CN114058273A - Resin-based film, adhesive tape and method for preparing conductive pole piece by using adhesive tape - Google Patents
Resin-based film, adhesive tape and method for preparing conductive pole piece by using adhesive tape Download PDFInfo
- Publication number
- CN114058273A CN114058273A CN202111313698.9A CN202111313698A CN114058273A CN 114058273 A CN114058273 A CN 114058273A CN 202111313698 A CN202111313698 A CN 202111313698A CN 114058273 A CN114058273 A CN 114058273A
- Authority
- CN
- China
- Prior art keywords
- resin
- based film
- adhesive tape
- film
- adhesive
- 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.)
- Pending
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- 229920005989 resin Polymers 0.000 title claims abstract description 206
- 239000011347 resin Substances 0.000 title claims abstract description 206
- 239000002390 adhesive tape Substances 0.000 title claims abstract description 96
- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 claims abstract description 15
- 239000012790 adhesive layer Substances 0.000 claims description 46
- 239000000853 adhesive Substances 0.000 claims description 44
- 230000001070 adhesive effect Effects 0.000 claims description 44
- 239000010410 layer Substances 0.000 claims description 39
- 239000000203 mixture Substances 0.000 claims description 37
- 238000011282 treatment Methods 0.000 claims description 26
- 239000000758 substrate Substances 0.000 claims description 18
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 7
- 239000000956 alloy Substances 0.000 claims description 7
- 229910001416 lithium ion Inorganic materials 0.000 claims description 7
- 230000005855 radiation Effects 0.000 claims description 7
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000002356 single layer Substances 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 3
- 210000002469 basement membrane Anatomy 0.000 claims description 2
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 44
- 239000000178 monomer Substances 0.000 description 22
- -1 polyethylene terephthalate Polymers 0.000 description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 16
- 150000001336 alkenes Chemical class 0.000 description 15
- 239000011149 active material Substances 0.000 description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- 238000003490 calendering Methods 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 11
- 229910052782 aluminium Inorganic materials 0.000 description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 11
- 229920001577 copolymer Polymers 0.000 description 11
- 239000003431 cross linking reagent Substances 0.000 description 11
- 230000001681 protective effect Effects 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- WWUVJRULCWHUSA-UHFFFAOYSA-N 2-methyl-1-pentene Chemical compound CCCC(C)=C WWUVJRULCWHUSA-UHFFFAOYSA-N 0.000 description 8
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 8
- OTTZHAVKAVGASB-UHFFFAOYSA-N hept-2-ene Chemical compound CCCCC=CC OTTZHAVKAVGASB-UHFFFAOYSA-N 0.000 description 8
- 229920005992 thermoplastic resin Polymers 0.000 description 8
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 6
- 125000002723 alicyclic group Chemical group 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 239000003292 glue Substances 0.000 description 6
- 229920000728 polyester Polymers 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
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- 238000012545 processing Methods 0.000 description 6
- 239000004831 Hot glue Substances 0.000 description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 5
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- 239000002904 solvent Substances 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
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- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 3
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- 239000004952 Polyamide Substances 0.000 description 3
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- 125000000217 alkyl group Chemical group 0.000 description 3
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- 238000005187 foaming Methods 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 3
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- VQOXUMQBYILCKR-UHFFFAOYSA-N 1-Tridecene Chemical compound CCCCCCCCCCCC=C VQOXUMQBYILCKR-UHFFFAOYSA-N 0.000 description 2
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- ADOBXTDBFNCOBN-UHFFFAOYSA-N 1-heptadecene Chemical compound CCCCCCCCCCCCCCCC=C ADOBXTDBFNCOBN-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- PJLHTVIBELQURV-UHFFFAOYSA-N 1-pentadecene Chemical compound CCCCCCCCCCCCCC=C PJLHTVIBELQURV-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 2
- LIMAEKMEXJTSNI-UHFFFAOYSA-N 2,3-dimethylpent-1-ene Chemical compound CCC(C)C(C)=C LIMAEKMEXJTSNI-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- 125000006539 C12 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 229920006257 Heat-shrinkable film Polymers 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000008064 anhydrides Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
-
- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/29—Laminated material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- 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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/33—Applications of adhesives in processes or use of adhesives in the form of films or foils for batteries or fuel cells
-
- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/50—Additional features of adhesives in the form of films or foils characterized by process specific features
- C09J2301/502—Additional features of adhesives in the form of films or foils characterized by process specific features process for debonding adherents
-
- 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
- C09J2423/00—Presence of polyolefin
- C09J2423/04—Presence of homo or copolymers of ethene
- C09J2423/046—Presence of homo or copolymers of ethene in the substrate
-
- 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
- C09J2427/00—Presence of halogenated polymer
- C09J2427/006—Presence of halogenated polymer in the substrate
-
- 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
- C09J2433/00—Presence of (meth)acrylic polymer
-
- 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
- C09J2467/00—Presence of polyester
- C09J2467/006—Presence of polyester in the substrate
-
- 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
- C09J2475/00—Presence of polyurethane
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to a resin-based film, an adhesive tape and a method for preparing a conductive pole piece by using the adhesive tape. The resin-based film or the adhesive tape using the resin-based film according to the present invention has improved removability in the production of electronic device components.
Description
Technical Field
The invention belongs to the field of electronic equipment element preparation, particularly relates to the field of energy storage electronic equipment element preparation, and more particularly relates to an adhesive tape for an electrode pole piece, a resin base film for the adhesive tape and a method for preparing the electrode pole piece by adopting the adhesive tape and the resin base film.
Background
The re-releasable adhesive tape has been used in the manufacture of various electronic device elements (e.g., semiconductor elements, electrode elements, etc.). By utilizing the removability of the removable adhesive tape, it is possible to perform temporary fixing, transfer, protection, and the like of the whole or a part of the elements during the process of manufacturing these elements.
In general, these removable adhesive tapes are required to have initial adhesive force satisfying requirements when they are bonded to an adherend and to have adhesive force decaying with time or after being subjected to external stimulus so as to be re-removable as needed.
For re-peeling, it is generally required that the adhesive tape can be entirely and rapidly peeled from the adherend surface under prescribed conditions, and such peeling is also required to neither cause damage (e.g., adherend surface breakage) and contamination (e.g., adhesive layer portion remaining on the adherend surface) of the adherend substrate nor cause a decrease in re-peeling quality or efficiency due to tearing of the base film of the adhesive tape. In particular, as electronic device components are becoming more miniaturized and miniaturized, the demand for re-peeling of the adhesive tape is becoming higher.
For example, cited document 1 discloses a pressure-sensitive adhesive sheet comprising an energy ray-curable pressure-sensitive adhesive layer of a layered structure and a heat-shrinkable film. This pressure-sensitive adhesive sheet, because the heat-shrinkable sheet shrinks under irradiation of energy rays, can prevent elongation or crease from being generated in the sheet such as under irradiation of ultraviolet light.
Further, with the mass industrial production of new energy devices, the manufacturing requirements for the electronic device components in the energy storage device are also increasing, both qualitatively and efficiently.
