CN105992691A - Laminated porous film, and production method therefor - Google Patents

Laminated porous film, and production method therefor Download PDF

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Publication number
CN105992691A
CN105992691A CN201480065581.5A CN201480065581A CN105992691A CN 105992691 A CN105992691 A CN 105992691A CN 201480065581 A CN201480065581 A CN 201480065581A CN 105992691 A CN105992691 A CN 105992691A
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CN
China
Prior art keywords
plasma membrane
porous
multiple aperture
lamination
polyethylene
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Granted
Application number
CN201480065581.5A
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Chinese (zh)
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CN105992691B (en
Inventor
水野直树
又野孝
又野孝一
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Toray Industries Inc
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Toray Battery Separator Film Co Ltd
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Publication of CN105992691A publication Critical patent/CN105992691A/en
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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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/32—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed at least two layers being foamed and next to each other
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/30—Extrusion nozzles or dies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/30—Extrusion nozzles or dies
    • B29C48/305—Extrusion nozzles or dies having a wide opening, e.g. for forming sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/911—Cooling
    • B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
    • B29C48/914—Cooling of flat articles, e.g. using specially adapted supporting means cooling drums
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
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    • B29C48/911—Cooling
    • B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
    • B29C48/915—Cooling of flat articles, e.g. using specially adapted supporting means with means for improving the adhesion to the supporting means
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    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/42—Acrylic resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/423—Polyamide resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
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    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
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    • H01M50/426—Fluorocarbon polymers
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
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    • H—ELECTRICITY
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    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
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    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • 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
    • H—ELECTRICITY
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    • 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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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
    • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
    • B29C55/14—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
    • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
    • B29C55/16—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial simultaneously
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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Cell Separators (AREA)
  • Laminated Bodies (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention provides a laminated porous film. The peel strength between the polyolefin porous film and the modified porous layers is extremely high, and thus the laminated porous film is suitable for high-speed processing. The polyolefin porous film has protrusions which comprise polyolefin, which satisfy 5 mum <=W <=50 mum (W being the size of the protrusions) and 0.5 mum <=H (H being the height of the protrusion), and which are irregularly dispersed on both surfaces of the polyolefin porous film at a density in the range of 3/cm<2> to 200/cm<2> inclusive per surface. A modified porous layer (A) laminates on one surface of a polyolefin porous film with the thickness of not more than 25 mum, and a modified porous layer (B) laminates on an opposite surface of the polyolefin porous film. At least the modified porous layer (A) includes inorganic particles and a binder having a tensile strength of at least 5 N/mm<2>.

Description

Lamination multiple aperture plasma membrane and manufacture method thereof
Technical field
The present invention relates to a kind of polyolefin porous plasma membrane and modification porous layer having and being suitable for modifying porous layer lamination Lamination multiple aperture plasma membrane and manufacture method thereof.The lamination multiple aperture plasma membrane of the present invention is a kind of electricity that can be used as diaphragm for lithium ion battery Pond barrier film.
Background technology
The micro-porous film being made up of thermoplastic resin be widely used as the separation film of material or selectivity through film and every From film etc..Such as, the battery separator, double used in lithium rechargeable battery, Ni-MH battery, nickel-cadmium cell, polymer battery Various filters, waterproof moisture permeable fabric, the medical materials such as electric layer capacitor barrier film, osmosis filtration film, ultrafilter membrane, micro-filtration membrane Material etc..Especially as Separator for Lithium-ion battery, being suitable for using polyethylene multiple aperture plasma membrane, it is by impregnation electrolyte And there is ion permeability, electrical insulating property is excellent, and has when battery mid-winter, at a temperature of about 120～150 DEG C Turn-off current, the hole occlusive effect of suppression excessive temperature rise.But, when continuing to for a certain reason heat up after the obturation of hole, have Time because of the contraction of film, rupture of membranes can occur.This phenomenon not only limits and occurs in polyethylene microporous film, uses and uses other During the micro-porous film of thermoplastic resin, when temperature is more than the melting point resin constituting this multiple aperture plasma membrane, just cannot avoid this phenomenon.
Particularly diaphragm for lithium ion battery is closely related with battery behavior, battery production and battery security, therefore Require that it has mechanical property, thermostability, permeability, dimensional stability, hole obturation characteristic (closing property) and melted rupture of membranes Characteristic (operating chacteristics) etc..Further, in order to improve the cycle characteristics of battery, the adhesion improving barrier film with electrode material is also required Property, in order to improve productivity, also require to improve electrolytic solution permeability etc..
Therefore, the research at polyolefin porous plasma membrane superimposed layer modification porous layer is carried out in the past.As modification porous layer In the resin that contains, applicable use has thermostability and the polyamide-imide resin of electrolytic solution permeability, polyimides simultaneously The fluorine-type resin etc. that resin, polyamide and electrode adhesiveness are excellent.Additionally, use more easy washing step, do Drying process and can the lamination modification water solublity of porous layer or water-dispersible adhesive being also widely used.
It addition, so-called modification porous layer refers in the present invention, containing give or improve thermostability and the adhesiveness of electrode material, And the layer of the resin of at least one in the function such as electrolytic solution permeability.
In patent documentation 1, a kind of composite porous film of publicity, it is by the polyethylene multiple aperture plasma membrane in thickness 9 μm Upper coating polyvinylidene fluoride, is properly embedded a part for polyvinylidene fluoride in the pore of polyethylene perforated membrane, sends out Wave anchor effect so that the peel strength at polyethylene perforated membrane and the coating layer interface of polyvinylidene fluoride (T-shaped stripping is strong Degree) it is 1.0～5.3N/25mm.
In patent documentation 2, a kind of barrier film of publicity, it is 16 μm and the polyethylene system through Corona discharge Treatment at thickness Multiple aperture plasma membrane is provided with heat-resisting porous layer, and this heat-resisting porous layer contains self-crosslinking acrylic and tabular boehmite, and And polyethylene multiple aperture plasma membrane is 1.1～3.0N/ with the heat-resisting porous layer peel strength (T-shaped peel strength) when 180 ° 10mm。
A kind of multi-layer porous plasma membrane of publicity in the embodiment 1 of patent documentation 3, it is prepared by the following: i.e. 200 DEG C time extrude the polyvinyl resin solution that is made up of compositions 50 mass parts and Liquid Paraffin 50 mass parts, this combination from extruder Thing is by polyethylene 47.5 mass parts of viscosity-average molecular weight 200,000, polypropylene 2.5 mass parts of viscosity-average molecular weight 400,000 and antioxygen Agent is constituted, and utilizes the chilling roll of homoiothermic to 25 DEG C to extract, while obtaining gluey article shaped, then implements two-way It is stretched to 7 × 6.4 times, makes vistanex perforated membrane.Then, at the surface stack of this vistanex multiple aperture plasma membrane by gathering The coating layer that vinyl alcohol, aluminium oxide particles are constituted, it is thus achieved that multi-layer porous plasma membrane.
A kind of non-aqueous secondary batteries barrier film of publicity in the embodiment 6 of patent documentation 4, it is prepared by the following: I.e. when 148 DEG C from extruder polyethylene extrusion resin solution, containing weight average molecular weight 4,150,000 He in this polyvinyl resin solution The mixing of weight average molecular weight 560,000, polyethylene composition 30 percentage by weight of weight ratio 1:9 and Liquid Paraffin and naphthalane is molten Agent 70 percentage by weight, cools down in a water bath, it is thus achieved that gluey article shaped, then implements biaxial tension to 5.5 × 11.0 times, it is thus achieved that Polyethylene porous plasma membrane.Then, then at this polyethylene porous plasma membrane surfaces lamination by bit-type fully aromatic polyamide and an oxidation The coating layer that aluminum particulate is constituted, it is thus achieved that non-aqueous secondary batteries barrier film.
A kind of multilayer porous film of publicity in the embodiment 1 of patent documentation 5, it is prepared by the following: i.e. use rolling Cylinder blender polyethylene 47 mass parts by Mv (viscosity-average molecular weight) 700,000 homopolymer, polyethylene 46 mass of Mv25 ten thousand homopolymer Polypropylene 7 mass parts of part and Mv40 ten thousand homopolymer is dry mixed.In straight polymer mixture 99 mass percent obtained Four [3-(3,5-di-t-butyl-4-hydroxyphenyl) propanoic acid] pentaerythritol ester 1 mass percent is added as antioxidant, will again Using the polyethylene composition melting mixing that rotary mixer is dry mixed, extrusion die casting is to the cooling rolling that surface temperature control is 25 DEG C On cylinder, it is thus achieved that the lamellar polyolefin composition of thickness 2000 μm, then implement biaxial tension to 7 × 7 times, it is thus achieved that polyethylene porous Plasma membrane, on the polyethylene porous plasma membrane obtained, the aqueous dispersions of Kaolin and latex is burnt till in coating, it is thus achieved that multilayer porous film.
[background technology document]
[patent documentation]
Patent documentation 1: Japanese Patent Laid-Open 2012-043762 publication.
Patent documentation 2: Japan Patent public table 2010-104127 publication again.
Patent documentation 3: No. 4931083 publication of Japanese Patent Laid.
Patent documentation 4: No. 4460028 publication of Japanese Patent Laid.
Patent documentation 5: Japanese Patent Laid-Open 2011-000832 publication.
Summary of the invention
[inventing problem to be solved]
From now on, in order to improve battery capacity, it is not only electrode slice, barrier film also must increase the face can being filled in container It is long-pending, it is therefore expected that filming can develop further.But, after advancing due to the filming of multiple aperture plasma membrane, easily at in-plane On deform, so sometimes in work in-process, rip cutting operation or battery assembling procedure, the multiple aperture plasma membrane superimposed layer of thin film Modification porous layer is peeling-off, is therefore more difficult to guarantee safety.
Additionally, in order to tackle cost degradation requirement, it is contemplated that battery assembling procedure high speed can be made.Adding at a high speed to obtain Work modifies the most less barrier films of fault such as porous layer stripping, it is desirable to having between polyolefin porous plasma membrane and modification porous layer can Bear the high-adhesiveness of High-speed machining.But, in order to improve adhesiveness, problems with can be there is, i.e. make modification porous layer contains After some resins fully permeate in polyolefin porous plasma membrane, vapour lock degree ascensional range can increase.
