環状ラクタムの開環重合物、アミノカルボン酸の重縮合物などが挙げられ、具体的にはポリ（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（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。
Hereinafter, the contents of the present invention will be described in detail.
Examples of the (a) polyamide resin of the present invention include polycondensates of dicarboxylic acids and diamines, ring-opening polymers of cyclic lactams, polycondensates of aminocarboxylic acids, and the like. Specific examples include poly (caprolactams). ) (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 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) Adipamide) (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 (tetramethyleneisophthalamide) (hereinafter abbreviated as polyamide 4I) and other aromatic components, and the above-mentioned aliphatic polyamides, polyamides containing aromatic components, and aliphatic polyamides and aromatics Mention may be made of polyamide copolymers and mixtures containing the components.
本発明により好ましいポリアミドは、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ので、融点が２４０℃以上で且つ２７０℃以下のポリアミド樹脂である。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、６６／６Ｉ／６Ｔ三元共重合ポリアミド、６６／６Ｉ／６三元共重合ポリアミドである。
最も好ましくは、成形性に加え、外観にも優れるイソフタル酸成分を含む、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る。具体的には、（１）ポリ（ヘキサメチレンアジパミド）単位６０〜９５重量％及びポリ（ヘキサメチレンイソフタルアミド）単位５〜４０重量％からなる共重合体；（２）ポリ（ヘキサメチレンアジパミド）単位５０〜９４重量％、ポリ（ヘキサメチレンイソフタルアミド）単位５〜４０重量％及びポリ（ヘキサメチレンアジパミド）以外の脂肪族ポリアミド単位１〜１０重量％からなる３元共重合体；（３）ポリ（ヘキサメチレンアジパミド）成分６０〜９５重量％及びポリ（ヘキサメチレンイソフタルアミド）成分５〜４０重量％を含有する混合ポリアミド；（４）ポリ（ヘキサメチレンアジパミド）成分５０〜９４重量％、ポリ（ヘキサメチレンイソフタルアミド）成分５〜４０重量％及びポリ（ヘキサメチレンアジパミド）以外の脂肪族ポリアミド成分１〜１０重量％を含有する混合ポリアミドが挙げられ、これらの芳香族成分を含むポリアミドは更に好ましい。また、上記（２）中のポリ（ヘキサメチレンアジパミド）以外の脂肪族ポリアミド単位及び（４）中のポリ（ヘキサメチレンアジパミド）以外の脂肪族ポリアミド成分としては、ポリ（カプロラクタム）即ちポリアミド６の単位及び成分などが挙げられる。
If the melting point of the polyamide preferred according to the present invention is too high, the flame retardant decomposes during melt processing and the gas component increases, so that melt processability is reduced. Moreover, since heat resistance, such as HDT in a molded article, will fall if melting | fusing point is too low, it is a polyamide resin whose melting | fusing point is 240 degreeC or more and 270 degrees C or less. For example, polyamide 66, polyamide MXD6, 66 / 6I copolymer polyamide, 66 / 6I / 6T terpolymer polyamide, 66 / 6I / 6 terpolymer polyamide.
Most preferred are 66 / 6I copolymer polyamide and 66 / 6I / 6 terpolymer polyamide containing an isophthalic acid component that is excellent in appearance as well as moldability. Specifically, (1) a copolymer comprising 60 to 95% by weight of poly (hexamethylene adipamide) units and 5 to 40% by weight of poly (hexamethylene isophthalamide) units; (2) poly (hexamethylene adipamide) A ternary copolymer comprising 50 to 94% by weight of a pamide) unit, 5 to 40% by weight of a poly (hexamethylene isophthalamide) unit, and 1 to 10% by weight of an aliphatic polyamide unit other than poly (hexamethylene adipamide). (3) mixed polyamide containing 60 to 95% by weight of poly (hexamethylene adipamide) component and 5 to 40% by weight of poly (hexamethylene isophthalamide) component; (4) poly (hexamethylene adipamide) component Fats other than 50-94% by weight, poly (hexamethylene isophthalamide) component 5-40% by weight and poly (hexamethylene adipamide) Include mixed polyamides containing 1 to 10 wt% family polyamide component, a polyamide containing these aromatic components is more preferred. The aliphatic polyamide unit other than poly (hexamethylene adipamide) in (2) and the aliphatic polyamide component other than poly (hexamethylene adipamide) in (4) include poly (caprolactam), Examples include units and components of polyamide 6.
本発明の（ｂ）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。
（ｂ）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燃焼時のドリップ抑制効果が高く、また、燃焼時に生成する不燃層（又は炭化層）強化を行い、発泡した不燃層（又は炭化層）の形状を維持し、高い難燃化を実現できるので好ましく使用される。
The reinforcing material (b) of the present invention is an optional component, and even if this component is not present, the object of the present invention is achieved, but this component is added to further improve flame retardancy and mechanical properties. can do.
(B) As reinforcing materials, 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, fired Examples thereof include fiber-like, granular, plate-like, or needle-like inorganic reinforcing materials such as 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 have a high drip suppression effect during combustion, and strengthen the incombustible layer (or carbonized layer) generated during combustion to maintain the shape of the foamed incombustible layer (or carbonized layer). It is preferably used because it can achieve high flame retardancy.
また、ガラス繊維は長繊維タイプのロービング、短繊維タイプのチョップドストランド、ミルドファイバー等から選択して用いることが出来る。ガラス繊維は表面処理した物を用いるのが好ましい。とりわけ、ガラス繊維を用いると、物性、難燃性に特に優れるため特に好ましい。そのなかでもガラス繊維の平均繊維径５〜３０μｍ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。
本発明の（ｃ）以下の式（Ｉ）で表されるホスフィン酸塩及び／又は以下の式（ＩＩ）で表されるジホスフィン酸塩（本明細書中では、ホスフィン酸塩と略記している）成分
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 it is particularly excellent in physical properties and flame retardancy. Among these, the average fiber diameter of the glass fiber is preferably 5 to 30 μm. Moreover, since the thing which processed the glass fiber surface for polyamide resins gave the outstanding physical property, it is still more preferable.
(C) The phosphinic acid salt represented by the following formula (I) and / or the diphosphinic acid salt represented by the following formula (II) (abbreviated as phosphinic acid salt in the present specification). )component
としては、ヨーロッパ特許出願公開第６９９７０８号公報や特開平０８−７３７２０号公報に記載されているように、ホスフィン酸と金属炭酸塩、金属水酸化物又は金属酸化物を用いて水溶液中で製造される。これらは、本質的にモノマー性化合物であるが、反応条件に依存して、環境によっては縮合度が１〜３のポリマー性ホスフィン酸塩も含まれる。
ホスフィン酸としては、ジメチルホスフィン酸、エチルメチルホスフィン酸、ジエチルホスフィン酸、メチル-n-プロピルホスフィン酸、メタンジ(メチルホスフィン酸)、ベンゼン−１，４−（ジメチルホスフィン酸）、メチルフェニルホスフィン酸及びジフェニルホスフィン酸等が挙げられる。
また金属成分としてはカルシウムイオン、マグネシウムイオン、アルミニウムイオン及び／又は亜鉛イオンを含む金属炭酸塩、金属水酸化物又は金属酸化物が挙げられる。
As described in European Patent Application Publication No. 699708 and Japanese Patent Application Laid-Open No. 08-73720, it is produced in an aqueous solution using phosphinic acid and metal carbonate, metal hydroxide or metal oxide. The These are essentially monomeric compounds, but depending on the reaction conditions, polymeric phosphinates having a degree of condensation of 1 to 3 are also included depending on the environment.
As phosphinic acid, dimethylphosphinic acid, ethylmethylphosphinic acid, diethylphosphinic acid, methyl-n-propylphosphinic acid, methandi (methylphosphinic acid), benzene-1,4- (dimethylphosphinic acid), methylphenylphosphinic acid and And diphenylphosphinic acid.
Examples of the metal component include metal carbonates, metal hydroxides or metal oxides containing calcium ions, magnesium ions, aluminum ions and / or zinc ions.
