JP4333486B2 - Polyamide resin composition and molded article comprising the composition - Google Patents
Polyamide resin composition and molded article comprising the composition Download PDFInfo
- Publication number
- JP4333486B2 JP4333486B2 JP2004164423A JP2004164423A JP4333486B2 JP 4333486 B2 JP4333486 B2 JP 4333486B2 JP 2004164423 A JP2004164423 A JP 2004164423A JP 2004164423 A JP2004164423 A JP 2004164423A JP 4333486 B2 JP4333486 B2 JP 4333486B2
- Authority
- JP
- Japan
- Prior art keywords
- polyamide resin
- mass
- resin composition
- product name
- parts
- 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.)
- Expired - Lifetime
Links
- 229920006122 polyamide resin Polymers 0.000 title claims description 82
- 239000011342 resin composition Substances 0.000 title claims description 62
- 239000000203 mixture Substances 0.000 title description 18
- 239000011256 inorganic filler Substances 0.000 claims description 20
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 20
- 150000001414 amino alcohols Chemical class 0.000 claims description 19
- 229920002292 Nylon 6 Polymers 0.000 claims description 14
- 239000001023 inorganic pigment Substances 0.000 claims description 10
- 229920000299 Nylon 12 Polymers 0.000 claims description 4
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 239000008188 pellet Substances 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 16
- -1 etc.) Substances 0.000 description 14
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 13
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- 238000002844 melting Methods 0.000 description 12
- 230000008018 melting Effects 0.000 description 12
- 239000002530 phenolic antioxidant Substances 0.000 description 12
- 238000002156 mixing Methods 0.000 description 11
- 239000000049 pigment Substances 0.000 description 11
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 10
- 229940102253 isopropanolamine Drugs 0.000 description 10
- 239000004594 Masterbatch (MB) Substances 0.000 description 9
- 229910000859 α-Fe Inorganic materials 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000003995 emulsifying agent Substances 0.000 description 7
- 230000006872 improvement Effects 0.000 description 7
- 229910052712 strontium Inorganic materials 0.000 description 7
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 6
- 239000006087 Silane Coupling Agent Substances 0.000 description 6
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 6
- GFIWSSUBVYLTRF-UHFFFAOYSA-N 2-[2-(2-hydroxyethylamino)ethylamino]ethanol Chemical compound OCCNCCNCCO GFIWSSUBVYLTRF-UHFFFAOYSA-N 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 239000007822 coupling agent Substances 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 3
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 3
- 239000008116 calcium stearate Substances 0.000 description 3
- 235000013539 calcium stearate Nutrition 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- LPRVNTWNHMSTPR-UHFFFAOYSA-M lithium;2-hydroxyoctadecanoate Chemical compound [Li+].CCCCCCCCCCCCCCCCC(O)C([O-])=O LPRVNTWNHMSTPR-UHFFFAOYSA-M 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 235000019359 magnesium stearate Nutrition 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 150000003141 primary amines Chemical group 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- GUYIZQZWDFCUTA-UHFFFAOYSA-N (pentadecachlorophthalocyaninato(2-))-copper Chemical compound [Cu+2].N1=C([N-]2)C3=C(Cl)C(Cl)=C(Cl)C(Cl)=C3C2=NC(C2=C(Cl)C(Cl)=C(Cl)C(Cl)=C22)=NC2=NC(C2=C(Cl)C(Cl)=C(Cl)C(Cl)=C22)=NC2=NC2=C(C(Cl)=C(C(Cl)=C3)Cl)C3=C1[N-]2 GUYIZQZWDFCUTA-UHFFFAOYSA-N 0.000 description 2
- CWKVFRNCODQPDB-UHFFFAOYSA-N 1-(2-aminoethylamino)propan-2-ol Chemical compound CC(O)CNCCN CWKVFRNCODQPDB-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 150000002171 ethylene diamines Chemical class 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000006247 magnetic powder Substances 0.000 description 2
- 239000006078 metal deactivator Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- PWHRZOCVKYGWMI-UHFFFAOYSA-N n'-[2-(2-aminoethylamino)ethyl]ethane-1,2-diamine;oxirane Chemical compound C1CO1.NCCNCCNCCN PWHRZOCVKYGWMI-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- KZFMOINJHMONLW-FOCLMDBBSA-N (2e)-4,7-dichloro-2-(4,7-dichloro-3-oxo-1-benzothiophen-2-ylidene)-1-benzothiophen-3-one Chemical compound S\1C(C(=CC=C2Cl)Cl)=C2C(=O)C/1=C1/C(=O)C(C(Cl)=CC=C2Cl)=C2S1 KZFMOINJHMONLW-FOCLMDBBSA-N 0.000 description 1
- ACJSMQZKXAMMRA-UHFFFAOYSA-N 1h-pyrrolo[3,2-b]pyrrol-5-one Chemical compound N1C=CC2=NC(=O)C=C21 ACJSMQZKXAMMRA-UHFFFAOYSA-N 0.000 description 1
- VESQWGARFWAICR-UHFFFAOYSA-N 2,2-dihydroxyoctadecanamide;ethene Chemical compound C=C.CCCCCCCCCCCCCCCCC(O)(O)C(N)=O VESQWGARFWAICR-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- JFGQHAHJWJBOPD-UHFFFAOYSA-N 3-hydroxy-n-phenylnaphthalene-2-carboxamide Chemical compound OC1=CC2=CC=CC=C2C=C1C(=O)NC1=CC=CC=C1 JFGQHAHJWJBOPD-UHFFFAOYSA-N 0.000 description 1
- ZEHOVWPIGREOPO-UHFFFAOYSA-N 4,5,6,7-tetrachloro-2-[2-(4,5,6,7-tetrachloro-1,3-dioxoinden-2-yl)quinolin-8-yl]isoindole-1,3-dione Chemical compound O=C1C(C(=C(Cl)C(Cl)=C2Cl)Cl)=C2C(=O)N1C(C1=N2)=CC=CC1=CC=C2C1C(=O)C2=C(Cl)C(Cl)=C(Cl)C(Cl)=C2C1=O ZEHOVWPIGREOPO-UHFFFAOYSA-N 0.000 description 1
- CGLVZFOCZLHKOH-UHFFFAOYSA-N 8,18-dichloro-5,15-diethyl-5,15-dihydrodiindolo(3,2-b:3',2'-m)triphenodioxazine Chemical compound CCN1C2=CC=CC=C2C2=C1C=C1OC3=C(Cl)C4=NC(C=C5C6=CC=CC=C6N(C5=C5)CC)=C5OC4=C(Cl)C3=NC1=C2 CGLVZFOCZLHKOH-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- SHBUUTHKGIVMJT-UHFFFAOYSA-N Hydroxystearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OO SHBUUTHKGIVMJT-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920001007 Nylon 4 Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- QJVKUMXDEUEQLH-UHFFFAOYSA-N [B].[Fe].[Nd] Chemical compound [B].[Fe].[Nd] QJVKUMXDEUEQLH-UHFFFAOYSA-N 0.000 description 1
- GXDVEXJTVGRLNW-UHFFFAOYSA-N [Cr].[Cu] Chemical compound [Cr].[Cu] GXDVEXJTVGRLNW-UHFFFAOYSA-N 0.000 description 1
- PRQMIVBGRIUJHV-UHFFFAOYSA-N [N].[Fe].[Sm] Chemical compound [N].[Fe].[Sm] PRQMIVBGRIUJHV-UHFFFAOYSA-N 0.000 description 1
- AUNAPVYQLLNFOI-UHFFFAOYSA-L [Pb++].[Pb++].[Pb++].[O-]S([O-])(=O)=O.[O-][Cr]([O-])(=O)=O.[O-][Mo]([O-])(=O)=O Chemical compound [Pb++].[Pb++].[Pb++].[O-]S([O-])(=O)=O.[O-][Cr]([O-])(=O)=O.[O-][Mo]([O-])(=O)=O AUNAPVYQLLNFOI-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- CJDPJFRMHVXWPT-UHFFFAOYSA-N barium sulfide Chemical compound [S-2].[Ba+2] CJDPJFRMHVXWPT-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- MYONAGGJKCJOBT-UHFFFAOYSA-N benzimidazol-2-one Chemical compound C1=CC=CC2=NC(=O)N=C21 MYONAGGJKCJOBT-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 235000012730 carminic acid Nutrition 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 229910000152 cobalt phosphate Inorganic materials 0.000 description 1
- KPLQYGBQNPPQGA-UHFFFAOYSA-N cobalt samarium Chemical compound [Co].[Sm] KPLQYGBQNPPQGA-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 description 1