From now on, cost degradation, high capacity may develop rapidly, and advance High-speed machining, the thin film of barrier film therewith Change, for above-mentioned requirements, when using conventional art, assemble modification porous layer in processing in rip cutting processing and battery and there will be local Peel off, it is therefore expected that safety will be increasingly difficult to ensure that.Particularly when vistanex multiple aperture plasma membrane is thinning, then it is difficult to Fully acquisition modification porous layer is for the anchor effect of vistanex multiple aperture plasma membrane, is therefore more difficult to guarantee safety.
Present inventors etc. are it is envisioned that battery separator is the most gradually advancing filming and the situation of cost degradation, and target exists In provide a kind of have be suitable for modification porous layer lamination polyolefin porous plasma membrane and modification porous layer lamination multiple aperture plasma membrane with And the described lamination multiple aperture plasma membrane as battery separator, this polyolefin porous plasma membrane and the peel strength pole modifying porous layer High-speed machining in height, and applicable rip cutting operation and battery assembling procedure.
In this specification, so-called peel strength refers to, 0 ° of stripping between polyolefin porous plasma membrane and modification porous layer is strong Degree, the value measured the most by the following method (following, the most referred to as 0 ° peel strength).
Fig. 1 shows to medelling and is in the polyolefin porous being stretched under testing machine (not shown) extended state The side situation of the lamination sample of plasma membrane and modification porous layer.1 is lamination sample, and 2 is polyolefin porous plasma membrane, and 3 is that modification is many Aperture layer, 4 is two-sided tape, and 5 and 5' is aluminium sheet, and the arrow in figure is draw direction.At size 50mm × 25mm, thickness 0.5mm The upper an equal amount of two-sided tape (4) that attaches of aluminium sheet (5), and thereon from length 25mm of described aluminium sheet (5) End starts the polyolefin porous plasma membrane (2) that the sample (1) (lamination multiple aperture plasma membrane) of width 50mm × length 100mm is cut in attaching Face so that it is overlapping 40mm, and cut the part stretched out.Then, a length of 100mm, width be 15mm, thickness be 0.5mm's Aluminium sheet one side (5') attaches two-sided tape, from the sample side of length 25mm of above-mentioned aluminium sheet (5) end start patch Attached so that it is overlapping 20mm.Thereafter, use cupping machine with draw speed 10mm/mi n by the most parallel with aluminium sheet for aluminium sheet (5) Ground stretches round about, intensity when mensuration modification porous layer is peeling-off.If peel strength in this evaluation methodology For more than 130N/15mm, even if then the thickness of polyolefin porous plasma membrane is below 10 μm, the modification porous layer of institute's lamination is the most almost Will not in transit or processing in peeling off phenomenon.
It was used as the T-shaped peel strength of the assay method of peel strength in the past or peel strength when 180 ° referred to, will be coated with Layer of cloth draws to the rear ramp of vertical direction or vertical direction with polyethylene porous film surface from polyethylene perforated membrane From time peeling force.According to this evaluation methodology, compared with the evaluation methodology that these are traditional, it is possible to evaluate rip cutting operation more practically With the friction patience in battery assembling procedure.
[solving the technological means of problem]
In order to solve above-mentioned problem, the lamination multiple aperture plasma membrane of the present invention has following structure.That is, one lamination Porous Film, the projection being wherein made up of polyolefin meets 5 μm≤W≤50 μm (W be protruding size) and 0.5 μm≤H, and (H is projection Height), with 3/cm2Above, 200/cm2Following density is dispersed on each face in two faces brokenly, and And a face superimposed layer modification porous layer A of the polyolefin porous plasma membrane below thickness 25 μm, lamination modification on opposing sides Porous layer B, at least modification porous layer A contain hot strength 5N/mm2Above binding agent and inorganic particulate.
The lamination multiple aperture plasma membrane of the present invention is preferably described hot strength 5N/mm2Above binding agent is polyvinyl alcohol or propylene Acid resin.
The lamination multiple aperture plasma membrane of the present invention is preferably described inorganic particulate and contains selected from calcium carbonate, aluminium oxide, titanium dioxide, sulphuric acid At least one in the group that barium, Muscovitum and boehmite are formed.
The thickness of the lamination multiple aperture plasma membrane of the present invention preferably polyolefin porous plasma membrane is below 20 μm.
The thickness of the lamination multiple aperture plasma membrane of the present invention preferably polyolefin porous plasma membrane is below 16 μm.
The lamination multiple aperture plasma membrane of the present invention is preferably and is used as battery separator.
In order to solve above-mentioned problem, the manufacture method of the lamination multiple aperture plasma membrane of the present invention has following structure.
A () adds molding solvent in vistanex after, carry out melting mixing, the operation of modulation vistanex solution.
B () extrudes described vistanex solution from T-shaped mould, the chilling roll using surface to eliminate molding solvent enters Row cooling, forms the operation of gluey article shaped, and described chilling roll is arranged in and is extruded as membranaceous vistanex solution Two sides.
C described gluey article shaped is stretched by () to operating direction and width, it is thus achieved that the operation of stretch-molded article.
D () removes described molding solvent from described stretch-molded article, be dried, it is thus achieved that the operation of Porous article shaped.
E described Porous article shaped is carried out heat treatment by (), it is thus achieved that the operation of polyolefin porous plasma membrane.F () uses containing stretching Intensity 5N/mm2Above binding agent, solubilized or disperse the solvent of described binding agent and the coating fluid of inorganic particulate, in institute State formation stack membrane, the operation being dried at least one face of polyolefin porous plasma membrane.
It is scraper that the manufacture method of the lamination multiple aperture plasma membrane of the present invention preferably molding solvent removes means.
It addition, modification porous layer A and modification porous layer B is the most referred to as modified porous layer by this specification sometimes.
[effect of invention]
According to the present invention, can obtain and there is the polyolefin porous plasma membrane the most excellent with the adhesiveness of modification porous layer and modify many The lamination multiple aperture plasma membrane of aperture layer and use battery that this lamination multiple aperture plasma membrane also will not be peeling-off when rapid transit with every Film.
Accompanying drawing explanation
Fig. 1 is the skeleton diagram of the assay method representing 0 ° of peel strength.
Fig. 2 is spherocrystal structure and the skeleton diagram of nucleus representing polyethylene in polyethylene porous plasma membrane.
Fig. 3 is the microphotograph of the ring-type trace of polyethylene spherocrystal in polyethylene porous plasma membrane.
Fig. 4 is to represent the T-shaped mould polyethylene extrusion resin solution from being arranged on extruder front end, and utilizes chilling roll Cool down, form the skeleton diagram of the operation of gluey article shaped.
Detailed description of the invention
Polyolefin porous plasma membrane used in the present invention by adjust specific vistanex solution, and Altitude control from The rate of cooling of the vistanex solution that extruder is extruded via T-shaped mould and obtain, there is shape sum in its surface Measure suitable projection.Further, will be containing inorganic particulate and hot strength 5N/mm2The modification porous stacking of above binding agent Layer is to time on this polyolefin porous plasma membrane, it is possible to obtain the most excellent stripping between polyolefin porous plasma membrane and modification porous layer strong Degree.
So-called projection in the present invention, with the projection adding such as inorganic particulate etc. in polyolefin porous plasma membrane and obtain There is essential distinction.The projection adding inorganic particulate in polyolefin porous plasma membrane and obtain is the most minimum, the need to In kind form the projection of more than height 0.5 μm, then must add the thickness of particle diameter and polyolefin porous plasma membrane equal or For the particle that it is above.But after adding this particle, polyolefin porous matter film strength can reduce, and unrealistic.
In the present invention, so-called projection refers to, makes a part for polyolefin porous plasma membrane grow into the convex of the suitable shape of protuberance Rise, the fundamental characteristics of polyolefin porous plasma membrane can't be reduced.
Additionally, it is so-called when spreading brokenly and manufacture polyolefin porous plasma membrane, before stretching process in the present invention Afterwards by knurling rolls obtain there is systematicness or periodically configuration exists significantly different.The punch process such as embossing processing Substantially form projection by the part beyond compression projection, be easily reduced vapour lock degree, electrolytic solution permeability, the most not Preferably.
The projection that in the present invention, so-called shape is suitable refers to, size be below more than 5 μm 50 μm and height be 0.5 μm with On projection.It is to say, 5 μm≤W≤50 μm (W is protruding size) and 0.5 μm≤H (H is protruding height).This convex Rise when modification porous layer is laminated on multiple aperture plasma membrane, the function of holder can be played, as a result of which it is, be obtained in that described 0 ° The lamination multiple aperture plasma membrane that peel strength is bigger.On the other hand, the upper limit of height is not particularly limited, but it is the most sufficient to reach 3.0 μm Enough.There is following trend, enough protruding quantity is the most, and the most above-mentioned 0 ° of peel strength is the highest.It is to say, 0 ° of stripping Intensity is affected by protruding quantity and the average height thereof that height is more than 0.5 μm.Protruding numerical lower limits be preferably 3/ cm2, more preferably 5/cm2, especially preferably 10/cm2.Protruding transformation is preferably 200/cm2, more preferably 150/cm2.Protruding height lower limit is preferably 0.5 μm, more preferably 0.8 μm, especially preferably 1.0 μm.
It addition, protruding size in the present invention and highly refer to the value recorded by following assay method.
In the present invention, the ascensional range of so-called vapour lock degree refers to, the vapour lock degree of polyolefin porous plasma membrane and lamination modification The difference of the vapour lock degree of the lamination multiple aperture plasma membrane of porous layer, preferably 100 seconds/below 100ccAir.
Hereinafter, the present invention is had polyolefin porous plasma membrane and the lamination multiple aperture plasma membrane of modification porous layer and is used as electricity The summary of the described lamination multiple aperture plasma membrane of pond barrier film illustrates, and certain present invention is not limited to this typical example.
