JP2014043525A - Metallic polyamide resin composition - Google Patents
Metallic polyamide resin composition Download PDFInfo
- Publication number
- JP2014043525A JP2014043525A JP2012187634A JP2012187634A JP2014043525A JP 2014043525 A JP2014043525 A JP 2014043525A JP 2012187634 A JP2012187634 A JP 2012187634A JP 2012187634 A JP2012187634 A JP 2012187634A JP 2014043525 A JP2014043525 A JP 2014043525A
- Authority
- JP
- Japan
- Prior art keywords
- polyamide resin
- resin composition
- polyamide
- organic solvent
- metallic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920006122 polyamide resin Polymers 0.000 title claims abstract description 107
- 239000011342 resin composition Substances 0.000 title claims abstract description 78
- 239000003960 organic solvent Substances 0.000 claims abstract description 37
- 239000000049 pigment Substances 0.000 claims abstract description 37
- 239000007788 liquid Substances 0.000 claims abstract description 21
- 238000000465 moulding Methods 0.000 claims abstract description 20
- 239000000654 additive Substances 0.000 claims abstract description 19
- 230000000996 additive effect Effects 0.000 claims abstract description 18
- 238000004040 coloring Methods 0.000 claims abstract description 13
- -1 liquid paraffin Substances 0.000 claims abstract description 11
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 8
- 229940057995 liquid paraffin Drugs 0.000 claims abstract description 7
- 239000002480 mineral oil Substances 0.000 claims abstract description 5
- 235000010446 mineral oil Nutrition 0.000 claims abstract description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 29
- 229910052782 aluminium Inorganic materials 0.000 claims description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 11
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 9
- 239000011707 mineral Substances 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 229920001451 polypropylene glycol Polymers 0.000 claims description 7
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 abstract description 10
- 230000014759 maintenance of location Effects 0.000 abstract description 8
- 229920002302 Nylon 6,6 Polymers 0.000 description 19
- 239000004952 Polyamide Substances 0.000 description 19
- 229920002647 polyamide Polymers 0.000 description 19
- 239000000203 mixture Substances 0.000 description 17
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 16
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 16
- 238000004898 kneading Methods 0.000 description 16
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 10
- 229910052802 copper Inorganic materials 0.000 description 10
- 239000010949 copper Substances 0.000 description 10
- 230000000379 polymerizing effect Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 8
- 239000005749 Copper compound Substances 0.000 description 8
- 150000001880 copper compounds Chemical class 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 239000011630 iodine Substances 0.000 description 8
- 229910052740 iodine Inorganic materials 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000002845 discoloration Methods 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- 239000001361 adipic acid Substances 0.000 description 5
- 235000011037 adipic acid Nutrition 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- 230000003746 surface roughness Effects 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 150000002497 iodine compounds Chemical class 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 235000015096 spirit Nutrition 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 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 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 229920000571 Nylon 11 Polymers 0.000 description 3
- 229920006121 Polyxylylene adipamide Polymers 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 3
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004880 explosion Methods 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 229920006131 poly(hexamethylene isophthalamide-co-terephthalamide) Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- JCUZDQXWVYNXHD-UHFFFAOYSA-N 2,2,4-trimethylhexane-1,6-diamine Chemical compound NCCC(C)CC(C)(C)CN JCUZDQXWVYNXHD-UHFFFAOYSA-N 0.000 description 2
- DPQHRXRAZHNGRU-UHFFFAOYSA-N 2,4,4-trimethylhexane-1,6-diamine Chemical compound NCC(C)CC(C)(C)CCN DPQHRXRAZHNGRU-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 2
- 229920000305 Nylon 6,10 Polymers 0.000 description 2
- 229920000572 Nylon 6/12 Polymers 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- YEOCHZFPBYUXMC-UHFFFAOYSA-L copper benzoate Chemical compound [Cu+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 YEOCHZFPBYUXMC-UHFFFAOYSA-L 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- PGMYKACGEOXYJE-UHFFFAOYSA-N pentyl acetate Chemical compound CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 2
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 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
- 239000012488 sample solution Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229920006012 semi-aromatic polyamide Polymers 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- HNSDLXPSAYFUHK-UHFFFAOYSA-N 1,4-bis(2-ethylhexyl) sulfosuccinate Chemical compound CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC HNSDLXPSAYFUHK-UHFFFAOYSA-N 0.000 description 1
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- MQWCXKGKQLNYQG-UHFFFAOYSA-N 4-methylcyclohexan-1-ol Chemical compound CC1CCC(O)CC1 MQWCXKGKQLNYQG-UHFFFAOYSA-N 0.000 description 1
- ZUHMEUFBTDOKPX-UHFFFAOYSA-N 6-[2-(4,6-diamino-1,3,5-triazin-2-yl)ethyl]-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(CCC=2N=C(N)N=C(N)N=2)=N1 ZUHMEUFBTDOKPX-UHFFFAOYSA-N 0.000 description 1
- 239000004953 Aliphatic polyamide Substances 0.000 description 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000001293 FEMA 3089 Substances 0.000 description 1
- 206010065042 Immune reconstitution inflammatory syndrome Diseases 0.000 description 1
- 229920006065 Leona® Polymers 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 229920003231 aliphatic polyamide Polymers 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229940107816 ammonium iodide Drugs 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- KCLGATRJYMEERW-UHFFFAOYSA-N benzene-1,3-dicarboxylic acid;copper Chemical compound [Cu].OC(=O)C1=CC=CC(C(O)=O)=C1 KCLGATRJYMEERW-UHFFFAOYSA-N 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 1
- ZCXLQZOQWCXFNN-UHFFFAOYSA-N copper;hexanedioic acid Chemical compound [Cu].OC(=O)CCCCC(O)=O ZCXLQZOQWCXFNN-UHFFFAOYSA-N 0.000 description 1
- LZJJVTQGPPWQFS-UHFFFAOYSA-L copper;propanoate Chemical compound [Cu+2].CCC([O-])=O.CCC([O-])=O LZJJVTQGPPWQFS-UHFFFAOYSA-L 0.000 description 1
- ZISLUDLMVNEAHK-UHFFFAOYSA-L copper;terephthalate Chemical compound [Cu+2].[O-]C(=O)C1=CC=C(C([O-])=O)C=C1 ZISLUDLMVNEAHK-UHFFFAOYSA-L 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 231100000206 health hazard Toxicity 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 description 1
- 229910001641 magnesium iodide Inorganic materials 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000010137 moulding (plastic) Methods 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- WSGCRAOTEDLMFQ-UHFFFAOYSA-N nonan-5-one Chemical compound CCCCC(=O)CCCC WSGCRAOTEDLMFQ-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
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- OBNAOHSAPQWLGU-UHFFFAOYSA-N phthalic acid;1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N)=N1.OC(=O)C1=CC=CC=C1C(O)=O OBNAOHSAPQWLGU-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920006110 poly(m-benzoyl4,4'-methylenebis(cyclohexylamine)) Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- LTURHSAEWJPFAA-UHFFFAOYSA-N sulfuric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OS(O)(=O)=O.NC1=NC(N)=NC(N)=N1 LTURHSAEWJPFAA-UHFFFAOYSA-N 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- BNEMLSQAJOPTGK-UHFFFAOYSA-N zinc;dioxido(oxo)tin Chemical compound [Zn+2].[O-][Sn]([O-])=O BNEMLSQAJOPTGK-UHFFFAOYSA-N 0.000 description 1
- BHTBHKFULNTCHQ-UHFFFAOYSA-H zinc;tin(4+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Sn+4] BHTBHKFULNTCHQ-UHFFFAOYSA-H 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、ポリアミド樹脂組成物に関する。 The present invention relates to a polyamide resin composition.
ポリアミド樹脂は、機械特性をはじめとして、成形加工性等において優れた特性を有するため、従来から自動車部品、電子電気部品、工業機械部品等各種部品に広く利用されている。さらに、ポリアミド樹脂からなる部品は、人の目に触れる部品にも好適に使用され、着色やシボなどの表面加工が幅広く行われている。中でも、メタリック調と言われるユニークな金属光沢感を付与する目的で鱗片状アルミニウム粉（以下「アルミフレーク」とも称す）に代表されるメタリック着色顔料を各種樹脂に配合することが行われている。メタリック着色顔料を配合した樹脂組成物は、自動車の内外装部品やパソコン筐体などに用いられている。 Polyamide resins have excellent properties in molding processability and the like including mechanical properties, and thus have been widely used for various parts such as automobile parts, electronic / electric parts, and industrial machine parts. Furthermore, parts made of polyamide resin are also suitably used for parts that can be seen by human eyes, and surface processing such as coloring and embossing is widely performed. Among these, for the purpose of imparting a unique metallic luster that is called metallic tone, metallic color pigments typified by scaly aluminum powder (hereinafter also referred to as “aluminum flakes”) are blended in various resins. Resin compositions containing metallic coloring pigments are used in automobile interior and exterior parts, personal computer casings, and the like.
このような樹脂組成物は、例えば、特許文献１や２などに開示されている。具体的には、特許文献１には、特定のメタリック顔料を配合した合成樹脂組成物が開示されており、特許文献２には、メタリック色を有する粒子を含有した特定の樹脂組成物が開示されている。また、特許文献２では、該樹脂組成物を自動車エンジンルーム内の部品（エンジンカバー）に使用することが提案されている。 Such a resin composition is disclosed in Patent Documents 1 and 2, for example. Specifically, Patent Document 1 discloses a synthetic resin composition containing a specific metallic pigment, and Patent Document 2 discloses a specific resin composition containing particles having a metallic color. ing. Patent Document 2 proposes that the resin composition is used for a part (engine cover) in an automobile engine room.
