CN100577412C - 多层层合体 - Google Patents
多层层合体 Download PDFInfo
- Publication number
- CN100577412C CN100577412C CN200580002188A CN200580002188A CN100577412C CN 100577412 C CN100577412 C CN 100577412C CN 200580002188 A CN200580002188 A CN 200580002188A CN 200580002188 A CN200580002188 A CN 200580002188A CN 100577412 C CN100577412 C CN 100577412C
- Authority
- CN
- China
- Prior art keywords
- multilayer laminate
- fluorine resin
- acid anhydrides
- mentioned
- layer
- 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 - Fee Related
Links
- 229920001577 copolymer Polymers 0.000 claims abstract description 56
- 150000008065 acid anhydrides Chemical group 0.000 claims abstract description 31
- 239000004734 Polyphenylene sulfide Substances 0.000 claims abstract description 22
- 229920000069 polyphenylene sulfide Polymers 0.000 claims abstract description 22
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000446 fuel Substances 0.000 claims abstract description 12
- 239000005977 Ethylene Substances 0.000 claims abstract description 10
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 73
- 239000011737 fluorine Substances 0.000 claims description 70
- 229920005989 resin Polymers 0.000 claims description 68
- 239000011347 resin Substances 0.000 claims description 68
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 66
- 239000000178 monomer Substances 0.000 claims description 35
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 24
- 230000004048 modification Effects 0.000 claims description 22
- 238000012986 modification Methods 0.000 claims description 22
- 150000001412 amines Chemical class 0.000 claims description 21
- -1 amino compound Chemical class 0.000 claims description 19
- 238000007334 copolymerization reaction Methods 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 7
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 claims description 5
- 238000010030 laminating Methods 0.000 claims description 5
- 150000008064 anhydrides Chemical class 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- 229920005992 thermoplastic resin Polymers 0.000 abstract description 41
- 238000001125 extrusion Methods 0.000 abstract description 3
- 239000006087 Silane Coupling Agent Substances 0.000 abstract 1
- 125000003277 amino group Chemical group 0.000 abstract 1
- 230000004888 barrier function Effects 0.000 abstract 1
- 239000000295 fuel oil Substances 0.000 abstract 1
- 125000005004 perfluoroethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 51
- 239000011229 interlayer Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 229920001707 polybutylene terephthalate Polymers 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 9
