CN110437686B - Electrolyte-resistant BOPA film and preparation method thereof - Google Patents
Electrolyte-resistant BOPA film and preparation method thereof Download PDFInfo
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
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- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
- C09D133/16—Homopolymers or copolymers of esters containing halogen atoms
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
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- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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Abstract
The invention relates to the field of nylon films for packaging films, in particular to an electrolyte-resistant BOPA film and a preparation method thereof, wherein the film consists of two layers of structures, namely a coating layer and a polyamide film layer, and the preparation method comprises the following steps: the coating layer is formed by coating water-based emulsion on the surface of the polyamide film layer; the water-based emulsion comprises the following components in percentage by mass: 45% -54% of aqueous fluorocarbon resin; 2.5 to 5.5 percent of water dispersible blocked isocyanate; 43% -51% of water; wherein the aqueous fluorocarbon resin is prepared by polymerizing a fluorine-containing monomer and cyclohexyl vinyl ether; the water dispersible blocked isocyanate is prepared by reacting methylene polyphenyl polyisocyanate with diethyl malonate for many times. The BOPA electrolyte-resistant film prepared by the preparation method has electrolyte-resistant and corrosion-resistant performances, the flexibility of the film is not affected, the pit punching forming depth of the film is not required to be reduced, and the phenomenon that a packaging film is easy to break is avoided.
Description
Technical Field
The invention relates to the field of nylon films for packaging films, in particular to an electrolyte-resistant BOPA film and a preparation method thereof.
Background
At present, the BOPA film has been widely used for the outer layer of the aluminum-plastic packaging film of the lithium ion polymer battery due to the excellent deep impact resistance and forming performance; in the production process of the lithium battery, the electrolyte is easy to pollute the aluminum-plastic packaging film of the lithium battery in the liquid injection process and the secondary sealing process, the polyamide material is not resistant to the electrolyte, the electrolyte is corroded and whitened when meeting, and when the electrolyte is polluted, the polyamide surface layer is damaged to cause defective products.
The common solution in the market is to compound a layer of PET film on the surface, which not only consumes time and labor and increases cost, but also reduces the overall toughness of the aluminum-plastic packaging film because the PET itself is hard and brittle, thereby reducing the cold-rolling forming depth, otherwise, the aluminum layer in the packaging film is easy to crack in the cold-rolling forming process.
Yet another approach is to use an electrolyte-resistant coating, such as the electrochemical cell packaging disclosed in the patent document "electrochemical cell packaging" of application number 201280055432.1, which discloses at least a laminate of: the protective layer is made of an epoxy resin having bisphenol A or bisphenol F as a unit in the skeleton, and the film has good electrolyte resistance and better flexibility than a film made by laminating one PET layer, but the composite film made of the film is still insufficient in overall toughness due to the electrolyte resistance coating being hard and is still easily broken during the drawing and molding process.
Disclosure of Invention
In order to solve the problem that the overall toughness of the packaging film is reduced and the packaging film is easy to crack due to the fact that a PET film is compounded in order to prevent the corrosion of electrolyte in the conventional aluminum-plastic packaging film in the background art, the invention provides an electrolyte-resistant BOPA film and a preparation method thereof, wherein the electrolyte-resistant BOPA film comprises a coating layer and a polyamide film layer, and the coating layer is formed by coating aqueous emulsion on the surface of the polyamide film layer; the water-based emulsion comprises the following components in percentage by mass:
45% -54% of aqueous fluorocarbon resin;
2.5 to 5.5 percent of water dispersible blocked isocyanate;
43% -51% of water;
wherein the aqueous fluorocarbon resin is prepared by polymerizing a fluorine-containing monomer and cyclohexyl vinyl ether; the water dispersible blocked isocyanate is prepared by reacting methylene polyphenyl polyisocyanate and diethyl malonate for many times.
On the basis of the scheme, the preparation method of the aqueous fluorocarbon resin comprises the following steps: adding quantitative deionized water, sodium alkyl benzene sulfonate, alkylphenol ethoxylates and sodium bicarbonate into a high-pressure reaction kettle, stirring and dissolving uniformly, then adding 10-15% of fluorine-containing monomer and 10-15% of cyclohexyl vinyl ether, stirring and mixing uniformly, heating to 58-62 ℃, adding 15% of potassium persulfate-ferrous chloride, automatically heating at the moment, controlling the temperature to be 75-85 ℃, adding the rest fluorine-containing monomer, cyclohexyl vinyl ether and the rest 85% of potassium persulfate-ferrous chloride after the temperature is stable, finishing the addition within 5h, and finishing the reaction when the system pressure is gradually reduced to be balanced. Cooling to 40 ℃, adding ammonia water, adjusting the pH value to 7-8, and filtering to obtain aqueous fluorocarbon resin; wherein, potassium persulfate-ferrous chloride is used as an initiator.
