CN118325498A - High-air-permeability adhesive tape and preparation method and application thereof - Google Patents
High-air-permeability adhesive tape and preparation method and application thereof Download PDFInfo
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- CN118325498A CN118325498A CN202410548019.3A CN202410548019A CN118325498A CN 118325498 A CN118325498 A CN 118325498A CN 202410548019 A CN202410548019 A CN 202410548019A CN 118325498 A CN118325498 A CN 118325498A
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- Prior art keywords
- adhesive tape
- filler
- porous
- permeability
- composition
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- 239000002390 adhesive tape Substances 0.000 title claims abstract description 107
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 239000000945 filler Substances 0.000 claims abstract description 89
- 239000010410 layer Substances 0.000 claims abstract description 53
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims abstract description 48
- 230000035699 permeability Effects 0.000 claims abstract description 46
- 239000000203 mixture Substances 0.000 claims abstract description 36
- 239000000758 substrate Substances 0.000 claims abstract description 35
- 239000003792 electrolyte Substances 0.000 claims abstract description 26
- 239000004745 nonwoven fabric Substances 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 16
- -1 carbonate compound Chemical class 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 14
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 14
- 239000011347 resin Substances 0.000 claims abstract description 14
- 229920005989 resin Polymers 0.000 claims abstract description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 229920001971 elastomer Polymers 0.000 claims abstract description 8
- 239000005060 rubber Substances 0.000 claims abstract description 8
- 229920005597 polymer membrane Polymers 0.000 claims abstract description 6
- 239000004034 viscosity adjusting agent Substances 0.000 claims abstract description 5
- 239000011248 coating agent Substances 0.000 claims description 55
- 238000000576 coating method Methods 0.000 claims description 55
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 42
- 239000007788 liquid Substances 0.000 claims description 38
- 239000002904 solvent Substances 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 23
- 239000012528 membrane Substances 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 13
- 229910052744 lithium Inorganic materials 0.000 claims description 13
- 238000005096 rolling process Methods 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- 238000004804 winding Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 6
- 238000013329 compounding Methods 0.000 claims description 5
- 229920002742 polystyrene-block-poly(ethylene/propylene) -block-polystyrene Polymers 0.000 claims description 5
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 claims description 5
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims description 5
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 4
- 229910001593 boehmite Inorganic materials 0.000 claims description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 4
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 4
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 229920006271 aliphatic hydrocarbon resin Polymers 0.000 claims description 3
- 229920006272 aromatic hydrocarbon resin Polymers 0.000 claims description 3
- 239000012948 isocyanate Substances 0.000 claims description 3
- 150000002513 isocyanates Chemical class 0.000 claims description 3
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 3
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 3
- 239000002480 mineral oil Substances 0.000 claims description 3
- 235000010446 mineral oil Nutrition 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 229920000098 polyolefin Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 239000000454 talc Substances 0.000 claims 1
- 229910052623 talc Inorganic materials 0.000 claims 1
- 230000001070 adhesive effect Effects 0.000 abstract description 7
- 230000010220 ion permeability Effects 0.000 abstract description 6
- 239000000853 adhesive Substances 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 22
- 239000000178 monomer Substances 0.000 description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 14
- 239000004743 Polypropylene Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 239000000523 sample Substances 0.000 description 13
- 239000003999 initiator Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000002791 soaking Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 238000005336 cracking Methods 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 238000007731 hot pressing Methods 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 229920002635 polyurethane Polymers 0.000 description 6
- 239000004814 polyurethane Substances 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 239000012790 adhesive layer Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 230000007774 longterm Effects 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 3
- VEBCLRKUSAGCDF-UHFFFAOYSA-N ac1mi23b Chemical compound C1C2C3C(COC(=O)C=C)CCC3C1C(COC(=O)C=C)C2 VEBCLRKUSAGCDF-UHFFFAOYSA-N 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 238000009423 ventilation Methods 0.000 description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 2
- IEVADDDOVGMCSI-UHFFFAOYSA-N 2-hydroxybutyl 2-methylprop-2-enoate Chemical compound CCC(O)COC(=O)C(C)=C IEVADDDOVGMCSI-UHFFFAOYSA-N 0.000 description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 2
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 208000027418 Wounds and injury Diseases 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 208000010392 Bone Fractures Diseases 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 206010017076 Fracture Diseases 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 1
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- QUZSUMLPWDHKCJ-UHFFFAOYSA-N bisphenol A dimethacrylate Chemical class C1=CC(OC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OC(=O)C(C)=C)C=C1 QUZSUMLPWDHKCJ-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 description 1
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- FFIUNPRXUCRYFU-UHFFFAOYSA-N tert-butyl pentaneperoxoate Chemical compound CCCCC(=O)OOC(C)(C)C FFIUNPRXUCRYFU-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Landscapes
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
A high-permeability adhesive tape and a preparation method and application thereof, wherein the adhesive tape comprises a porous substrate and a pressure-sensitive adhesive layer; the thickness of the porous base material is 5-50 μm, and the porous base material is at least one selected from porous polymer membrane and non-woven fabric; the thickness of the pressure-sensitive adhesive layer is 0.5-50 mu m, and the pressure-sensitive adhesive layer comprises at least one raw material composition of the composition (1) or the composition (2): the composition (1) comprises: 20-45% of rubber component, 5-25% of viscosity modifier, 30-75% of filler, and optional tackifying resin and carbonate compound; the composition (2) comprises: 20-70% of hydroxyl/carboxyl end-capped acrylate resin, 1-10% of curing agent, 25-75% of filler and optional carbonate compound; the particle size of the filler is 1nm-15 mu m; the initial air permeability of the adhesive tape is less than 350s/100cc, the air permeability after the adhesive tape is soaked in electrolyte is less than 370s/100cc, and the adhesive tape has good ion permeability and stable adhesive strength.
Description
Technical Field
The invention belongs to the technical field of battery adhesive tapes, and particularly relates to a high-air-permeability adhesive tape, and a preparation method and application thereof.