しかしながら、従前に使用されているメタリック着色顔料を配合した樹脂組成物には、湿潤処理の為に使用されるミネラルスピリットやソルベントナフサ等の有機溶剤が多く残留しているため、成形時の滞留安定性が悪いといった問題点や、成形品としたときにシルバーストリークのような外観不良が見られることがある。また使用者が該樹脂組成物から揮発した有機溶剤を吸引すると健康被害を引き起こすことが考えられ、この点でも好ましくない。 However, the resin composition containing the previously used metallic color pigments contains a lot of organic solvents such as mineral spirits and solvent naphtha used for the wet treatment, so that the retention stability during molding is stable. There is a case that the appearance is poor, such as a silver streak when a molded product is produced, or a problem that the property is poor. In addition, if the user sucks the organic solvent volatilized from the resin composition, it is considered that health damage is caused, which is not preferable.
本発明は、上記事情に鑑みなされたものであり、押出特性、成形時の滞留安定性および外観特性に優れ、有機溶剤の含有量が低減されたメタリック調ポリアミド樹脂組成物を提供することを目的とする。 The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a metallic polyamide resin composition excellent in extrusion characteristics, retention stability during molding and appearance characteristics, and having a reduced organic solvent content. And
本発明者らは、上記課題を解決すべく鋭意検討した結果、有機溶剤の代わりに特定の液状添加剤を使用したアルミペーストをポリアミド樹脂と溶融混練して得られる樹脂組成物によって上記課題が解決されることを見出した。 As a result of intensive studies to solve the above problems, the present inventors have solved the above problems by a resin composition obtained by melt-kneading an aluminum paste using a specific liquid additive instead of an organic solvent with a polyamide resin. I found out that
すなわち、本発明は、以下に関する。 That is, the present invention relates to the following.
［１］
（Ａ）ポリアミド樹脂と、
（Ｂ）メタリック着色顔料と、
（Ｃ）ミネラルオイル、流動パラフィンおよび非イオン性界面活性剤からなる群より選択される少なくとも１種の液状添加剤と、
（Ｄ）有機溶剤と、を含むポリアミド樹脂組成物であって、
該ポリアミド樹脂組成物中の（Ｄ）有機溶剤の含有量が５００ｐｐｍ以下である、ポリアミド樹脂組成物。
［２］
前記（Ｄ）有機溶剤が、ミネラルスピリット、ソルベントナフサ、キシレン、トルエン、メチルイソブチルケトンおよびイソプロピルアルコールからなる群より選択される少なくとも１種である、前記［１］に記載のポリアミド樹脂組成物。
［３］
前記（Ｂ）メタリック着色顔料が、アルミフレークである、前記［１］または［２］に記載のポリアミド樹脂組成物。
［４］
前記非イオン性界面活性剤が、ポリエチレングリコール、ポリエチレングリコールのエステル化誘導体、ポリプロピレングリコールおよびポリプロピレングリコールのエステル化誘導体からなる群より選択される少なくとも１種である、前記［１］〜［３］のいずれかに記載のポリアミド樹脂組成物。
［５］
前記（Ｃ）液状添加剤が、１気圧かつ０℃以上１００℃以下の条件で液状である、前記［１］〜［４］のいずれかに記載のポリアミド樹脂組成物。
［６］
（Ａ）ポリアミド樹脂１００質量部に対し、（Ｂ）メタリック着色顔料の含有量が０．１〜２０質量部、（Ｃ）液状添加剤の含有量が０．０１〜２質量部である、前記［１］〜［５］のいずれかに記載のポリアミド樹脂組成物。
［７］
前記［１］〜［６］のいずれかに記載のポリアミド樹脂組成物を成形して得られる、ポリアミド樹脂成形品。
[1]
(A) a polyamide resin;
(B) a metallic coloring pigment;
(C) at least one liquid additive selected from the group consisting of mineral oil, liquid paraffin, and nonionic surfactant;
(D) a polyamide resin composition comprising an organic solvent,
The polyamide resin composition whose content of the (D) organic solvent in this polyamide resin composition is 500 ppm or less.
[2]
The polyamide resin composition according to [1], wherein (D) the organic solvent is at least one selected from the group consisting of mineral spirit, solvent naphtha, xylene, toluene, methyl isobutyl ketone, and isopropyl alcohol.
[3]
The polyamide resin composition according to [1] or [2], wherein the (B) metallic color pigment is aluminum flakes.
[4]
[1] to [3], wherein the nonionic surfactant is at least one selected from the group consisting of polyethylene glycol, an esterified derivative of polyethylene glycol, polypropylene glycol, and an esterified derivative of polypropylene glycol. The polyamide resin composition according to any one of the above.
[5]
The polyamide resin composition according to any one of [1] to [4], wherein the liquid additive (C) is liquid under the conditions of 1 atm and 0 ° C to 100 ° C.
[6]
(A) The content of the (B) metallic color pigment is 0.1 to 20 parts by mass and the content of the (C) liquid additive is 0.01 to 2 parts by mass with respect to 100 parts by mass of the polyamide resin. The polyamide resin composition according to any one of [1] to [5].
[7]
A polyamide resin molded article obtained by molding the polyamide resin composition according to any one of [1] to [6].
本発明は、押出特性、成形時の滞留安定性および外観特性に優れ、有機溶剤の含有量が低減されたメタリック調ポリアミド樹脂組成物を提供することができる。 INDUSTRIAL APPLICABILITY The present invention can provide a metallic polyamide resin composition having excellent extrusion characteristics, retention stability during molding, and appearance characteristics, and having a reduced organic solvent content.
以下、本発明を実施するための形態（以下、「本実施形態」という。）について詳細に説明する。以下の本実施形態は、本発明を説明するための例示であり、本発明を以下の内容に限定する趣旨ではない。本発明は、その要旨の範囲内で適宜に変形して実施できる。 Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be implemented with appropriate modifications within the scope of the gist thereof.
≪ポリアミド樹脂組成物≫
本実施形態のポリアミド樹脂組成物は、
（Ａ）ポリアミド樹脂と、
（Ｂ）メタリック着色顔料と、
（Ｃ）ミネラルオイル、流動パラフィンおよび非イオン性界面活性剤からなる群より選択される少なくとも１種の液状添加剤と、
（Ｄ）有機溶剤と、を含むポリアミド樹脂組成物であって、
該ポリアミド樹脂組成物中の（Ｄ）有機溶剤の含有量が５００ｐｐｍ以下である。
≪Polyamide resin composition≫
The polyamide resin composition of this embodiment is
(A) a polyamide resin;
(B) a metallic coloring pigment;
(C) at least one liquid additive selected from the group consisting of mineral oil, liquid paraffin, and nonionic surfactant;
(D) a polyamide resin composition comprising an organic solvent,
The content of the organic solvent (D) in the polyamide resin composition is 500 ppm or less.
＜（Ａ）ポリアミド樹脂＞
本実施形態のポリアミド樹脂組成物を構成する（Ａ）ポリアミド樹脂（以下「ポリアミド樹脂（Ａ）」または「（Ａ）成分」と記載する場合もある。）は、特に制限はなく、従来公知のポリアミドを使用することができる。
<(A) Polyamide resin>
The polyamide resin (A) constituting the polyamide resin composition of the present embodiment (hereinafter sometimes referred to as “polyamide resin (A)” or “component (A)”) is not particularly limited and is conventionally known. Polyamide can be used.
（Ａ）ポリアミド樹脂としては、特に限定されないが、例えば、ε−カプロラクタム、アジピン酸、セバシン酸、ドデカン二酸、イソフタル酸、テレフタル酸、ヘキサメチレンジアミン、テトラメチレンジアミン、２−、メチルペンタメチレンジアミン、２，２，４−トリメチルヘキサメチレンジアミン、２，４，４−トリメチルヘキサメチレンジアミン、メタキシリレンジアミン、ビス（３−メチル−４アミノシクロヘキシル）メタン等のポリアミド形成性モノマーを適宜組み合わせて得られるホモポリマー単独、共重合体単独、ホモポリマー同士の混合物、共重合体同士の混合物、共重合体とホモポリマーとの混合物等を用いることができる。 (A) Although it does not specifically limit as a polyamide resin, For example, (epsilon) -caprolactam, adipic acid, sebacic acid, dodecanedioic acid, isophthalic acid, terephthalic acid, hexamethylenediamine, tetramethylenediamine, 2-, methylpentamethylenediamine , 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, metaxylylenediamine, bis (3-methyl-4-aminocyclohexyl) methane, and other polyamide-forming monomers Homopolymers alone, copolymers alone, mixtures of homopolymers, mixtures of copolymers, mixtures of copolymers and homopolymers, and the like can be used.
