JP2020152762A - 半芳香族ポリアミド樹脂組成物およびその成形体 - Google Patents
半芳香族ポリアミド樹脂組成物およびその成形体 Download PDFInfo
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- JP2020152762A JP2020152762A JP2019050187A JP2019050187A JP2020152762A JP 2020152762 A JP2020152762 A JP 2020152762A JP 2019050187 A JP2019050187 A JP 2019050187A JP 2019050187 A JP2019050187 A JP 2019050187A JP 2020152762 A JP2020152762 A JP 2020152762A
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- Prior art keywords
- polyamide resin
- semi
- aromatic polyamide
- component unit
- resin composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920006012 semi-aromatic polyamide Polymers 0.000 title claims abstract description 121
- 239000011342 resin composition Substances 0.000 title claims abstract description 71
- 229920005989 resin Polymers 0.000 claims abstract description 89
- 239000011347 resin Substances 0.000 claims abstract description 89
- -1 aluminum silicate compound Chemical class 0.000 claims abstract description 49
- 238000002844 melting Methods 0.000 claims abstract description 23
- 230000008018 melting Effects 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 16
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 60
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 48
- 125000004432 carbon atom Chemical group C* 0.000 claims description 29
- 125000001931 aliphatic group Chemical group 0.000 claims description 15
- 150000004985 diamines Chemical class 0.000 claims description 13
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 11
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims description 5
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 4
- 229920006122 polyamide resin Polymers 0.000 abstract description 44
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 description 15
- 239000011256 inorganic filler Substances 0.000 description 12
- 229910003475 inorganic filler Inorganic materials 0.000 description 12
- 239000003963 antioxidant agent Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- 125000005263 alkylenediamine group Chemical group 0.000 description 10
- 125000003118 aryl group Chemical group 0.000 description 10
- 230000009477 glass transition Effects 0.000 description 10
- 238000000465 moulding Methods 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 9
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 8
- 239000004952 Polyamide Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
- 229930195729 fatty acid Natural products 0.000 description 6
- 150000004665 fatty acids Chemical class 0.000 description 6
- 239000003063 flame retardant Substances 0.000 description 6