1. polyolefin porous plasma membrane
First, the polyolefin porous plasma membrane of the present invention is described.
The thickness of the polyolefin porous plasma membrane of the present invention is preferably below 25 μm, and the upper limit is more preferably 20 μm, especially preferably 16 μ m.Lower limit is 7 μm, preferably 9 μm.If the thickness of polyolefin porous plasma membrane above-mentioned preferably in the range of, then can keep can be real Film-strength and hole obturation function, the area of the unit volume of battery case can not be limited, and is suitable for will developing from now on The high capacity of battery.
The vapour lock degree upper limit of polyolefin porous plasma membrane is preferably 300sec/100ccAir, more preferably 200sec/ 100ccAir, especially preferably 150sec/100ccAir；Lower limit is preferably 50sec/100ccAir, more preferably 70sec/ 100ccAir, especially preferably 100sec/100ccAir.
The upper limit of the void content of polyolefin porous plasma membrane is preferably 70%, and more preferably 60%, especially preferably 55%.Under Limit is preferably 30%, more preferably 35%, especially preferably 40%.If vapour lock degree and void content above-mentioned preferably in the range of, Can have sufficient battery charging/discharging characteristic, particularly can have sufficient ion permeability (charge/discharge operation voltage) and enough Long battery life (closely related with the maintenance dose of electrolyte), it is possible to give full play to the function of battery, sufficient machine can be obtained Tool intensity and insulating properties, therefore, it is possible to the probability being short-circuited when reducing discharge and recharge.
The average pore size of polyolefin porous plasma membrane can to hole obturation performance produce considerable influence, the most preferably 0.01～ 1.0 μm, more preferably 0.05～0.5 μm, especially preferably 0.1～0.3 μm.If the average pore size of polyolefin porous plasma membrane is Above-mentioned preferred scope, then can obtain sufficient modify porous layer described 0 ° by the anchor effect of functional resin and peel off strong Degree, when lamination modification porous layer, vapour lock degree will not significantly deteriorate, and the response for the temperature of hole occlusion phenomena will not become Slowly, hole blocking temperature also will not go to side at higher temperature because of programming rate.
Polyolefin porous plasma membrane must have the function in obturation hole when discharge and recharge reaction occurs abnormal.Therefore, composition The fusing point (softening point) of resin is 70～150 DEG C, more preferably 80～140 DEG C, especially preferably 100～130 DEG C.If constituted Resin fusing point above-mentioned preferably in the range of, then it can be avoided that play hole obturation function when normal use and cause battery without Method uses, additionally, by playing hole obturation function when there is abnormal response, it can be ensured that safety.
As the vistanex of composition polyolefin porous plasma membrane, preferably polyethylene, polypropylene.In addition it is also possible to be One matter or the mixture of different vistanex of more than two kinds, such as polyethylene and polyacrylic mixture, it is also possible to be The copolymer of different alkene.This is because, in addition to the fundamental characteristics such as electrical insulating property, ion permeability, it also has hole and closes Plug effect, the meeting turn-off current when battery mid-winter, and suppress excessive intensification.Wherein, it is contemplated that excellent hole occlusive Can, particularly preferred polyethylene.
Hereinafter, as a example by polyethylene, describe the vistanex used in the present invention in detail.
Polyethylene can enumerate ultra-high molecular weight polyethylene, high density polyethylene (HDPE), medium density polyethylene and Low Density Polyethylene etc.. Additionally, polymerization catalyst also there is no particular restriction, Ziegler-Natta type catalyst, Karen Phillips class catalyst or cyclopentadienyl can be enumerated Metal-based catalysts etc..The homopolymer of ethylene is not only by these polyethylene, it is also possible to be the copolymerization containing other alpha-olefins a small amount of Thing.As the alpha-olefin beyond ethylene, preferably propylene, 1-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene, 1-octene, (methyl) acrylic acid, (methyl) acrylate and styrene etc..
Polyethylene can be one matter, but is preferably the mixture being made up of two or more polyethylene.Mix as polyethylene Compound, can use the mixture of the of more than two kinds ultra-high molecular weight polyethylene different containing weight average molecular weight (Mw), the most also The mixture of high density polyethylene (HDPE), medium density polyethylene or Low Density Polyethylene can be used.In addition it is also possible to use selected from super Two or more in the group that High molecular weight polyethylene, high density polyethylene (HDPE), medium density polyethylene and Low Density Polyethylene are formed The mixture of polyethylene.
As polyethylene mixture, being preferably by weight average molecular weight (Mw) is 5 × 105Above ultra-high molecular weight polyethylene It is 1 × 10 with Mw4Less than 5 × 105Polyethylene constitute mixture.The Mw of ultra-high molecular weight polyethylene is preferably 5 × 105～1 × 107, more preferably 1 × 106～15 × 106, especially preferably 1 × 106～5 × 106.It is 1 × 10 as Mw4Above And less than 5 × 105Polyethylene, any one of high density polyethylene (HDPE), medium density polyethylene and Low Density Polyethylene can be used, But particularly preferably use high density polyethylene (HDPE).It is 1 × 10 as Mw4Less than 5 × 105Polyethylene, Mw can be used not Same polyethylene of more than two kinds, it is possible to use the polyethylene of more than two kinds that density is different.By by the Mw of polyethylene mixture The upper limit be set to 15 × 106Below, it is possible to make to melt extrude and become easy.
In the present invention, the upper content limit of ultra-high molecular weight polyethylene is preferably 40 percentage by weights, more preferably 30 weight hundred Proportion by subtraction, especially preferably 10 percentage by weights；Lower limit is preferably 1 percentage by weight, and more preferably 2 percentage by weights are the most excellent Elect 5 percentage by weights as.
If the content of ultra-high molecular weight polyethylene is in the range of preferably, then can obtain highly sufficiently protruding.Utilizing should During bump stack modification porous layer, projection is understood as holder function, and relative to the face with polyethylene porous plasma membrane The power that direction applies abreast, it is possible to obtain extremely strong peel resistance.Even if additionally, making the thickness thin film of polyethylene porous plasma membrane Change, also can obtain sufficient hot strength.Hot strength is preferably more than 100MPa.The upper limit is not particularly limited.
The weight average molecular weight (Mw) of polyvinyl resin and molecular weight distribution ratio (Mw/Mn) of number-average molecular weight (Mn) are preferably In the range of 5～200, in the range of more preferably 10～100.If Mw/Mn is in the range of above-mentioned preferred scope, the most easily squeeze Go out polyvinyl resin solution, and sufficient amount of projection can be obtained.Further, at the thickness thin film making polyethylene porous plasma membrane Time, sufficient mechanical strength can be obtained.Mw/Mn is used as to weigh the yardstick of molecular weight distribution, say, that polyethylene is by single thing When matter is constituted, this value is the biggest, then the scope of molecular weight distribution is the biggest.When polyethylene is made up of one matter, Mw/Mn can be by poly- The multi-step polymerization of ethylene suitably adjusts.Additionally, suitably adjust also by the molecular weight and mixed proportion adjusting each composition The Mw/Mn of the mixture of polyethylene.
Described polyethylene porous plasma membrane can be monofilm, it is also possible to be by different two layers of molecular weight or average fine pore The Rotating fields more than constituted.When using by more than the two layers Rotating fields constituted, preferably at least one outermost polyethylene tree The molecular weight and molecualr weight distribution of fat meets described scope.If polyethylene porous plasma membrane is meeting the scope of above-mentioned various feature In, then can unrestricted choice manufacture method corresponding with purpose.
2. the manufacture method of polyolefin porous plasma membrane
As the manufacture method of polyolefin porous plasma membrane, have foaming, phase separation method, dissolving recrystallization, stretching perforate method, with And powder sintering etc., wherein in view of the homogenization of minute aperture, cost, preferably phase separation method.
It is taken as the manufacture method of phase separation method, include, for example by polyethylene is heated with molding solvent Melting mixing, extrudes the molten mixture obtained from T-shaped mould and cools down and form gluey article shaped, and to being obtained Gluey article shaped implement stretching at least one direction of principal axis, remove described molding solvent, thus the method obtaining multiple aperture plasma membrane Deng.
As the manufacture method by more than the two layers multilayer films constituted, such as, any one method following can be used to make: The polyethylene constituting a layer and b layer is carried out melting mixing with molding solvent respectively, by the molten mixture that obtained respectively from Extruder supply, to a T-shaped mould, makes the method that the gel film of each composition of composition is together extruded after forming one；And by structure The method carrying out thermal welding after becoming the gel film overlap of each layer.Coetrusion is readily available higher plunger bond strength, easily Forming intercommunicating pore at interlayer, the most easily maintain high osmosis, productivity is the most excellent, so more preferably.
Hereinafter, the manufacture method of polyolefin porous plasma membrane used in the present invention is described in detail.
The manufacture method of polyolefin porous plasma membrane used in the present invention contains following operation (a)～(e).
A () adds molding solvent in vistanex after, carry out melting mixing, the operation of modulation vistanex solution.
B () extrudes described polyethylene solution from T-shaped mould, the chilling roll using surface to eliminate molding solvent carries out cold But, forming the operation of gluey article shaped, described chilling roll is arranged in the two sides being extruded as membranaceous vistanex solution.
C described gluey article shaped is stretched by () to operating direction (MD) and width (T D), it is thus achieved that the work of stretch-molded article Sequence.
D () removes described molding solvent from described stretch-molded article, be dried, it is thus achieved that the operation of Porous article shaped.
E described Porous article shaped is carried out heat treatment by (), it is thus achieved that the operation of polyolefin porous plasma membrane.
And also can be arranged as required to sided corona treatment operation etc. after operation (a)～(e).
Hereinafter, to use polyvinyl resin as a example by vistanex, each operation is described.
The operation of (a) modulation polyvinyl resin solution
After adding molding solvent in polyvinyl resin, carry out melting mixing, modulate polyvinyl resin solution.
