CN115836111A - 无机增强聚酰胺树脂组合物 - Google Patents
无机增强聚酰胺树脂组合物 Download PDFInfo
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- CN115836111A CN115836111A CN202180048546.2A CN202180048546A CN115836111A CN 115836111 A CN115836111 A CN 115836111A CN 202180048546 A CN202180048546 A CN 202180048546A CN 115836111 A CN115836111 A CN 115836111A
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- Prior art keywords
- polyamide resin
- mass
- inorganic
- resin composition
- component
- Prior art date
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- 229920006122 polyamide resin Polymers 0.000 title claims abstract description 63
- 239000011342 resin composition Substances 0.000 title claims abstract description 39
- 229920005989 resin Polymers 0.000 claims abstract description 45
- 239000011347 resin Substances 0.000 claims abstract description 45
- 239000012779 reinforcing material Substances 0.000 claims abstract description 30
- 229920006039 crystalline polyamide Polymers 0.000 claims abstract description 24
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 16
- 229920006020 amorphous polyamide Polymers 0.000 claims abstract description 13
- 125000000524 functional group Chemical group 0.000 claims abstract description 5
- 125000003368 amide group Chemical group 0.000 claims abstract description 4
- 239000003365 glass fiber Substances 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 13
- 239000000835 fiber Substances 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- 229920013716 polyethylene resin Polymers 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 15
- 230000008094 contradictory effect Effects 0.000 abstract description 4
- 230000007774 longterm Effects 0.000 abstract description 4
- 239000012784 inorganic fiber Substances 0.000 abstract 1
- 238000005299 abrasion Methods 0.000 description 15
- 238000000034 method Methods 0.000 description 12
- -1 polyethylene Polymers 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 239000006087 Silane Coupling Agent Substances 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 6
- 239000000945 filler Substances 0.000 description 6
- 229920001903 high density polyethylene Polymers 0.000 description 6