Background
In the normal production process of the lithium battery, the positive electrode plate, the diaphragm and the negative electrode plate are coiled and then subjected to hot pressing, liquid injection, formation and other processes to prepare the battery cell. Because the pole piece has certain brittleness, the bending amplitude of the pole piece wound on the inner layer of the battery core at the corner of the battery core is often larger, larger stress exists, the active substance is easy to crack after being subjected to hot pressing and falls off, so that the yield and the use safety of the battery core are affected, or the situation that lithium is separated from the corner occurs in the battery circulation process is caused, the wound battery core is deformed, the pole piece at the corner is caused to have fracture risk, and the safety performance and the circulation performance of the battery are affected.
The adhesive tape is adhered on the pole piece at the corresponding position, so that the problems of hot-pressing cracking of the pole piece, lithium precipitation at the corner of the battery cell, deformation and cracking of the battery cell can be effectively prevented, and the adhesive tape can be used for preventing the adhesive tape base material from cracking. The adhesive tape used for the conventional lithium battery is generally electrolyte-resistant, the adhesive used for the adhesive layer is generally acrylic acid pressure-sensitive adhesive, hot melt adhesive and the like, the base material is generally PET, BOPP film and the like, and the adhesive layer is low in solubility in electrolyte and is not permeable to lithium ions, so that the use of the adhesive tape at the corners inside the battery core is limited.
The invention CN117363229A discloses an electrolyte-resistant lithium battery special-shaped adhesive tape and a preparation method thereof, wherein the adhesive tape comprises a three-dimensional matrix layer, and the matrix layer comprises the following active ingredients in parts by weight: 50-80 parts of natural rubber; 12-20 parts of styrene butadiene rubber; 7-10 parts of TPI; 4-7 parts of acrylic short fibers; 7-10 parts of micrometer filler; 32-45 parts of functional auxiliary agent; according to the invention, the adhesive force and the corrosion resistance against irregular shapes are improved by adding the filler and adopting the three-dimensional substrate layer to prepare the adhesive tape, but if the adhesive tape is used at the positions of corners of the battery core, and the like, lithium ions cannot pass through the adhesive tape and are separated out at the edge of the adhesive tape due to the fact that the adhesive tape is compact in structure and poor in ion permeability, so that the electric performance and the safety of the battery are reduced.
The invention CN115651554A discloses a battery diaphragm adhesive tape with a dissolvable adhesive layer and a preparation method thereof, wherein the battery diaphragm adhesive tape comprises a battery diaphragm and the adhesive layer arranged on the surface of the battery diaphragm, and the adhesive for forming the adhesive layer comprises the following raw materials in percentage by weight: 40-60% of solvent polyacrylate; 10-30% of polyvinyl acetate; 5-15% of polystyrene resin; initiator 0.1-0.5%; 0.5 to 1.0 percent of curing agent; 0-30% of solvent. The battery diaphragm adhesive tape glue layer provided by the invention can be rapidly and basically completely dissolved in electrolyte, normal migration of lithium ions is not blocked, but the used diaphragm substrate still has the problems of insufficient porosity and poor ion permeability, the adhesive tape after the adhesive tape is dissolved also has the falling risk, the adhesive property cannot be basically embodied, and the falling risk exists in the subsequent battery circulation process after the adhesive tape is dissolved, so that the problem of lithium precipitation cannot be avoided.
Therefore, how to select the materials and the structure of the conventional electrolyte-resistant battery diaphragm adhesive tape can provide enough joint strength and toughness, protect the pole piece from cracking under the action of stress in the hot pressing process, provide enough ion permeability in the battery circulation process, prevent the defects of pole piece deformation and the like caused by lithium precipitation of the battery, and become the problem to be solved urgently by the person skilled in the art.
Disclosure of Invention
In order to solve the problems, the invention provides a high-permeability adhesive tape, a preparation method and application thereof, wherein the high-permeability adhesive tape is formed by utilizing a porous substrate and a high-permeability pressure-sensitive adhesive layer, is particularly suitable for a lithium battery, provides excellent initial and bubble liquid permeability, provides sufficient ion permeability in the battery circulation process, and prevents defects such as lithium precipitation. The adhesive tape has enough and stable joint strength and toughness, and protects the pole piece from cracking under the action of stress in the hot pressing process.
In a first aspect, the present invention provides a highly breathable tape comprising a porous substrate and a pressure sensitive adhesive layer;
the thickness of the porous base material is 5-50 μm, and the porous base material is at least one selected from porous polymer membrane and non-woven fabric;
the thickness of the pressure-sensitive adhesive layer is 0.5-50 mu m, and the pressure-sensitive adhesive layer comprises at least one raw material composition of the composition (1) or the composition (2):
the composition (1) comprises, in weight percent: 20-45% of rubber component, 5-25% of viscosity modifier, 30-75% of filler, and optional tackifying resin and carbonate compound;
The composition (2) comprises, in weight percent: 20-70% of hydroxyl/carboxyl end-capped acrylate resin, 1-10% of curing agent, 25-75% of filler and optional carbonate compound;
The filler comprises a filler with the particle size of 1nm-15 mu m;
the initial air permeability of the high air permeability adhesive tape is less than 350s/100cc, and the air permeability after the adhesive tape is immersed in electrolyte is less than 370s/100cc.
The porous base material, the high-permeability pressure-sensitive adhesive layer and the like are utilized to form the high-permeability adhesive tape, so that on one hand, the porous base material is used for providing better long-term basic permeability, and the ion permeability and the adhesive property of the whole adhesive tape are optimized by preparing the raw material composition of the pressure-sensitive adhesive layer; on the other hand, by utilizing the physical and chemical properties and structural characteristics of the filler, a gap is formed between the filler and the resin matrix, so that the overall permeability of the adhesive tape is further increased. The mode of using the filler to increase the air permeability of the adhesive tape is obviously different from the purposes and effects of reinforcing, insulating/conducting and the like of the traditional filler.
Preferably, the porous polymer membrane is at least one selected from a porous PP membrane, a porous PE membrane, a porous PI membrane, a porous PAN membrane, a porous PVDF membrane and a porous PMMA membrane, and has a porosity of 30-85%;
The non-woven fabric comprises at least one of PP non-woven fabric, PE non-woven fabric, PET non-woven fabric and PTFE non-woven fabric, and the aperture is less than or equal to 10um.
