CN116373410A - Preparation process of high-punching-depth corrosion-resistant aluminum plastic film - Google Patents
Preparation process of high-punching-depth corrosion-resistant aluminum plastic film Download PDFInfo
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- CN116373410A CN116373410A CN202310496164.7A CN202310496164A CN116373410A CN 116373410 A CN116373410 A CN 116373410A CN 202310496164 A CN202310496164 A CN 202310496164A CN 116373410 A CN116373410 A CN 116373410A
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- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 111
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 238000005260 corrosion Methods 0.000 title claims abstract description 72
- 230000007797 corrosion Effects 0.000 title claims abstract description 58
- 239000002985 plastic film Substances 0.000 title claims abstract description 47
- 229920006255 plastic film Polymers 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000011888 foil Substances 0.000 claims abstract description 75
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000007822 coupling agent Substances 0.000 claims abstract description 48
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 35
- 239000004743 Polypropylene Substances 0.000 claims abstract description 21
- 229920001155 polypropylene Polymers 0.000 claims abstract description 21
- -1 polypropylene Polymers 0.000 claims abstract description 18
- 239000004677 Nylon Substances 0.000 claims abstract description 16
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920001778 nylon Polymers 0.000 claims abstract description 16
- 239000003112 inhibitor Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 239000000853 adhesive Substances 0.000 claims abstract description 9
- 230000001070 adhesive effect Effects 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 6
- 238000003825 pressing Methods 0.000 claims abstract description 5
- 238000004080 punching Methods 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000002161 passivation Methods 0.000 claims description 21
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 17
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 17
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 16
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- 239000004925 Acrylic resin Substances 0.000 claims description 15
- 229920000178 Acrylic resin Polymers 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000005238 degreasing Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 9
- 239000003792 electrolyte Substances 0.000 abstract description 19
- 238000000034 method Methods 0.000 abstract description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052744 lithium Inorganic materials 0.000 abstract description 9
- 238000009459 flexible packaging Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 91
- 230000000694 effects Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- 238000001514 detection method Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 229910001290 LiPF6 Inorganic materials 0.000 description 3
- 229910003077 Ti−O Inorganic materials 0.000 description 3
- 239000005030 aluminium foil Substances 0.000 description 3
- 239000012459 cleaning agent Substances 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003012 bilayer membrane Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 229910001512 metal fluoride Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 235000015393 sodium molybdate Nutrition 0.000 description 2
- 239000011684 sodium molybdate Substances 0.000 description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical group COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000012793 heat-sealing layer Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/02—Synthetic macromolecular fibres
- B32B2262/0261—Polyamide fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/752—Corrosion inhibitor
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Sealing Battery Cases Or Jackets (AREA)
- Laminated Bodies (AREA)
Abstract
The application relates to a preparation process of a high-punching-depth corrosion-resistant aluminum plastic film in the technical field of lithium battery flexible packaging. The preparation process comprises the following steps: s1, raw material pretreatment: passivating pretreatment is carried out on the aluminum foil layer by adopting a passivating agent, so that an anti-corrosion aluminum foil layer is obtained; carrying out plasma pretreatment on the nylon layer to obtain a rough nylon layer; corona pretreatment is carried out on the polypropylene layer to obtain a rough polypropylene layer; s2, smearing an adhesive between the rough nylon layer and the anti-corrosion aluminum foil layer and between the anti-corrosion aluminum foil layer and the rough polypropylene layer, and pressing to prepare an aluminum-plastic film; wherein, the passivating agent comprises the following components in parts by weight: 10-20 parts of fluorozirconic acid, 1-5 parts of molybdate, 15-40 parts of titanate coupling agent modified nano titanium dioxide, 0.5-3 parts of corrosion inhibitor and 30-60 parts of deionized water. The aluminum plastic film prepared by the method has the properties of high punching depth and electrolyte corrosion resistance, and has wide prospects in the market of lithium battery flexible packages.
Description
Technical Field
The application relates to the technical field of lithium battery flexible packaging, in particular to a preparation process of a high-punching-depth corrosion-resistant aluminum plastic film.
Background
The aluminum plastic film is a special packaging material for lithium ion batteries, is commonly used in soft package batteries and blade batteries, and mainly plays roles of protecting internal electrodes and isolating external environments. The aluminum plastic film is a multi-layer composite structure consisting of an outer nylon layer, an adhesive, an intermediate aluminum foil, an adhesive and an inner heat sealing layer. Has high barrier property, good cold stamping forming property, puncture resistance, electrolyte resistance stability and insulativity.
