WO2010058789A1 - Composition de résine de polyoléfine et ses applications - Google Patents

Composition de résine de polyoléfine et ses applications Download PDF

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Publication number
WO2010058789A1
WO2010058789A1 PCT/JP2009/069557 JP2009069557W WO2010058789A1 WO 2010058789 A1 WO2010058789 A1 WO 2010058789A1 JP 2009069557 W JP2009069557 W JP 2009069557W WO 2010058789 A1 WO2010058789 A1 WO 2010058789A1
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resin composition
polyolefin resin
mass
molecular weight
weight polyethylene
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PCT/JP2009/069557
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English (en)
Japanese (ja)
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昌太 阿部
森田　淳
和人 杉山
峰雄 久保
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三井化学株式会社
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Priority to JP2010539238A priority Critical patent/JPWO2010058789A1/ja
Priority to EP09827570.4A priority patent/EP2351790A4/fr
Priority to US13/127,723 priority patent/US8349957B2/en
Priority to CN2009801451000A priority patent/CN102209751B/zh
Publication of WO2010058789A1 publication Critical patent/WO2010058789A1/fr

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    • 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
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • 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
    • C08L23/04—Homopolymers or copolymers of ethene
    • 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
    • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/068—Ultra high molecular weight polyethylene
    • 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 polyolefin resin composition comprising an ultrahigh molecular weight polyethylene and a polymer containing a repeating unit derived from 4-methyl-1-pentene, and uses thereof. Specifically, it consists of a polyolefin resin composition excellent in mechanical characteristics and dimensional stability, particularly excellent in heat resistance, and the resin composition, and has excellent mechanical characteristics, dimensional stability and heat resistance, particularly in meltdown characteristics.
  • the present invention relates to an excellent film, a microporous membrane excellent in permeability and shutdown characteristics in addition to the above properties, and uses thereof.
  • Polyolefin microporous membranes include battery separators used in lithium secondary batteries, nickel-hydrogen batteries, nickel-cadmium batteries, polymer batteries, etc., separators for electrolytic capacitors, reverse osmosis filtration membranes, ultrafiltration membranes, microfiltration membranes, etc. It is widely used in various filters, breathable waterproof clothing, medical materials, etc.
  • the polyolefin microporous membrane When the polyolefin microporous membrane is used as a battery separator, particularly a lithium ion battery separator, its performance is deeply related to battery characteristics, battery productivity, and battery safety. Therefore, the polyolefin microporous membrane is required to have excellent mechanical characteristics, heat resistance, permeability, dimensional stability, shutdown characteristics, meltdown characteristics, and the like. For example, when the mechanical strength is low, when used as a battery separator, the voltage of the battery may decrease due to a short circuit of the electrodes.
  • a microporous film made of polyethylene alone has a low mechanical strength, and therefore a microporous film made of ultrahigh molecular weight polyethylene has been proposed to improve the mechanical strength.
  • Patent Document 1 Patent Document 2, and the like have proposed a separator made of a composition containing an ultrahigh molecular weight polyolefin as an essential component.
  • Patent Document 3 proposes a separator made of polyethylene and polypropylene.
  • Patent Document 4 proposes a microporous film made of polyethylene and a non-polyethylene thermoplastic resin.
  • polyethylene ultrahigh molecular weight polyethylene has been proposed, but what is used in this document is a polyethylene composition containing a high density polyethylene as a main component (a mixture of ultrahigh molecular weight polyethylene and high density polyethylene). And the molecular weight is not high.
  • Patent Document 5 proposes a polyolefin microporous porous membrane made of a mixture of polyethylene and polymethylpentene.
  • a polyolefin microporous porous membrane made of a mixture of polyethylene and polymethylpentene.
  • a mixture of high-density polyethylene and polymethylpentene polyolefin resin
  • the obtained microporous membrane is insufficient in terms of strength and heat resistance.
  • the document states that when ultra high molecular weight polyethylene is used, a uniform composition cannot be obtained unless the molecular weight of the whole system is 1,000,000 or less. Yes. For this reason, the document does not disclose that the performance of the microporous membrane can be improved by increasing the molecular weight of the polyolefin resin.
