CN109982844A - 复合构件 - Google Patents
复合构件 Download PDFInfo
- Publication number
- CN109982844A CN109982844A CN201780067783.7A CN201780067783A CN109982844A CN 109982844 A CN109982844 A CN 109982844A CN 201780067783 A CN201780067783 A CN 201780067783A CN 109982844 A CN109982844 A CN 109982844A
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- CN
- China
- Prior art keywords
- polyamide
- acid
- component
- unit
- poly
- 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.)
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- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 239000004952 Polyamide Substances 0.000 claims abstract description 168
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 93
- 239000011347 resin Substances 0.000 claims abstract description 83
- 229920005989 resin Polymers 0.000 claims abstract description 83
- 239000011737 fluorine Substances 0.000 claims abstract description 79
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 78
- 229920001971 elastomer Polymers 0.000 claims abstract description 76
- 239000000806 elastomer Substances 0.000 claims abstract description 72
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims abstract description 15
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims abstract description 15
- 229920006345 thermoplastic polyamide Polymers 0.000 claims abstract description 5
- -1 amine compounds Chemical class 0.000 claims description 178
- 229920002647 polyamide Polymers 0.000 claims description 162
- 229920001577 copolymer Polymers 0.000 claims description 93
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 91
- 229920000570 polyether Polymers 0.000 claims description 50
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 46
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 44
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 41
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 27
- 150000002430 hydrocarbons Chemical group 0.000 claims description 27
- 150000004985 diamines Chemical class 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 24
- 125000005647 linker group Chemical group 0.000 claims description 20
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 17
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 15
- 150000003951 lactams Chemical class 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 13
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 9
- 229920001451 polypropylene glycol Polymers 0.000 claims description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- 229940058401 polytetrafluoroethylene Drugs 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- PBLZLIFKVPJDCO-UHFFFAOYSA-N omega-Aminododecanoic acid Natural products NCCCCCCCCCCCC(O)=O PBLZLIFKVPJDCO-UHFFFAOYSA-N 0.000 claims description 6
- GUOSQNAUYHMCRU-UHFFFAOYSA-N 11-Aminoundecanoic acid Chemical compound NCCCCCCCCCCC(O)=O GUOSQNAUYHMCRU-UHFFFAOYSA-N 0.000 claims description 4
- 239000004677 Nylon Substances 0.000 claims description 4
- 125000002252 acyl group Chemical group 0.000 claims description 4
- 229920001778 nylon Polymers 0.000 claims description 4
- QHSJIZLJUFMIFP-UHFFFAOYSA-N ethene;1,1,2,2-tetrafluoroethene Chemical compound C=C.FC(F)=C(F)F QHSJIZLJUFMIFP-UHFFFAOYSA-N 0.000 claims description 3
- 229920006355 Tefzel Polymers 0.000 claims description 2
- VJHDPVWEDUCKRQ-UHFFFAOYSA-N 12-aminododecanoic acid Chemical compound NCCCCCCCCCCCC(O)=O.NCCCCCCCCCCCC(O)=O VJHDPVWEDUCKRQ-UHFFFAOYSA-N 0.000 claims 1
- 229920005992 thermoplastic resin Polymers 0.000 abstract description 10
- 239000000178 monomer Substances 0.000 description 77
- 229910052799 carbon Inorganic materials 0.000 description 63
- 238000000034 method Methods 0.000 description 53
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 45
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 44
- 238000006116 polymerization reaction Methods 0.000 description 43
- 239000010410 layer Substances 0.000 description 41
- 229920000642 polymer Polymers 0.000 description 41
- 229920003734 UBESTA® Polymers 0.000 description 40
- 125000000524 functional group Chemical group 0.000 description 39
- 238000004519 manufacturing process Methods 0.000 description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 36
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 33
- 239000000126 substance Substances 0.000 description 30
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 29
- 150000001721 carbon Chemical group 0.000 description 27
- 239000002253 acid Substances 0.000 description 24
- 239000002585 base Substances 0.000 description 22
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 21
- 239000000243 solution Substances 0.000 description 20
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 19
- 229920002635 polyurethane Polymers 0.000 description 18
- 239000004814 polyurethane Substances 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 16
- 239000005977 Ethylene Substances 0.000 description 16
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 16
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 16
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 15
- 125000004430 oxygen atom Chemical group O* 0.000 description 15
- 125000001118 alkylidene group Chemical group 0.000 description 14
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 14
- 238000009740 moulding (composite fabrication) Methods 0.000 description 14
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 14
- 238000002844 melting Methods 0.000 description 13
- 230000008018 melting Effects 0.000 description 13
- 238000002156 mixing Methods 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 12
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 12
- 150000002148 esters Chemical group 0.000 description 12
- 235000019441 ethanol Nutrition 0.000 description 12
- 125000001153 fluoro group Chemical group F* 0.000 description 12
- 229920005749 polyurethane resin Polymers 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 11
- 125000000217 alkyl group Chemical group 0.000 description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 230000035699 permeability Effects 0.000 description 11
