CN111479889B - 粘接剂、层叠体、电池用包装材料以及电池 - Google Patents
粘接剂、层叠体、电池用包装材料以及电池 Download PDFInfo
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- CN111479889B CN111479889B CN201880079869.6A CN201880079869A CN111479889B CN 111479889 B CN111479889 B CN 111479889B CN 201880079869 A CN201880079869 A CN 201880079869A CN 111479889 B CN111479889 B CN 111479889B
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- Prior art keywords
- anhydride
- acid
- olefin resin
- adhesive
- battery
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- 239000000853 adhesive Substances 0.000 title claims abstract description 74
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 73
- 239000005022 packaging material Substances 0.000 title claims abstract description 19
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 70
- 229910052751 metal Inorganic materials 0.000 claims abstract description 32
- 239000002184 metal Substances 0.000 claims abstract description 32
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 239000004593 Epoxy Substances 0.000 claims abstract description 12
- 239000000758 substrate Substances 0.000 claims description 53
- 229920000098 polyolefin Polymers 0.000 claims description 41
- -1 methylcyclohexene tetracarboxylic anhydride Chemical class 0.000 claims description 36
- 229920005989 resin Polymers 0.000 claims description 28
- 239000011347 resin Substances 0.000 claims description 28
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 18
- 239000011888 foil Substances 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 13
- 239000012790 adhesive layer Substances 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 13
- 239000011248 coating agent Substances 0.000 claims description 12
- 150000008064 anhydrides Chemical class 0.000 claims description 11
- 230000004048 modification Effects 0.000 claims description 8
- 238000012986 modification Methods 0.000 claims description 8
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 6
- 125000004018 acid anhydride group Chemical group 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 5
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 claims description 4
- 150000003512 tertiary amines Chemical class 0.000 claims description 4
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 claims description 3
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 claims description 3
- 239000002318 adhesion promoter Substances 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- KNDQHSIWLOJIGP-UMRXKNAASA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound O=C1OC(=O)[C@@H]2[C@H]1[C@]1([H])C=C[C@@]2([H])C1 KNDQHSIWLOJIGP-UMRXKNAASA-N 0.000 claims description 2
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 claims description 2
- BLBSJBOFNFNGLV-UHFFFAOYSA-N 3-ethyl-oxacyclononadecane-2,19-dione Chemical compound CCC1CCCCCCCCCCCCCCCC(=O)OC1=O BLBSJBOFNFNGLV-UHFFFAOYSA-N 0.000 claims description 2