（Ａ）ポリアミド樹脂の具体例としては、以下の例に限定されるものではないが、例えば、ポリアミド６、ポリアミド６６、ポリアミド６１０、ポリアミド６１２、ポリアミド１１、ポリアミド１２、ポリアミドＭＸＤ６、ヘキサメチレンジアミンとイソフタル酸とを重合してなるポリアミド（ポリアミド６Ｉ）、イソフタル酸とビス（３−メチル−４アミノシクロヘキシル）メタンとを重合してなるポリアミド（ポリアミドＰＡＣＭＩ）等のホモポリマー、アジピン酸とイソフタル酸とへキサメチレンジアミンとを重合してなるポリアミド（ポリアミド６６／６Ｉ共重合体）、アジピン酸とテレフタル酸とへキサメチレンジアミンとを重合してなるポリアミド（ポリアミド６６／６Ｔ共重合体）、アジピン酸とシクロヘキ酸とへキサメチレンジアミンとを重合してなるポリアミド（ポリアミド６６／６Ｃ共重合体）、イソフタル酸とテレフタル酸とヘキサメチレンジアミンとを重合してなるポリアミド（ポリアミド６Ｉ／６Ｔ共重合体）、アジピン酸とイソフタル酸とテレフタル酸とヘキサメチレンジアミンとを重合してなるポリアミド（ポリアミド６６／６Ｉ／６Ｔ共重合体）、テレフタル酸と２，２，４−トリメチルヘキサメチレンジアミンと２，４，４−トリメチルヘキサメチレンジアミンとを重合してなるポリアミド（ポリアミドＴＭＤＴ共重合体）、イソフタル酸とテレフタル酸とヘキサメチレンジアミンとビス（３−メチル−４アミノシクロヘキシル）メタンとを重合してなる共重合ポリアミド、およびイソフタル酸とテレフタル酸とヘキサメチレンジアミンとビス（３−メチル−４アミノシクロヘキシル）メタンとを重合してなる共重合ポリアミドとポリアミド６との混合物、ポリアミドＭＸＤ６とポリアミド６６との混合物等が挙げられる。 (A) Specific examples of the polyamide resin are not limited to the following examples. For example, polyamide 6, polyamide 66, polyamide 610, polyamide 612, polyamide 11, polyamide 12, polyamide MXD6, hexamethylenediamine Homopolymers such as polyamide (polyamide 6I) obtained by polymerizing isophthalic acid, polyamide (polyamide PACMI) obtained by polymerizing isophthalic acid and bis (3-methyl-4aminocyclohexyl) methane, adipic acid and isophthalic acid Polyamide obtained by polymerizing hexamethylenediamine (polyamide 66 / 6I copolymer), polyamide obtained by polymerizing adipic acid, terephthalic acid and hexamethylenediamine (polyamide 66 / 6T copolymer), adipic acid And cyclohexic acid and hexamethyle Polyamide obtained by polymerizing diamine (polyamide 66 / 6C copolymer), polyamide obtained by polymerizing isophthalic acid, terephthalic acid and hexamethylenediamine (polyamide 6I / 6T copolymer), adipic acid and isophthalic acid Polyamide obtained by polymerizing terephthalic acid and hexamethylenediamine (polyamide 66 / 6I / 6T copolymer), terephthalic acid, 2,2,4-trimethylhexamethylenediamine, and 2,4,4-trimethylhexamethylenediamine Polyamide (polyamide TMDT copolymer) obtained by polymerizing styrene, copolymer polyamide obtained by polymerizing isophthalic acid, terephthalic acid, hexamethylenediamine and bis (3-methyl-4aminocyclohexyl) methane, and isophthalic acid and terephthalic acid Acid, hexamethylenediamine and bis Mixture of copolymerized polyamide and a polyamide 6 obtained by polymerizing a 3-methyl-4-aminocyclohexyl) methane, mixtures of polyamide MXD6 and polyamide 66 and the like.
上述した各種ポリアミドの中でも、特に、ポリアミド６６やポリアミド６６／６Ｃ共重合体、ポリアミド６６／６Ｃ／６Ｉ共重合体、ポリアミド６６／６Ｔ共重合体、ポリアミド６６／６Ｔ／６Ｉ共重合体等の半芳香族ポリアミドは、融点が高く、より耐熱性の必要な部品を得る場合の材料として好適である。 Among the various polyamides mentioned above, in particular, half of polyamide 66, polyamide 66 / 6C copolymer, polyamide 66 / 6C / 6I copolymer, polyamide 66 / 6T copolymer, polyamide 66 / 6T / 6I copolymer, etc. Aromatic polyamide has a high melting point and is suitable as a material for obtaining parts that require more heat resistance.
また、ポリアミド６６／６Ｉ共重合体や、ポリアミドＭＸＤ６等の半芳香族ポリアミドや、これらの半芳香族ポリアミドと他の脂肪族ポリアミドとの混合物は、その共重合比、混合比により結晶化温度を適宜制御することができるため、結晶化温度を低下させることにより金型転写性が良好なものとなる。このような結晶化温度を低下させた（Ａ）成分を含むポリアミド樹脂組成物を用いて成形した成形品は外観に優れた成形品となる。 In addition, polyamide 66 / 6I copolymers, semi-aromatic polyamides such as polyamide MXD6, and mixtures of these semi-aromatic polyamides and other aliphatic polyamides have a crystallization temperature depending on their copolymerization ratio and mixing ratio. Since it can be appropriately controlled, mold transferability is improved by lowering the crystallization temperature. A molded product molded using the polyamide resin composition containing the component (A) having such a lowered crystallization temperature is a molded product having an excellent appearance.
また、ポリアミド６６とポリアミド６１２やポリアミド６１０等のエチレン基の長いポリアミドとの混合物は、高温高湿度下での耐加水分解性に優れることから、高温多湿な環境で使用される部品を得る場合のポリアミド樹脂組成物の構成成分として好適である。 In addition, since a mixture of polyamide 66 and a polyamide having a long ethylene group such as polyamide 612 or polyamide 610 is excellent in hydrolysis resistance under high temperature and high humidity, it is necessary to obtain a part used in a high temperature and high humidity environment. It is suitable as a constituent component of the polyamide resin composition.
上記ポリアミド６６の混合物の中でも、成形性、高温度下での機械的特性の観点から、ポリアミド６６成分を５０質量％以上含有する混合物がより好ましく、７０質量％以上含有する混合物がさらに好ましい。 Among the polyamide 66 mixtures, from the viewpoints of moldability and mechanical properties at high temperatures, a mixture containing 50% by mass or more of the polyamide 66 component is more preferable, and a mixture containing 70% by mass or more is more preferable.
前記（Ａ）ポリアミド樹脂は、従来公知の方法により重合できる。前記（Ａ）ポリアミド樹脂の製造方法としては、特に限定されないが、例えば、熱溶融法、ジカルボン酸ハライド成分とジアミン成分とを用いた溶液法等が挙げられる。特に、熱溶融法が好ましい。重合形態としてはバッチ式でも連続式でもよい。重合装置も特に制限されるものではなく、公知の装置、例えば、連続型反応器、オートクレーブ型反応器、タンブラー型反応器、ニーダー等の押出機型反応器がいずれも使用できる。 The (A) polyamide resin can be polymerized by a conventionally known method. The method for producing the (A) polyamide resin is not particularly limited, and examples thereof include a heat melting method and a solution method using a dicarboxylic acid halide component and a diamine component. In particular, the heat melting method is preferable. The polymerization form may be batch or continuous. The polymerization apparatus is not particularly limited, and any known apparatus such as a continuous reactor, an autoclave reactor, a tumbler reactor, a kneader or other extruder reactor can be used.
ポリアミド樹脂（Ａ）には、酸化防止剤として、銅化合物が添加されていてもよい。また、ポリアミド樹脂（Ａ）には、銅化合物に加えてヨウ素化合物が添加されていることが好ましい。 A copper compound may be added to the polyamide resin (A) as an antioxidant. Moreover, it is preferable that the iodine compound is added to the polyamide resin (A) in addition to the copper compound.
前記銅化合物としては、以下に限定されるものではないが、例えば、ヨウ化銅、臭化第一銅、臭化第二銅、塩化第一銅、酢酸銅、プロピオン酸銅、安息香酸銅、アジピン酸銅、テレフタル酸銅、イソフタル酸銅等が挙げられる。その中でもヨウ化銅および酢酸銅が好ましく、特にヨウ化銅がより好ましい。 Examples of the copper compound include, but are not limited to, copper iodide, cuprous bromide, cupric bromide, cuprous chloride, copper acetate, copper propionate, copper benzoate, Examples include copper adipate, copper terephthalate, and copper isophthalate. Among these, copper iodide and copper acetate are preferable, and copper iodide is more preferable.
ヨウ素化合物としては、以下に限定されるものではないが、例えば、ヨウ化カリウム、ヨウ化マグネシウム、ヨウ化アンモニウム等が挙げられ、その中でもヨウ化カリウムが好ましい。 Examples of the iodine compound include, but are not limited to, potassium iodide, magnesium iodide, ammonium iodide, and the like. Among these, potassium iodide is preferable.
これらの銅化合物、ヨウ素化合物は、それぞれ単独で用いてもよく、２種以上を混合して用いてもよい。 These copper compounds and iodine compounds may be used alone or in combination of two or more.
ポリアミド樹脂（Ａ）中の銅化合物の含有量は、銅に換算した濃度として、耐熱変色性の観点から、好ましくは４０ｐｐｍ以上２００ｐｐｍ以下とし、より好ましくは５０ｐｐｍ以上１７５ｐｐｍ以下であり、さらに好ましくは６０ｐｐｍ以上１５０ｐｐｍ以下である。 The content of the copper compound in the polyamide resin (A) is preferably 40 ppm or more and 200 ppm or less, more preferably 50 ppm or more and 175 ppm or less, and still more preferably 60 ppm, as the concentration converted to copper, from the viewpoint of heat discoloration. It is 150 ppm or less.
銅化合物の含有量が４０ｐｐｍを下回ると耐熱変色性が悪化し、銅化合物の含有量が２００ｐｐｍを超えても耐熱変色性の改善効果は変化しない。 When the content of the copper compound is less than 40 ppm, the heat discoloration deteriorates, and even if the content of the copper compound exceeds 200 ppm, the effect of improving the heat discoloration does not change.
