JP2007031505A - Black-colored polyamide resin composition and molded product thereof - Google Patents
Black-colored polyamide resin composition and molded product thereof Download PDFInfo
- Publication number
- JP2007031505A JP2007031505A JP2005214009A JP2005214009A JP2007031505A JP 2007031505 A JP2007031505 A JP 2007031505A JP 2005214009 A JP2005214009 A JP 2005214009A JP 2005214009 A JP2005214009 A JP 2005214009A JP 2007031505 A JP2007031505 A JP 2007031505A
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- JP
- Japan
- Prior art keywords
- polyamide resin
- resin composition
- weight
- black
- black colored
- 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 68
- 239000011342 resin composition Substances 0.000 title claims abstract description 53
- 239000000203 mixture Substances 0.000 claims abstract description 35
- 239000011256 inorganic filler Substances 0.000 claims abstract description 24
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 24
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 23
- 239000006229 carbon black Substances 0.000 claims abstract description 20
- 239000003365 glass fiber Substances 0.000 claims abstract description 19
- 239000010456 wollastonite Substances 0.000 claims abstract description 17
- 229910052882 wollastonite Inorganic materials 0.000 claims abstract description 17
- 239000010445 mica Substances 0.000 claims abstract description 14
- 229910052618 mica group Inorganic materials 0.000 claims abstract description 14
- 125000003277 amino group Chemical group 0.000 claims abstract description 12
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000460 chlorine Substances 0.000 claims abstract description 11
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 11
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000454 talc Substances 0.000 claims abstract description 10
- 229910052623 talc Inorganic materials 0.000 claims abstract description 10
- 239000004952 Polyamide Substances 0.000 claims description 26
- 229920002647 polyamide Polymers 0.000 claims description 26
- 238000004040 coloring Methods 0.000 claims description 11
- 238000000465 moulding Methods 0.000 claims description 10
- 239000005995 Aluminium silicate Substances 0.000 claims description 9
- 235000012211 aluminium silicate Nutrition 0.000 claims description 9
- 229920006012 semi-aromatic polyamide Polymers 0.000 claims description 9
- 239000004953 Aliphatic polyamide Substances 0.000 claims description 5
- 229920003231 aliphatic polyamide Polymers 0.000 claims description 5
- 239000012760 heat stabilizer Substances 0.000 claims description 5
- 239000011164 primary particle Substances 0.000 claims description 5
- 239000012778 molding material Substances 0.000 claims description 4
- 229910052622 kaolinite Inorganic materials 0.000 abstract description 3
- 239000000243 solution Substances 0.000 abstract description 3
- 238000002347 injection Methods 0.000 abstract description 2
- 239000007924 injection Substances 0.000 abstract description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 20
- 229920002302 Nylon 6,6 Polymers 0.000 description 19
- 230000007774 longterm Effects 0.000 description 18
- 238000000034 method Methods 0.000 description 18
- -1 aliphatic monocarboxylic acids Chemical class 0.000 description 16
- 238000012545 processing Methods 0.000 description 16
- 238000012360 testing method Methods 0.000 description 12
- 238000002156 mixing Methods 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 9
- 238000001746 injection moulding Methods 0.000 description 8
- 239000008188 pellet Substances 0.000 description 8
- 229920002292 Nylon 6 Polymers 0.000 description 7
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 7
- 229920000572 Nylon 6/12 Polymers 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 238000004898 kneading Methods 0.000 description 6
- 239000003381 stabilizer Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229920000299 Nylon 12 Polymers 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000012756 surface treatment agent Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 229920000305 Nylon 6,10 Polymers 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229920000571 Nylon 11 Polymers 0.000 description 2
- 229920000393 Nylon 6/6T Polymers 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 229920006038 crystalline resin Polymers 0.000 description 2
- NZNMSOFKMUBTKW-UHFFFAOYSA-N cyclohexanecarboxylic acid Chemical compound OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 229910001649 dickite Inorganic materials 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- YGANSGVIUGARFR-UHFFFAOYSA-N dipotassium dioxosilane oxo(oxoalumanyloxy)alumane oxygen(2-) Chemical compound [O--].[K+].[K+].O=[Si]=O.O=[Al]O[Al]=O YGANSGVIUGARFR-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000005562 fading Methods 0.000 description 2
- 229910052621 halloysite Inorganic materials 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 description 2
- 229910052627 muscovite Inorganic materials 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 229920005992 thermoplastic resin Polymers 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
- 239000012498 ultrapure water Substances 0.000 description 2
- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- YEYCMBWKTZNPDH-UHFFFAOYSA-N (2,2,6,6-tetramethylpiperidin-4-yl) benzoate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)C1=CC=CC=C1 YEYCMBWKTZNPDH-UHFFFAOYSA-N 0.000 description 1
- FEODVXCWZVOEIR-UHFFFAOYSA-N (2,4-ditert-butylphenyl) octyl hydrogen phosphite Chemical compound CCCCCCCCOP(O)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C FEODVXCWZVOEIR-UHFFFAOYSA-N 0.000 description 1
- VUDTWHRFAOFPBL-UHFFFAOYSA-N (3,5-ditert-butyl-4-hydroxyphenyl)methanesulfonic acid Chemical compound CC(C)(C)C1=CC(CS(O)(=O)=O)=CC(C(C)(C)C)=C1O VUDTWHRFAOFPBL-UHFFFAOYSA-N 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-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
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- OTCWVYFQGYOYJO-UHFFFAOYSA-N 1-o-methyl 10-o-(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate Chemical compound COC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 OTCWVYFQGYOYJO-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- VEPOHXYIFQMVHW-XOZOLZJESA-N 2,3-dihydroxybutanedioic acid (2S,3S)-3,4-dimethyl-2-phenylmorpholine Chemical compound OC(C(O)C(O)=O)C(O)=O.C[C@H]1[C@@H](OCCN1C)c1ccccc1 VEPOHXYIFQMVHW-XOZOLZJESA-N 0.000 description 1
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 1
- BGCSUUSPRCDKBQ-UHFFFAOYSA-N 2,4,8,10-tetraoxaspiro[5.5]undecane Chemical compound C1OCOCC21COCOC2 BGCSUUSPRCDKBQ-UHFFFAOYSA-N 0.000 description 1
- BVUXDWXKPROUDO-UHFFFAOYSA-N 2,6-di-tert-butyl-4-ethylphenol Chemical compound CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 BVUXDWXKPROUDO-UHFFFAOYSA-N 0.000 description 1
- GJDRKHHGPHLVNI-UHFFFAOYSA-N 2,6-ditert-butyl-4-(diethoxyphosphorylmethyl)phenol Chemical compound CCOP(=O)(OCC)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 GJDRKHHGPHLVNI-UHFFFAOYSA-N 0.000 description 1
- WSOMHEOIWBKOPF-UHFFFAOYSA-N 2,6-ditert-butyl-4-[(6-oxobenzo[c][2,1]benzoxaphosphinin-6-yl)methyl]phenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CP2(=O)C3=CC=CC=C3C3=CC=CC=C3O2)=C1 WSOMHEOIWBKOPF-UHFFFAOYSA-N 0.000 description 1
- FEXBEKLLSUWSIM-UHFFFAOYSA-N 2-Butyl-4-methylphenol Chemical compound CCCCC1=CC(C)=CC=C1O FEXBEKLLSUWSIM-UHFFFAOYSA-N 0.000 description 1
- HXIQYSLFEXIOAV-UHFFFAOYSA-N 2-tert-butyl-4-(5-tert-butyl-4-hydroxy-2-methylphenyl)sulfanyl-5-methylphenol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1SC1=CC(C(C)(C)C)=C(O)C=C1C HXIQYSLFEXIOAV-UHFFFAOYSA-N 0.000 description 1
- PFANXOISJYKQRP-UHFFFAOYSA-N 2-tert-butyl-4-[1-(5-tert-butyl-4-hydroxy-2-methylphenyl)butyl]-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(CCC)C1=CC(C(C)(C)C)=C(O)C=C1C PFANXOISJYKQRP-UHFFFAOYSA-N 0.000 description 1
- GPNYZBKIGXGYNU-UHFFFAOYSA-N 2-tert-butyl-6-[(3-tert-butyl-5-ethyl-2-hydroxyphenyl)methyl]-4-ethylphenol Chemical compound CC(C)(C)C1=CC(CC)=CC(CC=2C(=C(C=C(CC)C=2)C(C)(C)C)O)=C1O GPNYZBKIGXGYNU-UHFFFAOYSA-N 0.000 description 1
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 1
- YLUZWKKWWSCRSR-UHFFFAOYSA-N 3,9-bis(8-methylnonoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCC(C)C)OCC21COP(OCCCCCCCC(C)C)OC2 YLUZWKKWWSCRSR-UHFFFAOYSA-N 0.000 description 1
- 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 1
- ZDZYGYFHTPFREM-UHFFFAOYSA-N 3-[3-aminopropyl(dimethoxy)silyl]oxypropan-1-amine Chemical compound NCCC[Si](OC)(OC)OCCCN ZDZYGYFHTPFREM-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- QRLSTWVLSWCGBT-UHFFFAOYSA-N 4-((4,6-bis(octylthio)-1,3,5-triazin-2-yl)amino)-2,6-di-tert-butylphenol Chemical compound CCCCCCCCSC1=NC(SCCCCCCCC)=NC(NC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=N1 QRLSTWVLSWCGBT-UHFFFAOYSA-N 0.000 description 1
- PRWJPWSKLXYEPD-UHFFFAOYSA-N 4-[4,4-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butan-2-yl]-2-tert-butyl-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(C)CC(C=1C(=CC(O)=C(C=1)C(C)(C)C)C)C1=CC(C(C)(C)C)=C(O)C=C1C PRWJPWSKLXYEPD-UHFFFAOYSA-N 0.000 description 1
- KGCQNRKGLJTDKT-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-dibutyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-dibutylphenol Chemical compound CCCCC1=C(O)C(CCCC)=CC(CC=2C(=C(CC=3C=C(CCCC)C(O)=C(CCCC)C=3)C(C)=C(CC=3C=C(CCCC)C(O)=C(CCCC)C=3)C=2C)C)=C1 KGCQNRKGLJTDKT-UHFFFAOYSA-N 0.000 description 1
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 1
- NLRVQGZDJHUKOM-UHFFFAOYSA-N 6-methyl-4,6-bis(octylsulfanylmethoxy)cyclohexa-1,3-dien-1-ol Chemical compound C(CCCCCCC)SCOC1(CC(=CC=C1O)OCSCCCCCCCC)C NLRVQGZDJHUKOM-UHFFFAOYSA-N 0.000 description 1