The porous substrate can provide sufficient strength to the adhesive tape while maintaining good air permeability, and the air permeability of the substrate of the present invention is 350s/100cc or less, preferably 280s/100cc or less, and more preferably 240s/100cc or less.
Preferably, the filler is at least one selected from boehmite, talcum powder and silicon dioxide. Wherein the filler comprises a porous filler, the specific surface area is more than 2m 2/g, preferably more than 10m 2/g, and the preferred particle size is 10nm-10 mu m; and/or a compound filler, wherein the compound filler adopts a small-particle-size filler with the particle size of 1-600nm and a large-particle-size filler with the particle size of 700nm-15 mu m, preferably 700nm-10 mu m, according to the weight ratio (20-40): (60-80) compounding.
On the basis of using the filler to increase the air permeability, the invention screens out the preferable type and the using mode of the filler. Firstly, the types of the fillers are poor in compatibility between the fillers and the resin, a large amount of gaps are favorable for forming continuous channels, and the fillers can be obtained by adopting commercial products and further screening according to the particle size requirement. Secondly, when porous filler is adopted, a porous structure in the filler can form a ventilation channel; when the non-porous structure compound filler is adopted, gaps are formed on the surface of the filler by using rough surface and poor resin infiltration, and meanwhile, small-particle-size fillers are filled among gaps of large-particle-size fillers to communicate channels. The two fillers can be further compounded and used, namely, a mode of compounding the large-particle-diameter porous filler and the small-particle-diameter porous filler is adopted.
Optionally, the pressure-sensitive adhesive layer is patterned to cover the surface of the porous substrate, and the coverage area accounts for 10-50%, preferably 20-40% of the total area of the porous substrate. The patterned covering mode is adopted, so that the covering area is reduced, and the overall air permeability of the adhesive tape is further improved.
Specifically, although the material selection of the pressure-sensitive adhesive layer is not unique, the comprehensive adhesive property and the air permeability meet the conditions of internal use requirements of the lithium battery, and the following 2 compositions are preferably obtained:
first, in weight percent, the composition (1) comprises:
At least one rubber component selected from SIS, SEBS, SEPS, SBr, TPU; preferably, the styrene content in SIS, SEBS, SEPS, SBr is less than or equal to 40wt%;
the viscosity regulator is at least one selected from liquid polyolefin and naphthenic mineral oil;
The tackifying resin is selected from at least one of (hydrogenated) C5 resin, (hydrogenated) C9 resin and (hydrogenated) DCPD resin.
Second, the composition (2) comprises, in weight percent:
the hydroxyl/carboxyl terminated acrylate resin has a molecular weight of 20,000-500,000Da;
the curing agent is at least one of polyfunctional epoxy and polyfunctional isocyanate.
The hydroxyl/carboxyl terminated acrylate resin may be prepared by a thermal initiation method or a photoinitiation method. Wherein the acrylate monomer for hydroxyl end capping is selected from one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, propyl methacrylate, hydroxybutyl acrylate and hydroxybutyl methacrylate. The carboxyl end-capping acrylate monomer is at least one selected from acrylic acid and methacrylic acid.
Preferably, the content of the carbonate compound is 10-20%, and at least one of ethylene carbonate, propylene carbonate, methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate and methyl propyl carbonate is selected. The electrolyte solvent used in the lithium ion battery at present mainly comprises carbonate solvents such as dimethyl carbonate, ethylene carbonate, methyl ethyl carbonate and the like, a small amount of added carbonate compounds are easy to dissolve in the electrolyte, a swelling channel of a glue layer is increased, and the swelling rate/time, dissolution rate/time and the like of the pressure-sensitive adhesive layer are favorably regulated and controlled.
In a second aspect, the invention provides a method for preparing a high air permeability adhesive tape, comprising the following steps:
Step one, preparing pressure-sensitive adhesive layer coating liquid:
weighing each component according to the composition of the raw materials, and uniformly mixing each component with a solvent to obtain a coating liquid;
step two, coating film formation:
Coating the coating liquid on a porous substrate, and drying to form a pressure-sensitive adhesive layer to obtain a high-permeability adhesive tape; or alternatively
Coating the coating liquid on a release film, drying and transferring to a porous substrate to form a pressure-sensitive adhesive layer, so as to obtain the high-permeability adhesive tape;
Step three, tape winding:
and coating a release agent on the back surface of the porous substrate or arranging a release film on the surface of the pressure-sensitive adhesive layer, and rolling the adhesive tape to prepare the single-sided rolled high-permeability adhesive tape.
Preferably, the solvent is an organic solvent, including at least one of toluene, xylene, methylcyclohexane, ethyl acetate, butyl acetate, butanone, methyl isobutyl ketone, ethanol, and isopropanol, and the solid content of the coating liquid is 5-60wt%.
In a third aspect, the invention provides an application of the high-permeability adhesive tape in pole piece protection, pole lug protection and winding ending of a lithium battery.
The invention at least has the following beneficial effects:
(1) According to the invention, the high-permeability adhesive tape is prepared by laminating the pressure-sensitive adhesive layer on the porous substrate, and the adhesive tape provides sufficient mechanical strength and support for the pole piece in the application processes of electrode rolling and the like, so that the pole piece is protected from cracking in the subsequent hot pressing process, and the qualification rate of battery products is improved.
(2) The porous substrate, the high-permeability pressure-sensitive adhesive layer and the porous and/or compound filler are adopted, a large number of ventilation channels can be formed between the components, and the components, so that the shuttle of lithium ions is not influenced, the initial and long-term stable ventilation degree is provided for the adhesive tape, and the improvement of the energy density of the battery is facilitated.
(3) In the battery cycle process, the adhesive tape at the corner of the battery core has excellent lithium ion transmittance, so that the defects of lithium precipitation at the corner of the battery core, deformation of the battery core and the like can be avoided, and the service life of the battery is prolonged.
