WO2012046753A1 - ポリオレフィン系樹脂多孔フィルム - Google Patents
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- WO2012046753A1 WO2012046753A1 PCT/JP2011/072929 JP2011072929W WO2012046753A1 WO 2012046753 A1 WO2012046753 A1 WO 2012046753A1 JP 2011072929 W JP2011072929 W JP 2011072929W WO 2012046753 A1 WO2012046753 A1 WO 2012046753A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/027—Thermal properties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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- 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
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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
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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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
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/491—Porosity
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
- H01M50/406—Moulding; Embossing; Cutting
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
Definitions
- the present invention relates to a polyolefin-based resin porous film, and can be used as a packaging, sanitary, livestock, agricultural, architectural, medical, separation membrane, light diffusion plate, battery separator, and particularly for a non-aqueous electrolytic battery. It can be suitably used as a separator.
- Porous polypropylene film with many fine communication holes is used for separation membranes used for the production of ultrapure water, purification of chemicals, water treatment, waterproof and moisture-permeable films used for clothing and sanitary materials, and batteries. It is used in various fields such as battery separators.
- As a method for producing such a porous polypropylene film there has been known a method in which an inorganic filler such as calcium carbonate and barium sulfate is melt-mixed with polypropylene to form a film and then stretched and made porous.
- the porous film obtained by this method has a poorly dispersed portion due to the low compatibility of the inorganic filler with polypropylene, and pinholes are likely to occur when stretched and porous. There was a problem that the inorganic filler dropped off and contaminated the process.
- Patent Document 1 Japanese Patent No. 3443934
- Patent Document 2 International Publication No. 2002/066233
- Patent Document 3 describes a method for producing a polypropylene porous film by sequentially biaxially stretching a polypropylene containing acicular ⁇ crystals.
- a longitudinal stretch ratio (hereinafter referred to as “MD”) is used for the purpose of increasing air holes in the porous film and improving air permeability.
- MD stretching ratio A method of increasing the stretching ratio
- TD stretching ratio the transverse stretching ratio
- Patent Document 3 discloses a resin composition obtained by adding an inorganic substance to a ⁇ -crystal polypropylene resin, and Japanese Patent Application Laid-Open No.
- Patent Document 1 and Patent Document 2 in order to develop a high porosity and high air permeability, stretching at a higher magnification is required. There was a problem that the shrinkage rate was increased.
- Patent Document 3 and Patent Document 4 since a large amount of inorganic substances or resin particles are added, pinholes are likely to be generated at the time of stretching and porosity, and during production or use There was a problem that the inorganic material or resin particles dropped off and contaminated the production line. Further, the method described in Patent Document 5 has a problem that not only is it difficult to finely disperse the high melting point resin in polypropylene, but pinholes are easily generated.
- An object of the present invention is to solve the above problems. That is, an object is to provide a polyolefin resin porous film having high air permeability and high porosity.
- the present invention provides a polyolefin resin porous film composed of a resin composition (a) comprising a polyolefin resin as a main component and comprising organic-inorganic hybrid particles (f).
- the addition amount of the organic-inorganic hybrid particles (f) is 1% by mass or more and 10% by mass or less with respect to 100% by mass of the polyolefin resin.
- the air permeability is preferably 10 seconds / 100 ml or more and 200 seconds / 100 ml or less.
- At least a layer composed of the resin composition (a) and a layer composed of a resin composition (b) having a crystal melting peak temperature lower than that of the resin composition (a) are laminated. preferable.
- the present invention provides a separator for a non-aqueous electrolyte secondary battery using the polypropylene resin porous film.
- the present invention is a porous film having high air permeability characteristics and high porosity, and has excellent characteristics such as breakdown characteristics when used as a separator for a non-aqueous electrolyte secondary battery.
- the polyolefin resin porous film can be provided.
- the expression “main component” includes the intention to allow other components to be contained within a range that does not interfere with the function of the main component, unless otherwise specified.
- the content ratio of the components is not specified, but the main component includes 50% by mass or more, preferably 70% by mass or more, particularly preferably 90% by mass or more (including 100%) in the composition. It is.
- “X to Y” (X and Y are arbitrary numbers) is described, it means “preferably greater than X” and “preferably smaller than Y” with the meaning of “X to Y” unless otherwise specified. Is included.
- Polyolefin resin porous film examples of the polyolefin resin used in the polyolefin resin porous film include homopolymers or copolymers obtained by polymerizing ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexane and the like. Among these, a polypropylene resin and a polyethylene resin are preferable.
- Polypropylene resins include homopropylene (propylene homopolymer), or propylene and ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, etc. Random copolymers or block copolymers with ⁇ -olefins may be mentioned. Among these, homopolypropylene is more preferably used from the viewpoint of maintaining the mechanical strength and heat resistance of the laminated porous film.
- the polypropylene resin preferably has an isotactic pentad fraction (mmmm fraction) exhibiting stereoregularity of 80 to 99%. More preferably 83 to 98%, and still more preferably 85 to 97%. If the isotactic pentad fraction is too low, the mechanical strength of the film may be reduced.
- the upper limit of the isotactic pentad fraction is defined by the upper limit that can be obtained industrially at the present time, but this is not the case when a more regular resin is developed in the industrial level in the future. is not.
- the isotactic pentad fraction (mmmm fraction) is the same direction for all five methyl groups that are side chains with respect to the main chain of carbon-carbon bonds composed of any five consecutive propylene units. Means the three-dimensional structure located at or its proportion. Signal assignment of the methyl group region is as follows. It conformed to Zambelli et al (Macromolecules 8,687, (1975)).
- Mw / Mn which is a parameter indicating a molecular weight distribution
- Mw / Mn is 2.0 to 10.0. More preferred is 2.0 to 8.0, and still more preferred is 2.0 to 6.0. This means that the smaller the Mw / Mn is, the narrower the molecular weight distribution is.
- Mw / Mn is less than 2.0, problems such as a decrease in extrusion moldability occur, and it is difficult to produce industrially.
- Mw / Mn exceeds 10.0, low molecular weight components increase, and the mechanical strength of the laminated porous film tends to decrease.
- Mw / Mn is obtained by GPC (gel permeation chromatography) method.
- the melt flow rate (MFR) of the polypropylene resin is not particularly limited, but usually the MFR is preferably 0.5 to 15 g / 10 minutes, and 1.0 to 10 g / 10 minutes. It is more preferable. When the MFR is 0.5 g / 10 min or more, the resin has a high melt viscosity at the time of molding, and sufficient productivity can be ensured. On the other hand, the mechanical strength of the obtained polyolefin resin porous film can be sufficiently maintained by setting it to 15 g / 10 min or less. MFR is measured according to JIS K7210 under conditions of a temperature of 230 ° C. and a load of 2.16 kg.
- polypropylene resin examples include trade names “Novatech PP” “WINTEC” (manufactured by Nippon Polypro), “Notio” “Toughmer XR” (manufactured by Mitsui Chemicals), “Zeras” “Thermolan” (manufactured by Mitsubishi Chemical) , “Sumitomo Noblen”, “Tough Selenium” (manufactured by Sumitomo Chemical Co., Ltd.), “Prime TPO” (manufactured by Prime Polymer Co., Ltd.), “Adflex”, “Adsyl”, “HMS-PP (PF814)” (manufactured by Sun Allomer Co., Ltd.), “Versify” ",” Inspire “(manufactured by Dow Chemical Co., Ltd.), and other commercially available products can be used.
- the polypropylene resin preferably has ⁇ crystal activity.
- the ⁇ crystal activity can be regarded as an index indicating that the polypropylene resin produced ⁇ crystals in the film-like material before stretching. If the polypropylene resin in the film-like material before stretching produces ⁇ crystals, micropores can be easily formed by stretching, so that a polyolefin resin porous film having high air permeability can be obtained. Can do.
- the presence or absence of “ ⁇ crystal activity” is determined when the crystal melting peak temperature derived from the ⁇ crystal is detected by a differential scanning calorimeter described below and / or X-ray described later.
- a diffraction peak derived from a ⁇ crystal is detected by measurement using a diffractometer, it is determined to have “ ⁇ crystal activity”.
- the polyolefin-based resin porous film is heated at a heating rate of 10 ° C./min from 25 ° C. to 240 ° C. for 1 minute by a differential scanning calorimeter, and then cooled at a cooling rate of 10 ° C. from 240 ° C. to 25 ° C.
- the crystal melting peak temperature (Tm ⁇ ) derived from the ⁇ crystal of the polypropylene resin is detected. If it is, it is determined that it has ⁇ crystal activity.
- the ⁇ crystal activity of the polyolefin resin porous film is calculated by the following formula using the crystal heat of fusion derived from the ⁇ crystal of the polypropylene resin ( ⁇ Hm ⁇ ) and the crystal heat of heat derived from the ⁇ crystal ( ⁇ Hm ⁇ ). is doing.
- ⁇ crystal activity (%) [ ⁇ Hm ⁇ / ( ⁇ Hm ⁇ + ⁇ Hm ⁇ )] ⁇ 100
- the amount of heat of crystal melting derived from the ⁇ crystal ( ⁇ Hm ⁇ ) detected mainly in the range of 145 ° C. or higher and lower than 160 ° C., and mainly detected at 160 ° C. or higher and 170 ° C. or lower.
- the amount of heat of crystal melting ( ⁇ Hm ⁇ ) derived from the ⁇ crystal detected mainly in the range of 120 ° C. or more and less than 140 ° C. It can be calculated from the crystal melting calorie ( ⁇ Hm ⁇ ) derived from the ⁇ crystal detected in the range of from 0 ° C. to 165 ° C.
- the polyolefin resin porous film preferably has a high ⁇ crystal activity, and the ⁇ crystal activity is preferably 20% or more. More preferably, it is 40% or more, and particularly preferably 60% or more. If the polyolefin-based resin porous film has a ⁇ -crystal activity of 20% or more, it indicates that a large amount of ⁇ -crystals of polypropylene-based resin can be produced even in a film-like material before stretching, and it is fine and uniform by stretching. As a result, a separator for a lithium ion lithium battery having high mechanical strength and excellent air permeability can be obtained.
- the upper limit value of the ⁇ crystal activity is not particularly limited, but the higher the ⁇ crystal activity, the more effective the effect is obtained, so the closer it is to 100%, the better.
- the ⁇ crystal activity is the state of the entire polyolefin resin porous film even in the case where the polyolefin resin porous film of the present invention has a single-layer structure or when other porous layers are laminated. Can be measured.
- ⁇ crystal nucleating agent examples include those shown below, but are not particularly limited as long as they increase the formation and growth of ⁇ crystals of polypropylene resin, and two or more types are mixed. May be used.
- examples of the ⁇ crystal nucleating agent include amide compounds; tetraoxaspiro compounds; quinacridones; iron oxides having a nanoscale size; potassium 1,2-hydroxystearate, magnesium benzoate or magnesium succinate, magnesium phthalate, etc.
- Alkali or alkaline earth metal salts of carboxylic acids represented by: aromatic sulfonic acid compounds represented by sodium benzenesulfonate or sodium naphthalenesulfonate; diesters or triesters of dibasic or tribasic carboxylic acids; phthalocyanines Phthalocyanine pigments typified by blue, etc .; two-component compounds comprising component A which is an organic dibasic acid and component B which is an oxide, hydroxide or salt of a Group IIA metal in the periodic table; cyclic phosphorus compounds And magnesium compound Such composition comprising the like.
- specific types of nucleating agents are described in JP-A No. 2003-306585, JP-A No. 06-289656, and JP-A No. 09-194650.
- ⁇ crystal nucleating agent Commercially available products of ⁇ crystal nucleating agent are ⁇ crystal nucleating agent “NJESTER NU-100” manufactured by Shin Nippon Rika Co., Ltd.
- Specific examples of polypropylene resins to which ⁇ crystal nucleating agent is added include polypropylene “Bepol® B” manufactured by Aristech. -022SP ”, polypropylene manufactured by Borealis“ Beta ( ⁇ ) -PP BE60-7032 ”, polypropylene manufactured by Mayzo“ BNX BETAPP-LN ”, and the like.
- Organic inorganic hybrid particles (f) In the present invention, it is important that the organic-inorganic hybrid particles (f) comprise.
- the organic / inorganic hybrid particle (f) is a composite particle in which an organic polymer and an inorganic material are uniformly distributed in the same particle.
- the characteristics and flexibility of the inorganic material such as wear resistance and heat resistance It is a particle having both characteristics as an organic polymer. Since the particles (f) are contained, since the affinity with the polyolefin resin is high, the adhesion with the polyolefin resin is also good, and at the interface between the polyolefin resin and the particles (f). Delamination hardly occurs.
