TW201425514A - Polyurethane adhesive of packing material for battery, packing material for battery, container for battery and battery - Google Patents
Polyurethane adhesive of packing material for battery, packing material for battery, container for battery and battery Download PDFInfo
- Publication number
- TW201425514A TW201425514A TW102139675A TW102139675A TW201425514A TW 201425514 A TW201425514 A TW 201425514A TW 102139675 A TW102139675 A TW 102139675A TW 102139675 A TW102139675 A TW 102139675A TW 201425514 A TW201425514 A TW 201425514A
- Authority
- TW
- Taiwan
- Prior art keywords
- battery
- layer
- packaging material
- polyol
- adhesive
- Prior art date
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- 239000000853 adhesive Substances 0.000 title claims abstract description 51
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 50
- 239000004814 polyurethane Substances 0.000 title claims abstract description 37
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 37
- 239000000463 material Substances 0.000 title abstract description 19
- 238000012856 packing Methods 0.000 title abstract 4
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 75
- 229920005862 polyol Polymers 0.000 claims abstract description 52
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 48
- 150000003077 polyols Chemical class 0.000 claims abstract description 45
- 230000009477 glass transition Effects 0.000 claims abstract description 27
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 25
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 22
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 20
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 20
- 239000010410 layer Substances 0.000 claims description 123
- 239000005022 packaging material Substances 0.000 claims description 55
- 239000011888 foil Substances 0.000 claims description 38
- 229910052751 metal Inorganic materials 0.000 claims description 35
- 239000002184 metal Substances 0.000 claims description 35
- 239000012790 adhesive layer Substances 0.000 claims description 29
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 24
- 229920005989 resin Polymers 0.000 claims description 24
- 239000011347 resin Substances 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 22
- 239000002344 surface layer Substances 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000007822 coupling agent Substances 0.000 claims description 12
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 11
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 claims description 11
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 6
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 claims description 3
- 229930185605 Bisphenol Natural products 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 3
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 claims description 3
- 229920000098 polyolefin Polymers 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 239000004588 polyurethane sealant Substances 0.000 claims 4
- 125000003118 aryl group Chemical group 0.000 claims 1
- 238000004806 packaging method and process Methods 0.000 claims 1
- 229920006267 polyester film Polymers 0.000 claims 1
- 238000012360 testing method Methods 0.000 abstract description 16
- 239000000203 mixture Substances 0.000 abstract description 12
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 abstract description 6
- 239000006087 Silane Coupling Agent Substances 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 39
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- -1 m-xylylene Chemical group 0.000 description 24
- 239000000243 solution Substances 0.000 description 20
- 239000004848 polyfunctional curative Substances 0.000 description 18
- 239000002253 acid Substances 0.000 description 17
- 239000003822 epoxy resin Substances 0.000 description 17
- 229920000647 polyepoxide Polymers 0.000 description 17
- 238000000465 moulding Methods 0.000 description 12
- 229910052782 aluminium Inorganic materials 0.000 description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 11
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000005886 esterification reaction Methods 0.000 description 9
- 239000012948 isocyanate Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- 229920000728 polyester Polymers 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 7
- 230000001476 alcoholic effect Effects 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 239000004721 Polyphenylene oxide Substances 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 230000007774 longterm Effects 0.000 description 6
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 6
- 229920003986 novolac Polymers 0.000 description 6
- 229920000570 polyether Polymers 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- QUVMSYUGOKEMPX-UHFFFAOYSA-N 2-methylpropan-1-olate;titanium(4+) Chemical compound [Ti+4].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] QUVMSYUGOKEMPX-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 239000008151 electrolyte solution Substances 0.000 description 5
- 150000002513 isocyanates Chemical class 0.000 description 5
- 238000003475 lamination Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000005809 transesterification reaction Methods 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- 239000012496 blank sample Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 description 4
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 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 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 4
- 150000007519 polyprotic acids Polymers 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 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 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 3
- 238000005304 joining Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920000768 polyamine Polymers 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- 239000013638 trimer Substances 0.000 description 3
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 2
- MFAWEYJGIGIYFH-UHFFFAOYSA-N 2-[4-(trimethoxymethyl)dodecoxymethyl]oxirane Chemical compound C(C1CO1)OCCCC(C(OC)(OC)OC)CCCCCCCC MFAWEYJGIGIYFH-UHFFFAOYSA-N 0.000 description 2
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- RJGDLRCDCYRQOQ-UHFFFAOYSA-N anthrone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3CC2=C1 RJGDLRCDCYRQOQ-UHFFFAOYSA-N 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 150000004032 porphyrins Chemical class 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- 239000003981 vehicle Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 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 description 1
- ZBBLRPRYYSJUCZ-GRHBHMESSA-L (z)-but-2-enedioate;dibutyltin(2+) Chemical compound [O-]C(=O)\C=C/C([O-])=O.CCCC[Sn+2]CCCC ZBBLRPRYYSJUCZ-GRHBHMESSA-L 0.000 description 1
- ZGDSDWSIFQBAJS-UHFFFAOYSA-N 1,2-diisocyanatopropane Chemical compound O=C=NC(C)CN=C=O ZGDSDWSIFQBAJS-UHFFFAOYSA-N 0.000 description 1
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 1
- AZYRZNIYJDKRHO-UHFFFAOYSA-N 1,3-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC(C(C)(C)N=C=O)=C1 AZYRZNIYJDKRHO-UHFFFAOYSA-N 0.000 description 1
- IKYNWXNXXHWHLL-UHFFFAOYSA-N 1,3-diisocyanatopropane Chemical compound O=C=NCCCN=C=O IKYNWXNXXHWHLL-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- ATOUXIOKEJWULN-UHFFFAOYSA-N 1,6-diisocyanato-2,2,4-trimethylhexane Chemical compound O=C=NCCC(C)CC(C)(C)CN=C=O ATOUXIOKEJWULN-UHFFFAOYSA-N 0.000 description 1
- QGLRLXLDMZCFBP-UHFFFAOYSA-N 1,6-diisocyanato-2,4,4-trimethylhexane Chemical compound O=C=NCC(C)CC(C)(C)CCN=C=O QGLRLXLDMZCFBP-UHFFFAOYSA-N 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- YVXVGRFYPIUADZ-UHFFFAOYSA-N 1-isocyanato-1,3,3,5-tetramethylcyclohexane Chemical compound CC1CC(C)(C)CC(C)(N=C=O)C1 YVXVGRFYPIUADZ-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical group C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 description 1
- KQSMCAVKSJWMSI-UHFFFAOYSA-N 2,4-dimethyl-1-n,1-n,3-n,3-n-tetrakis(oxiran-2-ylmethyl)benzene-1,3-diamine Chemical compound CC1=C(N(CC2OC2)CC2OC2)C(C)=CC=C1N(CC1OC1)CC1CO1 KQSMCAVKSJWMSI-UHFFFAOYSA-N 0.000 description 1
- DXPIUHXKXUKZDK-UHFFFAOYSA-N 2,5-dimethyl-4,5-dihydro-1,3-oxazole Chemical compound CC1CN=C(C)O1 DXPIUHXKXUKZDK-UHFFFAOYSA-N 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- HMOZDINWBHMBSQ-UHFFFAOYSA-N 2-[3-(4,5-dihydro-1,3-oxazol-2-yl)phenyl]-4,5-dihydro-1,3-oxazole Chemical compound O1CCN=C1C1=CC=CC(C=2OCCN=2)=C1 HMOZDINWBHMBSQ-UHFFFAOYSA-N 0.000 description 1
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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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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- 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
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/117—Inorganic material
- H01M50/119—Metals
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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
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
- H01M50/126—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers
- H01M50/129—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers with two or more layers of only organic material
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/31—Heat sealable
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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
- B32B2553/00—Packaging equipment or accessories not otherwise provided for
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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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Sealing Battery Cases Or Jackets (AREA)
- Laminated Bodies (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
本發明是有關於一種用以形成電池用容器或電池用包裝的電池用包裝材用聚胺甲酸酯接著劑。另外,本發明是有關於一種使用上述電池用包裝材用聚胺甲酸酯接著劑而積層的電池用包裝材。而且,本發明是有關於一種將上述電池用包裝材成型而成的電池用容器、及具有上述電池用容器的電池。 The present invention relates to a polyurethane adhesive for a battery packaging material for forming a battery container or a battery package. Further, the present invention relates to a battery packaging material which is laminated using a polyurethane sealing material for a battery packaging material. Moreover, the present invention relates to a battery container in which the battery packaging material is molded, and a battery including the battery container.
由於行動電話、可攜式電腦等電子設備的急速的發展,而輕量且小型的鋰離子電池等二次電池的需求增大。作為二次電池的外裝體,先前使用金屬製罐,但就輕量化或生產性的觀點而言,積層塑膠膜或金屬箔等的包裝材逐漸成為主流。作為最簡易的包裝材,可列舉:如圖1所示的自外層側起依序積層外層側樹脂膜層(11)、外層側接著劑層(12)、金屬箔層(13)、內層側接著劑層(14)及包含熱密封層等的內面層(15)的積層體。作為電池用容器,例如如圖2所示般,有以外層側樹脂膜層(11)構 成凸面、內面層(15)構成凹面的方式將包裝材成型(拉深成型加工、突出成型加工等)者。藉由在電池用容器的凹面側封入電極或電解液等而將包裝材密封,而製造電池。 Due to the rapid development of electronic devices such as mobile phones and portable computers, the demand for secondary batteries such as lightweight and small-sized lithium ion batteries has increased. As the exterior body of the secondary battery, a metal can is used in the past, but from the viewpoint of weight reduction or productivity, a packaging material such as a laminated plastic film or a metal foil has gradually become mainstream. As the most simple packaging material, as shown in FIG. 1, the outer layer side resin film layer (11), the outer layer side adhesive layer (12), the metal foil layer (13), and the inner layer are sequentially laminated from the outer layer side. A laminate of a side adhesive layer (14) and an inner surface layer (15) including a heat seal layer or the like. As a battery container, for example, as shown in FIG. 2, there is an outer layer side resin film layer (11). The convex material and the inner surface layer (15) form a concave surface to form a packaging material (draw molding processing, protrusion molding processing, etc.). The battery is sealed by sealing an electrode or an electrolytic solution or the like on the concave side of the battery container to produce a battery.
作為電池用包裝材,揭示:在外層側積層耐熱性樹脂延伸膜層、在內層側積層熱塑性樹脂未延伸膜層、在所述兩膜之間積層鋁箔層而成的電池用容器用包裝材中,藉由在熱塑性樹脂未延伸膜層與鋁箔層之間使用特定接著劑層進行接著,而可提供成型性優異的電池盒用包裝材(專利文獻1)。 As a packaging material for a battery, a packaging material for a battery container in which an outer layer side heat-resistant resin stretched film layer, an inner layer side laminated thermoplastic resin unstretched film layer, and an aluminum foil layer are laminated between the two films is disclosed. By using a specific adhesive layer between the thermoplastic resin unstretched film layer and the aluminum foil layer, it is possible to provide a packaging material for a battery case having excellent moldability (Patent Document 1).
另外,作為電池用包裝材,揭示:至少依序積層基材層與鋁箔層以及熱接著性樹脂層的電池用外裝體,且具有特定範圍的環剛度(loop stiffness),使用厚度為80μm以上的經退火處理的鋁作為鋁箔層,而獲得成型性優異的外裝材,藉由上述外裝材而可提供確保了安全性能的鋰離子電池(專利文獻2)。 In addition, as a packaging material for a battery, a battery outer casing in which at least a base material layer, an aluminum foil layer, and a thermal adhesive resin layer are laminated in this order is provided, and a loop stiffness of a specific range is used, and a thickness of 80 μm or more is used. The annealed aluminum is used as an aluminum foil layer to obtain an exterior material having excellent moldability, and a lithium ion battery which ensures safety performance can be provided by the above-mentioned exterior material (Patent Document 2).
另外,作為用以包裝洗髮精等非食品的積層體形成用接著劑,揭示:含有包含玻璃轉移溫度為40℃以上的有機多元醇5重量%~50重量%及玻璃轉移溫度小於40℃的有機多元醇(其中,在其分子中不具有羧基)95重量%~50重量%的混合物的接著劑(專利文獻3)。 In addition, as an adhesive for forming a laminate for non-food products such as shampoo, it is disclosed that the organic polyol having a glass transition temperature of 40 ° C or higher is contained in an amount of 5 to 50% by weight and the glass transition temperature is less than 40 ° C. An adhesive of a mixture of 95% by weight to 50% by weight of an organic polyol (which does not have a carboxyl group in its molecule) (Patent Document 3).