At present, the preparation of the aluminum plastic film mainly comprises a dry method and a thermal method. The dry process is that aluminum and polypropylene are bonded by adhesive and then are directly pressed together, and the thermal process is that aluminum and polypropylene are bonded by polypropylene porous foaming material and then are slowly heated, boosted and hot pressed together. The aluminum plastic film prepared by the dry process has the main advantages of good deep drawing and forming effect, good appearance consistency, difficult occurrence of pinholes, fish eyes, impurities and other adverse conditions, and the thermal process can improve the adhesion between the aluminum foil layer and the polypropylene layer, so that the swelling and falling-off resistance of the electrolyte on the inner surface layer is greatly improved.
The high-punching-depth aluminum plastic film can improve the energy density of the battery, so that the active substances in the battery are increased by more bearing capacity. However, the electrolyte in the lithium battery has extremely strong corrosion performance, so that the surface of the aluminum plastic film can be corroded, the lithium battery is damaged, and explosion and fire can be caused under serious conditions. Therefore, there is a need to develop a corrosion-resistant high-impact deep-drawing aluminum plastic film to improve the safety of lithium batteries.
Disclosure of Invention
In order to solve the problem that the lithium battery safety is lower due to the fact that the aluminum-plastic film is easy to be corroded by electrolyte in the lithium battery, the application provides a preparation process of the high-punching-depth corrosion-resistant aluminum-plastic film, and the aluminum-plastic film prepared through the preparation process has better corrosion resistance.
The application provides a preparation process of a high-punching-depth corrosion-resistant aluminum plastic film, which adopts the following technical scheme:
a preparation process of a high-punching deep-drawing corrosion-resistant aluminum plastic film comprises the following preparation steps:
s1, raw material pretreatment: passivating pretreatment is carried out on the aluminum foil layer by adopting a passivating agent, so that an anti-corrosion aluminum foil layer is obtained; carrying out plasma pretreatment on the nylon layer to obtain a rough nylon layer; corona pretreatment is carried out on the polypropylene layer to obtain a rough polypropylene layer;
s2, smearing an adhesive between the rough nylon layer and the anti-corrosion aluminum foil layer and between the anti-corrosion aluminum foil layer and the rough polypropylene layer, and pressing to prepare an aluminum-plastic film;
wherein, the passivating agent comprises the following components in parts by weight:
10-20 parts of fluorozirconic acid, 1-5 parts of molybdate, 15-40 parts of titanate coupling agent modified nano titanium dioxide, 0.5-3 parts of corrosion inhibitor and 30-60 parts of deionized water.
By adopting the technical scheme, the nylon layer and the polypropylene layer are pretreated, so that the surfaces of the nylon layer and the polypropylene layer are rougher, the coverage area of the adhesive can be increased as much as possible, and the adhesive force between the nylon layer and the aluminum foil layer is increased. Meanwhile, the aluminum foil layer is passivated by using the passivating agent, so that the aluminum-plastic film has high deep-drawing and corrosion resistance, the possibility that the aluminum-plastic film is corroded by electrolyte is reduced, and the safety of the lithium battery is improved. In addition, the passivating agent in the application has less pollution to the environment and is more environment-friendly.
In the passivating agent, fluorozirconic acid and molybdate can cooperatively oxidize the aluminum foil layer to form a layer of metal oxide (ZrO 2 、MoO 3 And Al 2 O 3 ) Metal fluorides (AlF) 3 ) And an oxide film formed by the metal organic complex can reduce the contact area of the aluminum foil layer and the electrolyte and slow down the corrosion speed of the aluminum foil layer. The nano titanium dioxide modified by the titanate coupling agent can enhance the stability of other components, and can promote the oxide film to be better adhered to the surface of the aluminum foil layer due to the strong chemical bonding adsorptivity, high dispersibility and good film forming property of the nano titanium dioxide modified by the titanate coupling agent, so that the corrosion resistance of the aluminum foil layer is further improved. The corrosion inhibitor can form stable complex or passivation film on the surface of the aluminum foil layer, so that the corrosion speed of the aluminum foil layer is further slowed down.