- 230000001965 increasing effect 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
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229920002647 polyamide Polymers 0.000 description 6
- 229920000098 polyolefin Polymers 0.000 description 6
- 150000003440 styrenes Chemical class 0.000 description 6
- 239000004711 α-olefin Substances 0.000 description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 5
- 239000007983 Tris buffer Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 5
- 239000000395 magnesium oxide Substances 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000001361 adipic acid Substances 0.000 description 4
- 235000011037 adipic acid Nutrition 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000001273 butane Substances 0.000 description 3
- 125000002843 carboxylic acid group Chemical group 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- GEQHKFFSPGPGLN-UHFFFAOYSA-N cyclohexane-1,3-diamine Chemical compound NC1CCCC(N)C1 GEQHKFFSPGPGLN-UHFFFAOYSA-N 0.000 description 3
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 239000012760 heat stabilizer Substances 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000012488 sample solution Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- NSBGJRFJIJFMGW-UHFFFAOYSA-N trisodium;stiborate Chemical compound [Na+].[Na+].[Na+].[O-][Sb]([O-])([O-])=O NSBGJRFJIJFMGW-UHFFFAOYSA-N 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- HNURKXXMYARGAY-UHFFFAOYSA-N 2,6-Di-tert-butyl-4-hydroxymethylphenol Chemical compound CC(C)(C)C1=CC(CO)=CC(C(C)(C)C)=C1O HNURKXXMYARGAY-UHFFFAOYSA-N 0.000 description 2
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 2
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 2
- IGSBHTZEJMPDSZ-UHFFFAOYSA-N 4-[(4-amino-3-methylcyclohexyl)methyl]-2-methylcyclohexan-1-amine Chemical compound C1CC(N)C(C)CC1CC1CC(C)C(N)CC1 IGSBHTZEJMPDSZ-UHFFFAOYSA-N 0.000 description 2
- 239000004953 Aliphatic polyamide Substances 0.000 description 2
- 235000021357 Behenic acid Nutrition 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229920000106 Liquid crystal polymer Polymers 0.000 description 2
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- KEQFTVQCIQJIQW-UHFFFAOYSA-N N-Phenyl-2-naphthylamine Chemical compound C=1C=C2C=CC=CC2=CC=1NC1=CC=CC=C1 KEQFTVQCIQJIQW-UHFFFAOYSA-N 0.000 description 2
- 229910000503 Na-aluminosilicate Inorganic materials 0.000 description 2
- FRCLQKLLFQYUJJ-UHFFFAOYSA-N P(O)(O)O.P(O)(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)C)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1C(C)(C)C)C)C(C)(C)C Chemical compound P(O)(O)O.P(O)(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)C)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1C(C)(C)C)C)C(C)(C)C FRCLQKLLFQYUJJ-UHFFFAOYSA-N 0.000 description 2