[先前技術文獻] [Previous Technical Literature]
[專利文獻] [Patent Literature]
[專利文獻1]日本專利特開2010-92703號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2010-92703
[專利文獻2]日本專利特開2008-251342號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2008-251342
[專利文獻3]日本專利特開2001-322221號公報 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2001-322221
近年來,隨著車載或家庭蓄電等用途擴大,而要求二次電池的大容量化,並且對電池用包裝材要求成型性的良好性。另外,車載或家庭蓄電用途的二次電池設置於室外,而要求長期的耐用年數,並且要求包裝材的各塑膠膜或金屬箔等的層間的接著強度在長期耐久試驗後亦高、而且外觀亦無異常。 In recent years, with the expansion of applications such as in-vehicle or household power storage, it is required to increase the capacity of secondary batteries, and it is required to have good moldability for battery packaging materials. In addition, the secondary battery for in-vehicle or household power storage is installed outdoors, and the long-term durability is required, and the adhesion strength between the layers of each plastic film or metal foil of the packaging material is required to be high after the long-term durability test, and the appearance is also high. There is no abnormality.
本發明鑒於上述背景而成,課題是提供一種具有優異的成型性、在長期耐久性試驗後層間的接著強度亦高、外觀性優異的電池,電池用容器,電池用包裝材及電池用包裝材用聚胺甲酸酯接著劑。 The present invention has been made in view of the above circumstances, and it is an object of the invention to provide a battery having excellent moldability, high adhesion strength between layers after long-term durability test, and excellent appearance, battery container, battery packaging material, and battery packaging material. Use a polyurethane binder.
本發明鑒於上述課題而成,是有關於一種接著劑,其使用以特定比例包含玻璃轉移溫度不同的聚酯多元醇(A1)、聚酯多元醇(A2)的多元醇成分(A),作為用以形成聚胺甲酸酯的羥基成分,並含有相對於上述多元醇成分(A)的反應性官能基,而相當過量的異氰酸酯成分作為硬化劑。 In view of the above problems, the present invention relates to an adhesive comprising a polyol component (A) comprising a polyester polyol (A1) having a different glass transition temperature and a polyester polyol (A2) in a specific ratio. The hydroxyl component of the polyurethane is formed to contain a reactive functional group relative to the above polyol component (A), and a relatively large amount of the isocyanate component is used as a curing agent.
即,本發明是有關於一種電池用包裝材用聚胺甲酸酯接著劑,其含有主劑與聚異氰酸酯硬化劑,且其特徵在於:上述主劑含有多元醇成分(A)與矽烷偶合劑(B),上述多元醇成分(A)包含玻璃轉移溫度為40℃以上的聚酯多元醇(A1)5重量%~50重量%及玻璃轉移溫度小於40℃的聚酯多元醇(A2)95重量%~ 50重量%,上述聚異氰酸酯硬化劑中所含的異氰酸基相對於源自上述多元醇成分(A)的羥基與羧基的合計的當量比[NCO]/([OH]+[COOH])為10~30。 That is, the present invention relates to a polyurethane adhesive for a battery packaging material comprising a main component and a polyisocyanate curing agent, characterized in that the main component contains a polyol component (A) and a decane coupling agent. (B) The polyol component (A) comprises a polyester polyol (A2) 95 having a glass transition temperature of 40 ° C or more and a polyester polyol (A1) of 5 to 50% by weight and a glass transition temperature of less than 40 ° C. Weight%~ 50% by weight, the equivalent ratio of the isocyanato group contained in the above polyisocyanate curing agent to the total of the hydroxyl group and the carboxyl group derived from the above polyol component (A) [NCO] / ([OH] + [COOH]) It is 10~30.
本發明的電池用包裝材用聚胺甲酸酯接著劑較佳為進一步含有可與羧基反應的化合物(C)。 The polyurethane adhesive for a battery packaging material of the present invention preferably further contains a compound (C) which can react with a carboxyl group.
另外,本發明是有關於一種電池用包裝材,其依序積層外層側樹脂膜層(11)、外層側接著劑層(12)、金屬箔層(13)、內層側接著劑層(14)及內面層(15)而成,上述外層側接著劑層(12)由上述電池用包裝材用聚胺甲酸酯接著劑形成。 Further, the present invention relates to a battery packaging material which sequentially laminates an outer layer side resin film layer (11), an outer layer side adhesive layer (12), a metal foil layer (13), and an inner layer side adhesive layer (14). And the inner layer (15), wherein the outer layer side adhesive layer (12) is formed of the polyurethane packaging material for the battery packaging material.
而且,本發明是有關於一種電池用容器,其由上述電池用包裝材成型而成,且外層側樹脂膜層(11)構成凸面,內面層(15)構成凹面。 Further, the present invention relates to a battery container which is formed by molding the battery packaging material, and the outer layer side resin film layer (11) constitutes a convex surface, and the inner surface layer (15) constitutes a concave surface.
而且,本發明是有關於一種電池,其使用上述電池用容器而成。 Moreover, the present invention relates to a battery which is formed using the above container for a battery.
[發明的效果] [Effects of the Invention]
根據本發明,具有可提供具有優異的成型性、長期耐久性試驗後層間的接著強度亦高、外觀性優異的電池、電池用容器、電池用包裝材及電池用包裝材用聚胺甲酸酯接著劑的優異的效果。在依序積層外層側樹脂膜層(11)、外層側接著劑層(12)、金屬箔層(13)、內層側接著劑層(14)、內面層(15)而成的電池用包裝材中,為了形成外層側接著劑層,藉由使用本發明的聚胺甲酸酯接著劑,而可提供層間的接著強度優異、成型時膜無斷 裂、成型部不產生隆起、且耐久性試驗後上述性能亦優異的電池用包裝材。藉由使用上述電池用包裝材而成的電池用容器,而可提供可靠性優異的電池。 According to the present invention, it is possible to provide a battery, a battery container, a battery packaging material, and a polyurethane packaging material for a battery having excellent moldability and long-term durability test and having high adhesion strength and excellent appearance. The excellent effect of the subsequent agent. A battery for sequentially laminating an outer layer side resin film layer (11), an outer layer side adhesive layer (12), a metal foil layer (13), an inner layer side adhesive layer (14), and an inner surface layer (15) In the packaging material, in order to form the outer layer side adhesive layer, by using the polyurethane adhesive of the present invention, it is possible to provide excellent adhesion between layers and to form a film without breaking during molding. A battery packaging material which is excellent in the above-described performance after the crack test and the molded portion are not raised and has a durability test. By using the battery container made of the battery packaging material described above, it is possible to provide a battery excellent in reliability.
(11)‧‧‧外層側樹脂膜層 (11) ‧‧‧ outer layer resin film
(12)‧‧‧外層側接著劑層 (12) ‧‧‧Outer side adhesive layer
(13)‧‧‧金屬箔層 (13)‧‧‧metal foil layer
(14)‧‧‧內層側接著劑層 (14) ‧‧‧Inner layer of adhesive layer
(15)‧‧‧內面層 (15) ‧ ‧ inner layer
圖1是表示本發明的電池用包裝材的一個形態的示意性剖面圖。 Fig. 1 is a schematic cross-sectional view showing one embodiment of a battery packaging material of the present invention.
圖2是表示本發明的電池用容器的一個形態的示意性立體圖。 Fig. 2 is a schematic perspective view showing one embodiment of the battery container of the present invention.
以下,對本發明的實施形態進行詳細地說明。另外,本說明書中,「任意的數A~任意的數B」的記載是指數A及大於數A的範圍,且數B及小於數B的範圍。 Hereinafter, embodiments of the present invention will be described in detail. In the present specification, the description of "arbitrary number A to arbitrary number B" is a range of the index A and the number A, and the number B and the range of less than the number B.
本發明的聚胺甲酸酯接著劑用於形成用以獲得電池用容器的電池用包裝材。圖1表示本發明的電池用包裝材的一個形態的示意性剖面圖,圖2表示本發明的電池用容器的一個形態的示意性立體圖。電池用容器的形狀並無特別限定,除了如圖2所示的托盤狀者外,可例示:筒狀(圓筒、方筒、橢圓筒等)者。該些電池用容器是將扁平狀態的電池用包裝材進行成型加工而得。電池用容器的內側、即與電解液接觸的面為內面層(15)。作為內面層(15)的較佳的例子,可列舉熱密封層。藉由使用熱密封層,而使凸緣部的內面層(15)、與另外的構成電池用包裝材的內面層(15)或另外的電池用容器的凸緣部的內面層(15)對向、接觸, 並進行加熱,藉此可使內面層(15)彼此融接,而封入電解液。 The polyurethane adhesive of the present invention is used to form a battery packaging material for obtaining a battery container. Fig. 1 is a schematic cross-sectional view showing one embodiment of a battery packaging material according to the present invention, and Fig. 2 is a schematic perspective view showing one embodiment of the battery container of the present invention. The shape of the battery container is not particularly limited, and may be, for example, a cylindrical shape (cylinder, square tube, elliptical tube, etc.) other than the tray shape as shown in FIG. 2 . These battery containers are obtained by molding a battery packaging material in a flat state. The inner side of the battery container, that is, the surface in contact with the electrolytic solution is the inner surface layer (15). As a preferable example of the inner surface layer (15), a heat seal layer is mentioned. By using the heat seal layer, the inner surface layer (15) of the flange portion and the inner surface layer (15) constituting the battery packaging material or the inner surface layer of the flange portion of the other battery container ( 15) Opposite, contact, Heating is performed whereby the inner surface layers (15) are fused to each other to enclose the electrolyte.
電池用容器具備金屬箔(13)。在電池用容器中,通常 以金屬箔(13)為界,將靠近電解液之側稱為「內側」、將內側的層稱為「內層」、將遠離電解液之側稱為「外側」、將外側的層稱為「外層」。因此,在形成電池用容器的預定的電池用包裝材中,亦以金屬箔(13)為界,將位於靠近電解液處的預定之側稱為「內側」、將內側的層稱為「內層」、將位於遠離電解液處的預定之側稱為「外側」、將外側的層稱為「外層」。本發明的聚胺甲酸酯系接著劑適合作為將外層側樹脂膜層(11)與金屬箔層(13)積層(貼合)的用途。 The battery container is provided with a metal foil (13). In a battery container, usually The side of the metal foil (13) is referred to as "inside", the inner layer is referred to as "inner layer", the side away from the electrolyte is referred to as "outside", and the outer layer is referred to as "outside". "Outer layer." Therefore, in the predetermined battery packaging material for forming the battery container, the predetermined side located near the electrolyte solution is referred to as "inside" and the inner layer is referred to as "inside". The layer is referred to as "outside" on the predetermined side away from the electrolyte, and the outer layer is referred to as the "outer layer". The polyurethane-based adhesive of the present invention is suitable for use as a laminate (bonding) of the outer layer side resin film layer (11) and the metal foil layer (13).
本發明的聚胺甲酸酯系接著劑是使用主劑與硬化劑 者。可為在使用時將主劑與硬化劑混合的所謂的2液混合型接著劑,亦可為預先混合主劑與硬化劑的1液型接著劑。而且,還可為在使用時混合多種主劑及/或多種硬化劑的類型。 The polyurethane-based adhesive of the present invention uses a main agent and a hardener By. The so-called two-liquid mixing type adhesive in which the main component and the curing agent are mixed at the time of use may be a one-liquid type adhesive in which the main agent and the curing agent are mixed in advance. Moreover, it is also possible to mix a plurality of main agents and/or a plurality of hardeners at the time of use.
本發明的聚胺甲酸酯系接著劑含有多元醇成分(A)及 矽烷偶合劑(B)。多元醇成分(A)包含玻璃轉移溫度為40℃以上的聚酯多元醇(A1)5重量%~50重量%及玻璃轉移溫度小於40℃的聚酯多元醇(A2)95重量%~50重量%。多元醇成分(A)可在滿足本發明的目的、效果的範圍內進一步包含聚酯多元醇(A1)、聚酯多元醇(A2)以外的多元醇。 The polyurethane-based adhesive of the present invention contains the polyol component (A) and Decane coupling agent (B). The polyol component (A) comprises a polyester polyol (A1) having a glass transition temperature of 40 ° C or higher and 5 to 50% by weight and a polyester polyol (A2) having a glass transition temperature of less than 40 ° C, 95% by weight to 50% by weight. %. The polyol component (A) may further contain a polyol other than the polyester polyol (A1) or the polyester polyol (A2) within a range that satisfies the object and effect of the present invention.