In some specific embodiments, the passivating agent comprises 15-20 parts of fluorozirconic acid, 2-4 parts of molybdate, 25-35 parts of titanate coupling agent modified nano titanium dioxide, 1-3 parts of corrosion inhibitor and 40-55 parts of deionized water. The molybdate is selected from one or more of potassium molybdate, sodium molybdate and ammonium molybdate.
As preferable: the passivating agent also comprises 15-40 parts of acrylic resin.
Through adopting above-mentioned technical scheme, acrylic resin and molybdate cooperate and form bilayer membrane structure on the aluminium foil layer surface, and its outside is compact acrylic resin rete, has the isolation effect, and the inlayer is molybdate passive film, can improve the combination of acrylic resin rete and aluminium foil layer, and bilayer membrane can play the corrosion inhibition effect to the aluminium foil layer jointly.
In some preferred embodiments, the acrylic resin is present in the passivating agent in an amount of 20-30 parts.
As preferable: the weight ratio of the molybdate to the acrylic resin is 1 (5-20).
By adopting the technical scheme, when the weight ratio of the acrylic resin to the molybdate is controlled within the range, the synergistic effect between the acrylic resin and the molybdate can be better exerted, so that the corrosion resistance of the aluminum foil layer is better.
In some preferred embodiments, the weight ratio of molybdate to acrylic resin may be 1:10, 1:15, etc.
As preferable: the corrosion inhibitor comprises disodium ethylenediamine tetraacetate and triethanolamine.
By adopting the technical scheme, the disodium ethylenediamine tetraacetate is a metal chelating agent, the triethanolamine is a complexing agent, the disodium ethylenediamine tetraacetate and the triethanolamine cooperate with metal ions to form a complex, and a compact single-molecule protective film can be formed on the metal surface in the process of cooperation, so that the corrosion speed of the aluminum foil layer is slowed down, and the corrosion resistance of the aluminum foil layer is enhanced.
As preferable: the weight ratio of the disodium ethylenediamine tetraacetate to the triethanolamine is 1 (5-15).
In some preferred embodiments, the weight ratio of disodium edetate to triethanolamine in the corrosion inhibitor may be 1:5, 1:10, 1:15, or the like.
By adopting the technical scheme, when the weight ratio of the disodium ethylenediamine tetraacetate to the triethanolamine is controlled within the range, the synergistic effect between the disodium ethylenediamine tetraacetate and the triethanolamine can be better exerted, so that the corrosion resistance of the aluminum foil layer is better.
As preferable: the preparation method of the titanate coupling agent modified nano titanium dioxide comprises the following steps: putting nano titanium dioxide into an ethanol solution, and uniformly mixing to obtain a mixed solution; adding a titanate coupling agent into the mixed solution to obtain a modified solution; and (3) carrying out ultrasonic treatment and filtration on the modified liquid, and washing and drying the filtered precipitate to obtain the titanate coupling agent modified nano titanium dioxide.
By adopting the technical scheme, as nano titanium dioxide particles can be quickly agglomerated in water and the dispersibility is poor, the nano titanium dioxide is modified by using the titanate coupling agent through the method, the Ti-O bond can be formed with the hydroxyl on the surface of the nano titanium dioxide after the titanate coupling agent is hydrolyzed, the surface property of the nano titanium dioxide is changed, and the dispersibility is enhanced.
As preferable: the addition amount of the titanate coupling agent is 3-10% of the mass of the nano titanium dioxide.
By adopting the technical scheme, if the dosage of the titanate coupling agent is too small, the titanate coupling agent cannot completely react with the hydroxyl on the surface of the nano titanium dioxide, so that the modification effect is poor; however, if the dosage of the titanate coupling agent is too large, the titanium oxyalkane anion generated after the hydrolysis of the titanate coupling agent can attack Ti atoms in Ti-O bonds formed by the hydroxyl groups on the surface of the nano titanium dioxide and the titanate coupling agent to generate bridging, so that the nano titanium dioxide particles are agglomerated, the dispersion performance of the nano titanium dioxide is deteriorated, and the modification effect of the nano titanium dioxide is affected.
In some specific embodiments, the titanate coupling agent is added in an amount of 5% -8% of the mass of the nano-titania.