  • a polyolefin resin composition having excellent heat resistance and particularly suitable for a microporous membrane is desired in the market in addition to mechanical properties, permeability, dimensional stability, and shutdown properties.
  • An object of the present invention is to provide a polyolefin resin composition excellent in mechanical properties and dimensional stability, particularly excellent in heat resistance, and obtained from the polyolefin resin composition, so that mechanical properties, dimensional stability, It is an object to provide a film excellent in heat resistance, particularly excellent in meltdown characteristics, a microporous film excellent in permeability and shutdown characteristics in addition to the above characteristics, and use thereof.
  • the ultrahigh molecular weight polyethylene (A) having a specific intrinsic viscosity and a polymer (B) containing a repeating unit derived from 4-methyl-1-pentene (B) (
  • the polyolefin resin composition (C) having a specific amount may be referred to as polymethylpentene)
  • a resin composition can be obtained, and a film and a microporous membrane obtained from the polyolefin resin composition are excellent in mechanical properties, permeability, dimensional stability, and heat resistance, particularly in shutdown properties and meltdown properties.
  • the present invention was found.
  • the polyolefin resin composition (C) of the present invention has an intrinsic viscosity [ ⁇ ] measured in decalin at 135 ° C. according to (i) ASTM D4020 in 100% by mass of the polyolefin resin composition (C).
  • the ultra high molecular weight polyethylene (A) is 79 to 50% by mass with respect to 100% by mass of the polyolefin resin composition (C), and is a polymer containing repeating units derived from the 4-methyl-1-pentene ( B) is preferably 21 to 50% by mass.
  • the polyolefin resin composition (C) is preferably for a microporous membrane, particularly for a battery separator.
  • the composition for a microporous membrane of the present invention is characterized by comprising the polyolefin resin composition (C) and a plasticizer.
  • the film, microporous membrane and battery separator of the present invention are obtained from the polyolefin resin composition (C).
  • the method for producing a microporous membrane of the present invention includes extruding the polyolefin composition for a microporous membrane with a die and cooling to form a sheet, then stretching the sheet, and then extracting and removing the plasticizer, After the sheet is stretched, the plasticizer is extracted and removed, and further stretched.
  • seat is a gel form.
  • the polyolefin film obtained from the polyolefin resin composition of the present invention is excellent in mechanical properties, dimensional stability, heat resistance, particularly excellent in meltdown properties, and is microporous obtained from the polyolefin resin composition of the present invention. Since the membrane is excellent in permeability and shutdown characteristics in addition to the above properties, it can be suitably used, for example, as a battery separator for a lithium ion battery comprising a polyolefin microporous membrane. Therefore, the polyolefin resin composition of the present invention has an extremely high industrial value.
  • the polyolefin resin composition (C) according to the present invention contains a specific ultrahigh molecular weight polyethylene (A) and a polymer (B) containing a repeating unit derived from 4-methyl-1-pentene at a specific ratio. It becomes.
  • the ultrahigh molecular weight polyethylene (A) as the main component contained in the polyolefin resin composition (C) of the present invention is a homopolymer of ethylene having a specific intrinsic viscosity [ ⁇ ], or ethylene and propylene, 1-butene , 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 4-methyl-1-pentene or 3-methyl-1-pentene and other ⁇ -olefin copolymers.
  • a polymer containing ethylene as a main component is preferable in terms of excellent permeability and shutdown characteristics of the microporous membrane.
  • the lower limit of the intrinsic viscosity [ ⁇ ] of the ultrahigh molecular weight polyethylene (A) according to the present invention measured in decalin at 135 ° C. according to ASTM D4020 is 3.5 dl / g, preferably 4.0 dl / g, More preferably, it is 5.0 dl / g, More preferably, it is 8.0 dl / g, Most preferably, it is 10.0 dl / g.
  • the upper limit of the intrinsic viscosity [ ⁇ ] is 35 dl / g, preferably 30 dl / g, more preferably 26 dl / g, more preferably 23 dl / g, and particularly preferably 20 dl / g.
