CN103975035A - Polyurethane adhesive for packaging materials for batteries, packaging material for batteries, battery container, and battery - Google Patents
Polyurethane adhesive for packaging materials for batteries, packaging material for batteries, battery container, and battery Download PDFInfo
- Publication number
- CN103975035A CN103975035A CN201380003598.3A CN201380003598A CN103975035A CN 103975035 A CN103975035 A CN 103975035A CN 201380003598 A CN201380003598 A CN 201380003598A CN 103975035 A CN103975035 A CN 103975035A
- Authority
- CN
- China
- Prior art keywords
- battery
- packing material
- layer
- solid
- use packing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000005022 packaging material Substances 0.000 title abstract 5
- 239000000853 adhesive Substances 0.000 title abstract 4
- 230000001070 adhesive effect Effects 0.000 title abstract 4
- 239000004814 polyurethane Substances 0.000 title abstract 2
- 229920002635 polyurethane Polymers 0.000 title abstract 2
- 239000000463 material Substances 0.000 claims abstract description 80
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 76
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 34
- 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 24
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 21
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 21
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 13
- 239000010410 layer Substances 0.000 claims description 123
- 239000007787 solid Substances 0.000 claims description 65
- 238000012856 packing Methods 0.000 claims description 50
- 229920000768 polyamine Polymers 0.000 claims description 40
- 239000003351 stiffener Substances 0.000 claims description 40
- -1 glycidyl compound Chemical class 0.000 claims description 34
- 229910052751 metal Inorganic materials 0.000 claims description 27
- 239000002184 metal Substances 0.000 claims description 27
- 239000011521 glass Substances 0.000 claims description 25
- 239000000376 reactant Substances 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 24
- 239000002344 surface layer Substances 0.000 claims description 24
- 238000003475 lamination Methods 0.000 claims description 23
- 239000011888 foil Substances 0.000 claims description 22
- 229920005989 resin Polymers 0.000 claims description 22
- 239000011347 resin Substances 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 238000000465 moulding Methods 0.000 claims description 10
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 8
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 5
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 claims description 3
- 229930185605 Bisphenol Natural products 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229920000098 polyolefin Polymers 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 2
- 210000004379 membrane Anatomy 0.000 claims 1
- 210000000713 mesentery Anatomy 0.000 claims 1
- 229920006267 polyester film Polymers 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 17
- 238000012360 testing method Methods 0.000 abstract description 15
- 230000015572 biosynthetic process Effects 0.000 abstract description 10
- 229920005862 polyol Polymers 0.000 abstract description 8
- 150000003077 polyols Chemical class 0.000 abstract description 7
- 230000007774 longterm Effects 0.000 abstract description 4
- 230000009477 glass transition Effects 0.000 abstract 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 29
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 28
- 229910052757 nitrogen Inorganic materials 0.000 description 26
- 239000002253 acid Substances 0.000 description 23
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 22
- 239000003822 epoxy resin Substances 0.000 description 20
- 229920000647 polyepoxide Polymers 0.000 description 20
- 239000000243 solution Substances 0.000 description 20
- 230000001476 alcoholic effect Effects 0.000 description 12
- 239000008151 electrolyte solution Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000005030 aluminium foil Substances 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 9
- 230000032050 esterification Effects 0.000 description 9
- 238000005886 esterification reaction Methods 0.000 description 9
- 238000004519 manufacturing process Methods 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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000011229 interlayer Substances 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 230000032683 aging Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 239000012948 isocyanate Substances 0.000 description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 5
- 230000006837 decompression Effects 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000012793 heat-sealing layer Substances 0.000 description 5
- 150000002513 isocyanates Chemical class 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 229920000570 polyether Polymers 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 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 5
- 238000005809 transesterification reaction Methods 0.000 description 5
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 208000034189 Sclerosis Diseases 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
- 239000004205 dimethyl polysiloxane Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 4
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- 229960003742 phenol Drugs 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
- 238000010079 rubber tapping Methods 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 150000005846 sugar alcohols Polymers 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 229940106691 bisphenol a Drugs 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 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
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- 239000013638 trimer Substances 0.000 description 3
- 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 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-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
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- AYDQIZKZTQHYIY-UHFFFAOYSA-N OC(=O)C1(C)CC(C(O)=O)=CC=C1 Chemical compound OC(=O)C1(C)CC(C(O)=O)=CC=C1 AYDQIZKZTQHYIY-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 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
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000004568 cement Substances 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
- 239000013530 defoamer Substances 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-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
- 239000003292 glue Substances 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 239000005011 phenolic resin Substances 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
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000012545 processing 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
- 238000004381 surface treatment Methods 0.000 description 2
- 150000003512 tertiary amines Chemical class 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
- 239000002966 varnish Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- SHMHWONONAVWBU-ODZAUARKSA-N (z)-but-2-enedioic acid;tin Chemical compound [Sn].OC(=O)\C=C/C(O)=O SHMHWONONAVWBU-ODZAUARKSA-N 0.000 description 1
- YEBXJRBNPTUQKG-UHFFFAOYSA-N 1,1'-biphenyl;4,5-dihydro-1,3-oxazole Chemical compound C1CN=CO1.C1=CC=CC=C1C1=CC=CC=C1 YEBXJRBNPTUQKG-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-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
- 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 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
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 1
- ZEMPKEQAKRGZGQ-AAKVHIHISA-N 2,3-bis[[(z)-12-hydroxyoctadec-9-enoyl]oxy]propyl (z)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CC(O)CCCCCC)COC(=O)CCCCCCC\C=C/CC(O)CCCCCC ZEMPKEQAKRGZGQ-AAKVHIHISA-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
- ZPSNFVVCGMSWID-UHFFFAOYSA-N 2-isocyanatopropan-2-ylbenzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1 ZPSNFVVCGMSWID-UHFFFAOYSA-N 0.000 description 1
- GUXJXWKCUUWCLX-UHFFFAOYSA-N 2-methyl-2-oxazoline Chemical compound CC1=NCCO1 GUXJXWKCUUWCLX-UHFFFAOYSA-N 0.000 description 1
- ZXTHWIZHGLNEPG-UHFFFAOYSA-N 2-phenyl-4,5-dihydro-1,3-oxazole Chemical compound O1CCN=C1C1=CC=CC=C1 ZXTHWIZHGLNEPG-UHFFFAOYSA-N 0.000 description 1
- PZOJXKYWPGPWQC-UHFFFAOYSA-N 2h-1,3,5-oxadiazine Chemical class C1OC=NC=N1 PZOJXKYWPGPWQC-UHFFFAOYSA-N 0.000 description 1
- JRBJSXQPQWSCCF-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine Chemical compound C1=C(N)C(OC)=CC(C=2C=C(OC)C(N)=CC=2)=C1 JRBJSXQPQWSCCF-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- PGCBRGRKKOCPAN-UHFFFAOYSA-N 4-triethoxysilylbutanamide Chemical compound CCO[Si](OCC)(OCC)CCCC(N)=O PGCBRGRKKOCPAN-UHFFFAOYSA-N 0.000 description 1
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 1
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- ODYFMMXCYGDDCM-UHFFFAOYSA-N C1(=CC=CC=C1)C.C(CCCCCN=C=O)N=C=O Chemical compound C1(=CC=CC=C1)C.C(CCCCCN=C=O)N=C=O ODYFMMXCYGDDCM-UHFFFAOYSA-N 0.000 description 1
- GFXHFYHUJAATBP-UHFFFAOYSA-N CO[Si](OC)(OC)CCCC(N)=O Chemical compound CO[Si](OC)(OC)CCCC(N)=O GFXHFYHUJAATBP-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- UQBRAHLFLCMLBA-UHFFFAOYSA-N N=C=O.N=C=O.CC1=CC=CC(C)=C1 Chemical compound N=C=O.N=C=O.CC1=CC=CC(C)=C1 UQBRAHLFLCMLBA-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- JJLKTTCRRLHVGL-UHFFFAOYSA-L [acetyloxy(dibutyl)stannyl] acetate Chemical compound CC([O-])=O.CC([O-])=O.CCCC[Sn+2]CCCC JJLKTTCRRLHVGL-UHFFFAOYSA-L 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 229920006272 aromatic hydrocarbon resin Polymers 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- PQVXXMYLCJGDSU-UHFFFAOYSA-N benzene-1,2,3-triol ethane Chemical compound CC.OC=1C(=C(C=CC1)O)O PQVXXMYLCJGDSU-UHFFFAOYSA-N 0.000 description 1