- ADRNSOYXKABLGT-UHFFFAOYSA-N 8-methylnonyl diphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OCCCCCCCC(C)C)OC1=CC=CC=C1 ADRNSOYXKABLGT-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000004255 Butylated hydroxyanisole Substances 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- XEJHAXPBSKXOMR-UHFFFAOYSA-N CC[Ca] Chemical compound CC[Ca] XEJHAXPBSKXOMR-UHFFFAOYSA-N 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 1
- 101000576320 Homo sapiens Max-binding protein MNT Proteins 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920003189 Nylon 4,6 Polymers 0.000 description 1
- 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 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- 229920006121 Polyxylylene adipamide Polymers 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000007983 Tris buffer Substances 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
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- MMCPOSDMTGQNKG-UHFFFAOYSA-N anilinium chloride Chemical compound Cl.NC1=CC=CC=C1 MMCPOSDMTGQNKG-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052626 biotite Inorganic materials 0.000 description 1
- RSOILICUEWXSLA-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 RSOILICUEWXSLA-UHFFFAOYSA-N 0.000 description 1
- GVIVHQUGNYOZCA-UHFFFAOYSA-N bis(2,6-ditert-butyl-4-methylphenyl) hydrogen phosphite Chemical compound CC(C)(C)C1=CC(C)=CC(C(C)(C)C)=C1OP(O)OC1=C(C(C)(C)C)C=C(C)C=C1C(C)(C)C GVIVHQUGNYOZCA-UHFFFAOYSA-N 0.000 description 1
- SXXILWLQSQDLDL-UHFFFAOYSA-N bis(8-methylnonyl) phenyl phosphite Chemical compound CC(C)CCCCCCCOP(OCCCCCCCC(C)C)OC1=CC=CC=C1 SXXILWLQSQDLDL-UHFFFAOYSA-N 0.000 description 1
- 235000019282 butylated hydroxyanisole Nutrition 0.000 description 1
- CZBZUDVBLSSABA-UHFFFAOYSA-N butylated hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1.COC1=CC=C(O)C=C1C(C)(C)C CZBZUDVBLSSABA-UHFFFAOYSA-N 0.000 description 1
- 229940043253 butylated hydroxyanisole Drugs 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000012241 calcium silicate Nutrition 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- VZFUCHSFHOYXIS-UHFFFAOYSA-N cycloheptane carboxylic acid Natural products OC(=O)C1CCCCCC1 VZFUCHSFHOYXIS-UHFFFAOYSA-N 0.000 description 1
- GVJHHUAWPYXKBD-UHFFFAOYSA-N d-alpha-tocopherol Natural products OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- JFHGLVIOIANSIN-UHFFFAOYSA-N dimethyl butanedioate;1-(2-hydroxyethyl)-2,2,6,6-tetramethylpiperidin-4-ol Chemical compound COC(=O)CCC(=O)OC.CC1(C)CC(O)CC(C)(C)N1CCO JFHGLVIOIANSIN-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical class [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 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
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 150000002691 malonic acids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000009840 oxygen flask method Methods 0.000 description 1
- 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 1
- 229910052628 phlogopite Inorganic materials 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- BPILDHPJSYVNAF-UHFFFAOYSA-M sodium;diiodomethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(I)I BPILDHPJSYVNAF-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- NZNAAUDJKMURFU-UHFFFAOYSA-N tetrakis(2,2,6,6-tetramethylpiperidin-4-yl) butane-1,2,3,4-tetracarboxylate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CC(C(=O)OC1CC(C)(C)NC(C)(C)C1)C(C(=O)OC1CC(C)(C)NC(C)(C)C1)CC(=O)OC1CC(C)(C)NC(C)(C)C1 NZNAAUDJKMURFU-UHFFFAOYSA-N 0.000 description 1
- 229960000984 tocofersolan Drugs 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000002076 α-tocopherol Substances 0.000 description 1
- 235000004835 α-tocopherol Nutrition 0.000 description 1
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 description 1
Abstract
Description
本発明は、成形品外観、耐候性、機械的性質を損なうことなく、押出機や射出成形機のスクリュー、シリンダーおよび金型等の更なる長期使用を可能とする黒着色ポリアミド樹脂組成物に関する。 The present invention relates to a black-colored polyamide resin composition that enables further long-term use of screws, cylinders, molds and the like of extruders and injection molding machines without impairing the appearance, weather resistance, and mechanical properties of molded articles.
ポリアミド樹脂は、機械的及び熱的性質並びに耐油性に優れているため、自動車や電気・電子製品等の部品に広く用いられている。また、ポリアミド樹脂にガラス繊維を配合した強化ポリアミド樹脂は、機械的特性、耐熱性、耐薬品性等が大きく向上することにより、従来金属製であった部品を、軽量化および工程の合理化等の観点から強化ポリアミド樹脂製とすることも可能となり、近年積極的に検討が進められている。
特に、ガラス繊維単独、又はガラス繊維と他の無機充填材とを併用し、高濃度に配合した強化ポリアミド材料は、得られる成形品が高い剛性を有するばかりでなく、その組み合わせにより、成形品の表面平滑性を高めたり、振動特性に優れた材料が得られるために、幅広い用途に利用されている。
Polyamide resins are widely used in parts such as automobiles and electrical / electronic products because they are excellent in mechanical and thermal properties and oil resistance. Reinforced polyamide resin with glass fiber blended with polyamide resin greatly improves mechanical properties, heat resistance, chemical resistance, etc. From the viewpoint, it can be made of reinforced polyamide resin and has been actively studied in recent years.
In particular, a reinforced polyamide material containing glass fiber alone or a combination of glass fiber and another inorganic filler and blended at a high concentration is not only high in rigidity, but the combination of the resulting molded product Since materials having excellent surface smoothness and vibration characteristics can be obtained, they are used in a wide range of applications.
また、光沢性や耐候性を高めるためにニグロシン系化合物やカーボンブラック等の配合による黒色着色例が報告されている。
ポリアミド樹脂とニグロシン系化合物を配合した具体例として、半芳香族ポリアミドと脂肪族ポリアミド混合ポリアミドにガラス繊維、ワラストナイト、特定のカーボンブラック、銅化合物、アジン系染料を配合した組成物により、成形品光沢や漆黒度に優れ、且つ、屋外、特に降雨に曝される使用条件下でも、黒色の退色が少なく、ガラス繊維の浮きがない成形品を得ることができる低耐候変色で、機械的物性に優れた成形品を得ることができる組成物が開示されている。（例えば、特許文献１参照。）
Moreover, in order to improve glossiness and weather resistance, black coloring examples by blending a nigrosine compound, carbon black and the like have been reported.
As a specific example of blending a polyamide resin and a nigrosine compound, molding is performed with a composition in which a glass fiber, wollastonite, specific carbon black, a copper compound, and an azine dye are blended with a semi-aromatic polyamide and an aliphatic polyamide mixed polyamide. It has excellent luster and jetness, and has low weathering discoloration that can produce molded products with little black fading and no glass fiber floats even under outdoor conditions, especially under exposure to rain. The composition which can obtain the molded article excellent in is disclosed. (For example, refer to Patent Document 1.)
また、結晶性樹脂中に繊維状補強材と硫酸および／または燐酸でニグロシンを処理することにより得られる水不溶性のニグロシン系化合物を配合することにより、結晶性樹脂の成形中の流動性が良好でその成形精度に優れ、その成形物の表面光沢度等の外観及び表面形状が良好に改善される組成物が開示されている。（例えば、特許文献２参照。）
しかしながら、いずれの樹脂組成物も、加工装置の長期使用性に関しては触れられていない。
In addition, the water-insoluble nigrosine compound obtained by treating nigrosine with a fibrous reinforcing material and sulfuric acid and / or phosphoric acid in the crystalline resin improves the flowability during the molding of the crystalline resin. There has been disclosed a composition that is excellent in molding accuracy and in which appearance and surface shape such as surface glossiness of the molded article are improved satisfactorily. (For example, see Patent Document 2.)
However, none of the resin compositions is mentioned regarding the long-term usability of the processing apparatus.
本発明は、成形品外観、耐候性、機械的性質を損なうことなく、押出機や射出成形機のスクリュー、シリンダーおよび金型の更なる長期使用を可能にする黒着色ポリアミド樹脂組成物及びその成形品を提供することを目的とする。 The present invention relates to a black-colored polyamide resin composition that enables further long-term use of screws, cylinders, and molds of an extruder or an injection molding machine without impairing the appearance, weather resistance, and mechanical properties of the molded article, and molding thereof. The purpose is to provide goods.
本発明者は、上記課題を解決するために鋭意研究を重ねた結果、特定の末端基比率を持つポリアミド樹脂に特定の塩素濃度を有するニグロシンを配合させた組成物及びその成形品が、前記発明課題を達成し得ることを見出し、本発明を完成させるに至った。
即ち、本発明は以下に記載する通りのものである。
As a result of intensive research in order to solve the above-mentioned problems, the present inventor has obtained a composition in which a nigrosine having a specific chlorine concentration is blended with a polyamide resin having a specific end group ratio, and a molded product thereof. The present inventors have found that the problems can be achieved and have completed the present invention.
That is, the present invention is as described below.
（１）末端カルボキシル基濃度[ＣＯＯＨ]と末端アミノ基濃度[ＮＨ2]の関係が０．５＜[ＣＯＯＨ]／（[ＣＯＯＨ]＋[ＮＨ2]）＜０．８であるポリアミド樹脂１００重量部に対して、（Ｂ）含有塩素濃度が５０００ｐｐｍ以下であるニグロシンを０．０１〜１０重量部含むことを特徴とする黒着色ポリアミド樹脂組成物。
（２）（Ａ）ポリアミド樹脂が、（ａ１）半芳香族ポリアミドおよび／または（ａ２）脂肪族ポリアミドからなるポリアミドであることを特徴とする（１）記載の黒着色ポリアミド樹脂組成物。
（３）（１）または（２）記載の黒着色ポリアミド樹脂組成物３０〜９５重量％と、（Ｃ）無機充填材５〜７０重量％からなることを特徴とする黒着色ポリアミド樹脂組成物。
（４）前記（Ｃ）無機充填材が、下記（ｃ−１）と（ｃ−２）から構成され、且つ、（ｃ−１）に対する（ｃ−２）の重量比が０．２〜３の範囲にあることを特徴とする（３）記載の黒着色ポリアミド樹脂組成物。
（ｃ−１）ガラス繊維
（ｃ−２）ワラストナイト、タルク、カオリン、マイカから選ばれる少なくとも１種の無機充填材
（５）（１）または（２）記載の黒着色ポリアミド樹脂組成物６０〜９９.５重量％と、（Ｄ）カーボンブラック０.０５〜４０重量％からなることを特徴とする黒着色ポリアミド樹脂組成物。
(1) Polyamide resin 100 weight in which the relationship between terminal carboxyl group concentration [COOH] and terminal amino group concentration [NH 2 ] is 0.5 <[COOH] / ([COOH] + [NH 2 ]) <0.8 The black coloring polyamide resin composition characterized by including 0.01-10 weight part of nigrosine whose (B) containing chlorine concentration is 5000 ppm or less with respect to a part.
(2) The black colored polyamide resin composition according to (1), wherein the (A) polyamide resin is a polyamide comprising (a1) a semi-aromatic polyamide and / or (a2) an aliphatic polyamide.
(3) A black colored polyamide resin composition comprising 30 to 95% by weight of the black colored polyamide resin composition according to (1) or (2) and (C) 5 to 70% by weight of an inorganic filler.