また、銅化合物とヨウ素化合物とに含まれるヨウ素と銅とのモル比（ヨウ素／銅）は、ポリアミド樹脂（Ａ）の溶融時の銅金属析出抑制の観点から、５＜ヨウ素／銅≦３０が好ましい。これにより、射出成形後の成形品からのヨウ素溶出を抑え、さらに、射出成形機スクリューの腐食発生を抑えることが可能である。 The molar ratio of iodine to copper (iodine / copper) contained in the copper compound and iodine compound is 5 <iodine / copper ≦ 30 from the viewpoint of suppressing copper metal precipitation during melting of the polyamide resin (A). preferable. Thereby, it is possible to suppress iodine elution from the molded product after injection molding, and to further suppress the occurrence of corrosion of the injection molding machine screw.
より好ましい範囲は１３≦ヨウ素／銅≦２５であり、さらに好ましい範囲は１５≦ヨウ素／銅≦２２である。 A more preferable range is 13 ≦ iodine / copper ≦ 25, and a further preferable range is 15 ≦ iodine / copper ≦ 22.
ポリアミド樹脂（Ａ）中の銅の濃度は、以下の方法により定量できる。なお、以下の方法において用いた数値は具体例であり、以下に限定されるものではない。 The concentration of copper in the polyamide resin (A) can be quantified by the following method. In addition, the numerical value used in the following method is a specific example, and is not limited to the following.
まず、ポリアミド樹脂（Ａ）を０．５ｇ秤量し濃硫酸を２０ｍＬ加え、ヒーター上で湿式分解し冷却した後、過酸化水素５ｍＬを加え、ヒーター上で加熱し、全量が２〜３ｍＬになるまで濃縮する。 First, 0.5 g of polyamide resin (A) is weighed and 20 mL of concentrated sulfuric acid is added. After wet decomposition on the heater and cooling, 5 mL of hydrogen peroxide is added and heated on the heater until the total amount becomes 2-3 mL. Concentrate.
得られた濃縮液を再び冷却し、純水で希釈して５００ｍＬとする。 The obtained concentrated liquid is cooled again and diluted with pure water to 500 mL.
得られた水溶液から試料を精秤し、該試料について、測定装置としてＴｈｅｒｍｏＪａｒｒｅｌｌＡｓｈ製ＩＲＩＳ／ＩＰを用いて、高周波誘導結合プラズマ（ＩＣＰ）発光分析により波長でポリアミド樹脂（Ａ）中の銅の濃度を定量する。 A sample is precisely weighed from the obtained aqueous solution, and the concentration of copper in the polyamide resin (A) is measured at a wavelength by high frequency inductively coupled plasma (ICP) emission analysis using IRIS / IP manufactured by Thermo Jarrel Ash as a measuring device. Quantify.
具体的には、融合結合プラズマ（ＩＣＰ）発光分析法、高周波誘導結合法により得られるアルゴプラズマ中に試料を噴霧導入し、高温の熱エネルギーにより励起された原子による発光スペクトル（原子発光スペクトル）の波長および強度を測定して、元素の同定や定量分析を行うことによりポリアミド樹脂（Ａ）中の銅の濃度を定量できる。 Specifically, a sample is spray-introduced into an Argo plasma obtained by fusion coupled plasma (ICP) emission analysis method or high frequency inductive coupling method, and emission spectrum (atomic emission spectrum) of atoms excited by high-temperature thermal energy The concentration of copper in the polyamide resin (A) can be quantified by measuring the wavelength and intensity and performing element identification and quantitative analysis.
また、ポリアミド樹脂（Ａ）中のヨウ素の濃度は、以下の方法により定量できる。試料を精秤し、吸収液、例えば亜硝酸塩溶液中に入れ、その後、酸素リッチなフラスコ中で燃焼分解し、さらに当該吸収液を定浴し、ダイオネクス製ＩＣＳ−２０００、カラム：ＩｏｎＰａｃＡＧ１８ＡＳ１８、検出器：電気伝導度検出器を用い、イオンクロマトグラフ法にてポリアミド樹脂（Ａ）中のヨウ素の濃度を定量する。 Moreover, the density | concentration of the iodine in a polyamide resin (A) can be quantified with the following method. A sample is precisely weighed and placed in an absorbing solution, for example, a nitrite solution, and then combusted and decomposed in an oxygen-rich flask. Further, the absorbing solution is bathed, DIC-2000 manufactured by Dionex, column: IonPacAG18AS18, detector. : Using an electric conductivity detector, the concentration of iodine in the polyamide resin (A) is quantified by ion chromatography.
ポリアミド樹脂（Ａ）中のペレット水分率は、特に限定しないが、コンパウンド原料のポリアミド溶融時の分子量上昇を抑えるため、０．１質量％以上であることが好ましく、ポリアミド溶融時の加水分解を抑えるため、０．５質量％以下であることが好ましい。 The pellet moisture content in the polyamide resin (A) is not particularly limited, but is preferably 0.1% by mass or more in order to suppress an increase in molecular weight at the time of melting the polyamide of the compound raw material, and suppress hydrolysis at the time of melting the polyamide. Therefore, it is preferable that it is 0.5 mass% or less.
ペレット水分率はカールフィッシャー法水分計を用いて、ＪＩＳ Ｋ７２５１に準じて求めることができる。 The pellet moisture content can be determined according to JIS K7251 using a Karl Fischer moisture meter.
＜（Ｂ）メタリック着色顔料＞
（Ｂ）メタリック着色顔料の材料としては特に制限されるものではないが、例えば、アルミニウム、アルミフレーク、着色アルミニウム、パール顔料、カラーグラファイト、カラーガラスフレーク、スチール、銀、すず、ニッケル等が挙げられ、特に、アルミニウム、アルミフレークが好ましく、アルミフレークがより好ましい。
<(B) Metallic coloring pigment>
(B) Although it does not restrict | limit especially as a material of a metallic coloring pigment, For example, aluminum, aluminum flakes, colored aluminum, a pearl pigment, color graphite, color glass flakes, steel, silver, tin, nickel etc. are mentioned. In particular, aluminum and aluminum flakes are preferable, and aluminum flakes are more preferable.
（Ｂ）メタリック着色顔料は、入手しやすさ、コスト面、耐熱変色性の観点から、平均厚みを０．０５〜０．４μｍとすることが好ましい。 The (B) metallic color pigment preferably has an average thickness of 0.05 to 0.4 μm from the viewpoint of availability, cost, and heat discoloration.
厚みが０．０５μｍ未満であると入手しにくく、かつ高価であり、０．４μｍを上回るとポリアミド樹脂組成物の耐熱変色性が悪化する。 When the thickness is less than 0.05 μm, it is difficult to obtain and expensive, and when it exceeds 0.4 μm, the heat discoloration of the polyamide resin composition deteriorates.
これは、（Ｂ）メタリック着色顔料は、樹脂の熱変色を隠蔽する効果も有しているが、（Ｂ）メタリック着色顔料の厚みが大きくなり過ぎると、成形品の表面部分に存在する（Ｂ）メタリック着色顔料の数が減少し、これにより、当該（Ｂ）メタリック着色顔料の隠蔽効果が減少してしまい、外観上の熱変色性が悪化する傾向があるためである。 This is because (B) the metallic color pigment also has an effect of concealing the thermal discoloration of the resin, but when the thickness of the (B) metallic color pigment becomes too large, it exists on the surface portion of the molded product (B This is because the number of metallic color pigments is reduced, thereby reducing the concealing effect of the (B) metallic color pigment, and the thermal discoloration on appearance tends to deteriorate.
（Ｂ）メタリック着色顔料の平均厚みは、０．０５〜０．４μｍが好ましく、０．０８〜０．３５ｍがより好ましい。 (B) 0.05-0.4 micrometer is preferable and, as for the average thickness of a metallic coloring pigment, 0.08-0.35m is more preferable.
また、（Ｂ）メタリック着色顔料の平均厚み（ｔ）は、１ｇ当たりの水面拡散面積：ＷＣＡ（ｍ2／ｇ）を用いて次式により算出できる。 The average thickness (t) of the (B) metallic color pigment can be calculated by the following equation using the water surface diffusion area per gram: WCA (m 2 / g).
ｔ＝０．４／ＷＣＡ t = 0.4 / WCA
なお、水面拡散面積は、一定の予備処理、具体的には、メタリック着色顔料１ｇに、５質量％ステアリン酸のミネラルスピリット溶液を１〜２ｍｌ加え予備分散後、石油ベンジン５０ｍｌ加え混合し、４０〜４５℃で２時間加温後、フィルターで吸引濾過し、パウダー化したのち、ＪＩＳ−Ｋ−５９０６−１９９１に従って求めることができる。 In addition, the water surface diffusion area is a certain pretreatment, specifically, 1 to 2 ml of 5% by weight of mineral spirit solution of stearic acid is added to 1 g of the metallic coloring pigment, and after preliminary dispersion, 50 ml of petroleum benzine is added and mixed. After heating at 45 ° C. for 2 hours, the solution is suction filtered through a filter and powdered, and then obtained according to JIS-K-5906-1991.
また、（Ｂ）メタリック着色顔料の好ましい形状は、本実施形態のポリアミド樹脂組成物のメタリック感や、見た目の高級感の観点から、平均粒径５〜４０μｍのコイン状である。 Moreover, (B) The preferable shape of a metallic coloring pigment is a coin shape with an average particle diameter of 5-40 micrometers from a viewpoint of the metallic feeling of the polyamide resin composition of this embodiment, and a high-class appearance.
平均粒径５μｍを下回るとメタリック感が消失し、４０μｍを上回るとラメ調となり高級感が失われてしまう。 When the average particle size is less than 5 μm, the metallic feeling disappears, and when it exceeds 40 μm, it becomes lame and loses a high-class feeling.