  • the intrinsic viscosity [ ⁇ ] is a value smaller than 3.5 dl / g, the strength of the resulting film or microporous film made of the polyolefin resin composition (C) is lowered. On the other hand, if the intrinsic viscosity [ ⁇ ] is larger than 35 dl / g, it becomes difficult to form a film containing ultrahigh molecular weight polyethylene and a microporous film.
  • the mechanical properties and dimensional stability of the ultrahigh molecular weight polyethylene can be more effectively changed to the polyolefin resin composition (C). Can be granted.
  • the ultra high molecular weight polyethylene (A) can be obtained by a conventionally known method.
  • an ethylene monomer is added in the presence of a catalyst. It can be produced by changing the intrinsic viscosity and polymerizing in multiple stages.
  • the copolymer is a copolymer of 4-methyl-1-pentene and an ⁇ -olefin having 2 to 20 carbon atoms, preferably 5 to 20 carbon atoms, other than 4-methyl-1-pentene.
  • examples of the ⁇ -olefin having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, Examples thereof include 1-hexadecene, 1-heptadecene, 1-octadecene, 1-eicocene, and the like. These can be used alone or in combination of two or more.
  • 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-heptadecene and 1-octadecene are preferable, and since they have good rigidity and elastic modulus, 1-decene and 1-dodecene are preferable. Or 1-tetradecene is more preferred.
  • the repeating unit derived from 4-methyl-1-pentene is usually contained in an amount of 80% by mass or more, preferably 90 to 99% by mass, more preferably 95 to 99% by mass. Within the above range, the toughness during film stretching is excellent.
  • the MFR of polymethylpentene (B) measured according to ASTM D1238 at a load of 5.0 kg and a temperature of 260 ° C. is 0.1 to 220 g / 10 min, preferably 0.1 to 20 g / 10 min, more preferably 0.
  • the range is from 1 to 10 g / 10 min.
  • the polymethylpentene (B) can be produced using a known catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst.
  • a known catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst.
  • JP-A-2003-105022 It can be obtained by polymerizing 4-methyl-1-pentene and ethylene or the above ⁇ -olefin in the presence of a catalyst.
  • the polyolefin resin composition (C) of the present invention comprises, in 100% by mass of the polyolefin resin composition (C), more than 40% by mass of the ultrahigh molecular weight polyethylene (A) and 85% by mass or less, and the polymethylpentene ( B) 15% by mass or more and less than 60% by mass, preferably (A) 85 to 50% by mass, and polymethylpentene (B) 15 to 50% by mass, more preferably ultra high molecular weight polyethylene (A) 79 to 50% by mass.
  • ultra-high molecular weight polyethylene (A) and the polymethylpentene (B) are within the above ranges, in addition to the film having excellent mechanical properties, dimensional stability and heat resistance, particularly excellent meltdown properties, and the above properties, A microporous membrane having excellent permeability and shutdown characteristics can be obtained.
  • the film obtained from the polyolefin resin composition (C) in which the ultrahigh molecular weight polyethylene (A) and the polymethylpentene (B) are within the above ranges are excellent effects that have not been known so far with respect to heat resistance. It has become clear in the present invention that
  • the polyolefin resin composition (C) of the present invention is an additive added to a normal polyolefin, for example, a heat stabilizer, a weather stabilizer, a rust inhibitor, as long as the object of the present invention is not impaired.
  • a normal polyolefin for example, a heat stabilizer, a weather stabilizer, a rust inhibitor
  • Various stabilizers known per se such as copper damage resistance stabilizers, antistatic agents, flame retardants, crosslinking agents, crosslinking aids, antistatic agents, slip agents, antiblocking agents, antifogging agents, lubricants, dyes, pigments , Fillers, mineral oil softeners, petroleum resins, waxes and the like may be contained. These additives can be used alone or in combination of two or more.
  • polyolefin resins other than the ultrahigh molecular weight polyethylene (A) and polymethylpentene (B) used in the present invention can be included within the range not impairing the object of the present invention.
  • polyolefin resins include, but are not limited to, high density polyethylene, medium density polyethylene, low density polyethylene, and polypropylene polymers.
