WO2015087886A1 - ポリアミド組成物、成形品、led用反射板、及び熱による反射率の低下を抑制する方法 - Google Patents
ポリアミド組成物、成形品、led用反射板、及び熱による反射率の低下を抑制する方法 Download PDFInfo
- Publication number
- WO2015087886A1 WO2015087886A1 PCT/JP2014/082596 JP2014082596W WO2015087886A1 WO 2015087886 A1 WO2015087886 A1 WO 2015087886A1 JP 2014082596 W JP2014082596 W JP 2014082596W WO 2015087886 A1 WO2015087886 A1 WO 2015087886A1
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- WO
- WIPO (PCT)
- Prior art keywords
- polyamide
- polyamide composition
- acid
- metal
- dicarboxylic acid
- Prior art date
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- 239000004952 Polyamide Substances 0.000 title claims abstract description 385
- 229920002647 polyamide Polymers 0.000 title claims abstract description 385
- 239000000203 mixture Substances 0.000 title claims abstract description 215
- 238000000034 method Methods 0.000 title description 83
- 230000009467 reduction Effects 0.000 title description 3
- 238000002310 reflectometry Methods 0.000 title description 3
- 239000011574 phosphorus Substances 0.000 claims abstract description 56
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 56
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 43
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 43
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 40
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 40
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 10
- -1 phosphorus compound Chemical class 0.000 claims description 112
- 229910052751 metal Inorganic materials 0.000 claims description 77
- 239000002184 metal Substances 0.000 claims description 76
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 73
- 238000006116 polymerization reaction Methods 0.000 claims description 48
- 238000002844 melting Methods 0.000 claims description 41
- 230000008018 melting Effects 0.000 claims description 41
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 37
- 150000003839 salts Chemical class 0.000 claims description 36
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 36
- 125000002723 alicyclic group Chemical group 0.000 claims description 27
- 230000009477 glass transition Effects 0.000 claims description 21
- 239000011256 inorganic filler Substances 0.000 claims description 20
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 20
- 239000002667 nucleating agent Substances 0.000 claims description 20
- 238000002425 crystallisation Methods 0.000 claims description 19
- 230000008025 crystallization Effects 0.000 claims description 19
- 230000014759 maintenance of location Effects 0.000 claims description 15
- 239000000178 monomer Substances 0.000 claims description 12
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 claims description 11
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 9
- 238000000113 differential scanning calorimetry Methods 0.000 claims description 5
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 8
- 238000000465 moulding Methods 0.000 description 36
- 238000004519 manufacturing process Methods 0.000 description 35
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 34
- 229910052757 nitrogen Inorganic materials 0.000 description 34
- 125000004427 diamine group Chemical group 0.000 description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 31
- 238000002845 discoloration Methods 0.000 description 31
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 30
- 150000004985 diamines Chemical class 0.000 description 30
- 230000008569 process Effects 0.000 description 27
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 26
- 238000001125 extrusion Methods 0.000 description 26
- 239000000047 product Substances 0.000 description 26
- 239000002245 particle Substances 0.000 description 25
- 239000002994 raw material Substances 0.000 description 24
- 150000003951 lactams Chemical class 0.000 description 23
- 125000001142 dicarboxylic acid group Chemical group 0.000 description 21
- 150000001412 amines Chemical class 0.000 description 19
- 125000004432 carbon atom Chemical group C* 0.000 description 19
- 238000010438 heat treatment Methods 0.000 description 19
- 125000001424 substituent group Chemical group 0.000 description 19
- 239000000126 substance Substances 0.000 description 16
- 125000001931 aliphatic group Chemical group 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 14
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 14
- 239000003963 antioxidant agent Substances 0.000 description 14
- 238000002156 mixing Methods 0.000 description 14
- 239000008188 pellet Substances 0.000 description 14
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 13
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- 230000003078 antioxidant effect Effects 0.000 description 11
- 230000004927 fusion Effects 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 125000003118 aryl group Chemical group 0.000 description 9
- 239000000835 fiber Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 239000004611 light stabiliser Substances 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 229910052623 talc Inorganic materials 0.000 description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 150000003018 phosphorus compounds Chemical class 0.000 description 8
- 239000000454 talc Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 239000012943 hotmelt Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 239000000155 melt Substances 0.000 description 7
- 229910001507 metal halide Inorganic materials 0.000 description 7
- 150000005309 metal halides Chemical class 0.000 description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 7
- 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 7
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 description 6
- 239000007983 Tris buffer Substances 0.000 description 6
- 150000001342 alkaline earth metals Chemical class 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- 238000000691 measurement method Methods 0.000 description 6
- 150000002736 metal compounds Chemical class 0.000 description 6
- 229910001463 metal phosphate Inorganic materials 0.000 description 6
- 239000002530 phenolic antioxidant Substances 0.000 description 6
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 6
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 6
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 6
- GAGWMWLBYJPFDD-UHFFFAOYSA-N 2-methyloctane-1,8-diamine Chemical group NCC(C)CCCCCCN GAGWMWLBYJPFDD-UHFFFAOYSA-N 0.000 description 5
- 229920002292 Nylon 6 Polymers 0.000 description 5
- 229920002302 Nylon 6,6 Polymers 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 230000032683 aging Effects 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 125000003277 amino group Chemical group 0.000 description 5
- 150000004984 aromatic diamines Chemical group 0.000 description 5
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 5
- 238000004364 calculation method Methods 0.000 description 5
- 239000011247 coating layer Substances 0.000 description 5
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical group NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 5
- 150000003961 organosilicon compounds Chemical class 0.000 description 5
- 239000007790 solid phase Substances 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 4
- 239000000920 calcium hydroxide Substances 0.000 description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 4
- 229910001382 calcium hypophosphite Inorganic materials 0.000 description 4
- 229940064002 calcium hypophosphite Drugs 0.000 description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 4
- 239000000292 calcium oxide Substances 0.000 description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- QQHJDPROMQRDLA-UHFFFAOYSA-N hexadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCC(O)=O QQHJDPROMQRDLA-UHFFFAOYSA-N 0.000 description 4
- JJOJFIHJIRWASH-UHFFFAOYSA-N icosanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCCCC(O)=O JJOJFIHJIRWASH-UHFFFAOYSA-N 0.000 description 4
- 239000012770 industrial material Substances 0.000 description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 4
- 239000000347 magnesium hydroxide Substances 0.000 description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 4
- BNJOQKFENDDGSC-UHFFFAOYSA-N octadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCC(O)=O BNJOQKFENDDGSC-UHFFFAOYSA-N 0.000 description 4
- 150000002903 organophosphorus compounds Chemical class 0.000 description 4
- 229920005862 polyol Polymers 0.000 description 4
- 150000003077 polyols Chemical class 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- CNALVHVMBXLLIY-IUCAKERBSA-N tert-butyl n-[(3s,5s)-5-methylpiperidin-3-yl]carbamate Chemical compound C[C@@H]1CNC[C@@H](NC(=O)OC(C)(C)C)C1 CNALVHVMBXLLIY-IUCAKERBSA-N 0.000 description 4
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 238000011144 upstream manufacturing Methods 0.000 description 4
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 3
- 229910052582 BN Inorganic materials 0.000 description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 3
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 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 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000010445 mica Substances 0.000 description 3
- 229910052618 mica group Inorganic materials 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 239000000565 sealant Substances 0.000 description 3
- 239000001488 sodium phosphate Substances 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910052712 strontium Inorganic materials 0.000 description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- NZNAAUDJKMURFU-UHFFFAOYSA-N tetrakis(2,2,6,6-tetramethylpiperidin-4-yl) butane-1,2,3,4-tetracarboxylate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CC(C(=O)OC1CC(C)(C)NC(C)(C)C1)C(C(=O)OC1CC(C)(C)NC(C)(C)C1)CC(=O)OC1CC(C)(C)NC(C)(C)C1 NZNAAUDJKMURFU-UHFFFAOYSA-N 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- 239000010456 wollastonite Substances 0.000 description 3
- 229910052882 wollastonite Inorganic materials 0.000 description 3
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 2
- PBLZLIFKVPJDCO-UHFFFAOYSA-N 12-aminododecanoic acid Chemical compound NCCCCCCCCCCCC(O)=O PBLZLIFKVPJDCO-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- ZNRLMGFXSPUZNR-UHFFFAOYSA-N 2,2,4-trimethyl-1h-quinoline Chemical compound C1=CC=C2C(C)=CC(C)(C)NC2=C1 ZNRLMGFXSPUZNR-UHFFFAOYSA-N 0.000 description 2
- GXURZKWLMYOCDX-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.OCC(CO)(CO)CO GXURZKWLMYOCDX-UHFFFAOYSA-N 0.000 description 2
- WBWXVCMXGYSMQA-UHFFFAOYSA-N 3,9-bis[2,4-bis(2-phenylpropan-2-yl)phenoxy]-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C=1C=C(OP2OCC3(CO2)COP(OC=2C(=CC(=CC=2)C(C)(C)C=2C=CC=CC=2)C(C)(C)C=2C=CC=CC=2)OC3)C(C(C)(C)C=2C=CC=CC=2)=CC=1C(C)(C)C1=CC=CC=C1 WBWXVCMXGYSMQA-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
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
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- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 1
- ROPDWRCJTIRLTR-UHFFFAOYSA-L calcium metaphosphate Chemical compound [Ca+2].[O-]P(=O)=O.[O-]P(=O)=O ROPDWRCJTIRLTR-UHFFFAOYSA-L 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
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- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- BUZRUIZTMOKRPB-UHFFFAOYSA-N carboxycarbamic acid Chemical compound OC(=O)NC(O)=O BUZRUIZTMOKRPB-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
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- 125000001309 chloro group Chemical group Cl* 0.000 description 1
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- 238000004040 coloring Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
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- 150000001880 copper compounds Chemical class 0.000 description 1
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 description 1
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- XBZSBBLNHFMTEB-UHFFFAOYSA-N cyclohexane-1,3-dicarboxylic acid Chemical compound OC(=O)C1CCCC(C(O)=O)C1 XBZSBBLNHFMTEB-UHFFFAOYSA-N 0.000 description 1
- ZQWRZCZEOLZBQF-UHFFFAOYSA-N cyclopentane-1,3-diamine Chemical compound NC1CCC(N)C1 ZQWRZCZEOLZBQF-UHFFFAOYSA-N 0.000 description 1
- LNGJOYPCXLOTKL-UHFFFAOYSA-N cyclopentane-1,3-dicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)C1 LNGJOYPCXLOTKL-UHFFFAOYSA-N 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- PWZFXELTLAQOKC-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide;tetrahydrate Chemical compound O.O.O.O.[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O PWZFXELTLAQOKC-UHFFFAOYSA-A 0.000 description 1
- NEFBYIFKOOEVPA-UHFFFAOYSA-K dicalcium phosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])([O-])=O NEFBYIFKOOEVPA-UHFFFAOYSA-K 0.000 description 1
- 229910000390 dicalcium phosphate Inorganic materials 0.000 description 1
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- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
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- FSBVERYRVPGNGG-UHFFFAOYSA-N dimagnesium dioxido-bis[[oxido(oxo)silyl]oxy]silane hydrate Chemical compound O.[Mg+2].[Mg+2].[O-][Si](=O)O[Si]([O-])([O-])O[Si]([O-])=O FSBVERYRVPGNGG-UHFFFAOYSA-N 0.000 description 1
- OREAFAJWWJHCOT-UHFFFAOYSA-N dimethylmalonic acid Chemical compound OC(=O)C(C)(C)C(O)=O OREAFAJWWJHCOT-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- OGVJEUDMQQIAPV-UHFFFAOYSA-N diphenyl tridecyl phosphite Chemical compound C=1C=CC=CC=1OP(OCCCCCCCCCCCCC)OC1=CC=CC=C1 OGVJEUDMQQIAPV-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- DECIPOUIJURFOJ-UHFFFAOYSA-N ethoxyquin Chemical compound N1C(C)(C)C=C(C)C2=CC(OCC)=CC=C21 DECIPOUIJURFOJ-UHFFFAOYSA-N 0.000 description 1
- FPIQZBQZKBKLEI-UHFFFAOYSA-N ethyl 1-[[2-chloroethyl(nitroso)carbamoyl]amino]cyclohexane-1-carboxylate Chemical compound ClCCN(N=O)C(=O)NC1(C(=O)OCC)CCCCC1 FPIQZBQZKBKLEI-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
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- 125000005843 halogen group Chemical group 0.000 description 1
- PWSKHLMYTZNYKO-UHFFFAOYSA-N heptane-1,7-diamine Chemical compound NCCCCCCCN PWSKHLMYTZNYKO-UHFFFAOYSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- RTWNYYOXLSILQN-UHFFFAOYSA-N methanediamine Chemical compound NCN RTWNYYOXLSILQN-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 235000019691 monocalcium phosphate Nutrition 0.000 description 1
- 229910000150 monocalcium phosphate Inorganic materials 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 238000010137 moulding (plastic) Methods 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- LKPFBGKZCCBZDK-UHFFFAOYSA-N n-hydroxypiperidine Chemical compound ON1CCCCC1 LKPFBGKZCCBZDK-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
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- AXRSHKZFNKUGQB-UHFFFAOYSA-N octyl diphenyl phosphite Chemical class C=1C=CC=CC=1OP(OCCCCCCCC)OC1=CC=CC=C1 AXRSHKZFNKUGQB-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 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
- MFPCPCHVMQLDJN-UHFFFAOYSA-N phenyl ditridecyl phosphite Chemical compound CCCCCCCCCCCCCOP(OCCCCCCCCCCCCC)OC1=CC=CC=C1 MFPCPCHVMQLDJN-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229960003424 phenylacetic acid Drugs 0.000 description 1
- 239000003279 phenylacetic acid Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 150000003017 phosphorus Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920006123 polyhexamethylene isophthalamide Polymers 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- TURAMGVWNUTQKH-UHFFFAOYSA-N propa-1,2-dien-1-one Chemical group C=C=C=O TURAMGVWNUTQKH-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229920006012 semi-aromatic polyamide Polymers 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 239000000429 sodium aluminium silicate Substances 0.000 description 1
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 235000019983 sodium metaphosphate Nutrition 0.000 description 1
- KOUDKOMXLMXFKX-UHFFFAOYSA-N sodium oxido(oxo)phosphanium hydrate Chemical compound O.[Na+].[O-][PH+]=O KOUDKOMXLMXFKX-UHFFFAOYSA-N 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- WUPCFMITFBVJMS-UHFFFAOYSA-N tetrakis(1,2,2,6,6-pentamethylpiperidin-4-yl) butane-1,2,3,4-tetracarboxylate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CC(C(=O)OC1CC(C)(C)N(C)C(C)(C)C1)C(C(=O)OC1CC(C)(C)N(C)C(C)(C)C1)CC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 WUPCFMITFBVJMS-UHFFFAOYSA-N 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 230000010512 thermal transition Effects 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- GQUJEMVIKWQAEH-UHFFFAOYSA-N titanium(III) oxide Chemical compound O=[Ti]O[Ti]=O GQUJEMVIKWQAEH-UHFFFAOYSA-N 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- BWPNIANVWARHPR-UHFFFAOYSA-N tridecyl dihydrogen phosphite Chemical class CCCCCCCCCCCCCOP(O)O BWPNIANVWARHPR-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QOQNJVLFFRMJTQ-UHFFFAOYSA-N trioctyl phosphite Chemical class CCCCCCCCOP(OCCCCCCCC)OCCCCCCCC QOQNJVLFFRMJTQ-UHFFFAOYSA-N 0.000 description 1
- LTXMJHWSYUANCC-UHFFFAOYSA-N tris(2,4-ditert-butyl-5-methylphenyl) phosphite Chemical compound C1=C(C(C)(C)C)C(C)=CC(OP(OC=2C(=CC(=C(C)C=2)C(C)(C)C)C(C)(C)C)OC=2C(=CC(=C(C)C=2)C(C)(C)C)C(C)(C)C)=C1C(C)(C)C LTXMJHWSYUANCC-UHFFFAOYSA-N 0.000 description 1
- URRFGQHFJDWCFM-UHFFFAOYSA-N tris(2-butoxyethyl) phosphite Chemical compound CCCCOCCOP(OCCOCCCC)OCCOCCCC URRFGQHFJDWCFM-UHFFFAOYSA-N 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
- LUUMBHMWFNNZPH-UHFFFAOYSA-N tris(3,5-ditert-butyl-4-hydroxyphenyl) phosphite Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(OP(OC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)OC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 LUUMBHMWFNNZPH-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- KLNPWTHGTVSSEU-UHFFFAOYSA-N undecane-1,11-diamine Chemical compound NCCCCCCCCCCCN KLNPWTHGTVSSEU-UHFFFAOYSA-N 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0083—Nucleating agents promoting the crystallisation of the polymer matrix
-
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21V—FUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
- F21V7/00—Reflectors for light sources
- F21V7/22—Reflectors for light sources characterised by materials, surface treatments or coatings, e.g. dichroic reflectors
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/58—Optical field-shaping elements
- H01L33/60—Reflective elements
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/222—Magnesia, i.e. magnesium oxide
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/324—Alkali metal phosphate
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/325—Calcium, strontium or barium phosphate
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Definitions
- the present invention relates to a polyamide composition, a molded product, a reflector for LED, and a method for suppressing a decrease in reflectance due to heat.
- Polyamides represented by polyamide 6 (hereinafter also referred to as “PA6”) and polyamide 66 (hereinafter also referred to as “PA66”) and the like are excellent in molding processability, mechanical properties, and chemical resistance. Widely used as various parts materials for automobiles, electric and electronic, industrial materials, industrial materials, daily products and household products.
- polyamides are increasingly used in place of metals as exterior materials and interior materials for automobiles.
- Polyamides used for automobile exterior materials and interior materials are required to have higher levels of heat resistance, strength, appearance, and other characteristics.
- polyamides used as materials in the engine room are increasingly required to have high heat resistance in order to cope with the increasing tendency of the temperature in the engine room.
- SMT solder is progressing.
- Polyamides used for materials such as home appliances are required to have high heat resistance so that they can withstand the rise in the melting point of solder accompanying such lead-free soldering.
- PA6T terephthalic acid and hexamethylenediamine
- PA6T is a high melting point polyamide having a melting point of about 370 ° C.
- the polyamide undergoes thermal decomposition during the molding process to obtain a molded product having sufficient characteristics. There is a problem that it is difficult.
- PA6I amorphous aromatic polyamide
- 6T copolymer polyamide a high melting point semi-aromatic polyamide
- Patent Document 1 as a 6T copolymer polyamide, an aromatic polyamide composed of an aromatic dicarboxylic acid and an aliphatic diamine, and the aliphatic diamine is a mixture of hexamethylenediamine and 2-methylpentamethylenediamine (
- PA6T / 2MPDT is also disclosed.
- Patent Document 2 discloses a semi-alicyclic polyamide containing 1 to 40% of 1,4-cyclohexanedicarboxylic acid as a dicarboxylic acid unit. Electric and electronic members containing the semi-alicyclic polyamide are disclosed. It is disclosed that the solder heat resistance is improved.
- Patent Document 3 discloses a polyamide resin (hereinafter referred to as a dicarboxylic acid containing a terephthalic acid unit) and a diamine containing a 1,9-nonanediamine unit and / or a 2-methyl-1,8-octanediamine unit. , "PA9T”), a polyamide composition comprising titanium oxide, magnesium hydroxide, and a specific reinforcing material is disclosed, and it is disclosed that this polyamide composition is excellent in heat resistance. Has been.
- Patent Document 4 contains a semi-alicyclic polyamide blended with 70% or more of 1,4-cyclohexanedicarboxylic acid as a dicarboxylic acid unit, titanium oxide, and an inorganic filler, and their mass ratio.
- a polyamide composition having a predetermined value is disclosed, and it is disclosed that this polyamide composition is excellent in reflow resistance, heat resistance and the like.
- JP-T 6-503590 Japanese National Patent Publication No. 11-512476 JP 2006-257314 A JP 2011-219697 A
- the present inventors have found that a polyamide composition containing a polyamide, a metal hydroxide and / or a metal oxide, and a phosphorus compound is the above problem. As a result, the present invention has been completed. That is, the present invention is as follows.
- the (E) phosphorus compound is a metal salt, and the metal species of the metal salt is the same as the metal species of (C) a metal hydroxide and / or (D) a metal oxide, [1] to [1] to [7] The polyamide composition according to any one of [7]. [9] The polyamide composition according to any one of [1] to [8], wherein the (E) phosphorus compound is an alkaline earth metal salt. [10] (F) The polyamide composition according to any one of [1] to [9], further containing 5% by mass or more of an inorganic filler. [11] The polyamide composition according to any one of [1] to [10], further containing 0.001 to 15% by mass of a nucleating agent.
