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WO2009035161A2 - Filière et système distributeur associé - Google Patents

Filière et système distributeur associé Download PDF

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Publication number
WO2009035161A2
WO2009035161A2 PCT/JP2008/066935 JP2008066935W WO2009035161A2 WO 2009035161 A2 WO2009035161 A2 WO 2009035161A2 JP 2008066935 W JP2008066935 W JP 2008066935W WO 2009035161 A2 WO2009035161 A2 WO 2009035161A2
Authority
WO
WIPO (PCT)
Prior art keywords
passage
cross flow
die
flow manifold
communication
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2008/066935
Other languages
English (en)
Other versions
WO2009035161A3 (fr
Inventor
Soichiro Yamaguchi
Tetsuro Nogata
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tonen Chemical Corp
Original Assignee
Tonen Sekiyu Kagaku KK
Tonen Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US11/901,164 external-priority patent/US20090072434A1/en
Application filed by Tonen Sekiyu Kagaku KK, Tonen Chemical Corp filed Critical Tonen Sekiyu Kagaku KK
Priority to JP2010510594A priority Critical patent/JP5061238B2/ja
Publication of WO2009035161A2 publication Critical patent/WO2009035161A2/fr
Publication of WO2009035161A3 publication Critical patent/WO2009035161A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
    • B29C67/20—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 for porous or cellular articles, e.g. of foam plastics, coarse-pored
    • B29C67/202—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 for porous or cellular articles, e.g. of foam plastics, coarse-pored comprising elimination of a solid or a liquid ingredient
    • 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
    • B29C48/267—Intermediate treatments, e.g. relaxation, annealing or decompression step for the melt
    • 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
    • B29C48/31—Extrusion nozzles or dies having a wide opening, e.g. for forming sheets being adjustable, i.e. having adjustable exit sections
    • B29C48/313—Extrusion nozzles or dies having a wide opening, e.g. for forming sheets being adjustable, i.e. having adjustable exit sections by positioning the die lips
    • 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
    • B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
    • B29C71/02—Thermal after-treatment
    • B29C2071/022—Annealing
    • 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
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
    • 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
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/50—Details of extruders
    • B29C48/695—Flow dividers, e.g. breaker plates
    • B29C48/70—Flow dividers, e.g. breaker plates comprising means for dividing, distributing and recombining melt flows
    • B29C48/705—Flow dividers, e.g. breaker plates comprising means for dividing, distributing and recombining melt flows in the die zone, e.g. to create flow homogeneity
    • 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
    • B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
    • B29C71/0072—After-treatment of articles without altering their shape; Apparatus therefor for changing orientation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/06—PE, i.e. polyethylene
    • B29K2023/0658—PE, i.e. polyethylene characterised by its molecular weight
    • B29K2023/0683—UHMWPE, i.e. ultra high molecular weight polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/04—Condition, form or state of moulded material or of the material to be shaped cellular or porous
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/34—Electrical apparatus, e.g. sparking plugs or parts thereof
    • B29L2031/3468—Batteries, accumulators or fuel cells
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/712—Containers; Packaging elements or accessories, Packages
    • B29L2031/7146—Battery-cases