作為玻璃轉移溫度為40℃以上的聚酯多元醇(A1)、及玻璃轉移溫度小於40℃的聚酯多元醇(A2),例如使:間苯二甲 酸、對苯二甲酸、萘二甲酸、鄰苯二甲酸酐、己二酸、壬二酸、癸二酸、琥珀酸、戊二酸、四氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐、順丁烯二酸酐、衣康酸酐及其酯化合物等(以上匯總稱為多元酸成分)的單獨或混合物,與例如乙二醇、二乙二醇、三乙二醇、丙二醇、二丙二醇、1,6-己二醇、新戊二醇、1,4-丁二醇、1,4-環己烷二甲醇、三羥甲基丙烷、甘油、1,9-壬二醇、3-甲基-1,5-戊二醇、聚醚多元醇、聚碳酸酯多元醇、聚烯烴多元醇、丙烯酸系多元醇、聚胺甲酸酯多元醇等(以上匯總稱為多元醇成分)的單獨或混合物反應而得。 The polyester polyol (A1) having a glass transition temperature of 40 ° C or higher and the polyester polyol (A2) having a glass transition temperature of less than 40 ° C, for example, m-xylylene Acid, terephthalic acid, naphthalene dicarboxylic acid, phthalic anhydride, adipic acid, sebacic acid, sebacic acid, succinic acid, glutaric acid, tetrahydrophthalic anhydride, hexahydrophthalic acid An acid anhydride, maleic anhydride, itaconic anhydride, an ester compound thereof, and the like (collectively referred to as a polybasic acid component), alone or in combination with, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol 1,6-hexanediol, neopentyl glycol, 1,4-butanediol, 1,4-cyclohexanedimethanol, trimethylolpropane, glycerin, 1,9-nonanediol, 3- Methyl-1,5-pentanediol, polyether polyol, polycarbonate polyol, polyolefin polyol, acrylic polyol, polyurethane polyalcohol, etc. (collectively referred to as polyol components) It is obtained by reaction alone or in a mixture.
另外,作為聚酯多元醇(A1)、聚酯多元醇(A2)的較 佳的例子,可例示聚酯胺甲酸酯多元醇,其是使上述多元酸成分與上述多元醇成分反應而獲得聚酯多元醇,並使所得的聚酯多元醇與例如2,4-甲苯二異氰酸酯、2,6-甲苯二異氰酸酯、二甲苯二異氰酸酯、二苯基甲烷二異氰酸酯、異佛爾酮二異氰酸酯、1,5-萘二異氰酸酯、六亞甲基二異氰酸酯、氫化二苯基甲烷二異氰酸酯等聚異氰酸酯反應而得。 In addition, as a polyester polyol (A1), polyester polyol (A2) As a preferred example, a polyester urethane polyol can be exemplified by reacting the above polybasic acid component with the above polyol component to obtain a polyester polyol, and the obtained polyester polyol and, for example, 2,4-toluene Diisocyanate, 2,6-toluene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, 1,5-naphthalene diisocyanate, hexamethylene diisocyanate, hydrogenated diphenylmethane A polyisocyanate such as a diisocyanate is obtained by a reaction.
另外,作為聚酯多元醇(A1)、聚酯多元醇(A2)的較 佳的例子,可例示分子中(分子內部或分子末端)具有羧基的聚酯多元醇,其是使上述多元酸成分與上述多元醇成分反應而獲得聚酯多元醇,並使所得的聚酯多元醇與例如鄰苯二甲酸、偏苯三甲酸、均苯四甲酸等多元酸及該些的酸酐反應而得。 In addition, as a polyester polyol (A1), polyester polyol (A2) A preferred example is a polyester polyol having a carboxyl group in a molecule (inside or at a molecular end), which is obtained by reacting the above polybasic acid component with the above polyol component to obtain a polyester polyol, and obtaining the obtained polyester polyol. The alcohol is obtained by reacting a polybasic acid such as phthalic acid, trimellitic acid or pyromellitic acid with an acid anhydride thereof.
在主劑所含的多元醇成分(A)中,將玻璃轉移溫度為 40℃以上的聚酯多元醇(A1)設為5重量%~50重量%、較佳為10重量%~40重量%,將玻璃轉移溫度小於40℃的聚酯多元醇(A2)設為95重量%~50重量%、較佳為90重量%~60重量%,藉此可提高外層側樹脂膜層(11)與金屬箔層(13)的層間的接著強度,並獲得成型性良好的電池用包裝材。藉由將40℃以上的聚酯多元醇(A1)設為5重量%以上、將玻璃轉移溫度小於40℃的聚酯多元醇(A2)設為95重量%以下,而可獲得充分的成型性。 另外,藉由將40℃以上的聚酯多元醇(A1)設為50重量%以下、將玻璃轉移溫度小於40℃的聚酯多元醇(A2)設為50重量%以上,而可充分地獲得外層側樹脂膜層(11)與金屬箔層(13)的層間的接著強度。 In the polyol component (A) contained in the main component, the glass transition temperature is The polyester polyol (A1) at 40 ° C or higher is set to 5 wt% to 50 wt%, preferably 10 wt% to 40 wt%, and the polyester polyol (A2) having a glass transition temperature of less than 40 ° C is set to 95. The weight % to 50% by weight, preferably 90% by weight to 60% by weight, whereby the adhesion strength between the layers of the outer layer side resin film layer (11) and the metal foil layer (13) can be improved, and a battery having good moldability can be obtained. Use packaging materials. By setting the polyester polyol (A1) at 40° C. or higher to 5% by weight or more and the polyester polyol (A2) having a glass transition temperature of less than 40° C. to 95% by weight or less, sufficient moldability can be obtained. . In addition, the polyester polyol (A1) having a glass transition temperature of less than 40° C. is 50% by weight or more, and the polyester polyol (A2) having a glass transition temperature of less than 40° C. is 50% by weight or more. The bonding strength between the layers of the outer layer side resin film layer (11) and the metal foil layer (13).
作為玻璃轉移溫度為40℃以上的聚酯多元醇(A1)、及 玻璃轉移溫度小於40℃的聚酯多元醇(A2)的分子量,特別是數量平均分子量較佳為5,000~100,000,更佳為10,000~50,000。在工業上生產電池用包裝材時,將長條狀態者捲取成卷狀。並且,為了使捲取成卷狀的積層體中的接著劑層充分地硬化,而在維持為高溫的倉庫中老化數天。若聚酯多元醇(A1)、聚酯多元醇(A2)的數量平均分子量小於5,000,則老化前處於硬化中途的接著劑層的凝聚力低,因此有產生捲取狀態中出現滑動或隆起的外觀不良等加工異常的擔憂。另一方面,若聚酯多元醇(A1)、聚酯多元醇(A2)的數量平均分子量超過100,000,則有在稀釋溶劑中的溶解性變得缺乏,接著劑塗敷時的黏度變高,而塗敷性變得缺乏的擔 憂。 As a polyester polyol (A1) having a glass transition temperature of 40 ° C or higher, and The molecular weight of the polyester polyol (A2) having a glass transition temperature of less than 40 ° C, particularly the number average molecular weight, is preferably from 5,000 to 100,000, more preferably from 10,000 to 50,000. When the packaging material for a battery is industrially produced, the long state is taken up in a roll shape. Further, in order to sufficiently cure the adhesive layer in the laminated body wound in a roll shape, it is aged for several days in a warehouse maintained at a high temperature. When the number average molecular weight of the polyester polyol (A1) or the polyester polyol (A2) is less than 5,000, the cohesive force of the adhesive layer which is in the middle of hardening before aging is low, and thus the appearance of occurrence of slippage or bulging in the coiled state occurs. Worries such as poor processing. On the other hand, when the number average molecular weight of the polyester polyol (A1) or the polyester polyol (A2) exceeds 100,000, the solubility in the diluted solvent becomes insufficient, and the viscosity at the time of application of the adhesive becomes high. And the coating is becoming scarce worry.
聚酯多元醇(A1)、聚酯多元醇(A2)的玻璃轉移溫度 的測定是使用精工電子(Seiko Instruments)公司製造的示差掃描量熱儀(Differential Scanning Calorimeter,DSC)「RDC220」進行。分別量取約10mg的聚酯多元醇(A1)、聚酯多元醇(A2)放入至鋁鍋中,並設置於DSC裝置中藉由液氮冷卻至-100℃後,根據以10℃/min升溫而得的DSC圖表算出玻璃轉移溫度。在聚酯多元醇(A1)、聚酯多元醇(A2)溶解於溶劑時,將溶劑蒸餾除去進行乾燥後進行DSC測定。 Glass transition temperature of polyester polyol (A1) and polyester polyol (A2) The measurement was carried out using a Differential Scanning Calorimeter (DSC) "RDC220" manufactured by Seiko Instruments. About 10 mg of polyester polyol (A1) and polyester polyol (A2) were separately weighed into an aluminum pan and placed in a DSC apparatus and cooled to -100 ° C by liquid nitrogen, according to 10 ° C / The glass transition temperature was calculated from the DSC chart obtained by heating the min. When the polyester polyol (A1) or the polyester polyol (A2) is dissolved in a solvent, the solvent is distilled off, dried, and subjected to DSC measurement.
聚酯多元醇(A1)及聚酯多元醇(A2)的數量平均分子量是藉由凝膠滲透層析法(Gel Permeation Chromatography,GPC)的聚苯乙烯換算的值。例如將管柱(昭和電工公司製造的KF-805L、KF-803L、及KF-802)的溫度設為40℃,使用四氫呋喃(Tetrahydrofuran,THF)作為溶離液,將流速設為0.2mL/min,將檢測設為RI,將試樣濃度設為0.02%,使用聚苯乙烯作為標準試樣而進行。本發明的數量平均分子量記載藉由上述方法而測定的值。 The number average molecular weight of the polyester polyol (A1) and the polyester polyol (A2) is a polystyrene-equivalent value by Gel Permeation Chromatography (GPC). For example, the temperature of the column (KF-805L, KF-803L, and KF-802 manufactured by Showa Denko Co., Ltd.) is set to 40 ° C, and Tetrahydrofuran (THF) is used as the elution solution, and the flow rate is set to 0.2 mL/min. The detection was performed as RI, and the sample concentration was set to 0.02%, and polystyrene was used as a standard sample. The number average molecular weight of the present invention describes the value measured by the above method.
作為主劑所含的多元醇成分(A),亦可併用玻璃轉移溫 度為40℃以上的聚酯多元醇(A1)及玻璃轉移溫度小於40℃的聚酯多元醇(A2)以外的多元醇。例如可列舉:乙二醇或三羥甲基丙烷等低分子多元醇、及聚醚多元醇、聚碳酸酯多元醇、聚烯烴多元醇、丙烯酸系多元醇、或將該些單獨或併用2種以上與有機 異氰酸酯反應而得的聚胺甲酸酯多元醇等,可在不對接著強度或成型性造成不良影響的程度內使用。 As the polyol component (A) contained in the main component, it is also possible to use a glass to transfer temperature A polyester polyol (A1) having a degree of 40 ° C or higher and a polyol other than the polyester polyol (A2) having a glass transition temperature of less than 40 ° C. For example, a low molecular polyol such as ethylene glycol or trimethylolpropane, a polyether polyol, a polycarbonate polyol, a polyolefin polyol, an acrylic polyol, or two of them may be used alone or in combination. Above and organic The polyurethane urethane polyol obtained by the reaction of the isocyanate can be used to such an extent that it does not adversely affect the strength or moldability.