ホスフィン酸塩としてはジメチルホスフィン酸カルシウム、ジメチルホスフィン酸マグネシウム、ジメチルホスフィン酸アルミニウム、ジメチルホスフィン酸亜鉛、エチルメチルホスフィン酸カルシウム、エチルメチルホスフィン酸マグネシウム、エチルメチルホスフィン酸アルミニウム、エチルメチルホスフィン酸亜鉛、ジエチルホスフィン酸カルシウム、ジエチルホスフィン酸マグネシウム、ジエチルホスフィン酸アルミニウム、ジエチルホスフィン酸亜鉛、メチル−ｎ−プロピルホスフィン酸カルシウム、メチル−ｎ−プロピルホスフィン酸マグネシウム、メチル−ｎ−プロピルホスフィン酸アルミニウム、メチル−ｎ−プロピルホスフィン酸亜鉛、メタンジ（メチルホスフィン酸）カルシウム、メタンジ（メチルホスフィン酸）マグネシウム、メタンジ（メチルホスフィン酸）アルミニウム、メタンジ（メチルホスフィン酸）亜鉛、ベンゼン−１，４−（ジメチルホスフィン酸）カルシウム、ベンゼン−１，４−（ジメチルホスフィン酸）マグネシウム、ベンゼン−１，４−（ジメチルホスフィン酸）アルミニウム、ベンゼン−１，４−（ジメチルホスフィン酸）亜鉛、メチルフェニルホスフィン酸カルシウム、メチルフェニルホスフィン酸マグネシウム、メチルフェニルホスフィン酸アルミニウム、メチルフェニルホスフィン酸亜鉛、ジフェニルホスフィン酸カルシウム、ジフェニルホスフィン酸マグネシウム、ジフェニルホスフィン酸アルミニウム、ジフェニルホスフィン酸亜鉛が挙げられる。
特に難燃性、電気特性、ホスフィン酸合成の観点からジメチルホスフィン酸カルシウム、ジメチルホスフィン酸アルミニウム、ジメチルホスフィン酸亜鉛、エチルメチルホスフィン酸カルシウム、エチルメチルホスフィン酸アルミニウム、エチルメチルホスフィン酸亜鉛、ジエチルホスフィン酸カルシウム、ジエチルホスフィン酸アルミニウム、ジエチルホスフィン酸亜鉛が好ましい。
Phosphinates include calcium dimethylphosphinate, magnesium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, magnesium ethylmethylphosphinate, aluminum ethylmethylphosphinate, zinc ethylmethylphosphinate, diethyl Calcium phosphinate, magnesium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate, calcium methyl-n-propylphosphinate, magnesium methyl-n-propylphosphinate, methyl-n-propylphosphinate, methyl-n- Zinc propylphosphinate, methandi (methylphosphinic acid) calcium, methandi (methylphosphinic acid) mag Cium, methanedi (methylphosphinic acid) aluminum, methanedi (methylphosphinic acid) zinc, benzene-1,4- (dimethylphosphinic acid) calcium, benzene-1,4- (dimethylphosphinic acid) magnesium, benzene-1,4- (Dimethylphosphinic acid) aluminum, benzene-1,4- (dimethylphosphinic acid) zinc, calcium methylphenylphosphinate, magnesium methylphenylphosphinate, aluminum methylphenylphosphinate, zinc methylphenylphosphinate, calcium diphenylphosphinate, diphenyl Examples include magnesium phosphinate, aluminum diphenylphosphinate, and zinc diphenylphosphinate.
Calcium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, aluminum ethylmethylphosphinate, zinc ethylmethylphosphinate, diethylphosphinic acid, especially in terms of flame retardancy, electrical properties, and phosphinic acid synthesis Calcium, aluminum diethylphosphinate, and zinc diethylphosphinate are preferred.
本発明組成物を成形して得られる成形品の機械的強度、成形品外観の点でホスフィン酸塩の粒径は１００μｍ以下、好ましくは５０μｍ以下に粉砕した粉末を用いるのが良い。０．５〜２０μｍの粉末を用いると高い難燃性を発現するばかりでなく成形品の強度が著しく高くなるので特に好ましい。
また、ホスフィン酸塩は必ずしも完全に純粋である必要はなく、未反応物あるいは副生成物が多少残存していても良い。
ホスフィン酸塩は難燃剤として作用するが、メラミンとリン酸とから形成される付加物と併用することで少ない難燃剤量で優れた薄肉難燃性と優れた電気特性を発現する。
From the viewpoint of the mechanical strength and the appearance of the molded product obtained by molding the composition of the present invention, the phosphinic acid salt particle size is preferably 100 μm or less, preferably 50 μm or less. Use of a powder of 0.5 to 20 μm is particularly preferable because it not only exhibits high flame retardancy but also significantly increases the strength of the molded product.
Further, the phosphinic acid salt is not necessarily completely pure, and some unreacted products or by-products may remain.
The phosphinic acid salt acts as a flame retardant, but when used in combination with an adduct formed from melamine and phosphoric acid, it exhibits excellent thin-walled flame retardancy and excellent electrical properties with a small amount of flame retardant.
本発明の（ｄ）メラミンとリン酸とから形成される付加物としては、次の化学式（Ｃ３Ｈ６Ｎ６・ＨＰＯ３）ｎ、（ここでｎは縮合度を表す）で示されるもので、メラミンとリン酸、ピロリン酸、ポリリン酸との実質的に等モルの反応生成物から得られる物を意味し、製法には特に制約はない。通常、リン酸メラミンを窒素雰囲気下、加熱縮合して得られるポリリン酸メラミンを挙げることができる。ここでリン酸メラミンを構成するリン酸としては、具体的にはオルトリン酸、亜リン酸、次亜リン酸、メタリン酸、ピロリン酸、三リン酸、四リン酸等が挙げられるが、特にオルトリン酸、ピロリン酸を用いたメラミンとの付加物を縮合したポリリン酸メラミンが難燃剤としての効果が高く、好ましい。特に耐熱性の点からかかるポリリン酸メラミンの縮合度ｎは５以上が好ましい。また、ポリリン酸メラミンはポリリン酸とメラミンの等モルの付加塩であっても良く、メラミンとの付加塩を形成するポリリン酸としては、いわゆる縮合リン酸と呼ばれる鎖状ポリリン酸、環状ポリメタリン酸が挙げられる。これらポリリン酸の縮合度ｎには特に制約はなく通常３〜５０であるが、得られるポリリン酸メラミン付加塩の耐熱性の点でここに用いるポリリン酸の縮合度ｎは５以上が好ましい。かかるポリリン酸メラミン付加塩はメラミンとポリリン酸との混合物を例えば水スラリーとなし、よく混合して両者の反応生成物を微粒子状に形成させた後、このスラリーを濾過、洗浄、乾燥し、さらに必要であれば焼成し、得られた固形物を粉砕して得られる粉末である。 The adduct formed from (d) melamine and phosphoric acid according to the present invention is represented by the following chemical formula (C 3 H 6 N 6 .HPO 3 ) n (where n represents the degree of condensation). In this connection, it means a product obtained from a substantially equimolar reaction product of melamine and phosphoric acid, pyrophosphoric acid or polyphosphoric acid, and the production method is not particularly limited. Usually, melamine polyphosphate obtained by heat condensing melamine phosphate under nitrogen atmosphere can be mentioned. Specific examples of phosphoric acid constituting melamine phosphate include orthophosphoric acid, phosphorous acid, hypophosphorous acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, and tetraphosphoric acid. Melamine polyphosphate obtained by condensing an adduct with acid and melamine using pyrophosphoric acid has a high effect as a flame retardant and is preferable. In particular, the degree of condensation n of melamine polyphosphate is preferably 5 or more from the viewpoint of heat resistance. Melamine polyphosphate may be an equimolar addition salt of polyphosphoric acid and melamine. Examples of polyphosphoric acid forming an addition salt with melamine include chain polyphosphoric acid called cyclic phosphoric acid and cyclic polymetaphosphoric acid. Can be mentioned. The condensation degree n of these polyphosphoric acids is not particularly limited and is usually from 3 to 50. However, the condensation degree n of the polyphosphoric acid used here is preferably 5 or more from the viewpoint of the heat resistance of the resulting melamine addition salt. Such a melamine polyphosphate addition salt forms a mixture of melamine and polyphosphoric acid, for example, as an aqueous slurry, and mixes them well to form both reaction products in the form of fine particles. Then, the slurry is filtered, washed, dried, If necessary, it is a powder obtained by firing and pulverizing the obtained solid.
本発明組成物を成形して得られる成形品の機械的強度、成形品外観の点でポリリン酸メラミンの粒径は１００μｍ以下、好ましくは５０μｍ以下に粉砕した粉末を用いるのが良い。０．５〜２０μｍの粉末を用いると高い難燃性を発現するばかりでなく成形品の強度が著しく高くなるので特に好ましい。
また、ポリリン酸メラミンは必ずしも完全に純粋である必要はなく、未反応のメラミンあるいはリン酸、ポリリン酸が多少残存していても良い。
本発明の（ｅ）金属化合物としては、例えば、酸化亜鉛、酸化鉄、酸化カルシウム、酸化アルミニウム（アルミナ）、酸化ケイ素（シリカ）等の金属酸化物、水酸化マグネシウム、水酸化アルミニウム等の金属水酸化物、炭酸カルシウム、炭酸マグネシウム等の炭酸金属塩、ホウ酸亜鉛、ホウ酸マグネシウム、ホウ酸カルシウム、ホウ酸アルミニウム等のホウ酸金属塩が挙げられる。
From the viewpoint of the mechanical strength of the molded product obtained by molding the composition of the present invention and the appearance of the molded product, the particle size of melamine polyphosphate is preferably 100 μm or less, preferably 50 μm or less. Use of a powder of 0.5 to 20 μm is particularly preferable because it not only exhibits high flame retardancy but also significantly increases the strength of the molded product.
The melamine polyphosphate is not necessarily completely pure, and some unreacted melamine, phosphoric acid or polyphosphoric acid may remain.
Examples of the (e) metal compound of the present invention include metal oxides such as zinc oxide, iron oxide, calcium oxide, aluminum oxide (alumina) and silicon oxide (silica), and metal water such as magnesium hydroxide and aluminum hydroxide. Examples thereof include metal carbonates such as oxides, calcium carbonate and magnesium carbonate, and borate metal salts such as zinc borate, magnesium borate, calcium borate and aluminum borate.
