WO2010107023A1 - 多孔性ポリプロピレンフィルムおよびその製造方法 - Google Patents
多孔性ポリプロピレンフィルムおよびその製造方法 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/005—Shaping by stretching, e.g. drawing through a die; Apparatus therefor characterised by the choice of materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
- B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
- B29C55/14—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively
- B29C55/143—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively firstly parallel to the direction of feed and then transversely thereto
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
- H01M50/494—Tensile strength
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
- B29K2023/10—Polymers of propylene
- B29K2023/12—PP, i.e. polypropylene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/04—Condition, form or state of moulded material or of the material to be shaped cellular or porous
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
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- 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
- H01M50/443—Particulate material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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 porous polypropylene film excellent in quality and productivity, and having excellent battery characteristics when used in a separator of an electricity storage device, and a method for producing the same.
- Polypropylene films are used in various applications such as industrial materials, packaging materials, optical materials, and electrical materials due to their excellent mechanical, thermal, electrical, and optical properties.
- a porous polypropylene film having a void formed in the polypropylene film has excellent properties such as permeability and low specific gravity in addition to the properties as a polypropylene film.
- separators for batteries and electrolytic capacitors various separation membranes, clothing, moisture-permeable waterproof membranes for medical applications, reflectors for flat panel displays and heat-sensitive transfer recording sheets has been studied.
- a porous film is used as a separator, not only is the cost reduced by improving productivity, but also the recent lithium ion battery ignition accident requires further safety for the battery. High quality and reliability with less foreign matter are required.
- Porous methods can be broadly classified into wet methods and dry methods.
- wet method polypropylene is used as the matrix resin, the extractables to be extracted after sheeting are added and mixed, and only the additives are extracted using the good solvent of the extractables, creating voids in the matrix resin. It is a method to do.
- Various proposals have been made as wet methods (see Patent Document 1). The wet method is excellent in quality because it can reduce the viscosity of the resin composition and can be filtered with high precision, and can be cast at a low temperature, thereby reducing deterioration of the resin composition.
- the extraction process is complicated and a solvent treatment process is required, cost reduction is difficult.
- the porous polypropylene film produced by the various methods described above is used as a separator for an electricity storage device, particularly a lithium ion secondary battery
- the ⁇ crystal method usually forms voids by biaxial stretching, so it is compared with other methods.
- a high porosity can be achieved. Therefore, the internal resistance of the battery can be lowered, and it is particularly suitable for a separator for a high-output power storage device that requires a large current (see Patent Document 7).
- an object of the present invention is to provide a porous polypropylene film excellent in quality and productivity and exhibiting excellent battery characteristics when used in a separator of an electricity storage device, and a method for producing the same.
- the polypropylene film of the present invention has 0.5 or less portions per 1 m 2 where the transmitted light amount is 5 times or more with respect to the average transmitted light amount.
- porous polypropylene film of the present invention is excellent in quality and productivity and has a high porosity, it can be suitably applied as a separator for an electricity storage device.
- the porous polypropylene film of the present invention is a biaxially oriented polypropylene film and has through holes.
- a biaxially oriented polypropylene film produced by a dry method is preferable.
- a through-hole means the hole which penetrates both surfaces of a film and has air permeability.
- the ⁇ crystal method can be mentioned. Thereby, uniform physical properties and thinning can be achieved.
- the ⁇ crystal forming ability of the polypropylene resin is preferably 40 to 90%. If the ⁇ -crystal forming ability is less than 40%, the amount of ⁇ -crystals is small at the time of film production, so the number of voids formed in the film is reduced by utilizing the transition to ⁇ -crystal, and as a result, only a film with low air permeability is obtained. It may not be possible. On the other hand, in order to make the ⁇ crystal forming ability exceed 90%, it is necessary to add a large amount of a ⁇ crystal nucleating agent described later, or to make the stereoregularity of the polypropylene resin to be used extremely high. Industrial practical value is low, such as deterioration of stability. Industrially, the ⁇ -crystal forming ability is preferably 60 to 85%, particularly preferably 65 to 80%.
- a polypropylene resin having a high isotactic index is used, or a ⁇ crystal is selectively added by adding it to the polypropylene resin called a ⁇ crystal nucleating agent.
- the crystallization nucleating agent to be formed is preferably used as an additive.
- the ⁇ crystal nucleating agent include various pigment compounds and amide compounds. For example, amide compounds; tetraoxaspiro compounds; quinacridones; iron oxides having a nanoscale size; carboxylic acids represented by potassium 1,2-hydroxystearate, magnesium benzoate or succinate, magnesium phthalate, etc.
- amide compounds disclosed in JP-A-5-310665 can be preferably used. Specifically, it is an amide compound represented by the following general formula (1).
- R 1 NHCO—X—CONH—R 2 (1)
- X represents the following (2) or (3).
- R 1 and R 2 represent the same or different cycloalkyl groups having 5 to 12 carbon atoms.
- the polypropylene resin preferably contains 0.05 to 0.5% by mass of the ⁇ crystal nucleating agent with respect to the entire polypropylene resin. It is more preferable if it is -0.3 mass%.
- the polypropylene resin constituting the porous polypropylene film of the present invention preferably has a melt flow rate (hereinafter referred to as MFR, measurement conditions are 230 ° C., 2.16 kg) in the range of 2 to 30 g / 10 min. Furthermore, it is preferable that it is an isotactic polypropylene resin.
- MFR melt flow rate
- measurement conditions are 230 ° C., 2.16 kg
- the isotactic index is preferably 90 to 99.9%. If the isotactic index is less than 90%, the crystallinity of the resin is low, and it may be difficult to achieve high air permeability.
- polypropylene resin used in the present invention it is possible to use a homopolypropylene resin, as well as from the viewpoint of stability in the film-forming process, film-forming properties, and uniformity of physical properties, polypropylene with an ethylene component or butene, Resins obtained by copolymerizing ⁇ -olefin components such as hexene and octene in the range of 5% by mass or less can also be used.
- the form of introduction of the comonomer (copolymerization component) into polypropylene may be either random copolymerization or block copolymerization.
- the above polypropylene resin preferably contains high melt tension polypropylene in the range of 0.5 to 5% by mass from the viewpoint of improving the film forming property.
- High melt tension polypropylene is a polypropylene resin whose tension in the molten state is increased by mixing a high molecular weight component or a component having a branched structure into the polypropylene resin or by copolymerizing a long-chain branched component with polypropylene.
- This high melt tension polypropylene is commercially available.
- polypropylene resins PF814, PF633, and PF611 manufactured by Basell polypropylene resin WB130HMS manufactured by Borealis, and polypropylene resins D114 and D206 manufactured by Dow can be used.