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 10
- 125000001931 aliphatic group Chemical group 0.000 description 10
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 10
- 239000003505 polymerization initiator Substances 0.000 description 10
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 10
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 10
- 150000001412 amines Chemical class 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 9
- 238000000748 compression moulding Methods 0.000 description 9
- 238000009833 condensation Methods 0.000 description 9
- 230000005494 condensation Effects 0.000 description 9
- 239000012530 fluid Substances 0.000 description 9
- 229920006099 Vestamid® Polymers 0.000 description 8
- 125000005587 carbonate group Chemical group 0.000 description 8
- 238000007334 copolymerization reaction Methods 0.000 description 8
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000004970 Chain extender Substances 0.000 description 7
- 229920002292 Nylon 6 Polymers 0.000 description 7
- 229920000305 Nylon 6,10 Polymers 0.000 description 7
- 239000000654 additive Substances 0.000 description 7
- 125000004429 atom Chemical group 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229920002302 Nylon 6,6 Polymers 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 239000005062 Polybutadiene Substances 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 239000001361 adipic acid Substances 0.000 description 6
- 235000011037 adipic acid Nutrition 0.000 description 6
- 125000002723 alicyclic group Chemical group 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 125000005442 diisocyanate group Chemical group 0.000 description 6
- 230000006870 function Effects 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 6
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 6
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 5
- 239000002202 Polyethylene glycol Substances 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 5
- 239000000539 dimer Substances 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 125000005067 haloformyl group Chemical group 0.000 description 5
- 238000003780 insertion Methods 0.000 description 5
- 230000037431 insertion Effects 0.000 description 5
- 229920001684 low density polyethylene Polymers 0.000 description 5
- 239000004702 low-density polyethylene Substances 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 150000004978 peroxycarbonates Chemical class 0.000 description 5
- 229920002857 polybutadiene Polymers 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 229920005906 polyester polyol Polymers 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 150000005846 sugar alcohols Polymers 0.000 description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000006471 dimerization reaction Methods 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 4
- 239000003502 gasoline Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000008676 import Effects 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Chemical class 0.000 description 4
- 239000002184 metal Chemical class 0.000 description 4
- 229920002492 poly(sulfone) Polymers 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- 229920000515 polycarbonate Polymers 0.000 description 4
- 229920005862 polyol Polymers 0.000 description 4
- 150000003077 polyols Chemical class 0.000 description 4
- 239000004800 polyvinyl chloride Substances 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 4
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- GVNWZKBFMFUVNX-UHFFFAOYSA-N Adipamide Chemical compound NC(=O)CCCCC(N)=O GVNWZKBFMFUVNX-UHFFFAOYSA-N 0.000 description 3
- PLXMOAALOJOTIY-FPTXNFDTSA-N Aesculin Natural products OC[C@@H]1[C@@H](O)[C@H](O)[C@@H](O)[C@H](O)[C@H]1Oc2cc3C=CC(=O)Oc3cc2O PLXMOAALOJOTIY-FPTXNFDTSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- 229920006347 Elastollan Polymers 0.000 description 3
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 150000008064 anhydrides Chemical group 0.000 description 3
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 150000007942 carboxylates Chemical class 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 125000004093 cyano group Chemical group *C#N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 3
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 3
- 229960005082 etohexadiol Drugs 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 229920001903 high density polyethylene Polymers 0.000 description 3
- 239000004700 high-density polyethylene Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 3
- 229920006122 polyamide resin Polymers 0.000 description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 239000005056 polyisocyanate Substances 0.000 description 3
- 229920001228 polyisocyanate Polymers 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000007870 radical polymerization initiator Substances 0.000 description 3
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 3
- ZJVATSUMFCZSKA-QZOPMXJLSA-N (z)-docos-13-enoic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O ZJVATSUMFCZSKA-QZOPMXJLSA-N 0.000 description 2
- KHXKESCWFMPTFT-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptafluoro-3-(1,2,2-trifluoroethenoxy)propane Chemical compound FC(F)=C(F)OC(F)(F)C(F)(F)C(F)(F)F KHXKESCWFMPTFT-UHFFFAOYSA-N 0.000 description 2
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- KVWOTUDBCFBGFJ-UHFFFAOYSA-N tert-butyl 2-methylpropanoate Chemical compound CC(C)C(=O)OC(C)(C)C KVWOTUDBCFBGFJ-UHFFFAOYSA-N 0.000 description 1
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- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- ZFDIRQKJPRINOQ-UHFFFAOYSA-N transbutenic acid ethyl ester Natural products CCOC(=O)C=CC ZFDIRQKJPRINOQ-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/08—Polyurethanes from polyethers
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- B32B1/08—Tubular products
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- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/06—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of natural rubber or synthetic rubber