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- NEPKLUNSRVEBIX-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,4-dicarboxylate Chemical compound C=1C=C(C(=O)OCC2OC2)C=CC=1C(=O)OCC1CO1 NEPKLUNSRVEBIX-UHFFFAOYSA-N 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 229940043232 butyl acetate Drugs 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000000853 cresyl group Chemical class C1(=CC=C(C=C1)C)* 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- BRWZYZWZBMGMMG-UHFFFAOYSA-J dodecanoate tin(4+) Chemical class [Sn+4].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O BRWZYZWZBMGMMG-UHFFFAOYSA-J 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 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 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 235000013847 iso-butane Nutrition 0.000 description 1
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- CVKMFSAVYPAZTQ-UHFFFAOYSA-N methylhexanoic acid Natural products CCCCC(C)C(O)=O CVKMFSAVYPAZTQ-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- HRRDCWDFRIJIQZ-UHFFFAOYSA-N naphthalene-1,8-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=CC2=C1 HRRDCWDFRIJIQZ-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- BSWGGJHLVUUXTL-UHFFFAOYSA-N silver zinc Chemical compound [Zn].[Ag] BSWGGJHLVUUXTL-UHFFFAOYSA-N 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- 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
- H01M50/121—Organic material
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/095—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyurethanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B1/00—Layered products having a non-planar shape
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- 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
Provided is an adhesive which enables the formation of a packaging material for batteries, said packaging material having excellent moldability and high adhesive strength even after long-term endurance test. A polyurethane adhesive for packaging materials for batteries according to the present invention contains a base material and a polyisocyanate curing agent. The base material contains: (A) a polyol component that contains (A1) a polyester polyol having a glass transition temperature of 40 DEG C or more and (A2) a polyester polyol having a glass transition temperature less than 40 DEG C at a specific composition ratio; and (B) a silane coupling agent. The equivalent ratio of the isocyanate groups contained in the curing agent relative to the total of the hydroxyl groups and carboxyl groups derived from the polyol component (A), namely [NCO]/([OH] + [COOH]) is set to be 10-30.
Description
Technical field
The present invention relates to a kind of in order to form the polyamine manthanoate solid for battery use packing material of container or battery package for battery.In addition, the present invention relates to a kind ofly use above-mentioned battery use packing material with polyamine manthanoate solid and the battery use packing material of lamination.And, the present invention relates to a kind of battery that above-mentioned battery use packing material moulding is formed with container and there is the battery of container for above-mentioned battery.
Background technology
Due to the development rapidly of the electronicss such as mobil phone, portable computer, and the demand of light weight and small-sized secondary cells such as lithium ion battery increases.As the exterior body of secondary cell, use metal tank processed, but with regard to lightweight or productive viewpoint, the wrapping material of lamination plastic film or tinsel etc. become main flow gradually before.As the most easy wrapping material, can enumerate: the laminate of lamination outer layer side resin film layer (11), outer layer side adhesion agent layer (12), metal foil layer (13), internal layer side adhesion agent layer (14) and the internal surface layer (15) that comprises heat sealing layer etc. sequentially from outer layer side as shown in Figure 1.As battery container, for example as shown in Figure 2 as, have with outer layer side resin film layer (11) and form mode that convex surface, internal surface layer (15) form concave surface by wrapping material moulding (drawing and forming processing, outstanding forming process etc.) person.By enclosing electrode or electrolytic solution etc. and wrapping material are sealed by the concave side of container at battery, and manufacture battery.
As battery use packing material, disclose: outer layer side lamination heat-resistant resin extend rete, internal layer side lamination thermoplastic resin do not extend rete, lamination aluminium foil layer forms between described two films battery with container with in wrapping material, by extending at thermoplastic resin between rete and aluminium foil layer, do not use specific adhesion agent layer to follow, and the wrapping material for cell box (patent documentation 1) of formability excellence can be provided.
In addition, as battery use packing material, disclose: the battery exterior body of laminated base material layer and aluminium foil layer and hot adherence resin layer at least sequentially, and the ring stiffness (100p stiffness) with specified range, used thickness is that the more than 80 μ m aluminium through anneal is as aluminium foil layer, and the exterior material of acquisition formability excellence can provide by above-mentioned exterior material the lithium ion battery (patent documentation 2) of having guaranteed safety performance.
In addition, as in order to pack the laminate formation solid of the non-food products such as shampoo, disclose: contain and comprise the solid (patent documentation 3) that glass tansition temperature is the mixture of 40 ℃ of above organic polyhydric alcohol 5 % by weight～50 % by weight and glass tansition temperature organic polyhydric alcohol (wherein, not having carboxyl in its molecule) 95 % by weight～50 % by weight that are less than 40 ℃.
Prior art document
Patent documentation
Patent documentation 1: Japanese Patent Laid-Open 2010-92703 communique
Patent documentation 2: Japanese Patent Laid-Open 2008-251342 communique
Patent documentation 3: Japanese Patent Laid-Open 2001-322221 communique
Summary of the invention
The problem that invention wish solves
In recent years, along with the purposes such as vehicle-mounted or family's electric power storage expand, and require the high capacity of secondary cell, and battery use packing material is required to the formedness of formability.In addition, secondary cell vehicle-mounted or family's electric power storage purposes is arranged at outdoor, and requires long-term durable years, and the Bonding strength of interlayer that requires each plastic film of wrapping material or tinsel etc. after long-term long duration test also high and outward appearance also without extremely.
The present invention forms in view of above-mentioned background, problem be to provide a kind ofly there is excellent formability, the also excellent battery of high, aesthetic appearance of Bonding strength of interlayer after long durability test, battery container, polyamine manthanoate solid for battery use packing material and battery use packing material.
Solve the means that problem adopts
The present invention forms in view of above-mentioned problem, relate to a kind of solid, it uses the polyhydroxy reactant (A) that comprises the different polyester polyol of glass tansition temperature (A1), polyester polyol (A2) with specified proportion, as in order to form the hydroxyl composition of polyamine manthanoate, and contain the reactive functional group with respect to above-mentioned polyhydroxy reactant (A), and quite excessive isocyanate prepolymer composition is as stiffening agent.
, the invention relates to polyamine manthanoate solid for a kind of battery use packing material, it contains host and polymeric polyisocyanate stiffening agent, and it is characterized in that: above-mentioned host contains polyhydroxy reactant (A) and silane coupling agent (B), it is polyester polyol (A2) 95 % by weight～50 % by weight that 40 ℃ of above polyester polyol (A1) 5 % by weight～50 % by weight and glass tansition temperature are less than 40 ℃ that above-mentioned polyhydroxy reactant (A) comprises glass tansition temperature, isocyanato contained in above-mentioned polymeric polyisocyanate stiffening agent is 10～30 with respect to equivalence ratio [NCO]/([OH]+[COOH]) that is derived from the hydroxyl of above-mentioned polyhydroxy reactant (A) and the total of carboxyl.
Battery use packing material of the present invention with polyamine manthanoate solid be preferably further contain can with the compound (C) of carboxyl reaction.
In addition, the invention relates to a kind of battery use packing material, its sequentially lamination outer layer side resin film layer (11), outer layer side adhesion agent layer (12), metal foil layer (13), internal layer side adhesion agent layer (14) and internal surface layer (15) form, above-mentioned outer layer side adhesion agent layer (12) is formed with polyamine manthanoate solid by above-mentioned battery use packing material.