It is known that when preparing an electrode sheet in an energy storage device, it is generally necessary to plan a region for connecting a tab on the surface of a metal electrode sheet or electrode sheet after obtaining the electrode sheet. The position is further bonded using an adhesive tape for temporary protection. After that, the electrode sheet is coated with a composition containing an active material to form an active layer. Simultaneously with or after drying the active layer, the adhesive tape is peeled from the surface of the electrode sheet by utilizing the shrinkage caused by the heating of the adhesive tape, thereby exposing the solderable part.
For example, citation 2 discloses a method for preparing a lithium ion battery pole piece, which comprises: pasting heat shrinkable glue at the reserved position of a lug of the current collector, then coating active materials on the surfaces of the current collector and the heat shrinkable glue, and removing the heat shrinkable glue and active substances coated on the heat shrinkable glue after heating; the heat-shrinkable adhesive comprises a base material and a foaming bonding layer. The unidirectional heat shrinkage rate of the base material is 60-80%.
However, although various studies have been made in the related art on an adhesive tape used in the production of electronic components as described above, the improvement of the related art has not been sufficient to provide an adhesive tape having improved removability and improved production efficiency, and there is room for further investigation.
Cited documents:
cited document 1: japanese patent No.3073239
Cited document 2: CN105742565A
Cited document 3: CN113437259A
Cited document 4: CN112289980A
Cited document 5: CN106811143A
Disclosure of Invention
The invention is to solveProblem(s)
As described above, although the prior art has been studied as described above with respect to a releasable adhesive tape for electronic device component processing, in production practice, the following problems have also been found:
in the cited document 1, although the mechanical properties of the pressure-sensitive adhesive sheet are increased by utilizing the heat shrinkage to shrink the substrate, and thus the pressure-sensitive adhesive sheet can be prevented from breaking or the like, it is found that the overall removability is insufficient in the actual operation.
In the cited document 2, re-peeling is achieved by the combined action of the heat shrinkable film and the foamable component of the adhesive layer under heating, but the addition of the foamable component also raises a fear of increasing dimensional instability of the adhesive layer upon thermal history, and is particularly liable to cause poor processing at the edge portion, and is particularly disadvantageous for miniaturization or fine processing of the device. Similarly, both cited documents 3 and 5 use a resin film having heat shrinkability as a base film of an adhesive tape, and re-peeling of the adhesive tape is assisted by the heat shrinkability of the base film. However, in the cited documents 2,3 and 5, only the heat shrinkage rate of the base film in a certain temperature range is taken into consideration, and the stress state at the time of heat shrinkage is not examined, and in the specific application, it is found that, although a resin film satisfying the heat shrinkage rate specified in these documents is used as the base film, poor removability occurs, for example, peeling of the base film from the pressure-sensitive adhesive layer occurs at the time of heat shrinkage, and a removability failure occurs, or the pressure-sensitive adhesive layer remains on the surface of the adherend, and even removability cannot be performed.
Further, although the adhesive layer having heat-shrinkable properties is used as it is in cited document 4, it is found that in practical use, workability may be lowered by not using a base film, and the adhesive is likely to remain in a peeling process after heat shrinkage.
Therefore, based on the intensive practice and analysis of the prior art, the primary technical problem to be solved by the present invention is to provide a resin-based film suitable for use in an adhesive tape used in the production of electronic device components, particularly electrode components, which enables an adhesive tape containing the base film to have significantly improved removability in a re-peeling process by adjusting the shrinkage stress value and the gel fraction of the resin-based film.
Further, an object of the present invention is to provide an adhesive tape suitable for use in the production of electronic device components, particularly electrode components, which has good peeling efficiency when peeled again, and does not cause peeling failure or adhesive residue.
In addition, it is an object of the present invention to provide a method for producing an electronic device component, in particular an electrode component, which has improved production efficiency and improved product quality.
Means for solving the problems
After long-term intensive research by the inventor of the present invention, it is found that the technical problems can be solved by implementing the following technical scheme:
[1] the present invention first provides a resin base film for a re-releasable adhesive tape which is re-releasable via external stimulus after adhesion,
the resin-based film has:
the maximum shrinkage stress value in the MD direction is in a temperature range of 70 ℃ or more, and the maximum shrinkage stress value in the MD direction is 0.3-10 MPa,
and, the thickness of resin basilemma is 5 ~ 1000um, the gel fraction of resin basilemma is more than 10%.
[2] The resin-based film according to [1], wherein the maximum shrinkage stress value in the MD direction of the resin-based film occurs in a temperature range of 70 to 160 ℃.
[3] The resin-based film according to [1] or [2], wherein the resin-based film has a maximum shrinkage stress value in the MD direction of 0.5 to 9 MPa; the thickness of resin basal lamina is 10 ~ 300 um.
[4] The resin-based film according to any one of [1] to [3], wherein the resin-based film is a single-layer resin film or a multi-layer resin film; the gel rate of the resin-based film is 10-90%.
[5] The resin-based film according to [4], wherein at least one of the resin films has a shrinkage stress in the MD direction at 100 ℃ different from that of the other resin films.
[6] The resin-based film according to any one of [1] to [5], wherein the external stimulus includes at least one of a heat treatment or a radiation treatment or a combination thereof.
[7] Further, the present invention provides a releasable adhesive tape, wherein the adhesive tape comprises the resin base film according to any one of the above [1] to [6] and an adhesive layer formed on at least one surface of the resin base film.
[8] The adhesive tape according to [7], wherein the adhesive layer is formed by coating or sticking an adhesive composition on the surface of the resin base film, or is formed by co-extruding with the resin base film on the surface of the resin base film.
[9] Further, the present invention also provides a releasable adhesive tape, wherein the adhesive tape comprises a resin-based film layer and an adhesive layer formed on at least one surface of the resin-based film layer, wherein,
the maximum shrinkage stress value of the resin-based film in the MD direction is 0.3 to 10MPa,
and, after the adhesive tape is adhered to an adhered substrate, the following requirements are satisfied:
there is a temperature T in a temperature range of 70 ℃ or higher, and at this temperature T, the shrinkage stress value of the resin base film of the adhesive tape in the MD direction is 1.3 times or more the peeling force value of the adhesive layer from the adherend.
[10] The adhesive tape according to [9], wherein the substrate to be adhered is selected from a simple metal or an alloy of metals.
[11] The adhesive tape according to [9] or [10], wherein a maximum shrinkage stress value in the MD direction of the resin-based film in the adhesive tape occurs in a temperature range of 70 ℃ to 160 ℃.
[12] The adhesive tape according to any one of [9] to [11], wherein the resin-based film in the adhesive tape is a single-layer resin film or a multi-layer resin film; the gel rate of the resin-based film is 10-90%.
[13] The adhesive tape according to any one of [9] to [12], wherein the adhesive layer in the adhesive tape is formed by coating or adhering an adhesive composition on the surface of the resin base film, or the adhesive layer is formed by co-extruding with the resin base film on the surface of the resin base film.