- a polyamide composition having excellent whiteness, reflow resistance, heat discoloration resistance, extrusion processability, and molding process stability can be provided.
- the present embodiment a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail.
- the following this embodiment is an illustration for demonstrating this invention, and is not the meaning which limits this invention to the following content.
- the present invention can be implemented with various modifications within the scope of the gist.
- polyamide composition The polyamide composition of the present embodiment (hereinafter also simply referred to as “polyamide composition”) (A) polyamide, (C) metal hydroxide and / or (D) metal oxide 0.1 to 20% by mass, (E) 0.1 to 20% by mass of a phosphorus compound, Containing.
- the polyamide (A) used in the present embodiment has (a) a dicarboxylic acid unit and (b) a diamine unit.
- the total amount of the above-mentioned (a) dicarboxylic acid unit and (b) diamine unit is preferably 20 to 100 mol%, preferably 90 to 100 mol%, based on 100 mol% of all structural units of (A) polyamide. More preferably, it is more preferably 100 mol%.
- the ratio of the predetermined monomer unit constituting the polyamide (A) can be measured by nuclear magnetic resonance spectroscopy (NMR) or the like.
- NMR nuclear magnetic resonance spectroscopy
- the structural unit of (A) polyamide other than (a) dicarboxylic acid unit and (b) diamine unit is not particularly limited.
- (c) lactam and / or aminocarboxylic acid described later is used. The unit which consists of is mentioned.
- polyamide means a polymer having an amide (—NHCO—) bond in the main chain.
- (a) dicarboxylic acid units include, but are not limited to, (a-1) alicyclic dicarboxylic acid units, (a-2) aromatic dicarboxylic acid units, and (a-3) Aliphatic dicarboxylic acid units are mentioned.
- the (a) dicarboxylic acid unit preferably contains 50 to 100 mol% of the (a-1) alicyclic dicarboxylic acid unit (based on the total number of moles of dicarboxylic acid), more preferably 60 to 100 mol%. More preferably, it is contained in an amount of ⁇ 100 mol%, more preferably 100 mol%.
- the alicyclic dicarboxylic acid constituting the (a-1) alicyclic dicarboxylic acid unit is not limited to the following. Examples thereof include alicyclic dicarboxylic acids having 3 to 10 carbon atoms in the alicyclic structure, and alicyclic dicarboxylic acids having 5 to 10 carbon atoms in the alicyclic structure are preferable.
- alicyclic dicarboxylic acids examples include, but are not limited to, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, and the like. Can be mentioned. Among these, 1,4-cyclohexanedicarboxylic acid is preferable. By including such an alicyclic dicarboxylic acid, the heat resistance, low water absorption, rigidity and the like of the polyamide composition tend to be more excellent.
- the (a-1) alicyclic dicarboxylic acid constituting the alicyclic dicarboxylic acid unit may be used alone or in combination of two or more.
- the alicyclic group of the alicyclic dicarboxylic acid may be unsubstituted or may have a substituent.
- substituents include, but are not limited to, for example, 1 carbon atom such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group. -4 alkyl groups and the like.
- the alicyclic dicarboxylic acid constituting the alicyclic dicarboxylic acid unit includes a trans isomer and a cis geometric isomer.
- a trans isomer or a cis isomer may be used, or a mixture containing a trans isomer and a cis isomer in a predetermined ratio may be used.
- the trans isomer / cis isomer ratio (molar ratio) of the alicyclic dicarboxylic acid as the raw material monomer is preferably 50/50 to 0/100, more preferably 40/60 to 10/90. More preferably, it is 35/65 to 15/85.
- the trans / cis ratio (molar ratio) of the alicyclic dicarboxylic acid can be determined by liquid chromatography (HPLC) or nuclear magnetic resonance spectroscopy (NMR).
- the (a-1) alicyclic dicarboxylic acid unit in the polyamide has a trans isomer or a geometric isomer of a cis isomer.
- the ratio of the trans isomer in the whole (a-1) alicyclic dicarboxylic acid unit is referred to as “trans isomer ratio”.
- the trans isomer ratio is preferably 50 to 85 mol%, more preferably 50 to 80 mol%, and still more preferably 60 to 80 mol%.
- the polyamide composition of the present embodiment has a high melting point, toughness and rigidity, and in addition to the characteristics such as high thermal transition rigidity (Tg), However, it tends to have a property of simultaneously satisfying fluidity, which is a property contrary to heat resistance, and high crystallinity.
- Tg thermal transition rigidity
- these characteristics are obtained from a combination of (a) a dicarboxylic acid unit containing 50 mol% or more of 1,4-cyclohexanedicarboxylic acid and (b) a diamine unit containing 50 mol% or more of 2-methylpentamethylenediamine ( This is particularly noticeable in (A) polyamides which are A) polyamides and the trans isomer ratio is 50 to 85 mol%.
- the “trans isomer ratio” can be measured by the method described in Examples described later.
- Aromatic dicarboxylic acid unit (A-2)
- the aromatic dicarboxylic acid constituting the aromatic dicarboxylic acid unit is not limited to the following, and examples thereof include a dicarboxylic acid having a phenyl group or a naphthyl group.
- the aromatic group of the aromatic dicarboxylic acid may be unsubstituted or may have a substituent.
- the substituent is not particularly limited, and examples thereof include halogen groups such as an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, an arylalkyl group having 7 to 10 carbon atoms, a chloro group, and a bromo group.
- Aromatic dicarboxylic acids include, but are not limited to, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, and 5-sodium sulfo Examples thereof include aromatic dicarboxylic acids having 8 to 20 carbon atoms that are unsubstituted or substituted with a predetermined substituent such as isophthalic acid. (A-2) As the aromatic dicarboxylic acid constituting the aromatic dicarboxylic acid unit, only one kind may be used alone, or two or more kinds may be used in combination.
- the aliphatic dicarboxylic acid constituting the aliphatic dicarboxylic acid unit is not limited to the following, but examples thereof include malonic acid, dimethylmalonic acid, succinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylglutaric acid, 2,2-diethylsuccinic acid, 2,3-diethylglutaric acid, glutaric acid, 2,2-dimethylglutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid C3-20 linear or branched saturated aliphatic such as suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, eicosanedioic acid, and diglycolic acid
- the dicarboxylic acid unit other than the alicyclic dicarboxylic acid unit preferably includes (a-3) an aliphatic dicarboxylic acid unit, and includes an aliphatic dicarboxylic acid having 6 or more carbon atoms. More preferred.
- the polyamide composition tends to have better heat resistance, fluidity, toughness, low water absorption, rigidity, and the like.
- the (a-3) aliphatic dicarboxylic acid an aliphatic dicarboxylic acid having 10 or more carbon atoms is preferable. By using such a dicarboxylic acid, the heat resistance and low water absorption of the polyamide composition tend to be more excellent.
- the aliphatic dicarboxylic acid having 10 or more carbon atoms is not particularly limited, and examples thereof include sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, and eicosanedioic acid. Among these, sebacic acid and dodecanedioic acid are preferable from the viewpoint of heat resistance of the polyamide composition. (A-3) As the aliphatic dicarboxylic acid constituting the aliphatic dicarboxylic acid unit, only one kind may be used alone, or two or more kinds may be used in combination.
- the proportion (mol%) of the dicarboxylic acid other than the (a-1) alicyclic dicarboxylic acid unit in the (a) dicarboxylic acid unit is preferably 0 to 50 mol%, and preferably 0 to 40 mol%. More preferably, it is more preferably 0 to 30 mol%.
- the aliphatic dicarboxylic acid (a-3) having 10 or more carbon atoms is included, (a-1) 50 to 99.9 mol% of the alicyclic dicarboxylic acid and (a-3) the aliphatic dicarboxylic acid Is preferably 0.1 to 50 mol%, (a-1) 60 to 95 mol% of the alicyclic dicarboxylic acid and (a-3) 5 to 40 mol% of the aliphatic dicarboxylic acid. More preferably, (a-1) alicyclic dicarboxylic acid is 80 to 95 mol% and (a-3) aliphatic dicarboxylic acid is 5 to 20 mol%.
- Polyamide that satisfies the excellent heat resistance, fluidity, toughness, low water absorption, rigidity, etc. at the same time when the ratio of the aliphatic dicarboxylic acid unit (a-3) having 10 or more carbon atoms is in the above range. There is a tendency to obtain a composition.
- the dicarboxylic acid constituting the dicarboxylic acid unit is not limited to the compounds described as the dicarboxylic acid, and may be a compound equivalent to the dicarboxylic acid.
- the “compound equivalent to dicarboxylic acid” refers to a compound that can have the same dicarboxylic acid structure as the dicarboxylic acid structure derived from the dicarboxylic acid. Examples of such compounds include, but are not limited to, dicarboxylic acid anhydrides and halides.
- polyamide may further contain the unit derived from trivalent or more polyvalent carboxylic acid, such as trimellitic acid, trimesic acid, and pyromellitic acid, as needed.
- Trivalent or higher polyvalent carboxylic acids may be used alone or in combination of two or more.
- the (b) diamine unit is not limited to the following, but for example, (b-1) a diamine unit having a substituent branched from the main chain, (b-2) an aliphatic diamine unit, (b- 3) An alicyclic diamine unit, and (b-4) an aromatic diamine unit.
- the (b) diamine unit preferably contains (b-1) a diamine having a substituent branched from the main chain.
- the polyamide composition of the present embodiment has more excellent fluidity, toughness, rigidity, and the like. At the same time, it tends to be satisfactory. More preferably, the (b) diamine unit contains 50 mol% or more of the diamine unit having a substituent branched from the main chain (b-1).
- the “substituent branched from the main chain” in the diamine unit having a substituent branched from the main chain is not limited to the following, but for example, a methyl group, an ethyl group, n- Examples thereof include alkyl groups having 1 to 4 carbon atoms such as propyl group, isopropyl group, n-butyl group, isobutyl group, and tert-butyl group.
- the diamine constituting the diamine unit having a substituent branched from the main chain (b-1) is not limited to the following, but for example, 2-methylpentamethylenediamine (hereinafter referred to as “2- Methyl-1,5-diaminopentane ”), 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 2-methyloctamethylenediamine, and 2,4-dimethyloctane Examples thereof include branched saturated aliphatic diamines having 3 to 20 carbon atoms such as methylenediamine. Of these, 2-methylpentamethylenediamine is preferred.
- the polyamide composition tends to be excellent in heat resistance and rigidity.
- the diamine constituting the diamine unit having a substituent branched from the main chain (b-1) only one kind may be used alone, or two or more kinds may be used in combination.
- the proportion (mol%) of the diamine unit having a substituent branched from the main chain (b-1) in the diamine unit is preferably 50 to 100 mol%, more preferably 60 to 100 mol%. More preferably 85 to 100 mol%, still more preferably 90 to 100 mol%, and still more preferably 100 mol%.
- B When the ratio of the diamine unit having a substituent branched from the main chain in the diamine unit is within the above range, the polyamide composition tends to be excellent in fluidity, toughness, and rigidity. is there.
- the (b-2) aliphatic diamine constituting the aliphatic diamine unit is not limited to the following.
- straight chain saturated aliphatic diamines having 2 to 20 carbon atoms such as
- (B-3) Alicyclic diamine unit The (b-3) alicyclic diamine constituting the alicyclic diamine unit (hereinafter also referred to as “alicyclic diamine”) is not limited to the following. Examples include cyclohexanediamine, 1,3-cyclohexanediamine, and 1,3-cyclopentanediamine.
- the aromatic diamine constituting the (b-4) aromatic diamine unit is not limited to the following as long as it is an aromatic diamine, and examples thereof include metaxylylenediamine.
- diamine units (b-2) to (b-4) preferably an aliphatic diamine unit (excluding the (b-1) diamine unit) and (b-3) an alicyclic diamine unit ( b-3), more preferably a diamine unit (b-2) having a linear saturated aliphatic group having 4 to 13 carbon atoms, and more preferably a linear saturated aliphatic group having 6 to 10 carbon atoms.
- the total proportion (mol%) of the diamine units (b-2) to (b-4) is preferably 0 to 50 mol%, and preferably 0 to 40 mol%, with respect to the entire diamine unit (b). More preferred is 0 to 30 mol%.
- the polyamide composition tends to be excellent in fluidity, toughness, and rigidity.
- the (A) polyamide may further contain a trivalent or higher polyvalent aliphatic amine such as bishexamethylenetriamine, if necessary. Trivalent or higher polyvalent aliphatic amines may be used alone or in combination of two or more.
- the polyamide may further contain (c) a lactam unit (c-1) and / or an aminocarboxylic acid unit (c-2).
- a lactam unit (c-1) and / or an aminocarboxylic acid unit (c-2) By including such a unit, a polyamide composition that is superior in toughness tends to be obtained.
- the lactam and aminocarboxylic acid constituting the lactam unit (c-1) and the aminocarboxylic acid (c-2) refer to a lactam and aminocarboxylic acid capable of polycondensation.
- lactam and aminocarboxylic acid constituting the lactam unit (c-1) and the aminocarboxylic acid unit (c-2) are not limited to the following, but for example, lactam and amino acid having 4 to 14 carbon atoms Carboxylic acids are preferred, and lactams having 6 to 12 carbon atoms and aminocarboxylic acids are more preferred.
- the lactam constituting the lactam unit (c-1) is not limited to the following. Dodecanolactam) and the like. Among these, as the lactam, ⁇ -caprolactam, laurolactam and the like are preferable, and ⁇ -caprolactam is more preferable. By including such a lactam, it tends to be a polyamide composition having better toughness.
- the aminocarboxylic acid constituting the aminocarboxylic acid unit (c-2) is not limited to the following.
- ⁇ -aminocarboxylic acid or ⁇ , ⁇ - Examples include amino acids.
- the aminocarboxylic acid is preferably a linear or branched saturated aliphatic carboxylic acid having 4 to 14 carbon atoms in which the ⁇ position is substituted with an amino group.
- Examples of such aminocarboxylic acids include, but are not limited to, 6-aminocaproic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid.
- Examples of the aminocarboxylic acid include paraaminomethylbenzoic acid.
- lactam and aminocarboxylic acid constituting the lactam unit (c-1) and aminocarboxylic acid unit (c-2) may each be used alone or in combination of two or more. .
- the total ratio (mol%) of the lactam unit (c-1) and the aminocarboxylic acid unit (c-2) is preferably 0 to 20 mol%, more preferably 0 to It is 10 mol%, and more preferably 0 to 5%.
- the total ratio of the lactam unit (c-1) and the aminocarboxylic acid unit (c-2) is in the above range, effects such as improvement in fluidity tend to be obtained.
- the terminal of (A) polyamide used in this embodiment may be end-capped with a known end capping agent.
- a known end capping agent is also added as a molecular weight regulator in the production of (A) polyamide from the above-described dicarboxylic acid and diamine and lactam and / or aminocarboxylic acid used as necessary. Can do.
- end capping agent examples include, but are not limited to, acid anhydrides such as monocarboxylic acid, monoamine, and phthalic anhydride, monoisocyanates, monoacid halides, monoesters, and monoalcohols. Etc. Among these, monocarboxylic acid and monoamine are preferable.
- acid anhydrides such as monocarboxylic acid, monoamine, and phthalic anhydride
- monoisocyanates monoacid halides
- monoesters monoalcohols.
- monocarboxylic acid and monoamine are preferable.
- A Since the terminal of the polyamide is blocked with a terminal sealing agent, the polyamide composition tends to be more excellent in thermal stability. Only one type of end capping agent may be used alone, or two or more types may be used in combination.
- the monocarboxylic acid that can be used as the end-capping agent is not limited to the following as long as it has reactivity with an amino group that can be present at the end of the (A) polyamide.
- formic acid Aliphatic monocarboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, and isobutyric acid; cyclohexanecarboxylic acid, etc.
- aromatic monocarboxylic acids such as benzoic acid, toluic acid, ⁇ -naphthalenecarboxylic acid, ⁇ -naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, and phenylacetic acid.
- the said monocarboxylic acid may be used individually by 1 type, and may be used in combination of 2 or more type.
- the monoamine that can be used as the end-capping agent is not limited to the following as long as it has reactivity with the carboxyl group that can be present at the end of the (A) polyamide, but for example, methylamine, Aliphatic monoamines such as ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, and dibutylamine; alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; and aniline , Aromatic monoamines such as toluidine, diphenylamine, and naphthylamine. Only one monoamine may be used alone, or two or more monoamines may be used in combination.
- the polyamide composition containing (A) polyamide end-capped with a terminal capping agent tends to be excellent in heat resistance, fluidity, toughness, low water absorption, and rigidity.
- (A) Polyamide production method) (A) As a manufacturing method of polyamide, although not limited to the following, for example, (a) dicarboxylic acid which comprises a dicarboxylic acid unit, (b) diamine which comprises a diamine unit, and as needed It includes a step of polymerizing lactam and / or aminocarboxylic acid constituting the lactam unit (c-1) and / or aminocarboxylic acid unit (c-2) to obtain a polymer, and increasing the degree of polymerization of polyamide. It is preferable that the process of making it include is further included. Moreover, the sealing process which seals the terminal of the obtained polymer with a terminal sealing agent may be included as needed.
- thermoforming method As a concrete manufacturing method of polyamide, various methods are mentioned, for example so that it may illustrate below. 1) A method in which an aqueous solution of a dicarboxylic acid-diamine salt or a mixture of a dicarboxylic acid and a diamine, or a suspension of these waters is heated and polymerized while maintaining a molten state (hereinafter referred to as “hot melt polymerization method”). Say.). 2) A method of increasing the degree of polymerization of the polyamide obtained by the hot melt polymerization method while maintaining the solid state at a temperature below the melting point (hereinafter also referred to as “hot melt polymerization / solid phase polymerization method”).
- a method for increasing the degree of polymerization (hereinafter also referred to as “prepolymer / solid phase polymerization method”). 5) A method of polymerizing a dicarboxylic acid-diamine salt or a mixture of a dicarboxylic acid and a diamine while maintaining a solid state (hereinafter also referred to as “solid phase polymerization method”). 6) A method of polymerizing using a dicarboxylic acid halide component equivalent to dicarboxylic acid and a diamine component (hereinafter also referred to as “solution method”).
- the total molar amount of the diamine constituting the diamine unit is preferably 0.9 to 1.2, more preferably 0.95 to 1.1, and still more preferably 0.98 to 1. 05.
- (A) In the polyamide production method, it is preferable to increase the polymerization temperature or lengthen the polymerization time in order to increase the degree of polymerization and increase the melting point of the polyamide.
- (A) As a method for producing polyamide, it is easy to maintain the trans isomer ratio of the alicyclic dicarboxylic acid unit in the polyamide at 85% or less, and from the viewpoint of excellent color tone of the obtained polyamide, 1) hot melt polymerization and 2) hot melt polymerization / solid phase polymerization are preferred.
- the polymerization form is not particularly limited, and may be a batch type or a continuous type.
- the polymerization apparatus used for producing the polyamide is not particularly limited, and a known apparatus can be used. For example, an extruder type such as an autoclave type reactor, a tumbler type reactor, and a kneader. A reactor etc. are mentioned.
- an aqueous solution containing about 40 to 60% by mass of a raw material component of polyamide (dicarboxylic acid, diamine and, if necessary, lactam and / or aminocarboxylic acid) is heated at a temperature of 110 to 180 ° C. and about In a concentration tank operated at a pressure of 0.035 to 0.6 MPa (gauge pressure), the solution is concentrated to about 65 to 90% by mass to obtain a concentrated solution.
- a raw material component of polyamide dicarboxylic acid, diamine and, if necessary, lactam and / or aminocarboxylic acid
- the obtained concentrated solution is transferred to an autoclave, and heating is continued until the pressure in the autoclave reaches about 1.5 to 5.0 MPa (gauge pressure). Thereafter, in the autoclave, the pressure is maintained at about 1.5 to 5.0 MPa (gauge pressure) while draining water and / or gas components, and when the temperature reaches about 250 to 350 ° C., the pressure is reduced to atmospheric pressure ( Gauge pressure is 0 MPa). By reducing the pressure in the autoclave to atmospheric pressure and then reducing the pressure as necessary, by-product water can be effectively removed. Thereafter, the autoclave is pressurized with an inert gas such as nitrogen, and the polyamide melt is extruded from the autoclave as a strand. By cooling and cutting the extruded strand, (A) polyamide pellets are obtained.
- an inert gas such as nitrogen
- an aqueous solution containing about 40 to 60% by mass of a raw material component of polyamide (dicarboxylic acid, diamine and, if necessary, lactam and / or aminocarboxylic acid) is heated to about 40 to 100 ° C. in a container of a preliminary apparatus. Preheat.