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal 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
- B32B15/082—Layered products comprising a layer of metal comprising metal 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 comprising vinyl resins; comprising acrylic resins
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- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal 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
- B32B15/085—Layered products comprising a layer of metal comprising metal 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 comprising polyolefins
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- 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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal 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
- B32B15/095—Layered products comprising a layer of metal comprising metal 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 comprising polyurethanes
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/18—Layered products comprising a layer of metal comprising iron or steel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
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- B32B15/00—Layered products comprising a layer of metal
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- B32B21/00—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board
- B32B21/04—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B21/045—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood as the main or only constituent of a layer, which is next to another layer of the same or of a different material of natural rubber or synthetic rubber
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Abstract
提供具有包含含氟树脂的构件和包含热塑性树脂的构件、粘接性优异的复合构件。复合构件为包含热塑性聚氨酯及聚酰胺弹性体的第一构件与包含含氟树脂的第二构件直接接触而形成的。
Description
技术领域
本发明涉及复合构件。
背景技术
含氟树脂的耐热性、耐化学药品性、耐候性、非粘合性、低摩擦性及低介电特性等优异,因此在广泛的领域中使用,特别是耐化学药品性优异,因此化学溶液输送用管可以作为重要的用途而被列举出。但是,含氟树脂在粘接性、涂装性、印刷适性、染色性、柔软性等方面未必能够充分令人满意。因此,对将含氟树脂和其他热塑性树脂复合化而成的成形品进行了各种研究。例如,提出了将具有反应性官能团的含氟系聚合物和具有特定胺值的聚酰胺系树脂层叠的方法(例如,参照专利文献1~2)。另外,提出了将乙烯·四氟乙烯树脂的内层、包含乙烯-乙烯醇共聚物树脂的中间层、和包含树脂或弹性体的外层层叠的方法(例如,参照专利文献3)。
现有技术文献
专利文献
专利文献1:国际公开2004/110756号
专利文献2:日本特开2007-216387号公报
专利文献3:日本特开2011-62881号公报
发明内容
发明要解决的问题
对于专利文献1~2中记载的技术,需要具有反应性官能团的含氟系聚合物,难以应用于通用的含氟系聚合物。另外,专利文献3中记载的技术需要设置中间层。
本发明的课题在于,提供具有包含含氟树脂的构件和包含热塑性树脂的构件、两构件间的粘接性优异的复合构件。
用于解决问题的方案
用于解决前述课题的具体的方案如下,本发明包含以下的方式。
一种复合构件,其是包含热塑性聚氨酯及聚酰胺弹性体的第一构件与包含含氟树脂的第二构件直接接触而形成的。
以下示出复合构件的优选的方式。多个优选的方式可以进行组合。
[1]一种复合构件,其中,前述第一构件的聚酰胺弹性体含有率为49质量%以下。
[2]一种复合构件,其中,前述第一构件的聚酰胺弹性体含有率为30质量%以下。
[3]一种复合构件,其中,前述聚酰胺弹性体具有硬链段和软链段,前述硬链段具有由如下的化合物形成的聚酰胺结构单元,所述化合物为选自由用二胺与二羧酸形成的尼龙盐、下述式(2)所示的氨基羧酸化合物及下述式(3)所示的内酰胺化合物组成的组中的至少1种。
H2N-R1-COOH (2)
(式(2)及(3)中,R1表示包含烃链的连接基团,R2表示包含烃链的连接基团。)
[4]一种复合构件,其中,前述软链段具有聚醚结构单元。
[5]一种复合构件,其中,前述聚酰胺弹性体具有由选自由ω-月桂内酰胺、11-氨基十一烷酸及12-氨基十二烷酸组成的组中的至少1种形成的聚酰胺结构单元。
[6]一种复合构件,其中,前述软链段具有由选自由聚乙二醇、聚丙二醇、聚四亚甲基醚二醇及下述式(5)所示的XYX型三嵌段聚醚组成的组中的至少1种形成的聚醚结构单元。
(式(5)中,x表示1~20的整数,y表示4~50的整数,且z表示1~20的整数。)
[7]一种复合构件,其中,前述硬链段包含由前述聚酰胺结构单元和下述式(4)所示的二羧酸衍生的结构单元。
(式(4)中,R3表示包含烃链的连接基团,m表示0或1。)
[8]一种复合构件,其中,前述聚酰胺弹性体包含:
由下述式(1)所示的二胺化合物衍生的第一结构单元、
由下述式(2)所示的氨基羧酸化合物或下述式(3)所示的内酰胺化合物衍生的第二结构单元、和
由下述式(4)所示的二羧酸化合物衍生的第三结构单元。
H2N-R1-COOH (2)
(x表示1~20的整数,y表示4~50的整数,且z表示1~20的整数,R1表示包含烃链的连接基团,R2表示包含烃链的连接基团,R3表示包含烃链的连接基团,m表示0或1。)
[9]一种复合构件,其中,前述含氟树脂为选自由聚四氟乙烯、乙烯/四氟乙烯共聚物、聚偏氟乙烯、四氟乙烯/全氟烷基乙烯基醚共聚物、四氟乙烯/六氟丙烯共聚物及四氟乙烯/六氟丙烯/偏氟乙烯共聚物组成的组中的至少1种。
[10]一种层叠体,其包含复合构件。
[11]一种层叠管,其包含复合构件。
发明的效果
根据本发明,能够提供具有包含含氟树脂的构件和包含热塑性树脂的构件、两构件间的粘接性优异的复合构件。
具体实施方式
对于本说明书中组合物中的各成分的含量而言,在组合物中存在多种相当于各成分的物质的情况下,只要没有特别说明,就是指组合物中存在的该多种物质的合计量。
[复合构件]
本实施方式的复合构件是包含热塑性聚氨酯及聚酰胺弹性体的第一构件与包含含氟树脂的第二构件直接接触而形成的。第一构件不仅包含热塑性聚氨酯,还包含聚酰胺弹性体,且与包含含氟树脂的第二构件直接接触,从而形成第一构件与第二构件牢固地粘接而成为一体的复合构件。进而通过将复合构件成形为例如管状,从而能够构成柔软性、耐化学药品性、耐划痕性等优异的层叠管。
[第一构件]
第一构件包含热塑性聚氨酯及聚酰胺弹性体。第一构件的形态根据目的等来适宜选择,可以为块、薄膜、管、吹塑成形品、压制成形品、多层注射成形品(DSI法、DRI法、模内成形、嵌入成形、多色成形等)等中的任意者。第一构件的形态为薄膜状、管状等的情况下,其厚度可以设为例如10μm~10mm。
1.热塑性聚氨酯
第一构件中所含的热塑性聚氨酯(以下,也简称为“聚氨酯”)可以没有特别限制地使用公知的热塑性聚氨酯。
作为聚氨酯,可以使用使多元醇及多异氰酸酯反应而得到的聚氨酯;使多元醇、多异氰酸酯及扩链剂反应而得到的聚氨酯等。特别是聚氨酯优选为使二醇与二异氰酸酯反应或使二醇、二异氰酸酯及扩链剂反应而得到的聚氨酯。
作为多元醇,可以使用缩合系聚酯多元醇、内酯系聚酯多元醇、聚碳酸酯多元醇及聚醚多元醇等。
缩合系聚酯多元醇优选使用通过使用1种或2种以上的二羧酸和1种或2种以上的二醇得到的聚酯二醇。
作为二羧酸,可列举出戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、十二烷二酸等脂肪族二羧酸;环己烷二羧酸等脂环族二羧酸;对苯二甲酸、间苯二甲酸、邻苯二甲酸等芳香族二羧酸等,可以使用选自由这些二羧酸组成的组中的至少1种。这些当中,优选使用选自由己二酸、壬二酸、癸二酸等脂肪族二羧酸组成的组中的至少1种。需要说明的是,缩合系聚酯多元醇的形成中可以使用这些二羧酸的低级烷基酯来代替这些二羧酸的至少一部分。
作为二醇,可列举出乙二醇、1,2-丙二醇、1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、3-甲基-1,5-戊二醇、1,6-己二醇、1,7-庚二醇、1,8-辛二醇、2-甲基-1,8-辛二醇、1,9-壬二醇、1,10-癸二醇等脂肪族二醇;环己烷二甲醇、环己二醇等脂环式二醇,可以使用选自由这些二醇组成的组中的至少1种。这些当中,优选使用选自由3-甲基-1,5-戊二醇、2-甲基-1,8-辛二醇、1,9-壬二醇等脂肪族二醇组成的组中的至少1种。
作为内酯系聚酯多元醇,可列举出使β-丙内酯、新戊内酯、δ-戊内酯、ε-己内酯、甲基-ε-己内酯、二甲基-ε-己内酯、三甲基-ε-己内酯等内酯化合物与短链的二醇等羟基化合物一起反应而得到的聚酯二醇等。
作为聚碳酸酯多元醇,例如,优选通过低分子二醇与碳酸二烷基酯、碳酸亚烷基酯、碳酸二芳基酯等碳酸酯化合物的反应得到的聚碳酸酯二醇。对于作为聚碳酸酯二醇的制造原料的低分子二醇,可以使用作为聚酯二醇的制造原料而在前文中例示出的低分子的二醇。另外,作为碳酸二烷基酯,可列举出碳酸二甲酯、碳酸二乙酯等,作为碳酸亚烷基酯,可列举出碳酸亚乙酯等,作为碳酸二芳基酯,可列举出碳酸二苯酯等。
作为聚醚多元醇,可列举出聚氧化乙烯二醇、聚氧化丙烯二醇、聚氧四亚甲基二醇等聚醚二醇、聚氧化丙烯三醇等聚醚三醇等。除了上述多元醇以外,也可以使用公知的各种聚氨酯用多元醇。
聚氨酯可以优选使用以聚酯二醇和/或聚醚二醇为软链段的热塑性聚氨酯、例如聚酯系聚氨酯树脂和/或聚醚系聚氨酯树脂,从粘接性的观点出发,可以更优选使用聚酯系聚氨酯树脂。
聚氨酯中使用的多异氰酸酯没有特别限制,优选使用二异氰酸酯,可以使用聚氨酯、热塑性聚氨酯的制造中所用的二异氰酸酯中的任意者。
作为二异氰酸酯,可以使用四亚甲基二异氰酸酯、五亚甲基二异氰酸酯、六亚甲基二异氰酸酯、赖氨酸二异氰酸酯、环己基甲烷二异氰酸酯、2,2,4-三甲基六亚甲基二异氰酸酯或2,4,4-三甲基六亚甲基二异氰酸酯、异丙叉基双(4-环己基异氰酸酯)、甲基环己烷二异氰酸酯、异佛尔酮二异氰酸酯等脂肪族或脂环式二异氰酸酯、2,4-甲苯二异氰酸酯或2,6-甲苯二异氰酸酯、二苯基甲烷-4,4’-二异氰酸酯、3-甲基二苯基甲烷-4,4’-二异氰酸酯、间苯二异氰酸酯或对苯二异氰酸酯、氯亚苯基-2,4-二异氰酸酯、萘-1,5-二异氰酸酯、苯二亚甲基二异氰酸酯、四甲基苯二亚甲基二异氰酸酯等芳香族二异氰酸酯等,可以使用这些多异氰酸酯的1种或2种以上。其中,优选使用二苯基甲烷-4,4’-二异氰酸酯。
聚氨酯的制造中使用的扩链剂的种类没有特别限制,可以使用通常的聚氨酯的制造中以往使用的扩链剂中的任意者。作为扩链剂,优选使用分子中具有2个以上可与异氰酸酯基反应的活性氢原子的分子量300以下的低分子化合物。
作为扩链剂,可列举出乙二醇、丙二醇、1,4-丁二醇、1,6-己二醇、1,4-双(β-羟基乙氧基)苯、1,4-环己二醇、双-(β-羟基乙基)对苯二甲酸酯、苯二甲醇等二醇类;肼、乙二胺(ethylenediamine)、丙二胺、苯二甲胺、异佛尔酮二胺、哌嗪及其衍生物、苯二胺、甲苯二胺、二甲苯二胺、己二酸二酰肼、间苯二甲酸二酰肼等二胺类;氨基乙醇、氨基丙醇等氨基醇类等,可以使用1种或2种以上这些扩链剂。这些当中,优选使用碳数2~10的脂肪族二醇,更优选使用1,4-丁二醇。
第一构件中的聚氨酯的含有率例如为70质量%以上,优选80质量%以上、更优选90质量%以上、进一步优选95质量%以上。另外,聚氨酯的含有率例如不足100质量%,优选98质量%以下、更优选96质量%以下。
2.聚酰胺弹性体
聚酰胺弹性体的第一优选的方式如下。
第一构件中所含的聚酰胺弹性体具有硬链段和软链段,硬链段具有聚酰胺的结构单元。聚酰胺弹性体的软链段优选具有聚醚的结构单元。对于具有聚醚的结构单元作为软链段的聚酰胺弹性体,可列举出使硬链段和软链段通过酯键键合而成的聚醚聚酯聚酰胺弹性体、使硬链段和软链段通过酰胺键键合而成的聚醚聚酰胺弹性体。从表现本发明的效果的观点出发,优选使硬链段和软链段通过酰胺键键合而成的聚醚聚酰胺弹性体。