- organic-inorganic hybrid particles (f) examples include organic silicone fine particles.
- the organic silicone fine particles are composed of a polysiloxane crosslinked structure.
- This polysiloxane crosslinked structure is a structure in which siloxane units form a three-dimensional network structure.
- the present invention does not particularly limit the type and ratio of the siloxane units constituting the polysiloxane crosslinked structure.
- Examples of the polysiloxane crosslinked structure include siloxane units represented by the following chemical formula 1 and siloxane represented by the chemical formula 2 Unit, a siloxane unit represented by the chemical formula 3, a siloxane unit represented by the chemical formula 4, a siloxane unit represented by the chemical formula 5 and a siloxane unit represented by the chemical formula 6, and the following conditions 1 to 3: Those satisfying at the same time are preferred.
- R 1 , R 3 non-reactive hydrocarbon group
- R 2 , R 4 organic group having a reactive group selected from the following reactive group group reactive group group: acryloxy group, methacryloxy group, vinyl group and mercapto group
- the siloxane unit represented by Chemical Formula 1 is a silicic anhydride unit. Further, the siloxane unit represented by Chemical Formula 2 is a hydroxysiloxane unit.
- R 1 in Chemical formula 3 is a non-reactive hydrocarbon group.
- a non-reactive hydrocarbon group include an alkyl group, a cycloalkyl group, an aryl group, an alkylaryl group, an aralkyl group, and the like.
- a C 1 -C such as a methyl group, an ethyl group, a propyl group, etc. 3 alkyl groups are preferred, and methyl groups are more preferred.
- Examples of the siloxane unit represented by Chemical Formula 3 include a methylsiloxane unit, an ethylsiloxane unit, and a propylsiloxane unit, with a methylsiloxane unit being preferred.
- R 2 in Chemical formula 4 is an organic group having a specific reactive group.
- the specific reactive group include acryloxy group, methacryloxy group, vinyl group, and mercapto group.
- the organic group having such a reactive group are 1) an organic group having an acryloxy group such as 2-acryloxyethyl group, 3-acryloxypropyl group, etc., 2) 2-methacryloxyethyl group, 3-methacryloxypropyl group
- An organic group having a methacryloxy group such as 3) an organic group having a vinyl group such as a vinyl group, an allyl group, an isopropenyl group, or a 2-methylallyl group, and 4) an organic group having a mercapto group, such as a mercaptopropyl group or a mercaptoethyl group.
- the siloxane units represented by Chemical Formula 4 are: 1) siloxane units having an acryloxy group such as 2-acryloxyethylsiloxane units and 3-acryloxypropylsiloxane units, 2) 2-methacryloxyethylsiloxane units, 3-methacryloxy Siloxane units having a methacryloxy group such as propylsiloxane units, 3) siloxane units having a vinyl group such as vinylsiloxane units, allylsiloxane units, isopropenylsiloxane units, and 4) mercapto groups such as mercaptopropylsiloxane units and mercaptoethylsiloxane units.
- siloxane units having an acryloxy group and siloxane units having a methacryloxy group are preferable.
- R 3 in Chemical formula 5 is the same as described above for R 1 in Chemical formula 3 .
- R 4 in Chemical formula 6 is the same as described above for R 2 in Chemical formula 4 .
- Hydroxy siloxane units having inter alia acryloxy group, hydroxy siloxane unit preferably has a methacryloxy group.
- the organosilicone fine particles of the present invention are composed of the polysiloxane crosslinked structure as described above, and have a circular ring shape as a whole, with an average outer diameter of 0.05 to 15 ⁇ m and an average inner diameter. Is 0.01 to 10 ⁇ m, and the difference between the average value of the outer diameter and the average value of the inner diameter is in the range of 0.04 to 5 ⁇ m, but the average value of the outer diameter is 0.1 to 8 ⁇ m. Are preferably in the range of 0.05 to 6 ⁇ m, and the difference between the average value of the outer diameter and the average value of the inner diameter is in the range of 0.5 to 3 ⁇ m.
- both the average value of the outer diameter and the average value of the inner diameter are obtained by subjecting the organosilicone fine particles of the present invention to a scanning electron microscope and extracting 100 of the arbitrary 100 extracted from the secondary electron image. It is the value which measured the diameter and the internal diameter, respectively, and calculated
- the method for producing the organosilicone fine particles of the present invention is a method for producing the aforementioned organosilicone fine particles of the present invention, which is a silanol group-forming silicon compound represented by the following chemical formula 7, and a silanol group-forming property represented by the chemical formula 8:
- the silanol group-forming silicon compound represented by Chemical Formula 7 is a compound that results in the formation of the siloxane unit represented by Chemical Formula 1 and the siloxane unit represented by Chemical Formula 2.
- X in Chemical Formula 7 is 1) an alkoxyethoxy group having 1 to 4 carbon atoms such as a methoxy group or an ethoxy group, and 2) an alkoxyethoxy group having 1 to 4 carbon atoms such as a methoxyethoxy group or a butoxyethoxy group.
- an acyloxy group having 2 to 4 carbon atoms such as an acetoxy group or a propioxy group
- an N, N-dialkylamino group having an alkyl group having 1 to 4 carbon atoms such as a dimethylamino group or a diethylamino group
- a hydroxyl group such as a hydroxyl group
- a halogen atom such as a chlorine atom or a bromine atom
- 7) a hydrogen atom a hydrogen atom.
- Examples of the silanol group-forming silicon compound represented by Chemical Formula 7 include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, trimethoxyethoxysilane, tributoxyethoxysilane, tetraacetoxysilane, tetrapropoxysilane, tetraacetoxysilane, tetra (Dimethylamino) silane, tetra (diethylamino) silane, silanetetraol, chlorosilanetriol, dichlorodisianol, tetrachlorosilane, chlorotrihydrogensilane, and the like, among others, tetramethoxysilane, tetraethoxysilane, tetra Butoxysilane and tetrapropoxysilane are preferred.
- the silanol group-forming silicon compound represented by Chemical formula 8 is a compound that results in the formation of the siloxane unit represented by Chemical formula 3 and the siloxane unit represented by Chemical formula 5.
- R 5 in Chemical formula 8 is the same as described above for R 1 in Chemical formula 3
- Y in Chemical formula 8 is the same as described above for X in Chemical formula 7.
- Examples of the silanol group-forming silicon compound represented by Chemical Formula 8 include methyltrimethoxysilane, ethyltriethoxysilane, propyltributoxysilane, butyltributoxysilane, phenyltrimethoxyethoxysilane, methyltributoxysilane, methyltriacetoxysilane, Examples include methyltripropoxysilane, methyltriacetoxysilane, methyltri (dimethylamino) silane, methyltri (diethylamino) silane, methylsilanetriol, methylchlorodisianol, methyltrichlorosilane, and methyltrihydrogensilane.
- the average particle size of the organic-inorganic hybrid particles (f) is preferably 0.01 ⁇ m or more, more preferably 0.1 ⁇ m or more, and the upper limit is preferably 10.0 ⁇ m or less, more preferably 5.0 ⁇ m or less.
- An average particle size of 0.01 ⁇ m or more is preferable from the viewpoint of dispersibility of the organic-inorganic hybrid particles (f).
- the average particle diameter is 10.0 ⁇ m or more, the pore diameter becomes too large when stretched, which is not preferable from the viewpoint of becoming a pinhole or reducing the mechanical strength.
- the “average particle diameter” is a value measured according to a method using SEM.
- the amount of the organic-inorganic hybrid particles (f) added to the polyolefin resin is preferably 10% by mass or less with respect to 100% by mass of the polyolefin resin.
- the addition amount of the organic-inorganic hybrid particles (f) 10% by mass or less, the mechanical strength of the polyolefin-based resin porous film can be sufficiently secured, and the porous film is sufficiently contaminated by dropping of the particles. It is preferable because it can be suppressed.
- the lower limit of the addition amount of the organic-inorganic hybrid particles (f) is not particularly limited, but is preferably 1% by mass or more, and more preferably 3% by mass or more. If the addition amount of the organic-inorganic hybrid particles (f) is 1% by mass or more, it is preferable because high air permeability characteristics can be sufficiently obtained as compared with the case where the organic-inorganic hybrid particles (f) are not added.
- additives generally added to the resin composition can be added as appropriate within a range that does not significantly impair the effects of the present invention.
- the additive include recycling resin, silica, talc, kaolin, calcium carbonate, and the like, which are added for the purpose of improving and adjusting molding processability, productivity, and various physical properties of the laminated porous film.
- Inorganic particles such as, pigments such as titanium oxide and carbon black, flame retardants, weathering stabilizers, heat stabilizers, antistatic agents, melt viscosity improvers, crosslinking agents, lubricants, nucleating agents, plasticizers, anti-aging agents, Examples thereof include additives such as antioxidants, light stabilizers, ultraviolet absorbers, neutralizers, antifogging agents, antiblocking agents, slip agents, and coloring agents.
- additives such as antioxidants, light stabilizers, ultraviolet absorbers, neutralizers, antifogging agents, antiblocking agents, slip agents, and coloring agents.
- a low molecular weight compound from the viewpoint of air permeability characteristics.
- the low molecular weight compound include low molecular weight polypropylene, low molecular weight polyethylene, low molecular weight polystyrene, alicyclic saturated hydrocarbon resin, wax, and modified products thereof.
- These low molecular compounds can be selected as appropriate compounds by selecting the polyolefin resin of the present invention.
- the polyolefin resin is a polypropylene resin
- the low molecular weight compound is preferably a low molecular weight polypropylene.
- one or more of these low molecular weight compounds may be contained.
- the layer (A layer) which consists of the resin composition (a) which has the said polyolefin resin as a main component, and the layer (b) which consists of a resin composition (b) whose crystal melting peak temperature is lower than the said resin composition (a) ( B layer) is preferably laminated, and as the resin composition (a), a layer made of a resin composition containing a polypropylene resin as a main component, and as the resin composition (b), a polyethylene resin It is more preferable that a layer composed of a resin composition containing as a main component is laminated.
- shutdown characteristics By laminating the layer composed of the resin composition (b), shutdown characteristics (SD characteristics) can be imparted when used as a separator for a non-aqueous electrolyte secondary battery.
- Specific examples include a two-layer structure in which A layers / B layers are stacked, a three-layer structure in which A layers / B layers / A layers, or B layers / A layers / B layers are stacked.
- the physical properties of the polyolefin resin porous film of the present invention can be freely adjusted by the layer constitution, lamination ratio, composition of each layer, and production method.
- the density of the polyethylene resin is preferably 0.910 to 0.970 g / cm 3 , more preferably 0.930 to 0.970 g / cm 3 , and 0.940 to 0.970 g / cm 3. 3 is more preferable.
- a density of 0.910 g / cm 3 or more is preferable because it can have appropriate SD characteristics.
- it is 0.970 g / cm 3 or less, it can have an appropriate SD characteristic and is preferable in that the stretchability is maintained.
- the density is measured according to JIS K7112 using the density gradient tube method. can do.
- the melt flow rate (MFR) of the polyethylene resin is not particularly limited, but usually the MFR is preferably 0.03 to 30 g / 10 minutes, and preferably 0.3 to 10 g / 10 minutes. It is more preferable. If the MFR is 0.03 g / 10 min or more, the melt viscosity of the resin during the molding process is sufficiently low, which is excellent in productivity and preferable. On the other hand, if it is 30 g / 10 minutes or less, since sufficient mechanical strength can be obtained, it is preferable. MFR is measured in accordance with JIS K7210 under conditions of a temperature of 190 ° C. and a load of 2.16 kg.
- the polymerization catalyst for the polyethylene resin is not particularly limited, and may be any one such as a Ziegler type catalyst, a Philips type catalyst, or a Kaminsky type catalyst.
- a polymerization method of the polyethylene resin there are a one-stage polymerization, a two-stage polymerization, or a multistage polymerization more than that, and any method of the polyethylene resin can be used.
- the porosity promoting compound X is not limited, but specific examples thereof include a porosity promoting compound X selected from a modified polyolefin resin, an alicyclic saturated hydrocarbon resin or a modified product thereof, an ethylene copolymer, or a wax. It is more preferable that at least one of them is included. Among these, an alicyclic saturated hydrocarbon resin or a modified product thereof, an ethylene copolymer, or a wax, which is more effective when made porous, is more preferable, and a wax is more preferable from the viewpoint of moldability.