- the preheated aqueous solution is then transferred to a concentration vessel / reactor and concentrated to about 70-90% at a pressure of about 0.1-0.5 MPa (gauge pressure) and a temperature of about 200-270 ° C. obtain.
- the resulting concentrated solution is discharged into a flasher maintained at a temperature of about 200-350 ° C.
- the pressure in the flasher is reduced to atmospheric pressure (gauge pressure is 0 MPa). After reducing the pressure in the flasher to atmospheric pressure, the pressure is further reduced as necessary. Thereafter, the polyamide melt is extruded as a strand from the flasher. By cooling and cutting the extruded strand, (A) polyamide pellets can be obtained.
- the amino terminal is a polymer terminal having an amino group (—NH 2 group) and is derived from the raw material (b) diamine unit.
- the amount of the amino terminal is preferably 5 to 100 ⁇ equivalent / g, more preferably 5 to 70 ⁇ equivalent / g, and further preferably 5 to 50 ⁇ equivalent / g with respect to 1 g of (A) polyamide. Even more preferably, it is 5-30 ⁇ eq / g, and even more preferably 5-20 ⁇ eq / g.
- the polyamide composition tends to have more excellent whiteness, reflow resistance, heat discoloration resistance, light discoloration resistance, hydrolysis resistance, and heat retention stability.
- the amount of the amino terminus can be measured by neutralization titration.
- the carboxylic acid terminal is a polymer terminal having a carboxyl group (—COOH group) and is derived from the raw material (a) dicarboxylic acid.
- the amount of the carboxylic acid terminal is preferably 5 to 100 ⁇ equivalent / g, more preferably 5 to 70 ⁇ equivalent / g, and further preferably 5 to 50 ⁇ equivalent / g with respect to 1 g of (A) polyamide. Even more preferably, it is 5 to 30 ⁇ eq / g, and even more preferably 5 to 20 ⁇ eq / g.
- the polyamide composition tends to be more excellent in whiteness, reflow resistance, heat discoloration resistance, and light discoloration resistance.
- the amount of the carboxylic acid terminal can be measured by neutralization titration.
- the total amount of amino terminal and carboxylic acid terminal is preferably 10 to 200 ⁇ equivalent / g, more preferably 10 to 150 ⁇ equivalent / g, more preferably 1A of polyamide (A). It is 10 to 100 ⁇ eq / g, still more preferably 15 to 50 ⁇ eq / g, and still more preferably 20 to 40 ⁇ eq / g.
- the polyamide composition tends to be more excellent in whiteness, reflow resistance, heat discoloration resistance, and light discoloration resistance.
- the cyclic amino terminus is a polymer terminus having a cyclic amino group (a group represented by the following (formula 1)).
- R represents a substituent bonded to the carbon constituting the piperidine ring.
- Specific examples of R include a hydrogen atom, a methyl group, an ethyl group, and a t-butyl group.
- the amount of the cyclic amino terminus is preferably 30 ⁇ eq / g or more and 65 ⁇ eq / g or less, more preferably 30 ⁇ eq / g or more and 60 ⁇ eq / g or less, relative to 1 g of (A) polyamide. Preferably they are 35 microequivalent / g or more and 55 microequivalent / g or less.
- the polyamide composition of the present embodiment tends to have better toughness, hydrolysis resistance, and processability.
- the amount of the cyclic amino terminus can be measured using 1H-NMR. For example, there is a method of calculation based on the integral ratio of hydrogen bonded to carbon adjacent to the nitrogen atom of the heterocyclic ring of nitrogen and hydrogen bonded to carbon adjacent to the nitrogen atom of the amide bond of the polyamide main chain.
- the cyclic amino terminus can be generated by a dehydration reaction between a cyclic amine and a carboxylic acid terminus, and can also be generated by a deammonia reaction within the polymer molecule. It can also be produced by adding a diamine having a pentamethylenediamine skeleton, which is a raw material of polyamide, to cyclize by deammonia reaction.
- the cyclic amino terminal is preferably derived from a raw material diamine. Without adding cyclic amine as an end-capping agent at the initial stage of polymerization, the cyclic amino terminal is generated from the raw material diamine, so that the low molecular weight carboxylic acid terminal is prevented from being blocked at the initial stage of polymerization.
- the polymerization reaction rate of the polyamide is maintained high, and as a result, a high molecular weight product tends to be easily obtained.
- a cyclic amine is generated during the reaction, the carboxylic acid terminal is sealed with the cyclic amine at a later stage of the polymerization, so that a high molecular weight polyamide is easily obtained.
- a cyclic amine that generates a cyclic amino terminus can be generated as a by-product during the polymerization reaction of polyamide.
- the higher the reaction temperature the higher the reaction rate. Therefore, in order to make (A) the cyclic amino terminal of the polyamide a constant amount, it is preferable to promote the formation of a cyclic amine. Therefore, the reaction temperature for the polymerization of polyamide is preferably 300 ° C. or higher, and more preferably 320 ° C. or higher.
- the polymerization temperature, the time for the above reaction temperature of 300 ° C. or more during the polymerization step, the amount of amine added to form a cyclic structure, and the like are controlled appropriately.
- a method is mentioned.
- the end by the sealant is an end formed when a sealant is added during polymerization.
- the sealing agent include the above-described end sealing agents.
- the other terminal is a polymer terminal not classified in the above 1) to 4), such as a terminal generated by deammonia reaction at the amino terminal or a terminal generated by decarboxylation from the carboxylic acid terminal. It is done.
- the sulfuric acid relative viscosity ⁇ r at 25 ° C. can be used as an index of the molecular weight of the polyamide. The larger the ⁇ r, the higher the molecular weight of the (A) polyamide, and the smaller the ⁇ r, the lower the molecular weight of the (A) polyamide.
- the relative viscosity ⁇ r of sulfuric acid at 25 ° C. of the polyamide is preferably 1.5 to 7.0, more preferably 1.7 to 6.0, and even more preferably 1.9 to 5.5. is there.
- the sulfuric acid relative viscosity ⁇ r When the sulfuric acid relative viscosity ⁇ r is in the above range, it tends to be a polyamide composition having excellent mechanical properties such as toughness and rigidity, and moldability.
- the sulfuric acid relative viscosity ⁇ r at 25 ° C. can be measured in accordance with JIS-K6920 under the condition of 98% sulfuric acid concentration of 1%. More specifically, it can be measured by the method described in the following examples.
- the melting point Tm2 of the (A) polyamide is preferably 350 ° C. or lower, more preferably 340 ° C. or lower, still more preferably 335 ° C. or lower, and still more preferably 330 ° C. or lower.
- Tm2 of the (A) polyamide has a melting point Tm2 of 270 ° C. or higher, a polyamide composition having superior heat resistance tends to be obtained.
- fusing point Tm2 is 350 degrees C or less, it exists in the tendency which can suppress the thermal decomposition etc. of (A) polyamide in melt processing, such as extrusion and shaping
- the melting point Tm2 of the polyamide can be measured according to JIS-K7121 by the method described in the Examples below.
- the heat of fusion ⁇ H of the polyamide is preferably 10 J / g or more, more preferably 14 J / g or more, still more preferably 18 J / g or more, and even more preferably 20 J / g or more. Moreover, the upper limit of the heat of fusion ⁇ H is not particularly limited and is preferably as high as possible.
- the heat resistance of the polyamide composition tends to be further improved.
- the heat of fusion ⁇ H of the polyamide can be measured in accordance with JIS-K7121 by the method described in Examples below. Examples of the measuring device for the melting point Tm2 and the heat of fusion ⁇ H of the polyamide (A) described above include Diamond-DSC manufactured by PERKIN-ELMER.
- the glass transition temperature Tg of the polyamide is preferably 90 ° C. or higher, more preferably 110 ° C. or higher, still more preferably 120 ° C. or higher, even more preferably 130 ° C. or higher, and even more preferably. Is 135 ° C. or higher. Moreover, the glass transition temperature of (A) polyamide is preferably 170 ° C. or lower, more preferably 165 ° C. or lower, and further preferably 160 ° C. or lower. (A) When the glass transition temperature of polyamide is 90 ° C. or higher, a polyamide composition excellent in heat discoloration resistance and chemical resistance tends to be obtained. Moreover, when the glass transition temperature of (A) polyamide is 170 ° C.
- the glass transition temperature of polyamide can be measured according to JIS-K7121 as described in the following examples.
- Examples of the glass transition temperature measuring device include Diamond-DSC manufactured by PERKIN-ELMER.
- the polyamide composition of this embodiment may further contain (B) titanium oxide.
- (B) titanium oxide include, but are not limited to, titanium oxide (TiO), dititanium trioxide (Ti 2 O 3 ), and titanium dioxide (TiO 2 ). Of these, titanium dioxide is preferable.
- the crystal structure of titanium oxide is not particularly limited, but is preferably a rutile type from the viewpoint of light resistance of the polyamide composition.
- Titanium oxide is preferably in the form of particles, and the number average particle diameter of (B) titanium oxide is preferably 0.1 to 0.8 ⁇ m, more preferably 0.15 to 0.4 ⁇ m. More preferably 0.15 to 0.3 ⁇ m.
- the number average particle diameter of titanium oxide is 0.1 ⁇ m or more, the extrusion processability of the polyamide composition tends to be further improved.
- the number average particle diameter of titanium oxide is 0.8 ⁇ m or less, the toughness of the polyamide composition tends to be further improved.
- the number average particle diameter of titanium oxide can be measured by an electron micrograph.
- the polyamide composition is put in an electric furnace, the organic matter contained in the polyamide composition is incinerated, and, for example, 100 or more arbitrarily selected titanium oxides from the residue are observed with an electron microscope. By measuring the particle diameter, it is possible to determine the number average particle diameter of (B) titanium oxide.
- the method for producing titanium oxide is not limited to the following, and examples thereof include a so-called sulfuric acid method in which a titanium sulfate solution is hydrolyzed, or a so-called chlorine method in which titanium halide is vapor-phase oxidized.
- the titanium oxide has an inorganic coating layer and / or an organic coating layer on the surface.
- titanium oxide having an inorganic coating layer on the surface of titanium oxide and an organic coating layer on the inorganic coating layer is preferable.
- the titanium oxide particles may be coated using any known method.
- the inorganic coating is not limited to the following, but preferably includes, for example, a metal oxide.
- the organic coating is not limited to the following, but for example, it preferably contains one or more organic substances selected from the group consisting of carboxylic acids, polyols, alkanolamines, and organosilicon compounds.
- the surface of the (B) titanium oxide particles is more preferably coated using polyols and organosilicon compounds. From the viewpoint of reducing the generated gas, it is more preferable to coat using an organosilicon compound.
- titanium oxide only 1 type may be used independently and it may be used in combination of 2 or more types.
- the content of (B) titanium oxide in the polyamide composition of the present embodiment is preferably 5% by mass to 70% by mass and preferably 20% by mass to 70% by mass with respect to 100% by mass of the polyamide composition. More preferably, it is 25 to 60% by mass, and even more preferably 30 to 50% by mass. (B) When the content of titanium oxide is in the above range, the whiteness of the polyamide composition tends to be more excellent.
- the polyamide composition of this embodiment contains (C) a metal hydroxide and / or (D) a metal oxide described later.
- the metal hydroxide is represented by a general formula M (OH) x (M represents a metal element, and x represents a number corresponding to the multivalent value of M).
- the metal element M is preferably a monovalent or higher metal. Examples of the monovalent or higher metal include, but are not limited to, sodium, potassium, lithium, calcium, magnesium, barium, zinc, aluminum, strontium, and the like.
- the metal element M an alkaline earth metal is preferable.
- the (C) metal hydroxide contained in the polyamide composition of the present embodiment is not limited to the following, but examples include sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, Examples thereof include aluminum hydroxide, zinc hydroxide, and manganese hydroxide. Among these, from the viewpoint that the polyamide composition of the present embodiment is excellent in reflow resistance, extrusion process stability, and molding process stability, calcium hydroxide and magnesium hydroxide are preferable, and calcium hydroxide is more preferable.
- a metal hydroxide may be used individually by 1 type, and may use 2 or more types together.
- these (C) metal oxides may be subjected to surface treatment in order to improve adhesion and dispersibility.
- the surface treatment agent include, but are not limited to, for example, silane coupling agents such as aminosilane and epoxysilane, organosilicon compounds such as silicone; organic titanium compounds such as titanium coupling agents; organic acids and polyols And organic substances such as
- MxOy M represents a metal element
- M metal oxide having a specific element as the metal element M.
- the metal element M is preferably a monovalent or higher metal. Examples of the monovalent or higher metal include, but are not limited to, sodium, potassium, lithium, calcium, magnesium, barium, zinc, aluminum, strontium, and the like.
- an alkaline earth metal is preferable.
- the metal oxide (D) contained in the polyamide composition of the present embodiment is not limited to the following, but examples thereof include calcium oxide, magnesium oxide, aluminum oxide, zinc oxide, manganese oxide, and tin oxide. Etc. Among these, from the viewpoint that the polyamide composition of the present embodiment is excellent in heat discoloration resistance, extrusion processing stability, and molding processing stability, calcium oxide and magnesium oxide are preferable, and calcium oxide is more preferable.
- the (D) metal oxide may be used alone or as a mixture of two or more.
- the surface treatment agent include, but are not limited to, for example, silane coupling agents such as aminosilane and epoxysilane, organosilicon compounds such as silicone; organic titanium compounds such as titanium coupling agents; organic acids and polyols And organic substances such as
- the (C) metal hydroxide and / or (D) metal oxide in the polyamide composition of the present embodiment is preferably in the form of particles, and the average particle diameter is preferably 0.05 to 10 ⁇ m, more The thickness is preferably 0.1 to 5 ⁇ m. When the average particle diameter is in the above range, the effects of reflow resistance and heat discoloration can be obtained in the polyamide composition.
- the mass ratio of the particles of 30 ⁇ m or more to the whole particles of (C) metal hydroxide and / or (D) metal oxide is preferably 1% by mass or less, more preferably 0.1% by mass or less. is there.
- the purity of (C) metal hydroxide and / or (D) metal oxide in the polyamide composition is preferably 99% or more, more preferably 99.5% or more, and further preferably 99.9%. That's it. Due to the high purity, the whiteness, reflow resistance, and light discoloration resistance of the polyamide composition tend to be excellent.
- the content of the above-mentioned (C) metal hydroxide and / or (D) metal oxide is 0.1 to 20% by mass, preferably 0.1 to 10% by mass with respect to 100% by mass of the polyamide composition. %, More preferably 0.3 to 5% by mass, still more preferably 0.3 to 2% by mass, still more preferably 0.5 to 1.5% by mass, and still more preferably 0.5 to 1.0% by mass.
- the content of (C) metal hydroxide and / or (D) metal oxide is within the above range, the polyamide composition tends to be more excellent in heat discoloration resistance, extrusion process stability, and molding process stability. is there.
- the polyamide composition of this embodiment may further contain a metal compound other than the above-described (C) metal hydroxide and / or (D) metal oxide from the viewpoint of whiteness and heat discoloration.
- a metal compound other than (C) metal hydroxide and (D) metal oxide include, but are not limited to, metal carbonates and metal halides.
- metal element contained in (C) metal hydroxide and metal compounds other than (D) metal oxide For example, a monovalent or more metal element is preferable.
- metal elements include, but are not limited to, sodium, potassium, lithium, calcium, magnesium barium, zinc, aluminum, strontium, and the like.
- As the metal element an alkaline earth metal is preferable.
- (C) Metal hydroxide and / or (D) Metal oxide may be added during polymerization of (A) polyamide.
- (A) Polyamide composition mixed with (A) polyamide after polymerization of polyamide It is preferable to add at the time of manufacture. By adding it during the production of the polyamide composition, it is possible to reduce the thermal history, to suppress the decomposition of (C) metal hydroxide and / or (D) metal oxide, etc. A polyamide composition having excellent reflow properties, heat discoloration resistance, extrusion processability, and molding process stability can be obtained.
- the polyamide composition of this embodiment contains (E) a phosphorus compound.
- (E) phosphorus compounds include, but are not limited to, 1) phosphoric acid, phosphorous acid, hypophosphorous acid, and intramolecular and / or intermolecular condensates thereof, 2) Examples thereof include phosphoric acid, phosphorous acid, hypophosphorous acid, and metal salts of intramolecular and / or intermolecular condensates thereof.
- (E) phosphorus compound may be used individually by 1 type, and may be used in combination of 2 or more type.
- Examples of 1) phosphoric acid, phosphorous acid, hypophosphorous acid, and intramolecular and / or intermolecular condensates thereof are not limited to the following. Examples thereof include phosphoric acid, pyrophosphoric acid, and metalin. Examples thereof include acids, phosphorous acid, hypophosphorous acid, pyrophosphorous acid, and diphosphorous acid.
- the metal salts of phosphoric acid, phosphorous acid, hypophosphorous acid, and intramolecular and / or intermolecular condensates thereof in 2) are not limited to the following, but for example, in 1) Mention may be made of salts of phosphorus compounds with groups 1 and 2 of the periodic table, manganese, zinc and aluminum.
- More preferable (E) phosphorus compounds are selected from the group consisting of metal phosphates, metal phosphites, metal hypophosphites, intramolecular condensates of these metal salts, and intermolecular condensates of these metal salts. One or more selected.
- the polyamide composition of this embodiment tends to be superior in whiteness, heat discoloration resistance, heat reflow resistance, and light discoloration resistance.
- More preferable (E) phosphorus compounds are a phosphorus compound selected from phosphoric acid, phosphorous acid and hypophosphorous acid, group 1 (alkali metal) and group 2 (alkaline earth metal) of the periodic table, manganese , Zinc, and a metal selected from aluminum, or an intramolecular condensate of these metal salts or an intermolecular condensate of these metal salts. More preferably (E) a phosphorus compound is a metal salt containing a phosphorus compound selected from phosphoric acid, phosphorous acid and hypophosphorous acid, and a metal selected from Groups 1 and 2 of the periodic table. is there.
- the metal salt as the (E) phosphorus compound is not particularly limited, and examples thereof include monosodium phosphate, disodium phosphate, trisodium phosphate, monocalcium phosphate, dicalcium phosphate, phosphorus Tricalcium acid, sodium pyrophosphate, sodium metaphosphate, calcium metaphosphate, sodium hypophosphite, calcium hypophosphite and the like; their anhydrous salts; and their hydrates.
- sodium hypophosphite, calcium hypophosphite, and magnesium hypophosphite are preferable, and calcium hypophosphite and magnesium hypophosphite, which are alkaline earth metal salts, are more preferable.
- a phosphorus compound (E) it tends to be more excellent in whiteness, heat discoloration resistance, light discoloration resistance and extrusion processability.
- Phosphorus compound selected from the group consisting of the aforementioned metal phosphates, metal phosphates, metal hypophosphites, intramolecular condensates of these metal salts, and intermolecular condensates of these metal salts Is more preferably a metal hypophosphite salt.
- the phosphorus compound is a hypophosphite metal salt, a polyamide composition excellent in extrusion processability and molding process stability can be obtained.
- (E) Phosphorus compound metal selected from the group consisting of metal phosphates, metal phosphites, metal hypophosphites, intramolecular condensates of these metal salts, and intermolecular condensates of these metal salts
- the species is preferably the same as the metal species of (C) metal hydroxide and / or (D) metal oxide.
- the metal species of the phosphorus compound (E) is preferably an alkaline earth metal.
- the phosphorus compound is selected from the group consisting of metal salts, intramolecular condensates of metal salts, and intermolecular condensates of metal salts, and (E) the metal species of the phosphorus compound is (C) metal
- the metal species of the hydroxide and / or the (D) metal oxide are the same, a thermal stability is enhanced, and a polyamide composition excellent in extrusion processability and molding process stability can be obtained.
- an alkaline earth metal as the metal species of the (E) phosphorus compound, a more excellent effect can be obtained in the above characteristics.
- a metal salt that does not contain an anhydrous salt or hydrate as the phosphorus compound By using a metal salt that does not contain an anhydrous salt or hydrate as the phosphorus compound, the amount of water generated during processing can be suppressed, and a decrease in the molecular weight and gas generation of polyamide can be suppressed. .
- a metal salt having low deliquescence a polyamide composition excellent in whiteness, reflow resistance, heat discoloration resistance, extrusion processability, and molding process stability can be obtained.
- the phosphorus compound may include an organic phosphorus compound.
- organophosphorus compounds include, but are not limited to, pentaerythritol phosphite compounds, trioctyl phosphites, trilauryl phosphites, tridecyl phosphites, octyl diphenyl phosphites, trisisodecyls.