On the basis of the scheme, the preparation method of the water dispersible blocked isocyanate further comprises the following steps: adding methylene polyphenyl polyisocyanate, 1, 4-dihydroxyethoxy benzene, butanone and dibutyltin dilaurate into a reaction kettle for many times, heating to 85-90 ℃, reacting at a constant temperature, and measuring the-NCO group content in real time by using a n-dibutylamine method until the-NCO group content is 10-14%; cooling to room temperature, slowly adding diethyl malonate, heating to 70-75 ℃ after the addition is finished, keeping the temperature for reaction in the temperature range, finishing the reaction when the free-NCO content is basically zero, adding dimethyl ethanolamine serving as a neutralizing agent, neutralizing uniformly, adding water for dispersion, and finally extracting butanone to obtain the water-dispersible blocked isocyanate.
On the basis of the scheme, the fluorine-containing monomer is one or more of perfluoropropyl vinyl ether, perfluoroethyl vinyl ether, perfluoroalkyl methacrylate, perfluoroalkyl acrylate containing hetero atoms, perfluoroalkylamide methacrylate and perfluoroalkanesulfonyl acrylate.
On the basis of the scheme, the mass ratio of the sodium alkyl benzene sulfonate, the alkylphenol ethoxylates, the sodium bicarbonate, the fluorine-containing monomer, the cyclohexyl vinyl ether and the potassium persulfate-ferrous chloride is as follows: 0.0015-0.0020:1.2-1.5:0.10-0.15:12-15:30-35:0.02-0.03, wherein the mass ratio of the polymethylene polyphenyl polyisocyanate, the diethyl malonate, the 1, 4-dihydroxy ethoxybenzene, the butanone and the dibutyltin dilaurate is 3.5-6.5:3.5-6.5:1.0-2.0:4.0-5.0: 0.0005-0.001.
On the basis of the scheme, further, the thickness of the coating layer is 3-5 μm.
On the basis of the scheme, the thickness of the polyamide film layer is 15-25 μm.
On the basis of the scheme, the polyamide film layer is a biaxially oriented PA film.
On the basis of the scheme, the nylon resin of the polyamide membrane layer is prepared by mixing at least one or more of nylon 6, a copolymer of nylon 6 and nylon 6, nylon 612, nylon 610, nylon 12, nylon 1212 and poly-m-xylene adipamide.
The invention provides a preparation method of the electrolyte-resistant BOPA thin film, which comprises the following steps:
step a, carrying out corona treatment on the surface of a polyamide film after the polyamide film is longitudinally stretched to ensure that the corona value of the surface of the polyamide film is more than or equal to 48 dyn/cm;
b, coating a water-based emulsion on the corona surface of the polyamide film layer through an anilox roller, and drying at 140-200 ℃ to form a coating;
and c, drying at 140-200 ℃, and simultaneously transversely stretching and shaping the polyamide film to obtain the electrolyte-resistant BOPA film.
According to the electrolyte-resistant BOPA film and the preparation method thereof, the preparation method of the electrolyte-resistant BOPA film is simple and efficient through a specific coating layer formula and the preparation process provided by the technology, the coating liquid is firmly combined with the polyamide film layer, the crosslinking density of the aqueous fluorocarbon resin is improved once more due to the good corrosion resistance of the aqueous fluorocarbon resin and the good crosslinking performance of the water-dispersible end-capping isocyanate, so that the prepared BOPA film has strong electrolyte-resistant corrosion resistance, meanwhile, the film-forming performance of the coating layer is good due to the good crosslinking performance of the water-dispersible end-capping isocyanate, the flexibility of the BOPA film prepared by the method can be guaranteed to be not influenced, the depth of deep punching forming of the film is not required to be reduced in cold rolling forming, and the phenomenon that the packaging film is easy to break is avoided.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the following description will clearly and completely describe the embodiments of the present invention, and obviously, the described embodiments are a part of the embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The electrolyte-resistant BOPA film comprises a coating layer and a polyamide film layer, wherein the coating layer is formed by coating aqueous emulsion on the surface of the polyamide film layer; the water-based emulsion comprises the following components in percentage by mass:
45% -54% of aqueous fluorocarbon resin;
2.5 to 5.5 percent of water dispersible blocked isocyanate;
43% -51% of water;
wherein the aqueous fluorocarbon resin is prepared by polymerizing a fluorine-containing monomer and cyclohexyl vinyl ether; the water dispersible blocked isocyanate is prepared by reacting methylene polyphenyl polyisocyanate and diethyl malonate for many times.
The aqueous fluorocarbon resin has excellent corrosion resistance to electrolyte, the water dispersible blocked isocyanate has a crosslinking characteristic, and if the water dispersible blocked isocyanate is added too much, a formed coating layer is hard and brittle and affects toughness, so that the depth of a punched hole is easily reduced; if the amount of the water-dispersible blocked isocyanate is too small, the adhesion strength between the coating layer and the polyamide film is reduced, and the electrolyte resistance of the film is indirectly reduced.