- Examples of alicyclic saturated hydrocarbon resins and modified products thereof include petroleum resins, rosin resins, terpene resins, coumarone resins, indene resins, coumarone-indene resins, and modified products thereof.
- Examples of petroleum resins include aliphatic petroleum resins mainly containing C5 fraction, aromatic petroleum resins mainly containing C9 fraction, copolymer petroleum resins thereof, and alicyclic petroleum resins.
- Examples of the terpene resin include terpene resins and terpene-phenol resins from ⁇ -pinene
- examples of the rosin resin include rosin resins such as gum rosin and utudrodin, and esterified rosin resins modified with glycerin and pentaerythritol.
- the alicyclic saturated hydrocarbon resin and the modified product thereof have relatively good compatibility when mixed with a polyethylene resin, but a petroleum resin is more preferable in terms of color tone and thermal stability, and a hydrogenated petroleum resin is used. More preferably.
- Hydrogenated petroleum resin is obtained by hydrogenating petroleum resin by a conventional method.
- Examples thereof include hydrogenated aliphatic petroleum resins, hydrogenated aromatic petroleum resins, hydrogenated copolymer petroleum resins and hydrogenated alicyclic petroleum resins, and hydrogenated terpene resins.
- hydrogenated petroleum resins hydrogenated alicyclic petroleum resins obtained by copolymerizing and hydrogenating a cyclopentadiene compound and an aromatic vinyl compound are particularly preferable.
- Examples of commercially available hydrogenated petroleum resins include “ALCON” (manufactured by Arakawa Chemical Industries).
- the ethylene copolymer in the present invention is a compound obtained by copolymerizing ethylene and one or more of vinyl acetate, unsaturated carboxylic acid, unsaturated carboxylic acid anhydride, or carboxylic acid ester. It is.
- the ethylene copolymer preferably has an ethylene monomer unit content of 50% by mass or more, more preferably 60% by mass or more, and still more preferably 65% by mass or more.
- the content of ethylene monomer units is preferably 95% by mass or less, more preferably 90% by mass or less, and further preferably 85% by mass or less. If the content of the ethylene monomer unit is within a predetermined range, a porous structure can be formed more efficiently.
- ethylene copolymer those having an MFR (JIS K7210, temperature: 190 ° C., load: 2.16 kg) of 0.1 g / 10 min to 10 g / 10 min are preferably used.
- MFR JIS K7210, temperature: 190 ° C., load: 2.16 kg
- the MFR is 0.1 g / 10 min or more, the extrudability can be maintained satisfactorily.
- the MFR is 10 g / 10 min or less, the strength of the film is hardly lowered, which is preferable.
- the ethylene-based copolymers are “EVAFLEX” (Mitsui / DuPont Polychemical Co., Ltd.), “Novatech EVA” (Nippon Polyethylene Co., Ltd.) as an ethylene-vinyl acetate copolymer, and “NUC” as an ethylene-acrylic acid copolymer.
- the wax in the present invention is an organic compound that satisfies the following properties (a) and (b).
- the melting point is 40 ° C to 200 ° C.
- the melt viscosity at a temperature 10 ° C. higher than the melting point is 50 Pa ⁇ s or less.
- ⁇ For wax including polar or nonpolar wax, polypropylene wax, polyethylene wax and wax modifier.
- paraffin wax, polypropylene wax, polyethylene wax, and microcrystalline wax are preferable because a porous structure can be efficiently formed.
- Commercially available polypropylene waxes include “Mitsui High Wax” (manufactured by Mitsui Chemicals), “Biscol” (manufactured by Sanyo Chemical Industries), “Licocene” (manufactured by Clariant Japan), and polyethylene waxes such as “FT- 115 ”(manufactured by Nippon Seiwa Co., Ltd.) and microcrystalline waxes include“ Hi-Mic ”(manufactured by Nippon Seiwa Co., Ltd.).
- the blending amount of the porosity promoting compound X is set as a lower limit with respect to 100% by mass of the polyethylene resin contained in one layer when the interface between the polyethylene resin and the porosity promoting compound X is peeled to form micropores. 1 mass% or more is preferable, 5 mass% or more is more preferable, and 10 mass% or more is still more preferable.
- the upper limit is preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 30% by mass or less.
- thermoplastic resin may be used as long as the thermal characteristics of the porous film, specifically, the porosity is not impaired.
- thermoplastic resins include styrene resins such as styrene, AS resin, and ABS resin: polyvinyl chloride, fluorine resin, polyethylene terephthalate, polybutylene terephthalate, and polycarbonate.
- ester resins such as polyarylate
- Ether resins such as polyacetal, polyphenylene ether, polysulfone, polyethersulfone, polyetheretherketone or polyphenylene sulfide
- polyamides such as 6 nylon, 6-6 nylon, 6-12 nylon
- thermoplastic resins such as resins.
- thermoplastic elastomer examples include styrene / butadiene, polyolefin, urethane, polyester, polyamide, 1,2-polybutadiene, polyvinyl chloride, and ionomer.
- additives or other components that are generally blended in the resin composition may be included.
- the additive include recycling resin, silica, talc, kaolin, carbonic acid, etc., which are added for the purpose of improving / adjusting the processability, productivity, and various physical properties of the laminated porous film.
- Inorganic particles such as calcium, pigments such as titanium oxide and carbon black, flame retardants, weathering stabilizers, heat stabilizers, antistatic agents, melt viscosity improvers, crosslinking agents, lubricants, nucleating agents, plasticizers, anti-aging agents And additives such as antioxidants, light stabilizers, ultraviolet absorbers, neutralizers, antifogging agents, antiblocking agents, slip agents, and coloring agents.
- the nucleating agent is preferable because it has an effect of controlling the crystal structure of the polyethylene resin and reducing the porous structure at the time of stretching and opening.
- the method for producing the non-porous film is not particularly limited, and a known method may be used. For example, a method of melting a thermoplastic resin composition using an extruder, extruding from a T die, and cooling and solidifying with a cast roll. Is mentioned. Moreover, the method of cutting open the film-like thing manufactured by the tubular method and making it planar is also applicable.
- There are methods for stretching the nonporous film-like material such as a roll stretching method, a rolling method, a tenter stretching method, and a simultaneous biaxial stretching method, and these methods are used alone or in combination of two or more to perform uniaxial stretching or biaxial stretching. . Among these, sequential biaxial stretching is preferable from the viewpoint of controlling the porous structure.
- the production method is roughly classified into the following four types depending on the order of porous formation and lamination.
- (I) A method in which each layer is made porous, and then the layers made porous are laminated or bonded with an adhesive or the like.
- (II) A method of laminating each layer to produce a laminated nonporous film-like material, and then making the nonporous film-like material porous.
- (III) A method in which one of the layers is made porous and then laminated with another layer of a nonporous film to make it porous.
- (IV) A method of forming a laminated porous film by preparing a porous layer and then applying a coating such as inorganic / organic particles or depositing metal particles.
- a coating such as inorganic / organic particles or depositing metal particles.
- a method of forming a porous layer after preparing is particularly preferable.
- the pellets are put into an extruder and extruded from a T-die extrusion die to form a film.
- the type of T die is not particularly limited.
- the T die may be a multi-manifold type for two types and three layers or a feed block type for two types and three layers.
- the gap of the T die to be used is determined from the final required film thickness, stretching conditions, draft ratio, various conditions, etc., but is generally about 0.1 to 3.0 mm, preferably 0.5. -1.0 mm. If it is less than 0.1 mm, it is not preferable from the viewpoint of production speed, and if it is more than 3.0 mm, it is not preferable from the viewpoint of production stability because the draft rate increases.
- the extrusion temperature is appropriately adjusted depending on the flow characteristics and moldability of the resin composition, but is generally preferably 180 to 350 ° C, more preferably 200 to 330 ° C, and further preferably 220 to 300 ° C.
- a temperature of 180 ° C. or higher is preferable because the viscosity of the molten resin is sufficiently low, the moldability is excellent, and the productivity is improved.
- the temperature is set to 350 ° C. or lower, it is possible to suppress the deterioration of the resin composition, and hence the mechanical strength of the resulting polyolefin resin porous film.
- the cooling and solidification temperature by the cast roll is very important in the present invention, and the ratio of the ⁇ crystal of the polyolefin resin in the film can be adjusted.
- the cooling and solidifying temperature of the cast roll is preferably 80 to 150 ° C, more preferably 90 to 140 ° C, and still more preferably 100 to 130 ° C. It is preferable to set the cooling and solidification temperature to 80 ° C. or higher because the ratio of ⁇ crystals in the film can be sufficiently increased. Moreover, it is preferable to set the temperature to 150 ° C. or lower because troubles such as the extruded molten resin sticking to the cast roll and winding are unlikely to occur, and the film can be efficiently formed into a film.
- the ⁇ crystal ratio of the polyolefin resin of the film-like material before stretching is adjusted to 30 to 100% by setting the cast roll in the temperature range. More preferably, it is 40 to 100%, more preferably 50 to 100%, and most preferably 60 to 100%.
- a polyolefin-based resin porous film having good gas permeability can be obtained because it is easily made porous by the subsequent stretching operation.
- the ⁇ crystal ratio in the film before stretching is detected when the film is heated from 25 ° C. to 240 ° C. at a heating rate of 10 ° C./min using a differential scanning calorimeter.
- uniaxial stretching may be performed in the longitudinal direction or the transverse direction, or biaxial stretching may be performed.
- biaxial stretching simultaneous biaxial stretching may be sufficient and sequential biaxial stretching may be sufficient.
- sequential biaxial stretching is more preferable because the stretching conditions can be selected in each stretching step and the porous structure can be easily controlled.
- Biaxial stretching may be simultaneous biaxial stretching or sequential biaxial stretching, but the stretching conditions (magnification, temperature) can be easily selected in each stretching step, and the porous structure can be easily controlled. Biaxial stretching is more preferable.
- the longitudinal direction of the film and the film is referred to as “longitudinal direction”, and the direction perpendicular to the longitudinal direction is referred to as “lateral direction”.
- stretching in the longitudinal direction is referred to as “longitudinal stretching”
- stretching in the direction perpendicular to the longitudinal direction is referred to as “lateral stretching”.
- the stretching temperature needs to be appropriately selected depending on the composition of the resin composition to be used and the crystallization state, but it is preferable to select within the range of the following conditions.
- the stretching temperature needs to be changed appropriately depending on the composition of the resin composition to be used, the crystal melting peak temperature, the crystallinity, etc., but the stretching temperature in the longitudinal stretching is preferably about 0 to 130 ° C., More preferably, it is controlled in the range of 10 to 120 ° C., more preferably 20 to 110 ° C. Further, it is preferably 2 to 10 times, more preferably 3 to 8 times, still more preferably 4 to 7 times.
- the stretching temperature in transverse stretching is generally from 100 to 160 ° C., preferably from 110 to 150 ° C., more preferably from 120 to 140 ° C.
- the preferred longitudinal draw ratio is preferably 1.2 to 10 times, more preferably 1.5 to 8 times, still more preferably 2 to 7 times.
- the stretching speed in the stretching step is preferably 500 to 12000% / min, more preferably 1500 to 10,000% / min, and further preferably 2500 to 8000% / min.
- the area ratio is preferably 3 to 48 times, more preferably 5 to 40 times, and still more preferably 10 to 35 times. It is preferable that the area magnification is 3 times or more because sufficient air permeability characteristics can be obtained. Moreover, it is preferable for the area magnification to be 48 times or less because the occurrence of breakage of the porous film during production can be suppressed, and sufficient molding characteristics can be ensured.
- the polyolefin resin porous film thus obtained is preferably subjected to heat treatment for the purpose of improving dimensional stability.
- the effect of dimensional stability can be expected by setting the temperature to preferably 100 ° C. or higher, more preferably 120 ° C. or higher, and still more preferably 140 ° C. or higher.
- the heat treatment temperature is preferably 170 ° C. or lower, more preferably 165 ° C. or lower, and further preferably 160 ° C. or lower.
- a heat treatment temperature of 170 ° C. or lower is preferable because the polyolefin resin hardly melts by the heat treatment and the porous structure can be maintained.
- a relaxation treatment of 1 to 20% may be performed as necessary.
- a polyolefin resin porous film is obtained by cooling uniformly and winding up.
- the thickness of the polyolefin resin porous film of the present invention is preferably 5 to 100 ⁇ m. More preferably, it is 8 to 50 ⁇ m, and still more preferably 10 to 30 ⁇ m.
- the thickness of the polyolefin resin porous film of the present invention is preferably 5 to 100 ⁇ m. More preferably, it is 8 to 50 ⁇ m, and still more preferably 10 to 30 ⁇ m.