- XTBGPYSCCALXIA-UHFFFAOYSA-N 3-phenyl-oxacycloheptadecane-2,17-dione Chemical compound O=C1OC(=O)CCCCCCCCCCCCCC1C1=CC=CC=C1 XTBGPYSCCALXIA-UHFFFAOYSA-N 0.000 claims description 2
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 claims description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 2
- 239000011951 cationic catalyst Substances 0.000 claims description 2
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 2
- FLBJFXNAEMSXGL-UHFFFAOYSA-N het anhydride Chemical compound O=C1OC(=O)C2C1C1(Cl)C(Cl)=C(Cl)C2(Cl)C1(Cl)Cl FLBJFXNAEMSXGL-UHFFFAOYSA-N 0.000 claims description 2
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims description 2
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1 -dodecene Natural products CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 claims 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims 1
- CSHJJWDAZSZQBT-UHFFFAOYSA-N 7a-methyl-4,5-dihydro-3ah-2-benzofuran-1,3-dione Chemical compound C1=CCCC2C(=O)OC(=O)C21C CSHJJWDAZSZQBT-UHFFFAOYSA-N 0.000 claims 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims 1
- 229940069096 dodecene Drugs 0.000 claims 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 229940014800 succinic anhydride Drugs 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 26
- 238000000034 method Methods 0.000 description 25
- 239000002585 base Substances 0.000 description 24
- 229920001577 copolymer Polymers 0.000 description 17
- 239000003822 epoxy resin Substances 0.000 description 17
- 229920000647 polyepoxide Polymers 0.000 description 17
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 13
- 150000001336 alkenes Chemical class 0.000 description 13
- 239000000178 monomer Substances 0.000 description 13
- 229910052782 aluminium Inorganic materials 0.000 description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 11
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 11
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 11
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
- 239000003960 organic solvent Substances 0.000 description 10
- 238000007789 sealing Methods 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 239000006224 matting agent Substances 0.000 description 8
- 235000011007 phosphoric acid Nutrition 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 7
- 229920001225 polyester resin Polymers 0.000 description 7
- 239000004645 polyester resin Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 238000011282 treatment Methods 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 150000002009 diols Chemical class 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 229920006122 polyamide resin Polymers 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- 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
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
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- 125000000524 functional group Chemical group 0.000 description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 4