Preferably, the preparation method of the aqueous fluorocarbon resin comprises the following steps: adding quantitative deionized water, sodium alkyl benzene sulfonate, alkylphenol ethoxylates and sodium bicarbonate into a high-pressure reaction kettle, stirring and dissolving uniformly, then adding 10-15% of fluorine-containing monomer and 10-15% of cyclohexyl vinyl ether, stirring and mixing uniformly, heating to 58-62 ℃, adding 15% of potassium persulfate-ferrous chloride, automatically heating at the moment, controlling the temperature to be 75-85 ℃, adding the rest fluorine-containing monomer, cyclohexyl vinyl ether and the rest 85% of potassium persulfate-ferrous chloride after the temperature is stable, finishing the addition within 5h, and finishing the reaction when the system pressure is gradually reduced to be balanced. Cooling to 40 ℃, adding ammonia water, adjusting the pH value to 7-8, and filtering to obtain aqueous fluorocarbon resin; wherein, potassium persulfate-ferrous chloride is used as an initiator.
Preferably, the preparation method of the water dispersible blocked isocyanate comprises the following steps: adding methylene polyphenyl polyisocyanate, 1, 4-dihydroxyethoxy benzene, butanone and dibutyltin dilaurate into a reaction kettle for many times, heating to 85-90 ℃, reacting at a constant temperature, and measuring the-NCO group content in real time by using a n-dibutylamine method until the-NCO group content is 10-14%; cooling to room temperature, slowly adding diethyl malonate, heating to 70-75 ℃ after the addition is finished, keeping the temperature for reaction in the temperature range, finishing the reaction when the free-NCO content is basically zero, adding dimethyl ethanolamine serving as a neutralizing agent, neutralizing uniformly, adding water for dispersion, and finally extracting butanone to obtain the water-dispersible blocked isocyanate.
Preferably, the fluorine-containing monomer is one or more of perfluoropropyl vinyl ether, perfluoroethyl vinyl ether, perfluoroalkyl methacrylate, heteroatom-containing perfluoroalkyl acrylate, perfluoroalkylamide methacrylate and perfluoroalkanesulfonyl acrylate.
Preferably, the mass ratio of the sodium alkyl benzene sulfonate, the alkylphenol polyoxyethylene, the sodium bicarbonate, the fluorine-containing monomer, the cyclohexyl vinyl ether and the potassium persulfate-ferrous chloride is as follows: 0.0015-0.0020:1.2-1.5:0.10-0.15:12-15:30-35:0.02-0.03, wherein the mass ratio of the polymethylene polyphenyl polyisocyanate, the diethyl malonate, the 1, 4-dihydroxy ethoxybenzene, the butanone and the dibutyltin dilaurate is 3.5-6.5:3.5-6.5:1.0-2.0:4.0-5.0: 0.0005-0.001.
Preferably, the thickness of the coating layer is 3 μm to 5 μm.
When the thickness of the coating layer is less than 3 μm, the composite firmness of the coating layer and the polyamide film layer is insufficient, and when the thickness exceeds 3 μm, the appearance is prone to be poor due to uneven thickness, and the appearance is prone to have transverse striations and other defects. Therefore, in the technical scheme provided by the invention, the coating layer is controlled within a certain thickness range to ensure the compounding fastness.
Preferably, the thickness of the polyamide film layer is 15 μm to 25 μm.
The thickness of the polyamide film layer is controlled to be 15-25 mu m and the performance-to-cost ratio is high, namely the thickness of the BOPA film is as thin as possible on the premise of ensuring the basic performance of the BOPA film so as to reduce the production cost.
Preferably, the polyamide film layer is a biaxially oriented PA film.
Preferably, the nylon resin of the polyamide membrane layer is prepared by mixing at least one or more of nylon 6, copolymer of nylon 6 and nylon 6, nylon 612, nylon 610, nylon 12, nylon 1212 and poly-m-xylene adipamide.
The invention also provides a preparation method of the electrolyte-resistant BOPA thin film, which comprises the following steps:
step a, carrying out corona treatment on the surface of a polyamide film after the polyamide film is longitudinally stretched to ensure that the corona value of the surface of the polyamide film is more than or equal to 48 dyn/cm;
b, coating a water-based emulsion on the corona surface of the polyamide film layer through an anilox roller, and drying at 140-200 ℃ to form a coating layer;
and c, drying at 140-200 ℃, transversely stretching the polyamide film, and shaping to obtain the electrolyte-resistant BOPA film.