- it is 5 ⁇ m or more, substantially necessary electrical insulation can be obtained. For example, even when a large force is applied to the protruding portion of the electrode, Breaks through the separator for the electrolyte secondary battery and is not easily short-circuited.
- the electrical resistance of a polyolefin-type resin film can be made small if thickness is 100 micrometers or less, the performance of a battery can fully be ensured.
- the porosity is preferably 50% or more, and more preferably 55% or more.
- the porosity is 50% or more, low electrical resistance can be sufficiently secured when used as a separator for a non-aqueous electrolyte secondary battery, and even when used for high output applications, Since energy loss can be suppressed, it is preferable.
- the upper limit is preferably 90% or less, more preferably 85% or less, and still more preferably 80% or less. If the porosity is 90% or less, the mechanical strength of the polyolefin resin porous film can be sufficiently maintained, and it is also preferable from the viewpoint of secondary processing.
- the porosity is measured by the method described in the examples.
- the air permeability of the polyolefin resin porous film of the present invention is preferably 200 seconds / 100 ml or less. If the air permeability is 200 seconds / 100 ml or less, it indicates that the polyolefin-based resin porous film has communication properties, and not only has excellent air permeability properties but also is used as a separator for non-aqueous electrolyte secondary batteries. It is also effective from the viewpoint of output characteristics. On the other hand, the lower limit is not particularly limited, but the air permeability is more preferably 10 seconds / 100 ml or more.
- the air permeability represents the difficulty of air passing through in the film thickness direction, and is specifically expressed by the number necessary for 100 ml of air to pass through the film. Therefore, it means that the smaller the numerical value is, the easier it is to pass through, and the higher numerical value is, the easier it is to pass. That is, a smaller value means better communication in the thickness direction of the film, and a larger value means poor communication in the thickness direction of the film. Communication is the degree of connection of holes in the film thickness direction.
- the air permeability of the polyolefin resin porous film of the present invention is low, it can be used for various applications.
- a low air permeability means that lithium ions can be easily transferred, which is preferable because battery performance is excellent.
- the polyolefin resin porous film of the present invention preferably has SD characteristics when used as a separator for a non-aqueous electrolyte secondary battery.
- the air permeability after heating at 135 ° C. for 5 seconds is preferably 10,000 seconds / 100 ml or more, more preferably 25000 seconds / 100 ml or more, and further preferably 50000 seconds / 100 ml or more.
- the polyolefin resin porous film of the present invention preferably exhibits breakdown characteristics (BD characteristics) at 160 ° C. or higher. That is, in the polyolefin resin porous film of the present invention, the temperature (breakdown temperature) when the breakdown characteristics are manifested is preferably 160 ° C. or higher, more preferably 200 ° C. or higher, still more preferably 250 ° C. or higher. When the breakdown temperature is less than 160 ° C., there is no difference in the temperature at which the shutdown characteristics and breakdown characteristics are manifested.
- the polyolefin resin porous film of the present invention is used as a separator for a non-aqueous electrolyte secondary battery. When used, it is not preferable because a battery with sufficient safety cannot be provided.
- breakdown temperature refers to the lowest temperature among the temperatures at which the polyolefin resin porous film of the present invention breaks when heated by the method described in Examples.
- the thermal shrinkage rate (TD heat shrinkage rate) in the direction perpendicular to the flow direction of the porous film is preferably less than 10%.
- the polyolefin-based resin porous film is used as a separator for a non-aqueous electrolyte secondary battery, it is often incorporated into a non-aqueous electrolyte battery in a stacked form of positive electrode / separator / negative electrode / separator.
- a cylindrical battery generally referred to as 18650 cells is manufactured by winding the stacked units in a band shape.
- the TD heat shrinkage rate is preferably less than 10%.
- the thermal contraction rate (MD thermal contraction rate) in the flow direction is also less than 10% in order to prevent the risk of an internal short circuit similarly to the TD thermal contraction rate.
- a nonaqueous electrolyte secondary battery containing the polyolefin resin porous film of the present invention as a battery separator will be described with reference to FIG.
- Both electrodes of the positive electrode plate 21 and the negative electrode plate 22 are wound in a spiral shape so as to overlap each other via the battery separator 10, and the outside is stopped with a winding tape to form a wound body.
- the winding process will be described in detail.
- One end of the battery separator is passed between the slit portions 1 of the pin, and the pin is slightly rotated to wind one end of the battery separator around the pin. At this time, the surface of the pin is in contact with the heat-resistant layer of the battery separator.
- the positive electrode and the negative electrode are arranged so as to sandwich the battery separator, and the pins are rotated by a winding machine to wind the positive and negative electrodes and the battery separator. After winding, the pin is pulled out of the wound object.
- the wound body in which the positive electrode plate 21, the battery separator 10 and the negative electrode plate 22 are integrally wound is accommodated in a bottomed cylindrical battery case and welded to the positive and negative electrode lead bodies 24 and 25.
- the electrolyte is injected into the battery can, and after the electrolyte has sufficiently penetrated into the battery separator 10 or the like, the positive electrode lid 27 is sealed around the opening periphery of the battery can via the gasket 26, and precharging and aging are performed.
- a cylindrical non-aqueous electrolyte secondary battery is manufactured.
- an electrolytic solution in which a lithium salt is used as an electrolytic solution and is dissolved in an organic solvent is used.
- the organic solvent is not particularly limited.
- esters such as propylene carbonate, ethylene carbonate, butylene carbonate, ⁇ -butyrolactone, ⁇ -valerolactone, dimethyl carbonate, methyl propionate or butyl acetate, and nitriles such as acetonitrile.
- ethers such as tetrahydrofuran, 2-methyltetrahydrofuran or 4-methyl-1,3-dioxolane, or sulfolane.
- LiPF 6 lithium hexafluorophosphate
- an alkali metal or a compound containing an alkali metal integrated with a current collecting material such as a stainless steel net is used.
- the alkali metal include lithium, sodium, and potassium.
- the compound containing an alkali metal include an alloy of an alkali metal and aluminum, lead, indium, potassium, cadmium, tin or magnesium, a compound of an alkali metal and a carbon material, a low potential alkali metal and a metal oxide, and the like. Or a compound with a sulfide or the like.
- the carbon material may be any material that can be doped and dedoped with lithium ions, such as graphite, pyrolytic carbons, cokes, glassy carbons, a fired body of an organic polymer compound, Mesocarbon microbeads, carbon fibers, activated carbon and the like can be used.
- a carbon material having an average particle size of 10 ⁇ m is mixed with a solution in which vinylidene fluoride is dissolved in N-methylpyrrolidone to form a slurry, and this negative electrode mixture slurry is passed through a 70-mesh net. After removing the large particles, uniformly apply to both sides of the negative electrode current collector made of a strip-shaped copper foil having a thickness of 18 ⁇ m and dry, and then compression-molded with a roll press machine, cut, strip-shaped negative electrode plate and We use what we did.
- lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, manganese dioxide, metal oxide such as vanadium pentoxide or chromium oxide, metal sulfide such as molybdenum disulfide, etc. are used as active materials.
- These positive electrode active materials are combined with conductive additives and binders such as polytetrafluoroethylene as appropriate, and finished with a current collector material such as a stainless steel mesh as a core material. It is done.
- a strip-like positive electrode plate produced as follows is used as the positive electrode. That is, lithium graphite oxide (LiCoO 2 ) is added with phosphorous graphite as a conductive additive at a mass ratio of 90: 5 (lithium cobalt oxide: phosphorous graphite) and mixed, and this mixture and polyvinylidene fluoride are mixed with N Mix with a solution in methylpyrrolidone to make a slurry.
- This positive electrode mixture slurry is passed through a 70-mesh net to remove large particles, and then uniformly applied to both sides of a positive electrode current collector made of an aluminum foil having a thickness of 20 ⁇ m, dried, and then compressed by a roll press. After forming, it is cut into a strip-like positive electrode plate.
- the longitudinal direction of the polyolefin-based resin porous film is referred to as “longitudinal direction”, and the direction perpendicular to the longitudinal direction is referred to as “lateral direction”.
- the longitudinal direction of the polyolefin-based resin porous film is referred to as “longitudinal direction”, and the direction perpendicular to the longitudinal direction is referred to as “lateral direction”.
- Air permeability (Gurley value) The air permeability (second / 100 ml) was measured at room temperature in accordance with JIS P8117. Next, the obtained air permeability value was evaluated as follows. ⁇ : Air permeability is 10 to 200 seconds / 100ml X: Air permeability is less than 10 seconds / 100 ml, or more than 200 seconds / 100 ml
- Porosity is a numerical value indicating the proportion of the space portion in the polyolefin resin porous film. The porosity is determined by measuring the substantial amount W1 of the polyolefin resin porous film, calculating the mass W0 when the porosity is 0% from the density and thickness of the resin composition, and calculating from these values based on the following formula: did.
- Porosity Pv (%) ⁇ (W0 ⁇ W1) / W0 ⁇ ⁇ 100 Next, the obtained porosity value was evaluated as follows. ⁇ : Porosity is 55 to 90% X: Porosity is less than 55% or more than 90%
- the sample in a state constrained to was immersed and heated for 5 seconds. Immediately after heating, it is immersed in a separately prepared cooling bath filled with 25 ° C. glycerin and cooled for 5 minutes, and then washed with 2-propanol (manufactured by Nacalai Tesque, special grade) and acetone (manufactured by Nacalai Tesque, special grade). And dried in an air atmosphere at 25 ° C. for 15 minutes. The air permeability of the sample after drying was measured according to the method (2). Based on the above measurement, the evaluation was made according to the following criteria, and the evaluation of “ ⁇ ” was regarded as having a shutdown characteristic. ⁇ : 50,000 seconds / 100 ml or more ⁇ : 10,000 seconds / 100 ml or more, less than 50000 seconds / 100 ml ⁇ : less than 10,000 seconds / 100 ml
- the presence or absence of ⁇ -crystal activity was evaluated according to the following criteria depending on whether or not a peak was detected at 145 to 160 ° C., which is the crystal melting peak temperature (Tm ⁇ ) derived from ⁇ -crystal of the polypropylene resin at the time of re-heating. .
- Tm ⁇ crystal melting peak temperature
- X When Tm ⁇ is not detected within the range of 145 ° C to 160 ° C (no ⁇ crystal activity) The ⁇ crystal activity was measured with a sample amount of 10 mg in a nitrogen atmosphere.
- the set temperature was changed to 100 ° C., and the mixture was gradually cooled to 100 ° C. over 10 minutes or more.
- the display temperature reaches 100 ° C.
- the sample is taken out and cooled for 5 minutes in an atmosphere of 25 ° C. while being restrained by two aluminum plates.
- Wide-angle X-ray diffraction measurement was performed on a 40 mm ⁇ circular portion.
- -Wide-angle X-ray diffraction measurement device manufactured by Mac Science, model number: XMP18A X-ray source: CuK ⁇ ray, output: 40 kV, 200 mA Scanning method: 2 ⁇ / ⁇ scan, 2 ⁇ range: 5 ° to 25 °, scanning interval: 0.05 °, scanning speed: 5 ° / min
- the presence or absence of ⁇ crystal activity was evaluated as follows from the peak derived from the (300) plane of ⁇ crystal of the polypropylene resin.
- Example 1 As a ⁇ -crystal nucleating agent, 100% by mass of polypropylene resin (Nippon Polypro, Novatec PP FY6HA, MFR: 2.4 g / 10 min, melting point: 158 ° C.) as a ⁇ crystal nucleating agent is 3,9-bis [4- (N -Cyclohexylcarbamoyl) phenyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 0.2% by mass, organic-inorganic hybrid particles (SPT014, manufactured by Takemoto Yushi Co., Ltd., average particle size: 0.3 ⁇ m Is added to the same direction twin screw extruder (Toshiba Machine Co., Ltd., caliber: 40 mm ⁇ , L / D: 32), melt kneaded at a set temperature of 300 ° C., and extruded from a strand die. The strands were cooled and solidified in water, and the strands
- Example 2 A polyolefin resin porous film was produced in the same manner as in Example 1 except that the amount of organic-inorganic hybrid particles (SPT014, Takemoto Yushi Co., Ltd., average particle size: 0.3 ⁇ m) added was 3 mass%. The resulting polyolefin resin porous film was evaluated for physical properties, and the results are summarized in Table 1.
- Example 4 A polyolefin resin porous film was produced in the same manner as in Example 1 except that 1% by mass of organic / inorganic hybrid particles (SPT013, manufactured by Takemoto Yushi Co., Ltd., average particle size: 0.6 ⁇ m) was added. The resulting polyolefin resin porous film was evaluated for physical properties, and the results are summarized in Table 1.