Definitions

  • This disclosure relates generally to an extrusion apparatus for producing a film or sheet of thermoplastic material.
  • Extrusion dies are used in manufacturing processes to make a variety of goods. Some dies, for example, are used to form thin films, sheets or other elongated shapes of plastic material. Techniques have been developed for melt laminating which involves joining two or more diverse materials (e.g., thermoplastic materials) from separate molten layers under pressure within a die to emerge as a single laminated material. Such processes make use of the laminar flow principle which enables two or more molten layers under proper operating conditions to join in a common flow channel without intermixing at the contacting interfaces. These multiple layer extrusion systems have come into use as a convenient way to provide for the formation of multiple layers of similar or dissimilar materials from polymer melts.
  • materials e.g., thermoplastic materials
  • a die assembly for extruding polymer melts can be modular and is typically assembled from a plurality of parts and then set in a die station as an integral device.
  • a die assembly can comprise a first die part and a second die part, which together form the components that allow a fluid to enter the assembly and be properly emitted therefrom.
  • the first die part includes a first lip and the second die part includes a second lip, these lips defining a feed gap therebetween that determines the thickness of the fluid film emitted therefrom.
  • Center feed extrusion dies are commonly used in today's plastics industry.
  • center feed extrusion dies have a tear drop-shaped, flat manifold, which may be in a form known as a coat hanger manifold, a fish tail manifold, or a T- type manifold.
  • this type of die may further include a flow pressure-compensating preland channel.
  • a die assembly for extruding polymer melts can have a fixed feed gap or a flexible feed gap.
  • the lips are not movable relative to each other, so that the thickness of the feed gap will always be the same dimension.
  • a flexible feed gap one lip is movable relative to the other lip so as to enable adjustment of the feed gap along the width of the assembly.
  • a flexible feed gap is typically accomplished by assembling the first die part so that it contains a flexible web between its rear portion and its front portion (to which the first lip is attached), as well as means for moving the front portion in localized areas. Movement of the front portion results in the adjustment of the position of the lip relative to the other lip and, thus, the thickness of the feed gap in the relevant localized area.
  • Microporous polyolefin membranes are useful as separators for primary batteries and secondary batteries such as lithium ion secondary batteries, lithium-polymer secondary batteries, nickel-hydrogen secondary batteries, nickel- cadmium secondary batteries, nickel-zinc secondary batteries, silver-zinc secondary batteries, etc.
  • secondary batteries such as lithium ion secondary batteries, lithium-polymer secondary batteries, nickel-hydrogen secondary batteries, nickel- cadmium secondary batteries, nickel-zinc secondary batteries, silver-zinc secondary batteries, etc.
  • the membrane's performance significantly affects the properties, productivity and safety of the battery.
  • microporous polyolefin membrane should have suitably well-balanced permeability, mechanical properties, dimensional stability, shutdown properties, meltdown properties, etc.
  • well-balanced means that the optimization of one of these characteristics does not result in a significant degradation in another.
  • the batteries it is desirable for the batteries to have a relatively low shutdown temperature and a relatively high meltdown temperature for improved battery safety, particularly for batteries exposed to high temperatures under operating conditions. Consistent dimensional properties, such as film thickness, are essential to high performing films. A separator with high mechanical strength is desirable for improved battery assembly and fabrication, and for improved durability.
  • microporous polyolefm membranes consisting essentially of polyethylene (i.e., they contain polyethylene only with no significant presence of other species) have relatively low meltdown temperatures. Accordingly, proposals have been made to provide microporous polyolefin membranes made from polymer solutions which contain mixed resins of polyethylene and polypropylene, and multi-layer, microporous polyolefin membranes having polyethylene layers and polypropylene layers in order to increase meltdown temperature. The use of these polymer solutions containing such mixed resins and the production of multilayer films having layers of differing polyolefins can make the production of films having consistent dimensional properties, such as film thickness, all the more difficult.
  • JP U3048972 proposes an extrusion die design said to eliminate flow divergence within the extrusion manifold.
  • the proposed die design is provided with two manifolds to form two slit currents.
  • the molten polymer is fed into a first inlet at an end of a first manifold and a second inlet at the end of a second manifold on the opposite side of the first inlet.
  • Two slit currents flow together inside the die. It is theorized that due to the absence of flow divergence of the melt inside the manifold, it may be possible to achieve uniform flow distribution within the die. This is said to result in improved thickness uniformity in the transverse direction the film or the sheet.
  • JP7-216118A discloses a battery separator formed from a porous film comprising polyethylene and polypropylene as indispensable components and having at least two microporous layers each with different polyethylene content.
  • the polyethylene content is 0 to 20% by weight in one microporous layer, 21 to 60% by weight in the other microporous layer, and 2 to 40% by weight in the overall film.
  • the battery separator has relatively high shutdown-starting temperature and mechanical strength.
  • WO 2004/089627 discloses a microporous polyolef ⁇ n membrane made of polyethylene and polypropylene comprising two or more layers, the polypropylene content being more than 50% and 95% or less by mass in at least one surface layer, and the polyethylene content being 50 to 95% by mass in the entire membrane.
  • WO 2005/113657 discloses a microporous polyolefin membrane having conventional shutdown properties, meltdown properties, dimensional stability and high- temperature strength. The membrane is made using a polyolefin composition comprising (a) composition comprising lower molecular weight polyethylene and higher molecular weight polyethylene, and (b) polypropylene. This microporous polyolefin membrane is produced by a so-called "wet process".