- Phosphite phenyl diisodecyl phosphite, phenyl di (tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl phosphite, diphenyl (tridecyl) phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2 , 4-Di-tert-butylphenyl) phosphite, Tris (2,4-di-tert-butyl-5-methylphenyl) phosphite, Tris (butoxyethyl) phosphite, 4,4′-butyryl Den-bis (3-methyl-6-t-butylphenyl-tetra-tridecyl) diphosphite, tetra (C12-C15 mixed alkyl) -4,
- a pentaerythritol type phosphite compound tris (2,4-di-t-butylphenyl), from the viewpoint of further improving the heat aging resistance of the polyamide composition and reducing the generated gas.
- Phosphites are preferred, and pentaerythritol phosphite compounds are more preferred.
- pentaerythritol phosphite compound examples include, but are not limited to, for example, 2,6-di-t-butyl-4-methylphenyl-phenyl-pentaerythritol diphosphite, 2,6-diphosphite.
- pentaerythritol type phosphite compounds listed above bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-) Ethylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-amyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-octyl-4-methylphenyl) penta Erythritol diphosphite and bis (2,4-dicumylphenyl) pentaerythritol diphosphite are preferred.
- the content of the (E) phosphorus compound in the polyamide composition of the present embodiment is 0.1 to 20.0 mass% with respect to 100 mass% of the polyamide composition. It is preferably 0.2 to 7.0% by mass, more preferably 0.5 to 3.0% by mass, still more preferably 0.5 to 2.5% by mass, and even more preferably 0.5%. It is -2.0 mass%, More preferably, it is 0.5-1.5 mass%.
- the content of the (E) phosphorus compound in the polyamide composition of this embodiment is preferably greater than (C) metal hydroxide and / or (D) metal oxide. (E) When the content of the phosphorus compound is within the above range, the polyamide composition of the present embodiment tends to be excellent in whiteness, reflow resistance, heat discoloration resistance, extrusion stability, and molding stability. It is in.
- the phosphorus compound (E) is preferably contained in an amount such that the phosphorus element concentration is 1,400 to 20,000 ppm relative to the polyamide composition. More preferably, it is contained in an amount of 20,000 ppm, more preferably in an amount of 3,000 to 20,000 ppm, and even more preferably in an amount of 3,000 to 10,000 ppm. More preferably, it is contained in an amount of 4,000 to 6,000 ppm.
- concentration derived from the (E) phosphorus type compound contained in a polyamide composition can be measured with the measuring method of the metal element density
- (E) Phosphorus compound may be added during polymerization of (A) polyamide, but after (A) polyamide is polymerized, (C) metal hydroxide and / or (D) metal oxide described above, It is preferable to add at the time of manufacture of the polyamide composition to be mixed. By adding it during the production of the polyamide composition, it is possible to reduce the thermal history, (E) it is possible to suppress the decomposition of the phosphorus compound, whiteness, reflow resistance, heat discoloration resistance, extrusion processability And a polyamide composition excellent in molding process stability can be obtained.
- (C) metal hydroxide and / or (D) metal oxide, (E) phosphorus compound is a total value of metal element concentrations derived from these components (however, phosphorus element Is preferably included in an amount of 1,000 to 40,000 ppm, more preferably in an amount of 2,000 to 30,000 ppm, and an amount of 3,000 to 25,000 ppm. More preferably, it is contained in an amount of 4,000 to 20,000 ppm, more preferably in an amount of 5,000 to 10,000 ppm.
- the metal element concentration can be measured by the method for measuring the metal element concentration described in the examples.
- the polyamide composition of the present embodiment may contain a phenol-based antioxidant and / or an amine-based antioxidant from the viewpoint of thermal stability.
- phenolic antioxidants include, but are not limited to, hindered phenol compounds.
- Phenol-based antioxidants, particularly hindered phenol compounds have the property of imparting heat resistance and light resistance to resins such as polyamide and fibers.
- hindered phenol compound examples include, but are not limited to, for example, N, N′-hexane-1,6-diylbis [3- (3,5-di-t-butyl-4-hydroxy Phenylpropionamide), pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis (3,5-di-t-butyl) -4-hydroxy-hydrocinnamamide), triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 3,9-bis ⁇ 2- [3- ( 3-tert-butyl-4-hydroxy-5-methylphenyl) propynyloxy] -1,1-dimethylethyl ⁇ -2,4,8,10-tetraoxapyro [5,5] undeca 3,5-di-t-butyl-4-hydroxybenzyl
- the hindered phenol compound may be N, N′-hexane-1,6-diylbis [3- (3,5-di-t-butyl-4-hydroxyphenylpropion). Amide)] is preferred.
- the phenolic antioxidant mentioned above may be used individually by 1 type, and may be used in combination of 2 or more type.
- the content of the phenolic antioxidant in the polyamide composition of the present embodiment is preferably 0 to 1% by mass, more preferably 0.01 to 1% by mass with respect to 100% by mass of the polyamide composition. More preferably, it is 0.1 to 1% by mass.
- the polyamide composition of the present embodiment tends to be superior in heat aging resistance and lower in the amount of generated gas.
- amine-based antioxidants include, but are not limited to, poly (2,2,4-trimethyl-1,2-dihydroquinoline, 6-ethoxy-1,2-dihydro-2, 2,4-trimethylquinoline, phenyl- ⁇ -naphthylamine, 4,4-bis ( ⁇ , ⁇ -dimethyldendyl) diphenylamine, (p-toluenesulfonylamido) diphenylamine, N, N′-diphenyl-p-phenylenediamine, N, N′-di- ⁇ -naphthyl-p-phenylenediamine, N, N′-di (1,4-dimethylpentyl) -p-phenylenediamine, N-phenyl-N′-isopropyl-p-phenylenediamine, N-phenyl-N′-1,3-dimethylbutyl-p-phenylenediamine, N- (1-methylheptyl
- the content of the amine-based antioxidant in the polyamide composition of the present embodiment is preferably 0 to 1% by mass, more preferably 0.01 to 1% by mass with respect to 100% by mass of the polyamide composition. More preferably, it is 0.1 to 1% by mass.
- the content of the amine-based antioxidant is within the above range, the polyamide composition tends to be more excellent in heat aging resistance and lower in the amount of generated gas.
- the polyamide composition of the present embodiment may further contain (F) an inorganic filler other than the above-described (B) titanium oxide from the viewpoint of mechanical properties such as strength and rigidity.
- (F) As an inorganic filler, although not limited to the following, for example, glass fiber, carbon fiber, calcium silicate fiber, potassium titanate fiber, aluminum borate fiber, glass flake, talc, kaolin, mica , Hydrotalcite, calcium carbonate, zinc carbonate, zinc oxide, calcium monohydrogen phosphate, wollastonite, silica, zeolite, alumina, boehmite, aluminum hydroxide, silicon oxide, magnesium oxide, calcium silicate, sodium aluminosilicate, Examples include magnesium silicate, ketjen black, acetylene black, furnace black, carbon nanotube, graphite, brass, copper, silver, aluminum, nickel, iron, calcium fluoride, montmorillonite, swellable fluoromica, and apatite.
- the inorganic filler is preferably at least one selected from the group consisting of glass fiber, potassium titanate fiber, talc, wollastonite, kaolin, mica, calcium carbonate, and clay. Calcium carbonate is more preferable.
- the number average particle diameter of the inorganic filler is preferably 0.1 to 0.8 ⁇ m, more preferably 0.15 to 0.4 ⁇ m, from the viewpoint of the whiteness, toughness and extrusion processability of the polyamide composition. More preferably, it is 0.15 to 0.3 ⁇ m. By including such (F) inorganic filler, the mechanical strength, appearance, whiteness and the like of the polyamide composition of the present embodiment tend to be more excellent.
- An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type.
- the content of the (F) inorganic filler in the polyamide composition of the present embodiment is preferably 5 to 50% by mass, more preferably 10 to 50% by mass with respect to 100% by mass of the polyamide composition. More preferably, it is 15 to 40% by mass.
- (F) When content of an inorganic filler exists in said range, the intensity
- the polyamide composition of this embodiment may further contain an amine light stabilizer from the viewpoint of light stability.
- amine light stabilizers include, but are not limited to, 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetra Methylpiperidine, 4-acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (phenylacetoxy) -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6, 6-tetramethylpiperidine, 4-methoxy-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6 6-tetramethylpiperidine, 4-benzyloxy-2,2,6,6-tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethyl Peridine, 4- (ethylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (cyclohexylcarbamoyloxy
- amine light stabilizer examples include bis (2,2,6,6-tetramethyl-4-piperidyl) carbonate, bis (2,2,6,6-tetramethyl-4-piperidyl) oxalate, bis (2 , 2,6,6-tetramethyl-4-piperidyl) malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-) Piperidyl) adipate, bis (2,2,6,6-tetramethyl-4-piperidyl) terephthalate, N, N′-bis-2,2,6,6-tetramethyl-4-piperidinyl-1,3-benzene Dicarboxyamide and tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate are preferred.
- bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, N, N′-bis-2,2,6,6-tetramethyl-4 are used as amine light stabilizers.
- -Piperidinyl-1,3-benzenedicarboxamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate are more preferred
- N, N ′ -Bis-2,2,6,6-tetramethyl-4-piperidinyl-1,3-benzenedicarboxamide is more preferred.
- the content of the amine light stabilizer in the polyamide composition of the present embodiment is preferably 0 to 2% by mass, more preferably 0.01 to 2% by mass with respect to 100% by mass of the polyamide composition. More preferably, it is 0.1 to 2% by mass.
- the content of the amine light stabilizer is within the above range, the light stability and heat aging resistance of the polyamide composition can be further improved, and the amount of generated gas can be further reduced.
- the polyamide composition of the present embodiment preferably further contains a nucleating agent from the viewpoint of releasability.
- a nucleating agent is effective to increase the crystallization temperature measured by thermal differential scanning analysis (DSC) by addition, and to improve the spherulite of the obtained molded product or make the size uniform.
- nucleating agent examples include, but are not limited to, talc, boron nitride, mica, kaolin, calcium carbonate, barium sulfate, silicon nitride, carbon black, potassium titanate, and molybdenum disulfide. Can be mentioned.
- a nucleating agent may be used individually by 1 type, and may combine 2 or more types.
- talc, boron nitride, and carbon black are preferable from the viewpoint of the nucleating agent effect, more preferably talc and boron nitride, and further preferably talc.
- the nucleating agent is preferably in the form of particles, and the number average particle diameter of the nucleating agent is preferably 0.01 to 10 ⁇ m, more preferably 0.5 to 5 ⁇ m, and still more preferably 0.00. 5 to 3 ⁇ m. When the number average particle diameter of the nucleating agent is within the above range, the nucleating effect tends to be further improved.
- the number average particle size of the nucleating agent is measured by dissolving the molded article of the polyamide composition of the present embodiment with a solvent in which polyamide such as formic acid is soluble, and, for example, 100 or more of the obtained insoluble components.
- a nucleating agent can be arbitrarily selected, and can be obtained by observing with an optical microscope or a scanning electron microscope.
- the blending amount of the nucleating agent is preferably 0.001 to 15% by mass, more preferably 0.001 to 5% by mass, further preferably 100% by mass with respect to 100% by mass of the polyamide composition of the present embodiment. Is 0.001 to 3% by mass, and more preferably 0.5 to 2.5% by mass.
- the polyamide composition of this embodiment may further contain other components as necessary.
- other components include, but are not limited to, colorants such as pigments and dyes (including colored master batches), mold release agents, flame retardants, fibrillating agents, lubricants, and optical brighteners.
- Plasticizer copper compound, alkali metal halide compound, antioxidant, stabilizer, UV absorber, antistatic agent, fluidity improver, filler, reinforcing agent, spreading agent, nucleating agent, rubber, reinforcing Agents and other polymers.
- suitable content ratios for the respective components are various. A person skilled in the art can easily set a suitable content for each of the other components described above.
- the method for producing the polyamide composition of the present embodiment is not particularly limited, and the (A) polyamide, (C) metal hydroxide and / or (D) metal oxide, (E) phosphorus compound, and further necessary.
- Each raw material containing (B) titanium oxide, phenol-based antioxidant and / or amine-based antioxidant, (F) inorganic filler, amine-based light stabilizer, nucleating agent, and other components according to A method of mixing the components can be used.
- the mixing method of (A) polyamide and (B) titanium oxide is not limited to the following. ) Mixing polyamide, etc. and (B) titanium oxide using a tumbler, Henschel mixer, etc., supplying the resulting mixture to a melt kneader and kneading, or by using a single or twin screw extruder (A) The method etc. which mix
- the same method can also be used when (C) a metal hydroxide and / or (D) a metal oxide, (E) a phosphorus compound, (A) polyamide or the like and (C) a metal hydroxide. And / or (D) a metal oxide and (E) a phosphorus compound are mixed, and the resulting mixture is supplied to a melt kneader and kneaded, or in a molten state with a single or twin screw extruder.
- A A method of blending (C) a metal hydroxide and / or (D) a metal oxide, (E) a phosphorus-based compound from the side feeder into the polyamide (A).
- a method of blending from a side feeder is preferable.
- the polyamide composition tends to have excellent whiteness, reflow resistance, heat discoloration resistance, light discoloration resistance, and molding process stability.
- the same method can be used also when (F) inorganic filler is blended, (A) polyamide or the like and (F) inorganic filler are mixed, and the resulting mixture is supplied to a melt kneader.
- examples thereof include a kneading method and a method of blending (F) an inorganic filler from a side feeder into (A) polyamide or the like that has been melted with a single or twin screw extruder.
- the method of supplying each component of the polyamide composition to the melt kneader may be a method of supplying all the components to the same supply port at a time, or a method of supplying each component from a different supply port. Good.
- the melt kneading temperature is preferably 250 to 375 ° C. as the resin temperature.
- the melt kneading time is preferably 0.25 to 5 minutes.
- the apparatus for melt kneading is not particularly limited, and a known apparatus such as a single or twin screw extruder, a Banbury mixer, a mixing roll, or the like can be used.
- the 25 ° C. sulfuric acid relative viscosity ⁇ r, the melting point Tm2, the heat of fusion ⁇ H, and the glass transition temperature Tg of the polyamide composition of the present embodiment can be measured by the same method as that for the polyamide (A). Specifically, it can measure by the method as described in the Example mentioned later. Moreover, when the measured value in a polyamide composition exists in the range similar to a preferable range as a measured value of the said polyamide, the polyamide composition excellent in heat resistance, a moldability, and chemical resistance can be obtained.
- the crystallization peak temperature Tc (° C.) obtained when the polyamide composition of the present embodiment is cooled at 100 ° C./min is preferably 240 to 290 ° C.
- the crystallization peak temperature Tc (° C.) of the polyamide composition is more preferably 245 ° C. or more, further preferably 250 ° C. or more, still more preferably 255 ° C. or more, and still more preferably 260 ° C. or more. is there.
- the crystallization peak temperature Tc (° C.) of the polyamide composition is more preferably 280 ° C. or less, more preferably 275 ° C. or less, and further preferably 270 ° C. or less.
- the crystallization peak temperature Tc (° C.) of the polyamide composition is 240 ° C. or higher, a polyamide composition having excellent releasability at the time of molding can be obtained.
- the crystallization peak temperature Tc (° C.) of the polyamide composition is 290 ° C. or less, the gate seal at the time of molding does not become too fast, and the polyamide composition can satisfactorily mold fine parts such as thin molded products. Can be obtained.
- the melting point crystallization peak temperature Tc of the polyamide composition used in the present embodiment can be measured according to JIS-K7121 by the method described in Examples below. Examples of the measuring device for the crystallization peak temperature Tc include Diamond-DSC manufactured by PERKIN-ELMER.
- the difference (Tc ⁇ Tg) between the crystallization peak temperature Tc (° C.) obtained when cooled at 100 ° C./min and the glass transition temperature Tg is preferably 90 ° C. or more. More preferably, it is 95 ° C. or higher, more preferably 100 ° C. or higher, still more preferably 105 ° C. or higher, and still more preferably 110 ° C. or higher.
- the difference (Tc ⁇ Tg) between the crystallization peak Tc (° C.) obtained when the polyamide composition of the present embodiment is cooled at 100 ° C./min and the glass transition temperature Tg is larger, the temperature range for crystallization is wider.
- the upper limit of the difference (Tc ⁇ Tg) between the crystallization peak temperature Tc (° C.) obtained when the polyamide composition of the present embodiment is cooled at 100 ° C./min and the glass transition temperature Tg is not particularly limited, It is preferable that it is 300 degrees C or less.
- the molded product of this embodiment contains the above-mentioned polyamide composition.
- the molded product of this embodiment is excellent in reflow resistance, heat discoloration resistance, and light discoloration resistance, and can be suitably used for a reflector or the like.
- the molded product of this embodiment can be obtained, for example, by molding the above-described polyamide composition by a known molding method.
- the known molding method is not limited to the following, for example, press molding, injection molding, gas assist injection molding, welding molding, extrusion molding, blow molding, film molding, hollow molding, multilayer molding, and Commonly known plastic molding methods such as melt spinning can be mentioned.
- the molded product of this embodiment is excellent in heat resistance, moldability, mechanical strength, and low water absorption by including the above-described polyamide composition. Therefore, the above-mentioned polyamide composition can be suitably used as various parts materials for automobiles, electric and electronic use, industrial materials, daily use and household goods, and also suitably used for extrusion applications. be able to.
- the molded product of this embodiment is preferably a metal halide lamp type light resistance tester having a reflectance retention of 95% or more after being exposed for 1000 hours at a position at 100 ° C. and an illuminance of 10 mW / cm 2 . More preferably, it is 98% or more, More preferably, it is 99% or more.
- maintenance rate of a molded article can be measured by the method described in the Example mentioned later.
- the molded product of this embodiment can be used as various component materials. Although it is not limited to the following for automobiles, for example, intake system parts, cooling system parts, fuel system parts, interior parts, exterior parts, electrical parts and the like can be mentioned.
- Examples of the automobile intake system parts include, but are not limited to, an air intake manifold, an intercooler inlet, an exhaust pipe cover, an inner bush, a bearing retainer, an engine mount, an engine head cover, a resonator, and a throttle body. It is done.
- Examples of the automobile cooling system parts include, but are not limited to, a chain cover, a thermostat housing, an outlet pipe, a radiator tank, an oil netter, and a delivery pipe.
- Automotive fuel system parts include, but are not limited to, fuel delivery pipes and gasoline tank cases.
- automobile interior parts include, but are not limited to, instrument panels, console boxes, glove boxes, steering wheels, trims, and the like.
- automobile exterior parts include, but are not limited to, malls, lamp housings, front grills, mud guards, side bumpers, door mirror stays, roof rails, and the like.
- automobile electrical components include, but are not limited to, connectors, wire harness connectors, motor components, lamp sockets, sensor on-vehicle switches, and combination switches.
- connectors For electrical and electronic use, it is not limited to the following.
- connectors For electrical and electronic use, it is not limited to the following.
- switches, relays printed wiring boards, electronic component housings, outlets, noise filters, coil bobbins, LED reflectors, LED reflectors, etc.
- motor end caps For electrical and electronic use, it is not limited to the following.
- motor end caps For example, connectors, switches, relays, printed wiring boards, electronic component housings, outlets, noise filters, coil bobbins, LED reflectors, LED reflectors, etc.
- motor end caps for example, connectors, switches, relays, printed wiring boards, electronic component housings, outlets, noise filters, coil bobbins, LED reflectors, LED reflectors, etc.
- motor end caps for example, connectors, switches, relays, printed wiring boards, electronic component housings, outlets
- Industrial equipments are not limited to the following, but examples include gears, cams, insulating blocks, valves, power tool parts, agricultural equipment parts, engine covers, and the like.
- buttons, food containers, office furniture, and the like may be mentioned.
- Extrusion applications include, but are not limited to, for example, films, sheets, filaments, tubes, rods, and hollow molded products.
- a molded product containing the polyamide composition of the present embodiment can be suitably used as a reflector.
- the (A) polyamide, the (C) metal hydroxide and / or (D) metal oxide, and (E) a phosphorus compound are used in combination, thereby reflecting by heat.
- the decrease in rate can be effectively suppressed.
- the said reflectance it can measure by the method described in the Example mentioned later, and in the reflector containing the polyamide composition of this embodiment, the fall of a reflectance can be suppressed effectively by the combination mentioned above. Has been verified in an example described later.
- the number average particle diameter of (B) titanium oxide was measured as follows by an electron micrograph method.
- the polyamide compositions of Examples and Comparative Examples to be described later are placed in an electric furnace, the organic matter contained in the polyamide composition is incinerated, and 100 or more titanium oxides arbitrarily selected from the residue are observed with an electron microscope. And the number average particle diameter of (B) titanium oxide was calculated
- (C) Metal hydroxide (C-1) Calcium hydroxide purity 99.9% (Wako Pure Chemical Industries, Ltd.) (C-2) Magnesium hydroxide purity 99.9% (manufactured by Wako Pure Chemical Industries, Ltd.)