As molding solvent, can abundant polyethylene dissolving, be not particularly limited.Include, for example nonane, decane, 11 The aliphatic such as alkane, dodecane and Liquid Paraffin or cyclic hydrocarbon or the boiling point mineral oil fractions etc. corresponding with them, but in order to obtain Obtain the non-volatile solvents such as the gluey article shaped that solvent is stable, preferably Liquid Paraffin.Heating for dissolving can use with polyethylene The temperature that compositions is completely dissolved is stirred or the most uniformly mixes, the method carrying out dissolving.In an extruder Or when stirring while dissolving in solvent, this temperature can be according to the polymer used and solvent difference, but preference Such as the scope of 140～250 DEG C.
The total amount of polyvinyl resin and molding solvent is set to 100 weight portions, and the concentration of polyvinyl resin is 25～40 Weight portion, preferably 28～35 weight portions.If the concentration of polyvinyl resin above-mentioned preferably in the range of, then can be formed enough The nucleus for forming projection of quantity, and sufficient amount of projection can be formed.Additionally, energy during polyethylene extrusion resin solution Enough repression of swellings and inside contracting at T-shaped mould outlet, maintain mouldability and the self-sustained of extrusion molding body.
Method as melting mixing is not particularly limited, the most mixing.The method is suitable for In the highly concentrated solution modulating above-mentioned polyethylene.Melt temperature is preferably the scope of the fusing point+10 DEG C～+100 DEG C at polyethylene In.General melt temperature is preferably in the range of 160～230 DEG C, in the range of more preferably 170～200 DEG C.Herein, fusing point Refer to according to differential scanning calorimetry (DSC), the value tried to achieve based on JIS K7121.Molding solvent can advance mixing beginning Row adds, it is possible to is added implementing melting mixing in mixing from the midway of extruder again, but preferably advances mixing beginning Row adds, and makes it become solution in advance.During melting mixing, in order to prevent the oxidation of polyethylene, preferably add antioxidant.
B () forms the operation of gluey article shaped
From T-shaped mould, extrude the polyvinyl resin solution through melting mixing, use surface to utilize molding solvent to remove hands Section eliminates the chilling roll of molding solvent and cools down, and forms gluey article shaped.Directly from extruder or by other The polyvinyl resin solution through melting mixing extruded from T-shaped mould by extruder.As T-shaped mould, generally use and there is length The T-shaped mould of the thin slice of square Oral incision.
Then, utilize cold-producing medium that the surface temperature of the chilling roll of a pair rotation is set as 20 DEG C to 40 DEG C, make from T-shaped The two sides being extruded as membranaceous polyvinyl resin solution in mould contacts this chilling roll, thus forms gluey article shaped.Squeezed The polyvinyl resin solution gone out is preferably cooled to less than 25 DEG C.
It is important that control the cooling substantially implementing in the temperature range of crystallization for forming projection in the present invention Speed.
About forming so-called protruding mechanism in the present invention, present inventor etc. considers as follows.Polyvinyl resin after melting While extruding from T-shaped mould with the resin solution of molding solvent, polyethylene starts crystallization, by connecing with chilling roll Touch and cool down rapidly, accelerating crystallization rate.Now, the spherocrystal (Fig. 2) of the symmetrical structure with nucleus can be formed.Chilling roll Surface and described melted after polyvinyl resin between heat-transfer rate less time, crystallization rate is slow, as a result of which it is, form tool There is the spherocrystal of relatively small crystal nucleus.When heat-transfer rate is fast, the spherocrystal with bigger nucleus can be formed.The nucleus of these spherocrystals is in rear operation Projection can be formed during i.e. TD (width) and/or MD (operating direction) stretching.Additionally, spherocrystal can be apparent in poly-second with ring-type trace Alkene multiple aperture plasma membrane surface (Fig. 3).
In the present invention, such as, the cooling in the temperature range of crystallization is substantially implemented with polyvinyl resin solution surface Speed is more than 10 DEG C/sec, the polyvinyl resin solution that cooling is extruded, it is thus achieved that gluey article shaped.Rate of cooling is preferably 20 More than DEG C/sec, more preferably more than 30 DEG C/sec, especially preferably more than 50 DEG C/sec.By implementing this cooling, it is possible to fixing It is able to the structure of microphase-separated for polyethylene mutually by solvent, forms tool on the surface of the gluey article shaped contacted with chilling roll There is the spherocrystal of relatively macronucleus, and form the projection that shape is suitable after the stretch.By the heat conduction system according to vistanex solution The thermal conductivity of number, thickness, molding solvent, chilling roll and air is simulated, it is possible to deduce on chilling roll is cold But speed.
In order to control rate of cooling in the present invention, it is important that trying one's best in advance, it is poly-with extrude from T-shaped mould to remove Vinyl solution contact part chilling roll surface on accompanying molding solvent.It is to say, as shown in Figure 4, Polyvinyl resin solution cools off by being wound on the chilling roll of rotation, and forms gluey article shaped, but is forming glue Shape article shaped after being detached, can adhere to molding solvent on chilling roll surface, and would generally in this state again Contact with polyvinyl resin solution.But, if adhering to a large amount of molding solvent on chilling roll surface, then can be because of its heat insulation effect Really, make rate of cooling slack-off, it is difficult to form projection.It is important, therefore, that again connect with polyvinyl resin solution at chilling roll Before Chuing, remove molding solvent as far as possible.
The method (also referred to as molding solvent removes means) removing molding solvent from chilling roll there is no limit especially Fixed, it is preferable to employ following methods, i.e. make the width contact cooling cylinder abreast of scraper and gluey article shaped, scrape Molding solvent, so that it is guaranteed that extremely contact in the period of gluey article shaped after just scraping scraper, will not be on chilling roll surface Observe molding solvent.Or may be used without utilizing compressed air to carry out dispelling, attracting, or combine the side of these methods etc. Method removes.Wherein, the method using scraper to scrape is easier to implement, and the most preferably, compared with 1, uses multi-disc scraper more The removing efficiency of molding solvent can be improved, the most particularly preferably.
The material of scraper, for molding solvent is had patience, is not particularly limited, but compared with metal scraper, It is preferably resin-made or rubber system.During this is because use metal, chilling roll may be caused cut.As resin-made Scraper, can enumerate polyester system, polyacetals system and polyethylene etc..
Even if the temperature of chilling roll is set smaller than 20 DEG C, due to the effect of heat insulation of molding solvent, it is only such Sufficient rate of cooling can not be obtained, moreover, the most also can be attached on chilling roll cause glue because of condensation The rough surface of article shaped.
Chilling roll is 2 chilling rolls being arranged in polyvinyl resin solution two sides, and the most each diameter of cylinder is different. Additionally, the height that position is set of the polyvinyl resin solution outlet relative to T-shaped mould, the rotary shaft of 2 chilling rolls To arrange position height different.Be preferably the little chilling roll of diameter rotary shaft to arrange position height big compared to diameter Chilling roll is closer to the allocation position of the polyvinyl resin solution outlet of T-shaped mould.This is to reduce from T-shaped mould as far as possible The polyvinyl resin solution outlet allocation position of tool contacts to earth position to polyvinyl resin solution on the big chilling roll of diameter Distance.Such as, by the configuration shown in Fig. 4, the polyvinyl resin solution extruded from T-shaped mould can be made substantially to implement crystallization Rate of cooling in the temperature range changed reaches more than 10 DEG C/sec.
During extrusion, the thickness of polyvinyl resin solution is preferably below 1500 μm, below more preferably 1000 μm, the most excellent Elect below 800 μm as.If within the above range, then the face of chilling roll side is cold for the thickness of polyvinyl resin solution during extrusion But speed will not be slack-off, the most preferably.
C () obtains the operation of stretch-molded article
Then, this glue article shaped is stretched to operating direction (MD) and width (T D), makes stretch-molded article.Stretching Refer to that the gluey article shaped of heating utilizes the combination of common tenter frame process, drum process or these methods, to MD and TD this two Stretching is implemented with regulation multiplying power in individual direction.Stretching can be to stretch (simultaneously bi-directionally stretching) to MD and TD simultaneously or gradually draw Stretch.When gradually stretching, it is also possible to do not consider the order of MD and TD, at least one in MD and TD is drawn with multi-level approach Stretch.Draft temperature is the fusing point less than+10 DEG C of polyolefin composition.Stretching ratio is different because of raw-material thickness, but preferably face During multiplying power it is more than 9 times, more preferably 16～400 times.If MD and TD stretches (simultaneously bi-directionally stretching) simultaneously, then it is preferably 3 × 3,5 × 5 modes identical with MD with the TD multiplying powers such as 7 × 7 stretch.If face multiplying power above-mentioned preferably in the range of, then draw Stretch fully, the multiple aperture plasma membrane of high resiliency, high intensity can be obtained.Additionally, by regulation draft temperature, additionally it is possible to obtain desired Vapour lock degree.
D () obtains the operation of Porous article shaped
Stretch-molded article after utilizing cleaning solvent to process stretching, removes the molding solvent of residual, it is thus achieved that multiple aperture plasma membrane.As Cleaning solvent, can use the fluorinations such as the hydrocarbon such as pentane, hexane, heptane, the chlorinated hydrocabon such as dichloromethane, carbon tetrachloride, borontrifluoride ethane Hydrocarbon and the ethers such as diethyl ether, dioxane etc. have the material of effumability.These cleaning solvents can polyethylene accordingly molten The molding solvent used in solution suitably selects, and is used alone or as a mixture.Cleaning method can use and be immersed in cleaning solvent And carry out extracting method, the method spraying cleaning solvent, attract from the opposition side of stretch-molded article cleaning solvent method or The method etc. that they are combined by person.Implement above-mentioned cleaning, until the residual solvent in stretch-molded article i.e. stretch-molded article is less than 1 Percentage by weight.Then, cleaning solvent is dried, the drying means of cleaning solvent can use heat drying, air-dry etc. side Method.
E () obtains the operation of polyethylene porous plasma membrane
Heat treatment will be carried out, it is thus achieved that polyethylene porous plasma membrane by the Porous article shaped being dried acquisition.Heat treatment can use and draw Any one in width machine mode, cylinder mode, calendering mode and free way.It is preferably the temperature range at 90～150 DEG C Inside carry out heat treatment.If heat treatment temperature above-mentioned preferably in the range of, then can reduce obtained polyolefin porous plasma membrane Percent thermal shrinkage and substantially ensure that vapour lock degree.The holdup time of heat treatment step is not particularly limited, but usually more than 1 second Less than 10 minutes, preferably 3 seconds to less than 2 minutes.