(4) By setting the porous base material and the pressure-sensitive adhesive layer for patterning, selecting the filler, adding the carbonate compound and the like, the foam swelling rate/time, dissolution rate/time, air permeability, peeling strength and other parameters of the adhesive tape can be adjusted, so that various application requirements are met.
Drawings
Fig. 1 is a schematic structural view of a high air permeability adhesive tape according to the present invention.
Reference numerals: 1-pressure-sensitive adhesive layer, 2-porous substrate.
Detailed Description
In order to better understand the above technical solutions, the following detailed description will be given with reference to the accompanying drawings and specific embodiments. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The terminology used in the embodiments of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used in this application and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise, the "plurality" generally includes at least two.
It should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a product or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such product or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a commodity or device comprising such elements.
Referring to FIG. 1, the present invention provides a high air permeability adhesive tape with stable adhesion, comprising a porous substrate 2 and a pressure sensitive adhesive layer 1, wherein the initial air permeability of the adhesive tape is less than 350s/100cc, and the air permeability after soaking in an electrolyte is less than 370s/100cc. The soaking electrolyte comprises the following steps: placing the adhesive tape into a container filled with electrolyte solvent, sealing, baking at 80-90deg.C for 20-30hrs, and taking out to wipe off the surface solvent. The electrolyte solvent comprises the following components in percentage by mass: ethylene carbonate EC: ethyl methyl carbonate emc= (30-70): (10-50): (10-40), preferably, the electrolyte solvent comprises the following specific components in parts by mass: diethyl carbonate DEC:50%, ethylene carbonate EC:30%, ethyl methyl carbonate EMC:20%.
1. A porous base material 2 having a thickness of 5 to 50 μm and selected from at least one of a porous polymer separator and a nonwoven fabric, wherein the porous base material 2 has an air permeability of less than 350s/100cc, preferably 280s/100cc or less, more preferably 240s/100cc or less:
A porous polymer membrane selected from at least one of a porous PP membrane, a porous PE membrane, a porous PI membrane, a porous PAN membrane, a porous PVDF membrane and a porous PMMA membrane, and has a porosity of 30-85%;
The non-woven fabric comprises at least one of PP non-woven fabric, PE non-woven fabric, PET non-woven fabric and PTFE non-woven fabric, and the aperture is less than or equal to 10um.
2. A pressure-sensitive adhesive layer 1 having a thickness of 0.5 to 50 μm, the pressure-sensitive adhesive layer 1 being capable of entirely covering the porous substrate 2, see fig. 1; may also be laminated in a pattern on the porous substrate 2, for example with a coverage area of less than 50%, preferably 10-50%, more preferably 20-40% of the total area of the porous substrate 2;
comprises at least one raw material composition of the composition (1) or the composition (2):
composition (1), in weight percent, comprising: 20-45% of rubber component, 5-25% of viscosity modifier, 30-75% of filler, and optional tackifying resin and carbonate compound;
Preferably, the method comprises the steps of:
(1.1) at least one of the rubber components selected from SIS, SEBS, SEPS, SBr, TPU; preferably, the styrene content in SIS, SEBS, SEPS, SBr is less than or equal to 40wt%;
(1.2) the viscosity modifier is selected from at least one of liquid polyolefin and naphthenic mineral oil;
(1.3) the tackifying resin is selected from at least one of (hydrogenated) C5 resins, (hydrogenated) C9 resins, (hydrogenated) DCPD resins.
Composition (2), comprising in weight percent: 20-70% of hydroxyl/carboxyl end-capped acrylate resin, 1-10% of curing agent, 25-75% of filler and optional carbonate compound;
Preferably, the method comprises the steps of:
(2.1) the molecular weight of the hydroxy/carboxy terminated acrylate resin is from 20,000 to 500,000Da;
(2.2) the curing agent is at least one selected from the group consisting of multifunctional epoxy and multifunctional isocyanate.
Wherein, the hydroxyl/carboxyl end-capped acrylate resin can be prepared by adopting a thermal initiation method or a photoinitiation method.
A thermally initiated process for preparing a hydroxy/carboxy terminated acrylate resin comprising:
I) Heating the reaction kettle to 40-50 ℃, adding 3-6 parts of acrylate prepolymer, 80-120 parts of common acrylate monomer and 140-160 parts of solvent in parts by weight, and stirring at a speed of 30-60rpm for 30-90min;
II) heating to 55-65 ℃ and introducing nitrogen, then dropwise adding part (about 5-8 parts, 50-65% of the total solution) of a thermal initiator solution (solid content 0.5-1.5 wt.%) and
140-150 Parts of solvent and stirring at 20-60rpm for at least 4 hours;
III) when the viscosity reaches 9,000+/-200 cps and the molecular weight reaches 12,000+/-300 Da, adding 140-155 parts of another part (about 2-4 parts and accounting for 25-35% of the total solution) of the thermal initiator solution and the solvent, heating to 70-75 ℃ and continuing to react for at least 3 hours;
IV) when the viscosity and the molecular weight reach the requirements (for example, the viscosity reaches 14,000+/-200 cps, the molecular weight reaches 40,000+/-300 Da), adding the rest of the thermal initiator solution (about 0.5-1.5 parts, accounting for 10-15% of the total amount of the solution), 145-155 parts of solvent and 1-3 parts of acrylate monomer for end capping, and reacting for 3-5 hours;
v) discharging when the viscosity and molecular weight reach the requirements (for example, the viscosity reaches 20,000+/-200 cps, and the molecular weight reaches 50,000+/-300 Da).