  • the polyolefin resin composition (C) is an additive in which ultra-high molecular weight polyethylene (A) and polymethylpentene (B) are blended within the above range, and further, as long as the purpose of the present invention is not impaired. Or mixed with a Banbury mixer, Henschel mixer or the like with the polyolefin resin added, and melted and kneaded using a single screw extruder, double screw extruder, kneader, etc., and granulated or pulverized be able to.
  • the melting temperature in this melt-kneading is usually 160 to 300 ° C., preferably 180 to 280 ° C.
  • the polyolefin resin composition (C) is useful as a raw material for films, microporous membranes, and battery separators, and in particular, battery separators such as lithium secondary batteries, nickel-hydrogen batteries, nickel-cadmium batteries, and polymer batteries. Useful for use.
  • a film comprising the polyolefin resin composition (C) of the present invention (also referred to as a polyolefin film) is obtained by subjecting the polyolefin resin composition (C) to a known method such as a press molding method, an extrusion molding method, an inflation method, or a calendar method. It can be manufactured by film forming.
  • the measurement result of the 50 ⁇ m penetration temperature of TMA by a penetration method with a test load of 50 g and a heating rate of 5.0 ° C./min is different for the film comprising the polyolefin resin composition (C) of the present invention. It became clear for the first time in the present invention that excellent heat resistance greatly deviated from the usual results measured with a mixed composition between resins.
  • the measurement result of the penetration temperature of a film composed of a mixed composition between different resins is expected to be below the additivity line shown in FIG. 3 according to Fox's equation.
  • the details of Fox's formula are described in Bulletin of the American Physical Society, Series 2 (Bulletin of the American Physical Society, Series 2) Vol. 1, No. 3, p. 123 (1956).
  • the film made of the polyolefin resin composition (C) obtained from the present invention has an ultrahigh molecular weight because a convex line can be drawn above the expected additivity line as shown in the plot in FIG.
  • heat resistance is 10 ° C or higher, and depending on the mixing ratio of polymethylpentene (B), 20 ° C or higher is excellent.
  • a characteristic is that it exhibits high heat resistance.
  • the mass ratio of polymethylpentene (B) is 15% by mass or more, preferably 21% by mass or more in 100% by mass of the polyolefin resin composition (C), the polyolefin resin composition obtained from the present invention. It has been found from the results of FIG. 3 that the film made of the product (C) exhibits specifically excellent heat resistance. The reason is not clear, but the following reasons are presumed. That is, it is considered that the polymethylpentene (B) needs to form a continuous layer in order to maintain the film shape (heat resistance) at a high temperature. Ultra high molecular weight polyethylene (A) and polymethylpentene (B) are used in order to form a continuous layer structure by mixing these two polymers. Methyl pentene (B) is considered necessary and its mass ratio is assumed to be the amount described above.
  • the film composed of the polyolefin resin composition (C) of the present invention has a continuous phase in which the phase of ultrahigh molecular weight polyethylene (A) and the phase of polymethylpentene (B) are both.
  • the assumed cause of the specific expression of heat resistance is considered to have been confirmed.
  • the ultrahigh molecular weight polyethylene (A) and the polymethylpentene (B) are within the above range in the polyolefin resin composition (C) of the present invention, the polyethylene (A) and the polymethylpentene (B) Since both of these phases form a continuous phase, the film obtained from the polyolefin resin composition (C) has the mechanical strength and dimensional stability of the ultrahigh molecular weight polyethylene (A) and the heat resistance of the polymethylpentene (B). An excellent film having both properties can be obtained. In addition, such a characteristic cannot be acquired when either the ultrahigh molecular weight polyethylene (A) or the polymethylpentene (B) phase is discontinuous.
  • the film made of the polyolefin resin composition (C) of the present invention can also be used in the form of a multilayer film of the polyolefin resin composition (C) and another resin. It can be manufactured by a method, an extrusion lamination method, a heat lamination method, or the like.
  • the microporous membrane made of the polyolefin resin composition (C) of the present invention is composed of ultrahigh molecular weight polyethylene (A) and polymethylpentene (B) in a specific amount, like the above-described film. Preferably used.
  • the microporous film obtained from the polyolefin resin composition (C) has the mechanical strength, dimensional stability, permeability and shutdown characteristics of the ultrahigh molecular weight polyethylene (A) and the heat resistance of the polymethylpentene (B).