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 8
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 230000003252 repetitive effect Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000008676 import Effects 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 229940117958 vinyl acetate Drugs 0.000 description 5
- 101100137463 Bacillus subtilis (strain 168) ppsA gene Proteins 0.000 description 4
- 101100464932 Bacillus subtilis (strain 168) ppsC gene Proteins 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 101100342406 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) PRS1 gene Proteins 0.000 description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 101150056693 pps1 gene Proteins 0.000 description 4
- 101100464927 Bacillus subtilis (strain 168) ppsB gene Proteins 0.000 description 3
- 101100464936 Bacillus subtilis (strain 168) ppsD gene Proteins 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- 150000002221 fluorine Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 229920006324 polyoxymethylene Polymers 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- AVYGCQXNNJPXSS-UHFFFAOYSA-N 2,5-dichloroaniline Chemical compound NC1=CC(Cl)=CC=C1Cl AVYGCQXNNJPXSS-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- 229920000106 Liquid crystal polymer Polymers 0.000 description 2
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007705 chemical test Methods 0.000 description 2
- 239000012933 diacyl peroxide Substances 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 229920002313 fluoropolymer Polymers 0.000 description 2
- 239000004811 fluoropolymer Substances 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000005001 laminate film Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229920001470 polyketone Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 1
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 description 1
- UHMWWIKRVZTBBR-UHFFFAOYSA-N 1-chloro-1,1,2,2,3-pentafluoropropane Chemical compound FCC(F)(F)C(F)(F)Cl UHMWWIKRVZTBBR-UHFFFAOYSA-N 0.000 description 1
- YACLCMMBHTUQON-UHFFFAOYSA-N 1-chloro-1-fluoroethane Chemical class CC(F)Cl YACLCMMBHTUQON-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- FGRJGEWVJCCOJJ-UHFFFAOYSA-N 2,2-dimethylaziridine Chemical compound CC1(C)CN1 FGRJGEWVJCCOJJ-UHFFFAOYSA-N 0.000 description 1
- BRPSAOUFIJSKOT-UHFFFAOYSA-N 2,3-dichloroaniline Chemical class NC1=CC=CC(Cl)=C1Cl BRPSAOUFIJSKOT-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- RPBWMJBZQXCSFW-UHFFFAOYSA-N 2-methylpropanoyl 2-methylpropaneperoxoate Chemical compound CC(C)C(=O)OOC(=O)C(C)C RPBWMJBZQXCSFW-UHFFFAOYSA-N 0.000 description 1
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 description 1
