TW202035566A - 玻璃纖維強化聚醯胺樹脂組成物、以及由此組成物構成之車輛內裝用或車輛外裝用成形品 - Google Patents
玻璃纖維強化聚醯胺樹脂組成物、以及由此組成物構成之車輛內裝用或車輛外裝用成形品 Download PDFInfo
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- TW202035566A TW202035566A TW109105055A TW109105055A TW202035566A TW 202035566 A TW202035566 A TW 202035566A TW 109105055 A TW109105055 A TW 109105055A TW 109105055 A TW109105055 A TW 109105055A TW 202035566 A TW202035566 A TW 202035566A
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- Prior art keywords
- polyamide resin
- glass fiber
- mass
- resin composition
- parts
- Prior art date
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- 229920006122 polyamide resin Polymers 0.000 title claims abstract description 54
- 239000011342 resin composition Substances 0.000 title claims abstract description 42
- 239000011521 glass Substances 0.000 title abstract description 10
- 239000003365 glass fiber Substances 0.000 claims abstract description 50
- 229920005989 resin Polymers 0.000 claims abstract description 40
- 239000011347 resin Substances 0.000 claims abstract description 40
- 239000006229 carbon black Substances 0.000 claims abstract description 21
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 19
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 19
- 239000010445 mica Substances 0.000 claims abstract description 18
- 229910052618 mica group Inorganic materials 0.000 claims abstract description 18
- 229920006020 amorphous polyamide Polymers 0.000 claims abstract description 17
- 239000005749 Copper compound Substances 0.000 claims abstract description 15
- 150000001880 copper compounds Chemical class 0.000 claims abstract description 15
- 229920006177 crystalline aliphatic polyamide Polymers 0.000 claims abstract description 15
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 12
- 229920006012 semi-aromatic polyamide Polymers 0.000 claims description 7
- -1 polyhexamethylene dixylene Polymers 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 8
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- 239000010456 wollastonite Substances 0.000 description 6
- 229910052882 wollastonite Inorganic materials 0.000 description 6