The photoinitiation method for preparing the hydroxyl/carboxyl terminated acrylate resin comprises the following steps:
I) Adding 3-6 parts of acrylate prepolymer, 80-120 parts of common acrylate monomer and 140-160 parts of solvent into a reaction kettle, and stirring at a speed of 30-60rpm for 30-90min;
II) introducing nitrogen, then adding part (about 4-6 parts, 45-55% of the total solution) of photoinitiator solution (solid content 0.5-1.5 wt%) and solvent 140-150 parts, stirring at 20-40rpm for at least 30min;
III) irradiating the side wall of the reaction kettle with ultraviolet light (for example, the wavelength of 365nm of the LED) at a distance of 10+/-1 cm and a power of 5-15mW/cm 2, adding 140-150 parts of the photoinitiator solution and the solvent when the viscosity reaches 9,000+/-200 cps and the molecular weight reaches 12,000+/-300 Da, and increasing the rotating speed to 55-65rpm;
IV) when the viscosity and molecular weight reach the requirements (for example, the viscosity reaches 14,000+/-200 cps, the molecular weight reaches 40,000+/-300 Da), adding the rest photoinitiator solution (about 0.5-1.5 parts, accounting for 10-20% of the total solution), 145-155 parts of solvent and 1-3 parts of end-capping acrylate monomer;
v) when the viscosity and molecular weight meet the requirements (for example, the viscosity reaches 20,000.+ -. 2)
200Cps, molecular weight up to 50,000.+ -. 300 Da), stopping irradiation and discharging.
Among them, the acrylate prepolymer is preferably a difunctional acrylate prepolymer: epoxy modified polyurethanes, polyether polyurethanes, polyester polyurethanes, polycarbonate polyurethane acrylate resins, and the like, and having a molecular weight of 2,000 to 6,000Da;
And (3) a photoinitiator: 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, 1-hydroxycyclohexyl phenyl ketone, alpha-dimethoxy-alpha-phenyl acetophenone, 2, 4-dihydroxybenzophenone, and the like. The addition amount of the photoinitiator is 0.1% -0.5% of the sum of the prepolymer and the monomer.
Thermal initiator: azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, dibenzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, t-butyl peroxybenzoate, t-butyl peroxyvalerate, and the like. The addition amount of the thermal initiator is 0.1% -0.5% of the sum of the prepolymer and the monomer.
Common acrylate monomers: tricyclodecane dimethanol diacrylate, triethylene glycol dimethacrylate, ethoxylated bisphenol A acrylate, ethoxylated bisphenol A dimethacrylate, and propoxylated neopentyl glycol diacrylate.
Hydroxyl-terminated acrylate monomer: one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, propyl methacrylate, hydroxybutyl acrylate, and hydroxybutyl methacrylate.
Carboxyl-terminated acrylate monomer: at least one of acrylic acid and methacrylic acid.
Solvent: ethyl acetate, butyl acetate, toluene, methyl isobutyl ketone, butanone, and the like.
In the compositions (1) and (2), the content of the carbonate compound is preferably 10 to 20%, and at least one of the carbonate compounds selected from the group consisting of ethylene carbonate, propylene carbonate, methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate and methyl propyl carbonate is preferably used.
The filler is at least one selected from boehmite, talcum powder and silicon dioxide, and adopts a porous filler and/or compound filler form;
A porous filler having a porosity of 20% or more, a specific surface area of 2m 2/g or more, preferably 10m 2/g or more, and a preferable particle diameter of 10nm to 10 μm; more preferably, a boehmite-based porous filler is used, D10 is 10nm to 2 μm, D50 is 50nm to 3 μm, and D90 is 100nm to 5 μm;
The compound filler adopts small-particle-size filler with the particle size of 1-600nm and large-particle-size filler with the particle size of 700nm-15 mu m, preferably 700nm-10 mu m, according to the weight ratio (20-40): (60-80) compounding. Wherein, during compounding, the small-particle-size filler and the large-particle-size filler can be the same or different types, and the compounded filler can also be porous filler.
The preparation method for the high-permeability adhesive tape comprises the following steps:
Step one, preparing a pressure-sensitive adhesive layer 1 coating solution:
Weighing each component according to the composition of the raw materials, and uniformly mixing each component with a solvent to obtain a coating liquid; the solvent is an organic solvent, and is selected from at least one of toluene, xylene, methylcyclohexane, ethyl acetate, butyl acetate, butanone, methyl isobutyl ketone, ethanol and isopropanol, and the solid content of the coating liquid is 5-60wt%.
Step two, coating film formation:
the coating liquid is coated on the porous substrate 2, and the porous substrate 2 is dried to form the pressure-sensitive adhesive layer 1, so that the high-permeability adhesive tape is obtained.
Or the coating liquid is coated on a release film, dried and transferred to a porous substrate 2 to form a pressure-sensitive adhesive layer 1, so as to obtain the high-permeability adhesive tape, and the performance of the obtained product is basically similar to that of the direct coating mode.
When the pressure-sensitive adhesive layer 1 is patterned to cover the surface of the porous substrate 2, the coating solution can be coated and dried on the porous substrate 2 to obtain a certain pattern, or coated on the release film to obtain a certain pattern, and after drying, the pattern on the release film is transferred to the porous substrate 2.
Step three, tape winding:
And coating a release agent on the back surface of the porous substrate 2 or arranging a release film on the surface of the pressure-sensitive adhesive layer 1, and rolling the adhesive tape to prepare the single-sided rolled high-permeability adhesive tape.
The initial air permeability of the high air permeability adhesive tape is less than 350s/100cc, and the air permeability after being soaked in electrolyte is less than 370s/100cc. And the peeling strength is reduced by less than 15 percent, preferably less than 10 percent, before and after the electrolyte is soaked, so that the adhesive tape has higher adhesiveness and electrolyte stability, and long-term stable use of the adhesive tape in a battery is ensured.
The following examples are given in Table A for reference only and are not intended to limit the invention.