- JPVNTYZOJCDQBK-UHFFFAOYSA-N 3-ethenoxypropan-1-amine Chemical compound NCCCOC=C JPVNTYZOJCDQBK-UHFFFAOYSA-N 0.000 description 1
- CAMBAGZYTIDFBK-UHFFFAOYSA-N 3-tert-butylperoxy-2-methylpropan-1-ol Chemical compound CC(CO)COOC(C)(C)C CAMBAGZYTIDFBK-UHFFFAOYSA-N 0.000 description 1
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical compound NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000005263 alkylenediamine group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- QGEOKXWFGANCJL-UHFFFAOYSA-N ethenyl acetate;hydrochloride Chemical compound Cl.CC(=O)OC=C QGEOKXWFGANCJL-UHFFFAOYSA-N 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000002828 fuel tank Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- LIBWSLLLJZULCP-UHFFFAOYSA-N n-(3-triethoxysilylpropyl)aniline Chemical compound CCO[Si](OCC)(OCC)CCCNC1=CC=CC=C1 LIBWSLLLJZULCP-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000005634 peroxydicarbonate group Chemical group 0.000 description 1
- 229920001596 poly (chlorostyrenes) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B1/00—Layered products having a non-planar shape
- B32B1/08—Tubular products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/286—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysulphones; polysulfides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
- B32B27/322—Layered products comprising a layer of synthetic resin comprising polyolefins comprising halogenated polyolefins, e.g. PTFE
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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Abstract
提供了阻燃料性、耐燃油性、机械强度以及层间粘合力均优良的多层层合体。它是直接层压由含有酸酐残基的含氟树脂(例如，四氟乙烯/乙烯/(全氟乙基)乙烯/衣康酸酐共聚物)形成的层与由胺改性的热塑性树脂(例如，用含有氨基的硅烷偶联剂改性的聚苯硫醚)形成的层而形成的多层层合体。该多层层合体可通过共挤出成形来制造，由于层间粘合力优良，因此可适用于燃料软管等的用途。
Description
技术领域
本发明涉及阻燃料性、耐燃油性、机械强度以及层间粘合力均优良的多层层合体。
背景技术
聚四氟乙烯、四氟乙烯/全氟(乙烯基醚烷基乙烯基醚)系共聚物、乙烯/四氟乙烯系共聚物等氟系聚合物(以下，亦称为含氟树脂)耐热性、耐化学性、耐油性、耐气候性、气密性、阻燃料性、脱模性、非粘着性、防污性等均优良，被使用在半导体工业或汽车工业等各种领域。伴随着用途的不断广泛化，在需要提高含氟树脂的机械强度、降低成本的情况下，研究了含氟树脂与含氟树脂以外的机械强度优良的热塑性树脂形成的多层层合体。
特别是作为汽车的燃料输送用软管，要求具有阻燃料性、耐燃油性、机械强度等，提出了在内层使用阻燃料性以及耐燃油性优良的含氟树脂，在外层使用机械强度优良的聚酰胺的多层层压软管(例如，参考日本专利特开平2-107371号公报以及日本专利特开平5-8353号公报)。为了适应今后的排气限制强化，提出了含氟树脂与聚酰胺之间插入阻燃料性非常优良的热塑性树脂的中间层而形成的多层层压软管(参考日本专利特开2003-127256号公报以及日本专利特开2000-329266号公报)。作为构成中间层的热塑性树脂，有聚苯硫醚、聚对苯二甲酸乙二酯、聚对苯二甲酸丁二醇酯、聚萘二甲酸乙二酯等。但是该多层层压软管中，含氟树脂层与中间层的热塑性树脂层之间的粘合强度不充分。
另外，公知有含氟树脂与热塑性树脂形成的多层层压膜(例如，参照日本专利特开2002-67241号公报以及日本专利特开2001-138338号公报)，提出了脱模膜等的用途。但是，由于该多层层压膜是通过电晕处理含氟树脂膜的表面后涂敷粘合剂再层压热塑性树脂膜的工序制造的，因此生产性不高。
发明的揭示
发明要解决的课题
本发明是以上述背景为基础来开发的，目的是提供层间粘合力以及生产性均优良的多层层合体。
解决课题的手段
本发明是解决上述课题的发明，以下述内容为要点。
(1)多层层合体，其特征在于，具有直接层压由含有酸酐残基的含氟树脂形成的层与由胺改性的热塑性树脂形成的层而形成的层压结构。
(2)如上述(1)所述的多层层合体，其特征在于，上述含氟树脂是乙烯/四氟乙烯系共聚物。