And, the invention relates to a kind of battery container, it is formed by above-mentioned battery use packing material moulding, and outer layer side resin film layer (11) forms convex surface, internal surface layer (15) formation concave surface.
And, the invention relates to a kind of battery, it uses above-mentioned battery to form with container.
The effect of invention
According to the present invention, have can provide there is excellent formability, the Bonding strength battery that also high, aesthetic appearance is excellent, the excellent effect of container, battery use packing material and battery use packing material use polyamine manthanoate solid battery for of interlayer after long durability test.In the battery use packing material that sequentially lamination outer layer side resin film layer (11), outer layer side adhesion agent layer (12), metal foil layer (13), internal layer side adhesion agent layer (14), internal surface layer (15) form, in order to form outer layer side adhesion agent layer, the polyamine manthanoate solid of the application of the invention, and can provide the Bonding strength of interlayer excellent, film does not produce also excellent battery use packing material of above-mentioned performance after protuberance and endurance test without fracture, forming part during moulding.By the battery container that uses above-mentioned battery use packing material to form, and can provide the battery of reliability excellence.
Accompanying drawing explanation
[Fig. 1] means the schematic cross sectional view of a form of battery use packing material of the present invention.
[Fig. 2] means the schematic perspective view of a form of container for battery of the present invention.
Embodiment
Below, example of the present invention is described in detail.In addition, in this specification sheets, the record of " count arbitrarily A～count arbitrarily B " is Index A and the scope that is greater than several A, and number B and be less than the scope of several B.
Polyamine manthanoate solid of the present invention is used to form to obtain the battery use packing material of container for battery.Fig. 1 represents the schematic cross sectional view of a form of battery use packing material of the present invention, and Fig. 2 represents the schematic perspective view of a form of container for battery of the present invention.Battery is not particularly limited by the shape of container, except as shown in Figure 2 hypocraterimorphous, and can illustration: tubular (cylinder, square tube, cylindroid etc.).Those battery containers are the battery use packing material of flat form is carried out to forming process and obtain.Battery is internal surface layer (15) with the inner side of container, the face that contacts with electrolytic solution.As the preferably example of internal surface layer (15), can enumerate heat sealing layer.By using heat sealing layer, and make the internal surface layer (15) of flange part, with the internal surface layer (15) of other formation battery use packing material or other battery by internal surface layer (15) subtend of the flange part of container, contact, and heat, can make by this internal surface layer (15) fuse each other, and enclose electrolytic solution.
Battery possesses tinsel (13) with container.At battery, with in container, the tinsel (13) of conventionally take is boundary, and the side near electrolytic solution is called to " inner side ", the layer of inner side is called to " internal layer ", the side away from electrolytic solution is called to " outside ", the layer in outside is called to " skin ".Therefore, forming battery with in the predetermined battery use packing material of container, also the tinsel (13) of take is boundary, and the predetermined side being positioned near electrolytic solution place is called to " inner side ", the layer of inner side is called to " internal layer ", the predetermined side being positioned at away from electrolytic solution place is called to " outside ", the layer in outside is called to " skin ".Polyamine manthanoate of the present invention is that solid is suitable as the purposes with metal foil layer (13) lamination (laminating) by outer layer side resin film layer (11).
Polyamine manthanoate of the present invention is that solid is to use host and stiffening agent.Can be the so-called 2 liquid mixed type solids that in use host mixed with stiffening agent, also can be the 1 liquid type solid that is pre-mixed host and stiffening agent.And, also can be the type of mixing in use multiple host and/or multiple stiffening agent.
Polyamine manthanoate of the present invention is that solid contains polyhydroxy reactant (A) and silane coupling agent (B).It is polyester polyol (A2) 95 % by weight～50 % by weight that 40 ℃ of above polyester polyol (A1) 5 % by weight～50 % by weight and glass tansition temperature are less than 40 ℃ that polyhydroxy reactant (A) comprises glass tansition temperature.Polyhydroxy reactant (A) can further comprise polyester polyol (A1), polyester polyol (A2) polyvalent alcohol in addition in the scope that meets object of the present invention, effect.
As glass tansition temperature, be 40 ℃ of above polyester polyols (A1), and the glass tansition temperature polyester polyol (A2) that is less than 40 ℃, for example make: m-phthalic acid, terephthalic acid, naphthalic acid, Tetra hydro Phthalic anhydride, hexanodioic acid, nonane diacid, sebacic acid, succsinic acid, pentanedioic acid, Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, MALEIC ANHYDRIDE, independent or the mixture of itaconic anhydride and ester cpds etc. thereof (gather above and be called polyprotonic acid composition), with for example ethylene glycol, Diethylene Glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1, 6-hexylene glycol, neopentyl glycol, 1, 4-butyleneglycol, 1, 4-cyclohexanedimethanol, TriMethylolPropane(TMP), glycerine, 1, 9-nonanediol, 3-methyl isophthalic acid, 5-pentanediol, polyether glycol, polycarbonate polyol, polyolefin polyhydric alcohol, acrylic acid series multiple alcohol, polyamine manthanoate polyvalent alcohol etc. (gather above and be called polyhydroxy reactant) separately or mixture reaction and obtaining.
In addition, preferably example as polyester polyol (A1), polyester polyol (A2), can illustration polyesteramine manthanoate polyvalent alcohol, it is above-mentioned polyprotonic acid composition is reacted with above-mentioned polyhydroxy reactant and obtain polyester polyol, and make the polyester polyol of gained and for example 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, Xylene Diisocyanate, diphenylmethanediisocyanate, isophorone diisocyanate, 1, the polymeric polyisocyanates such as 5-naphthalene diisocyanate, hexamethylene diisocyanate, hydrogenated diphenyl methane diisocyanate react and obtain.
In addition, preferably example as polyester polyol (A1), polyester polyol (A2), in can illustration molecule, (intramolecule or molecular end) has the polyester polyol of carboxyl, it is to make above-mentioned polyprotonic acid composition react with above-mentioned polyhydroxy reactant and obtain polyester polyol, and the polyester polyol that makes gained and polyprotonic acids such as phthalic acid, trimellitic acid, Pyromellitic Acid and those anhydride reaction and obtain.
In the contained polyhydroxy reactant of host (A), by glass tansition temperature, be that 40 ℃ of above polyester polyols (A1) are made as 5 % by weight～50 % by weight, are preferably 10 % by weight～40 % by weight, the polyester polyol (A2) that glass tansition temperature is less than to 40 ℃ is made as 95 % by weight～50 % by weight, is preferably 90 % by weight～60 % by weight, can improve by this Bonding strength of the interlayer of outer layer side resin film layer (11) and metal foil layer (13), and obtain the battery use packing material of good forming ability.By 40 ℃ of above polyester polyols (A1) are made as 5 % by weight above, glass tansition temperature be less than to the polyester polyol (A2) of 40 ℃ be made as below 95 % by weight, and can obtain sufficient formability.In addition, by 40 ℃ of above polyester polyols (A1) are made as 50 % by weight following, glass tansition temperature is less than more than the polyester polyol (A2) of 40 ℃ is made as 50 % by weight, and can obtain fully the Bonding strength of outer layer side resin film layer (11) and the interlayer of metal foil layer (13).
The molecular weight of the polyester polyol (A2) that the polyester polyols (A1) more than being 40 ℃ as glass tansition temperature and glass tansition temperature are less than 40 ℃, particularly number average molecular weight is preferably 5,000～100,000, be more preferred from 10,000～50,000.When industrial production battery use packing material, rectangular state person is coiled into web-like.And, for the adhesion agent layer that makes to coil in the laminate of web-like is hardened fully, and in being maintained the warehouse of high temperature aging a couple of days.If the number average molecular weight of polyester polyol (A1), polyester polyol (A2) is less than 5,000, the aging front cohesive force in sclerosis adhesion agent layer is midway low, therefore has to produce to batch the abnormal worries of processing such as bad order that occur slip or protuberance in state., if the number average molecular weight of polyester polyol (A1), polyester polyol (A2) surpasses 100,000, there is solvability in diluting solvent shortages that become separately-aspect, and viscosity during solid coating uprises, and the become worry of shortage of screening characteristics.