- Example 5 A polyolefin-based resin porous film was produced in the same manner as in Example 1 except that 5% by mass of organic-inorganic hybrid particles (SPT013, manufactured by Takemoto Yushi Co., Ltd., average particle size: 0.6 ⁇ m) were added. The resulting polyolefin resin porous film was evaluated for physical properties, and the results are summarized in Table 1.
- Example 1 instead of the organic / inorganic hybrid particles (f), a polyolefin-based polymer was prepared in the same manner as in Example 1 except that 5% by mass of alumina (Sumicorundum AA-07, Sumitomo Chemical Co., Ltd., average particle size: 0.7 ⁇ m) was added. An attempt was made to produce a porous resin film, but an avatar that was thought to be caused by poor dispersibility of alumina during extrusion from a T-die was generated, so that a good nonporous film-like product could not be obtained.
- alumina Sudicorundum AA-07, Sumitomo Chemical Co., Ltd., average particle size: 0.7 ⁇ m
- Example 2 A polyolefin-based resin porous film was produced in the same manner as in Example 1 except that 3% by mass of polymethylpentene (TPX RT-18, manufactured by Mitsui Chemicals, Inc.) was added instead of the organic / inorganic hybrid particles (f). The resulting polyolefin resin porous film was evaluated for physical properties, and the results are summarized in Table 1.
- TPX RT-18 polymethylpentene
- Example 3 A polyolefin-based resin porous film was produced in the same manner as in Example 1 except that 3% by mass of polycarbonate (Taflon A1900, manufactured by Idemitsu Kosan Co., Ltd.) was added instead of the organic-inorganic hybrid particles (f). The resulting polyolefin resin porous film was evaluated for physical properties, and the results are summarized in Table 1.
- Example 4 A polyolefin resin porous film was produced in the same manner as in Example 1 except that the organic-inorganic hybrid particles (f) were not added. The resulting polyolefin resin porous film was evaluated for physical properties, and the results are summarized in Table 1.
- Example 6 As the A layer, a polypropylene resin (Novatech PP FY6HA, MFR: 2.4 g / 10 min, melting point: 158 ° C.) 100% by mass with respect to 100% by mass as a ⁇ -nucleating agent, 3,9-bis [ 0.2% by mass of 4- (N-cyclohexylcarbamoyl) phenyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, organic-inorganic hybrid particles (SPT014, Takemoto Yushi Co., Ltd., average particle size : 0.3 ⁇ m) is added to 3% by mass, then charged into the same-direction twin screw extruder (manufactured by Toshiba Machine Co., Ltd., caliber: 40 mm ⁇ , L / D: 32), melt-kneaded at a set temperature of 300 ° C., and a strand die After further extrusion, the strand was cooled and solidified in water, and the strand was
- high-density polyethylene manufactured by Prime Polymer Co., Ltd., Hi-Zex 3600F, MFR: 1.0 g / 10 min, melting point: 133 ° C.
- resin composition constituting the B layer.
- Example 7 A polyolefin-based resin porous film was produced in the same manner as in Example 6 except that the amount of organic / inorganic hybrid particles (SPT014, manufactured by Takemoto Yushi Co., Ltd., average particle size: 0.3 ⁇ m) was changed to 5% by mass for layer A. did. The resulting polyolefin resin porous film was evaluated for physical properties, and the results are summarized in Table 2.
- Example 5 For layer A, the same as in Example 6 except that 5% by mass of alumina (Sumicorundum AA-03, manufactured by Sumitomo Chemical Co., Ltd., average particle size: 0.3 ⁇ m) was added instead of the organic-inorganic hybrid particles (f).
- alumina Sudicorundum AA-03, manufactured by Sumitomo Chemical Co., Ltd., average particle size: 0.3 ⁇ m
- Example 6 A polyolefin resin porous film was produced in the same manner as in Example 6 except that the organic-inorganic hybrid particles (f) were not added. The resulting polyolefin resin porous film was evaluated for physical properties, and the results are summarized in Table 2.
- Example 8 As a ⁇ -crystal nucleating agent, 100% by mass of polypropylene resin (Nippon Polypro, Novatec PP FY6HA, MFR: 2.4 g / 10 min, melting point: 158 ° C.) as a ⁇ crystal nucleating agent is 3,9-bis [4- (N -Cyclohexylcarbamoyl) phenyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 0.2% by mass, organic-inorganic hybrid particles (SPT014, manufactured by Takemoto Yushi Co., Ltd., average particle size: 0.3 ⁇ m ) Is added to the same direction twin screw extruder (Toshiba Machine Co., Ltd., caliber: 40 mm ⁇ , L / D: 32), melt kneaded at a set temperature of 300 ° C., and extruded from a strand die. The strands were cooled and solidified in water, and the strands were
- the polypropylene resin composition was extruded from a T-die and cooled and solidified with a casting roll at 127 ° C. to prepare a nonporous film-like material.
- the non-porous film-like material was stretched 4.6 times in the longitudinal direction using a longitudinal stretching machine, stretched 3 times in the lateral direction at 150 ° C. by a lateral stretching machine, and then subjected to heat setting / relaxation treatment.
- the resulting polyolefin resin porous film was evaluated for physical properties, and the results are summarized in Table 3.
- Example 9 A polyolefin-based resin porous film was produced in the same manner as in Example 8, except that the nonporous membrane was stretched four times in the transverse direction at 150 ° C. by a transverse stretching machine. The resulting polyolefin resin porous film was evaluated for physical properties, and the results are summarized in Table 3.
- Example 10 A polyolefin-based resin porous film was produced in the same manner as in Example 8, except that the nonporous membrane was stretched 5 times in the transverse direction at 150 ° C. by a transverse stretching machine. The resulting polyolefin resin porous film was evaluated for physical properties, and the results are summarized in Table 3.
- Example 12 A polyolefin-based resin porous film was produced in the same manner as in Example 8, except that the nonporous membrane was stretched 7 times in the transverse direction at 150 ° C. by a transverse stretching machine. The resulting polyolefin resin porous film was evaluated for physical properties, and the results are summarized in Table 3.
- Example 5 A polyolefin resin porous film was produced in the same manner as in Example 8 except that the organic-inorganic hybrid particles (f) were not added. The resulting polyolefin resin porous film was evaluated for physical properties, and the results are summarized in Table 3.