Table A
1. Self-made hydroxyl-terminated acrylate resin by a thermal initiation method, comprising:
i) The reaction kettle is heated to 45 ℃,5 parts of polyurethane acrylic ester prepolymer (molecular weight about 5,000Da, brand UN-9000 PEP), 100 parts of tricyclodecane dimethanol diacrylate monomer (brand SR833 s) and 150 parts of ethyl acetate are added in parts by weight, and stirring is carried out at a speed of 45rpm for 60 minutes;
II) heating to 60 ℃ and introducing nitrogen, then dropwise adding part (about 6 parts, accounting for 60% of the total solution) of a thermal initiator solution (solid content 1.0 wt%) and 150 parts of ethyl acetate, and stirring at 45rpm for 5 hours; the thermal initiator adopts azobisisobutyronitrile, and the addition amount is 0.2% of the sum of the mass of the prepolymer and the mass of the monomer;
III) when the viscosity reaches 9,000+/-100 cps and the molecular weight reaches 12,000+/-150 Da, adding the other part (about 2.5 parts, accounting for 25 percent of the total solution) of the thermal initiator solution and 150 parts of ethyl acetate, heating to 70 ℃ and continuing to react for 4 hours;
IV) when the viscosity reaches 14,000+/-100 cps and the molecular weight reaches 40,000+/-150 Da, adding residual thermal initiator solution (about 1.5 parts, accounting for 15% of the total solution), 150 parts of ethyl acetate and 2 parts of hydroxyethyl acrylate monomer for end capping, and reacting for 4 hours;
v) discharging when the viscosity reaches 200,000+/-100 cps and the molecular weight reaches 310,000+/-150 Da.
2. The self-made carboxyl end-capped acrylic resin by a photoinitiation method comprises the following steps:
I) 5 parts of polyurethane acrylic ester prepolymer (molecular weight of about 5,000Da, brand No-9000 PEP), 100 parts of tricyclodecane dimethanol diacrylate monomer and 150 parts of ethyl acetate are stirred at a speed of 45rpm for 60 minutes;
II) introducing nitrogen, then adding part (about 5 parts, 50% of the total solution) of photoinitiator solution (solid content 1.2 wt%) and 150 parts of ethyl acetate, stirring at 30rpm for 45min; the photoinitiator is2, 4, 6-trimethyl benzoyl-diphenyl phosphine oxide, and the addition amount is 0.25% of the sum of the prepolymer and the monomer;
III) irradiating the side wall of the reaction kettle by using ultraviolet light with the wavelength of 365nm of an LED, wherein the distance is 10+/-1 cm, the power is 10mW/cm 2, when the viscosity reaches 9,000+/-100 cps and the molecular weight reaches 12,000+/-150 Da, adding the other part (about 4 parts, accounting for 40 percent of the total amount of the solution) of the photoinitiator solution and 150 parts of ethyl acetate, and increasing the rotating speed to 60rpm;
IV) when the viscosity reaches 14,000+/-100 cps and the molecular weight reaches 40,000+/-150 Da, adding the rest photoinitiator solution (about 1.0 part, accounting for 10 percent of the total solution), 150 parts of ethyl acetate, 1 part of acrylic monomer for end capping and 1 part of methacrylic monomer;
V) stopping irradiation and discharging when the viscosity reaches 200,000+/-100 cps and the molecular weight reaches 320,000+/-150 Da.
Preparation example 1:
the preparation method of the high-permeability adhesive tape sample comprises the following steps:
Step one, preparing pressure-sensitive adhesive layer coating liquid:
weighing the components according to the raw material proportion of the component (1), and uniformly mixing the components with a solvent to obtain a coating liquid; the solvent is toluene, and the solid content of the coating liquid is 15%;
step two, coating film formation:
Coating the coating liquid on a release film, drying and transferring to a porous PP film substrate to form a pressure-sensitive adhesive layer, so as to obtain the high-permeability adhesive tape;
Step three, tape winding:
And coating a release agent on the back surface of the porous PP film, and rolling the adhesive tape to prepare the high-permeability adhesive tape with one-sided rolling.
Preparation example 1 corresponds to the samples of examples 1-1 to 1-11, wherein the porous PP film has a porosity of 45±10%;
comparative examples 1-1, 1-2 and 1-3:
Comparative examples 1-1 differ from examples 1-3 in that no filler was used;
comparative examples 1-2 differ from examples 1-3 in that the filler amount was increased by about 75.8% by weight of the filler calculated;
comparative examples 1-3 differ from examples 1-3 in that only the filler XH-SiO 2 -800 was used. Specific parameters are shown in tables 1-1-1 and 1-1-2:
TABLE 1-1
TABLE 1-1-2
Preparation example 2:
the preparation method of the high-permeability adhesive tape sample comprises the following steps:
Step one, preparing pressure-sensitive adhesive layer coating liquid:
weighing the components according to the raw material proportion of the component (1), and uniformly mixing the components with a solvent to obtain a coating liquid; the solvent is toluene, and the solid content of the coating liquid is 15%;
step two, coating film formation:
coating the coating liquid on a release film, drying and transferring to a PP non-woven fabric substrate to form a pressure-sensitive adhesive layer, so as to obtain the high-permeability adhesive tape;
Step three, tape winding:
coating a release agent on the back of the PP non-woven fabric, and rolling the adhesive tape to prepare the high-permeability adhesive tape with one-sided rolling.
Preparative example 2 corresponds to the samples of examples 1-12 to 1-18;
comparative examples 1 to 4, 1 to 5 and 1 to 6:
Comparative examples 1 to 4 differ from examples 1 to 13 in that no filler was used;
Comparative examples 1-5 differ from examples 1-13 in that the filler amount was increased by about 75.6% by weight of the filler calculated;
Comparative examples 1 to 6 differ from examples 1 to 13 in that only the filler XH-SiO 2 -800 was used. Specific parameters are shown in tables 1-2:
TABLE 1-2
Preparation example 3:
the preparation method of the high-permeability adhesive tape sample comprises the following steps:
Step one, preparing pressure-sensitive adhesive layer coating liquid:
Weighing the components according to the raw material proportion of the component (2), and uniformly mixing the components with a solvent to obtain a coating liquid; the solvent is ethyl acetate, and the solid content of the coating liquid is 20%.
Step two, coating film formation:
Coating the coating liquid on a release film, drying and transferring to a porous PP film substrate to form a pressure-sensitive adhesive layer, so as to obtain the high-permeability adhesive tape;
Step three, tape winding:
And coating a release agent on the back surface of the porous PP film, and rolling the adhesive tape to prepare the high-permeability adhesive tape with one-sided rolling.