- the polypropylene resin used in the present invention comprises 80 to 99 parts by mass of polypropylene and an ethylene / ⁇ -olefin copolymer 20 to 20% from the viewpoint of improving void formation efficiency during biaxial stretching and improving air permeability by increasing the pore size. It is preferable to use a mixture having a mass ratio of 1 part by mass.
- examples of the ethylene / ⁇ -olefin copolymer include linear low-density polyethylene and ultra-low-density polyethylene, and among them, a copolymer polyethylene obtained by copolymerizing octene-1 and having a melting point of 60 to 90 ° C.
- a resin (copolymerized PE resin) can be preferably used.
- the copolymerized polyethylene include commercially available resins such as “Engage (registered trademark)” (type names: 8411, 8452, 8100, etc.) manufactured by Dow Chemical.
- the copolymer polyethylene resin contains 1 to 10% by mass when the entire polypropylene resin constituting the film of the present invention is 100% by mass, and the porosity and average through-hole diameter described below are controlled within a preferable range. Since it becomes easy to do, it is preferable. From the viewpoint of the mechanical properties of the film, it is more preferably 1 to 7% by mass.
- the number of the portions where the transmitted light amount is 5 times or more with respect to the average transmitted light amount is 0.5 or less per 1 m 2 .
- a portion where the amount of transmitted light is 5 times or more may cause a short circuit when used as a separator.
- the number of transmitted light quantity is more than 5 times per 1 m 2 , the yield deteriorates and the productivity decreases. It is more preferable that the number of transmitted light amounts be 5 times or more is 0.3 or less per 1 m 2 .
- the porous polypropylene film of this invention is 1 or less per 1 m ⁇ 2 > that the transmitted light quantity becomes 3 times or more and less than 5 times with respect to an average transmitted light quantity.
- the portion where the amount of transmitted light is 3 times or more and less than 5 times is not a problem when a separate shutdown layer is provided from the viewpoint of safety or when it is used for a low output battery, but when high output such as in-vehicle use is required A short circuit may occur and the battery life may be reduced.
- the number of transmitted light amounts of 3 times or more and less than 5 times exceeds 1 per 1 m 2 , the yield may deteriorate and the productivity may decrease. It is more preferable that the number of transmitted light amounts be 3 times or more and less than 5 times is 0.5 or less per 1 m 2 .
- the filtration accuracy is preferably 50 ⁇ m, that is, it is possible to remove foreign matters of 50 ⁇ m or more. More preferably, it is 20 micrometers, Most preferably, it is 10 micrometers. If the filtration accuracy exceeds 50 ⁇ m, the foreign matter that has passed through the filter medium may be the starting point and coarse voids or pinholes may be generated.
- a polypropylene resin has a high viscosity when melted
- the leaf disk type filter has a complicated flow path, a resin staying portion occurs. When this staying portion is generated on the downstream side of the filter, particles or additives added to the polypropylene resin may aggregate or thermally deteriorate at that portion, which may be the starting point of coarse voids or pinholes.
- the inclusion of the amide compound represented by the above general formula (1) increases the ⁇ crystal forming ability of polypropylene which is a cause of porosity, while the amide compound contained therein is crystallized in the molten polypropylene resin in which the amide compound is retained. In some cases, it grows and flows into the film, resulting in a film defect, and the amide compound may cause a decrease in productivity.
- the frequency may increase when continuous film formation is performed, which causes a deterioration in productivity.
- the filtration accuracy is made finer as it goes downstream, but in the present invention, the filtration accuracy of the flat filter is coarser than that of the high-precision filtration filter described above.
- the roughness is preferably 1.8 to 3 times.
- the filter area of the flat filter cannot be increased, so that the filtration pressure increases and the filter is damaged, and if the discharge rate is lowered to suppress the increase in filtration pressure, the residence time is reduced. Increasing the defects may increase. If it exceeds 3 times, particles passing through the filter medium and aggregates of additives may be the starting point and coarse voids and pinholes may be generated.
- the filtration accuracy of the flat filter is preferably 100 ⁇ m, that is, it can remove foreign matters of 100 ⁇ m or more, more preferably 50 ⁇ m, and most preferably 20 ⁇ m. If the filtration accuracy exceeds 100 ⁇ m, particles passing through the filter medium and aggregates of additives may be the starting point and coarse voids and pinholes may be generated. Since the flat filter cannot increase the filtration area, the filtration accuracy is often about 20 ⁇ m.
- the position where the flat filter is installed is preferably as downstream as possible, and is preferably immediately before the die or when the feed block is used for lamination.
- the coarse voids and pinholes generated from the aggregates of particles and additives are portions where the amount of transmitted light is high, which may deteriorate the battery characteristics when used as a separator.
- Sintered metal, porous ceramics, sand, wire mesh, etc. can be used for the filter medium used for high-precision filtration filters and flat plate filters.
- the amide compound represented by the above general formula (1) is included as a ⁇ crystal nucleating agent, the ⁇ crystal nucleating agent grows in a needle shape, so that a sintered metal or porous material is used rather than a screen filter such as a wire mesh. It is preferable to use a sintered filter made of conductive ceramic because the defect frequency can be effectively reduced.
- the melt extrusion temperature is preferably 190 ° C to 240 ° C. More preferably, it is 200 ° C to 230 ° C, and further preferably 200 ° C to 220 ° C.
- the temperature exceeds 240 ° C.
- the particles and additives added to the polypropylene resin are aggregated, which may be the starting point of coarse voids and pinholes. If it is less than 190 degreeC, the fluidity
- the raw material hopper may be purged with nitrogen, or an antioxidant may be added to the raw material.
- the porous polypropylene film of the present invention preferably has a porosity of 60 to 85% from the viewpoint of ionic conductivity when used as a separator.
- the porosity is less than 60%, the electric resistance increases when used as a separator, and when used for a high output, heat may be generated and energy may be lost.
- the porosity exceeds 85%, the strength of the film becomes too low, and the handleability may be inferior, for example, the film may be broken when wound together with the electrode to be stored inside the battery.
- the film porosity is more preferably 65 to 80%, and particularly preferably 65 to 75%.
- the polypropylene resin and the copolymer polyethylene resin were mixed at a specific ratio. It becomes easy to achieve by using a resin, and can be effectively achieved by employing specific biaxial stretching conditions described later. In a wet method or a uniaxially stretched film, it is difficult to obtain a porous film having such low cost, high porosity, and practical strength.
- the air resistance is preferably 10 to 500 seconds / 100 ml.
- the air permeation resistance is the air permeation resistance (Gurley) defined in JIS P8117 (1998).
- the air permeation resistance is a value evaluated using this JIS B-type testing machine. If the air permeability resistance is less than 10 seconds / 100 ml, the film strength is low, and pinholes are easily generated when used as a separator, causing a short circuit or tearing when wound for storage inside the battery. May be inferior in handleability. If the air permeation resistance exceeds 500 seconds / 100 ml, the ion conductivity is poor. From the viewpoint of exhibiting excellent ionic conductivity as a separator, the air permeation resistance is more preferably 30 to 300 seconds / 100 ml, and particularly preferably 50 to 200 seconds / 100 ml.