- VVOLVFOSOPJKED-UHFFFAOYSA-N copper phthalocyanine Chemical compound [Cu].N=1C2=NC(C3=CC=CC=C33)=NC3=NC(C3=CC=CC=C33)=NC3=NC(C3=CC=CC=C33)=NC3=NC=1C1=CC=CC=C12 VVOLVFOSOPJKED-UHFFFAOYSA-N 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 150000002148 esters Chemical class 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
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [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
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 description 1
- 229940072106 hydroxystearate Drugs 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 235000019239 indanthrene blue RS Nutrition 0.000 description 1
- UHOKSCJSTAHBSO-UHFFFAOYSA-N indanthrone blue Chemical compound C1=CC=C2C(=O)C3=CC=C4NC5=C6C(=O)C7=CC=CC=C7C(=O)C6=CC=C5NC4=C3C(=O)C2=C1 UHOKSCJSTAHBSO-UHFFFAOYSA-N 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 1
- GWVMLCQWXVFZCN-UHFFFAOYSA-N isoindoline Chemical compound C1=CC=C2CNCC2=C1 GWVMLCQWXVFZCN-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- DKXULEFCEORBJK-UHFFFAOYSA-N magnesium;octadecanoic acid Chemical compound [Mg].CCCCCCCCCCCCCCCCCC(O)=O DKXULEFCEORBJK-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 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
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 1
- AQGNVWRYTKPRMR-UHFFFAOYSA-N n'-[2-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCNCCN AQGNVWRYTKPRMR-UHFFFAOYSA-N 0.000 description 1
- 229910001172 neodymium magnet Inorganic materials 0.000 description 1
- DGBWPZSGHAXYGK-UHFFFAOYSA-N perinone Chemical compound C12=NC3=CC=CC=C3N2C(=O)C2=CC=C3C4=C2C1=CC=C4C(=O)N1C2=CC=CC=C2N=C13 DGBWPZSGHAXYGK-UHFFFAOYSA-N 0.000 description 1
- PJQYNUFEEZFYIS-UHFFFAOYSA-N perylene maroon Chemical compound C=12C3=CC=C(C(N(C)C4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)N(C)C(=O)C4=CC=C3C1=C42 PJQYNUFEEZFYIS-UHFFFAOYSA-N 0.000 description 1
- ZZSIDSMUTXFKNS-UHFFFAOYSA-N perylene red Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N(C(=O)C=1C2=C3C4=C(OC=5C=CC=CC=5)C=1)C(=O)C2=CC(OC=1C=CC=CC=1)=C3C(C(OC=1C=CC=CC=1)=CC1=C2C(C(N(C=3C(=CC=CC=3C(C)C)C(C)C)C1=O)=O)=C1)=C2C4=C1OC1=CC=CC=C1 ZZSIDSMUTXFKNS-UHFFFAOYSA-N 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910000938 samarium–cobalt magnet Inorganic materials 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 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
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、ポリアミド樹脂に無機充填材や顔料を高濃度で配合しても、流動性に優れたポリアミド樹脂組成物に関する。 The present invention relates to a polyamide resin composition having excellent fluidity even when an inorganic filler or pigment is blended in a high concentration with a polyamide resin.
無機充填材を高濃度で配合したポリアミド樹脂組成物は、ポリアミド樹脂の配合比率が低いため、樹脂組成物の溶融時の流動性が著しく低下する問題があった。また、このような流動性の低いものを成形加工に用いる際には、その形状に制限を受けたり、取り個数を減らしたりする必要があった。また、ポリアミド樹脂に無機充填材や顔料を高濃度で配合したマスターバッチも同様に、ポリアミド樹脂の配合比率が低いため、樹脂組成物の流動性が著しく低下する問題があった。このような流動性の低いマスターバッチを用いた場合、無機充填材や顔料のほぐれ不良を生じる問題がある。 The polyamide resin composition containing a high concentration of the inorganic filler has a problem that the flowability at the time of melting of the resin composition is remarkably lowered because the blending ratio of the polyamide resin is low. Further, when such a low fluidity material is used for molding, it is necessary to be restricted by its shape or to reduce the number of products. Similarly, a master batch in which an inorganic filler or a pigment is blended at a high concentration with a polyamide resin has a problem that the fluidity of the resin composition is remarkably lowered because the blending ratio of the polyamide resin is low. When such a masterbatch with low fluidity is used, there is a problem that the looseness of the inorganic filler and the pigment occurs.
上記のような問題を解決する方法として、ポリアミド樹脂組成物中のポリアミド樹脂の配合比率を高くし、流動性を高める方法が一般的である。しかし、無機充填材や顔料の配合比率が低下するため、充分な性能が得られない問題があった。また、ポリアミド樹脂組成物をマスターバッチとして用いた場合、ポリアミド樹脂の配合量が多いため、マスターバッチの配合量によっては、成形品の特性が大きく左右される問題やマスターバッチが低濃度であるため、マスターバッチの使用量が増加し、コストアップにつながる問題があった。 As a method of solving the above problems, a method of increasing the blending ratio of the polyamide resin in the polyamide resin composition and increasing the fluidity is common. However, since the blending ratio of the inorganic filler and the pigment is lowered, there is a problem that sufficient performance cannot be obtained. Also, when the polyamide resin composition is used as a masterbatch, the amount of polyamide resin is large, so depending on the amount of masterbatch, the properties of the molded product are greatly affected and the masterbatch is low in concentration. There was a problem that the usage amount of the master batch increased and the cost was increased.
この問題を解決するため、比較的分子量が低いポリアミド樹脂を用いて、流動性を高める方法が提案されている。しかし、溶融時の流動性の向上は充分でなく、ポリアミド樹脂が低分子量であるため、成形品の強度が低下する問題もあった（例えば、特許文献１を参照。）。 In order to solve this problem, a method for improving fluidity using a polyamide resin having a relatively low molecular weight has been proposed. However, the improvement in fluidity at the time of melting is not sufficient, and the polyamide resin has a low molecular weight, so that there is a problem that the strength of the molded product is reduced (for example, see Patent Document 1).
また、ポリアミド樹脂組成物の溶融時の流動性を向上するため、可塑剤や滑剤を添加する方法が提案されている。しかし、この方法で高い流動性を維持しつつ、高濃度で無機充填材や顔料等のポリアミド樹脂に非相溶の化合物を配合するには、より多くの可塑剤や滑剤を添加する必要があり、結果として成形品の性能低下や加工性の低下を生じ、充分に満足できるものではなかった（例えば、特許文献２及び特許文献３を参照。）。 Moreover, in order to improve the fluidity | liquidity at the time of the melt | dissolution of a polyamide resin composition, the method of adding a plasticizer and a lubricant is proposed. However, it is necessary to add more plasticizers and lubricants to blend incompatible compounds with polyamide resins such as inorganic fillers and pigments at high concentrations while maintaining high fluidity by this method. As a result, the performance of the molded product and the workability are deteriorated, which is not fully satisfactory (for example, see Patent Document 2 and Patent Document 3).
本発明が解決しようとする課題は、ポリアミド樹脂に無機充填材や顔料を高濃度で配合しても、流動性に優れ、良好な成形性を有するポリアミド樹脂組成物を提供し、マスターバッチとして使用した際には優れた希釈性を有するポリアミド樹脂組成物を提供することである。 The problem to be solved by the present invention is to provide a polyamide resin composition having excellent flowability and good moldability even when blended with a high concentration of an inorganic filler or pigment in a polyamide resin, and used as a masterbatch When it does, it is providing the polyamide resin composition which has the outstanding dilution property.
本発明者らは、上記課題を解決すべく鋭意検討を重ねた結果、無機充填材や顔料を高濃度で配合したポリアミド樹脂組成物に、特定のアミノアルコール類を添加することで、溶融時の流動性が飛躍的に向上できることを見出した。すなわち、本発明は、（Ａ）ポリアミド樹脂、
（Ｂ）無機充填材及び／又は顔料及び
（Ｃ）下記一般式（１）で表されるアミノアルコール類
を含有することを特徴とするポリアミド樹脂組成物を提供するものである。
As a result of intensive studies to solve the above problems, the present inventors have added a specific amino alcohol to a polyamide resin composition containing a high concentration of inorganic fillers and pigments. We found that the fluidity can be improved dramatically. That is, the present invention provides (A) a polyamide resin,
The present invention provides a polyamide resin composition comprising (B) an inorganic filler and / or a pigment and (C) an amino alcohol represented by the following general formula (1).