As preferable: the conditions of the ultrasonic treatment are as follows: ultrasonic temperature: 40-60 ℃; ultrasonic time: 0.5-1.5h.
By adopting the technical scheme, the temperature can influence the hydrolysis and condensation of the titanate coupling agent, and when the temperature is lower, the hydrolysis speed and the condensation speed of the titanate coupling agent are very low, and the unhydrolyzed titanate coupling agent cannot be coated on the surface of the nano titanium dioxide, so that the modification effect of the nano titanium dioxide is poor in a certain time. When the temperature is higher, the hydrolysis speed and the condensation speed of the titanate coupling agent are both fast, and a part of the hydrolyzed titanyl anions can generate self-condensation reaction, so that the titanate coupling agent coated on the surface of the nano titanium dioxide is reduced, and the modification effect of the nano titanium dioxide is affected.
In addition, as the ultrasonic time increases, the titanate coupling agent forms more Ti-O bonds with the hydroxyl groups on the surface of the nano titanium dioxide, so that the dispersibility of the modified nano titanium dioxide is obviously increased, but the adsorption process of the titanate coupling agent on the surface of the nano titanium dioxide comprises two stages: the single-molecule adsorption layer is formed and the micelle is formed, so that the titanate coupling agent can form the micelle on the surface of the nano titanium dioxide to influence the dispersibility of the nano titanium dioxide along with the increase of ultrasonic time. After 1h of ultrasound, the dispersibility of the nano titanium dioxide modified by the titanate coupling agent is the best.
In some preferred embodiments, the conditions of the sonication are as follows: the ultrasonic temperature is 50 ℃ and the ultrasonic time is 1h.
As preferable: the passivation pretreatment comprises the following steps:
t1, degreasing and cleaning the aluminum foil layer;
t2, performing double-sided passivation treatment on the cleaned aluminum foil layer by using a passivating agent to obtain a passivated aluminum foil layer;
and T3, cleaning the passivated aluminum foil layer by using deionized water, and drying to obtain the anti-corrosion aluminum foil layer.
By adopting the technical scheme, firstly, the cleaning agent is used for removing stains on the surface of the aluminum foil layer, so that on one hand, the pollution of the passivating agent is avoided, the effectiveness of the passivating agent is influenced, and on the other hand, the aluminum foil layer can be fully contacted and reacted with the passivating agent. And then passivating the aluminum foil layer by using a passivating agent to cover the surface of the aluminum foil layer with an oxide film and a complex as much as possible, and slowing down the corrosion speed of the aluminum foil layer by electrolyte, thereby improving the corrosion resistance of the aluminum plastic film.
As preferable: the temperature of the double-sided passivation treatment is 35-50 ℃.
By adopting the technical scheme, the passivation film formed by passivating the aluminum foil layer at the temperature by fluorozirconic acid and molybdate has better corrosion resistance, so that the aluminum foil layer has better corrosion resistance.
In some preferred embodiments, the temperature of the double sided passivation process is 40 ℃.
In summary, the present application includes at least one of the following beneficial technical effects:
1. the passivation solution is used for passivating the aluminum foil layer, a compact oxide film formed by metal oxide, metal fluoride and metal complex is formed on the surface of the aluminum foil layer under the synergistic effect of the components of the passivation solution, and an acrylic resin film is covered on the outer layer of the oxide film, so that the contact between the electrolyte and the aluminum foil layer can be blocked, the corrosion rate of the aluminum foil layer is slowed down, and the corrosion resistance of the aluminum plastic film is improved;
2. the nano titanium dioxide modified by the titanate coupling agent is added into the passivating agent, so that the stability of the passivating solution is improved, the oxide film can be more uniformly and firmly attached to the surface of the aluminum foil layer, and the corrosion resistance of the aluminum plastic film is further improved.
Detailed Description
In order that the present application may be more readily understood, the following examples are presented in conjunction with the following detailed description, which are intended to be illustrative only and are not intended to limit the scope of application of the present application. The starting materials or components used in the present application may be prepared by commercial or conventional methods unless specifically indicated.