本発明に好ましい金属化合物としては、助難燃剤として燃焼時に熱源である炎から樹脂への熱を遮断すること（断熱能力）によって、樹脂の分解で燃料となるガスの発生を抑制し、難燃性を高めるのに必要な不燃層（又は炭化層）の形成効率が高く、即ち難燃性に優れ、更に３００℃以上の熱加工時での安定性にも優れるので、ｘＺｎＯ・ｙＢ２Ｏ３・ｚＨ２Ｏ（ｘ＞０、ｙ＞０、ｚ≧０）で表されるホウ酸亜鉛が挙げられる。更に好ましくは
、２ＺｎＯ・３Ｂ２Ｏ３・３．５Ｈ２Ｏ、４ＺｎＯ・Ｂ２Ｏ３・Ｈ２Ｏ、２ＺｎＯ・３Ｂ２Ｏ３で表されるホウ酸亜鉛が挙げられる。
さらには、これらのホウ酸金属化合物はシラン系カップリング剤、チタネート系カップリング剤等の表面処理剤で処理されていてもよい。また、平均粒径は、好ましくは３０μｍ以下であり、更に好ましくは、１５μｍ以下であり、特に好ましくは７μｍ以下である。
As a preferred metal compound for the present invention, as an auxiliary flame retardant, the heat from the flame, which is a heat source during combustion, is blocked (adiabatic ability), thereby suppressing the generation of gas serving as a fuel in the decomposition of the resin, and flame retardant Since the formation efficiency of the incombustible layer (or carbonized layer) necessary for enhancing the property is high, that is, excellent in flame retardancy and also excellent in stability during heat processing at 300 ° C. or higher, xZnO · yB 2 O 3 · zH 2 O (x> 0 , y> 0, z ≧ 0) zinc borate represented by like. More preferably, 2ZnO · 3B 2 O 3 · 3.5H 2 O, 4ZnO · B 2 O 3 · H 2 O, the zinc borate represented by 2ZnO · 3B 2 O 3 and the like.
Further, these metal borate compounds may be treated with a surface treatment agent such as a silane coupling agent or a titanate coupling agent. The average particle size is preferably 30 μm or less, more preferably 15 μm or less, and particularly preferably 7 μm or less.
本発明の（ｆ）（ｂ）〜（ｅ）成分以外の金属化合物としては、難燃性以外の特性を向上させるための成分であり、熱安定剤、変色防止剤、耐候性改良剤、離型剤、滑剤、ポリマーの重合触媒としての働きをもつ金属化合物であり、例えば、銅化合物、ナトリウム化合物、ヨウ化カリウム、カリウム化合物、カルボン酸金属塩が挙げられる。
本発明に好ましい（ｆ）（ｂ）〜（ｅ）成分以外の金属化合物としては、熱安定剤、変色防止剤、耐候性改良剤、離型剤、滑剤、ポリマーの重合触媒としての効果と高温での付着物量の抑制への効果の点から、ヨウ化銅、臭化銅、酢酸銅などの銅化合物、次亜リン酸ナトリウム、亜リン酸ナトリウム、リン酸ナトリウム、アルミン酸ナトリウム等のナトリウム化合物、ヨウ化カリウム、臭化カリウム等のカリウム化合物、乳酸マンガン、ステアリン酸カルシウム、ステアリン酸アルミニウム、ステアリン酸亜鉛、ステアリン酸リチウム、モンタン酸ナトリウム、モンタン酸カルシウム、モンタン酸亜鉛、モンタン酸リチウム等のカルボン酸金属塩が挙げられる。
The metal compounds other than the components (f), (b) to (e) of the present invention are components for improving properties other than flame retardancy, and are heat stabilizers, discoloration inhibitors, weather resistance improvers, release agents. It is a metal compound that functions as a mold agent, a lubricant, and a polymer polymerization catalyst. Examples thereof include a copper compound, a sodium compound, potassium iodide, a potassium compound, and a carboxylic acid metal salt.
As metal compounds other than the components (f), (b) to (e) preferred in the present invention, heat stabilizers, discoloration inhibitors, weather resistance improvers, release agents, lubricants, polymer polymerization effects and high temperatures Copper compounds such as copper iodide, copper bromide, and copper acetate, sodium compounds such as sodium hypophosphite, sodium phosphite, sodium phosphate, and sodium aluminate , Potassium compounds such as potassium iodide and potassium bromide, carboxylic acids such as manganese lactate, calcium stearate, aluminum stearate, zinc stearate, lithium stearate, sodium montanate, calcium montanate, zinc montanate, lithium montanate Metal salts are mentioned.
本発明の（ｇ）炭素−炭素不飽和結合を含む脂肪酸アミドは任意成分であり、本成分が無くとも、本発明の目的は達成されるが、更なる成形時の流動性、離型性、成形品の難燃性、靭性、高温での付着物量の抑制効果の向上を図る際には、本成分を添加することができる。
（ｇ）炭素−炭素不飽和結合を含む脂肪酸アミドとしては、例えば、オレイン酸アミド、エルカ酸アミド、Ｎ−ステアリルエルカ酸アミド、Ｎ−オレイルパルミチン酸アミド、エチレンビスオレイン酸アミド、エチレンビスエルカ酸アミド等が挙げられる。
本発明に好ましい炭素−炭素不飽和結合を含む脂肪酸アミドとしては、成形時の流動性、離型性、成形品の難燃性、靭性、高温での付着物量の抑制への効果の点から、オレイン酸アミド、エルカ酸アミド、Ｎ−ステアリルエルカ酸アミド、Ｎ−オレイルパルミチン酸アミド等の炭素−炭素不飽和結合を含む脂肪酸とアミンとから形成される脂肪酸アミドが挙げられる。
更に好ましくは、炭素−炭素不飽和結合を含む脂肪酸と第一級アミンとから形成される脂肪酸アミドが挙げられる。最も好ましくは、Ｎ−ステアリルエルカ酸アミドである。
また、炭素−炭素不飽和結合を含む脂肪酸アミドは必ずしも完全に純粋である必要はなく、未反応物あるいは副生成物が多少残存していても良い。
(G) The fatty acid amide containing a carbon-carbon unsaturated bond of the present invention is an optional component, and even without this component, the object of the present invention can be achieved. This component can be added to improve the flame retardancy, toughness, and the effect of suppressing the amount of deposits at high temperatures.
(G) Examples of the fatty acid amide containing a carbon-carbon unsaturated bond include oleic acid amide, erucic acid amide, N-stearyl erucic acid amide, N-oleyl palmitic acid amide, ethylene bisoleic acid amide, and ethylene biserucic acid. Examples include amides.
As the fatty acid amide containing a carbon-carbon unsaturated bond preferable for the present invention, from the viewpoint of the flowability during molding, mold release properties, flame retardancy of molded products, toughness, and the effect of suppressing the amount of deposits at high temperatures, Examples include fatty acid amides formed from fatty acids containing carbon-carbon unsaturated bonds such as oleic acid amide, erucic acid amide, N-stearyl erucic acid amide, N-oleyl palmitic acid amide, and amines.
More preferably, the fatty acid amide formed from the fatty acid containing a carbon-carbon unsaturated bond and a primary amine is mentioned. Most preferred is N-stearyl erucamide.
The fatty acid amide containing a carbon-carbon unsaturated bond is not necessarily completely pure, and some unreacted product or by-product may remain.
本発明の好ましい態様として、成分（ａ）、（ｂ）、（ｃ）、（ｄ）、（ｅ）及び（ｆ）からなる難燃性ポリアミド樹脂組成物において、（ａ）ポリアミド樹脂の割合は、２４〜８０重量％の範囲である。２４重量％未満では成形加工性、機械的物性が損なわれ、８０重量％を越えると難燃性、剛性の低下を生じる恐れがある。より好ましくは、４０〜７０重量％、更に好ましくは、４５〜６５重量％である。
（ｂ）強化材の割合は、０〜６０重量％の範囲である。６０重量％を越えると混練時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。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る。より好ましくは、１０〜５０重量％であり、これは、１０重量％未満よりも強度、難燃性に一層大きな効果が得られるためである。更に好ましくは、１５〜３０重量％である。
As a preferred embodiment of the present invention, in the flame-retardant polyamide resin composition comprising components (a), (b), (c), (d), (e) and (f), the proportion of (a) the polyamide resin is 24 to 80% by weight. If it is less than 24% by weight, moldability and mechanical properties are impaired, and if it exceeds 80% by weight, flame retardancy and rigidity may be lowered. More preferably, it is 40-70 weight%, More preferably, it is 45-65 weight%.
(B) The proportion of the reinforcing material is in the range of 0 to 60% by weight. If it exceeds 60% by weight, problems such as generation of cracked gas during kneading and adhesion of contaminating substances to the molding die during molding will occur. In addition, the mechanical properties are significantly lowered and the appearance of the molded product is deteriorated. More preferably, it is 10 to 50% by weight, which is because a greater effect can be obtained on strength and flame retardancy than less than 10% by weight. More preferably, it is 15 to 30% by weight.