- the porous polypropylene film of the present invention preferably has a total film thickness of 10 to 50 ⁇ m. If the total thickness is less than 10 ⁇ m, the film may break during use. If it exceeds 50 ⁇ m, the volume ratio of the porous film in the electricity storage device becomes too high, and it may be impossible to obtain a high energy density.
- the total film thickness is more preferably 12 to 30 ⁇ m, still more preferably 14 to 25 ⁇ m.
- Porous polypropylene film of the present invention is preferably break strength E M in the longitudinal direction is not less than 65 MPa.
- the pressure is less than 65 MPa, the film may be stretched, wrinkled or broken in the process of processing the electricity storage device using the separator, and productivity may be reduced. From the viewpoint of workability at the time of winding the battery, it is more preferably 70 MPa or more.
- the upper limit of the breaking strength in the longitudinal direction is not particularly limited, but is practically about 150 MPa or less.
- the porous polypropylene film of the present invention preferably has a breaking strength E T in the width direction of 45 MPa or more. If it is less than 45 MPa, the difference from the breaking strength in the longitudinal direction becomes large, and the porous polypropylene film may be easily torn in the longitudinal direction.
- the upper limit of the breaking strength in the width direction is not particularly limited, but is practically about 150 MPa or less.
- the breaking strength can be controlled by the crystallinity of polypropylene, the porosity of the resulting porous film, the orientation state (orientation state in the film plane), and the like. It becomes stronger by decreasing the porosity within 60 to 85%, and weaker by increasing it.
- the higher the plane orientation the higher the strength, so the control of the orientation state is important.
- the planar orientation of the porous film can be increased as the stretching condition is higher or low temperature.
- an antioxidant In the porous polypropylene film of the present invention, an antioxidant, a heat stabilizer, an antistatic agent, a lubricant composed of inorganic or organic particles, an antiblocking agent, a filler, a non-blocking agent, and the like are used as long as the effects of the present invention are not impaired.
- Various additives such as a compatible polymer may be contained.
- the method for producing the porous polypropylene film of the present invention will be specifically described.
- the manufacturing method of the film of this invention is not limited to this.
- a polypropylene resin 94 parts by mass of a commercially available homopolypropylene resin having an MFR of 8 g / 10 minutes, 1 part by mass of a commercially available MFR of 2.5 g / 10 minutes and a high melt tension polypropylene resin, and an ultra low density polyethylene having a melt index of 18 g / 10 minutes.
- N, N′-dicyclohexyl-2,6-naphthalenedicarboxyamide which is a ⁇ crystal nucleating agent
- the melting temperature is preferably 270 to 300 ° C. It is preferable to remove foreign matters by providing a high-accuracy filter that can remove foreign matters of, for example, 50 ⁇ m or more on the downstream side of the twin-screw extruder.
- the above-mentioned mixed raw material is supplied to a single-screw melt extruder, and melt extrusion is performed at 190 to 240 ° C. And after removing a foreign material, a modified polymer, etc. with the filter installed in the middle of the polymer pipe
- it is preferable to remove a foreign matter by providing a high-accuracy filter that can remove a foreign matter of 50 ⁇ m or more.
- the surface temperature of the cast drum for obtaining the unstretched sheet is preferably 105 to 130 ° C. from the viewpoint of controlling the ⁇ crystal fraction in the unstretched sheet to be high.
- the end portion is sprayed with spot air to be in close contact with the drum. Further, air may be blown over the entire surface using an air knife as necessary based on the state of close contact of the entire sheet on the drum.
- the obtained unstretched sheet is biaxially stretched to form pores (through holes) in the film.
- a biaxial stretching method the film is stretched in the longitudinal direction of the film and then stretched in the width direction, or the sequential biaxial stretching method of stretching in the longitudinal direction after stretching in the width direction, or the longitudinal direction and the width direction of the film are stretched almost simultaneously. Any simultaneous biaxial stretching method can be used. It is preferable to employ a sequential biaxial stretching method from the viewpoint that it is easy to obtain a highly permeable film, and it is particularly preferable to stretch in the width direction after stretching in the longitudinal direction.
- an unstretched sheet is controlled to a temperature at which it can be stretched in the longitudinal direction.
- a temperature control method a method using a temperature-controlled rotating roll, a method using a hot air oven, or the like can be adopted.
- the stretching temperature in the longitudinal direction it is preferable to employ a temperature of 110 to 140 ° C., more preferably 120 to 135 ° C., from the viewpoint of film characteristics and uniformity.
- the draw ratio is preferably 3 to 10 times, more preferably 4 to 6 times, still more preferably 4.5 to 5.8 times. When the draw ratio is less than 3 times, the porosity may be lowered to deteriorate the battery characteristics, and the productivity may be lowered.
- the stretching ratio As the stretching ratio is increased, the porosity is increased. However, if the stretching ratio exceeds 10 times, the film may be easily broken in the next transverse stretching step.
- the stretching temperature in the longitudinal direction at which a particularly high porosity film can be obtained is 120 to 125 ° C.
- the uniaxially stretched polypropylene film is introduced by holding the film end by a tenter-type stretcher and stretched in the width direction to obtain a biaxially stretched film.
- the stretching temperature is preferably 130 to 155 ° C, and more preferably 145 to 150 ° C because a high porosity can be obtained.
- the stretching ratio in the width direction is preferably 3 to 10 times, more preferably 4 to 8 times. When the draw ratio is less than 3 times, the porosity may be lowered to deteriorate the battery characteristics, and the productivity may be lowered. Moreover, the higher the stretching ratio, the higher the porosity. However, if the stretching ratio exceeds 10 times, the film may be easily broken.
- the transverse stretching speed at this time is preferably 500 to 6,000% / min, more preferably 1,000 to 5,000% / min. It is particularly preferable that the stretching speed is as low as 2,000% / min or less.
- heat setting is performed in the stenter as it is, and the temperature is preferably from the transverse stretching temperature to 160 ° C. and the heat setting time is preferably 5 to 30 seconds. Further, the heat setting may be performed while relaxing in the longitudinal direction and / or the width direction of the film, and in particular, the relaxation rate in the width direction is preferably 7 to 12% from the viewpoint of thermal dimensional stability.
- the porous polypropylene film of the present invention is excellent in productivity and not only has a high porosity, but also can control extremely small voids and foreign matter defects in the separator film that affect battery characteristics. Therefore, it can be preferably used as a separator for a non-aqueous electrolyte secondary battery such as a lithium ion secondary battery, which is particularly demanding of safety.
- ⁇ -crystal forming ability 5 mg of resin or film was sampled in an aluminum pan and measured using a differential scanning calorimeter (Seiko Denshi Kogyo RDC220).