就提高對金屬箔等金屬系原材料的接著強度的觀點而 言,本發明的聚胺甲酸酯接著劑包含矽烷偶合劑(B)。作為矽烷偶合劑(B),例如可列舉:乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷等具有乙烯基的三烷氧基矽烷;3-胺基丙基三乙氧基矽烷、N-(2-胺基乙基)3-胺基丙基三甲氧基矽烷等具有胺基的三烷氧基矽烷;3-縮水甘油氧基丙基三甲氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-縮水甘油氧基丙基三乙氧基矽烷等具有縮水甘油基的三烷氧基矽烷。該些分別可單獨使用,或任意地組合2種以上而使用。相對於多元醇成分(A)的固體成分100重量份,矽烷偶合劑(B)的添加量較佳為0.1重量份~5重量份,更佳為0.5重量份~3重量份。在矽烷偶合劑(B)的添加量小於0.1重量份時,缺乏因添加矽烷偶合劑引起的對金屬箔的接著強度提高效果,即便添加5重量份以上,亦無法期待再有其以上的性能的提高。 From the viewpoint of improving the adhesion strength to metal materials such as metal foils The polyurethane adhesive of the present invention comprises a decane coupling agent (B). Examples of the decane coupling agent (B) include a trialkoxysilane having a vinyl group such as vinyltrimethoxydecane or vinyltriethoxysilane; 3-aminopropyltriethoxydecane, N -Trialkyloxydecane having an amine group such as (2-aminoethyl) 3-aminopropyltrimethoxydecane; 3-glycidoxypropyltrimethoxydecane, 2-(3,4- A trialkoxydecane having a glycidyl group such as epoxycyclohexyl)ethyltrimethoxydecane or 3-glycidoxypropyltriethoxydecane. These may be used individually or in combination of two or more types arbitrarily. The amount of the decane coupling agent (B) to be added is preferably from 0.1 part by weight to 5 parts by weight, more preferably from 0.5 part by weight to 3 parts by weight, per 100 parts by weight of the solid component of the polyol component (A). When the amount of the decane coupling agent (B) added is less than 0.1 part by weight, the effect of improving the adhesion strength to the metal foil due to the addition of the decane coupling agent is lacking, and even if 5 parts by weight or more is added, the above performance cannot be expected. improve.
為了維持耐久性試驗後的接著強度、或更有效地抑制因 膜的隆起引起的外觀不良,本發明的聚胺甲酸酯接著劑可進一步使用可與羧基反應的化合物(C)。可與羧基反應的化合物(C)可包含於主劑中,亦可包含於硬化劑中,另外還可在將主劑與硬化劑混合時添加。作為可與羧基反應的化合物(C),較佳為分子內具有縮水甘油基的化合物、或具有碳二醯亞胺基的化合物、或具 有噁唑啉基的化合物。藉由使用可與羧基反應的化合物(C),而與在長期耐久性試驗中接著劑層中的酯鍵分解而產生的羧酸反應,從而可抑制因接著劑層的分子量降低引起的凝聚力降低,並抑制接著強度的降低或外觀不良的產生。 In order to maintain the strength of the adhesion after the durability test, or to more effectively suppress the cause The appearance of the film is poor, and the polyurethane (5) which can react with a carboxyl group can be further used for the polyurethane adhesive of the present invention. The compound (C) which can be reacted with a carboxyl group may be contained in the main component or may be contained in the hardening agent, and may also be added when the main agent and the hardener are mixed. The compound (C) which can react with a carboxyl group is preferably a compound having a glycidyl group in the molecule, or a compound having a carbodiimide group, or A compound having an oxazoline group. By using the compound (C) reactive with a carboxyl group, it reacts with a carboxylic acid generated by decomposition of an ester bond in the adhesive layer in the long-term durability test, thereby suppressing a decrease in cohesive force due to a decrease in molecular weight of the adhesive layer. And suppressing the decrease in the strength of the subsequent or the occurrence of poor appearance.
作為分子內具有縮水甘油基的化合物,可列舉:雙酚A 型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、溴化雙酚A型環氧樹脂、氫化雙酚A型環氧樹脂、聯苯酚型環氧樹脂、聯二甲苯酚型環氧樹脂、苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、溴化苯酚酚醛清漆型環氧樹脂、雙酚A的酚醛清漆型環氧樹脂、三羥基苯基甲烷型環氧樹脂、四酚基乙烷型環氧樹脂、含有萘骨架的苯酚酚醛清漆型環氧樹脂、含有二環戊二烯骨架的苯酚酚醛清漆型環氧樹脂等縮水甘油醚化合物;對苯二甲酸二縮水甘油酯等縮水甘油酯化合物;大賽璐化學工業(DAICEL CHEMICAL INDUSTRIES)公司製造的EHPE-3150等脂環式環氧樹脂;三縮水甘油基異三聚氰酸酯等雜環式環氧樹脂;N,N,N',N'-四縮水甘油基間二甲苯二胺等縮水甘油胺類;或(甲基)丙烯酸縮水甘油酯與具有乙烯性不飽和雙鍵的化合物的共聚物等。該些可單獨使用,亦可併用2種以上。 As a compound having a glycidyl group in the molecule, bisphenol A can be cited. Epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, brominated bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, biphenol epoxy resin, dimethyl Phenol type epoxy resin, phenol novolac type epoxy resin, cresol novolak type epoxy resin, brominated phenol novolak type epoxy resin, phenol novolak type epoxy resin of bisphenol A, trishydroxyphenylmethane type An epoxy resin, a tetraphenol ethane type epoxy resin, a phenol novolac type epoxy resin containing a naphthalene skeleton, a glycidyl ether compound such as a phenol novolac type epoxy resin containing a dicyclopentadiene skeleton; a glycidyl ester compound such as diglycidyl formate; an alicyclic epoxy resin such as EHPE-3150 manufactured by DAICEL CHEMICAL INDUSTRIES; a heterocyclic epoxy such as triglycidyl isocyanurate a resin; a glycidylamine such as N,N,N',N'-tetraglycidyl-m-xylenediamine; or a copolymer of glycidyl (meth)acrylate and a compound having an ethylenically unsaturated double bond; . These may be used alone or in combination of two or more.
作為分子內具有碳二醯亞胺基的化合物,可列舉:N,N'- 二-鄰甲苯甲醯基碳二醯亞胺、N,N'-二苯基碳二醯亞胺、N,N'-二-2,6-二甲基苯基碳二醯亞胺、N,N'-雙(2,6-二異丙基苯基)碳二醯亞胺、N,N'-二辛基癸基碳二醯亞胺、N-三基-N'-環己基碳二醯亞胺、 N,N'-二-2,2-二-第三丁基苯基碳二醯亞胺、N-三基-N'-苯基碳二醯亞胺、N,N'-二-對硝基苯基碳二醯亞胺、N,N'-二-對胺基苯基碳二醯亞胺、N,N'-二-對羥基苯基碳二醯亞胺、N,N'-二-環己基碳二醯亞胺、及N,N'-二-對甲苯甲醯基碳二醯亞胺等。 As a compound having a carbodiimide group in the molecule, N, N'- Di-o-tolylcarbyl carbodiimide, N,N'-diphenylcarbodiimide, N,N'-di-2,6-dimethylphenylcarbodiimide, N , N'-bis(2,6-diisopropylphenyl)carbodiimide, N,N'-dioctyldecylcarbodiimide, N-triyl-N'-cyclohexyl carbon Diterpenoid N,N'-di-2,2-di-t-butylphenylcarbodiimide, N-triyl-N'-phenylcarbodiimide, N,N'-di-p-nitro Phenyl carbodiimide, N,N'-di-p-aminophenylcarbodiimide, N,N'-di-p-hydroxyphenylcarbodiimide, N,N'-di - cyclohexylcarbodiimide, and N,N'-di-p-tolylcarbenylcarbodiimide.
作為分子內具有噁唑啉基的化合物,可列舉: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-噁唑啉等單噁唑啉化合物,2,2'-(1,3-伸苯基)-雙(2-噁唑啉)、2,2'-(1,2-伸乙基)-雙(2-噁唑啉)、2,2'-(1,4-伸丁基)-雙(2-噁唑啉)、2,2'-(1,4-伸苯基)-雙(2-噁唑啉)等。 As a compound having an oxazoline group in the molecule, a 2-oxazole can be cited. Porphyrin, 2-methyl-2-oxazoline, 2-phenyl-2-oxazoline, 2,5-dimethyl-2-oxazoline, 2,4-diphenyl-2-oxazole Monooxazoline compound such as porphyrin, 2,2'-(1,3-phenylene)-bis(2-oxazoline), 2,2'-(1,2-extended ethyl)-bis (2) -oxazoline), 2,2'-(1,4-butylene)-bis(2-oxazoline), 2,2'-(1,4-phenylene)-bis(2-oxo Oxazoline) and the like.
作為可與羧基反應的化合物(C),較佳為雙酚型環氧化合物,較佳為數量平均分子量為400~5,000的雙酚型環氧樹脂。若環氧樹脂的數量平均分子量小於400,則有接著劑層變得柔軟而無法獲得充分的耐久性的傾向。若環氧樹脂的數量平均分子量大於5,000,則有與聚酯多元醇的相容性降低,並產生外觀不良的擔憂。另外,相對於多元醇成分(A)100重量份,可與羧基反應的化合物(C)較佳為含有1重量份~100重量份,更佳為含有5重量份~50重量份。 The compound (C) which can react with a carboxyl group is preferably a bisphenol type epoxy compound, and preferably a bisphenol type epoxy resin having a number average molecular weight of 400 to 5,000. When the number average molecular weight of the epoxy resin is less than 400, the adhesive layer tends to be soft and sufficient durability cannot be obtained. When the number average molecular weight of the epoxy resin is more than 5,000, the compatibility with the polyester polyol is lowered, and there is a concern that the appearance is poor. Further, the compound (C) which can react with the carboxyl group is preferably contained in an amount of from 1 part by weight to 100 parts by weight, more preferably from 5 parts by weight to 50 parts by weight per 100 parts by weight of the polyol component (A).
此外,作為接著劑用途,可在主劑、或硬化劑中調配公知的添加劑。例如可使用反應促進劑。例如可列舉:二丁基二乙酸錫、二丁基二月桂酸錫、二辛基二月桂酸錫、二丁基二順丁烯二酸錫等金屬系觸媒;1,8-二氮雜-雙環(5,4,0)十一碳烯-7,1,5-二氮雜雙環(4,3,0)壬烯-5、6-二丁基胺基-1,8-二氮雜雙環(5,4,0)十一碳 烯-7等三級胺;如三乙醇胺的反應性三級胺等,可使用選自該些組群的1種或2種以上反應促進劑。 Further, as an adhesive application, a known additive may be blended in the main agent or the curing agent. For example, a reaction accelerator can be used. For example, a metal catalyst such as dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate or dibutyltin maleate; 1,8-diaza -bicyclo(5,4,0)undecene-7,1,5-diazabicyclo(4,3,0)decene-5,6-dibutylamino-1,8-diaza Heterobicyclo (5,4,0) eleven carbon A tertiary amine such as alkene-7; a reactive tertiary amine such as triethanolamine; and one or more reaction accelerators selected from the group may be used.
為了提高層壓外觀,亦可在主劑中調配公知的均化劑或消泡劑。作為均化劑,例如可列舉:聚醚改質聚二甲基矽氧烷、聚酯改質聚二甲基矽氧烷、芳烷基改質聚甲基烷基矽氧烷、聚酯改質含有羥基的聚二甲基矽氧烷、聚醚酯改質含有羥基的聚二甲基矽氧烷、丙烯酸系共聚物、甲基丙烯酸系共聚物、聚醚改質聚甲基烷基矽氧烷、丙烯酸烷基酯共聚物、甲基丙烯酸烷基酯共聚物、卵磷脂等。作為消泡劑,可列舉:矽酮樹脂、矽酮溶液、烷基乙烯醚與丙烯酸烷基酯以及甲基丙烯酸烷基酯的共聚物等公知者。 In order to improve the appearance of the laminate, a known leveling agent or antifoaming agent may be formulated in the main agent. Examples of the leveling agent include polyether modified polydimethyl siloxane, polyester modified polydimethyl siloxane, aralkyl modified polymethyl alkyl siloxane, and polyester modification. Hydroxy-containing polydimethyl siloxane, polyether ester modified hydroxy-containing polydimethyl siloxane, acrylic copolymer, methacrylic copolymer, polyether modified polymethylalkyl hydrazine Oxyalkane, alkyl acrylate copolymer, alkyl methacrylate copolymer, lecithin, and the like. Examples of the antifoaming agent include those known as an anthrone resin, an anthrone solution, a copolymer of an alkyl vinyl ether, an alkyl acrylate, and an alkyl methacrylate.