  • an extrusion die for producing an extrudate comprising polymer and diluent from a mixture comprising the polymer, and the diluent.
  • the extrusion die includes a die outlet through which the mixture is extruded, a feed entrance in communication with a feed splitter for dividing the mixture into a first portion and a second portion, and a cross flow manifold comprising: a first cross flow manifold section for receiving the first portion of the mixture, the first cross flow manifold section comprising a first passage having a first axis positioned within a first plane of the extrusion die, a second passage in communication with the first passage and having a second axis positioned within a second plane of the extrusion die, and a third passage in communication with the second passage and having a third axis positioned within a third plane of the extrusion die, the third passage in communication with the die outlet, and a second cross flow manifold section for receiving the second portion of the mixture, the second cross
  • a process for producing an extrudate comprising polymer and diluent includes the steps of combining at least one polyolefin and a diluent (e.g., a solvent) to prepare a polyolefin solution, and extruding the polyolefin solution through an extrusion die to form an extrudate, the extrusion die comprising (i) a die outlet through which a melt stream of the polyolefin solution is extruded as a film or sheet, (ii) a feed entrance in communication with a feed splitter for dividing the polyolefin solution into a first portion and a second portion, (iii) a cross flow manifold comprising: a first cross flow manifold section for receiving the first portion, the first cross flow manifold section comprising a first passage having a first axis positioned within a first plane of the extrusion die, a second passage in communication with the first passage and having
  • a diluent e.g
  • the invention is based in part on the discovery that extrusion die manifold design can influence the shape memory phenomena in the extrusion of polymer solutions.
  • the cross flow manifold is provided with a flow path of a length sufficient to moderate or substantially eliminate the shape memory characteristics of the thermoplastic material.
  • the first cross flow manifold section and the second cross flow manifold section of the cross flow manifold each have a flow path that substantially traverses the extrusion die's length at least two times.
  • the die outlet is a slotted die outlet which includes a first die lip and a second die lip, the first die lip including a flexible lip bar having actuatable means located along a length thereof.
  • the actuatable means of the first die lip includes a plurality of individual lip bolts effective for varying the width of the slotted die outlet in a region adjacent a point of adjustment.
  • FIG. 1 is an exploded perspective view of an extrusion die having a cross flow manifold system for producing an extrudate of thermoplastic material, in accordance herewith.
  • FIG. 2 is a partially exploded perspective view of the extrusion die having a cross flow manifold system of FIG. 1 , showing a pair of die end plates for positioning I 0 on the die, in accordance herewith.
  • FIG. 3 is a schematic view of an extrusion die for producing an extrudate of thermoplastic material showing the respective flow paths of the thermoplastic material, in accordance herewith.
  • FIG. 4 is a side view of an extrusion die for producing an extrudate of is thermoplastic material showing a flexible lip bar having actuatable means, in accordance herewith.
  • FIG. 5 is a perspective view of a coat hanger extrusion die showing the flow path of the thermoplastic material.
  • FIG. 6 is a perspective view of a cross flow extrusion die showing the flow 20 path of the thermoplastic material.
  • FIGS. 1-6 wherein like numerals are used to designate like parts throughout.
  • Extrusion die 10 for producing an extrudate comprising thermoplastic material e.g., polymer and diluent, in accordance herewith, is shown.
  • Extrusion die 10 includes a die outlet 12, which may be a slotted die outlet, as shown, through which a mixture of polymer and diluent may be extruded as a film or sheet (extrudate).
  • extrusion die 10 is provided with a first die section 14, a second die section 16, and a third die section 18 and a cross flow manifold 20 that traverses a plurality of passageways formed within first die section 14, second die section 16, and third die section 18.
  • cross flow manifold 20 includes a feed entrance 22 and a feed splitter 24 for feeding the plurality of passageways of cross flow manifold 20 in communication with die outlet 12.
  • a feed stream ofo polymer solution F is split into a first stream Sl and a second stream S2, the first stream Sl feeding cross flow manifold section 26 and the second stream S2 feeding cross flow manifold section 28.
  • First die section 14 includes a first side 30, a second side 32, a first end 34 and a second end 36, with portions of cross flow manifold 20 formed within each.
  • Second die section 16 includes an interior side 38 and third die section 18 includes an interior side 40, with portions of cross flow manifold 20 formed within each.
  • first end plate 42 and second end plate 44 are also provided with portions of cross flow manifold 20 formed within each.
  • cross flow manifold section 26 includes a first passage 26aQ having a first axis positioned within a first plane 50 formed by first side 30 of first die section 14 and interior side 38 of second die section 16, a second passage 26b having a second axis positioned within a second plane 52 formed between first end 34 of first die section 14 and a first end plate 42 (see FIG. 2) and a third passage 26c having a third axis positioned within a third plane 54 formed between second side 32 of first dies section 14 and interior side 40 of third die section 18.
  • first passage 26aQ having a first axis positioned within a first plane 50 formed by first side 30 of first die section 14 and interior side 38 of second die section 16
  • a second passage 26b having a second axis positioned within a second plane 52 formed between first end 34 of first die section 14 and a first end plate 42 (see FIG. 2)
  • a third passage 26c having a third axis positioned within a third plane 54 formed between second side 32 of first dies section 14
  • cross flow manifold section 28 may be provided with a first passage 28a having a first axis positioned within third plane 54 formed between second side 32 of first die section 14 and interior side 40 of third die section 18, a second passage 28b having a second axis positioned within a fourth plane 56 formed between second end 36 of first die section 14 and a second end plate 44 (see FIG.