- 239000004700 high-density polyethylene Substances 0.000 description 6
- 239000008188 pellet Substances 0.000 description 6
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 229920002292 Nylon 6 Polymers 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000000314 lubricant Substances 0.000 description 5
- 239000010687 lubricating oil Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000002344 surface layer Substances 0.000 description 5
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 229920002302 Nylon 6,6 Polymers 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 239000013077 target material Substances 0.000 description 4
- LWBHHRRTOZQPDM-UHFFFAOYSA-N undecanedioic acid Chemical compound OC(=O)CCCCCCCCCC(O)=O LWBHHRRTOZQPDM-UHFFFAOYSA-N 0.000 description 4
- PGGROMGHWHXWJL-UHFFFAOYSA-N 4-(azepane-1-carbonyl)benzamide Chemical compound C1=CC(C(=O)N)=CC=C1C(=O)N1CCCCCC1 PGGROMGHWHXWJL-UHFFFAOYSA-N 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910052882 wollastonite Inorganic materials 0.000 description 3
- 239000010456 wollastonite Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- PBLZLIFKVPJDCO-UHFFFAOYSA-N 12-aminododecanoic acid Chemical compound NCCCCCCCCCCCC(O)=O PBLZLIFKVPJDCO-UHFFFAOYSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- ZZYZUFNSKAIYCJ-UHFFFAOYSA-N 3-[(3-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1C(N)CCCC1CC1CC(N)CCC1 ZZYZUFNSKAIYCJ-UHFFFAOYSA-N 0.000 description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 2
- XVDXXIFPRDPQBG-UHFFFAOYSA-N 4-(2,2,3-trimethylazepane-1-carbonyl)benzamide Chemical compound CC1(C)C(C)CCCCN1C(=O)C1=CC=C(C(N)=O)C=C1 XVDXXIFPRDPQBG-UHFFFAOYSA-N 0.000 description 2
- IGSBHTZEJMPDSZ-UHFFFAOYSA-N 4-[(4-amino-3-methylcyclohexyl)methyl]-2-methylcyclohexan-1-amine Chemical compound C1CC(N)C(C)CC1CC1CC(C)C(N)CC1 IGSBHTZEJMPDSZ-UHFFFAOYSA-N 0.000 description 2
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 125000004018 acid anhydride group Chemical group 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 2