The invention also provides the following examples and comparative examples:
[ example 1 ]
Longitudinally stretching three layers of co-extruded and cast polyamide film layers through an extruder, performing corona treatment after stretching to obtain a film with a corona value of 48dyn/cm, coating aqueous emulsion on the corona surface of the polyamide film layer through an anilox roller by using aqueous fluorocarbon resin of 50.0 percent, water dispersible blocked isocyanate of 2.5 percent and pure water of 47.5 percent, feeding the polyamide film layer into an oven, drying and transversely stretching the polyamide film layer at 160-180 ℃, and shaping to obtain an electrolyte-resistant BOPA film;
wherein the content of the first and second substances,
the aqueous fluorocarbon resin is prepared by polymerizing perfluoropropyl vinyl ether and cyclohexyl vinyl ether emulsion by adopting the preparation method of the aqueous fluorocarbon resin;
the water dispersible blocked isocyanate is prepared by reacting polymethylene polyphenyl polyisocyanate with diethyl malonate by adopting the preparation method of the water dispersible blocked isocyanate;
the aqueous fluorocarbon resin, the water dispersible blocked isocyanate and the water are weighed according to the proportion, and are mixed and uniformly stirred to obtain the aqueous emulsion of the coating layer.
The thickness of the coating layer is 5 μm; the polyamide film layer is a biaxially oriented PA film with the thickness of 25 mu m, and the resin adopted by the polyamide film layer is nylon 6.
[ example 2 ]
Longitudinally stretching three layers of co-extruded and cast polyamide film layers through an extruder, performing corona treatment after stretching to obtain a film with a corona value of 48dyn/cm, coating aqueous emulsion on the corona surface of the polyamide film layer through a anilox roller by using aqueous fluorocarbon resin of 53.0 percent, water dispersible blocked isocyanate of 3 percent and pure water of 44 percent, feeding the polyamide film layer into an oven, drying and transversely stretching the polyamide film layer at 160-180 ℃, and shaping to obtain an electrolyte-resistant BOPA film;
wherein the content of the first and second substances,
the aqueous fluorocarbon resin is prepared by polymerizing perfluoroalkyl methacrylate and cyclohexyl vinyl ether emulsion by adopting the preparation method of the aqueous fluorocarbon resin;
the water dispersible blocked isocyanate is prepared by reacting polymethylene polyphenyl polyisocyanate with diethyl malonate by adopting the preparation method of the water dispersible blocked isocyanate;
the aqueous fluorocarbon resin, the water dispersible blocked isocyanate and the water are weighed according to the proportion, and are mixed and uniformly stirred to obtain the aqueous emulsion of the coating layer.
The thickness of the coating layer is 5 μm; the polyamide film layer is a biaxially oriented PA film with the thickness of 25 mu m, and the resin adopted by the polyamide film layer is nylon 6.
[ example 3 ]
Longitudinally stretching three layers of co-extruded and cast polyamide film layers through an extruder, performing corona treatment after stretching to obtain a film with a corona value of 48dyn/cm, coating aqueous emulsion on the corona surface of the polyamide film layer through a anilox roller by using aqueous fluorocarbon resin of 45.0 percent, water dispersible blocked isocyanate of 5 percent and pure water of 50 percent, feeding the polyamide film layer into an oven, drying and transversely stretching the polyamide film layer at 160-180 ℃, and shaping to obtain an electrolyte-resistant BOPA film;
wherein the content of the first and second substances,
the aqueous fluorocarbon resin is prepared by emulsion polymerization of perfluoroalkyl amide methacrylate and cyclohexyl vinyl ether;
the water dispersible blocked isocyanate is prepared by reacting polymethylene polyphenyl polyisocyanate with diethyl malonate by adopting the preparation method of the water dispersible blocked isocyanate;
the aqueous fluorocarbon resin, the water dispersible blocked isocyanate and the water are weighed according to the proportion, and are mixed and uniformly stirred to obtain the aqueous emulsion of the coating layer.
The thickness of the coating layer is 5 μm; the polyamide film layer is a biaxially oriented PA film with the thickness of 25 mu m, and the resin adopted by the polyamide film layer is nylon 6.
[ example 4 ]
The film obtained in example 1 was dry-compounded with 40 μm of AL and 40 μm of CPP to form a battery packaging composite film.
Comparative example 1
Longitudinally stretching three layers of co-extruded and cast polyamide film layers through an extruder, performing corona treatment after stretching to obtain a film with a corona value of 48dyn/cm, coating aqueous emulsion on the corona surface of the polyamide film layer through an anilox roller by using aqueous emulsion obtained by mutually matching 50.0% of aqueous fluorocarbon resin, 7% of water-dispersible blocked isocyanate and 43.0% of pure water, feeding the polyamide film layer into an oven, drying and transversely stretching the polyamide film layer at 160-180 ℃, and shaping to obtain an electrolyte-resistant BOPA film;
wherein the content of the first and second substances,
the aqueous fluorocarbon resin is prepared by polymerizing perfluoroethyl vinyl ether and cyclohexyl vinyl ether emulsion by adopting the preparation method of the aqueous fluorocarbon resin;
the water dispersible blocked isocyanate is prepared by reacting polymethylene polyphenyl polyisocyanate with diethyl malonate by adopting the preparation method of the water dispersible blocked isocyanate;
the aqueous fluorocarbon resin, the water dispersible blocked isocyanate and the water are weighed according to the proportion, and are mixed and uniformly stirred to obtain the aqueous emulsion of the coating layer.