[14] Furthermore, the invention also provides a preparation method of the conductive pole piece, wherein the method comprises the following steps:
a step of bonding, using the adhesive tape according to any one of the above [7] to [13], or the resin-based film according to any one of the above [1] to [6], to a region of the conductive electrode sheet having the adhesive; and
and a re-peeling step of subjecting the adhesive tape or the region having the adhesive to an external stimulus to re-peel it from the conductive electrode sheet.
[15] The method of [14], wherein the external stimulus comprises at least one of heat treatment, radiation treatment, or a combination thereof.
[16] In addition, the present invention also provides a method for producing a pole piece for a lithium ion battery, wherein the method comprises the method according to [14] or [15] above.
ADVANTAGEOUS EFFECTS OF INVENTION
Through the implementation of the technical scheme, the invention can obtain the following technical effects:
1) the resin-based film and the adhesive tape formed based on the resin-based film provided by the invention can show improved re-peeling characteristics in the re-peeling process mainly due to the optimization of conditions such as internal stress of the resin-based film when undergoing shrinkage, namely, the peeling of the substrate film and the adhesive layer can be avoided, and the poor peeling of the adhesive layer from the surface of an adherend can also be avoided;
2) the resin base film can be more easily formed into a curled shape during re-peeling and the problem of splashing can be avoided mainly by optimizing the shrinkage stress of the resin base film, so that the re-peeling efficiency can be improved;
3) the adhesive tape based on the resin-based film of the present invention does not require the use of a foamable component in the adhesive layer to assist re-peeling, and therefore, can have an improved appearance of the edge of the protected region, avoiding poor edge morphology.
Drawings
FIG. 1 Structure of adhesive tape in one embodiment of the invention
FIG. 2a use of the resin-based film in application example 1
FIG. 2b use of the resin-based film in application example 2
Detailed Description
The present invention will be described in detail below. The technical features described below are explained based on typical embodiments and specific examples of the present invention, but the present invention is not limited to these embodiments and specific examples. It should be noted that:
in the present specification, the numerical range represented by "numerical value a to numerical value B" means a range including the end point numerical value A, B.
In the present specification, the numerical ranges indicated by "above" or "below" mean the numerical ranges including the numbers.
In the present specification, the meaning of "may" includes both the meaning of performing a certain process and the meaning of not performing a certain process.
As used herein, the term "optional" or "optional" is used to indicate that certain substances, components, performance steps, application conditions, and the like are used or not used.
As used herein, "room temperature" means an indoor ambient temperature of "20 ℃.
In the present specification, the unit names used are all international standard unit names, and the "%" used means weight or mass% content, if not specifically stated.
In the present specification, the term "substantially" is used to indicate that the standard deviation from the theoretical model or theoretical data is within 5%, preferably 3%, and more preferably 1%.
In the present specification, the "MD" direction means the machine direction or the line direction, and the "TD" direction means the direction perpendicular to the machine direction or the water flow direction.
In the present specification, the term "surface" refers to the main surface of the resin film, i.e., the two opposing surfaces having the largest area.
In the present specification, reference to "some particular/preferred embodiments," "other particular/preferred embodiments," "embodiments," and the like, means that a particular element (e.g., feature, structure, property, and/or characteristic) described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various embodiments.
< first aspect >
In a first aspect of the present invention, a resin-based film is provided. The resin-based film is particularly suitable for an adhesive tape used in the production of electronic device components (e.g., semiconductor components, electrode components, etc.). The resin base film of the present invention can impart excellent removability to the pressure-sensitive adhesive tape mainly by adjusting the shrinkage stress in a specific temperature range.
(composition of resin original film)
The resin base film of the present invention can be obtained by subjecting a resin base film to a stress treatment. The composition of the resin original film is not particularly limited, and may be formed mainly of various organic polymer materials.
As for the kind of the above organic polymer material usable in the present invention, from the viewpoint of facilitating the heat shrinkability of the resin-based film and the adhesion to the adhesive layer, it may be selected from: one or more of polyolefin, modified polyolefin, polyester, polyamide, polyimide, polyurethane, and the like.
For polyolefins or modified polyolefins, in some specific embodiments, they may be selected from homopolymers and copolymers of ethylene, propylene, monochloroethylene, dichloroethylene, vinyl fluoride, styrene, halogenated styrene, olefins having an alicyclic structure (norbornene-type monomers), their halides, and the like. In other specific embodiments, there are no particular restrictions in principle on the other comonomers that can also be used in the copolymers described above, and these may be, for example, unsaturated monomers of the acrylate type, or of the ester type formed by vinyl alcohol.
For the polyester, it may be chosen from polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene terephthalate-1, 4-cyclohexanedimethanol ester (PET-G) or mixtures thereof in any proportion. In some preferred embodiments, it is preferred to use a polyester mixture formed from them, and the content of PET is preferably 50 mass% or more, based on the total mass of both.
Polyamides and polyimides can be obtained by condensation reactions only using aromatic or alicyclic di/polybasic acids and di/polybasic amines. In addition, in order to further improve the transparency (which is advantageous for radiation treatment and the like) of these materials, alicyclic structures and/or fluorine-containing groups may be introduced into their structures.
For the polyurethane, polyester type as well as polyether type polyurethane materials can be used.
The resin original film may contain, in addition to the matrix resin of the organic polymer material, other optional additives such as an inorganic/metal filler, a leveling agent, an antistatic agent, a flame retardant, and an antioxidant.
By performing a film forming treatment on the composition having the above composition, a resin original film can be obtained.
(formation of resin-based film)
The resin-based film of the present invention can be obtained by subjecting a resin original film to a stress treatment. The stress treatment for the present invention may generally include a calendering treatment, a stretching treatment, or a combination thereof.
The calendering treatment is not particularly limited, and the raw resin film may be mechanically calendered in one direction or in a plurality of (orthogonal) directions at a temperature of usually not higher than 130 ℃, preferably in the range of 70 to 120 ℃, more preferably in the range of 90 to 110 ℃. The specific rolling method is not particularly limited, and depends mainly on the structure of the rolling mill.
Typically, the resin raw film may be subjected to a calendering process by being placed between two rolls facing each other in a calender. The degree of calendering is adjusted by adjusting the distance between the twin rolls at the rate of operation of the twin rolls and the thickness uniformity of the calendered film is ensured. In other embodiments, some stretching may be aided simultaneously with calendering.
Further, as for the elongation of the resin film after the calendering treatment, in some specific embodiments of the present invention, the elongations in the MD and TD directions may be 30% to 400%, respectively, preferably, 50% to 300%, respectively, and more preferably, 60% to 200%. By controlling the calendering elongation in the MD and/or TD direction, the shrinkage stress of the calendered resin base film in the corresponding direction can be regulated and controlled. In some preferred embodiments, the shrinkage stress at 70 ℃ in the MD and TD directions can be adjusted to be in the range of 0.3 to 30MPa, preferably 0.5 to 15MPa, more preferably 1 to 10MPa or 1.2 to 9MPa by adjusting the elongation in the MD and TD directions.
The number of rolling treatments is not particularly limited, and one or more single-or multi-directional rolling treatments may be performed.