- (E) Phosphorus compound) (E-1) Calcium hypophosphite (manufactured by Wako Pure Chemical Industries, Ltd., decomposition start temperature 340 ° C.) (E-2) Sodium hypophosphite monohydrate (manufactured by Wako Pure Chemical Industries, Ltd., decomposition start temperature 300 ° C.)
- ((F) inorganic filler) (F) Wollastonite (number average fiber diameter 8 ⁇ m)
- the number average fiber diameter of the (F) inorganic filler is arbitrarily determined from the residue by putting the polyamide compositions of Examples and Comparative Examples described later into an electric furnace, incinerating the organic substances contained in the polyamide composition, and The number average fiber diameter was calculated
- Phenol-based antioxidant (trade name: IRGANOX (registered trademark) 1098, manufactured by BASF)
- mol% of alicyclic dicarboxylic acid unit (a-1) (mol number of alicyclic dicarboxylic acid added as raw material monomer / mol number of all dicarboxylic acids added as raw material monomer) ⁇ 100
- Aromatic dicarboxylic acid unit (a-2) (number of moles of aromatic dicarboxylic acid added as raw material monomer / number of moles of all dicarboxylic acids added as raw material monomer) ⁇ 100
- the temperature of the endothermic peak (melting peak) appearing at this time was defined as Tm1 (° C.).
- Tm1 The temperature of the endothermic peak (melting peak) appearing at this time was defined as Tm1 (° C.).
- the temperature was maintained for 2 minutes at the highest temperature rise. At this maximum temperature, the polyamide was in a molten state. Thereafter, the temperature is lowered to 30 ° C. at a temperature lowering rate of 100 ° C./min.
- the exothermic peak appearing at this time is defined as a crystallization peak, and the crystallization peak temperature is defined as Tc.
- the temperature was increased from 30 ° C. to 300 to 350 ° C. according to the melting point of the sample at a temperature increase rate of 20 ° C./min.
- the maximum peak temperature of the endothermic peak (melting peak) appearing at this time was the melting point Tm2 (° C.), and the total peak area was the heat of fusion ⁇ H (J / g).
- the endothermic peak temperature having the maximum ⁇ H was defined as the melting point Tm2 (° C.).
- Tm2 melting point
- Metal element concentration By ICP emission spectroscopic analysis (ICPS-8100, manufactured by Shimadzu Corporation), (C) metal hydroxide, (D) metal oxide, and (E) phosphorus compound contained in the polyamide composition.
- the metal element concentration derived is measured, and the total value (excluding phosphorus element) of the metal element concentration derived from the components (C), (D) and (E) contained in the polyamide composition and the polyamide composition The phosphorus element concentration derived from the contained component (E) was calculated.
- the vessel of the autoclave (hereinafter, simply referred to as "tank".) Pressure is, as a gauge pressure (hereinafter, all the pressure in the tank was expressed as a gauge pressure.)
- a gauge pressure hereinafter, all the pressure in the tank was expressed as a gauge pressure.
- the pressure in the tank was reduced to atmospheric pressure (gauge pressure was 0 kg / cm 2 ) over 60 minutes.
- the heater temperature was adjusted so that the final temperature of the resin temperature (liquid temperature) in the tank was about 345 ° C.
- the inside of the tank was maintained for 10 minutes under a reduced pressure of 100 torr with a vacuum apparatus. Then, the inside of the tank was pressurized with nitrogen, and the product was discharged in a strand form from the lower nozzle (nozzle). Furthermore, the strand-like product was cooled with water and cut to obtain pellets of polyamide (polyamide pellets).
- the obtained polyamide was dried in a nitrogen stream to adjust the moisture content to less than about 0.2% by mass, and then each property of the polyamide was measured based on the above measurement method.
- the polyamide (PA-1) had a melting point Tm2 of 327 ° C., a glass transition temperature Tg of 150 ° C., a trans isomer ratio of 71%, and a sulfuric acid relative viscosity of 25 ° C. of 3.1.
- Heating was continued until the pressure in the autoclave tank reached about 2.5 kg / cm 2 as a gauge pressure. At this time, the liquid temperature was about 145 ° C. Heating was continued while removing water out of the system to keep the pressure in the tank at about 2.5 kg / cm 2, and the solution was concentrated until the concentration of the aqueous solution in the tank was about 75% by mass. The removal of water was stopped and heating was continued until the pressure in the tank reached about 30 kg / cm 2 . While maintaining the pressure in the tank at about 30 kg / cm 2 , while continuing to remove water from the system, heating was continued until the temperature reached about 50 ° C. (about 290 ° C.) lower than the final temperature (about 340 ° C.).
- the pressure in the tank was reduced to atmospheric pressure (gauge pressure was 0 kg / cm 2 ) over 90 minutes.
- the heater temperature was adjusted so that the final temperature of the resin temperature (liquid temperature) in the tank was about 340 ° C.
- the inside of the tank was maintained for 30 minutes under a reduced pressure of 400 torr with a vacuum apparatus. Then, the inside of the tank was pressurized with nitrogen, and the product was discharged in a strand form from the lower nozzle (nozzle). Further, the strand-like product was cooled with water and cut to obtain a pellet-like polyamide (hereinafter also referred to as “PA-2”).
- PA-2 pellet-like polyamide
- the obtained polyamide was dried in a nitrogen stream to adjust the moisture content to less than about 0.2% by mass, and then each property of the polyamide was measured based on the above measurement method.
- the polyamide (PA-2) had a melting point Tm2 of 316 ° C., a glass transition temperature Tg of 119 ° C., a trans isomer ratio of 70%, and a sulfuric acid relative viscosity at 25 ° C. of 2.4.
- the obtained polyamide was dried in a nitrogen stream to adjust the moisture content to less than about 0.2% by mass, and then each property of the polyamide was measured based on the above measurement method.
- the polyamide (PA-3) has a melting point Tm2 of 334 ° C., a heat of fusion ⁇ H of 35 J / g, a glass transition temperature Tg of 121 ° C., a trans isomer ratio of 70%, and a sulfuric acid relative viscosity of 25 ° C. 2.3.
- the internal temperature of the autoclave was raised to 210 ° C. over 2 hours. At that time, the autoclave was raised to 22kg / cm 2. After the reaction was continued for 1 hour, the internal temperature of the autoclave was raised to 230 ° C. Thereafter, the internal temperature of the autoclave was kept constant at 230 ° C. for 2 hours, and the reaction was carried out while gradually removing water vapor and maintaining the pressure in the autoclave at 22 kg / cm 2 . Next, the pressure in the autoclave was lowered to 10 kg / cm 2 over 30 minutes, and the reaction was further continued for 1 hour to obtain a prepolymer. The obtained prepolymer was dried at 100 ° C.
- polyamide (PA-4) Each characteristic of the polyamide (PA-4) was measured based on the above measurement method. As a result of the measurement, the polyamide (PA-4) had a melting point Tm2 of 298 ° C., a glass transition temperature Tg of 122 ° C., and a sulfuric acid relative viscosity of 2.6 ° C. of 2.6.
- the polyamide (PA-1) obtained in Production Example 1 was used as a raw material for the polyamide composition after drying in a nitrogen stream and adjusting the water content to about 0.2% by mass.
- a twin screw extruder [ZSK-26MC: manufactured by Coperion (Germany)] was used as an apparatus for producing the polyamide composition.
- the twin screw extruder has an upstream supply port in the first barrel from the upstream side of the extruder, a downstream first supply port in the sixth barrel, and a downstream second supply in the ninth barrel. Had a mouth.
- L / D extruder cylinder length / extruder cylinder diameter
- the number of barrels was 12.
- the temperature from the upstream supply port to the die was set to the melting point Tm2 + 20 ° C. of each (A) polyamide produced in the above production example, the screw rotation speed was set to 250 rpm, and the discharge amount was set to 25 kg / h. .
- the obtained polyamide composition pellets were dried in a nitrogen stream, and the water content in the polyamide composition was reduced to 500 ppm or less.
- Various evaluations were performed as described above using the polyamide composition after adjusting the water content. The evaluation results are shown in Tables 1 and 2 below.
- the polyamide compositions of Examples 1 to 14 have extrusion processability, initial reflectance, reflectance retention after the reflow process, reflectance retention after the heat treatment, and reflection during the metal halide exposure test. It was found that the rate retention was high. Further, as shown in Table 2, the polyamide compositions of Examples 15 to 19 are excellent by containing (C) a metal hydroxide and / or (D) a metal oxide and (E) a phosphorus compound. It was found that the moldability can be realized.
- the polyamide composition in the case where an appropriate amount of a nucleating agent such as talc is contained as the polyamide composition of the present invention is further excellent in plasticization stability, and It was found that the crystallization speed is high and the molding process can be performed with a short molding cycle. Further, when the crystal state of the surface of the molded articles of the polyamide compositions of Examples 1 to 15 and 17 to 19 was confirmed by differential scanning calorimetry (DSC), it was found that the crystals were sufficiently crystallized in the mold. Furthermore, from the above results, it was shown that the polyamide composition of the present invention is excellent in each reflectance retention rate, and thus can be suitably used for a reflector for LED.
- DSC differential scanning calorimetry
- the polyamide composition of the present invention has industrial applicability as various parts materials for automobiles, electric and electronic use, industrial materials, daily use and household goods.
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Abstract
Description
すなわち本発明は下記の通りである。
(A)ポリアミドと、
(C)金属水酸化物及び/又は(D)金属酸化物0.1~20質量%と、
(E)リン系化合物0.1~20質量%と、
を、含有する、ポリアミド組成物。
〔2〕