Preparation example 3 corresponds to the samples of examples 2-1 to 2-12, wherein the porous PP film has a porosity of 45±10%;
Comparative examples 2-1, 2-2 and 2-3:
comparative example 2-1 differs from example 2-2 in that no filler was used;
Comparative example 2-2 differs from example 2-2 in that the filler amount was increased by about 75.3% by weight of the filler in terms of the filler;
Comparative example 2-3 differs from example 2-2 in that only the filler XH-SiO 2 -800 was used. Specific parameters are shown in tables 2-1-1 and 2-1-2:
TABLE 2-1
TABLE 2-1-2
Preparation example 4:
the preparation method of the high-permeability adhesive tape sample comprises the following steps:
Step one, preparing pressure-sensitive adhesive layer coating liquid:
Weighing the components according to the raw material proportion of the component (2), and uniformly mixing the components with a solvent to obtain a coating liquid; the solvent is ethyl acetate, and the solid content of the coating liquid is 20%;
step two, coating film formation:
coating the coating liquid on a release film, drying and transferring to a PP non-woven fabric substrate to form a pressure-sensitive adhesive layer, so as to obtain the high-permeability adhesive tape;
Step three, tape winding:
coating a release agent on the back of the PP non-woven fabric, and rolling the adhesive tape to prepare the high-permeability adhesive tape with one-sided rolling.
Preparation example 4 samples corresponding to examples 2-13 to 2-19;
comparative examples 2-4, 2-5 and 2-6:
comparative examples 2 to 4 differ from examples 2 to 14 in that no filler was used;
Comparative examples 2-5 differ from examples 2-14 in that the filler amount was increased by about 75.7% by weight of the filler calculated;
Comparative examples 2 to 6 differ from examples 2 to 14 in that only the filler XH-SiO 2 -800 was used. Specific parameters are shown in Table 2-2:
TABLE 2-2
The testing method comprises the following steps:
(1) Peel Strength test method-before soaking liquid
The testing method comprises the following steps: cleaning an aluminum foil to be tested by using isopropanol, airing, and cutting a tape sample into strips with the width of 24mm and the length of 100 mm; sticking the surface to be measured of the adhesive tape sample strip to the aluminum foil to be measured, avoiding bubbles or wrinkles, and slowly pressing three back and forth by using a 2kg pressing wheel at a speed of 300 mm/min; attaching the back surface (non-adhesive tape surface) of the aluminum foil to the stainless steel plate by using a double-sided adhesive tape, starting timing by a timer, and maintaining for 20min; one end of the stainless steel plate is fixed on a lower clamp of the tension machine and is perpendicular to a horizontal plane, and the equipment is cleared; the other clamp clamps the substrate of the tape sample bar, the peeling test is carried out according to the speed of 304.8mm/min, and a section (not shorter than 80 mm) with stable data is selected for calculating the peeling strength in N/m.
(2) Method for testing peel strength after soaking
The testing method comprises the following steps: cleaning an aluminum foil to be tested by using isopropanol, airing, cutting a tape sample into strips with the width of 24mm and the length of 100mm, attaching the surface to be tested of the tape strip to the aluminum foil to be tested, avoiding bubbles or wrinkles, and slowly pressing three back and forth by using a 2kg pressing wheel at the speed of 300 mm/min; the timer starts to count and maintains for 20min; placing into a container filled with electrolyte solvent (specific components and proportions of the electrolyte solvent are diethyl carbonate DEC:50%, ethylene carbonate EC:30%, ethylmethyl carbonate EMC: 20%) and passing through the liquid surface, sealing, baking at 85deg.C for 24hrs, and taking out to wipe off the surface solvent; attaching the back surface (non-adhesive tape surface) of the aluminum foil to the stainless steel plate by using a double-sided adhesive tape, starting timing by a timer, and standing for 20min; one end of the stainless steel plate is fixed on a lower clamp of the tension machine and is perpendicular to a horizontal plane, and the equipment is cleared; the other clamp clamps the substrate of the adhesive tape sample, the peeling test is carried out at a speed of 304.8mm/min, and a section (not shorter than 80 mm) with stable data is selected for calculating the peeling strength in N/m.
(3) Air permeability testing method
Cutting the adhesive tape sample into round films with the diameter of more than 10cm or square films with the side length of more than 10 cm; opening a device switch, and propping the sliding barrel against the top of the sliding barrel; rotating the sliding barrel, wherein the infrared probe is perpendicular to the central axis of a 100ml test area; placing the film to be tested on a test seat and screwing; the screen displays "TIMER SEEKING STARTING MARK", and after pressing the "RESET" key, the slide is released to begin the test. After the test is completed, the values in the screen are read in s/100cc. The air permeability after soaking is tested by firstly putting a square film which is cut into a round shape with the diameter of more than 10cm or with the side length of more than 10cm into a container which is filled with electrolyte solvent (the specific components and proportion of the electrolyte solvent are that diethyl carbonate DEC is 50%, ethylene carbonate EC is 30% and ethylmethyl carbonate EMC is 20%) and the container is not over the liquid level, sealing and putting the container into 85 ℃ for baking for 24hrs, taking out and wiping the surface solvent, and then testing the air permeability according to the steps.
The test results for the foregoing examples are shown in tables 1-3, 1-4 and 2-3, 2-4, where NA represents that no effective test can be performed:
Tables 1 to 3
Tables 1 to 4
As can be seen from tables 1-3 and 1-4, when composition (1) is selected, the pressure-sensitive adhesive layer comprising the rubber component gives the tape a good initial air permeability, and particularly when the filler percentage is 40-65%, the tape retains a good air permeability after the electrolyte is immersed; the error condition is considered, the change of the peel strength of the adhesive tape before and after soaking is very small, and the overall specification shows that the pressure-sensitive adhesive layer has higher adhesiveness and electrolyte stability, so that the long-term stable use of the adhesive tape in a battery is ensured. Among them, comparative examples 1-1 and 1-4, which do not contain filler, do not have a filler content of comparative examples 1-2 and 1-5 too high, and comparative examples 1-3 and 1-6 only select a single particle size non-porous filler XH-SiO 2 -800, which cannot make the adhesive tape compatible with breathability and adhesiveness. In the proper range of filler levels, examples 1-10 and 1-17 have lower filler levels and slightly less air permeability than other examples of the same type, but are also able to meet most application requirements.
