Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/409—Separators, membranes or diaphragms characterised by the material
  • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/409—Separators, membranes or diaphragms characterised by the material
  • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/409—Separators, membranes or diaphragms characterised by the material
  • H01M50/411—Organic material
  • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
  • H01M50/426—Fluorocarbon polymers
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/409—Separators, membranes or diaphragms characterised by the material
  • H01M50/411—Organic material
  • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/409—Separators, membranes or diaphragms characterised by the material
  • H01M50/411—Organic material
  • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
  • H01M50/417—Polyolefins
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
  • H01M50/491—Porosity
• • 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

Definitions

• the present invention relates to a separator for a lithium ion secondary battery with a process film in which a porous film is formed on a process film and a method for producing the same.
• Lithium ion secondary batteries are widely used as power sources for portable devices because of their high energy density. In recent years, with the reduction in size, weight, and performance of portable devices, there has been an increasing demand for higher performance and improved safety of lithium ion secondary batteries. Lithium ion secondary batteries are also spreading to large-size applications such as electric vehicles and household power storage systems.
• a lithium ion secondary battery is configured by providing a separator between a positive electrode and a negative electrode.
• a porous film of polyolefin resin formed by stretching is generally used.
• the porous membrane of polyolefin-based resin shrinks when the inside of the battery becomes high temperature and there is a risk of short circuit, various improvements have been made in the past in order to prevent such short circuit.
• Patent Document 1 discloses a separator in which a first porous layer mainly composed of a thermoplastic resin such as a polyolefin-based resin and a second porous layer mainly composed of fine particles are laminated. ing.
• Patent Documents 2 and 3 disclose a method of forming a porous film using a polyimide resin or an aramid fiber nonwoven fabric.
• these separators have a problem that the manufacturing method becomes complicated and the manufacturing cost increases due to an increase in the number of processes and the use of expensive materials.
• a porous film is formed by applying a slurry for forming a porous film containing a binder and fine particles on a process film and drying the slurry.
• a method of peeling a film from a process film is known (see, for example, Patent Documents 4 and 5).
• a polyester film coated with silicone may be used to facilitate peeling of the porous membrane from the process film.
• a porous film composed of a predetermined binder and fine particles is not sufficiently peelable with respect to a normal silicone release agent. For this reason, even if a normal silicone coat film is used as the process film, the porous film cannot be peeled off from the process film satisfactorily, and problems such as breakage of the porous film during peeling may occur.
• high-speed peeling is required for industrialization, but when the porous film is peeled from the process film at high speed, the peeling performance tends to deteriorate, and the porous film is damaged, so the performance as a lithium ion battery separator. Is likely to drop, and short circuits are likely to occur.
• the porous membrane has a problem in that when the slurry for forming a porous membrane is dried on the process film, the film shrinks with the process film and curls. Furthermore, when the porous membrane is thin, the above-mentioned curling and breakage at the time of peeling are likely to occur. For this reason, when a normal silicone coat film is used as the process film, it may be difficult to reduce the thickness of the porous membrane. Especially in applications where high durability and electrical insulation are required, it may be desirable to use a fluororesin binder as the binder, but the porous film using a fluororesin binder is likely to curl. It was difficult to reduce the thickness of the porous film.
• This invention is made
• the subject of this invention is able to peel without damaging a porous membrane from a process film, and suppresses the curl which generate
• the present inventors set the elastic modulus of the cured layer of the silicone resin composition of the process film and the bending resistance of the process film to a predetermined value. It has been found that it is possible to prevent breakage when the porous film is peeled off from the process film, and that the separator for a lithium ion secondary battery with a process film having a porous film of a resin binder is less likely to be curled. It was. That is, the present invention provides the following (1) to (12).
• a lithium ion secondary battery comprising a process film having a cured layer of a silicone resin composition, and a porous film provided on the cured layer and containing fine particles (A) and a resin binder (B)
• a separator The separator for lithium ion secondary batteries with a process film whose elastic modulus of the said hardened layer is 0.15 GPa or more, and the bending resistance of the said process film by the Gurley method is 0.3 mN or more.
• the porous film was formed by applying a porous film forming composition containing fine particles (A), a resin binder (B) and a solvent (C) on the cured layer and drying.