本發明的聚胺甲酸酯接著劑包含聚異氰酸酯作為硬化 劑。聚異氰酸酯可為藉由有機溶劑將聚異氰酸酯稀釋的狀態者,亦可為未稀釋的狀態者。作為聚異氰酸酯,例如可列舉:三亞甲基二異氰酸酯、四亞甲基二異氰酸酯、六亞甲基二異氰酸酯、1,2-丙烯二異氰酸酯、1,2-丁烯二異氰酸酯、2,3-丁烯二異氰酸酯、1,3-丁烯二異氰酸酯、2,4,4-三甲基六亞甲基二異氰酸酯或2,2,4-三甲基六亞甲基二異氰酸酯、2,6-二異氰酸酯甲基己酸酯等脂肪族二異氰酸酯,1,4-環己烷二異氰酸酯、1,3-環己烷二異氰酸酯、3-異氰酸酯甲基-3,5,5-三甲基環己基異氰酸酯、4,4'-亞甲基雙(環己基異氰酸酯)、甲基2,4-環己烷二異氰酸酯、甲基2,6-環己烷二異氰酸酯、1,4-雙(異氰酸酯甲基)環己烷、1,3-雙(異氰酸酯甲基)環己烷等脂環式二異氰酸酯,間苯二異氰酸酯、對苯二異氰酸酯、4,4'-二 苯基二異氰酸酯、1,5-萘二異氰酸酯、4,4'-二苯基甲烷二異氰酸酯、2,4-甲苯二異氰酸酯或2,6-甲苯二異氰酸酯或其混合物、4,4'-甲苯胺二異氰酸酯、聯茴香胺二異氰酸酯、4,4'-二苯醚二異氰酸酯等芳香族二異氰酸酯,1,3-二甲苯二異氰酸酯或1,4-二甲苯二異氰酸酯或其混合物、ω,ω'-二異氰酸基-1,4-二乙基苯、1,3-雙(1-異氰酸基-1-甲基乙基)苯或1,4-雙(1-異氰酸基-1-甲基乙基)苯或其混合物等芳香脂肪族二異氰酸酯,三苯基甲烷-4,4',4"-三異氰酸酯、苯-1,3,5-三異氰酸酯、甲苯-2,4,6-三異氰酸酯等有機三異氰酸酯,4,4'-二苯基二甲基甲烷-2,2',5,5'-四異氰酸酯等有機四異氰酸酯等聚異氰酸酯單體,由上述聚異氰酸酯單體衍生的二聚物、三聚物,縮二脲、脲基甲酸酯,由二氧化碳與上述聚異氰酸酯單體獲得的具有2,4,6-噁二嗪三酮環的聚異氰酸酯、例如與乙二醇、丙二醇、丁二醇、己二醇、新戊二醇、1,6-己二醇、3-甲基-1,5-戊二醇、3,3'-二羥甲基丙烷、環己烷二甲醇、二乙二醇、三乙二醇、二丙二醇、甘油、三羥甲基丙烷、季戊四醇、山梨糖醇等分子量小於200的低分子多元醇的加成物,或與分子量為200~20,000的聚酯多元醇、聚醚酯多元醇、聚酯醯胺多元醇、聚己內酯多元醇、聚戊內酯多元醇、丙烯酸系多元醇、聚碳酸酯多元醇、聚羥基烷烴、蓖麻油、聚胺甲酸酯多元醇等的加成物等。其中,就包裝材的生產性、及成型性的觀點而言,更佳為由芳香族二異氰酸酯衍生的有機聚異氰酸酯。 The polyurethane adhesive of the present invention comprises polyisocyanate as a hardening Agent. The polyisocyanate may be in a state in which the polyisocyanate is diluted by an organic solvent, or may be in an undiluted state. Examples of the polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butene diisocyanate, and 2,3-butylene. Eicyl diisocyanate, 1,3-butene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-di Aliphatic diisocyanate such as isocyanate methyl hexanoate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate 4,4'-methylenebis(cyclohexyl isocyanate), methyl 2,4-cyclohexane diisocyanate, methyl 2,6-cyclohexane diisocyanate, 1,4-bis(isocyanate methyl) An alicyclic diisocyanate such as cyclohexane or 1,3-bis(isocyanatemethyl)cyclohexane, isophthalic diisocyanate, p-phenylene diisocyanate, 4,4'-di Phenyl diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate or 2,6-toluene diisocyanate or mixtures thereof, 4,4'-A An aromatic diisocyanate such as aniline diisocyanate, dianisidine diisocyanate or 4,4'-diphenyl ether diisocyanate, 1,3-xylene diisocyanate or 1,4-dimethylbenzene diisocyanate or a mixture thereof, ω, ω '-Diisocyanyl-1,4-diethylbenzene, 1,3-bis(1-isocyanato-1-methylethyl)benzene or 1,4-bis(1-isocyanate) Aromatic aliphatic diisocyanate such as -1-methylethyl)benzene or a mixture thereof, triphenylmethane-4,4',4"-triisocyanate, benzene-1,3,5-triisocyanate, toluene-2 , an organic triisocyanate such as 4,6-triisocyanate, or a polyisocyanate monomer such as an organic tetraisocyanate such as 4,4'-diphenyldimethylmethane-2,2',5,5'-tetraisocyanate, or the like Isocyanate monomer-derived dimer, trimer, biuret, allophanate, polyisocyanate having 2,4,6-oxadiazinetrione ring obtained from carbon dioxide and the above polyisocyanate monomer, For example with ethylene glycol, propylene glycol, Glycol, hexanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 3,3'-dimethylolpropane, cyclohexanedimethanol, An adduct of a low molecular weight polyol having a molecular weight of less than 200 such as diethylene glycol, triethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, pentaerythritol or sorbitol, or a polyester having a molecular weight of 200 to 20,000 Polyol, polyether ester polyol, polyester decylamine polyol, polycaprolactone polyol, polyvalerolactone polyol, acrylic polyol, polycarbonate polyol, polyhydroxyalkane, castor oil, polyamine An adduct of a formic acid ester or the like, etc., is preferably an organic polyisocyanate derived from an aromatic diisocyanate from the viewpoint of productivity of the packaging material and moldability.
本發明的聚胺甲酸酯接著劑中,聚異氰酸酯硬化劑(2) 中所含的異氰酸基相對於主劑(1)中所含的多元醇成分(A)所具有的羥基與羧基的合計的當量比[NCO]/([OH]+[COOH]),較佳為10~30,更佳為15~25。即,相對於羥基與羧基的合計1莫耳,異氰酸基小於10莫耳時,無法獲得充分的成型性,若超過30莫耳,則在硬化時間、衛生性、經濟性的方面不利。 Polyisocyanate hardener (2) in the polyurethane adhesive of the present invention The equivalent ratio [NCO]/([OH]+[COOH]) of the total of the hydroxyl group and the carboxyl group which the polyhydric alcohol group contained in the polyol component (A) contained in the main component (1), It is preferably 10 to 30, more preferably 15 to 25. That is, when the total amount of the hydroxyl group and the carboxyl group is 1 mol, and the isocyanate group is less than 10 mol, sufficient moldability cannot be obtained, and if it exceeds 30 mol, it is disadvantageous in terms of curing time, hygiene, and economy.
本發明的電池用包裝材例如可藉由通常所用的方法而 製造。例如使用本發明的聚胺甲酸酯接著劑積層外層側樹脂膜層(11)與金屬箔層(13),而獲得中間積層體。繼而,可使用內層側接著劑(14)在中間積層體的金屬箔層(13)面積層內面層(15)。 或者使用內層側接著劑積層金屬箔層(13)與內面層(15),而獲得中間積層體。繼而,可使用本發明的聚胺甲酸酯接著劑,積層中間積層體的金屬箔層(13)與外層側樹脂膜層(11)。為前者時,本發明的聚胺甲酸酯接著劑塗佈於外層側樹脂膜層(11)或金屬箔層(13)的任一基材的單面上,使溶劑揮發後,在加熱加壓下在接著劑層上重疊另一基材,繼而在常溫或加溫下進行老化,使接著劑層硬化即可。接著劑層量較佳為1g/m2~15g/m2左右。為後者時,亦同樣,本發明的聚胺甲酸酯接著劑塗佈於外層側樹脂膜層(11)或中間積層體的金屬箔層(13)面的任一面即可。 The packaging material for a battery of the present invention can be produced, for example, by a method generally used. For example, the outer layer side resin film layer (11) and the metal foil layer (13) are laminated using the polyurethane adhesive of the present invention to obtain an intermediate laminate. Then, the inner layer side adhesive (14) may be used to laminate the inner metal layer (13) of the metal foil layer (13) in the middle layer. Alternatively, an inner layer side laminate is used to laminate the metal foil layer (13) and the inner surface layer (15) to obtain an intermediate laminate. Then, the metal foil layer (13) of the intermediate laminate and the outer layer side resin film layer (11) can be laminated using the polyurethane adhesive of the present invention. In the former case, the polyurethane adhesive of the present invention is applied to one surface of any of the outer layer side resin film layer (11) or the metal foil layer (13), and the solvent is volatilized and then heated. The other substrate is superposed on the adhesive layer by pressing, and then aged at normal temperature or under heating to cure the adhesive layer. The amount of the layer is preferably from about 1 g/m 2 to about 15 g/m 2 . In the latter case, the polyurethane adhesive of the present invention may be applied to either the outer layer side resin film layer (11) or the metal foil layer (13) surface of the intermediate laminate.
將聚胺甲酸酯系接著劑塗敷於基材時,為了將塗佈液調整為適度的黏度,而可在乾燥步驟中在不對基材造成影響的範圍內包含溶劑。作為溶劑,可列舉:丙酮、甲基乙基酮、甲基異丁基酮、環己酮等酮系化合物,乙酸甲酯、乙酸乙酯、乙酸丁酯、 乳酸乙酯、乙酸甲氧基乙酯等酯系化合物,二乙醚、乙二醇二甲醚等醚系化合物,甲苯、二甲苯等芳香族化合物,戊烷、己烷等脂肪族化合物,二氯甲烷、氯苯、氯仿等鹵化烴化合物,乙醇、異丙醇、正丁醇等醇類,水等。該些溶劑可單獨使用,亦可併用2種以上。 When the polyurethane-based adhesive is applied to the substrate, in order to adjust the coating liquid to an appropriate viscosity, the solvent can be contained in the drying step without affecting the substrate. Examples of the solvent include ketone compounds such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; methyl acetate, ethyl acetate, and butyl acetate; An ester compound such as ethyl lactate or methoxyethyl acetate; an ether compound such as diethyl ether or ethylene glycol dimethyl ether; an aromatic compound such as toluene or xylene; an aliphatic compound such as pentane or hexane; A halogenated hydrocarbon compound such as methane, chlorobenzene or chloroform; an alcohol such as ethanol, isopropanol or n-butanol; or the like. These solvents may be used singly or in combination of two or more.
在本發明中作為塗敷聚胺甲酸酯系接著劑的裝置,可列 舉:缺角輪塗佈機(comma coater)、乾式貼合機、輥式刮刀塗佈機(roll knife coater)、模塗機、輥塗機、棒塗機、凹版輥式塗佈機、逆輥塗佈機、刮刀塗佈機(blade coater)、凹版塗佈機、微凹版塗佈機等。 In the present invention, as a device for applying a polyurethane-based adhesive, it can be listed. Lift: comma coater, dry laminator, roll knife coater, die coater, roll coater, bar coater, gravure roll coater, reverse A roll coater, a blade coater, a gravure coater, a micro gravure coater, or the like.
構成本發明的電池用外裝材的外層側樹脂膜層(11)並無特別限定,較佳為使用包含聚醯胺或聚酯的延伸膜。另外,亦可藉由碳黑或氧化鈦等顏料進行著色。另外,亦可塗佈防裂痕塗佈劑等塗佈劑、或油墨等。另外,亦可預先積層2層以上的膜。膜層的厚度並無特別限定,較佳為12μm~100μm。 The outer layer side resin film layer (11) constituting the battery exterior material of the present invention is not particularly limited, and a stretch film containing polyamine or polyester is preferably used. Further, it may be colored by a pigment such as carbon black or titanium oxide. Further, a coating agent such as a crack preventing coating agent, or an ink or the like may be applied. Further, two or more layers of the film may be laminated in advance. The thickness of the film layer is not particularly limited, but is preferably from 12 μm to 100 μm.
構成本發明的電池用外裝材的金屬箔層(13)並無特別限定,較佳為鋁箔層。膜層的厚度並無特別限定,較佳為20μm~80μm。另外,較佳為在金屬箔表面進行藉由磷酸鹽、鉻酸鹽、氟化物、三嗪硫醇化合物、異氰酸酯化合物等的表面處理,藉由實施表面處理,而可抑制因電池的電解液或電解液的影響引起的在金屬箔面的層間的隆起。 The metal foil layer (13) constituting the exterior material for a battery of the present invention is not particularly limited, and is preferably an aluminum foil layer. The thickness of the film layer is not particularly limited, but is preferably 20 μm to 80 μm. Further, it is preferred to subject the surface of the metal foil to surface treatment by a phosphate, a chromate, a fluoride, a triazine thiol compound, an isocyanate compound or the like, and by performing a surface treatment, the electrolyte solution of the battery or the battery can be suppressed. The bulging between the layers of the metal foil surface caused by the influence of the electrolyte.