Ｒ１〜Ｒ５は、水素原子、−ＣＨ２ＣＨ２ＯＨ、−ＣＨ２ＣＨ（ＣＨ３）ＯＨからなる群のいずれかであり、かつ少なくとも１つは、−ＣＨ２ＣＨ２ＯＨ又は
−ＣＨ２ＣＨ（ＣＨ３）ＯＨである。］
R 1 to R 5 are each selected from the group consisting of a hydrogen atom, —CH 2 CH 2 OH, —CH 2 CH (CH 3 ) OH, and at least one of —CH 2 CH 2 OH or —CH 2 CH (CH 3 ) OH. ]
本発明のポリアミド樹脂組成物は、ポリアミド樹脂に無機充填材や顔料を高濃度で配合しても、流動性に優れ、良好な成形性を有する。また、高い機械強度を有するが、溶融時の流動性が低い高分子量のポリアミド樹脂を用いても高い流動性が得られるため、高い機械強度を有する成形品を得ることもできる。そのため、高い磁気特性を得る目的で高濃度に磁性粉を配合したボンド磁石や、コストダウンの目的で高濃度に顔料を配合した着色用マスターバッチに非常に有用である。 The polyamide resin composition of the present invention has excellent flowability and good moldability even when an inorganic filler or pigment is blended in high concentration with the polyamide resin. In addition, since high fluidity can be obtained even when a high molecular weight polyamide resin having high mechanical strength but low fluidity at the time of melting is used, a molded product having high mechanical strength can also be obtained. Therefore, it is very useful for a bonded magnet in which magnetic powder is blended at a high concentration for the purpose of obtaining high magnetic characteristics, and a coloring masterbatch in which a pigment is blended at a high concentration for the purpose of cost reduction.
本発明を以下に詳しく説明する。本発明で用いられるポリアミド樹脂（Ａ）としては、特に限定するものではないが、例えば、ポリアミド６、ポリアミド１２、ポリアミド６，６、ポリアミド６，１０、ポリアミド１１、ポリアミド４，６、ポリアミド４，１２、ポリアミドＭＸＤ、芳香族ポリアミド、ポリアミドエラストマー及びこれらの共重合体が挙げられる。これらの中でも、ポリアミド６、ポリアミド１２、ポリアミド６，６及びその共重合体が好ましい。これらのポリアミド樹脂は、単独で用いることも、２種以上を併用することもできる。また、溶融時の流動性が低い高分子量のポリアミド樹脂を用いても高い流動性が得られるため、従来は使用が困難であった高分子量のポリアミド樹脂も用いることができる。 The present invention is described in detail below. The polyamide resin (A) used in the present invention is not particularly limited. For example, polyamide 6, polyamide 12, polyamide 6,6, polyamide 6,10, polyamide 11, polyamide 4,6, polyamide 4, 12, polyamide MXD, aromatic polyamide, polyamide elastomer and copolymers thereof. Among these, polyamide 6, polyamide 12, polyamide 6,6 and a copolymer thereof are preferable. These polyamide resins can be used alone or in combination of two or more. Moreover, since high fluidity is obtained even when a high molecular weight polyamide resin having low fluidity at the time of melting is used, a high molecular weight polyamide resin that has been difficult to use can also be used.
本発明で用いられる成分（Ｂ）の無機充填材としては、例えば、炭酸カルシウム、タルク、カオリン、マイカ、ワラストナイト、珪酸カリウム、ハイドロタルサイト、ゼオライト、シリカ、アルミナ、ガラス（フレーク状、球状、バルーン等）、カーボンファイバー、金属及びこれらの合金（鉄、アルミニウム、ニッケル、銅、タングステン等）、磁性粉（フェライト系、ネオジウム−鉄−ボロン系、サマリウム−コバルト系、サマリウム−鉄−窒素系、アルミニウム−ニッケル−コバルト系）等が挙げられる。これらの無機充填材は、単独で用いることも２種以上を併用することもできる。 Examples of the inorganic filler of the component (B) used in the present invention include calcium carbonate, talc, kaolin, mica, wollastonite, potassium silicate, hydrotalcite, zeolite, silica, alumina, glass (flakes, spheres) , Balloon, etc.), carbon fiber, metal and alloys thereof (iron, aluminum, nickel, copper, tungsten, etc.), magnetic powder (ferrite, neodymium-iron-boron, samarium-cobalt, samarium-iron-nitrogen) , Aluminum-nickel-cobalt system) and the like. These inorganic fillers can be used alone or in combination of two or more.
本発明で用いられる成分（Ｂ）の顔料は、例えば、酸化物系（亜鉛華、酸化チタン、弁柄、鉄黒、酸化クロム等）、複合酸化物系（チタンイエロー、亜鉛−鉄分ブラウン、チタンコバルトグリーン、コバルトグリーン、コバルオブルー、銅−クロム系ブラック、銅−鉄ブラック等）、クロム酸系（黄鉛、モリブテートオレンジ等）、フェロシアン系（紺青等）、硫化物系（カドミウムイエロー、カドミウムレッド、硫化亜鉛等）、硫化バリウム、群青、炭酸カルシウム、コバルトバイオレット、黄色酸化鉄、カーボンブラック、アゾ顔料（レーキレット、パーマネントレッド、ブリリアントカーミン、カルシウムレーキ、ナフトールＡＳレッド、ベンズイミダゾロンイエロー、ジスアゾイエローＨＲ、ビラゾロンレッド、縮合アゾイエロー、縮合アゾレッド、縮合アゾブラウン、ニッケルアゾイエロー等）、銅フタロシアニン（銅フタロシアニンブルー、銅フタロシアニングリーン、臭素化銅フタロシアニングリーン等）、縮合多環顔料（アンスラキノンイエロー、ジアンスラキノリルレッド、インダンスレンブルー、チオインジゴボルドー、ペリノンオレンジ、ペリレンスカーレット、ペリレンレッド、ペリレンマルーン、キナクリドンレッド、キナクリドンマゼンタ、キナクリドンスカーレット、ジオキサジンバイオレット、インインドリノンイエロー、インインドリノンイエロー、キノフタロンイエロー、イソインドリンイエロー、ジケトピロロピロールレッド等）が挙げられる。これらの顔料は、単独で用いることも、２種以上を併用することもできる。また、これらの顔料は、上記の無機充填材と併用することもできる。 The pigment of the component (B) used in the present invention is, for example, an oxide type (zinc white, titanium oxide, dial, iron black, chromium oxide, etc.), complex oxide type (titanium yellow, zinc-iron brown, titanium). Cobalt green, cobalt green, kovalu blue, copper-chromium black, copper-iron black, etc., chromic acid (yellow lead, molybdate orange, etc.), ferrocyanic (bitumen, etc.), sulfide (cadmium yellow, cadmium) Red, zinc sulfide, etc.), barium sulfide, ultramarine, calcium carbonate, cobalt violet, yellow iron oxide, carbon black, azo pigments (lakelet, permanent red, brilliant carmine, calcium lake, naphthol AS red, benzimidazolone yellow, disazo yellow HR, virazolone red, condensed azo yellow, Azo red, condensed azo brown, nickel azo yellow, etc.), copper phthalocyanine (copper phthalocyanine blue, copper phthalocyanine green, brominated copper phthalocyanine green, etc.), condensed polycyclic pigments (anthraquinone yellow, dianthraquinolyl red, indanthrene) Blue, thioindigo Bordeaux, perinone orange, perylene scarlet, perylene red, perylene maroon, quinacridone red, quinacridone magenta, quinacridone scarlet, dioxazine violet, inindolinone yellow, inindolinone yellow, quinophthalone yellow, isoindoline yellow, di Ketopyrrolopyrrole red, etc.). These pigments can be used alone or in combination of two or more. These pigments can also be used in combination with the above inorganic filler.