• the separator for lithium ion secondary batteries with a process film as described in said (1) which is what.
• a porous film-forming composition containing fine particles (A) and a resin binder (B) is applied onto the cured layer of a process film having a cured layer of a silicone resin composition, and dried. It is a manufacturing method of the separator for lithium ion secondary batteries with a process film which obtains the separator for lithium ion secondary batteries with a process film, Comprising: The elastic modulus of the said hardened layer is 0.15 GPa or more, and the Gurley method of the said process film The manufacturing method of the separator for lithium ion secondary batteries with a process film whose bending resistance by 0.3 is 0.3 mN or more.
• a separator for a lithium ion secondary battery with a process film that prevents curling that occurs during the formation of the porous film and breakage of the porous film that occurs when the porous film is peeled from the process film can be provided.
• the separator with a process film of the present invention includes a base film, a process film having a cured layer of a silicone resin composition provided on one surface of the base film, and a fine film provided on the cured layer.
• A the separator for lithium ion secondary batteries which consists of a porous film containing a resin binder (B).
• the fine particles (A) can be used without particular limitation as long as they have heat resistance and electrical insulation and are chemically and electrochemically stable.
• heat resistance means that substantial dimensional change and chemical composition change due to softening or the like do not occur at least at 150 ° C.
• chemically stable means that there is no change in form in the electrolytic solution and no change in composition due to a chemical reaction.
• electrochemically stable means that a side reaction due to an electrochemical redox reaction does not occur in a lithium ion secondary battery.
• the fine particles (A) are not particularly limited, and examples thereof include boehmite, silica, titanium oxide, magnesium oxide, and alumina. Preferably, boehmite is used.
• the fine particles (A) may be modified for the purpose of improving electrical insulation and dispersibility in a solvent. These fine particles may be used alone or in combination of two or more.
• the size of the fine particles (A) is desirably an average particle size of 0.1 ⁇ m or more and 5 ⁇ m or less.
• the average particle size is 0.1 ⁇ m or more, the pore size of the porous membrane becomes an appropriate size, the ionic conductivity in the porous membrane is improved, and the battery characteristics of the lithium ion secondary battery can be improved. .
• the average particle diameter is 5 ⁇ m or less, the pore diameter of the porous film is prevented from becoming too large, and short-circuiting due to lithium dendride hardly occurs.
• the average particle size of the fine particles (A) is the number average particle size measured with a laser diffraction particle size distribution meter.
• the resin binder (B) may be any resin that has heat resistance and electrical insulation, is chemically and electrochemically stable, and can favorably adhere the fine particles (A).
• the resin binder (B) is not particularly limited, and various types can be used.
• polyester resins such as ethyl cellulose, polyvinyl alcohol, polyvinyl butyral, polyvinyl pyrrolidone, urethane resins, epoxy resins, and polyethylene terephthalate.
• the resin binder (B) is preferably a fluorine-based resin such as polyfluorinated fluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, or polyvinyl fluoride, and more preferably polyvinylidene fluoride.
• a fluorine-based resin such as polyfluorinated fluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, or polyvinyl fluoride, and more preferably polyvinylidene fluoride.
• high durability and electrical insulation can be imparted to the porous membrane by using a fluororesin.
• the porous membrane is likely to curl and more easily damaged when peeled off from the process film. Damage can be prevented appropriately.
• the molecular weight of the resin binder (B) is preferably a weight average molecular weight of 100,000 to 2,000,000, more preferably 500,000 to 1,500,000.
• the weight average molecular weight is a standard polystyrene equivalent value measured by gel permeation chromatography (GPC).
• the fine particles (A) in the porous film are preferably 40% by volume or more and 85% by volume or less, more preferably 60% by volume or more and 80% by volume or less.
• the porous film within the volume ratio range has a good peeling force with respect to the cured layer of the process film.
• the volume ratio to the above lower limit or more, the porosity of the porous membrane becomes appropriate, and the ionic conductivity in the porous membrane is improved, and the battery characteristics of the lithium ion secondary battery are good. Can be.
• the volume ratio of the resin binder (B) can be set to a predetermined value or more, and the strength of the porous film can be kept good.