- 229910002113 barium titanate Inorganic materials 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000011231 conductive filler Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- 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 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 229910003472 fullerene Inorganic materials 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 description 2
- 229960001545 hydrotalcite Drugs 0.000 description 2
- 229910003437 indium oxide Inorganic materials 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 2
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- DJZKNOVUNYPPEE-UHFFFAOYSA-N tetradecane-1,4,11,14-tetracarboxamide Chemical compound NC(=O)CCCC(C(N)=O)CCCCCCC(C(N)=O)CCCC(N)=O DJZKNOVUNYPPEE-UHFFFAOYSA-N 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 2
- 239000003981 vehicle Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- GUOSQNAUYHMCRU-UHFFFAOYSA-N 11-Aminoundecanoic acid Chemical compound NCCCCCCCCCCC(O)=O GUOSQNAUYHMCRU-UHFFFAOYSA-N 0.000 description 1
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- PAOXFRSJRCGJLV-UHFFFAOYSA-N 2-[4-(2-aminoethyl)piperazin-1-yl]ethanamine Chemical compound NCCN1CCN(CCN)CC1 PAOXFRSJRCGJLV-UHFFFAOYSA-N 0.000 description 1
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- ZKLHYNVZTMYNHM-UHFFFAOYSA-N 3-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CC(N)CCC1 ZKLHYNVZTMYNHM-UHFFFAOYSA-N 0.000 description 1
- XUSNPFGLKGCWGN-UHFFFAOYSA-N 3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-amine Chemical compound NCCCN1CCN(CCCN)CC1 XUSNPFGLKGCWGN-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- OZUBMBIDHPBIDL-UHFFFAOYSA-N 4-Propylcyclohexylamine Chemical compound CCCC1CCC(N)CC1 OZUBMBIDHPBIDL-UHFFFAOYSA-N 0.000 description 1
- IMRKOERSTLKEAO-UHFFFAOYSA-N 4-methyldec-1-ene Chemical compound CCCCCCC(C)CC=C IMRKOERSTLKEAO-UHFFFAOYSA-N 0.000 description 1
- MBRGOFWKNLPACT-UHFFFAOYSA-N 5-methylnonane-1,9-diamine Chemical compound NCCCCC(C)CCCCN MBRGOFWKNLPACT-UHFFFAOYSA-N 0.000 description 1
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 1
- 239000004953 Aliphatic polyamide Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229920006060 Grivory® Polymers 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 229920003354 Modic® Polymers 0.000 description 1