（Ｂ）メタリック着色顔料の平均粒径は、セイシン企業株式会社製レーザーミクロンサイザーＬＭＳ−２４を用いて測定することができる。 (B) The average particle diameter of the metallic coloring pigment can be measured using a Laser Micron Sizer LMS-24 manufactured by Seishin Enterprise Co., Ltd.
本実施形態のポリアミド樹脂組成物において、（Ｂ）メタリック着色顔料の含有量は、成形品の輝度の観点から、ポリアミド樹脂（Ａ）１００質量部に対して０．１〜２０質量部が好ましく、より好ましくは０．５〜１０質量部、さらに好ましくは１〜５質量部である。 In the polyamide resin composition of the present embodiment, the content of the (B) metallic color pigment is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the polyamide resin (A) from the viewpoint of the brightness of the molded product. More preferably, it is 0.5-10 mass parts, More preferably, it is 1-5 mass parts.
前記（Ｂ）メタリック着色顔料は、平均表面粗さＲａが２０ｎｍ以下であることが好ましい。 The (B) metallic color pigment preferably has an average surface roughness Ra of 20 nm or less.
（Ｂ）メタリック着色顔料の平均表面粗さは、以下の方法により測定できる。 (B) The average surface roughness of the metallic color pigment can be measured by the following method.
（Ｂ）メタリック着色顔料の表面形態観察装置としては、原子間力顕微鏡、Ｔｏｐｏｍｅｔｒｉｘ製、ＴＭＸ−２０１０を使用することができる。 (B) As an apparatus for observing the surface form of a metallic color pigment, an atomic force microscope, manufactured by Topometrix, TMX-2010 can be used.
先ず、前処理として、測定用試料の（Ｂ）メタリック着色顔料を過剰のメタノール、またはクロロホルムで超音波洗浄し、その後、真空乾燥し、再度アセトンに分散、Ｓｉウェハー上に滴下し、自然乾燥を行う。 First, as a pretreatment, the (B) metallic color pigment of the sample for measurement is ultrasonically washed with excess methanol or chloroform, then vacuum-dried, dispersed again in acetone, dripped on a Si wafer, and naturally dried. Do.
次に、上記原子間力顕微鏡で測定を行うが、このとき、表面粗さの定量は、（Ｂ）メタリック着色顔料が他の（Ｂ）メタリック着色顔料と重なり合っていないものを選択し、５μｍ四方の視野につき表面粗さ曲線を３００スキャンにより測定し、粗さ曲線の算出術平均粗さ（基準長さ５μｍ内での標高の絶対値の算術平均）を求める。 Next, the measurement is performed with the atomic force microscope. At this time, the surface roughness is determined by selecting (B) a metallic colored pigment that does not overlap with another (B) metallic colored pigment, and measuring 5 μm square. The surface roughness curve is measured by 300 scans per field of view, and the calculated average roughness of the roughness curve (arithmetic average of the altitude values within the reference length of 5 μm) is obtained.
通常、測定に用いる基準長さは、平均粒径によるが、本実施形態のポリアミド樹脂組成物に含有されている（Ｂ）メタリック着色顔料においては、５μｍを選択することが好適である。 Normally, the reference length used for measurement depends on the average particle diameter, but it is preferable to select 5 μm for the (B) metallic color pigment contained in the polyamide resin composition of the present embodiment.
（Ｂ）メタリック着色顔料の平均表面粗さＲａは２０ｎｍ以下が好ましく、より好ましくは１５ｎｍ以下である。 (B) The average surface roughness Ra of the metallic color pigment is preferably 20 nm or less, more preferably 15 nm or less.
（Ｂ）メタリック着色顔料の平均粗さＲａが２０ｎｍ以下のとき、本実施形態のポリアミド樹脂組成物を用いて成形された成形品表面での正反射率、すなわち表面光沢度が大きくなり、極めて優れた輝度、メタリック感が得られる。 (B) When the average roughness Ra of the metallic color pigment is 20 nm or less, the regular reflectance on the surface of the molded product molded using the polyamide resin composition of the present embodiment, that is, the surface glossiness is increased, which is extremely excellent. Brightness and metallic feel.
（Ｂ）メタリック着色顔料の中には、アルミニウムのように消防法により危険物第２類の金属粉Ａに指定されているものがある。特にドライアルミニウムは粉塵爆発の危険性があるが、後述の（Ｃ）液状添加剤または（Ｄ）有機溶剤によって濡らすことによりこの粉塵爆発の危険性を大幅に低減することができる。 (B) Some metallic coloring pigments are designated as hazardous powder type 2 metal powder A by the Fire Service Act, such as aluminum. Dry aluminum in particular has a risk of dust explosion, but the danger of dust explosion can be greatly reduced by wetting with (C) liquid additive or (D) organic solvent described later.
＜（Ｃ）液状添加剤＞
本実施形態に用いる（Ｃ）液状添加剤は、ミネラルオイル、流動パラフィンおよび非イオン性界面活性剤からなる群より選択される少なくとも１種である。
<(C) Liquid additive>
The (C) liquid additive used in the present embodiment is at least one selected from the group consisting of mineral oil, liquid paraffin, and nonionic surfactant.
ここでいう非イオン性界面活性剤としては、特に限定されないが、例えば、ポリエチレングリコール、ポリエチレングリコールのエステル化誘導体、ポリプロピレングリコール、およびポリプロピレングリコールのエステル化誘導体からなる群より選択される少なくとも１種であることが好ましい。（Ｃ）液状添加剤としては、流動パラフィンや、ポリオキシエチレングリコール、ポリオキシプロピレングリコールが溶融混練時の耐熱安定性や入手の容易性から好ましい。 The nonionic surfactant here is not particularly limited, but for example, at least one selected from the group consisting of polyethylene glycol, an esterified derivative of polyethylene glycol, polypropylene glycol, and an esterified derivative of polypropylene glycol. Preferably there is. As the liquid additive (C), liquid paraffin, polyoxyethylene glycol, and polyoxypropylene glycol are preferable from the viewpoint of heat resistance stability during melt kneading and availability.
（Ｃ）液状添加剤の性状については、１気圧かつ０℃以上１００℃以下の条件で液状であることが好ましく、１気圧かつ５℃以上４０℃以下の条件で液状であることがより好ましい。 (C) About the property of a liquid additive, it is preferable that it is a liquid on the conditions of 1 atmosphere and 0 degreeC or more and 100 degrees C or less, and it is more preferable that it is a liquid on the conditions of 1 atmosphere and 5 degrees C or more and 40 degrees C or less.
本実施形態のポリアミド樹脂組成物において、液状添加剤（Ｃ）の含有量は、外観の観点から、ポリアミド樹脂（Ａ）１００質量部に対して０．０１〜２質量部であることが好ましく、０．０１〜１質量部であることがより好ましく、さらに好ましくは０．０１〜０．５質量部である。 In the polyamide resin composition of the present embodiment, the content of the liquid additive (C) is preferably 0.01 to 2 parts by mass with respect to 100 parts by mass of the polyamide resin (A) from the viewpoint of appearance, More preferably, it is 0.01-1 mass part, More preferably, it is 0.01-0.5 mass part.
＜（Ｄ）有機溶剤＞
本実施形態のポリアミド樹脂組成物中の（Ｄ）有機溶剤の含有量は５００ｐｐｍ以下である。
<(D) Organic solvent>
Content of the (D) organic solvent in the polyamide resin composition of this embodiment is 500 ppm or less.
例えば、アルミを含むポリアミド樹脂組成物において、有機溶剤は、通常、アルミペーストの原料であるアルミ粉を湿潤させて粉塵爆発の危険性を大幅に低減させるために使用される。しかしながら、ポリアミド樹脂組成物中に有機溶剤が一定量以上残留していると成形時の滞留安定性が悪いといった問題点や、成形品としたときにシルバーストリークのような外観不良が見られることがある。また使用者がポリアミド樹脂組成物から揮発した有機溶剤を吸引すると健康被害を引き起こすことが考えられる。 For example, in a polyamide resin composition containing aluminum, an organic solvent is usually used to wet aluminum powder, which is a raw material of the aluminum paste, to greatly reduce the risk of dust explosion. However, there is a problem that the retention stability at the time of molding is poor if a certain amount or more of the organic solvent remains in the polyamide resin composition, and appearance defects such as silver streaks are seen when it is formed into a molded product. is there. In addition, if the user sucks an organic solvent that has volatilized from the polyamide resin composition, it is considered to cause a health hazard.
以上の観点から本実施形態のポリアミド樹脂組成物は、上述したとおり、（Ｃ）液状添加剤を用いることにより、ポリアミド樹脂組成物中の（Ｄ）有機溶剤の含有量を低減させ、上述の問題を改善している。 From the above viewpoint, the polyamide resin composition of the present embodiment, as described above, reduces the content of the organic solvent (D) in the polyamide resin composition by using the (C) liquid additive, and the above-mentioned problems. Has improved.
本実施形態のポリアミド樹脂組成物中の（Ｄ）有機溶剤の含有量は、５００ｐｐｍ以下であり、３００ｐｐｍ以下であることが好ましく、より好ましくは１００ｐｐｍ以下である。ポリアミド樹脂組成物中の（Ｄ）有機溶剤の含有量の下限は、小さい方が好ましいが、例えば、０．１ｐｐｍ以上である。なお、本実施形態において、ポリアミド樹脂組成物中の（Ｄ）有機溶剤の含有量は、後述の実施例に記載の方法により測定することができる。 The content of the organic solvent (D) in the polyamide resin composition of the present embodiment is 500 ppm or less, preferably 300 ppm or less, more preferably 100 ppm or less. The lower limit of the content of the (D) organic solvent in the polyamide resin composition is preferably smaller, but is, for example, 0.1 ppm or more. In addition, in this embodiment, content of the (D) organic solvent in a polyamide resin composition can be measured by the method as described in the below-mentioned Example.