（ｃ）ホスフィン酸塩の割合は、１〜３０重量％の範囲である。１重量％未満では難燃効果が充分でなく、３０重量％を越えると混練時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。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る。より好ましくは、４〜２４重量％、更に好ましくは、５〜１８重量％である。
（ｄ）メラミンとリン酸とから形成される付加物の割合は、１〜３０重量％の範囲である。１重量％未満では難燃効果が充分でなく、３０重量％を越えると混練時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。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る。より好ましくは、４〜２４重量％、更に好ましくは、５〜１８重量％である。
（ｅ）金属化合物の割合は、０．１〜１０重量％の範囲である。０．１重量％未満では混練時や成型加工時に分解ガスが発生するなどの問題が生じる。１０重量％を越えると成形加工時に流動性が低下したり、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る。より好ましくは、０．３〜３重量％であり、更に好ましくは、０．５〜１．５重量％である。
(C) The ratio of the phosphinic acid salt is in the range of 1 to 30% by weight. If it is less than 1% by weight, the flame retardant effect is not sufficient, and if it exceeds 30% by weight, decomposition gas is generated during kneading, fluidity is lowered during molding processing, and many contaminants adhere to the molding die. Problem arises. In addition, the mechanical properties are significantly lowered and the appearance of the molded product is deteriorated. More preferably, it is 4 to 24% by weight, and further preferably 5 to 18% by weight.
(D) The ratio of the adduct formed from melamine and phosphoric acid is in the range of 1 to 30% by weight. If it is less than 1% by weight, the flame retardant effect is not sufficient, and if it exceeds 30% by weight, decomposition gas is generated during kneading, fluidity is lowered during molding processing, and many contaminants adhere to the molding die. Problem arises. In addition, the mechanical properties are significantly lowered and the appearance of the molded product is deteriorated. More preferably, it is 4 to 24% by weight, and further preferably 5 to 18% by weight.
(E) The ratio of the metal compound is in the range of 0.1 to 10% by weight. If it is less than 0.1% by weight, problems such as generation of decomposition gas occur during kneading or molding. If it exceeds 10% by weight, the fluidity is lowered during the molding process, the mechanical properties are remarkably lowered, and the appearance of the molded product is deteriorated. More preferably, it is 0.3-3 weight%, More preferably, it is 0.5-1.5 weight%.
（ｆ）（ｂ）〜（ｅ）成分以外の金属化合物の割合は、０．００１〜０．０５重量％の範囲である。０．００１重量％未満だと熱安定剤、変色防止剤、耐候性改良剤、離型剤、滑剤、ポリマーの重合触媒等の効果が充分でなく、０．０５重量％を超えると成形品の高温での付着物量が多くなり好ましくない。より好ましくは０．００１５重量％以上０．０３重量％以下の範囲であり、更に好ましくは、０．００２〜０．０１５重量％である。
（ｇ）炭素−炭素不飽和結合を含む脂肪酸アミドは、任意成分であるが添加する際の割合は０．０１〜１重量％が好ましい。０．０１重量％未満だと離型性、流動性等の向上の効果が小さく、１重量％を越えると難燃性の低下、混練時にポリマー中にとけきれずに、押出機から液状であふれたり、滴ったりする恐れがある。より好ましくは、０．０３〜０．５重量％、更に好ましくは、０．０５〜０．３重量％である。
(F) The proportion of the metal compound other than the components (b) to (e) is in the range of 0.001 to 0.05% by weight. If it is less than 0.001% by weight, the effects of heat stabilizer, anti-discoloring agent, weather resistance improver, mold release agent, lubricant, polymer polymerization catalyst, etc. are not sufficient. The amount of deposits at high temperatures is undesirably high. More preferably, it is the range of 0.0015 weight% or more and 0.03 weight% or less, More preferably, it is 0.002-0.015 weight%.
(G) The fatty acid amide containing a carbon-carbon unsaturated bond is an optional component, but the proportion when added is preferably 0.01 to 1% by weight. If it is less than 0.01% by weight, the effect of improving releasability, fluidity, etc. is small. If it exceeds 1% by weight, the flame retardancy is reduced, and it does not melt into the polymer during kneading, and overflows in liquid form from the extruder. There is a risk of dripping. More preferably, it is 0.03 to 0.5 weight%, More preferably, it is 0.05 to 0.3 weight%.
本発明の強化された難燃性ポリアミド樹脂組成物の製造方法は、特に限定はなく、ポリアミド樹脂、強化材（任意成分）、ホスフィン酸塩、メラミンとリン酸とから形成される付加物、金属化合物、（ｂ）〜（ｅ）成分以外の金属化合物等を常用の単軸又は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、ポリアミド樹脂、（ｂ）〜（ｅ）成分以外の金属化合物を添加した後に、ホスフィン酸塩、メラミンとリン酸とから形成される付加物、金属化合物、強化材（任意成分）を添加し混練するのが好ましい。また、ポリアミド樹脂、（ｂ）〜（ｅ）成分以外の金属化合物を添加した後に、ホスフィン酸塩、メラミンとリン酸とから形成される付加物、金属化合物を添加し十分に溶融混練された後に強化材（任意成分）を添加するのが更に好ましい。
さらに、（ｂ）〜（ｅ）成分以外の金属化合物の添加方法は、特に限定はないが、例えば、溶融混練時にポリアミド樹脂ペレットとブレンドして押出機に供給する方法、ポリアミド樹脂重合の際（重合前又は重合中）に（ｂ）〜（ｅ）成分以外の金属化合物等を添加して製造したポリアミド樹脂を押出機に供給する方法、予め、押出機などで高濃度の（ｂ）〜（ｅ）成分以外の金属化合物等とポリアミド樹脂を溶融混練したマスターバッチを押出機に供給する方法が挙げられる。
The method for producing the reinforced flame-retardant polyamide resin composition of the present invention is not particularly limited, and is an addition product formed from polyamide resin, reinforcing material (optional component), phosphinate, melamine and phosphoric acid, metal A compound, a metal compound other than the components (b) to (e), etc. is used at a temperature of 200 to 350 ° C., depending on the melting point of the resin, etc., using a kneader such as a conventional single or biaxial extruder or kneader. In order to maintain mechanical properties, after adding a metal compound other than the polyamide resin and the components (b) to (e), the phosphinic acid salt, melamine and phosphoric acid are used. It is preferable to add and knead the adduct formed, the metal compound, and the reinforcing material (optional component). In addition, after adding a metal compound other than the polyamide resin and the components (b) to (e), an phosphinate, an adduct formed from melamine and phosphoric acid, and a metal compound are added and sufficiently melt-kneaded. It is more preferable to add a reinforcing material (optional component).
Furthermore, the method for adding the metal compound other than the components (b) to (e) is not particularly limited. For example, a method of blending with polyamide resin pellets at the time of melt kneading and supplying them to an extruder, (Before or during polymerization) A method of supplying a polyamide resin produced by adding a metal compound other than the components (b) to (e) to the extruder, in advance with a high concentration of (b) to (b) e) A method of supplying a master batch obtained by melt-kneading a metal compound other than the component and a polyamide resin to the extruder may be mentioned.
本発明の難燃性ポリアミド樹脂組成物には、本発明の目的を損なわない範囲で、他の成分、例えば難燃剤、エラストマー、フィブリル化剤、顔料、染料等の着色剤や、ポリアミド樹脂の一般的な熱安定剤である、ヒンダードフェノール系、ヒンダードアミン系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、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。
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。ここでの電気・電子用途部品とは、例えば、コネクター、ブレーカー、電磁開閉器、プラグ、スイッチ等の高い難燃性と高い電気特性が要求され、成形品の高温での付着物量ができるだけ抑制されたものが望まれる部品を意味する。
In the flame-retardant polyamide resin composition of the present invention, other components such as flame retardants, elastomers, fibrillating agents, pigments, dyes and other colorants, and polyamide resins in general are within the range not impairing the object of the present invention. Organic heat stabilizers typified by hindered phenols and hindered amine oxidative degradation inhibitors, weather resistance improvers, nucleating agents, plasticizers, antistatic agents, fluidity improvers, filling Agents, reinforcing agents, spreading agents, other polymers, etc. can be added at any stage.
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. The electrical / electronic parts used here are required to have high flame resistance and high electrical properties such as connectors, breakers, electromagnetic switches, plugs, switches, etc. Means a desired part.