- 241000180701 Nitzschia <flatworm> Species 0.000 description 1
- 229920000571 Nylon 11 Polymers 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
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Abstract
提供一种无机增强聚酰胺树脂组合物,其兼具高刚性和耐冲击性(高韧性)的相互矛盾的机械特性,流动性优异,进一步将无机纤维增强材料作为滑动对象材料时的长时间的耐磨损性(高滑动)优异。一种无机增强聚酰胺树脂组合物,其特征在于,其含有结晶性聚酰胺树脂(A)10~55质量%、非晶性聚酰胺树脂(B)1~20质量%、无机增强材料(C)40~70质量%以及具有能够与聚酰胺树脂的末端基和/或主链酰胺基反应的反应性官能团的改性聚烯烃树脂(D)0.5~10质量%,(A)成分和(D)成分的混合质量比满足0.01≤(D)/(A)≤0.2,并且(A)成分和(B)成分的混合质量比满足0.05≤(B)/(A)≤0.7。
Description
技术领域
本发明涉及一种高刚性高韧性的无机增强聚酰胺树脂组合物,具体是,涉及一种无机增强聚酰胺树脂组合物,其在由含有无机增强材料的树脂组合物构成的成形品作为对象材料时,长时间的耐磨损性优异。
背景技术
聚酰胺树脂由于机械特性、耐热性、耐冲击性、耐化学品性优异,而被广泛用于汽车部件、电机部件、电子部件、家庭杂货等。其中,已知的是以添加了玻璃纤维为代表的无机增强材料的聚酰胺树脂,刚性、强度、耐热性大幅提升,特别是,刚性与添加量呈比例提升。因此,无机纤维增强聚酰胺树脂组合物被广泛用作电子电机设备和机动车领域中的内部部件以及外部部件。近年,特别是由于电子电机部件中的制品壁厚的薄壁化,车辆用部件的小尺寸化,所要求的振动特性的水平日益提高。
另外,聚酰胺树脂除了机械特性,由于耐磨损性也优异,因此被广泛用于齿轮、凸轮轴承等各领域的滑动部件中。为了得到更优异的滑动特性,已知有混合二硫化钼、石墨以及氟树脂等固体润滑剂和各种润滑油、硅油等液体润滑剂等(例如,非专利文献1)。但是,这些滑动改良剂中,固体润滑剂的话需要混合大量的固体润滑剂,有显著降低作为基础的聚酰胺树脂的韧性的缺点。液体润滑剂虽然能够以相对少的量、高效地赋予滑动性,但存在多数情况下,与作为基础的树脂的相容性差,常有成形品的表面被这些液体润滑剂污染的情况,用途受到限制的缺点。
另外,作为改善诸如混合各种润滑剂配合导致的缺点的方法,提出了混合改性苯乙烯系共聚物和特定范围的分子量的改性高密度聚乙烯的方法(专利文献1),使用高粘度聚酰胺树脂的同时,混合改性聚乙烯的方法等(专利文献2)。
通过相关聚酰胺树脂组合物,能够提供没有上述这些缺点,滑动特性优异的成形品。这些聚酰胺树脂,在对象材料为金属的情况下,能够发挥大的滑动性提升效果。
现有技术文献
非专利文献
非专利文献1:福本修《塑料材料讲座〔16〕聚酰胺树脂(プラスチック材料講座〔16〕ポリアミド樹脂)》日刊工业新闻社(1970年)
专利文献
专利文献1:日本特开平8-157714号公报
专利文献2:WO2008/075699号公报
发明内容
发明要解决的问题
但是,近年,相对于成形品的薄壁化、成形品形状的复杂化的趋势导致需求高刚性高韧性材料,而尚未获得具有可满足该需求的充分机械特性的材料。此外进一步,近年,在成形品的轻量化过程中,在对象材料从金属变成彼此为相同的树脂时,为了提高刚性,这些聚酰胺树脂中大量填充无机增强材料的情况下,会发生由于存在于表面的无机增强材料导致对象材料被削下的问题。因此,无法得到充分满足高刚性和高滑动两者的材料。
本发明是鉴于上述现有技术的现状而发明的,其目的是,提供一种无机增强聚酰胺树脂组合物,其兼具高刚性和耐冲击性(高韧性)的相互矛盾的机械特性,流动性优异,进一步将无机纤维增强材料作为滑动对象材料时的长时间的耐磨损性(高滑动)优异。
解决问题的技术方案
本发明者们着眼于无机增强聚酰胺树脂之间的滑动中,影响磨损量的要因是成形品表面析出的无机增强材料的量,影响更大的是无机增强材料的端面和断裂面突出表面的量,以及由于无机增强材料变多而产生的树脂部分的脆性,为了实现上述课题进行了深入的研究,结果发现,从多方面的视角出发,通过平衡的选取配比无机增强聚酰胺树脂组合物中非晶性聚酰胺和改性聚烯烃,能够全部解决上述课题,完成了本发明。
即本发明,具有以下构成。
[1]
一种无机增强聚酰胺树脂组合物,其特征在于,其为含有结晶性聚酰胺树脂(A)10~55质量%、非晶性聚酰胺树脂(B)1~20质量%、无机增强材料(C)40~70质量%、以及具有能够与聚酰胺树脂的末端基团和/或主链酰胺基反应的反应性官能团的改性聚烯烃树脂(D)0.5~10质量%的无机增强聚酰胺树脂组合物,
(A)成分和(D)成分的混合质量比满足0.01≤(D)/(A)≤0.2、且(A)成分和(B)成分的混合质量比满足0.05≤(B)/(A)≤0.7。