- Comparative Example 6 A polyolefin-based resin porous film was produced in the same manner as in Comparative Example 5 except that the nonporous membrane was stretched 5 times in the transverse direction at 150 ° C. by a transverse stretching machine. The resulting polyolefin resin porous film was evaluated for physical properties, and the results are summarized in Table 3.
- Comparative Example 7 A polyolefin-based resin porous film was produced in the same manner as in Comparative Example 5, except that the nonporous membrane was stretched 6 times in the transverse direction at 150 ° C. with a transverse stretching machine. The resulting polyolefin resin porous film was evaluated for physical properties, and the results are summarized in Table 3.
- Comparative Example 8 A polyolefin-based resin porous film was produced in the same manner as in Comparative Example 5 except that the nonporous membrane was stretched 7 times in the transverse direction at 150 ° C. with a transverse stretching machine. The resulting polyolefin resin porous film was evaluated for physical properties, and the results are summarized in Table 3.
- the polyolefin resin porous film obtained in any of the examples had high air permeability and a high porosity.
- inorganic particles such as alumina are added instead of the organic-inorganic hybrid particles (f)
- the polyolefin resin porous film to which the organic-inorganic hybrid particles (f) were added was able to obtain even higher transmission characteristics when the area magnification was increased.
- the organic-inorganic hybrid particles (f) were not added as in Comparative Examples 5 to 8, the air permeability characteristics were deteriorated by increasing the area magnification.
- the polyolefin resin porous film of the present invention can be applied to various uses that require air permeability.
Abstract
Description
前記要望に対し、特許2883726号公報(特許文献3)ではβ晶ポリプロピレン樹脂に無機物を、特開平9-176352号公報(特許文献4)ではβ晶ポリプロピレン樹脂に樹脂粒子を添加した樹脂組成物をシート化し、特定の延伸条件で延伸することにより多孔性フィルムを得る製造方法が提案されている。
また、特開2005-171230号公報(特許文献5)では、β晶ポリプロピレン樹脂に対して、ポリプロピレンに非相溶で高融点樹脂を0.2~10重量部を添加することが提案されている。
また、特許文献3、特許文献4に記載の方法では、無機物もしくは樹脂粒子が大量に添加されているために、延伸多孔化の際にピンホールが発生しやすいことや、製造中もしくは使用中に無機物もしくは樹脂粒子が脱落して製造ラインを汚染させるという問題があった。
また、特許文献5に記載の方法では、前記高融点樹脂をポリプロピレンに微分散させることが困難なだけでなく、ピンホールが発生しやすいという問題を有していた。
なお、本発明において、「主成分」と表現した場合には、特に記載しない限り、当該主成分の機能を妨げない範囲で他の成分を含有することを許容する意を包含し、特に当該主成分の含有割合を特定するものではないが、主成分は組成物中の50質量%以上、好ましくは70質量%以上、特に好ましくは90質量%以上(100%含む)を占める意を包含するものである。
また、「X~Y」(X,Yは任意の数字)と記載した場合、特にことわらない限り「X以上Y以下」の意と共に、「好ましくはXより大きい」及び「好ましくはYより小さい」の意を包含するものである。
ポリオレフィン系樹脂多孔フィルムで用いるポリオレフィン系樹脂として、エチレン、プロピレン、1-ブテン、4-メチル-1-ペンテン、1-ヘキサンなどを重合した単独重合体または共重合体が挙げられる。この中でも、ポリプロピレン系樹脂、ポリエチレン系樹脂が好ましい。
ポリプロピレン系樹脂としては、ホモプロピレン(プロピレン単独重合体)、またはプロピレンとエチレン、1-ブテン、1-ペンテン、1-へキセン、1-へプテン、1-オクテン、1-ノネンもしくは1-デセンなどα-オレフィンとのランダム共重合体またはブロック共重合体などが挙げられる。この中でも、積層多孔フィルムの機械的強度、耐熱性などを維持する観点から、ホモポリプロピレンがより好適に使用される。
アイソタクチックペンタッド分率(mmmm分率)とは、任意の連続する5つのプロピレン単位で構成される炭素-炭素結合による主鎖に対して側鎖である5つのメチル基がいずれも同方向に位置する立体構造あるいはその割合を意味する。メチル基領域のシグナルの帰属は、A.Zambelli et al(Macromolecules8,687,(1975))に準拠した。
β晶活性は、延伸前の膜状物においてポリプロピレン系樹脂がβ晶を生成していたことを示す一指標と捉えることができる。延伸前の膜状物中のポリプロピレン系樹脂がβ晶を生成していれば、延伸を施すことで微細孔が容易に形成されるため、高い透気特性を有するポリオレフィン系樹脂多孔フィルムを得ることができる。
具体的には、示差走査型熱量計でポリオレフィン系樹脂多孔フィルムを25℃から240℃まで加熱速度10℃/分で昇温後1分間保持し、次に240℃から25℃まで冷却速度10℃/分で降温後1分間保持し、更に25℃から240℃まで加熱速度10℃/分で再昇温させた際に、ポリプロピレン系樹脂のβ晶に由来する結晶融解ピーク温度(Tmβ)が検出された場合、β晶活性を有すると判断している。
β晶活性度(%)=〔ΔHmβ/(ΔHmβ+ΔHmα)〕×100
例えば、ポリプロピレン系樹脂がホモポリプロピレンの場合は、主に145℃以上160℃未満の範囲で検出されるβ晶由来の結晶融解熱量(ΔHmβ)と、主に160℃以上170℃以下に検出されるα晶由来の結晶融解熱量(ΔHmα)から計算することができる。また、例えばエチレンが1~4モル%共重合されているランダムポリプロピレンの場合は、主に120℃以上140℃未満の範囲で検出されるβ晶由来の結晶融解熱量(ΔHmβ)と、主に140℃以上165℃以下の範囲に検出されるα晶由来の結晶融解熱量(ΔHmα)から計算することができる。
β晶活性度の上限値は特に限定されないが、β晶活性度が高いほど前記効果がより有効に得られるので100%に近いほど好ましい。
詳細には、ポリプロピレン系樹脂の融点を超える温度である170℃~190℃の熱処理を施し、徐冷してβ晶を生成・成長させたポリオレフィン系樹脂多孔フィルムについて広角X線測定を行い、ポリプロピレン系樹脂のβ晶の(300)面に由来する回折ピークが2θ=16.0°~16.5°の範囲に検出された場合、β晶活性が有ると判断している。
ポリプロピレン系樹脂のβ晶構造と広角X線回折に関する詳細は、Macromol.Chem.187,643-652(1986)、Prog.Polym.Sci.Vol.16,361-404(1991)、Macromol.Symp.89,499-511(1995)、Macromol.Chem.75,134(1964)、及びこれらの文献中に挙げられた参考文献を参照することができる。広角X線回折を用いたβ晶活性の詳細な評価方法については、後述の実施例にて示す。
本発明で用いるβ晶核剤としては以下に示すものが挙げられるが、ポリプロピレン系樹脂のβ晶の生成・成長を増加させるものであれば特に限定される訳ではなく、また2種類以上を混合して用いても良い。
β晶核剤としては、例えば、アミド化合物;テトラオキサスピロ化合物;キナクリドン類;ナノスケールのサイズを有する酸化鉄;1,2-ヒドロキシステアリン酸カリウム、安息香酸マグネシウムもしくはコハク酸マグネシウム、フタル酸マグネシウムなどに代表されるカルボン酸のアルカリもしくはアルカリ土類金属塩;ベンゼンスルホン酸ナトリウムもしくはナフタレンスルホン酸ナトリウムなどに代表される芳香族スルホン酸化合物;二もしくは三塩基カルボン酸のジエステル類もしくはトリエステル類;フタロシアニンブルーなどに代表されるフタロシアニン系顔料;有機二塩基酸である成分Aと周期律表第IIA族金属の酸化物、水酸化物もしくは塩である成分Bとからなる二成分系化合物;環状リン化合物とマグネシウム化合物からなる組成物などが挙げられる。そのほか核剤の具体的な種類については、特開2003-306585号公報、特開平06-289566号公報、特開平09-194650号公報に記載されている。
本発明において、有機無機ハイブリッド粒子(f)が含んでなることが重要である。
有機無機ハイブリッド粒子(f)とは、有機高分子と無機材料とが同一粒子内に均一に分布した複合体粒子であって、耐摩耗性、耐熱性等、無機材料としての特性と、柔軟性等の有機高分子としての特性を併せ持つ粒子である。
前記粒子(f)が含まれていることによって、ポリオレフィン系樹脂との親和性が高いため、ポリオレフィン系樹脂との接着性も良好であり、ポリオレフィン系樹脂と前記粒子(f)との界面での層間剥離が起こりにくい。そのため、非水電解液二次電池用セパレータとして使用する場合、優れた電池特性を有することができる。また、前記粒子(f)同士の凝集が少なく、分散性に優れているため、無機粒子もしくは有機粒子よりも少量の添加によって、高い開孔効果を得ることができる。
一方で、前記粒子(f)を含有していないポリオレフィン系樹脂多孔フィルムでは、高い面積倍率で延伸すると、形成された空孔に歪みが生じるために、空孔が扁平して最終的には閉塞する。これは、前記界面が存在しないために、透気特性が悪化したものと考えられる。
SiO4/2
Si(OH)O3/2
R1(OH)O3/2
R2(OH)O3/2
R3Si(OH)O2/2
R4Si(OH)O2/2
R1,R3:非反応性炭化水素基
R2,R4:下記の反応性基群から選ばれる反応性基を有する有機基
反応性基群:アクリロキシ基、メタクリロキシ基、ビニル基及びメルカプト基
SiX4
R5SiY3
R6SiZ3
R5:非反応性炭化水素基
R6:下記の反応性基群から選ばれる反応性基を有する有機基
反応性基群:アクリロキシ基、メタクリロキシ基、ビニル基及びメルカプト基
X,Y,Z:炭素数1~4のアルコキシ基、炭素数1~4のアルコキシ基を有するアルコキシエトキシ基、炭素数2~4のアシロキシ基、炭素数1~4のアルキル基を有するN,N-ジアルキルアミノ基、ヒドロキシル基、ハロゲン原子又は水素原子
また化5中のR3について前記したように、結果としてヒドロキシ=メチルシロキサン単位を形成することとなるシラノール基形成性ケイ素化合物が好ましい。
なお、本実施の形態において「平均粒径」とは、SEMを用いる方法に準じて測定される値である。
一方、前記有機無機ハイブリッド粒子(f)の添加量の下限は、特に限定されないが、1質量%以上がより好ましく、3質量%以上が更に好ましい。前記有機無機ハイブリッド粒子(f)の添加量が1質量%以上であれば、前記有機無機ハイブリッド粒子(f)が無添加の場合と比べて、高い透気特性が十分に得られるために好ましい。
本発明においては、前述した成分のほか、本発明の効果を著しく阻害しない範囲内で、一般に樹脂組成物に配合される添加剤を適宜添加できる。前記添加剤としては、成形加工性、生産性および積層多孔フィルムの諸物性を改良・調整する目的で添加される、耳などのトリミングロス等から発生するリサイクル樹脂やシリカ、タルク、カオリン、炭酸カルシウム等の無機粒子、酸化チタン、カーボンブラック等の顔料、難燃剤、耐候性安定剤、耐熱安定剤、帯電防止剤、溶融粘度改良剤、架橋剤、滑剤、核剤、可塑剤、老化防止剤、酸化防止剤、光安定剤、紫外線吸収剤、中和剤、防曇剤、アンチブロッキング剤、スリップ剤または着色剤などの添加剤が挙げられる。具体的には、「プラスチックス配合剤」のP154~P158に記載されている酸化防止剤、P178~P182に記載されている紫外線吸収剤、P271~P275に記載されている帯電防止剤としての界面活性剤、P283~P294に記載されている滑剤などが挙げられる。
本発明において、ポリオレフィン系樹脂多孔フィルムは、単層でも積層でも構わないが、2層以上に積層させることが好ましい。
ポリオレフィン系樹脂多孔フィルムの層構成は、ポリオレフィン系樹脂を主成分とする樹脂組成物(a)からなる層(A層)を少なくとも1層存在すれば、特に限定されるものではない。また、ポリオレフィン系樹脂多孔フィルムの機能を妨げない範囲で他の層(B層)を積層することもできる。強度保持層、耐熱層(高融解温度樹脂層)、シャットダウン層(低融解温度樹脂層)などを積層させた構成が挙げられる。例えば、非水電解液二次電池用セパレータとして用いる際には、特開平04-181651号公報に記載されているような高温雰囲気化で孔閉塞し、電池の安全性を確保する低融点樹脂層を積層させることが好ましい。
中でも、前記ポリオレフィン系樹脂を主成分とする樹脂組成物(a)からなる層(A層)と、当該樹脂組成物(a)より結晶融解ピーク温度が低い樹脂組成物(b)からなる層(B層)とが積層されているものが好ましく、前記樹脂組成物(a)として、ポリプロピレン系樹脂を主成分とする樹脂組成物からなる層と、前記樹脂組成物(b)として、ポリエチレン系樹脂を主成分とする樹脂組成物からなる層とが積層されているものが更に好ましい。前記樹脂組成物(b)からなる層を積層させることで、非水電解液二次電池用セパレータとして用いる際に、シャットダウン特性(SD特性)が付与させることができる。