(3)如上述(1)或(2)所述的多层层合体，其特征在于，相对于构成含氟树脂的全部聚合单元，上述含氟树脂中的酸酐残基含量为0.01～3摩尔％。
(4)如上述(1)～(3)所述的多层层合体，其特征在于，上述含氟树脂是使含氟单体与具有聚合性不饱和键的酸酐共聚而得的含氟聚合物。
(5)如上述(4)所述的多层层合体，其特征在于，上述具有聚合性不饱和键的酸酐选自马来酸酐、衣康酸酐、柠康酸酐以及5-降冰片烯-2，3-二羧酸酐的1种或1种以上。
(6)如上述(1)～(5)中任一项所述的多层层合体，上述热塑性树脂是基于选自聚苯硫醚、聚对苯二甲酸乙二酯、聚对苯二甲酸丁二醇酯、聚萘二甲酸乙二酯、聚萘二甲酸丁二醇酯、液晶高分子、聚乙烯醇、乙烯/乙烯醇共聚物、脂肪族聚酮、聚缩醛以及聚烯烃的至少1种的树脂。
(7)如上述(1)～(6)中任一项所述的多层层合体，其特征在于，上述胺改性的热塑性树脂是聚苯硫醚。
(8)如上述(1)～(7)中任一项所述的多层层合体，其特征在于，上述胺改性的热塑性树脂由将具有氨基的化合物与热塑性树脂熔融混炼制造而得。
(9)如上述(8)所述的多层层合体，其特征在于，上述具有氨基的化合物是具有氨基的硅烷偶联剂。
(10)如上述(1)～(9)中任一项所述的多层层合体，其特征在于，多层层合体是燃料输送用软管。
(11)上述(1)～(10)中任一项所述的多层层合体的制造方法，其特征在于，将含有酸酐残基的含氟树脂与胺改性的热塑性树脂共挤出成形。
发明的效果
本发明的多层层合体阻燃料性、耐燃油性均非常优良，机械强度、层间粘合力也优良。另外，多层层合体的生产性优良。在表面还有含氟树脂的层时，该表面脱模性、非粘着性、防污性等均优良。
实施发明的最佳方式
本发明中，作为含有酸酐残基的含氟树脂，较好为在主链、侧链、高分子末端具有酸酐残基的含氟树脂。在此，酸酐残基是具有以酸酐为基础的结构的官能团。相对于构成含氟树脂的全部聚合单元，酸酐残基的含量较好为0.01～3摩尔％，更好为0.05～2摩尔％，最好为0.1～1摩尔％。
作为向含氟树脂中导入酸酐残基的方法，可例举如使含氟单体与具有聚合性不饱和键的酸酐(以下，称为AM单体)共聚的方法、在可向高分子末端导入酸酐残基的聚合引发剂或者链转移剂的存在下聚合含氟单体的方法、在自由基产生剂的存在下熔融混合AM单体与含氟树脂将该酸酐接枝聚合到含氟树脂的方法。较好为，使含氟单体与AM单体共聚的方法。
本发明中，当含有酸酐残基的含氟树脂是将含氟单体与AM单体共聚而得的含氟共聚物时，相对于全部聚合单元，基于AM单体的重复单元的含量较好为0.01～3摩尔％，更好为0.05～2摩尔％，最好为0.1～1摩尔％。
作为AM单体，较好为选自马来酸酐、衣康酸酐(以下，称为IAH)、柠康酸酐(以下，称为CAH)以及5-降冰片烯-2，3-二羧酸酐(以下，称为NAH)的1种或1种以上。更好为选自IAH、CAH以及NAH的1种或1种以上，最好为IAH。
上述含氟共聚物中，也可含有基于AM单体水解而得的衣康酸、柠康酸、5-降冰片烯-2，3-二羧酸、马来酸等二羧酸的重复单元。含有基于该二羧酸的重复单元时，作为上述基于AM单体的重复单元表示基于AM单体的重复单元与基于二羧酸的重复单元的合计量。
作为本发明中的含氟树脂，可例举如含氟单体的聚合物、共聚物，或者含氟单体与含氟单体以外的单体形成的共聚物。
作为含氟单体，可例举如四氟乙烯(以下，称为TFE)、三氟乙烯、1，1-二氟乙烯(以下，称为VDF)、氟化乙烯、氯三氟乙烯(以下，称为CTFE)、六氟丙烯(以下，称为HFP)、CF2＝CFRf(在此，Rf为碳原子数为2～10的多氟烷基)、CH2＝CX(CF2)nY(在此，X以及Y分别独立地表示氢或氟原子、n是2～8的整数)表示的化合物等含氟烯烃、CF2＝CFO(CF2)2F、CF2＝CFO(CF2)3F(以下，称为PPVE)等全氟(烷基乙烯基醚)、CF2＝CFOCH2CF3等含有氢原子的(多氟烷基)三氟乙烯基醚等。较好为选自TFE、VDF、PPVE以及CH2＝CX(CF2)nY的1种或1种以上。更好为TFE。含氟单体可单独使用1种，也可将2种或2种以上并用。
作为上述CH2＝CX(CF2)nY表示的化合物，较好为n＝2～4的化合物。作为具体例，可例举如CH2＝CF(CF2)2F、CH2＝CF(CF2)3F、CH2＝CF(CF2)4F、CH2＝CF(CF2)2H、CH2＝CF(CF2)3H、CH2＝CF(CF2)4H、CH2＝CH(CF2)2F、CH2＝CH(CF2)3F、CH2＝CH(CF2)4F、CH2＝CH(CF2)2H、CH2＝CH(CF2)3H、CH2＝CH(CF2)4H等。更好为CH2＝CF(CF2)2F、CH2＝CH(CF2)2F、CH2＝CH(CF2)2H或者CH2＝CF(CF2)2H，最好为CH2＝CH(CF2)2F。共聚该化合物而得的含氟树脂阻燃料性、耐应力开裂性等优良。
作为含氟单体以外的单体，可例举如乙烯(以下，称为E)、丙烯、丁烯等烃系烯烃、乙基乙烯基醚、丁基乙烯基醚、甲基乙烯氧基丁基碳酸酯(メチルビニロキシブチルカ一ボネ一ト)、缩水甘油乙烯基醚等乙烯基醚；醋酸乙烯酯、氯醋酸乙烯酯、丁酸乙烯酯、三甲基乙酸乙烯酯、苯甲酸乙烯酯、丁烯酸乙烯酯等乙烯酯等。较好为E。可单独使用1种含氟单体以外的单体，也可将2种或2种以上并用。
作为含氟树脂的具体例，可例举如TFE/E系共聚物、TFE/HFP系共聚物、TFE/PPVE系共聚物、TFE/VDF/HFP系共聚物、TFE/VDF系共聚物、CTFE/E系共聚物等。较好为TFE/E系共聚物。作为TFE/E系共聚物，较好为TFE/E/CH2＝CH(CF2)4F共聚物或者TFE/E/CH2＝CH(CF2)2F共聚物，更好为TFE/E/CH2＝CH(CF2)2F共聚物。
另外，作为含有基于AM单体的重复单元的聚合物的较好具体例，可例举如TFE/PPVE/IAH共聚物、TFE/PPVE/CAH共聚物、TFE/PPVE/NAH共聚物、TFE/HFP/IAH共聚物、TFE/HFP/CAH共聚物、TFE/HFP/NAH共聚物、TFE/VdF/IAH共聚物、TFE/VdF/CAH共聚物、TFE/CH2＝CH(CF2)4F/IAH/E共聚物、TFE/CH2＝CH(CF2)4F/CAH/E共聚物、TFE/CH2＝CH(CF2)2F/IAH/E共聚物、TFE/CH2＝CH(CF2)2F/CAH/E共聚物、CTFE/CH2＝CH(CF2)4F/IAH/E共聚物、CTFE/CH2＝CH(CF2)4F/CAH/E共聚物、CTFE/CH2＝CH(CF2)2F/IAH/E共聚物、CTFE/CH2＝CH(CF2)2F/CAH/E共聚物、TFE/HFP/PPVE/IAH共聚物、TFE/HFP/PPVE/CAH共聚物、TFE/HFP/PPVE/NAH共聚物等。