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- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
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- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
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- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
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- 239000002202 Polyethylene glycol Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
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- 125000001931 aliphatic group Chemical group 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
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- 150000002148 esters Chemical class 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
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- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
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- 229920001223 polyethylene glycol Polymers 0.000 description 3
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- GRWFGVWFFZKLTI-IUCAKERBSA-N (-)-α-pinene Chemical compound CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 description 2
- GWQOYRSARAWVTC-UHFFFAOYSA-N 1,4-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=C(C(C)(C)OOC(C)(C)C)C=C1 GWQOYRSARAWVTC-UHFFFAOYSA-N 0.000 description 2
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- ODBCKCWTWALFKM-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhex-3-yne Chemical compound CC(C)(C)OOC(C)(C)C#CC(C)(C)OOC(C)(C)C ODBCKCWTWALFKM-UHFFFAOYSA-N 0.000 description 2
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- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
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- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 2
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
- H01M50/105—Pouches or flexible bags
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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
- B32B15/085—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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/26—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Laminated Bodies (AREA)
- Adhesives Or Adhesive Processes (AREA)
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Abstract
本申请提供将烯烃树脂这样的非极性基材与金属基材粘接的粘接性、耐热性优异的粘接剂、使用该粘接剂所得到的耐热性优异的层叠体、电池用包装材料。本申请涉及一种粘接剂、该粘接剂用预混物、使用该粘接剂的层叠体、电池用包装材料和电池，上述粘接剂包含烯烃树脂(A)、含环氧化合物的固化剂(B)和酸酐(C)，相对于烯烃树脂(A)100质量份，酸酐(C)的配合量为0.05质量份以上且10质量份以下。
Description
技术领域
本发明涉及粘接剂，更具体而言，涉及适于将树脂基材与金属基材粘接的聚烯烃系粘接剂、使用该粘接剂所得到的层叠体、二次电池用外包装材料和电池。
背景技术
以锂离子电池为代表的二次电池采用封入正极、负极以及它们间的电解液等的构成。此外已知：作为用于封入用来将正极和负极的电引出至外部的引线的封入袋，使用使塑料与热封层和金属基材贴合的层叠体，上述热封层包含烯烃树脂，上述金属基材包含铝箔等金属箔、金属蒸镀层(专利文献1、2)。
现有技术文献
专利文献
专利文献1：日本特开平09－283101号公报
专利文献2：日本特开2007－294381号公报
发明内容
发明要解决的课题
然而，烯烃树脂为非极性，因此与金属基材的粘接是困难的。此外，在使用上述层叠体来组装电池时，将位于电池元件周缘的密封层彼此热熔接而将电池元件密封，由此将电池元件封住。因此，对于使热封层与金属基材贴合的粘接剂而言，除了需要将烯烃树脂这样的非极性基材与金属基材粘接的粘接性以外，还需要耐热性。