- the temperature is raised from room temperature to 260 ° C. at a rate of 10 ° C./minute (first run) in a nitrogen atmosphere, held for 10 minutes, and then cooled to 20 ° C. at a rate of 10 ° C./minute.
- the melting peak observed when the temperature is raised again (second run) at 10 ° C./min after holding for 5 minutes the melting having a peak in the temperature range of 145 to 157 ° C. is the melting peak of ⁇ crystal, 158 ° C.
- the melting at which the peak is observed is regarded as the melting peak of the ⁇ crystal, and the respective heats of fusion are determined from the base line drawn with reference to the flat portion on the high temperature side and the area of the region surrounded by the peak.
- the value calculated by the following formula is the ⁇ crystal forming ability.
- the heat of fusion was calibrated using indium.
- ⁇ crystal forming ability (%) [ ⁇ H ⁇ / ( ⁇ H ⁇ + ⁇ H ⁇ )] ⁇ 100
- the ⁇ crystal fraction in the state of the sample can be calculated by calculating the abundance ratio of the ⁇ crystal in the same manner from the melting peak observed in the first run.
- MFR Melt flow rate
- the film was cut into a size of 30 mm ⁇ 40 mm and used as a sample.
- an electronic hydrometer SD-120L manufactured by Mirage Trading Co., Ltd.
- the specific gravity was measured in an atmosphere having a room temperature of 23 ° C. and a relative humidity of 65%. The measurement was performed three times, and the average value was defined as the specific gravity ⁇ of the film.
- the measured film was hot-pressed at 280 ° C. and 5 MPa, and then rapidly cooled with water at 25 ° C. to prepare a sheet from which pores were completely erased.
- the specific gravity of this sheet was measured in the same manner as described above, and the average value was defined as the specific gravity (d) of the resin.
- the obtained film was slit with a width of 210 mm, and the transmitted light amount of the film was measured with a defect detector equipped with an unwinder and a winder.
- a cylindrical rod lens having a length of 750 mm and a diameter of 10 mm was used as the light source, and light from a 250 W metal halide light source was incident from the end surface of the rod lens.
- a light source was placed 15 mm away from one side of the film, and the amount of irradiated light was detected from the other side. The distance between the detector and the film was 250 mm.
- the film width direction was run at 5 m / min, and the amount of light transmitted through the film was measured at a full width for a length of 500 m.
- the frequency of the portion where the transmitted light amount is 5 times or more compared to the average transmitted light amount is A / 1 m 2
- the frequency of the portion where the transmitted light amount is 3 times or more and less than 5 times compared to the average transmitted light amount is B / 1 m 2 .
- the average transmitted light amount the transmitted light amount for a length of 1 m was measured for each of the core portion and the unwinding portion of the film after the slit, and the average value was used.
- the measurement area was increased 10 times, and the frequency was obtained.
- Battery characteristics evaluation Long-term characteristics at normal temperature A lithium cobalt oxide (LiCoO 2 ) positive electrode having a thickness of 40 ⁇ m manufactured by Hosen Co., Ltd. was used and cut into a width of 200 mm and a length of 4,000 mm. Further, a graphite negative electrode having a thickness of 50 ⁇ m manufactured by Hosen Co., Ltd. was used and cut into a width of 200 mm and a length of 4,000 mm.
- LiCoO 2 lithium cobalt oxide
- a graphite negative electrode having a thickness of 50 ⁇ m manufactured by Hosen Co., Ltd. was used and cut into a width of 200 mm and a length of 4,000 mm.
- the above belt-like positive electrode is overlapped with the sheet-like negative electrode through the separator film of each Example / Comparative Example, wound into a spiral shape to form a spiral electrode body, and then a bottomed cylindrical battery
- the electrolytic solution dissolved so as to be L was poured into the battery case. The opening of the battery case was sealed and the battery was precharged to produce a cylindrical organic electrolyte secondary battery.
- a battery was produced for each example and comparative example.
- Each manufactured secondary battery was charged to 4.2 V at 16,000 mA in an atmosphere of 25 ° C. (Charging operation was 3.5 hours, and constant current charging up to 4.2 V reached 4.2 V. Thereafter, a constant voltage charge was performed), and a charge / discharge operation of discharging at 1,600 mA up to 2.7 V was repeated three times, and then charged again at 16,000 mA to 4.2 V. Thereafter, the secondary battery was left without being charged and discharged in an atmosphere at 25 ° C., and the voltage value after 50 hours was measured. Battery characteristics were good when the value obtained by the formula of [(voltage value after 50 hours) / (initial voltage value (4.2 V))] ⁇ 100 was 95% or more. 100 test pieces were measured, and the frequency of batteries with good battery characteristics was determined and evaluated according to the following criteria. A: 90% or more B: 80% or more and less than 90% C: less than 80%.
- A Long-term characteristics evaluation at normal temperature, the same operation was performed except that the ambient temperature left for 50 hours was 60 ° C., and evaluation was performed according to the following criteria.
- (C) Output characteristics A lithium cobalt oxide (LiCoO 2 ) positive electrode having a thickness of 40 ⁇ m manufactured by Hosen Co., Ltd. was used and punched into a circle having a diameter of 15.9 mm. Further, a graphite negative electrode having a thickness of 50 ⁇ m manufactured by Hosen Co., Ltd. was used and punched into a circle having a diameter of 16.2 mm. Next, the separators of the examples and comparative examples were punched out to a diameter of 24 mm.
- LiCoO 2 lithium cobalt oxide
- the negative electrode, the separator, and the positive electrode were stacked in this order so that the positive electrode active material and the negative electrode active material face each other, and stored in a small stainless steel container with a lid (HS cell manufactured by Hosen Co., Ltd.).
- the container and the lid are insulated, the container is in contact with the negative electrode copper foil, and the lid is in contact with the positive electrode aluminum foil.
- a battery was produced for each example and comparative example.
- Breaking strength According to JIS K 7127 (1999, test piece type 2), using a film strength / elongation measuring device (AMF / RTA-100) manufactured by Orientec Co., Ltd., at 25 ° C. and 65% RH.
- the breaking strength was measured. Specifically, a porous polypropylene film was cut into a size of 15 cm in the longitudinal direction and 1 cm in the width direction, stretched at an original length of 50 mm, and a tensile speed of 300 mm / min, and the breaking strength (unit: MPa) was measured. The same measurement was performed five times for the same sample, and the average value of the obtained breaking strengths was taken as the breaking strength in the longitudinal direction of the sample. Further, the longitudinal direction and the width direction of the sample were interchanged, and the breaking strength in the width direction was similarly measured.
- ⁇ -crystal nucleating agent content A porous polypropylene film is added to decalin to extract amide compounds, antioxidants and the like in polypropylene resin, and then quantified by high performance liquid chromatography. A standard polypropylene resin with a known amount of amide compound and antioxidant added in advance is prepared, the same measurement is performed, and a calibration curve is prepared to determine the concentration of the amide compound in polypropylene. did.