The thickness of the coating layer is 5 μm; the polyamide film layer is a biaxially oriented PA film with the thickness of 25 mu m, and the resin adopted by the polyamide film layer is nylon 6.
Comparative example 2
Longitudinally stretching three layers of co-extruded and cast polyamide film layers through an extruder, performing corona treatment after stretching to obtain a film with a corona value of 48dyn/cm, coating the water-based emulsion on the corona surface of the polyamide film layer through an anilox roller by using water-based fluorocarbon resin of 40.0 percent, water-dispersed blocked isocyanate of 7 percent and pure water of 53.0 percent, feeding the polyamide film layer into an oven, drying and transversely stretching the polyamide film layer at 160-180 ℃, and shaping to obtain an electrolyte-resistant BOPA film;
wherein the content of the first and second substances,
the aqueous fluorocarbon resin is prepared by polymerizing perfluoropropyl vinyl ether and cyclohexyl vinyl ether emulsion by adopting the preparation method of the aqueous fluorocarbon resin;
the water dispersible blocked isocyanate is prepared by reacting polymethylene polyphenyl polyisocyanate with diethyl malonate by adopting the preparation method of the water dispersible blocked isocyanate;
the aqueous fluorocarbon resin, the water dispersible blocked isocyanate and the water are weighed according to the proportion, and are mixed and uniformly stirred to obtain the aqueous emulsion of the coating layer.
The thickness of the coating layer is 5 μm; the polyamide film layer is a biaxially oriented PA film with the thickness of 25 mu m, and the resin adopted by the polyamide film layer is nylon 6.
Comparative example 3
Longitudinally stretching three layers of co-extruded and cast polyamide film layers through an extruder, performing corona treatment after stretching to obtain a film with a corona value of 48dyn/cm, coating the water-based emulsion on the corona surface of the polyamide film layer through an anilox roller by using water-based emulsion obtained by blending 50.0% of water-based fluorocarbon resin and 50.0% of pure water, feeding the polyamide film layer into an oven, drying and transversely stretching the polyamide film layer at 160-180 ℃, and shaping to obtain an electrolyte-resistant BOPA film;
wherein the content of the first and second substances,
the aqueous fluorocarbon resin is prepared by polymerizing acrylic acid perfluoroalkanesulfonyl and cyclohexyl vinyl ether emulsion by adopting the preparation method of the aqueous fluorocarbon resin;
and weighing the aqueous fluorocarbon resin and the water in proportion, mixing and uniformly stirring to obtain the aqueous emulsion of the coating layer.
The thickness of the coating layer is 5 μm; the polyamide film layer is a biaxially oriented PA film with the thickness of 25 mu m, and the resin adopted by the polyamide film layer is nylon 6.
Comparative example 4
Longitudinally stretching three layers of co-extruded and cast polyamide film layers through an extruder, performing corona treatment after stretching to obtain a film with a corona value of 48dyn/cm, coating aqueous emulsion on the corona surface of the polyamide film layer through an anilox roller by using aqueous fluorocarbon resin of 50.0 percent, water dispersible blocked isocyanate of 2.5 percent and pure water of 47.5 percent, feeding the polyamide film layer into an oven, drying and transversely stretching the polyamide film layer at 160-180 ℃, and shaping to obtain an electrolyte-resistant BOPA film;
wherein the content of the first and second substances,
the aqueous fluorocarbon resin is conventional aqueous fluorocarbon resin and is prepared by copolymerization and emulsification of vinylidene fluoride and methyl methacrylate as main monomers;
the water dispersible blocked isocyanate is prepared by reacting polymethylene polyphenyl polyisocyanate with diethyl malonate;
the aqueous fluorocarbon resin, the water dispersible blocked isocyanate and the water are weighed according to the proportion, and are mixed and uniformly stirred to obtain the aqueous emulsion of the coating layer.
The thickness of the coating layer is 5 μm; the polyamide film layer is a biaxially oriented PA film with the thickness of 25 mu m, and the resin adopted by the polyamide film layer is nylon 6.
Comparative example 5
Longitudinally stretching three layers of co-extruded and cast polyamide film layers through an extruder, performing corona treatment after stretching to obtain a film with a corona value of 48dyn/cm, coating aqueous emulsion on the corona surface of the polyamide film layer through an anilox roller by using aqueous emulsion obtained by mutually matching 50.0% of aqueous fluorocarbon resin, 2.5% of aqueous curing agent and 47.5% of pure water, feeding the polyamide film layer into an oven, drying and transversely stretching the polyamide film layer at 160-180 ℃, and shaping to obtain an electrolyte-resistant BOPA film;
wherein the content of the first and second substances,
the aqueous fluorocarbon resin is prepared by emulsion polymerization of perfluoropropyl vinyl ether and cyclohexyl vinyl ether;
the waterborne curing agent is prepared by using isophorone diisocyanate and sodium bisulfite as main raw materials;
the aqueous fluorocarbon resin, the aqueous curing agent and the water are weighed according to the proportion, and are uniformly stirred after being mixed, so that the aqueous emulsion of the coating layer can be obtained.