本发明是鉴于这样的状况而完成的，目的在于提供将烯烃树脂这样的非极性基材与金属基材粘接的粘接性、耐热性优异的粘接剂。此外，目的在于提供使用这样的粘接剂所得到的层叠体、使用该层叠体所得到的二次电池外包装材料以及电池。
用于解决课题的手段
本发明涉及一种粘接剂，其包含烯烃树脂(A)、含环氧化合物的固化剂(B)和酸酐(C)，相对于烯烃树脂(A)100质量份，酸酐(C)的配合量为0.05质量份以上且10质量份以下。
发明效果
本发明的粘接剂的将烯烃树脂这样的非极性基材与金属基材粘接的粘接性、耐热性优异。此外，本发明的层叠体的粘接性、耐热性优异。
具体实施方式
＜粘接剂＞
本发明的粘接剂包含烯烃树脂(A)、含环氧化合物的固化剂(B)和酸酐(C)。以下，针对本发明的粘接剂的各成分进行具体说明。
作为本发明的粘接剂中使用的烯烃树脂(A)，可举出烯烃单体的均聚物、共聚物、烯烃单体与其他单体的共聚物、这些聚合物的氢化物、卤化物、导入了酸、羟基等官能团的改性物等以烃骨架作为主体的聚合物，能够使用1种或组合使用2种以上。优选使用具有酸基或酸酐基的结晶性烯烃树脂、具有羟基的结晶性烯烃树脂。
作为具有酸基或酸酐基的结晶性烯烃树脂，可举出：作为烯烃系单体、与烯键式不饱和羧酸或烯键式不饱和羧酸酐的共聚物的酸改性烯烃树脂(A－1)；作为对聚烯烃用烯键式不饱和羧酸或烯键式不饱和羧酸酐进行了接枝改性的树脂的酸改性烯烃树脂(A－2)。
作为酸改性烯烃树脂(A－1)的制备中使用的烯烃系单体，可举出碳原子数2～8的烯烃，例如乙烯、丙烯、异丁烯、1－丁烯、4－甲基－1－戊烯、己烯、乙烯基环己烷等。在它们中，从特别是粘接强度变得良好的方面出发，优选碳原子数3～8的烯烃，更优选丙烯和1－丁烯，尤其是并用丙烯与1－丁烯在对溶剂的耐性优异、粘接强度优异的方面是优选的。
作为在与烯烃系单体的共聚中使用的烯键式不饱和羧酸或烯键式不饱和羧酸酐，可举出例如：丙烯酸、甲基丙烯酸、马来酸、衣康酸、柠康酸、中康酸、马来酸酐、4－甲基环己－4－烯－1,2－二羧酸酐、双环[2.2.2]辛－5－烯－2,3－二羧酸酐、1,2,3,4,5,8,9,10－八氢萘－2,3－二羧酸酐、2－辛－1,3－二酮螺[4.4]壬－7－烯、双环[2.2.1]庚－5－烯－2,3－二羧酸酐、马来海松酸、四氢邻苯二甲酸酐、甲基双环[2.2.1]庚－5－烯－2,3－二羧酸酐、甲基－降冰片烯－5－烯－2,3－二羧酸酐、降冰片(日文：ノルボルン)－5－烯－2,3－二羧酸酐等。在它们中，特别是从与烯烃系单体的反应性，共聚后的酸酐的反应性优异，且该化合物自身的分子量小、制成共聚物的情况下的官能团浓度变高的方面出发，优选马来酸酐。它们可以单独使用或并用2种以上来使用。
酸改性烯烃树脂(A－1)的制备中，除烯烃系单体、烯键式不饱和羧酸或烯键式不饱和羧酸酐以外，还可以并用其他带有烯键式不饱和基的化合物，例如苯乙烯、丁二烯、异戊二烯等。
作为酸改性烯烃树脂(A－2)的制备中使用的聚烯烃，可举出碳原子数2～8的烯烃的均聚物、共聚物、碳原子数2～8的烯烃与其他单体的共聚物等，具体而言，可举出例如：高密度聚乙烯(HDPE)、低密度聚乙烯(LDPE)、线性低密度聚乙烯树脂等聚乙烯、聚丙烯、聚异丁烯、聚(1－丁烯)、聚(4－甲基－1－戊烯)、聚乙烯基环己烷、乙烯·丙烯嵌段共聚物、乙烯·丙烯无规共聚物、乙烯·1－丁烯共聚物、乙烯·4－甲基－1－戊烯共聚物、乙烯·己烯共聚物等α－烯烃共聚物、乙烯·乙酸乙烯酯共聚物、乙烯·甲基丙烯酸甲酯共聚物、乙烯·乙酸乙烯酯·甲基丙烯酸甲酯共聚物、丙烯·1－丁烯共聚物等。在它们中，从特别是粘接强度变得良好的方面出发，优选碳原子数3～8的烯烃的均聚物、2种以上碳原子数3～8的烯烃的共聚物，更优选丙烯的均聚物或丙烯·1－丁烯共聚物，尤其是丙烯·1－丁烯共聚物在对溶剂的耐性优异、粘接强度优异的方面是优选的。
作为与聚烯烃的接枝改性中使用的烯键式不饱和羧酸或烯键式不饱和羧酸酐，能够使用：与上述的酸改性烯烃树脂(A－1)的制备中、和烯烃系单体的共聚所使用的烯键式不饱和羧酸或烯键式不饱和羧酸酐同样的物质。从接枝改性后的官能团的反应性高、且经接枝改性的聚烯烃的官能团浓度升高的方面出发，优选马来酸酐。它们可以单独使用或并用2种以上来使用。
为了通过接枝改性使烯键式不饱和羧酸或烯键式不饱和羧酸酐与聚烯烃反应，具体而言，可举出：将聚烯烃熔融，在其中添加烯键式不饱和羧酸或烯键式不饱和羧酸酐(接枝单体)而进行接枝反应的方法；将聚烯烃溶解于溶剂而制成溶液，在其中添加烯键式不饱和羧酸或烯键式不饱和羧酸酐(接枝单体)而进行接枝反应的方法；将溶解于有机溶剂的聚烯烃与烯键式不饱和羧酸或烯键式不饱和羧酸酐混合，以聚烯烃的软化温度或熔点以上的温度加热，在熔融状态下同时进行自由基聚合与夺氢反应的方法等。
在任意的情况下，为了使接枝单体高效地进行接枝共聚，优选在自由基引发剂的存在下实施接枝反应。接枝反应通常以60～350℃的条件进行。自由基引发剂的使用比例相对于改性前的聚烯烃100重量份，通常为0.001～1重量份的范围。
作为自由基引发剂，优选有机过氧化物，可举出例如：过氧化苯甲酰、二氯过氧化苯甲酰、过氧化二异丙苯、二叔丁基过氧化物、2,5－二甲基－2,5－二(过氧化苯甲酸酯)己炔－3、1,4－双(叔丁基过氧化异丙基)苯、过氧化月桂酰、过氧化乙酸叔丁酯、2,5－二甲基－2,5－二(叔丁基过氧化)己炔－3、2,5－二甲基－2,5－二(叔丁基过氧化)己烷、过氧化苯甲酸叔丁酯、过氧化苯乙酸叔丁酯、过氧化异丁酸叔丁酯、过氧化仲辛酸叔丁酯、过氧化新戊酸叔丁酯、过氧化新戊酸枯基酯和过氧化二乙基乙酸叔丁酯等。也能够使用其他偶氮化合物，例如偶氮二异丁腈、偶氮异丁酸二甲酯等。
自由基引发剂只要根据接枝反应的工艺来选定最合适的自由基引发剂即可，通常优选使用过氧化二异丙苯、二叔丁基过氧化物、2,5－二甲基－2,5－二(叔丁基过氧化)己炔－3、2,5－二甲基－2,5－二(叔丁基过氧化)己烷、1,4－双(叔丁基过氧化异丙基)苯等二烷基过氧化物。
使用酸改性烯烃树脂(A－1)、酸改性烯烃树脂(A－2)作为烯烃树脂(A)的情况下，从金属层的密合性进一步提高、耐电解质性优异的方面出发，优选使用具有1～200mgKOH/g的酸值的物质。
作为具有羟基的烯烃树脂(A－3)，可举出：聚烯烃与含羟基(甲基)丙烯酸酯、含羟基乙烯基醚的共聚物；对聚烯烃用含羟基(甲基)丙烯酸酯、含羟基乙烯基醚进行了接枝改性的树脂。聚烯烃能够使用与烯烃树脂(A－2)的制备中使用的聚烯烃同样的物质。作为改性方法，能够使用与酸改性烯烃树脂(A－1)、(A－2)的制备方法同样的方法。
作为改性中使用的含羟基(甲基)丙烯酸酯，可举出：(甲基)丙烯酸羟乙酯、(甲基)丙烯酸羟丙酯、(甲基)丙烯酸甘油酯、内酯改性(甲基)丙烯酸羟乙酯、聚乙二醇单(甲基)丙烯酸酯、聚丙二醇单(甲基)丙烯酸酯等。
作为含羟基乙烯基醚，可举出2－羟乙基乙烯基醚、二乙二醇单乙烯基醚、4－羟丁基乙烯基醚等。