• the thickness of the porous membrane is not particularly limited, but is preferably 10 ⁇ m or more and 30 ⁇ m or less. By setting the film thickness to 10 ⁇ m or more, the strength of the porous film can be made sufficient. In addition, by setting the film thickness to 30 ⁇ m or less, the ion conduction path can be set to an appropriate length, and the battery characteristics of the lithium ion secondary battery can be improved.
• the porosity of the porous membrane is not particularly limited, but is preferably 30% or more and 80% or less. By setting the porosity to 30% or more, it is possible to prevent the ionic conductivity from decreasing. Moreover, it can prevent that the intensity
• the cured layer of the silicone resin composition may be any material that is stable with respect to the composition for forming a porous film and can appropriately peel the porous film.
• “stable with respect to the composition for forming a porous film” means that the composition for forming a porous film undergoes a morphological change or a chemical reaction during the production process of the porous film. It means that no change occurs.
• the silicone resin composition is not particularly limited as long as the cured layer can have a predetermined elastic modulus as described later, and various types can be used. Examples thereof include, but are not limited to, an addition reaction type silicone resin, a crosslinking agent, and an addition reaction type silicone resin composition containing a catalyst. Further, if desired, a photosensitizer, an addition reaction inhibitor, a release adjusting agent such as silicone gum or silicone varnish, and an adhesion improving agent may be added.
• addition reaction type silicone resin there is no restriction
• the crosslinking agent is for curing the silicone resin composition, and examples thereof include polyorganosiloxane having at least two functional groups having hydrogen atoms bonded to silicon atoms in one molecule.
• the amount of the crosslinking agent used is preferably 0.3 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the addition reaction type silicone resin.
• the catalyst a platinum-based catalyst is usually used.
• platinum-based catalyst examples include particulate platinum, particulate platinum adsorbed on a carbon powder carrier, chloroplatinic acid, alcohol-modified chloroplatinic acid, olefin complexes of chloroplatinic acid, palladium, rhodium catalyst, and the like.
• the usage-amount of a catalyst is about 1 mass ppm or more and about 1000 mass ppm or less as a platinum-type metal in the total amount of an addition reaction type silicone resin and a crosslinking agent.
• a photosensitizer there is no restriction
• the addition reaction inhibitor is a component used for imparting storage stability of the silicone resin composition at room temperature.
• the thickness of the cured layer of the silicone resin composition is not particularly limited, but is preferably 40 nm or more and 300 nm or less.
• the film thickness is preferably 40 nm or more and 300 nm or less.
• the cured layer of the silicone resin composition in the process film has an elastic modulus of 0.15 GPa or more.
• the elastic modulus is preferably 0.20 GPa or more, more preferably 0.25 GPa or more.
• the resin binder in the porous film forming composition soaks into the cured layer of the silicone resin composition, and the process film has sufficient releasability from the porous film. There is a possibility that it cannot be done.
• the elastic modulus is 0.25 GPa or more, the peeling performance is further improved, and the peeling performance at the time of high-speed peeling can be particularly improved.
• the elastic modulus of the cured layer of the silicone resin composition is not particularly limited, but is generally about 1.0 GPa or less, preferably 0.5 GPa or less for a polyorganosiloxane having a functional group from the viewpoint of composition.
• the elastic modulus of the cured layer can be measured by a known method, but in the present specification, it is an elastic modulus measured by a nanoindenter from the surface of the cured layer, and the method described in the examples. Can be sought.
• a base film that does not undergo substantial dimensional change or chemical composition change due to softening or the like with respect to a predetermined drying temperature is used.
• a base film There is no restriction
• the thickness of the base film is not particularly limited as long as a predetermined bending resistance can be obtained as will be described later, but is, for example, 50 ⁇ m or more and 150 ⁇ m or less, preferably 60 ⁇ m or more and 120 ⁇ m or less. If the thickness of the base film is within the above range, a predetermined bending resistance described later can be easily obtained.
• the releasability on the cured layer side of the process film is such that the porous film does not peel from the process film in the slit process or winding process after the porous film is formed, and the porous film is peeled off from the process film.
• the peeling step it is sufficient that the porous film does not change its shape or breakage occurs.
• the peeling force when peeling the porous membrane from the process film at a peeling speed of 0.3 m / min and 10 m / min at a peeling angle of 180 ° is 10 mN / 50 mm or more and 400 mN at each peeling speed.