- 239000004952 Polyamide Substances 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 150000004985 diamines Chemical class 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229920002647 polyamide Polymers 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 4
- 229920002292 Nylon 6 Polymers 0.000 description 4
- 229920002302 Nylon 6,6 Polymers 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000012779 reinforcing material Substances 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 229920001684 low density polyethylene Polymers 0.000 description 3
- 239000004702 low-density polyethylene Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 229920006060 Grivory® Polymers 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 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
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 238000005562 fading Methods 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- XJIAZXYLMDIWLU-UHFFFAOYSA-N undecane-1,1-diamine Chemical compound CCCCCCCCCCC(N)N XJIAZXYLMDIWLU-UHFFFAOYSA-N 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- GUOSQNAUYHMCRU-UHFFFAOYSA-N 11-Aminoundecanoic acid Chemical compound NCCCCCCCCCCC(O)=O GUOSQNAUYHMCRU-UHFFFAOYSA-N 0.000 description 1
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 description 1
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 1
- XDOLZJYETYVRKV-UHFFFAOYSA-N 7-Aminoheptanoic acid Chemical compound NCCCCCCC(O)=O XDOLZJYETYVRKV-UHFFFAOYSA-N 0.000 description 1
- VWPQCOZMXULHDM-UHFFFAOYSA-N 9-aminononanoic acid Chemical compound NCCCCCCCCC(O)=O VWPQCOZMXULHDM-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004953 Aliphatic polyamide Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- HTLZVHNRZJPSMI-UHFFFAOYSA-N N-ethylpiperidine Chemical compound CCN1CCCCC1 HTLZVHNRZJPSMI-UHFFFAOYSA-N 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920003189 Nylon 4,6 Polymers 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 229920000572 Nylon 6/12 Polymers 0.000 description 1
- 229920006152 PA1010 Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920010741 Ultra High Molecular Weight Polyethylene (UHMWPE) Polymers 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
- 238000010521 absorption reaction Methods 0.000 description 1
- HVYLDJKDVOOTHV-UHFFFAOYSA-N acetic acid;2-iminoethanethiol Chemical compound CC(O)=O.CC(O)=O.SCC=N HVYLDJKDVOOTHV-UHFFFAOYSA-N 0.000 description 1