[2]
根据[1]所述的无机增强聚酰胺树脂组合物,其特征在于,所述结晶性聚酰胺树脂(A)含有:结晶性聚酰胺树脂(A1),以及熔点比结晶性聚酰胺树脂(A1)高20℃以上的结晶性聚酰胺树脂(A2);(A1)成分和(A2)成分的混合质量比为0.1≤(A2)/(A1)≤0.5。
[3]
根据[1]或[2]中任一项所述的无机增强聚酰胺树脂组合物,其特征在于,所述改性聚烯烃树脂(D)为改性聚乙烯树脂。
[4]
根据[1]~[3]中任一项所述的无机增强聚酰胺树脂组合物,其特征在于,所述无机增强材料(C)为数均纤维长度为140μm以上的玻璃纤维。
发明效果
本发明的聚酰胺树脂组合物,由于兼具高刚性和耐冲击性的相互矛盾的机械特性,能够用于代替金属和薄壁化成形品,另外,由于作为流动性优异,进一步将无机纤维增强材料用作对象材料时的长时间的耐磨损性优异的高刚性高滑动材料,能够广泛地用于高滑动部件,由于能够容易地生产代替金属的无机增强聚酰胺树脂组合物及其成形品,用于电子电机部件的壳体和机动车内装以及外装的车辆用部件等中,可以实现前所未有的小型化。
具体实施方式
以下,就本发明的无机增强聚酰胺树脂组合物进行详细说明。
作为本发明中的结晶性聚酰胺树脂(A),只要是主链中具有酰胺键(-NHCO-)的结晶性聚合物没有特别限定,例如,可以例举聚酰胺6(NY6)、聚酰胺66(NY66)、聚酰胺46(NY46)、聚酰胺11(NY11)、聚酰胺12(NY12)、聚酰胺610(NY610)、聚酰胺612(NY612)、聚己二酰间苯二甲胺(MXD6)、对苯二甲酰己二胺聚合物(6T)、对苯二甲酰/己二酰己二胺聚合物(6T/66)、对苯二甲酰己二胺与ε-己内酰胺共聚物(6T/6)、对苯二甲酰三甲基己二胺聚合物(TMD-T)、己二酰/间苯二甲酰间苯二甲胺共聚物(MXD-6/I)、对苯二甲酰三甲基己二胺与ε-己内酰胺共聚物(TMD-T/6)、间苯二甲酰二氨基二环己基甲烷胺(CA)与十二内酰胺共聚物等结晶性聚酰胺树脂,或者是这些的混合物等,并不仅限于这些。本发明中,优选脂肪族聚酰胺,更优选为聚酰胺6、聚酰胺66。此外,使用2种聚酰胺时,通过使用两者的熔点相差20℃以上的不同物质,在控制固化速度方面是优选的。进一步,更优选结晶性聚酰胺树脂(A)包含结晶性聚酰胺树脂(A1)和熔点比结晶性聚酰胺树脂(A1)高20℃以上的结晶性聚酰胺树脂(A2),(A1)成分和(A2)成分的混合比为0.1≤(A2)/(A1)≤0.5。优选的一种方式是结晶性聚酰胺树脂(A1)为聚酰胺6,结晶性聚酰胺树脂(A2)为聚酰胺66。
本发明中,结晶性聚酰胺树脂(A)的相对粘度没有特别限定,可使用在96%硫酸溶液(聚酰胺树脂浓度1g/dl、温度25℃)下测定的相对粘度在1.5~3.5的范围的制品。优选为1.5~3.3。更优选为1.5~2.8。若为该范围,能够赋予树脂组合物即使在高度填充无机增强材料时也能注射成形的流动性,也能成型为小型/薄壁的成形品,也能够充分具有作为树脂的韧性。为得到相对粘度为1.5~3.5的聚酰胺树脂,可调节制造条件聚合为相对粘度为1.8~3.5的聚酰胺树脂,或是在制造相对粘度大于3.5的聚酰胺树脂后,使用降粘剂切断聚酰胺分子链的方法。作为降粘剂,脂肪族二羧酸、芳香族二羧酸等是有效的,具体能够例举草酸、丙二酸、琥珀酸、己二酸、壬二酸、癸二酸、邻苯二甲酸、对苯二甲酸等。相对于聚酰胺树脂100质量份,其添加量为混合0.1~3质量份左右通过熔融混炼得到。
本发明的聚酰胺树脂组合物中的结晶性聚酰胺树脂(A)含有率为10~55质量%。优选为15~45质量%、更优选为20~40质量%。
本发明中使用的非晶性聚酰胺树脂(B)是基于JIS K7121用差示扫描量热仪(DSC)测定时,不显示明确熔点之物。
作为构成非晶性聚酰胺树脂(B)的单体的具体例,可以例举双(4-氨基环己基)甲烷(有时简称为PACM)、双(3-氨基环己基)甲烷、双(3-甲基-4-氨基环己基)甲烷(MACM有时简称为)、2,2-双(4-氨基环己基)丙烷、异佛尔酮二胺、四亚甲基二胺、六亚甲基二胺、十一亚甲基二胺、十二亚甲基二胺、2,2,4/2,4,4-三甲基六亚甲基二胺(TMD)、5-甲基九亚甲基二胺、1,3-双(氨基甲基)环己烷、1,4-双(氨基甲基)环己烷、3-氨基环己基-4-氨基环己基甲烷、1-氨基-3-氨基甲基-3,5,5-三甲基环己烷、双(氨基丙基)哌嗪、双(氨基乙基)哌嗪等二胺类,此外作为二羧酸类,可以例举己二酸、辛二酸、壬二酸、癸二酸、十一烷二酸、十二烷二酸(有时简称为12)、十三烷二酸、十四烷二酸(有时简称为14)等碳原子数为4~36的直链状或具有烷基侧链的脂肪族二羧酸,对苯二甲酸(有时简称为T)、间苯二甲酸(有时简称为I)等芳香族二羧酸。作为氨基羧酸类,可以例举ε-己内酰胺、ω-月桂内酰胺(LL)等内酰胺类,6-氨基己酸、11-氨基十一烷酸、12-氨基十二烷酸等氨基羧酸等。