前記(A)ポリアミドが、270~350℃の融点を有する、前記〔1〕に記載のポリアミド組成物。
〔3〕
前記(A)ポリアミドは、脂環族ジカルボン酸を50モル%以上含むジカルボン酸を重合単量体としたポリアミドである、前記〔1〕又は〔2〕に記載のポリアミド組成物。
〔4〕
前記脂環族ジカルボン酸が、1,4-シクロヘキサンジカルボン酸を含む、前記〔3〕に記載のポリアミド組成物。
〔5〕
(B)酸化チタンを5質量%以上、さらに含有する、前記〔1〕乃至〔4〕のいずれか一に記載のポリアミド組成物。
〔6〕
前記(C)金属水酸化物がアルカリ土類金属の水酸化物である、前記〔1〕乃至〔5〕のいずれか一に記載のポリアミド組成物。
〔7〕
前記(D)金属酸化物がアルカリ土類金属の酸化物である、前記〔1〕乃至〔6〕のいずれか一に記載のポリアミド組成物。
〔8〕
前記(E)リン系化合物が金属塩であり、当該金属塩の金属種が、(C)金属水酸化物及び/又は(D)金属酸化物の金属種と同一である、前記〔1〕乃至〔7〕のいずれか一に記載のポリアミド組成物。
〔9〕
前記(E)リン系化合物がアルカリ土類金属塩である、前記〔1〕乃至〔8〕のいずれか一に記載のポリアミド組成物。
〔10〕
(F)無機充填材を5質量%以上、さらに含有する、前記〔1〕乃至〔9〕のいずれか一に記載のポリアミド組成物。
〔11〕
造核剤を0.001~15質量%、さらに含有する、前記〔1〕乃至〔10〕のいずれか一に記載のポリアミド組成物。
〔12〕
ポリアミド組成物中に含まれる(E)リン系化合物由来のリン元素濃度が、1,400~20,000ppmであり、JIS-K7121に準じた示差走査熱量測定において、100℃/minで冷却したときに得られる結晶化ピーク温度Tcとガラス転移温度Tgとの差(Tc-Tg)が100℃以上である、前記〔1〕乃至〔11〕のいずれか一に記載のポリアミド組成物。
〔13〕
前記〔1〕乃至〔12〕のいずれか一に記載のポリアミド組成物を含む、成形品。
〔14〕
メタルハライドランプ式耐光性試験機で100℃、照度が10mW/cm2となる位置で1000時間暴露した後の反射率保持率が95%以上である、前記〔13〕に記載の成形品。
〔15〕
前記〔1〕乃至〔12〕のいずれか一に記載のポリアミド組成物を含む、LED用反射板。
本実施形態のポリアミド組成物(以下、単に「ポリアミド組成物」ともいう。)は、
(A)ポリアミドと、
(C)金属水酸化物及び/又は(D)金属酸化物0.1~20質量%と、
(E)リン系化合物0.1~20質量%と、
を、含有する。
本実施形態において用いられる(A)ポリアミドは、(a)ジカルボン酸単位と、(b)ジアミン単位と、を有する。
上記(a)ジカルボン酸単位及び(b)ジアミン単位の合計量は、(A)ポリアミドの全構成単位100モル%に対して、20~100モル%であることが好ましく、90~100モル%であることがより好ましく、100モル%であることがさらに好ましい。
(A)ポリアミドにおいて、上記(a)ジカルボン酸単位及び(b)ジアミン単位以外の(A)ポリアミドの構成単位としては、特に限定されないが、例えば、後述する(c)ラクタム及び/又はアミノカルボン酸からなる単位が挙げられる。
(a)ジカルボン酸単位としては、以下に限定されるものではないが、例えば、(a-1)脂環族ジカルボン酸単位、(a-2)芳香族ジカルボン酸単位、及び(a-3)脂肪族ジカルボン酸単位が挙げられる。
(a)ジカルボン酸単位は、(a-1)脂環族ジカルボン酸単位を50~100モル%含むことが好ましく(ジカルボン酸全モル数基準)、60~100モル%含むことがより好ましく、70~100モル%含むことがさらに好ましく、100モル%含むことがさらにより好ましい。
(a)ジカルボン酸単位中の(a-1)脂環族ジカルボン酸単位の割合(モル%)が上記範囲であることにより、耐熱性、流動性、靭性、低吸水性、及び剛性等を同時に満足する、ポリアミド組成物を得ることができる。
前記(a-1)脂環族ジカルボン酸単位(以下、「脂環式ジカルボン酸単位」ともいう。)を構成する脂環族ジカルボン酸としては、以下に限定されるものではないが、例えば、脂環構造の炭素数が3~10の脂環族ジカルボン酸が挙げられ、脂環構造の炭素数が5~10の脂環族ジカルボン酸が好ましい。
このような脂環族ジカルボン酸としては、以下に限定されるものではないが、例えば、1,4-シクロヘキサンジカルボン酸、1,3-シクロヘキサンジカルボン酸、及び1,3-シクロペンタンジカルボン酸等が挙げられる。この中でも、1,4-シクロヘキサンジカルボン酸が好ましい。
このような脂環族ジカルボン酸を含むことにより、ポリアミド組成物の耐熱性、低吸水性、及び剛性等がより優れる傾向にある。
なお、(a-1)脂環族ジカルボン酸単位を構成する脂環族ジカルボン酸は、1種のみを単独で用いてもよいし、2種類以上を組み合わせて用いてもよい。
この置換基としては、以下に限定されるものではないが、例えば、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、及びtert-ブチル基等の炭素数1~4のアルキル基等が挙げられる。
原料モノマーとしての脂環族ジカルボン酸としては、トランス体とシス体とのどちらか一方を用いてもよく、トランス体とシス体とを所定の比率で含む混合物として用いてもよい。
なお、脂環族ジカルボン酸は、高温で異性化し、トランス体とシス体が一定の比率になることが知られており、シス体の脂環族ジカルボン酸の方がトランス体の脂環族ジカルボン酸に比べて、脂環族ジカルボン酸とジアミンとの当量塩の水溶性が高い傾向にある。このことから、原料モノマーとしての脂環族ジカルボン酸のトランス体/シス体比(モル比)は、好ましくは50/50~0/100であり、より好ましくは40/60~10/90であり、さらに好ましくは35/65~15/85である。
脂環族ジカルボン酸のトランス体/シス体比(モル比)は、液体クロマトグラフィー(HPLC)や核磁気共鳴分光法(NMR)により求めることができる。
(A)ポリアミド中において、(a-1)脂環族ジカルボン酸単位全体におけるトランス異性体の比率を、「トランス異性体比率」という。トランス異性体比率は、好ましくは50~85モル%であり、より好ましくは50~80モル%であり、さらに好ましくは60~80モル%である。
トランス異性体比率が上記範囲内にあることにより、本実施形態のポリアミド組成物は、高融点、靭性及び剛性により優れるという特徴に加えて、高いガラス転移温度(Tg)による熱時剛性と、通常では耐熱性と相反する性質である流動性と、高い結晶性とを同時に満足するという性質を持つ傾向にある。
これらの特徴は、1,4-シクロヘキサンジカルボン酸を50モル%以上含む(a)ジカルボン酸単位と、2-メチルペンタメチレンジアミンを50モル%以上含む(b)ジアミン単位との組み合わせから得られる(A)ポリアミドであって、かつ前記トランス異性体比率が50~85モル%である(A)ポリアミドで特に顕著である。
前記「トランス異性体比率」は、後述する実施例に記載する方法により測定することができる。
(a-2)芳香族ジカルボン酸単位を構成する芳香族ジカルボン酸としては、以下に限定されるものではないが、例えば、フェニル基、ナフチル基を有するジカルボン酸が挙げられる。芳香族ジカルボン酸の芳香族基は、無置換でも置換基を有していてもよい。
この置換基としては、特に限定されないが、例えば、炭素数1~4のアルキル基、炭素数6~10のアリール基、炭素数7~10のアリールアルキル基、クロロ基及びブロモ基等のハロゲン基、炭素数1~6のシリル基、並びにスルホン酸基及びその塩(ナトリウム塩等)等が挙げられる。
芳香族ジカルボン酸としては、以下に限定されるものではないが、テレフタル酸、イソフタル酸、ナフタレンジカルボン酸、2-クロロテレフタル酸、2-メチルテレフタル酸、5-メチルイソフタル酸、及び5-ナトリウムスルホイソフタル酸等の無置換又は所定の置換基で置換された炭素数8~20の芳香族ジカルボン酸等が挙げられる。
(a-2)芳香族ジカルボン酸単位を構成する芳香族ジカルボン酸は、1種のみを単独で用いてもよく、2種以上を組み合わせて用いてもよい。
(a-3)脂肪族ジカルボン酸単位を構成する脂肪族ジカルボン酸としては、以下に限定されるものではないが、例えば、マロン酸、ジメチルマロン酸、コハク酸、2,2-ジメチルコハク酸、2,3-ジメチルグルタル酸、2,2-ジエチルコハク酸、2,3-ジエチルグルタル酸、グルタル酸、2,2-ジメチルグルタル酸、アジピン酸、2-メチルアジピン酸、トリメチルアジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、ドデカン二酸、テトラデカン二酸、ヘキサデカン二酸、オクタデカン二酸、エイコサン二酸、及びジグリコール酸等の炭素数3~20の直鎖又は分岐状飽和脂肪族ジカルボン酸等が挙げられる。
このようなジカルボン酸を用いることにより、ポリアミド組成物の耐熱性、流動性、靭性、低吸水性、及び剛性等がより優れる傾向にある。
中でも、(a-3)脂肪族ジカルボン酸としては、炭素数が10以上である脂肪族ジカルボン酸が好ましい。このようなジカルボン酸を用いることにより、ポリアミド組成物の耐熱性及び低吸水性等がより優れる傾向にある。
炭素数が10以上である脂肪族ジカルボン酸としては、特に限定されないが、例えば、セバシン酸、ドデカン二酸、テトラデカン二酸、ヘキサデカン二酸、オクタデカン二酸、及びエイコサン二酸等が挙げられる。この中でも、ポリアミド組成物の耐熱性等の観点で、セバシン酸及びドデカン二酸が好ましい。
(a-3)脂肪族ジカルボン酸単位を構成する脂肪族ジカルボン酸は、1種のみを単独で用いてもよく、2種以上を組み合わせて用いてもよい。
炭素数10以上の脂肪族ジカルボン酸単位(a-3)の割合が上記範囲であることにより、より優れた、耐熱性、流動性、靭性、低吸水性、及び剛性等を同時に満足する、ポリアミド組成物が得られる傾向にある。
ここで「ジカルボン酸と等価な化合物」とは、上記ジカルボン酸に由来するジカルボン酸構造と同様のジカルボン酸構造となり得る化合物をいう。このような化合物としては、以下に限定されるものではないが、例えば、ジカルボン酸の無水物及びハロゲン化物等が挙げられる。
3価以上の多価カルボン酸は、1種のみを単独で用いてもよいし、2種類以上を組み合わせて用いてもよい。
(b)ジアミン単位としては、以下に限定されるものではないが、例えば、(b-1)主鎖から分岐した置換基を持つジアミン単位、(b-2)脂肪族ジアミン単位、(b-3)脂環式ジアミン単位、及び(b-4)芳香族ジアミン単位等が挙げられる。
(b)ジアミン単位は、前記(b-1)主鎖から分岐した置換基を持つジアミンを含むことが好ましい。
(b)ジアミン単位が、前記(b-1)主鎖から分岐した置換基を持つジアミン単位を含むことにより、本実施形態のポリアミド組成物は、より優れた、流動性、靭性及び剛性等を同時に満足できる傾向にある。
(b)ジアミン単位は、前記(b-1)主鎖から分岐した置換基を持つジアミン単位を50モル%以上含むことがより好ましい。
(b-1)主鎖から分岐した置換基を持つジアミン単位における前記「主鎖から分岐した置換基」としては、以下に限定されるものではないが、例えば、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、及びtert-ブチル基等の炭素数1~4のアルキル基等が挙げられる。
これらの中でも、2-メチルペンタメチレンジアミンが好ましい。このような(b-1)主鎖から分岐した置換基を持つジアミン単位を含むことにより、耐熱性及び剛性等により優れるポリアミド組成物となる傾向にある。
なお、(b-1)主鎖から分岐した置換基を持つジアミン単位を構成するジアミンは、1種のみを単独で用いてもよいし、2種類以上を組み合わせて用いてもよい。
(b)ジアミン単位中の(b-1)主鎖から分岐した置換基を持つジアミン単位の割合が、上記範囲であることにより、流動性、靭性、及び剛性により優れるポリアミド組成物となる傾向にある。
前記(b-2)脂肪族ジアミン単位を構成する脂肪族ジアミン(ただし、前記(b-1)主鎖から分岐した置換基を持つジアミンを除く)としては、以下に限定されるものではないが、例えば、エチレンジアミン、プロピレンジアミン、テトラメチレンジアミン、ペンタメチレンジアミン、ヘキサメチレンジアミン、ヘプタメチレンジアミン、オクタメチレンジアミン、ノナメチレンジアミン、デカメチレンジアミン、ウンデカメチレンジアミン、ドデカメチレンジアミン、及びトリデカメチレンジアミン等の炭素数2~20の直鎖飽和脂肪族ジアミン等が挙げられる。
前記(b-3)脂環族ジアミン単位を構成する脂環族ジアミン(以下、「脂環式ジアミン」ともいう。)としては、以下に限定されるものではないが、例えば、1,4-シクロヘキサンジアミン、1,3-シクロヘキサンジアミン、及び1,3-シクロペンタンジアミン等が挙げられる。
前記(b-4)芳香族ジアミン単位を構成する芳香族ジアミンとしては、芳香族を含有するジアミンであれば以下に限定されるものではないが、例えば、メタキシリレンジアミン等が挙げられる。
このようなジアミンを用いることにより、耐熱性、流動性、靭性、低吸水性、及び剛性等により優れるポリアミド組成物となる傾向にある。
なお、ジアミンは、1種のみを単独で用いてもよいし、2種類以上を組み合わせて用いてもよい。
(b)ジアミン単位中のジアミン単位(b-2)~(b-4)の合計割合が、上記範囲であることにより、流動性、靭性、及び剛性により優れるポリアミド組成物となる傾向にある。
3価以上の多価脂肪族アミンは、1種のみ単独で用いてもよいし、2種類以上を組み合わせて用いてもよい。
(A)ポリアミドは、(c)ラクタム単位(c-1)及び/又はアミノカルボン酸単位(c-2)をさらに含有することができる。
このような単位を含むことにより、靭性により優れるポリアミド組成物が得られる傾向にある。なお、ここでラクタム単位(c-1)及びアミノカルボン酸(c-2)を構成するラクタム及びアミノカルボン酸とは、重(縮)合可能なラクタム及びアミノカルボン酸をいう。
中でも、ラクタムとしては、ε-カプロラクタム、ラウロラクタム等が好ましく、ε-カプロラクタムがより好ましい。このようなラクタムを含むことにより、靭性により優れるポリアミド組成物となる傾向にある。
前記アミノカルボン酸としては、ω位がアミノ基で置換された炭素数4~14の直鎖又は分岐状飽和脂肪族カルボン酸が好ましい。このようなアミノカルボン酸としては、以下に限定されるものではないが、例えば、6-アミノカプロン酸、11-アミノウンデカン酸、及び12-アミノドデカン酸等が挙げられる。また、アミノカルボン酸としては、パラアミノメチル安息香酸等も挙げられる。
ラクタム単位(c-1)及びアミノカルボン酸単位(c-2)の合計割合が上記範囲であることにより、流動性の向上等の効果が得られる傾向にある。
本実施形態において用いる(A)ポリアミドの末端は、公知の末端封止剤により末端封止されていてもよい。
このような末端封止剤は、上述したジカルボン酸とジアミンと、必要に応じて用いるラクタム及び/又はアミノカルボン酸とから、(A)ポリアミドを製造する際に、分子量調節剤としても添加することができる。
この中でも、モノカルボン酸、及びモノアミンが好ましい。(A)ポリアミドの末端が末端封止剤で封鎖されていることにより、熱安定性により優れるポリアミド組成物となる傾向にある。
末端封止剤は、1種のみを単独で用いてもよいし、2種類以上を組み合わせて用いてもよい。
前記モノカルボン酸は、1種のみを単独で用いてもよいし、2種類以上を組み合わせて用いてもよい。
モノアミンは、1種のみを単独で用いてもよいし、2種類以上を組み合わせて用いてもよい。
(A)ポリアミドの製造方法としては、以下に限定されるものではないが、例えば、(a)ジカルボン酸単位を構成するジカルボン酸と、(b)ジアミン単位を構成するジアミンと、必要に応じてラクタム単位(c-1)及び/又はアミノカルボン酸単位(c-2)を構成するラクタム及び/又はアミノカルボン酸と、を重合して重合体を得る工程を含むものとし、ポリアミドの重合度を上昇させる工程を、さらに含むことが好ましい。また、必要に応じて、得られた重合体の末端を末端封止剤により封止する封止工程を含んでいてもよい。
1)ジカルボン酸-ジアミン塩、又はジカルボン酸とジアミンとの混合物の水溶液、あるいはこれらの水の懸濁液を加熱し、溶融状態を維持したまま重合させる方法(以下、「熱溶融重合法」ともいう。)。
2)熱溶融重合法で得られたポリアミドを融点以下の温度で固体状態を維持したまま重合度を上昇させる方法(以下、「熱溶融重合・固相重合法」ともいう。)。
3)ジカルボン酸-ジアミン塩、又はジカルボン酸とジアミンとの混合物の水溶液、あるいはこれらの水の懸濁液を加熱し、析出したプレポリマーをさらにニーダー等の押出機で再び溶融して重合度を上昇させる方法(以下、「プレポリマー・押出重合法」ともいう。)。
4)ジカルボン酸-ジアミン塩、又はジカルボン酸とジアミンとの混合物の水溶液、あるいはこれらの水の懸濁液を加熱し、析出したプレポリマーをさらにポリアミドの融点以下の温度で固体状態を維持したまま重合度を上昇させる方法(以下、「プレポリマー・固相重合法」ともいう。)。
5)ジカルボン酸-ジアミン塩、又はジカルボン酸とジアミンとの混合物を固体状態を維持したまま重合させる方法(以下、「固相重合法」ともいう。)。
6)ジカルボン酸と等価なジカルボン酸ハライド成分とジアミン成分を用いて重合させる方法(以下、「溶液法」ともいう。)。
重合反応中の(b)ジアミン単位を構成するジアミンの反応系外への逃散分もモル比においては考慮して、(a)ジカルボン酸単位を構成するジカルボン酸全体のモル量1に対して、(b)ジアミン単位を構成するジアミン全体のモル量は、0.9~1.2であることが好ましく、より好ましくは0.95~1.1であり、さらに好ましくは0.98~1.05である。
特に、ポリアミド中の脂環族ジカルボン酸単位のトランス異性体比率を80%以下に維持して重合することにより、さらに色調や引張伸度に優れ、高融点のポリアミドを得られる傾向にある。
(A)ポリアミドの製造に用いる重合装置としては、特に限定されるものではなく、公知の装置を用いることができ、例えば、オートクレーブ型の反応器、タンブラー型反応器、及びニーダー等の押出機型反応器等が挙げられる。
まず、例えば、ポリアミドの原料成分(ジカルボン酸、ジアミン、及び、必要に応じて、ラクタム及び/又はアミノカルボン酸)を、約40~60質量%含有する水溶液を、110~180℃の温度及び約0.035~0.6MPa(ゲージ圧)の圧力で操作される濃縮槽で、約65~90質量%に濃縮して濃縮溶液を得る。
次いで、得られた濃縮溶液をオートクレーブに移し、当該オートクレーブにおける圧力が約1.5~5.0MPa(ゲージ圧)になるまで加熱を続ける。
その後、オートクレーブにおいて、水及び/又はガス成分を抜きながら圧力を約1.5~5.0MPa(ゲージ圧)に保ち、温度が約250~350℃に達した時点で、大気圧まで降圧する(ゲージ圧は、0MPa)。
オートクレーブ内の圧力を大気圧に降圧後、必要に応じて減圧することにより、副生する水を効果的に除くことができる。
その後、オートクレーブを窒素等の不活性ガスで加圧し、オートクレーブからポリアミド溶融物をストランドとして押し出す。押し出されたストランドを、冷却、カッティングすることにより、(A)ポリアミドのペレットを得る。
まず、ポリアミドの原料成分(ジカルボン酸、ジアミン、及び、必要に応じて、ラクタム及び/又はアミノカルボン酸)を約40~60質量%含有する水溶液を、予備装置の容器において約40~100℃まで予備加熱する。次いで、予備加熱した水溶液を濃縮槽/反応器に移し、約0.1~0.5MPa(ゲージ圧)の圧力及び約200~270℃の温度で約70~90%に濃縮して濃縮溶液を得る。
得られた濃縮溶液を約200~350℃の温度に保ったフラッシャーに排出する。
その後、フラッシャー内の圧力を大気圧まで降圧する(ゲージ圧は、0MPa)。フラッシャー内の圧力を大気圧に降圧後、必要に応じてさらに減圧する。その後、フラッシャーからポリアミド溶融物をストランドとして押し出す。押し出されたストランドを、冷却、カッティングすることにより、(A)ポリアミドのペレットを得ることができる。
本実施形態に用いる(A)ポリアミドのポリマー末端としては、特に限定されないが、以下のように分類され、定義することができる。
すなわち、1)アミノ末端、2)カルボン酸末端、3)環状アミノ末端、4)封止剤による末端、5)その他の末端である。
アミノ末端の量は、(A)ポリアミド1gに対して、好ましくは5~100μ当量/gであり、より好ましくは5~70μ当量/gであり、さらに好ましくは5~50μ当量/gであり、さらにより好ましくは5~30μ当量/gであり、よりさらに好ましくは、5~20μ当量/gである。
アミノ末端の量が上記の範囲であることにより、ポリアミド組成物の白色度、耐リフロー性、耐熱変色性、耐光変色性、耐加水分解性、及び熱滞留安定性がより優れる傾向にある。アミノ末端の量は、中和滴定により測定することができる。
カルボン酸末端の量は、(A)ポリアミド1gに対して、好ましくは5~100μ当量/gであり、より好ましくは5~70μ当量/gであり、さらに好ましくは5~50μ当量/gであり、さらにより好ましくは5~30μ当量/gであり、よりさらに好ましくは、5~20μ当量/gである。カルボン酸末端の量が上記の範囲であることにより、ポリアミド組成物の白色度、耐リフロー性、耐熱変色性、及び耐光変色性がより優れる傾向にある。カルボン酸末端の量は、中和滴定により測定することができる。
下記(式1)中でRはピペリジン環を構成する炭素に結合する置換基を示す。Rの具体例としては、水素原子、メチル基、エチル基、t-ブチル基などが挙げられる。
また、例えば、原料のペンタメチレンジアミン骨格を有するジアミンの脱アンモニア反応により環化したピペリジンがポリマー末端に結合してもこの環状アミノ基の末端となる。これらの構造は、モノマーとして、ペンタメチレンジアミン骨格を有するものを含む場合にとることがある。
環状アミノ末端の量が上記の範囲であることにより、本実施形態のポリアミド組成物は、靭性、耐加水分解性、及び加工性がより優れる傾向にある。
本実施形態において、環状アミノ末端は、原料のジアミンに由来することが好ましい。
環状アミンを末端封止剤として重合初期に添加せずに、原料のジアミンに由来して環状アミノ末端が生成することにより、低分子量のカルボン酸末端を重合初期の段階で封止することが回避され、ポリアミドの重合反応速度が高く維持され、結果として高分子量体が得られやすい傾向にある。このように、反応の途中で環状アミンが生成する場合、重合後期の段階で環状アミンによりカルボン酸末端を封止することになるため、高分子量のポリアミドが得られ易くなる。
(A)ポリアミドの分子量の指標としては、25℃の硫酸相対粘度ηrを利用できる。ηrが大きいほど(A)ポリアミドの分子量が高く、小さいほど(A)ポリアミドの分子量が低い。
(A)ポリアミドの25℃の硫酸相対粘度ηrは、好ましくは1.5~7.0であり、より好ましくは1.7~6.0であり、さらに好ましくは1.9~5.5である。
硫酸相対粘度ηrが上記範囲であることにより、靭性及び剛性等の機械物性並びに成形性等により優れるポリアミド組成物となる傾向にある。なお、25℃の硫酸相対粘度ηrは、JIS-K6920に従って、98%硫酸中濃度1%の条件下で測定することができる。より具体的には、下記実施例に記載する方法により測定することができる。
また、(A)ポリアミドの融点Tm2は、好ましくは350℃以下であり、より好ましくは340℃以下であり、さらに好ましくは335℃以下であり、よりさらに好ましくは330℃以下である。
(A)ポリアミドの融点Tm2が270℃以上であることにより、耐熱性により優れるポリアミド組成物を得ることができる傾向にある。
また、(A)ポリアミドの融点Tm2が350℃以下であることにより、押出、成形等の溶融加工における(A)ポリアミドの熱分解等をより抑制することができる傾向にある。