- 229920003231 aliphatic polyamide Polymers 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229960002684 aminocaproic acid Drugs 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229910052626 biotite Inorganic materials 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 1
- WXCZUWHSJWOTRV-UHFFFAOYSA-N but-1-ene;ethene Chemical compound C=C.CCC=C WXCZUWHSJWOTRV-UHFFFAOYSA-N 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- WXYNCCWBUXKSBG-UHFFFAOYSA-N copper;nitric acid Chemical compound [Cu].O[N+]([O-])=O WXYNCCWBUXKSBG-UHFFFAOYSA-N 0.000 description 1
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 description 1
- GEBVYLHOCNKBAH-UHFFFAOYSA-N copper;propan-2-one Chemical compound [Cu].CC(C)=O GEBVYLHOCNKBAH-UHFFFAOYSA-N 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- FWBOFUGDKHMVPI-UHFFFAOYSA-K dicopper;2-oxidopropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[O-]C(=O)CC([O-])(C([O-])=O)CC([O-])=O FWBOFUGDKHMVPI-UHFFFAOYSA-K 0.000 description 1
- 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 1
- 239000000975 dye Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 229920006225 ethylene-methyl acrylate Polymers 0.000 description 1
- 239000005043 ethylene-methyl acrylate Substances 0.000 description 1
- 229920005676 ethylene-propylene block copolymer Polymers 0.000 description 1
- 229920005674 ethylene-propylene random copolymer Polymers 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 239000012213 gelatinous substance Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 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
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 229910052627 muscovite Inorganic materials 0.000 description 1
- ZETYUTMSJWMKNQ-UHFFFAOYSA-N n,n',n'-trimethylhexane-1,6-diamine Chemical compound CNCCCCCCN(C)C ZETYUTMSJWMKNQ-UHFFFAOYSA-N 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229910052628 phlogopite Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001627 poly(4-methyl styrene) Polymers 0.000 description 1
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 229920003251 poly(α-methylstyrene) Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
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- C—CHEMISTRY; METALLURGY