また、前記成分（Ｂ）の無機充填材又は顔料は、その表面をカップリング剤で処理すると、ポリアミド樹脂中での分散性や機械特性が向上できるので好ましい。このようなカップリング剤としては、シラン系、アルミニウム系、チタン系のものを用いることができる。本発明では、バインダー樹脂としてポリアミド樹脂を使用するため、カップリング剤の中でも、ポリアミド樹脂と反応性を有するもの、又は相溶性に優れるものが好ましい。このようなカップリング剤としては、例えば、３−アミノプロピルトリエトキシシラン、３−グリシドキシプロピルトリメトキシシラン、３−グリシドキシプロピルメチルジメトキシシラン、Ｎ−２−（アミノエチル）−３−アミノプロピルトリメトキシシラン、Ｎ−２−（アミノエチル）−３−アミノプロピルメルジメトキシシラン、３−アミノプロピルトリエトキシシラン、１,３,５−Ｎ−トリス（３−トリメトキシシリルプロピル）イソシアヌレート、ビニルトリメトキシシラン、ビニルトリエトキシシラン、アルキルアセトアセテートアルミニウムジイソプロピレート等が挙げられる。 Further, the inorganic filler or pigment of the component (B) is preferably treated with a coupling agent on the surface because dispersibility and mechanical properties in the polyamide resin can be improved. As such a coupling agent, a silane-based, aluminum-based, or titanium-based one can be used. In the present invention, since a polyamide resin is used as the binder resin, among the coupling agents, those having reactivity with the polyamide resin or those having excellent compatibility are preferable. Examples of such a coupling agent include 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, N-2- (aminoethyl) -3- Aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmerdimethoxysilane, 3-aminopropyltriethoxysilane, 1,3,5-N-tris (3-trimethoxysilylpropyl) isocyanurate Vinyltrimethoxysilane, vinyltriethoxysilane, alkyl acetoacetate aluminum diisopropylate and the like.
本発明のポリアミド樹脂組成物では、配合する無機充填剤や顔料の粒子径にもよるが、フェライト（比重５．１、平均粒子径１．５μｍ）のような無機充填剤の場合、配合比率がポリアミド樹脂組成物中５５体積％以上で、ポリアミド樹脂組成物の溶融時の流動性の向上効果が大きく、特に６０体積％を超える場合、流動性の向上効果が著しい。また、カーボンブラック（比重１．８、平均粒子径１０〜５０ｎｍ）では、配合比率がポリアミド樹脂組成物中２０体積％以上で、ポリアミド樹脂組成物の溶融時の流動性の向上効果が大きく、特に２５体積％を超える場合、流動性の向上効果が著しい。 In the polyamide resin composition of the present invention, depending on the particle size of the inorganic filler and pigment to be blended, in the case of an inorganic filler such as ferrite (specific gravity 5.1, average particle size 1.5 μm), the blending ratio is When the volume of the polyamide resin composition is 55% by volume or more, the effect of improving the fluidity at the time of melting of the polyamide resin composition is large, and particularly when the volume exceeds 60% by volume, the effect of improving the fluidity is remarkable. Carbon black (specific gravity 1.8, average particle diameter 10 to 50 nm) has a blending ratio of 20% by volume or more in the polyamide resin composition, and has a large effect of improving fluidity when the polyamide resin composition is melted. When it exceeds 25 volume%, the improvement effect of fluidity | liquidity is remarkable.
本発明で用いられるアミノアルコール類（Ｃ）は、下記一般式（１）で表されるものである。このようなアミノアルコール類は、エチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ペンタエチレンヘキサミン、ヘキサエチレンヘプタミン等のエチレンジアミン類に、エチレンオキサイド又はプロピレンオキサイドを付加させることにより得られる。本発明では、前記アミノアルコール類（Ｃ）は、流動性向上剤として働く。なお、一般式（１）中のｎが６以上のものは、ポリアミド樹脂組成物の溶融時の流動性を向上する効果が低いため好ましくない。 The amino alcohol (C) used in the present invention is represented by the following general formula (1). Such amino alcohols can be obtained by adding ethylene oxide or propylene oxide to ethylenediamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine and the like. In the present invention, the amino alcohol (C) functions as a fluidity improver. In addition, it is not preferable that n in the general formula (1) is 6 or more because the effect of improving the fluidity at the time of melting of the polyamide resin composition is low.
Ｒ１〜Ｒ５は、水素原子、−ＣＨ２ＣＨ２ＯＨ、−ＣＨ２ＣＨ（ＣＨ３）ＯＨからなる群のいずれかであり、かつ少なくとも１つは、−ＣＨ２ＣＨ２ＯＨ又は
−ＣＨ２ＣＨ（ＣＨ３）ＯＨである。］
R 1 to R 5 are each selected from the group consisting of a hydrogen atom, —CH 2 CH 2 OH, —CH 2 CH (CH 3 ) OH, and at least one of —CH 2 CH 2 OH or —CH 2 CH (CH 3 ) OH. ]
前記アミノアルコール類（Ｃ）は、前記エチレンジアミン類１分子中に、エチレンオキサイド又はプロピレンオキサイドが１つ以上付加したものであるが、特に末端１級アミンに付加したものは、ポリアミド樹脂組成物の溶融時の流動性の向上効果が高くなるので好ましい。また、末端の１級アミンへのエチレンオキサイド又はプロピレンオキサイドの付加数が１〜３のものが好ましく、さらには、末端１級アミンへの付加数が１〜２のものが最も流動性を向上するので、特に好ましい。なお、付加するエチレンオキサイドとプロピレンオキサイドとの間で、流動性向上の効果に差がないため、これらの２種を付加させたものも用いることができる。 The amino alcohols (C) are those obtained by adding one or more ethylene oxides or propylene oxides in one molecule of the ethylene diamines. Particularly, those added to terminal primary amines are melts of the polyamide resin composition. This is preferable because the effect of improving the fluidity at the time becomes high. Further, those having 1 to 3 additions of ethylene oxide or propylene oxide to the terminal primary amine are preferred, and those having 1 to 2 additions to the terminal primary amine most improve the fluidity. Therefore, it is particularly preferable. In addition, since there is no difference in the effect of fluidity | liquidity improvement between the ethylene oxide and propylene oxide to add, what added these 2 types can also be used.
ポリアミド樹脂組成物の溶融時の流動性の向上効果を充分に得るため、前記アミノアルコール類（Ｃ）のポリアミド樹脂組成物中の配合比率は、０．０５質量％以上が好ましい。また、曲げ強度等の機械特性やマスターバッチとして用いた際の希釈性が要求される場合には、成分（Ｂ）の無機充填材や顔料の種類によって異なるが、前記アミノアルコール類（Ｃ）のポリアミド樹脂組成物中の配合比率は、概ね１.５質量％以下にするのが好ましい。 In order to sufficiently obtain the effect of improving the fluidity when the polyamide resin composition is melted, the blending ratio of the amino alcohols (C) in the polyamide resin composition is preferably 0.05% by mass or more. In addition, when mechanical properties such as bending strength and dilutability when used as a masterbatch are required, the amino alcohols (C) may vary depending on the type of the inorganic filler or pigment of the component (B). The blending ratio in the polyamide resin composition is preferably about 1.5% by mass or less.
本発明のポリアミド樹脂組成物においては、本発明の趣旨を損なわない範囲で、酸化防止剤、帯電防止剤、光安定剤、紫外線吸収剤、金属不活性剤、滑剤、着色剤、分散剤等の添加剤類を適宜配合することができる。 In the polyamide resin composition of the present invention, an antioxidant, an antistatic agent, a light stabilizer, an ultraviolet absorber, a metal deactivator, a lubricant, a colorant, a dispersant, etc., as long as the gist of the present invention is not impaired. Additives can be appropriately blended.
本発明のポリアミド樹脂組成物の成形方法としては、例えば、押出成形、射出成形、モノフィラ等の一般的な成形方法を用いることができる。 As a method for molding the polyamide resin composition of the present invention, for example, a general molding method such as extrusion molding, injection molding, or monofilament can be used.
以下に実施例及び比較例を挙げて、本発明をさらに具体的に説明するが、本発明はこれら実施例に限定されるものではない。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to these examples.
以下の実施例１〜５は、成分（Ｂ）として無機充填材を高濃度に配合した例である。 Examples 1 to 5 below are examples in which an inorganic filler is blended at a high concentration as the component (B).