具体的にはA層/B層を積層した2層構造、A層/B層/A層、若しくは、B層/A層/B層として積層した3層構造などが例示できる。また、他の機能を持つ層と組み合わせて3種3層の様な形態も可能である。この場合、他の機能を持つ層との積層順序は特に問わない。更に層数としては4層、5層、6層、7層と必要に応じて増やしても良い。
ポリエチレン系樹脂としては、具体的に超低密度ポリエチレン、低密度ポリエチレン、高密度ポリエチレン、線状低密度ポリエチレン、また分子量に特徴のある超高分子量ポリエチレンのようなホモポリマーポリエチレンだけでなく、エチレンプロピレン共重合体、またはポリエチレン系樹脂と他のポリオレフィン系樹脂とのコポリマーポリエチレンが挙げられる。中でも、ホモポリマーポリエチレン、或いはα-オレフィンコモノマー含量が2モル%以下のコポリマーポリエチレンが好ましく、ホモポリマーポリエチレンであることが更に好ましい。α-オレフィンコモノマーの種類については特に制限はない。
MFRはJIS K7210に従い、温度190℃、荷重2.16kgの条件で測定している。
ポリエチレン系樹脂に、多孔化を促進させる多孔化促進化合物Xを添加することが好ましい。前記多孔化促進化合物Xを添加することにより、より効率的に多孔構造を得ることができ、孔の形状や孔径を制御しやすくなる。
前記多孔化促進化合物Xは限定しないが、具体的に例示すると、変性ポリオレフィン樹脂、脂環族飽和炭化水素樹脂若しくはその変性体、エチレン系共重合体、またはワックスから選ばれる多孔化促進化合物Xのうち少なくとも1種が含まれていることがより好ましい。中でも、多孔化でより効果の大きい脂環族飽和炭化水素樹脂若しくはその変性体、エチレン系共重合体、またはワックスがより好ましく、成形性の観点からワックスが更に好ましい。
(ア)融点が40℃~200℃である。
(イ)融点より10℃高い温度での溶融粘度が50Pa・s以下である。
中でも、核剤はポリエチレン系樹脂の結晶構造を制御し、延伸開孔時の多孔構造を細かくするという効果があるため好ましい。市販されているものとして、「ゲルオールD」(新日本理化社製)、「アデカ スタブ」(旭電化工業社製)、「Hyperform」(ミリケンケミカル社製)、または「IRGACLEAR D」(チバ スペシャルケミカルズ社製)等が挙げられる。また、核剤の添加されたポリエチレン系樹脂の具体例としては、「リケマスター」(理研ビタミン社製)等が商業的に入手できる。
次に本発明のポリオレフィン系樹脂多孔フィルムの製造方法について説明するが、本発明はかかる製造方法により製造される多孔フィルムのみに限定されるものではない。
無孔膜状物の延伸方法については、ロール延伸法、圧延法、テンター延伸法、同時二軸延伸法などの手法があり、これらを単独あるいは2つ以上組み合わせて一軸延伸あるいは二軸延伸を行う。中でも、多孔構造制御の観点から逐次二軸延伸が好ましい。
(I)各層を多孔化したのち、多孔化された各層をラミネートしたり接着剤等で接着したりして積層する方法。
(II)各層を積層して積層無孔膜状物を作製し、ついで当該無孔膜状物を多孔化する方法。
(III)各層のうちいずれか1層を多孔化したのち、もう1層の無孔膜状物と積層し、多孔化する方法。
(IV)多孔層を作製した後、無機・有機粒子などのコーティング塗布や、金属粒子の蒸着などを行うことにより積層多孔フィルムとする方法。
本発明においては、その工程の簡略さ、生産性の観点から(II)の方法を用いることが好ましく、なかでも2層の層間接着性を確保するために、共押出で積層無孔膜状物を作製した後、多孔化する方法が特に好ましい。
まずポリオレフィン系樹脂と、必要であれば熱可塑性樹脂、添加剤の混合樹脂組成物を作製する。例えば、ポリプロピレン系樹脂、β晶核剤、無機有機ハイブリッド粒子および所望によりその他添加物等の原材料を、好ましくはヘンシェルミキサー、スーパーミキサー、タンブラー型ミキサー等を用いて、または袋の中に全成分を入れてハンドブレンドにて混合した後、一軸あるいは二軸押出機、ニーダー等、好ましくは二軸押出機で溶融混練後、カッティングしてペレットを得る。
Tダイの種類としては特に限定されない。例えば本発明の積層多孔フィルムが2種3層の積層構造をとる場合、Tダイは2種3層用マルチマニホールドタイプでも構わないし、2種3層用フィードブロックタイプでも構わない。
使用するTダイのギャップは、最終的に必要なフィルムの厚み、延伸条件、ドラフト率、各種条件等から決定されるが、一般的には0.1~3.0mm程度、好ましくは0.5~1.0mmである。0.1mm未満では生産速度という観点から好ましくなく、また3.0mmより大きければ、ドラフト率が大きくなるので生産安定性の観点から好ましくない。
キャストロールによる冷却固化温度は本発明において非常に重要であり、膜状物中のポリオレフィン系樹脂のβ晶の比率を調整することができる。キャストロールの冷却固化温度は好ましくは80~150℃、より好ましくは90~140℃、更に好ましくは100~130℃である。冷却固化温度を80℃以上とすることで、膜状物中のβ晶の比率を十分に増加させることができるために好ましい。また、150℃以下とすることで、押出された溶融樹脂がキャストロールへ粘着し巻き付いてしまうなどのトラブルが起こりにくく、効率よく膜状物化することが可能であるので好ましい。
延伸前の膜状物中のβ晶比率は、示差走査型熱量計を用いて、該膜状物を25℃から240℃まで加熱速度10℃/分で昇温させた際に、検出されるポリオレフィン系樹脂のα晶由来の結晶融解熱量(ΔHmα)とβ晶由来の結晶融解熱量(ΔHmβ)を用いて下記式で計算される。
β晶比率(%)=〔ΔHmβ/(ΔHmβ+ΔHmα)〕×100
ついで、得られた無孔膜状物を少なくとも二軸延伸することがより好ましい。二軸延伸は同時二軸延伸であってもよいし、逐次二軸延伸であってもよいが、各延伸工程で延伸条件(倍率、温度)を簡便に選択でき、多孔構造を制御し易い逐次二軸延伸がより好ましい。なお、膜状物及びフィルムの長手方向を「縦方向」、長手方向に対して垂直方向を「横方向」と称する。また、長手方向への延伸を「縦延伸」、長手方向に対して垂直方向への延伸を「横延伸」と称する。
一方、横延伸での延伸温度は概ね100~160℃、好ましくは110~150℃、更に好ましくは120~140℃である。また、好ましい縦延伸倍率は1.2~10倍が好ましく、より好ましくは1.5~8倍、更に好ましくは2~7倍である。前記範囲内で横延伸することで、縦延伸により形成された空孔起点を適度に拡大させ、微細な多孔構造を発現させることができる。
前記延伸工程の延伸速度としては、500~12000%/分が好ましく、1500~10000%/分がさらに好ましく、2500~8000%/分であることが更に好ましい。
本発明のポリオレフィン系樹脂多孔フィルムの厚みは5~100μmが好ましい。より好ましくは8~50μm、更に好ましくは10~30μmである。非水電解液二次電池用セパレータとして使用する場合、5μm以上であれば、実質的に必要な電気絶縁性を得ることができ、例えば電極の突起部分に大きな力がかかった場合でも、非水電解液二次電池用セパレータを突き破って短絡しにくく安全性に優れる。また、厚みが100μm以下であれば、ポリオレフィン系樹脂フィルムの電気抵抗を小さくすることができるので、電池の性能が十分に確保することができる。
一方、上限については、90%以下が好ましく、85%以下がより好ましく、80%以下が更に好ましい。空孔率が90%以下であれば、ポリオレフィン系樹脂多孔フィルムの機械的強度を十分に保持することができる上に、二次加工の観点からも好ましい。なお、空孔率は実施例に記載の方法で測定されている。
透気度は、フィルム厚み方向の空気の通り抜け難さを表し、具体的には100mlの空気が当該フィルムを通過するのに必要な数で表現されている。そのため、数値が小さい方が通り抜け易く、数値が大きい方が通り抜け難いことを意味する。すなわち、その数値が小さい方がフィルムの厚み方向の連通性が良いことを意味し、その数値が大きい方がフィルムの厚み方向の連通性が悪いことを意味する。連通性とはフィルム厚み方向の孔のつながり度合いである。本発明のポリオレフィン系樹脂多孔フィルムの透気度が低ければ様々な用途に使用することができる。例えば電池用セパレータとして使用した場合、透気度が低いということはリチウムイオンの移動が容易であることを意味し、電池性能に優れるため好ましい。
すなわち、本発明のポリオレフィン系樹脂多孔フィルムにおいて、ブレイクダウン特性が発現時の温度(ブレイクダウン温度)は160℃以上が好ましく、より好ましくは200℃以上、更に好ましくは250℃以上である。ブレイクダウン温度が160℃未満では、シャットダウン特性、ブレイクダウン特性のそれぞれの特性が発現される温度に差が無く、例えば本発明のポリオレフィン系樹脂多孔フィルムを、非水電解液二次電池用セパレータとして使用した場合、十分に安全性を確保された電池を提供することはできないために好ましくない。一方、ブレイクダウン温度の高温側については特に制限はないが、300℃以下がより好ましい。
ここで、「ブレイクダウン温度」とは、実施例に記載の方法で加熱したときに本発明のポリオレフィン系樹脂多孔フィルムが破膜する温度のうち最も低い温度をいう。
続いて、本発明の前記ポリオレフィン系樹脂多孔フィルムを電池用セパレータとして収容している非水電解液二次電池について、図1に参照して説明する。
正極板21、負極板22の両極は電池用セパレータ10を介して互いに重なるようにして渦巻き状に捲回し、巻き止めテープで外側を止めて捲回体としている。
前記捲回工程について詳しく説明する。電池用セパレータの片端をピンのスリット部1の間に通し、ピンを少しだけ回転させて電池用セパレータの一端をピンに巻きつけておく。この時、ピンの表面と電池用セパレータの耐熱層とが接触している。その後、電池用セパレータを間に挟むようにして正極と負極を配置し、捲回機によってピンを回転させて、正負極と電池用セパレータを捲回する。捲回後、ピンは捲回物から引き抜かれる。
なかでも、エチレンカーボネート1質量部に対してメチルエチルカーボネートを2質量部混合した溶媒中に六フッ化リン酸リチウム(LiPF6)を1.0mol/Lの割合で溶解した電解質が好ましい。
負極に炭素材料を用いる場合、炭素材料としてはリチウムイオンをドープ、脱ドープできるものであればよく、例えば黒鉛、熱分解炭素類、コークス類、ガラス状炭素類、有機高分子化合物の焼成体、メソカーボンマイクロビーズ、炭素繊維、活性炭などを用いることができる。
1/1000mmのダイアルゲージにて、面内を不特定に30箇所測定し、その平均値を厚みとした。
JIS P8117に準拠して透気度(秒/100ml)を室温で測定した。次に、得られた透気度の値を以下のように評価した。
○:透気度が10~200秒/100ml
×:透気度が10秒/100ml未満、もしくは200秒/100mlを超える
空孔率は、ポリオレフィン系樹脂多孔フィルム中の空間部分の割合を示す数値である。空孔率は、ポリオレフィン系樹脂多孔フィルムの実質量W1を測定し、樹脂組成物の密度と厚みから、空孔率0%の場合の質量W0を計算し、それらの値から下記式に基づき算出した。
空孔率Pv(%)={(W0-W1)/W0}×100
次に、得られた空孔率の値を以下のように評価した。
○:空孔率が55~90%
×:空孔率が55%未満、もしくは90%を超える
ポリオレフィン系樹脂多孔フィルムから、横方向に対して長さ150mm、幅10mmの形状で試験片を切り出し、長さ方向に対して100mmの間隔で標線を入れた。作製した試験片を、標線の外側をクリップで挟んで吊るした状態にて、105℃に設定したオーブン(大栄科学精器製作所社製、DK-1M)に入れた。1時間後、試験片を取り出し、標線の間隔L(mm)を測定した。下記式に基づいて、熱収縮率を算出した。
熱収縮率(%)=100-L
ポリオレフィン系樹脂多孔フィルムを縦60mm×横60mm角に切り出し、図2(a)に示すように中央部にφ40mmの円状の穴を空けたアルミ板(材質:JIS A5052、サイズ:縦60mm、横60mm、厚さ1mm)2枚の間にはさみ、図2(b)に示すように周囲をクリップで固定した。
次に、グリセリン(ナカライテスク社製、1級)を底面から100mmとなるまで満たした、135℃のオイルバス(アズワン社製、OB-200A)の中央部に、積層多孔フィルムをアルミ板2枚に拘束した状態のサンプルを浸漬し、5秒間加熱した。加熱後直ちに、別途用意した25℃のグリセリンを満たした冷却槽に浸漬して5分間冷却した後、2-プロパノール(ナカライテスク社製、特級)、アセトン(ナカライテスク社製、特級)で洗浄し、25℃の空気雰囲気下にて15分間乾燥した。乾燥後のサンプルについて、透気度を前記(2)の方法に従い測定した。前記測定により、以下の基準で評価を行い、評価が「○」となったものを、シャットダウン特性を有するとした。
○:50000秒/100ml以上
△:10000秒/100ml以上、50000秒/100ml未満
×:10000秒/100ml未満
図2(a)、(b)と同様の方法でアルミ板2枚に固定した状態のフィルムを180℃に設定したオ-ブン(タバイエスペック社製、タバイギヤオ-ブン『GPH200(商品名)』、ダンパー閉状態)に入れ、オーブン設定温度が180℃に再び達してから2分後に取り出し、フィルムの状態を確認して形状維持性能を判断した。
フィルムが破膜した場合は「×」、形状が維持されている場合は「○」と評価した。
(7)示差走査型熱量測定(DSC)
得られたポリオレフィン系樹脂多孔フィルムをパーキンエルマー社製の示差走査型熱量計(DSC-7)をもちいて、25℃から240℃まで走査速度10℃/分で昇温後1分間保持し、次に240℃~25℃まで走査速度10℃/分で降温後1分間保持し、次に25℃から240℃まで走査速度10℃/分で再昇温させた。この再昇温時にポリプロピレン系樹脂のβ晶に由来する結晶融解ピーク温度(Tmβ)である145~160℃にピークが検出されるか否かによりβ晶活性の有無を以下の基準にて評価した。
○:Tmβが145℃~160℃の範囲内に検出された場合(β晶活性あり)
×:Tmβが145℃~160℃の範囲内に検出されなかった場合(β晶活性なし)
なお、β晶活性の測定は、試料量10mgで、窒素雰囲気下にて行った。
得られたポリオレフィン系樹脂多孔フィルムを縦60mm×横60mm角に切り出し、図2(a)に示すように中央部が40mmφの円状に穴の空いたアルミ板(材質:JIS A5052、サイズ:縦60mm、横60mm、厚み1mm)2枚の間にはさみ、図2(b)に示すように周囲をクリップで固定した。
ポリオレフィン系樹脂多孔フィルムをアルミ板2枚に拘束した状態のサンプルを設定温度180℃、表示温度180℃である送風定温恒温器(ヤマト科学株式会社製、型式:DKN602)に入れ3分間保持した後、設定温度を100℃に変更し、10分以上の時間をかけて100℃まで徐冷を行った。表示温度が100℃になった時点でサンプルを取り出し、アルミ板2枚に拘束した状態のまま25℃の雰囲気下で5分間冷却して得られたサンプルについて、以下の測定条件で、中央部の40mmφの円状の部分について広角X線回折測定を行った。