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］
（ａ）成分 ポリアミド樹脂
（ａ−１）：製造例１のポリアミド６６／６Ｉ（ＰＡ６６／６Ｉ） （共重合成分のモル比 ６６：６Ｉ＝８５：１５） 硫酸相対粘度２．３８
（ａ−２）：製造例２のポリアミド６６（ＰＡ６６） 硫酸相対粘度２．７９
（ｂ）成分 強化材
（ｂ−１）：ガラス繊維（ＧＦ） 日本電気硝子（株）製 商品名 ＥＣＳ０３Ｔ２７５Ｈ／ＰＬ（平均繊維径１０．５μｍ）
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) Component Polyamide Resin (a-1): Polyamide 66 / 6I of Production Example 1 (PA66 / 6I) (Molar ratio of copolymerization component 66: 6I = 85: 15) Sulfuric acid relative viscosity 2.38
(A-2): Polyamide 66 of Production Example 2 (PA66) Sulfuric acid relative viscosity 2.79
(B) Component Reinforcing material (b-1): Glass fiber (GF) Product name manufactured by Nippon Electric Glass Co., Ltd. ECS03T275H / PL (average fiber diameter 10.5 μm)
（ｃ）成分 ホスフィン酸塩
（ｃ−１）：特開平０８−７３７２０号公報に記載されている製法を参考にして、製造されたジエチルホスフィン酸アルミニウム（以下、ＤＥＰＡｌと記載する）。
（ｄ）成分 メラミンとリン酸とから形成される付加物
（ｄ−１）：ポリリン酸メラミン（以下、ＭＰＰと記載する） チバ・スペシャリティー・ケミカルズ（株）製 商品名 Ｍｅｌａｐｕｒ２００／７０
（ｅ）成分 金属化合物
（ｅ−１）：ホウ酸亜鉛 ２ＺｎＯ・３Ｂ２Ｏ３ （ホウ酸亜鉛Ａ） Ｕ．Ｓ． Ｂｏｒａｘ社製 商品名 Ｆｉｒｅｂｒａｋｅ ５００
（ｅ−２）：酸化カルシウム （酸化Ｃａ） 入交産業（株）製 商品名 ミクロンライム
Component (c) Phosphinic acid salt (c-1): Aluminum diethylphosphinate (hereinafter referred to as DEPAl) produced with reference to the production method described in JP-A-08-73720.
(D) Component Adduct formed from melamine and phosphoric acid (d-1): Melamine polyphosphate (hereinafter referred to as MPP) Ciba Specialty Chemicals Co., Ltd. Product name Melapur 200/70
(E) Component Metal compound (e-1): Zinc borate 2ZnO.3B 2 O 3 (Zinc borate A) S. Product name Firebrake 500 made by Borax
(E-2): Calcium oxide (Ca oxide) Product name made by Iryo Sangyo Co., Ltd. Micron lime
（ｆ）成分 （ｂ）〜（ｅ）成分以外の金属化合物
（ｆ−１）：ステアリン酸カルシウム（ステアリン酸Ｃａ） 日本油脂（株）製 商品名 ステアリン酸カルシウム
（ｆ−２）：モンタン酸ナトリウム（モンタン酸Ｎａ） クラリアントジャパン（株）
商品名 Ｌｉｃｏｍｏｎｔ ＮａＶ １
（ｆ−３）：次亜リン酸ナトリウム 和光純薬工業（株）製 商品名 次亜リン酸ナトリウム一水和物
（ｆ−４）：乳酸マンガン キシダ化学（株）製 商品名 乳酸マンガン（ＩＩ）（3水和物）
（ｇ）成分 炭素−炭素不飽和結合を含む脂肪酸アミド
（ｇ−１）Ｎ−ステアリルエルカ酸アミド 日本精化（株）製 商品名 ＳＮＴ−４０（ｈ）成分 その他成分
（ｈ−１）ヒンダードフェノール系熱安定剤（熱安定剤）Ｎ，Ｎ‘−ヘキサメチレンビス（３，５−ジ−ｔ−ブチル−４−ヒドロキシ−ヒドロシンナマイド） チバ・スペシャリティー・ケミカルズ（株）製 商品名 ｉｒｇａｎｏｘ１０９８
Component (f) Metal compounds other than components (b) to (e) (f-1): Calcium stearate (Ca stearate) Product name: Calcium stearate (f-2): Sodium montanate (Montan) Acid Na) Clariant Japan Co., Ltd.
Product Name Licomont NaV 1
(F-3): Sodium hypophosphite manufactured by Wako Pure Chemical Industries, Ltd. Product name Sodium hypophosphite monohydrate (f-4): Manganese lactate manufactured by Kishida Chemical Co., Ltd. Product name Manganese lactate (II ) (Trihydrate)
(G) Component Fatty acid amide containing carbon-carbon unsaturated bond (g-1) N-stearyl erucic acid amide Nippon Seika Co., Ltd. Product name SNT-40 (h) Component Other components (h-1) Hindered Phenol heat stabilizer (heat stabilizer) N, N′-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide) Ciba Specialty Chemicals Co., Ltd. Product name irganox 1098
（製造例１）
アジピン酸とヘキサメチレンジアミンの等モル塩２．００ｋｇとイソフタル酸とヘキサメチレンジアミンの等モル塩０．３５ｋｇ、アジピン酸０．１ｋｇ、および純水２．５ｋ
ｇを５Ｌのオートクレーブの中に仕込み良く撹拌した。充分窒素置換した後、撹拌しながら温度を室温から２２０℃まで約１時間かけて昇温した。この際、オートクレーブ内の水蒸気による自然圧で内圧はゲージ圧で１．７６ＭＰａになるが、１．７６ＭＰａ以上の圧にならないよう水を反応系外に除去しながら加熱を続けた。更に２時間後内温が２６０℃に到達した時点で加熱を止め、オートクレーブのバルブを閉止し、約８時間かけて室温まで冷却した。冷却後オートクレーブを開け、約２ｋｇのポリマーを取りだし粉砕した。得られた粉砕ポリマーを、１０Ｌのエバポレーターに入れ窒素気流下、２００℃で１０時間固相重合した。固相重合によって得られたポリアミドは、融点２４５℃、硫酸相対粘度２．３８であった。
(Production Example 1)
2.00 kg of equimolar salt of adipic acid and hexamethylenediamine, 0.35 kg of equimolar salt of isophthalic acid and hexamethylenediamine, 0.1 kg of adipic acid, and 2.5 k of pure water
g was charged in a 5 L autoclave and stirred well. After sufficiently purging with nitrogen, the temperature was raised from room temperature to 220 ° C. over about 1 hour with stirring. Under the present circumstances, although the internal pressure became 1.76 MPa by the natural pressure by the water vapor | steam in an autoclave, it continued heating, removing water out of a reaction system so that it might not become a pressure of 1.76 MPa or more. After 2 hours, when the internal temperature reached 260 ° C., the heating was stopped, the autoclave valve was closed, and the system was cooled to room temperature over about 8 hours. After cooling, the autoclave was opened, and about 2 kg of polymer was taken out and pulverized. The obtained pulverized polymer was placed in a 10 L evaporator and subjected to solid phase polymerization at 200 ° C. for 10 hours under a nitrogen stream. The polyamide obtained by solid phase polymerization had a melting point of 245 ° C. and a sulfuric acid relative viscosity of 2.38.
（製造例２）
アジピン酸とヘキサメチレンジアミンの等モル塩２．４０ｋｇとアジピン酸０．１ｋｇ、および純水２．５ｋｇを５Ｌのオートクレーブの中に仕込み良く撹拌した。充分窒素置換した後、撹拌しながら温度を室温から２２０℃まで約１時間かけて昇温した。この際、オートクレーブ内の水蒸気による自然圧で内圧はゲージ圧で１．７６ＭＰａになるが、１．７６ＭＰａ以上の圧にならないよう水を反応系外に除去しながら加熱を続けた。更に２時間後内温が２６０℃に到達したら、加熱は続けながら、オートクレーブのバルブの開閉調整を行い、ゆっくり約４０分かけて、内圧が０．２ＭＰａになるまで降圧する。その後、約８時間かけて室温まで冷却した。冷却後オートクレーブを開け、約２ｋｇのポリマーを取りだし粉砕した。得られたポリアミドは、融点２６４℃、硫酸相対粘度２．７９であった。
(Production Example 2)
2.40 kg of equimolar salt of adipic acid and hexamethylenediamine, 0.1 kg of adipic acid and 2.5 kg of pure water were charged into a 5 L autoclave and stirred well. After sufficiently purging with nitrogen, the temperature was raised from room temperature to 220 ° C. over about 1 hour with stirring. Under the present circumstances, although the internal pressure became 1.76 MPa by the natural pressure by the water vapor | steam in an autoclave, it continued heating, removing water out of a reaction system so that it might not become a pressure of 1.76 MPa or more. When the internal temperature reaches 260 ° C. after 2 hours, the autoclave valve is adjusted to be opened and closed while heating is continued, and the pressure is slowly lowered over about 40 minutes until the internal pressure becomes 0.2 MPa. Then, it cooled to room temperature over about 8 hours. After cooling, the autoclave was opened, and about 2 kg of polymer was taken out and pulverized. The obtained polyamide had a melting point of 264 ° C. and a sulfuric acid relative viscosity of 2.79.
［測定方法］
（１）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。なお試験片は長さ１２７ｍｍ、幅１２．７ｍｍ、厚みは１／１６インチと１／３２インチの２種類を射出成形機（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
平均燃焼時間（秒）とは、各サンプル１０秒間接炎を２回即ち計２０回接炎後に試験片の炎が消えるまでの平均燃焼時間、最大燃焼時間（秒）とは、同じく計２０回接炎後に試験片の炎が消えるまでの最大燃焼時間を意味する。
[Measuring method]
(1) Flame retardancy (UL-94VB)
Measurements were made using the method of UL94 (standard established by Under Writers Laboratories Inc., USA). The test pieces were 127 mm long, 12.7 mm wide, and 1/16 inch and 1/32 inch thick by 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 the clamp that holds the specimen and the average burning time (seconds) is 10 seconds for each sample. The average combustion time until the flame of the test piece disappears after the indirect flame is applied twice, that is, 20 times in total, the maximum combustion time (seconds) is the maximum combustion until the flame of the test piece disappears after 20 times of flame contact. Means time.