Further, in heat treatment step, it is contemplated that thermal contraction, it is preferably at operating direction (MD), width (TD) sizing is implemented in the two direction, and at least one direction in MD, TD is shunk.At least one side in MD, TD Shrinkage factor in time shrinking is preferably 0.01～50%, more preferably 3～20%.
Additionally, it is possible to after operation (a)～(e), it is arranged as required to sided corona treatment operation or hydrophiling operation etc. and gives merit The operation of energy.
3. modification porous layer
It follows that modification porous layer used in the present invention is illustrated.
The lamination multiple aperture plasma membrane of the present invention is a face superimposed layer modification porous layer A at said polyolefins multiple aperture plasma membrane, in phase The lamination multiple aperture plasma membrane of reverse side superimposed layer modification porous layer B.
Modification porous layer A and modification porous layer B can be identical porous layer, it is also possible to different.It is essential, however, that extremely Modification porous layer A contains inorganic particulate and hot strength 5N/mm less2Above binding agent.Only modification porous layer A contains inorganic grain Son and hot strength 5N/mm2During above binding agent, in order to play the effect of the present invention, it is preferably in rip cutting operation or transport In the rear operation such as operation, apply the side lamination modification porous layer A of higher stress in the contact because of cylinder or horizontal bar etc..
In the present invention, so-called modification porous layer refers to, gives or improve thermostability and the adhesiveness of electrode material, Yi Ji electricity Solve the layer of at least one in the functions such as liquid permeability.At least modification porous layer A contains inorganic particulate and hot strength 5N/mm2 Above binding agent.By using hot strength 5N/mm2Above binding agent, it is possible to because polyolefin porous plasma membrane surfaces exists The cooperative effect of tension stress of projection and this binding agent obtain the lamination multiple aperture plasma membrane that described 0 ° of peel strength is the most excellent.Additionally, Compared with the vapour lock degree of polyolefin porous plasma membrane, the vapour lock degree of the lamination multiple aperture plasma membrane of the present invention is not substantially increased.This is because Even if not permeating a large amount of binding agent in the pore of polyolefin porous plasma membrane, it is also possible to obtain sufficient 0 ° of peel strength.
The hot strength lower limit of binding agent is preferably 10N/mm2, more preferably 20N/mm2, especially preferably 30N/mm2.On Limit is not particularly limited, but reaches 100N/mm2Enough.The hot strength of binding agent refers to be recorded by following method Value.
As hot strength 5N/mm used in the present invention2Above binding agent, as long as hot strength is 5N/mm2Above, Then it is not particularly limited, include, for example polyvinyl alcohol, cellulose ether resinoid, acrylic resin etc..As cellulose ether Resinoid, can enumerate carboxymethyl cellulose (CMC), hydroxyethyl cellulose (HEC), carboxyethyl cellulose, methylcellulose, ethyl Cellulose, cyanethyl cellulose, hydrogen-oxygen ethyl cellulose etc., as acrylic resin, preferably cross-linking type acrylic acid resin. Additionally, it be also possible to use the aqueous solution or aqueous dispersions sold on market.As product sold on market, include, for example day new Chemical conversion (strain) system " POVACOA T " (registered trade mark), East Asia synthesis (strain) system " JURYMER " (registered trade mark) AT-510, ET- 410, FC-60, SEK-301, great achievement fine chemistry industry (strain) U processed W-223SX, UW-550CS, DIC (strain) WE-301, EC- 906EF, CG-8490 etc..Wherein, it is however preferred to have electrode adhesion, high with the affinity of nonaqueous electrolytic solution, and thermostability is suitable When, there is the polyvinyl alcohol of bigger hot strength, acrylic resin.
The binding agent used as modification porous layer B, can be identical with modification porous layer A, it is also possible to different.Such as, When giving excellent thermostability, the thermostability trees such as polyamide-imide resin, polyimide resin, polyamide can be used Fat；When giving electrode adhesiveness, the fluorine-type resin such as polyvinylidene fluoride and derivant thereof etc. can be used.
In order to reduce the bending of lamination multiple aperture plasma membrane, it is important that add in the coating fluid for forming modification porous layer Add inorganic particulate.The coating fluid of this specification contains hot strength 5N/mm2Above binding agent, inorganic particulate and solubilized Or disperse the solvent of described binding agent, it is used for forming modification porous layer.
As the addition upper limit of inorganic particulate, preferably 98 percentage by weights, more preferably 95 percentage by weights.Lower limit It is preferably 80 percentage by weights, more preferably 85 percentage by weights.If the addition of inorganic particulate above-mentioned preferably in the range of, Then can fully obtain the effect reducing bending, in the cumulative volume of modification porous layer, ratio shared by functional resin is optimal, and energy Enough sufficient 0 ° of peel strengths obtaining modification porous layer.
As inorganic particulate, calcium carbonate, calcium phosphate, amorphous silica, crystalline glass filler, kaolinite can be enumerated Soil, Talcum, titanium dioxide, aluminium oxide, silica-alumina composite oxide particle, barium sulfate, calcium fluoride, lithium fluoride, boiling Stone, molybdenum sulfide, Muscovitum and boehmite etc..And it is possible to be added as needed on thermostability cross-linked polymer particle.As heat-resisting Sexual intercourse linked polymer particle, can enumerate crosslinked polystyrene particle, crosslinked acrylic resin particle and crosslinked methacrylic Acid methyl ester class particle etc..
The shape of inorganic particulate can enumerate spherical, the most spherical, tabular, needle-like, polyhedron-shaped, is not particularly limited.
The mean diameter of these inorganic particulates is preferably more than 1.5 times of the average fine pore of polyolefin porous plasma membrane, and 50 Below Bei.More preferably more than 2.0 times, less than 20 times.If the mean diameter of particle above-mentioned preferably in the range of, then deposit mixed Under the state of heat-resistant resin and particle, will not block the pore of polyolefin porous plasma membrane, its result can maintain vapour lock degree, and And still prevent this particle in battery assembling procedure and come off, cause the significant deficiency of battery.
Binding agent at least has the effect making inorganic particulate combine and makes polyolefin porous plasma membrane and modification porous layer In conjunction with effect.Solvent include, for example water, alcohols, acetone or n-methyl pyrrolidone etc..By adding nothing in coating fluid Machine particle, additionally it is possible to acquisition prevents the effect of the internal short-circuit caused because of the growth of the ingotism of inside battery electrode (dendrite preventing effectiveness) and the effect such as reduction percent thermal shrinkage, imparting sliding.
As long as the solid concentration of coating fluid can even spread, then there is no particular restriction, preferably 50 percentage by weights Above, below 98 percentage by weights, more than more preferably 80 percentage by weights, below 95 percentage by weights.If coating fluid Solid concentration above-mentioned preferably in the range of, then can prevent modifying porous layer and become fragile, it is thus achieved that sufficient 0 ° of stripping of modification porous layer From intensity.
The thickness of modification porous layer is preferably 1～5 μm, more preferably 1～4 μm, especially preferably 1～3 μm.If modification The thickness of porous layer above-mentioned preferably in the range of, then the lamination multiple aperture plasma membrane obtained after lamination modification porous layer can ensure that at fusing point Rupture of membranes intensity when more than melting/shrink and insulating properties, and sufficient hole obturation function can be obtained, prevent abnormal response.This Outward, may also suppress winding volume, be suitable for the high capacity of battery.And bent by suppression, it is possible to directly improve battery and assemble The productivity of operation.The thickness of modification porous layer A with B can be identical, it is also possible to different, the difference of thickness is preferably below 0.5 μm, Below especially preferably 0.3 μm.
In view of battery behavior, the void content of modification porous layer is preferably 30～90%, more preferably 40～70%.Pass through Suitably adjust the concentration of inorganic particulate, binder concn etc., desired void content can be obtained.
The thickness upper limit of the lamination multiple aperture plasma membrane obtained after lamination modification porous layer is preferably 25 μm, more preferably 20 μm. Lower limit is preferably more than 6 μm, more than more preferably 7 μm.If the thickness of lamination multiple aperture plasma membrane above-mentioned preferably in the range of, then fold The lamination multiple aperture plasma membrane obtained after layer modification porous layer can ensure that sufficient mechanical strength and insulating properties.Additionally, can by minimizing The electrode area being filled in container, it is possible to avoid capacity to reduce.
The vapour lock degree of lamination multiple aperture plasma membrane is one of most important characteristic, and preferably 50～600sec/100ccAir are more excellent Elect 100～500sec/100ccAir as, especially preferably 100～400sec/100ccAir.By adjusting modification porous layer Void content, adjusts binding agent and immerses the degree of polyolefin porous plasma membrane, can obtain desired vapour lock degree.If lamination Porous The vapour lock degree of film above-mentioned preferably in the range of, then be obtained in that sufficient insulating properties, and foreign matters from being blocked, short circuit can be prevented and break Film.Additionally, by controlling membrane resistance, additionally it is possible to obtain the charge-discharge characteristic in scope that can be practical, life characteristic.
4. modification porous layer is laminated to the method on polyolefin porous plasma membrane
It follows that the method that modification porous layer is laminated on polyolefin porous plasma membrane is illustrated to the present invention.
Modification porous layer is laminated to the method on polyolefin porous plasma membrane and can use well-known method.Specifically, logical Cross following method to be applied on polyolefin porous plasma membrane with regulation thickness by described coating fluid, can be by baking temperature 40～80 DEG C, the method that is dried under conditions of 5 seconds to 60 seconds drying time obtains.Additionally, it be also possible to use following methods, i.e. use following Binding agent is laminated to the polyolefin porous matter of regulation by rubbing method with the coating fluid that solvable and with water mixing solvent carries out dissolving On film, it is placed under specific humidity environment, makes the solvent phase by binding agent mixes with water separate, and it is (solidifying to put into water-bath Gu bath) in make adhesive.