Preparation example 1
The preparation method of the titanate coupling agent modified nano titanium dioxide comprises the following steps: and (3) putting the nano titanium dioxide into an ethanol solution with the concentration of 75% for uniform mixing to obtain a mixed solution, and then adding a titanate coupling agent into the mixed solution to obtain a modified solution. And (3) placing the modified solution into a water bath kettle with the temperature of 50 ℃ and carrying out ultrasonic treatment on the modified solution for 1h, filtering, washing the precipitate by using deionized water, and drying the precipitate in an oven with the temperature of 120 ℃ for 10h to obtain the titanate coupling agent modified nano titanium dioxide. Wherein 5g of nano titanium dioxide and 0.3g of titanate coupling agent are added into each 1L of ethanol solution, and the addition amount of the titanate coupling agent is 6% of the mass of the nano titanium dioxide.
Preparation example 2
The preparation process is basically the same as that of preparation example 1, except that: 5g of nano titanium dioxide and 0.4g of titanate coupling agent are added into each 1L of ethanol solution, and the addition amount of the titanate coupling agent is 8% of the mass of the nano titanium dioxide.
Preparation example 3
The preparation process is basically the same as that of preparation example 1, except that: 5g of nano titanium dioxide and 1g of titanate coupling agent are added into each 1L of ethanol solution, and the addition amount of the titanate coupling agent is 5% of the mass of the nano titanium dioxide.
Examples 1 to 5
A preparation process of a high-punching deep-drawing corrosion-resistant aluminum plastic film specifically comprises the following steps:
preparing a passivating agent: according to the components and the addition amounts thereof shown in Table 1, the components were mixed and stirred to be dispersed uniformly to prepare the passivating agent. Wherein the corrosion inhibitor is disodium ethylenediamine tetraacetate and triethanolamine, and the weight ratio of the disodium ethylenediamine tetraacetate to the triethanolamine is 1:5.
Pretreatment of raw materials: carrying out plasma pretreatment on the nylon layer by using a plasma surface processor, wherein the plasma treatment frequency is 10kHz, the treatment voltage is 8KV, and the treatment power is 8m/min to obtain a rough nylon layer; and (3) carrying out corona pretreatment on the polypropylene layer by using a corona treatment machine, wherein the corona power is 1.5KVA, and the corona time is 30s, so as to obtain the rough polypropylene layer. And (3) removing grease stains on the surface of the aluminum foil layer by using an aluminum material cleaning agent RSB-108, cleaning by using deionized water, immersing the cleaned aluminum foil layer into a passivating agent at 40 ℃ for double-sided passivation treatment, and taking out after immersing for 3min to obtain the passivated aluminum foil layer. And cleaning the passivated aluminum foil layer by using deionized water, and putting the cleaned aluminum foil layer into an oven for drying at 120 ℃ for 4 hours to obtain the anti-corrosion aluminum foil layer.
And (3) pressing an aluminum plastic film: and uniformly coating polyurethane adhesive between the rough nylon layer and the anti-corrosion aluminum foil layer and between the anti-corrosion aluminum foil layer and the rough polypropylene layer, overlapping and bonding the three layers, and then pressing to prepare the aluminum plastic film.
TABLE 1 addition amount (kg) of the components of the passivating agents of examples 1-5
In Table 1, in examples 3-5, the weight ratios of sodium molybdate to acrylic resin were 1:10, 1:15 and 1:25, respectively.
Example 6
The difference between this example and example 4 is that in the passivating agent, the corrosion inhibitor is disodium ethylenediamine tetraacetate, and the remainder is the same as in example 4.
Example 7
The difference between this example and example 4 is that in the passivating agent, the corrosion inhibitor is triethanolamine, and the remainder is the same as in example 4.
Example 8
The difference between this example and example 4 is that the weight ratio of disodium ethylenediamine tetraacetate to triethanolamine in the corrosion inhibitor is 1:10, and the remainder is the same as in example 4.
Example 9
The difference between this example and example 4 is that the weight ratio of disodium ethylenediamine tetraacetate to triethanolamine in the corrosion inhibitor is 1:15, and the remainder is the same as in example 4.
Example 10
The difference between this example and example 4 is that the weight ratio of disodium ethylenediamine tetraacetate to triethanolamine in the corrosion inhibitor is 1:20, and the remainder is the same as in example 4.
Example 11
This example differs from example 8 in that the titanate coupling agent modified nano-titania in the passivating agent is the titanate coupling agent modified nano-titania prepared in preparation example 2, and the remainder is the same as in example 8.