  • first cross flow manifold section 26 of cross flow manifold 20 and the second cross flow manifold section 28 of cross flow manifold 20 each have a pressure manifold 26d and 28d, respectively, in communication with die outlet 12.
  • first plane and the third plane and the second plane and the fourth plane may be aligned in substantially parallel spaced relationships, respectively.
  • substantially parallel spaced relationship is meant that the opposing planes (i.e., first and third and second and fourth) do not intersect within the outer boundaries of extrusion die 10.
  • microporous membrane films and sheets from the polyolefin solution described hereinbelow, a surprising characteristic of these materials is their inherent propensity for shape memory similar to that which is observed in the extrusion of polymer melts. Other films and sheets formed from other polymer besides polyolefin may also exhibit these characteristics.
  • shape- memory plastics have a thermoplastic phase and a "frozen” phase. The initial shape is “memorized” in the frozen phase, with the shape-memory effect permitting its recovery from whatever temporary shape the plastic has been formed into.
  • a polymer chain has an ideal spatial configuration (Gaussian coil) in a melt state or in a solution without perturbation.
  • the polymer When the polymer is deformed by an external force, e.g., shear flow, the polymer relaxes its shape returns to the ideal Gaussian coil by allowing itself to diffuse in the polymer axis direction.
  • the relaxation time strongly depends on the number of entanglements, therefore, the higher the molecular weight of the polymer and the higher the polymer concentration of the solution is, the longer the relaxation time required.
  • cross flow manifold section 26 and cross flow manifold section 28 of cross flow manifold 20 each have a flow path of a length sufficient to substantially eliminate the shape memory characteristics of the thermoplastic material.
  • a portion of the combined polymer (e.g., polyolefin) and diluent traverses first cross flow manifold section 26 of the cross flow manifold 20 and second cross flow manifold section 28 of cross flow manifold 20 a distance substantially equivalent to the extrusion die's length more than once.
  • cross flow manifold section 26 and cross flow manifold section 28 of cross flow manifold 20 each have a flow path that substantially traverses the length of extrusion die 10 at least two times.
  • die outlet 12 of extrusion die 10 which may be a slotted die outlet, may be provided with a first die lip 46 and a second die lip 48, first die lip 46 including a flexible lip bar 60 having externally actuatable means 62 located along a length thereof.
  • externally actuatable means 62 includes a plurality of individual lip bolts 64, each lip bolt 64 effective for varying the width of slotted die outlet 12 in a region adjacent to a point of adjustment.
  • this difficulty stems from the fact that when a coat hanger manifold (CH) die 100 is used for the extrusion of a monolayer microporous membrane film or sheet 102, shape-memory effects in the extrudate cause a thickness non- uniformity along the transverse direction of the extrudate.
  • shape-memory effects in the extrudate tend to act in a direction perpendicular to the flow of the polyolefm solution S in the die manifold 104. Since, in coat hanger manifold die 100, the primary direction of flow in the manifold is toward the die lip 106, the shape-memory effect tends to occur in the transverse direction of the extrudate. This causes a redistribution of material in the extrudate toward the extrudate's center along the transverse direction.
  • the extrusion dies and manifold systems disclosed herein are useful in forming microporous membrane films and sheets. These films and sheets find particular utility in the critical field of battery separators.
  • the multi-layer films and sheets described hereinbelow can be produced using a monolayer die and manifold system of the type described hereinabove to produce a monolayer film or sheet, with additional layers laminated thereto in a conventional manner. Co-extrusion can also be used, where a compound die (e.g., one having at least two outlets in close proximity) has at least one component die having the manifold system of the invention.
  • the multi-layer, microporous membrane comprises two layers.
  • the first layer e.g., the skin, top or upper layer of the membrane
  • the second layer e.g., the bottom or lower or core layer of the membrane
  • the membrane can have a planar top layer when viewed from above on an axis approximately perpendicular to the transverse and longitudinal (machine) directions of the membrane, with the bottom planar layer hidden from view by the top layer.
  • the extrusion dies described herein are also useful for producing monolayer microporous membranes, e.g., monolayer polyethylene microporous membranes and/or monolayer polyolefin membranes of the type disclosed in PCT Publication WO2007/132942, for example, which is incorporated by reference herein in its entirety.
  • the multi-layer, microporous membrane comprises three or more layers, wherein the outer layers (also called the "surface” or “skin” layers) comprise the first microporous layer material and at least one core or intermediate layer comprises the second microporous layer material.
  • the multilayer, microporous polyolefin membrane comprises two layers
  • the first layer consists essentially of the first microporous layer material
  • the second layer consists essentially of the second microporous layer material.
  • the multilayer, microporous polyolefin membrane comprises three or more layers
  • the outer layers consist essentially of the first microporous layer material and at least one intermediate layer consists essentially of (or consists of) the second microporous layer material.
  • Such membranes are described in PCT Publication WO2008/016174, US2008/0057388, and US2008/0057389, which are incorporated by reference herein in their entirety.
  • the first microporous layer material contains a first polyethylene (“PE-I”) having an Mw value of less than about 1 x 10 6 or a second polyethylene (“UHMWPE-I”) having an Mw value of at least about 1 x 10 .
  • the first microporous layer material can contain a first polypropylene (“PP- 1").
  • the first microporous layer material comprises one of (i) a polyethylene (PE), (ii) an ultra high molecular weight polyethylene (UHMWPE), (iii) PE-I and PP-I , or (iv) PE-I, UHMWPE-I, and PP-I .