（実施例１）
ポリアミド６（宇部興産株式会社製の製品名「ウベスタＰ−１０１１Ｆ」）６．１質量部、タングステンパウダー（光正製の製品名「ＦＷ−１ ＴＹＰＥ１５０」）９３質量部をシランカップリング剤（信越化学工業株式会社製の製品名「ＫＢＥ−９０３」）０．５質量部で処理したもの、金属不活性剤（チバ・スペシャリティ・ケミカルズ株式会社製の製品名「ＭＤ１０２４」）０．２質量部、フェノール系酸化防止剤（チバ・スペシャリティ・ケミカルズ株式会社製の製品名「イルガノックス１０９８」）０．１質量部及びＮ−（β−アミノエチル）エタノールアミン（日本乳化剤工業株式会社製の製品名「アミノアルコールＥＡ」）０．１質量部をミキサーで混合後、押出機で混練、賦形して、ポリアミド樹脂組成物のペレットを得た。また、同様にしてＮ−（β−アミノエチル）エタノールアミンを配合しないポリアミド樹脂組成物のペレットも得た。
Example 1
6.1 parts by mass of polyamide 6 (product name “Uvesta P-1011F” manufactured by Ube Industries, Ltd.) and 93 parts by mass of tungsten powder (product name “FW-1 TYPE150” manufactured by Kosei) were added to a silane coupling agent (Shin-Etsu Chemical). Product name “KBE-903” manufactured by Kogyo Co., Ltd.) treated with 0.5 part by mass, metal deactivator (product name “MD1024” manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.2 part by mass, phenol 0.1 part by weight of a series antioxidant (product name “Irganox 1098” manufactured by Ciba Specialty Chemicals Co., Ltd.) and N- (β-aminoethyl) ethanolamine (product name “amino” manufactured by Nippon Emulsifier Industry Co., Ltd.) Alcohol EA ") 0.1 parts by mass was mixed with a mixer, and then kneaded and shaped with an extruder to obtain polyamide resin composition pellets. Moreover, the pellet of the polyamide resin composition which does not mix | blend N-((beta) -aminoethyl) ethanolamine similarly was obtained.
（実施例２）
ポリアミド６（宇部興産株式会社製の製品名「ウベスタＰ−１０１０」）９．１５質量部、ストロンチウムフェライト（日本弁柄工業株式会社製の製品名「ＮＦ−１１０」）９０質量部をシランカップリング剤（信越化学工業株式会社製の製品名「ＫＢＥ−９０３」）０．５質量部で処理したもの、フェノール系酸化防止剤（チバ・スペシャリティ・ケミカルズ株式会社製の製品名「イルガノックス１０９８」）０．１質量部及びＮ−（β−アミノエチル）イソプロパノールアミン（日本乳化剤工業株式会社製の製品名「アミノアルコールＰＡ」）０．２５質量部をミキサーで混合後、押出機で混練、賦形して、ポリアミド樹脂組成物のペレットを得た。また、同様にしてＮ−（β−アミノエチル）イソプロパノールアミンを配合しないポリアミド樹脂組成物のペレットも得た。
(Example 2)
9.15 parts by mass of polyamide 6 (product name “Uvesta P-1010” manufactured by Ube Industries Co., Ltd.) and 90 parts by mass of strontium ferrite (product name “NF-110” manufactured by Nippon Valve Industry Co., Ltd.) Agent (Shin-Etsu Chemical Co., Ltd. product name "KBE-903") treated with 0.5 parts by mass, phenolic antioxidant (Ciba Specialty Chemicals Co., Ltd. product name "Irganox 1098") 0.1 parts by mass and 0.25 part by mass of N- (β-aminoethyl) isopropanolamine (product name “Aminoalcohol PA” manufactured by Nippon Emulsifier Industry Co., Ltd.) were mixed with a mixer, then kneaded with an extruder and shaped. Thus, pellets of the polyamide resin composition were obtained. Moreover, the pellet of the polyamide resin composition which does not mix | blend N-((beta) -aminoethyl) isopropanolamine similarly was obtained.
（実施例３）
ポリアミド６（宇部興産株式会社製の製品名「ウベスタＰ−１０１０」）８．３質量部、ストロンチウムフェライト（日本弁柄工業株式会社製の製品名「ＮＦ−１１０」）９０質量部をシランカップリング剤（信越化学工業株式会社製の製品名「ＫＢＥ−９０３」）０．５質量部で処理したもの、フェノール系酸化防止剤（チバ・スペシャリティ・ケミカルズ株式会社製の製品名「イルガノックス１０９８」）０．１質量部及びＮ−（β−アミノエチル）イソプロパノールアミン（日本乳化剤工業株式会社製の製品名「アミノアルコールＰＡ」）１．１質量部をミキサーで混合後、押出機で混練、賦形して、ポリアミド樹脂組成物のペレットを得た。また、同様にしてＮ−（β−アミノエチル）イソプロパノールアミンを配合しないポリアミド樹脂組成物のペレットも得た。
(Example 3)
Silane coupling of 8.3 parts by mass of polyamide 6 (product name “Uvesta P-1010” manufactured by Ube Industries Co., Ltd.) and 90 parts by mass of strontium ferrite (product name “NF-110” manufactured by Nippon Valve Industrial Co., Ltd.) Agent (Shin-Etsu Chemical Co., Ltd. product name "KBE-903") treated with 0.5 parts by mass, phenolic antioxidant (Ciba Specialty Chemicals Co., Ltd. product name "Irganox 1098") 0.1 parts by mass and 1.1 parts by mass of N- (β-aminoethyl) isopropanolamine (product name “Amino Alcohol PA” manufactured by Nippon Emulsifier Industry Co., Ltd.) were mixed with a mixer, then kneaded with an extruder and shaped. Thus, pellets of the polyamide resin composition were obtained. Moreover, the pellet of the polyamide resin composition which does not mix | blend N-((beta) -aminoethyl) isopropanolamine similarly was obtained.
（実施例４）
ポリアミド６,６（宇部興産株式会社製の製品名ウベスタ２０１５Ｂ）５９．１５質量部、ガラス繊維（日東紡績株式会社製の製品名「ＣＳ３ＰＥ４５４」）４０質量部をシランカップリング剤（信越化学工業株式会社製の製品名「ＫＢＥ−９０３」）０．５質量部で処理したもの、フェノール系酸化防止剤（チバ・スペシャリティ・ケミカルズ株式会社製の製品名「イルガノックス１０９８」）０．１質量部及び１，２−ビス（２−ヒドロキシエチルアミノ）エタン（日本乳化剤工業株式会社製の製品名「アミノアルコールＡ−ＥＡＤ」）０．２５質量部をミキサーで混合後、押出機で混練、賦形して、ポリアミド樹脂組成物のペレットを得た。また、同様にして１，２−ビス（２−ヒドロキシエチルアミノ）エタンを配合しないポリアミド樹脂組成物のペレットも得た。
(Example 4)
59,15 parts by mass of polyamide 6,6 (product name Uvesta 2015B manufactured by Ube Industries, Ltd.) and 40 parts by mass of glass fiber (product name “CS3PE454” manufactured by Nitto Boseki Co., Ltd.) were added to a silane coupling agent (Shin-Etsu Chemical Co., Ltd.). Company product name “KBE-903”) treated with 0.5 parts by mass, phenolic antioxidant (product name “Irganox 1098” manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.1 parts by mass and 0.25 parts by mass of 1,2-bis (2-hydroxyethylamino) ethane (product name “Amino Alcohol A-EAD” manufactured by Nippon Emulsifier Industry Co., Ltd.) was mixed with a mixer, then kneaded with an extruder and shaped. Thus, a pellet of the polyamide resin composition was obtained. Similarly, pellets of polyamide resin composition not containing 1,2-bis (2-hydroxyethylamino) ethane were also obtained.