構成本發明的電池用外裝材的內面層(15)並無 特別限定,較佳為包含含有選自由聚乙烯、聚丙烯、烯烴系共聚物、該些的酸變成物及離聚物所組成的組群的至少1種熱塑性樹脂的未延伸膜的熱密封層。熱密封層的厚度並無特別限定,較佳為20μm~150μm。 The inner layer (15) constituting the exterior material for a battery of the present invention does not have In particular, it is preferably a heat-sealing layer comprising an unstretched film containing at least one thermoplastic resin selected from the group consisting of polyethylene, polypropylene, olefin-based copolymers, acid-based compounds and ionomers. . The thickness of the heat seal layer is not particularly limited, but is preferably 20 μm to 150 μm.
形成構成本發明的電池用外裝材的內層側接著劑層 (14)的接著劑並無特別限定,較佳為金屬箔層(13)與內面層(15)的接著強度不會因電池的電解液而降低者,可使用公知的接著劑。例如,可藉由凹版塗佈機等使將聚烯烴樹脂與多官能異氰酸酯組合而成的接著劑或將多元醇與多官能異氰酸酯組合而成的接著劑塗佈於金屬箔層上,使溶劑乾燥,在加熱加壓下在接著劑層上重疊內面層(15),繼而,在常溫或加溫下進行老化而使金屬箔層(13)與內面層(15)貼合。或者可藉由T模擠出機將酸改質聚丙烯等接著劑熔融擠出至金屬箔層(13)上形成接著劑層,在上述接著劑層上重疊內面層(15),而使金屬箔層(13)與內面層(15)貼合。在外層側接著劑層(12)及內層側接著劑層(14)兩者必須進行老化時,可匯總進行老化。 Forming an inner layer side adhesive layer constituting the exterior material for a battery of the present invention The adhesive agent of (14) is not particularly limited, and it is preferable that the adhesive strength of the metal foil layer (13) and the inner surface layer (15) is not lowered by the electrolyte solution of the battery, and a known adhesive can be used. For example, an adhesive obtained by combining a polyolefin resin and a polyfunctional isocyanate or an adhesive obtained by combining a polyol and a polyfunctional isocyanate may be applied onto a metal foil layer by a gravure coater or the like to dry the solvent. The inner surface layer (15) is superposed on the adhesive layer under heat and pressure, and then aged at normal temperature or under heating to bond the metal foil layer (13) to the inner surface layer (15). Alternatively, an adhesive such as acid-modified polypropylene may be melt-extruded onto the metal foil layer (13) by a T-die extruder to form an adhesive layer, and the inner surface layer (15) may be superposed on the adhesive layer. The metal foil layer (13) is bonded to the inner surface layer (15). When both the outer layer side adhesive layer (12) and the inner layer side adhesive layer (14) must be aged, the aging can be collectively performed.
本發明的電池用容器可使用上述電池用外裝材,以外層 側樹脂膜層(11)構成凸面、內面層(15)構成凹面的方式,進行成型而得。 The battery container of the present invention can use the above-mentioned battery exterior material, and the outer layer The side resin film layer (11) is formed by forming a convex surface and the inner surface layer (15) is a concave surface.
繼而,列舉實施例及比較例對本發明進行更具體地說明。實施例及比較例中的%均是指質量%。 Next, the present invention will be more specifically described by way of examples and comparative examples. The % in both the examples and the comparative examples means mass%.
(合成例1)投入間苯二甲酸166.0g、對苯二甲酸166.0g、 乙二醇85.6g、新戊二醇95.6g,在200℃~220℃下進行6小時酯化反應,餾出特定量的水後,添加鈦酸四異丁酯0.12g,並緩慢地減壓,在1.3hPa~2.6hPa、230℃~250℃下進行6小時酯交換反應,而獲得數量平均分子量為20,000、玻璃轉移溫度(Tg)為60℃的聚酯多元醇。藉由乙酸乙酯將該聚酯多元醇調整為不揮發成分為50%,而獲得羥值為2.71mgKOH/g、酸值為0.1mgKOH/g的聚酯多元醇溶液(1)。 (Synthesis Example 1) 166.0 g of isophthalic acid and 166.0 g of terephthalic acid were charged. 85.6 g of ethylene glycol and 95.6 g of neopentyl glycol were subjected to esterification reaction at 200 ° C to 220 ° C for 6 hours, and after distilling off a specific amount of water, 0.12 g of tetraisobutyl titanate was added, and the pressure was slowly reduced. A 6-hour transesterification reaction was carried out at 1.3 hPa to 2.6 hPa and 230 ° C to 250 ° C to obtain a polyester polyol having a number average molecular weight of 20,000 and a glass transition temperature (Tg) of 60 °C. The polyester polyol was adjusted to have a nonvolatile content of 50% by ethyl acetate to obtain a polyester polyol solution (1) having a hydroxyl value of 2.71 mgKOH/g and an acid value of 0.1 mgKOH/g.
另外,數量平均分子量、玻璃轉移溫度藉由如上述所述 的方法利用GPC及DSC而求出。另外,酸值、羥值以如下方式而求出。 In addition, the number average molecular weight and the glass transition temperature are as described above. The method is obtained by using GPC and DSC. Further, the acid value and the hydroxyl value were determined in the following manner.
<酸值(AV)的測定>在具塞錐形瓶中精密地量取試樣(聚酯多元醇溶液)約1g,添加甲苯/乙醇(容量比:甲苯/乙醇=2/1)混合液100mL進行溶解。於其中添加酚酞試劑作為指示劑,並保持30秒鐘。然後,藉由0.1N醇性氫氧化鉀溶液進行滴定直至溶液呈現淡紅色為止。酸值藉由下式而求出(單位:mgKOH/g)。 <Measurement of Acid Value (AV)> About 1 g of a sample (polyester polyol solution) was accurately weighed in a stoppered conical flask, and a mixed solution of toluene/ethanol (capacity ratio: toluene/ethanol = 2/1) was added. 100 mL was dissolved. A phenolphthalein reagent was added thereto as an indicator and held for 30 seconds. Then, titration was carried out by a 0.1 N alcoholic potassium hydroxide solution until the solution appeared reddish. The acid value was determined by the following formula (unit: mgKOH/g).
酸值(mgKOH/g)=(5.611×a×F)/S Acid value (mgKOH/g) = (5.611 × a × F) / S
其中,S:試樣的採集量(g) Among them, S: sample collection amount (g)
a:0.1N醇性氫氧化鉀溶液的消耗量(mL) a: consumption of 0.1N alcoholic potassium hydroxide solution (mL)
F:0.1N醇性氫氧化鉀溶液的滴定度 F: titer of 0.1N alcoholic potassium hydroxide solution
<羥值(OHV)的測定>在具塞錐形瓶中精密地量取試 樣(聚酯多元醇溶液)約1g,添加甲苯/乙醇(容量比:甲苯/乙醇=2/1)混合液100mL進行溶解。繼而準確地添加5mL乙醯化劑(藉由吡啶溶解乙酸酐25g,製成容量為100mL的溶液),攪拌約1小時。於其中添加酚酞試劑作為指示劑,持續30秒鐘。然後,藉由0.1N醇性氫氧化鉀溶液進行滴定直至溶液呈現淡紅色為止。羥值藉由下式而求出(單位:mgKOH/g)。 <Measurement of hydroxyl value (OHV)>Precision measurement in a conical flask About 1 g of the sample (polyester polyol solution) was added, and 100 mL of a mixed solution of toluene/ethanol (capacity ratio: toluene/ethanol = 2/1) was added and dissolved. Then, 5 mL of an acetamidine agent (25 g of acetic anhydride was dissolved in pyridine to prepare a solution having a capacity of 100 mL) was added, and the mixture was stirred for about 1 hour. A phenolphthalein reagent was added thereto as an indicator for 30 seconds. Then, titration was carried out by a 0.1 N alcoholic potassium hydroxide solution until the solution appeared reddish. The hydroxyl value was determined by the following formula (unit: mgKOH/g).
羥值(mgKOH/g)=[{(b-a)×F×28.25}/S]+D Hydroxyl value (mgKOH/g) = [{(b-a) × F × 28.25} / S] + D
其中,S:試樣的採集量(g) Among them, S: sample collection amount (g)
a:0.1N醇性氫氧化鉀溶液的消耗量(mL) a: consumption of 0.1N alcoholic potassium hydroxide solution (mL)
b:空白實驗的0.1N醇性氫氧化鉀溶液的消耗量(mL) b: consumption of 0.1N alcoholic potassium hydroxide solution in blank experiment (mL)
F:0.1N醇性氫氧化鉀溶液的滴定度 F: titer of 0.1N alcoholic potassium hydroxide solution
D:酸值(mgKOH/g) D: acid value (mgKOH/g)
(合成例2)投入間苯二甲酸149.4g、對苯二甲酸149.4g、乙二醇71.3g、新戊二醇119.6g,在200℃~220℃下進行6小時酯化反應,餾出特定量的水後,添加癸二酸40.4g,繼而進行6小時酯化反應。餾出特定量的水後,添加鈦酸四異丁酯0.13g,並緩慢地減壓,在1.3hPa~2.6hPa、230℃~250℃下進行6小時酯交換反應,而獲得數量平均分子量為19,800、Tg為45℃的聚酯多元醇。繼而藉由乙酸乙酯將該聚酯多元醇調整為不揮發成分為50%,而獲得羥值為2.33mgKOH/g、酸值為0.5mgKOH/g的聚酯 多元醇溶液(2)。 (Synthesis Example 2) 149.4 g of isophthalic acid, 149.4 g of terephthalic acid, 71.3 g of ethylene glycol, and 119.6 g of neopentyl glycol were placed, and the esterification reaction was carried out at 200 ° C to 220 ° C for 6 hours to distill off the specificity. After the amount of water, 40.4 g of sebacic acid was added, followed by an esterification reaction for 6 hours. After distilling off a specific amount of water, 0.13 g of tetraisobutyl titanate was added, and the pressure was gradually reduced, and the transesterification reaction was carried out at 1.3 hPa to 2.6 hPa and 230 ° C to 250 ° C for 6 hours to obtain a number average molecular weight of 19,800, polyester polyol having a Tg of 45 °C. Then, the polyester polyol was adjusted to have a nonvolatile content of 50% by ethyl acetate to obtain a polyester having a hydroxyl value of 2.33 mgKOH/g and an acid value of 0.5 mgKOH/g. Polyol solution (2).
(合成例3)投入間苯二甲酸83.2g、對苯二甲酸83.2g、乙二醇142.6g,在200℃~220℃下進行8小時酯化反應,餾出特定量的水後,添加壬二酸188g,繼而進行4小時酯化反應。餾出特定量的水後,添加鈦酸四異丁酯0.13g,並緩慢地減壓,在1.3hPa~2.7hPa、230℃~250℃下進行3小時酯交換反應,而獲得數量平均分子量為22,000、Tg為-5℃的聚酯多元醇。藉由乙酸乙酯將該聚酯多元醇調整為不揮發成分為50%,而獲得羥值為2.45mgKOH/g、酸值為0.1mgKOH/g的聚酯多元醇溶液(3)。 (Synthesis Example 3) 83.2 g of isophthalic acid, 83.2 g of terephthalic acid, and 142.6 g of ethylene glycol were charged, and an esterification reaction was carried out at 200 ° C to 220 ° C for 8 hours to distill a specific amount of water, and then hydrazine was added. Diacid 188 g, followed by a 4 hour esterification reaction. After distilling off a specific amount of water, 0.13 g of tetraisobutyl titanate was added, and the pressure was gradually reduced, and the transesterification reaction was carried out at 1.3 hPa to 2.7 hPa and 230 ° C to 250 ° C for 3 hours to obtain a number average molecular weight of 22,000 polyester polyol having a Tg of -5 °C. The polyester polyol was adjusted to have a nonvolatile content of 50% by ethyl acetate to obtain a polyester polyol solution (3) having a hydroxyl value of 2.45 mgKOH/g and an acid value of 0.1 mgKOH/g.