Example 12
This example differs from example 8 in that the titanate coupling agent-modified nano-titania in the passivating agent is the titanate coupling agent-modified nano-titania prepared in preparation example 3, and the remainder is the same as in example 8.
Example 13
The difference between this example and example 8 is that the grease stains on the surface of the aluminum foil layer are removed by using an aluminum treatment cleaning agent, then the aluminum foil layer is cleaned by using deionized water, the cleaned aluminum foil layer is immersed in a passivating agent at 25 ℃ for double-sided passivation treatment, and the aluminum foil layer is taken out after 3min of immersion, so that the passivated aluminum foil layer is obtained. The procedure is as in example 8.
Comparative example 1
This comparative example differs from example 8 in that the titanate coupling agent modified nano-titania in the passivating agent is replaced with nano-titania in equal amounts, and the remainder is the same as in example 8.
Test case
The aluminum plastic films and the passivated aluminum foil layers prepared in examples 1 to 13 and comparative example 1 were tested, specifically, the electrolyte resistance of the aluminum foil layer/polypropylene layer was tested and the salt spray test was performed, and the test results are shown in table 2.
The method for detecting the electrolyte resistance of the aluminum foil layer/polypropylene layer comprises the following steps: preparing 1mol/L LiPF6 electrolyte (the solute is 1mol/L LiPF6, the solvent is dimethyl carbonate, ethylene carbonate and diethyl carbonate, and the weight ratio of the two is 1:1:1), cutting the aluminum plastic films prepared in examples 1-13 and comparative example 1 into strips with the width of 15mm and the length of 100mm, placing the strips into the LiPF6 electrolyte, standing for 7 days at the temperature of 85 ℃, taking out, cleaning, and detecting the peeling strength of the aluminum foil layer/polypropylene layer according to the soft composite plastic material peeling test method of GB/T8808-1988, wherein the stretching speed is (300+/-50) mm/min.
In addition, the salt spray test is required to be performed according to the artificial atmosphere corrosion test-salt spray test (NSS) in the national standard GB/T10125-1997. The test samples were the passivated aluminum foil layers in examples 1-13 and comparative example 1,the solution used in the test was 5% NaCl solution, pH 7.0, maintained at 35℃per 80cm 2 The settling amount is 1-2ml/h, spraying is continuously carried out for 21 days, and the time for starting to change the color on the surface of the passivated aluminum foil layer is recorded.
TABLE 2
From the test results in Table 2, it is found that the peel strength of the electrolyte resistance of the aluminum plastic films prepared in examples 1 to 13 and comparative example 1 is 7.9 to 12.1N/15mm, and the discoloration time of the passivated aluminum foil layer in the salt spray test is at least 330 hours. From the detection data of examples 1-3, the passivation effect of the passivation agent added with the acrylic resin on the aluminum foil layer is better, the corrosion resistance of the prepared passivation aluminum foil layer is stronger, and the prepared aluminum plastic film has higher electrolyte peeling strength. From the detection data of examples 3-5, when the weight ratio of the acrylic resin to the molybdate in the passivating agent is 15:1, the peel strength of the prepared aluminum plastic film against electrolyte is higher.
From the detection data of examples 4 and 6-10, when the corrosion inhibitor in the passivating agent is disodium ethylenediamine tetraacetate and triethanolamine, and the weight ratio of the disodium ethylenediamine tetraacetate to the triethanolamine is 1:10, the prepared passivated aluminum foil layer has better corrosion resistance, and the prepared aluminum plastic film has higher electrolyte peeling strength. From the detection data of examples 8, 11-12 and comparative example 1, compared with nano titanium dioxide, the addition of the nano titanium dioxide modified by the titanate coupling agent is more beneficial to improving the corrosion resistance of the aluminum plastic film, and when the addition amount of the titanate coupling agent is 6% of the mass of the nano titanium dioxide in the preparation process of the nano titanium dioxide modified by the titanate coupling agent, the prepared nano titanium dioxide modified by the titanate coupling agent can enable the passivation effect of the passivation agent on the aluminum foil layer to be better, and the electrolyte peeling resistance of the finally prepared aluminum plastic film to be enhanced. From the detection data of examples 8 and 13, the passivation effect of the passivation agent on the aluminum foil layer is better at 40 ℃, the corrosion resistance of the prepared passivation aluminum foil layer is better, and the peel strength of the prepared aluminum plastic film against electrolyte is higher.