使用具有羟基的烯烃树脂(A－3)作为烯烃树脂(A)的情况下，从金属层的密合性进一步提高、耐电解质性优异的方面出发，优选使用具有1～200mgKOH/g的羟值的物质。
可以将上述的酸改性烯烃树脂(A－2)、具有羟基的烯烃树脂(A－3)的制备中使用的聚烯烃不经改性而直接用作烯烃树脂(A)。
为了使粘接性良好，烯烃树脂(A)的重均分子量优选为40,000以上。此外，为了确保适度的流动性，烯烃树脂(A)的重均分子量优选为150,000以下。
需要说明的是，本发明中，重均分子量(Mw)、数均分子量(Mn)为通过下述条件的凝胶渗透色谱(GPC)所测定的值。
测定装置：东曹株式会社制HLC－8320GPC
柱：东曹株式会社制TSKgel 4000HXL、TSKgel 3000HXL、TSKgel2000HXL、TSKgel1000HXL
检测器：RI(示差折射仪)
数据处理：东曹株式会社制Multi Station GPC－8020modelII
测定条件：柱温40℃
溶剂四氢呋喃
流速0.35ml/分钟
标准：单分散聚苯乙烯
试样：将换算成树脂固体成分为0.2质量％的四氢呋喃溶液用微型过滤器进行了过滤的产物(100μl)。
烯烃树脂(A)的熔点优选为50℃以上，更优选为60℃以上，进一步优选为65℃以上。烯烃树脂(A)的熔点优选为120℃以下，更优选为90℃以下，进一步优选为85℃以下。
烯烃树脂的熔点通过DSC(差示扫描热量分析)进行测定。具体而言，以10℃/min从降温到达温度升温至升温到达温度后，以10℃/min冷却至降温到达温度，从而消除热历史之后，再次以10℃/min升温至升温到达点。将第2次升温时的峰值温度作为熔点。此外，降温到达温度设定为比结晶化温度低50℃以上的温度，升温到达温度设为比熔点温度高30℃左右以上的温度。降温到达温度、升温到达温度进行试测定来决定。
作为固化剂(B)，使用环氧化合物。只要为分子内具有环氧基的化合物则没有特别限定，可举出例如：乙二醇、丙二醇、己二醇、新戊二醇、三羟甲基乙烷、三羟甲基丙烷、季戊四醇、甘油、二甘油、山梨糖醇、螺二醇或氢化双酚A等脂肪族多元醇的聚缩水甘油醚型环氧树脂；
双酚A型环氧树脂、双酚F型环氧树脂、双酚S型环氧树脂、双酚AD型环氧树脂等双酚型环氧树脂；
作为苯酚酚醛树脂、甲酚酚醛树脂的缩水甘油醚的、酚醛型环氧树脂等芳香族环氧树脂；
作为双酚A、双酚F、双酚S、双酚AD等芳香族系多羟基化合物的环氧乙烷或环氧丙烷加成物的、多元醇的聚缩水甘油醚；
聚乙二醇、聚丙二醇或聚四亚甲基二醇等聚醚多元醇的聚缩水甘油醚型环氧树脂；双(3,4－环氧环己基甲基)己二酸酯、3,4－环氧环己基甲基－3’,4’－环氧环己基羧酸酯等环状脂肪族型聚环氧树脂；
丙烷三羧酸、丁烷四羧酸、己二酸、邻苯二甲酸、对苯二甲酸或偏苯三酸等多羧酸的聚缩水甘油酯型环氧树脂；
丁二烯、己二烯、辛二烯、十二碳二烯、环辛二烯、α－蒎烯或乙烯基环己烯等烃系二烯的双环氧树脂；
聚丁二烯或聚异戊二烯等二烯聚合物的环氧树脂；
四缩水甘油基二氨基二苯基甲烷、三缩水甘油基对氨基苯酚、四缩水甘油基双氨基甲基环己烷、二缩水甘油基苯胺、四缩水甘油基间苯二甲胺等缩水甘油胺型环氧树脂；
含有三嗪、乙内酰脲等杂环的环氧树脂。
这些环氧树脂可以单独使用，也可以2种以上组合使用。
此外，本发明中使用的环氧化合物优选为1分子中具备2个以上的环氧基和1个以上的羟基、且重均分子量为3000以下的环氧化合物。
作为固化剂(B)，可以并用环氧树脂以外的化合物。作为能与环氧树脂并用的其他固化剂，可举出：多官能异氰酸酯化合物、含氮丙啶基化合物、碳二亚胺、噁唑啉、氨基树脂等。
作为多官能异氰酸酯化合物，可举出：2,4－甲苯二异氰酸酯、2,6－甲苯二异氰酸酯、苯二亚甲基二异氰酸酯、二苯基甲烷二异氰酸酯、异佛尔酮二异氰酸酯、1,5－萘二异氰酸酯、六亚甲基二异氰酸酯、双(4－异氰酸根合环己基)甲烷或氢化二苯基甲烷二异氰酸酯等二异氰酸酯、以及由它们衍生的化合物即上述二异氰酸酯的异氰脲酸酯体、加成物、缩二脲型、缩脲二酮体、脲基甲酸酯体、具有异氰酸酯残基的预聚物(由二异氰酸酯与多元醇所得到的低聚物)、或它们的复合物等。
可以使上述那样的多官能异氰酸酯化合物的一部分异氰酸酯基、与对异氰酸酯基具有反应性的化合物进行反应，使用所得的化合物作为固化剂。作为对异氰酸酯基具有反应性的化合物，可举出：丁胺、己胺、辛胺、2－乙基己胺、二丁胺、乙二胺、苄胺、苯胺等含氨基的化合物类；甲醇、乙醇、丙醇、异丙醇、丁醇、己醇、辛醇、2－乙基己醇、十二烷醇、乙二醇、丙二醇、苯甲醇、苯酚等含羟基化合物类；烯丙基缩水甘油醚、2－乙基己基缩水甘油醚、苯基缩水甘油醚、新戊二醇二缩水甘油醚、1,6－己二醇缩水甘油醚、环己烷二甲醇二缩水甘油醚等具有环氧基的化合物类；乙酸、丁酸、己酸、辛酸、琥珀酸、己二酸、癸二酸、邻苯二甲酸等含羧酸的化合物等。
作为含氮丙啶基化合物，可举出例如：N,N’－六亚甲基－1,6－双(1－氮丙啶羧基酰胺)、N,N’－二苯基甲烷－4,4’－双(1－氮丙啶羧基酰胺)、三羟甲基丙烷－三－β－氮丙啶基丙酸酯)、N,N’－甲苯－2,4－双(1－氮丙啶羧基酰胺)、三亚乙基三聚氰胺、三羟甲基丙烷－三－β－(2－甲基氮丙啶)丙酸酯、双间苯二甲酰－1－2－甲基氮丙啶、三－1－氮丙啶基氧化膦、三－1－2－甲基氮丙啶氧化膦等。
作为碳二亚胺，可举出：N,N’－二－邻甲苯酰碳二亚胺、N,N’－二苯基碳二亚胺、N,N’－二－2,6－二甲基苯基碳二亚胺、N,N’－双(2,6－二异丙基苯基)碳二亚胺、N,N’－双十八烷基碳二亚胺、N－甲苯基－N’－环己基碳二亚胺、N,N’－二－2,2－叔丁基苯基碳二亚胺、N－甲苯基－N’－苯基碳二亚胺、N,N’－二－对氨基苯基碳二亚胺、N,N’－二－对羟基苯基碳二亚胺、N,N’－二－环己基碳二亚胺，N,N’－二－对甲苯基碳二亚胺等。
作为噁唑啉，可举出：2－噁唑啉、2－甲基－2－噁唑啉、2－苯基－2－噁唑啉、2,5－二甲基－2－噁唑啉、2,4－二苯基－2－噁唑啉等单噁唑啉化合物、2,2’－(1,3－亚苯基)－双(2－噁唑啉)、2,2’－(1,2－亚乙基)－双(2－噁唑啉)、2,2’－(1,4－亚丁基)－双(2－噁唑啉)、2,2’－(1,4－亚苯基)－双(2－噁唑啉)等。
作为氨基树脂，可举出蜜胺树脂、苯并胍胺树脂、脲树脂等。
固化剂(B)的配合量相对于烯烃树脂(A)100质量份，优选为0.01质量份以上，更优选为0.1质量份以上，进一步优选为0.5质量份以上。此外，固化剂(B)的配合量相对于烯烃树脂(A)100质量份，优选为10质量份以下，更优选为8质量份以下，进一步优选为5质量份以下。由此，能够显现出优异的粘接性和耐药剂性。