The mensuration of the glass tansition temperature of polyester polyol (A1), polyester polyol (A2) is that the differential scanning calorimeter (Differential ScanningCalorimeter, DSC) " RDC220 " that uses Seiko electronics (Seiko Instruments) company to manufacture carries out.The polyester polyol (A1), the polyester polyol (A2) that measure respectively about 10mg are put into aluminum pot, and are arranged in DSC device by cooled with liquid nitrogen after-100 ℃, according to the DSC chart obtaining that heats up with 10 ℃/min, calculate glass tansition temperature.When polyester polyol (A1), polyester polyol (A2) are dissolved in solvent, solvent distillation is removed after being dried and carried out DSC mensuration.
The number average molecular weight of polyester polyol (A1) and polyester polyol (A2) is by the value of the polystyrene conversion of gel permeation chromatography (Gel Permeation Chromatography, GPC).For example the temperature of tubing string (KF-805L, KF-803L and KF-802 that Zhao He electrician company manufactures) is made as to 40 ℃, use tetrahydrofuran (THF) (Tetrahydrofuran, THF) as eluat, flow velocity is made as to 0.2mL/min, detection is made as to RI, sample solution concentration is made as to 0.02%, uses polystyrene to carry out as standard test specimen.Number average molecular weight of the present invention is recorded the value of measuring by aforesaid method.
As the contained polyhydroxy reactant of host (A), can and be also the polyvalent alcohol in addition of polyester polyol (A2) that 40 ℃ of above polyester polyols (A1) and glass tansition temperature are less than 40 ℃ with glass tansition temperature.Such as enumerating: the low molecular polylols such as ethylene glycol or TriMethylolPropane(TMP) and polyether glycol, polycarbonate polyol, polyolefin polyhydric alcohol, acrylic acid series multiple alcohol or by those separately or and with two or more, react with organic isocyanate and must polyamine manthanoate polyvalent alcohol etc., can Bonding strength or formability not caused in dysgenic degree and used.
With regard to improving metals such as tinsels, be with regard to the viewpoint of raw-material Bonding strength, polyamine manthanoate solid of the present invention comprises silane coupling agent (B).As silane coupling agent (B), such as enumerating: vinyltrimethoxy silane, vinyltriethoxysilane etc. has the trialkoxy silane of vinyl; 3-aminocarbonyl propyl triethoxyl silane, N-(2-amido ethyl) 3-aminocarbonyl propyl Trimethoxy silane etc. have the trialkoxy silane of amido; 3-glycidoxypropyltrimewasxysilane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 3-glycidoxypropyl triethoxyl silane etc. have the trialkoxy silane of glycidyl.Those can be used alone respectively, or at random combine two or more and use.With respect to solids component 100 weight parts of polyhydroxy reactant (A), the addition of silane coupling agent (B) is preferably 0.1 weight part～5 weight part, is more preferred from 0.5 weight part～3 weight part.When the addition of silane coupling agent (B) is less than 0.1 weight part, lack the raising of the Bonding strength to the tinsel effect causing because adding silane coupling agent, even if more than adding 5 weight parts, also cannot expect to have again the raising of its above performance.
In order to maintain the Bonding strength after endurance test or more effectively to suppress the bad order that the protuberance because of film causes, polyamine manthanoate solid of the present invention can enter-walk to use can with the compound (C) of carboxyl reaction.Can be contained in host with the compound (C) of carboxyl reaction, also can be contained in stiffening agent, also can when host is mixed with stiffening agent, add in addition.As can with the compound (C) of carboxyl reaction, be preferably and in molecule, there is the compound of glycidyl or there is the compound of carbon imide base or there is the compound of oxazoline group.By use can with the compound (C) of carboxyl reaction, and decompose and the carboxylic acid reaction of generation with the ester bond in adhesion agent layer in long durability test, thereby can suppress to reduce because of the molecular weight of adhesion agent layer the cohesive force reduction causing, and suppress the reduction of Bonding strength or the generation of bad order.
As the compound in molecule with glycidyl, can enumerate: bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, brominated bisphenol a type epoxy resin, bisphenol-A epoxy resin, united phenol-type epoxy resin, di-toluene phenol-type epoxy resin, phenol novolak type epoxy resin, cresols phenolic resin varnish type epoxy resin, bromination phenol novolak type epoxy resin, the phenolic resin varnish type epoxy resin of dihydroxyphenyl propane, trihydroxybenzene methylmethane type epoxy resin, four phenolic group ethane type epoxy resin, the phenol novolak type epoxy resin that contains naphthalene skeleton, the glycidyl ether compounds such as phenol novolak type epoxy resin that contain Dicyclopentadiene (DCPD) skeleton, the epihydric alcohol ester compounds such as terephthalic acid diglycidyl ester, the alicyclic epoxy resins such as EHPE-3150 that Daicel chemical industry (DAICEL CHEMICAL INDUSTRIES) company manufactures, the hetero ring type epoxy resin such as triglycidylisocyanurates, N, N, N ', the Racemic glycidol amines such as N '-four glycidyl group m-xylene diamine, or (methyl) glycidyl acrylate and the multipolymer etc. with the compound of ethene unsaturated double-bond.Those can be used alone, and also can and use two or more.
As the compound in molecule with carbon imide base, can enumerate: N, N '-bis--adjacent toluyl carbon imide, N, N '-phenylbenzene carbon imide, N, N '-bis--2, 6-3,5-dimethylphenyl carbon imide, N, N '-bis-(2, 6-diisopropyl phenyl) carbon imide, N, N '-dioctyl decyl carbon imide, N-tri-bases-N '-cyclohexyl carbon imide, N, N '-bis--2, 2-bis--tributyl phenyl carbons imide, N-tri-bases-N '-phenyl carbons imide, N, N '-bis--p-nitrophenyl carbon imide, N, N '-bis--to aminocarbonyl phenyl carbon imide, N, N '-bis--p-hydroxybenzene carbon imide, N, N '-bis--cyclohexyl carbon imide, and N, N '-bis--to toluyl carbon imide etc.
As the compound in molecule with oxazoline group, can enumerate: 2-oxazoline, 2-methyl-2-oxazoline, 2-phenyl-2-oxazoline, 2,5-dimethyl-2-oxazoline, 2, the monosubstituted oxazolyl quinoline compounds such as 4-phenylbenzene-2-oxazoline, 2,2 '-(1,3-phenylene)-bis-(2-oxazolines), 2,2 '-(1,2-ethylidene)-bis-(2-oxazolines), 2,2 '-(tetramethylene)-bis-(2-oxazolines), 2,2 '-(Isosorbide-5-Nitrae-phenylene)-bis-(2-oxazolines) etc.
As can with the compound (C) of carboxyl reaction, be preferably bisphenol type epoxy compounds, be preferably number average molecular weight and be 400～5,000 bisphenol-type epoxy resin.If the number average molecular weight of epoxy resin is less than 400, there is adhesion agent layer to become soft and cannot obtain the tendency of sufficient weather resistance.If the number average molecular weight of epoxy resin is greater than 5,000, has with the consistency of polyester polyol and reduce, and produce the worry of bad order.In addition, with respect to polyhydroxy reactant (A) 100 weight parts, can be preferably and contain 1 weight part～100 weight part with the compound (C) of carboxyl reaction, be more preferred from and contain 5 weight part～50 weight parts.
In addition,, as solid purposes, can in host or stiffening agent, allocate known additive.For example can use reaction promotor.Such as enumerating: the metals such as dibutyl tin acetate, dibutyl tin dilaurate, dioctyl two tin laurates, dibutyl two maleic acid tin are catalyst; 1,8-diaza-dicyclo (5,4,0), ten-carbene-7,1,5-diazabicyclo (4,3,0) nonene-5,6-dibutyl amido-1,8-diazabicyclo (5,4,0) ten-carbene-7 tertiary amine such as grade; As reactive tertiary amine of trolamine etc., can use the one kind or two or more reaction promotor that is selected from those cohorts.