(A)ポリアミドの融点Tm2は、後述の実施例に記載の方法により、JIS-K7121に準じて測定することができる。
(A)ポリアミドの融解熱量ΔHが10J/g以上であることにより、ポリアミド組成物の耐熱性がより向上する傾向にある。
(A)ポリアミドの融解熱量ΔHは、後述の実施例に記載の方法により、JIS-K7121に準じて測定することができる。
上述した(A)ポリアミドの融点Tm2及び融解熱量ΔHの測定装置としては、例えば、PERKIN-ELMER社製Diamond-DSC等が挙げられる。
また、(A)ポリアミドのガラス転移温度は、好ましくは170℃以下であり、より好ましくは165℃以下であり、さらに好ましくは160℃以下である。
(A)ポリアミドのガラス転移温度が90℃以上であることにより、耐熱変色性や耐薬品性に優れるポリアミド組成物を得ることができる傾向にある。また、(A)ポリアミドのガラス転移温度が170℃以下であることにより、外観のよい成形品を得ることができる傾向にある。
(A)ポリアミドのガラス転移温度は、下記実施例に記載するように、JIS-K7121に準じて測定することができる。
ガラス転移温度の測定装置としては、例えば、PERKIN-ELMER社製Diamond-DSC等が挙げられる。
本実施形態のポリアミド組成物は、(B)酸化チタンをさらに含有してもよい。
(B)酸化チタンとしては、以下に限定されるものではないが、例えば、酸化チタン(TiO)、三酸化二チタン(Ti2O3)、及び二酸化チタン(TiO2)等が挙げられる。
中でも、二酸化チタンが好ましい。
(B)酸化チタンの数平均粒子径が0.1μm以上であることにより、ポリアミド組成物の押出加工性がより向上する傾向にある。
(B)酸化チタンの数平均粒子径が0.8μm以下であることにより、ポリアミド組成物の靱性がより向上する傾向にある。
(B)酸化チタンの数平均粒子径は、電子顕微鏡写真法により測定することができる。例えば、ポリアミド組成物を電気炉に入れて、ポリアミド組成物中に含まれる有機物を焼却処理し、残渣分から、例えば任意に選択した100個以上の酸化チタンを、電子顕微鏡で観察して、これらの粒子径を測定することにより、(B)酸化チタンの数平均粒子径を求めることが可能である。
特に、(B)酸化チタンの表面に無機コーティング層を有し、該無機コーティング層上に有機コーティング層を有する(B)酸化チタンが好ましい。
前記無機コーティングとしては、以下に限定されるものではないが、例えば、金属酸化物を含むことが好ましい。
中でも、ポリアミド組成物の耐光性及び押出加工性の観点から、(B)酸化チタン粒子の表面は、ポリオール類、有機ケイ素化合物を使用してコーティングされることがより好ましく、ポリアミド組成物の加工時の発生ガスの低減の観点から、有機ケイ素化合物を使用してコーティングされることがさらに好ましい。
(B)酸化チタンの含有量が上記範囲であることにより、ポリアミド組成物の白色度がより優れる傾向にある。
本実施形態のポリアミド組成物は、(C)金属水酸化物及び/又は後述する(D)金属酸化物を含有する。
(C)金属水酸化物は、一般式M(OH)xで表される(Mは、金属元素を示し、xは、Mの多価に対応する数を示す。)。
前記金属元素Mは、1価以上の金属であることが好ましい。前記1価以上の金属としては、以下に限定されるものではないが、例えば、ナトリウム、カリウム、リチウム、カルシウム、マグネシウム、バリウム、亜鉛、アルミニウム、ストロンチウム等が挙げられる。金属元素Mとしては、アルカリ土類金属が好ましい。
(C)金属水酸化物は、1種のみを単独で用いてもよく、2種以上を併用してもよい。
表面処理剤としては、以下に限定されるものではないが、例えば、アミノシラン、エポキシシランなどのシランカップリング剤、シリコーン等の有機珪素化合物;チタンカップリング剤等の有機チタン化合物;有機酸、ポリオール等の有機物などが挙げられる。
金属酸化物は、一般式MxOy(Mは、金属元素を示し、x及びyは、それぞれ、0<x≦5、0<y≦5であり、Mの多価×x=2×yを満たす数である。)で表される。
本実施形態のポリアミド組成物においては、金属元素Mとして、特定の元素を有する(D)金属酸化物を用いることが好ましい。
前記金属元素Mは、1価以上の金属であることが好ましい。前記1価以上の金属としては、以下に限定されるものではないが、例えば、ナトリウム、カリウム、リチウム、カルシウム、マグネシウム、バリウム、亜鉛、アルミニウム、ストロンチウム等が挙げられる。金属元素としては、アルカリ土類金属が好ましい。
前記(D)金属酸化物は、一種のみを単独で用いてもよく、二種以上の混合物として用いてもよい。
表面処理剤としては、以下に限定されるものではないが、例えば、アミノシラン、エポキシシランなどのシランカップリング剤、シリコーン等の有機珪素化合物;チタンカップリング剤等の有機チタン化合物;有機酸、ポリオール等の有機物などが挙げられる。
(C)金属水酸化物及び/又は(D)金属水酸化物全体に対する30μm以上の粒子の質量割合を上記範囲内とすることにより、ポリアミド組成物において、耐リフロー性、耐熱変色性の効果が得られる。
(C)金属水酸化物及び/又は(D)金属酸化物の含有量が上記の範囲内であることにより、ポリアミド組成物は耐熱変色性、押出加工安定性、成形加工安定性により優れる傾向にある。
(C)金属水酸化物、(D)金属酸化物以外の金属化合物としては、以下に限定されるものではないが、例えば、金属炭酸塩、金属ハロゲン化物等が挙げられる。
(C)金属水酸化物、(D)金属酸化物以外の金属化合物に含まれる金属元素としては、特に限定されないが、例えば、1価以上の金属元素が好ましい。このような金属元素としては、以下に限定されるものではないが、例えば、ナトリウム、カリウム、リチウム、カルシウム、マグネシウムバリウム、亜鉛、アルミニウム、ストロンチウム等を挙げることができる。金属元素として、アルカリ土類金属が好ましい。
本実施形態のポリアミド組成物は、(E)リン系化合物を含有する。
(E)リン系化合物としては、以下に限定されるものではないが、例えば、1)リン酸、亜リン酸、次亜リン酸、並びにそれらの分子内及び/又は分子間縮合物、2)リン酸、亜リン酸、次亜リン酸、並びにそれらの分子内及び/又は分子間縮合物の金属塩類等が挙げられる。
なお、(E)リン系化合物は、1種のみを単独で用いてもよく、2種以上を組み合わせて用いてもよい。
前記2)のリン酸、亜リン酸、次亜リン酸、並びにそれらの分子内及び/又は分子間縮合物の金属塩類としては、以下に限定されるものではないが、例えば、前記1)のリン化合物と周期律表第1族及び第2族、マンガン、亜鉛、アルミニウムとの塩を挙げることができる。
よりさらに好ましい(E)リン系化合物は、リン酸、亜リン酸及び次亜リン酸から選ばれるリン化合物と、周期律表第1族及び第2族から選ばれる金属と、を含む金属塩である。
これらの中でも、次亜リン酸ナトリウム、次亜リン酸カルシウム、次亜リン酸マグネシウムが好ましく、より好ましくはアルカリ土類金属塩である次亜リン酸カルシウム、次亜リン酸マグネシウムである。このような(E)リン系化合物を用いることにより、白色度、耐熱変色性、耐光変色性及び押出加工性により優れる傾向にある。
特に、前記(E)リン系化合物の金属種としては、アルカリ土類金属であることが好ましい。
(E)リン系化合物が金属塩、金属塩の分子内縮合物、及び金属塩の分子間縮合物からなる群より選ばれるものであり、かつ(E)リン化合物の金属種が(C)金属水酸化物及び/又は(D)金属酸化物の金属種が同一であることにより、熱安定性が高まり、押出加工性、及び成形加工安定性に優れるポリアミド組成物を得ることができる。さらに、(E)リン系化合物の金属種としてアルカリ土類金属を用いることにより、上記特性において、より一層優れた効果が得られる。
(E)リン系化合物として、無水塩、水和物を含まない金属塩を使用することにより、加工時に発生する水分量を抑えることができ、ポリアミドの分子量低下やガス発生を抑制することができる。また、(E)リン系化合物として、無水塩、水和物を含まない金属塩を用いることにより、白色度、耐リフロー性、耐熱変色性、押出加工性、及び成形加工安定性に優れるポリアミド組成物を得ることができる。
(E)リン系化合物として潮解性の低い金属塩を用いることにより、ポリアミド組成物の製造時に各原料成分を混合する際に作業性が低下や原料成分中の水分量が高くなることによる、加工時のポリアミドの分子量低下やガス発生を抑制することができる。潮解性の低い金属塩を用いることにより、白色度、耐リフロー性、耐熱変色性、押出加工性、及び成形加工安定性に優れるポリアミド組成物を得ることができる。
前記有機リン系化合物としては、以下に限定されるものではないが、例えば、ペンタエリスリトール型ホスファイト化合物、トリオクチルホスファイト、トリラウリルホスファイト、トリデシルホスファイト、オクチルジフェニルホスファイト、トリスイソデシルホスファイト、フェニルジイソデシルホスファイト、フェニルジ(トリデシル)ホスファイト、ジフェニルイソオクチルホスファイト、ジフェニルイソデシルホスファイト、ジフェニル(トリデシル)ホスファイト、トリフェニルホスファイト、トリス(ノニルフェニル)ホスファイト、トリス(2,4-ジ-t-ブチルフェニル)ホスファイト、トリス(2,4-ジ-t-ブチル-5-メチルフェニル)ホスファイト、トリス(ブトキシエチル)ホスファイト、4,4’-ブチリデン-ビス(3-メチル-6-t-ブチルフェニル-テトラ-トリデシル)ジホスファイト、テトラ(C12~C15混合アルキル)-4,4’-イソプロピリデンジフェニルジホスファイト、4,4’-イソプロピリデンビス(2-t-ブチルフェニル)-ジ(ノニルフェニル)ホスファイト、トリス(ビフェニル)ホスファイト、テトラ(トリデシル)-1,1,3-トリス(2-メチル-5-t-ブチル-4-ヒドロキシフェニル)ブタンジホスファイト、テトラ(トリデシル)-4,4’-ブチリデンビス(3-メチル-6-t-ブチルフェニル)ジホスファイト、テトラ(C1~C15混合アルキル)-4,4’-イソプロピリデンジフェニルジホスファイト、トリス(モノ,ジ混合ノニルフェニル)ホスファイト、9,10-ジ-ヒドロ-9-オキサ-9-オキサ-10-ホスファフェナンスレン-10-オキサイド、トリス(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)ホスファイト、水素化-4,4’-イソプロピリデンジフェニルポリホスファイト、ビス(オクチルフェニル)-ビス(4,4’-ブチリデンビス(3-メチル-6-t-ブチルフェニル))・1,6-ヘキサノールジホスファイト、ヘキサトリデシル-1,1,3-トリス(2-メチル-4-ヒドロキシ-5-t-ブチルフェニル)ジホスファイト、トリス(4,4’-イソプロピリデンビス(2-t-ブチルフェニル))ホスファイト、トリス(1,3-ステアロイルオキシイソプロピル)ホスファイト、2,2-メチレンビス(4,6-ジ-t-ブチルフェニル)オクチルホスファイト、2,2-メチレンビス(3-メチル-4,6-ジ-t-ブチルフェニル)2-エチルヘキシルホスファイト、テトラキス(2,4-ジ-t-ブチル-5-メチルフェニル)-4,4’-ビフェニレンジホスファイト、及びテトラキス(2,4-ジ-t-ブチルフェニル)-4,4’-ビフェニレンジホスファイトが挙げられる。
前記有機リン系化合物は、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
前記ペンタエリスリトール型ホスファイト化合物は、1種のみを単独で用いてもよく、2種以上を組み合わせて用いてもよい。
本実施形態のポリアミド組成物中の(E)リン系化合物の含有量は、(C)金属水酸化物及び/又は(D)金属酸化物よりも多く含有している方が好ましい。
(E)リン系化合物の含有量が上記の範囲内であることにより、本実施形態のポリアミド組成物は白色度、耐リフロー性、耐熱変色性、押出加工安定性、成形加工安定性に優れる傾向にある。
ポリアミド組成物中に含まれる(E)リン系化合物由来のリン元素濃度が上記範囲であることにより、ポリアミド組成物は白色度、耐リフロー性、耐熱変色性、押出加工安定性、成形加工安定性に優れる。
なお、ポリアミド組成物中に含まれる(E)リン系化合物由来のリン元素濃度は、後述する実施例に記載されている金属元素濃度の測定方法により測定することができる。
前記金属元素濃度が上記範囲であることにより、ポリアミド組成物が、耐リフロー性、耐光変色性がより優れる傾向にある。
なお、金属元素濃度は、実施例に記載されている金属元素濃度の測定方法により測定することができる。
本実施形態のポリアミド組成物は、熱安定性の観点から、フェノール系酸化防止剤及び/又はアミン系酸化防止剤を含有していてもよい。
中でも、耐熱エージング性向上の観点から、前記ヒンダードフェノール化合物としては、N,N’-へキサン-1,6-ジイルビス[3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニルプロピオンアミド)]が好ましい。
なお、上述したフェノール系酸化防止剤は、1種のみを単独で用いてもよく、2種以上を組み合わせて用いてもよい。
フェノール系酸化防止剤の含有量が上記の範囲内であることにより、本実施形態のポリアミド組成物は、耐熱エージング性により優れ、発生ガス量のより低いものとなる傾向にある。
なお、本実施形態において、アミン系酸化防止剤とは、芳香族アミン系化合物を含む。アミン系酸化防止剤は、1種のみを単独で用いてもよく、2種以上を組み合わせて用いてもよい。
アミン系酸化防止剤の含有量が上記の範囲内であることにより、ポリアミド組成物は、耐熱エージング性により優れ、発生ガス量のより低いものとなる傾向にある。
本実施形態のポリアミド組成物は、強度剛性等の機械物性の観点から、上述した(B)酸化チタン以外の(F)無機充填材をさらに含有していてもよい。
これらの中でも、(F)無機充填材としては、ガラス繊維、チタン酸カリウム繊維、タルク、ウォラストナイト、カオリン、マイカ、炭酸カルシウム及びクレーからなる群より選ばれる1種以上が好ましく、ウォラストナイト、炭酸カルシウムがより好ましい。
(F)無機充填剤の数平均粒子径は、ポリアミド組成物の白色度、靭性及び押出加工性の観点から、好ましくは0.1~0.8μm、より好ましくは0.15~0.4μm、さらに好ましくは0.15~0.3μmである。
このような(F)無機充填材を含むことにより、本実施形態のポリアミド組成物の機械的強度、外観、白色度等がより優れる傾向にある。
(F)無機充填材は、1種のみを単独で用いてもよく、2種以上を組み合わせて用いてもよい。
(F)無機充填材の含有量が上記の範囲内であることにより、本実施形態のポリアミド組成物の強度、剛性及び靭性をよりバランス良く保つことができる。
上記観点から(F)無機充填材の含有量は5質量%以上であることが好ましく、より好ましくは10質量%以上、さらに好ましくは15質量%以上である。
本実施形態のポリアミド組成物は、光安定性の観点から、アミン系光安定剤をさらに含有していてもよい。
前記アミン系光安定剤は、1種のみを単独で用いてもよく、2種以上を組み合わせて用いてもよい。
これらの中でも、アミン系光安定剤としては、ビス(2,2,6,6-テトラメチル-4-ピペリジル)セバケート、N,N’-ビス-2,2,6,6-テトラメチル-4-ピペリジニル-1,3-ベンゼンジカルボキシアミド、テトラキス(2,2,6,6-テトラメチル-4-ピペリジル)-1,2,3,4-ブタンテトラカルボキシラートがより好ましく、N,N’-ビス-2,2,6,6-テトラメチル-4-ピペリジニル-1,3-ベンゼンジカルボキシアミドがさらに好ましい。
本実施形態のポリアミド組成物は、離型性の観点から、造核剤をさらに含有することが好ましい。
前記「造核剤」とは、添加により熱示差走査分析(DSC)で測定される結晶化温度を上昇させる効果や、得られる成形品の球晶を微細化又はサイズの均一化に効果が得られる物質のことを意味する。
造核剤は、1種のみを単独で用いてもよく、2種以上を組み合わせてもよい。
前記造核剤の中でも、造核剤効果の観点で、タルク、窒化ホウ素、及びカーボンブラックが好ましく、より好ましくはタルク、窒化ホウ素であり、さらに好ましくはタルクである。
造核剤の数平均粒子径が上記範囲内であることにより、造核効果がより向上する傾向にある。
造核剤の数平均粒子径の測定は、本実施形態のポリアミド組成物の成形品をギ酸などのポリアミドが可溶な溶媒で溶解し、得られた不溶成分の中から、例えば100個以上の造核剤を任意に選択し、光学顕微鏡や走査型電子顕微鏡などで観察し、求めることができる。
造核剤の配合量をポリアミド組成物100質量%に対して0.001質量%以上とすることにより、本実施形態のポリアミド組成物の耐熱性が良好に向上し、また、配合量を15質量%以下とすることにより、靭性に優れるポリアミド組成物を得ることができる。
本実施形態のポリアミド組成物は、上記した成分の他に、必要に応じてさらに、その他の成分を添加してもよい。
その他の成分としては、以下に限定されるものではないが、例えば、顔料及び染料等の着色剤(着色マスターバッチ含む)、離型剤、難燃剤、フィブリル化剤、潤滑剤、蛍光増白剤、可塑化剤、銅化合物、ハロゲン化アルカリ金属化合物、酸化防止剤、安定剤、紫外線吸収剤、帯電防止剤、流動性改良剤、充填剤、補強剤、展着剤、核剤、ゴム、強化剤並びに他のポリマー等が挙げられる。
ここで、上記その他の成分は、それぞれ性質が大きく異なるため、各成分についての好適な含有率は様々である。そして、当業者であれば、上記した他の成分ごとの好適な含有率は容易に設定可能である。
本実施形態のポリアミド組成物の製造方法としては、特に限定されず、前記(A)ポリアミド、(C)金属水酸化物及び/又は(D)金属酸化物、(E)リン系化合物、さらに必要に応じて、(B)酸化チタン、フェノール系酸化防止剤及び/又はアミン系酸化防止剤、(F)無機充填材、アミン系光安定剤、造核剤、前記その他の成分等を含む各原料成分を混合する方法を用いることができる。
(C)金属水酸化物及び/又は(D)金属酸化物、(E)リン系化合物の混合方法としては、サイドフィダーから配合する方法の方が好ましい。サイドフィダーから配合する方法によりポリアミド組成物を製造することにより、ポリアミド組成物の白色度、耐リフロー性、耐熱変色性、耐光変色性、及び成形加工安定性が優れたものとなる傾向にある。
本実施形態のポリアミド組成物の25℃の硫酸相対粘度ηr、融点Tm2、融解熱量ΔH、ガラス転移温度Tgは、前記(A)ポリアミドにおける測定方法と同様の方法により測定することができる。具体的には、後述する実施例に記載の方法により測定することができる。
また、ポリアミド組成物における測定値が、前記ポリアミドの測定値として好ましい範囲と同様の範囲にあることにより、耐熱性、成形性、及び耐薬品性により優れるポリアミド組成物を得ることができる。
ポリアミド組成物の結晶化ピーク温度Tc(℃)は、より好ましくは245℃以上であり、さらに好ましくは250℃以上であり、さらにより好ましくは255℃以上であり、よりさらに好ましくは260℃以上である。また、ポリアミド組成物の結晶化ピーク温度Tc(℃)は、より好ましくは280℃以下であり、より好ましくは275℃以下であり、さらに好ましくは270℃以下である。
ポリアミド組成物の結晶化ピーク温度Tc(℃)が240℃以上であることにより、成形時の離型性に優れるポリアミド組成物を得ることができる。また、ポリアミド組成物の結晶化ピーク温度Tc(℃)が290℃以下であることにより、成形時のゲートシールが速すぎることがなく、薄肉成形品等の微細部品を良好に成形できるポリアミド組成物を得ることができる。
本実施形態に用いるポリアミド組成物の融点結晶化ピーク温度Tcの測定は、後述の実施例に記載の方法により、JIS-K7121に準じて行うことができる。
結晶化ピーク温度Tcの測定装置としては、例えば、PERKIN-ELMER社製Diamond-DSC等が挙げられる。
本実施形態のポリアミド組成物の100℃/minで冷却したときに得られる結晶化ピークTc(℃)とガラス転移温度Tgとの差(Tc-Tg)が大きいほど、結晶化できる温度範囲が広く、金型内で十分に結晶化しやすいことを意味する。
本実施形態のポリアミド組成物の100℃/minで冷却したときに得られる結晶化ピーク温度Tc(℃)と、ガラス転移温度Tgとの差(Tc-Tg)が90℃以上であるポリアミド組成物は、成形時の離型性に優れる。本実施形態のポリアミド組成物の100℃/minで冷却したときに得られる結晶化ピーク温度Tc(℃)と、ガラス転移温度Tgとの差(Tc-Tg)の上限は、特に限定されないが、300℃以下であることが好ましい。
本実施形態の成形品は、上述のポリアミド組成物を含む。
本実施形態の成形品は、耐リフロー性、耐熱変色性、耐光変色性に優れ、反射板等に好適に用いることができる。
本実施形態の成形品は、例えば、上述のポリアミド組成物を公知の成形方法で成形することにより得ることができる。
当該公知の成形方法としては、以下に限定されるものではないが、例えば、プレス成形、射出成形、ガスアシスト射出成形、溶着成形、押出成形、吹込成形、フィルム成形、中空成形、多層成形、及び溶融紡糸等、一般に知られているプラスチック成形方法を挙げることができる。
当該反射率保持率を95%以上とするためには、(E)リン系化合物を含有することが有効である。
また、成形品の反射率保持率は、後述する実施例に記載する方法により測定することができる。
自動車用としては、以下に限定されるものではないが、例えば、吸気系部品、冷却系部品、燃料系部品、内装部品、外装部品、及び電装部品等が挙げられる。
上記のように本実施形態のポリアミド組成物を含有する成形品は、反射板として好適に用いることができる。
当該反射板においては、前記(A)ポリアミドと、前記(C)金属水酸化物及び/又は(D)金属酸化物と、(E)リン系化合物とを、組み合わせて用いることにより、熱による反射率の低下を効果的に抑制することができる。
前記反射率については、後述する実施例に記載する方法により測定することができ、上述した組み合わせにより、本実施形態のポリアミド組成物を含有する反射板において、効果的に反射率の低下が抑制できることは、後述する実施例において検証されている。
なお、本実施例において、1kg/cm2は、0.098MPaを意味する。
((A)ポリアミド(PA-1))
本実施例、比較例において用いる(A)ポリアミドは、下記(a)及び(b)を適宜用いて製造した。
<(a)ジカルボン酸>
(a-1)1,4-シクロヘキサンジカルボン酸(CHDA)(イーストマンケミカル社製、商品名:1,4-CHDA HPグレード(トランス体/シス体=25/75))
(a-2)テレフタル酸(和光純薬工業社製)
<(b)ジアミン>
(b-1)2-メチルペンタメチレンジアミン(2MC5DA)(東京化成工業製)
(b-2)1,9-ノナメチレンジアミン(C9DA)(アルドリッチ社製)
(b-3)2-メチルオクタメチレンジアミン(2MC9DA)(特開平05-17413号公報に記載されている製法を参考にして製造した。)
(B-1)TiO2(石原産業社製、商品名:タイペーク(登録商標)CR-63、数平均粒子径:0.21μm、コーティング:アルミナ、シリカ及びシロキサン化合物)
なお、(B)酸化チタンの数平均粒子径は、電子顕微鏡写真法により以下のとおり測定した。
後述する実施例及び比較例のポリアミド組成物を電気炉に入れて、ポリアミド組成物中に含まれる有機物を焼却処理し、残渣分から、任意に選択した100個以上の酸化チタンを、電子顕微鏡で観察して、これらの粒子径を測定することにより、(B)酸化チタンの数平均粒子径を求めた。
(C-1)水酸化カルシウム 純度99.9% (和光純薬工業社製)
(C-2)水酸化マグネシウム 純度99.9% (和光純薬工業社製)
(D-1)酸化カルシウム 純度99.9% (和光純薬工業社製)
(D-2)酸化マグネシウム 和光一級 (和光純薬工業社製)