The stretching treatment is not particularly limited, and generally, in order to ensure the stretching efficiency and uniformity, the stretching treatment is performed at a temperature of 70 to 180 ℃. In some specific embodiments, the elongation in the MD and/or TD direction is adjusted by uniaxial or biaxial stretching to adjust the shrinkage stress in the corresponding direction of the stretched resin base film. The stretching treatment may be carried out by obtaining a resin raw film and then raising the temperature again, or may be carried out by producing a raw film by, for example, an extrusion method and simultaneously carrying out hot stretching. In some embodiments of the present invention, the elongation in the MD and TD directions may be 30% to 700%, respectively, preferably 50% to 400%, and more preferably 60% to 300%, respectively, in the stretching treatment. Further, in a preferred embodiment, the shrinkage stress at 70 ℃ in the MD and TD directions of the resin base film can be adjusted to 0.3 to 30MPa, preferably 0.5 to 15MPa, more preferably 1 to 10MPa or 1.2 to 9MPa by the stretching.
The number of times of the stretching treatment is not particularly limited, and one or more times of the unidirectional or multidirectional stretching treatment may be performed.
Further, from the viewpoint of increasing the internal stress of the resin base film to improve the uniformity of the thickness of the resin base film, it is preferable to perform stress treatment on the resin base film using at least a calendering treatment process.
Further, the resin-based film obtained by the stress treatment of the present invention can be fixed by rapidly cooling to room temperature to fix the internal stress to alleviate the stress relaxation existing during storage before use.
(Properties of resin-based film)
In the present invention, the resin base film satisfying the requirements of the present invention can be obtained by controlling or adjusting the stress treatment mode and the elongation in the stress processing direction (for example, MD and TD directions).
In some specific embodiments, the maximum shrinkage stress value of the resin-based film of the present invention in the MD direction is 70 ℃ or more, preferably 80 to 160 ℃, more preferably 90 to 150 ℃, and for example, the peak of the shrinkage stress occurs at 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃ or 160 ℃. If the maximum stress value in the MD direction occurs in a range lower than 70 ℃, the adhesive tape using the resin-based film is difficult to accomplish re-peeling in a subsequent re-peeling process. This is mainly because the resin base film shrinks prematurely during the temperature rise of the re-peeling process, but the adhesive layer still has a high peeling force at this time, and thus re-peeling failure is easily caused.
Further, the maximum achievable shrinkage stress of the resin-based film in the present invention is 0.3 to 10MPa, preferably 0.5 to 9MPa, more preferably 0.8 to 8.5MPa, and even more preferably 1 to 8MPa, at a temperature of 70 ℃ or higher. If the maximum shrinkage stress is less than 0.3MPa, there is a difficulty in completing re-peeling of the adhesive tape by wrinkling or curling caused by shrinkage; if the maximum shrinkage stress is too large, on the one hand, there is an increase in processing difficulty in terms of processing of the resin film, and on the other hand, there is a problem that the adhesive tape is scattered or adhesive remains during the re-peeling of the adhesive tape.
In other specific embodiments, the total shrinkage (stable shrinkage) at 70 ℃ or higher for the resin-based film of the present invention is not particularly limited. In a preferred embodiment, the total shrinkage in the MD direction may be 40% or more, preferably 50% to 80%. If the total shrinkage is too low, the adhesive tape re-peeling efficiency may be reduced even if the shrinkage stress is satisfactory.
Further, the resin-based film of the present invention may be a single resin film or a multilayer resin film in some specific embodiments.
Further, in the case of a multilayer resin film, it may be a resin film having 2 to 5 layers, preferably a resin film having 2 or 3 layers. For multilayer resin films, the film layers may be the same film layer or different film layers. In some preferred embodiments, at least one of the film layers has a shrinkage stress (particularly, a shrinkage stress in the MD direction) that is different from the other resin films at the same temperature (e.g., at 100 ℃).
In a preferred embodiment of the present invention, the resin base film may be a laminated film formed by two resin films in view of the formation of a form advantageous for the removability of the adhesive tape after the shrinkage of the resin base film. More preferably, one resin film of the two film layers has a greater shrinkage stress than the other resin film at the same temperature, thereby facilitating the formation of a curled structure after shrinkage.
Further, it is necessary and advantageous for the resin-based film of the present invention to have a defined shrinkage stress and mechanical properties to be satisfied such that a certain total gel fraction is present in the resin-based film. The total gel fraction is a gel fraction calculated for the whole resin-based film, and if the resin-based film is a multilayer resin film, it is calculated for the whole multilayer resin film.
In some specific embodiments of the present invention, the gel fraction of the resin-based film is 10% or more, preferably 20% or more, and if the gel fraction is too low, there is a fear that the shrinkage stress defined in the present invention is difficult to obtain and the mechanical stress of the resin film is too low (easy to tear); the upper limit of the gel fraction is not particularly limited, but may be controlled to 90% or less, preferably 80% or less, and there is a concern that an excessively high gel fraction may adversely affect the processability of the resin base film. To achieve the above-described gel fraction, the organic polymeric material can be crosslinked, typically by chemical or radiation processes, including but not limited to chemical crosslinking (peroxide crosslinking), radiation crosslinking, silane crosslinking, and ultraviolet light crosslinking.
The overall average thickness of the resin-based film of the present invention is not particularly limited, but may be 5 to 1000 μm, preferably 8 to 500 μm, more preferably 10 to 300 μm, and still more preferably 15 to 100 μm in view of facilitating re-peeling. If the average thickness is too low, the mechanical properties of the resin-based film may be insufficient and the distribution may be uneven; if the average thickness is too high, the rigidity may be too high, and shrinkage/curling may be insufficient, and the irradiation efficiency may be impaired when the resin-based film is used as an adhesive tape later.
< second aspect >
In a second aspect of the present invention, there is provided a releasable adhesive tape having a resin-based film layer and an adhesive layer formed on at least one major surface of the resin-based film layer.
As for the resin-based film, preferably, the resin-based film layer provided in the above-described first aspect may be used. When the resin-based film layer is a multilayer film, at least the surface having a smaller shrinkage stress at the same temperature in the two surface films of the multilayer film has an adhesive layer.
Referring to the present invention, fig. 1 illustrates the structure of an adhesive tape according to some specific embodiments of the present invention. Wherein the resin film 1 and the resin film 2 form a laminated resin-based film, and the surface of the resin film 2 has an adhesive layer. It is preferable that the shrinkage stress of the resin film 1 is larger than that of the resin film 2 under the same temperature condition (for example, at 100 ℃).
(Binder)
The kind of the adhesive that can be used in the present invention is not particularly limited, and pressure sensitive adhesives and hot melt adhesive types that are commonly used in the art can be used.
The pressure-sensitive adhesive may be specifically selected from crosslinkable adhesives such as acrylic pressure-sensitive adhesives, silicone pressure-sensitive adhesives, polyester pressure-sensitive adhesives, polyurethane pressure-sensitive adhesives, polyamide pressure-sensitive adhesives, and rubber pressure-sensitive adhesives. Among these, as a preferable aspect of the present invention, an acrylic pressure-sensitive adhesive, a silicone pressure-sensitive adhesive, and a rubber pressure-sensitive adhesive can be used.