  • UHMWPE-I can preferably have an Mw in the range of from about 1 x 10 6 to about 15 x 10 6 or from about 1 x 10 6 to about 5 x 10 6 or from about 1 x 10 6 to about 3 x 10 6 ,and preferably contain greater than about 1 wt.%, or about 15 wt.% to 40 wt.%, on the basis of total amount of PE-I and UHMWPE-I in order to obtain a microporous layer having a hybrid structure as described in WO2008/016174, and can be at least one of homopolymer or copolymer.
  • PP-I can be at least one of a homopolymer or copolymer, or can preferably contain no more than about 25 wt.%, on the basis of total amount of the first layer microporous material.
  • the Mw of polyolefin in the first microporous layer material can have about 1 x 10 ⁇ or less, or in the range of from about 1 x 10 5 to about 1 x 10 ⁇ or from about 2 x 10 5 to about 1 x 10 6 in order to obtain a microporous layer having a hybrid structure defined in the later section.
  • PE-I can preferably have an Mw ranging from about 1 x 10 to about 5 x 10 5 , or from about 2 x 10 5 to about 4 x 10 5 , and can be one or more of a high-density polyethylene, a medium-density polyethylene, a branched low-density polyethylene, or a linear low- density polyethylene, and can be at least one of a homoporymer or copolymer.
  • the second microporous layer material comprises one of: (i) a fourth polyethylene having an Mw of at least about 1 x 10 6 , (UHMWPE-2), (ii) a third polyethylene having an Mw that is less than 1 x 10 6 and UHMWPE-2 and the fourth polyethylene, wherein the fourth polyethylene is present in an amount of at least about 8% by mass based on the combined mass of the third and fourth polyethylene; (iii) UHMWPE-2 and PP-2, or (iv) PE-2, UHMWPE-2, and PP-2.
  • UHMWPE-2 can contain at least about 8 wt.%, or at least about 20 wt.%, or at least about 25 wt.%, based on the total amount of UHMWPE-2, PE-2 and PP-2 in order to produce a relatively strong multi-layer, microporous polyolefin membrane.
  • PP-2 can be at least one of a homopolymer or copolymer, and can contain 25 wt.% or less, or in the range of from about 2% to about 15%, or in the range of from about 3% to about 10%, based on the total amount of the second microporous layer material.
  • preferable PE-2 can be the same as PE-I, but can be selected independently.
  • preferable UHMWPE-2 can be the same as UHMWPE-I, but can be selected independently.
  • each of the first and second layer materials can optionally contain one or more additional polyolefms, and/or a polyethylene wax, e.g., one having an Mw in the range of about 1 x 10 3 to about 1 x 10 4 , as described in US2008/0057388.
  • a process for producing a two-layer microporous polyolefin membrane wherein an extrusion die and manifold system of the type disclosed herein is employed.
  • the microporous polyolefin membrane has at least three layers and is produced through the use of an extrusion die and manifold system of the type disclosed herein. The production of the microporous polyolef ⁇ n membrane will be mainly described in terms of two-layer and three-layer membrane.
  • a three-layer microporous polyolefm membrane comprises first and third microporous layers constituting the outer layers of the microporous polyolefm membrane and a second (core) layer situated between (and optionally in planar contact with) the first and third layers.
  • the first and third layers are produced from a first polyolefm solution and the second (core) layer is produced from a second polyolefin solution.
  • a method for producing the multi-layer, microporous polyolefin membrane is provided.
  • the method comprises the steps of (1) combining (e.g., by melt- blending) a first polyolefm composition and at least one diluent (e.g., a membrane- forming solvent) to prepare a first mixture of polyolefin and diluent, e.g., a first polyolefin solution, (2) combining a second polyolefin composition and at least a second diluent (e.g., a second membrane-forming solvent) to prepare a second mixture of polyolefm and diluent, e.g., a second polyolefin solution, (3) extruding the first and second polyolefin solutions through at least one die of the type disclosed herein to form a multi-layer extrudate, (4) optionally cooling the multi-layer extrudate to form a cooled extrudate, (5) removing at least a portion of the membrane-forming solvent from the extrudate or cooled extrudate to form the multilayer membrane, and
  • the first polyolefin composition comprises polyolefin resins as described above that can be combined, e.g., by dry mixing or melt blending with an appropriate membrane-forming solvent to produce the first polyolefin solution.
  • the first polyolefin solution can contain various additives such as one or more antioxidant, fine silicate powder (pore-forming material), etc., as disclosed in WO2008/016174, US2008/0057388, and US2008/0057389, for example.
  • additives such as one or more antioxidant, fine silicate powder (pore-forming material), etc., as disclosed in WO2008/016174, US2008/0057388, and US2008/0057389, for example.
  • the first and second diluents can be solvents that are liquid at room temperature. Suitable diluents include those described in WO2008/016174, US2008/0057388, and US2008/0057389, for example.
  • the resins, etc., used to produce to the first polyolefin composition are melt-blended in, e.g., a double screw extruder or mixer.
  • a conventional extruder or mixer or mixer-extruder
  • a double-screw extruder can be used to combine the resins, etc., to form the first polyolefin composition.
  • the diluent can be added to the polyolefin composition (or alternatively to the resins used to produce the polyolefin composition) at any convenient point in the process.
  • the solvent can be added to the polyolefin composition (or its components) at any of (i) before starting melt-blending, (ii) during melt blending of the first polyolefin composition, or (iii) after melt-blending, e.g., by supplying the first membrane-forming solvent to the melt-blended or partially melt- blended polyolefin composition in a second extruder or extruder zone located downstream of the extruder zone used to melt-blend the polyolefin composition.
  • the amount of the first polyolefin composition in the first polyolefin solution is not critical. In one form, the amount of first polyolefin composition in the first polyolefin solution can range from about 1 wt.% to about 75 wt.%, based on the weight of the polyolefin solution, for example from about 20 wt.% to about 70 wt.%. The remainder of the polyolefin solution can be the solvent.
  • the polyolefin solution can be about 30 wt.% to about 80 wt.% solvent (or diluent) based on the weight of the polyolefin solution.
  • the second polyolefin solution can be prepared by the same methods used to prepare the first polyolefin solution.
  • the second polyolefin solution can be prepared by melt-blending a second polyolefin composition with a second membrane- forming solvent.
  • the amount of the second polyolefin composition in the second polyolefin solution is not critical.