本実施形態に用いる（Ｄ）有機溶剤としては、一般的に工業的に使用される有機溶剤であれば特に限定されず、例えば、トルエン、キシレン、スチレン、クロルベンゼン、オルト−クロルベンゼン、ジクロロメタン、クロロホルム、四塩化炭素、１，２−ジクロルエタン、１，１，１−トリクロルエタン、１，２−ジクロルエチレン、トリクロルエチレン、テトラクロルエチレン、イソプロピルアルコール、１−ブタノール、２−ブタノール、イソブチルアルコール、イソペンチルアルコール、酢酸メチル、酢酸エチル、酢酸ノルマループロピル、酢酸イソプロピル、酢酸ノルマルーブチル、酢酸イソブチル、酢酸ノルマルーペンチル、酢酸イソペンチル、１，４−ジオキサン、テトラヒドロフラン、メチルエチルケトン、メチルーノルマルーブチルケトン、メチルイソブチルケトン、エチレングリコールーモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノーノルマルーブチルエーテル、エチレングリコールモノエチルエーテルアセテート、シクロヘキサン、メチルシクロヘキサン、メチルシクロヘキサノール、ノルマルヘキサン、コールタールナフサ、石油エーテル、ソルベントナフサ、石油ベンジン、テレビン油、ミネラルスピリット、クレゾール等が挙げられる。中でも（Ｄ）有機溶剤としては、ミネラルスピリット、ソルベントナフサ、キシレン、トルエン、メチルイソブチルケトン、イソプロピルアルコールであることが好ましい。これらの（Ｄ）有機溶剤は、１種単独で用いてもよく、２種以上併用してもよい。 The organic solvent (D) used in the present embodiment is not particularly limited as long as it is an organic solvent that is generally used industrially. For example, toluene, xylene, styrene, chlorobenzene, ortho-chlorobenzene, dichloromethane, Chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,2-dichloroethylene, trichloroethylene, tetrachloroethylene, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, Isopentyl alcohol, methyl acetate, ethyl acetate, normal propyl acetate, isopropyl acetate, normal butyl acetate, isobutyl acetate, normal pentyl acetate, isopentyl acetate, 1,4-dioxane, tetrahydrofuran, methyl ethyl ketone, methyl normal Butyl ketone, methyl isobutyl ketone, ethylene glycol-monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-normal-butyl ether, ethylene glycol monoethyl ether acetate, cyclohexane, methylcyclohexane, methylcyclohexanol, normal hexane, coal tar naphtha, petroleum ether Solvent naphtha, petroleum benzine, turpentine oil, mineral spirit, cresol and the like. Among these, (D) the organic solvent is preferably mineral spirit, solvent naphtha, xylene, toluene, methyl isobutyl ketone, or isopropyl alcohol. These (D) organic solvents may be used alone or in combination of two or more.
〔添加剤〕
本実施形態のポリアミド樹脂組成物には、必要に応じて本発明の目的を損なわない範囲で慣用的に用いられる添加剤を加えることができる。当該添加剤としては、特に限定されないが、例えば、ガラス繊維や炭素繊維などの無機繊維；水酸化アルミニウム、水酸化マグネシウム、ホウ酸亜鉛、すず酸亜鉛、ヒドロキシすず酸亜鉛、ポリリン酸アンモニウム、シアヌル酸メラミン、サクシノグアナミン、ポリリン酸メラミン、硫酸メラミン、フタル酸メラミン、リン酸アルミニウム等の難燃剤；チタンホワイト、カーボンブラック等の顔料や着色剤；ヒンダードフェノールやヒンダードアミンに代表される熱安定剤；高級脂肪酸金属塩、高級脂肪酸アミド、高級脂肪酸エステル等の滑剤；種々の可塑剤；帯電防止剤等が挙げられる。
〔Additive〕
In the polyamide resin composition of the present embodiment, additives that are conventionally used can be added as needed as long as the object of the present invention is not impaired. Although it does not specifically limit as said additive, For example, inorganic fiber, such as glass fiber and carbon fiber; Aluminum hydroxide, magnesium hydroxide, zinc borate, zinc stannate, zinc hydroxy stannate, ammonium polyphosphate, cyanuric acid Flame retardants such as melamine, succinoguanamine, melamine polyphosphate, melamine sulfate, melamine phthalate and aluminum phosphate; pigments and colorants such as titanium white and carbon black; heat stabilizers typified by hindered phenols and hindered amines; Lubricants such as higher fatty acid metal salts, higher fatty acid amides, higher fatty acid esters; various plasticizers; antistatic agents and the like.
≪ポリアミド樹脂組成物の製造方法≫
本実施形態のポリアミド樹脂組成物は、上記（Ａ）〜（Ｄ）成分を含む原料成分を溶融混練することにより製造することができる。当該溶融混練を行う装置としては、一般に実用されている混練機が適用できる。例えば、一軸または多軸混練押出機、バンバリーミキサー、ロール等が用いられる。当該溶融混練の方法は、全原料成分を同時に混練する方法、あらかじめ原料成分を予備混練したブレンド物を用いて混練する方法、更に押出し機の途中から逐次、各原料成分をフィードし、混練する方法のいずれでもよい。当該溶融混練の温度は、（Ａ）〜（Ｄ）成分のいずれかのうちで最も高い融点あるいは軟化点より１〜１００℃高い温度が好ましく、１０〜６０℃高い温度がより好ましく、２０〜５０℃高い温度がさらに好ましい。すなわち、本実施形態では、製造時にすべての樹脂を溶融し混合することが好ましい。融点または軟化点はＪＩＳ Ｋ７１２１に準じた示差走査熱量（ＤＳＣ）測定で求めることができる。ポリアミド樹脂組成物の引張伸度および生産性の観点から、当該溶融混練の温度は、前記温度範囲が好ましい。
≪Method for producing polyamide resin composition≫
The polyamide resin composition of this embodiment can be manufactured by melt-kneading the raw material component containing said (A)-(D) component. As a device for performing the melt-kneading, generally used kneaders can be applied. For example, a single-screw or multi-screw kneading extruder, a Banbury mixer, a roll, or the like is used. The melt kneading method includes a method of kneading all raw material components simultaneously, a method of kneading using a blend obtained by pre-kneading raw material components in advance, and a method of feeding and kneading each raw material component sequentially from the middle of the extruder. Either of these may be used. The temperature of the melt kneading is preferably 1 to 100 ° C. higher than the highest melting point or softening point of any of the components (A) to (D), more preferably 10 to 60 ° C., more preferably 20 to 50 ° C. Even higher temperatures are more preferred. That is, in this embodiment, it is preferable to melt and mix all the resins at the time of manufacture. The melting point or softening point can be determined by differential scanning calorimetry (DSC) measurement according to JIS K7121. From the viewpoint of the tensile elongation and productivity of the polyamide resin composition, the temperature of the melt kneading is preferably within the above temperature range.
≪成形品≫
本実施形態のポリアミド樹脂成形品は、上述のポリアミド樹脂組成物を成形して得られる。
≪Molded product≫
The polyamide resin molded product of the present embodiment is obtained by molding the above-described polyamide resin composition.
当該成形方法としては、特に限定されないが、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、及び溶融紡糸など、一般に知られているプラスチック成形方法が挙げられる。 The molding method is not particularly limited, but is generally known, for example, press molding, injection molding, gas assist injection molding, welding molding, extrusion molding, blow molding, film molding, hollow molding, multilayer molding, and melt spinning. A plastic molding method.
本実施形態のポリアミド樹脂成形品は、上述のポリアミド樹脂組成物から得られるので、特に表面外観に優れる。したがって、本実施形態のポリアミド樹脂成形品は、自動車部品、電気及び電子部品、家電部品、ＯＡ機器部品、携帯機器部品、産業機器部品、建材、日用品及び家庭品などの各種部品として好適に用いることができる。 Since the polyamide resin molded article of this embodiment is obtained from the above-mentioned polyamide resin composition, it is particularly excellent in surface appearance. Therefore, the polyamide resin molded product of the present embodiment is preferably used as various parts such as automobile parts, electric and electronic parts, home appliance parts, OA equipment parts, portable equipment parts, industrial equipment parts, building materials, daily necessities, and household goods. Can do.
以下、本発明を実施例により更に詳細に説明するが、本発明は以下の実施例に制限されるものではない。なお、以下の実施例および比較例において行った物性評価は以下のように行った。 EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not restrict | limited to a following example. In addition, the physical property evaluation performed in the following Examples and Comparative Examples was performed as follows.
（１）押出特性
実施例および比較例においてポリアミド樹脂組成物を、押出機を用いて製造した際に、（ａ）押出機周辺での有機溶剤臭による環境悪化、（ｂ）押出機のダイス部での異物発生、の２点について評価を行った。評価のランクは以下に記載の通りとし、数字が少ないほど良好であった。
(1) Extrusion characteristics When the polyamide resin composition was produced using an extruder in the examples and comparative examples, (a) environmental deterioration due to organic solvent odor around the extruder, (b) die part of the extruder Evaluation was made on two points of foreign matter generation. The rank of evaluation was as described below, and the smaller the number, the better.
（ａ）環境悪化
１：溶剤臭はほとんどなく、問題なく作業できた。
２：溶剤臭はあるが、問題なく作業できた。
３：溶剤臭があり、作業に支障があった。
(A) Environmental deterioration 1: There was almost no solvent odor and it was able to work without a problem.