硬链段中的聚酰胺结构单元优选由聚酰胺形成性单体[选自由用二胺与二羧酸形成的尼龙盐、下述式(2)所示的氨基羧酸化合物及下述式(3)所示的内酰胺化合物组成的组中的至少1种]形成的结构单元。
硬链段也可以由两末端基具有羧基的聚酰胺衍生,也可以是包含由聚酰胺结构单元和下述式(4)所示的二羧酸衍生的结构单元的链段。
作为下述式(2)所示的氨基羧酸化合物,可列举出6-氨基己酸、7-氨基庚酸、8-氨基辛酸、10-氨基癸酸、11-氨基十一烷酸、12-氨基十二烷酸等碳数5~20的脂肪族ω-氨基羧酸等。
作为用二胺与二羧酸形成的尼龙盐的二胺,可列举出乙二胺、三亚甲基二胺、四亚甲基二胺、六亚甲基二胺、七亚甲基二胺、八亚甲基二胺、九亚甲基二胺、十亚甲基二胺、十一亚甲基二胺、十二亚甲基二胺、2,2,4-三甲基己烷-1,6-二胺、2,4,4-三甲基己烷-1,6-二胺、3-甲基戊烷-1,5-二胺等碳数2~20的脂肪族二胺等二胺化合物。
作为用二胺与二羧酸形成的尼龙盐的二羧酸,可列举出与后述的下述式(4)所示的二羧酸化合物同样的化合物。
作为下述式(3)所示的内酰胺化合物,可列举出ε-己内酰胺、ω-庚内酰胺、ω-十一烷内酰胺、ω-月桂内酰胺、2-吡咯烷酮等碳数5~20的脂肪族内酰胺等。
这些当中,从由低吸水带来的尺寸稳定性、耐化学药品性、机械特性的观点出发,优选ω-月桂内酰胺、11-氨基十一烷酸或12-氨基十二烷酸。
作为下述式(4)所示的二羧酸化合物,可以使用选自脂肪族、脂环族及芳香族二羧酸中的至少一种二羧酸或它们的衍生物。
作为下述式(4)所示的二羧酸的具体例,可列举出草酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、十二烷二酸等碳数2~25的直链脂肪族二羧酸、或、将通过甘油三酯的分馏得到的不饱和脂肪酸二聚化而得到的碳数14~48的二聚化脂肪族二羧酸(二聚酸)及它们的氢化物(氢化二聚酸)等脂肪族二羧酸;1,4-环己烷二羧酸等脂环族二羧酸;及,对苯二甲酸、间苯二甲酸等芳香族二羧酸。作为二聚酸及氢化二聚酸,可以使用Unichema公司制商品名“Pripol 1004”、“Pripol 1006”、“Pripol 1009”、“Pripol 1013”等。
在下述式(4)所示的二羧酸的存在下、通过常规方法使上述聚酰胺结构单元开环聚合或缩聚,由此能够得到两末端具有羧基的聚酰胺。硬链段的二羧酸可以作为分子量调节剂来使用。
硬链段的数均分子量优选为300~15000,从柔软性、成形性的观点出发,更优选为300~6000。
需要说明的是,本说明书中,数均分子量为基于依据JIS K 1557测定的羟值算出的数均分子量。具体而言,测定羟值,通过末端基定量法,用(56.1×1000×元数)/羟值来算出(该式中,羟值的单位为[mgKOH/g])。前述式中,元数为1分子中的羟基的数量。
软链段优选具有聚醚的结构单元,例如,可列举出聚乙二醇、聚丙二醇、聚四亚甲基醚二醇及下述式(5)所示的XYX型三嵌段聚醚等。这些可以单独使用或使用2种以上,这些当中,更优选下述式(5)所示的XYX型三嵌段聚醚。另外,可以使用通过使氨等与聚醚的末端反应而得到的聚醚二胺等。软链段的数均分子量优选为200~6000、更优选为650~2000。
下述式(5)中,x及z各自独立地优选1~18的整数、更优选1~16的整数、进一步优选1~14的整数、特别优选1~12的整数。另外,y优选5~45的整数、更优选6~40的整数、进一步优选7~35的整数、特别优选8~30的整数。
作为上述硬链段与上述软链段的组合,可列举出上述中举出的硬链段与软链段的各个组合。其中,优选月桂内酰胺的开环缩聚物/聚乙二醇的组合、月桂内酰胺的开环缩聚物/聚丙二醇的组合、月桂内酰胺的开环缩聚物/聚四亚甲基醚二醇的组合、及月桂内酰胺的开环缩聚物/XYX型三嵌段聚醚的组合,特别优选月桂内酰胺的开环缩聚物/XYX型三嵌段聚醚的组合。
H2N-R1-COOH (2)
上述式(2)~(5)中,x表示1~20的整数、y表示4~50的整数、且z表示1~20的整数,R1表示包含烃链的连接基团,R2表示包含烃链的连接基团,R3表示包含烃链的连接基团,m表示0或1。
上述硬链段与上述软链段的比例(重量比)优选为硬链段/软链段=95/5~20/80。为该范围时,容易避免自成形体的渗出,也容易确保充分的柔软性。硬链段/软链段(重量比)更优选为95/5~25/75、特别优选为50/50~30/70。
上述硬链段/软链段(重量比)小于上述范围的情况下,有时聚酰胺成分的结晶性变低,有时强度、弹性模量等机械物性降低,因此不优选。上述硬链段/软链段(重量比)比上述范围大的情况下,有时难以表现橡胶弹性、柔软性等作为弹性体的功能、性能,因此不优选。
作为如上所述的聚酰胺弹性体的市售品,例如可列举出Daicel-Evonik Ltd.制商品名“Diamide(注册商标)E1947”、“Diamide(注册商标)E47”、“Diamide(注册商标)E47H”、“Diamide(注册商标)E55”、“Diamide(注册商标)E55H”、“Diamide(注册商标)E62”、“Diamide(注册商标)E62H”、“Diamide(注册商标)E73K2”、“Diamide(注册商标)E75K2”、“Diamide(注册商标)EX9200”、“Diamide(注册商标)MSP-S”、“Diamide(注册商标)X4442W2”、“Diamide(注册商标)ZE7000”、“Diamide(注册商标)ZE7200”、“VESTAMID(注册商标)E47-S1”、“VESTAMID(注册商标)E47-S4”、“VESTAMID(注册商标)E55-S4”、“VESTAMID(注册商标)E58-S4”、“VESTAMID(注册商标)E62-S1”、“VESTAMID(注册商标)E62-S4”、“VESTAMID(注册商标)EX9200”、“VESTAMID(注册商标)EX9202”、ARKEMA K.K.制商品名“Pebax”系列、EMS-CHEMIE(Japan)Ltd.制商品名“Grilflex(注册商标)EBG”、“Grilflex(注册商标)ELG”、“Grilon(注册商标)ELX”、宇部兴产株式会社制商品名“UBESTA XPA(注册商标)”系列、例如“UBESTA XPA 9040X1、UBESTA XPA 9040F1、UBESTA XPA 9048X1、UBESTAXPA 9048F1、UBESTA XPA 9055X1、UBESTA XPA 9055F1、UBESTA XPA 9063X1、UBESTA XPA9063F1、UBESTA XPA 9068X1、UBESTA XPA 9068F1、UBESTA XPA 9040X2、UBESTA XPA9048X2、UBESTA XPA 9040F2、UBESTA XPA 9048F2、UBESTA XPA 9068TF1、UBESTA XPA9063TF1、UBESTA XPA 9055TF1、UBESTA XPA 9048TF1”(宇部兴产株式会社制)等。
其中,优选宇部兴产株式会社制商品名“UBESTA XPA(注册商标)”系列。
聚酰胺弹性体可以单独使用,也可以组合使用2种以上。
作为聚醚聚酰胺弹性体的制造方法,举出一例时,可以使用如下方法:该方法包括使聚酰胺形成性单体、XYX型三嵌段聚醚二胺及二羧酸这三种成分在加压和/或常压下熔融聚合、根据需要进一步在减压下进行熔融聚合的工序,进而,可以使用如下方法:该方法包括使聚酰胺形成性单体、XYX型三嵌段聚醚二胺及二羧酸这三种成分同时在加压和/或常压下熔融聚合、根据需要进一步在减压下进行熔融聚合的工序。需要说明的是,也可以利用使聚酰胺形成性单体与二羧酸这两种成分先聚合,接着与XYX型三嵌段聚醚二胺聚合的方法。
在聚醚聚酰胺弹性体的制造时,原料的投入方法没有特别限制,相对于聚酰胺形成性单体及XYX型三嵌段聚醚二胺,聚酰胺形成性单体优选为20~95重量%、进一步优选为25~95重量%、特别优选为30~50重量%的范围,XYX型三嵌段聚醚二胺优选为5~80重量%、进一步优选为5~75重量%、特别优选为50~70重量%的范围。原料中,XYX型三嵌段聚醚二胺与二羧酸优选以XYX型三嵌段聚醚二胺的氨基与二羧酸的羧基几乎为等摩尔的方式投入。
对于聚醚聚酰胺弹性体的制造,对于聚合温度,可以在优选150~300℃、进一步优选160~280℃、特别优选180~250℃下进行。聚合温度低于上述温度时,聚合反应慢,大于上述温度时,容易引起热解,有时得不到良好的物性的聚合物。
对于聚醚聚酰胺弹性体,使用ω-氨基羧酸作为聚酰胺形成性单体的情况下,可以通过包括如下工序的方法来制造:所述工序为基于常压熔融聚合的工序、或基于常压熔融聚合和继其之后的减压熔融聚合。
另一方面,作为聚酰胺形成性单体,使用内酰胺、或由二胺和二羧酸合成的物质和/或它们的盐的情况下,可以通过使适量的水共存、包括0.1~5MPa的加压下的熔融聚合且包括继其之后的常压熔融聚合和/或减压熔融聚合的方法来制造。
对于聚醚聚酰胺弹性体,对于聚合时间,通常可以以0.5~30小时进行制造。若聚合时间比上述范围短,则分子量的上升不充分,若长,则有时引起由热解导致的着色等,任意情况下都得不到具有期望的物性的聚醚聚酰胺弹性体。
对于聚醚聚酰胺弹性体的制造,可以以间歇式、也可以以连续式来实施,另外,可以单独使用或适宜组合使用分批式反应釜、一槽式乃至多槽式的连续反应装置、管状连续反应装置等。
聚醚聚酰胺弹性体的制造中,为了分子量调节、成形加工时的熔融粘度稳定,根据需要可以添加月桂胺、硬脂胺、六亚甲基二胺、间苯二甲胺等单胺及二胺、乙酸、苯甲酸、硬脂酸、己二酸、癸二酸、十二烷二酸等单羧酸或二羧酸等。对于它们的用量,优选以最终得到的弹性体的相对粘度成为1.2~3.5(0.5重量/容量%间甲酚溶液、25℃)的范围的方式来适宜添加。
聚醚聚酰胺弹性体的制造中,上述的单胺及二胺、单羧酸及二羧酸等的添加量优选设为不阻碍得到的聚醚聚酰胺弹性体的特性的范围。
聚醚聚酰胺弹性体的制造中,根据需要可以添加磷酸、焦磷酸、多聚磷酸等作为催化剂,另外,可以添加亚磷酸、次磷酸、及它们的碱金属盐、碱土金属盐等无机系磷化合物来发挥催化剂和耐热剂这两者的效果。添加量通常相对于投入原料为50~3000ppm。
聚酰胺弹性体的第二优选的方式如下。
第一构件中所含的聚酰胺弹性体优选为如下的聚合物,其包含:由下述式(1)所示的二胺化合物衍生的第一结构单元、由下述式(2)所示的氨基羧酸化合物或下述式(3)所示的内酰胺化合物衍生的第二结构单元、及由下述式(4)所示的二羧酸化合物衍生的第三结构单元。
H2N-R1-COOH (2)
上述式(1)~(4)中,x表示1~20的整数、y表示4~50的整数、且z表示1~20的整数,R1表示包含烃链的连接基团,R2表示包含烃链的连接基团,R3表示包含烃链的连接基团,m表示0或1。
构成聚酰胺弹性体第一结构单元是由式(1)所示的二胺化合物衍生出的。式(1)所示的二胺化合物为XYX型三嵌段聚醚二胺化合物,可以使用通过在聚(氧四亚甲基)二醇等的两末端加成环氧丙烷来形成聚丙二醇后,使氨等与该聚丙二醇的末端反应而制造的聚醚二胺等。
式(1)中,x及z为1~20,优选为1~18、更优选为1~16、进一步优选为1~14、特别优选的是1~12,y为4~50,优选为5~45、更优选为6~40、进一步优选为7~35、特别优选的是8~30。另外,作为x、y及z的组合,可以优选例示出x为2~6的范围、y为6~12的范围、z为1~5的范围的组合、或者x为2~10的范围、y为13~28的范围、z为1~9的范围的组合等。
作为二胺化合物的具体例,可列举出美国HUNTSMAN公司制XTJ-533(上述式(1)中,x为约12、y为约11、z为约11)、XTJ-536(式(1)中,x为约8.5、y为约17、z为约7.5)、以及XTJ-542(上述式(1)中,x为约3、y为约9、z为约2)等。
另外,作为XYX型三嵌段聚醚二胺化合物,也可列举出XYX-1(式(1)中,x为约3、y为约14、z为约2)、XYX-2(式(1)中,x为约5、y为约14、z为约4)、以及XYX-3(上述式(1)中,x为约3、y为约19、z为约2)等。
聚酰胺弹性体中的第一结构单元的含有率例如为2~87质量%,优选为7~78质量%。
第二结构单元是由式(2)所示的氨基羧酸化合物或式(3)所示的内酰胺化合物衍生出的。式(2)中,R1表示包含烃链的连接基团,优选为碳数2~20的脂肪族、脂环族或芳香族的烃基或碳数2~20的亚烷基,更优选为碳数3~18的上述烃基或碳数3~18的亚烷基,进一步优选为碳数4~15的上述烃基或碳数4~15的亚烷基,特别优选为碳数10~15的上述烃基或碳数10~15的亚烷基。
式(3)中,R2表示包含烃链的连接基团,优选为碳数3~20的脂肪族、脂环族或芳香族的烃基或碳数3~20的亚烷基,更优选为碳数3~18的上述烃基或碳数3~18的亚烷基,进一步优选为碳数4~15的上述烃基或碳数4~15的亚烷基,特别优选为碳数10~15的上述烃基或碳数10~15的亚烷基。
式(2)所示的氨基羧酸化合物为ω-氨基羧酸,作为ω-氨基羧酸的具体例,可列举出6-氨基己酸、7-氨基庚酸、8-氨基辛酸、10-氨基癸酸、11-氨基十一烷酸、12-氨基十二烷酸等碳数5~20的脂肪族ω-氨基羧酸等。
作为式(3)所示的内酰胺化合物的具体例,可列举出ε-己内酰胺、ω-庚内酰胺、ω-十一烷内酰胺、ω-十二烷内酰胺、2-吡咯烷酮等碳数5~20的脂肪族内酰胺等
聚酰胺弹性体中的第二结构单元的含有率例如为10~95质量%,优选为15~90质量%、更优选为15~85质量%、进一步优选为15~80质量%。
第三结构单元是由式(4)所示的二羧酸化合物衍生出的。式(4)中,R3表示包含烃链的连接基团,优选为碳数1~20的脂肪族、脂环族或芳香族的烃基或碳数1~20的亚烷基,进一步优选为碳数1~15的上述烃基或碳数1~15的亚烷基,更优选为碳数2~12的上述烃基或碳数2~12的亚烷基,特别优选为碳数4~10的上述烃基或碳数4~10的亚烷基。另外,m表示0或1。
作为二羧酸化合物,可以使用选自脂肪族、脂环族及芳香族二羧酸中的至少1种二羧酸或它们的衍生物。
