WO2016132808A1 - 微多孔プラスチックフィルムの製造方法 - Google Patents
微多孔プラスチックフィルムの製造方法 Download PDFInfo
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- WO2016132808A1 WO2016132808A1 PCT/JP2016/051778 JP2016051778W WO2016132808A1 WO 2016132808 A1 WO2016132808 A1 WO 2016132808A1 JP 2016051778 W JP2016051778 W JP 2016051778W WO 2016132808 A1 WO2016132808 A1 WO 2016132808A1
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- 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
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
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- 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
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- 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
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- 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
- B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
- B29C48/10—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels flexible, e.g. blown foils
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- 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
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- 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
- B29C48/885—External treatment, e.g. by using air rings for cooling tubular films
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- 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
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- 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
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- 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
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- 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
- B29C55/18—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets by squeezing between surfaces, e.g. rollers
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- 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
- B29C55/20—Edge clamps
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
- H01M50/406—Moulding; Embossing; Cutting
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/491—Porosity
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- 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
- B29C48/91—Heating, e.g. for cross linking
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- 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
- B29C48/919—Thermal treatment of the stream of extruded material, e.g. cooling using a bath, e.g. extruding into an open bath to coagulate or cool the material
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- 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
- B29K2105/0002—Condition, form or state of moulded material or of the material to be shaped monomers or prepolymers
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- 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
- B29K2105/041—Microporous
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- 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
- B29L2007/00—Flat articles, e.g. films or sheets
- B29L2007/008—Wide strips, e.g. films, webs
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a method for producing a microporous plastic film.
- Microporous plastic films are widely used as separators for electrochemical elements such as separation membranes used for separation and selective permeation of substances, alkaline secondary batteries, lithium secondary batteries, fuel cells and capacitors. In particular, it is suitably used as a separator for lithium ion batteries.
- Patent Document 1 Conventionally, as a method for producing a microporous film using a plastic mainly made of polyolefin as a raw material, there are wet methods as shown in Patent Document 1 and Patent Document 2, for example.
- a diluent such as liquid paraffin is added to the polymer, kneaded and dispersed, discharged onto a cooling drum from the die, and formed into a gel sheet by cooling and solidifying, and then the roller method for the purpose of improving the strength.
- the film is stretched uniaxially or biaxially using a tenter method, and then the diluent is extracted to obtain a microporous film.
- the longitudinal stretch ratio can be freely changed by changing the roller speed. Since it can be stretched, the mechanical properties of the microporous plastic film can be improved.
- the diluent should bleed out from the gel sheet surface with pressure due to heat and tension, and this diluent should be transported and stretched while interposing at the boundary between the film and the roller.
- Patent Document 1 In order to stretch this gel sheet, the sheet that has been sufficiently cooled to below the crystallization end temperature of the polymer is heated and stretched to the extent that it does not exceed the melting point again (for example, above the crystal dispersion temperature as in Patent Document 2). I do.
- Patent Document 1 it is possible to avoid the slip by applying a tension exceeding the longitudinal stretching tension between the longitudinal stretching machine and the lateral stretching machine (tenter), and particularly when a tension of 20% or more of the stretching tension is applied. It is good. According to the knowledge of the inventor of the present application, when a tension exceeding the stretching tension is applied, the sheet is pulled downstream on the side of the transverse stretching machine, conversely promoting slipping, and slipping cannot be prevented.
- An object of the present invention is to provide a method for producing a microporous plastic film having excellent physical properties and mechanical properties by stretching while preventing slipping at high speed and high productivity.
- the present invention is a method in which a diluent and a polyolefin polymer are kneaded with an extruder, the polymer kneaded with the diluent is discharged from a die into a sheet shape, and a sheet discharged from the die is obtained. After cooling and solidifying on the drum, the solidified sheet is heated again and stretched in the sheet conveying direction by a plurality of rollers.
- both ends of the sheet are held by clips
- the roller (B) in the transport direction downstream of the plurality of rollers, and this roller The largest magnification of the stretching in the sheet conveyance direction between the roller (A) driven by the motor on the upstream side in one conveyance direction of (B).
- a method for producing a microporous plastic film, wherein stretching is performed so that a ratio of a traveling speed of a clip on the most upstream side in the transport direction of the tenter to a peripheral speed of the roller (B) is within a range of ⁇ 3% to + 3%. provide.