• the peeling force By setting the peeling force to the above lower limit or more, it is possible to prevent the porous film from being lifted off from the process film and being peeled off when the slit process or the winding process after the porous film formation is not intended. . Moreover, by setting it as the said upper limit or less, when peeling a porous film from a process film, it can prevent that a shape change arises in a porous film, or a damage arises.
• the arithmetic average roughness of the cured layer surface of the process film is preferably 15.0 nm or less.
• the porous film formed on the cured layer of the process film is prevented from biting into the cured layer, and a shape change occurs when the porous film is peeled off. It is prevented that damage occurs.
• the maximum cross-sectional height of the hardened layer surface of a process film is 200.0 nm or less.
• the porous film formed on the cured layer of the process film is prevented from biting into the cured layer, and a shape change occurs when the porous film is peeled off. It is prevented that damage occurs.
• the process film of the present invention has a bending resistance by the Gurley method of 0.3 mN or more.
• the porous film is formed by applying and drying the porous film-forming composition on the process film. In this drying process, the porous film tends to undergo heat shrinkage. However, if the bending resistance is less than 0.3 mN, the process film cannot sufficiently resist the heat shrinkage. A big curl will arise in a separator with a film.
• the process film having the bending resistance is sufficiently resistant to the heat shrinkage of the porous film, and the bending resistance is 0.5 mN or more so that curling can be more effectively suppressed. It is preferable, and it is more preferable that it is 0.75 mN or more.
• the bending resistance is preferably 4.0 mN or less, and more preferably 2.0 mN or less so that the separator with a process film to be obtained can be wound into a roll.
• the bending resistance by the Gurley method means a value measured in accordance with the JIS L-1096 A method (Gurley method).
• a porous film-forming composition containing fine particles (A) and a resin binder (B) is applied onto a cured layer of a process film by a known method, It can be produced by drying at a temperature. At this time, the drying temperature is 120 to 180 ° C., and the drying time is, for example, 60 to 300 seconds.
• the application method is not particularly limited, and examples thereof include dip coating, die coating, bar coating, and doctor blade.
• the composition for forming a porous film contains the solvent (C) in addition to the fine particles (A) and the resin binder (B), and the fine particles (A) are dispersed in the solvent (C) to disperse the resin binder (B). Alternatively, it is dissolved.
• the solvent (C) is not particularly limited as long as it can uniformly disperse the fine particles (A) and can uniformly disperse or dissolve the resin binder (B), and various solvents can be used.
• N-methylpyrrolidone dimethylacetamide, dimethylformamide, tetrahydrofuran, dimethyl sulfoxide, triethyl phosphate, methyl ethyl ketone, methyl isobutyl ketone and the like can be mentioned, and N-methylpyrrolidone (NMP) is preferably used.
• the cured layer of the process film preferably has a contact angle with respect to the solvent (C) used for forming the porous film of 55 ° or more and 75 ° or less.
• C solvent
• the cured layer of the process film preferably has a contact angle with respect to the solvent (C) used for forming the porous film of 55 ° or more and 75 ° or less.
• the solid content concentration of the composition for forming a porous film is not particularly limited, but is preferably 20% by mass or more and 60% by mass or less. By setting the solid content concentration within the above range, the viscosity of the composition for forming a porous film becomes an appropriate value, and a necessary coating amount for obtaining a predetermined film thickness can be obtained.
• the composition can be applied uniformly.
• the separator with a process film manufactured as described above is slit as necessary so as to have an appropriate width and length, and then wound into a roll.
• the method of obtaining a laminated electrode body used for a lithium ion secondary battery by laminating a positive electrode and a negative electrode on a porous film using the separator with a process film of the present invention is not particularly limited. A method is mentioned.
• the separator with a roll-formed process film is unwound and the process film is wound on a take-up roll to peel the porous film from the process film, and the positive electrode and the negative electrode are laminated on the peeled porous film. To do. At this time, the positive electrode and the negative electrode may or may not be unwound from the roll.
• the elastic modulus of the cured layer of the silicone resin composition is set to 0.15 GPa or more and the bending resistance of the process film is set to 0.3 mN or more to curl the separator with the process film. Can be prevented, and furthermore, damage to the porous membrane that occurs when the porous membrane is peeled from the process film can be prevented.