作为上述单体的组合的优选例,可以例举双(4-氨基环己基)甲烷(PACM)、双(3-氨基环己基)甲烷、双(3-甲基-4-氨基环己基)甲烷(MACM)、2,2-双(4-氨基-)环己基)丙烷等脂环族二胺与十一烷二酸、十二烷二酸、十三烷二酸、十四烷二酸等二羧酸的组合,具体可以例举12MACM、14MACM、10MACM/11、12MACM/I、I/MACM/LL、T/TMD、6T6I等聚合物或共聚物或者是混合物等,并不仅限于这些。
例如,结晶性聚酰胺树脂(A)为聚酰胺6时,优选为6T6I。
非晶性聚酰胺树脂的相对粘度(96%硫酸法),没有特别限定,优选范围为1.8~2.4。更优选为1.9~2.2的范围。
本发明的聚酰胺树脂组合物中的非晶性聚酰胺树脂(B)的含有率为1~20质量%。非晶性聚酰胺树脂(B)的配比量小于1质量%时,模具内的冷却固化速度变得过快,填料的上浮、流痕等外观不良变得严重,耐磨损性也变差。
另一方面,非晶性聚酰胺树脂(B)的配比量大于20质量%时,冷却固化速度变得过慢,脱模性变差,与模具密贴而无法脱模,在成形品表面出现脱模褶皱。进一步,结晶性变得过差,机械强度、冲击强度可能会变差。非晶性聚酰胺树脂(B)的含有率优选为2~15质量%、更优选为3~10质量%。
另外,本发明中,(A)成分和(B)成分的质量比需要满足下述式。
0.05≤(B)/(A)≤0.7
本发明中,通过使(B)/(A)在该范围中,能够得到更高水平的良好外观的成形品,(B)/(A)优选为0.08以上、0.4以下,更优选为0.10以上、0.2以下。
本发明中的无机增强材料(C)最有效地改良了强度和刚性以及耐热性等物性,具体可以例举玻璃纤维、碳纤维、氧化铝纤维、碳化硅纤维、氧化锆纤维等纤维状制品,硼酸铝、钛酸钾等晶须类,针状硅灰石,磨碎纤维等。另外,除了这些之外,可以使用玻璃珠、玻璃鳞片、玻璃中空微球、二氧化硅、滑石、高岭土、硅灰石、云母、氧化铝、水滑石、蒙脱石、石墨、碳纳米管、富勒烯、氧化锌、氧化铟、氧化锡、氧化铁、氧化钛、氧化镁、氢氧化铝、氢氧化镁、红磷、碳酸钙、钛酸钾、锆钛酸铅、钛酸钡、氮化铝、氮化硼、硼酸锌、硼酸铝、硫酸钡、硫酸镁、以层间剥离为目的而施以有机处理的层状硅酸盐等填充材料作为无机增强材料(C)。这些之中,特别优选使用玻璃纤维、碳纤维等。这些无机增强材料(C),可以仅为1种,也可以组合2种以上。
作为无机增强材料(C)使用纤维状增强材料时,在上述之中,特别优选使用玻璃纤维、碳纤维等。这些纤维状增强材料,优选为用有机硅烷系化合物、有机钛系化合物、有机硼烷系化合物以及环氧系化合物等硅烷偶联剂预处理之物,特别优选容易与羧酸基或和羧酸酐基反应之物。由于通过混合了以硅烷偶联剂处理的玻璃纤维的聚酰胺系树脂组合物能够得到机械特性和外观特性优异的成形品,因而是优选的。另外,即使在其他纤维状增强材料中,在未进行硅烷偶联剂处理的情况下,也能够后添加使用。
无机增强材料(C)为玻璃纤维时,能够优选使用切断为纤维长度1~20mm程度的短切原丝状的制品。作为玻璃纤维的截面形状,能够使用圆形截面以及非圆形截面的玻璃纤维。作为玻璃纤维的截面形状,从物性方面,优选非圆形截面的玻璃纤维。作为非圆形截面的玻璃纤维,相对于纤维长度的长度方向的垂直截面中可包括略椭圆系、略长圆系、略茧形系,扁平度优选为1.5~8。该扁平度是指,假设相对于玻璃纤维的长度方向垂直的截面中外接的最小面积的长方形,以该长方形的长边的长度作为长径,短边的长度作为短径时,长径/短径之比。对于玻璃纤维的粗度没有特别限定,短径为1~20μm、长径为2~100μm左右。
本发明的聚酰胺树脂组合物中的玻璃纤维的数均纤维长度,优选为140~700μm、更优选为180~400μm。通过使玻璃纤维长度为该范围,高强度、高刚性且流动性稳定。若在上述范围外,则其变得难以在聚酰胺树脂表面上取向填充,纤维端面会在表面露出,有耐磨损性降低的可能性。
玻璃纤维优选为以硅烷系、钛酸盐系等硅烷偶联剂处理之物,特别是优选使用以硅烷系硅烷偶联剂处理之物。
作为优选的硅烷系硅烷偶联剂,能够例举γ-缩水甘油氧基丙基三甲氧基硅烷、γ-缩水甘油氧基丙基甲基二乙氧基硅烷、β-(3,4-环氧环己基)乙基三甲氧基硅烷、γ-苯胺基丙基三甲氧基硅烷、γ-(2-氨基乙基)氨基丙基三甲氧基硅烷、γ-甲基丙烯酰氧基丙基三甲氧基硅烷、乙烯基三甲氧基硅烷、γ-巯基丙基三甲氧基硅烷等,特别是优选γ-缩水甘油氧基丙基三甲氧基硅烷、γ-苯胺基丙基三甲氧基硅烷、γ-(2-氨基乙基)氨基丙基三甲氧基硅烷、γ-甲基丙烯酰氧基丙基三甲氧基硅烷。
相对于总树脂组合物100质量%,无机增强材料(C)的配比量为40~70质量%、优选为45~67质量%、更优选为50~65质量%、进一步优选为55~65质量%。配比量若大于70质量%,生产性变差。另外,若小于40质量%,有时无法充分发挥增强材料的效果。
作为无机增强材料(C)之外的填充材(填料),除了增强用填料的之外,根据目的,能够使用导电性填料、磁性填料、阻燃填料、导热填料。具体可以例举玻璃珠、玻璃鳞片、玻璃中空微球、二氧化硅、滑石、高岭土、硅灰石、云母、氧化铝、水滑石、蒙脱石、羟基磷灰石、石墨、碳纳米管、富勒烯、氧化锌、氧化铟、氧化锡、氧化铁、氧化钛、氧化镁、氢氧化铝、氢氧化镁、红磷、碳酸钙、钛酸钾、锆钛酸铅、钛酸钡、氮化铝、氮化硼、硼酸锌、硼酸铝、硫酸钡、硫酸镁、硫化锌、铁、铝、铜、银等。这些填充材,不仅可以仅单独使用1种,也可以组合多种使用。作为形状,没有特别限定,可以使用针状、球状、板状、无定形等。