作为二羧酸的具体例,可列举出草酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、十二烷二酸等碳数2~25的直链脂肪族二羧酸、或将通过甘油三酯的分馏得到的不饱和脂肪酸二聚化而得到的碳数14~48的二聚化脂肪族二羧酸(二聚酸)及它们的氢化物(氢化二聚酸)等脂肪族二羧酸;1,4-环己烷二羧酸等脂环族二羧酸;及对苯二甲酸、间苯二甲酸等芳香族二羧酸。作为二聚酸及氢化二聚酸,可以使用Unichema公司制商品名“Pripol 1004”、“Pripol 1006”、“Pripol 1009”、“Pripol 1013”等。
聚酰胺弹性体中的第一结构单元和第三结构单元的合计量的比例优选为5~90质量%、更优选为10~85质量%、进一步优选为15~85质量%、特别优选为20~85质量%、最优选为30~85质量。
聚酰胺弹性体可以还包含由除式(1)所示的二胺化合物以外的第二二胺化合物衍生的第四结构单元。作为第二二胺化合物,可列举出选自脂肪族二胺、脂环式二胺及芳香族二胺、或它们的衍生物中的至少1种。
作为第二二胺的具体例,可列举出乙二胺、三亚甲基二胺、四亚甲基二胺、六亚甲基二胺、七亚甲基二胺、八亚甲基二胺、九亚甲基二胺、十亚甲基二胺、十一亚甲基二胺、十二亚甲基二胺、2,2,4-三甲基六亚甲基二胺、2,4,4-三甲基六亚甲基二胺、3-甲基五亚甲基二胺等碳数2~20的脂肪族二胺等二胺化合物。
聚酰胺弹性体的详情及其制造方法例如可以参照日本特开2012-211251号公报。另外,聚酰胺弹性体可以使用市售品。作为市售品,例如可以使用“UBESTA XPA 9040X1、UBESTA XPA 9040F1、UBESTA XPA 9048X1、UBESTA XPA 9048F1、UBESTA XPA 9055X1、UBESTA XPA 9055F1、UBESTA XPA 9063X1、UBESTA XPA 9063F1、UBESTA XPA 9068X1、UBESTA XPA 9068F1、UBESTA XPA 9040X2、UBESTA XPA 9048X2、UBESTA XPA 9040F2、UBESTA XPA 9048F2、UBESTA XPA 9068TF1、UBESTA XPA 9063TF1、UBESTA XPA 9055TF1、UBESTA XPA 9048TF1”(宇部兴产株式会社制)等。
第一构件中的聚酰胺弹性体的含有率优选为49质量%以下、更优选30质量%以下、进一步优选17质量%以下、最优选10质量%以下。另外,聚酰胺弹性体的含有率例如优选为0.01质量%以上、更优选2质量%以上、进一步优选4质量%以上。聚酰胺弹性体的含有率为上述范围时,能够得到粘接性更优异的复合构件。
对于第一构件中的聚酰胺弹性体与聚氨酯的含有比(质量比),从粘接性的观点出发,例如为1:10000~3:7、优选1:50~3:17、更优选1:20~1:9。
第一构件在不损害特性的范围内可以包含除聚氨酯以外的其他热塑性聚合物、具有柔软性的热塑性聚合物、除上述聚酰胺弹性体以外的弹性体、橡胶等。另外,聚氨酯树脂组合物在不阻碍其特性的范围内可以包含耐热剂、紫外线吸收剂、光稳定剂、抗氧化剂、抗静电剂、润滑剂、增滑剂、结晶成核剂、增粘剂、密封性改良剂、防雾剂、脱模剂、增塑剂、颜料、染料、香料、阻燃剂、加强材料等。
作为第一构件的制造方法,可以使用公知的各种方法。例如,可以将用于形成第一构件的聚氨酯及聚酰胺弹性体等混合后,进行熔融混炼,经过挤出成形、注射成形、压制成形等而制造成第一构件。需要说明的是,也可以不进行熔融混炼,在混合后经过挤出成形、注射成形、压制成形等而制造成第一构件。另外,混合通常是使用亨舍尔混合机、螺带式混合机、V型混合机等来均匀地进行混合。熔融混炼中通常使用班伯里密炼机、捏合机、辊、单螺杆或双螺杆等多螺杆混炼挤出机等。利用熔融混炼法的情况下,将聚氨酯和聚酰胺弹性体与根据需要的其他添加剂以规定的配混比例均匀混合后进行熔融混炼即可。对于熔融混炼温度,可以根据使用的聚氨酯及聚酰胺弹性体的种类,考虑反应速度及反应的选择性等来适宜选择,优选为140~300℃、更优选为150~270℃。熔融混炼可以在常压下、减压下、加压下中的任意条件下进行,其时间为通常的利用双螺杆挤出机的混炼时间、例如为20秒~3分钟左右,但不限定于此。
[第二构件]
第二构件包含含氟树脂。对于第二构件的形态,根据目的等来适宜选择,可以为块、薄膜、管、吹塑成形品、压制成形品、多层注射成形品(DSI法、DRI法、模内成形、嵌入成形、多色成形等)等中的任意者。第二构件的形态为薄膜状、管状等的情况下,其厚度例如可以设为10μm~25mm。
含氟树脂为具有至少1种由含氟单体衍生的重复单元的聚合物(均聚物或共聚物)。只要为可热熔融加工的含氟树脂,就没有特别限定。
此处作为含氟单体,可列举出四氟乙烯(TFE)、三氟乙烯、偏氟乙烯(VDF)、氟乙烯(VF)、氯三氟乙烯(CTFE)、三氯氟乙烯、六氟丙烯(HFP)、CF2=CFORf1所示的全氟烷基乙烯基醚(此处,Rf1表示碳原子数1~10的任选包含醚性氧原子的全氟烷基。)、CF2=CF-OCH2-Rf2(此处,Rf2表示碳原子数1~10的任选包含醚性氧原子的全氟烷基。)、CF2=CF(CF2)pOCF=CF2(此处,p表示1或2。)、CH2=CX1(CF2)nX2(此处,X1及X2彼此独立地表示氢原子或氟原子,n为2~10的整数。)等。这些可以使用1种或2种以上。
作为上述通式CF2=CFORf1的具体例,可列举出
CF2=CFOCF2(全氟(甲基乙烯基醚):PMVE)、
CF2=CFOCF2CF3(全氟(乙基乙烯基醚):PEVE)、
CF2=CFOCF2CF2CF3(全氟(丙基乙烯基醚):PPVE)、
CF2=CFOCF2CF2CF2CF3(全氟(丁基乙烯基醚):PBVE)、
CF2=CFO(CF2)8F(全氟(辛基乙烯基醚):POVE)等全氟(烷基乙烯基醚)(以下,有时称为PAVE。)。这些当中,优选CF2=CFOCF2、CF2=CFOCF2CF2CF3。
另外,上述通式CH2=CX1(CF2)nX2(此处,X1及X2彼此独立地表示氢原子或氟原子,n为2~10的整数。)所示的化合物中的n小于前述的值时,有时含氟系聚合物的改性(例如,共聚物的成形时的裂纹产生的抑制、成形品的裂纹产生的抑制)不充分,另一方面,超过前述的值时,在聚合反应性的方面不利。
具体而言,可列举出CH2=CF(CF2)2F、CH2=CF(CF2)3F、CH2=CF(CF2)4F、CH2=CF(CF2)5F、CH2=CF(CF2)8F、CH2=CF(CF2)2H、CH2=CF(CF2)3H、CH2=CF(CF2)4H、CH2=CF(CF2)5H、CH2=CF(CF2)8H、CH2=CH(CF2)2F、CH2=CH(CF2)3F、CH2=CH(CF2)4F、CH2=CH(CF2)5F、CH2=CH(CF2)8F、CH2=CH(CF2)2H、CH2=CH(CF2)3H、CH2=CH(CF2)4H、CH2=CH(CF2)5H、CH2=CH(CF2)8H等。这些可以使用1种或2种以上。
这些当中,从兼顾树脂B的防化学溶液透过性和耐裂纹性的方面出发,更优选为CH2=CH(CF2)nF或CH2=CF(CF2)nH所示的化合物且式中的n为2~4。
含氟树脂可以在上述含氟单体基础上还含有基于非含氟单体的聚合单元。作为非含氟单体,可列举出乙烯、丙烯、异丁烯等碳原子数2~4的烯烃、氯乙烯、偏氯乙烯、乙酸乙烯酯、氯乙酸乙烯酯、乳酸乙烯酯、丁酸乙烯酯、特戊酸乙烯酯、苯甲酸乙烯酯、巴豆酸乙烯酯、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、巴豆酸甲酯等乙烯基酯、甲基乙烯基醚(MVE)、乙基乙烯基醚(EVE)、丁基乙烯基醚(BVE)、异丁基乙烯基醚(IBVE)、环己基乙烯基醚(CHVE)、缩水甘油基乙烯基醚等乙烯基醚等。这些可以使用1种或2种以上。其中,优选乙烯、丙烯、乙酸乙烯酯,更优选乙烯。
含氟树脂中,从耐热性、耐化学药品性、防化学溶液透过性的方面出发,优选为选自由如下的共聚物组成的组中的至少1种:
至少包含四氟乙烯单元(TFE单元)的聚合物(聚四氟乙烯)、
至少包含四氟乙烯单元(TFE单元)及乙烯单元(E单元)的共聚物(乙烯/四氟乙烯共聚物)、
至少包含偏氟乙烯单元(VDF单元)的聚合物(聚偏氟乙烯)、
至少包含四氟乙烯单元(TFE单元)及全氟烷基乙烯基醚单元(PAVE单元)的共聚物(四氟乙烯/全氟烷基乙烯基醚共聚物)、
至少包含四氟乙烯单元(TFE单元)及六氟丙烯单元(HFP单元)的共聚物(四氟乙烯/六氟丙烯共聚物)、
至少包含四氟乙烯单元(TFE单元)、六氟丙烯单元(HFP单元)及偏氟乙烯单元(VDF单元)的共聚物(四氟乙烯/六氟丙烯/偏氟乙烯共聚物)、至少包含四氟乙烯单元(TFE单元)及六氟丙烯单元(HFP单元)和/或上述式CF2=CFORf1所示的全氟烷基乙烯基醚(PAVE单元)的共聚物(四氟乙烯/六氟丙烯/PAVE共聚物、
至少包含氯三氟乙烯单元(CTFE单元)的共聚物、
以及至少包含氯三氟乙烯单元(CTFE单元)及四氟乙烯单元(TFE单元)的共聚物,
优选为选自由聚四氟乙烯、乙烯/四氟乙烯共聚物、聚偏氟乙烯、四氟乙烯/全氟烷基乙烯基醚共聚物、四氟乙烯/六氟丙烯共聚物、及四氟乙烯/六氟丙烯/偏氟乙烯共聚物组成的组中的至少1种。
作为至少包含偏氟乙烯单元(VDF单元)的共聚物(以下,也称为“VDF共聚物”),例如可列举出:偏氟乙烯均聚物(聚偏氟乙烯(PVDF));包含VDF单元和TFE单元,且相对于除后述含官能团单体以外的单体整体,VDF单元的含量为30~99摩尔%、且TFE单元的含量为1~70摩尔%的共聚物;包含VDF单元和TFE单元、及三氯氟乙烯单元,且相对于除后述含官能团单体以外的单体整体,VDF单元的含量为10~90摩尔%、TFE单元的含量为0~90摩尔%、且三氯氟乙烯单元的含量为0~30摩尔%的共聚物;包含VDF单元和TFE单元、及HFP单元,且VDF单元的含量为10~90摩尔%、TFE单元的含量为0~90摩尔%、且HFP单元的含量为0~30摩尔%的共聚物(VDF/TFE/HFP共聚物)等。
上述VDF/TFE/HFP共聚物中,相对于除后述含官能团单体以外的单体整体,优选VDF单元的含量为15摩尔%以上且84摩尔%以下、TFE单元的含量为15摩尔%以上且84摩尔%以下、且HFP单元的含量为0摩尔%以上且30摩尔%以下。
作为至少包含四氟乙烯单元(TFE单元)及乙烯单元(E单元)的共聚物(以下,也称为“ETFE共聚物”),例如,可列举出TFE单元的含量为20摩尔%以上的聚合物,进而可列举出TFE单元的含量为20~80摩尔%、E单元的含量为20~80摩尔%且源自可与它们共聚的单体的单元的含量为0~60摩尔%的共聚物等。
作为上述可共聚的单体,可列举出六氟丙烯(HFP)、上述通式CF2=CFORf1(此处,Rf1表示碳原子数1~10的任选包含醚性氧原子的全氟烷基。)、上述通式CH2=CX1(CF2)nX2(此处,X1及X2彼此独立地表示氢原子或氟原子,n为2~10的整数。)等。这些可以使用1种或2种以上。
作为至少包含四氟乙烯单元(TFE单元)及乙烯单元(E单元)的共聚物,优选包含源自上述通式CH2=CX1(CF2)nX2(此处,X1及X2彼此独立地表示氢原子或氟原子,n为2~10的整数。)、六氟丙烯(HFP)等氟烯烃的氟烯烃单元和/或源自上述通式CF2=CFORf1(此处,Rf1表示碳原子数1~10的任选包含醚性氧原子的全氟烷基。)所示的PAVE的PAVE单元的共聚物,优选的是,相对于除后述含官能团单体以外的单体整体,TFE单元的含量为20~80摩尔%,E单元的含量为20~80摩尔%,源自上述通式CH2=CX1(CF2)nX2(此处,X1及X2彼此独立地表示氢原子或氟原子,n为2~10的整数。)、六氟丙烯(HFP)等氟烯烃的氟烯烃单元和/或源自上述通式CF2=CFORf1(此处,Rf1表示碳原子数1~10的任选包含醚性氧原子的全氟烷基。)所示的PAVE的PAVE单元的合计含量为0~60摩尔%。
作为至少包含四氟乙烯单元(TFE单元)及乙烯单元(E单元)的共聚物,例如可列举出:包含TFE单元和E单元、及源自上述通式CH2=CX1(CF2)nX2(此处,X1及X2彼此独立地表示氢原子或氟原子,n为2~10的整数。)所示的氟烯烃的氟烯烃单元,且相对于除后述含官能团单体以外的单体整体,TFE单元的含量为30~70摩尔%、E单元的含量为20~55摩尔%、且源自上述通式CH2=CX1(CF2)nX2(此处,X1及X2彼此独立地表示氢原子或氟原子,n为2~10的整数。)所示的氟烯烃的氟烯烃单元的含量为0~10摩尔%的共聚物;包含TFE单元和E单元和HFP单元、及源自可与它们共聚的单体的单元,且TFE单元的含量为30~70摩尔%、E单元的含量为20~55摩尔%、HFP单元的含量为1~30摩尔%、且源自可与它们可共聚的单体的单元的含量为0~10摩尔%的共聚物;包含TFE单元和E单元、及源自上述通式CF2=CFORf1(此处,Rf1表示碳原子数1~10的任选包含醚性氧原子的全氟烷基。)所示的PAVE的PAVE单元,且TFE单元的含量为30~70摩尔%、E单元的含量为20~55摩尔%、且源自上述通式CF2=CFORf1(此处,Rf1表示碳原子数1~10的任选包含醚性氧原子的全氟烷基。)所示的PAVE的PAVE单元的含量为0~10摩尔%的共聚物等。
作为至少包含四氟乙烯单元(TFE单元)和六氟丙烯单元(HFP单元)和/或源自上述通式CF2=CFORf1(此处,Rf1表示碳原子数1~10的任选包含醚性氧原子的全氟烷基。)所示的PAVE的PAVE单元的共聚物(以下,有时称为TFE/HFP/PAVE共聚物。),例如,可列举出:
包含TFE单元及HFP单元,且相对于除后述含官能团单体以外的单体整体,TFE单元的含量为70摩尔%以上且95摩尔%以下、优选为85摩尔%以上且93摩尔%以下、HFP单元的含量为5摩尔%以上且30摩尔%以下、优选为7摩尔%以上且15摩尔%以下的共聚物;
包含TFE单元及1种或2种以上源自上述通式CF2=CFORf1(此处,Rf1表示碳原子数1~10的任选包含醚性氧原子的全氟烷基。)所示的PAVE的PAVE单元,且相对于除后述含官能团单体以外的单体整体,TFE单元的含量为70摩尔%以上且95摩尔%以下、且1种或2种以上源自上述通式CF2=CFORf1(此处,Rf1表示碳原子数1~10的任选包含醚性氧原子的全氟烷基。)所示的PAVE的PAVE单元的含量为5摩尔%以上且30摩尔%以下的共聚物;