2: Although there was a solvent odor, it was able to work without problems.
3: There was a solvent odor, which hindered work.
（ｂ）異物発生
１：異物発生はほとんどなく、連続して生産可能であった。
２：異物が発生し、ストランドのロープ切れが見られた。
３：異物が多く発生し、ストランドのロープ切れが多く発生した。
(B) Generation of foreign matter 1: Almost no foreign matter was generated, and continuous production was possible.
2: Foreign matter was generated, and strand rope breakage was observed.
3: A lot of foreign matters were generated, and a lot of strands were broken.
（２）ポリアミド樹脂組成物中の（Ｄ）有機溶剤の含有量
実施例および比較例において得られたポリアミド樹脂組成物のペレットを凍結粉砕し、粉砕物を得た。ねじ付三角フラスコに前記粉砕物１ｇを入れて、１０ｍｌのクロロホルムで熱抽出（５０度、１時間）を行い、試料溶液を作成した。この試料溶液をガスクロマトグラフで分析を行い、外部標準法にて有機溶剤の定量を行った。
(2) Content of (D) Organic Solvent in Polyamide Resin Composition The polyamide resin composition pellets obtained in the examples and comparative examples were freeze pulverized to obtain a pulverized product. 1 g of the pulverized product was put into a conical flask with a screw and subjected to heat extraction (50 ° C., 1 hour) with 10 ml of chloroform to prepare a sample solution. This sample solution was analyzed with a gas chromatograph, and the organic solvent was quantified by an external standard method.
（３）成形時の滞留安定性
射出成形機（住友重工業株式会社製、ＳＥ５０Ｄ）を用いて、シリンダー設定温度２９０℃、金型温度８０℃、スクリュー回転数２５０ｒｐｍ、射出時間１０秒、冷却時間１５秒、背圧２０％の条件で、実施例および比較例において得られたポリアミド樹脂組成物を射出成形し、幅６０ｍｍ長さ９０ｍｍ厚さ１ｍｍの平板を得た。連続成形の際に５分間中断時間を設け、その間にノズルから噴出がない場合を○、噴出があった場合を×として、成形時の滞留安定性を評価した。
(3) Residence stability during molding Using an injection molding machine (SE50D, manufactured by Sumitomo Heavy Industries, Ltd.), a cylinder set temperature of 290 ° C., a mold temperature of 80 ° C., a screw rotation speed of 250 rpm, an injection time of 10 seconds, and a cooling time of 15 The polyamide resin compositions obtained in the examples and comparative examples were injection molded under the conditions of second and back pressure of 20% to obtain a flat plate having a width of 60 mm, a length of 90 mm, and a thickness of 1 mm. In the continuous molding, an interruption time of 5 minutes was provided, and during this period, the case where there was no ejection from the nozzle was evaluated as ◯, and the case where there was an ejection was evaluated as x, and the residence stability during molding was evaluated.
（４）外観特性
上記（３）で得られた平板の表面に、シルバーストリークが発生しているか否かにより外観特性を評価した。シルバーストリークが発生していない場合を○、発生した場合を×とした。
(4) Appearance characteristics Appearance characteristics were evaluated based on whether or not silver streaks occurred on the surface of the flat plate obtained in (3) above. The case where silver streak did not occur was marked with ◯, and the case where it occurred was marked with x.
実施例および比較例で用いた各成分は、以下のものを用いた。 The following were used for each component used in the examples and comparative examples.
・ポリアミド樹脂
（Ａ１）ポリアミド６６（旭化成ケミカルズ株式会社製レオナ１３００）
Polyamide resin (A1) Polyamide 66 (Leona 1300 manufactured by Asahi Kasei Chemicals Corporation)
・アルミペースト
アルミペースト１：（Ｂ１）平均粒径２０μｍのアルミフレーク１００質量部、（Ｃ１）流動パラフィン１０質量部、（Ｄ１）ミネラルスピリット１質量部からなる。
アルミペースト２：（Ｂ１）平均粒径２０μｍのアルミフレーク１００質量部、（Ｃ２）ポリエチレングリコール１０質量部、（Ｄ１）ミネラルスピリット１質量部からなる。
アルミペースト３：（Ｂ１）平均粒径２０μｍのアルミフレーク１００質量部、（Ｄ１）ミネラルスピリット１０質量部からなる。
Aluminum paste Aluminum paste 1: (B1) 100 parts by mass of aluminum flakes having an average particle diameter of 20 μm, (C1) 10 parts by mass of liquid paraffin, and (D1) 1 part by mass of mineral spirits.
Aluminum paste 2: (B1) 100 parts by mass of aluminum flakes having an average particle diameter of 20 μm, (C2) 10 parts by mass of polyethylene glycol, and (D1) 1 part by mass of mineral spirits.
Aluminum paste 3: (B1) 100 parts by mass of aluminum flakes having an average particle diameter of 20 μm, and (D1) 10 parts by mass of mineral spirits.
なお、アルミフレークの平均粒径は、セイシン企業株式会社製レーザーミクロンサイザーＬＭＳ−２４を用いて測定した。また、上記ポリエチレングリコールは、株式会社ＡＤＥＫＡ製 アデカＰＥＧ４００を使用した。 The average particle size of the aluminum flakes was measured using a Laser Micron Sizer LMS-24 manufactured by Seishin Enterprise Co., Ltd. The polyethylene glycol used was ADEKA PEG400 manufactured by ADEKA Corporation.
［実施例１］
（Ａ１）ポリアミド６６を１００質量部と、アルミペースト１を１１．１質量部と、を混合し、混合物を得た。単軸押出機（田辺プラスチック機械製ＶＳ６５−３６）を用いて、２９０℃、スクリュー回転数１００ｒｐｍ、吐出量１００ｋｇ／ｈ、真空ベントを用いない条件下で、前記混合物の溶融混練を行い、ポリアミド樹脂組成物を得た。得られたポリアミド樹脂組成物の評価結果を表１に示す。
[Example 1]
(A1) 100 parts by mass of polyamide 66 and 11.1 parts by mass of aluminum paste 1 were mixed to obtain a mixture. Using a single screw extruder (VS65-36, manufactured by Tanabe Plastic Machine), the mixture was melt-kneaded under the conditions of 290 ° C., screw rotation speed 100 rpm, discharge rate 100 kg / h, no vacuum vent, and polyamide resin A composition was obtained. The evaluation results of the obtained polyamide resin composition are shown in Table 1.
［実施例２］
アルミペースト１をアルミペースト２に変更した以外は、実施例１と同様にして溶融混練を行い、ポリアミド樹脂組成物を得た。得られたポリアミド樹脂組成物の評価結果を表１に示す。
[Example 2]
Except for changing the aluminum paste 1 to the aluminum paste 2, melt-kneading was performed in the same manner as in Example 1 to obtain a polyamide resin composition. The evaluation results of the obtained polyamide resin composition are shown in Table 1.
［比較例１］
原料として、（Ａ１）ポリアミド６６を１００質量部と、アルミペースト３を１１質量部と、を用いた以外は、実施例１と同様にして溶融混練を行い、ポリアミド樹脂組成物を得た。得られたポリアミド樹脂組成物の評価結果を表１に示す。
[Comparative Example 1]
Except that 100 parts by mass of (A1) polyamide 66 and 11 parts by mass of aluminum paste 3 were used as raw materials, melt kneading was performed in the same manner as in Example 1 to obtain a polyamide resin composition. The evaluation results of the obtained polyamide resin composition are shown in Table 1.
［実施例３］
真空ベントを−８００ｈｐａの条件で用いた以外は、実施例１と同様にして溶融混練を行い、ポリアミド樹脂組成物を得た。得られたポリアミド樹脂組成物の評価結果を表１に示す。
[Example 3]
Except for using a vacuum vent under the condition of -800 hpa, melt kneading was performed in the same manner as in Example 1 to obtain a polyamide resin composition. The evaluation results of the obtained polyamide resin composition are shown in Table 1.
［比較例２］
原料として、（Ａ１）ポリアミド６６を１００質量部と、アルミペースト３を１１質量部と、を用いた以外は、実施例３と同様にして溶融混練を行い、ポリアミド樹脂組成物を得た。得られたポリアミド樹脂組成物の評価結果を表１に示す。
[Comparative Example 2]
Except that 100 parts by mass of (A1) polyamide 66 and 11 parts by mass of aluminum paste 3 were used as raw materials, melt kneading was performed in the same manner as in Example 3 to obtain a polyamide resin composition. The evaluation results of the obtained polyamide resin composition are shown in Table 1.
実施例１〜３で得られたポリアミド樹脂組成物は、押出特性、成形時の滞留安定性および外観特性のいずれもが優れていた。また、実施例１〜３で得られたポリアミド樹脂組成物は、有機溶剤の含有量も少なく良好であった。一方、比較例１および２で得られたポリアミド樹脂組成物は、押出特性、滞留安定性および外観特性の少なくともいずれかが劣っていた。さらに比較例２で得られたポリアミド樹脂組成物は、有機溶剤の含有量は少ないものの押出特性が悪いことが明らかとなった。以上より、本実施形態のポリアミド樹脂組成物は、押出特性、滞留安定性および外観特性に優れ、有機溶剤の含有量が低減されていることが確認された。 The polyamide resin compositions obtained in Examples 1 to 3 were excellent in extrusion characteristics, retention stability during molding, and appearance characteristics. In addition, the polyamide resin compositions obtained in Examples 1 to 3 were good with a small content of organic solvent. On the other hand, the polyamide resin compositions obtained in Comparative Examples 1 and 2 were inferior in at least one of extrusion characteristics, residence stability, and appearance characteristics. Furthermore, the polyamide resin composition obtained in Comparative Example 2 was found to have poor extrusion characteristics although it contained a small amount of organic solvent. From the above, it was confirmed that the polyamide resin composition of the present embodiment was excellent in extrusion characteristics, retention stability and appearance characteristics, and the content of the organic solvent was reduced.