The thickness of the coating layer is 5 μm; the polyamide film layer is a biaxially oriented PA film with the thickness of 25 mu m, and the resin adopted by the polyamide film layer is nylon 6.
Comparative example 6
Longitudinally stretching three layers of co-extruded and cast polyamide film layers through an extruder, performing corona treatment after stretching to obtain a film with a corona value of 48dyn/cm, coating a water-based emulsion obtained by mutually matching 50.0% of water-based curing agent, 5% of water-based curing agent and 45.0% of pure water on the corona surface of the polyamide film layer through an anilox roller, feeding the polyamide film layer into an oven, drying and transversely stretching the polyamide film layer at 160-180 ℃, and shaping to obtain an electrolyte-resistant BOPA film;
wherein the content of the first and second substances,
the aqueous fluorocarbon resin is conventional aqueous fluorocarbon resin and is prepared by copolymerization and emulsification of vinylidene fluoride and methyl methacrylate as main monomers;
the aqueous curing agent is prepared from isophorone diisocyanate and sodium bisulfite as main raw materials.
The aqueous fluorocarbon resin, the water dispersible blocked isocyanate and the water are weighed according to the proportion, and are mixed and uniformly stirred to obtain the aqueous emulsion of the coating layer.
The thickness of the coating layer is 5 μm; the polyamide film layer is a biaxially oriented PA film with the thickness of 25 mu m, and the resin adopted by the polyamide film layer is nylon 6.
Comparative example 7
Longitudinally stretching three layers of co-extruded and cast polyamide film layers through an extruder, performing corona treatment after stretching to obtain a film with a corona value of 48dyn/cm, coating a water-based emulsion obtained by mutually matching 50.0% of water-based polyurethane resin, 5% of water-based curing agent and 45.0% of pure water on the corona surface of the polyamide film layer through a anilox roller, feeding the polyamide film layer into an oven, drying and transversely stretching the polyamide film layer at 160-180 ℃, and shaping to obtain an electrolyte-resistant BOPA film;
wherein the content of the first and second substances,
the aqueous fluorocarbon resin is conventional aqueous fluorocarbon resin and is prepared by copolymerizing and emulsifying tetrafluoroethylene, chlorotrifluoroethylene, hexafluoroethylene and vinyl versatate as main monomers;
the water-based curing agent is prepared by taking hexamethylene diisocyanate and acetanilide as main raw materials.
The waterborne polyurethane resin, the waterborne curing agent and the water are weighed according to the proportion, and are mixed and uniformly stirred to obtain the waterborne emulsion of the coating layer.
The thickness of the coating layer is 5 μm; the polyamide film layer is a biaxially oriented PA film with the thickness of 25 mu m, and the resin adopted by the polyamide film layer is nylon 6.
Comparative example 8
The commercially available aluminum-plastic composite film for the PET/AL/PP electrolyte-resistant lithium battery is produced by Jiangsu Bairuier packaging material Co.Ltd, and has the model of BR-li.
The electrolyte resistance test before deep drawing is carried out on the films prepared in the above examples and comparative examples, and the specific test operation is as follows:
2ml of an electrolyte (ethylene carbonate (EC): dimethyl carbonate (DMC): methyl ethyl carbonate (EMC) = 1: 1: 1: 1) was dropped onto the coating layers of examples 1 to 4 and comparative examples 1 to 8, 1mol of lithium hexafluorophosphate (LiPF 6) was added thereto, and after 48 hours, the dropped electrolyte was wiped off by a wipe stained with alcohol, and then the film surface was observed for corrosion by eyes, and the test results are shown in Table 1;
the films prepared in the above examples and comparative examples are subjected to electrolyte resistance test at vertex angle after deep drawing, and the specific test operation is as follows:
after punching the films of examples 1 to 3 and comparative examples 1 to 7 to a depth of 6.5mm, 2ml of an electrolyte (ethylene carbonate (EC): dimethyl carbonate (DMC): methyl ethyl carbonate (EMC) = 1: 1: 1) was added to a liquid containing 1mol of lithium hexafluorophosphate (LiPF 6)) was dropped onto four corners, and after 48 hours, the dropped electrolyte was wiped off with a wiping cloth soaked with alcohol, and then the corrosion of the film surface was observed by eyes, and the test results are shown in table 1;
after drawing 8.5mm deep in example 4 and comparative example 8, 2ml of an electrolyte (ethylene carbonate (EC): dimethyl carbonate (DMC): methyl ethyl carbonate (EMC) = 1: 1: 1) was added to a liquid containing 1mol of lithium hexafluorophosphate (LiPF 6)) was dropped onto four corners, and after 48 hours, the dropped electrolyte was wiped off with a wiper stained with alcohol, and then the corrosion of the film surface was observed by eyes, and the test results are shown in table 1;
TABLE 1
| Evaluation of electrolyte resistance before drawing | Evaluation of electrolyte resistance of vertex angle after deep punching | |
| Example 1 | O | O |
| Example 2 | O | O |
| Example 3 | O | O |
| Example 4 | 0 | 0 |
| Comparative example 1 | O | * |