  • an excellent microporous film having both permeability and meltdown characteristics can be obtained.
  • such a characteristic cannot be acquired when either the ultrahigh molecular weight polyethylene (A) or the polymethylpentene (B) phase is discontinuous.
  • the phase of the ultra high molecular weight polyethylene (A) is not good. It has also been found to be continuous (dispersed phase).
  • the microporous membrane made of the polyolefin resin composition obtained at such a ratio is insufficient in permeability and does not exhibit shutdown characteristics. Also, the mechanical strength and dimensional stability are not sufficient. Therefore, ultra high molecular weight polyethylene (A) needs to consist of 50 mass% or more.
  • the polyolefin microporous membrane according to a preferred embodiment of the present invention has the following physical properties. (1) When the film is compressed at 90 ° C. for 5 minutes under a pressure of 2.2 MPa by a pressing machine, the film thickness variation rate before compression is 15% or less. When the film thickness fluctuation rate exceeds 15%, there is a possibility that a short circuit may occur when used as a battery separator, or battery productivity may decrease due to a decrease in yield.
  • the porosity is 25 to 80%. When the porosity is less than 25%, good air permeability cannot be obtained. On the other hand, if it exceeds 80%, the battery safety and impedance cannot be balanced. The porosity is measured by a mass method.
  • the air permeability converted from the Gurley value is 20 to 550 seconds / 100 cc when the film thickness is 16 ⁇ m.
  • the air permeability is 20 to 550 seconds / 100 cc
  • the battery capacity is increased and the cycle characteristics of the battery are also improved.
  • the air permeability exceeds 550 seconds / 100 cc
  • the battery capacity decreases when the polyolefin microporous membrane is used as a battery separator.
  • the air permeability is less than 20 seconds / 100 cc, shutdown is not sufficiently performed when the temperature inside the battery rises.
  • the puncture strength is 2450 mN / 16 ⁇ m or more. If the puncture strength is less than 2450 mN / 16 ⁇ m, a short circuit may occur when the polyolefin microporous membrane is incorporated in a battery as a battery separator.
  • the puncture strength is obtained from the maximum load value when a microporous membrane is pierced at a speed of 2 mm / sec using a needle having a diameter of 1 mm (0.5 mmR).
  • the thermal shrinkage after exposure for 8 hours at 105 ° C. is 5% or less in both the machine direction (MD) and the vertical direction (TD).
  • MD machine direction
  • TD vertical direction
  • the shutdown temperature is 120 to 140 ° C. Note that the shutdown temperature indicates a temperature at which the air permeability becomes 100,000 seconds / 100 cc or more when heated to a predetermined temperature.
  • the meltdown temperature is 165 ° C. or higher, preferably 165 to 190 ° C. In addition, meltdown temperature shows the temperature which film-breaks when it heats up to predetermined temperature.
  • the method for producing a microporous membrane comprising the polyolefin resin composition (C) of the present invention is as follows: (A) a step of melt-kneading ultrahigh molecular weight polyethylene (A), polymethylpentene (B) and a plasticizer to prepare a polyolefin composition; (B) a step of extruding a polyolefin composition from a die and cooling to form a gel sheet; (C) A stretching / plasticizer removing step, and (d) a step of drying the obtained film.
  • plasticizer known ones can be used as long as they are liquid or solid and become liquid at a high temperature and can be extracted into a washing solvent described later.
  • a plasticizer that is liquid at room temperature is used as the plasticizer, stretching at a relatively high magnification tends to be possible.
  • a liquid plasticizer is not particularly limited, but is an aliphatic or cyclic hydrocarbon such as nonane, decane, decalin, paraxylene, undecane, dodecane, or liquid paraffin, and a mineral oil fraction having a boiling point corresponding thereto.
  • liquid phthalates such as dibutyl phthalate and dioctyl phthalate can be used at room temperature.
  • a non-volatile liquid plasticizer such as liquid paraffin.