（２）電気特性（ＣＴＩ）
ＩＥＣ Ｐｕｂｌｉｃａｔｉｏｎ １１２規格の方法で、日立化成工業（株）製耐トラッキング試験機 ＨＡＴ−５００−３型の装置を用いて、耐トラッキング試験を行った。なお試験片は６５ｍｍ×９０ｍｍ×３．０ｍｍ（厚み３．０ｍｍ）とし、射出成形機（東芝機械製：ＩＳ１５０）を用いて成形して得た。測定の概要は試験片を装置にセットし、試験片表面に接触させた二本の電極によって１００〜６００Ｖの電圧を印加し、その電極間に０．１％塩化アンモニウム水溶液を３０秒毎に滴下し、試験片がトラッキングを起こすことなく、５０滴の間絶縁破壊しない最大電圧（ＣＴＩ）を測定し、その値を示した。
この値が高いほど耐トラッキング性に優れる。
（３）機械特性
射出成形機（日精工業（株）製：ＰＳ４０Ｅ）を用いて、ＡＳＴＭ Ｄ７９０の曲げ試験片（厚さ３ｍｍ）を成形し、ＡＳＴＭ Ｄ７９０に準拠した方法で曲げ試験を実施し、曲げ強度、曲げ弾性率を求めた。
(2) Electrical characteristics (CTI)
The tracking resistance test was performed by the method of IEC Publication 112 standard using the apparatus of the tracking resistance tester HAT-500-3 manufactured by Hitachi Chemical Co., Ltd. The test piece was 65 mm × 90 mm × 3.0 mm (thickness 3.0 mm), and was obtained by molding using an injection molding machine (Toshiba Machine: IS150). The outline of the measurement is that a test piece is set in the apparatus, a voltage of 100 to 600 V is applied by two electrodes brought into contact with the surface of the test piece, and a 0.1% ammonium chloride aqueous solution is dropped between the electrodes every 30 seconds. The maximum voltage (CTI) at which the test piece did not break down for 50 drops was measured without causing tracking, and the value was shown.
The higher this value, the better the tracking resistance.
(3) Mechanical properties Using an injection molding machine (manufactured by Nissei Kogyo Co., Ltd .: PS40E), a bending test piece (thickness 3 mm) of ASTM D790 is molded, and a bending test is carried out by a method based on ASTM D790, Bending strength and flexural modulus were determined.
（４）付着試験（成形品の高温での付着物量）
成形品の高温での付着物量の測定を行った。ここでの高温とは、成形品が溶融しない状態での高温を指し、特に限定はしないが、この試験は、１２０℃で行った。
大洋化学工業（株）製のヒーティングブロック ＤＲＹ ＴＨＥＲＭＯ ＵＮＩＴ ＴＡＨ−１８に、直径１５ｍｍの穴の空いた金属ブロックを装着した装置を用いた。
ガラス製の試験管（外径１５ｍｍ、内径１３ｍｍ、長さ１５０ｍｍ）に機械特性を測定する為の試験片を細かく砕いたものを３ｇ入れ、その試験管を上記装置の金属ブロックの穴に７５ｍｍ程差込み、金属ブロックを装置のヒーターで１２０℃に加熱し、その状態で２００時間維持した。その後、金属ブロックの上に出て、外気にて冷却されている試験管の部分（ガラス内側）が白く曇っている度合いを目視により観測した。
○：あまり白く曇っていない。（付着量が少ない）
△：白く曇っている。（付着量が中程度）
×：かなり白く曇っている。（付着量が多い）
また参考として、難燃剤や金属化合物のみ（ｃ−１、ｄ−１、ｅ−１、ｅ−２、）を３ｇとり、上記の試験管にガラス面が紛体で汚れないようにして入れ、同様の条件で試験を行い、試験管の金属ブロックの上に出ている部分（ガラス内側）が白く曇っている度合いを目視により観測したが、ほとんど曇っていなかった。
従って、上記の白く曇る現象は、ポリアミド樹脂と難燃剤成分などを溶融混練して得られた組成物のペレットで、はじめて起きる現象である。
(4) Adhesion test (Amount of deposits at high temperature of molded products)
The amount of deposits at a high temperature of the molded product was measured. The high temperature here refers to a high temperature in a state where the molded product does not melt, and is not particularly limited, but this test was performed at 120 ° C.
A device in which a metal block with a hole having a diameter of 15 mm was attached to a heating block DRY THERMO UNIT TAH-18 manufactured by Taiyo Chemical Industry Co., Ltd. was used.
A glass test tube (outer diameter 15 mm, inner diameter 13 mm, length 150 mm) containing 3 g of finely crushed test pieces for measuring mechanical properties is put into a hole in a metal block of the above apparatus about 75 mm. The metal block was heated to 120 ° C. with the heater of the apparatus and maintained in that state for 200 hours. Thereafter, the degree of the test tube portion (inside of the glass) that had come out on the metal block and was cooled by outside air was visually observed.
○: Not very white and cloudy. (Small amount of adhesion)
Δ: White and cloudy. (Medium amount of adhesion)
X: It is quite white and cloudy. (A large amount of adhesion)
For reference, 3 g of flame retardant and metal compound only (c-1, d-1, e-1, e-2) are taken and placed in the above test tube so that the glass surface is not contaminated with powder. The test was carried out under the conditions described above, and the degree of clouding of the portion (inside the glass) on the metal block of the test tube that was clouded white was visually observed.
Therefore, the above white clouding phenomenon occurs for the first time in a pellet of a composition obtained by melt-kneading a polyamide resin and a flame retardant component.
（５）離型性
上記（１）の難燃性評価用にＵＬ試験片成形する際の離型性を示した。基準は以下の通り。またこれを組成物の離型性の指標とした。
離型性の評価基準（成形サイクル時間：射出＝５秒、冷却＝１５秒、トータル＝約２６秒、シリンダー温度＝２６０℃（ポリアミド樹脂がａ−１での組成物の時）
○：問題なく離型する。（全自動での成形が可能なレベル）
△：問題なく離型する時と離型しないときがある。（半自動では成形可能なレベル）
×：ほとんど離型せず、成形品の取り出しに人手が必要。
(5) Releasability The releasability when forming a UL test piece for the flame retardancy evaluation of (1) above was shown. The standards are as follows. This was also used as an index of mold releasability of the composition.
Evaluation criteria for releasability (molding cycle time: injection = 5 seconds, cooling = 15 seconds, total = about 26 seconds, cylinder temperature = 260 ° C. (when polyamide resin is a composition in a-1)
○: Release without problems. (Full automatic molding is possible)
(Triangle | delta): It may be when it releases without a problem, and it may not release. (Semi-automatic moldable level)
X: Almost no mold release, requiring manual operation to take out the molded product.
（６）耐熱変色性
それぞれの組成物のペレットをオーブン中で２０分間１３０℃加熱（空気雰囲気下）を行い、その後の変色を観察した。
耐熱変色性の評価基準
○：ペレットの熱変色が小さい。
×：ペレットの熱変色が大きい。
(6) Heat-resistant discoloration The pellets of each composition were heated in an oven at 130 ° C. for 20 minutes (in an air atmosphere), and the subsequent discoloration was observed.
Evaluation criteria for heat discoloration ○: Thermal discoloration of the pellet is small.
X: The thermal discoloration of a pellet is large.
（比較例１）
表１に示す組成物を得た。
原材料はａ−１が５２．９重量％、ｂ−１が２５．０重量％、ｃ−１が１４．０重量％、ｄ−１が７．０重量％、ｅ−１が１．０重量％、ｈ−１が０．１重量％となるように用意し、上流側に１ヶ所（以下ｔｏｐ−Ｆと略記）と、押出機中央部並びにダイに近い下流側の２ヶ所に供給口（以下押出機中央部をｓｉｄｅ−１、ダイに近い下流側をｓｉｄｅ−２とそれぞれ略記）を有する二軸押出機（東芝機械製：ＴＥＭ３５）を用いてシリンダー設定温度２４０℃、スクリュー回転１００ｒｐｍ、吐出量３０ｋｇ／ｈｒの条件下で、ａ
−１、ｈ−１の二成分を予めブレンドしたものをｔｏｐ−Ｆから、ｃ−１、ｄ−１、ｅ−１の三成分を予めブレンドしたものをｓｉｄｅ−１から、ｂ−１はｓｉｄｅ−２から合計の吐出量が３０ｋｇ／ｈｒになるようにそれぞれ調節して供給し、溶融混練してストランド状に取り出し、ストランドバス（水槽）で冷却後、カッターで造粒しポリアミド樹脂組成物ペレットを得た。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、０．１２％以下になるようにした。
得られたペレットを前記した測定方法にて難燃性（ＵＬ−９４ＶＢ）、電気特性（ＣＴＩ）、機械特性、成形品の高温での付着物量、離型性を調べた。その結果を表１に示す。
(Comparative Example 1)
The composition shown in Table 1 was obtained.