| Comparative example 2 | * | ** |
| Comparative example 3 | *** | *** |
| Comparative example 4 | * | ** |
| Comparative example 5 | O | ** |
| Comparative example 6 | * | *** |
| Comparative example 7 | * | *** |
| Comparative example 8 | O | *** |
(wherein "O" indicates no whitening of the film surface, "+" indicates slight whitening; "+" indicates moderate whitening, and "+" indicates severe whitening)
From the test results in table 1, the following conclusions can be drawn:
the electrolyte resistance of the examples 1-4 is better than that of the comparative examples 1-8, and the vertex angles of the examples 1-4 before and after the punching depth of 6.5mm can achieve the electrolyte resistance for 48h without whitening;
comparative example 1 although electrolyte resistance can be achieved before deep drawing, the electrolyte test at the top corner after deep drawing turns white, which shows that after deep drawing, the coating layer is broken or has pinholes, so that the electrolyte permeates into the BOPA film through the holes to turn white, therefore, when the adding proportion of the water dispersible blocked isocyanate is too high, the coating is too hard, the impact depth of the film is reduced, and the film is easy to break;
the film of comparative example 2 shows slight whitening under the action of the electrolyte before deep drawing, which shows that the aqueous fluorocarbon resin has corrosion resistance, and the electrolyte resistance is reduced when the addition proportion is too low;
the film of comparative example 3 shows severe whitening under the action of the electrolyte before deep drawing, which indicates that no water-dispersible blocked isocyanate exists, the crosslinking density is not sufficient, and the film does not have electrolyte resistance only by being coated with aqueous fluorocarbon resin, and finally the film is severely whitened in the electrolyte resistance test;
the film in comparative example 4 shows slight whitening under the action of the electrolyte before deep drawing, which shows that the electrolyte resistance of the aqueous fluorocarbon resin prepared by the conventional fluorine-containing monomer is poorer than that of the aqueous fluorocarbon resin prepared by the fluorine-containing monomer provided by the invention.
In comparative example 5, the film was not whitened under the action of the electrolyte before being subjected to deep drawing, but the electrolyte at the apex angle was moderately whitened after the film was subjected to deep drawing, which indicates that the coating layer was broken or had pinholes after the film was subjected to deep drawing, and thus it was found that the conventional water-dispersible blocked isocyanate prepared from isophorone diisocyanate and sodium bisulfite was used, and compared with the film made from the aqueous fluorocarbon resin prepared by reacting methylene polyphenyl polyisocyanate with diethyl malonate many times, which was provided by the present invention, the film had poor flexibility and high hardness, and the coating layer was broken or had pinholes after the film was subjected to deep drawing, so that the electrolyte permeated into the BOPA film through the pinholes, resulting in whitening.
The aqueous emulsions used in comparative examples 6 and 7 were prepared from a conventional aqueous fluorocarbon resin and a conventional aqueous curing agent, and the electrolyte resistance of the resulting films before and after drawing were inferior to those of the examples.
The packaging composite film prepared in example 4 has good electrolyte resistance before and after drawing, which indicates that the packaging composite film has good flexibility; the comparative example 8 is a commercially available PET/AL/PP electrolyte-resistant film, which has good electrolyte resistance before deep drawing, but the electrolyte resistance of the vertex angle after deep drawing is poor, and the film is severely whitened, so that the electrolyte-resistant BOPA film provided by compounding the BOPA film has better electrolyte resistance and flexibility than a battery packaging composite film prepared by adopting a conventional method of compounding one layer of PET.
Therefore, the electrolyte-resistant BOPA film provided by the invention not only has simple and efficient preparation method of coating liquid and coating process through a specific coating layer formula and the preparation process provided by the technology, and the coating liquid is firmly combined with the polyamide film layer, the aqueous fluorocarbon resin provided by the invention has good corrosion resistance, and the excellent crosslinking performance of the water dispersible blocked isocyanate provided by the invention improves the crosslinking density of the aqueous fluorocarbon resin, so that the prepared BOPA film has strong electrolyte resistance and corrosion resistance, meanwhile, the water dispersible blocked isocyanate has excellent crosslinking performance, so that the film forming property of the coating layer is good, the flexibility of the BOPA film prepared by the method can be ensured not to be influenced, the electrolyte resistance film has good electrolyte resistance before and after the punching depth, and avoids the phenomenon that the packaging film of the existing electrolyte resistance composite film is easy to break.