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Abstract
本發明目的在於提供一種玻璃纖維強化聚醯胺樹脂組成物,其分別地以(17~30):(10~16):(3~8):(10~25):(20~50):(1~8)之質量比來含有結晶性脂肪族聚醯胺樹脂(A)、非晶性聚醯胺樹脂(B)、丙烯酸系樹脂(C)、雲母(D)、玻璃纖維(E)、及碳黑之母料(F);該(A)和(B)之質量比(B)/(A)符合0.50~0.61;且令該(A)~(F)成分之合計含量為100質量份時,含有0.005~1.0質量份之比例之銅化合物(G)。藉此玻璃纖維強化聚醯胺樹脂組成物,可得到表面外觀(紋理面之均勻性)非常優異,且具有即使經耐候試驗後仍可維持優異表面外觀之耐候性之成形品。
Description
本發明關於玻璃纖維強化聚醯胺樹脂組成物,可製得成形品外觀非常優異,且處在暴露於屋外,尤其暴露於降雨的使用條件下,耐候性仍優異之成形品。
聚醯胺樹脂因機械特性、熱性質以及耐藥品性優異,而廣泛用於汽車、電、電子製品等之零件。此外,由於對聚醯胺樹脂摻合了玻璃纖維而成之強化聚醯胺樹脂組成物,機械特性、耐熱性、耐藥品性等可大幅改善,考量輕量化及步驟之合理化等之觀點,就金屬替代材料而言,已積極探討使用強化聚醯胺樹脂組成物。
由經高濃度摻合玻璃纖維、矽灰石等之強化聚醯胺樹脂組成物可輕易提供具高剛性之成形品,但有耐候性差之缺點,為了可在屋外用方面使用而必須改善。就相關改善耐候性之方法而言,例如,有人提出專利文獻1~3。
專利文獻1揭示對於聚己二醯間二甲苯二胺摻合丙烯酸系樹脂及含環氧基化合物。然而,由於此方法中含環氧基化合物為必要,若在成形時蓄積的話,會有產生凝膠狀物、熔融流動性降低等成形品之外觀損傷的缺點,且耐候性亦不充分。專利文獻2揭示以結晶性之半芳香族聚醯胺作為主體,使其含有玻璃纖維、矽灰石、碳黑及銅化合物。由於該樹脂組成物係以半芳香族聚醯胺作為主體,有提高成形樹脂溫度之必要,此外,由於摻合了矽灰石,有必須避免螺桿磨損之問題等製造上之缺點,且由雲母取代矽灰石的話,耐候暴露後之黑色的褪色、耐候性之改善效果不充分,有改善之餘地。專利文獻3揭示以結晶性之半芳香族聚醯胺作為主體,使其含有玻璃纖維、矽灰石、特定之碳黑及銅化合物。該樹脂組成物亦與專利文獻2有同樣之缺點,且必須使用特定之碳黑,以脂肪族聚醯胺作為主體的話,耐候暴露後之黑色的褪色、耐候性之改善效果不充分,有改善之餘地。
針對上述之課題,如專利文獻4所示,其揭示藉由對結晶性脂肪族聚醯胺樹脂以特定之比例組合非晶性聚醯胺樹脂、丙烯酸系樹脂、雲母、玻璃纖維、碳黑、及銅化合物,可得到耐候性優異之玻璃纖維強化聚醯胺樹脂組成物。然而,專利文獻4揭示的玻璃纖維強化聚醯胺樹脂組成物,雖耐候性有一定程度優異,但有無法得到非常讓人滿意的成形品之外觀或耐候性之情形。
[先前技術文獻]
[專利文獻]
[專利文獻1]日本專利3442502號公報
[專利文獻2]日本特開2000-273299號公報
[專利文獻3]日本特開2002-284990號公報
[專利文獻4]日本專利6172415號公報
[發明所欲解決之課題]
前述專利文獻4之玻璃纖維強化聚醯胺樹脂組成物,若按公知市場的要求,耐候性、成形品外觀還算符合要求之等級,惟,並無法認定其符合近年來更高的要求,尤其成形品之紋理面之均勻性的要求、暴露在嚴苛的使用環境之情形仍可維持優異成形品外觀之耐候性的要求,此仍為課題。
本發明係鑑於此新課題而創造,目的在於提供一種玻璃纖維強化聚醯胺樹脂組成物,藉此可得到表面外觀(紋理面之均勻性)極為優異,且具有即使處在暴露於屋外,尤其暴露於降雨的使用條件下仍可維持優異表面外觀之耐候性之成形品。
[解決課題之手段]
本案發明人為了達成該目的而深入研究之結果,發現以特定之比例來摻和(含有)結晶性脂肪族聚醯胺樹脂、非晶性聚醯胺樹脂、丙烯酸系樹脂、雲母、玻璃纖維、碳黑、及銅化合物,可提供一種玻璃纖維強化聚醯胺樹脂組成物,藉此可得到表面外觀(紋理面之均勻性)非常優異,且具有可維持優異表面外觀之耐候性之成形品,進而完成本發明。
亦即,本發明採用下列之構成。
(1)一種玻璃纖維強化聚醯胺樹脂組成物,其特徵在於,分別地以(17~30):(10~16):(3~8):(10~25):(20~50):(1~8)之質量比來含有結晶性脂肪族聚醯胺樹脂(A)、非晶性聚醯胺樹脂(B)、丙烯酸系樹脂(C)、雲母(D)、玻璃纖維(E)、及碳黑之母料(F);該(A)和(B)之質量比(B)/(A)符合0.50~0.61;且令該(A)~(F)成分之合計含量為100質量份時,含有0.005~1.0質量份之比例之銅化合物(G)。
(2)如(1)之玻璃纖維強化聚醯胺樹脂組成物,其中,非晶性聚醯胺樹脂(B)為半芳香族聚醯胺。
(3)一種車輛內裝用或車輛外裝用成形品,係由如(1)或(2)之玻璃纖維強化聚醯胺樹脂組成物構成。
(4)如(3)之車輛內裝用或車輛外裝用成形品,其係選自於由外把手、外門把手、輪蓋、車頂縱樑、門鏡底座、室內鏡臂、天窗導流板、散熱器風扇、散熱器格柵、軸承保持架、控制台盒、遮陽板臂、擾流板、及移門滑軌蓋構成之群組。
[發明之效果]
本發明之玻璃纖維強化聚醯胺樹脂組成物,表面外觀(紋理面之均勻性)非常優異,且具有即使處在暴露於屋外,尤其暴露於降雨的使用條件下仍可維持優異表面外觀之耐候性之成形品。
以下,具體地說明本發明。首先,針對本發明所使用之各成分進行說明。