- the total draw ratio in the sheet conveying direction is 4 to 12 times, and the ratio of the peripheral speed of the roller (B) to the peripheral speed of the roller (A) is 2 to
- the ratio of the circumferential speed of the roller (B) to the circumferential speed of the roller (A) divided by the total draw ratio in the sheet conveying direction is 0.3 or more.
- a microporous plastic film having excellent physical properties and mechanical properties can be obtained with high productivity by preventing slippage even in the wet roller stretching method.
- FIG. 1 is a schematic side view of a manufacturing process of a microporous plastic film according to an embodiment of the present invention.
- a polyolefin solution in which a polyolefin resin is mixed with a diluent and heated and melted is prepared.
- the diluent determines the structure for microporous formation of the microporous plastic film, and also improves the stretchability when stretching the film (for example, reduction of plaque at the stretch ratio for strength development). Contribute.
- the diluent is not particularly limited as long as it is a substance that can be mixed or dissolved in the polyolefin resin. In the melt-kneaded state, it is miscible with the polyolefin, but a solid solvent may be mixed with the diluent at room temperature. Examples of such a solid diluent include stearyl alcohol, seryl alcohol, and paraffin wax.
- the diluent is preferably a liquid at room temperature in order to prevent unevenness due to stretching and to be applied later.
- Liquid diluents include nonane, decane, decalin, para-xylene, undecane, dodecane, liquid paraffins and other aliphatics; cycloaliphatic or aromatic hydrocarbons; and mineral oils whose boiling point is between those of these compounds Distillates; and liquid phthalates such as dibutyl phthalate and dioctyl phthalate at room temperature.
- a non-volatile diluent such as liquid paraffin is more preferable.
- the viscosity of the liquid diluent is preferably 20 to 200 cSt at 40 ° C.
- the blending ratio of the polyolefin resin and the diluent is preferably 10 to 50% by mass from the viewpoint of improving the extrudate moldability by setting the total of the polyolefin resin and the diluent to 100% by mass.
- the extruder 21 with a screw like FIG. 1 etc. can be used.
- the preferable range of the temperature of the polyolefin resin solution in the extruder varies depending on the resin.
- the polyethylene composition has a temperature of 140 to 250 ° C.
- polypropylene includes 190 to 270 ° C.
- the temperature is indirectly grasped by installing a thermometer in the extruder or in the cylinder part, and the heater temperature, rotation speed, and discharge amount of the cylinder part are appropriately adjusted so as to reach the target temperature.
- the polyolefin resin solution melt-kneaded by the extruder 21 is discharged in a sheet form from the slit portion of the base 23 while being measured by the gear pump 22 as necessary.
- the discharged gel sheet 12 contacts the cooling drum 31 and solidifies.
- the gel-like sheet 12 forms a crystal structure in the polyolefin portion, and this structure becomes a pillar portion that supports the holes of the microporous plastic film 11 later.
- the gel sheet 12 contains the diluent kneaded in the extruder 21 and is in a gel state.
- a part of the diluent is bleed out from the surface of the sheet by cooling the gel-like sheet 12, so that the surface is conveyed on the cooling drum 31 while the surface is wet by the diluent.
- the thickness of the gel-like sheet 12 is preferably adjusted by adjusting the speed of the cooling drum with respect to the flow rate from the mouthpiece slit portion corresponding to the discharge amount.
- the temperature of the cooling drum 31 affects the crystal structure of the gel-like sheet 12, and is preferably 15 to 40 ° C. This is because the final cooling temperature of the gel sheet 12 is preferably set to be equal to or lower than the crystallization end temperature. Since the higher-order structure is fine, the molecular orientation easily proceeds in the subsequent stretching.
- the cooling time can be supplemented by appropriately increasing the diameter of the cooling drum 31, adding another cooling drum 32 in addition to the cooling drum 31, or adding a plurality of cooling drums. At this time, in order to densify and homogenize the crystal structure in the gel-like sheet 12, it is preferable to determine the conveying speed, the drum temperature, the drum size, and the number of drums in consideration of the cooling speed.
- the temperature of the drum 31 may be set to a low value such as 20 ° C.
- the temperature of the drum 31 may be set to a low value such as 20 ° C.