作为酸酐(C)，可举出：环状脂肪族酸酐、芳香族酸酐、不饱和羧酸酐等，能够使用1种或组合使用2种以上。更具体而言，可举出例如：邻苯二甲酸酐、偏苯三酸酐、均苯四酸酐、二苯甲酮四羧酸酐、十二碳烯琥珀酸酐、聚己二酸酐、聚壬二酸酐、聚癸二酸酐、聚(乙基十八烷二酸)酐、聚(苯基十六烷二酸)酐、四氢邻苯二甲酸酐、甲基四氢邻苯二甲酸酐、甲基六氢邻苯二甲酸酐、六氢邻苯二甲酸酐、甲基降冰片烯二酸酐(日文：メチルハイミック酸無水物)、三烷基四氢邻苯二甲酸酐、甲基环己烯二羧酸酐、甲基环己烯四羧酸酐、乙二醇双偏苯三酸酯二酐、氯桥酸酐、纳迪克酸酐(日文：ナジック酸無水物)、甲基纳迪克酸酐、5－(2,5－二氧代四氢－3－呋喃基)－3－甲基－3－环己烷－1,2－二羧酸酐、3,4－二羧基－1,2,3,4－四氢－1－萘琥珀酸二酐、1－甲基－二羧基－1,2,3,4－四氢－1－萘琥珀酸二酐等。
此外，作为酸酐(C)，可以使用将上述化合物用二醇改性了的产物。作为能够用于改性的二醇，可举出：乙二醇、丙二醇、新戊二醇等亚烷基二醇类；聚乙二醇、聚丙二醇、聚四亚甲基醚二醇等聚醚二醇类等。此外，也能够使用它们中的2种以上的二醇和/或聚醚二醇的共聚聚醚二醇。
酸酐(C)的配合量相对于烯烃树脂(A)100质量份，优选为0.05质量份以上，更优选为0.8质量份以上。此外，酸酐(C)的配合量相对于烯烃树脂(A)100质量份，优选为10质量份以下，更优选为8质量份以下。由此，能够提高粘接剂与金属的密合性，制成初始强度和热封后的粘接强度优异的粘接剂。
本发明的粘接剂的粘接性、耐热性优异的理由尚不确定，但推测如下。本发明中使用的酸酐(C)具有极性基，对金属基材的亲和性优异。此外，分子量较小，因此相对地容易移动。可认为其在涂敷的粘接剂完全固化为止的期间移动到金属基材侧，发挥所谓的锚定剂那样的效果，由此有助于粘接性、耐热性的提高。另一方面，认为当粘接剂所含的酸酐(C)的量过多时，酸酐(C)会在金属基材与粘接剂之间近似地形成强度低的层，因此导致粘接性降低。
本发明的粘接剂除上述各成分外，可通过进一步配合有机溶剂(D)而确保流动性，显现合适的涂敷性。作为这样的有机溶剂，只要是能够通过涂敷粘接剂时的干燥工序中的加热而使其挥发除去的有机溶剂则没有特别限定，可举出例如：甲苯、二甲苯等芳香族系有机溶剂；正己烷、正庚烷等脂肪族系有机溶剂；环己烷、甲基环己烷等脂环族系有机溶剂；三氯乙烯、二氯乙烯、氯苯、氯仿等卤素系有机溶剂；甲乙酮、甲基异丁基酮、环己酮等酮系溶剂；乙酸乙酯、乙酸丁酯等酯系溶剂；乙醇、甲醇、正丙醇、2－丙醇(异丙基醇)、丁醇、己醇等醇系溶剂；二异丙醚、丁基溶纤剂、四氢呋喃、二噁烷、丁基卡必醇等醚系溶剂；二乙二醇单甲醚、三乙二醇单甲醚、丙二醇单甲醚等二醇醚系溶剂；乙二醇单甲醚乙酸酯、丙二醇单甲醚乙酸酯、二乙二醇单乙醚乙酸酯等二醇酯系溶剂等，它们可以单独使用，也可以并用2种以上。
从即使在使用非氯系的烯烃树脂、具有酸基或酸酐基的烯烃树脂、具有羟基的烯烃树脂作为烯烃树脂(A)的情况下其溶解性也优异的方面出发，优选使用将脂环族系有机溶剂、酯系有机溶剂和醇系溶剂混合的混合溶剂。特别是，从使用具有酸基或酸酐基的烯烃树脂的情况下其溶解性也优异的方面出发，优选使用将甲基环己烷、乙酸乙酯和异丙醇混合的混合溶剂。
作为有机溶剂的使用量，优选为如下比例，即，相对于烯烃树脂(A)和有机溶剂(D)的合计质量，烯烃树脂(A)比例成为10～30质量％。由此，能够制成涂敷性、对金属膜的浸润性优异的粘接剂。
本发明的粘接剂能够根据需要使用增粘剂、增塑剂、热塑性弹性体、反应性弹性体、磷酸化合物、硅烷偶联剂、粘接促进剂等各种添加剂。这些添加剂的含量在不损害本发明粘接剂的功能的范围内酌情调节即可。
在此，作为可使用的增粘剂，可举出例如：松香系或松香酯系增粘剂、萜烯系或萜烯酚系增粘剂、饱和烃树脂、香豆酮系增粘剂、香豆酮茚系增粘剂、苯乙烯树脂系增粘剂、二甲苯树脂系增粘剂、酚树脂系增粘剂、石油树脂系增粘剂等。它们可以分别单独使用，也可以并用两种以上。
作为增塑剂，可举出：聚异戊二烯、聚丁烯、操作油等，作为热塑性弹性体，可举出苯乙烯·丁二烯共聚物(SBS)、苯乙烯·丁二烯共聚物的氢化物(SEPS)、SBBS、苯乙烯·异戊二烯共聚合的氢化物(SEPS)、苯乙烯嵌段共聚物(TPS)、烯烃系弹性体(TPO)等，作为反应性弹性体，可举出将这些弹性体进行了酸改性的产物。
作为磷酸化合物，可举出例如：次磷酸、亚磷酸、正磷酸、连二磷酸等磷酸类；例如偏磷酸、焦磷酸、三聚磷酸、多磷酸、超磷酸等缩合磷酸类；例如正磷酸单甲酯、正磷酸单乙酯、正磷酸单丙酯、正磷酸单丁酯、正磷酸单－2－乙基己酯、正磷酸单苯酯、亚磷酸单甲酯、亚磷酸单乙酯、亚磷酸单丙酯、亚磷酸单丁酯、亚磷酸单2－乙基己酯、亚磷酸单苯酯、正磷酸二－2－乙基己酯、正磷酸二苯酯、亚磷酸二甲酯、亚磷酸二乙酯、亚磷酸二丙酯、亚磷酸二丁酯、亚磷酸二－2－乙基己酯、亚磷酸二苯酯等单酯化物、二酯化物；由缩合磷酸与醇类形成的单酯化物、二酯化物；对例如上述的磷酸类加成了例如环氧乙烷、环氧丙烷等环氧化合物的产物；对例如脂族族或芳香族的二缩水甘油醚加成了上述的磷酸类所得到的环氧磷酸酯类等。
作为硅烷偶联剂，能够举出例如：γ－氨基丙基三乙氧基硅烷、γ－氨基丙基三甲氧基硅烷、N－β(氨基乙基)－γ－氨基丙基三甲氧基硅烷、N－β(氨基乙基)－γ－氨基丙基三甲基二甲氧基硅烷、N－苯基－γ－氨基丙基三甲氧基硅烷等氨基硅烷；β－(3,4－环氧环己基)乙基三甲氧基硅烷、γ－环氧丙氧基丙基三甲氧基硅烷、γ－环氧丙氧基丙基三乙氧基硅烷等环氧硅烷；乙烯基三(β－甲氧基乙氧基)硅烷、乙烯基三乙氧基硅烷、乙烯基三甲氧基硅烷、γ－甲基丙烯酰氧基丙基三甲氧基硅烷等乙烯基硅烷；六甲基二硅氮烷、γ－巯基丙基三甲氧基硅烷等。
作为粘接促进剂，可举出：2－甲基咪唑、1,2－二甲基咪唑、2－苯基－4－甲基咪唑、2－乙基－4－甲基咪唑、1－苄基－2－甲基咪唑、1－氰乙基－2－乙基－4－甲基咪唑等咪唑系化合物；三乙胺、三亚乙基二胺、N’－甲基－N－(2－二甲基氨基乙基)哌嗪、1,8－二氮杂双环[5.4.0]十一碳烯(DBU)、1,5－二氮杂双环[4.3.0]－壬烯、6－二丁基氨基－1,8－二氮杂双环[5.4.0]十一碳烯等叔胺类、以及将这些叔胺类用酚、辛酸、季盐化四苯基硼酸盐等制成胺盐的化合物；三烯丙基锍六氟锑酸盐、二烯丙基碘鎓六氟锑酸盐等阳离子催化剂；三丁基膦、甲基二苯基膦、三苯基膦、三(4－甲基苯基)膦、三(4－丁基苯基)膦、二苯基膦、苯基膦等有机膦化合物等。它们可以单独使用，也可以并用2种以上。
能够通过将上述各成分混合而制备本发明的粘接剂。此时，可以将各成分同时混合而制成粘接剂，但从粘接剂的稳定性、操作性优异的方面出发，先将除固化剂(B)以外的成分预先混合而制备预混物，在使用粘接剂时再混合固化剂(B)的二液型粘接剂是优选的。
本发明的粘接剂的将烯烃树脂这样的非极性基材与金属基材粘接的粘接性、耐热性优异。
＜层叠体＞
本发明的层叠体包含第1基材、第2基材、以及配置在第1基材与第2基材之间并使第1基材与第2基材贴合的粘接层。粘接层为上述的粘接剂的固化涂膜。除第1基材、第2基材以外，还可以进一步包含其他基材。使第1基材与其他基材、第2基材与其他基材贴合的粘接层可以是本发明的粘接剂的固化涂膜，也可以不是。