The above-mentioned embodiments are specific examples of the present invention, and are only examples for illustrating the present invention, but are not limited to the above-mentioned embodiments. On the contrary, it is intended that those skilled in the art should be able to make various other changes and modifications without departing from the technical spirit of the present invention, and it does not affect the essence of the present invention.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. An electrolyte-resistant BOPA film, characterized in that: the coating comprises a coating layer and a polyamide film layer, wherein the coating layer is formed by coating aqueous emulsion on the surface of the polyamide film layer, and the aqueous emulsion comprises the following components in percentage by mass:
45% -54% of aqueous fluorocarbon resin;
2.5 to 5.5 percent of water dispersible blocked isocyanate;
43% -51% of water;
the waterborne fluorocarbon resin is prepared by polymerizing a fluorine-containing monomer and cyclohexyl vinyl ether, wherein the fluorine-containing monomer is one or more of fluorine-containing alkyl vinyl ester, fluorine-containing alkyl vinyl ether, fluorine-containing alkyl allyl ester or fluorine-containing alkyl propenyl ether; the water dispersible blocked isocyanate is prepared by reacting methylene polyphenyl polyisocyanate and diethyl malonate for many times.
2. An electrolyte resistant BOPA film according to claim 1, wherein: the preparation method of the water-based fluorocarbon resin comprises the following steps: adding water, sodium alkyl benzene sulfonate, alkylphenol ethoxylates and sodium bicarbonate into a reaction container, uniformly stirring, adding part of fluorine-containing monomer and part of cyclohexyl vinyl ether, heating to 58-62 ℃, and adding part of potassium persulfate-ferrous chloride; controlling the temperature to be 75-85 ℃, adding the rest fluorine-containing monomer, the rest cyclohexyl vinyl ether and the rest potassium persulfate-ferrous chloride for reaction, cooling to 40 ℃ after the reaction is finished, adding ammonia water, adjusting the pH value to be 7-8, and filtering to obtain the aqueous fluorocarbon resin.
3. An electrolyte resistant BOPA film according to claim 2, wherein: the preparation method of the water dispersible blocked isocyanate comprises the following steps: adding methylene polyphenyl polyisocyanate, 1, 4-dihydroxy ethoxy benzene, butanone and dibutyltin dilaurate into a reaction vessel for many times, heating to 85-90 ℃, adding diethyl malonate for reaction at 70-75 ℃, adding dimethylethanolamine for neutralization after the reaction is finished, adding water for dispersion, and extracting butanone to obtain the water-dispersible blocked isocyanate.
4. An electrolyte-resistant BOPA film according to claim 3, wherein: the mass ratio of the sodium alkyl benzene sulfonate, the alkylphenol polyoxyethylene, the sodium bicarbonate, the fluorine-containing monomer, the cyclohexyl vinyl ether and the potassium persulfate-ferrous chloride is as follows: 0.0015-0.0020:1.2-1.5:0.10-0.15:12-15:30-35:0.02-0.03, wherein the mass ratio of the polymethylene polyphenyl polyisocyanate, the diethyl malonate, the 1, 4-dihydroxy ethoxybenzene, the butanone and the dibutyltin dilaurate is 3.5-6.5:3.5-6.5:1.0-2.0:4.0-5.0: 0.0005-0.0010.
5. An electrolyte resistant BOPA film according to claim 1, wherein: the fluorine-containing monomer is one or more of perfluoropropyl vinyl ether, perfluoroethyl vinyl ether, perfluoroalkyl methacrylate, perfluoroalkyl acrylate containing hetero atoms and perfluoroalkylamide methacrylate.
6. An electrolyte resistant BOPA film according to claim 1, wherein: the thickness of the coating layer is 3-5 μm.
7. An electrolyte resistant BOPA film according to claim 1, wherein: the thickness of the polyamide film layer is 15-25 μm.
8. An electrolyte resistant BOPA film according to claim 1, wherein: the polyamide film layer is a biaxially oriented PA film.
9. An electrolyte resistant BOPA film according to claim 1, wherein: the nylon resin of the polyamide membrane layer is prepared by mixing at least one or more of nylon 6, copolymer of nylon 6 and nylon 6, nylon 612, nylon 610, nylon 12, nylon 1212 and poly-m-xylene adipamide.
10. A method of making an electrolyte resistant BOPA film according to any of claims 1-8, comprising the steps of:
step a, carrying out corona treatment on the surface of a polyamide film after the polyamide film is longitudinally stretched to ensure that the corona value of the surface of the polyamide film is more than or equal to 48 dyn/cm;
b, coating a water-based emulsion on the corona surface of the polyamide film layer through an anilox roller, and drying at 140-200 ℃ to form a coating;
and c, drying at 140-200 ℃, and simultaneously transversely stretching and shaping the polyamide film to obtain the electrolyte-resistant BOPA film.
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