  • a plasticizer that is solid and liquid at high temperatures. In the hot melt kneaded state, it is mixed with the polyolefin resin composition, but at room temperature, a solid plasticizer may be mixed with a liquid plasticizer. Examples of such a plasticizer include higher aliphatic alcohols such as paraffin wax, stearyl alcohol, and seryl alcohol that are solid at room temperature.
  • the method of melt kneading is not particularly limited, but is usually performed by uniformly kneading in a twin screw extruder. This method is suitable for preparing highly concentrated solutions of polyolefins.
  • the melting temperature is usually 160 to 300 ° C, preferably 180 to 280 ° C.
  • the blending ratio of the polyolefin resin composition (C) and the plasticizer is 1 to 50 parts by mass, preferably 20 to 40 parts by mass, with the total amount being 100 parts by mass. Part.
  • (B) Sheet forming step The melt-kneaded polyolefin composition is directly or via another extruder, or once cooled and pelletized, and then extruded from the die again via the extruder.
  • a sheet die is usually used, but a double cylindrical hollow die, an inflation die, or the like can also be used.
  • the melting temperature at the time of extrusion is usually 140 to 280 ° C.
  • the molded product is formed by cooling the solution thus extruded from the die. In this manner, a phase separation structure in which the polyolefin phase is microphase-separated by the plasticizer can be fixed.
  • the molded product is preferably a gel.
  • the sheet is preferably a gel.
  • Stretching is performed at a predetermined magnification by heating the sheet and then using a normal tenter method, roll method, inflation method, rolling method, or a combination of these methods.
  • the stretching may be uniaxial stretching or biaxial stretching, but biaxial stretching is preferred.
  • biaxial stretching any of simultaneous biaxial stretching, sequential stretching or multistage stretching (for example, a combination of simultaneous biaxial stretching and sequential stretching) may be used, but simultaneous biaxial stretching is particularly preferable.
  • the mechanical strength is improved by stretching.
  • the stretching ratio varies depending on the thickness of the sheet, but when performing uniaxial stretching, it is preferably 2 times or more, more preferably 3 to 30 times. In biaxial stretching, it is preferably at least 3 times or more in any direction, preferably 9 times or more in terms of surface magnification, and more preferably 25 times or more in terms of surface magnification. By setting the surface magnification to 9 times or more, the puncture strength is improved.
  • the stretching temperature is usually 100 to 140 ° C, preferably 110 to 120 ° C.
  • a cleaning solvent is used to remove (wash) the plasticizer. Since the polyolefin phase is phase-separated from the plasticizer, a porous film can be obtained by extracting and removing the plasticizer.
  • the removal (washing) of the plasticizer can be performed using a known washing solvent.
  • Known cleaning solvents include, for example, chlorinated hydrocarbons such as methylene chloride and carbon tetrachloride, hydrocarbons such as pentane, hexane and heptane, fluorinated hydrocarbons such as ethane trifluoride, ethers such as diethyl ether and dioxane, Examples include readily volatile solvents such as methyl ethyl ketone.
  • the washing method can be performed by a method of immersing the stretched film or sheet in a washing solvent, a method of showering the washing film on the stretched film or sheet, or a combination thereof.
  • the washing with the washing solvent is preferably carried out until the remaining plasticizer is less than 1 part by mass with respect to the added amount.
  • the film obtained by stretching and removing the plasticizer can be dried by a heat drying method or an air drying method.
  • the drying temperature is preferably a temperature not higher than the crystal dispersion temperature of polyethylene, and particularly preferably a temperature lower by 5 ° C. or more than the crystal dispersion temperature.
  • the washing solvent remaining in the polyolefin microporous membrane is contained with respect to 100 parts by mass of the membrane weight after drying.
  • the amount is preferably 5 parts by mass or less, and more preferably 3 parts by mass or less. If the drying is insufficient and a large amount of the washing solvent remains in the film, it is not preferable because the porosity decreases and the permeability deteriorates in the subsequent heat treatment.
  • the battery separator constituted by the microporous membrane made of the polyolefin resin composition (C) of the present invention has a microporous blocking temperature (shutdown temperature) of 140 ° C. or lower and a temperature at which membrane breakage occurs (meltdown temperature) of 165.