Raw materials are 52.9% by weight for a-1, 25.0% by weight for b-1, 14.0% by weight for c-1, 7.0% by weight for d-1, 1.0% for e-1. % And h-1 are 0.1% by weight, and supply ports are provided at one location on the upstream side (hereinafter abbreviated as top-F) and two locations on the downstream side near the center of the extruder and the die ( Hereinafter, using a twin screw extruder (manufactured by Toshiba Machine: TEM35) having a central portion of the extruder as side-1 and a downstream side close to the die as side-2, cylinder set temperature 240 ° C., screw rotation 100 rpm, discharge Under the condition of an amount of 30 kg / hr, a
-1 and h-1 are pre-blended from top-F, c-1, d-1, and e-1 are pre-blended from side-1 and b-1 is side. -2 to adjust the total discharge amount to be 30 kg / hr, respectively, melt and knead to take out into strands, cool in a strand bath (water tank), granulate with a cutter, and polyamide resin composition pellets Got. Further, the immersion length of the strands in the strand bath was adjusted so that the pellet moisture was 0.12% or less.
The obtained pellets were examined for flame retardancy (UL-94VB), electrical properties (CTI), mechanical properties, the amount of deposits at high temperatures of the molded product, and releasability by the measurement method described above. The results are shown in Table 1.
（実施例１）
原材料はａ−１が５２．８７重量％、ｂ−１が２５．０重量％、ｃ−１が１４．０重量％、ｄ−１が７．０重量％、ｅ−１が１．０重量％、ｆ−１が０．０３重量％、ｈ−１が０．１重量％となるように用意し、比較例１と同条件下で、ａ−１、ｆ−１、ｈ−１の三成分を予めブレンドしたものをｔｏｐ−Ｆから、ｃ−１、ｄ−１、ｅ−１の三成分を予めブレンドしたものをｓｉｄｅ−１から、ｂ−１はｓｉｄｅ−２から合計の吐出量が３０ｋｇ／ｈｒになるようにそれぞれ調節して供給し、溶融混練してストランド状に取り出し、ストランドバス（水槽）で冷却後、カッターで造粒しポリアミド樹脂組成物ペレットを得た。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、０．１２％以下になるようにした。
得られたペレットを前記した測定方法にて難燃性（ＵＬ−９４ＶＢ）、電気特性（ＣＴＩ）、機械特性、成形品の高温での付着物量、離型性を調べた。その結果を表１に示す。
Example 1
The raw materials are 52.87% by weight for a-1, 25.0% by weight for b-1, 14.0% by weight for c-1, 7.0% by weight for d-1, 1.0% for e-1. %, F-1 is 0.03% by weight, and h-1 is 0.1% by weight. Under the same conditions as in Comparative Example 1, three of a-1, f-1, and h-1 are prepared. Pre-blended components from top-F, c-1, d-1, and e-1 blended in advance from side-1, b-1 from side-2 Each was adjusted and supplied so as to be 30 kg / hr, melt kneaded, taken out into a strand shape, cooled in a strand bath (water tank), granulated with a cutter, and a polyamide resin composition pellet was obtained. Further, the immersion length of the strands in the strand bath was adjusted so that the pellet moisture was 0.12% or less.
The obtained pellets were examined for flame retardancy (UL-94VB), electrical properties (CTI), mechanical properties, the amount of deposits at high temperatures of the molded product, and releasability by the measurement method described above. The results are shown in Table 1.
（比較例２）
原材料のａ−１の量を５２．７重量％、ｆ−１の量を０．２重量％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。
得られたペレットを前記した測定方法にて難燃性（ＵＬ−９４ＶＢ）、電気特性（ＣＴＩ）、機械特性、成形品の高温での付着物量、離型性を調べた。その結果を表１に示す。
（実施例２）
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。
得られたペレットを前記した測定方法にて難燃性（ＵＬ−９４ＶＢ）、電気特性（ＣＴＩ）、機械特性、成形品の高温での付着物量、離型性を調べた。その結果を表１に示す。
(Comparative Example 2)
The amount of raw material a-1 was changed to 52.7% by weight, and the amount of f-1 was changed to 0.2% by weight. Other than that was melt-kneaded in the same manner as in Example 1 to obtain polyamide resin composition pellets.
The obtained pellets were examined for flame retardancy (UL-94VB), electrical properties (CTI), mechanical properties, the amount of deposits at high temperatures of the molded product, and releasability by the measurement method described above. The results are shown in Table 1.
(Example 2)
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.
The obtained pellets were examined for flame retardancy (UL-94VB), electrical properties (CTI), mechanical properties, the amount of deposits at high temperatures of the molded product, and releasability by the measurement method described above. The results are shown in Table 1.
（比較例３）
原材料のａ−１の量を５２．７重量％、ｆ−２の量を０．２重量％に変更した。それ以外は、実施例２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。
得られたペレットを前記した測定方法にて難燃性（ＵＬ−９４ＶＢ）、電気特性（ＣＴＩ）、機械特性、成形品の高温での付着物量、離型性を調べた。その結果を表１に示す。
（比較例４）
原材料はａ−２が５２．８重量％、ｂ−１が２５．０重量％、ｃ−１が１４．０重量％、ｄ−１が７．０重量％、ｅ−１が１．０重量％、ｇ−１が０．１重量％、ｈ−１が０．１重量％となるように用意し、比較例１と同条件下で、ａ−１、ｇ−１、ｈ−１の三成分を予めブレンドしたものをｔｏｐ−Ｆから、ｃ−１、ｄ−１、ｅ−１の三成分を予めブレンドしたものをｓｉｄｅ−１から、ｂ−１はｓｉｄｅ−２から合計の吐出量が３０ｋｇ／ｈｒになるようにそれぞれ調節して供給し、溶融混練してストランド状に取り出し、ストランドバス（水槽）で冷却後、カッターで造粒しポリアミド樹脂組成物ペレットを得た。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、０．１２％以下になるようにした。
得られたペレットを前記した測定方法にて難燃性（ＵＬ−９４ＶＢ）、電気特性（ＣＴＩ）、機械特性、成形品の高温での付着物量、耐熱変色性を調べた。その結果を表１に示
す。
(Comparative Example 3)
The amount of raw material a-1 was changed to 52.7% by weight, and the amount of f-2 was changed to 0.2% by weight. Other than that was melt-kneaded in the same manner as in Example 2 to obtain polyamide resin composition pellets.
The obtained pellets were examined for flame retardancy (UL-94VB), electrical properties (CTI), mechanical properties, the amount of deposits at high temperatures of the molded product, and releasability by the measurement method described above. The results are shown in Table 1.
(Comparative Example 4)
The raw materials are 52.8 wt% for a-2, 25.0 wt% for b-1, 14.0 wt% for c-1, 7.0 wt% for d-1, 1.0 wt for e-1. %, G-1 is 0.1% by weight, and h-1 is 0.1% by weight. Under the same conditions as in Comparative Example 1, three of a-1, g-1, and h-1 are prepared. Pre-blended components from top-F, c-1, d-1, and e-1 blended in advance from side-1, b-1 from side-2 Each was adjusted and supplied so as to be 30 kg / hr, melt kneaded, taken out into a strand shape, cooled in a strand bath (water tank), granulated with a cutter, and a polyamide resin composition pellet was obtained. Further, the immersion length of the strands in the strand bath was adjusted so that the pellet moisture was 0.12% or less.
The obtained pellets were examined for flame retardancy (UL-94VB), electrical properties (CTI), mechanical properties, the amount of deposits at high temperatures and heat discoloration by the above-described measurement methods. The results are shown in Table 1.
（実施例３）
原材料はａ−１が５２．７９７重量％、ｂ−１が２５．０重量％、ｃ−１が１４．０重量％、ｄ−１が７．０重量％、ｅ−１が１．０重量％、ｆ−３が０．００３重量％、ｇ−１が０．１重量％、ｈ−１が０．１重量％となるように用意し、比較例１と同条件下で、ａ−１、ｆ−１、ｇ−１、ｈ−１の四成分を予めブレンドしたものをｔｏｐ−Ｆから、ｃ−１、ｄ−１、ｅ−１の三成分を予めブレンドしたものをｓｉｄｅ−１から、ｂ−１はｓｉｄｅ−２から合計の吐出量が３０ｋｇ／ｈｒになるようにそれぞれ調節して供給し、溶融混練してストランド状に取り出し、ストランドバス（水槽）で冷却後、カッターで造粒しポリアミド樹脂組成物ペレットを得た。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、０．１２％以下になるようにした。
得られたペレットを前記した測定方法にて難燃性（ＵＬ−９４ＶＢ）、電気特性（ＣＴＩ）、機械特性、成形品の高温での付着物量、耐熱変色性を調べた。その結果を表１に示す。
(Example 3)
The raw materials are 52.797% by weight for a-1, 25.0% by weight for b-1, 14.0% by weight for c-1, 7.0% by weight for d-1, 1.0% for e-1. %, F-3 is 0.003% by weight, g-1 is 0.1% by weight, and h-1 is 0.1% by weight. , F-1, g-1, and h-1 are blended in advance from top-F, and c-1, d-1, and e-1 are blended in advance from side-1. , B-1 are adjusted and supplied from side-2 so that the total discharge amount is 30 kg / hr, melt kneaded and taken out into a strand shape, cooled in a strand bath (water tank), and granulated with a cutter. Polyamide resin composition pellets were obtained. Further, the immersion length of the strands in the strand bath was adjusted so that the pellet moisture was 0.12% or less.