包含TFE单元和HFP单元、及1种或2种以上源自上述通式CF2=CFORf1(此处,Rf1表示碳原子数1~10的任选包含醚性氧原子的全氟烷基。)所示的PAVE的PAVE单元,且相对于除后述含官能团单体以外的单体整体,TFE单元的含量为70摩尔%以上且95摩尔%以下、HFP单元和1种或2种以上源自上述通式CF2=CFORf1(此处,Rf1表示碳原子数1~10的任选包含醚性氧原子的全氟烷基。)所示的PAVE的PAVE单元的合计含量为5摩尔%以上且30摩尔%以下的共聚物等。
至少包含氯三氟乙烯单元(CTFE单元)的共聚物是指具有CTFE单元[-CFCl-CF2-]、且由乙烯单元(E单元)和/或含氟单体单元构成的氯三氟乙烯共聚物(以下,也称为“CTFE共聚物(1)”)。
作为上述CTFE共聚物(1)中的含氟单体,只要为除CTFE以外的含氟单体,没有特别限定,可列举出四氟乙烯(TFE)、偏氟乙烯(VDF)、六氟丙烯(HFP)、上述通式CF2=CFORf1(此处,Rf1表示碳原子数1~10的任选包含醚性氧原子的全氟烷基。)所示的PAVE、上述通式CH2=CX1(CF2)nX2(此处,X1及X2彼此独立地表示氢原子或氟原子,n为2~10的整数。)所示的氟烯烃等。这些可以使用1种或2种以上。
作为CTFE共聚物(1),没有特别限定,例如可列举出CTFE/PAVE共聚物、CTFE/TFE/PAVE共聚物、CTFE/VDF共聚物、CTFE/HFP共聚物、CTFE/E共聚物、CTFE/TFE/E共聚物、CTFE/TFE/HFP/PAVE共聚物、CTFE/TFE/VDF/PAVE共聚物等,这些当中,优选CTFE/TFE/PAVE共聚物、CTFE/TFE/HFP/PAVE共聚物。
CTFE共聚物(1)中的CTFE单元的含量优选为15~70摩尔%、更优选为18~65摩尔%。另一方面,E单元和/或含氟单体单元的含量相对于单体整体优选为30~85摩尔%、更优选为35~82摩尔%。
至少包含氯三氟乙烯单元(CTFE单元)及四氟乙烯单元(TFE单元)的共聚物是指由CTFE单元[-CFCl-CF2-]及TFE单元[-CF2-CF2-]、以及可与CTFE及TFE共聚的单体单元构成的氯三氟乙烯共聚物(以下,也称为“CTFE共聚物(2)”)。
作为上述CTFE共聚物(2)中的可共聚的单体,只要为除CTFE及TFE以外的单体,就没有特别限定,可列举出偏氟乙烯(VDF)、六氟丙烯(HFP)、上述通式CF2=CFORf1(此处,Rf1表示碳原子数1~10的任选包含醚性氧原子的全氟烷基。)所示的PAVE、上述通式CH2=CX1(CF2)nX2(此处,X1及X2彼此独立地表示氢原子或氟原子,n为2~10的整数。)所示的氟烯烃等含氟单体、乙烯、丙烯、异丁烯等碳原子数2~4的烯烃、乙酸乙烯酯、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯等乙烯基酯、甲基乙烯基醚(MVE)、乙基乙烯基醚(EVE)、丁基乙烯基醚(BVE)等乙烯基醚等非含氟单体。这些可以使用1种或2种以上。这些当中,优选上述通式CF2=CFORf1(此处,Rf1表示碳原子数1~10的任选包含醚性氧原子的全氟烷基。)所示的PAVE,更优选全氟(甲基乙烯基醚)(PMVE)、全氟(丙基乙烯基醚)(PPVE),从耐热性的观点出发,进一步优选PPVE。
作为CTFE共聚物(2),没有特别限定,例如,可列举出CTFE/TFE共聚物、CTFE/TFE/HFP共聚物、CTFE/TFE/VDF共聚物、CTFE/TFE/PAVE共聚物、CTFE/TFE/E共聚物、CTFE/TFE/HFP/PAVE共聚物、CTFE/TFE/VDF/PAVE共聚物等,这些当中,优选CTFE/TFE/PAVE共聚物、CTFE/TFE/HFP/PAVE共聚物。
CTFE共聚物(2)中的CTFE单元及TFE单元的合计含量相对于单体整体,优选为90~99.9摩尔%,上述可与CTFE及TFE共聚的单体单元的含量优选为0.1~10摩尔%。上述可与CTFE及TFE共聚的单体单元的含量小于前述的值时,有时成形性、耐环境应力裂纹性差,另一方面,若超过前述的值,则有时化学溶液低透过性、耐热性、机械特性差。
CTFE共聚物(2)中的CTFE单元的含量相对于上述CTFE单元和TFE单元的合计量100摩尔%优选为15~80摩尔%、更优选为17~70摩尔%、进一步优选为19~65摩尔%。CTFE单元的含量小于前述的值时,有时化学溶液低透过性变得不充分,另一方面,若超过前述的值,则有时耐燃料裂纹性降低、生产率降低。
CTFE共聚物(2)中,上述可与CTFE及TFE共聚的单体为PAVE的情况下,PAVE单元的含量相对于除后述含官能团单体以外的单体整体优选为0.5~7.0摩尔%、更优选为1.0~5.0摩尔%。
CTFE/TFE共聚物(2)中,上述可与CTFE及TFE共聚的单体为HFP和PAVE的情况下,HFP单元和PAVE单元的合计含量相对于除后述含官能团单体以外的单体整体优选为0.5摩尔%以上且7.0摩尔%以下、更优选为1.0摩尔%以上且5.0摩尔%以下。
TFE/HFP/PAVE共聚物、CTFE共聚物(1)、CTFE共聚物(2)的防化学溶液透过性、特别是对含醇汽油的阻隔性非常优异。含醇汽油透过系数为如下的值:在投入有将异辛烷、甲苯、及乙醇以45:45:10的容积比混合而成的异辛烷/甲苯/乙醇混合溶剂的透过系数测定用杯中,投入由测定对象树脂得到的片,根据60℃下测定的质量变化算出的值。TFE/HFP/PAVE共聚物、CTFE共聚物(1)、CTFE共聚物(2)的上述含醇汽油透过系数优选为1.5g·mm/(m2·天)以下、更优选为0.01g·mm/(m2·天)以上且1.0g·mm/(m2·天)以下、进一步优选为0.02g·mm/(m2·天)以上且0.8g·mm/(m2·天)以下。
含氟树脂可以通过利用以往以来的聚合方法使构成聚合物的单体(共)聚合来获得。其中,主要使用基于自由基聚合的方法。即对于聚合的引发,只要是以自由基方式进行,手段就没有任何限制,例如利用有机、无机自由基聚合引发剂、热、光或电离辐射线等来引发。
含氟树脂的制造方法没有特别限制,可以使用利用通常使用的自由基聚合引发剂的聚合方法。作为聚合方法,可以采用本体聚合、使用氟化烃、氯化烃、氟氯化烃、醇、烃等有机溶剂的溶液聚合、使用水性介质及根据需要的适当的有机溶剂的悬浮聚合、使用水性介质及乳化剂的乳液聚合等公知的方法。
另外,聚合可以使用一槽乃至多槽式的搅拌型聚合装置、管型聚合装置,以间歇式或连续式操作来实施。
作为自由基聚合引发剂,半衰期为10小时的分解温度优选为0℃以上且100℃以下、更优选为20℃以上且90℃以下。作为具体例,可列举出2,2’-偶氮双异丁腈、2,2’-偶氮双(2,4-二甲基戊腈)、2,2’-偶氮双(2-甲基戊腈)、2,2’-偶氮双(2-环丙基丙腈)、2,2’-偶氮双异丁酸二甲酯、2,2’-偶氮双[2-(羟基甲基)丙腈]、4,4’-偶氮双(4-氰基戊烯酸)等偶氮化合物、过氧化氢、叔丁基过氧化氢、过氧化氢异丙苯等过氧化氢、二叔丁基过氧化物、过氧化二异丙苯等二烷基过氧化物、过氧化乙酰、过氧化异丁酰、过氧化辛酰、过氧化苯甲酰、过氧化月桂酰等非氟系二酰基过氧化物、甲乙酮过氧化物、环己酮过氧化物等酮过氧化物、过氧化二碳酸二异丙酯等过氧化二碳酸酯、过氧化特戊酸叔丁酯、过氧化异丁酸叔丁酯、过氧化乙酸叔丁酯等过氧化酯、(Z(CF2)pCOO)2(此处,Z为氢原子、氟原子或氯原子,p为1~10的整数。)所示的化合物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等。这些可以使用1种或2种以上。
另外,制造含氟树脂时,为了调整分子量,还优选使用通常的链转移剂。作为链转移剂,可列举出甲醇、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、1,2-二氯-1,1,2,2-四氟乙烷、1,1-二氯-1-氟乙烷、1,1,2-三氯-1,2,2-三氟乙烷等氯氟烃、戊烷、己烷、环己烷等烃、四氯化碳、氯仿、二氯甲烷、氯甲烷等氯代烃。这些可以使用1种或2种以上。
对聚合条件没有特别限定,聚合温度优选为0~100℃、更优选为20~90℃。为了避免聚合物中的乙烯-乙烯链生成导致的耐热性的降低,通常优选低温。对于聚合压力,根据使用的溶剂的种类、量及蒸汽压、聚合温度等其他聚合条件来适宜确定,优选为0.1~10MPa、更优选为0.5~3MPa。聚合时间优选为1~30小时。
另外,含氟树脂的分子量没有特别限定,优选室温下为固体的聚合物,且其自身可以作为热塑性树脂、弹性体等来使用。分子量通过聚合中使用的单体的浓度、聚合引发剂的浓度、链转移剂的浓度、温度来控制。
在比含氟树脂的熔点高50℃的温度且5kg载荷下的熔体流动速率优选为0.5g/10分钟以上且200g/10分钟以下、更优选为1g/10分钟以上且100g/10分钟以下。
另外,含氟树脂可以通过选择含氟单体及其他单体的种类、组成比等来调节聚合物的熔点、玻璃化转变温度。
含氟树脂的熔点可以根据目的、用途、使用方法来适宜选择,与第一构件共挤出的情况下,优选接近第一构件中所含的树脂的成形温度。因此,优选适宜调节前述含氟单体、其他单体与后述的含官能团单体的比例,使含氟树脂的熔点最优化。
此处,对于熔点,使用差示扫描量热测定装置,将试样加热至预估的熔点以上的温度,接着,对试样以每1分钟10℃的速度进行降温,冷却至30℃,以原样放置约1分钟后,以每1分钟10℃的速度进行升温,将由此测定的熔解曲线的峰值的温度定义为熔点。
本发明中使用的含氟树脂优选分子结构内具有对氨基具有反应性的官能团。该官能团可以被含有在含氟树脂的分子末端或侧链或主链中的任意处。另外,该官能团可以在含氟树脂中单独或组合使用2种以上。其官能团的种类、含量由与包含含氟系树脂的第二构件直接接触的第一构件的种类、形状、用途、要求的构件间粘接性、粘接方法、官能团导入方法等来适宜决定。
作为对氨基具有反应性的官能团,可列举出选自羧基、酸酐基或羧酸盐、磺基或磺酸盐、环氧基、氰基、碳酸酯基、及卤代甲酰基的组中的至少1种。特别优选选自由羧基、酸酐基或羧酸盐、环氧基、碳酸酯基、及卤代甲酰基组成的组中的至少1种。
作为在含氟树脂中导入具有反应性的官能团的方法,可列举出:(i)在含氟树脂的聚合时使具有官能团的可共聚的单体共聚的方法、(ii)利用聚合引发剂、链转移剂等在聚合时向含氟树脂的分子末端导入官能团的方法、(iii)使含有具有反应性的官能团和可接枝化的官能团的化合物(接枝化合物)与含氟系聚合物接枝的方法等。这些导入方法可以单独使用或适宜组合使用。考虑到复合构件的构件间粘接性的情况下,优选由上述(i)、(ii)制造的含氟树脂。对于(iii),可以参照日本特开平7-18035号公报、日本特开平7-25952号公报、日本特开平7-25954号公报、日本特开平7-173230号公报、日本特开平7-173446号公报、日本特开平7-173447号公报、日本特表平10-503236号公报中的制造方法。以下,对(i)在含氟系聚合物的聚合时使具有官能团的可共聚的单体共聚的方法、(ii)利用聚合引发剂等向含氟系聚合物的分子末端导入官能团的方法进行说明。
(i)在含氟树脂的制造时使具有官能团的可共聚的单体(以下,有时简记为含官能团单体。)共聚的方法中,使用含有选自由羧基、酸酐基或羧酸盐、羟基、磺基或磺酸盐、环氧基、及氰基组成的组中的至少1种以上官能团的单体作为聚合单体。作为含官能团单体,可列举出含官能团的非氟单体、含官能团的含氟单体等。
作为含官能团的非氟单体,可列举出丙烯酸、卤代丙烯酸(其中,不包括氟)、甲基丙烯酸、卤代甲基丙烯酸(其中,不包括氟)、马来酸、卤代马来酸(其中,不包括氟)、富马酸、卤代富马酸(其中,不包括氟)、衣康酸、柠康酸、巴豆酸、内双环-[2.2.1]-5-庚烯-2,3-二羧酸等不饱和羧酸、其酯等衍生物、马来酸酐、衣康酸酐、琥珀酸酐、柠康酸酐、内双环-[2.2.1]-5-庚烯-2,3-二羧酸酐等含羧基单体、丙烯酸缩水甘油酯、甲基丙烯酸缩水甘油酯、缩水甘油醚等含环氧基单体等。这些可以使用1种或2种以上。对于含官能团的非氟单体,考虑与使用的含氟单体的共聚反应性来决定。通过选择适当的含官能团的非氟单体,从而聚合良好地进行,容易均匀地导入至含官能团的非氟单体的主链中,结果有未反应单体少、能够减少杂质的优点。
作为含官能团的含氟单体,可列举出通式X3X4C=CX5-(R7)n-Y(此处,Y表示选自由-COOM(M表示氢原子或碱金属。)、源自羧基的基团、-SO3M(M表示氢原子或碱金属。)、源自磺酸的基团、环氧基、及-CN组成的组中的官能团,X3、X4及X5相同或不同、表示氢原子或氟原子(其中,X3、X4及X5同为氢原子的情况下,n=1、R7中包含氟原子。)、R7表示碳原子数1以上且40以下的亚烷基、碳原子数1以上且40以下的含氟氧亚烷基、具有醚键的碳原子数1以上且40以下的含氟亚烷基、或具有醚键的碳原子数1以上且40以下的含氟氧亚烷基,n为0或1。)所示的不饱和化合物等。
对于作为上述通式中的Y的源自羧基的基团,例如,可列举出通式-C(=O)Q1(式中,Q1表示-OR8、-NH2、F、Cl、Br或I,R8表示碳原子数1以上且20以下的烷基或碳原子数6以上且22以下的芳基。)所示的基团等。
对于作为上述通式中的Y的源自磺酸的基团,例如,可列举出通式-SO2Q2(式中Q2表示-OR9、-NH2、F、Cl、Br或I,R9表示碳原子数1以上且20以下的烷基或碳原子数6以上且22以下的芳基。)所示的基团等。
前述Y优选-COOH、-SO3H、-SO3Na、-SO2F或-CN。
作为含官能团的含氟单体,例如,具有羰基的官能团的情况下,可列举出全氟丙烯酸氟化物、1-氟丙烯酸氟化物、丙烯酸氟化物、1-三氟甲基丙烯酸氟化物、全氟丁烯酸等。这些可以使用1种或2种以上。