TFE/E系共聚物中，基于TFE的聚合单元/基于E的聚合单元的摩尔比较好为30/70～70/30，更好为45/55～65/35，最好为50/50～65/35。如果基于TFE的聚合单元/基于E的聚合单元的摩尔比过小，则多层层合体的耐热性、耐气候性、耐化学性、气密性、阻燃料性等不充分，如摩尔比过大，则多层层合体的机械强度、熔融成形性等不充分。如在该范围内，则多层层合体的耐热性、耐气候性、耐化学性、气密性、阻燃料性、机械强度、熔融成形性等均优良。
当TFE/E系共聚物含有基于TFE以及E以外的单体的聚合单元时，相对于氟系聚合物中全部聚合单元，基于TFE以及E以外的单体的聚合单元的含量较好为0.01～20摩尔％，更好为0.05～15摩尔％，最好为0.1～10摩尔％。
本发明中含氟树脂的体积流速(以下，称为Q值。)较好为0.1～1000mm3/秒，更好为5～500mm3/秒，最好为10～200mm3/秒。Q值是表示含氟共聚物的熔融流动性的指标，成为分子量的基准。Q值大表示分子量低，小表示分子量高。Q值是使用岛津制作所制流速测定仪，在比含氟树脂的熔点高50℃的温度下，于负荷7kg下，从直径2.1mm、长8mm的孔板(orifice)中挤出时的含氟共聚物的挤出速度。如在该范围内，则含氟树脂挤出成形性、机械强度均优良。
作为本发明中含氟树脂的制造方法，可例举如悬浮聚合、溶液聚合、乳液聚合、本体聚合等方法。特好为自由基聚合，更好为在自由基聚合引发剂、链转移剂、聚合介质的存在下，聚合含氟单体的溶液聚合。
作为自由基聚合引发剂，较好为半衰期为10小时、温度为0～100℃的引发剂，更好为20～90℃的引发剂。作为具体例，可例举如、偶氮二异丁腈等偶氮化合物；过氧化二碳酸二异丙酯等过氧化二碳酸酯；叔丁基过氧化新戊酸酯、过异丁酸叔丁酯、过乙酸叔丁酯等过氧化酯；异丁酰基过氧化物、辛酰基过氧化物、苯甲酰基过氧化物、月桂酰基过氧化物等非氟系二酰基过氧化物；(Z(CF2)pCOO)2(在此，Z为氢原子、氟原子或者氯原子，p为1～10的整数)等含氟二酰基过氧化物；过硫酸钾、过硫酸钠、过硫酸铵等无机过氧化物。
作为聚合介质，可例举如氟化烃、氯化烃、氟氯烃、醇、烃等有机溶媒；水性介质等。作为链转移剂，可例举如甲醇、乙醇等醇；1，3-二氯-1，1，2，2，3-五氟丙烷、1，1-二氯-1-氟乙烷等氯氟烃；戊烷、己烷、环己烷等烃等。聚合条件没有特别的限定，聚合温度较好为0～100℃，更好为20～90℃。聚合压力较好为0.1～10MPa，更好为0.5～3MPa。聚合时间较好为1～30小时，更好为2～10小时。
使用本发明的多层层合体作为燃料输送用软管时，与燃料接触的内层较好为由具有导电性的含氟树脂形成的内层，更好为由含有导电性炭黑的含氟树脂形成的内层。作为导电性尺度的表面电阻率较好小于等于1×109Ω/□，特好为小于等于1×105Ω/□。
作为本发明中的热塑性树脂，较好为选自聚苯硫醚、聚对苯二甲酸乙二酯、聚对苯二甲酸丁二醇酯、聚萘二甲酸乙二酯、聚萘二甲酸丁二醇酯、液晶高分子、聚乙烯醇、乙烯/乙烯醇共聚物、脂肪族聚酮、聚缩醛以及聚烯烃的至少1种。更好为选自聚苯硫醚、聚对苯二甲酸乙二酯、聚对苯二甲酸丁二醇酯、聚萘二甲酸乙二酯以及聚萘二甲酸丁二醇酯的至少1种。
本发明中的胺改性是指使用各种方法，使上述热塑性树脂与具有氨基的化合物反应。作为胺改性的热塑性树脂，较好为含有氨基的热塑性树脂。作为胺改性的方法，可例举如在制造热塑性树脂时，共聚具有氨基的单体的方法；聚合时使用具有氨基的引发剂或者链转移剂，在热塑性树脂的高分子链末端导入氨基的方法；在热塑性树脂中接枝聚合具有氨基的单体的方法；使热塑性树脂与氨气接触，在高分子链末端导入氨基的方法；将热塑性树脂与具有氨基的化合物或者具有氨基的热塑性树脂熔融混炼，在热塑性树脂中导入氨基的方法等。作为胺改性的方法，较好为将热塑性树脂与具有氨基的化合物熔融混炼，在树脂中导入氨基的方法。
作为上述具有氨基的化合物，可例举如3-氨丙基三乙氧基硅烷、N-苯基-3-氨丙基三乙氧基硅烷、N-(2-氨乙基)-3-氨丙基三甲氧基硅烷、3-氨丙基甲基二甲氧基硅烷等具有氨基的硅烷偶联剂、n-己胺等碳原子数1～20的烷基胺类、六亚甲基二胺等碳原子数1～20的亚烷基二胺类、氨丙基乙烯基醚、2，2’-偶氮二异丁脒二盐酸盐(2，2’-アゾビス(2-メチルプロピオンアミジン)ジヒドロクロライド)等。较好为具有氨基的硅烷偶联剂。
特好为用具有氨基的硅烷偶联剂将聚苯硫醚改性。改性时具有氨基的硅烷偶联剂的使用量较好是相对于聚苯硫醚100质量份为0.1～15质量份，更好为1～10质量份。如在该范围内，则与含有酸酐残基的含氟树脂的粘合性优良。
作为胺改性的方法，较好为共聚具有氨基的单体的方法，或者在聚合时使用具有氨基的链转移剂向热塑性树脂的高分子链末端导入氨基的方法。
例如，热塑性树脂是聚苯硫醚的情况时，当用1，4-二氯苯和硫化钠来制造聚苯硫醚时，通过添加2，5-二氯苯胺等具有氨基的二氯苯类(具有氨基的单体)得到具有氨基侧链的聚苯硫醚。另外，通过添加4-氯苯胺(具有氨基的阻聚剂)等得到末端基具有氨基的聚苯硫醚。相对于所使用的1，4-二氯苯，具有氨基的单体的使用量较好为0.05～10摩尔％，更好为0.1～5摩尔％。另外，相对于所使用的1，4-二氯苯，具有氨基的链转移剂的使用量较好为0.01～10摩尔％，更好为0.1～5摩尔％。
作为本发明的多层层合体的制造方法，较好为将具有酸酐残基的含氟树脂与胺改性的热塑性树脂共挤出成形的方法，或者将由含有酸酐残基的含氟树脂形成的膜与由胺改性的热塑性树脂形成的膜层压的方法。更好为共挤出成形的方法。共挤出成形中，将该含氟树脂与该热塑性树脂从不同的挤出机的吐出口吐出，通过在使它们以熔融状态接触的同时通过模具，将该含氟树脂与该热塑性树脂直接层压成形为多层层压软管。