In order to improve lamination outward appearance, also can in host, allocate known levelling agent or defoamer.As levelling agent, such as enumerating: polyethers upgrading polydimethylsiloxane, polyester upgrading polydimethylsiloxane, the poly-methyl alkyl siloxane of aralkyl upgrading, the polydimethylsiloxane that polyester upgrading contains hydroxyl, polydimethylsiloxane, acrylic copolymer, methacrylic acid based copolymer, the polyethers upgrading that polyether ester upgrading contains hydroxyl gather methyl alkyl siloxane, alkyl acrylate copolymer, alkyl methacrylate multipolymer, Yelkin TTS etc.As defoamer, can enumerate: the multipolymer of silicone resin, silicone solution, alkyl vinyl ether and alkyl acrylate and alkyl methacrylate etc. are known.
Polyamine manthanoate solid of the present invention comprises polymeric polyisocyanate as stiffening agent.Polymeric polyisocyanate can be state polymeric polyisocyanate being diluted by organic solvent, also can be undiluted state.As polymeric polyisocyanate, for example, can enumerate: trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 1,2-propylene vulcabond, 1,2-butylene vulcabond, 2,3-butene diisocyanate, 1,3-butene diisocyanate, 2,4,4-trimethyl hexamethylene diisocyanate or 2,2,4-trimethyl hexamethylene diisocyanate, the aliphatic diisocyanates such as 2,6-vulcabond methylhexanoic acid ester, Isosorbide-5-Nitrae-cyclohexyl diisocyanate, 1,3-cyclohexyl diisocyanate, 3-isocyanic ester methyl-3,5,5-3-methyl cyclohexanol based isocyanate, 4,4 '-methylene-bis (cyclohexyl isocyanate), methyl 2,4-cyclohexyl diisocyanate, methyl 2,6-cyclohexyl diisocyanate, Isosorbide-5-Nitrae-bis-(isocyanic ester methyl) hexanaphthene, the ester ring type vulcabond such as two (isocyanic ester methyl) hexanaphthenes of 1,3-, m-benzene diisocyanate, PPDI, 4,4 '-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4,4 '-diphenylmethanediisocyanate, 2,4 toluene diisocyanate or 2,6-tolylene diisocyanate or its mixture, 4,4 '-Tolylamine vulcabond, dianisidine vulcabond, 4, the 4 '-aromatic diisocyanates such as phenyl ether vulcabond, 1,3-Xylene Diisocyanate or Isosorbide-5-Nitrae-Xylene Diisocyanate or its mixture, ω, ω '-bis-isocyanato-Isosorbide-5-Nitrae-diethylbenzene, the aromatic-aliphatic vulcabond such as two (1-isocyanato-1-methylethyl) benzene of 1,3-or Isosorbide-5-Nitrae-bis-(1-isocyanato-1-methylethyl) benzene or its mixture, triphenyl methane-4,4 ', 4 ' '-triisocyanate, benzene-1,3,5-triisocyanate, Toluene-2,4-diisocyanate, organic triisocyanates such as 4,6-triisocyanate, 4,4 '-phenylbenzene dimethylmethane-2,2 ', 5, the 5 '-polymeric polyisocyanate monomers such as organic tetraisocyanate such as tetraisocyanate, by the dipolymer of above-mentioned polymeric polyisocyanate monomer derived, trimer, biuret, allophanate, the polymeric polyisocyanate with 2,4,6-oxadiazines triketone ring being obtained by carbonic acid gas and above-mentioned polymeric polyisocyanate monomer, for example, with ethylene glycol, propylene glycol, butyleneglycol, hexylene glycol, neopentyl glycol, 1,6-hexylene glycol, 3-methyl isophthalic acid, 5-pentanediol, 3,3 '-dihydroxy methylpropane, cyclohexanedimethanol, Diethylene Glycol, triethylene glycol, dipropylene glycol, glycerine, TriMethylolPropane(TMP), tetramethylolmethane, Sorbitol Powder equimolecular quantity is less than the affixture of 200 low molecular polylol, or with molecular weight be 200～20,000 polyester polyol, polyester ether polylol, polyester amide polyol, polycaprolactone polyol, poly-valerolactone polyvalent alcohol, acrylic acid series multiple alcohol, polycarbonate polyol, poly-hydroxyl alkane, Viscotrol C, the affixture of polyamine manthanoate polyvalent alcohol etc. etc.Wherein, with regard to the productivity of wrapping material and the viewpoint of formability, be more preferred from the organic polymeric polyisocyanate being derived by aromatic diisocyanate.
In polyamine manthanoate solid of the present invention, the equivalence ratio [NCO] of the hydroxyl that in polymeric polyisocyanate stiffening agent (2), contained isocyanato has with respect to polyhydroxy reactant (A) contained in host (1) and the total of carboxyl/([OH]+[COOH]), be preferably 10～30, be more preferred from 15～25.That is, with respect to 1 mole of the total of hydroxyl and carboxyl, when isocyanato is less than 10 moles, cannot obtain sufficient formability, if surpass 30 moles, unfavorable aspect setting time, wholesomeness, economy.
Battery use packing material of the present invention for example can be manufactured by common method used.For example use polyamine manthanoate solid lamination outer layer side resin film layer of the present invention (11) and metal foil layer (13), and laminate in the middle of obtaining.Then, can use internal layer side solid (14) at metal foil layer (13) the area layer internal surface layer (15) of middle laminate.Or use internal layer side solid lamination metal foil layer (13) and internal surface layer (15), and laminate in the middle of obtaining.Then, can use polyamine manthanoate solid of the present invention, the metal foil layer (13) of laminate and outer layer side resin film layer (11) in the middle of lamination.For the former time, polyamine manthanoate solid of the present invention is coated on the one side of arbitrary base material of outer layer side resin film layer (11) or metal foil layer (13), make after solvent evaporates, under heating and pressurizing in adhesion agent layer overlapping another base material, then at normal temperature or carry out agingly under heating, make adhesion agent layer sclerosis.Adhesion agent layer amount is preferably 1g/m
2～15g/m
2left and right.During for the latter, also same, polyamine manthanoate solid of the present invention is coated arbitrary of metal foil layer (13) face of outer layer side resin film layer (11) or middle laminate.
By polyamine manthanoate, be solid while being coated on base material, for coating fluid being adjusted into appropriate viscosity, and can in drying step, in the scope base material not being impacted, comprise solvent.As solvent, can enumerate: the ketone based compounds such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone, the ester based compounds such as methyl acetate, ethyl acetate, butylacetate, ethyl lactate, acetic acid methoxyl group ethyl ester, the ether such as diethyl ether, glycol dimethyl ether based compound, the aromatics such as toluene, dimethylbenzene, the fatty compoundss such as pentane, hexane, the halogenated hydrocarbon compounds such as methylene dichloride, chlorobenzene, chloroform, the alcohols such as ethanol, Virahol, propyl carbinol, water etc.Those solvents can be used alone, and also can and use two or more.
As coating polyamine manthanoate, be the device of solid in the present invention, can enumerate: unfilled corner wheel coating machine (comma coater), dry adhered machine, roll-type knife coater (roll knife coater), mould are coated with machine, roller coating machine, excellent painting machine, intaglio plate roll coater, contrary roll-coater, knife coater (blade coater), intaglio plate coating machine, nick version coating machine etc.
Form battery of the present invention and be not particularly limited with the outer layer side resin film layer (11) of exterior material, be preferably and use the stretchable film that comprises polymeric amide or polyester.In addition, also can be undertaken painted by pigment such as carbon black or titanium oxide.In addition, also can be coated with the coating agents such as anti-slight crack coating agent or ink etc.In addition, also above film of 2 layers of laminations in advance.The thickness of rete is not particularly limited, and is preferably 12 μ m～100 μ m.