It should be noted that the above-described embodiments are only for explaining the present application, and do not constitute any limitation to the present application. The present application has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the present application as defined within the scope of the claims of the present application, and the invention may be modified without departing from the scope and spirit of the present application. Although the present application is described herein with reference to particular methods, materials and embodiments, the present application is not intended to be limited to the particular examples disclosed herein, but rather, the present application is intended to extend to all other methods and applications having the same functionality.
Claims (10)
1. A preparation process of a high-punching deep-drawing corrosion-resistant aluminum plastic film is characterized by comprising the following steps of: the preparation method comprises the following preparation steps:
s1, raw material pretreatment: passivating pretreatment is carried out on the aluminum foil layer by adopting a passivating agent, so that an anti-corrosion aluminum foil layer is obtained; carrying out plasma pretreatment on the nylon layer to obtain a rough nylon layer; corona pretreatment is carried out on the polypropylene layer to obtain a rough polypropylene layer;
s2, smearing an adhesive between the rough nylon layer and the anti-corrosion aluminum foil layer and between the anti-corrosion aluminum foil layer and the rough polypropylene layer, and pressing to prepare an aluminum-plastic film;
wherein, the passivating agent comprises the following components in parts by weight:
10-20 parts of fluorozirconic acid, 1-5 parts of molybdate, 15-40 parts of titanate coupling agent modified nano titanium dioxide, 0.5-3 parts of corrosion inhibitor and 30-60 parts of deionized water.
2. The process for preparing the high-punching-depth corrosion-resistant aluminum plastic film according to claim 1, which is characterized in that: the passivating agent also comprises 15-40 parts of acrylic resin.
3. The process for preparing the high-punching-depth corrosion-resistant aluminum plastic film according to claim 2, which is characterized in that: the weight ratio of the molybdate to the acrylic resin is 1 (5-20).
4. A process for preparing a high-impact-depth corrosion-resistant aluminum-plastic film according to any one of claims 1 to 3, wherein: the corrosion inhibitor comprises disodium ethylenediamine tetraacetate and triethanolamine.
5. The process for preparing the high-punching-depth corrosion-resistant aluminum-plastic film according to claim 4, which is characterized in that: the weight ratio of the disodium ethylenediamine tetraacetate to the triethanolamine is 1 (5-15).
6. A process for preparing a high-impact-depth corrosion-resistant aluminum-plastic film according to any one of claims 1 to 3, wherein: the preparation method of the titanate coupling agent modified nano titanium dioxide comprises the following steps: putting nano titanium dioxide into an ethanol solution, and uniformly mixing to obtain a mixed solution; adding a titanate coupling agent into the mixed solution to obtain a modified solution; and (3) carrying out ultrasonic treatment and filtration on the modified liquid, and washing and drying the filtered precipitate to obtain the titanate coupling agent modified nano titanium dioxide.
7. The process for preparing the high-punching-depth corrosion-resistant aluminum-plastic film according to claim 6, which is characterized in that: the addition amount of the titanate coupling agent is 3-10% of the mass of the nano titanium dioxide.
8. The process for preparing the high-punching-depth corrosion-resistant aluminum-plastic film according to claim 6, which is characterized in that: the conditions of the ultrasonic treatment are as follows: the ultrasonic temperature is 40-60 ℃ and the ultrasonic time is 0.5-1.5h.
9. A process for preparing a high-impact-depth corrosion-resistant aluminum-plastic film according to any one of claims 1 to 3, wherein: the passivation pretreatment comprises the following steps:
t1, degreasing and cleaning the aluminum foil layer;
t2, performing double-sided passivation treatment on the cleaned aluminum foil layer by using a passivating agent to obtain a passivated aluminum foil layer;
and T3, cleaning the passivated aluminum foil layer by using deionized water, and drying to obtain the anti-corrosion aluminum foil layer.
10. The process for preparing the high-impact deep-drawing corrosion-resistant aluminum-plastic film according to claim 9, which is characterized in that: the temperature of the double-sided passivation treatment is 35-50 ℃.
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| CN116666647B (en) * | 2023-08-01 | 2024-04-12 | 宁德时代新能源科技股份有限公司 | Positive electrode current collector, preparation method, positive electrode plate, secondary battery and power utilization device |
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