本发明的多层层合体中，由含氟树脂形成的层与由热塑性树脂形成的层之间的层间粘合力非常优良。例如，本发明的多层层合体具有大于等于2.0N/cm，特别是大于等于3.5N/cm的层间粘合力，另外，即使是简易粘合强度，也大于等于0.1N/cm，特别是大于等于0.5N/cm。本发明的多层层合体的层间粘合力优良的原因并非十分明确，认为是由以下原因引起的，即，在成形时，通过将由该含氟树脂形成的层与由该热塑性树脂形成的层以熔融状态接触，含氟树脂所含的酸酐残基与热塑性树脂所含的氨基反应，形成酰胺酸键，再通过脱水反应形成酰亚胺键等，在两层之间形成了化学键。
本发明的多层层合体具有将由含有酸酐残基的含氟树脂形成的层与由胺改性的热塑性树脂形成的层直接层压而得的层压结构。作为本发明的多层层合体，较好为将由含有酸酐残基的含氟树脂形成的层与由胺改性的热塑性树脂形成的层直接层压而得的2层层合体。另外，在该2层层合体再层压其它热塑性树脂形成的层或其它含氟树脂(除了含有酸酐残基的含氟树脂)而得的多层层合体也较好。另外，也较好为具有将上述2层层合体多重层叠的结构的多层层合体。
作为本发明的多层层合体，更好为在该2层层合体的由胺改性的热塑性树脂形成的层的一侧，再层压由其它热塑性树脂形成的层而形成的具有3层或者3层以上层数的层合体。该情况时，可得到成本低、机械强度或阻化学试液性均优良的多层层合体。作为其它的热塑性树脂，可例举如聚对苯二甲酸乙二酯、聚对苯二甲酸丁二醇酯、聚萘二甲酸乙二酯、聚萘二甲酸丁二醇酯等聚酯类；聚乙烯、聚丙烯等等聚烯烃类；乙烯/醋酸乙烯共聚物；聚醋酸乙烯；聚乙烯醇；乙烯/乙烯醇共聚物；聚苯乙烯；聚氯化乙烯；聚丙烯腈、聚甲醛、聚苯硫醚、聚苯醚、聚碳酸酯、聚酰胺酰亚胺、聚酰亚胺、聚醚酰亚胺、聚砜、多芳基化合物、聚酰胺等。
另外，作为本发明的多层层合体，更好为在该2层层合体的由含有酸酐残基的含氟树脂形成的层一侧，再层压其它含氟树脂而得的具有3层或者3层以上的层数的层合体。这种情况时，可得到阻燃料性、阻化学试液性均优良的多层层合体。作为其它的含氟树脂的具体例，可例举如TFE/E系共聚物、TFE/HFP系共聚物、TFE/PPVE系共聚物、TFE/VDF/HFP系共聚物、TFE/VDF系共聚物、CTFE/E系共聚物等。
本发明的多层层合体的厚度，较好为10μm～2cm，更好为50μm～1cm。另外，由含有酸酐残基的含氟树脂形成的层的厚度较好为5μm～5000μm，更好为50μm～500μm。另外，由胺改性的热塑性树脂形成的层的厚度，较好为5μm～1.5cm，更好为50μm～1cm。
以下，例举实施例以及比较例来说明本发明，但本发明不限于此。另外，层间粘合力的评价方法如下听述。
[层间粘合力(N/cm)]
纵向切断2层层压软管，制成8mm×15cm的长方形试料。在内层与外层之间的层间剥离所得试料的一端，将剥离的边端部分固定在拉伸试验机(オリエンテツク公司制)的夹具中，以进行180°剥离时的剥离强度为层间粘合力。
[简易粘合强度(N/cm)]
将压力成形所得的厚度为100μm的具有酸酐基的含氟树脂膜以及胺改性的聚苯硫醚膜重合，脉冲热封口机使两膜热熔着得到层压膜。将该层压膜的没有熔着的边端部分用拉伸试验机(オリエンテツク公司制)的夹盘固定，进行180°剥离时的剥离强度为简易粘合力。
[合成例1]
将聚苯硫醚(大日本油墨化学工业公司制LD-10、熔融粘度1000Pa·s，以下称为PPS1)6.0kg与作为具有氨基的硅烷偶联剂的N-(2-氨乙基)-3-氨丙基三甲氧基硅烷(信越化学工业公司制KBM-603，以下称为KBM-603)143g充分混合，使用料筒温度设定在300℃的双轴挤出机挤出成形，得到胺改性的聚苯硫醚(以下，称为PPS2)的颗粒(以下，称为颗粒1)4.8kg。PPS2的红外吸收光谱中，在3300cm-1检出氨基的吸收。
[合成例2]
向内容积为500ml的不锈钢制反应釜中添加N-甲基吡咯烷酮(以下，称为NMP)128.8g、Na2S·9H2O 117.2g、NaOH 0.16g，一边通入氮气一边在约2小时内升温至205℃进行脱水。之后将反应釜冷却至150℃，向其中添加使1，4-二氯苯70g以及2，5-二氯苯胺8g溶解至NMP40g中所得的液体，在1小时内升温至250℃，在250℃使之反应2小时。将反应釜冷却至室温，将内容物用60℃的温水洗浄，接着在100℃干燥，通过将所得的固形成分在220℃进行退火1小时，得到聚苯硫醚(以下，称为PPS3)。在PPS3的红外吸收光谱中，于3370cm-1检出氨基的吸收。
[合成例3]
将聚苯硫醚(大日本油墨化学工业制LC-5、熔融粘度300Pa·s)39g与0.93g的KBM-603在试验混炼机(ラボプラストミル)(东洋精机制作所制)中，于300℃、以70rpm熔融混炼2分钟，得到胺改性聚苯硫醚(以下，称为PPS4)。
[实施例1]
作为含有酸酐残基的含氟树脂，使用含有衣康酸酐残基的TFE/E共聚物(共聚组成：基于TFE的聚合单元/基于E的聚合单元/基于衣康酸酐的聚合单元/基于C2F5CH＝CH2的聚合单元＝58.1/39.0/0.8/2.1(摩尔比))(以下，称为含氟树脂1)。
向形成外层的料筒中供给颗粒1，向形成内层的料筒中供给含氟树脂1，使之分别移送至料筒的输送段。在颗粒1以及含氟树脂1的输送段中的加热温度为300℃、十字头模的温度为300℃的条件下进行共挤出成形，得到2层层压软管。该层压软管的外径为8mm、内径为6mm、厚度为1mm，PPS2的外层、含氟树脂1的内层的厚度分别为0.5mm、0.5mm。该层压软管中层间粘合力为4.5N/cm。
[比较例1]
除了将颗粒1变更为PPS1之外，与实施例1同样实施，得到2层层压软管。该层压软管的外径为8mm、内径为6mm、厚度为1mm，PPS1的外层、含氟树脂1的内层的厚度分别为0.5mm、0.5mm。该层压软管的外层与内层完全不粘合，层间粘合力为0N/cm。
[实施例2～4]
测定含氟树脂1的膜与PPS3或者PPS4的膜的简易粘合强度。含氟树脂1与PPS3的简易粘合强度为0.7N/cm，含氟树脂1与PPS4的简易粘合强度为8.1N/cm。
[比较例2]
测定含氟树脂1的膜与PPS1的膜的简易粘合强度，但是两膜完全没有粘合，可简单剥离，不能测定剥离强度。
产业上利用的可能性
本发明的多层层合体可成形为膜、板、管、软管、罐、瓶等各种形状。特别适用于燃料输送用软管、燃料罐、保护膜、载体膜、膜结构物用膜、脱模膜、固化板等用途。