对于含氟树脂中的含官能团单体的含量,从确保充分的构件间粘接性、不会由使用环境条件导致构件间粘接性的降低、充分确保耐热性、防止高温下的加工时粘接不良、着色、发泡、防止高温下的使用时由分解导致的剥离、着色/发泡、溶出等的发生的观点出发,相对于全部聚合单元,优选为0.05摩尔%以上且20摩尔%以下、更优选为0.05摩尔%以上且10摩尔%以下、进一步优选为0.1摩尔%以上且5摩尔%以下。若含官能团单体的含量处于前述范围,则制造时的聚合速度不会降低,并且含氟系聚合物(E)与层叠的对象材料的粘接性优异。含官能团单体的添加法没有特别限定,可以在聚合开始时进行一次性添加,也可以在聚合中进行连续添加。添加方法根据聚合引发剂的分解反应性和聚合温度来适宜选择,优选在聚合中随着含官能团单体因聚合而被消耗,连续地或断续地向聚合槽内供给所消耗的量,将该含官能团单体的浓度维持在该范围。
另外,只要满足上述含量,则也可以为导入有官能团的含氟树脂与未导入官能团的含氟系聚合物的混合物。
(ii)利用聚合引发剂等向含氟树脂的分子末端导入官能团的方法中,官能团导入到含氟系聚合物的分子链的单末端或两末端。作为导入至末端的官能团,优选碳酸酯基、卤代甲酰基。
作为含氟树脂的末端基而导入的碳酸酯基,通常为具有-OC(=O)O-的键的基团,具体而言,为-OC(=O)O-R10基[R10为氢原子、有机基团(例如,碳原子数1以上且20以下烷基、具有醚键的碳原子数2以上且20以下的烷基等)、或为I、II、VII族元素。]的结构,可列举出-OC(=O)OCH3、-OC(=O)OC3H7、-OC(=O)OC8H17、-OC(=O)OCH2CH2OCH2CH3等。卤代甲酰基具体而言为-COZ[Z为卤素元素。]的结构,可列举出-COF、-COCl等。这些可以使用1种或2种以上。
另外,为了向聚合物的分子末端导入碳酸酯基,可以采用使用聚合引发剂、链转移剂的各种方法,从经济性、耐热性、耐化学药品性等性能的观点出发,可以优选采用使用过氧化物、特别是过氧化碳酸酯、过氧化酯作为聚合引发剂的方法。根据该方法,可以将源自过氧化物的羰基、例如源自过氧化碳酸酯的碳酸酯基、源自过氧化酯的酯基、或将这些官能团转化而成的卤代甲酰基等导入到聚合物末端中。这些聚合引发剂中,从能够降低聚合温度、引发反应时不伴有副反应的方面出发,更优选使用过氧化碳酸酯。
为了向聚合物的分子末端导入卤代甲酰基,可以采用各种方法,例如,可以通过对末端具有前述碳酸酯基的含氟系聚合物的碳酸酯基进行加热使其热解(脱羧)来得到。
作为过氧化碳酸酯,可列举出过氧化碳酸二异丙酯、过氧化碳酸二正丙酯、叔丁基过氧化异丙基碳酸酯、叔丁基过氧化甲基丙烯酰氧基乙基碳酸酯、双(4-叔丁基环己基)过氧化二碳酸酯、二-2-乙基己基过氧化二碳酸酯等。这些可以使用1种或2种以上。
过氧化碳酸酯的用量根据目标聚合物的种类(组成等)、分子量、聚合条件、使用的引发剂的种类而不同,从适当地控制聚合速度、确保充分的聚合速度的观点出发,相对于通过聚合得到的全部聚合物100质量份,优选为0.05质量份以上且20质量份以下、更优选为0.1质量份以上且10质量份以下。聚合物的分子末端的碳酸酯基含量可以通过调整聚合条件来控制。聚合引发剂的添加法没有特别限定,可以在聚合开始时进行一次性添加,可以在聚合中进行连续添加。根据聚合引发剂的分解反应性和聚合温度来适宜选择添加方法。
对于含氟树脂中的相对于主链碳原子数106个的末端官能团的个数,从确保充分的构件间粘接性、不会由使用环境条件导致构件间粘接性的降低、充分确保耐热性、防止高温下的加工时粘接不良、着色、发泡、防止高温下的使用时由分解导致的剥离、着色/发泡、溶出等的发生的观点出发,优选为150个以上且3,000个以下、更优选为200个以上且2,000个以下、进一步优选为300个以上且1,000个以下。另外,只要满足上述官能团数,可以为导入有官能团的含氟系聚合物与未导入官能团的含氟树脂的混合物。
如上所述,本发明中使用的含氟树脂可以为导入有对氨基具有反应性的官能团的含氟树脂。如上所述,导入有官能团的含氟树脂其自身能维持含氟树脂特有的耐热性、耐水性、低摩擦性、耐化学药品性、耐候性、防污性、防化学溶液透过性等优异的特性,在生产率、成本方面是有利的。
进而,通过使分子链中含有对氨基具有反应性的官能团,从而在复合构件中,能够针对构件间粘接性不充分或不可能粘接的各种材料,在不进行表面处理等特别的处理、粘接性树脂的覆盖等的情况下直接赋予与其他构件的优异的构件间粘接性。
含氟树脂组合物根据目的、用途等,可以在不损害其性能的范围内配混无机质粉末、玻璃纤维、碳纤维、金属氧化物、或碳等各种填充剂。另外,除填充剂以外,还可以混合颜料、紫外线吸收剂等任意添加剂。除添加剂以外,还可以配混其他氟系树脂、热塑性树脂等树脂、合成橡胶等,能实现机械特性的改善、耐候性的改善、外观性的赋予、静电的防止、成形性改善等。
含氟树脂组合物中的含氟树脂的含有率例如为70质量%以上,优选80质量%以上、更优选90质量%以上。
本实施方式的复合构件是第一构件与第二构件直接接触而形成的。作为复合构件的具体例,可列举出层叠管、多层薄膜、多层吹塑成形品、多层压制成形品、多层注射成形品(DSI法、DRI法、模内成形、嵌入成形、多色成形等)等层叠体。
复合构件为层叠管的情况下,层叠管由如下的至少2层以上构成:所述至少2层包含由第一构件形成的层和由第二构件形成的层。对于层叠管,作为优选的实施方式,由第一构件形成的层配置于层叠管的最外层。通过使由第一构件形成的层配置于最外层,从而得到柔软性、耐振动性优异的层叠管。
层叠管必须包含由第二构件形成的层,该层与层叠管的由第一构件形成的层直接接触并配置于其内侧。通过具有由第二构件形成的层,从而能够构成防化学溶液透过性、耐化学药品性等优异的层叠管。
对于层叠管的外径,考虑化学溶液等的流量,以不增大化学溶液透过性、且能够维持通常的管的破坏压力、并且能维持管的安装操作容易性及使用时的耐振动性良好的程度的柔软性的厚度来设计壁厚,没有限定。优选外径为1.5~150mm、内径为1~100mm、壁厚为0.25~25mm。
对于层叠管,各层的厚度没有特别限制,可以根据构成各层的聚合物的种类、层叠管的整体的层数、用途等来调节,考虑层叠管的防化学溶液透过性、低温耐冲击性、柔软性等特性来决定各个层的厚度。通常,由第一构件形成的层及由第二构件形成的层的厚度相对于层叠管整体的厚度各自优选为3~90%。考虑防化学溶液透过性及柔软性、成本等,由第二构件形成的层的厚度相对于层叠管整体的厚度更优选为1~50%、进一步优选为5~30%。
对于层叠管的整体的层数,只要为包含由第一构件形成的层及由第二构件形成的层的至少2层,就没有特别限定。为了赋予进一步的功能、或得到经济上有利的层叠管,层叠管除了由第一构件形成的层及由第二构件形成的层这2层以外,还可以具有1层或2层以上包含其他热塑性树脂的层。
作为构成层叠管中除上述以外的其他层的热塑性树脂,可列举出聚酰胺系树脂、聚烯烃系树脂、聚酯系树脂、聚醚系树脂、聚砜系树脂、聚硫醚系树脂、聚酮系树脂、聚腈系树脂、聚甲基丙烯酸酯系树脂、聚乙烯基酯系树脂、聚氯乙烯系树脂、纤维素系树脂、聚碳酸酯系树脂、聚酰亚胺系树脂等。
作为聚酰胺系树脂,具体而言,可列举出聚己内酰胺(聚酰胺6)、聚十一烷内酰胺(聚酰胺11)、聚十二烷内酰胺(聚酰胺12)、聚己二酰乙二胺(聚酰胺26)、聚丁二酰丁二胺(聚酰胺44)、聚戊二酰丁二胺(聚酰胺45)、聚己二酰丁二胺(聚酰胺46)、聚壬二酰丁二胺(聚酰胺49)、聚癸二酰丁二胺(聚酰胺410)、聚十二烷二酰丁二胺(聚酰胺412)、聚丁二酰戊二胺(聚酰胺54)、聚戊二酰戊二胺(聚酰胺55)、聚己二酰戊二胺(聚酰胺56)、聚壬二酰戊二胺(聚酰胺59)、聚癸二酰戊二胺(聚酰胺510)、聚十二烷二酰戊二胺(聚酰胺512)、聚对苯二甲酰戊二胺(聚酰胺5T)、聚间苯二甲酰戊二胺(聚酰胺5I)、聚六氢对苯二甲酰戊二胺(聚酰胺5T(H))、聚萘二甲酰戊二胺(聚酰胺5N)、聚丁二酰己二胺(聚酰胺64)、聚戊二酰己二胺(聚酰胺65)、聚己二酰己二胺(聚酰胺66)、聚壬二酰己二胺(聚酰胺69)、聚癸二酰己二胺(聚酰胺610)聚十二烷二酰己二胺(聚酰胺612)、聚对苯二甲酰己二胺(聚酰胺6T)、聚间苯二甲酰己二胺(聚酰胺6I)、聚六氢对苯二甲酰己二胺(聚酰胺6T(H))、聚萘二甲酰己二胺(聚酰胺6N)、聚对苯二甲酰2-甲基戊二胺(聚酰胺M5T)、聚间苯二甲酰2-甲基戊二胺(聚酰胺M5I)、聚六氢对苯二甲酰2-甲基戊二胺(聚酰胺M5T(H))、聚萘二甲酰2-甲基戊二胺(聚酰胺M5N)、聚乙二酰壬二胺(聚酰胺92)、聚己二酰壬二胺(聚酰胺96)、聚壬二酰壬二胺(聚酰胺99)、聚癸二酰壬二胺(聚酰胺910)、聚十二烷二酰壬二胺(聚酰胺912)、聚对苯二甲酰壬二胺(聚酰胺9T)、聚间苯二甲酰壬二胺(聚酰胺9I)、聚六氢对苯二甲酰壬二胺(聚酰胺9T(H))、聚萘二甲酰壬二胺(聚酰胺9N)、聚乙二酰2-甲基辛二胺(聚酰胺M82)、聚己二酰2-甲基辛二胺(聚酰胺M86)、聚壬二酰2-甲基辛二胺(聚酰胺M89)、聚癸二酰2-甲基辛二胺(聚酰胺M810)、聚十二烷二酰2-甲基辛二胺(聚酰胺M812)、聚对苯二甲酰2-甲基辛二胺(聚酰胺M8T)、聚间苯二甲酰2-甲基辛二胺(聚酰胺M8I)、聚六氢对苯二甲酰2-甲基辛二胺(聚酰胺M8T(H))、聚萘二甲酰2-甲基辛二胺(聚酰胺M8N)、聚乙二酰三甲基己二胺(聚酰胺TMH2)、聚己二酰三甲基己二胺(聚酰胺TMH6)、聚壬二酰三甲基己二胺(聚酰胺TMH9)、聚癸二酰三甲基己二胺(聚酰胺TMH10)、聚十二烷二酰三甲基己二胺(聚酰胺TMH12)、聚对苯二甲酰三甲基己二胺(聚酰胺TMHT)、聚间苯二甲酰三甲基己二胺(聚酰胺TMHI)、聚六氢对苯二甲酰三甲基己二胺(聚酰胺TMHT(H))、聚萘二甲酰三甲基己二胺(聚酰胺TMHN)、聚乙二酰癸二胺(聚酰胺102)、聚己二酰癸二胺(聚酰胺106)、聚壬二酰癸二胺(聚酰胺109)、聚癸二酰癸二胺(聚酰胺1010)、聚十二烷二酰癸二胺(聚酰胺1012)、聚对苯二甲酰癸二胺(聚酰胺10T)、聚间苯二甲酰癸二胺(聚酰胺10I)、聚六氢对苯二甲酰癸二胺(聚酰胺10T(H))、聚萘二甲酰癸二胺(聚酰胺10N)、聚乙二酰十二烷二胺(聚酰胺122)、聚己二酰十二烷二胺(聚酰胺126)、聚壬二酰十二烷二胺(聚酰胺129)、聚癸二酰十二烷二胺(聚酰胺1210)、聚十二烷二酰十二烷二胺(聚酰胺1212)、聚对苯二甲酰十二烷二胺(聚酰胺12T)、聚间苯二甲酰十二烷二胺(聚酰胺12I)、聚六氢对苯二甲酰十二烷二胺(聚酰胺12T(H))、聚萘二甲酰十二烷二胺(聚酰胺12N)、聚己二酰间苯二甲胺(聚酰胺MXD6)、聚辛二酰间苯二甲胺(聚酰胺MXD8)、聚壬二酰间苯二甲胺(聚酰胺MXD9)、聚癸二酰间苯二甲胺(聚酰胺MXD10)、聚十二烷二酰间苯二甲胺(聚酰胺MXD12)、聚对苯二甲酰间苯二甲胺(聚酰胺MXDT)、聚间苯二甲酰间苯二甲胺(聚酰胺MXDI)、聚萘二甲酰间苯二甲胺(聚酰胺MXDN)、聚双(4-氨基环己基)甲烷十二烷二酰胺(聚酰胺PACM12)、聚双(4-氨基环己基)甲烷对苯二甲酰胺(聚酰胺PACMT)、聚双(4-氨基环己基)甲烷间苯二甲酰胺(聚酰胺PACMI)、聚双(3-甲基-4-氨基环己基)甲烷十二烷二酰胺(聚酰胺二甲基PACM12)、聚异佛尔酮己二酰胺(聚酰胺IPD6)、聚异佛尔酮十二烷二酰胺(聚酰胺IPD12)、聚异佛尔酮对苯二甲酰胺(聚酰胺IPDT)、聚异佛尔酮间苯二甲酰胺(聚酰胺IPDI)、使用这些原料单体的聚酰胺共聚物。需要说明的是,聚酰胺树脂的具体例的上述括号内的名称是基于JIS K 6920-1:2000“塑料-聚酰胺(PA)成形用及挤出用材料-第1部:命名系统和规范符号的基础”。
作为聚烯烃系树脂,具体而言,可列举出高密度聚乙烯(HDPE)、中密度聚乙烯(MDPE)、低密度聚乙烯(LDPE)、直链状低密度聚乙烯(LLDPE)、超高分子量聚乙烯(UHMWPE)、聚丙烯(PP)、乙烯/丙烯共聚物(EPR)、乙烯/丁烯共聚物(EBR)、乙烯/丙烯/二烯共聚物(EPDM)、聚丁二烯(BR)、丁二烯/丙烯腈共聚物(NBR)、聚异戊二烯(IR)、丁烯/异戊二烯共聚物、乙烯/乙酸乙烯酯共聚物(EVA)、乙烯/乙酸乙烯酯共聚物皂化物(EVOH)、乙烯/丙烯酸共聚物(EAA)、乙烯/甲基丙烯酸共聚物(EMAA)、乙烯/丙烯酸甲酯共聚物(EMA)、乙烯/甲基丙烯酸甲酯共聚物(EMMA)、乙烯/丙烯酸乙酯共聚物(EEA)等。进而也可列举出丙烯酸、甲基丙烯酸、马来酸、富马酸、衣康酸、巴豆酸、中康酸、柠康酸、戊烯二酸、顺式-4-环己烯-1,2-二羧酸、内双环-[2.2.1]-5-庚烯-2,3-二羧酸等羧基及其金属盐(Na、Zn、K、Ca、Mg)、马来酸酐、衣康酸酐、柠康酸酐、内双环-[2.2.1]-5-庚烯-2,3-二羧酸酐等酸酐基、丙烯酸缩水甘油酯、甲基丙烯酸缩水甘油酯、乙基丙烯酸缩水甘油酯(glycidyl ethacrylate)、衣康酸缩水甘油酯、柠康酸缩水甘油酯等含有环氧基等官能团的上述聚烯烃系树脂。
作为聚酯系树脂,具体而言,可列举出聚对苯二甲酸丁二醇酯(PBT)、聚对苯二甲酸乙二醇酯(PET)、聚间苯二甲酸乙二醇酯(PEI)、PET/PEI共聚物、聚对苯二甲酸丙二醇酯(PTT)、聚芳酯(PAR)、聚萘二甲酸丁二醇酯(PBN)、聚萘二甲酸乙二醇酯(PEN)、液晶聚酯(LCP)、聚乳酸(PLA)、聚乙醇酸(PGA)等。
作为聚醚系树脂,具体而言,可列举出聚缩醛(POM)、聚苯醚(PPO)等。
作为聚砜系树脂,具体而言,可列举出聚砜(PSF)、聚醚砜(PES)等。
作为聚硫醚系树脂,具体而言,可列举出聚亚苯基硫醚(PPS)、聚硫醚砜(PTES)等。
作为聚酮系树脂,具体而言,可列举出聚醚醚酮(PEEK)、聚芳醚酮(PAEK)等。
作为聚腈系树脂,具体而言,可列举出聚丙烯腈(PAN)、聚甲基丙烯腈、丙烯腈/苯乙烯共聚物(AS)、甲基丙烯腈/苯乙烯共聚物、丙烯腈/丁二烯/苯乙烯共聚物(ABS)、甲基丙烯腈/苯乙烯/丁二烯共聚物(MBS)等。
作为聚甲基丙烯酸酯系树脂,具体而言,可列举出聚甲基丙烯酸甲酯(PMMA)、聚甲基丙烯酸乙酯(PEMA)等。
作为聚乙烯基酯系树脂,具体而言,可列举出聚乙酸乙烯酯(PVAc)等。
作为聚氯乙烯系树脂,具体而言,可列举出聚偏氯乙烯(PVDC)、聚氯乙烯(PVC)、氯乙烯/偏氯乙烯共聚物、偏氯乙烯/甲基丙烯酸酯共聚物等。
作为纤维素系树脂,具体而言,可列举出乙酸纤维素、丁酸纤维素等。
作为聚酰亚胺系树脂,具体而言,可列举出热塑性聚酰亚胺(PI)、聚酰胺酰亚胺(PAI)、聚醚酰亚胺等。
层叠管中,从构成第一构件的聚氨酯树脂组合物的熔融稳定性的观点出发,上述例示的热塑性树脂中,优选使用熔点为230℃以下的聚酯系树脂、聚酰胺系树脂、聚硫醚系树脂。