作为第1基材、第2基材、其他基材，能够使用例如：纸、由烯烃系树脂、丙烯腈－丁二烯－苯乙烯共聚物(ABS树脂)、聚氯乙烯系树脂、氟系树脂、聚(甲基)丙烯酸系树脂、碳酸酯系树脂、聚酰胺系树脂、聚酰亚胺系树脂、聚亚苯基醚系树脂、聚亚苯基硫醚系树脂、聚酯系树脂得到的合成树脂膜、铜箔、铝箔之类的各种金属箔等。
本发明的粘接剂的将烯烃树脂这样的非极性基材与金属基材粘接的粘接性优异，因此优选第1基材和第2基材中的一者为非极性的基材，另一者为金属基材，但不限定于此。
本发明的层叠体可通过对第1基材和第2基材的一者涂布本发明的粘接剂，接着层叠另一者，使粘接剂固化而得到。优选在涂布粘接剂后至将第1基材与第2基材层叠为止的期间设置干燥工序。
作为粘接剂的涂敷方式，能够使用凹版涂布机方式、微凹版涂布机方式、反向涂布机方式、棒涂机方式、辊涂机方式、模头涂布机方式等。粘接剂的涂布量优选调节为使干燥后的涂布重量成为0.5～20.0g/m2。当低于0.5g/m2时，连续均一涂布性容易降低，当高于20.0g/m2时，涂布后的溶剂脱离性也降低，容易产生操作性降低、残留溶剂的问题。
优选第1基材与第2基材层叠时的层压辊的温度为25～120℃、压力为3～300kg/cm2。
优选在将第1基材与第2基材贴合后设置老化工序。老化条件优选为25～100℃、12～240小时。
＜电池用包装材料＞
作为一个例子，本发明的电池用包装材料包含第1基材、第2基材、第3基材、使第1基材与第2基材贴合的第1粘接层、以及使第2基材与第3基材贴合的第2粘接层。第1基材为聚烯烃膜，第2基材为金属箔。第3基材为尼龙、聚酯等的树脂膜。第1粘接层是本发明的粘接剂的固化涂膜。第2粘接层可以是本发明的粘接剂的固化涂膜，也可以不是。在第3基材的与设置第2粘接层相反一侧，可以进一步经由或不经由粘接层地配置其他基材，也可以设置涂层。也可以不设置其他基材、涂层。
作为聚烯烃膜，可以从以往公知的烯烃树脂中酌情选择。例如，没有特别限定，能够使用聚乙烯、聚丙烯、乙烯丙烯共聚物等。优选为未拉伸膜。聚烯烃膜的膜厚没有特别限定，优选为10μm以上，更优选为20μm以上，进一步优选为25μm以上。此外，优选为100μm以下，更优选为95μm以下，进一步优选为90μm以下。
第1基材在制造后述的电池时作为使本发明的电池用包装材料彼此热封贴合时的密封层发挥功能。
作为金属箔，可举出铝、铜、镍等。这些金属箔可以实施有喷砂处理、研磨处理、脱脂处理、蚀刻处理、基于防锈剂浸渍或喷雾的表面处理、3价铬化学转化处理、磷酸盐化学转化处理、硫化物化学转化处理、阳极氧化覆膜形成、氟树脂涂敷等表面处理。在它们中，从密合性保持性能(耐环境劣化性)、防腐蚀性优异的方面出发，优选实施有3价铬化学转化处理。此外，从防止腐蚀的方面出发，该金属膜的厚度优选为10～100μm的范围。
作为能够用作第3基材的树脂膜，可举出：聚酯树脂、聚酰胺树脂、环氧树脂、丙烯酸类树脂、氟树脂、聚氨酯树脂、硅树脂、酚醛树脂、以及它们的混合物、共聚物等的树脂膜。在它们中，优选地举出聚酯树脂、聚酰胺树脂，更优选地举出双轴拉伸聚酯树脂、双轴拉伸聚酰胺树脂。作为聚酯树脂，具体而言，可举出：聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚萘二甲酸乙二醇酯、聚萘二甲酸丁二醇酯、共聚聚酯、聚碳酸酯等。此外，作为聚酰胺树脂，具体而言，可举出：尼龙6、尼龙6,6、尼龙6与尼龙6,6的共聚物、尼龙6,10、聚己二酰间苯二甲胺(MXD6)等。
涂层能够利用例如聚偏氯乙烯、聚酯树脂、氨基甲酸酯树脂、丙烯酸类树脂、环氧树脂等形成。优选利用二液固化型树脂形成。作为形成涂层的二液固化型树脂，可举出例如二液固化型氨基甲酸酯树脂、二液固化型聚酯树脂、二液固化型环氧树脂等。此外，在涂层中可以配合消光剂。
作为消光剂，可举出例如粒径0.5nm～5μm左右的微粒。针对消光剂的材质没有特别限制，可举出例如金属、金属氧化物、无机物、有机物等。此外，针对消光剂的形状也没有特别限制，可举出例如球状、纤维状、板状、无定型、气球状等。作为消光剂，具体而言，可举出：滑石、二氧化硅、石墨、高岭土、Montmorillonoid(日文：モンモリロイド)、蒙脱石(日文：モンモリロナイト)、合成云母、水滑石、硅胶、沸石、氢氧化铝、氢氧化镁、氧化锌、氧化镁、氧化铝、氧化钕、氧化锑、氧化钛、氧化铈、硫酸钙、硫酸钡、碳酸钙、硅酸钙、碳酸锂、苯甲酸钙、草酸钙、硬脂酸镁、炭黑、碳纳米管类、高熔点尼龙、交联丙烯酸类、交联苯乙烯、交联聚乙烯、苯并胍胺、金、铝、铜、镍等。这些消光剂可以1种单独使用，也可以组合使用2种以上。在这些消光剂中，从分散稳定性、成本等的观点出发，优选地举出二氧化硅、硫酸钡、氧化钛。此外，对于消光剂，可以在表面实施有绝缘处理、高分散性处理等各种表面处理。
将这样的层叠体以制成电池时作为第1基材的聚烯烃膜处于比第3基材更靠的内侧的方式进行成型，成为本发明的二次电池外包装材料。作为成型方法，没有特别限制，可举出以下这样的方法作为例子。
·加热压空成型法：使电池用包装材料被具有供给高温、高压气体的孔的下模具与具有袋状凹部的上模具夹持，一边使其加热软化一边供给气体而形成凹部的方法。
·预加热平板式压空成型法：使电池用包装材料加热软化后，被具有供给高压气体的孔的下模具与具有袋状凹部的上模具夹持，供给气体而形成凹部的方法。
·筒式真空成型法：将电池用包装材料用加热筒部分性地加热软化后，将具有袋状凹部的筒的该凹部抽真空，从而成型凹部的方法。
·顶针(日文：ピン)成型法：将底材片加热软化后用袋状的凹凸模具进行压接的方法。
·预加热柱塞辅助压空成型法：使电池用包装材料加热软化后，被具有供给高压气体的孔的下模具与具有袋状凹部的上模具夹持，供给气体而形成凹部的方法，且在成型时使凸形的柱塞上升和下降来辅助成型。
从成型后的底材的壁厚均匀的方面出发，优选作为加热真空成型法的预加热柱塞辅助压空成型法。
像这样得到的本发明的电池用包装材料能够适宜地用作密封并收纳正极、负极、电解质等电池元件的电池用容器。
＜电池＞
本发明的电池可通过如下方式得到：对具备正极、负极和电解质的电池元件，在使上述正极和负极各自所连接的金属端子突出到外侧的状态下，以电池元件的周缘能够形成凸缘部(密封层彼此接触的区域)的方式用本发明的电池用包装材料覆盖，将上述法兰部的密封层彼此热封而使其密封。
作为使用本发明的电池用包装材料所得到的电池，可以为一次电池、二次电池中的任一种，优选为二次电池。作为二次电池，没有特别限制，可举出例如：锂离子电池、锂离子聚合物电池、铅蓄电池、镍·氢蓄电池、镍·镉蓄电池、镍·铁蓄电池、镍·锌蓄电池、氧化银·锌蓄电池、金属空气电池、多价阳离子电池、电容器(日文：コンデンサー)、电容器(日文：キャパシター)等。这些二次电池中，作为本发明的电池用包装材料的适宜的应用对象，可举出锂离子电池和锂离子聚合物电池。
实施例
以下，通过实施例和比较例来说明本发明，但本发明不限定于此。配合组成其他的数值只要没有明确记载，则为质量基准。
(实施例1)