  • the difference between the meltdown temperature and the shutdown temperature is 25 ° C or more, and the safety is very high as compared with the conventional battery separator.
  • the microporous membrane of the present invention has excellent characteristics as described above.
  • the battery separator of the present invention is particularly useful as a lithium battery separator because it is very useful in terms of safety.
  • the separator of the present invention has a homogeneous three-dimensional porous structure composed of fine pores, not only excellent safety (heat resistance, shutdown characteristics and meltdown characteristics), but also mechanical characteristics, It has excellent porosity and permeability, and is useful as a separator for primary batteries and secondary batteries, such as lithium secondary batteries, nickel-hydrogen batteries, nickel-cadmium batteries, and polymer batteries.
  • TMA temperature at the time of 50 ⁇ m penetration was measured by a penetration method with a test load of 50 g and a heating rate of 5.0 ° C./min.
  • FIG. 2 shows a portion where a phase of ultra high molecular weight polyethylene (A) is continuous (portion indicated by oblique lines).
  • Ultra high molecular weight polyethylene (A) was obtained by the following method. [Preparation of solid catalyst component] Anhydrous magnesium chloride 47.6 g (0.5 mol), decane 0.25 liter, and 2-ethylhexyl alcohol 0.23 liter (1.5 mol) were heated at 130 ° C. for 2 hours to obtain a homogeneous solution. To this solution, 7.4 ml (50 mmol) of ethyl benzoate was added. After cooling the homogeneous solution to room temperature, the whole amount was dropped into 1.5 liters of titanium tetrachloride maintained at ⁇ 5 ° C. over 1 hour with stirring.
  • the reactor used was a 3 L glass separable flask, and the stirring speed was 950 rpm. After completion of the insertion, the temperature of the mixed solution was raised to 90 ° C., and the reaction was performed at 90 ° C. for 2 hours. After completion of the reaction, the solid part was collected by filtration and washed thoroughly with hexane to obtain a highly active finely powdered titanium catalyst component. The composition of the catalyst component thus obtained was 3.9% by mass of titanium.
  • the temperature of the mixture was raised to 110 ° C. over 4.5 hours, and when it reached 110 ° C., 5.2 ml of 2-isobutyl-2-isopropyl-1,3-dimethoxypropane was added, Thereby, it was kept under stirring at the same temperature for 2 hours.
  • the solid part was collected by hot filtration, and the solid part was resuspended in 1000 ml of titanium tetrachloride, and then heated again at 110 ° C. for 2 hours. After completion of the reaction, the solid part was again collected by hot filtration, and washed thoroughly with 90 ° C.
  • the solid titanium catalyst component prepared by the above operation was stored as a decanslurry, but a part of this was dried for the purpose of examining the catalyst composition.
  • the composition of the catalyst component thus obtained was 3.0% by mass of titanium, 17.0% by mass of magnesium, 57% by mass of chlorine, 18.8% by mass of 2-isobutyl-2-isopropyl-1,3-dimethoxypropane.
  • 2-ethylhexyl alcohol was 1.3% by mass.
  • the powder was taken out from the polymerization vessel, filtered and washed, and then dried to obtain a polymer containing a repeating unit derived from 4-methyl-1-pentene (polymethylpentene (B)). .
  • the yield of the obtained polymer (polymethylpentene (B)) was 26 kg, the MFR (load 5.0 kg, temperature 260 ° C.) was 7 g / 10 min, and the density was 940 kg / m 3 .
  • the decene-1 content was 2.4% by mass.
  • the set temperatures C1, C2, and C3 are cylinder temperatures from the bottom of the hopper toward the nozzle tip, and D1 indicates the die temperature.
  • the obtained pellets were inserted into a mold having a thickness of 500 ⁇ m, and the pressure was increased to 10 MPa at a press temperature of 270 ° C. using a press molding machine. After preheating for 5 minutes, depressurization and pressure increase (10 MPa) processes were performed 10 times. Repeated. Next, the pressure was again increased to 10 MPa and held for 5 minutes, and after depressurization, the pressure was increased to 10 MPa with a press molding machine at 50 ° C. and cooled to obtain a film having a thickness of 500 ⁇ m.