本發明中,聚醯胺樹脂之結晶性/非晶性,係聚醯胺樹脂依據JIS K 7121:2012在升溫速度20℃/分鐘進行DSC測定時,表示明確的熔點峰部者為結晶性,未表示者為非晶性。
本發明之玻璃纖維強化聚醯胺樹脂組成物含有結晶性脂肪族聚醯胺樹脂(A)、非晶性聚醯胺樹脂(B)、丙烯酸系樹脂(C)、雲母(D)、玻璃纖維(E)、及碳黑之母料(F),且(A)、(B)、(C)、(D)、(E)、及(F)之各成分之質量比分別為(17~30):(10~16):(3~8):(10~25):(20~50):(1~8)之質量比,前述(A)和(B)之比(B)/(A)必須符合0.50~0.61。此外,本發明之玻璃纖維強化聚醯胺樹脂組成物令(A)~(F)成分之合計含量為100質量份時,含有0.005~1.0質量份之比例之銅化合物(G)。
就結晶性脂肪族聚醯胺樹脂(A)而言,可列舉如:將內醯胺或ω-胺基羧酸、二羧酸及二胺等作為原料,藉由它們的聚縮合而得到之聚醯胺樹脂,或它們的共聚物、混合物。就內醯胺或ω-胺基羧酸而言,可列舉例如:ε-己內醯胺、6-胺基己酸、ω-庚內醯胺(ω-enantolactam)、7-胺基庚酸、11-胺基十一酸、9-胺基壬酸、α-吡咯啶酮、α-哌啶等。就二羧酸而言,可列舉如:戊二酸、己二酸、壬二酸、癸二酸、辛二酸等,就二胺而言,可列舉如:丁二胺、己二胺、辛二胺、癸二胺、十一烷二胺、十二烷二胺等。就結晶性脂肪族聚醯胺樹脂(A)之具體例而言,宜為聚醯胺6、聚醯胺12、聚醯胺66、聚醯胺46、聚醯胺610、聚醯胺612、聚醯胺1010。
結晶性脂肪族聚醯胺樹脂(A)之相對黏度(96%硫酸法)宜為1.7~2.5之範圍。較理想為1.8~2.2之範圍,更理想為1.9~2.1之範圍。又,藉由相對黏度在此範圍內,可符合作為樹脂的韌性、流動性。
結晶性脂肪族聚醯胺樹脂(A)之含有比例,令本發明之玻璃纖維強化聚醯胺樹脂組成物中之(A)成分和後述之(B)~(F)成分之合計含量為100質量份時,宜為17~30質量份,較理想為18~28質量份,更理想為20~25質量份。
就非晶性聚醯胺樹脂(B)而言,係在DSC測定時的熱分析圖中未確認到結晶之熔解峰部的聚醯胺樹脂,就構成成分之二羧酸而言,可列舉如:對苯二甲酸、間苯二甲酸、己二酸、癸二酸等,就二胺而言,可列舉如:丁二胺、己二胺、間苯二甲二胺、對苯二甲二胺、十一烷二胺、十二烷二胺、2-甲基戊二胺、三甲基己二胺、胺乙基六氫吡𠯤、二胺甲基環己烷等。它們之中,考量同時符合高彎曲彈性率及高耐衝擊性,則宜為半芳香族聚醯胺。就半芳香族聚醯胺而言,宜為對苯二甲酸和間苯二甲酸及己二胺作為原料之聚醯胺6T/6I、對苯二甲酸和己二酸及己二胺作為原料之聚醯胺6T/66等較理想。就非晶性聚醯胺樹脂(B)而言,宜為聚醯胺6T/6I尤其理想。
非晶性聚醯胺樹脂(B)之相對黏度(96%硫酸法),無特別限制,理想範圍為1.6~2.4,更理想範圍為1.7~2.3。
非晶性聚醯胺樹脂(B)之含有比例,令本發明之玻璃纖維強化聚醯胺樹脂組成物中之(A)、(B)成分及後述之(C)~(F)成分之合計含量為100質量份時,宜為10~16質量份,較理想為10~15質量份,更理想為11~15質量份。
此外,前述(A)和(B)之質量比(B)/(A)必須符合0.50~0.61。質量比(B)/(A)宜為0.51~0.60。藉由結晶性脂肪族聚醯胺樹脂(A)及非晶性聚醯胺樹脂(B)之含量符合上述,且質量比(B)/(A)符合上述,從而可使聚醯胺樹脂組成物在熔融擠壓特性、機械特性、熱特性方面優異,可使由聚醯胺樹脂組成物得到之成形品之外觀(紋理面之均勻性)非常優異。此外,(B)/(A)為0.50~0.61之比時,可展現高彈性率,且能使在生產時之股線(Strand)穩定。
如上述,藉由使結晶性脂肪族聚醯胺樹脂(A)含有非晶性聚醯胺樹脂(B),耐候性改善效果可增大。理由可推論係因為丙烯酸系樹脂(C)之分散性、相容性會產生變化。
就丙烯酸系樹脂(C)而言,可列舉出甲基丙烯酸酯之均聚物或共聚物。就共聚物而言,宜含有甲基丙烯酸酯50質量%以上,更宜為70質量%以上。就甲基丙烯酸酸酯單體而言,具體可列舉如:甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯、甲基丙烯酸丁酯等之甲基丙烯酸烷基酯;如甲基丙烯酸-β-羥乙酯、N,N-二甲基胺乙基甲基丙烯酸酯等在烷基上的氫經羥基、胺基等取代之甲基丙烯酸烷基酯衍生物。此外,就與這些甲基丙烯酸酯單體進行共聚合之單體而言,可列舉如:丙烯酸甲酯、苯乙烯、α-甲基苯乙烯、丙烯腈等乙烯基單體。這些丙烯酸系樹脂(C)之中,尤其理想為聚甲基丙烯酸甲酯或聚甲基丙烯酸乙酯。
關於丙烯酸系樹脂(C)之熔融流動性,在230℃、37.3N條件下之熔體流動速率(MFR),宜為5g/10min以上,10g/10min以上較理想,15g/10min以上更理想。
丙烯酸系樹脂(C)之含有比例,於令本發明之玻璃纖維強化聚醯胺樹脂組成物中之(A)~(C)成分及後述(D)~(F)成分之合計含量為100質量份時,宜為3~8質量份,較理想為3~7質量份,更理想為4~6質量份。丙烯酸系樹脂(C)之含有比例在上述範圍內的話,可使由聚醯胺樹脂組成物得到之成形品之外觀(紋理面之均勻性)更為極優異,且耐候性亦可更優異。