- Air permeability resistance (Gurley) A square with a side length of 100 mm was cut out from the separators obtained in the examples and comparative examples. The permeation time of 100 ml of air was measured three times at 23 ° C.
- the average value of the permeation time was defined as the air resistance (Gurley) of the film.
- the measurement was stopped when the permeation time of 25 ml of air exceeded 30 minutes (1,800 seconds), and the air resistance (Gurley) was 120. It was judged that the minute / 100 ml (7,200 seconds / 100 ml) was exceeded.
- the raw material fed to a twin-screw extruder from the weighing hopper was melt-kneaded at 300 ° C., discharged from a die in a strand shape, cooled and solidified in a water bath at 25 ° C., cut into a chip shape, and used as a chip raw material. This was used as a raw material resin for a porous polypropylene film.
- This chip was supplied to a single screw extruder (discharge amount: 15 kg / hr) and melt extrusion was performed at 235 ° C.
- Foreign matter was removed with a leaf disk type filter in which 10 sheets of a 20 ⁇ m cut sintered filter (filtration area: 65000 mm 2 ) were set, and then a 50 ⁇ m cut wire mesh screen filter (filtration area: 18000 mm 2 ) was passed.
- the sheet was discharged from a T-die to a cast drum whose surface temperature was controlled at 120 ° C. and cast so as to be indirectly on the drum for 15 seconds to obtain an unstretched sheet.
- the ⁇ -crystal forming ability of the unstretched film was 80%.
- preheating was performed using a ceramic roll heated to 125 ° C., and the film was stretched 5 times in the longitudinal direction of the film.
- the end portion was introduced into a tenter type stretching machine by holding it with a clip, and the film was stretched 6.5 times at 150 ° C. at a stretching speed of 1,800% / min.
- heat treatment was performed at 155 ° C. for 7 seconds while relaxing 10% in the width direction to obtain a porous polypropylene film having a thickness of 25 ⁇ m.
- Table 1 shows the physical properties of the obtained film.
- the sample for evaluating physical properties was a sample collected after film formation for 10 hours under the above conditions.
- the obtained separator had good defect quality and air permeability, and the battery characteristics were good in both long-term characteristics and output characteristics.
- Example 2 A porous polypropylene film was obtained with the raw material composition and film forming conditions described in Example 1 except that a static mixer was used instead of the screen filter of 50 ⁇ m cut in Example 1. Since a static mixer was used in place of the screen filter, the obtained separator had a slightly higher frequency of defects than that of Example 1, and the long-term characteristics at high temperatures were slightly lowered, resulting in Evaluation B. The output characteristics were good.
- Example 3 A porous polypropylene film was obtained with the raw material composition and film forming conditions described in Example 1 except that a static mixer was installed on the downstream side of the screen filter of 50 ⁇ m cut in Example 1. Since the screen filter and the static mixer were installed in series, the obtained separator had less defect frequency compared to Example 1, both defect quality and air permeability were good, and battery characteristics were good in both long-term characteristics and output characteristics. Met.
- Example 4 A porous polypropylene film was obtained with the raw material composition and film forming conditions described in Example 1 except that the temperature during melt extrusion in Example 1 was 200 ° C. Since the temperature at the time of melt extrusion was set to a preferable temperature, the obtained separator had fewer defect frequencies than Example 1, both defect quality and air permeability were good, and battery characteristics were good in both long-term characteristics and output characteristics. there were.
- Example 5 A porous polypropylene film was obtained using the raw material composition and film forming conditions described in Example 1, except that a 40 ⁇ m cut sintered filter was used instead of the 20 ⁇ m cut sintered filter in Example 1. Since the filter accuracy was changed to a 40 ⁇ m cut, the obtained separator had a slightly higher frequency of defects than that of Example 1, and the long-term characteristics at room temperature and high temperature were slightly lowered, resulting in Evaluation B. The output characteristics were good.
- Example 6 A porous polypropylene film was formed under the same raw material composition and film forming conditions as described in Example 1 except that a flat plate sintered filter (filtering area: 18000 mm 2 ) of 50 ⁇ m cut was used instead of the screen filter of 50 ⁇ m cut in Example 1. Obtained. By changing the wire mesh filter to a sintered filter, the obtained separator significantly improved the defect quality compared to Example 1. The battery characteristics were good in both long-term characteristics and output characteristics.
- Example 7 A porous polypropylene film was obtained with the raw material composition and film forming conditions described in Example 1, except that the temperature at the time of melt extrusion in Example 1 was 200 ° C. and the addition amount of the ⁇ crystal nucleating agent was 0.03 parts by mass. It was. The obtained separator had good defect quality and good long-term characteristics. However, since there were few ⁇ crystal nucleating agents, the air permeability was lowered and the output characteristics were evaluated as B.
- Example 8 A porous polypropylene film was obtained with the raw material composition and film forming conditions described in Example 1, except that the draw ratio in the longitudinal direction was changed to 2.8 times in Example 1. Since the obtained separator had a low draw ratio, the frequency of defects was improved and long-term characteristics were good. However, since the longitudinal draw ratio was low, the air permeability was lowered, and the output characteristics were evaluated as B. Moreover, since the strength was reduced, workability during battery assembly was also reduced.
- Example 9 A porous polypropylene film was obtained with the raw material composition and film forming conditions described in Example 1 except that the draw ratio in the width direction was changed to 2.8 times in Example 1. Since the obtained separator had a low draw ratio, the frequency of defects was improved and long-term characteristics were good. However, since the width direction draw ratio was low, the air permeability was lowered, and the output characteristics were evaluated as B. Moreover, since the strength was reduced, workability during battery assembly was also reduced.
- Example 1 A porous polypropylene film was obtained using the raw material composition and film forming conditions described in Example 1, except that the 20 ⁇ m cut sintered filter and the 50 ⁇ m cut screen filter were not used in Example 1. Since the obtained separator had a high defect frequency, the long-term characteristics deteriorated.
- Example 2 A porous polypropylene film was obtained with the raw material composition and film forming conditions described in Example 1, except that the screen filter of 50 ⁇ m cut was not used in Example 1. Since the obtained separator had a high defect frequency, the long-term characteristics deteriorated.
- Example 3 (Comparative Example 3)
- the temperature at the time of melt extrusion was 200 ° C.
- a porous polypropylene film was obtained with the raw material composition and film forming conditions described in Example 1 except that a 50 ⁇ m cut screen filter was not used. Since the obtained separator had a high defect frequency, the long-term characteristics deteriorated.