(合成例4)投入間苯二甲酸132.8g、乙二醇42.7g、新戊二醇71.8g、1,6-己二醇108.6g,在200℃~230℃下進行6小時酯化反應,餾出特定量的水後,添加己二酸175.2g,繼而進行6小時酯化反應。餾出特定量的水後,添加鈦酸四異丁酯0.13g,並緩慢地減壓,在1.3hPa~2.6hPa、230℃~250℃下進行3小時酯交換反應,而獲得聚酯多元醇。為了使所得的該聚酯多元醇的羥基的約90%與均苯四甲酸酐反應,而相對於該聚酯多元醇的總量,添加均苯四甲酸酐7.7g,在180℃下反應約2小時。使用液相層析法確認反應體系中不殘存未反應的均苯四甲酸酐,而獲得數量平均分子量為18,000、Tg為-20℃的經均苯四甲酸酐改質的聚酯多元醇。藉由乙酸乙酯將經均苯四甲酸酐改質的聚酯多元醇調整為不揮發成分為50%,而獲得羥值為0.31mgKOH/g、酸值為2.8mgKOH/g的聚酯多元醇溶液(4)。 (Synthesis Example 4) 132.8 g of isophthalic acid, 42.7 g of ethylene glycol, 71.8 g of neopentyl glycol, and 108.6 g of 1,6-hexanediol were charged, and the esterification reaction was carried out at 200 ° C to 230 ° C for 6 hours. After distilling off a specific amount of water, 175.2 g of adipic acid was added, followed by an esterification reaction for 6 hours. After distilling off a specific amount of water, 0.13 g of tetraisobutyl titanate was added, and the pressure was gradually reduced, and the transesterification reaction was carried out at 1.3 hPa to 2.6 hPa and 230 ° C to 250 ° C for 3 hours to obtain a polyester polyol. . In order to react about 90% of the hydroxyl group of the obtained polyester polyol with pyromellitic anhydride, 7.7 g of pyromellitic anhydride is added relative to the total amount of the polyester polyol, and the reaction is carried out at 180 ° C. 2 hours. It was confirmed by liquid chromatography that unreacted pyromellitic anhydride remained in the reaction system, and a trimenic acid anhydride-modified polyester polyol having a number average molecular weight of 18,000 and a Tg of -20 ° C was obtained. The polyester polyol modified with the pyromellitic anhydride was adjusted to have a nonvolatile content of 50% by ethyl acetate to obtain a polyester polyol having a hydroxyl value of 0.31 mgKOH/g and an acid value of 2.8 mgKOH/g. Solution (4).
(合成例5)投入間苯二甲酸132.8g、乙二醇44.6g、 新戊二醇74.8g、1,6-己二醇113.3g,在200℃~230℃下進行6小時酯化反應,餾出特定量的水後,添加己二酸175.2g,繼而進行6小時酯化反應。餾出特定量的水後,添加鈦酸四異丁酯0.13g,並緩慢地減壓,在1.3hPa~2.6hPa、230℃~250℃下進行3小時酯交換反應,而獲得聚酯多元醇。相對於藉由乙酸乙酯將該聚酯多元醇調整為不揮發成分為80%而得的聚酯多元醇溶液600g,而添加甲苯二異氰酸酯3.2g,在80℃下進行8小時反應,而獲得數量平均分子量為20,000、Tg為-10℃的聚酯聚胺甲酸酯多元醇。繼而,藉由乙酸乙酯將該聚酯多元醇調整為不揮發成分為50%,而獲得羥值為2.71mgKOH/g、酸值為0.1mgKOH/g的聚酯多元醇溶液(5)。 (Synthesis Example 5) 132.8 g of isophthalic acid and 44.6 g of ethylene glycol were charged. 74.8 g of neopentyl glycol and 113.3 g of 1,6-hexanediol were subjected to esterification reaction at 200 ° C to 230 ° C for 6 hours to distill a specific amount of water, and then 175.2 g of adipic acid was added, followed by 6 hours. Esterification reaction. After distilling off a specific amount of water, 0.13 g of tetraisobutyl titanate was added, and the pressure was gradually reduced, and the transesterification reaction was carried out at 1.3 hPa to 2.6 hPa and 230 ° C to 250 ° C for 3 hours to obtain a polyester polyol. . 600 g of a polyester polyol solution obtained by adjusting the polyester polyol to 80% of a nonvolatile content by ethyl acetate, and 3.2 g of toluene diisocyanate was added, and the reaction was carried out at 80 ° C for 8 hours to obtain a reaction. A polyester polyurethane polyol having a number average molecular weight of 20,000 and a Tg of -10 °C. Then, the polyester polyol was adjusted to have a nonvolatile content of 50% by ethyl acetate to obtain a polyester polyol solution (5) having a hydroxyl value of 2.71 mgKOH/g and an acid value of 0.1 mgKOH/g.
[主劑(1)的製造]調配聚酯多元醇溶液(1)60g(固 體成分為30g)、與聚酯多元醇溶液(3)140g(固體成分為70g)、以及KBM-403(矽烷偶合劑)1g後,添加乙酸乙酯136g,而獲得不揮發成分為30%的主劑(1)。主劑(1)的羥值與酸值的合計為約1.56mgKOH/g。 [Production of main agent (1)] Formulated with polyester polyol solution (1) 60g (solid 30 g of the body component, and 140 g of the polyester polyol solution (3) (solid content: 70 g) and KBM-403 (decane coupling agent), 1 g of ethyl acetate, 136 g of ethyl acetate was added to obtain a nonvolatile content of 30%. The main agent (1). The total of the hydroxyl value and the acid value of the main agent (1) was about 1.56 mgKOH/g.
[主劑(2)~主劑(11)的製造]以與主劑(1)的情形 相同的方式,以表1所示的比例(g)調配聚酯多元醇溶液(1)~聚酯多元醇溶液(5)以及下述所示的矽烷偶合劑、及可與羧基反應的化合物後,並以不揮發成分為30%的方式添加乙酸乙酯,而獲得主劑(2)~主劑(11)。 [Production of the main agent (2) to the main agent (11)] in the case of the main agent (1) In the same manner, in the ratio (g) shown in Table 1, the polyester polyol solution (1) to the polyester polyol solution (5) and the decane coupling agent shown below, and the compound reactive with the carboxyl group are blended. Ethyl acetate was added in such a manner that the nonvolatile content was 30%, and the main component (2) to the main agent (11) was obtained.
矽烷偶合劑 Decane coupling agent
KBM-403:3-縮水甘油氧基丙基三甲氧基矽烷(信越矽利光(Shin-Etsu Silicones)公司製造) KBM-403: 3-glycidoxypropyltrimethoxydecane (manufactured by Shin-Etsu Silicones)
KBM-903:3-胺基丙基三甲氧基矽烷(日本尤尼卡(Nippon Unicar)公司製造) KBM-903: 3-aminopropyltrimethoxydecane (manufactured by Nippon Unicar Co., Ltd.)
可與羧基反應的成分 a component reactive with a carboxyl group
YD-012:雙酚A型環氧樹脂(新日鐵化學公司製造) YD-012: bisphenol A type epoxy resin (manufactured by Nippon Steel Chemical Co., Ltd.)
(硬化劑的製造) (Manufacture of hardener)
硬化劑(1):將藉由乙酸乙酯稀釋甲苯二異氰酸酯的與三羥甲基丙烷的加合物而製成的固體成分為50%的樹脂溶液作為硬化劑(1)。硬化劑(1)的NCO%為8.6%。 Hardener (1): A resin solution having a solid content of 50% prepared by diluting an adduct of toluene diisocyanate with trimethylolpropane with ethyl acetate as a curing agent (1). The NCO% of the hardener (1) was 8.6%.
硬化劑(2):將藉由乙酸乙酯稀釋六亞甲基二異氰酸酯的三聚物而製成的固體成分為50%的樹脂溶液作為硬化劑(2)。硬化劑(2)的NCO%為8.6%。 Hardener (2): A resin solution having a solid content of 50% prepared by diluting a trimer of hexamethylene diisocyanate with ethyl acetate as a curing agent (2). The NCO% of the hardener (2) was 8.6%.
硬化劑(3):將混合有硬化劑(1)50重量份、硬化劑(2)50重量份的固體成分為50%的樹脂溶液作為硬化劑(3)。硬化劑(3)的NCO%為8.6%。 Hardener (3): A resin solution containing 50 parts by weight of a curing agent (1) and 50 parts by weight of a curing agent (2) and a solid content of 50% is used as a curing agent (3). The NCO% of the hardener (3) was 8.6%.
(實施例1~實施例13、比較例1~比較例4)以表2所示的比例(g)調配主劑與硬化劑後,以不揮發成分為30%的方式,添加乙酸乙酯,而獲得聚胺甲酸酯接著劑。硬化劑中的異氰酸基相對於主劑所含的羥值與酸值的合計的當量[NCO]/([OH]+[COOH]),以如下方式求出。 (Examples 1 to 13 and Comparative Examples 1 to 4) The main component and the curing agent were blended at a ratio (g) shown in Table 2, and then ethyl acetate was added so that the nonvolatile content was 30%. A polyurethane binder is obtained. The equivalent [NCO]/([OH]+[COOH]) of the isocyanate group in the hardener to the total value of the hydroxyl value and the acid value contained in the main component was determined as follows.
[NCO]/([OH]+[COOH]) [NCO]/([OH]+[COOH])
=[561×(硬化劑的NCO%)×(相對於主劑100g的硬化劑調配量(g))]/[(主劑的羥值與酸值的合計(mgKOH/g))×42×100] = [561 × (NCO% of hardener) × (hardener amount (g) with respect to 100 g of main agent)] / [(Total value of hydroxyl value and acid value of main agent (mgKOH/g)) × 42 × 100]
在厚度為40μm的鋁箔的一個面上,以塗佈量:5g/平 方米的量藉由乾式貼合機塗佈上述聚胺甲酸酯接著劑作為外層用接著劑,使溶劑揮發後,積層厚度為30μm的延伸聚醯胺膜。繼而,在所得的積層膜的鋁箔的另一個面上,以塗佈量:5g/平方米的量藉由乾式貼合機塗佈下述內層用接著劑,使溶劑揮發後,積層厚度為30μm的未延伸聚丙烯膜,然後,進行60℃、7天的硬化(老化),使外層用及內層用接著劑硬化而獲得電池用包裝材。 On one side of an aluminum foil having a thickness of 40 μm, the coating amount is 5 g/flat The amount of square meter was applied to the above-mentioned polyurethane adhesive by a dry laminator as an adhesive for the outer layer, and after evaporating the solvent, an extended polyamine film having a thickness of 30 μm was laminated. Then, on the other surface of the obtained aluminum foil of the laminated film, the following adhesive for the inner layer was applied by a dry laminator at a coating amount of 5 g/m 2 to volatilize the solvent, and the thickness of the laminate was A 30 μm unstretched polypropylene film was then cured (aging) at 60 ° C for 7 days, and the outer layer and the inner layer were cured with an adhesive to obtain a battery packaging material.
*內層用接著劑 *Beneer for the inner layer
以重量比計為主劑/硬化劑=100/10調配如下的主劑與硬化劑,並以不揮發成分為30%的方式添加甲苯製成內層用接著劑,上述主劑是在容器中加入Tuftec M1913(側鏈具有羧基的苯乙烯-乙烯-丁二烯-苯乙烯(Styrene-Ethylene-Butadiene-Styrene,SEBS)、旭化成化學(Asahi Kasei Chemicals)公司製造、苯乙烯含量為30重量%、羧基量為0.19mmol/g、每1分子中含有11.4個羧基):55份、以及作為黏著賦予劑(B)的荒川化學工業公司製造的完全氫化C9樹脂Arkon P-140(軟化點為140℃、無酸值):45份,藉由甲苯/甲基乙基酮=8/2的混合溶劑進行稀釋並在50℃ 下加熱攪拌3小時而得;上述硬化劑是藉由甲苯稀釋六亞甲基二異氰酸酯的三聚物而製成的固體成分為50%的溶液。 The main agent and the hardener are prepared by adding the following main agent/hardener=100/10 by weight ratio, and toluene is added in such a manner that the non-volatile content is 30%, and the above-mentioned main agent is in the container. Tuftec M1913 (Styrene-Ethylene-Butadiene-Styrene (SEBS), manufactured by Asahi Kasei Chemicals Co., Ltd., having a styrene content of 30% by weight, Arkon P-140, a completely hydrogenated C9 resin manufactured by Arakawa Chemical Industries Co., Ltd., which has a carboxyl group content of 0.19 mmol/g, containing 11.4 carboxyl groups per molecule): 55 parts, and a softening point of 140 ° C, which is an adhesion-imparting agent (B). , no acid value): 45 parts, diluted by a mixed solvent of toluene / methyl ethyl ketone = 8 / 2 at 50 ° C The mixture was heated and stirred for 3 hours; the hardener was a 50% solid solution prepared by diluting a trimer of hexamethylene diisocyanate with toluene.