• the porous film of the present invention is less likely to be damaged or curled, and thus has excellent handleability and is easily thinned.
• the measuring method of each physical property in the present invention is as follows.
• (1) Elastic modulus of cured layer The process film having a cured layer of the silicone resin composition was allowed to stand for 24 hours under conditions of a temperature of 23 ° C and a relative humidity of 50%, and then the elastic modulus of the cured layer was measured. At this time, the process film was fixed on a glass plate using Bond Quick 5 manufactured by Konishi Co., Ltd., and measured at a temperature of 23 ° C. and a relative humidity of 50% using NanoInstant SA2 manufactured by NTS from the surface of the cured layer. went.
• the elastic modulus of the cured layer was calculated as an average value of 20 points measured within a depth range of 5 to 10 nm from the surface of the cured layer.
• (3) Contact angle of cured layer of process film to solvent (NMP) A process film having a cured layer of the silicone resin composition is allowed to stand for 24 hours at a temperature of 23 ° C. and a relative humidity of 50%. The contact angle was measured. The measurement was performed using DSA100S manufactured by KRUSS.
• CD direction means the direction orthogonal to the flow direction of the manufacturing line of a process film and a separator with a process film.
• Average particle size The number average particle size of the fine particles (A) was calculated by laser diffraction particle size distribution measurement. For the measurement, LA-920 manufactured by Horiba Ltd. was used. The number average particle diameter is calculated from the refractive index of the solvent and the fine particles (A) after the fine particles (A) are dispersed in water and diluted so that the transmittance at 532 nm is 70 to 90%.
• the resin binder (B) was dissolved in tetrahydrofuran and measured at a temperature of 40 ° C. using gel permeation chromatography (GPC) to calculate a standard polystyrene equivalent value.
• GPC gel permeation chromatography
• HLC-8020 manufactured by Tosoh Corporation was used, and TSKguardcolumnHXL-H, TSKgelGMHXL ( ⁇ 2), and TSKgelG2000HXL, which are GPC columns manufactured by Tosoh Corporation, were passed in order.
• Example 1 The fine particles (A) have a density of 2.96 g / cm 3 , boehmite fine particles having an average particle diameter of 0.2 ⁇ m, and the resin binder (B) has a density of 1.78 g / cm 3 and a weight average molecular weight of 1,000,000 polyfluorination. Vinylidene is blended so that the fine particles (A) in the total solids are 70% by volume, and N-methylpyrrolidone as the solvent (C) is put in a container so that the total solids concentration is 30% by mass. By stirring with a mechanical stirrer for 2 hours, a uniformly dispersed slurry-like composition for forming a porous film was prepared.
• a 75 ⁇ m-thick polyethylene terephthalate film which is a base film
• a cured layer of a process film (trade name “PDS752160”, manufactured by Lintec Corporation) having a cured layer of a silicone resin composition
• the porous film-forming composition was uniformly applied using a comma coater so that the film thickness after drying was 20 ⁇ m, and dried at 150 ° C. for 150 seconds to produce a separator with a process film.
• Example 2 The point which used the process film (The product name "PDS1002160” by Lintec Corporation) which has the hardened layer of a silicone resin composition on one surface of the polyethylene terephthalate film of thickness 100 micrometers which is a base film as a process film. Except for the above, a separator with a process film was produced in the same manner as in Example 1.
• Example 3 Other than the use of a process film (trade name “PLD752060”, manufactured by Lintec Corporation) having a cured layer of a silicone resin composition on one surface of a 75 ⁇ m-thick polyethylene terephthalate film, which is a base film, as the process film Produced a separator with a process film in the same manner as in Example 1.
• a process film trade name “PLD752060”, manufactured by Lintec Corporation
• Example 4 Other than the use of a process film having a cured layer of a silicone resin composition on one surface of a 100 ⁇ m-thick polyethylene terephthalate film as a process film (product name “PLD1002060” manufactured by Lintec Corporation) as the process film Produced a separator with a process film in the same manner as in Example 1.