- GIATZHZBSIMOEE-UHFFFAOYSA-N P(O)(O)O.P(O)(O)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C Chemical compound P(O)(O)O.P(O)(O)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C GIATZHZBSIMOEE-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 239000004697 Polyetherimide Substances 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229920003231 aliphatic polyamide Polymers 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229940116226 behenic acid Drugs 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 239000000404 calcium aluminium silicate Substances 0.000 description 2
- 235000012215 calcium aluminium silicate Nutrition 0.000 description 2
- WNCYAPRTYDMSFP-UHFFFAOYSA-N calcium aluminosilicate Chemical compound [Al+3].[Al+3].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O WNCYAPRTYDMSFP-UHFFFAOYSA-N 0.000 description 2
- 229940078583 calcium aluminosilicate Drugs 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000010411 cooking Methods 0.000 description 2
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 230000017525 heat dissipation Effects 0.000 description 2
- 229920006015 heat resistant resin Polymers 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000012766 organic filler Substances 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229920001601 polyetherimide Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000429 sodium aluminium silicate Substances 0.000 description 2
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- SDVHRXOTTYYKRY-UHFFFAOYSA-J tetrasodium;dioxido-oxo-phosphonato-$l^{5}-phosphane Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)P([O-])([O-])=O SDVHRXOTTYYKRY-UHFFFAOYSA-J 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- CNUJLMSKURPSHE-UHFFFAOYSA-N trioctadecyl phosphite Chemical compound CCCCCCCCCCCCCCCCCCOP(OCCCCCCCCCCCCCCCCCC)OCCCCCCCCCCCCCCCCCC CNUJLMSKURPSHE-UHFFFAOYSA-N 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 2
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Landscapes
- Polyamides (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
[1]示差走査型熱量計(DSC)により測定される融点が290〜330℃である半芳香族ポリアミド樹脂(A)と、ケイ酸アルミニウム化合物(B)と、を含み、前記ケイ酸アルミニウム化合物(B)の含有量は、半芳香族ポリアミド組成物の全質量を100質量%としたとき、20質量%以上80質量%以下である、半芳香族ポリアミド樹脂組成物。
[2]前記ケイ酸アルミニウム化合物(B)は、ケイ酸アルミニウムアミノシランである、[1]に記載の半芳香族ポリアミド樹脂組成物。
[3]前記半芳香族ポリアミド樹脂(A)は、20〜100モル%の、テレフタル酸成分単位(a−1)と、0〜80モル%の、テレフタル酸以外の芳香族カルボン酸成分単位(a−2)または炭素原子数4〜20の脂肪族ジカルボン酸成分単位(a−3)と、を含むジカルボン酸成分単位[a](ただし、半芳香族ポリアミド樹脂(A)に含まれるジカルボン酸成分単位の総モル数を100モル%とする。)と、ジアミン成分単位[b]と、からなる繰り返し単位を有する、[1]または[2]に記載の半芳香族ポリアミド樹脂組成物。