As a specific example of the acrylic pressure-sensitive adhesive, a homopolymer or a copolymer of an alkyl (meth) acrylate, which may be, for example, C1-C30 alkyl (meth) acrylate, preferably C1-C20 alkyl (meth) acrylate, may be included. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isopropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, and the like can be mentioned. In addition, as for the other unsaturated monomer copolymerizable with the above-mentioned alkyl (meth) acrylate, another monomer including a carboxyl group-or acid anhydride group-containing monomer or an olefin monomer may be mentioned. Specifically, (meth) acrylic acid, itaconic acid, fumaric acid, or maleic anhydride; hydroxyl group-containing monomers such as 2-hydroxyethyl (meth) acrylate; amino group-containing monomers such as morphinol (meth) acrylate; amide group-containing monomers such as (meth) acrylamide; cyano group-containing monomers such as (meth) acrylonitrile; or (meth) acrylates containing alicyclic hydrocarbon groups such as isobornyl (meth) acrylate; C1-C20 olefins such as ethylene, propylene, butadiene, styrene, and olefins having an alicyclic structure.
As the acrylic pressure-sensitive adhesive, particularly preferred is a copolymer of one or more C1 to C12 alkyl (meth) acrylates such as ethyl acrylate, butyl acrylate or 2-ethylhexyl acrylate, and at least one copolymerizable monomer selected from the group consisting of hydroxyl group-containing monomers such as 2-hydroxyethyl acrylate and carboxyl group-or anhydride group-containing monomers such as acrylic acid, or a copolymer of one or more C1 to C12 alkyl (meth) acrylates, alicyclic hydrocarbon group-containing (meth) acrylates, and at least one copolymerizable monomer selected from the group consisting of hydroxyl group-containing monomers and carboxyl group-or anhydride group-containing monomers.
For the acrylic pressure-sensitive adhesive, which is generally prepared, for example, by photopolymerizing (for example, with ultraviolet light) the above-mentioned monomer components (and polymerization initiator) in the presence of a solvent, it is a liquid prepolymer having a high viscosity. The crosslinked pressure-sensitive adhesive composition can be obtained by adding a crosslinking agent to the above prepolymer. The crosslinking agent may be added at the time of preparing the prepolymer. The crosslinking-type acrylic pressure-sensitive adhesive composition can also be obtained by adding a crosslinking agent and a solvent (which is unnecessary in the case of using an acrylic polymer solution) to an acrylic polymer obtained by polymerizing the above-mentioned monomer components or a solution thereof.
The crosslinking agent is not particularly limited, and may be selected from isocyanate-based crosslinking agents, melamine-based crosslinking agents, epoxy-based crosslinking agents, acrylate-based crosslinking agents (polyfunctional acrylates), isocyanate group-containing (meth) acrylates, and the like. Examples of the acrylate-type crosslinking agent include hexanediol diacrylate, 1, 4-butanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate and dipentaerythritol hexaacrylate. Examples of the (meth) acrylate having an isocyanate group include 2-isocyanatoethyl acrylate and 2-isocyanatoethyl methacrylate. Among them, Ultraviolet (UV) -reactive crosslinking agents such as acrylate-type crosslinking agents (polyfunctional acrylates) or (meth) acrylates having an isocyanate group are preferable.
The silicone pressure-sensitive adhesive is not particularly limited, and may be a polymer obtained by hydrolysis and condensation of an organic silane monomer, and the polymer may have an unsaturated reactive group.
For the rubber-based pressure-sensitive adhesive, a natural rubber component or an artificial rubber component, or a mixture thereof can be used.
For acrylic pressure-sensitiveAdhesives, polysiloxane-based pressure-sensitive adhesives and rubber-based pressure-sensitive adhesives, the weight average molecular weight of the soluble portion of which may be 30X 10 in some preferred embodiments4～14×105The gel fraction may be 20 to 95%.
As the hot-melt adhesive that can be used in the present invention, typically, various resins having thermoplastic properties can be used.
Examples of the thermoplastic resin include homopolymers of olefins such as ethylene, propylene, butene, hexene, and cycloolefin, copolymers of 2 or more olefins, and copolymers of 1 or more olefins and 1 or more (other than olefin) polymerizable monomers copolymerizable with the olefins; other resins having thermoplastic properties, and the like. For these thermoplastic resins, it is generally required to develop initial adhesion in the range of 40 ℃ to 100 ℃, preferably 40 ℃ to 60 ℃.
Examples of the thermoplastic resin include acrylic resins such as ethylene-ethyl acrylate copolymers, styrene resins such as butadiene-styrene copolymers, acrylonitrile-styrene copolymers, polystyrene, styrene-butadiene-styrene copolymers, styrene-isoprene-styrene copolymers, and styrene-acrylic copolymers.
In addition, other thermoplastic resins that may also be used include: vinyl chloride-based resins, vinyl fluoride-based resins such as polyvinyl fluoride and polyvinylidene fluoride, amide-based resins such as 6-nylon, 6-nylon and 12-nylon, saturated ester-based resins such as polyethylene terephthalate and polybutylene terephthalate, polycarbonates, polyphenylene oxides, polyphenylene sulfides, thermoplastic silicone resins, thermoplastic polyurethane resins, polyether ether ketones, polyether imides, thermoplastic epoxy resins, phenol resins, and modified products thereof.
As the thermoplastic resin, 2 or more different thermoplastic resins may be mixed and used.
Among the thermoplastic resins, a polyolefin resin or a copolymer of 1 or more kinds of olefins and 1 or more kinds of polymerizable monomers (other than olefins) copolymerizable with the olefins can be preferably used from the viewpoint of forming the adhesive layer by coextrusion as described below.
The olefin constituting the polyolefin resin is preferably a homopolymer or copolymer of ethylene, propylene, an α -olefin having 4 to 20 carbon atoms, a cycloolefin, an alicyclic vinyl compound such as an aromatic vinyl compound or vinylcyclohexane, or a polyene compound.
Specific examples of the α -olefin having 4 to 20 carbon atoms include 1-butene, 2-methyl-1-propene, 1-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene, 2-ethyl-1-butene, 2, 3-dimethyl-1-butene, 3-dimethyl-1-butene, 2-methyl-1-pentene, 2, 3-dimethyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-heptene, 2-methyl-1-hexene, 2, 3-dimethyl-1-pentene, 2-ethyl-1-pentene, 2-methyl-1-pentene, 1-butene, 2-methyl-1-pentene, 1-butene, 2-methyl-1-pentene, and mixtures thereof, 2-methyl-3-ethylene-1-butene, 1-octene, 2-ethyl-1-hexene, 3-dimethyl-1-hexene, 2-propyl-1-heptene, 2-methyl-3-ethyl-1-heptene, 2,3, 4-trimethyl-1-pentene, 2-propyl-1-pentene, 2, 3-diethyl-1-butene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, etc.