(E-1)次亜リン酸カルシウム(和光純薬工業社製、分解開始温度 340℃)
(E-2)次亜リン酸ナトリウム一水和物(和光純薬工業社製、分解開始温度 300℃)
(F)ウォラストナイト(数平均繊維径8μm)
なお、(F)無機充填材の数平均繊維径は、後述する実施例及び比較例のポリアミド組成物を電気炉に入れて、ポリアミド組成物中に含まれる有機物を焼却処理し、残渣分から、任意に選択した100本以上のガラス繊維を、SEMで観察して、これらのガラス繊維の繊維径を測定することにより数平均繊維径を求めた。
フェノール系酸化防止剤(BASF社製、商品名:IRGANOX(登録商標)1098)
エポキシ変性反応性シリコーンオイル(信越化学工業社製、商品名:KF-105、粘度(25℃)15mm2/s、官能基当量=490g/mol)
タルク(日本タルク社製、商品名:MICRO ACE(登録商標)L-1 平均粒子径 5μm)
[脂環族ジカルボン酸単位(a-1)のモル%の計算]
脂環族ジカルボン酸単位(a-1)のモル%は、下記式を用いて計算により求めた。
式:脂環族ジカルボン酸単位(a-1)のモル%=(原料モノマーとして加えた脂環族ジカルボン酸のモル数/原料モノマーとして加えた全てのジカルボン酸のモル数)×100
芳香族ジカルボン酸単位(a-2)のモル%は、下記式を用いて計算により求めた。
式:芳香族ジカルボン酸単位(a-2)=(原料モノマーとして加えた芳香族ジカルボン酸のモル数/原料モノマーとして加えた全てのジカルボン酸のモル数)×100
(1)ポリアミドの融点Tm2(℃)、融解熱量ΔH(J/g)、結晶化ピーク温度Tc(℃)
JIS-K7121に準じて、PERKIN-ELMER社製Diamond-DSCを用いて、ポリアミドの融点Tm2(℃)、及び融解熱量ΔH(J/g)を測定した。
具体的には、以下のとおり測定した。
まず、窒素雰囲気下、サンプル約10mgを、室温からサンプルの融点に応じて300~350℃まで、昇温速度20℃/minで昇温した。このときに現れる吸熱ピーク(融解ピーク)の温度をTm1(℃)とした。次に、昇温の最高温度で温度を2分間保った。この最高温度ではポリアミドは溶融状態であった。その後、降温速度100℃/minで30℃まで降温する。このときに現れる発熱ピークを結晶化ピークとし、結晶化ピーク温度をTcとする。その後、30℃で2分間保持した後、30℃からサンプルの融点に応じて300~350℃まで、昇温速度20℃/minで昇温した。このときに現れる吸熱ピーク(融解ピーク)の最高ピーク温度を融点Tm2(℃)とし、その全ピーク面積を融解熱量ΔH(J/g)とした。なお、ピークが複数ある場合には、ΔHが1J/g以上のものをピークとみなし、最大のΔHを有する吸熱ピ-ク温度を融点Tm2(℃)とした。例えば、吸熱ピーク温度295℃(ΔH=20J/g)と、吸熱ピーク温度325℃(ΔH=25J/g)との二つのピークが存在する場合、融点Tm2は325℃とし、ΔH=25J/gとした。
(A)ポリアミド中の(a-1)脂環族ジカルボン酸に由来する部分のトランス異性体比率を以下のとおり測定した。
ポリアミド30~40mgをヘキサフルオロイソプロパノール重水素化物1.2gに溶解し、得られた溶液を用いて1H-NMRで前記トランス異性体比率を測定した。
(a-1)脂環族ジカルボン酸が1,4-シクロヘキサンジカルボン酸の場合、トランス異性体に由来する1.98ppmのピーク面積と、シス異性体に由来する1.77ppm及び1.86ppmのピーク面積と、の比率からトランス異性体比率を求めた。
JIS-K7121に準じて、PERKIN-ELMER社製Diamond-DSCを用いてガラス転移温度Tg(℃)を測定した。具体的には以下のとおり測定した。サンプルをホットステージ(Mettler社製EP80)で溶融させて、得られた溶融状態のサンプルを、液体窒素を用いて急冷し、固化させ、測定用サンプルとした。その測定用サンプル10mgを、前記DSCにより、昇温スピード20℃/minの条件下、30~350℃の範囲で昇温して、該昇温の際に観測されるガラス転移温度Tg(℃)を測定した。
JIS-K6810に準じて25℃の硫酸相対粘度ηrの測定を実施した。
具体的には、98%硫酸を用いて、1%の濃度の溶解液((ポリアミド1g)/(98%硫酸100mL)の割合)を作製し、得られた溶解液を用いて25℃の温度条件下で硫酸相対粘度ηrを測定した。
ICP発光分光分析法(島津製作所製ICPS-8100)により、ポリアミド組成物中に含まれる(C)金属水酸化物、(D)金属酸化物、(E)リン系化合物に由来する金属元素濃度を測定し、ポリアミド組成物中に含まれる(C)、(D)、(E)成分に由来する金属元素濃度の合算値(リン元素を除く)と、ポリアミド組成物中に含まれる(E)成分に由来するリン元素濃度を算出した。
XRDにより測定した。測定装置はPANalytical社製X‘Pert PRO MPDを使用した。検出器はX‘Celeratorを用いた。金属化合物単体の回折パターンから、金属化合物を同定した。含有量はX線回折のピーク面積から算出した。
後述する実施例及び比較例で製造したポリアミド組成物のペレットを、射出成形機[PS-40E:日精樹脂株式会社製]を用いて成形することにより、長さ60mm×幅60mm×厚さ1.0mmの成形片を作製した。
当該成形の際、射出+保圧時間10秒、冷却時間15秒、金型温度を120℃、溶融ポリアミド組成物の温度を(A)ポリアミドの融点Tm2+10℃に設定した。
得られた成形片の波長450nmの光に対する反射率を日立分光光度計(U-3310)により測定した。
後述する実施例及び比較例で製造したポリアミド組成物のペレットを、射出成形機[PS-40E:日精樹脂株式会社製]を用いて成形することにより、長さ60mm×幅60mm×厚さ1.0mmの成形片を作製した。
当該成形の際、射出+保圧時間10秒、冷却時間15秒、金型温度を120℃、溶融樹脂温度を(A)ポリアミドの融点Tm2+10℃に設定した。得られた成形片を、熱風リフロー炉(280℃×10秒)で3回加熱処理(リフロー工程)した。
当該加熱処理(リフロー工程)前後の成形片の、450nmの光に対する反射率を日立分光光度計(U-3310)により測定し、リフロー工程後の反射率保持率を算出した。
上記により得られたリフロー工程後の成形片を、150℃の熱風乾燥機中で72時間加熱処理した。
熱処理後の成形片の、450nmの光に対する反射率を日立分光光度計(U-3310)により測定し、熱処理前における反射率と対比して反射率保持率を算出した。
上記熱処理後の反射率保持率(%)測定により得られた熱処理後の成形片を、100℃のメタルハライドランプ式耐光性試験機(岩崎電気株式会社製)にて、1000時間、メタルハライド暴露処理した。成形片を設置した位置での照度は10mW/cm2であった。
このメタルハライド暴露処理前後の成形片に対して波長450nmの光を照射し、その光の反射率を日立分光光度計(U-3310)により測定し、反射率保持率を算出した。
後述する実施例及び比較例で製造したポリアミド組成物のペレットを、スクリュー径26mmの二軸押出機により押出加工した。
該押出加工の際、シリンダーの温度を(A)ポリアミドのTm2+20℃に設定し、スクリュー回転数300rpm、吐出量25kg/hに設定した。
押出開始から20分間に発生するストランド切れの回数を測定した。
該ストランド切れの回数が少ないほど、押出加工性に優れると判断した。
後述する実施例及び比較例で製造したポリアミド組成物のペレットを、射出成形機[PS-40E:日精樹脂株式会社製]を用いて成形することにより、長さ60mm×幅60mm×厚さ1.0mmの成形品を作製した。
当該成形の際、射出+保圧時間2秒、冷却時間6秒、金型温度を130℃、溶融樹脂温度を(A)ポリアミドの融点Tm2+10℃に設定した。
成形性の評価判定は下記の通りとした。問題なく成形品が得られることは、生産性の向上に繋がると評価した。
◎:問題なく成形品が得られた。
○:問題なく離型し成形品が得られるがバリが発生した。
△:時々スプルーが金型に残った。
×:離型性が不十分であり、成形品が金型に貼り付いたり変形したりした。
(製造例1)
CHDA896g(5.20モル)、及び2MC5DA604g(5.20モル)を蒸留水1500gに溶解させ、原料モノマーの等モル50質量%の水混合液を作製した。
得られた水混合液と、溶融重合時の添加物である、2MC5DA15g(0.15モル)とを内容積5.4Lのオートクレーブ(日東高圧製)に仕込んだ。
次に、オートクレーブ内の液温(内温)が50℃になるまで加温した。
その後、オートクレーブ内を窒素置換した。
オートクレーブの槽内(以下、単に「槽内」ともいう。)の圧力が、ゲージ圧として(以下、槽内の圧力は全てゲージ圧として表記した。)、約2.5kg/cm2になるまで加熱を続けた。このとき液温は約145℃であった。
槽内の圧力を約2.5kg/cm2に保つため水を系外に除去しながら、加熱を続けて、槽内の水溶液の濃度が約85質量%になるまで濃縮した。
水の除去を止め、槽内の圧力が約30kg/cm2になるまで加熱を続けた。
槽内の圧力を約30kg/cm2に保つため水を系外に除去しながら、最終温度(約345℃)より50℃低い温度(約295℃)になるまで加熱を続けた。さらに加熱を続けながら、槽内の圧力を60分間かけて大気圧(ゲージ圧は0kg/cm2)になるまで降圧した。槽内の樹脂温度(液温)の最終温度が約345℃になるようにヒーター温度を調整した。
槽内の樹脂温度はその状態のまま、槽内を真空装置で100torrの減圧下に10分維持した。その後、槽内を窒素で加圧し、下部紡口(ノズル)から生成物をストランド状にして排出した。さらにストランド状の生成物を、水冷、カッティングを行いペレット状のポリアミド(ポリアミドペレット)を得た。
前記溶融重合を用いて得られたポリアミドペレット10kgを円錐型リボン真空乾燥機(株式会社大川原製作所製、商品名リボコーンRM-10V)に入れ、該真空乾燥機内を十分に窒素置換した。
該真空乾燥機内に1L/分で窒素を流したまま、ポリアミドペレットを攪拌しながら260℃で6時間、加熱した。その後、窒素を流通したまま該真空乾燥機内の温度を約50℃まで下げて、ポリアミドペレットを、ペレット状のまま該真空乾燥機から取り出し、ポリアミド(以下、「PA-1」ともいう。)を得た。
得られたポリアミドを、窒素気流中で乾燥し水分率を約0.2質量%未満に調整してから、該ポリアミドの各特性を上記測定方法に基づいて測定した。
該測定の結果、ポリアミド(PA-1)は、融点Tm2が327℃、ガラス転移温度Tgが150℃、トランス異性体比率が71%、25℃の硫酸相対粘度が3.1であった。
CHDA782g(4.54モル)とC9DA575g(3.63モル)と2MC9DA144g(0.91モル)とを蒸留水1500gに溶解させ、原料モノマーの等モル50質量%の水混合液を作製した。
得られた水混合液と、溶融重合時の添加物である、C9DA11g(0.07モル)とを内容積5.4Lのオートクレーブ(日東高圧製)に仕込んだ。
次に、オートクレーブ内の液温(内温)が50℃になるまで加温した。
その後、オートクレーブ内を窒素置換した。オートクレーブの槽内の圧力が、ゲージ圧として、約2.5kg/cm2になるまで加熱を続けた。このとき液温は約145℃であった。
槽内の圧力を約2.5kg/cm2に保つため水を系外に除去しながら、加熱を続けて、槽内の水溶液の濃度が約75質量%になるまで濃縮した。水の除去を止め、槽内の圧力が約30kg/cm2になるまで加熱を続けた。
槽内の圧力を約30kg/cm2に保つため水を系外に除去しながら、最終温度(約340℃)より50℃低い温度(約290℃)になるまで加熱を続けた。さらに加熱を続けながら、槽内の圧力を90分間かけて大気圧(ゲージ圧は0kg/cm2)になるまで降圧した。
槽内の樹脂温度(液温)の最終温度が約340℃になるようにヒーター温度を調整した。槽内の樹脂温度はその状態のまま、槽内を真空装置で400torrの減圧下に30分維持した。その後、槽内を窒素で加圧し、下部紡口(ノズル)から生成物をストランド状にして排出した。さらにストランド状の生成物を、水冷、カッティングを行いペレット状のポリアミド(以下、「PA-2」ともいう。)を得た。
得られたポリアミドを、窒素気流中で乾燥し水分率を約0.2質量%未満に調整してから、該ポリアミドの各特性を上記測定方法に基づいて測定した。
該測定の結果、ポリアミド(PA-2)は、融点Tm2が316℃、ガラス転移温度Tgが119℃、トランス異性体比率が70%、25℃の硫酸相対粘度が2.4であった。
原料のジカルボン酸として1,4-シクロヘキサンジカルボン酸(CHDA)750g(4.35モル)を用い、原料のジアミンとして1,10-ジアミノデカン(C10DA)750g(4.35モル)を用い、溶融重合時の添加物として、C10DA 15g(0.09モル)を用い、樹脂温度(液温)の最終温度355℃としたこと以外は、製造例1に記載した方法と同様にして重合を実施し、ポリアミド(以下、「PA-3」ともいう。)を得た。
得られたポリアミドを、窒素気流中で乾燥し水分率を約0.2質量%未満に調整してから、該ポリアミドの各特性を上記測定方法に基づいて測定した。
該測定の結果、ポリアミド(PA-3)は、融点Tm2が334℃、融解熱量ΔHが35J/g、ガラス転移温度Tgが121℃、トランス異性体比率が70%、25℃の硫酸相対粘度が2.3であった。
ポリアミド9T(以下、「PA-4」とも略記する)を、特開平7-228689号公報の実施例1に記載された方法に従って製造した。
その際、原料のジカルボン酸として、テレフタル酸を用い、原料ジアミンとして、1,9-ノナメチレンジアミン及び2-メチルオクタメチレンジアミン[1,9-ノナメチレンジアミン:2-メチルオクタメチレンジアミン=80:20(モル比)]を用いた。
具体的には、上記の各原料及び蒸留水等を20リットル容のオートクレーブに入れて水混合液を得た。次に、該オートクレーブ内を窒素で置換した。その後、該オートクレーブ内の水混合液を、100℃で30分間撹拌した。
次に、2時間かけて該オートクレーブの内部温度を210℃まで昇温した。その際、オートクレーブは22kg/cm2まで昇圧した。
そのまま1時間反応を続けた後、該オートクレーブの内部温度を230℃に昇温した。その後2時間、オートクレーブの内部温度を230℃で恒温し、水蒸気を徐々に抜いてオートクレーブの内の圧力を22kg/cm2に保ちながら反応させた。
次に、30分かけてオートクレーブの内の圧力を10kg/cm2まで下げ、さらに1時間反応させて、プレポリマーを得た。
得られたプレポリマーを、100℃、減圧下で12時間乾燥し、2mm以下の大きさまで粉砕した。粉砕したプレポリマーを、230℃、0.1mmHg下にて、10時間固相重合し、ポリアミド(PA-4)を得た。
該ポリアミド(PA-4)の各特性を上記測定方法に基づいて測定した。
該測定の結果、ポリアミド(PA-4)は、融点Tm2が298℃、ガラス転移温度Tgが122℃、25℃の硫酸相対粘度が2.6であった。
テレフタル酸を、ジカルボン酸単位(a)を構成するジカルボン酸単位として用い、1,10-ジアミノデカン(C10DA)を、ジアミン単位(b)を構成するジアミンとして用いたこと以外は、製造例1と同様の操作を行い、ポリアミド10T(以下、「PA-5」ともいう。)を得た。該ポリアミドの各特性を上記測定方法に基づいて測定した。
該測定の結果、融点Tm2は315℃、融解熱量ΔHは43J/g、ガラス転移温度Tgは116℃、25℃の硫酸相対粘度は2.0であった。
(実施例1~19及び比較例1~10)
上記製造例1~5で得られたポリアミド(PA-1)~(PA-5)と、上記各原材料とを、下記表1、表2に記載の種類及び割合で用いて、ポリアミド組成物を以下のとおり製造した。
該二軸押出機は、押出機上流側から1番目のバレルに上流側供給口を有し、6番目のバレルに下流側第1供給口を有し、9番目のバレルに下流側第2供給口を有していた。また、該二軸押出機において、L/D(押出機のシリンダーの長さ/押出機のシリンダー径)は48であり、バレル数は12であった。
該二軸押出機において、上流側供給口からダイまでの温度を上記製造例にて製造した各(A)ポリアミドの融点Tm2+20℃に設定し、スクリュー回転数250rpm、吐出量25kg/hに設定した。
次に、表1に示すポリアミド組成物を製造する場合には、前記二軸押出機の下流側第1供給口より、下記表1に記載の種類及び割合で(B)酸化チタンを供給した。
さらに二軸押出機の下流側第2供給口より、下記表1、表2に記載の種類及び割合で(F)無機充填材を供給した。
上記のとおり供給した原料を二軸押出機で溶融混練してポリアミド組成物のペレットを作製した。
得られたポリアミド組成物のペレットを、窒素気流中で乾燥し、ポリアミド組成物中の水分量を500ppm以下にした。
水分量を調整した後のポリアミド組成物を用いて上記のとおり各種評価を実施した。
評価結果を下記表1、表2に示す。
また、表2に示すように、実施例15~19のポリアミド組成物は、(C)金属水酸化物及び/又は(D)金属酸化物と、(E)リン系化合物を含有することにより優れた成形性が実現できることが分かった。
特に、実施例15と16を対比することにより、本発明のポリアミド組成物として、タルク等の造核剤を適量含有させた場合のポリアミド組成物は、より一層、可塑化安定性に優れ、かつ結晶化速度が速く、短い成形サイクルで成形加工できることが分かった。
さらに、実施例1~15、17~19のポリアミド組成物の成形品の表面の結晶状態を示差走査熱量測定(DSC)で確認すると、型内で十分に結晶化していることが分かった。
さらにまた、以上の結果から、本発明のポリアミド組成物は、各反射率保持率に優れるため、LED用反射板に好適に用いることができることが示された。
Claims (15)
- (A)ポリアミドと、
(C)金属水酸化物及び/又は(D)金属酸化物0.1~20質量%と、
(E)リン系化合物0.1~20質量%と、
を、含有する、ポリアミド組成物。 - 前記(A)ポリアミドが、270~350℃の融点を有する、請求項1に記載のポリアミド組成物。
- 前記(A)ポリアミドは、脂環族ジカルボン酸を50モル%以上含むジカルボン酸を重合単量体としたポリアミドである、請求項1又は2に記載のポリアミド組成物。
- 前記脂環族ジカルボン酸が、1,4-シクロヘキサンジカルボン酸を含む、請求項3に記載のポリアミド組成物。
- (B)酸化チタンを5質量%以上、さらに含有する、請求項1乃至4のいずれか一項に記載のポリアミド組成物。
- 前記(C)金属水酸化物がアルカリ土類金属の水酸化物である、請求項1乃至5のいずれか一項に記載のポリアミド組成物。
- 前記(D)金属酸化物がアルカリ土類金属の酸化物である、請求項1乃至6のいずれか一項に記載のポリアミド組成物。
- 前記(E)リン系化合物が金属塩であり、当該金属塩の金属種が、(C)金属水酸化物及び/又は(D)金属酸化物の金属種と同一である、請求項1乃至7のいずれか一項に記載のポリアミド組成物。
- 前記(E)リン系化合物がアルカリ土類金属塩である、請求項1乃至8のいずれか一項に記載のポリアミド組成物。
- (F)無機充填材を5質量%以上、さらに含有する、請求項1乃至9のいずれか一項に記載のポリアミド組成物。
- 造核剤を0.001~15質量%、さらに含有する、請求項1乃至10のいずれか一項に記載のポリアミド組成物。
- ポリアミド組成物中に含まれる(E)リン系化合物由来のリン元素濃度が、1,400~20,000ppmであり、JIS-K7121に準じた示差走査熱量測定において、100℃/minで冷却したときに得られる結晶化ピーク温度Tcとガラス転移温度Tgとの差(Tc-Tg)が100℃以上である、請求項1乃至11のいずれか一項に記載のポリアミド組成物。
- 請求項1乃至12のいずれか一項に記載のポリアミド組成物を含む、成形品。
- メタルハライドランプ式耐光性試験機で100℃、照度が10mW/cm2となる位置で1000時間暴露した後の反射率保持率が95%以上である、請求項13に記載の成形品。
- 請求項1乃至12のいずれか一項に記載のポリアミド組成物を含む、LED用反射板。
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CN201480066203.9A CN105849196B (zh) | 2013-12-13 | 2014-12-09 | 聚酰胺组合物、成型品、led用反射板和抑制由热导致的反射率降低的方法 |
JP2015552469A JP6099767B2 (ja) | 2013-12-13 | 2014-12-09 | ポリアミド組成物、成形品、led用反射板、及び熱による反射率の低下を抑制する方法 |
EP14870028.9A EP3081598B8 (en) | 2013-12-13 | 2014-12-09 | Polyamide composition, molded article, reflective board for leds, and method for preventing heat-induced reflectivity reduction |
US15/100,717 US20160304696A1 (en) | 2013-12-13 | 2014-12-09 | Polyamide composition, molded article, reflective plate for led, and method for suppressing reduction in reflectance due to heat |
KR1020167014851A KR101821512B1 (ko) | 2013-12-13 | 2014-12-09 | 폴리아미드 조성물, 성형품, led 용 반사판, 및 열에 의한 반사율의 저하를 억제하는 방법 |
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JP2017014397A (ja) * | 2015-07-01 | 2017-01-19 | 旭化成株式会社 | ポリアミド組成物、成形品、及びled用反射板 |
CN107735454A (zh) * | 2015-06-29 | 2018-02-23 | 株式会社可乐丽 | Led反射板用聚酰胺组合物、led反射板、具备该反射板的发光装置 |
JP7460390B2 (ja) | 2020-02-21 | 2024-04-02 | 株式会社クラレ | 半芳香族ポリアミド繊維 |
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JP7039166B2 (ja) * | 2016-09-30 | 2022-03-22 | 東京応化工業株式会社 | 樹脂組成物、硬化物の製造方法、及び硬化物 |
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KR101821512B1 (ko) | 2018-01-23 |
CN105849196A (zh) | 2016-08-10 |
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US20160304696A1 (en) | 2016-10-20 |
JP6099767B2 (ja) | 2017-03-22 |
EP3081598B8 (en) | 2020-08-12 |
EP3081598B1 (en) | 2020-06-10 |
EP3081598A4 (en) | 2016-12-14 |
KR20160085799A (ko) | 2016-07-18 |
TWI631181B (zh) | 2018-08-01 |
TW201525065A (zh) | 2015-07-01 |
EP3081598A1 (en) | 2016-10-19 |
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