另外,也可以层叠除热塑性树脂以外的任意基材、例如纸、金属系材料、无拉伸、单轴或双轴拉伸塑料薄膜或片、织布、无纺布、金属棉、木材等。作为金属系材料,可列举出铝、铁、铜、镍、金、银、钛、钼、镁、锰、铅、锡、铬、铍、钨、钴等金属、金属化合物及包含2种以上上述物质的不锈钢等合金钢、铝合金、黄铜、青铜等铜合金、镍合金等合金类等。
本发明的层叠管的层数为2层以上,但根据管制造装置的机构来判断,优选为8层以下、更优选为2层~7层、进一步优选为2层~5层。
作为层叠管的制造方法,可列举出如下方法:使用与层的数目或材料的数量相对应的挤出机,进行熔融挤出,在模内或模外同时进行层叠的方法(共挤出法);或,暂时预先制造单层管或通过上述方法制造的层叠管,在外侧依次根据需要使用粘接剂将树脂一体化来进行层叠的方法(涂覆法)。作为层叠管的成形方法,优选利用共挤出成形。
另外,得到的层叠管为复杂的形状的情况下、成形后施加加热弯曲加工而制成成形品的情况下,为了去除成形品的残留应变,也可以在形成上述的层叠管后,在比构成前述管的树脂的熔点之中最低的熔点更低的温度下进行0.01~10小时热处理,从而得到目标的成形品。
层叠管可以具有波形区域。波形区域为形成为波形形状、波纹形状、折叠(accordion)形状、或波浪(corrugated)形状等的区域。对于波形区域,不仅可以在层叠管全长中具有,还可以在中间的适宜区域局部具有。波形区域可以如下形成:首先,成形为直管状的管后,接着进行模制成形,制成规定的波形形状等,由此容易地形成。通过具有所述波形区域,从而具有冲击吸收性,安装性变容易。进而,例如,可以附加连接器等必要的部件,或通过弯曲加工来制成L字、U字的形状等。
考虑到与砂石飞溅(日语:石ハネ)、其他部件的磨耗、耐火性,可以在这样成形的层叠管的外周的全部或一部分配设由表氯醇橡胶(ECO)、丙烯腈/丁二烯橡胶(NBR)、NBR与聚氯乙烯的混合物、氯磺化聚乙烯橡胶、氯化聚乙烯橡胶、丙烯酸类橡胶(ACM)、氯丁橡胶(CR)、乙烯/丙烯橡胶(EPR)、乙烯/丙烯/二烯橡胶(EPDM)、NBR与EPDM的混合物橡胶、氯乙烯系、烯烃系、酯系等的热塑性弹性体等构成的实心的或海绵状的保护构件(protector)。保护构件可以通过已知的方法制成海绵状的多孔体。通过制成多孔体,从而能够形成轻量、绝热性优异的保护部。另外,也能够减小材料成本。或者可以添加玻璃纤维等来改善其强度。保护构件的形状没有特别限定,通常为筒状构件或具有用于容纳层叠管的凹部的块状构件。筒状构件的情况下,可以在预先制作的筒状构件中后续插入层叠管、或在层叠管上覆盖挤出筒状构件,从而使两者密合来制作。为了使两者粘接,在保护构件内表面或前述凹面根据需要涂布粘接剂,将层叠管插入或嵌装于其中,使两者密合,由此形成层叠管与保护构件一体化而成的结构体。另外,也可以用金属等进行加强。
对于层叠管而言,以汽车部件、内燃机用途、电动工具外壳类等机械部件为首,可列举出工业材料、产业材料、电气/电子部件、医疗、食品、家庭/办公用品、建筑材料相关部件、家具用部件等各种用途。
另外,本发明的层叠管的防化学溶液透过性优异,因此适合作为化学溶液输送用管。作为化学溶液,例如,可列举出苯、甲苯、二甲苯等芳香族烃系溶剂、甲醇、乙醇、丙醇、丁醇、戊醇、乙二醇、丙二醇、二乙二醇、苯酚、甲酚、聚乙二醇、聚丙二醇等醇、酚类溶剂、二甲醚、二丙醚、甲基叔丁基醚、二噁烷、四氢呋喃等醚系溶剂、氯仿、二氯甲烷、三氯乙烯、二氯化乙烯、全氯乙烯、单氯乙烷、二氯乙烷、四氯乙烷、全氯乙烷、氯苯等卤素系溶剂、丙酮、甲乙酮、二乙基酮、苯乙酮等酮系溶剂、汽油、灯油、柴油、含氧汽油、含胺汽油、酸性汽油、蓖麻油基制动液、二醇醚系制动液、硼酸酯系制动液、极寒地用制动液、硅油系制动液、矿物油系制动液、动力转向油、含硫化氢油、挡风玻璃清洗液、引擎冷却液、尿素溶液、甘油溶液、药品、墨、涂料、饮料等。
层叠管适合作为输送上述化学溶液的管,具体而言,可列举出冷却水用管、制冷剂等用冷却管、空调制冷剂用管、地热管、灭火器及灭火设备用管、医疗用冷却设备用管、墨、涂料散布管、进给管、回油管(return tube)、蒸发管、加油管、ORVR管、备用管、弯管等燃料管、油管、制动管、挡风玻璃清洗液用管、散热器管、石油挖掘管、加油站用地下埋设管等化学溶液管。
另外,可以用作Freon-11、Freon-12、Freon-21、Freon-22、Freon-113、Freon-114、Freon-115、Freon-134A、Freon-32、Freon-123、Freon-124、Freon-125、Freon-143A、Freon-141b、Freon-142b、Freon-225、Freon-C318、Freon-502、氯甲烷、氯乙烷、空气、氢、氮、氧、二氧化碳、甲烷、丙烷、异丁烷、正丁烷、氩气、氦气、氙气等各种气体输送用管。
实施例
以下,示出实施例及比较例,具体对本发明进行说明,但本发明不限定于此。
[制造例1聚酰胺弹性体1(PAE-1)的制造]
在具备搅拌机、温度计、压力计、氮气导入口、压力调整装置及聚合物取出口的70L的压力容器中,投入ε-己内酰胺(宇部兴产株式会社制)14.3kg、己二酸(Asahi KaseiChemicals Corporation制)0.74kg、Elastamine RT-1000(美国Huntsman公司制、数均分子量约1000、XYX型三嵌段聚醚二胺化合物)10.0kg、次磷酸钠11.2g、及IRGANOX 245(BASF公司制受阻酚系抗氧化剂)80g。对容器内进行氮气置换后,开始加热。自槽内温度到达230℃的时刻起进一步进行5小时加热搅拌,一边将反应水蒸馏去除到体系外,一边进行聚合反应。反应结束后,从聚合物取出口将无色透明的聚合物以线料状排出到水中,利用造粒机进行切割,得到约13kg的PAE-1。
[制造例2聚酰胺弹性体2(PAE-2)的制造]
利用与制造例1相同的装置,投入六亚甲基二胺80%水溶液(Asahi KaseiChemicals Corporation制)4.88kg、十二烷二酸(宇部兴产株式会社制)9.87kg、Elastamine RT-1000(美国Huntsman公司制、数均分子量约1000、XYX型三嵌段聚醚二胺化合物)9.2kg、脱气水1kg、亚磷酸11.5g、IRGANOX 24569g。对容器内进行氮气置换后,在氮气气流下开始加热。自槽内温度到达230℃的时刻起进一步进行5小时加热搅拌,一边将反应水蒸馏去除到体系外,一边进行聚合反应。用2小时降低温度后,进一步进行3小时聚合反应。反应结束后,通过与制造例1同样的方法取出,得到约13kg的PAE-2。
[实施例及比较例]
(第一构件、第二构件的制作)
按照表1及表2的比例将聚氨酯树脂和聚酰胺弹性体混合,使用单螺杆挤出机进行熔融混炼,对PAE-1、PAE-2,在230℃且以下的条件下进行压制成形,在使用除PAE-1、PAE-2以外的聚酰胺弹性体的情况下在200℃且以下的条件下进行压制成形,得到厚度1mm的第一构件。对表1的参考例在170℃且以下的条件下进行压制成形。
对含氟树脂在250℃且以下的条件下进行压制成形,得到厚度1mm的第二构件。
机械压力:2MPa(预热时)、5MPa(成形时)、250kg/cm2(冷却时)
时间:120秒(预热时)、120秒(成形时)、120秒(冷却时)
(复合构件的制作)
用双层铝箔覆盖第二构件的面的一半,在其上层叠第一构件,对于温度,表1中设为260℃、表2中设为250℃,在上述的压力及时间下进行压制成形,对于表1,得到厚度3mm的复合构件,对于表2,得到厚度2mm的复合构件。
[评价]
(剥离试验)
对得到的复合构件,使用万能材料试验机(ORIENTEC CORPORATION制、TensilonUTM III-200),以50mm/分钟的拉伸速度实施180°剥离试验(依据JIS K 6854-2)。根据S-S曲线的最大点读取剥离强度。另外,目视观察剥离试验后的复合构件的剥离状态。将结果示于表1及表2。
[表1]
表1中,剥离表示在第一构件与第二构件的接触面两者发生了剥离。
[表1中使用的材料]
聚氨酯树脂:醚系聚氨酯树脂
聚酰胺弹性体:UBESTA XPA(商标)9040X1(宇部兴产株式会社制)
含氟树脂:AH3000(旭硝子株式会社制、ETFE)
根据表1的结果可知,第一构件包含聚氨酯树脂及聚酰胺弹性体时,第一构件与第二构件的粘接性提高。
[表2]
表2中,母材破坏表示第一构件及第二构件中的至少一者发生了断裂破坏,剥离表示在第一构件与第二构件的接触面两者发生了剥离。
另外,质量%为相对于第一构件及第二构件各自的值。
表2中的缩写如下。
<热塑性聚氨酯>
ET385-50:聚醚系聚氨酯树脂、制品名“Elastollan(商标)ET385-50”、BASF公司制
1195A10TR:聚醚系聚氨酯树脂、制品名“Elastollan(商标)1195A10TR”BASF公司制
ET690-10:聚酯系聚氨酯树脂、制品名“Elastollan(商标)ET690-10”、BASF公司制
<聚酰胺弹性体>
PEBAX3533:包含月桂内酰胺的开环缩聚物及聚四亚甲基醚二醇的聚酰胺弹性体、制品名“PEBAX(商标)3533”ARKEMA K.K.制
PAE1200U:包含月桂内酰胺的开环缩聚物及源自氢化二聚酸的结构单元的聚酰胺弹性体、制品名“UBEPAE1200U”、宇部兴产株式会社制
9040X1:具有月桂内酰胺的开环缩聚物及XYX型三嵌段聚醚结构的聚酰胺弹性体、制品名“UBESTA XPA(注册商标)9040X1”、宇部兴产株式会社制
PAE-1:制造例1中得到的PAE-1
PAE-2:制造例2中得到的PAE-2
<含氟树脂>
AH2000:制品名“ETFE AH2000”、旭硝子株式会社制
根据实施例4~8可知,作为第一构件,在热塑性聚氨酯中配混聚酰胺弹性体时,无论聚酰胺弹性体的种类为何,第一构件与第二构件的粘接性都提高。
根据实施例10~13可知,第一构件中的聚酰胺弹性体的量越少,剥离强度越高。
根据实施例4~13可知,无论第一构件中的热塑性聚氨酯的种类为何,在进一步配混聚酰胺弹性体时,第一构件与第二构件的粘接性都提高。
与此相对,根据比较例2~7可知,作为第一构件仅使用热塑性聚氨酯的情况下及作为第一构件仅使用聚酰胺弹性体的情况下,第一构件与第二构件的粘接性不充分。
Claims (12)
1.一种复合构件,其是包含热塑性聚氨酯及聚酰胺弹性体的第一构件与包含含氟树脂的第二构件直接接触而形成的。
2.根据权利要求1所述的复合构件,其中,所述第一构件的聚酰胺弹性体含有率为49质量%以下。
3.根据权利要求2所述的复合构件,其中,所述第一构件的聚酰胺弹性体含有率为30质量%以下。
4.根据权利要求1~3中任一项所述的复合构件,其中,所述聚酰胺弹性体具有硬链段和软链段,所述硬链段具有由如下的化合物形成的聚酰胺结构单元,所述化合物为选自由用二胺与二羧酸形成的尼龙盐、下述式(2)所示的氨基羧酸化合物及下述式(3)所示的内酰胺化合物组成的组中的至少1种,
H2N-R1-COOH (2)
式(2)及(3)中,R1表示包含烃链的连接基团,R2表示包含烃链的连接基团。
5.根据权利要求4所述的复合构件,其中,所述软链段具有聚醚结构单元。
6.根据权利要求4或5所述的复合构件,其中,所述聚酰胺弹性体具有由选自由ω-月桂内酰胺、11-氨基十一烷酸及12-氨基十二烷酸组成的组中的至少1种形成的聚酰胺结构单元。
7.根据权利要求4~6中任一项所述的复合构件,其中,所述软链段具有由选自由聚乙二醇、聚丙二醇、聚四亚甲基醚二醇及下述式(5)所示的XYX型三嵌段聚醚组成的组中的至少1种形成的聚醚结构单元,
式(5)中,x表示1~20的整数,y表示4~50的整数,且z表示1~20的整数。
8.根据权利要求4~7中任一项所述的复合构件,其中,所述硬链段包含由所述聚酰胺结构单元和下述式(4)所示的二羧酸衍生的结构单元,
式(4)中,R3表示包含烃链的连接基团,m表示0或1。
9.根据权利要求1~3中任一项所述的复合构件,其中,所述聚酰胺弹性体包含:
由下述式(1)所示的二胺化合物衍生的第一结构单元、
由下述式(2)所示的氨基羧酸化合物或下述式(3)所示的内酰胺化合物衍生的第二结构单元、和
由下述式(4)所示的二羧酸化合物衍生的第三结构单元,
H2N-R1-COOH (2)
x表示1~20的整数,y表示4~50的整数,且z表示1~20的整数,R1表示包含烃链的连接基团,R2表示包含烃链的连接基团,R3表示包含烃链的连接基团,m表示0或1。
10.根据权利要求1~3中任一项所述的复合构件,其中,所述含氟树脂为选自由聚四氟乙烯、乙烯/四氟乙烯共聚物、聚偏氟乙烯、四氟乙烯/全氟烷基乙烯基醚共聚物、四氟乙烯/六氟丙烯共聚物及四氟乙烯/六氟丙烯/偏氟乙烯共聚物组成的组中的至少1种。
11.一种层叠体,其包含权利要求1~3中任一项所述的复合构件。
12.一种层叠管,其包含权利要求1~3中任一项所述的复合构件。
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CN114231026A (zh) * | 2021-12-21 | 2022-03-25 | 天津金发新材料有限公司 | 一种聚酰胺复合材料及其制备方法 |
CN114231026B (zh) * | 2021-12-21 | 2023-12-01 | 天津金发新材料有限公司 | 一种聚酰胺复合材料及其制备方法 |
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EP3533607B1 (en) | 2021-09-29 |
JP6939810B2 (ja) | 2021-09-22 |
US20190241737A1 (en) | 2019-08-08 |
EP3533607A1 (en) | 2019-09-04 |
WO2018079768A1 (ja) | 2018-05-03 |
EP3533607A4 (en) | 2020-07-01 |
KR20190078575A (ko) | 2019-07-04 |
JPWO2018079768A1 (ja) | 2019-09-19 |
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