  • the amount of second polyolefin composition in the second polyolefin solution can range from about 1 wt.% to about 75 wt.%, based on the weight of the second polyolefin solution, for example from about 20 wt.% to about 70 wt.%.
  • the remainder of the polyolefin solution can be the solvent.
  • the polyolefin solution can be about 30 wt.% to about 80 wt.% solvent (or diluent) based on the weight of the polyolefin solution.
  • extrusion dies of the type disclosed herein are used for forming an extrudate that can be co-extruded or laminated.
  • extrusion dies which can be adjacent or connected, are used to form the extrudates.
  • the first and second sheet dies are connected to first and second extruders, respectively, where the first extruder contains the first polyolefin solution and the second extruder contains the second polyolefin solution.
  • lamination if used is generally easier to accomplish when the extruded first and second polyolefin solution are still at approximately the extrusion temperature.
  • first, second, and third dies are connected to first, second and third extruders, where the first and third dies contain the first polyolefin solutions, and the second die contains the second polyolefin solution.
  • a laminated extrudate is formed constituting outer layers comprising the extruded first polyolefm solution and one intermediate comprising the extruded second polyolefin solution.
  • the first, second, and third dies are connected to first, second, and third extruders, where the second die contains the first polyolefin solution, and the first and third dies contain the second polyolefin solution.
  • a laminated extrudate is formed constituting outer layers comprising the extruded second polyolefin solution and one intermediate comprising extruded first polyolefin solution.
  • the die gaps are generally not critical.
  • extrusion dies of the type disclosed herein can have a die gap of about 0.1 mm to about 5 mm.
  • Die temperature and extruding speed are also non-critical parameters.
  • the dies can be heated to a die temperature ranging from about 140 0 C to about 250 0 C during extrusion.
  • the extruding speed can range, for example, from about 0.2 m/minute to about 15 m/minute.
  • the thickness of the layers of the layered extrudate can be independently selected.
  • the resultant sheet can have relatively thick skin or surface layers compared to the thickness of an intermediate layer of the layered extrudate.
  • the multi-layer extrudate can be cooled. Cooling rate and cooling temperature are not particularly critical. Suitable cooling methods are described in WO2008/016174, US2008/0057388, and US2008/0057389, for example. [0068] In one form, at least a portion of the first and second membrane-forming solvents are removed (or displaced) from the multi-layer extrudate in order to form the multi-layer, microporous membrane. Suitable methods for removing the solvents (diluents) are described in WO2008/016174, US2008/0057388, and US2008/0057389, for example. A washing solvent can be used, for example.
  • any remaining volatile species in the membrane e.g., the washing solvent
  • Suitable methods for removing the volatile species are disclosed in WO2008/016174, US2008/0057388, and US2008/0057389, for example.
  • the extrudate Prior to the step for removing the membrane-forming solvents, the extrudate can be stretched in order to obtain an oriented extrudate. Suitable methods for stretching the extrudate or cooled extrudate are disclosed in WO2008/016174, US2008/0057388, and US2008/0057389, for example.
  • the extrudate can be treated with a hot solvent as described in WO 2000/20493.
  • the microporous membrane can be stretched at least monoaxially after removal of at least a portion of the diluent.
  • the stretching method selected is not critical, and conventional stretching methods can be used such as by a tenter method, etc.
  • the stretching of the dry microporous polyolefm membrane can be called dry-stretching, re- stretching, or dry-orientation. Suitable stretching methods are disclosed in WO2008/016174, US2008/0057388, and US2008/0057389, for example.
  • the stretching magnification is not critical.
  • the stretching magnification of the microporous membrane can range from about 1.1 fold to about 2.5 or about 1.1 to 2.0 fold in at least one lateral (planar) direction. Biaxial stretching can be used, and the stretching magnification need not by symmetric.
  • the microporous membrane can be heat-treated and/or annealed.
  • the microporous membrane can also be cross-linked if desired [e.g., by ionizing radiation rays such as a-rays, (3-rays, 7-rays, electron beams, etc.)] or can be subjected to a hydrophilic treatment [i.e., a treatment which makes the microporous polyolefin membrane more hydrophilic (e.g., a monomer-grafting treatment, a surfactant treatment, a corona-discharging treatment, etc.)].
  • a hydrophilic treatment i.e., a treatment which makes the microporous polyolefin membrane more hydrophilic (e.g., a monomer-grafting treatment, a surfactant treatment, a corona-discharging treatment, etc.)].
  • a hydrophilic treatment i.e., a treatment which makes the microporous polyolefin membrane more hydrophilic (e.g., a monomer-grafting treatment, a
  • microporous membrane such as those described in WO2008/016174 (for multi-layer membranes) and in WO2007/132942 (for monolayer membranes) can also be used.
  • All patents, test procedures, and other documents cited herein, including priority documents, are fully incorporated by reference to the extent such disclosure is not inconsistent and for all jurisdictions in which such incorporation is permitted.
  • [0077] While the illustrative forms disclosed herein have been described with particularity, it will be understood that various other modifications will be apparent to and can be readily made by those skilled in the art without departing from the spirit and scope of the disclosure.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne une filière destinée à la production d'un extrudat de matière thermoplastique. La filière comprend une sortie de filière par laquelle un flux fondu de la matière thermoplastique est extrudé, une entrée d'alimentation en communication avec un diviseur d'alimentation destiné à diviser la matière thermoplastique en une première partie et en une seconde partie, ainsi qu'un distributeur à écoulement transversal comprenant une première section de distributeur à écoulement transversal destinée à recevoir la première partie de la matière thermoplastique, un deuxième passage en communication avec le premier passage, et un troisième passage en communication avec le deuxième passage.
PCT/JP2008/066935 2007-09-14 2008-09-12 Filière et système distributeur associé Ceased WO2009035161A2 (fr)