Form battery of the present invention and be not particularly limited with the metal foil layer (13) of exterior material, be preferably aluminium foil layer.The thickness of rete is not particularly limited, and is preferably 20 μ m～80 μ m.In addition, be preferably in metal foil surface and carry out by the surface treatment of phosphoric acid salt, chromic salt, fluorochemical, triazine thiol compound, isocyanate compound etc., by implementing surface treatment, and can suppress the protuberance of the interlayer in metal foil surfaces that causes because of the electrolytic solution of battery or the impact of electrolytic solution.
Form battery of the present invention and be not particularly limited with the internal surface layer (15) of exterior material, be preferably the heat sealing layer that comprises the not stretchable film that contains at least a kind of thermoplastic resin that selects free polyethylene, polypropylene, olefin copolymer, those acid to become the cohort that thing and ionomer form.The thickness of heat sealing layer is not particularly limited, and is preferably 20 μ m～150 μ m.
Forming formation battery of the present invention is not particularly limited with the solid of the internal layer side adhesion agent layer (14) of exterior material, be preferably that the Bonding strength of metal foil layer (13) and internal surface layer (15) can not reduce because of the electrolytic solution of battery, can use known solid.For example, can make solid that polyolefin resin and polyfunctional isocyanate are combined or the solid that polyvalent alcohol and polyfunctional isocyanate combine is coated on metal foil layer by intaglio plate coating machine etc., make solvent seasoning, under heating and pressurizing in adhesion agent layer overlapping internal surface layer (15), then, at normal temperature or under heating, carry out aging and metal foil layer (13) and internal surface layer (15) are fitted.Or can the solids such as sour upgrading polypropylene be melt extruded to the upper adhesion agent layer that forms of metal foil layer (13) by T mould forcing machine, overlapping internal surface layer (15) in above-mentioned adhesion agent layer, and make metal foil layer (13) and internal surface layer (15) laminating.Both must carry out when aging at outer side joint, agent layer (12) and internal layer side adhesion agent layer (14), can gather carry out aging.
Battery of the present invention can be used above-mentioned battery exterior material with container, with outer layer side resin film layer (11), forms the mode that convex surface, internal surface layer (15) form concave surface, carries out moulding and obtains.
Then, enumerate embodiment and comparative example is described more specifically the present invention.% in embodiment and comparative example all refers to quality %.
(synthesis example 1) drops into m-phthalic acid 166.0g, terephthalic acid 166.0g, ethylene glycol 85.6g, neopentyl glycol 95.6g, at 200 ℃～220 ℃, carry out 6 hours esterifications, distillate after the water of specified quantitative, add tetrabutyl titanate 0.12g, and decompression lentamente, at 1.3hPa～2.6hPa, 230 ℃～250 ℃, carry out 6 hours transesterification reactions, and obtain that number average molecular weight is 20,000, glass tansition temperature (Tg) is the polyester polyol of 60 ℃.By ethyl acetate, this polyester polyol being adjusted into nonvolatile component is 50%, and obtain hydroxyl value, is the polyester polyols alcoholic solution (1) that 2.71mgKOH/g, acid number are 0.1mgKOH/g.
In addition, number average molecular weight, glass tansition temperature utilize GPC and DSC to obtain by method as described above.In addition, acid number, hydroxyl value are obtained as follows.
The mensuration > of < acid number (AV) critically measures the about 1g of sample (polyester polyols alcoholic solution) in tool plug Erlenmeyer flask, adds toluene/ethanol (volume ratio: toluene/ethanol=2/1) mixed solution 100mL dissolves.In wherein adding phenolphthalein reagent as indicator, and kept for 30 seconds.Then, by 0.1N alcohol potassium hydroxide solution, carry out titration until solution presents incarnadine.Acid number is obtained (unit: mgKOH/g) by following formula.
Acid number (mgKOH/g)=(5.611 * a * F)/S
Wherein, S: the collection capacity of sample (g)
The consumption (mL) of a:0.1N alcohol potassium hydroxide solution
The titre of F:0.1N alcohol potassium hydroxide solution
The mensuration > of < hydroxyl value (OHV) critically measures the about 1g of sample (polyester polyols alcoholic solution) in tool plug Erlenmeyer flask, adds toluene/ethanol (volume ratio: toluene/ethanol=2/1) mixed solution 100mL dissolves.Then add exactly 5mL acetylizing agent (dissolving diacetyl oxide 25g by pyridine, the solution that the capacity of making is 100mL), stir about 1 hour.In wherein adding phenolphthalein reagent as indicator, continued for 30 seconds.Then, by 0.1N alcohol potassium hydroxide solution, carry out titration until solution presents incarnadine.Hydroxyl value is obtained (unit: mgKOH/g) by following formula.
Hydroxyl value (mgKOH/g)=[(b-a) * F * 28.25}/S]+D
Wherein, S: the collection capacity of sample (g)
The consumption (mL) of a:0.1N alcohol potassium hydroxide solution
B: the consumption (mL) of the 0.1N alcohol potassium hydroxide solution of blank assay
The titre of F:0.1N alcohol potassium hydroxide solution
D: acid number (mgKOH/g)
(synthesis example 2) drops into m-phthalic acid 149.4g, terephthalic acid 149.4g, ethylene glycol 71.3g, neopentyl glycol 119.6g, at 200 ℃～220 ℃, carry out 6 hours esterifications, distillate after the water of specified quantitative, add sebacic acid 40.4g, then carry out 6 hours esterifications.Distillate after the water of specified quantitative, add tetrabutyl titanate 0.13g, and decompression lentamente, at 1.3hPa～2.6hPa, 230 ℃～250 ℃, carry out 6 hours transesterification reactions, and obtain that number average molecular weight is 19,800, Tg is the polyester polyol of 45 ℃.Then by ethyl acetate, this ripple private interests ester polyol being adjusted into nonvolatile component is 50%, and obtain hydroxyl value, is the polyester polyols alcoholic solution (2) that 2.33mgKOH/g, acid number are 0.5mgKOH/g.
(synthesis example 3) drops into m-phthalic acid 83.2g, terephthalic acid 83.2g, ethylene glycol 142.6g, carries out 8 hours esterifications at 200 ℃～220 ℃, distillates after the water of specified quantitative, adds nonane diacid 188g, then carries out 4 hours esterifications.Distillate after the water of specified quantitative, add tetrabutyl titanate 0.13g, and decompression lentamente, at 1.3hPa～2.7hPa, 230 ℃～250 ℃, carry out 3 hours transesterification reactions, and obtain that number average molecular weight is 22,000, Tg is the polyester polyol of-5 ℃.By ethyl acetate, this polyester polyol being adjusted into nonvolatile component is 50%, and obtain hydroxyl value, is the polyester polyols alcoholic solution (3) that 2.45mgKOH/g, acid number are 0.1mgKOH/g.
(synthesis example 4) drops into m-phthalic acid 132.8g, ethylene glycol 42.7g, neopentyl glycol 71.8g, 1,6-hexylene glycol 108.6g carries out 6 hours esterifications at 200 ℃～230 ℃, distillates after the water of specified quantitative, add hexanodioic acid 175.2g, then carry out 6 hours esterifications.Distillate after the water of specified quantitative, add tetrabutyl titanate 0.13g, and decompression lentamente, at 1.3hPa～2.6hPa, 230 ℃～250 ℃, carry out 3 hours transesterification reactions, and obtain polyester polyol.For make gained this polyester polyol hydroxyl approximately 90% with Pyromellitic Acid anhydride reactant, and with respect to the total amount of this polyester polyol, add pyromellitic dianhydride 7.7g, at 180 ℃, react approximately 2 hours.Use liquid chromatography to confirm not remaining unreacted pyromellitic dianhydride in reaction system, and obtain that number average molecular weight is 18,000, Tg is the polyester polyol through pyromellitic dianhydride upgrading of-20 ℃.By ethyl acetate, the polyester polyol through pyromellitic dianhydride upgrading being adjusted into nonvolatile component is 50%, and obtain hydroxyl value, is the polyester polyols alcoholic solution (4) that 0.31mgKOH/g, acid number are 2.8mgKOH/g.