[4]前記ジカルボン酸成分単位[a]は、20〜100モル%の、テレフタル酸成分単位(a−1)と、0〜80モル%の、テレフタル酸以外の芳香族カルボン酸成分単位(a−2)と、を含む(ただし、半芳香族ポリアミド樹脂(A)に含まれるジカルボン酸成分単位の総モル数を100モル%とする。)、[3]に記載の半芳香族ポリアミド樹脂組成物。
[5]前記ジカルボン酸成分単位[a]は、45〜100モル%の、テレフタル酸成分単位(a−1)と、0〜80モル%の、炭素原子数4〜20の脂肪族ジカルボン酸成分単位(a−3)と、を含む(ただし、半芳香族ポリアミド樹脂(A)に含まれるジカルボン酸成分単位の総モル数を100モル%とする。)、[3]に記載の半芳香族ポリアミド樹脂組成物。
[6][1]〜[5]のいずれかに記載の半芳香族ポリアミド樹脂組成物から得られる、成形体。
本発明の半芳香族ポリアミド樹脂組成物は、半芳香族ポリアミド樹脂(A)と、ケイ酸アルミニウム化合物(B)と、を少なくとも含む。
半芳香族ポリアミド樹脂(A)は、その示差走査型熱量計(DSC)により測定される融点(Tm)が290〜330℃である。上記融点(Tm)は、290〜305℃であることが好ましい。
[η]=ηSP/(C*(1+0.205ηSP))
[η]:極限粘度(dl/g)
ηSP:比粘度
C:試料濃度(g/dl)
t:試料溶液の流下秒数(秒)
t0:ブランク硫酸の流下秒数(秒)
ηSP=(t−t0)/t0
ケイ酸アルミニウム化合物(B)は、半芳香族ポリアミド樹脂組成物の熱電動性および機械的特性を高めることができる。一方で、ケイ酸アルミニウム化合物(B)は、半芳香族ポリアミド樹脂組成物の電導性への影響が少ない。
上記の半芳香族ポリアミド樹脂組成物は、本発明の効果を損なわない範囲で、前述の成分以外の他の成分をさらに含んでいてもよい。他の成分の例には、半芳香族ポリアミド樹脂(A)以外の他の耐熱性樹脂、無機充填材、有機充填剤、有機難燃剤、酸化防止剤(耐熱安定剤)、熱安定剤、耐候性安定剤、帯電防止剤、スリップ防止剤、アンチブロッキング剤、防曇剤、滑剤、顔料、染料、天然油、合成油、ワックスおよび脂肪酸金属塩などの添加剤が含まれる。
上記半芳香族ポリアミド樹脂組成物は、上記の比率の半芳香族ポリアミド樹脂(A)およびケイ酸アルミニウム化合物(B)、ならびに必要に応じてその他の成分を、公知の方法、例えばヘンシェルミキサー、Vブレンダー、リボンブレンダー若しくはタンブラーブレンダーなどで混合する方法、および混合後さらに一軸押出機、多軸押出機、ニーダー若しくはバンバリーミキサーなどで溶融混練し、その後、造粒若しくは粉砕する方法などにより製造することができる。
上記のようにして調製した半芳香族ポリアミド樹脂組成物を用いて、通常の溶融成形法、例えば圧縮成形法、射出成形法および押し出し成形法などを利用することにより、所望の形状の成形体を製造することができる。
1−1.半芳香族ポリアミド樹脂(A−1)の調製
1,6−ジアミノヘキサン2800g(24.1モル)、テレフタル酸1787g(10.8モル)、アジピン酸1921g(13.1モル)、次亜リン酸ナトリウム一水和物5.7gおよび蒸留水554gを内容量13.6Lのオートクレーブに入れ、窒素置換した。190℃から攪拌を開始し、3時間かけて内部温度を250℃まで昇温した。このとき、オートクレーブの内圧を3.01MPaまで昇圧した。このまま1時間反応を続けた後、オートクレーブ下部に設置したスプレーノズルから大気放出して低次縮合物を抜き出した。抜き出した低次縮合物を室温まで冷却し、その後、粉砕機で1.5mm以下の粒径まで粉砕し、110℃で24時間乾燥した。得られた低次縮合物の水分量は3600ppm、極限粘度[η]は0.14dl/gであった。
1,6−ジアミノヘキサン2800g(24.3モル)、テレフタル酸2774g(16.7モル)、イソフタル酸1196g(7.2モル)、安息香酸36.6g(0.3モル)、次亜リン酸ナトリウム一水和物5.7gおよび蒸留水545gを内容量13.6Lのオートクレーブに入れ、窒素置換した。190℃から攪拌を開始し、3時間かけて内部温度を250℃まで昇温させた。このとき、オートクレーブの内圧を3.03MPaまで昇圧させた。このまま1時間反応を続けた後、オートクレーブ下部に設置したスプレーノズルから大気放出して低次縮合物を抜き出した。抜き出した低次縮合物を室温まで冷却し、その後、低次縮合物を粉砕機で1.5mm以下の粒径まで粉砕し、110℃で24時間乾燥させた。得られた低次縮合物の水分量は4100ppm、極限粘度[η]は0.15dl/gであった。
得られた半芳香族ポリアミド樹脂0.5gを96.5%硫酸溶液50mlに溶解させた。得られた溶液の、25℃±0.05℃の条件下での流下秒数を、ウベローデ粘度計を使用して測定し、「数式:[η]=ηSP/(C(1+0.205ηSP))」に基づき算出した。
[η]:極限粘度(dl/g)
ηSP:比粘度
C:試料濃度(g/dl)
t:試料溶液の流下秒数(秒)
t0:ブランク硫酸の流下秒数(秒)
ηSP=(t−t0)/t0
半芳香族ポリアミド樹脂の融点(Tm)およびガラス転移温度(Tg)は、JIS K7121に準じて測定した。具体的には、PerkinElemer社製DSC7を用いて、約5mgの半芳香族ポリアミド樹脂を測定用アルミニウムパン中に密封し、室温から10℃/minで340℃まで加熱した。半芳香族ポリアミド樹脂を完全融解させるために、340℃で5分間保持し、次いで、10℃/minで30℃まで冷却した。30℃で5分間置いた後、10℃/minで340℃まで2度目の加熱を行なった。この2度目の加熱でのピーク温度(℃)をポリアミド樹脂(A)の融点(Tm)とし、ガラス転移に相当する変位点をガラス転移温度(Tg)とした。
充填剤として、ケイ酸アルミニウムアミノシラン(Quarzwerke GmbH社製、SILATHERM 1360−400 AST(「SILATHERM」は同社の登録商標))、または酸化マグネシウム(宇部マテリアルズ社製、RF−50−AC, RF−10−AC)を用いた。