（実施例５）
ポリアミド１２（宇部興産株式会社製の製品名「ウベスタ１０１３」）２４．１５質量部、シリカ（マイクロン製の製品名「Ｓ−ＣＯ」）７５質量部をシランカップリング剤（信越化学工業株式会社製の製品名「ＫＢＥ−９０３」）０．５質量部で処理したもの、フェノール系酸化防止剤（チバ・スペシャリティ・ケミカルズ株式会社製の製品名「イルガノックス１０９８」）０．１質量部、ステアリン酸マグネシウム（大日化学工業株式会社製の製品名「ダイワックスＭＳ」）０．１５質量部及びトリエチレンテトラミンのエチレンオキサイド２分子付加物（トリエチレンテトラミン１分子にエチレンオキサイド２分子を付加反応させた生成物から低沸点成分を除去した混合物で、主成分は１,４−ビス（２−ヒドロキシエチルアミノ）トリエチレンジアミン）０．１質量部をミキサーで混合後、押出機で混練、賦形して、ポリアミド樹脂組成物のペレットを得た。また、同様にしてトリエチレンテトラミンのエチレンオキサイド２分子付加物を配合しないポリアミド樹脂組成物のペレットも得た。
(Example 5)
24.15 parts by mass of polyamide 12 (product name “Uvesta 1013” manufactured by Ube Industries, Ltd.) and 75 parts by mass of silica (product name “S-CO” manufactured by Micron) were combined with a silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd.). Product name “KBE-903”) treated with 0.5 part by mass, phenolic antioxidant (product name “Irganox 1098” manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.1 part by mass, stearic acid Magnesium (product name "Daiwax MS" manufactured by Dainichi Chemical Industry Co., Ltd.) 0.15 parts by mass and triethylenetetramine ethylene oxide bimolecular adduct (2 molecules of ethylene oxide were added to 1 molecule of triethylenetetramine) A mixture obtained by removing low-boiling components from the product, the main component being 1,4-bis (2-hydroxyethylamino) tri Ethylenediamine) 0.1 parts by mass was mixed with a mixer and then kneaded and shaped with an extruder to obtain polyamide resin composition pellets. Similarly, pellets of a polyamide resin composition not containing an ethylene oxide bimolecular adduct of triethylenetetramine were also obtained.
以下の実施例６〜８は、成分（Ｂ）として顔料を高濃度に配合したマスターバッチの例である。 Examples 6 to 8 below are examples of master batches in which a pigment is blended at a high concentration as the component (B).
（実施例６）
ポリアミド６（宇部興産株式会社製の製品名「ウベスタＰ−１０１１Ｆ」）２３.７質量部、酸化チタン(デュポン株式会社製の製品名「タイピュアＲ１０１」)７５質量部をシランカップリング剤（信越化学工業株式会社製の製品名「ＫＢＥ−９０３」）０．５質量部で処理したもの、フェノール系酸化防止剤（チバ・スペシャリティ・ケミカルズ株式会社製の製品名「イルガノックス１０９８」）０．１質量部、ステアリン酸マグネシウム（大日化学工業株式会社製の製品名「ダイワックスＭＳ」）０．２質量部及び１,２−ビス（２−ヒドロキシエチルアミノ）エタン（日本乳化剤工業株式会社製の製品名「アミノアルコールＡ−ＥＡＤ」）０．５質量部をミキサーで混合後、押出機で混練、賦形して、ポリアミド樹脂組成物のペレットを得た。また、同様にして１,２−ビス（２−ヒドロキシエチルアミノ）エタンを配合しないポリアミド樹脂組成物のペレットも得た。
(Example 6)
23.7 parts by mass of polyamide 6 (product name “Uvesta P-1011F” manufactured by Ube Industries, Ltd.) and 75 parts by mass of titanium oxide (product name “Typure R101” manufactured by DuPont) were combined with a silane coupling agent (Shin-Etsu Chemical). Kogyo Co., Ltd. product name “KBE-903”) treated with 0.5 parts by mass, phenolic antioxidant (Ciba Specialty Chemicals product name “Irganox 1098”) 0.1 mass Parts, magnesium stearate (product name “Daiwax MS” manufactured by Dainichi Chemical Co., Ltd.) 0.2 parts by mass and 1,2-bis (2-hydroxyethylamino) ethane (product manufactured by Nippon Emulsifier Industry Co., Ltd.) Name "amino alcohol A-EAD") 0.5 parts by mass is mixed with a mixer, and then kneaded and shaped with an extruder to obtain polyamide resin composition pellets. It was. Similarly, pellets of a polyamide resin composition not containing 1,2-bis (2-hydroxyethylamino) ethane were also obtained.
（実施例７）
ポリアミド６（宇部興産株式会社製の製品名「ウベスタＰ−１０１１Ｆ」）５８．５質量部、カーボンブラック（三菱化学株式会社製の製品名「＃３０」）４０質量部をシランカップリング剤（信越化学工業株式会社製の製品名「ＫＢＥ−９０３」）０．５質量部で処理したもの、フェノール系酸化防止剤（チバ・スペシャリティ・ケミカルズ株式会社製の製品名「イルガノックス１０９８」）０．１質量部、ステアリン酸マグネシウム（大日化学工業株式会社製の製品名「ダイワックスＭＳ」）０．２質量部及びＮ−（β−アミノエチル）エタノールアミン（日本乳化剤工業株式会社製の製品名「アミノアルコールＥＡ」）０．７質量部をミキサーで混合後、押出機で混練、賦形して、ポリアミド樹脂組成物のペレットを得た。また、同様にしてＮ−（β−アミノエチル）エタノールアミンを配合しないポリアミド樹脂組成物のペレットも得た。
(Example 7)
58.5 parts by mass of polyamide 6 (product name “Uvesta P-1011F” manufactured by Ube Industries, Ltd.) and 40 parts by mass of carbon black (product name “# 30” manufactured by Mitsubishi Chemical Corporation) were combined with a silane coupling agent (Shin-Etsu). Chemical product, product name “KBE-903”) treated with 0.5 parts by mass, phenolic antioxidant (product name “Irganox 1098”, manufactured by Ciba Specialty Chemicals) 0.1 Parts by weight, 0.2 parts by weight of magnesium stearate (product name “Daiwax MS” manufactured by Dainichi Chemical Co., Ltd.) and N- (β-aminoethyl) ethanolamine (product name manufactured by Nippon Emulsifier Industry Co., Ltd.) Aminoalcohol EA ") 0.7 parts by mass was mixed with a mixer, then kneaded and shaped with an extruder to obtain polyamide resin composition pellets. Moreover, the pellet of the polyamide resin composition which does not mix | blend N-((beta) -aminoethyl) ethanolamine similarly was obtained.
（実施例８）
ポリアミド６（宇部興産株式会社製の製品名「ウベスタＰ−１０１１Ｆ」）５７．７質量部、カーボンブラック（三菱化学株式会社製の製品名「＃３０」）４０質量部をシランカップリング剤（信越化学工業株式会社製の製品名「ＫＢＥ−９０３」）０．５質量部で処理したもの、フェノール系酸化防止剤（チバ・スペシャリティ・ケミカルズ株式会社製の製品名「イルガノックス１０９８」）０．１質量部、ステアリン酸マグネシウム（大日化学工業製ダイワックスＭＳ）０．２質量部及びＮ−（β−アミノエチル）エタノールアミン（日本乳化剤工業株式会社製の製品名「アミノアルコールＥＡ」）１.５質量部をミキサーで混合後、押出機で混練、賦形して、ポリアミド樹脂組成物のペレットを得た。また、同様にしてＮ−（β−アミノエチル）エタノールアミンを配合しないポリアミド樹脂組成物のペレットも得た。
(Example 8)
57.7 parts by mass of polyamide 6 (product name “Uvesta P-1011F” manufactured by Ube Industries, Ltd.) and 40 parts by mass of carbon black (product name “# 30” manufactured by Mitsubishi Chemical Corporation) were combined with a silane coupling agent (Shin-Etsu). Chemical product, product name “KBE-903”) treated with 0.5 parts by mass, phenolic antioxidant (product name “Irganox 1098”, manufactured by Ciba Specialty Chemicals) 0.1 Parts by mass, magnesium stearate (diewax MS manufactured by Dainichi Chemical Co., Ltd.) 0.2 parts by mass and N- (β-aminoethyl) ethanolamine (product name “Amino Alcohol EA” manufactured by Nippon Emulsifier Industry Co., Ltd.) After mixing 5 parts by mass with a mixer, the mixture was kneaded and shaped with an extruder to obtain polyamide resin composition pellets. Moreover, the pellet of the polyamide resin composition which does not mix | blend N-((beta) -aminoethyl) ethanolamine similarly was obtained.
以下の比較例１〜５は、本発明のアミノアルコール類（Ｃ）に代え、他の流動性向上剤を用いた例である。 The following Comparative Examples 1 to 5 are examples using other fluidity improvers in place of the amino alcohols (C) of the present invention.