(synthesis example 5) drops into m-phthalic acid 132.8g, ethylene glycol 44.6g, neopentyl glycol 74.8g, 1,6-hexylene glycol 113.3g carries out 6 hours esterifications at 200 ℃～230 ℃, distillates after the water of specified quantitative, add hexanodioic acid 175.2g, then carry out 6 hours esterifications.Distillate after the water of specified quantitative, add tetrabutyl titanate 0.13g, and decompression lentamente, at 1.3hPa～2.6hPa, 230 ℃～250 ℃, carry out 3 hours transesterification reactions, and obtain polyester polyol.With respect to this polyester polyol being adjusted into nonvolatile component by ethyl acetate, be the 80% polyester polyols alcoholic solution 600g obtaining, and interpolation tolylene diisocyanate 3.2g, at 80 ℃, carry out reaction in 8 hours, and obtain that number average molecular weight is 20,000, Tg is the polyester polyamine manthanoate polyvalent alcohol of-10 ℃.Then, by ethyl acetate, this polyester polyol being adjusted into nonvolatile component is 50%, and obtain hydroxyl value, is the polyester polyols alcoholic solution (5) that 2.71mgKOH/g, acid number are 0.1mgKOH/g.
[manufacture of host (1)] allotment polyester polyols alcoholic solution (1) 60g (solids component is 30g), with polyester polyols alcoholic solution (3) 140g (solids component is 70g) and KBM-403 (silane coupling agent) 1g after, add ethyl acetate 136g, and obtain the host (1) that nonvolatile component is 30%.The hydroxyl value of host (1) and acid number add up to about 1.56mgKOH/g.
[manufacture of host (2)～host (11)] is in the identical mode of the situation with host (1), with the ratio shown in table 1 (g) allotment polyester polyols alcoholic solution (1)～polyester polyols alcoholic solution (5) and following shown in silane coupling agent and can with the compound of carboxyl reaction after, and take the mode that nonvolatile component is 30% and add ethyl acetate, and obtain host (2)～host (11).
Silane coupling agent
KBM-403:3-glycidoxypropyltrimewasxysilane (silicon profit light (Shin-EtsuSilicones) company of SHIN-ETSU HANTOTAI manufactures)
KBM-903:3-aminocarbonyl propyl Trimethoxy silane (manufacture of Japanese You Nika (Nippon Unicar) company)
Can with the composition of carboxyl reaction
YD-012: bisphenol A type epoxy resin (manufacture of chemical company of Nippon Steel)
(manufacture of stiffening agent)
Stiffening agent (1): will dilute resin solution that the solids component made from adducts TriMethylolPropane(TMP) tolylene diisocyanate is 50% by ethyl acetate as stiffening agent (1).The NCO% of stiffening agent (1) is 8.6%.
Stiffening agent (2): the resin solution that the solids component that the trimer that dilutes hexamethylene diisocyanate by ethyl acetate is made is 50% is as stiffening agent (2).The NCO% of stiffening agent (2) is 8.6%.
Stiffening agent (3): the resin solution that is 50% using the solids component that is mixed with stiffening agent (1) 50 weight part, stiffening agent (2) 50 weight parts is as stiffening agent (3).The NCO% of stiffening agent (3) is 8.6%.
(embodiment 1～embodiment 13, comparative example 1～comparative example 4) allocated after host and stiffening agent with the ratio shown in table 2 (g), and the mode that the nonvolatile component of take is 30% is added ethyl acetate, and obtains polyamine manthanoate solid.Isocyanato in stiffening agent, with respect to equivalent [NCO]/([OH]+[COOH]) of the total of the contained hydroxyl value of host and acid number, is obtained as follows.
[NCO]/([OH]＋[COOH])
=[561 * (NCO% of stiffening agent) * (with respect to the stiffening agent allotment amount (g) of host 100g)]/[(hydroxyl value of host and the total of acid number (mgKOH/g)) * 42 * 100]
At thickness, be on a face of aluminium foil of 40 μ m, the amount of glue spread: 5g/ square metre of usining is coated with above-mentioned polyamine manthanoate solid as skin solid by dry adhered machine, makes after solvent evaporates, and lamination thickness is the extension polyamide membrane of 30 μ m.Then, on another face of the aluminium foil of the laminated film of gained, with the amount of glue spread: 5g/ square metre, by dry adhered machine, be coated with following internal layer solid, make after solvent evaporates, lamination thickness is the not extended polypropylene film of 30 μ m, then, carry out the sclerosis (aging) of 60 ℃, 7 days, make outer using and solid sclerosis and acquisition battery use packing material for internal layer.
* internal layer solid
With weight ratio, count following host and the stiffening agent of host/stiffening agent=100/10 allotment, and take mode that nonvolatile component is 30% and add toluene and make internal layer solid, above-mentioned host is in container, to add Tuftec M1913 (side chain has styrene-ethylene-butadiene-styrene (Styrene-Ethylene-Butadiene-Styrene of carboxyl, SEBS), chemistry (Asahi KaseiChemicals) company of Asahi Chemical Industry manufactures, styrene content is 30 % by weight, carboxyl amount is 0.19mmol/g, in every 1 molecule, contain 11.4 carboxyls): 55 parts, and the complete hydrogenation C9 Resin A rkon P-140 manufacturing as the Huang Chuan chemical industrial company of sticking together imparting agent (B) (softening temperature is 140 ℃, without acid number): 45 parts, mixed solvent by toluene/methyl ethyl ketone=8/2 dilute and at 50 ℃ heated and stirred within 3 hours, obtain, above-mentioned stiffening agent is the solution that the solids component made by the trimer of dilution with toluene hexamethylene diisocyanate is 50%.
According to following evaluation assessment, the battery use packing material obtaining is in the above described manner carried out to performance evaluation.
< humidity resistance is tested forward and backward lamination strength > and battery use packing material is cut into the size of 200mm * 15mm, in temperature, be under 20 ℃, the relative humidity environment that is 65%, use tensile testing machine to take load speed and as 300mm/ minute, carry out the stripping test of T mould.Mean value with each 5 test films represents to extend the stripping strength (N/15mm width) (lamination strength before humidity resistance test) between polyamide membrane and aluminium foil.
In addition, battery use packing material is added in 70 ℃, the constant temperature and humidity cabinet of 90%RH environment, after standing 168 hours, battery use packing material self-constant temperature constant humidity groove is taken out, in the mode with identical before test, measure lamination strength (lamination strength after humidity resistance test).According to the mean value of each stripping strength, carry out the evaluation of following 4 grades.
◎: 6N/15mm above (excellent in practicality)
Zero: 4N/15mm is above and be less than 6N/15mm (practical region)
△: 2N/15mm is above and be less than 4N/15mm (practical lower limit)
*: be less than 2N/15mm
Above result is shown in to table 2 in the lump.
< formability evaluation assessment > cuts into battery use packing material the size of 80mm * 80mm, and as blank sample (by forming material, starting material).To above-mentioned blank sample, straight mould (straight mold) that can free variation by forming height is given prominence to 1 section of moulding, by producing the fracture of aluminium foil or the protuberance of each interlayer and maximum forming height is evaluated formability.The tapping and plugging machine of the mould using in addition, be shaped as square that a limit is 30mm, corner R for 2mm, tapping and plugging machine shoulder R be 1mm, mould shoulder R:1mm.According to the height of moulding, carry out the evaluation of following 4 grades.
◎: 6mm above (excellent in practicality)
Zero: 4mm is above and be less than 6mm (practical region)
△: 2mm is above and be less than 4mm (practical lower limit)
*: be less than 2mm
Above result is shown in to table 2 in the lump.