(4) The (C) inorganic filler is composed of the following (c-1) and (c-2), and the weight ratio of (c-2) to (c-1) is 0.2-3. The black colored polyamide resin composition according to (3), which is in the range of
(C-1) Glass fiber (c-2) At least one inorganic filler selected from wollastonite, talc, kaolin and mica (5) The black colored polyamide resin composition 60 according to (1) or (2) A black-colored polyamide resin composition comprising ˜99.5% by weight and (D) 0.05 to 40% by weight of carbon black.
（６）（３）または（４）記載の黒着色ポリアミド樹脂組成物９０〜９９.５重量％と、（Ｄ）カーボンブラック０.０５〜１０重量％からなることを特徴とする黒着色ポリアミド樹脂組成物。
（７）（Ｄ）カーボンブラックのアグリゲート径が５０〜１２０ｎｍ、一次粒子径が２０ｎｍ以下であることを特徴とする（５）または（６）記載載の黒着色ポリアミド樹脂組成物。
（８）（１）〜（７）記載の黒着色ポリアミド樹脂組成物１００重量部と、（Ｅ）有機系０．０１〜０．５重量部からなることを特徴とする黒着色ポリアミド樹脂組成物。
（９）（１）〜（８）に記載の黒着色ポリアミド樹脂組成物を成形して得られる成形体。
（１０）黒着色ポリアミド樹脂組成物が、アウターハンドル、アウタードアハンドル、ホイールキャップ、ルーフレール、ドアミラーベース、ルームミラーアーム、サンルーフデフレクター、ラジエーターファン、ラジエーターグリル、ベアリングリテーナー、コンソールボックス、サンバイザーアーム、スポイラー、スライドドアレールカバー、机及び椅子の脚、座受け、肘掛け、車椅子部品、ドアハンドル、手摺り、浴室等の握り棒または窓用ノブの成形材料として用いられることを特徴とする（１）〜（８）のいずれかに記載の黒着色ポリアミド樹脂組成物。
(6) A black colored polyamide resin comprising 90 to 99.5% by weight of the black colored polyamide resin composition according to (3) or (4) and (D) 0.05 to 10% by weight of carbon black Composition.
(7) The black colored polyamide resin composition according to (5) or (6), wherein (D) carbon black has an aggregate diameter of 50 to 120 nm and a primary particle diameter of 20 nm or less.
(8) A black colored polyamide resin composition comprising 100 parts by weight of the black colored polyamide resin composition according to (1) to (7) and (E) 0.01 to 0.5 part by weight of an organic system. .
(9) A molded product obtained by molding the black colored polyamide resin composition according to (1) to (8).
(10) The black colored polyamide resin composition has an outer handle, an outer door handle, a wheel cap, a roof rail, a door mirror base, a rear mirror arm, a sunroof deflector, a radiator fan, a radiator grill, a bearing retainer, a console box, a sun visor arm, and a spoiler. It is used as a molding material for sliding door rail covers, desk and chair legs, seats, armrests, wheelchair parts, door handles, handrails, bathroom grips, and knobs for windows (1) to ( The black colored polyamide resin composition according to any one of 8).
本発明の黒着色ポリアミド樹脂組成物は、成形品外観、耐候性、機械的性質を損なうことなく、押出機や射出成形機のスクリュー、シリンダーおよび金型の長期使用を可能にすることから、アウターハンドル、アウタードアハンドル、ホイールキャップ、ルーフレール、ドアミラーベース、ルームミラーアーム、サンルーフデフレクター、ラジエーターファン、ラジエーターグリル、ベアリングリテーナー、コンソールボックス、サンバイザーアーム、スポイラー、スライドドアレールカバー、机及び椅子の脚、座受け、肘掛け、車椅子部品、ドアハンドル、手摺り、浴室等の握り棒、窓用ノブ等の成形用材料として好適に用いることができる。 Since the black colored polyamide resin composition of the present invention enables long-term use of screws, cylinders and molds of extruders and injection molding machines without impairing the appearance, weather resistance, and mechanical properties of the molded product, Handle, outer door handle, wheel cap, roof rail, door mirror base, rear mirror arm, sunroof deflector, radiator fan, radiator grill, bearing retainer, console box, sun visor arm, spoiler, sliding door rail cover, desk and chair legs, seat It can be suitably used as a molding material for receiving parts, armrests, wheelchair parts, door handles, handrails, grip bars for bathrooms, window knobs, and the like.
以下に本発明を詳しく説明する。
本発明の（Ａ）ポリアミド樹脂の具体例としては、ポリアミド６、ポリアミド６６、ポリアミド４６、ポリアミド１１，ポリアミド１２，ポリアミド６１０、ポリアミド６１２、ポリアミド６／６６、ポリアミド６／６１２、ポリアミドＭＸＤ，６（ＭＸＤ：ｍ−キシリレンジアミン）、ポリアミド６／ＭＸＤ，６、ポリアミド６６／ＭＸＤ６、ポリアミド６Ｔ、ポリアミド６Ｉ、ポリアミド６／６Ｔ、ポリアミド６／６Ｉ、ポリアミド６６／６Ｔ、ポリアミド６６／６Ｉ、ポリアミド６／６Ｔ／６Ｉ、ポリアミド６６／６Ｔ／６Ｉ、ポリアミド６／１２／６Ｔ、ポリアミド６６／１２／６Ｔ、ポリアミド６／１２／６Ｉ、ポリアミド６６／１２／６Ｉなどが挙げられ、複数のポリアミドを押出機等で共重合化したポリアミド類も使用することができる。
これらは、もちろん２種以上組み合わせて使用しても構わない。
The present invention is described in detail below.
Specific examples of the polyamide resin (A) of the present invention include polyamide 6, polyamide 66, polyamide 46, polyamide 11, polyamide 12, polyamide 610, polyamide 612, polyamide 6/66, polyamide 6/612, polyamide MXD, 6 ( MXD: m-xylylenediamine), polyamide 6 / MXD, 6, polyamide 66 / MXD6, polyamide 6T, polyamide 6I, polyamide 6 / 6T, polyamide 6 / 6I, polyamide 66 / 6T, polyamide 66 / 6I, polyamide 6 / 6T / 6I, polyamide 66 / 6T / 6I, polyamide 6/12 / 6T, polyamide 66/12 / 6T, polyamide 6/12 / 6I, polyamide 66/12 / 6I, etc. Polyamides copolymerized with Can.
Of course, two or more of these may be used in combination.
本発明の（Ａ）ポリアミド樹脂として、特に好ましい例としては、（ａ１）半芳香族ポリアミドおよび／または（ａ２）脂肪族ポリアミドからなるポリアミドであって、（ａ１）半芳香族ポリアミドとしては、結晶性半芳香族ポリアミド、又は結晶性半芳香族ポリアミドと非晶性半芳香族ポリアミドとの混合物のいずれの場合も本発明に用いることができる。
本発明において特に好ましい半芳香族ポリアミド（ａ１）の例としては６６成分が６０〜９５重量％、６成分が０〜１０重量％及び６Ｉ成分が５〜４０重量％の範囲であるポリアミド６６／６／６Ｉ共重合体を挙げることができる。
６Ｉ成分は、成形品外観、耐候性に優れた成形品を得るという観点から、５重量％以上が好ましく、成形時の生産性の観点から、４０重量％以下が好ましい。
また、６成分は、吸水による機械的特性、熱時の剛性の観点から、１０重量％以下であることが好ましい。
Particularly preferred examples of the (A) polyamide resin of the present invention include (a1) a semi-aromatic polyamide and / or (a2) a polyamide comprising an aliphatic polyamide, and (a1) a semi-aromatic polyamide includes crystals. Any of the crystalline semi-aromatic polyamide or the mixture of the crystalline semi-aromatic polyamide and the amorphous semi-aromatic polyamide can be used in the present invention.
Examples of particularly preferred semi-aromatic polyamides (a1) in the present invention are polyamide 66/6 in which 66 component is in the range of 60 to 95% by weight, 6 component is in the range of 0 to 10% by weight and 6I component is in the range of 5 to 40% by weight. / 6I copolymer.
The 6I component is preferably 5% by weight or more from the viewpoint of obtaining a molded article having excellent appearance and weather resistance, and preferably 40% by weight or less from the viewpoint of productivity during molding.
Moreover, it is preferable that 6 components is 10 weight% or less from a viewpoint of the mechanical characteristic by water absorption and the rigidity at the time of a heat | fever.
次に脂肪族ポリアミド（ａ２）について説明する。これらの例としてはポリアミド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６６／６共重合体、またはこれらのブレンド物等が挙げられる。
好ましくはポリアミド６、ポリアミド６１０、ポリアミド６１２、ポリアミド１２、ポリアミド６６／６共重合体、またはこれらのブレンド物等であり、これらのポリアミドを用いることにより、ガラス繊維及び無機フィラーの配合量が多い場合においても、外観の良好な成形品を得ることができる。
Next, the aliphatic polyamide (a2) will be described. Examples thereof include polyamide 6, polyamide 66, polyamide 610, polyamide 612, polyamide 11, polyamide 12, polyamide 66/6 copolymer, or a blend thereof.
Preferred are polyamide 6, polyamide 610, polyamide 612, polyamide 12, polyamide 66/6 copolymer, or blends thereof. When these polyamides are used, the amount of glass fiber and inorganic filler is large. In this case, a molded product having a good appearance can be obtained.
本発明に用いるポリアミド（Ａ）の好ましいポリアミドの末端カルボキシル基濃度[ＣＯＯＨ]と末端アミノ基濃度[ＮＨ2]との関係は、成形性、成形品外観の観点から、[ＣＯＯＨ]／（[ＣＯＯＨ]＋[ＮＨ2]）が０．５より大きく、加工装置の更なる長期使用の観点から０．８より小さいことが好ましい。 The relationship between the terminal carboxyl group concentration [COOH] and the terminal amino group concentration [NH 2 ] of the preferred polyamide of the polyamide (A) used in the present invention is [COOH] / ([COOH] from the viewpoint of moldability and molded product appearance. ] + [NH 2 ]) is preferably larger than 0.5 and smaller than 0.8 from the viewpoint of further long-term use of the processing apparatus.
本発明に用いるポリアミド樹脂の末端基濃度の制御方法としては、公知の方法を用いることができ、例えば重合時にモノカルボン酸、ジカルボン酸又はモノアミンを所定量添加することが挙げられる。具体的な例としては、酢酸、カプリル酸、カプロン酸、ウンデカン酸、ステアリン酸等の脂肪族モノカルボン酸、シクロヘキサンカルボン酸、メチルシクロカルボン酸等の脂環式モノカルボン酸、安息香酸等の芳香族モノカルボン酸、マロン酸、コハク酸、アジピン酸等の脂肪族ジカルボン酸、ヘキシルアミン、オクチルアミン、デシルアミン等の脂肪族モノアミンが利用できる。 As a method for controlling the terminal group concentration of the polyamide resin used in the present invention, a known method can be used. For example, a predetermined amount of monocarboxylic acid, dicarboxylic acid or monoamine is added during polymerization. Specific examples include aliphatic monocarboxylic acids such as acetic acid, caprylic acid, caproic acid, undecanoic acid and stearic acid, alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid and methylcyclocarboxylic acid, and aromatics such as benzoic acid. Aliphatic monocarboxylic acids, malonic acids, aliphatic dicarboxylic acids such as succinic acid and adipic acid, and aliphatic monoamines such as hexylamine, octylamine and decylamine can be used.
本発明に用いるポリアミドの分子量は、機械的特性、成形性、表面光沢性の観点から、硫酸溶液粘度ηｒ（９５．５％硫酸１００ｍｌにポリマー１ｇを溶解し、オストワルト型粘度計を用いて２５℃で測定する。）で１．５〜３．５、好ましくは１．８〜３．０、更に好ましくは、２．０〜２．８である。 The molecular weight of the polyamide used in the present invention is determined from the viewpoints of mechanical properties, moldability, and surface gloss, by dissolving the sulfuric acid solution viscosity ηr (1 g of polymer in 100 ml of 95.5% sulfuric acid at 25 ° C using an Ostwald viscometer 1.5) to 3.5, preferably 1.8 to 3.0, and more preferably 2.0 to 2.8.
本発明の（Ｂ）成分であるニグロシンとしては、ＣＯＬＯＲ ＩＮＤＥＸにＣ．Ｉ．ＳＯＬＶＥＮＴ ＢＬＡＣＫ ５及びＣ．Ｉ．ＳＯＬＶＥＮＴＢＬＡＣＫ ７として記載されているような黒色アジン系縮合混合物を用いることができる。その合成は、例えば、アニリン、アニリン塩酸塩及びニトロベンゼンを、塩化鉄の存在下、反応温度１６０乃至１８０℃で酸化及び脱水縮合することにより得られる。 As nigrosine which is the component (B) of the present invention, COLOR INDEX and C.I. I. SOLVENT BLACK 5 and C.I. I. A black azine-based condensation mixture such as that described as SOLVENTBLACK 7 can be used. The synthesis can be obtained, for example, by oxidizing and dehydrating condensation of aniline, aniline hydrochloride and nitrobenzene at a reaction temperature of 160 to 180 ° C. in the presence of iron chloride.
ニグロシンは、種々の異なる化合物の混合物として生成するが、各種のトリフェナジンオキサジン及びフェナジンアジン等のアジン系化合物の混合物と推定されている。
本発明におけるニグロシンに含有される塩素濃度としては、加工装置の長期使用の観点から、５０００ｐｐｍ以下が好ましい。ここでいうニグロシンに含有される塩素濃度とは、イオンクロマトグラフィーにより分析、測定した塩素濃度である。
Nigrosine is produced as a mixture of various different compounds, and is assumed to be a mixture of various azine compounds such as triphenazine oxazine and phenazine azine.
The chlorine concentration contained in nigrosine in the present invention is preferably 5000 ppm or less from the viewpoint of long-term use of the processing apparatus. The chlorine concentration contained in nigrosine here is the chlorine concentration analyzed and measured by ion chromatography.
また、本発明におけるニグロシン（Ｂ）の添加量は、ポリアミド（Ａ）１００重量部に対して０．０１〜１０重量部である。
本発明におけるニグロシンの添加量は、成形品の光沢性の観点から、０．０１重量部以上、加工装置の長期使用の観点から、１０重量部以下が好ましい。更に好ましくは、０.０１〜１重量部である。
Moreover, the addition amount of nigrosine (B) in this invention is 0.01-10 weight part with respect to 100 weight part of polyamide (A).
The addition amount of nigrosine in the present invention is preferably 0.01 parts by weight or more from the viewpoint of gloss of the molded product, and 10 parts by weight or less from the viewpoint of long-term use of the processing apparatus. More preferably, the content is 0.01 to 1 part by weight.
本発明の（Ｃ）成分である無機充填材は、ガラス繊維、炭素繊維、マイカ、タルク、カオリン、ウオラストナイト、炭酸カルシウム、チタン酸カリウム等から選ばれる少なくとも１種の無機充填材であり、特に（ｃ−１）ガラス繊維と（ｃ−２）ワラストナイト、タルク、カオリン、マイカから選ばれる少なくとも１種の無機充填材を併用することが好ましい。 The inorganic filler which is the component (C) of the present invention is at least one inorganic filler selected from glass fiber, carbon fiber, mica, talc, kaolin, wollastonite, calcium carbonate, potassium titanate and the like, In particular, it is preferable to use (c-1) glass fiber and (c-2) at least one inorganic filler selected from wollastonite, talc, kaolin and mica.
無機充填材は、ポリアミドとの接着性を向上させる目的で従来公知の表面処理剤で表面処理して用いてもかまわない。表面処理剤の種類としてはアミノ基やエポキシ基を含有するシラン系カップリング剤やチタネート系カップリング剤等を例示できる。このような表面処理剤は、予め無機充填材表面に処理することもできるし、ポリアミドと無機充填材を混合する際に添加してもかまわない。 The inorganic filler may be used after surface treatment with a conventionally known surface treatment agent for the purpose of improving the adhesion to polyamide. Examples of the surface treatment agent include silane coupling agents and titanate coupling agents containing amino groups and epoxy groups. Such a surface treating agent can be pretreated on the surface of the inorganic filler, or may be added when the polyamide and the inorganic filler are mixed.
本発明で用いられる（ｃ−１）ガラス繊維は、通常熱可塑性樹脂に使用されているものを使うことができ、繊維径や長さに特に制限はなく、例えば平均繊維径が５〜３０μｍのチョップドストランド、ロービング、ミルドファイバーのいずれでも良い。チョップドストランドを用いる場合には、その長さが０．１から６ｍｍの範囲で適宜選択すればよい。
これらのガラス繊維は、またその表面に通常公知の集束剤やシラン系カップリング剤を付着させたものを用いることも好ましく利用できる。例えばγ−アミノプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、Ｎ−β（アミノエチル）−γ−アミノプロピルトリメトキシシラン、ビニルトリエトキシシラン、γ−グリシドキシプロピルトリメトキシシランなどを利用できる。
As the (c-1) glass fiber used in the present invention, those usually used in thermoplastic resins can be used, and there is no particular limitation on the fiber diameter and length, for example, the average fiber diameter is 5 to 30 μm. Any of chopped strand, roving, and milled fiber may be used. When using chopped strands, the length may be appropriately selected within the range of 0.1 to 6 mm.
For these glass fibers, it is also possible to preferably use a glass fiber with a generally known sizing agent or silane coupling agent attached to its surface. For example, use of γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, etc. it can.
本発明の（ｃ−２）成分は、ワラストナイト、タルク、カオリン、マイカから選ばれる少なくとも１種の無機充填材である。
ワラストナイトは、化学名がメタケイ酸カルシウムであり、白色針状結晶の鉱物である。通常、ＳｉＯ２を４０〜６０重量％、ＣａＯを４０〜５５重量％含有し、その他にＦｅ２Ｏ３、Ａｌ２Ｏ３、ＭｇＯ、Ｎａ２Ｏ、Ｋ２Ｏ等の成分を含有するものである。
The component (c-2) of the present invention is at least one inorganic filler selected from wollastonite, talc, kaolin and mica.
Wollastonite has the chemical name calcium metasilicate and is a mineral of white needle-like crystals. Usually, it contains 40 to 60% by weight of SiO 2 and 40 to 55% by weight of CaO, and additionally contains components such as Fe 2 O 3 , Al 2 O 3 , MgO, Na 2 O and K 2 O. is there.
ワラストナイトは、吸油量２０〜５０ｃｃ／１００ｇ、嵩比重が０．１〜１．０、繊維長が０．１〜１０００μｍ、繊維径が０．１〜５０μｍのものを用いることができる。
本発明におけるワラストナイトの平均粒子径は、成形品の表面外観の観点から、５０μｍ以下が好ましく、さらに好ましくは５〜３０μｍである。
Wollastonite having an oil absorption of 20 to 50 cc / 100 g, a bulk specific gravity of 0.1 to 1.0, a fiber length of 0.1 to 1000 μm, and a fiber diameter of 0.1 to 50 μm can be used.
The average particle diameter of wollastonite in the present invention is preferably 50 μm or less, more preferably 5 to 30 μm, from the viewpoint of the surface appearance of the molded product.
ここでいう、平均粒子径は、攪拌し、場合によっては更に超音波照射した純水中に透過率が８５％になるように分散させたワラストナイトをレーザ回折／散乱式粒度分布装置などを用いて導出する方法において粒度分布累積の５０％に相当する粒子径を示す。
尚、これらのワラストナイトは、天然に存在するものを粉砕、場合によっては分級したものでも、合成品でも使用できる。また、ハンター白色度が６０以上で、ポリアミドへの耐候性を悪化させない意味で高純水へ１０％スラリーとした際のスラリーのｐＨ値が６〜８のものを好ましく用いることができる。
As used herein, the average particle diameter is determined by using a laser diffraction / scattering particle size distribution device or the like for wollastonite that has been stirred and optionally further dispersed in pure water irradiated with ultrasonic waves so that the transmittance is 85%. The particle diameter corresponding to 50% of the cumulative particle size distribution in the method derived using the method is shown.
These wollastonites can be used in the form of pulverized, classified in some cases, or synthetic products. In addition, those having a Hunter whiteness of 60 or more and a pH value of 6 to 8 when the slurry is made into 10% slurry in high-purity water in the sense that the weather resistance to polyamide is not deteriorated can be preferably used.
さらに、本発明におけるワラストナイトは、ポリアミドとの接着性を向上させる目的で従来公知の表面処理剤で表面処理をして用いてもかまわない。表面処理剤の種類としてはアミノ基やエポキシ基を含有するシラン系カップリング剤やチタネート系カップリング剤等を例示できる。このような表面処理剤は、予めワラストナイト表面に処理することもできるし、ポリアミドとワラストナイトを混合する際に添加してもかまわない。
タルクは、４ＳｉＯ２・３ＭｇＯ・Ｈ２Ｏの化学式で表され、含水ケイ酸マグネシウムと呼ばれる。通常はタルク鉱石をさまざまな手法で粉砕し、０．１〜２０μｍ程度の粒子径のものがプラスチック用充填材として使用される。好ましいタルクの径は０．５〜５μｍである。
Furthermore, the wollastonite in the present invention may be used after surface treatment with a conventionally known surface treatment agent for the purpose of improving the adhesion to polyamide. Examples of the surface treatment agent include silane coupling agents and titanate coupling agents containing amino groups and epoxy groups. Such a surface treating agent can be pretreated on the surface of wollastonite, or may be added when the polyamide and wollastonite are mixed.
Talc is represented by a chemical formula of 4SiO 2 .3MgO.H 2 O and is called hydrous magnesium silicate. Usually, talc ore is pulverized by various methods, and those having a particle size of about 0.1 to 20 μm are used as plastic fillers. A preferable talc diameter is 0.5 to 5 μm.
カオリンは、化学組成がＡｌ２Ｓｉ２Ｏ５（ＯＨ）４で、２八面体型１：１層状の積み重なり方が異なるカオリナイト、ディッカイト、ナクライト、ハロイサイトがあるがいずれも使用することができる。通常、ポリアミドに配合するカオリンは脱水した構造の焼成カオリンが成形体の揮発成分を減少させることや、成形体加工時の安定性向上の観点から好ましい。粒子径は、通常０．１〜３μｍ程度のものが好適に用いられる。また、白色度の高いものほど成形体の色調への影響が少なく好ましい。 Kaolin has a chemical composition of Al 2 Si 2 O 5 (OH) 4 , and there are kaolinite, dickite, nacrite, and halloysite, which are different from each other in the two-octahedral 1: 1 layer stacking method, and any of them can be used. Usually, the kaolin blended with the polyamide is preferred from the viewpoint of reducing the volatile components of the molded body and improving the stability during processing of the molded body, because the calcined kaolin having a dehydrated structure. A particle size of usually about 0.1 to 3 μm is preferably used. Moreover, the higher the whiteness, the less the influence on the color tone of the molded product, which is preferable.
マイカは、産地や合成法により結晶構造や化学組成が異なるが特に限定されない。本発明に使用されるマイカの主成分はＳｉＯ２であり、結晶構造は、ＳｉＯ４四面体が六角網目の板状に連なり、この板が２枚で一組となっているものである。また、その板間に八面***をとるイオン（例えばＡｌ３＋、Ｍｇ２＋）がイオン結合している。これをタブレットといい、これが層をなして積み重なっており、タブレット間にアルカリ金属またはアルカリ土類金属のイオン（例えばＫ＋、Ｌｉ＋、Ｎａ＋）がイオン結合している。 Mica varies in crystal structure and chemical composition depending on the production area and synthesis method, but is not particularly limited. The main component of the mica used in the present invention is SiO 2 , and the crystal structure is such that the SiO 4 tetrahedron is connected in a hexagonal mesh plate shape, and this plate is a set of two sheets. Further, ions having octahedral positions (for example, Al 3+ , Mg 2+ ) are ionically bonded between the plates. This is called a tablet, which is stacked in layers, and ions of alkali metal or alkaline earth metal (for example, K + , Li + , Na + ) are ion-bonded between the tablets.
マイカには白雲母、金雲母、黒雲母、人造雲母などがあり、いずれを使用してもかまわないが、より白色に近い白雲母、人造雲母が好適に用いられる。マイカはタブレット間のイオン結合が弱いことからこれを利用して薄片状に粉砕される。この厚みの幅に対する比率が高いほど成形体の剛性を向上できるため、好ましく使用できる。通常粒子径としては、１〜３０μｍ程度のマイカが外観と剛性のバランスに優れるため好ましく用いることができる。 Mica includes muscovite, phlogopite, biotite, and artificial mica. Any of these may be used, but muscovite and artificial mica that are closer to white are preferably used. Mica is pulverized into flakes using the weak ionic bond between tablets. Since the rigidity of a molded object can be improved, so that the ratio with respect to the width | variety of this thickness is high, it can use preferably. In general, mica having a particle diameter of about 1 to 30 μm is preferably used because it has a good balance between appearance and rigidity.
本発明の（ｃ）無機充填材の配合量は５〜７０重量％であり、好ましくは１０〜６５重量％である。無機充填材の配合量は強度剛性の観点から、５重量％以上、樹脂組成物の流動性、成形品の表面光沢性の観点から７０重量％以下が好ましい。 The blending amount of the inorganic filler (c) of the present invention is 5 to 70% by weight, preferably 10 to 65% by weight. The blending amount of the inorganic filler is preferably 5% by weight or more from the viewpoint of strength rigidity and 70% by weight or less from the viewpoint of the fluidity of the resin composition and the surface gloss of the molded product.
本発明では、（Ｃ）無機充填材が（ｃ−１）ガラス繊維と（ｃ−２）ワラストナイト、タルク、カオリン、マイカから選ばれる少なくとも１種の無機充填材とを併用し、且つ（ｃ−１）に対する（ｃ−２）の重量比を０．２〜３とする。（ｃ−１）に対する（ｃ−２）の重量比は、屋外に暴露された場合のガラス繊維の浮きを抑制するという観点から、０．２以上、強度及び剛性の観点から、３以下が好ましい。 In the present invention, (C) the inorganic filler is a combination of (c-1) glass fiber and (c-2) at least one inorganic filler selected from wollastonite, talc, kaolin and mica, and ( The weight ratio of (c-2) to c-1) is 0.2-3. The weight ratio of (c-2) to (c-1) is preferably 0.2 or more and 3 or less from the viewpoint of strength and rigidity from the viewpoint of suppressing the float of the glass fiber when exposed outdoors. .
本発明の（Ｄ）成分であるカーボンブラックは、オイルファーネス法、ガスファーネス法、チャネル法又はサーマル法のいずれの製法で製造されたものも使用でき、特に限定されるものではない。
本発明におけるカーボンブラックは、アグリゲート径が５０〜１２０ｎｍ、一次粒子径が２０ｎｍ以下のものがしぼ平板と光沢平板の耐候暴露後の耐変色性（耐黒退色性）の観点から、好ましく用いられる。
本発明のカーボンブラックのアグリゲート径とは、電子顕微鏡で測定されるカーボンブラック凝集粒子の長径と短径を４００個以上の凝集体から測定し、円相当径に換算したものである。
The carbon black which is the component (D) of the present invention can be produced by any of the oil furnace method, gas furnace method, channel method or thermal method, and is not particularly limited.
In the present invention, carbon black having an aggregate diameter of 50 to 120 nm and a primary particle diameter of 20 nm or less is preferably used from the viewpoint of discoloration resistance (black fading resistance) after weathering exposure of grained and glossy flat plates. .
The aggregate diameter of the carbon black of the present invention is obtained by measuring the major axis and the minor axis of carbon black aggregated particles measured with an electron microscope from 400 or more aggregates and converting them to equivalent circle diameters.
本発明のカーボンブラックの一次粒子径は透過型もしくは走査型電子顕微鏡により観察し、視野内に観察されたカーボンブラックの一次粒子を４００個以上測定し、その平均により求めることができる。また、カーボンブラックは、日本工業規格Ｋ６２２１に定められた９５０℃で７分間加熱した際の減量（揮発分）が０．５〜５％、吸油量（ジブチルフタレートを用いた測定値）が５０〜１５０ｃｃ／１００ｇ、窒素吸着比表面積が１２０〜１５０ｍ２／ｇの範囲であるものを好ましく使用できる。 The primary particle diameter of the carbon black of the present invention can be determined by observing with a transmission or scanning electron microscope, measuring 400 or more primary particles of carbon black observed in the field of view, and averaging them. Carbon black has a weight loss (volatile content) of 0.5 to 5% when heated at 950 ° C. for 7 minutes as defined in Japanese Industrial Standard K6221, and an oil absorption (measured value using dibutyl phthalate) of 50 to 50%. Those having 150 cc / 100 g and a nitrogen adsorption specific surface area in the range of 120 to 150 m 2 / g can be preferably used.
本発明におけるカーボンブラックの添加量は、黒着色ポリアミド樹脂組成物に対して、０．０５〜４０重量％、無機充填材を配合した黒着色ポリアミド樹脂組成物に対しては、０．０５〜１０重量％が好ましい。カーボンブラックの添加量は、耐候性試験後のガラス繊維浮き上がりを抑制するという観点から、上記０．０５重量％以上、強度及び剛性の観点から、上記１０重量％以下が好ましい。 The addition amount of carbon black in the present invention is 0.05 to 40% by weight with respect to the black colored polyamide resin composition, and 0.05 to 10% with respect to the black colored polyamide resin composition containing the inorganic filler. % By weight is preferred. The amount of carbon black added is preferably 0.05% by weight or more and 10% by weight or less from the viewpoints of strength and rigidity from the viewpoint of suppressing glass fiber lift after the weather resistance test.
本発明の（Ｅ）成分である有機系熱安定剤は、必須成分ではないが、ポリアミド樹脂組成物の熱エージング性改良効果、特に成形品を高い温度で長期間放置した場合の機械的特性の低下を抑制したり、成形片表面の変色を抑制したりする作用効果を有するものであり、フェノール系安定剤、リン系安定剤、アミン系安定剤などが挙げられる。これらを二種以上併用してもよい。
本発明における有機熱安定剤の添加量は、黒着色ポリアミド樹脂組成物１００重量部に対して０．０１〜０．５重量部である。
The organic heat stabilizer which is the component (E) of the present invention is not an essential component, but the effect of improving the heat aging property of the polyamide resin composition, particularly the mechanical properties when the molded product is left at a high temperature for a long period of time. It has the effect of suppressing the decrease or discoloration of the surface of the molded piece, and examples thereof include phenol-based stabilizers, phosphorus-based stabilizers, and amine-based stabilizers. Two or more of these may be used in combination.
The addition amount of the organic heat stabilizer in the present invention is 0.01 to 0.5 parts by weight with respect to 100 parts by weight of the black colored polyamide resin composition.
具体的にはフェノール系安定剤としては、ヒンダードフェノール系化合物を好適に用いることができる。例えば、トリエチレングリコール−ビス［３−（３−ｔ−ブチル−５−メチル−４−ヒドロキシフェニル）プロピオネート、４，４‘−ブチリデンビス（３−メチル−６−ｔ−ブチルフェノール）、１，６−ヘキサンジオール−ビス［３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート、２，４−ビス−（ｎ−オクチルチオ）−６−（４−ヒドロキシ−３，５−ジ−ｔ−ブチルアニリノ）−１，３，５−トリアジン、ペンタエリスリチル−テトラキス［３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、２，２―チオ−ジエチレンビス［３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、オクタデシル−３−（３，５―ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネートを例示できる。 Specifically, a hindered phenol compound can be suitably used as the phenol stabilizer. For example, triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate, 4,4′-butylidenebis (3-methyl-6-t-butylphenol), 1,6- Hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di- t-butylanilino) -1,3,5-triazine, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3 -(3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxypheny ) Propionate can be exemplified.
また、２，２−チオビス（４−メチル−６−１−ブチルフェノール）、Ｎ，Ｎ’−ヘキサメチレンビス（３，５−ジ−ｔ−ブチル−４−ヒドロキシンナマミド）、３，５―ジ−ｔ−ブチル−４−ヒドロキシーベンジルフォスファスフォネート−ジエチルエステル、１，３，５−トリメチル−２，４、６―トリス（３，５−ジ−ブチル−４−ヒドロキシベンジル）ベンゼン、ビス（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジルスルホン酸エチルカルシウム、トリス−（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）−イソシアヌレイト、２，６−ジ−ｔ―ブチルーｐ―クレゾール、ブチル化ヒドロキシアニソール、２，６−ジ−ｔ―ブチルー４−エチルフェノール、ステアリルーβ−（３，５−ジ−ｔ−ブチルー４−ヒドロキシフェニル）プロピオネートである。 In addition, 2,2-thiobis (4-methyl-6-1-butylphenol), N, N′-hexamethylenebis (3,5-di-tert-butyl-4-hydroxynnamamide), 3,5- Di-t-butyl-4-hydroxy-benzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-butyl-4-hydroxybenzyl) benzene, Ethyl calcium bis (3,5-di-t-butyl-4-hydroxybenzylsulfonate, tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, 2,6-di- t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, stearyl-β- (3,5-di-t-butyl-4-hydroxyl Nil) is a propionate.
また、２，２‘−メチレンビス−（４−メチル−６−ｔ−ブチルフェノール）、２，２’―メチレンービス−（４−エチル−６−ｔ−ブチルフェノール）、４，４‘―チオビス−（３−メチル−６−ｔ―ブチルフェノール）、オクチル化ジフェニルアミン、２，４−ビス［（オクチルチオ）メチル］−Ｏ−クレゾール、イソオクチル−３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート、４，４’−ブチリデンビス（３−メチル−６−ｔ−ブチルフェノール、３，９−ビス［１，１−ジメチル−２−［β−（３−ｔ−ブチル−４−ヒドロキシ−５−メチルフェニル）プロピオニルオキシ］エチル］２，４，８，１０−テトラオキサスピロ［５，５］ウンデカンである。 In addition, 2,2′-methylenebis- (4-methyl-6-tert-butylphenol), 2,2′-methylenebis- (4-ethyl-6-tert-butylphenol), 4,4′-thiobis- (3- Methyl-6-tert-butylphenol), octylated diphenylamine, 2,4-bis [(octylthio) methyl] -O-cresol, isooctyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate 4,4′-butylidenebis (3-methyl-6-tert-butylphenol, 3,9-bis [1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) ) Propionyloxy] ethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane.
また、１，１，３−トリス（２−メチル−４−ヒドロキシ−５−ｔ−ブチルフェニル）ブタン、１，３，５−トリメチル−２，４，６−トリス（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）ベンゼン、ビス［３，３‘−ビス−（４’−ヒドロキシー３‘−Ｔ−ブチルフェニル）ブチリックアシッド］グリコールエステル、１，３，５−トリス（３’，５‘−ジ−ｔ−ブチルー４’―ヒドロキシベンジル）−ｓｅｃ−トリアジン−２，４，６―（１Ｈ，３Ｈ，５Ｈ）トリオン、ｄ−α−トコフェロールなどを例示することができる。
またリン系安定剤としては、有機リン系化合物を好適に用いることができる。例えば、テトラキス（２，４−ジ−ｔ−ブチルフェニル）−４，４‘−ビフェニレンフォスフォナイト、ビス（２，６−ジ−ｔ−ブチル−４−メチルフェニル）ペンタエリスリトール−ジ−ホスファイト、２，２−メチレンビス（４，６−ジ−ｔ−ブチルフェニル）オクチルホスファイト、トリフェニルホスファイト、トリス（２，４−ジ−ｔ―ブチルフェニル）フォスファイト、ジフェニルイソデシルフォスファイト、フェニルジイソデシルフォスファイトである。
In addition, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t -Butyl-4-hydroxybenzyl) benzene, bis [3,3′-bis- (4′-hydroxy-3′-T-butylphenyl) butyric acid] glycol ester, 1,3,5-tris (3 ′, Examples thereof include 5′-di-t-butyl-4′-hydroxybenzyl) -sec-triazine-2,4,6- (1H, 3H, 5H) trione, d-α-tocopherol and the like.
As the phosphorus stabilizer, an organic phosphorus compound can be suitably used. For example, tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylene phosphonite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, triphenyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, diphenylisodecyl phosphite, phenyl Diisodecyl phosphite.
また、４，４−ブチリデン−ビス（３−メチル−６−ｔ−ブチルフェニル−ジ−トリデシル）フォスファイト、サイクリックネオペンタンテトライルビス（オクタデシルホスファイト）、サイクリックネオペンタンテトライルビス（２，６−ジ−ｔ−ブチル−４−メチルフェニル）ホスファイト、トリス（ノニル・フェニル）ホスファイト、ジイソデシルペンタエリスリトールジフォスファイト、９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキサイド、１０−（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）−９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキサイド、１０−デシロキシ−９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレンなどを例示することができる。 In addition, 4,4-butylidene-bis (3-methyl-6-tert-butylphenyl-di-tridecyl) phosphite, cyclic neopentanetetrayl bis (octadecyl phosphite), cyclic neopentanetetrayl bis (2 , 6-di-t-butyl-4-methylphenyl) phosphite, tris (nonylphenyl) phosphite, diisodecylpentaerythritol diphosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 -Oxide, 10- (3,5-di-tert-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10- Illustrative examples include dihydro-9-oxa-10-phosphaphenanthrene Door can be.
またアミン系安定剤としては、ヒンダードアミン系化合物を好適に用いることができる。例えば、コハク酸ジメチル−１−（２−ヒドロキシエチル）−４−ヒドロキシ−２，２，６，６−テトラメチルピペリジン重縮合物、ポリ−［［６−（１，１，３，３−テトラメチルブチル）イミノー１，３，５−トリアジンー２，４−ジイル］［２，２，６，６−テトラメチル−４−ピペリジル］イミノ］ヘキサメチレン［［２，２，５，６−テトラメチル−４−ピペリジル］イミノ］２−（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）−２−ｎ−ブチルマロン酸ビス（１，２，２，６，６−ペンタメチル−４−ピペリジル）である。 As the amine stabilizer, a hindered amine compound can be suitably used. For example, dimethyl succinate-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly-[[6- (1,1,3,3-tetra Methylbutyl) imino 1,3,5-triazine-2,4-diyl] [2,2,6,6-tetramethyl-4-piperidyl] imino] hexamethylene [[2,2,5,6-tetramethyl- 4-piperidyl] imino] 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6-pentamethyl-4-piperidyl) It is.
また、テトラキス（２，２，６，６−テトラメチル−４−ピペリジル）１，２，３，４−ブタンテトラカルボキシレート、ビス−２，２，６，６−テトラメチル−４−ピペリジル−セバケート、ビス（１，２，２，６，６−ペンタメチル−４−ピペリジル）セバケート、メチル（１，２，２，６，６−ペンタメチル−４−ピペリジル）セバケート、１−［２−［３−（３．５−ジ−ｔ−ブチルー４−ヒドロキシフェニル）プロピオニルオキシ］エチル］−４−［３−（３，５−ｔ−ブチル−ヒドロキシフェニル）プロピオニルオキシ］２，２，６，６−テトラメチルピペリジン、４−ベンゾイルオキシ−２，２，６，６−テトラメチルピペリジンなどを例示することができる。 Tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, bis-2,2,6,6-tetramethyl-4-piperidyl-sebacate Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, methyl (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1- [2- [3- ( 3.5-di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-t-butyl-hydroxyphenyl) propionyloxy] 2,2,6,6-tetramethyl Examples include piperidine and 4-benzoyloxy-2,2,6,6-tetramethylpiperidine.
本発明の黒着色ポリアミド樹脂組成物および成形体は、上記（Ａ）〜（Ｅ）成分および必要に応じて用いられる各種の添加剤を混合し、混練して製造すればよい。
その際、配合、混合、及び混練方法やそれらの順序には特に制限はなく、通常用いられる混合機、例えばヘンシェルミキサー、タンブラー、リボンブレンダー等で混合すればよい。混練機としては、通常、単軸又は２軸の押出機が用いられる。本発明による成形品は、押出機により、通常まず上記本発明の樹脂組成物からなるペレットを製造し、このペレットを圧縮成形、射出成形、押出成形等により任意の形状に成形して所望の樹脂製品とすることによって得られる。
本発明は射出成形条件を特に限定するものではないが、成形温度が２５０℃〜３１０℃、金型温度が４０℃〜１２０℃で成形することが好ましい。
The black colored polyamide resin composition and molded product of the present invention may be produced by mixing and kneading the components (A) to (E) and various additives used as necessary.
In that case, there is no restriction | limiting in particular in a mixing | blending, mixing, kneading | mixing method, and those order, What is necessary is just to mix with a normally used mixer, for example, a Henschel mixer, a tumbler, a ribbon blender, etc. As the kneader, a single-screw or twin-screw extruder is usually used. The molded product according to the present invention is usually produced by first producing pellets comprising the resin composition of the present invention with an extruder, and molding the pellets into an arbitrary shape by compression molding, injection molding, extrusion molding, or the like. It is obtained by making it into a product.
Although the present invention does not particularly limit the injection molding conditions, it is preferable to mold at a molding temperature of 250 ° C. to 310 ° C. and a mold temperature of 40 ° C. to 120 ° C.
また、本発明の組成物は、それを得るための混合順序に特に制限はなく、例えば、（Ａ）〜（Ｅ）を一括して混練する方法、（Ａ）と（Ｃ）とを溶融混練後、（Ｂ）と（Ｄ）を混練する方法等が挙げられ、また、全部を溶融混練せずに、いわゆるペレットブレンドとしては、（Ａ）の一部と（Ｃ）とを混練したものと、（Ａ）の残りと（Ｂ）と（Ｄ）を混練したものを、ペレットブレンドして加工に供する方法等を例示できる。また、予め、（Ａ）に（Ｂ）と（Ｄ）を高濃度で含むマスターペレットを製造しておき、これと（Ａ）と（Ｃ）からなる組成物とを再混練又はペレットブレンドして用いても差し支えない。また、有機系熱安定剤（Ｆ）の添加方法に関しては、特に制限はなく、添加することができる。 Further, the composition of the present invention is not particularly limited in the mixing order for obtaining the composition. For example, the method of kneading (A) to (E) at once, (A) and (C) are melt-kneaded. Thereafter, there is a method of kneading (B) and (D), and as a so-called pellet blend without melting and kneading the whole, a part of (A) and (C) are kneaded. A method of subjecting the remainder of (A) and (B) and (D) to kneading with pellets for processing, etc. can be exemplified. In addition, a master pellet containing (B) and (D) at a high concentration in (A) is prepared in advance, and this and a composition comprising (A) and (C) are re-kneaded or pellet blended. It can be used. Moreover, there is no restriction | limiting in particular regarding the addition method of an organic type heat stabilizer (F), It can add.
本発明のポリアミド樹脂組成物には、必要に応じ本発明の目的を損なわない範囲に於いて通常のポリアミド樹脂に添加される酸化防止剤、紫外線吸収剤、熱安定剤、光劣化防止剤、可塑剤、滑剤、離型剤、核剤、難燃剤、銅フタロシアニン誘導体等の着色用染料等を添加することもできるし、他の熱可塑性樹脂をブレンドしても良い。
本発明による組成物は、例えば、アウターハンドル、アウタードアハンドル、ホイールキャップ、ルーフレール、ドアミラーベース、ルームミラーアーム、サンルーフデフレクター、ラジエーターファン、ラジエーターグリル、ベアリングリテーナー、コンソールボックス、サンバイザーアーム、スポイラー、スライドドアレールカバー、机及び椅子の脚、座受け、肘掛け、車椅子部品、ドアハンドル、手摺り、浴室等の握り棒、窓用ノブ、グレーティング材等工業用成形品及び雑貨用成形品に特に好ましく利用できる。
The polyamide resin composition of the present invention includes an antioxidant, an ultraviolet absorber, a heat stabilizer, a photodegradation inhibitor, a plasticizer added to a normal polyamide resin as long as the purpose of the present invention is not impaired. An agent, a lubricant, a release agent, a nucleating agent, a flame retardant, a coloring dye such as a copper phthalocyanine derivative, or the like may be added, or another thermoplastic resin may be blended.