- the material of the surface of the cooling drum 31 is preferably a material having excellent shape stability and easy processing accuracy so that the roller speed is constant. Examples of such a material include metals, ceramics, fiber composite materials, and the like.
- the surface is preferably a metal excellent in heat conduction to the film.
- the roller internal structure of the cooling drums 31 and 32 is provided with a flow path through which the refrigerant flows, and also includes a heat pump and various cooling devices that have been used conventionally. Is preferred.
- the rollers are rotationally driven at a speed set by a rotational driving means such as a motor, and a transmission mechanism is appropriately provided between the rollers so that draw tension and relaxation can be applied according to the expansion and contraction of the sheet.
- a rotational driving means such as a motor
- a transmission mechanism is appropriately provided between the rollers so that draw tension and relaxation can be applied according to the expansion and contraction of the sheet.
- a motor may be individually disposed on each roller, and the speed may be adjusted with accuracy by an inverter or a servo to provide the same function as the speed change mechanism.
- the gel-like sheet 12 is in contact with the first cooling drum 31 that is the cooling drum that the upper surface side is discharged from the base 23 and first contacts, and is rapidly cooled by the refrigerant at the above temperature.
- the surface opposite to the surface in contact with the first cooling drum 31 is gradually cooled by air in FIG.
- the cooling rate can be increased also for the opposite surface by cooling with forced convection by an air nozzle or an air chamber. it can. This is particularly suitable when the conveyance speed is high, or when the thickness of the gel-like sheet is large and the heat conduction to the cooling drum 31 is not sufficient. Further, it is possible to improve the cooling capacity of the opposite surface by disposing a refrigerant nip roller that allows the refrigerant to flow inside on the side opposite to the cooling drum 31.
- contact means such as a nip roller, a jet nozzle, a suction chamber, and electrostatic application, so that the wet gel-like sheet 12 may not be cooled and meandering due to lubrication. Good.
- contact means such as a nip roller, a jet nozzle, a suction chamber, and electrostatic application, so that the wet gel-like sheet 12 may not be cooled and meandering due to lubrication. Good.
- These close contact means are preferable because they improve the running performance, increase the cooling efficiency of the gel-like sheet 12, and facilitate the setting of the cooling rate and the final cooling temperature.
- the surface of the nip roller is a flexible rubber-like elastic body so that the gel-like sheet 12 can be uniformly pressed against uneven thickness of the gel-like sheet 12, deflection of the roller, and slight unevenness of the surface.
- the flexible rubber-like elastic body is not particularly limited, but a general vulcanized rubber such as nitrile butyl rubber (NBR), chloroprene rubber (CR), ethylene propylene rubber (EPDM), hyperon rubber (CSM) and the like are suitable. is there.
- the gel-like sheet 12 and the conveying roller temperature are high, specifically, when the temperature is 80 ° C. or higher, the EPDM and CSM are particularly preferable. At higher temperatures, silicone rubber and fluororubber are suitable in addition to the vulcanized rubber. In this case, selecting a rubber that is less swelled by the diluent can prevent the roller shape from becoming distorted over time.
- the both ends of the uniaxially stretched sheet 13 are continuously clipped with conventional clips.
- the sheet is gripped and stretched in the width direction of the sheet (a direction perpendicular to the conveying direction) while conveying the sheet in the traveling direction while heating and keeping warm in the oven 5.
- a speed difference may be provided between the rollers to stretch the gel sheet 12 in the longitudinal direction.
- a stretching roller is disposed, and stretching may be performed between the stretching roller 421 and the stretching roller 422, between the stretching roller 422 and the stretching roller 423, or both.
- stretching is performed with either one, it is a one-stage stretching, but when stretching with both, a two-stage stretching is performed.
- properties such as strength and air permeability as a microporous film and high productivity can be realized.
- the sheet conveying direction stretching (hereinafter referred to as longitudinal stretching) step is composed of a roller having a conventional surface such as a metal and a temperature control mechanism such as a heater in the same manner as the cooling drum, and the driving is the same.
- pass you may arrange
- the idler roller since the coefficient of friction between the wet film and the roller is small, it is preferable that the idler roller be provided with a bearing or reduce inertia loss so that the rotational force is small, and should not be provided more than necessary. Is also preferable.
- the internal structures of the temperature raising roller group 41 and the drawing roller group 42 are also preferably heated by providing a flow path of a heat medium such as steam or pressurized hot water inside the rollers, similarly to the cooling drum 31.