The weather resistance > of < forming composition cuts into battery use packing material the size of 80mm * 80mm, and as blank sample (by forming material, starting material).To above-mentioned blank sample, straight mould that can free variation by forming height be take forming height and is given prominence to the moulding of 1 stage as 3mm.Then, the battery through moulding is added in the constant temperature and humidity cabinet under 70 ℃, 90%RH environment to standing 168 hours with container.Self-constant temperature constant humidity groove takes out battery container, confirms the outward appearance of container for battery, evaluates and whether produces protuberance.The tapping and plugging machine of the mould using in addition, be shaped as square that a limit is 30mm, corner R for 2mm, tapping and plugging machine shoulder R be 1mm, mould shoulder R:1mm.
Zero: without protuberance
*: produce protuberance
Above result is shown in to table 2 in the lump.
Known according to the result of table 2, by using with respect to the hydroxyl that is derived from polyhydroxy reactant (A) in the host that comprises polyhydroxy reactant (A) and silane coupling agent (B) and the total of carboxyl, and in the scope that the equivalence ratio of contained isocyanato is 10～30 in above-mentioned stiffening agent, allocate the polyamine manthanoate solid for battery use packing material that polymeric polyisocyanate stiffening agent forms, and the battery use packing material that can provide humidity resistance to test forward and backward lamination strength, formability excellence, it is 40 that above-mentioned polyhydroxy reactant (A) contains glass tansition temperature.Polyester polyol (A1) 5 % by weight～50 % by weight and glass tansition temperature more than ℃ are less than 40.℃ polyester polyol (A2) 95 % by weight～50 % by weight.Also known in addition, by using above-mentioned battery use packing material can form the forming composition of excellent in te pins of durability with the battery use packing material of polyamine manthanoate solid.
Comparative example 1 humidity resistance test forward and backward lamination strength aspect and no less than embodiment, but with respect to the hydroxyl that is derived from polyhydroxy reactant (A) in host and the total of carboxyl, the equivalence ratio of the isocyanato while comprising polymeric polyisocyanate stiffening agent in above-mentioned stiffening agent is too small, so insufficient formability, the weather resistance of forming composition is also poor.In addition, in comparative example 3, with respect to the hydroxyl that is derived from polyhydroxy reactant (A) in host and the total of carboxyl, even if the equivalence ratio of the isocyanato while comprising polymeric polyisocyanate stiffening agent in above-mentioned stiffening agent is appropriate, the ratio of components of polyester polyol (A1), polyester polyol (A2) is also incorrect, so the poor durability of forming composition.
Utilizability in industry
Polyamine manthanoate solid of the present invention can be widely used as to form the solid of container or battery package for battery.Particularly be suitable as to form the solid of container or battery package for battery that the secondary cells such as lithium ion battery, lithium ion polymer battery, lead storage battery, alkaline cell, oxidation silver zinc storage battery, metal-air battery, polyvalent cation battery, electrical condenser (condenser), electric capacity (capacitor) use.Polyamine manthanoate solid of the present invention is for by identical or different raw-material by convered structure bonder, for example, can for plastic cement, be preferably that starting material are engaging of raw-material multilayer laminated boards body with metal.Certainly, being also suitable for plastic cement is that starting material joint, metal is each other starting material joints each other.Use solid of the present invention and the formability of laminate excellent, environmental resistance is high, under the condition of outdoor exposure, also can suppress through time reduction, the long-term strong cohesiveness of Bonding strength excellent strength, face shaping also excellent.Therefore; also can be used as the solid that blister pack (Press Through Package, PTP) or steel plate etc. need the outdoor industry purposes laminates such as fabrication such as the laminate of formability or protection walls material, roof material, solar cell panel material, window material, outdoor floor material, illumination protection material, automobile component to use.
This application case advocates take that the Japanese patent application case Patent 2012-242154 applying on November 1st, 2012 is basic right of priority, and the full content of its announcement is incorporated herein.
Nomenclature
(11): outer layer side resin film layer
(12): outer layer side adhesion agent layer
(13): metal foil layer
(14): internal layer side adhesion agent layer
(15): internal surface layer
Claims (9)
1. a polyamine manthanoate solid for battery use packing material, it contains host and polymeric polyisocyanate stiffening agent, and it is characterized in that:
Described host comprise polyhydroxy reactant (A), with silane coupling agent (B), it is polyester polyol (A2) 95 % by weight～50 % by weight that 40 ℃ of above polyester polyol (A1) 5 % by weight～50 % by weight and glass tansition temperature are less than 40 ℃ that described polyhydroxy reactant (A) contains glass tansition temperature
Isocyanato contained in described polymeric polyisocyanate stiffening agent is 10～30 with respect to equivalence ratio [NCO]/([OH]+[COOH]) that is derived from the hydroxyl of described polyhydroxy reactant (A) and the total of carboxyl.
2. polyamine manthanoate solid for battery use packing material according to claim 1, wherein further contain can with the compound (C) of described carboxyl reaction.
3. polyamine manthanoate solid for battery use packing material according to claim 2, wherein said can with the compound (C) of described carboxyl reaction for have glycidyl compound, there is at least one of compound of carbon imide base and oxazoline group.
4. polyamine manthanoate solid for battery use packing material according to claim 3, the wherein said compound with described glycidyl is bisphenol type epoxy compounds.
5. according to polyamine manthanoate solid for the battery use packing material described in any one in claim 1-4, wherein said polymeric polyisocyanate stiffening agent contains fragrant family polymeric polyisocyanate.
6. a battery use packing material, its sequentially lamination outer layer side resin film layer (11), outer layer side adhesion agent layer (12), metal foil layer (13), internal layer side adhesion agent layer (14) and internal surface layer (15) form, it is characterized in that:
Described outer layer side adhesion agent layer (12) is formed with polyamine manthanoate solid by the battery use packing material as described in any one in claim 1-5.
7. battery use packing material according to claim 6, wherein said outer layer side resin film layer (11) is polyamide membrane and/or polyester film, described internal surface layer (15) is polyolefine mesentery.
8. a battery container, it is formed by the battery use packing material moulding as described in claim 6 or 7, and outer layer side resin film layer (11) forms convex surface, and internal surface layer (15) forms concave surface.
9. a battery, it uses battery as claimed in claim 8 to form with container.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| JP2012242154A JP5267718B1 (en) | 2012-11-01 | 2012-11-01 | Polyurethane adhesive for battery packaging material, battery packaging material, battery container and battery |
| JP2012-242154 | 2012-11-01 | ||
| PCT/JP2013/006460 WO2014068986A1 (en) | 2012-11-01 | 2013-10-31 | Polyurethane adhesive for packaging materials for batteries, packaging material for batteries, battery container, and battery |
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| CN103975035A true CN103975035A (en) | 2014-08-06 |
| CN103975035B CN103975035B (en) | 2016-04-06 |
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| CN201380003598.3A Active CN103975035B (en) | 2012-11-01 | 2013-10-31 | Battery use packing material polyurethane(s) solid, battery use packing material, battery container and battery |
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| JP (1) | JP5267718B1 (en) |
| KR (1) | KR101475456B1 (en) |
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| WO (1) | WO2014068986A1 (en) |
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| CN109642141A (en) * | 2016-09-06 | 2019-04-16 | Dic株式会社 | Bonding agent, blister package laminated body and the blister package using it |
| CN110072964B (en) * | 2016-12-20 | 2021-05-25 | Dic株式会社 | Adhesive for battery packaging material, battery container, and battery |
| CN110072964A (en) * | 2016-12-20 | 2019-07-30 | Dic株式会社 | Battery use packing material bonding agent, battery use packing material, battery container and battery |
| TWI749129B (en) * | 2016-12-20 | 2021-12-11 | 日商迪愛生股份有限公司 | Adhesives for battery packaging materials, battery packaging materials, battery containers and batteries |
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| CN110978688B (en) * | 2019-10-23 | 2022-04-19 | 明基材料（芜湖）有限公司 | Composite packaging material for lithium battery |
| CN110819291A (en) * | 2019-12-06 | 2020-02-21 | 中国乐凯集团有限公司 | Polyurethane adhesive for battery flexible package |
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Also Published As
| Publication number | Publication date |
|---|---|
| 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 |
| TW201425514A (en) | 2014-07-01 |
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