本發明之玻璃纖維強化聚醯胺樹脂組成物中,丙烯酸系樹脂(C)之含有比例相對於聚醯胺樹脂(A)和(B)之合計100質量份,宜為7~25質量份。丙烯酸系樹脂(C)之含有比例未達上述範圍的話,改善耐候性之效果會變小,另一方面,超過上述範圍的話,強度、剛性、耐溶劑性、耐熱性的降低會有增大之傾向。
就雲母(D)而言,可列舉如:白雲母、金雲母、黑雲母、人造雲母等,可任意使用。雲母之形狀與橢圓相近且將長徑和短徑的平均作為粒徑時,考量到外觀與剛性之平衡,雲母之粒徑宜為約1~30μm。
雲母(D)之含有比例,於令本發明之玻璃纖維強化聚醯胺樹脂組成物中之(A)~(D)成分及後述(E)及(F)成分之合計含量為100質量份時,宜為10~25質量份,較理想為15~22質量份。雲母(D)之含有比例未達上述範圍的話,改善成形品之外觀之效果會變小,另一方面,超過上述範圍的話,流動性或機械強度會有劣化傾向。
玻璃纖維(E)之剖面可為圓形或扁平任一者。就扁平剖面玻璃纖維而言,相對於纖維之長手方向為垂直之剖面中包含略橢圓形、略長圓形、略繭形,扁平度宜為1.5~8,進一步2~5較理想。此處之扁平度係在假定相對於玻璃纖維之長手方向為垂直之剖面外接的最小面積為長方形並將此長方形之長邊的長度作為長徑且短邊之長度作為短徑時長徑/短徑之比。扁平度未達上述範圍的話,與圓形剖面之玻璃纖維在形狀上不會有大差異,故導致會有無法充分改善成形物之耐衝擊性之情形。另一方面,扁平度超過上述範圍的話,聚醯胺樹脂中體積密度會增高而無法在聚醯胺樹脂中均勻地分散,有成形物之耐衝擊性無法充分改善之情形。本發明中,藉由使用具有略長圓形之剖面且扁平度為2~5之玻璃纖維,可使其展現更高之機械物性。
玻璃纖維(E)之含有比例,於令本發明之玻璃纖維強化聚醯胺樹脂組成物中之(A)、(B)、(C)、(D)、(E)成分及後述(F)成分之合計含量為100質量份時,宜為20~50質量份,較理想為25~45質量份,更理想為30~45質量份。玻璃纖維(E)之含有比例未達上述範圍的話,成形品之剛性會不足,另一方面,超過上述範圍的話,會有無法展現與含量相符之補強效果之傾向。
製造本發明之玻璃纖維強化聚醯胺樹脂組成物時,尤其使用扁平剖面玻璃纖維時,宜以玻璃纖維(E)之0.1~1.0質量%之比例添加聚醯胺反應性矽烷偶聯劑。為了使聚醯胺用切股之集束劑和基體樹脂之黏接性改善,會預先將少量矽烷偶聯劑含在纖維束中。然而,預先可附著在纖維束之胺基矽烷偶聯劑之量,由於為了讓纖維束在擠壓時不會發生解纖不良而有上限,故進行更添加補足不足的部分為理想。
就碳黑之母料(F)中之碳黑而言,無特別限制,可列舉例如:熱碳黑、槽製碳黑、乙炔碳、導電碳黑、爐黑等。符合平均粒子徑落在10~40μm之範圍、BET吸著法的比表面積落在50~300m2
/g之範圍、使用鄰苯二甲酸二丁酯之吸油量的測定值落在50cc/100g~150cc/100g之範圍之條件為理想。母料中含有30~60質量%之碳黑為理想。
就碳黑之母料(F)之基礎樹脂而言,除了低密度聚乙烯(LDPE)、高密度聚乙烯(HDPE)、超高分子量聚乙烯(UHMWPE)等為代表的各種聚乙烯以外,還可列舉出:乙烯-丙烯之無規共聚物及嵌段共聚物、乙烯-丁烯之無規共聚物及嵌段共聚物等乙烯和α-烯烴的共聚物;乙烯-丙烯酸甲酯、乙烯-丙烯酸丁酯等乙烯和不飽和羧酸酯的共聚物;乙烯-乙酸乙烯酯等乙烯和脂肪族乙烯酯的共聚物等聚乙烯系樹脂、聚苯乙烯;聚(α-甲基苯乙烯)、聚(對甲基苯乙烯)等均聚物、苯乙烯-丙烯腈共聚物(AS樹脂)、苯乙烯單體和馬來醯亞胺、N-苯基馬來醯亞胺等馬來醯亞胺系單體、或丙烯醯胺等丙烯醯胺系單體的共聚物等。
碳黑之母料(F)之含有比例,於令本發明之玻璃纖維強化聚醯胺樹脂組成物中之(A)~(F)成分之合計含量為100質量份時宜為1~8質量份,較宜為2~6質量份,更理想為3~6質量份。作為碳黑之含量,宜為0.3~4.5質量份,較宜為0.5~3.0質量份。碳黑之母料(F)之含有比例未達上述範圍的話,對於耐候性的貢獻會減少,另一方面,超過上述範圍的話,會有損害機械強度、剛性之傾向。
就銅化合物(G)而言,可列舉如:氯化銅、溴化銅、碘化銅、乙酸銅、乙醯丙酮銅、碳酸銅、硼氟化銅、檸檬酸銅、氫氧化銅、硝酸銅、硫酸銅、草酸銅等。本發明之玻璃纖維強化聚醯胺樹脂組成物中,銅化合物(G)之含有比例,於令本發明之玻璃纖維強化聚醯胺樹脂組成物中之(A)~(F)之成分之合計含量為100質量份時,宜為0.005~1.0質量份,較宜為0.01~0.5質量份。銅化合物(G)之含有比例未達上述範圍的話,耐熱老化性會有劣化之傾向,另一方面,超過上述範圍的話,並不會改善到比該耐熱老化性還要更好,有物性降低之傾向。
本發明亦可以和銅化合物併用的方式來含有鹵化鹼化合物作為穩定劑。就此鹵化鹼化合物而言,可列舉如:溴化鋰、碘化鋰、溴化鉀、碘化鉀、溴化鈉及碘化鈉,尤宜為碘化鉀。
此外,本發明之玻璃纖維強化聚醯胺樹脂組成物只要在不損及本發明之特性之範圍,除了上述(A)~(G)之必須成分以外,還可含有纖維狀強化材、無機填充材、作為光或熱穩定劑之苯酚系氧化防止劑或磷系抗氧化劑、脫模劑、結晶成核劑、潤滑劑、阻燃劑、抗靜電劑、顏料、染料等之任意成分。本發明之玻璃纖維強化聚醯胺樹脂組成物中,(A)~(G)之必須成分以外之任意成分之合計含量宜為最大10質量%。本發明之玻璃纖維強化聚醯胺樹脂組成物中,(A)~(G)之必須成分占合計之90質量%以上為理想,占95質量%以上更理想。此外,考量耐候性之觀點,令本發明之玻璃纖維強化聚醯胺樹脂組成物之(A)~(F)之成分之合計含量為100質量份時,矽灰石理想為5質量份以下,不含則更理想。