Tables 2 to 3
Tables 2 to 4
As can be seen from tables 2-3 and 2-4, when composition (2) is selected, the pressure-sensitive adhesive layer comprising the hydroxyl/carboxyl terminated acrylate resin component gives the tape a good initial air permeability, particularly when the filler percentage is 40-65%, and the tape retains good air permeability after the electrolyte is immersed; the error condition is considered, the change of the peel strength of the adhesive tape before and after soaking is very small, and the overall specification shows that the pressure-sensitive adhesive layer has higher adhesiveness and electrolyte stability, so that the long-term stable use of the adhesive tape in a battery is ensured. Among them, comparative examples 2-1 and 2-4, which do not contain filler, do not have a filler content of comparative examples 2-2 and 2-5 too high, and comparative examples 2-3 and 2-6, which are only selected from the non-porous filler XH-SiO 2 -800 having a single particle size, do not allow the adhesive tape to have both breathability and adhesiveness. In the proper range of filler content, examples 2-11 and 2-18 have lower filler content and slightly less air permeability than other examples of the same type, but can meet most application requirements.
In contrast, the samples of the examples corresponding to the composition (1) and the composition (2) were selected to have better initial air permeability and bubble air permeability of the adhesive tape, while the sample of the example selected to the composition (2) was higher in peel strength as a whole than the sample of the example selected to the composition (1). The usage is selected according to specific usage environment and requirement.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, the present invention includes the preferred embodiments and all the variations and modifications associated therewith. It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit and scope of the invention, and it is intended that the invention encompass such modifications and variations as fall within the scope of the invention and its equivalents.
Claims (10)
1. The high-permeability adhesive tape is characterized by comprising a porous base material and a pressure-sensitive adhesive layer;
the thickness of the porous base material is 5-50 μm, and the porous base material is at least one selected from porous polymer membrane and non-woven fabric;
the thickness of the pressure-sensitive adhesive layer is 0.5-50 mu m, and the pressure-sensitive adhesive layer comprises at least one raw material composition of the composition (1) or the composition (2):
the composition (1) comprises, in weight percent:
20-45% of rubber component, 5-25% of viscosity modifier, 30-75% of filler, and optional tackifying resin and carbonate compound;
the composition (2) comprises, in weight percent:
20-70% of hydroxyl/carboxyl end-capped acrylate resin, 1-10% of curing agent, 25-75% of filler and optional carbonate compound;
The filler comprises a filler with the particle size of 1nm-15 mu m;
The initial air permeability of the high air permeability adhesive tape is less than 350s/100cc, and the air permeability after the high air permeability adhesive tape is immersed in electrolyte is less than 370s/100cc.
2. The high permeability adhesive tape according to claim 1, wherein the porous polymer membrane is at least one selected from the group consisting of porous PP membrane, porous PE membrane, porous PI membrane, porous PAN membrane, porous PVDF membrane, and porous PMMA membrane, and has a porosity of 30-85%;
The non-woven fabric comprises at least one of PP non-woven fabric, PE non-woven fabric, PET non-woven fabric and PTFE non-woven fabric, and the aperture is less than or equal to 10 mu m.
3. The high permeability adhesive tape according to claim 1 or 2, wherein the filler is at least one selected from boehmite, talc and silica.
4.A high permeability adhesive tape according to claim 3, wherein said filler comprises a porous filler having a specific surface area of 2m 2/g or more; and/or
The compound filler adopts small-particle-size filler with the particle size of 1-600nm and large-particle-size filler with the particle size of 700-15 mu m according to the weight ratio of (20-40): (60-80) compounding.
5. A high permeability adhesive tape according to claim 3, wherein composition (1) comprises, in weight percent:
At least one rubber component selected from SIS, SEBS, SEPS, SBr, TPU;
the viscosity regulator is at least one selected from liquid polyolefin and naphthenic mineral oil;
The tackifying resin is selected from at least one of (hydrogenated) C5 resin, (hydrogenated) C9 resin and (hydrogenated) DCPD resin.
6. A high permeability adhesive tape according to claim 3, wherein composition (2) comprises, in weight percent:
the hydroxyl/carboxyl terminated acrylate resin has a molecular weight of 20,000-500,000Da;
the curing agent is at least one of polyfunctional epoxy and polyfunctional isocyanate.
7. The high-permeability adhesive tape according to claim 5 or 6, wherein the content of the carbonate compound is 10 to 20% and is at least one selected from the group consisting of ethylene carbonate, propylene carbonate, ethylmethyl carbonate, dimethyl carbonate, diethyl carbonate and methylpropyl carbonate.
8. A method of preparing the high air permeability adhesive tape according to any one of claims 1 to 7, comprising the steps of:
Step one, preparing pressure-sensitive adhesive layer coating liquid:
weighing each component according to the composition of the raw materials, and uniformly mixing each component with a solvent to obtain a coating liquid;
step two, coating film formation:
Coating the coating liquid on a porous substrate, and drying to form a pressure-sensitive adhesive layer to obtain a high-permeability adhesive tape; or alternatively
Coating the coating liquid on a release film, drying and transferring to a porous substrate to form a pressure-sensitive adhesive layer, so as to obtain the high-permeability adhesive tape;
Step three, tape winding:
and coating a release agent on the back surface of the porous substrate or arranging a release film on the surface of the pressure-sensitive adhesive layer, and rolling the adhesive tape to prepare the single-sided rolled high-permeability adhesive tape.
9. The method according to claim 8, wherein the solvent is an organic solvent including at least one of toluene, xylene, methylcyclohexane, ethyl acetate, butyl acetate, butanone, methyl isobutyl ketone, ethanol, and isopropanol, and the solid content of the coating liquid is 5to 60wt%.
10. Use of the high air permeability adhesive tape of any one of claims 1-7 in lithium battery pole piece protection, tab protection, winding and winding.
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