本发明中的改性聚烯烃树脂(D)是指对以下聚烯烃树脂改性之物。即,可以例举高密度聚乙烯、低密度聚乙烯、超高分子量聚乙烯、直链状低密度聚乙烯、聚丙烯、聚(1-丁烯)、聚(4-甲基戊烯)等烯烃系树脂。从耐磨损性的观点,这些聚烯烃系树脂中最优选的是高密度聚乙烯。改性聚烯烃树脂(D)的数均分子量优选为5~40万。
本发明中的改性前的高密度聚乙烯优选为数均分子量为5~40万、密度为0.94kg/cm2以上的高密度聚乙烯。数均分子量若小于5万,所得成形品的耐磨损性变得不充分,分子量若大于40万,变得难以成形,并不优选。
本发明中的高密度聚乙烯,在不损害其性质的范围内,可以与其他单体共聚,例如,丙烯、1-丁烯、戊烯、4-甲基-1-戊烯、己烯、辛烯、癸烯等α-烯烃,丁二烯、异戊二烯等二烯类,环戊烯、环己烯、环戊二烯等环烯烃类,丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯等丙烯酸酯类。
改性聚烯烃树脂(D)为提升其与聚酰胺树脂的相容性,具有能够与聚酰胺树脂的末端基团和/或主链酰胺基反应的反应性官能团。能够与聚酰胺树脂反应的官能团是指具体可以例举羧酸基、酸酐基、环氧基、恶唑啉基、氨基、异氰酸酯基等,这些之中,由于酸酐基与聚酰胺树脂的反应性高而特别优选,其中优选马来酸酐。
改性聚烯烃树脂(D)的配比量为总树脂组合物中0.1~10质量%,优选为0.5~7质量%、更优选为1~5质量%。适量混合改性聚烯烃树脂(D)时,通过滑动时的摩擦,在成形品的最表层形成由强韧的改性聚烯烃形成的覆盖层,抑制聚酰胺的脆性磨损,从而能够防止无机纤维增强材料突出表层。改性聚烯烃的熔点优选比聚酰胺树脂(A)以及(B)更低。这是因为相比聚酰胺树脂可由于摩擦热更先熔解容易形成表面覆盖层。若聚酰胺树脂组合物中聚酰胺树脂小于0.1质量%,无法形成充分厚度的覆盖层,耐磨损性的提升效果变低。若大于10质量%,由于表层的改性烯烃树脂浓度变高,降低了表层硬度,摩擦系数变大。进一步,使得无机增强聚酰胺树脂组合物的机械特性降低。
另外,本发明中,(A)成分和(D)成分的质量比需要满足下述式。
0.01≤(D)/(A)≤0.2
(D)/(A)优选为0.03以上、0.18以下,更优选为0.04以上、0.15以下,进一步优选为0.05以上、0.12以下。(D)/(A)若为0.01以下,无法形成充分厚度的覆盖层,耐磨损性的提升效果变低。
若大于0.2,由于表层的改性烯烃树脂浓度变高,表层硬度下降摩擦系数变大。进一步,无机增强聚酰胺树脂组合物的机械特性降低。
本发明的无机增强聚酰胺树脂组合物以差示扫描量热仪(DSC)测定的降温结晶温度(TC2)优选为170℃≤(TC2)≤190℃。另外,降温结晶温度(TC2)的测定,是使用差示扫描量热仪(DSC),通过在氮气流下以20℃/分钟的升温速度升温至300℃,在该温度下保持5分钟后,以10℃/分钟的速度降温至100℃测定时所得的峰温度。
进一步,降温结晶温度(TC2)不满足170℃≤(TC2)≤190℃时,由于聚酰胺树脂组合物的结晶化速度,导致无法得到更高水平的良好的成形品外观。
另外,本发明的无机增强聚酰胺树脂组合物中,可以根据需要添加耐热稳定剂、抗氧化剂、紫外吸收剂、光稳定剂、增塑剂、润滑剂、结晶成核剂、脱模剂、防静电剂、阻燃剂、颜料、染料或其他种类的聚合物等。本发明的无机增强聚酰胺树脂组合物,以所述(A)、(B)、(C)以及(D)成分的总计,优选为占90质量%以上、更优选为占95质量%以上。
作为本发明的聚酰胺树脂组合物的制造方法,只要是能够将本发明中的各成分的配比量正确地控制在上述的所定范围的熔融混炼挤出法就没有特别限定,优选使用单螺杆挤出机、双螺杆挤出机。
在将混合的树脂颗粒的形状、表观比重、摩擦系数等差异程度大的树脂颗粒投入挤出机的料斗部时,优选采用以下方法。
即,将结晶性聚酰胺树脂(A)、非晶性聚酰胺树脂(B)、改性聚烯烃树脂(D)预先混合投入挤出机的料斗部,将无机增强材料(C)以侧进料的方式投入的制造方法。
实施例
以下,通过实施例对本发明进一步详细地说明,但本发明不限于这些实施例。
本发明的实施例、比较例中使用的原材料如下所述。
(A)结晶性聚酰胺树脂
A1:聚酰胺6……东洋纺制“T-860”(RV2.0)熔点225℃
A2:聚酰胺66……东丽制“CM3000EF”(RV2.4)熔点265℃
(B)非晶性聚酰胺树脂
B:聚酰胺6T6I……EMS公司制“Grivory G21”(RV2.0)
(C)无机增强材料
C:玻璃纤维……日本电器硝子公司制“ECS03T-275H”
(D):改性聚烯烃
D1:马来酸酐改性聚乙烯……三菱化学制“MODIC DH0200”
D2:马来酸酐改性聚丙烯……普瑞曼聚合物公司制“MMP-006”
D3:未改性聚乙烯……普瑞曼聚合物公司制“6203B”
(E)其他添加剂
脱模剂:褐煤酸钙……日东化成工业制“CS-6CP”