Priority Applications (1)

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JP2010510594A JP5061238B2 (ja) 2007-09-14 2008-09-12 押出金型および押出金型用マニホールド

Applications Claiming Priority (8)

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US11/901,164 US20090072434A1 (en) 2007-09-14 2007-09-14 Coextrusion die and manifold system therefor
US11/901,164 2007-09-14
US97368207P 2007-09-19 2007-09-19
US97368107P 2007-09-19 2007-09-19
US60/973,682 2007-09-19
US60/973,681 2007-09-19
US97668807P 2007-10-01 2007-10-01
US60/976,688 2007-10-01

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WO2009035161A2 true WO2009035161A2 (fr) 2009-03-19
WO2009035161A3 WO2009035161A3 (fr) 2009-05-22

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PCT/JP2008/066920 Ceased WO2009035152A2 (fr) 2007-09-14 2008-09-12 Matrice d'extrusion à répartiteur de flux transversal de type amélioré
PCT/JP2008/066935 Ceased WO2009035161A2 (fr) 2007-09-14 2008-09-12 Filière et système distributeur associé
PCT/JP2008/066922 Ceased WO2009035154A2 (fr) 2007-09-14 2008-09-12 Matrice de co-extrusion et système de répartiteur correspondant
PCT/JP2008/067047 Ceased WO2009035167A2 (fr) 2007-09-14 2008-09-12 Matrice d'extrusion à système de réglage de lèvre de matrice en porte-à-faux