- Example 4 The raw material composition described in Example 1, except that a screen filter of 15 ⁇ m cut was used instead of the screen filter of 50 ⁇ m cut in Example 1, and the discharge rate was changed to 3 kg / hr to prevent breakage of the screen filter, A porous polypropylene film was obtained under the film forming conditions. In addition, at the same discharge amount as in Example 1, the pressure loss before and after the screen filter was high, and film formation was difficult. The separator obtained had a lower discharge rate and increased residence time, so the frequency of defects increased and the long-term characteristics deteriorated.
- Example 5 A porous polypropylene film was formed under the same raw material composition and film forming conditions as described in Example 1, except that a leaf disk type filter in which 10 sheets of 15 ⁇ m cut sintered filters were set instead of the 50 ⁇ m cut screen filter in Example 1 was installed. Obtained. Since a flat plate type filter was not installed, the obtained separator had a higher frequency of defects and deteriorated long-term characteristics.
- the film quality is excellent, so that it can be suitably used as a separator for an electricity storage device.
- the comparative example there are many defects that cause deterioration of battery evaluation, and it is difficult to use as a separator for an electricity storage device.
- the porous polypropylene film of the present invention is excellent in quality and productivity, and has a high porosity, so that it can be suitably used as a separator for a lithium ion battery.
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Abstract
Description
式中、Xは下記(2)又は(3)を表す。R1,R2は、同一又は異なる炭素数5~12のシクロアルキル基を表す。
樹脂またはフィルム5mgを試料としてアルミニウム製のパンに採取し、示差走査熱量計(セイコー電子工業製RDC220)を用いて測定した。まず、窒素雰囲気下で室温から260℃まで10℃/分で昇温(ファーストラン)し、10分間保持した後、20℃まで10℃/分で冷却する。5分保持後、再度10℃/分で昇温(セカンドラン)した際に観測される融解ピークにについて、145~157℃の温度領域にピークが存在する融解をβ晶の融解ピーク、158℃以上にピークが観察される融解をα晶の融解ピークとして、高温側の平坦部を基準に引いたベースラインとピークに囲まれる領域の面積から、それぞれの融解熱量を求める。α晶の融解熱量をΔHα、β晶の融解熱量をΔHβとしたとき、以下の式で計算される値をβ晶形成能とする。なお、融解熱量の校正はインジウムを用いて行った。
・β晶形成能(%) = 〔ΔHβ / (ΔHα + ΔHβ)〕 × 100
なお、ファーストランで観察される融解ピークから同様にβ晶の存在比率を算出することで、その試料の状態でのβ晶分率を算出することができる。
ポリプロピレン樹脂のMFRは、JIS K 7210(1995)の条件M(230℃、2.16kg)に準拠して測定する。ポリエチレン樹脂は、JIS K 7210(1995)の条件D(190℃、2.16kg)に準拠して測定する。
フィルムを30mm×40mmの大きさに切取り試料とした。電子比重計(ミラージュ貿易(株)製SD-120L)を用いて、室温23℃、相対湿度65%の雰囲気にて比重の測定を行った。測定を3回行い、平均値をそのフィルムの比重ρとした。
次に、測定したフィルムを280℃、5MPaで熱プレスを行い、その後、25℃の水で急冷して、空孔を完全に消去したシートを作成した。このシートの比重を上記した方法で同様に測定し、平均値を樹脂の比重(d)とした。なお、後述する実施例においては、いずれの場合も樹脂の比重dは0.91であった。フィルムの比重と樹脂の比重から、以下の式により空孔率を算出した。
・空孔率(%) = 〔( d - ρ ) / d 〕 × 100。
得られたフィルムを幅210mmでスリットし、巻出機と巻取機を備えた欠点検出器でフィルムの透過光量を測定した。光源には、長さ750mm、直径φ10mmの円柱状のロッドレンズを用い、ロッドレンズの端面から250Wのメタルハライド光源の光を入射した。フィルムの一方の面から光源を15mm離して設置し、照射した光の光量をもう一方の面から検出した。検出器とフィルムの距離は250mmとした。検出器としてはエレクトロセンサリデバイス(株)社製CCDラインセンサカメラE7450Dとニコン社製カメラレンズAiMicro-Nikkor55mmF2.8Sをフィルム幅方向に2台用い、以下の条件で検査した。フィルムを5m/分で走行させ、フィルムの透過光量を長さ500mについて全幅で測定した。表には平均透過光量に比べ、透過光量が5倍以上となる部分の頻度をA個/1m2、平均透過光量に比べ、透過光量が3倍以上5倍未満となる部分の頻度をB個/1m2として記載した。ここで、平均透過光量はスリット後のフィルムの巻き芯部分と巻き外部分についてそれぞれ長さ1m分の透過光量を測定し、その平均値を用いた。
また、上記操作で透過光量が平均透過光量に比べ、5倍以上および3倍以上5倍未満となる部分が検出されなかった場合は、測定面積を10倍にして検査を行い、頻度を求めた。
・幅方向分解能 :20μm/pixel
・長さ方向分解能:20μm/pixel
・視野幅 :中央部200mm幅
・スキャンレート:9,500
・絞り :16F。
(A)常温での長期特性
宝泉(株)製の厚みが40μmのリチウムコバルト酸化物(LiCoO2)正極を使用し、幅200mm、長さ4,000mmに切断した。また、宝泉(株)製の厚みが50μmの黒鉛負極を使用し、幅200mm、長さ4,000mmに切断した。