稳定剂:溴化铜
各种评价方法如下所述。评价结果示于表1。
(1)聚酰胺树脂的相对粘度(RV)(96%硫酸溶液法)
使用乌氏粘度管,在25℃下96质量%硫酸溶液中,以聚酰胺树脂浓度1g/dl进行测定。
(2)聚酰胺树脂的熔点
使用差示扫描量热仪(Seiko Instruments株式会社制、EXSTAR 6000),在升温速度20℃/分钟下测定,求出吸热峰的温度。
(4)熔融指数(MFR):
根据ISO1133进行测定。测定温度:275℃、载重:5kg
(5)弯曲强度
根据ISO178进行测定。
(6)夏比耐冲击强度
根据ISO179-1进行测定。
(7)数均纤维长度
颗粒中残存玻璃纤维长度通过以下方法进行测定。
由于玻璃纤维高填充材料中的玻璃纤维之间的干涉多,测定时玻璃纤维容易破损,难以正确求出纤维长度,本发明中为了正确测定玻璃纤维长度,将熔融混炼得到的颗粒在650℃下高热2小时,不损坏玻璃纤维将玻璃纤维以灰分取出,将所得玻璃纤维浸入水中,将分散的玻璃纤维取出制为切片,随机选择1000个以上的玻璃纤维在数码显微镜(株式会社HIROX制KH-7700)下80倍观察的数均纤维长度。
(8)磨损特性
使用推力(thrust)式磨损试验机,使通过注射成形得到的聚酰胺树脂组合物的平板(尺寸:50mm×50mm)和与平板相同材质的圆筒成形品(外径20mm、内径14.4mm、接触面积1.51cm2)接触60分钟,在负载载重55.5kgf/cm2、速度5cm/sec的条件下连续滑动。之后,从磨损前后的平板和圆筒成形品的质量差和总磨损距离,算出每单位距离换算得到的磨损量(mg/km)和基于磨损试验时的结束的载重值算出的滑动摩擦系数。
(9)成形品外观的评价方法:
作为成形品外观,以下述方法测定评价镜面光泽度。
使用镜面加工100mm×100mm×3mm(厚度)的模具,在树脂温度280℃,模具温度80℃下制作成形品,根据JIS Z-8714测定入射角60度的光泽度。(数值越高,光泽度越好)
光泽度的测定结果根据下述判定标准进行评价。
◎:97以上
〇:95以上、小于97
△:90以上、小于95
×:小于90
实施例1~5、7、比较例1~6
铜化合物使用溴化铜水溶液。以表1所示的组成那样,将无机增强材料以外的各原料预混合,从双螺杆挤出机(TEM―75SS、芝浦机械)的料斗部投加,无机增强材料从双螺杆挤出机的第2侧进料器投加,该双螺杆挤出机在挤出机的上游侧起第1料筒(barrel)上设置主进料器(料斗部),进一步第4料筒上具有第1侧进料器、第8料筒上具有第2侧进料器。在双螺杆挤出机的料筒温度为280℃、螺杆旋转数为180rpm下进行混合,制成颗粒。所得颗粒,用热风干燥机干燥至水分率0.05%以下为止后,评价各种特性。评价结果如表1所示。
实施例6
除了将无机增强材料从双螺杆挤出机的第1侧进料器投加之外,与实施例1进行同样化合,制成颗粒。所得颗粒,用热风干燥机干燥至水分率0.05%以下为止后,评价各种特性。评价结果如表1所示。
[表1]
由表1的结果可知,本发明范围内的实施例1~7,机械特性、耐磨损性以高水平取得了平衡。另一方面,不含改性聚烯烃或非晶性聚酰胺树脂的比较例1、2耐磨损性和成形外观不良。(D)/(A)在范围外的比较例3机械特性降低,(B)/(A)在范围外的比较例4,玻璃上浮明显等成形品外观差,耐磨损性也变低。
工业上的可利用性
本发明的聚酰胺树脂组合物,由于兼具高刚性和耐冲击性的相互矛盾的机械特性,能够用于代替金属和薄壁化的成形品,另外,流动性优异,进一步由于是由含有无机纤维增强材料的树脂组合物构成的成形品作为对象材料时的长时间的耐磨损性优异高刚性高滑动材料,能够用于广泛用途的高滑动部件,由于容易生产能够代替金属的无机增强聚酰胺树脂组合物及其成形品,因此可用于电子电机部件的壳体、机动车内装以及外装,实现在车辆用部件等中至今尚未有的低尺寸化,极其有用。
Claims (4)
1.一种无机增强聚酰胺树脂组合物,其特征在于,其含有:10~55质量%的结晶性聚酰胺树脂A、1~20质量%的非晶性聚酰胺树脂B、40~70质量%的无机增强材料C,以及0.5~10质量%的改性聚烯烃树脂D,所述改性聚烯烃树脂D具有能够与聚酰胺树脂的末端基团和/或主链酰胺基反应的反应性官能团,
A成分和D成分的混合质量比满足0.01≤(D)/(A)≤0.2,并且A成分和B成分的混合质量比满足0.05≤(B)/(A)≤0.7。
2.根据权利要求1所述的无机增强聚酰胺树脂组合物,其特征在于,所述结晶性聚酰胺树脂A含有:结晶性聚酰胺树脂A1,以及熔点比结晶性聚酰胺树脂A1高20℃以上的结晶性聚酰胺树脂A2;
A1成分和A2成分的混合质量比为0.1≤(A2)/(A1)≤0.5。
3.根据权利要求1或2所述的无机增强聚酰胺树脂组合物,其特征在于,所述改性聚烯烃树脂D为改性聚乙烯树脂。
4.根据权利要求1~3中任一项所述的无机增强聚酰胺树脂组合物,其特征在于,所述无机增强材料C为数均纤维长度为140μm以上的玻璃纤维。
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