・広角X線回折測定装置:マックサイエンス社製、型番:XMP18A
・X線源:CuKα線、出力:40kV、200mA
・走査方法:2θ/θスキャン、2θ範囲:5°~25°、走査間隔:0.05°、走査速度:5°/min
得られた回折プロファイルについて、ポリプロピレン系樹脂のβ晶の(300)面に由来するピークより、β晶活性の有無を以下のように評価した。
○:ピークが2θ=16.0~16.5°の範囲に検出された場合(β晶活性あり)
×:ピークが2θ=16.0~16.5°の範囲に検出されなかった場合(β晶活性なし)
なお、ポリオレフィン系樹脂多孔フィルムが60mm×60mm角に切り出せない場合は、中央部に40mmφの円状の穴にポリオレフィン系樹脂多孔フィルムが設置されるように調整し、サンプルを作成しても構わない。
ポリプロピレン系樹脂(日本ポリプロ社製、ノバテックPP FY6HA、MFR:2.4g/10分、融点:158℃)100質量%に対して、β晶核剤として、3,9-ビス[4-(N-シクロヘキシルカルバモイル)フェニル]-2,4,8,10-テトラオキサスピロ[5.5]ウンデカンを0.2質量%、有機無機ハイブリッド粒子(SPT014、竹本油脂社製、平均粒径:0.3μm)を1質量%添加後、同方向二軸押出機(東芝機械株式会社製、口径:40mmφ、L/D:32)に投入し、設定温度300℃で溶融混練してストランドダイより押出した後、ストランドを水中で冷却固化し、カッターによりストランドをカットし、ポリプロピレン系樹脂組成物のペレットを作製した。
前記無孔膜状物を、縦延伸機を用いて縦方向に4.6倍延伸し、横延伸機にて150℃で横方向に2倍延伸後、熱固定/弛緩処理を行った。
得られたポリオレフィン系樹脂多孔フィルムについて物性評価を行い、その結果を表1にまとめた。
有機無機ハイブリッド粒子(SPT014、竹本油脂社製、平均粒径:0.3μm)の添加量を3質量%とした以外は実施例1と同様の方法によりポリオレフィン系樹脂多孔フィルムを製造した。
得られたポリオレフィン系樹脂多孔フィルムについて物性評価を行い、その結果を表1にまとめた。
機無機ハイブリッド粒子(SPT014、竹本油脂社製、平均粒径:0.3μm)の添加量を5質量%とした以外は実施例1と同様の方法によりポリオレフィン系樹脂多孔フィルムを製造した。
得られたポリオレフィン系樹脂多孔フィルムについて物性評価を行い、その結果を表1にまとめた。
有機無機ハイブリッド粒子(SPT013、竹本油脂社製、平均粒径:0.6μm)を1質量%添加とした以外は実施例1と同様の方法によりポリオレフィン系樹脂多孔フィルムを製造した。
得られたポリオレフィン系樹脂多孔フィルムについて物性評価を行い、その結果を表1にまとめた。
有機無機ハイブリッド粒子(SPT013、竹本油脂社製、平均粒径:0.6μm)を5質量%添加とした以外は実施例1と同様の方法によりポリオレフィン系樹脂多孔フィルムを製造した。
得られたポリオレフィン系樹脂多孔フィルムについて物性評価を行い、その結果を表1にまとめた。
有機無機ハイブリッド粒子(f)の代わりに、アルミナ(スミコランダムAA-07、住友化学社製、平均粒径:0.7μm)を5質量%添加した以外は実施例1と同様の方法によりポリオレフィン系樹脂多孔フィルムを製造しようとしたが、Tダイより押出時にアルミナの分散性不良が起因と思われるアバタが発生したため、良好な無孔膜状物が得られなかった。
有機無機ハイブリッド粒子(f)の代わりに、ポリメチルペンテン(TPX RT-18 三井化学社製)を3質量%添加とした以外は実施例1と同様の方法によりポリオレフィン系樹脂多孔フィルムを製造した。
得られたポリオレフィン系樹脂多孔フィルムについて物性評価を行い、その結果を表1にまとめた。
有機無機ハイブリッド粒子(f)の代わりに、ポリカーボネート(タフロンA1900、出光興産社製)を3質量%添加した以外は実施例1と同様の方法によりポリオレフィン系樹脂多孔フィルムを製造した。
得られたポリオレフィン系樹脂多孔フィルムについて物性評価を行い、その結果を表1にまとめた。
有機無機ハイブリッド粒子(f)を添加しなかった以外は、実施例1と同様の方法によりポリオレフィン系樹脂多孔フィルムを製造した。
得られたポリオレフィン系樹脂多孔フィルムについて物性評価を行い、その結果を表1にまとめた。
A層として、ポリプロピレン系樹脂(日本ポリプロ社製、ノバテックPP FY6HA、MFR:2.4g/10分、融点:158℃)100質量%に対して、β晶核剤として、3,9-ビス[4-(N-シクロヘキシルカルバモイル)フェニル]-2,4,8,10-テトラオキサスピロ[5.5]ウンデカンを0.2質量%、有機無機ハイブリッド粒子(SPT014、竹本油脂社製、平均粒径:0.3μm)を3質量%添加後、同方向二軸押出機(東芝機械株式会社製、口径:40mmφ、L/D:32)に投入し、設定温度300℃で溶融混練してストランドダイより押出した後、ストランドを水中で冷却固化し、カッターによりストランドをカットし、ポリプロピレン系樹脂組成物のペレットを作製した。
前記積層膜状物を、縦延伸機を用いて縦方向に4.2倍延伸し、その後、横延伸機にて95℃で横方向に2.0倍延伸後、熱固定/弛緩処理を行った。
得られたポリオレフィン系樹脂多孔フィルムについて物性評価を行い、その結果を表2にまとめた。
A層について、有機無機ハイブリッド粒子(SPT014、竹本油脂社製、平均粒径:0.3μm)の添加量を5質量%とした以外は実施例6と同様の方法によりポリオレフィン系樹脂多孔フィルムを製造した。
得られたポリオレフィン系樹脂多孔フィルムについて物性評価を行い、その結果を表2にまとめた。
A層について、有機無機ハイブリッド粒子(f)の代わりに、アルミナ(スミコランダムAA-03、住友化学社製、平均粒径:0.3μm)を5質量%添加した以外は実施例6と同様の方法によりポリオレフィン系樹脂多孔フィルムを製造しようとしたが、2種3層のフィードブロックを通じて積層成型用の口金より押出時に、アルミナの分散性不良が起因と思われるアバタが発生したため、良好な積層膜状物が得られなかった。
有機無機ハイブリッド粒子(f)を添加しなかった以外は、実施例6と同様の方法によりポリオレフィン系樹脂多孔フィルムを製造した。
得られたポリオレフィン系樹脂多孔フィルムについて物性評価を行い、その結果を表2にまとめた。
ポリプロピレン系樹脂(日本ポリプロ社製、ノバテックPP FY6HA、MFR:2.4g/10分、融点:158℃)100質量%に対して、β晶核剤として、3,9-ビス[4-(N-シクロヘキシルカルバモイル)フェニル]-2,4,8,10-テトラオキサスピロ[5.5]ウンデカンを0.2質量%、有機無機ハイブリッド粒子(SPT014、竹本油脂社製、平均粒径:0.3μm)を3質量%添加後、同方向二軸押出機(東芝機械株式会社製、口径:40mmφ、L/D:32)に投入し、設定温度300℃で溶融混練してストランドダイより押出した後、ストランドを水中で冷却固化し、カッターによりストランドをカットし、ポリプロピレン系樹脂組成物のペレットを作製した。
前記無孔膜状物を、縦延伸機を用いて縦方向に4.6倍延伸し、横延伸機にて150℃で横方向に3倍延伸後、熱固定/弛緩処理を行った。
得られたポリオレフィン系樹脂多孔フィルムについて物性評価を行い、その結果を表3にまとめた。
前記無孔膜状物を、横延伸機にて150℃で横方向に4倍に延伸した以外は実施例8と同様の方法によりポリオレフィン系樹脂多孔フィルムを製造した。
得られたポリオレフィン系樹脂多孔フィルムについて物性評価を行い、その結果を表3にまとめた。
前記無孔膜状物を、横延伸機にて150℃で横方向に5倍に延伸した以外は実施例8と同様の方法によりポリオレフィン系樹脂多孔フィルムを製造した。
得られたポリオレフィン系樹脂多孔フィルムについて物性評価を行い、その結果を表3にまとめた。
前記無孔膜状物を、横延伸機にて150℃で横方向に6倍に延伸した以外は実施例8と同様の方法によりポリオレフィン系樹脂多孔フィルムを製造した。
得られたポリオレフィン系樹脂多孔フィルムについて物性評価を行い、その結果を表3にまとめた。
前記無孔膜状物を、横延伸機にて150℃で横方向に7倍に延伸した以外は実施例8と同様の方法によりポリオレフィン系樹脂多孔フィルムを製造した。
得られたポリオレフィン系樹脂多孔フィルムについて物性評価を行い、その結果を表3にまとめた。
有機無機ハイブリッド粒子(f)を添加しなかった以外は、実施例8と同様の方法によりポリオレフィン系樹脂多孔フィルムを製造した。
得られたポリオレフィン系樹脂多孔フィルムについて物性評価を行い、その結果を表3にまとめた。
前記無孔膜状物を、横延伸機にて150℃で横方向に5倍に延伸した以外は比較例5と同様の方法によりポリオレフィン系樹脂多孔フィルムを製造した。
得られたポリオレフィン系樹脂多孔フィルムについて物性評価を行い、その結果を表3にまとめた。
前記無孔膜状物を、横延伸機にて150℃で横方向に6倍に延伸した以外は比較例5と同様の方法によりポリオレフィン系樹脂多孔フィルムを製造した。
得られたポリオレフィン系樹脂多孔フィルムについて物性評価を行い、その結果を表3にまとめた。
前記無孔膜状物を、横延伸機にて150℃で横方向に7倍に延伸した以外は比較例5と同様の方法によりポリオレフィン系樹脂多孔フィルムを製造した。
得られたポリオレフィン系樹脂多孔フィルムについて物性評価を行い、その結果を表3にまとめた。
一方、比較例1、5のように、有機無機ハイブリッド粒子(f)の代わりに、アルミナのような無機粒子を添加すると、無機粒子の分散性不良のために成形できず、ポリオレフィン系樹脂多孔フィルムが得られなかった。
また、比較例2、3のように、有機無機ハイブリッド粒子(f)の代わりに、ポリオレフィン系樹脂に対して非相溶である熱可塑性樹脂を添加した場合、および、比較例4、6のように、有機無機ハイブリッド粒子(f)が添加されていない場合、得られるポリオレフィン系樹脂多孔フィルムは、透気特性が不十分で、空孔率も実施例よりも低くなった。
21 正極板
22 負極板
24 正極リード体
25 負極リード体
26 ガスケット
27 正極蓋
31 アルミ板
32 サンプル
33 クリップ
34 フィルム縦方向
35 フィルム横方向
Claims (9)
- ポリオレフィン系樹脂を主成分とし、かつ、有機無機ハイブリッド粒子(f)を含んでなる樹脂組成物(a)から構成されるポリオレフィン系樹脂多孔フィルム。
- 前記有機無機ハイブリッド粒子(f)の添加量が、前記ポリオレフィン系樹脂100質量%に対して1質量%以上10質量%以下であることを特徴とする請求項1に記載のポリオレフィン系樹脂多孔フィルム。
- 前記有機無機ハイブリット粒子(f)として、ポリシロキサン架橋構造体からなる有機シリコーン微粒子を用い、該有機シリコーン微粒子は平均粒径が0.01~10μmのリング形状であることを特徴とする請求項1または請求項2に記載のポリオレフィン系樹脂多孔フィルム。
- 透気度が10秒/100ml以上200秒/100ml以下であることを特徴とする請求項1乃至請求項3のいずれか1項に記載のポリオレフィン系樹脂多孔フィルム。
- 空孔率が55~90%であることを特徴とする請求項1乃至請求項4のいずれか1項に記載のポリオレフィン系樹脂多孔フィルム。
- 少なくとも前記樹脂組成物(a)からなる層と、前記樹脂組成物(a)より結晶融解ピーク温度が低い樹脂組成物(b)からなる層とが積層されていることを特徴とする請求項1乃至請求項5のいずれか1項に記載のポリオレフィン系樹脂多孔フィルム。
- 前記ポリオレフィン系樹脂が、β晶活性を有するポリプロピレン系樹脂であることを特徴とする請求項1乃至請求項6のいずれか1項に記載のポリオレフィン系樹脂多孔フィルム。
- 請求項1乃至請求項7のいずれか1項に記載のポリオレフィン系樹脂多孔フィルムを用いた非水電解液二次電池用セパレータ。
- 請求項8に記載の非水電解液二次電池用セパレータを用いた非水電解液二次電池。
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JP2017513996A (ja) * | 2014-04-25 | 2017-06-01 | トレオファン・ジャーマニー・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング・ウント・コンパニー・コマンデイトゲゼルシャフト | 粒子含有多孔質層を備えた二軸配向フィルム |
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KR101504436B1 (ko) * | 2013-11-29 | 2015-03-19 | 롯데케미칼 주식회사 | 이차전지 분리막용 폴리프로필렌 수지 조성물 |
JP5931290B2 (ja) * | 2014-01-07 | 2016-06-08 | 三菱樹脂株式会社 | 積層多孔フィルム、非水電解液二次電池用セパレータ、及び非水電解液二次電池 |
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WO2020027172A1 (ja) * | 2018-07-31 | 2020-02-06 | 日東電工株式会社 | 板状の複合材料 |
EP4068488A1 (en) | 2018-10-11 | 2022-10-05 | Asahi Kasei Kabushiki Kaisha | Lithium ion battery using crosslinkable separator |
CN115172985A (zh) | 2018-10-11 | 2022-10-11 | 旭化成株式会社 | 蓄电装置用分隔件的制造方法 |
CN112909431B (zh) * | 2021-01-22 | 2022-09-09 | 中国科学技术大学 | 锂离子电池复合隔膜及其制备方法、锂离子电池 |
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Also Published As
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EP2626380A4 (en) | 2014-04-23 |
US9115277B2 (en) | 2015-08-25 |
US20130236793A1 (en) | 2013-09-12 |
EP2626380A1 (en) | 2013-08-14 |
KR20130047752A (ko) | 2013-05-08 |
KR101514901B1 (ko) | 2015-04-23 |
CN103140544A (zh) | 2013-06-05 |
JP5705868B2 (ja) | 2015-04-22 |
JPWO2012046753A1 (ja) | 2014-02-24 |
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