使100份作为烯烃树脂(A)的TOYO－TAC PMA－L、0.05份三苯基膦、1.0份FTR－8120、0.1份作为酸酐(C)的EPICLON B－570－H溶解于混合溶剂(甲基环己烷/乙酸乙酯/异丙醇＝71/8/1)，使不挥发成分为20％。接着加入2.0份作为含环氧化合物的固化剂(B)的Denacol EX－321，充分搅拌而制备实施例1的粘接剂。
将制备的粘接剂用棒涂机以2g/m2(干燥)的涂布量涂布于铝箔(ToyoAluminiumK.K.制铝箔“1N30H”：膜厚30μm)的光泽面，80℃干燥1分钟后，与未拉伸聚烯烃膜(Okamoto株式会社制“ET－20”，膜厚：40μm)以100℃进行贴合。接着，对铝箔的消光面用棒凃机以4g/m2(干燥)的涂布量涂布以“DICDRY LX－906”(DIC株式会社制)为主剂、以“KW－75”(DIC株式会社制)为固化剂、按照重量比成为主剂/固化剂＝100/10的方式配合而成的粘接剂，之后层叠厚度25μm的拉伸聚酰胺膜。其后，80℃进行2天的保养(老化)，得到层压物。
(实施例2～10)
将铝箔和未拉伸聚烯烃膜的贴合中使用的粘接剂的配合变更为表1、2中记载的配合，除此以外，与实施例1同样地制备粘接剂，得到层压物。
(比较例1～5)
将铝箔和未拉伸聚烯烃膜的贴合中使用的粘接剂的配合变更为表3中记载的配合，除此以外，与实施例1同样地制备粘接剂，得到层压物。
需要说明的是，实施例、比较例中使用的化合物的细节如下所述。
TOYO－TAC PMA－L：马来酸酐改性烯烃树脂，酸值：35mgKOH/g，熔点：70℃，东洋纺公司制
TOYO－TAC PMA－KE：马来酸酐改性烯烃树脂，酸值：44mgKOH/g，熔点：80℃，东洋纺公司制
FTR8120：苯乙烯树脂，三井化学公司制
EPICRON B－570－H：甲基四氢邻苯二甲酸酐，DIC公司制
YH－306：三烷基四氢邻苯二甲酸酐，三菱化学公司制
Denacol EX－321：三羟甲基丙烷聚缩水甘油醚型环氧树脂，NagaseChemteX公司制
EPICLON 860：双酚A型环氧树脂，DIC公司制
EPICLON N－665：甲酚酚醛型环氧树脂，DIC公司制
需要说明的是，烯烃树脂的酸值为使用FT－IR(日本分光公司制，FT－IR4200)，用根据基于马来酸酐的氯仿溶液制作的校正曲线所得到的系数(f)、马来酸酐改性聚烯烃溶液中的马来酸酐的酸酐环的伸缩峰(1780cm－1)的吸光度(I)和马来酸的羰基的伸缩峰(1720cm－1)的吸光度(II)根据下式算出的值。下式中，马来酸酐的分子量设为98.06，氢氧化钾的分子量设为56.11。
[数学式1]
(初始粘接强度的测定)
使用株式会社岛津制作所的“Autogragh AGS－J”，以剥离速度50mm/min、剥离宽度15mm、剥离形态T型的条件评价所述层压物的铝箔与未拉伸聚烯烃膜的界面的粘接强度。
(耐热性)
即使要测定热封后的层压物的粘接强度，也会有聚烯烃膜破损，不在聚烯烃膜与铝箔之间、而在经热封的聚烯烃膜彼此之间剥离的情况。基于热封前后的粘接强度的比较来评价耐热性不一定正确。因此，针对耐热性，像以下那样评价。
将上述层压物的未拉伸聚烯烃膜侧向内折，以190℃3秒的条件用热封棒将未拉伸聚烯烃膜彼此接触触碰。接着，使用株式会社岛津制作所的“Autogragh AGS－J”，评价以剥离速度500mm/min、剥离宽度15mm、剥离形态T型的条件剥离1cm时的界面。
◎：未拉伸聚烯烃膜/未拉伸聚烯烃膜间的剥离为90％以上(实用上特别优异)
○：未拉伸聚烯烃膜/未拉伸聚烯烃膜间的剥离为60％以上且小于90％(实用上优异)
△：未拉伸聚烯烃膜/未拉伸聚烯烃膜间的剥离为50％以上且小于60％(实用区域)
×：未拉伸聚烯烃膜/未拉伸聚烯烃膜间的剥离小于50％
[表1]
[表2]
[表3]
由表1～表3可以看出，与比较例的粘接剂相比，本发明的粘接剂的耐热性优异。
产业上的可利用性
本发明的粘接剂将烯烃树脂这样的非极性基材与金属基材粘接的粘接性、耐热性优异，使用本发明的粘接剂所得到的层叠体能够适宜地用于例如电池用包装材料。此外，作为本发明的粘接剂的用途，不限于电池用包装材料、用于其的层叠体，能够广泛地应用于家电外板、家具用原材料、建筑内装用材料等需要非极性的基材与金属基材的粘接性的领域。
Claims (9)
1.一种粘接剂，其包含烯烃树脂(A)、含环氧化合物的固化剂(B)和酸酐(C)，
所述烯烃树脂(A)选自具有酸基或酸酐基的结晶性烯烃树脂、具有羟基的结晶性烯烃树脂，
相对于所述烯烃树脂(A)100质量份，所述酸酐(C)的配合量为0.05质量份以上且10质量份以下，
相对于所述烯烃树脂(A)100质量份，所述固化剂(B)的配合量为0.01质量份以上且1.0质量份以下。
2.根据权利要求1所述的粘接剂，其中，所述酸酐(C)包含选自酸酐和酸酐的二醇改性物中的至少1种，所述酸酐为选自邻苯二甲酸酐、偏苯三酸酐、均苯四酸酐、二苯甲酮四羧酸酐、十二碳烯琥珀酸酐、聚己二酸酐、聚壬二酸酐、聚癸二酸酐、聚(乙基十八烷二酸)酐、聚(苯基十六烷二酸)酐、四氢邻苯二甲酸酐、甲基四氢邻苯二甲酸酐、甲基六氢邻苯二甲酸酐、六氢邻苯二甲酸酐、甲基降冰片烯二酸酐、三烷基四氢邻苯二甲酸酐、甲基环己烯二羧酸酐、甲基环己烯四羧酸酐、乙二醇双偏苯三酸酯二酐、氯桥酸酐、纳迪克酸酐、甲基纳迪克酸酐、5－(2,5－二氧代四氢－3－呋喃基)－3－甲基－3－环己烷－1,2－二羧酸酐、3,4－二羧基－1,2,3,4－四氢－1－萘琥珀酸二酐、1－甲基－二羧基－1,2,3,4－四氢－1－萘琥珀酸二酐中的至少1种。
3.根据权利要求1所述的粘接剂，其特征在于，所述烯烃树脂(A)具有酸基或羟基。
4.根据权利要求1～3中任一项所述的粘接剂，其特征在于，包含选自咪唑系化合物、叔胺类、叔胺类的盐、阳离子催化剂、有机膦化合物中的至少1种粘接促进剂。
5.一种预混物，其为包含烯烃树脂(A)、含环氧化合物的固化剂(B)和酸酐(C)的粘接剂用预混物，所述预混物包含所述烯烃树脂(A)和所述酸酐(C)，所述烯烃树脂(A)选自具有酸基或酸酐基的结晶性烯烃树脂、具有羟基的结晶性烯烃树脂，相对于所述烯烃树脂(A)100质量份，所述酸酐(C)的含量为0.05质量份以上且10质量份以下。
6.一种层叠体，其特征在于，包含第1基材、第2基材、以及使所述第1基材与所述第2基材贴合的粘接层，所述粘接层为权利要求1～4中任一项所述的粘接剂的固化涂膜。
7.一种电池用包装材料，其特征在于，包含：
聚烯烃膜、
树脂膜、
配置在所述聚烯烃膜与所述树脂膜之间的金属箔、以及
配置在所述聚烯烃膜与所述金属箔之间的粘接层，
所述粘接层为权利要求1～4中任一项所述的粘接剂的固化涂膜。
8.一种电池用容器，其是将权利要求7所述的电池用包装材料成型而成的。
9.一种电池，其使用了权利要求8所述的电池用容器。
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