As the method for applied coating solution, include, for example dip coating, reverse roll rubbing method, gravure coating process, identical painting Cloth method, roll brush rubbing method, spraying process, air knife coating method, Meyer rod coating method, pipe scraper for coating method, knife coating and mold pressing Rubbing methods etc., these methods can be implemented alone or in combination.
The lamination multiple aperture plasma membrane of the present invention preserves the most in the dry state, but is difficult to enter under absolute dry condition When row preserves, implement the drying under reduced pressure process of less than 100 DEG C the most immediately before use.
The lamination multiple aperture plasma membrane of the present invention can be used as Ni-MH battery, nickel-cadmium cell, nickel-zinc cell, smee cell, lithium secondary The secondary cell such as battery, lighium polymer secondary battery and plastic film capacitor, ceramic capacitor, double layer capacitor etc. Barrier film, be particularly preferably used as the barrier film of lithium rechargeable battery.Illustrate as a example by lithium rechargeable battery below.
Lithium rechargeable battery is across barrier film lamination positive pole and negative pole, and barrier film contains electrolyte (electrolyte).The knot of electrode Structure is not particularly limited, and can be well-known structure.Such as, the electricity of discoid positive pole arranging opposed with negative pole can be used The electrode structure (lamination-type) of electrode structure (coin shape), flat positive pole and negative pole alternative stacked and the positive pole of banding with The structures such as the electrode structure (rollback type) of negative pole overlap rollback.
Positive pole typically has collector body and the positive electrode active material layer containing positive active material, wherein this positive-active Material occlusion release can be formed at the lithium ion on surface of collector body.As positive active material, transiting metal oxidation can be enumerated Thing, lithium and the inorganic compound etc. such as the composite oxides (lithium composite xoide) of transition metal and transient metal sulfide.Make For transition metal, V, Mn, Fe, Co and Ni etc. can be enumerated.In positive active material, as the preference of lithium composite xoide Son, can enumerate with lithium nickelate, cobalt acid lithium, LiMn2O4, α-NaFeO2Type structure is the Layered Lithium composite oxides etc. of parent.
Negative pole has collector body and the negative electrode active material layer containing negative electrode active material, wherein this negative electrode active material It is formed on the surface of collector body.As negative electrode active material, native graphite, Delanium, coke class and white carbon black can be enumerated Deng carbonaceous material.Electrolyte can obtain in organic solvent by being dissolved by lithium salts.As lithium salts, LiClO can be enumerated4、 LiPF6、LiAsF6、LiSbF6、LiBF4、LiCF3SO3、LiN(CF3SO2)2、LiC(CF3SO2)3、Li2B10Cl10、LiN (C2F5SO2)2、LiPF4(CF3)2、LiPF3(C2F5)3, lower aliphatic carboxylic acid's lithium salts and LiAlCl4 etc..These can individually make With, it is possible to two or more is used in mixed way.As organic solvent, can enumerate ethylene carbonate, Allyl carbonate, Ethyl methyl carbonate, The boiling points such as gamma-butyrolacton and the higher organic solvent of dielectric constant, oxolane, 2-methyltetrahydrofuran, dimethoxy, two The boiling points such as oxygen five cycloalkanes, dimethyl carbonate, diethyl carbonate and the relatively low organic solvent of viscosity.These can be used alone, it is possible to 2 Plant use mixed above.Especially because the viscosity of the organic solvent of high-k is higher, Jie of low viscous organic solvent Electric constant is relatively low, it is advantageous to both be used in mixed way.
During assembled battery, electrolyte can be made to contain in the barrier film being dipped into the present invention, give ion permeability to barrier film.Generally, Impregnation process is implemented by normal temperatures micro-porous film being impregnated into electrolyte.Such as when assembling cylinder battery, first depend on Sequence lamination positive plate, barrier film (composite porous film) and negative plate, batch this laminated body from one end, forms rollback type electrode Element.Then, this electrode member is inserted battery can, is impregnated with above-mentioned electrolyte, and also served as by pad riveting there is relief valve The battery cover of positive terminal such that it is able to obtain battery.
Embodiment
Hereinafter, show embodiment, the present invention is specifically described, but the present invention is not exposed to any of these embodiments Limit.It addition, the measured value in embodiment is the value measured by the following method.
1. hot strength (the N/mm of binding agent2)
The binding agent used in embodiment and comparative example fully dissolves or moisture is scattered in solvable solvent, puts it into JIS No. 2 shape test films of K7113 regulation make of in dumbbell mould, carry out natural drying with 25 DEG C and make dried thickness be about 100 μ M, and carry out vacuum drying (vacuum 3mmHg) in 8 hours with 25 DEG C, after fully removing solvent, the coupons obtained is used Make stretching strength determination.Use cupping machine ((strain) Shimadzu Seisakusho Ltd. Autograph AGS-J LOAD CELLS capacity 1kN) it is measured by following condition.Sample thin film, condition determination are as follows, carry out 3 times and measure, and are averaged value as viscous The hot strength of mixture.
Chuck spacing: 40mm
Test speed: 20mm/min
Mensuration environment: temperature 20 DEG C, relative humidity 60%
2. the quantity of projection
Use burnt (confocal point) microscope (Lasert ec company HD 100) of the copolymerization being arranged on non-shock table, make light source steady After Ding, measure protruding quantity and size.
(step)
(1), on any one face (being set to A face) of the battery separator obtained in embodiment and comparative example, superfine oiliness is used The square-shaped frame of 1cm × 1cm drawn by pen.
(2) by drawing facing up of above-mentioned square-shaped frame, it is placed on sample stage, and uses the subsidiary electrostatic of Laser Scanning Confocal Microscope Bonder so that it is be adhesively fixed on sample stage.
(3) object lens using multiplying power to be 5 times, make the ring-type trace of the spherocrystal from polyethylene shown in Fig. 3 show on a monitor For 2D image (in this device be referred to as R EAL picture), and adjusting sample stage position, the part making the color of ring-type trace the denseest is positioned at The approximate centre of monitor picture.When being connected to 2 ring-type traces, it is directed at its contact.By the spherocrystal from described polyethylene The major diameter of ring-type trace is more than the 0.2mm person mensuration object as height of projection.In described 2D image, light is made to be marked on major diameter side Upwards it is directed at the two ends of ring-type trace, reads the length of its major diameter.
(4) object lens are changed 20 times of lens into, and make the central part of focus alignment monitor picture (this device make monitor picture Central part show the brightest), height (in this device be referred to as REF SET) on the basis of this height and position.
(5) described altitude datum being set to 0 μm, the measurement range of short transverse is set as its upper and lower 15 μm.During additionally, will scan Between be set to 120 seconds, STEP displacement is set to 0.1 μm/Step, reads 3D data.
(6), after reading 3D data, video data processes uses image (being referred to as Z-image in this device), and it is (smooth to implement smoothing processing Condition: filter disc size 3 × 3, substrate types SMOOTH3_0, number of times is 1 time).Additionally, always according to needs, at level correction picture In implement level correction.
(7) in data process image, cursor is placed in the horizontal direction (the brightest portion, position by the highest projection Point), make the section profile corresponding with described cursor show in section profile image.
(8) in section profile image, in vertical direction, the flex point of the both sides of 2 cursor alignment bumps is made, with between two cursors Distance is as protruding size.
(9) in section profile image, in horizontal direction, make summit and the flex point of protruding both sides of 2 cursor alignment bumps The height difference of the flex point of protruding both sides (time take relatively low one), using the distance between two cursors as protruding height.
(10) repeating described operation in the square-shaped frame of described 1cm × 1cm, counting size is below more than 5 μm, 50 μm, height Degree is the protruding quantity of below more than 0.5 μm, 3.0 μm, calculates the every 1cm in A face2Protruding number, and calculate the height of this projection Degree meansigma methods is as the average height of projection in A face.Opposing face (being set to B face) for A face also implements same operation, calculates B The protruding number in face and average height of projection.
3. modify 0 ° of peel strength of porous layer
In order to arbitrary face (such as A face) is measured, peels off the modification porous layer in opposing face (B face) in advance with adhesive tape, make to gather One surface of alkene multiple aperture plasma membrane is exposed, as sample.
Fig. 1 schematically shows evaluation methodology.1 is lamination sample, and 2 is polyolefin porous plasma membrane, and 3 is modification porous layer, and 4 are Two-sided tape, 5 and 5 ' is aluminium sheet, and the arrow in figure is draw direction.At size 50mm × 25mm, the aluminium sheet 5 of thickness 0.5mm On, attach the two-sided tape (Nichiban Co., Ltd. NW-K50) 4 that size is identical.Thereon attach be cut into width 50mm × Sample 1 (battery separator) the i.e. face of polyolefin porous plasma membrane 2 of length 100mm so that it is from length 25mm of described aluminium sheet 5 End on one side starts overlapping 40mm, and cuts extension.Then, at length 100mm, width 15mm, the aluminum of thickness 0.5mm The one side of plate 5 ' attaches two-sided tape, from the sample side of length 25mm of described aluminium sheet 5 end start to attach so that it is Overlapping 20mm.Then, the aluminium sheet 5 and aluminium sheet 5 ' of clamping sample are installed to cupping machine ((strain) Shimadzu Seisakusho Ltd. Au Tograph AGS-J 1kN), stretch aluminium sheet 5 and aluminium sheet 5 ' with the draw speed of 10mm/min the most round about, Measure intensity when modification porous layer is peeled off.Implement this mensuration at any the 3 of interval more than 30cm in the longitudinal direction, put down Average is as 0 ° of peel strength of A face modification porous layer.B face is calculated similarly 0 ° of peel strength of modification porous layer.
4. thickness
Use contact film thickness gauge (Mitutoyo Co., Ltd. LIGHTOMATI C series318), measured value at 20 is taken Meansigma methods, thus calculate thickness.Use superhard sphere gauge headIt is measured increasing the weight of the condition of 0.01N.