Examples of the cycloolefin include norbornene derivatives to which an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a butyl group or the like is introduced, such as bicyclo [2.2.1] hept-2-ene, 6-alkylbicyclo [2.2.1] hept-2-ene, 5, 6-dialkylbicyclo [2.2.1] hept-2-ene, 1-alkylbicyclo [2.2.1] hept-2-ene, 7-alkylbicyclo [2.2.1] hept-2-ene or the like which is generally called norbornene.
Examples of the aromatic vinyl compound include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2, 4-dimethylstyrene, o-ethylstyrene, and p-ethylstyrene.
Examples of the "1 or more kinds of olefins and 1 or more kinds of polymerizable monomers (other than olefins) copolymerizable with the olefins" include polar vinyl compounds and derivatives of aromatic vinyl compounds. The derivative is a compound in which an aromatic vinyl is bonded with another substituent, and examples thereof include a substituted styrene in which a hydroxyl group, an alkoxy group, a carboxyl group, an acyloxy group, a halogen or the like is introduced into a benzene ring of styrene, such as hydroxystyrene, t-butoxystyrene, vinylbenzoic acid, vinylbenzylacetate, o-chlorostyrene, p-chlorostyrene, and vinylbiphenyl compounds such as 4-hydroxy-4' -vinylbiphenyl. Examples of the polar vinyl compound include acrylic compounds such as methyl acrylate, methyl methacrylate, and ethyl acrylate, and vinyl acetate and vinyl chloride.
In some preferred embodiments of the present invention, it is preferable to use Ethylene Vinyl Acetate (EVA) as the thermoplastic resin of the present invention in view of convenience of use and recycling and solvent resistance.
Further, for the pressure-sensitive adhesive of the present invention, other components or auxiliaries may be used as needed in addition to the above-mentioned main polymer components. For example, crosslinking catalysts, tackifying resins (such as rosin derivative resins, polyterpene resins, petroleum resins, or oil-soluble phenol resins), tackifiers, plasticizers, fillers, inorganic fillers, organic fillers, coupling agents, anti-aging agents, antistatic agents, foaming agents, antioxidants, and the like.
It is noted that the foamable component is an optional but not absolutely necessary component to the composition of the adhesive of the invention. In other words, the technical solution of the present invention does not need to use the foaming component in principle, which is a different feature from the prior art that uses the foaming component to assist the re-peeling.
(adhesive layer)
The mode of forming the pressure-sensitive adhesive layer of the present invention is not particularly limited. This may be performed using a method for forming an adhesive layer, which is conventional in the art.
In some specific embodiments, the adhesive composition may be formed into a coating liquid or a coating slurry by means of a solvent or the like, and then formed on at least one surface of the above-described resin base film by means of spray coating or spin coating or the like.
In some preferred embodiments, the adhesive may also be applied in a solid or semi-solid form to at least one surface of the resin-based film. For example, the adhesive layer may be formed using an adhesive in the form of a "double-sided tape". For such double-sided adhesive tape, a laminate in which two layers of pressure-sensitive adhesive are listed as a mode is preferable. Among them, one pressure-sensitive adhesive layer may be based on an acrylic pressure-sensitive adhesive, and the other pressure-sensitive adhesive layer may be based on a silicone pressure-sensitive adhesive. In use, the acrylic pressure-sensitive adhesive side of the double-sided tape is bonded to one surface of the resin base film of the present invention, and the silicone pressure-sensitive adhesive faces the surface to which the tape is bonded.
In the case of the adhesive layer used in the form of the "double-sided tape", it may be formed using only one type of pressure-sensitive adhesive.
In addition, the above-mentioned "double-sided tape" may or may not have a support layer or a protective layer before use. Typical support layers may be polyester materials such as PET, but also fibres such as tissue or non-woven, preferably with a melting point above 120 ℃, and in general the use of a support layer facilitates the preservation of the adhesive layer and is convenient to use; the protective layer is also not particularly limited, and a resin film, paper, nonwoven fabric, or the like which is generally used in the art can be used.
In other preferred embodiments, the adhesive (especially a hot-melt adhesive) may also be coextruded by coextrusion while forming the original film (or while simultaneously stretching). In some preferred embodiments, the layered structure shown in fig. 1, a resin-based film having two resin films, and an adhesive layer formed of a hot melt adhesive may be formed by co-extrusion.
The thickness of the pressure-sensitive adhesive layer of the present invention is not particularly limited, and the average thickness of the pressure-sensitive adhesive layer may be 5 to 800. mu.m, preferably 10 to 500. mu.m, and more preferably 20 to 300. mu.m, from the viewpoint of facilitating re-peeling.
(Properties of adhesive tape)
In the present invention, in order to realize the re-peeling property satisfying the requirements of the present invention, the adhesive tape satisfies the following conditions: the temperature T is present in a temperature range of 70 ℃ or more, preferably 80 ℃ or more, and at this temperature T, the shrinkage stress value of the resin base film of the adhesive tape in the MD direction is 1.3 times or more the peeling force value of the adhesive layer from the substrate to be bonded. The present inventors have found that when the above conditions are satisfied, the pressure-sensitive adhesive tape can be easily and conveniently peeled off again from the surface of an adherend by an external stimulus, thereby avoiding the problems of peeling failure such as adhesive residue and tape breakage.
The temperature T may be a certain temperature value, such as 90 ℃, 100 ℃ or 110 ℃, or may be a temperature range composed of one or more continuous temperature values, such as all temperature values within a range of 90 to 130 ℃ or 100 to 120 ℃.
In some preferred embodiments, the temperature T can be any or all of 90 to 120 ℃ (i.e., the above-described relationship between the shrinkage stress and the peel force values of the present invention is met or exists in the range of 90 to 120 ℃), and more preferably the temperature T is 100 ℃.
For bonded substrates, the metal is usually elemental or an alloy thereof. In some specific embodiments, the bonded substrate may be copper, aluminum, iron or an alloy thereof, preferably, the bonded substrate is aluminum or an aluminum alloy.
In the present invention, the relationship between the shrinkage stress value of the resin base film of the adhesive tape at 70 ℃ or higher and the peeling stress value of the adhesive layer and the adherend base is set as described above, based on the following findings:
when the adhesive layer is bonded with the substrate to be bonded, the adhesive layer and the substrate to be bonded have an initial peeling force. Further, the temperature of the adhesive tape is increased by external stimulation such as heating or irradiation, and the peeling force of the adhesive layer from the substrate to be adhered is generally decreased with the increase in temperature. Meanwhile, the resin base film of the adhesive tape is heated to shrink under a shrinking stress, and the shrinking stress increases with an increase in temperature. The normal operation temperature for re-peeling may be 70 ℃ or higher. At this time, if the adhesive tape satisfies the above condition, it means that the shrinkage stress of the resin base film significantly exceeds the peeling force of the adhesive layer from the substrate to be adhered, and therefore, with the wrinkling or curling of the resin base film due to shrinkage, the adhesive tape can be easily peeled again from the substrate to be adhered.
In addition, the peeling force of the pressure-sensitive adhesive layer with respect to the adherend is not particularly limited in principle as long as the above-described conditions are satisfied. In some preferred embodiments, the peel force of the adhesive layer from the substrate to be bonded is not more than 0.4MPa, preferably 0.05 to 0.3MPa at 70 ℃ or higher, for example, 80 ℃, 90 ℃ or 100 ℃.