• a process film having a cured layer of a silicone resin composition on one surface of a 100 ⁇ m-thick polyethylene terephthalate film product name “PLD1002060” manufactured by Lintec Corporation
• Example 5 The point which used the process film (the product name "PLS75T161" by Lintec Co., Ltd.) which has the hardened layer of a silicone resin composition on one surface of the 75-micrometer-thick polyethylene terephthalate film which is a base film as a process film. Except for the above, a separator with a process film was produced in the same manner as in Example 1.
• Example 6 The point which used the process film (the product name "PLS100T161" by Lintec Co., Ltd.) which has the hardened layer of a silicone resin composition on one surface of the 100-micrometer-thick polyethylene terephthalate film which is a base film as a process film. Except for the above, a separator with a process film was produced in the same manner as in Example 1.
• Comparative Example 1 The point which used the process film (the product name "PDS382160” by the Lintec Co., Ltd. product) which has the hardened layer of a silicone resin composition on one surface of the 38-micrometer-thick polyethylene terephthalate film which is a base film as a process film. Except for the above, a separator with a process film was produced in the same manner as in Example 1.
• Comparative Example 2 The point which used the process film (the product name "PDS252160” by Lintec Corporation) which has the hardened layer of a silicone resin composition on one surface of the 25-micrometer-thick polyethylene terephthalate film which is a base film as a process film. Except for the above, a separator with a process film was produced in the same manner as in Example 1.
• Comparative Example 5 As a process film, a process film (trade name “NF SP-PET 381031” manufactured by Lintec Corporation) having a cured layer of a silicone resin composition on one surface of a 38 ⁇ m-thick polyethylene terephthalate film as a base film is used. A separator with a process film was produced in the same manner as in Example 1 except for the points used.
• NF SP-PET 381031 manufactured by Lintec Corporation
• Comparative Example 6 As a process film, a process film (trade name “NF SP-PET 251031” manufactured by Lintec Corporation) having a cured layer of a silicone resin composition on one surface of a 25 ⁇ m-thick polyethylene terephthalate film as a base film is used. A separator with a process film was produced in the same manner as in Example 1 except for the points used.
• NF SP-PET 251031 manufactured by Lintec Corporation
• Comparative Example 7 As a process film, a process film having a cured layer of a silicone resin composition on one side of a 38 ⁇ m-thick polyethylene terephthalate film as a base film (product name “NF SP-PET38T103-1”, manufactured by Lintec Corporation) ) was used in the same manner as in Example 1 except that a separator with a process film was produced.
• Comparative Example 8 As a process film, a process film having a cured layer of an alkyd resin composition on one surface of a 50 ⁇ m thick polyethylene terephthalate film as a base film (trade name “SP-PFS50AL-5”, manufactured by Lintec Corporation) A separator with a process film was produced in the same manner as in Example 1 except that was used.
• Comparative Example 9 Separator with process film as in Example 1 except that a polyethylene terephthalate film (trade name “PET38T-100”, manufactured by Mitsubishi Plastics, Inc.) having a thickness of 38 ⁇ m without a cured layer was used as the process film. Manufactured.
• a polyethylene terephthalate film (trade name “PET38T-100”, manufactured by Mitsubishi Plastics, Inc.) having a thickness of 38 ⁇ m without a cured layer was used as the process film.
• the separators with process films according to Examples 1 to 4 were peeled off from the process film because the cured layer had a good elastic modulus and the process film had a suitable bending resistance.
• the porous film was not changed in shape or damaged, and the amount of curling generated in the separator with the process film could be suppressed.
• the elastic modulus of the cured layer was slightly low and the releasability at high speed of the process film was not good, the releasability at low speed was good and the porous film was damaged. The film could be peeled without changing its shape, and the amount of curling could be suppressed because of its good bending resistance.
• the separators with a process film according to Comparative Examples 1 to 9 had poor curling softness of the process film, so that a large curl was generated in the porous film, and the performance was inferior to those of Examples 1 to 6.
• Comparative Examples 5 to 9 since the elastic modulus of the cured layer was low or the cured silicone layer was not provided, the releasability was poor, and the porous film was damaged during peeling.

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• 2013
  • 2013-03-05 WO PCT/JP2013/056027 patent/WO2013146126A1/fr not_active Ceased
  • 2013-03-27 TW TW102110910A patent/TW201405917A/zh unknown

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