5. average pore size
Make to measure using the following method the average pore size of polyolefin porous plasma membrane.Use two-sided tape that sample is fixed on mensuration electricity consumption Chi Shang, makes platinum or gold vacuum evaporation several minutes, with suitable multiplying power, the surface of film is implemented SEM and measure.Obtain being measured by SEM Image at optional 10, using this at 10 the meansigma methods in aperture as the average pore size of sample.
6. vapour lock degree (sec/100ccAir)
Use the Gurley formula air permeability testing machine Type B of TESTER Industry Co., Ltd, by polyolefin porous plasma membrane or lamination It is fixed between clamping plate and keyset to multiple aperture plasma membrane corrugationless, and implements to measure according to JIS P8117.Sample is made 10cm Square, measuring point be the central part of sample and 4 jiaos amount at 5, use its meansigma methods as vapour lock degree.It addition, one side of sample Length less than 10cm time, it is possible to use with the value at 5cm measuring space 5.The ascensional range of vapour lock degree is calculated according to following formula.
The ascensional range of vapour lock degree=(Y)-(X) sec/100ccAir
Vapour lock degree (X) sec/100ccAir of polyolefin porous plasma membrane
Vapour lock degree (Y) sec/100ccAir of lamination multiple aperture plasma membrane
7. the void content of polyolefin porous plasma membrane
Prepare the square sample of 10cm, measure this volume of sample (cm3) and quality (g), according to the result obtained, use following formula Calculate void content (%).
Void content=(1-mass/(resin density × volume of sample)) × 100
8. rub resistance
While the cylinder shape lamination multiple aperture plasma membrane obtained in embodiment and comparative example is spread out, rip cutting is implemented at two ends and adds Work.Use microtome (Nishimura Seisakusho Co., Ltd.'s WA177A type), at speed 20m/ minute, the bar of tension force 60N/100mm Rip cutting processing is implemented under part.In processing, the cylinder contacted with coated face is 2 hard plating rollers (being all free roll).Then, Rollback implemented the cylinder shape lamination multiple aperture plasma membrane of rip cutting processing, the visual and magnifier with a scale of use amplification 10 times (PEAK company SCALE LUPE × 10), count the stripping number of non-compliances of the modification porous layer of more than major diameter 0.5mm, according to following Determinating reference is evaluated.Evaluating area is width 100mm × length 500m.(regulation length when width is less than 100mm, to reach Evaluation area to same).
Determinating reference
Zero (the best): less than 5
△ (well): 6～15
× (bad): more than 16
Embodiment 1
Obtain by ultra-high molecular weight polyethylene (UH MWPE) 2 percentage by weights that weight average molecular weight is 2,000,000 and Weight-average molecular Amount is compositions (Mw/Mn=16.0) 100 weight portion of high density polyethylene (HDPE) (H DPE) the 98 percentage by weight composition of 350,000 In, add the polyethylene composition (fusing point 135 DEG C) of antioxidant 0.375 weight portion.By this polyethylene composition 30 weight Part puts into double screw extruder.Supply Liquid Paraffin 70 weight portion from the side feeder of this double screw extruder, melt Mixing, modulation polyvinyl resin solution the most in an extruder.Then, from the T-shaped mould being arranged on extruder front end, with 190 DEG C, extrusion thickness 825 μm polyethylene extrusion resin solution, utilize be arranged in polyvinyl resin solution both sides (with reference to Fig. 4), Chilling roll internal cooling coolant-temperature gage is maintained at 2 chilling rolls of 25 DEG C, and extraction is extruded into membranaceous polyethylene tree Lipoprotein solution, forms gluey article shaped.Now, in each chilling roll, leaving chilling roll from gluey article shaped Put between the point that the polyvinyl resin solution extruded from T-shaped mould is connected with chilling roll, make 1 polyester scraper with gluey The width of article shaped contact cooling cylinder abreast, scrapes attachment Liquid Paraffin onto a chilled roll, among other applications.Then, adjust This glue article shaped, to reach desired vapour lock degree, is implemented simultaneously bi-directionally to stretch, it is thus achieved that draw by joint temperature with 5 × 5 times Stretch article shaped.Utilize dichloromethane to clean the stretch-molded article obtained, remove the Liquid Paraffin of residual, after being dried, obtain Obtain Porous article shaped.Then, multiple aperture plasma membrane is maintained on stenter, only constriction 10% on TD (width) direction, The heat treatment 3 seconds when 90 DEG C, it is thus achieved that thickness 16 μm, void content 45%, average pore size 0.15 μm, vapour lock degree 240s/ The polyethylene porous plasma membrane of 100ccAir.
(allotment of coating fluid A)
Polyvinyl alcohol (average degree of polymerization 1700, saponification degree more than 99%), average particle is coordinated respectively with the weight rate of 6:54:40 The aluminium oxide particles of footpath 0.5 μm and ion exchange water, with zirconium oxide bead (Dongli Ltd.'s system " Toravseram " (registrar Mark) beadlet, diameter 0.5mm) together put in the container of polypropylene, ((strain) Toyo Seiki makes institute to utilize paint shaker System) disperse 6 hours.Then, the filter filtering the limit 5 μm is used to filter, it is thus achieved that coating fluid (a).
(allotment of coating fluid B)
By trimellitic anhydride (TMA) 1 mole, o-tolidine diisocyanate (T ODI) 0.8 mole, 2,4-toluene diisocyanate Acid esters (TDI) 0.2 mole and potassium fluoride 0.01 mole together load with thermometer, cooling with METHYLPYRROLIDONE Pipe, nitrogen ingress pipe four-hole boiling flask in, make solid concentration reach 14%, stir after 5 hours when 100 DEG C, utilize N-first Base-2-Pyrrolidone is diluted, and makes solid concentration reach 14%, synthesizing polyamides imide resin solution.Obtained The logarithmic viscosity number of polyamide-imide resin is 1.35dl/g, and glass transition temperature is 320 DEG C.
It is the aluminium oxide particles of 0.5 μm, METHYLPYRROLIDONE by polyamideimide resin solution and mean diameter Coordinate with the weight rate of 26:34:40 respectively, with zirconium oxide bead (Dongli Ltd.'s system, " Toravseram " (registration Trade mark) beadlet, diameter 0.5mm) together put in polypropylene container, utilize paint shaker ((strain) Toyo Seiki make institute System) disperse 6 hours.Then, the filter filtering the limit 5 μm is used to filter, it is thus achieved that coating fluid (b).Intaglio plate is utilized to be coated with Method on a face (being set to A face) of described polyethylene porous plasma membrane with dried thickness 2 μm applied coating solution (a) so that it is logical The hot-air drying stove crossing 50 DEG C is dried for 10 seconds.Then, opposing face (being set to B face) is coated with dried thickness 2.5 μm Cloth so that it is by temperature 25 DEG C, absolute humidity 12g/m3Damping district after 5 seconds, be immersed in containing METHYLPYRROLIDONE In the aqueous solution of 5 percentage by weights 10 seconds.Further, after utilizing pure water to clean so that it is entered by the hot-air drying stove of 70 DEG C Row is dried, it is thus achieved that the lamination multiple aperture plasma membrane of final thickness 20.5 μm.
Embodiment 2
Except being the height of 350,000 by ultra-high molecular weight polyethylene (UHMW PE) that weight average molecular weight is 2,000,000 with weight average molecular weight The proportioning of density polyethylene (HDPE) is changed to beyond 10:90 (percentage by weight), obtains lamination porous similarly to Example 1 Plasma membrane.
Embodiment 3
Except being the height of 350,000 by ultra-high molecular weight polyethylene (UHMW PE) that weight average molecular weight is 2,000,000 with weight average molecular weight The proportioning of density polyethylene (HDPE) is changed to beyond 20:80 (percentage by weight), obtains lamination porous similarly to Example 1 Plasma membrane.
Embodiment 4
Except being the height of 350,000 by ultra-high molecular weight polyethylene (UHMW PE) that weight average molecular weight is 2,000,000 with weight average molecular weight The proportioning of density polyethylene (HDPE) is changed to beyond 30:70 (percentage by weight), obtains lamination porous similarly to Example 1 Plasma membrane.
Embodiment 5
Except being the height of 350,000 by ultra-high molecular weight polyethylene (UHMW PE) that weight average molecular weight is 2,000,000 with weight average molecular weight The proportioning of density polyethylene (HDPE) is changed to beyond 40:60 (percentage by weight), obtains lamination porous similarly to Example 1 Plasma membrane.
Embodiment 6
In addition to 2 polyester scrapers are contacted 2 chilling rolls with the interval of 20mm, obtain folded similarly to Example 1 Layer multiple aperture plasma membrane.
Embodiment 7
In addition to 3 polyester scrapers are contacted 2 chilling rolls with the interval of respective 20mm, obtain similarly to Example 1 Obtain lamination multiple aperture plasma membrane.
Embodiment 8
Coordinate by water soluble acrylic acid ester polyol and water-dispersible polyisocyanates (solidification with the weight rate of 10:40:50 respectively Agent) constitute biliquid curable aqueous propenoic methyl carbamate resin (solid concentration 45 mass percent), mean diameter The aluminium oxide particles of 0.5 μm and ion exchange water, with zirconium oxide bead (Dongli Ltd.'s system, " Toravseram " (registrar Mark) beadlet, diameter 0.5mm) together put in the container of polypropylene, ((strain) Toyo Seiki makes institute to utilize paint shaker System) disperse 6 hours.Then, the filter filtering the limit 5 μm is used to filter, it is thus achieved that coating fluid (c).Except by coating fluid A () replaces to beyond coating fluid (c), obtain two sides lamination modification porous layer similarly to Example 1, final thickness 20.5 μm Lamination multiple aperture plasma membrane.
Embodiment 9
(day is newly changed to coordinate the copolymer of polyvinyl alcohol and acrylic acid, methyl methacrylate with the weight rate of 5:45:50 respectively Become (strain) system " POVACOAT " (registered trade mark)), the aluminium oxide particles of mean diameter 0.5 μm and solvent (ion exchange water: ethanol =70:30), with zirconium oxide bead (Dongli Ltd.'s system " Toravse ram " (registered trade mark) beadlet, diameter 0.5mm) together Put in the container of polypropylene, utilize paint shaker ((strain) Toyo Seiki makes made) dispersion 6 hours.Then, use The filter filtering the limit 5 μm filters, it is thus achieved that coating fluid (d).In addition to coating fluid (a) is replaced to coating fluid (d), It is coated similarly to Example 1, it is thus achieved that two sides lamination modification porous layer, the lamination multiple aperture plasma membrane of final thickness 20.5 μm.