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012011751A (ja) * 2010-07-05 2012-01-19 Asahi Kasei E-Materials Corp 積層多孔フィルム及びその製造方法

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5204147B2 (ja) * 2010-04-08 2013-06-05 株式会社日本製鋼所 押出成形用フラットダイ
KR101143556B1 (ko) 2011-07-25 2012-05-09 삼원금형정공주식회사 냉각수로가 형성된 립형성코어를 가지는 사출금형
JP7213275B2 (ja) * 2021-01-08 2023-01-26 日本碍子株式会社 押出成形用ダイ及び押出成形機

Family Cites Families (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3308222A (en) * 1964-08-19 1967-03-07 Midland Ross Corp Sheet extrusion die
US3559239A (en) * 1968-02-27 1971-02-02 American Can Co Multilayer extrusion die
JPS5035112Y1 (fr) * 1973-06-25 1975-10-13
US4003689A (en) * 1975-09-15 1977-01-18 Celanese Corporation Die-gap adjusting means
JPS591179B2 (ja) * 1978-08-24 1984-01-10 東洋紡績株式会社 多層フイルム製造用押出しダイ
KR890002683B1 (ko) * 1984-04-27 1989-07-24 클뢰렌 피터 동시압출성형 방법 및 멀티매니폴드(multimanifold)압출성형 다이
DE3641438A1 (de) * 1986-03-27 1987-10-01 Brown Inc John Mechanismus zum einstellen einer formlippe
US4789513A (en) * 1987-06-05 1988-12-06 P.C.E. Corp. Coextrusion apparatus and process
JPS63307925A (ja) * 1987-06-09 1988-12-15 Toshiba Mach Co Ltd 波状プロファイルを有するプラスチックシ−トの成形方法
JPH01150517A (ja) * 1987-12-08 1989-06-13 Toshiba Mach Co Ltd プラスチック押出成形用ｔダイ
DE3805774A1 (de) * 1988-02-24 1989-09-07 Sigmund Boos Schlitzduese, insbesondere breitschlitzduese, fuer extrudieranlagen in der kunststoffindustrie
JPH0723234Y2 (ja) * 1989-11-30 1995-05-31 三菱重工業株式会社 押出成形用ダイリップ調整装置
KR910019750A (ko) * 1990-05-09 1991-12-19 피터 클로렌 2세 압출장치
JPH0531930U (ja) * 1991-10-02 1993-04-27 株式会社日本製鋼所 押出成形用ｔダイ
JP3112358B2 (ja) * 1992-10-13 2000-11-27 三菱樹脂株式会社 共押出用フラットダイ
US5320679A (en) * 1993-07-28 1994-06-14 Eastman Kodak Company Coating hopper with criss-cross flow circuit
US5329964A (en) * 1993-09-09 1994-07-19 Eastman Kodak Company Criss-cross hopper including non-contacting inserts
JPH09174660A (ja) * 1995-12-28 1997-07-08 Fuji Photo Film Co Ltd 複層シート又は複層フィルムの成形ダイ装置
US6186765B1 (en) * 1997-03-31 2001-02-13 Toshiba Kikai Kabushiki Kaisha Apparatus for forming a molded multilayer product
JP3048972U (ja) * 1997-11-17 1998-05-29 東燃化学株式会社 フラットダイ
JP2000127227A (ja) * 1998-10-29 2000-05-09 Teijin Ltd フィルムの押出装置及び製造方法
JP2002292660A (ja) * 2001-04-02 2002-10-09 Konica Corp セルロースエステルフィルムの製造装置
JP2003285367A (ja) * 2002-03-27 2003-10-07 Fuji Photo Film Co Ltd 溶液製膜方法及びその製造物
JP4385832B2 (ja) * 2004-04-08 2009-12-16 東レ株式会社 シート押出成形用口金およびシート製造方法
HUE041980T2 (hu) * 2005-10-24 2019-06-28 Toray Industries Poliolefin többrétegû mikropórusos film, eljárás az elõállítására és akkumulátor-szeparátor

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012011751A (ja) * 2010-07-05 2012-01-19 Asahi Kasei E-Materials Corp 積層多孔フィルム及びその製造方法

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WO2009035152A3 (fr) 2009-06-04
JP2010538859A (ja) 2010-12-16
JP5062920B2 (ja) 2012-10-31
WO2009035154A2 (fr) 2009-03-19
WO2009035154A3 (fr) 2009-05-22
JP2010538858A (ja) 2010-12-16
WO2009035167A3 (fr) 2009-07-30
WO2009035152A2 (fr) 2009-03-19
WO2009035161A3 (fr) 2009-05-22
JP5127000B2 (ja) 2013-01-23
JP2010538860A (ja) 2010-12-16
JP2010538857A (ja) 2010-12-16
WO2009035167A2 (fr) 2009-03-19

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