4−1.ポリアミド樹脂組成物1の調製
34質量部の半芳香族ポリアミド樹脂(A−1)と、65質量部のケイ酸アルミニウムアミノシランと、充填材としての0.7質量部のタルクおよび滑剤としての0.7質量部のモンタン酸カルシウム(日東化成工業社製、CS−8CP)をタンブラーブレンダーにて混合し、30mmφのベント式二軸スクリュー押出機を用いて300〜335℃のシリンダー温度条件で溶融混練した。その後、混練物をストランド状に押出し、水槽で冷却させた。その後、ペレタイザーでストランドを引き取り、カットすることでペレット状のポリアミド樹脂組成物を得た。
半芳香族ポリアミド樹脂(A−1)を半芳香族ポリアミド樹脂(A−2)とした以外はポリアミド樹脂組成物1の調製と同様にして、ポリアミド樹脂組成物2を得た。
ケイ酸アルミニウムアミノシランを酸化マグネシウムとした以外はポリアミド樹脂組成物1の調製と同様にして、ポリアミド樹脂組成物3を得た。
半芳香族ポリアミド樹脂(A−1)を、脂肪族ポリアミド樹脂(東レ社製、アミランCM3001−N(66ナイロン、融点(Tm):265℃)とした以外はポリアミド樹脂組成物1の調製と同様にして、ポリアミド樹脂組成物4を得た。
半芳香族ポリアミド樹脂(A−1)の配合量を89質量部とし、ケイ酸アルミニウムアミノシランの配合量を10質量部とした以外はポリアミド樹脂組成物1の調製と同様にして、ポリアミド樹脂組成物5を得た。
半芳香族ポリアミド樹脂(A−1)を、脂肪族ポリアミド樹脂(東レ社製、アミランCM3001−N)とした以外はポリアミド樹脂組成物5の調製と同様にして、ポリアミド樹脂組成物6を得た。
得られた半芳香族ポリアミド樹脂組成物の、熱伝導率、引張強度、曲げ強度、曲げ弾性率、および荷重たわみ温度(HDT)を、以下の方法で評価した。
面方向の熱伝導率λ(単位:W/mK)は、熱拡散率α、密度ρおよび比熱Cpを下記方法により求め、その積として次式で算出した。
λ=α・ρ・Cp
λ:熱伝導率(W/(m・K))
α:熱拡散率(m2/sec)
ρ:密度(g/m3)
Cp:比熱(J/g・K)
なお、熱拡散率αは、実施例、比較例で得られた評価用成形片の樹脂の流れ方向について、レーザーフラッシュ法熱定数測定装置(アドバンス理工株式会社製 LaserPit)を用いて測定した。密度ρは自動比重計(アルファーミラージュ株式会社製 D−H100)を用いて測定した。比熱Cpは示差走査熱量計(パーキンエルマー社製 Diamond DSC)を用い、昇温速度10℃/分の条件で測定した。
得られたポリアミド樹脂組成物を、下記の射出成形機を用いて、下記成形条件で成形して、厚み3.2mmの(A)STMダンベル型試験片Type Iを得た。
(成形条件)
成形機:住友重機械工業社製 SG50M3
成形機シリンダー温度:ポリアミド樹脂組成物の融点(Tm)+10℃
金型温度:120℃
射出設定速度:60mm/sec
得られた試験片を、温度23℃、窒素雰囲気下で24時間放置した。次いで、ASTMD638に準拠して、温度23℃、相対湿度50%の雰囲気下で引張試験を行い、引張強度(単位:MPa)を測定した。
下記の射出成形機を用い、下記の成形条件で作製した厚さ3.2mmの試験片を、スパンを100mmに固定して、35℃から昇温速度120℃/hrで1.8MPaの圧力をかけた。たわみ量が0.254mmになった際の温度を荷重たわみ温度(単位:℃)とした。
成形機:株式会社ソディック プラスティック製、ツパールTR40S3A
成形機シリンダー温度:ポリアミド樹脂(A)の融点(Tm)+15℃
金型温度:ポリアミド樹脂(A)のガラス転移温度(Tg)+20℃
Claims (6)
- 示差走査型熱量計(DSC)により測定される融点が290〜330℃である半芳香族ポリアミド樹脂(A)と、
ケイ酸アルミニウム化合物(B)と、
を含み、
前記ケイ酸アルミニウム化合物(B)の含有量は、半芳香族ポリアミド組成物の全質量を100質量%としたとき、20質量%以上80質量%以下である、
半芳香族ポリアミド樹脂組成物。 - 前記ケイ酸アルミニウム化合物(B)は、ケイ酸アルミニウムアミノシランである、請求項1に記載の半芳香族ポリアミド樹脂組成物。
- 前記半芳香族ポリアミド樹脂(A)は、
20〜100モル%の、テレフタル酸成分単位(a−1)と、
0〜80モル%の、テレフタル酸以外の芳香族カルボン酸成分単位(a−2)または炭素原子数4〜20の脂肪族ジカルボン酸成分単位(a−3)と、
を含むジカルボン酸成分単位[a](ただし、半芳香族ポリアミド樹脂(A)に含まれるジカルボン酸成分単位の総モル数を100モル%とする。)と、
ジアミン成分単位[b]と、からなる繰り返し単位を有する、
請求項1または2に記載の半芳香族ポリアミド樹脂組成物。 - 前記ジカルボン酸成分単位[a]は、
20〜100モル%の、テレフタル酸成分単位(a−1)と、
0〜80モル%の、テレフタル酸以外の芳香族カルボン酸成分単位(a−2)と、
を含む(ただし、半芳香族ポリアミド樹脂(A)に含まれるジカルボン酸成分単位の総モル数を100モル%とする。)、
請求項3に記載の半芳香族ポリアミド樹脂組成物。 - 前記ジカルボン酸成分単位[a]は、
45〜100モル%の、テレフタル酸成分単位(a−1)と、
0〜80モル%の、炭素原子数4〜20の脂肪族ジカルボン酸成分単位(a−3)と、
を含む(ただし、半芳香族ポリアミド樹脂(A)に含まれるジカルボン酸成分単位の総モル数を100モル%とする。)、
請求項3に記載の半芳香族ポリアミド樹脂組成物。 - 請求項1〜5のいずれか一項に記載の半芳香族ポリアミド樹脂組成物から得られる、成形体。
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JP2008505223A (ja) * | 2004-07-01 | 2008-02-21 | ソルヴェイ アドバンスド ポリマーズ リミテッド ライアビリティ カンパニー | 芳香族ポリアミド組成物および該組成物から製造した物品 |
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