Embodiment 10
KF polymer #1120 (Kureha Kagaku Kogyo K.K.'s system, poly-inclined difluoro is coordinated respectively with the weight rate of 14:19:67 Vinyl solution (fusing point 175 DEG C, 12%N-methylpyrrolidone solution)) and the aluminium oxide particles of mean diameter 0.5 μm, METHYLPYRROLIDONE, with zirconium oxide bead (Dongli Ltd.'s system " Tor avseram " (registered trade mark) beadlet, diameter 0.5mm) together put in the container of polypropylene, utilize paint shaker ((strain) Toyo Seiki makes made) dispersion 6 hours. Then, the filter filtering the limit 5 μm is used to filter, allotment varnish (e).Except coating fluid (b) is replaced to coating fluid Beyond (e), it is coated similarly to Example 1, it is thus achieved that two sides lamination modification porous layer, the lamination of final thickness 20.5 μm is many Hole plasma membrane.
Embodiment 11
In addition to the internal cooling coolant-temperature gage of chilling roll is remained 35 DEG C, obtain lamination porous similarly to Example 1 Plasma membrane.
Embodiment 12
Except adjusting the extrusion capacity of polyvinyl resin solution, it is thus achieved that beyond the polyethylene porous plasma membrane of thickness 20 μm, with embodiment 1 Similarly, it is thus achieved that the lamination multiple aperture plasma membrane of final thickness 24.5 μm.
Embodiment 13
Except adjusting the extrusion capacity of polyvinyl resin solution, it is thus achieved that beyond the polyethylene porous plasma membrane of thickness 12 μm, with embodiment 1 Similarly, it is thus achieved that the lamination multiple aperture plasma membrane of final thickness 16.5 μm.
Embodiment 14
Except adjusting the extrusion capacity of polyvinyl resin solution, it is thus achieved that beyond the polyethylene porous plasma membrane of thickness 9 μm, with embodiment 1 Similarly, it is thus achieved that the lamination multiple aperture plasma membrane of final thickness 13.5 μm.
Embodiment 15
Except polyethylene composition 26 weight portion being put into double screw extruder, and supply from the side feeder of double screw extruder Answer Liquid Paraffin 74 weight portion, carry out beyond melting mixing, obtain lamination multiple aperture plasma membrane similarly to Example 1.
Embodiment 16
Except polyethylene composition 35 weight portion being put into double screw extruder, and supply from the side feeder of double screw extruder Answer Liquid Paraffin 65 weight portion, carry out beyond melting mixing, obtain lamination multiple aperture plasma membrane similarly to Example 1.
Embodiment 17
In coating fluid (a), aluminium oxide particles is replaced to Titanium particles (mean diameter 0.38 μm), mixes coating fluid (f).In addition to using coating fluid (f) to substitute coating fluid (a), obtain lamination multiple aperture plasma membrane similarly to Example 1.
Embodiment 18
In coating fluid (a), aluminium oxide particles is replaced to tabular boehmite particulate (mean diameter 1.0 μm), mixes coating Liquid (g).In addition to using coating fluid (g) to substitute coating fluid (a), obtain lamination multiple aperture plasma membrane similarly to Example 1.
Embodiment 19
In addition to two sides all uses coating fluid (a), obtain lamination multiple aperture plasma membrane similarly to Example 1.
Comparative example 1
The polyvinyl resin solution extruded from T-shaped mould except utilizing 2 chilling rolls to cool down, and obtaining gluey article shaped Time, the most do not use scraper for 2 chilling rolls, do not scrape beyond attachment Liquid Paraffin onto a chilled roll, among other applications, with embodiment 1 Similarly obtain lamination multiple aperture plasma membrane.
Comparative example 2
Except using in the combination being made up of high density polyethylene (HDPE) (HDP E) 100 percentage by weights that weight average molecular weight is 350,000 Thing (Mw/Mn=16.0) 100 weight portion with the addition of the polyethylene composition (fusing point 135 DEG C) of antioxidant 0.375 weight portion In addition, lamination multiple aperture plasma membrane is obtained similarly to Example 1.
Comparative example 3
Except the internal cooling coolant-temperature gage of chilling roll is remained 0 DEG C, and do not use beyond scraper, similarly to Example 1 Ground obtains lamination multiple aperture plasma membrane.
Comparative example 4
Except the polyvinyl resin solution utilizing chilling roll cooling to extrude from T-shaped mould is changed into during remaining the water of 25 DEG C Impregnate beyond 1 minute, obtain lamination multiple aperture plasma membrane similarly to Example 1.
Comparative example 5
Although attempted polyethylene composition 50 weight portion used in embodiment 1 is put into double screw extruder, and from double spiral shells Side feeder supply Liquid Paraffin 50 weight portion of bar extruder, carries out melting mixing, in an extruder modulation polyethylene tree Lipoprotein solution, and extrude from T-shaped mould, but fail to extrude the most membranaceous.
Comparative example 6
In addition to the internal cooling coolant-temperature gage of chilling roll is remained 50 DEG C, obtain lamination porous similarly to Example 1 Plasma membrane.
Comparative example 7
By trimellitic anhydride (TMA) 1 mole, o-tolidine diisocyanate (T ODI) 0.8 mole, 2,4-toluene diisocyanate Acid esters (TDI) 0.2 mole and potassium fluoride 0.01 mole together load with thermometer, cooling with METHYLPYRROLIDONE Pipe, nitrogen ingress pipe four-hole boiling flask in, make solid concentration reach 14%, stir after 5 hours when 100 DEG C, utilize N-first Base-2-Pyrrolidone is diluted, and makes solid concentration reach 14%, synthesizing polyamides imide resin solution.
It is the aluminium oxide particles of 0.5 μm, METHYLPYRROLIDONE difference by polyamideimide resin solution and mean diameter Coordinate with the weight rate of 13:47:40, with zirconium oxide bead (Dongli Ltd.'s system " Toravseram (registered trade mark) pearl Grain ", diameter 0.5mm) together put in polypropylene container, utilize paint shaker ((strain) Toyo Seiki make made) dispersion 6 hours.Then, the filter filtering the limit 5 μm is used to filter, it is thus achieved that coating fluid (h).Except coating fluid (a) is replaced Become beyond coating fluid (h), obtain the lamination multiple aperture plasma membrane of final thickness 20.5 μm similarly to Example 1.
Embodiment 1～19, comparative example 1～7 manufacturing condition as shown in table 1.
[table 1]
The polyolefin porous plasma membrane obtained in embodiment 1～19, comparative example 1～7 and the characteristic such as table 2 of lamination multiple aperture plasma membrane Shown in.
[table 2]
Symbol description
1 lamination multiple aperture plasma membrane
2 polyolefin porous plasma membranes
3 modification porous layers
4 two-sided tapes
5 aluminium sheets
5 ' aluminium sheets
The nucleus of 6 polyethylene spherocrystals
7 T-shaped moulds
8 vistanex solution
9 chilling rolls
9 ' chilling rolls
10 scrapers
11 gluey article shaped

Claims (8)

1. a lamination multiple aperture plasma membrane, it is characterised in that the projection being made up of polyolefin meets 5 μm≤W≤50 μm and 0.5 μm ≤ H, with 3/cm2Above, 200/cm2Following density is dispersed on each face in two faces brokenly, and One face superimposed layer modification porous layer A of the polyolefin porous plasma membrane below thickness 25 μm, lamination modification porous on opposing sides Layer B, at least modification porous layer A contain hot strength 5N/mm2Above binding agent and inorganic particulate, wherein W is the big of projection Little, H is protruding height.
Lamination multiple aperture plasma membrane the most according to claim 1, it is characterised in that described hot strength 5N/mm2Above bonding Agent is polyvinyl alcohol or acrylic resin.
3. according to the lamination multiple aperture plasma membrane described in claim 1 or claim 2, it is characterised in that described inorganic particulate contains At least one in the group that calcium carbonate, aluminium oxide, titanium dioxide, barium sulfate, Muscovitum and boehmite are formed.
4. according to the lamination multiple aperture plasma membrane according to any one of claims 1 to 3, it is characterised in that described polyolefin porous matter The thickness of film is below 20 μm.
5. according to the lamination multiple aperture plasma membrane according to any one of claims 1 to 3, it is characterised in that described polyolefin porous matter The thickness of film is below 16 μm.
6. according to the lamination multiple aperture plasma membrane according to any one of Claims 1 to 5, it is characterised in that as battery separator.
7. a manufacture method for lamination multiple aperture plasma membrane, in order to the lamination Porous according to any one of manufacturing claims 1～6 Film, it is characterised in that contain:
A () adds molding solvent in vistanex after, carry out melting mixing, the operation of modulation vistanex solution；
B () extrudes described vistanex solution from T-shaped mould, use surface to eliminate the cooling rolling of vistanex solution Cylinder cools down, and forms the operation of gluey article shaped, and it is molten that described chilling roll is arranged in the vistanex being extruded as membranaceous The two sides of liquid；
C described gluey article shaped is stretched by () to operating direction and width, it is thus achieved that the operation of stretch-molded article；
D () removes described molding solvent from described stretch-molded article, be dried, it is thus achieved that the operation of Porous article shaped；
E described Porous article shaped is carried out heat treatment by (), it is thus achieved that the operation of polyolefin porous plasma membrane；And
F () uses containing hot strength 5N/mm2Above binding agent, solubilized or disperse the solvent of described binding agent and inorganic The coating fluid of particle, forms stack membrane, the operation being dried at least one face of described polyolefin porous plasma membrane.
The manufacture method of lamination multiple aperture plasma membrane the most according to claim 7, it is characterised in that molding in described operation (b) It is scraper by the removing means of solvent.
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