另外，将作为本申请的要求优先权基础的日本专利愿2004-5585号(2004年1月13日向日本特许厅提出申请)的全部说明书的内容在此引用作为本发明的说明书的内容。
Claims (8)
1.多层层合体，其特征在于，具有将由含有酸酐残基的含氟树脂形成的层与由胺改性的聚苯硫醚形成的层直接层压而构成的层压结构，上述含氟树脂是使含氟单体与具有聚合性不饱和键的酸酐共聚所得的含氟共聚物。
2.如权利要求1所述的多层层合体，其特征在于，上述含氟树脂是乙烯/四氟乙烯系共聚物。
3.如权利要求1或2所述的多层层合体，其特征在于，相对于构成含氟树脂的全部聚合单元，上述含氟树脂中的酸酐残基含量为0.01～3摩尔％。
4.如权利要求1所述的多层层合体，其特征在于，上述具有聚合性不饱和键的酸酐为选自马来酸酐、衣康酸酐、柠康酸酐以及5-降冰片烯-2，3-二酸酐的1种或1种以上。
5.如权利要求1所述的多层层合体，其特征在于，上述胺改性的聚苯硫醚通过将具有氨基的化合物与聚苯硫醚熔融混炼而制得。
6.如权利要求5所述的多层层合体，其特征在于，上述具有氨基的化合物是具有氨基的硅烷偶联剂。
7.如权利要求1所述的多层层合体，其特征在于，多层层合体是燃料输送用软管。
8.权利要求1～7中任一项所述的多层层合体的制造方法，其特征在于，将含有酸酐残基的含氟树脂与胺改性的聚苯硫醚共挤出成形，上述含氟树脂是使含氟单体与具有聚合性不饱和键的酸酐共聚所得的含氟共聚物。
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| JP2004005585 | 2004-01-13 | ||
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| JP (1) | JP4697596B2 (zh) |
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| BR (1) | BRPI0506781B1 (zh) |
| DE (1) | DE602005027535D1 (zh) |
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| US7959836B2 (en) * | 2005-03-02 | 2011-06-14 | Eastman Chemical Company | Process for the preparation of transparent, shaped articles containing polyesters comprising a cyclobutanediol |
| ATE433467T1 (de) * | 2005-04-19 | 2009-06-15 | Asahi Glass Co Ltd | Mehrschichtiges schlauchhaltiges fluorcopolymer |
| RU2412822C2 (ru) * | 2005-06-14 | 2011-02-27 | Асахи Гласс Компани, Лимитед | Многослойный материал из фторсодержащей смолы |
| JO2945B1 (en) * | 2006-09-13 | 2016-03-15 | سميث كلاين بيتشام كوربوريشن | Methods of giving prolonged hypoglycemic agents |
| JP2009006575A (ja) * | 2007-06-28 | 2009-01-15 | Nissan Motor Co Ltd | 多層ホース |
| CN101386218B (zh) * | 2007-09-14 | 2011-06-22 | 四川得阳化学有限公司 | 聚苯硫醚纤维复合层压板材的制造方法 |
| EP2209625B1 (en) | 2007-11-14 | 2019-03-20 | Dow Global Technologies LLC | Multi-layered article |
| US20100036073A1 (en) * | 2008-08-08 | 2010-02-11 | E. I. Du Pont De Nemours And Company | Non-Melt-Flowable Perfluoropolymer Comprising Repeating Units Arising From Tetrafluoroethylene and a Monomer Having a Functional Group and a Polymerizable Carbon-Carbon Double Bond |
| US20100034919A1 (en) * | 2008-08-08 | 2010-02-11 | E. I. Du Pont De Nemours And Company | Melt Processible Semicrystalline Fluoropolymer having Repeating Units Arising from Tetrafluoroethylene, Hexafluoropropylene, and Hydrocarbon Monomer Having a Carboxyl Group and a Polymerizable Carbon-Carbon Double Bond and Multi-Layer Articles Comprising a Layer of the Melt Processible Semicrystalline Fluoropolymer |
| US20100036074A1 (en) * | 2008-08-08 | 2010-02-11 | E. I. Du Pont De Nemours And Company | Melt-Flowable Fluoropolymer Comprising Repeating Units Arising from Tetrafluoroethylene and a Hydrocarbon Monomer Having a Functional Group and a Polymerizable Carbon-Carbon Double Bond |