< third aspect >
In a third aspect of the present invention, there is provided a method for producing an electronic device component, particularly an electrode component, by using the resin-based film in the above-described first aspect or using the removable adhesive tape in the above-described second aspect.
In some embodiments, the present invention provides a method for preparing a conductive pole piece for a lithium ion secondary battery.
Specifically, the conductive sheet generally includes a current collector, an active material composition formed on a surface of the current collector, and a tab electrically connected to the current collector.
As for the current collector, there is no particular limitation, and a simple metal or an alloy material thereof may be used. In some preferred embodiments, metallic copper, aluminum or alloys thereof may be used, and more preferably, aluminum or aluminum alloys may be used.
The composition of the active material composition is not particularly limited, and may include an electrode active material containing lithium ions that can be accommodated and extracted, a binder component, and other optional conductive components. As the electrode active material, a positive electrode active material such as a metal oxide, preferably a metal element containing one or more of Li, Co, Ni, Mn, a rare earth metal element, and the like; the negative electrode active material may be, for example, a carbon-based material (graphite, etc.) or a silicon-based material (silicon dioxide, etc.).
In some specific embodiments of the present invention, the method for preparing the conductive pole piece may include a step of adhesion and a step of re-peeling.
Wherein the step of bonding comprises: forming a protective region on at least a portion of the current collector, thereby coating the surface of the current collector with a composition containing an active material;
the step of re-peeling comprises: the adhesive tape in the protective area is then peeled off.
Further, the step of forming the protective zone may be a pre-designed zone reserved for tab attachment where protection is provided to prevent ingress of the active composition.
As for a specific method for forming the protection region, the following method may be adopted in the present invention:
in the first embodiment, the adhesive composition of the present invention is applied to a region to be protected to form an adhesive layer, and then a resin-based film is bonded to the surface of the adhesive layer. Further, the form of the adhesive layer is not particularly limited, and the adhesive composition may be applied (sprayed or spin-coated) to the protective region, or one surface of an adhesive which is a double-sided tape may be bonded to the protective region. For resin-based films, alignment with the adhesive layer should be maintained to avoid poor handling of the protective areas during subsequent application of the active material.
In the second embodiment, the adhesive composition of the present invention and a resin-based film are formed in advance into an adhesive tape, and then the adhesive tape, which is optionally cut, is attached to the protective region. The method for forming the adhesive tape is not particularly limited, and the adhesive layer may be coated on or adhered to the surface of the resin-based film, or the adhesive tape having the hot melt adhesive layer obtained by the co-extrusion process may be directly used.
In the above manner, the adhesive tape with the resin base film is formed in the protective region, and in some preferred embodiments, the total thickness of the adhesive tape may be 10 to 1200 μm, preferably 15 to 800 μm, and more preferably 20 to 300 μm.
Further, with respect to the method of coating the active material composition on the surface of the current collector, there is no particular limitation, and the above composition may be coated in the form of slurry. And, at the time of coating, allowing the above composition to be coated on a part or all of the surface of the resin-based film in the protected region.
In the step of peeling the adhesive tape of the protective region of the present invention, the active material composition slurry is dried and the adhesive tape is peeled off, usually accompanied by an external stimulus to the conductive sheet.
In some specific embodiments, the external stimulus comprises one of a heat treatment, an irradiation treatment, or a combination thereof.
Generally, by the above-mentioned external stimulus, temperature rise of the conductive sheet is caused, which leads to evaporation of the solvent in the active material composition slurry, curing of the adhesive component; and to cause crosslinking, softening or melting of the adhesive of the invention, and shrinkage of the dimensions of the resin-based film.
The temperature caused by the external stimulus (re-peeling temperature) may be generally 70 ℃ or higher, preferably 90 ℃ or higher, and more preferably 100 ℃ or higher, and the upper limit of the temperature is generally not more than 200 ℃, and may be 160 ℃ or lower, preferably 150 ℃ or lower, and more preferably 140 ℃ or lower, depending on the composition or properties of the active material composition slurry.
In the above temperature range, by satisfying the relationship between the shrinkage stress value of the resin base film of the present invention and the peeling force of the adhesive layer, the adhesive tape can be easily peeled from the protective region with wrinkles, preferably with curling, due to the volume shrinkage of the resin base film, exposing the protective region not coated with the active material composition. The time during which the volume shrinkage occurs is usually controlled to 0.1 to 3 seconds by adjusting the shrinkage stress in the MD direction of the resin base film.
Further, in the protection area, a tab is connected by bonding or welding.
The electrode sheet obtained by the above method of the present invention can be preferably used for a positive electrode or a negative electrode of a lithium ion secondary battery.
Examples
The present invention will be further specifically described below by way of examples:
< test methods >
1. Testing of shrinkage stress:
the test specimens were cut into 25mm by 200mm strips along the flow line (MD), and then the two ends of the specimens were clamped on a tensile machine which was heated at constant temperature, with a distance of 150mm between the upper and lower clamps.
The force generated by the test sample in the environment of 100 ℃ and the calculation formula of the shrinkage stress value are as follows:
shrinkage stress test value/(mm thickness of sample 25 mm).
2.180 ° peel stress (hereinafter referred to as "peel force"):
the test sample was cut into 25mm by 200mm strips along the flow line direction, and then the sample was attached to an Al plate by reciprocating 2 times with a 2Kg roller, and the peel force was measured.
The calculation formula of the sample peeling internal stress is as follows:
peel stress test value/(mm thickness of sample 25 mm).
3. Evaluation of Heat resistance:
the test samples were cut into 25mm by 200mm strips along the flow line, then the samples were placed in an oven at 140 ℃ for 10min, taken out and cooled to observe changes in appearance:
if the alloy is obviously melted, the heat resistance is poor, and the label is multiplied;
slightly melting, marked with ≈ mark;
no melting, marked-.
4. Gel fraction test method:
wrapping the material with tetrafluoroethylene film, placing in 70 deg.C trichloroethylene, taking out after 24hr, weighing the weight before and after, and calculating the gel fraction by the formula:
gel fraction (tetrafluoroethylene and film weight before impregnation-tetrafluoroethylene and film weight after impregnation)/tetrafluoroethylene and film weight before impregnation x 100%.
5. Curling of the adhesive tape:
effect of curling form
The samples were cut into 30mm by 10mm strips with the long side in the direction of shrinkage (MD), then laminated to aluminum foil, heated at 100 ℃ by 2min, tested for height after crimp, and then the crimp score was calculated according to the following formula:
curl score ═ (after curl product height-before curl product width)/before curl product width (10mm) if curl score is: 0.15 to 0.4 excellent in curl;
if the curl score is: 0.05 to <0.15 is O, and the curl shape is normal;
if the curl score is: <0.05 is ×, curl morphology is poor.
6. Adherend adhesion:
the initial adhesion was good: marked with ∘;
poor initial adhesion: identified by x.