  • Example 6 A film was obtained in the same manner as in Example 1 except that ultrahigh molecular weight polyethylene (A) having an intrinsic viscosity [ ⁇ ] of 8.0 dl / g was used. The results are shown in Table 2.
  • Example 7 A film was obtained in the same manner as in Example 1 except that ultrahigh molecular weight polyethylene (A) having an intrinsic viscosity [ ⁇ ] of 20.0 dl / g was used. The results are shown in Table 2.
  • Example 8 A film was obtained in the same manner as in Example 1 except that ultrahigh molecular weight polyethylene (A) having an intrinsic viscosity [ ⁇ ] of 26.0 dl / g was used. The results are shown in Table 2.
  • Example 1 A film was obtained in the same manner as in Example 1 except that the ultrahigh molecular weight polyethylene (A) was changed to 100 parts by mass. The results are shown in Table 3.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Cell Separators (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

L'invention porte sur une composition de résine de polyoléfine de propriétés mécaniques et de stabilité dimensionnelle supérieures, en particulier de résistance à la chaleur supérieure, sur un film de propriétés mécaniques, de stabilité dimensionnelle et de résistance à la chaleur supérieures, en particulier de propriétés de fusion supérieures, et sur une membrane microporeuse ayant, en plus des propriétés mentionnées ci-dessus, une transparence et des propriétés d'arrêt supérieures, ainsi que sur les applications de cette membrane. La composition de résine de polyoléfine (C) est caractérisée par le fait que 100 % en masse de la composition de résine de polyoléfine (C) contiennent 85 à 50 % en masse d'un polyéthylène d'ultra-haute masse moléculaire (A) d'une viscosité intrinsèque spécifiée et 15 à 50 % en masse d'un polymère (B) contenant des unités répétitives provenant du 4-méthyl-1-pentène.
PCT/JP2009/069557 2008-11-19 2009-11-18 Composition de résine de polyoléfine et ses applications WO2010058789A1 (fr)

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EP09827570.4A EP2351790A4 (fr) 2008-11-19 2009-11-18 Composition de résine de polyoléfine et ses applications
US13/127,723 US8349957B2 (en) 2008-11-19 2009-11-18 Polyolefin resin composition and uses thereof
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CN102956858A (zh) * 2011-08-21 2013-03-06 比亚迪股份有限公司 一种电池隔膜及其制备方法
WO2013031795A1 (fr) * 2011-08-31 2013-03-07 三井化学株式会社 Composition de résine polyoléfinique et ses applications
JP2013083766A (ja) * 2011-10-07 2013-05-09 Hamamatsu Photonics Kk ミクロ相分離構造体フィルムの製造方法
WO2018164056A1 (fr) 2017-03-08 2018-09-13 東レ株式会社 Film microporeux polyoléfinique

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TWI638718B (zh) 2017-08-31 2018-10-21 財團法人工業技術研究院 複合膜及其製造方法與包括複合膜的電池
CN112549717A (zh) * 2020-12-03 2021-03-26 深圳大学 一种复合布及其制备方法与应用
CN113121902B (zh) * 2021-03-23 2022-11-22 江西铜业股份有限公司 一种快速成型超高分子量聚乙烯管及其制备方法

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WO2012102129A1 (fr) * 2011-01-25 2012-08-02 東レバッテリーセパレータフィルム株式会社 Membrane microporeuse, son procédé de production, et séparateur pour pile l'utilisant
CN102956858A (zh) * 2011-08-21 2013-03-06 比亚迪股份有限公司 一种电池隔膜及其制备方法
WO2013031795A1 (fr) * 2011-08-31 2013-03-07 三井化学株式会社 Composition de résine polyoléfinique et ses applications
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KR101583166B1 (ko) * 2011-08-31 2016-01-06 미쓰이 가가쿠 가부시키가이샤 폴리올레핀 수지 조성물 및 그 용도
JP2013083766A (ja) * 2011-10-07 2013-05-09 Hamamatsu Photonics Kk ミクロ相分離構造体フィルムの製造方法
WO2018164056A1 (fr) 2017-03-08 2018-09-13 東レ株式会社 Film microporeux polyoléfinique

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