| JP2012526142A (ja) * | 2009-05-08 | 2012-10-25 | スリーエム イノベイティブ プロパティズ カンパニー | 口腔ケア方法及びキット |
| CN102959341B (zh) * | 2010-06-29 | 2015-09-30 | 三菱工程塑料株式会社 | 树脂制罐 |
| CN102673882B (zh) * | 2012-06-06 | 2014-11-05 | 浙江金石包装有限公司 | 一种液体包装复合膜及其制备方法 |
| KR101526244B1 (ko) * | 2013-04-11 | 2015-06-10 | 이동권 | 폴리케톤 및 폴리올레핀 기반의 접착부재 및 이를 포함하는 접착 구조체 |
| EP3305523B1 (en) | 2015-06-05 | 2021-10-20 | AGC Inc. | Laminate |
| JP2020535986A (ja) * | 2017-09-28 | 2020-12-10 | サン−ゴバン パフォーマンス プラスティックス コーポレイション | 燃料管及びその製造方法および使用方法 |
| US10902696B2 (en) | 2018-09-18 | 2021-01-26 | Aristocrat Technologies Australia Pty Limited | Wheel display with moveable segments |
| US10713880B2 (en) | 2018-09-18 | 2020-07-14 | Aristocrat Technologies Australia Pty Limited | Electronic gaming machine with dynamic display |
| US11710368B2 (en) | 2021-02-26 | 2023-07-25 | Aristocrat Technologies, Inc. | Electronic gaming machine with dynamic display |
| CN113187819A (zh) * | 2021-04-20 | 2021-07-30 | 怀宁吉利来精密机械科技有限公司 | 高性能粘合复合自润滑复合材料和复合轴承 |
| US20220379578A1 (en) * | 2021-05-28 | 2022-12-01 | AGC Inc. | Fuel filler pipe |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH10311461A (ja) * | 1997-05-12 | 1998-11-24 | Asahi Glass Co Ltd | 燃料ホース |
| EP1165669B1 (en) * | 1999-03-02 | 2004-01-21 | 3M Innovative Properties Company | Compositions for fluoropolymer bonding to non-fluorinated polymers |
| EP1270208B1 (en) * | 2000-02-10 | 2019-01-30 | Daikin Industries, Ltd. | Laminated resin |
| US20030099799A1 (en) | 2000-03-03 | 2003-05-29 | Masaki Koike | Resin hose for fuel |
| JP2001285905A (ja) * | 2000-03-29 | 2001-10-12 | Hitachi Commun Syst Inc | マトリックススイッチ回路 |
| JP4209595B2 (ja) * | 2000-04-24 | 2009-01-14 | 旭硝子株式会社 | 燃料用ホース |
| DE60119505T2 (de) * | 2000-04-24 | 2006-09-21 | Asahi Glass Co., Ltd. | Kraftstoffschlauch |
| KR100387850B1 (ko) * | 2000-12-29 | 2003-06-18 | 현대자동차주식회사 | 폴리아미드 수지 조성물 및 이를 이용한 합성수지제품 |
| JP2004285905A (ja) * | 2003-03-20 | 2004-10-14 | Tokai Rubber Ind Ltd | 自動車用燃料ホース |
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Also Published As
| Publication number | Publication date |
|---|---|
| EP1704998A4 (en) | 2008-03-12 |
| WO2005068191A1 (ja) | 2005-07-28 |
| CN1910045A (zh) | 2007-02-07 |
| JPWO2005068191A1 (ja) | 2007-12-27 |
| EP1704998A1 (en) | 2006-09-27 |
| BRPI0506781B1 (pt) | 2015-06-02 |
| BRPI0506781A (pt) | 2007-05-22 |
| EP1704998B1 (en) | 2011-04-20 |
| US20070056681A1 (en) | 2007-03-15 |
| JP4697596B2 (ja) | 2011-06-08 |
| US7514132B2 (en) | 2009-04-07 |
| DE602005027535D1 (de) | 2011-06-01 |
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