就本發明之玻璃纖維強化聚醯胺樹脂組成物之製造方法而言,無特別限制,可利用公知的混練方法將各成分進行熔融混練而得。具體而言,混練裝置亦無限制,可列舉例如:單軸或雙軸之擠壓機、混練機、捏合機等,考量到生產面尤其以雙軸擠壓機為理想。螺桿排列亦無特別限制,但為了更均勻分散各成分而設置捏合區為理想。就具體之方法而言,對於聚醯胺樹脂(A)、(B)、及丙烯酸系樹脂(C)之混合物,將碳黑之母料(F)、銅化合物(G)、其他任意成分利用攪拌器和其預混合,從料筒將其投入至單軸或雙軸之擠壓機後,在聚醯胺樹脂(A)、(B)及丙烯酸系樹脂(C)中至少一部分呈熔融之狀態時,對於熔融混合物中利用進料將雲母(D)、玻璃纖維(E)投入至單軸或雙軸之擠壓機,熔融混練後吐出股線狀再進行冷卻,裁切而製得。
本發明之玻璃纖維強化聚醯胺樹脂組成物,由於係藉由如上述之組成而製得,故特徵在於具有如下列所示優異耐候性。亦即,使用了氙弧燈耐候試驗機之耐候試驗(依據JIS K-7350-2後之色差ΔE宜為3.5以下,較宜為2.5以下,更宜為2.0以下。耐候試驗之詳情如後述之實施例記載的步驟。藉由色差ΔE為上述值以下,可耐受暴露於降雨之屋外之用途。
[實施例]
本發明的效果可由下列的實施例而具體表示,但只要不脫離本發明之技術思想,則不受限於下列實施例。又,實施例中之特性值的評價係根據下列方法而進行。
(1)聚醯胺樹脂之相對黏度:將聚醯胺樹脂0.25g溶解於96%之硫酸25ml,將此溶液10ml放入至奧士華黏度管,在20℃之條件進行測定並藉由下式而算出。
RV=T/T0
RV:相對黏度、T:樣品溶液的落下時間、T0:溶劑的落下時間
(2)彎曲強度,彎曲彈性率:依據ISO-178而進行測定。
(3)紋理面均勻表面性:使用經紋理加工的板狀的模具(紋理深度:30μm),利用射出成形機(東芝機械股份有限公司製,IS80)在樹脂溫度285℃、模具溫度80℃之條件進行成形,製作出厚度2.5mm之成形品後,以肉眼判斷紋理面的表面性。
[判斷基準]
○:整個表面皆有良好的紋理轉印性,無光澤斑。
△:雖整個表面皆有良好的紋理轉印性,但部分有光澤斑。
╳:有部分之紋理轉印性不同,有光澤斑。
(4)耐候性之評價
色差ΔE:針對經上述(3)而製得之附紋理面之成形品,依據JIS K-7350-2,使用氙弧燈耐候試驗機(Suga Test Instruments Co.,Ltd.製XL75),進行耐候試驗(黑盤溫度:63±2℃、相對濕度:50±5%、照射方法:120分鐘中18分鐘降雨(水噴射)、照射時間:1250小時、照射度:波長300nm~400nm 60W/m2
・S、光學濾鏡:(內)石英,(外)硼矽酸鹽♯275)。針對耐候試驗前後之紋理平板,使用東京電色公司製分光測色計TC-1500SX進行測定L、a、b值,進而算出色差ΔE。
耐候試驗後之成形品表面外觀(強化材露出的有無):依據下述之基準進行判斷。
[判斷基準]
○:無觀察到強化材之露出。
△:稍微觀察到強化材之露出。
╳:觀察到強化材之露出。
耐候試驗後之成形品表面之紋理狀態:依據下述之基準進行判斷。
[判斷基準]
○:可清楚觀察到紋理之模樣。
△:紋理之模樣有一部分不明顯。
╳:紋理之模樣不明顯。
使用的原料如下述。
・結晶性脂肪族聚醯胺樹脂(A)
PA6:聚醯胺6,MEIDA公司製「M2000」,相對黏度2.0
PA66:聚醯胺66,Rhodia 公司製「Stabamide 23AE」,相對黏度2.4
・非晶性聚醯胺樹脂(B)
G21:聚醯胺6T6I,瑞士遠東(EMS)股份有限公司製「Grivory G21」,相對黏度2.0
G16:聚醯胺6T6I,瑞士遠東(EMS)股份有限公司製「Grivory G16」,相對黏度1.8
・丙烯酸系樹脂(C)
聚甲基丙烯酸甲酯,可樂麗股份有限公司製「PARAPET GF」
・雲母(D)
Repco公司製「S-325」
・玻璃纖維(E)
日本電氣硝子股份有限公司製「T-275H」(圓形剖面玻璃纖維切股:直徑11μm)
・碳黑之母料(F)
SUMIKA COLOR CO., LTD.製「EPC-840」,基礎樹脂LDPE樹脂,碳黑含量43質量%
・銅化合物(G)
溴化銅(II):和光純藥公司製純度99.9%
<實施例1~9、比較例1~4>
以表1所示含有比例將雲母(D)、玻璃纖維(E)以外之成分進行乾摻,使用科倍隆公司製排出式雙軸擠壓機「STS35mm」(滾筒12區塊構成)並以缸筒溫度280℃、螺桿轉速250rpm之擠壓條件進行熔融混合,然後,再以側進料的方式供給雲母(D)、玻璃纖維並進行熔融混練。將從擠壓機被擠壓出的股線予以急速冷卻並利用絞線機進行丸粒化。將得到的丸粒在100℃之條件乾燥12小時後,利用射出成形機(東芝機械股份有限公司製,IS80)在缸筒溫度285℃、模具溫度90℃之條件成形為紋理平板來供評價。評價結果亦表示於表1。
[表1]
單 位 | 實 施 例 1 | 實 施 例 2 | 實 施 例 3 | 實 施 例 4 | 實 施 例 5 | 實 施 例 6 | 實 施 例 7 | 實 施 例 8 | 實 施 例 9 | 比 較 例 1 | 比 較 例 2 | 比 較 例 3 | 比 較 例 4 | ||