The obtained pellets were examined for flame retardancy (UL-94VB), electrical properties (CTI), mechanical properties, the amount of deposits at high temperatures and heat discoloration by the above-described measurement methods. The results are shown in Table 1.
（比較例５）
原材料のａ−２の量を５２．７２重量％、ｆ−３の量を０．０８重量％に変更した。それ以外は、実施例３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。
得られたペレットを前記した測定方法にて難燃性（ＵＬ−９４ＶＢ）、電気特性（ＣＴＩ）、機械特性、成形品の高温での付着物量、耐熱変色性を調べた。その結果を表１に示す。
（実施例４）
原材料のｆ−３をｆ−４に変更した。それ以外は、実施例３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。
得られたペレットを前記した測定方法にて難燃性（ＵＬ−９４ＶＢ）、電気特性（ＣＴＩ）、機械特性、成形品の高温での付着物量、耐熱変色性を調べた。その結果を表１に示す。
(Comparative Example 5)
The amount of raw material a-2 was changed to 52.72% by weight, and the amount of f-3 was changed to 0.08% by weight. Other than that was melt-kneaded similarly to Example 3 to obtain polyamide resin composition pellets.
The obtained pellets were examined for flame retardancy (UL-94VB), electrical properties (CTI), mechanical properties, the amount of deposits at high temperatures and heat discoloration by the above-described measurement methods. The results are shown in Table 1.
Example 4
The raw material f-3 was changed to f-4. Other than that was melt-kneaded similarly to Example 3 to obtain polyamide resin composition pellets.
The obtained pellets were examined for flame retardancy (UL-94VB), electrical properties (CTI), mechanical properties, the amount of deposits at high temperatures and heat discoloration by the above-described measurement methods. The results are shown in Table 1.
（実施例５）
原材料のｅ−１をｅ−２に変更した。それ以外は、実施例４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。
得られたペレットを前記した測定方法にて難燃性（ＵＬ−９４ＶＢ）、電気特性（ＣＴＩ）、機械特性、成形品の高温での付着物量、耐熱変色性を調べた。その結果を表１に示す。
（比較例６）
原材料のａ−２の量を５２．７２重量％、ｆ−４の量を０．０８重量％に変更した。それ以外は、実施例４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。
得られたペレットを前記した測定方法にて難燃性（ＵＬ−９４ＶＢ）、電気特性（ＣＴＩ）、機械特性、成形品の高温での付着物量、耐熱変色性を調べた。その結果を表１に示す。
(Example 5)
The raw material e-1 was changed to e-2. Other than that was melt-kneaded in the same manner as in Example 4 to obtain polyamide resin composition pellets.
The obtained pellets were examined for flame retardancy (UL-94VB), electrical properties (CTI), mechanical properties, the amount of deposits at high temperatures and heat discoloration by the above-described measurement methods. The results are shown in Table 1.
(Comparative Example 6)
The amount of raw material a-2 was changed to 52.72% by weight, and the amount of f-4 was changed to 0.08% by weight. Other than that was melt-kneaded in the same manner as in Example 4 to obtain polyamide resin composition pellets.
The obtained pellets were examined for flame retardancy (UL-94VB), electrical properties (CTI), mechanical properties, the amount of deposits at high temperatures and heat discoloration by the above-described measurement methods. The results are shown in Table 1.
本発明は、燃焼時にハロゲン化水素ガスの発生がなく、薄肉難燃性、電気特性、押出加工性、離型性、流動性等の成形加工性、機械特性が優れており、更に成形品の高温での付着物量が抑制された難燃性ポリアミド樹脂組成物を提供できるため、高い難燃性、高い電気特性、高い靭性、さらには易成形性を要求され、更に成形品の高温での付着物量ができるだけ抑制されたもの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 does not generate hydrogen halide gas at the time of combustion, has excellent thin film flame retardancy, electrical properties, extrusion processability, mold release properties, flowability, and other molding processability and mechanical properties. Since it is possible to provide a flame-retardant polyamide resin composition with a reduced amount of deposits at high temperatures, high flame retardancy, high electrical properties, high toughness, and easy moldability are required. This is very useful in the field of application where a material whose amount is suppressed as much as possible 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.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10505875A (en) * | 1994-09-21 | 1998-06-09 | デーエスエム・メラプル・ベスローテン・フェンノートシャップ | Flame retardant glass fiber reinforced polyamide resin composition containing melamine- or melem-phosphoric acid reaction product as flame retardant |
| JP2001072978A (en) * | 1999-07-22 | 2001-03-21 | Clariant Gmbh | Flame retardant combination |
| JP2001081317A (en) * | 1999-09-16 | 2001-03-27 | Asahi Kasei Corp | Flame retardant polyamide resin composition and its molded product |
| JP2002201361A (en) * | 2000-12-28 | 2002-07-19 | Wakoo Jushi Kk | Flame-retardant resin composition |
| JP2002275370A (en) * | 2001-03-21 | 2002-09-25 | Asahi Kasei Corp | Flame-retardant polyamide resin composition |
| JP2002284987A (en) * | 2001-03-26 | 2002-10-03 | Asahi Kasei Corp | Flame-retardant polyamide composition |
| JP2004510863A (en) * | 2000-10-05 | 2004-04-08 | チバ スペシャルティ ケミカルズ ホールディング インコーポレーテッド | Halogen-free flame retardant composition and flame retardant polyamide composition |
| JP2004263188A (en) * | 2003-03-03 | 2004-09-24 | Clariant Gmbh | Flame retarder-stabiliser-combination for thermoplastic polymer |
| JP2005105167A (en) * | 2003-09-30 | 2005-04-21 | Toray Ind Inc | Polyamide resin composition |
| JP2005113146A (en) * | 2003-10-07 | 2005-04-28 | Clariant Gmbh | Phosphorus-containing flame-retardant aggregate |
-
2005
- 2005-07-20 JP JP2005209679A patent/JP4993425B2/en not_active Expired - Fee Related
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10505875A (en) * | 1994-09-21 | 1998-06-09 | デーエスエム・メラプル・ベスローテン・フェンノートシャップ | Flame retardant glass fiber reinforced polyamide resin composition containing melamine- or melem-phosphoric acid reaction product as flame retardant |
| JP2001072978A (en) * | 1999-07-22 | 2001-03-21 | Clariant Gmbh | Flame retardant combination |
| JP2001081317A (en) * | 1999-09-16 | 2001-03-27 | Asahi Kasei Corp | Flame retardant polyamide resin composition and its molded product |
| JP2004510863A (en) * | 2000-10-05 | 2004-04-08 | チバ スペシャルティ ケミカルズ ホールディング インコーポレーテッド | Halogen-free flame retardant composition and flame retardant polyamide composition |
| JP2002201361A (en) * | 2000-12-28 | 2002-07-19 | Wakoo Jushi Kk | Flame-retardant resin composition |
| JP2002275370A (en) * | 2001-03-21 | 2002-09-25 | Asahi Kasei Corp | Flame-retardant polyamide resin composition |
| JP2002284987A (en) * | 2001-03-26 | 2002-10-03 | Asahi Kasei Corp | Flame-retardant polyamide composition |
| JP2004263188A (en) * | 2003-03-03 | 2004-09-24 | Clariant Gmbh | Flame retarder-stabiliser-combination for thermoplastic polymer |
| JP2005105167A (en) * | 2003-09-30 | 2005-04-21 | Toray Ind Inc | Polyamide resin composition |
| JP2005113146A (en) * | 2003-10-07 | 2005-04-28 | Clariant Gmbh | Phosphorus-containing flame-retardant aggregate |
Cited By (32)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI419913B (en) * | 2007-03-30 | 2013-12-21 | Mitsui Chemicals Inc | Flame-retardant polyamide composition |
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| US20100116542A1 (en) * | 2007-04-17 | 2010-05-13 | Seiren Co., Ltd. | Flame retardant metal coated fabric, and electromagnetic wave shielding gasket |
| WO2008125968A3 (en) * | 2007-04-17 | 2009-02-12 | Seiren Co Ltd | Metal-coated fabric |
| JP2008285804A (en) * | 2007-04-17 | 2008-11-27 | Seiren Co Ltd | Flame-retardant metal-coated fabric and gasket for shielding electromagnetic wave by using the same |
| KR101159440B1 (en) | 2007-09-21 | 2012-06-22 | 미쓰이 가가쿠 가부시키가이샤 | Flame-retardant polyamide composition |
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| JP2009275217A (en) * | 2008-04-14 | 2009-11-26 | Asahi Kasei Chemicals Corp | Polyamide composition |
| CN102257071A (en) * | 2008-12-22 | 2011-11-23 | 三井化学株式会社 | Flame-retardant polyamide composition |
| JPWO2010073595A1 (en) * | 2008-12-22 | 2012-06-07 | 三井化学株式会社 | Flame retardant polyamide composition |
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| EP2361952A1 (en) * | 2008-12-22 | 2011-08-31 | Mitsui Chemicals, Inc. | Flame-retardant polyamide composition |
| WO2010073595A1 (en) * | 2008-12-22 | 2010-07-01 | 三井化学株式会社 | Flame-retardant polyamide composition |
| JP5761998B2 (en) * | 2008-12-22 | 2015-08-12 | 三井化学株式会社 | Flame retardant polyamide composition |
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