根據下述評價法對以上述方式而得的電池用包裝材進行性能評價。 The battery packaging material obtained in the above manner was evaluated for performance according to the following evaluation method.
<耐濕熱性試驗前、後的層壓強度>將電池用包裝材切割成200mm×15mm的大小,在溫度為20℃、相對濕度為65%的環境下,使用拉伸試驗機以負荷速度為300mm/分鐘進行T模剝離試驗。以各5個試驗片的平均值表示延伸聚醯胺膜與鋁箔間的剝離強度(N/15mm寬度)(耐濕熱性試驗前的層壓強度)。 <Lamination strength before and after the heat and humidity resistance test> The battery packaging material was cut into a size of 200 mm × 15 mm, and the tensile tester was used at a load speed in an environment of a temperature of 20 ° C and a relative humidity of 65%. T die peel test was performed at 300 mm/min. The peel strength (N/15 mm width) between the stretched polyamide film and the aluminum foil (the laminate strength before the moisture resistance test) was expressed by the average value of each of the five test pieces.
另外,將電池用包裝材加入至70℃、90%RH環境的恆溫恆濕槽中,靜置168小時後,將電池用包裝材自恆溫恆濕槽取出,以與試驗前相同的方式,測定層壓強度(耐濕熱性試驗後的層壓強度)。根據各剝離強度的平均值,進行以下4個等級的評價。 In addition, the battery packaging material was placed in a constant temperature and humidity chamber at 70 ° C and 90% RH atmosphere, and after standing for 168 hours, the battery packaging material was taken out from the constant temperature and humidity chamber, and measured in the same manner as before the test. Lamination strength (lamination strength after moisture and heat resistance test). The following four levels of evaluation were performed based on the average value of each peel strength.
◎:6N/15mm以上(實用上優異) ◎: 6N/15mm or more (excellent in practical use)
○:4N/15mm以上、且小於6N/15mm(實用區域) ○: 4N/15mm or more and less than 6N/15mm (practical area)
△:2N/15mm以上、且小於4N/15mm(實用下限) △: 2N/15mm or more and less than 4N/15mm (practical lower limit)
×:小於2N/15mm ×: less than 2N/15mm
將以上結果一併表示於表2。 The above results are shown together in Table 2.
<成型性評價法>將電池用包裝材切割成80mm×80mm的大小,並作為空白樣品(被成型材、原材料)。對上述空白樣品,藉由成型高度可自由變動的直型模具(straight mold)進行突出1段成型,藉由未產生鋁箔的斷裂、或各層間的隆起及最大 的成型高度評價成型性。另外,所使用的模具的打孔機形狀為一條邊為30mm的正方形、角隅R為2mm、打孔機肩R為1mm、模肩R:1mm。根據成型的高度,進行以下4個等級的評價。 <Formability Evaluation Method> The battery packaging material was cut into a size of 80 mm × 80 mm, and used as a blank sample (formed material, raw material). For the above blank sample, a one-stage molding is performed by a straight mold having a freely variable molding height, by which no fracture of the aluminum foil occurs, or ridges between the layers and the maximum The molding height is evaluated for moldability. Further, the shape of the punch used for the mold was a square having a side of 30 mm, a corner 隅R of 2 mm, a punching shoulder R of 1 mm, and a shoulder R of 1 mm. Based on the height of the molding, the following four grades were evaluated.
◎:6mm以上(實用上優異) ◎: 6mm or more (excellent in practical use)
○:4mm以上、且小於6mm(實用區域) ○: 4 mm or more and less than 6 mm (practical area)
△:2mm以上、且小於4mm(實用下限) △: 2 mm or more and less than 4 mm (practical lower limit)
×:小於2mm ×: less than 2mm
將以上結果一併表示於表2。 The above results are shown together in Table 2.
<成型物的耐久性>將電池用包裝材切割成80mm×80mm的大小,並作為空白樣品(被成型材、原材料)。對上述空白樣品,藉由成型高度可自由變動的直型模具以成型高度為3mm進行突出1階段成型。繼而,將經成型的電池用容器加入至70℃、90%RH環境下的恆溫恆濕槽中,靜置168小時。自恆溫恆濕槽取出電池用容器,確認電池用容器的外觀,評價是否產生隆起。另外,所使用的模具的打孔機形狀為一條邊為30mm的正方形、角隅R為2mm、打孔機肩R為1mm、模肩R:1mm。 <Durability of Molded Article> The battery packaging material was cut into a size of 80 mm × 80 mm, and used as a blank sample (formed material, raw material). For the blank sample described above, a one-stage molding was performed by a straight mold having a freely variable molding height at a molding height of 3 mm. Then, the formed battery container was placed in a constant temperature and humidity chamber at 70 ° C and 90% RH, and allowed to stand for 168 hours. The battery container was taken out from the constant temperature and humidity chamber, and the appearance of the battery container was confirmed, and whether or not bulging occurred was evaluated. Further, the shape of the punch used for the mold was a square having a side of 30 mm, a corner 隅R of 2 mm, a punching shoulder R of 1 mm, and a shoulder R of 1 mm.
○:無隆起 ○: no uplift
×:產生隆起 ×: Create a bulge
將以上結果一併表示於表2。 The above results are shown together in Table 2.
根據表2的結果可知,藉由使用相對於包含多元醇成分(A)及矽烷偶合劑(B)的主劑中的源自多元醇成分(A)的羥基與羧基的合計,而在上述硬化劑中所含的異氰酸基的當量比為10~30的範圍內調配聚異氰酸酯硬化劑而成的電池用包裝材用聚胺甲酸酯接著劑,而可提供耐濕熱性試驗前、後的層壓強度、成型性優異的電池用包裝材,上述多元醇成分(A)含有玻璃轉移溫度為40℃以上的聚酯多元醇(A1)5重量%~50重量%及玻璃轉移溫度小於40℃的聚酯多元醇(A2)95重量%~50重量%。另外亦可知,由使用上述電池用包裝材用聚胺甲酸酯接著劑的電池用包裝材可形成耐久性優異的成型物。 According to the results of Table 2, it is understood that the above hardening is carried out by using the total of the hydroxyl group and the carboxyl group derived from the polyol component (A) in the main component containing the polyol component (A) and the decane coupling agent (B). The polyurethane adhesive for battery packaging materials prepared by blending a polyisocyanate curing agent in an equivalent ratio of isocyanate groups in the range of 10 to 30, and providing a heat and humidity resistance test before and after The battery packaging material having excellent lamination strength and moldability, the polyol component (A) containing 5% by weight to 50% by weight of the polyester polyol (A1) having a glass transition temperature of 40 ° C or higher and a glass transition temperature of less than 40 The polyester polyol (A2) at °C is 95% by weight to 50% by weight. In addition, it is also known that a battery packaging material using the polyurethane adhesive for a battery packaging material described above can form a molded article having excellent durability.
比較例1在耐濕熱性試驗前、後的層壓強度的方面並不遜於實施例,但相對於主劑中的源自多元醇成分(A)的羥基與羧基的合計,在上述硬化劑中包含聚異氰酸酯硬化劑時的異氰酸基的當量比過小,因此成型性差,成型物的耐久性亦差。另外,比較例3中,相對於主劑中的源自多元醇成分(A)的羥基與羧基的合計,在上述硬化劑中包含聚異氰酸酯硬化劑時的異氰酸基的當量比即便恰當,聚酯多元醇(A1)、聚酯多元醇(A2)的組成比亦不恰當,因此成型物的耐久性差。 Comparative Example 1 is not inferior to the examples in terms of the lamination strength before and after the moisture heat resistance test, but is in the above hardener with respect to the total of the hydroxyl group and the carboxyl group derived from the polyol component (A) in the main component. When the polyisocyanate curing agent is contained, the equivalent ratio of the isocyanate groups is too small, so the moldability is poor, and the durability of the molded article is also poor. In addition, in Comparative Example 3, the equivalent ratio of the isocyanate group in the case where the polyisocyanate curing agent is contained in the curing agent is appropriate, in the total amount of the hydroxyl group and the carboxyl group derived from the polyol component (A) in the main component. The composition ratio of the polyester polyol (A1) and the polyester polyol (A2) is also inappropriate, and thus the durability of the molded article is poor.
[產業上之可利用性] [Industrial availability]
本發明的聚胺甲酸酯接著劑可廣泛地用作用以形成電池用容器或電池用包裝的接著劑。特別是適合作為用以形成鋰離子電池、鋰離子聚合物電池、鉛蓄電池、鹼電池、氧化銀-鋅蓄電 池、金屬空氣電池、多價陽離子電池、電容器(condenser)、電容(capacitor)等二次電池用的電池用容器或電池用包裝的接著劑。本發明的聚胺甲酸酯接著劑是用於將相同或不同原材料的被黏接體接合者,例如可較佳地用於塑膠系原材料與金屬系原材料的多層積層體的接合。當然,亦適於塑膠系原材料彼此的接合、金屬系原材料彼此的接合。使用本發明的接著劑而得的積層物的成型性優異、環境耐性高、在室外暴露的條件下亦可抑制經時的接著強度的降低、長期的強接著強度優異、外觀形狀亦優異。因此,亦可用作泡殼包裝(Press Through Package,PTP)或鋼板等需要成型性的積層物、或防護壁材、屋頂材、太陽電池面板材、窗材、室外地板材、照明保護材、汽車構件等建造物等室外產業用途積層物用的接著劑。 The polyurethane adhesive of the present invention can be widely used as an adhesive for forming a battery container or a battery package. Especially suitable for forming lithium ion batteries, lithium ion polymer batteries, lead storage batteries, alkaline batteries, silver oxide-zinc storage A battery container for a secondary battery such as a pool, a metal air battery, a polyvalent cation battery, a condenser, or a capacitor, or an adhesive for a battery package. The polyurethane adhesive of the present invention is used for bonding a bonded body of the same or different raw materials, and for example, can be preferably used for joining a multilayered laminate of a plastic-based raw material and a metal-based raw material. Of course, it is also suitable for joining of plastic-based raw materials and joining of metal-based raw materials. The laminate obtained by using the adhesive of the present invention is excellent in moldability, high in environmental resistance, and can suppress deterioration of the adhesive strength over time, excellent long-term strong bonding strength, and excellent appearance shape even under outdoor exposure conditions. Therefore, it can also be used as a laminate of a need for formability such as a press through package (PTP) or a steel plate, or a protective wall material, a roofing material, a solar cell panel, a window material, an outdoor floor panel, a lighting protection material, An adhesive for laminates for outdoor industrial applications such as construction materials such as automobile components.
該申請案主張以2012年11月1日申請的日本專利申請案特願2012-242154為基礎的優先權,並將其揭示的全部內容併入本文中。 The priority of the Japanese Patent Application No. 2012-242154, filed on Nov. 1, 2012, is hereby incorporated by reference.
(11)‧‧‧外層側樹脂膜層 (11) ‧‧‧ outer layer resin film
(12)‧‧‧外層側接著劑層 (12) ‧‧‧Outer side adhesive layer
(13)‧‧‧金屬箔層 (13)‧‧‧metal foil layer
(14)‧‧‧內層側接著劑層 (14) ‧‧‧Inner layer of adhesive layer
(15)‧‧‧內面層 (15) ‧ ‧ inner layer
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2012
- 2012-11-01 JP JP2012242154A patent/JP5267718B1/en active Active
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2013
- 2013-10-31 CN CN201380003598.3A patent/CN103975035B/en active Active
- 2013-10-31 KR KR1020147009623A patent/KR101475456B1/en active IP Right Grant
- 2013-10-31 WO PCT/JP2013/006460 patent/WO2014068986A1/en active Application Filing
- 2013-11-01 TW TW102139675A patent/TWI600736B/en active
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TWI553950B (en) * | 2014-09-17 | 2016-10-11 | 迪愛生股份有限公司 | Adhesive for the laminating, the laminate using it and rechargeable battery |
TWI759309B (en) * | 2016-06-24 | 2022-04-01 | 日商昭和電工包裝股份有限公司 | Exterior material for power storage device, method for producing the same, and power storage device |
Also Published As
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CN103975035B (en) | 2016-04-06 |
JP5267718B1 (en) | 2013-08-21 |
JP2014091770A (en) | 2014-05-19 |
KR20140084030A (en) | 2014-07-04 |
TWI600736B (en) | 2017-10-01 |
WO2014068986A1 (en) | 2014-05-08 |
KR101475456B1 (en) | 2014-12-22 |
CN103975035A (en) | 2014-08-06 |
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