次に、上記の帯状正極を、各実施例・比較例のセパレータ用フィルムを介して、上記シート状負極と重ね、渦巻状に巻回して渦巻状電極体としたのち、有底円筒状の電池ケース内に充填し、正極および負極のリード体の溶接を行った後、この容器内に、エチレンカーボネート:ジメチルカーボネート=3:7(体積比)の混合溶媒に溶質としてLiPF6を濃度1モル/Lとなるように溶解させた電解液を電池ケース内に注入した。電池ケースの開口部を封口し、電池の予備充電を行い、筒形の有機電解液二次電池を作製した。各実施例・比較例につき、電池を作製した。
[(50時間後の電圧値)/(初期電圧値(4.2V))]×100 の計算式で得られる値が95%以上のものを電池特性良好とした。試験個数は100個測定し、電池特性良好となった電池の頻度を求め以下の基準で評価した。
A:90%以上
B:80%以上90%未満
C:80%未満。
上記(A)常温での長期特性評価において、50時間放置する雰囲気温度を60℃とする以外は同様の操作を行い、以下の基準で評価した。
A:90%以上
B:80%以上90%未満
C:80%未満。
宝泉(株)製の厚みが40μmのリチウムコバルト酸化物(LiCoO2)正極を使用し、直径15.9mmの円形に打ち抜いた。また、宝泉(株)製の厚みが50μmの黒鉛負極を使用し、直径16.2mmの円形に打ち抜いた。次に、各実施例・比較例のセパレータを直径24mmに打ち抜いた。正極活物質と負極活物質面が対向するように、下から負極、セパレータ、正極の順に重ね、蓋付ステンレス金属製小容器(宝泉(株)製のHSセル)に収納した。容器と蓋とは絶縁され、容器は負極の銅箔と、蓋は正極のアルミ箔と接している。この容器内にエチレンカーボネート:ジメチルカーボネート=3:7(体積比)の混合溶媒に溶質としてLiPF6を濃度1モル/Lとなるように溶解させた電解液を注入して密閉した。各実施例・比較例につき、電池を作製した。
[(16,000mAでの放電容量)/(1,600mAでの放電容量)]×100 の計算式で得られる値を以下の基準で評価した。なお、試験個数は20個測定し、その平均値で評価した。
A:85%以上
B:80%以上85%未満
C:80%未満。
JIS K 7127(1999、試験片タイプ2)に準じて、(株)オリエンテック製フィルム強伸度測定装置(AMF/RTA-100)を用いて、25℃、65%RHにて破断強度を測定した。具体的には、多孔性ポリプロピレンフィルムを長手方向:15cm、幅方向:1cmのサイズに切り出し、原長50mm、引張り速度300mm/分で伸張して、破断強度(単位:MPa)を測定した。同じサンプルについて同様の測定を5回行い、得られた破断強度の平均値を当該サンプルの長手方向の破断強度とした。また、サンプルの長手方向と幅方向を入れ替えて同様に幅方向の破断強度を測定した。
多孔性ポリプロピレンフィルムをデカリンに加えてポリプロピレン樹脂中のアミド系化合物や酸化防止剤などを抽出させたのち、高速液体クロマトグラフィーにより定量する。なお、予め秤量したアミド系化合物、酸化防止剤の添加量が既知の標準ポリプロピレン樹脂を作成し、同様の測定を行い、検量線を作成しておくことで、ポリプロピレン中のアミド系化合物濃度を定量した。
(8)透気抵抗(ガーレー)
実施例および比較例で得たセパレータから1辺の長さ100mmの正方形を切取り試料とした。JIS P 8117(1998)のB形のガーレー試験機を用いて、23℃、相対湿度65%にて、100mlの空気の透過時間の測定を3回行った。透過時間の平均値をそのフィルムの透気抵抗度(ガーレー)とした。なお、透気抵抗度(ガーレー)が悪いサンプルの場合は、25mlの空気の透過時間が30分(1,800秒)を超えた時点で測定を中止し、透気抵抗度(ガーレー)が120分/100ml(7,200秒/100ml)を超えていると判断した。
住友化学(株)製ホモポリプロピレンFLX80E4(以下、PP-1と表記、MFR=8)94質量部、高溶融張力ポリプロピレン樹脂であるBasell製ポリプロピレンPF-814(以下、HMS-PPと表記、MFR=2.5)1質量部、エチレン-オクテン-1共重合体であるダウ・ケミカル製 Engage8411(メルトインデックス:18g/10分、以下、単にPEと表記)5質量部、β晶核剤であるN,N’-ジシクロヘキシル-2,6-ナフタレンジカルボキシアミド(新日本理化(株)製、Nu-100、以下、単にβ晶核剤と表記)0.2質量部、酸化防止剤であるチバ・スペシャリティ・ケミカルズ製IRGANOX1010、IRGAFOS168を各々0.15、0.1質量部を、この比率で混合されるように計量ホッパーから二軸押出機に原料供給した。300℃で溶融混練を行い、ストランド状にダイから吐出して、25℃の水槽にて冷却固化し、チップ状にカットしてチップ原料とした。これを多孔性ポリプロピレンフィルムの原料樹脂とした。
実施例1で50μmカットのスクリーンフィルターの代わりにスタティックミキサーを用いた以外は実施例1に記載した原料組成、製膜条件で多孔性ポリプロピレンフィルムを得た。
スクリーンフィルターの代わりにスタティックミキサーを用いたため、得られたセパレータは実施例1に比べて欠点頻度がやや多くなり、高温での長期特性が若干低下し、評価Bとなった。出力特性は良好であった。
実施例1で50μmカットのスクリーンフィルターの下流側にスタティックミキサーを設置した以外は実施例1に記載した原料組成、製膜条件で多孔性ポリプロピレンフィルムを得た。
スクリーンフィルターとスタッティクミキサーを直列して設置したので、得られたセパレータは実施例1に比べて欠点頻度が少なく、欠点品位、透気性共に良好であり、電池特性は長期特性、出力特性共に良好であった。
実施例1で溶融押出時の温度を200℃とした以外は実施例1に記載した原料組成、製膜条件で多孔性ポリプロピレンフィルムを得た。
溶融押出温時の温度を好ましい温度にしたので、得られたセパレータは実施例1に比べて欠点頻度が少なく、欠点品位、透気性共に良好であり、電池特性は長期特性、出力特性共に良好であった。
実施例1で20μmカットの焼結フィルターの代わりに40μmカットの焼結フィルターを用いた以外は実施例1に記載した原料組成、製膜条件で多孔性ポリプロピレンフィルムを得た。
フィルター精度を40μmカットに変更したため、得られたセパレータは実施例1に比べて欠点頻度がやや多くなり、常温および高温での長期特性が若干低下し、評価Bとなった。出力特性は良好であった。
実施例1で50μmカットのスクリーンフィルターの代わりに50μmカットの平板型焼結フィルター(濾過面積:18000mm2)を用いた以外は実施例1に記載した原料組成、製膜条件で多孔性ポリプロピレンフィルムを得た。
金網フィルターを焼結フィルターに変更したことで、得られたセパレータは実施例1に比べて欠点品位が大幅に改善した。電池特性は長期特性、出力特性共に良好であった。
実施例1で溶融押出時の温度を200℃とし、β晶核剤の添加量を0.03質量部とした以外は実施例1に記載した原料組成、製膜条件で多孔性ポリプロピレンフィルムを得た。
得られたセパレータは欠点品位が良好であり、長期特性が良好であったが、β晶核剤が少ないため透気性が低下し、出力特性が評価Bとなった。
実施例1で長手方向の延伸倍率を2.8倍に変更する以外は実施例1に記載した原料組成、製膜条件で多孔性ポリプロピレンフィルムを得た。
得られたセパレータは延伸倍率が低いため欠点頻度は向上し、長期特性が良好であったが、長手方向延伸倍率が低いため透気性が低下し、出力特性が評価Bとなった。また、強度が低下したため、電池組立時の加工性も低下した。
実施例1で幅方向の延伸倍率を2.8倍に変更する以外は実施例1に記載した原料組成、製膜条件で多孔性ポリプロピレンフィルムを得た。
得られたセパレータは延伸倍率が低いため欠点頻度は向上し、長期特性が良好であったが、幅方向延伸倍率が低いため透気性が低下し、出力特性が評価Bとなった。また、強度が低下したため、電池組立時の加工性も低下した。
実施例1で20μmカットの焼結フィルターおよび50μmカットのスクリーンフィル
ターを使用しない以外は実施例1に記載した原料組成、製膜条件で多孔性ポリプロピレンフィルムを得た。
得られたセパレータは欠点頻度が高くなったため、長期特性が悪化した。
実施例1で50μmカットのスクリーンフィルターを使用しない以外は実施例1に記載した原料組成、製膜条件で多孔性ポリプロピレンフィルムを得た。