本発明のポリアミド組成物は、押出特性、成形時の滞留安定性および外観特性に優れ、有機溶剤の含有量が低減されている為、様々な機械工業部品、電気電子部品などの産業用材料として有用である。 The polyamide composition of the present invention is excellent in extrusion characteristics, retention stability during molding, and appearance characteristics, and has a reduced organic solvent content, so that it can be used as an industrial material such as various mechanical and electrical parts. Useful.
Claims (7)
（Ｂ）メタリック着色顔料と、
（Ｃ）ミネラルオイル、流動パラフィンおよび非イオン性界面活性剤からなる群より選択される少なくとも１種の液状添加剤と、
（Ｄ）有機溶剤と、を含むポリアミド樹脂組成物であって、
該ポリアミド樹脂組成物中の（Ｄ）有機溶剤の含有量が５００ｐｐｍ以下である、ポリアミド樹脂組成物。 (A) a polyamide resin;
(B) a metallic coloring pigment;
(C) at least one liquid additive selected from the group consisting of mineral oil, liquid paraffin, and nonionic surfactant;
(D) a polyamide resin composition comprising an organic solvent,
The polyamide resin composition whose content of the (D) organic solvent in this polyamide resin composition is 500 ppm or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012187634A JP5968163B2 (en) | 2012-08-28 | 2012-08-28 | Metallic polyamide resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012187634A JP5968163B2 (en) | 2012-08-28 | 2012-08-28 | Metallic polyamide resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2014043525A true JP2014043525A (en) | 2014-03-13 |
| JP5968163B2 JP5968163B2 (en) | 2016-08-10 |
Family
ID=50395039
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2012187634A Active JP5968163B2 (en) | 2012-08-28 | 2012-08-28 | Metallic polyamide resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5968163B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017127649A1 (en) | 2016-01-21 | 2017-07-27 | Ticona Llc | Polyamide composition containing a metallic pigment |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5837045A (en) * | 1981-08-31 | 1983-03-04 | Denki Kagaku Kogyo Kk | Abs resin composition |
| JPS59501550A (en) * | 1982-08-16 | 1984-08-30 | カ−ン、ジョ−ジ・エム | Free-flowing granular material consisting of metal particles covered with a coating |
| JPS6220574A (en) * | 1985-07-19 | 1987-01-29 | Toyo Alum Kk | Metallic pigment to be incorporated into synthetic resin |
| JPH11240591A (en) * | 1997-11-11 | 1999-09-07 | Silberline Ltd | Method for packaging metallic pigment, method for transporting the same, method for powder-coating object, and metallic pigment delivery system |
| JPH11315205A (en) * | 1998-02-12 | 1999-11-16 | Toray Ind Inc | Metallically pre-dyed polyamide resin composition |
| JP2000086889A (en) * | 1998-09-17 | 2000-03-28 | Toyobo Co Ltd | Metallic polyamide resin composition |
| JP2003312195A (en) * | 2002-04-24 | 2003-11-06 | Daicel Chem Ind Ltd | Transfer sheet |
| JP2005171155A (en) * | 2003-12-12 | 2005-06-30 | Ito Seiyu Kk | Pigment sedimentation-preventing agent for water-borne coating and method for producing the same |
| JP2009235028A (en) * | 2008-03-28 | 2009-10-15 | Ube Ind Ltd | Cosmetic composition containing colored polyamide fine particle |
| US20110034610A1 (en) * | 2009-08-07 | 2011-02-10 | Ticona, Llc | Low Formaldehyde Emission Polyacetal Composition |
-
2012
- 2012-08-28 JP JP2012187634A patent/JP5968163B2/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4461865A (en) * | 1981-08-31 | 1984-07-24 | Denki Kagaku Kogyo Kabushiki Kaisha | ABS Resin composition |
| JPS5837045A (en) * | 1981-08-31 | 1983-03-04 | Denki Kagaku Kogyo Kk | Abs resin composition |
| JPS59501550A (en) * | 1982-08-16 | 1984-08-30 | カ−ン、ジョ−ジ・エム | Free-flowing granular material consisting of metal particles covered with a coating |
| US4544600A (en) * | 1982-08-16 | 1985-10-01 | Silberline Manufacturing Company, Inc. | Resin compositions containing metals such as aluminum |
| JPS6220574A (en) * | 1985-07-19 | 1987-01-29 | Toyo Alum Kk | Metallic pigment to be incorporated into synthetic resin |
| US6134863A (en) * | 1997-11-11 | 2000-10-24 | Silberline Limited | Process for packaging metal pigment powder |
| JPH11240591A (en) * | 1997-11-11 | 1999-09-07 | Silberline Ltd | Method for packaging metallic pigment, method for transporting the same, method for powder-coating object, and metallic pigment delivery system |
| JPH11315205A (en) * | 1998-02-12 | 1999-11-16 | Toray Ind Inc | Metallically pre-dyed polyamide resin composition |
| JP2000086889A (en) * | 1998-09-17 | 2000-03-28 | Toyobo Co Ltd | Metallic polyamide resin composition |
| JP2003312195A (en) * | 2002-04-24 | 2003-11-06 | Daicel Chem Ind Ltd | Transfer sheet |
| JP2005171155A (en) * | 2003-12-12 | 2005-06-30 | Ito Seiyu Kk | Pigment sedimentation-preventing agent for water-borne coating and method for producing the same |
| JP2009235028A (en) * | 2008-03-28 | 2009-10-15 | Ube Ind Ltd | Cosmetic composition containing colored polyamide fine particle |
| US20110034610A1 (en) * | 2009-08-07 | 2011-02-10 | Ticona, Llc | Low Formaldehyde Emission Polyacetal Composition |
| JP2011038097A (en) * | 2009-08-07 | 2011-02-24 | Ticona Llc | Low formaldehyde emission polyacetal composition |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017127649A1 (en) | 2016-01-21 | 2017-07-27 | Ticona Llc | Polyamide composition containing a metallic pigment |
| CN108699290A (en) * | 2016-01-21 | 2018-10-23 | 提克纳有限责任公司 | Daiamid composition containing metallic pigments |
| EP3405520A4 (en) * | 2016-01-21 | 2019-09-18 | Ticona LLC | Polyamide composition containing a metallic pigment |
| US11608423B2 (en) | 2016-01-21 | 2023-03-21 | Ticona Llc | Polyamide composition containing a metallic pigment |
| US20230227624A1 (en) * | 2016-01-21 | 2023-07-20 | Ticona Llc | Polyamide Composition Containing a Metallic Pigment |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5968163B2 (en) | 2016-08-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5909534B2 (en) | Polyester resin composition and camera module including the same | |
| TWI363076B (en) | Flame retardant composition having improved fluidity, resin composition thereof, and molded article therefrom | |
| CN100564450C (en) | A kind of flame retardant resistance and shock-resistance thermoplastic resin excellent constituent | |
| CN103333478A (en) | Halogen-free flame-retardant polycarbonate and preparation method thereof | |
| CN107043516A (en) | Dark heat-proof ABS resin composition with improvement weatherability | |
| JP2017061675A (en) | Polyamide compositions | |
| WO2023020413A1 (en) | High-toughness flame-retardant polycarbonate alloy composition, and preparation method therefor and application thereof | |
| JP5968163B2 (en) | Metallic polyamide resin composition | |
| JP6194687B2 (en) | Composition comprising polyamide resin, copper compound and potassium halide, and molded article comprising the same | |
| CN110423461B (en) | Low-water-absorption flame-retardant glass fiber reinforced PA6 composite material and preparation method thereof | |
| WO2024082521A1 (en) | Polycarbonate alloy material, preparation method therefor and use thereof | |
| CN111500011A (en) | Household flame-retardant weather-resistant high-gloss ABS material and preparation method thereof | |
| JP5887100B2 (en) | Polyamide resin composition | |
| WO1996025460A1 (en) | Crystalline polyolefin resin composition and electrical insulation parts made from said composition | |
| CN113429734A (en) | Novel flame-retardant ABS material and preparation method thereof | |
| CN115028958A (en) | Flame-retardant ABS (acrylonitrile-butadiene-styrene) modified material as well as preparation method and application thereof | |
| CN110483941B (en) | Low-smoke environment-friendly 5 VA-grade flame-retardant ABS material and preparation method thereof | |
| JP2019006866A (en) | Polybutylene terephthalate-based resin composition and molded product | |
| JP2023504245A (en) | Flame-retardant polyester molding composition | |
| CN109467907A (en) | A kind of PC/PMMA/PBT composite material and preparation method | |
| KR101360118B1 (en) | Low volatile and flame retardant polyester resin composition and molded article thereof | |
| CN104672843A (en) | Halogen-free flame retardant antistatic modified PC and preparation method thereof | |
| KR100894276B1 (en) | Polyprophilene resin composition with advanced tensile strength and weather proof property | |
| JP2018177847A (en) | Vinylidene chloride resin composition, resin blend, and molding | |
| CN108219448A (en) | A kind of thermoplastic resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20150302 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20151117 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20151209 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20160205 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20160303 |
|
| A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A712 Effective date: 20160401 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20160428 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20160523 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20160614 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20160705 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5968163 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |