WO2014007260A1 - Film en polypropylène poreux, séparateur pour dispositifs de stockage de l'électricité, et dispositif de stockage de l'électricité - Google Patents

Film en polypropylène poreux, séparateur pour dispositifs de stockage de l'électricité, et dispositif de stockage de l'électricité Download PDF

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WO2014007260A1
WO2014007260A1 PCT/JP2013/068169 JP2013068169W WO2014007260A1 WO 2014007260 A1 WO2014007260 A1 WO 2014007260A1 JP 2013068169 W JP2013068169 W JP 2013068169W WO 2014007260 A1 WO2014007260 A1 WO 2014007260A1
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polypropylene film
porous polypropylene
film
separator
porous
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PCT/JP2013/068169
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English (en)
Japanese (ja)
Inventor
大 西村
今西　康之
大倉　正寿
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東レ株式会社
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Priority to KR1020147033038A priority Critical patent/KR20150035548A/ko
Priority to CN201380030174.6A priority patent/CN104395382B/zh
Priority to JP2013552793A priority patent/JP5626486B2/ja
Publication of WO2014007260A1 publication Critical patent/WO2014007260A1/fr

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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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • 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
    • 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
    • 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
    • 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
    • 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 provides a porous polypropylene film capable of suppressing an increase in separator resistance and exhibiting excellent battery characteristics when a functional layer that imparts or improves performance such as heat resistance and adhesion to an electrode is provided, and
  • the present invention relates to a power storage device separator using a porous polypropylene film, and a power storage device using the power storage device separator.
  • Porous polypropylene films are being considered for use in a wide range of applications, including separators for batteries and electrolytic capacitors, various separation membranes, clothing, moisture-permeable waterproof membranes for medical applications, reflectors for flat panel displays, and thermal transfer recording sheets.
  • a porous film is suitable as a separator for lithium ion batteries widely used in mobile devices such as notebook personal computers, mobile phones, and digital cameras.
  • lithium-ion batteries have been used in electric vehicles and hybrid vehicles, and as the output of batteries increases and the capacity increases, studies on coating porous films with inorganic particle layers and heat-resistant resin layers are actively conducted. (For example, refer to Patent Documents 1 and 2). Further, since the size of the battery is increased and the area to be used is increased, cost reduction is also strongly desired.
  • a ⁇ -crystal method can be cited as a dry method and a method capable of forming a film with high productivity by biaxial stretching.
  • the ⁇ crystal method is a method in which voids are formed in a film by utilizing the crystal density difference and crystal transition between ⁇ type crystal ( ⁇ crystal) and ⁇ type crystal ( ⁇ crystal), which are polymorphs of polypropylene.
  • Many proposals have been made (see, for example, Patent Documents 3 to 5).
  • many proposals have been made on a method of coating a functional layer such as a heat-resistant layer on the surface of a porous polypropylene film by the ⁇ crystal method (see, for example, Patent Documents 6 to 15).
  • a ⁇ -crystal porous polypropylene film is coated with a coating material containing an inorganic or organic material that forms a functional layer
  • the pore structure may change depending on the solvent used, or a component having a binder function may be a base material.
  • the air resistance changes due to, for example, remaining in the film.
  • the use of a high molecular weight polypropylene resin is restricted from the viewpoint of pressure at the time of melt extrusion, etc., so that it is more organic than polyethylene films such as Patent Documents 1 and 2.
  • the resistance to the solvent was low, and the solvent of the coating material for the functional layer had to be limited to an aqueous system.
  • the object of the present invention is to solve the above-mentioned problems. That is, to provide a porous polypropylene film capable of suppressing an increase in separator resistance and exhibiting excellent battery characteristics when a functional layer that imparts or improves performance such as heat resistance and adhesion to an electrode is provided. is there.
  • the present invention provides a porous polypropylene film mainly composed of a polypropylene resin, the separator resistance R1 ( ⁇ ) of the porous polypropylene film, and the porous
  • the separator resistance R2 ( ⁇ ) after applying and drying a coating simulation liquid composed of a functional polymer and an organic solvent on a polypropylene film satisfies the following formula (1).
  • porous polypropylene film of the present invention When the porous polypropylene film of the present invention is provided with a functional layer that imparts or improves performance such as heat resistance and adhesion with an electrode, it suppresses an increase in separator resistance and can exhibit excellent battery characteristics. It can be suitably used as a separator for an electricity storage device.
  • FIG. 1 is an equivalent circuit diagram used when measuring the separator resistance.
  • the porous polypropylene film of the present invention comprises a polypropylene resin composition containing a polypropylene resin as a main component.
  • a polypropylene resin as a main component, it is possible to satisfy the heat resistance necessary for preventing a short circuit of the battery when used as a separator for an electricity storage device.
  • having a polypropylene resin as a main component means that the proportion of the polypropylene resin in all the components constituting the porous polypropylene film is 50% by mass or more, preferably 80% by mass or more, more preferably It is 90 mass% or more, More preferably, it is 95 mass% or more.
  • the porous polypropylene film of the present invention has pores that penetrate from one surface of the film toward the other surface and have air permeability (hereinafter referred to as through-holes).
  • Examples of the method for forming the through hole include an extraction method, a lamellar stretching method, a ⁇ crystal method, and the like. From the viewpoint of productivity and uniformity of physical properties in the longitudinal direction and the width direction, the ⁇ crystal method is preferable.
  • the ⁇ crystal method uses a cast sheet of a polypropylene resin composition having a ⁇ crystal as a crystal structure, and longitudinally stretches the cast sheet to transfer the crystal structure of the ⁇ crystal to an ⁇ crystal and This is a technique for obtaining a film having through-holes by forming ⁇ -crystal fibrils oriented in the film direction and cleaving the fibrils in a transverse stretching process to form a network structure.
  • the cast sheet means an unstretched sheet obtained by molding a molten polypropylene resin composition into a sheet shape on a cast drum.
  • a ⁇ crystal nucleating agent to the polypropylene resin composition to enhance the ⁇ crystal forming ability. Since the ⁇ -crystal forming ability is high, the portion of the crystal structure that causes crystal transition to the ⁇ -crystal increases, and the number of voids formed in the film can be increased. In addition, by controlling the raw material containing the ⁇ crystal nucleating agent, the orientation and denseness of the polypropylene crystals are improved, and the pores are uniformly and densely opened, whereby the porous polypropylene film is used as a separator for an electricity storage device. Reduction of separator resistance can be achieved.
  • the ⁇ -crystal forming ability of the porous polypropylene film is preferably 60% or more from the viewpoint of the through-hole formability. More preferred is 65 to 90%, and particularly preferred is 65 to 85%.
  • the ⁇ crystal forming ability is less than 60%, the amount of ⁇ crystals is small, so that the number of voids formed in the film using the transition to ⁇ crystal is reduced, and the separator resistance of the film may be inferior.
  • a method of controlling the ⁇ crystal formation ability to 60% or more a method using a polypropylene resin having a high isotactic index, a ⁇ crystal is selectively formed by adding it to a polypropylene resin called a ⁇ crystal nucleating agent.
  • a method of using a ⁇ crystal nucleating agent described later, or a ⁇ crystal nucleating agent described later in a polypropylene resin having a high isotactic index it is preferable to use the method used as
  • Examples of the ⁇ crystal nucleating agent used in the present invention include alkali or alkaline earth metal salts of carboxylic acids such as calcium 1,2-hydroxystearate and magnesium succinate, and N, N′-dicyclohexyl-2,6-naphthalene.
  • Amide compounds represented by carboxamide tetraoxaspiro compounds such as 3,9-bis [4- (N-cyclohexylcarbamoyl) phenyl] -2,4,8,10-tetraoxaspiro [5.5] undecane
  • aromatic sulfonic acid compounds such as sodium benzene sulfonate and sodium naphthalene sulfonate, imide carboxylic acid derivatives, and quinacridone pigments, particularly amide compounds disclosed in JP-A-5-310665. It is preferable to use it.
  • the content of the ⁇ crystal nucleating agent varies depending on the ⁇ crystal nucleating agent to be used, but when the amide compound is used, it is 0.05 to 0.5 based on the whole polypropylene composition.
  • the content is preferably 0.1% by mass, more preferably 0.1 to 0.3% by mass, and particularly preferably 0.22 to 0.3% by mass in order to have the effects described later. If it is less than 0.05% by mass, the formation of ⁇ crystals becomes insufficient, and the separator resistance of the porous polypropylene film may increase.
  • an isotactic polypropylene resin having a melt flow rate (hereinafter referred to as MFR) of 2 to 30 g / 10 min is used as the polypropylene resin from the viewpoint of extrusion moldability and uniform pore formation.
  • MFR is an index indicating the melt viscosity of a resin defined in JIS K 7210 (1995), and is a physical property value indicating the characteristics of a polyolefin resin. In the present invention, it refers to a value measured at 230 ° C. and 2.16 kg.
  • the isotactic index of the polypropylene resin is preferably in the range of 90 to 99.9%, more preferably 95 to 99%.
  • the isotactic index is less than 90%, the crystallinity of the resin is lowered, the film forming property may be lowered, and the strength of the film may be inferior.
  • the polypropylene resin used in the present invention is made of the above-mentioned isotopic material from the viewpoint of suppressing the increase in separator resistance when a functional layer is provided that makes the pore structure uniform and imparts or improves performance such as heat resistance and adhesion to electrodes.
  • tactic polypropylene it is preferable to add low molecular weight isotactic polypropylene having an MFR of 70 g / 10 min or more, preferably 100 g / 10 min or more, more preferably 500 g / 10 min or more.
  • the upper limit is that the MFR is 5000 g / 10 min.
  • the MFR exceeds 5000 g / 10 min, it may be difficult to homogenize with the above-described isotactic polypropylene.
  • low molecular weight isotactic polypropylene having an MFR of 70 g / 10 min or more has not been used in the field of films because it has poor film-forming properties and causes a decrease in strength.
  • the low molecular weight isotactic polypropylene is 0.1 to 50% by mass, preferably 1 to 20% by mass, more preferably 2 to 10% by mass, and most preferably 2%.
  • the content of ⁇ 5% by mass can suppress an increase in separator resistance when a functional layer that imparts or improves performance such as heat resistance and adhesion to an electrode is provided.
  • the cause is still unknown, but low molecular weight polypropylene added in small amounts increases the molecular chain end concentration at the crystal interface and promotes pore formation at the crystal interface in longitudinal stretching, that is, it functions as a hole opening aid.
  • the coating composition is difficult to clog, or even if clogged, a large number of through-holes are formed. It is presumed that the increase in separator resistance can be suppressed in order to survive.
  • the melting point of the low molecular weight isotactic polypropylene resin having an MFR of 70 g / 10 min or more is preferably 130 ° C. or more, more preferably 140 ° C. or more, and further preferably 150 ° C. or more.
  • the melting point is lower than 130 ° C., the openability of the porous polypropylene film may be lowered.
  • Examples of the low molecular weight isotactic polypropylene having the above-described properties include commercially available polypropylene resins S10AL, S10CL, J13B manufactured by Prime Polymer, and polypropylene resin 6936G1 manufactured by ExxonMobil.
  • the polypropylene resin composition forming the porous polypropylene film of the present invention includes an antioxidant, a heat stabilizer, an antistatic agent, a lubricant composed of inorganic or organic particles, and a blocking agent within the range that does not impair the effects of the present invention.
  • You may contain various additives, such as an inhibitor, a filler, and an incompatible polymer.
  • an antioxidant for the purpose of suppressing oxidative deterioration due to the thermal history of the polypropylene resin.
  • the addition amount of the antioxidant is preferably 2 parts by mass or less, more preferably 1 part by mass or less, still more preferably 0.5 parts by mass or less with respect to 100 parts by mass of the polypropylene resin composition.
  • the polypropylene resin composition for forming the porous polypropylene film of the present invention can contain a pore-forming aid composed of inorganic particles or organic particles within a range not impairing the effects of the present invention.
  • the porous polypropylene film of the present invention has a separator resistance R1 ( ⁇ ) of the porous polypropylene film, and after applying a solution containing a functional polymer that is a coating simulation liquid and an organic solvent to the porous polypropylene film,
  • the separator resistance R2 ( ⁇ ) of the film after drying the organic solvent satisfies the following formula (1).
  • the separator resistance means an electric resistance obtained by preparing an evaluation cell by a method described later and calculating a Cole-Cole plot measured by an AC impedance method from the equivalent circuit shown in FIG.
  • a functional layer that imparts or improves performance such as heat resistance and adhesion to an electrode is provided on a conventionally produced porous polypropylene film
  • a functional polymer having a binder function as an inorganic particle or organic particle.
  • PVdF polyvinylidene fluoride
  • EOA ethylene-acrylic acid copolymer
  • SBR fluorine-based rubber Styrene butadiene rubber
  • cross-linked acrylic resin polyurethane, polyvinyl butyral, polyethylene, polyvinyl alcohol, polytetrafluoroethylene, polyvinyl pyrrolidone, polyimide, polyamide, polysulfide, polyvinyl methyl ether, polyethylene
  • organic solvents eg, acetone, N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), cyclohexanone, ⁇ -butyrolactone (GBL), dimethylace
  • PVdF resin which is one kind of functional polymer
  • acetone which is one kind of solvent.
  • the dissolved coating simulation solution is applied and dried by the method described later to prepare a simulated coating film for evaluation.
  • Small R2 / R1 is considered to indicate that the functional polymer clogs the pores, and that the resistance increase due to the structure change at the time of solvent swelling and solvent drying hardly occurs.
  • R2 / R1 can be used as an index of the degree of increase in resistance relative to the base material when a functional layer for imparting or improving the performance is provided.
  • R2 / R1 satisfies the formula (1)
  • the film can suppress an increase in separator resistance when a functional layer that imparts or improves performance such as heat resistance and adhesion to an electrode is provided.
  • the value of R2 / R1 exceeds 1.2, it means that resistance is likely to increase when a functional layer that imparts or improves performance such as heat resistance and adhesion to electrodes is provided.
  • There are industrial disadvantages such as restrictions.
  • the addition amount of the ⁇ crystal nucleating agent in the raw material is within the above-mentioned range, the above-mentioned raw material is used, the temperature of the cast drum, the draw ratio and the temperature in the longitudinal direction.
  • the transverse stretching speed, the temperature and time in the heat treatment step, and the relaxation rate in the relaxation zone can be obtained within the ranges described below.
  • the ratio PMD / PTD of the breaking strength PMD in the longitudinal direction and the breaking strength PTD in the width direction preferably satisfies the following formula (2).
  • the direction parallel to the film forming direction is referred to as the film forming direction, the longitudinal direction, the MD direction, or simply MD, and the direction perpendicular to the film forming direction in the film plane is the width direction and the TD direction.
  • the value of PMD / PTD is preferably 0.7 ⁇ PMD / PTD ⁇ 1.6, and more preferably 0.8 ⁇ PMD / PTD ⁇ 1.4.
  • the addition amount of the ⁇ crystal nucleating agent in the raw material should be within the above-mentioned range, the above-mentioned raw material is used, the temperature of the cast drum, and the longitudinal direction.
  • the stretching ratio and temperature, the transverse stretching speed, the temperature and time in the heat treatment step, and the relaxation rate in the relaxation zone can be controlled within the ranges described below.
  • breaking strength itself of the porous polypropylene film is low, the safety may be inferior or the process suitability in the coating process and the battery assembly process may be insufficient.
  • the breaking strength is preferably 60 MPa or more in both the longitudinal direction and the width direction. More preferably, both are 80 MPa or more, and more preferably both are 100 MPa or more.
  • the amount of ⁇ crystal nucleating agent in the raw material is set in the above-described range, the above-described raw material is used, and the cast drum
  • the temperature, the stretching ratio and temperature in the longitudinal direction, the transverse stretching speed, the temperature and time in the heat treatment step, and the relaxation rate in the relaxation zone can be controlled within the ranges described below.
  • the porous polypropylene film of the present invention preferably has an air permeability resistance of 10 to 1,000 seconds / 100 ml, more preferably 50 to 500 seconds / 100 ml, and 80 to 300 seconds / 100 ml. Particularly preferred.
  • air permeation resistance is less than 10 seconds / 100 ml, mechanical strength such as breaking strength, which is an indicator of process suitability, may be lowered.
  • breaking strength which is an indicator of process suitability
  • the output characteristics may be deteriorated particularly when used as a separator for a high-power storage device.
  • the air permeation resistance is determined by setting the addition amount of the ⁇ crystal nucleating agent in the raw material within the above-described range, using the above-described raw material, the temperature of the cast drum, the stretching ratio and temperature in the longitudinal direction, the transverse stretching speed, and the heat treatment step It is possible to control by controlling the temperature and time of each of them and the relaxation rate in the relaxation zone within the range described later.
  • the porous polypropylene film of the present invention preferably has a film thickness of 5 to 30 ⁇ m. If the thickness is less than 5 ⁇ m, the film may break during use. If the thickness exceeds 30 ⁇ m, the separator resistance increases and the output characteristics may deteriorate when used as a separator, and the porous film occupies the power storage device. In some cases, the volume ratio of becomes high, and a high energy density cannot be obtained.
  • the film thickness is more preferably 10 to 25 ⁇ m, still more preferably 12 to 20 ⁇ m.
  • the porous polypropylene film of the present invention preferably has a porosity of 40 to 85% from the viewpoint of achieving both battery characteristics and strength. More preferably, it is 50 to 80%, and particularly preferably 55 to 75%.
  • the porosity is less than 40%, the separator resistance may increase particularly when used as a separator for a high-power electricity storage device.
  • the porosity exceeds 85%, mechanical strength such as elastic modulus and tensile strength may be lowered.
  • the porosity is determined by setting the amount of ⁇ -crystal nucleating agent in the raw material within the above-mentioned range, using the above-described raw material, the temperature of the cast drum, the stretching ratio and temperature in the longitudinal direction, the transverse stretching speed, and the heat treatment step. It is possible to control by controlling the temperature and time of each of them and the relaxation rate in the relaxation zone within the range described later.
  • the porous polypropylene film of the present invention preferably has a heat shrinkage in the width direction of 10% or less when heat-treated at 135 ° C. for 60 minutes. More preferably, it is 5% or less, More preferably, it is 3% or less.
  • a heat shrinkage rate when heat-treated at 135 ° C. for 60 minutes exceeds 10%, it may be inferior in safety when used as a separator for an electricity storage device.
  • polyethylene is applied to the surface of the porous polyolefin film of the present invention.
  • the porous polyolefin film as the base material may shrink and the battery may short circuit is there.
  • the lower limit is 0.1%.
  • the heat shrinkage ratio is within the above-mentioned range for the amount of ⁇ -crystal nucleating agent in the raw material, the raw material is used, the temperature of the cast drum, the stretching ratio and temperature in the longitudinal direction, the transverse stretching speed, and the heat treatment step. It is possible to control by controlling the temperature and time of each of them and the relaxation rate in the relaxation zone within the range described later.
  • the porous polypropylene film of the present invention may have a laminated structure for the purpose of imparting various effects.
  • the number of laminations may be two-layer lamination, three-layer lamination, or a larger number of laminations.
  • As a lamination method there are a feed block method by co-extrusion, a multi-manifold method, a method of laminating porous films by lamination, and the lamination method may be selected according to the physical properties of the resin to be laminated.
  • a laminated structure for example, a layer containing polyethylene may be laminated for the purpose of imparting a shutdown property at a low temperature, or a layer containing particles may be laminated for the purpose of imparting strength or heat resistance.
  • the method for producing the porous polypropylene film of the present invention will be described based on a specific example.
  • the manufacturing method of the film of this invention is not limited to this.
  • polypropylene resin 94.5 parts by mass of commercially available homopolypropylene resin with MFR 8 g / 10 min, 5 parts by mass of commercially available low molecular weight polypropylene resin with MFR 1,000 g / 10 min, and N, N′-dicyclohexyl-2 as ⁇ crystal nucleating agent , 6-Naphthalenedicarboxamide 0.3 parts by mass, “IRGANOX (registered trademark)” 1010 as an antioxidant, 0.1 parts by mass of “IRGAFOS (registered trademark)” 168, and 0.05 mg of calcium behenate as a lubricant Feed the raw material from the weighing hopper to the twin screw extruder so that the mass part is mixed at this ratio, melt and knead, discharge the strand from the die, cool and solidify in a 25 ° C water bath, cut into chips Thus, a polypropylene resin composition (a) is prepared. At this time, the melting temperature is preferably 280 to 310 ° C.
  • the polypropylene resin composition (a) is supplied to a single screw extruder, and melt extrusion is performed at 200 to 230 ° C. And after removing a foreign material, a modified polymer, etc. with the filter installed in the middle of the polymer pipe
  • a plurality of extruders are used to form a laminated structure by a feed block method or a multi-manifold method, and then discharged from a T-die onto a cast drum. It can be a sheet.
  • the cast drum preferably has a surface temperature of 105 to 130 ° C.
  • the forming of the end portion of the sheet affects the subsequent stretchability, and therefore it is preferable that 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 from the state in which the entire sheet is in close contact with the drum.
  • the obtained cast sheet is biaxially oriented to form pores in the film.
  • a biaxial orientation 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 in which the film is stretched in the width direction and then stretched in the longitudinal direction.
  • the simultaneous biaxial stretching method can be used, but it is preferable to adopt the sequential biaxial stretching method in that it is easy to obtain a film having a balance between the separator resistance and the mechanical strength, particularly after stretching in the longitudinal direction.
  • the film is preferably stretched in the width direction.
  • stretching is performed in the longitudinal direction while controlling the temperature of the cast sheet.
  • 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 is preferably 90 to 140 ° C., more preferably 100 to 130 ° C., and particularly preferably 115 to 125 ° C., from the viewpoint of achieving both the R2 / R1 value and the mechanical strength. If it is less than 90 degreeC, a film may fracture
  • the separator resistance decreases.
  • film breakage is likely to occur in the next transverse stretching process, and the air permeability resistance becomes too low and the mechanical strength may decrease. is there.
  • the transverse stretching temperature is preferably 130 to 155 ° C., more preferably 145 to 155 ° C., from the viewpoint of achieving both the R2 / R1 value and the mechanical strength. If it is less than 130 degreeC, a film may fracture
  • the draw ratio in the width direction is preferably 2 to 12 times from the viewpoint of improving the tensile strength. More preferably, it is 4 to 11 times, and further preferably 7 to 10 times. If it is less than twice, the air resistance may increase or the tensile strength in the width direction may decrease. If it exceeds 12 times, the film may break.
  • the transverse stretching speed at this time is preferably 500 to 6,000% / min, more preferably 1,000 to 5,000% / min.
  • the area ratio (longitudinal stretch ratio ⁇ transverse stretch ratio) is preferably high, specifically 20 times or more, more preferably 30 times or more. 45 times or more is particularly preferable.
  • the area magnification is low, specifically, when it is less than 20 times, it is difficult to reduce air resistance and improve mechanical strength.
  • the upper limit of the area magnification is not particularly provided, but if it exceeds 60 times, the film forming property is deteriorated and may be easily broken.
  • the heat treatment step includes a heat setting zone (hereinafter referred to as HS1 zone) in which heat treatment is performed with the width after transverse stretching, and a relaxation zone (hereinafter referred to as Rx zone) in which heat treatment is performed while relaxing the film by narrowing the width of the tenter.
  • HS1 zone heat setting zone
  • Rx zone relaxation zone
  • HS2 zone heat fixing zone
  • the temperature of the HS1 zone is preferably 140 to 165 ° C., more preferably 150 to 160 ° C. from the viewpoint of achieving both R2 / R1 value and mechanical strength. If it is lower than 140 ° C., the thermal shrinkage in the width direction may increase. If the temperature exceeds 165 ° C, the relaxation of the orientation of the film is too large, so that the relaxation rate cannot be increased in the subsequent Rx zone, and it may be difficult to achieve both R2 / R1 and mechanical strength. In some cases, the air resistance is increased due to melting of the polymer.
  • the heat treatment time in the HS1 zone is preferably 0.1 seconds or more and 10 seconds or less from the viewpoint of achieving both the thermal shrinkage in the width direction and the productivity.
  • the relaxation rate in the Rx zone in the present invention is preferably from 5 to 35%, more preferably from 10 to 25%, from the viewpoint of reducing the heat shrinkage rate in addition to the improvement of the value of R2 / R1 and mechanical strength. preferable. If the relaxation rate is less than 5%, the thermal shrinkage rate may increase. If it exceeds 35%, air resistance may increase, and thickness unevenness and flatness in the width direction may decrease.
  • the temperature of the Rx zone is preferably 155 to 170 ° C., more preferably 160 to 165 ° C., from the viewpoint of the value of R2 / R1 and the reduction of the heat shrinkage rate.
  • the temperature of the Rx zone is less than 155 ° C., the shrinkage stress for relaxation is lowered, and the above-described high relaxation rate may not be achieved, and the thermal shrinkage rate in the width direction may be increased.
  • the temperature exceeds 170 ° C. the polymer around the pores may melt due to high temperature, and the separator resistance may increase.
  • the relaxation rate in the Rx zone is preferably 100 to 1,000% / min, and more preferably 150 to 500% / min.
  • the relaxation rate is less than 100% / min, it is necessary to slow down the film forming rate or increase the tenter length, which may be inferior in productivity. If it exceeds 1,000% / min, the speed at which the film shrinks becomes slower than the speed at which the rail width of the tenter shrinks, the film flutters in the tenter and breaks, or the physical properties in the width direction are uneven and the flatness is lowered. There is a case.
  • the temperature of the HS2 zone is preferably 155 to 165 ° C, more preferably 160 to 165 ° C, from the viewpoint of achieving both the R2 / R1 value and the mechanical strength.
  • the temperature is lower than 155 ° C., the tension of the film after thermal relaxation becomes insufficient, which may cause uneven physical properties in the width direction and a decrease in flatness, or increase the heat shrinkage rate in the width direction.
  • the higher the temperature of the HS zone 2 the higher the mechanical strength tends to be. If it exceeds 165 ° C., the polymer around the pores may melt due to the high temperature and the separator resistance may increase.
  • the heat treatment time in the HS2 zone is preferably 0.1 seconds or more and 10 seconds or less from the viewpoint of physical property unevenness in the width direction and flatness and productivity.
  • the film after the heat setting step is removed by slitting the ears gripped by the tenter clip, and wound around the core with a winder to obtain a product. Thereafter, a coating layer may be provided on at least one side to form a porous film having a functional layer.
  • the porous polypropylene film of the present invention has a low R2 / R1 value of the separator resistance ratio before and after application of the application simulation liquid, a functional layer is formed using a coating liquid containing an organic solvent.
  • a coating liquid containing an organic solvent As the coating method, various methods can be used. For example, at least one organic solvent selected from acetone, ethanol, tetrahydrofuran, N-methyl-2-pyrrolidone and the like is used as a solvent,
  • the porous polypropylene of the present invention is prepared using a die coating method or a gravure coating method by adding a functional polymer for binding them and an additive such as a thickener as necessary to prepare a coating solution.
  • a porous film having a functional layer can be obtained by coating on at least one side of the film and drying the organic solvent using a drying oven.
  • the porous polypropylene film of the present invention not only has excellent heat resistance, mechanical strength, and productivity, but also has excellent extrusion stability, so that it can be used for packaging products, sanitary products, agricultural products, building products, medical products, separation membranes, light. Although it can be used for diffuser plates and reflective sheet applications, it is difficult to increase resistance when a functional layer that imparts or improves performance such as heat resistance and adhesion to electrodes is used. Can be preferably used.
  • examples of the electricity storage device include a non-aqueous electrolyte secondary battery represented by a lithium ion secondary battery, and an electric double layer capacitor such as a lithium ion capacitor.
  • the separator for an electricity storage device formed by laminating a functional layer on the porous polypropylene film of the present invention is not only excellent in separator resistance and productivity, but also excellent in heat resistance and short circuit resistance. It can be preferably used as a power storage device separator for power supply devices such as electric vehicles and hybrid electric vehicles.
  • the separator using the porous polypropylene film of the present invention, the positive electrode, the negative electrode, and the electrolytic solution can be suitably used for power supplies of industrial equipment and automobiles because of the excellent characteristics of the separator.
  • the bar coating machine # 10 manufactured by Matsuo Sangyo Co., Ltd. was moved in the longitudinal direction (bar coating method) to apply the coating liquid. It was dried with hot air at 1 ° C. for 1 minute. Thereafter, the four corners were cut off to obtain a coating simulation film.
  • the coating simulation liquid was prepared without mixing additives such as heat-resistant resin, inorganic particles, and thickeners that form the functional layer. Was used. The characteristics were measured and evaluated by the following methods.
  • the thickness of the porous polypropylene film was measured using a contact-type film thickness meter, Mitsutyo Lightmatic VL-50A (10.5 mm ⁇ carbide spherical surface probe, measuring load 0.06 N). The measurement was performed 10 times at different locations, and the average value was taken as the thickness of the porous polypropylene film.
  • Air permeability resistance A square having a size of 100 mm ⁇ 100 mm was cut from a porous polypropylene film or a coating simulation film, and used as a sample. Using a JIS P 8117 (1998) B-type Gurley tester, the permeation time of 100 ml of air was measured at 23 ° C. and a relative humidity of 65%. The measurement was performed three times by changing the sample, and the average value of the permeation time was taken as the air resistance of the film.
  • R1 or R2 A porous polypropylene film or a coating simulation film was punched into a circle having a diameter of 24 mm. From the bottom, SUS plate with a diameter of 16 mm, porous polypropylene film or coating simulation film, SUS plate with a diameter of 16 mm are stacked in this order, and a stainless steel small container with a lid (manufactured by Hosen Co., Ltd., HS cell, spring pressure 1 kgf). Stowed. The container and the lid are insulated, and the container and the lid are in contact with the SUS plate.
  • the melting of the ⁇ crystal is the melting peak of the ⁇ crystal
  • the melting peak of the ⁇ crystal is taken as the melting peak of the base
  • a sample prepared under the following conditions is determined to have ⁇ -crystal forming ability when the K value calculated from each diffraction peak intensity of the diffraction profile obtained by the 2 ⁇ / ⁇ scan is 0.3 or more.
  • sample preparation conditions and the measurement conditions of the wide angle X-ray diffraction method are shown below.
  • ⁇ sample The direction of the film is aligned, and the samples are stacked so that the sample thickness after hot press preparation is about 1 mm.
  • This sample is sandwiched between two aluminum plates having a thickness of 0.5 mm, and is hot-pressed at 280 ° C. for 3 minutes to be melted and compressed to make the polymer chain substantially non-oriented.
  • the obtained sheet is crystallized by being immersed in boiling water at 100 ° C. for 5 minutes immediately after being taken out together with the aluminum plate. Then, a sample obtained by cutting a sheet obtained by cooling in an atmosphere at 25 ° C. is used for measurement.
  • ⁇ Wide-angle X-ray diffraction method measurement conditions In accordance with the above conditions, an X-ray diffraction profile is obtained by 2 ⁇ / ⁇ scanning.
  • the K value is an empirical value indicating the ratio of ⁇ crystals.
  • K H ⁇ 1 / ⁇ H ⁇ 1 + (H ⁇ 1 + H ⁇ 2 + H ⁇ 3) ⁇
  • the structure of the polypropylene crystal type ( ⁇ crystal, ⁇ crystal), the obtained wide-angle X-ray diffraction profile, etc. are described in, for example, Edward P. Moore Jr. Written by "Polypropylene Handbook", Industrial Research Committee (1998), p.
  • MFR Melt flow rate
  • Breaking strength A porous polypropylene film was cut into a rectangle having a length of 150 mm and a width of 10 mm and used as a sample. In addition, the length direction of 150 mm was matched with the width direction of the film. Using a tensile tester (Orientec Tensilon UCT-100), the initial chuck distance was 50 mm, the tensile speed was 300 mm / min, and a tensile test was performed in the width direction of the film. A load applied to the film when the sample broke was read, and a value obtained by dividing the load by the cross-sectional area of the sample before the test (film thickness ⁇ width (10 mm)) was used as an index of the breaking strength. The measurement was performed 5 times for each sample, and the average value was evaluated.
  • a tensile tester Orientec Tensilon UCT-100
  • Tm Melting point (Tm) of polypropylene resin 5 mg of polypropylene resin used for the porous polypropylene film was sampled in an aluminum pan and measured using a differential scanning calorimeter (Seiko Denshi Kogyo RDC220). First, the temperature was raised from room temperature to 220 ° C. at 40 ° C./min in a nitrogen atmosphere (first run), held for 5 minutes, and then cooled to 20 ° C. at 10 ° C./min (first run). The melting peak observed when the temperature was raised again (second run) at 10 ° C./min after holding for 5 minutes was taken as the melting point of the polypropylene resin.
  • the obtained polypropylene composition (I) is supplied to a uniaxial melt extruder, melt extruded at 210 ° C., foreign matter is removed with a 60 ⁇ m cut sintered filter, and the surface temperature is adjusted to 122 ° C. with a T-die.
  • a cast sheet was obtained by discharging to a controlled cast drum.
  • preheating was performed using a ceramic roll heated to 123 ° C., and the film was stretched 5.0 times in the longitudinal direction of the film.
  • the edge part was hold
  • heat treatment was performed at 150 ° C. for 2 seconds while maintaining the distance between the clips after stretching (HS1 zone), and further relaxation was performed to achieve a relaxation rate of 17% at 163 ° C. for 5 seconds (Rx zone). Heat treatment was performed at 163 ° C. for 5 seconds while maintaining the distance between the clips (HS2 zone).
  • gripped with the clip was cut and removed, and the porous polypropylene film of thickness 21 micrometers and air permeation resistance 140 second / 100 ml was obtained.
  • the air resistance of the coating simulation film prepared using this porous polypropylene film was 290 seconds / 100 ml.
  • Example 2 In Example 1, a porous polypropylene film having a thickness of 22 ⁇ m was obtained by the same raw material and film forming method as in Example 1 except that the draw ratio in the longitudinal direction was 4.5 times.
  • a porous polypropylene film having a thickness of 22 ⁇ m was obtained by the same film forming method as in Example 1 using a chip of the polypropylene composition (II).
  • a chip of the polypropylene resin composition (III) a porous polypropylene film having a thickness of 23 ⁇ m was obtained by the same film forming method as in Example 1.
  • Example 7 In Example 1, heat treatment (HS1 zone) was performed at 163 ° C. for 2 seconds while maintaining the distance between the clips after stretching in the width direction at 9.5 times at a transverse stretching speed of 1,800% / min in the width direction. Except for the above, a porous polypropylene film having a thickness of 21 ⁇ m was obtained by the same raw material and film forming method as in Example 1.
  • the mixture is melt-kneaded, discharged from a die, cooled and solidified in a 25 ° C. water bath, cut into chips, and a polypropylene resin composition (VI) chip is formed. Obtained.
  • a chip of the polypropylene resin composition (VI) a porous polypropylene film having a thickness of 23 ⁇ m was obtained by the same film forming method as in Example 1.
  • the raw material is supplied from the weighing hopper to the twin screw extruder so that the parts are mixed at this ratio, melt kneaded at 240 ° C., discharged from the die in a strand shape, cooled and solidified in a 25 ° C.
  • the edge part was hold
  • heat treatment was performed at 150 ° C. for 2 seconds (HS1 zone) while maintaining the distance between the clips after stretching (HS1 zone), and further relaxed at a relaxation rate of 17% at 163 ° C. for 5 seconds (Rx zone). Heat treatment was performed at 163 ° C. for 5 seconds while keeping the distance (HS2 zone). Then, the ear
  • Example 3 (Comparative Example 3)
  • heat treatment was performed at 150 ° C. for 2 seconds while maintaining the distance between the clips after stretching in the width direction (HS1 zone), and further relaxation was performed so that the relaxation rate became 5% at 153 ° C. for 5 seconds (Rx zone).
  • a porous polypropylene film having a thickness of 21 ⁇ m was obtained by the same raw material and film forming method as in Example 1 except that heat treatment was performed at 153 ° C. for 5 seconds (HS2 zone) while maintaining the distance between the clips after relaxation. .
  • the value of R2 / R1 is low, and thus the function of imparting or improving the performance such as heat resistance and adhesion to the electrode. It can be suitably used as a base material for a separator for an electricity storage device having a layer.
  • the value of R2 / R1 is high, and it is difficult to use it as a base material for an electricity storage device separator having a functional layer that imparts or improves performance such as heat resistance and adhesion to electrodes.
  • porous polypropylene film of the present invention When the porous polypropylene film of the present invention is provided with a functional layer that imparts or improves performance such as heat resistance and adhesion with an electrode, it suppresses an increase in separator resistance and can exhibit excellent battery characteristics. It can be suitably used as a separator for an electricity storage device.

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  • Electrochemistry (AREA)
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  • Engineering & Computer Science (AREA)
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Abstract

Cette invention a pour objectif de pourvoir à un film en polypropylène poreux qui supprime l'accroissement de la résistance du séparateur dans les cas où ledit film en polypropylène poreux est pourvu d'une couche fonctionnelle, qui confère ou améliore des propriétés telles que la résistance thermique et l'adhérence à une électrode. Pour ce faire, le film en polypropylène poreux selon l'invention est principalement constitué d'une résine polypropylène, et est caractérisé en ce que la résistance de séparateur (R1 (Ω)) du film en polypropylène poreux et sa résistance de séparateur (R2 (Ω)) après application d'un liquide de revêtement simulé qui est composé d'un polymère fonctionnel et d'un solvant organique sur le film en polypropylène poreux et séchage dudit liquide de revêtement simulé ainsi appliqué satisfont la formule (1). R2/R1 ≤ 1,2 (1)
PCT/JP2013/068169 2012-07-04 2013-07-02 Film en polypropylène poreux, séparateur pour dispositifs de stockage de l'électricité, et dispositif de stockage de l'électricité WO2014007260A1 (fr)

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CN201380030174.6A CN104395382B (zh) 2012-07-04 2013-07-02 多孔性聚丙烯膜、蓄电装置用隔膜及蓄电装置
JP2013552793A JP5626486B2 (ja) 2012-07-04 2013-07-02 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

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WO2017038843A1 (fr) * 2015-08-31 2017-03-09 凸版印刷株式会社 Feuille décorative et procédé de fabrication de feuille décorative
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TWI770004B (zh) * 2016-03-29 2022-07-11 日商東麗股份有限公司 聚烯烴微多孔膜及其製造方法以及電池用隔膜及其製造方法
CN107522941A (zh) * 2017-07-28 2017-12-29 广东圆融新材料有限公司 一种耐热透明抗冲pvdf/pp合金材料及其制备方法
CN109422613B (zh) * 2017-08-29 2021-06-11 中国石油化工股份有限公司 从裂解汽油中分离所得粗苯乙烯的脱色方法及装置
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KR20220165920A (ko) * 2021-06-09 2022-12-16 주식회사 엘지에너지솔루션 접착력이 개선된 이차전지용 분리막

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