The composition according to the present invention includes, for example, an outer handle, an outer door handle, a wheel cap, a roof rail, a door mirror base, a rear mirror arm, a sunroof deflector, a radiator fan, a radiator grill, a bearing retainer, a console box, a sun visor arm, a spoiler, and a slide. Door rail covers, desk and chair legs, seats, armrests, wheelchair parts, door handles, handrails, grip bars for bathrooms, knobs for windows, grating materials, etc. .
以下の実施例により本発明をさらに詳しく説明するが、本発明はこれら実施例により何ら限定されるものではない。なお、実施例及び比較例に用いた測定方法及び原材料を以下に示す。 The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In addition, the measuring method and raw material which were used for the Example and the comparative example are shown below.
［硫酸相対粘度の測定］
９５．５％硫酸１００ｍｌに試料１ｇを溶解し、オストワルト型粘度計を用いて２５℃で測定した。
［末端カルボキシル基濃度［ＣＯＯＨ］の測定］
試料を１７０±５℃のベンジルアルコールに溶解し、０.１Ｎの苛性ソーダで滴定した。指示薬として、フェノールフタレインを使用した。
［末端アミノ基濃度［ＮＨ２］の測定］
試料をフェノールに溶解し、０．０２Ｎ塩酸で電位差滴定を行った。
[Measurement of relative viscosity of sulfuric acid]
1 g of a sample was dissolved in 100 ml of 95.5% sulfuric acid and measured at 25 ° C. using an Ostwald viscometer.
[Measurement of terminal carboxyl group concentration [COOH]]
The sample was dissolved in benzyl alcohol at 170 ± 5 ° C. and titrated with 0.1N caustic soda. Phenolphthalein was used as an indicator.
[Measurement of terminal amino group concentration [NH 2 ]]
The sample was dissolved in phenol and subjected to potentiometric titration with 0.02N hydrochloric acid.
［ニグロシンに含有する塩素濃度の測定］
染料中に含まれる塩素濃度は、試料１０ｍｇを用い、吸収液として超純水２５ｍｌを用いた酸素フラスコ燃焼法により得られた試料溶液を１０倍に希釈して、ダイオネクス社製ＤＸ−５００イオンクロマトグラフィーを用いて測定した。測定の諸条件を以下に記す。
カラム ＩｏｎＰａｃ ＡＧ１２Ａ、ＡＳ１２Ａ（４ｍｍφ×２５０ｍｍ）
溶離液 ： ０.３ｍＭ ＮａＨＣＯ３＋ ２.７ｍＭ Ｎａ２ＣＯ３
溶離液流量 ： １.２ｍｌ／ｍｉｎ
検出器 ： 電気伝導度検出器
[Measurement of chlorine concentration in nigrosine]
The concentration of chlorine contained in the dye was 10-fold of the sample, 10-fold dilution of the sample solution obtained by the oxygen flask combustion method using 25 ml of ultrapure water as the absorbing solution, and DX-500 ion chromatograph manufactured by Dionex. Measured using graphy. The measurement conditions are described below.
Column IonPac AG12A, AS12A (4mmφ × 250mm)
Eluent: 0.3 mM NaHCO 3 + 2.7 mM Na 2 CO 3
Eluent flow rate: 1.2 ml / min
Detector: Electric conductivity detector
［機械物性］
東芝機械（株）製ＩＳ−５０ＥＰ射出成形機を用いて、スクリュー回転数２００ｒｐｍ、樹脂温度２９０℃の成形条件にて、厚さ３ｍｍのＡＳＴＭタイプ１を成形し、この成形片を物性測定用試料とし、それぞれＡＳＴＭ Ｄ６３８及びＤ７９０に従って引張破断強さ、及び曲げ弾性率を測定した。
[Mechanical properties]
Using an IS-50EP injection molding machine manufactured by Toshiba Machine Co., Ltd., a 3 mm thick ASTM type 1 was molded under molding conditions of a screw speed of 200 rpm and a resin temperature of 290 ° C., and this molded piece was used as a sample for measuring physical properties. The tensile strength at break and the flexural modulus were measured according to ASTM D638 and D790, respectively.
［外観］
東芝機械（株）社製ＩＳ１５０Ｅ射出成形機を用いて、シリンダー温度２９０℃、金型温度１２０℃で、充填時間が約１．５秒になるように射出圧力、及び速度を適宜調整し、１００×９０×３ｍｍの射出成形板を得た。この平板を用い、光沢計（ＨＯＲＩＢＡ製ＩＧ３２０）を用いてＪＩＳ−Ｋ７１５０に準じて６０度グロスを測定した。
[appearance]
Using an IS150E injection molding machine manufactured by Toshiba Machine Co., Ltd., the injection pressure and speed were appropriately adjusted so that the filling time was about 1.5 seconds at a cylinder temperature of 290 ° C. and a mold temperature of 120 ° C. A x90 x 3 mm injection-molded plate was obtained. Using this flat plate, 60 degree gloss was measured according to JIS-K7150 using a gloss meter (IG320 manufactured by HORIBA).
［加工装置の長期使用性］
８０℃で２４時間乾燥した樹脂ペレットを金属性密閉試験容器に入れ、その中央に樹脂ペレットと接触するように試験片（表面研磨を施した炭素鋼（ＳＳ４００）（２０ｍｍ×１０ｍｍ×２ｍｍ））を入れ、試験温度２８０℃、試験時間６時間という条件にて、試験を行った。なお、試験容器内は試験前に窒素ガスによる置換を行った。評価方法としては、試験後の試験片を取り出し、試験片の表面を金属顕微鏡で分析し、損傷部分を次のような計算方法を用いて、試験後の重量減少として換算し、評価した。
重量減少量＝７.８６×Ａ×Ｂ
Ｂ＝π×（平均穴半径）２×平均掘れ深さ
ここで、Ａは穴の個数、Ｂは平均穴体積を意味する。
[Long-term usability of processing equipment]
The resin pellet dried at 80 ° C. for 24 hours is placed in a metal sealed test container, and a test piece (carbon steel (SS400) (20 mm × 10 mm × 2 mm) subjected to surface polishing) subjected to surface polishing) is placed in contact with the resin pellet at the center. The test was conducted under the conditions of a test temperature of 280 ° C. and a test time of 6 hours. The inside of the test container was replaced with nitrogen gas before the test. As an evaluation method, the test piece after the test was taken out, the surface of the test piece was analyzed with a metallographic microscope, and the damaged part was converted and evaluated as a weight loss after the test using the following calculation method.
Weight loss = 7.86 x A x B
B = π × (average hole radius) 2 × average digging depth Here, A means the number of holes and B means the average hole volume.
＜原材料＞
[Ａ]ポリアミド樹脂
Ａ１：ポリアミド６６樹脂（以下ＰＡ６６と略記）
硫酸相対粘度 ２.４
末端カルボキシル基濃度 ９４（ミリ等量／ｋｇ）
末端アミノ基濃度 ４０（ミリ等量／ｋｇ）
Ａ２：ＰＡ６６
硫酸相対粘度 ２.４
末端カルボキシル基濃度 １１３（ミリ等量／ｋｇ）
末端アミノ基濃度 ２５（ミリ等量／ｋｇ）
Ａ３：ポリアミド６６／６Ｉ（以下ＰＡ６６／６Ｉと略記）
硫酸相対粘度 ２.１
末端カルボキシル基濃度 １０２（ミリ等量／ｋｇ）
末端アミノ基濃度 ４４（ミリ等量／ｋｇ）
Ａ４：ポリアミド６６／６Ｉ
硫酸相対粘度 ２.１
末端カルボキシル基濃度 １２０（ミリ等量／ｋｇ）
末端アミノ基濃度 ３５（ミリ等量／ｋｇ）
Ａ５：ポリアミド６６／６Ｉ
硫酸相対粘度 ２.１
末端カルボキシル基濃度 １３０（ミリ等量／ｋｇ）
末端アミノ基濃度 ２５（ミリ等量／ｋｇ）
<Raw materials>
[A] Polyamide resin A1: Polyamide 66 resin (hereinafter abbreviated as PA66)
Sulfuric acid relative viscosity 2.4
Terminal carboxyl group concentration 94 (milli equivalent / kg)
Terminal amino group concentration 40 (milli equivalent / kg)
A2: PA66
Sulfuric acid relative viscosity 2.4
Terminal carboxyl group concentration 113 (mm equivalent / kg)
Terminal amino group concentration 25 (milli equivalent / kg)
A3: Polyamide 66 / 6I (hereinafter abbreviated as PA66 / 6I)
Sulfuric acid relative viscosity 2.1
Terminal carboxyl group concentration 102 (mm equivalent / kg)
Terminal amino group concentration 44 (milli equivalent / kg)
A4: Polyamide 66 / 6I
Sulfuric acid relative viscosity 2.1
Terminal carboxyl group concentration 120 (milli equivalent / kg)
Terminal amino group concentration 35 (milli equivalent / kg)
A5: Polyamide 66 / 6I
Sulfuric acid relative viscosity 2.1
Terminal carboxyl group concentration 130 (mm equivalent / kg)
Terminal amino group concentration 25 (milli equivalent / kg)
[Ｂ]ニグロシン
Ｂ１：中央合成化学（株）製 商品名 オイルブラックＳ
含有塩素濃度 ８００（ｐｐｍ）
Ｂ２：オリエント化学（株）製 商品名 ヌビアンブラックＰＡ９８０１
含有塩素濃度 ２００００（ｐｐｍ）
[B] Nigrosine
B1: Chuo Synthetic Chemical Co., Ltd. Product name Oil Black S
Concentration of chlorine 800 (ppm)
B2: Product name: Nubian Black PA9801 manufactured by Orient Chemical Co., Ltd.
Concentration of contained chlorine 20000 (ppm)
［Ｃ］無機充填材
（ｃ−１）ガラス繊維
日本電気硝子（株）製；商品名 Ｔ−２７５Ｈ 平均繊維径＝１０.５μｍ
（ｃ−２）無機充填材
ワラストナイト ナイコ社製；商品名 Ｎｙｇｌｏｓ８ 平均粒子径＝８μｍ
[Ｄ]カーボンブラック
三菱化学（株）製 商品名 ＃９８０
[C] Inorganic filler (c-1) glass fiber
Manufactured by Nippon Electric Glass Co., Ltd .; trade name T-275H Average fiber diameter = 10.5 μm
(C-2) Inorganic filler Wollastonite manufactured by Nyco; trade name Nyglos8 average particle size = 8 μm
[D] Carbon black
Product name # 980 manufactured by Mitsubishi Chemical Corporation
［実施例１］
（Ａ）ポリアミドとしてＡ１を９５重量部、（Ｂ）ニグロシンとしてＢ１を５重量部混合して、東芝機械（株）製ＴＥＭ３５φ２軸押出機（設定温度２９０℃、スクリュー回転数３００ｒｐｍ）にフィードホッパーより供給し、紡口より押し出された溶融混練物をストランド状で冷却し、ペレタイズして黒着色ポリアミド樹脂組成物を得た。得られた組成物の加工装置の長期使用性を前記方法にて評価した。その組成及び評価結果を表１に示す。得られた組成物は加工装置の長期使用性に優れる。
[Example 1]
(A) 95 parts by weight of A1 as polyamide and (B) 5 parts by weight of B1 as nigrosine are mixed into a TEM35φ twin screw extruder (set temperature 290 ° C., screw rotation speed 300 rpm) manufactured by Toshiba Machine Co., Ltd. from a feed hopper. The melt-kneaded material supplied and extruded from the spinning nozzle was cooled in a strand shape and pelletized to obtain a black colored polyamide resin composition. The long-term usability of the processing apparatus for the obtained composition was evaluated by the above method. The composition and evaluation results are shown in Table 1. The obtained composition is excellent in long-term usability of the processing apparatus.