（比較例１）
ポリアミド６（宇部興産株式会社製の製品名「ウベスタＰ−１０１０」）９．１５質量部、ストロンチウムフェライト（日本弁柄工業株式会社製の製品名「ＮＦ−１１０」）９０質量部をシランカップリング剤（信越化学工業株式会社製の製品名「ＫＢＥ−９０３」）０．５質量部で処理したもの、フェノール系酸化防止剤（チバ・スペシャリティ・ケミカルズ株式会社製の製品名「イルガノックス１０９８」）０．１質量部及びエチレンジアミン（和光純薬工業株式会社製）０．２５質量部をミキサーで混合後、押出機で混練、賦形して、ポリアミド樹脂組成物のペレットを得た。また、同様にしてエチレンジアミンを配合しないポリアミド樹脂組成物のペレットも得た。
(Comparative Example 1)
9.15 parts by mass of polyamide 6 (product name “Uvesta P-1010” manufactured by Ube Industries Co., Ltd.) and 90 parts by mass of strontium ferrite (product name “NF-110” manufactured by Nippon Valve Industry Co., Ltd.) Agent (Shin-Etsu Chemical Co., Ltd. product name "KBE-903") treated with 0.5 parts by mass, phenolic antioxidant (Ciba Specialty Chemicals Co., Ltd. product name "Irganox 1098") After mixing 0.1 part by mass and 0.25 part by mass of ethylenediamine (manufactured by Wako Pure Chemical Industries, Ltd.) with a mixer, the mixture was kneaded and shaped with an extruder to obtain polyamide resin composition pellets. Moreover, the pellet of the polyamide resin composition which does not mix | blend ethylenediamine similarly was obtained.
（比較例２）
ポリアミド６（宇部興産株式会社製の製品名「ウベスタＰ−１０１０」）９．１質量部、ストロンチウムフェライト（日本弁柄工業株式会社製の製品名「ＮＦ−１１０」）９０質量部をシランカップリング剤（信越化学工業株式会社製の製品名「ＫＢＥ−９０３」）０．５質量部で処理したもの、フェノール系酸化防止剤（チバ・スペシャリティ・ケミカルズ株式会社製の製品名「イルガノックス１０９８」）０．１質量部、トルエンスルホン酸アミド（富士アミドケミカル株式会社製の製品名「トップサイザー１号Ｓ」）０.２重量部及びステアリン酸カルシウム（大日本インキ化学工業株式会社製の製品名「Ｃａ-Ｓｔｅａｒａｔｅ」）０.１質量部をミキサーで混合後、押出機で混練、賦形して、ポリアミド樹脂組成物のペレットを得た。また、同様にしてトルエンスルホン酸アミドとステアリン酸カルシウムを配合しないポリアミド樹脂組成物のペレットも得た。
(Comparative Example 2)
Silane coupling of 9.1 parts by mass of polyamide 6 (product name “Uvesta P-1010” manufactured by Ube Industries Co., Ltd.) and 90 parts by mass of strontium ferrite (product name “NF-110” manufactured by Nippon Valve Industrial Co., Ltd.) Agent (Shin-Etsu Chemical Co., Ltd. product name "KBE-903") treated with 0.5 parts by mass, phenolic antioxidant (Ciba Specialty Chemicals Co., Ltd. product name "Irganox 1098") 0.1 parts by mass, 0.2 part by weight of toluenesulfonic acid amide (product name “Topsizer No. 1 S” manufactured by Fujiamide Chemical Co., Ltd.) and calcium stearate (product name “Ca manufactured by Dainippon Ink and Chemicals, Inc.) -Stearate ") 0.1 parts by mass was mixed with a mixer, and then kneaded and shaped with an extruder to obtain polyamide resin composition pellets. Similarly, pellets of a polyamide resin composition not containing toluenesulfonic acid amide and calcium stearate were also obtained.
（比較例３）
ポリアミド６（宇部興産株式会社製の製品名「ウベスタＰ−１０１０」）９．１５質量部、ストロンチウムフェライト（日本弁柄工業株式会社製の製品名「ＮＦ−１１０」）９０質量部をシランカップリング剤（信越化学工業株式会社製の製品名「ＫＢＥ−９０３」）０．５質量部で処理したもの、フェノール系酸化防止剤（チバ・スペシャリティ・ケミカルズ株式会社製の製品名「イルガノックス１０９８」）０．１質量部及びパラオキシ安息香酸メチル（和光純薬工業株式会社製）０．２５質量部をミキサーで混合後、押出機で混練、賦形して、ポリアミド樹脂組成物のペレットを得た。また、同様にしてパラオキシ安息香酸メチルを配合しないポリアミド樹脂組成物のペレットも得た。
(Comparative Example 3)
9.15 parts by mass of polyamide 6 (product name “Uvesta P-1010” manufactured by Ube Industries Co., Ltd.) and 90 parts by mass of strontium ferrite (product name “NF-110” manufactured by Nippon Valve Industry Co., Ltd.) Agent (Shin-Etsu Chemical Co., Ltd. product name "KBE-903") treated with 0.5 parts by mass, phenolic antioxidant (Ciba Specialty Chemicals Co., Ltd. product name "Irganox 1098") 0.1 parts by mass and 0.25 parts by mass of methyl paraoxybenzoate (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed with a mixer, then kneaded with an extruder and shaped to obtain polyamide resin composition pellets. Moreover, the pellet of the polyamide resin composition which does not mix | blend methyl paraoxybenzoate similarly was also obtained.
（比較例４）
ポリアミド６（宇部興産株式会社製の製品名「ウベスタＰ−１０１０」）９．１５質量部、ストロンチウムフェライト（日本弁柄工業株式会社製の製品名「ＮＦ−１１０」）９０質量部をシランカップリング剤（信越化学工業株式会社製の製品名「ＫＢＥ−９０３」）０．５質量部で処理したもの、フェノール系酸化防止剤（チバ・スペシャリティ・ケミカルズ株式会社製の製品名「イルガノックス１０９８」）０．１質量部及びヒドロキシステアリン酸リチウム（株式会社耕正製の製品名「ヒドロキシステアリン酸リチウム」）０．２５質量部をミキサーで混合後、押出機で混練、賦形して、ポリアミド樹脂組成物のペレットを得た。また、同様にしてヒドロキシステアリン酸リチウムを配合しないポリアミド樹脂組成物のペレットも得た。
(Comparative Example 4)
9.15 parts by mass of polyamide 6 (product name “Uvesta P-1010” manufactured by Ube Industries Co., Ltd.) and 90 parts by mass of strontium ferrite (product name “NF-110” manufactured by Nippon Valve Industry Co., Ltd.) Agent (Shin-Etsu Chemical Co., Ltd. product name "KBE-903") treated with 0.5 parts by mass, phenolic antioxidant (Ciba Specialty Chemicals Co., Ltd. product name "Irganox 1098") 0.1 parts by mass and 0.25 parts by mass of lithium hydroxystearate (product name “lithium hydroxystearate” manufactured by Kosho Co., Ltd.) are mixed with a mixer, then kneaded and shaped with an extruder to form a polyamide resin composition A product pellet was obtained. Similarly, pellets of a polyamide resin composition not containing lithium hydroxystearate were also obtained.
（比較例５）
ポリアミド６（宇部興産株式会社製の製品名「ウベスタＰ−１０１０」）９．１５質量部、ストロンチウムフェライト（日本弁柄工業株式会社製の製品名「ＮＦ−１１０」）９０質量部をシランカップリング剤（信越化学工業株式会社製の製品名「ＫＢＥ−９０３」）０．５質量部で処理したもの、フェノール系酸化防止剤（チバ・スペシャリティ・ケミカルズ株式会社製の製品名「イルガノックス１０９８」）０．１質量部及びエチレンビスヒドロキシステアリン酸アマイド（コグニスジャパン株式会社製の製品名「ＬＯＸＩＯＬ ＶＰＮ２１２」）０．２５質量部をミキサーで混合後、押出機で混練、賦形して、ポリアミド樹脂組成物のペレットを得た。また、同様にしてエチレンビスヒドロキシステアリン酸アマイドを配合しないポリアミド樹脂組成物のペレットも得た。
(Comparative Example 5)
9.15 parts by mass of polyamide 6 (product name “Uvesta P-1010” manufactured by Ube Industries Co., Ltd.) and 90 parts by mass of strontium ferrite (product name “NF-110” manufactured by Nippon Valve Industry Co., Ltd.) Agent (Shin-Etsu Chemical Co., Ltd. product name "KBE-903") treated with 0.5 parts by mass, phenolic antioxidant (Ciba Specialty Chemicals Co., Ltd. product name "Irganox 1098") 0.1 parts by mass and 0.25 parts by mass of ethylenebishydroxystearic acid amide (product name “LOXIOL VPN212” manufactured by Cognis Japan Co., Ltd.) are mixed with a mixer, kneaded with an extruder, and shaped to form a polyamide resin composition A product pellet was obtained. Similarly, pellets of a polyamide resin composition not containing ethylene bishydroxystearic acid amide were also obtained.