組 成 | 結晶性脂肪族聚醯胺樹脂(A)PA6 | 質量份 | 21.5 | 22.5 | 21.5 | 24 | 21.5 | 20.5 | 21.5 | 0 | 21.5 | 23.5 | 24 | 23.5 | 21.5 |
結晶性脂肪族聚醯胺樹脂(A)PA66 | 質量份 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 21.5 | 0 | 0 | 0 | 0 | 0 | |
非晶性聚醯胺樹脂(B) G21 | 質量份 | 12.5 | 11.5 | 13 | 14.5 | 12.5 | 11.5 | 12.5 | 12.5 | 0 | 10.5 | 14.5 | 14.5 | 17 | |
非晶性聚醯胺樹脂(B) G16 | 質量份 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 12.5 | 0 | 0 | 0 | 0 | |
丙烯酸系樹脂(C) | 質量份 | 4 | 4 | 4 | 3.5 | 4 | 6 | 4 | 4 | 4 | 4 | 2 | 4 | 2 | |
雲母(D) | 質量份 | 20 | 20 | 20 | 20 | 16 | 20 | 21 | 20 | 20 | 20 | 20 | 20 | 20 | |
玻璃纖維(E) | 質量份 | 37.5 | 37.5 | 37.5 | 33.5 | 41.5 | 37.5 | 38.5 | 37.5 | 37.5 | 37.5 | 35 | 35 | 37.5 | |
碳黑之母料(F) | 質量份 | 4.5 | 4.5 | 4 | 4.5 | 4.5 | 4.5 | 2.5 | 4.5 | 4.5 | 4.5 | 4.5 | 3 | 2 | |
銅化合物(G) | 質量份 | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | |
(B)/(A) | - | 0.58 | 0.51 | 0.60 | 0.60 | 0.58 | 0.56 | 0.58 | 0.58 | 0.58 | 0.45 | 0.60 | 0.62 | 0.79 | |
評價結果 | 彎曲強度 | MPa | 280 | 280 | 280 | 275 | 290 | 280 | 285 | 280 | 280 | 280 | 278 | 280 | 283 |
彎曲彈性率 | GPa | 18 | 18 | 18 | 17 | 19 | 18 | 18 | 18 | 18 | 18 | 18 | 18 | 18 | |
紋理面均勻表面性 | - | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ╳ | ○ | △ | △ | |
耐 候 性 | 色差 ΔE | - | 2.0 | 2.0 | 2.0 | 2.3 | 2.0 | 1.3 | 2.1 | 2.0 | 2.0 | 2.0 | 3.1 | 2.1 | 3.7 |
強化材露出的有無 | - | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | △ | △ | △ | ╳ | |
試驗後之紋理的狀態 | - | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ╳ | △ | △ | ╳ |
從表1可知,實施例1~9之試驗片,其耐候試驗前後的色差ΔE小,表面外觀(紋理面之均勻性)非常優異,且具有即使耐候試驗後仍可維持優異之表面外觀之耐候性。另一方面,比較例1之試驗片,其無法得到符合期望之表面外觀(紋理面之均勻性)。比較例2之試驗片則雖表面外觀(紋理面之均勻性)優異,但在耐候試驗後無法維持優異之表面外觀。比較例3、4之試驗片,其表面外觀(紋理面之均勻性)稍差,在耐候試驗後無法維持表面外觀。
[產業上利用性]
本發明之玻璃纖維強化聚醯胺樹脂組成物可適當地使用於外把手、外門把手、輪蓋、車頂縱樑、門鏡底座、室內鏡臂、天窗導流板、散熱器風扇、散熱器格柵、軸承保持架、控制台盒、遮陽板臂、擾流板、移門滑軌蓋等車輛用之內裝、外裝零件用途。
Claims (4)
- 一種玻璃纖維強化聚醯胺樹脂組成物,其特徵在於, 分別地以(17~30):(10~16):(3~8):(10~25):(20~50):(1~8)之質量比來含有結晶性脂肪族聚醯胺樹脂(A)、非晶性聚醯胺樹脂(B)、丙烯酸系樹脂(C)、雲母(D)、玻璃纖維(E)、及碳黑之母料(F); 該(A)和(B)之質量比(B)/(A)符合0.50~0.61;且 令該(A)~(F)成分之合計含量為100質量份時,含有0.005~1.0質量份之比例之銅化合物(G)。
- 如請求項1之玻璃纖維強化聚醯胺樹脂組成物,其中,非晶性聚醯胺樹脂(B)為半芳香族聚醯胺。
- 一種車輛內裝用或車輛外裝用成形品,係由如請求項1或2之玻璃纖維強化聚醯胺樹脂組成物構成。
- 如請求項3之車輛內裝用或車輛外裝用成形品,其係選自於由外把手、外門把手、輪蓋、車頂縱樑、門鏡底座、室內鏡臂、天窗導流板、散熱器風扇、散熱器格柵、軸承保持架、控制台盒、遮陽板臂、擾流板、及移門滑軌蓋構成之群組。
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