得られたセパレータは欠点頻度が高くなったため、長期特性が悪化した。
実施例1で溶融押出時の温度を200℃とし、50μmカットのスクリーンフィルターを使用しない以外は実施例1に記載した原料組成、製膜条件で多孔性ポリプロピレンフィルムを得た。
得られたセパレータは欠点頻度が高くなったため、長期特性が悪化した。
実施例1で50μmカットのスクリーンフィルターの代わりに15μmカットのスクリーンフィルターを使用し、また、スクリーンフィルターの破損を防ぐため吐出量を3kg/hrと変更する以外は実施例1に記載した原料組成、製膜条件で多孔性ポリプロピレンフィルムを得た。なお、実施例1と同じ吐出量ではスクリーンフィルター前後の圧損が高くなり、製膜は困難であった。
得られたセパレータは吐出量が低くなり滞留時間が増えたため欠点頻度が高くなり、長期特性が悪化した。
実施例1で50μmカットのスクリーンフィルターに代えて15μmカットの焼結フィルターを10枚セットしたリーフディスク型フィルターを設置する以外は実施例1に記載した原料組成、製膜条件で多孔性ポリプロピレンフィルムを得た。
平板型のフィルターを設置していないため、得られたセパレータは欠点頻度が高くなり、長期特性が悪化した。
Claims (9)
- 平均透過光量に対し透過光量が5倍以上となる部分が1m2当たり0.5個以下である多孔性ポリプロピレンフィルム。
- 平均透過光量に対し透過光量が3倍以上5倍未満となる部分が1m2当たり1個以下である請求項1の多孔性ポリプロピレンフィルム。
- 多孔性ポリプロピレンフィルムが乾式法で製造されてなる請求項1または2のいずれかの多孔性ポリプロピレンフィルム。
- 空孔率が60~85%である、請求項1~3のいずれかの多孔性ポリプロピレンフィルム。
- 多孔性ポリプロピレンフィルムがβ晶形成能40~90%のポリプロピレン樹脂を含む、請求項1~4のいずれかの多孔性ポリプロピレンフィルム。
- 多孔性ポリプロピレンフィルムを構成するポリプロピレン樹脂中に、該ポリプロピレン樹脂全体に対してβ晶核剤を0.05~0.5質量%含有する請求項1~5のいずれかの多孔性ポリプロピレンフィルム。
- 長手方向の破断強度EMが65MPa以上であり、幅方向の破断強度ETが45MPa以上である請求項1~6のいずれかの多孔性ポリプロピレンフィルム。
- 請求項1~7のいずれかの多孔性ポリプロピレンフィルムの製造方法であって、乾式法により製膜されたポリプロピレンフィルムを、長手方向および幅方向にそれぞれ3倍以上10倍以下延伸する多孔性ポリプロピレンフィルムの製造方法。
- 乾式法により製膜されたポリプロピレンフィルムが、β晶形成能40~90%のポリプロピレン樹脂を含む、請求項8の多孔性ポリプロピレンフィルムの製造方法。
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EP10753515.5A EP2410006A4 (en) | 2009-03-17 | 2010-03-16 | Porous polypyryl film and method for its production |
US13/203,879 US20110319511A1 (en) | 2009-03-17 | 2010-03-16 | Porous polypropylene film and production method thereof |
JP2010513514A JP5736777B2 (ja) | 2009-03-17 | 2010-03-16 | 多孔性ポリプロピレンフィルムおよびその製造方法 |
CN2010800047370A CN102282203B (zh) | 2009-03-17 | 2010-03-16 | 多孔聚丙烯膜及其制造方法 |
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WO2012105661A1 (ja) * | 2011-02-03 | 2012-08-09 | 東レ株式会社 | 多孔性ポリプロピレンフィルム、蓄電デバイス用セパレータおよび蓄電デバイス |
JP2012531009A (ja) * | 2009-06-20 | 2012-12-06 | トレオファン・ジャーマニー・ゲーエムベーハー・ウント・コンパニー・カーゲー | シャットダウン機能を有する電池用微孔質ホイル |
JP2013100458A (ja) * | 2011-10-14 | 2013-05-23 | Toray Ind Inc | 多孔性ポリオレフィンフィルムおよび蓄電デバイス |
JP2015004017A (ja) * | 2013-06-21 | 2015-01-08 | 三菱樹脂株式会社 | 多孔性フィルム、それを利用した電池用セパレータおよび電池 |
WO2018164056A1 (ja) | 2017-03-08 | 2018-09-13 | 東レ株式会社 | ポリオレフィン微多孔膜 |
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CN106159171A (zh) * | 2016-08-29 | 2016-11-23 | 无锡市宝来电池有限公司 | 一种耐腐蚀的锂离子电池隔膜材料 |
WO2019057325A1 (de) * | 2017-09-20 | 2019-03-28 | Treofan Germany Gmbh & Co. Kg | Separator-folie mit verbesserten mechanischen eigenschaften |
WO2019158266A1 (de) * | 2018-02-16 | 2019-08-22 | Treofan Germany Gmbh & Co. Kg | Separator-folie mit verbesserten mechanischen eigenschaften |
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CN103339175A (zh) * | 2011-02-03 | 2013-10-02 | 东丽株式会社 | 多孔性膜、蓄电器件用隔板及蓄电器件 |
US9287543B2 (en) | 2011-02-03 | 2016-03-15 | Toray Industries, Inc. | Porous film, separator for electric storage device, and electric storage device |
JP2013100458A (ja) * | 2011-10-14 | 2013-05-23 | Toray Ind Inc | 多孔性ポリオレフィンフィルムおよび蓄電デバイス |
JP2015004017A (ja) * | 2013-06-21 | 2015-01-08 | 三菱樹脂株式会社 | 多孔性フィルム、それを利用した電池用セパレータおよび電池 |
WO2018164056A1 (ja) | 2017-03-08 | 2018-09-13 | 東レ株式会社 | ポリオレフィン微多孔膜 |
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JPWO2010107023A1 (ja) | 2012-09-20 |
CN102282203A (zh) | 2011-12-14 |
CN102282203B (zh) | 2013-04-03 |
EP2410006A4 (en) | 2015-08-19 |
US20110319511A1 (en) | 2011-12-29 |
KR20110131213A (ko) | 2011-12-06 |
EP2410006A1 (en) | 2012-01-25 |
JP5736777B2 (ja) | 2015-06-17 |
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