上記で得られたポリアミド樹脂組成物の評価を以下の方法で行った。 The polyamide resin composition obtained above was evaluated by the following method.
（流動性の評価）
上記の実施例１〜８及び比較例１〜５で、成分（Ｃ）を配合したポリアミド樹脂組成物と成分（Ｃ）を配合しなかったポリアミド樹脂組成物のそれぞれのメルトフローレート（ＭＦＲ）を所定条件（実施例１〜４、比較例１〜３：２７０℃×９８ＭＰａ、実施例５，６、比較例４，５：２８０℃×２１．２ＭＰａ）で、メルトインデクサー（東洋精機製セミオートメルトインデクサー）を用いて測定した。得られたＭＦＲ値を用いて次式より算出されるＭＦＲ比から、以下の基準で流動性を評価した。
◎：顕著に改善（ＭＦＲ比が２０以上）
○：かなり改善（ＭＦＲ比が１０以上２０未満）
△：若干改善（ＭＦＲ比が５を超えて１０未満）
×：改善なし（ＭＦＲ比が５以下）
(Evaluation of liquidity)
In each of Examples 1 to 8 and Comparative Examples 1 to 5, the respective melt flow rates (MFR) of the polyamide resin composition containing the component (C) and the polyamide resin composition not containing the component (C) are shown. Under predetermined conditions (Examples 1 to 4, Comparative Examples 1 to 3: 270 ° C. × 98 MPa, Examples 5 and 6, Comparative Examples 4 and 5: 280 ° C. × 21.2 MPa), a melt indexer (Toyo Seiki semi-auto melt) It was measured using an indexer. From the MFR ratio calculated from the following equation using the obtained MFR value, the fluidity was evaluated according to the following criteria.
A: Remarkably improved (MFR ratio is 20 or more)
○: considerably improved (MFR ratio of 10 or more and less than 20)
Δ: Slightly improved (MFR ratio exceeds 5 and less than 10)
X: No improvement (MFR ratio is 5 or less)
実施例の評価結果を表1及び２に、比較例の評価結果を表３に示す。 The evaluation results of the examples are shown in Tables 1 and 2, and the evaluation results of the comparative examples are shown in Table 3.
表１及び２中の流動性向上剤の略号は、それぞれ以下のものを表す。
ＥＡ：Ｎ−（β−アミノエチル）エタノールアミン
ＰＡ：Ｎ−（β−アミノエチル）イソプロパノールアミン
Ａ−ＥＡＤ：１，２−ビス（２−ヒドロキシエチルアミノ）エタン
ＴＥＴＡ−２ＥＯ：トリエチレンテトラミンのエチレンオキサイド２分子付加物
The abbreviations of fluidity improvers in Tables 1 and 2 represent the following.
EA: N- (β-aminoethyl) ethanolamine PA: N- (β-aminoethyl) isopropanolamine A-EAD: 1,2-bis (2-hydroxyethylamino) ethane TETA-2EO: triethylenetetramine ethylene Oxide bimolecular adduct
表１及び２の結果から、本発明のポリアミド樹脂組成物は、無機充填材や顔料を高濃度で配合した場合においても、流動性向上剤としてアミノアルコール類（Ｃ）を配合することにより、飛躍的に溶融時の流動性が向上することが分かった。 From the results of Tables 1 and 2, the polyamide resin composition of the present invention is a leap forward by blending amino alcohols (C) as a fluidity improver even when blended with a high concentration of inorganic fillers and pigments. In particular, the fluidity at the time of melting was improved.
また、表３の結果から、以下のことが分かった。 Moreover, the following was found from the results in Table 3.
比較例１は、実施例２で用いたアミノアルコール類（Ｃ）であるＮ−（β−アミノエチル）イソプロパノールアミンの代わりに、流動性向上剤としてエチレンジアミンを配合した例である。このポリアミド樹脂組成物の溶融時の流動性は、ほとんど向上しなかった。 Comparative Example 1 is an example in which ethylenediamine was blended as a fluidity improver instead of N- (β-aminoethyl) isopropanolamine, which is the amino alcohol (C) used in Example 2. The fluidity at the time of melting of this polyamide resin composition was hardly improved.
比較例２は、実施例２で用いたアミノアルコール類（Ｃ）であるＮ−（β−アミノエチル）イソプロパノールアミンの代わりに、流動性向上剤としてトルエンスルホン酸アミド及びステアリン酸カルシウムを配合した例である。このポリアミド樹脂組成物では、溶融時の流動性は、ほとんど向上しなかった。 In Comparative Example 2, instead of N- (β-aminoethyl) isopropanolamine, which is the amino alcohol (C) used in Example 2, toluenesulfonic acid amide and calcium stearate were blended as fluidity improvers. is there. In this polyamide resin composition, the fluidity at the time of melting hardly improved.
比較例３は、実施例２で用いたアミノアルコール類（Ｃ）であるＮ−（β−アミノエチル）イソプロパノールアミンの代わりに、流動性向上剤としてパラオキシ安息香酸エステルを配合した例である。このポリアミド樹脂組成物では、溶融時の流動性の向上はわずかであった。 In Comparative Example 3, paraoxybenzoic acid ester was blended as a fluidity improver in place of N- (β-aminoethyl) isopropanolamine, which is the amino alcohol (C) used in Example 2. With this polyamide resin composition, the improvement in fluidity upon melting was slight.
比較例４は、実施例２で用いたアミノアルコール類（Ｃ）であるＮ−（β−アミノエチル）イソプロパノールアミンの代わりに、流動性向上剤としてヒドロキシステアリン酸リチウムを配合した例である。このポリアミド樹脂組成物では、溶融時の流動性の向上が若干見られたが、充分なものではなかった。 Comparative Example 4 is an example in which lithium hydroxystearate was blended as a fluidity improver instead of N- (β-aminoethyl) isopropanolamine, which is the amino alcohol (C) used in Example 2. In this polyamide resin composition, a slight improvement in fluidity at the time of melting was observed, but it was not sufficient.
比較例５は、実施例２で用いたアミノアルコール類（Ｃ）であるＮ−（β−アミノエチル）イソプロパノールアミンの代わりに、流動性向上剤としてエチレンビスヒドロキシステアリン酸アマイドを配合した例である。このポリアミド樹脂組成物では、溶融時の流動性の向上が若干見られたが、充分なものではなかった。
Comparative Example 5 is an example in which ethylenebishydroxystearic acid amide was blended as a fluidity improver in place of N- (β-aminoethyl) isopropanolamine which is the amino alcohol (C) used in Example 2. . In this polyamide resin composition, a slight improvement in fluidity at the time of melting was observed, but it was not sufficient.
Claims (3)
（Ｂ）無機充填材及び／又は顔料及び
（Ｃ）下記一般式（１）で表されるアミノアルコール類
を含有することを特徴とするポリアミド樹脂組成物。
Ｒ１〜Ｒ５は、水素原子、−ＣＨ２ＣＨ２ＯＨ、−ＣＨ２ＣＨ（ＣＨ３）ＯＨからなる群のいずれかであり、かつ少なくとも１つは、−ＣＨ２ＣＨ２ＯＨ又は
−ＣＨ２ＣＨ（ＣＨ３）ＯＨである。］ (A) polyamide resin,
(B) An inorganic filler and / or pigment, and (C) an amino alcohol represented by the following general formula (1).
R 1 to R 5 are each selected from the group consisting of a hydrogen atom, —CH 2 CH 2 OH, —CH 2 CH (CH 3 ) OH, and at least one of —CH 2 CH 2 OH or —CH 2 CH (CH 3 ) OH. ]
A molded article comprising the polyamide resin composition according to claim 1 or 2.
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