7. The residual glue condition:
the test sample was cut into strips of 100mm by 50mm along the flow line (MD), then the sample was attached to an aluminum foil, placed in an oven at 140 ℃ for 10min, taken out, cooled, and the tape was peeled off.
If the aluminum foil surface has offset printing, the heat resistance is poor, and the mark is multiplied;
if the surface has no trace, it is marked with ∘.
8. Difficulty in cleaning:
the samples were cut into 30mm by 10mm strips along the flow line (MD) and then attached to aluminum foil, heated at 140 c for 2min, and the heated aluminum foil and samples were removed.
And blowing a sample on the surface of the aluminum foil by using a blower with the air speed of 30 m/s, wherein if the sample is displaced, the mark can be easily swept, and if the sample is not moved, the mark is difficult to sweep.
< materials >
Resin-based film: single-layer vinyl chloride films, PET-G films and double-layer LDPE/EVA films prepared by a rolling method or a stretching method;
adhesive: commercially available acrylic pressure sensitive adhesives and polyurethane hot melts;
examples 1 to 6 and comparative examples 1 to 4
Adhesive tapes were prepared according to the compositions of table 1 and the tests of table 2 were performed, wherein the resin base layer was a single-layer resin-based film prepared by a stretching method.
Table 1:
table 2:
example 7 and comparative example 5
Adhesive tapes were prepared according to the compositions of table 3 and the tests of table 4 were performed, wherein the resin base layer was a two-layer resin-based film prepared by calendering.
Table 3:
table 4:
application example
Application examples 1 and 2 show the case where the resin base film of the present invention is used as a base film of an adhesive tape. Among them, the case where the stress of the resin-based film used in application example 1 and application example 2 and the commercially available conventional adhesive changes with temperature is as follows:
the following fig. 2a and 2b show the use of the resin-based film in application example 1 and application example 2, respectively, in which different commercially available acrylic adhesives were blended, and show the relationship between the film shrinkage stress and the peeling force (180 ° at the aluminum interface) of the adhesive with temperature change.
As can be seen from fig. 2a, the maximum shrinkage stress of the resin-based film occurs at around 125 ℃, and it is considered that good re-peeling can be performed at this temperature in accordance with a commonly used commercially available adhesive.
As can be seen from fig. 2b, the maximum shrinkage stress of the resin-based film occurs at around 150 ℃, and it is considered that good re-peeling can be performed at this temperature in accordance with a commonly used commercially available adhesive.
It should be noted that, although the technical solutions of the present invention are described by specific examples, those skilled in the art can understand that the present disclosure should not be limited thereto.
Having described embodiments of the present disclosure, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the disclosed embodiments. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments. The terminology used herein is chosen in order to best explain the principles of the embodiments, the practical application, or improvements made to the technology in the marketplace, or to enable others of ordinary skill in the art to understand the embodiments disclosed herein.
Industrial applicability
The preparation methods of the resin-based film, the adhesive tape and the conductive pole piece can be industrially prepared or implemented.
Claims (16)
1. A resin-based film characterized by being a resin-based film for a re-releasable adhesive tape which is re-releasable via external stimulus after adhesion,
the resin-based film has:
the maximum shrinkage stress value in the MD direction is in a temperature range of 70 ℃ or more, and the maximum shrinkage stress value in the MD direction is 0.3-10 MPa,
and, the thickness of resin basilemma is 5 ~ 1000um, the gel fraction of resin basilemma is more than 10%.
2. The resin-based film according to claim 1, wherein the maximum shrinkage stress value in the MD direction of the resin-based film is in a temperature range of 70 to 160 ℃.
3. The resin-based film according to claim 1 or 2, wherein the resin-based film has a maximum shrinkage stress value in the MD direction of 0.5 to 9 MPa; the thickness of resin basal lamina is 10 ~ 300 um.
4. The resin-based film according to any one of claims 1 to 3, wherein the resin-based film is a single resin film or a multilayer resin film; the gel rate of the resin-based film is 10-90%.
5. The resin-based film according to claim 4, wherein at least one of the resin films has a different shrinkage stress in the MD at 100 ℃ from the other resin films.
6. The resin-based film according to any one of claims 1 to 5, wherein the external stimulus comprises at least one of a heat treatment or a radiation treatment or a combination thereof.
7. A releasable adhesive tape comprising the resin-based film according to any one of claims 1 to 6 and an adhesive layer formed on at least one surface of the resin-based film.
8. The adhesive tape as claimed in claim 7, wherein the adhesive layer is formed by coating or adhering an adhesive composition on the surface of the resin-based film, or is formed by co-extruding the adhesive composition with the resin-based film on the surface of the resin-based film.
9. A releasable adhesive tape comprising a resin-based film layer and an adhesive layer formed on at least one surface of the resin-based film layer, wherein,
the maximum shrinkage stress value of the resin-based film in the MD direction is 0.3 to 10MPa,
and, after the adhesive tape is adhered to an adhered substrate, the following requirements are satisfied:
there is a temperature T in a temperature range of 70 ℃ or higher, and at this temperature T, the shrinkage stress value of the resin base film of the adhesive tape in the MD direction is 1.3 times or more the peeling force value of the adhesive layer from the adherend.
10. The adhesive tape of claim 9, wherein said substrate is selected from the group consisting of elemental metals and alloys of metals.
11. The adhesive tape according to claim 9 or 10, wherein the maximum shrinkage stress value in the MD direction of the resin-based film in the adhesive tape is in a temperature range of 70 ℃ to 160 ℃.
12. The adhesive tape according to any one of claims 9 to 11, wherein the resin-based film in the adhesive tape is a single-layer resin film or a multi-layer resin film; the gel rate of the resin-based film is 10-90%.
13. The adhesive tape according to any one of claims 9 to 12, wherein the adhesive layer is formed by coating or adhering an adhesive composition on the surface of the resin base film, or is formed by co-extruding the adhesive composition with the resin base film on the surface of the resin base film.
14. A preparation method of a conductive pole piece is characterized by comprising the following steps:
a step of bonding, in which the adhesive tape according to any one of claims 7 to 13 is used to bond the conductive pole piece, or the resin-based film according to any one of claims 1 to 6 is used to bond the region with the adhesive on the conductive pole piece; and
and a re-peeling step of subjecting the adhesive tape or the region having the adhesive to an external stimulus to re-peel it from the conductive electrode sheet.
15. The method of claim 14, wherein the external stimulus comprises at least one of heat treatment, radiation treatment, or a combination thereof.
16. A method of making a pole piece for a lithium ion battery, the method comprising the method of claim 14 or 15.
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| CN202210573260.2A CN114854317B (en) | 2021-11-08 | 2021-11-08 | Adhesive tape and method for preparing conductive pole piece by using same |
| CN202111313698.9A CN114058273A (en) | 2021-11-08 | 2021-11-08 | Resin-based film, adhesive tape and method for preparing conductive pole piece by using adhesive tape |
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| CN202111313698.9A CN114058273A (en) | 2021-11-08 | 2021-11-08 | Resin-based film, adhesive tape and method for preparing conductive pole piece by using adhesive tape |
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| CN114854317B (en) | 2024-06-11 |
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