［比較例１〜３］
使用する（Ａ）ポリアミド、（Ｂ）ニグロシンを変えた以外は、実施例１と同様に実施し、黒着色ポリアミド樹脂組成物を得た。その組成及び評価結果を表１に示す。得られた組成物は実施例１と比較して加工装置の長期使用性に劣る。
[Comparative Examples 1-3]
Except having changed (A) polyamide and (B) nigrosine to be used, it implemented similarly to Example 1 and obtained the black coloring polyamide resin composition. The composition and evaluation results are shown in Table 1. The obtained composition is inferior to the long-term usability of the processing apparatus as compared with Example 1.
［実施例２、３］
使用する（Ａ）ポリアミドを変えた以外は、実施例１と同様に実施し、黒着色ポリアミド樹脂組成物を得た。その組成及び評価結果を表２に示す。得られた組成物は加工装置の長期使用性に優れる。
[Examples 2 and 3]
(A) Except having changed the polyamide used, it implemented similarly to Example 1 and obtained the black coloring polyamide resin composition. The composition and evaluation results are shown in Table 2. The obtained composition is excellent in long-term usability of the processing apparatus.
［比較例４〜６］
使用する（Ａ）ポリアミド、（Ｂ）ニグロシンを変えた以外は、実施例２と同様に実施し、黒着色ポリアミド樹脂組成物を得た。その組成及び評価結果を表２に示す。得られた組成物は実施例２または３と比較して加工装置の長期使用性に劣る。
[Comparative Examples 4 to 6]
Except having changed (A) polyamide and (B) nigrosine to be used, it implemented similarly to Example 2 and obtained the black coloring polyamide resin composition. The composition and evaluation results are shown in Table 2. The obtained composition is inferior to the long-term usability of the processing apparatus as compared with Example 2 or 3.
［実施例４］
（Ａ）ポリアミドとしてＡ３を４０重量部、（Ｄ）カーボンブラックを１．５重量部、（Ｂ）ニグロシンとしてＢ１を０.３重量部混合して、東芝機械（株）製ＴＥＭ３５φ２軸押出機（設定温度２９０℃、スクリュー回転数３００ｒｐｍ）にフィードホッパーより供給し、更にサイドフィード口を２カ所設け、上流側のサイドフィード口より無機充填材としてワラストナイトを２５重量部供給し、下流側のサイドフィード口よりガラス繊維を３５重量部供給し、紡口より押し出された溶融混練物をストランド状で冷却し、ペレタイズして黒着色ポリアミド樹脂組成物を得た。得られた組成物を前記の方法にて評価した。その組成及び評価結果を表３に示す。成形品は機械物性、成形品外観に優れ、加工装置の長期使用性も優れる。
[Example 4]
(A) 40 parts by weight of A3 as polyamide, (D) 1.5 parts by weight of carbon black, (B) 0.3 part by weight of B1 as nigrosine, and a TEM35φ twin screw extruder manufactured by Toshiba Machine Co., Ltd. (Set temperature 290 ° C., screw rotation speed 300 rpm) from the feed hopper, further provided with two side feed ports, and supplied 25 parts by weight of wollastonite as an inorganic filler from the upstream side feed port, 35 parts by weight of glass fiber was supplied from the side feed port, and the melt-kneaded product extruded from the spinneret was cooled in a strand shape and pelletized to obtain a black colored polyamide resin composition. The obtained composition was evaluated by the method described above. The composition and evaluation results are shown in Table 3. Molded products have excellent mechanical properties and appearance of molded products, and excellent long-term usability of processing equipment.
［実施例５］
（Ａ）ポリアミドをＡ４に変えた以外は、実施例４と同様に実施し、黒着色ポリアミド樹脂組成物を得た。その組成及び評価結果を表３に示す。成形品は実施例４と同様に機械物性、成形品外観に優れ、加工装置の長期使用性も優れる。
[Example 5]
(A) Except having changed polyamide to A4, it implemented similarly to Example 4 and obtained the black coloring polyamide resin composition. The composition and evaluation results are shown in Table 3. The molded product is excellent in mechanical properties and appearance of the molded product as in Example 4, and is excellent in long-term usability of the processing apparatus.
［比較例７〜９］
使用する（Ａ）ポリアミド、（Ｂ）ニグロシンを変えた以外は、実施例４と同様に実施し、黒着色ポリアミド樹脂組成物を得た。その組成及び評価結果を表３に示す。成形品は機械物性、成形品外観に優れるものの、実施例４または５と比較して加工装置の長期使用性に劣る。
[Comparative Examples 7 to 9]
Except having changed (A) polyamide and (B) nigrosine to be used, it implemented similarly to Example 4 and obtained the black coloring polyamide resin composition. The composition and evaluation results are shown in Table 3. Although the molded product is excellent in mechanical properties and appearance of the molded product, it is inferior in long-term usability of the processing apparatus as compared with Example 4 or 5.
［比較例１０］
（Ｂ）ニグロシンを添加しない以外は、実施例４と同様に実施し、黒着色ポリアミド樹脂組成物を得た。その組成及び評価結果を表３に示す。成形品は機械物性、耐候性、加工装置の長期使用性に優れるものの、実施例４または５と比較して、成形品外観に劣る。
[Comparative Example 10]
(B) Except not adding nigrosine, it implemented like Example 4 and obtained the black coloring polyamide resin composition. The composition and evaluation results are shown in Table 3. Although the molded product is excellent in mechanical properties, weather resistance, and long-term usability of the processing apparatus, it is inferior in appearance to the molded product as compared with Example 4 or 5.
本発明によって得られた黒着色ポリアミド樹脂組成物は、成形品外観、耐候性、機械的性質を損なうことなく、押出機や射出成形機のスクリュー、シリンダーおよび金型の長期使用を可能にすることから、アウターハンドル、アウタードアハンドル、ホイールキャップ、ルーフレール、ドアミラーベース、ルームミラーアーム、サンルーフデフレクター、ラジエーターファン、ラジエーターグリル、ベアリングリテーナー、コンソールボックス、サンバイザーアーム、スポイラー、スライドドアレールカバー、机及び椅子の脚、座受け、肘掛け、車椅子部品、ドアハンドル、手摺り、浴室等の握り棒、窓用ノブ等の成形用材料として好適に用いられる。 The black colored polyamide resin composition obtained by the present invention enables long-term use of screws, cylinders and molds of extruders and injection molding machines without impairing the appearance, weather resistance, and mechanical properties of molded products. Outer handle, outer door handle, wheel cap, roof rail, door mirror base, rear mirror arm, sunroof deflector, radiator fan, radiator grill, bearing retainer, console box, sun visor arm, spoiler, sliding door rail cover, desk and chair It is suitably used as a molding material for legs, seats, armrests, wheelchair parts, door handles, handrails, grip bars for bathrooms, knobs for windows, and the like.
Claims (10)
（ｃ−１）ガラス繊維
（ｃ−２）ワラストナイト、タルク、カオリン、マイカから選ばれる少なくとも１種の無機充填材 The (C) inorganic filler is composed of the following (c-1) and (c-2), and the weight ratio of (c-2) to (c-1) is in the range of 0.2 to 3. The black colored polyamide resin composition according to claim 3, wherein the composition is a black colored polyamide resin composition.
(C-1) Glass fiber (c-2) At least one inorganic filler selected from wollastonite, talc, kaolin and mica
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| JP2010150533A (en) * | 2008-11-25 | 2010-07-08 | Asahi Kasei Chemicals Corp | Polyamide resin composition and molded article thereof |
| JP2010270327A (en) * | 2009-04-22 | 2010-12-02 | Asahi Kasei Chemicals Corp | Glass fiber-reinforced polyamide resin composition |
| JP2014074150A (en) * | 2012-10-02 | 2014-04-24 | Ems-Patent Ag | Polyamide molding compound and use thereof in the production of molded product |
| WO2014203606A1 (en) * | 2013-06-20 | 2014-12-24 | 旭化成ケミカルズ株式会社 | Polyamide resin composition and molding |
| JP2015013984A (en) * | 2013-06-05 | 2015-01-22 | 旭化成ケミカルズ株式会社 | Polyamide resin composition and molded body |
| JP2015059222A (en) * | 2013-09-20 | 2015-03-30 | エボニック インダストリーズ アクチエンゲゼルシャフトＥｖｏｎｉｋ Ｉｎｄｕｓｔｒｉｅｓ ＡＧ | Molding material based on partially aromatic copolyamide |
| JP2015059221A (en) * | 2013-09-20 | 2015-03-30 | エボニック インダストリーズ アクチエンゲゼルシャフトＥｖｏｎｉｋ Ｉｎｄｕｓｔｒｉｅｓ ＡＧ | Molding material based on partially aromatic copolyamide |
| JP2018059019A (en) * | 2016-10-07 | 2018-04-12 | 三菱エンジニアリングプラスチックス株式会社 | Molding and method for producing molding |
| CN109722021A (en) * | 2018-12-29 | 2019-05-07 | 上海普利特复合材料股份有限公司 | A kind of piano is black, damage resistant nylon material and preparation method thereof |
| JP2023024548A (en) * | 2016-10-07 | 2023-02-16 | 三菱エンジニアリングプラスチックス株式会社 | Molding and method for producing molding |
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| JP2010270327A (en) * | 2009-04-22 | 2010-12-02 | Asahi Kasei Chemicals Corp | Glass fiber-reinforced polyamide resin composition |
| JP2014074150A (en) * | 2012-10-02 | 2014-04-24 | Ems-Patent Ag | Polyamide molding compound and use thereof in the production of molded product |
| JP2015013984A (en) * | 2013-06-05 | 2015-01-22 | 旭化成ケミカルズ株式会社 | Polyamide resin composition and molded body |
| US9783677B2 (en) | 2013-06-20 | 2017-10-10 | Asahi Kasei Chemicals Corporation | Polyamide resin composition and molded body |
| JPWO2014203606A1 (en) * | 2013-06-20 | 2017-02-23 | 旭化成株式会社 | Polyamide resin composition and molded body |
| WO2014203606A1 (en) * | 2013-06-20 | 2014-12-24 | 旭化成ケミカルズ株式会社 | Polyamide resin composition and molding |
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| JP2015059221A (en) * | 2013-09-20 | 2015-03-30 | エボニック インダストリーズ アクチエンゲゼルシャフトＥｖｏｎｉｋ Ｉｎｄｕｓｔｒｉｅｓ ＡＧ | Molding material based on partially aromatic copolyamide |
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