- a heat medium such as steam or pressurized hot water inside the rollers
- the roller is supported by a bearing so that it can be rotated, and in order to supply a heat medium inside, a rotatable joint (generally called a rotary joint) for supplying a heat medium that does not disturb the rotation of the roller is used as a shaft. It may be connected to the end and connected to the heat medium supply pipe.
- the stretching ratio varies depending on the thickness of the gel sheet, but the stretching in the sheet conveying direction is preferably performed at 5 to 12 times.
- the area magnification is preferably 30 times or more, more preferably 40 times or more, and still more preferably 60 times or more.
- the stretching temperature is preferably below the melting point of the polyolefin resin, and more preferably in the range of (polyolefin resin crystal dispersion temperature Tcd) to (polyolefin resin melting point).
- Tcd polyolefin resin crystal dispersion temperature
- the temperature is from 80 to 130 ° C, more preferably from 100 to 125 ° C. After stretching, cooling is performed below these temperatures.
- the uniaxially stretched sheet 13 or the biaxially stretched sheet 14 obtained in this way is finely washed by removing the diluent by a conventional technique, for example, the method described in International Publication No. 2008-016174 pamphlet, and drying.
- a porous plastic film 11 is obtained.
- a dry stretching step 7 may be provided after the cleaning step 6 and reheated and restretched.
- the redrawing step 7 may be either a roller type or a tenter type.
- physical properties can be adjusted and residual strain can be removed by performing heat treatment in the same step.
- the surface of the microporous plastic film 11 may be subjected to surface treatment such as corona discharge or functional coating such as heat-resistant particles.
- the diluent contained in the gel-like sheet 12 bleeds out by being cooled by the cooling drums 31 and 32. Further, the diluent bleeds out even under the pressure due to the conveying tension here. For the same reason, after discharging from the base 23, the surfaces of the gel-like sheet 12 and the stretched films 13 and 14 are wet with the diluent until the diluent is removed and washed in the washing step 6.
- the gel-like sheet 12 is heated to the stretching temperature by the temperature raising roller group 41 in the longitudinal stretching step 4 and the like, but the bleeding out of the diluent is accelerated by the temperature rise.
- bleed out increases from the cooling drum 31 to the upstream of the longitudinal stretching step 4, that is, from the temperature raising roller group 41.
- a pan (not shown) may be installed in order to collect and discard or reuse the diluent.
- the heating roller group 41 and the stretching roller group 42 are common in that the temperature of the gel-like sheet 12 is raised and heated and the roller rotation speed can be made variable. Since this is a roller for substantially stretching the sheet 12, it is a roller for providing a difference in peripheral speed for causing the gel-like sheet 12 to be permanently deformed in the traveling direction. More specifically, a roller that gives a circumferential speed difference of 3% or more with respect to an upstream roller is defined as a roller that substantially extends, that is, a stretching roller group 42.
- a gripping force (frictional force) is required between the roller and the gel-like sheet 12, and in particular, the stretching roller group 42 has a high tension due to stretching.
- a high gripping force that is balanced with the stretching tension is required.
- the diluent bleed out as described above is interposed between the roller and the gel-like sheet 12 and becomes in a lubricated state, which causes a reduction in gripping force necessary for conveyance and stretching.
- the longitudinal stretching step 42 stretching is performed between the first stretching roller 421 and the second stretching roller 422, between the second stretching roller 422 and the third stretching roller 423, or both.
- the downstream stretching tension is borne and balanced by the clip that grips the end of the uniaxially stretched sheet 13 mainly in the transverse stretching step 5.
- the second stretching roller 422 is considered as the stretching roller (B) because it becomes the most downstream roller in the transport direction for stretching.
- the first stretching roller 421 on the upstream side in the transport direction is the stretching roller (A).
- the stretching roller (A) and the stretching roller (B) stretching is performed at the largest magnification in the sheet conveyance direction.
- the ratio of the traveling speed of the uppermost clip in the transport direction of the transverse stretching step 5 to the circumferential speed of the stretching roller (B), that is, the second stretching roller 422 ((the traveling speed of the clip ⁇ the circumferential speed of the stretching roller (B)).
- Speed) / peripheral speed of stretching roller (B) in the range of ⁇ 3% to + 3% the stretching tension on the downstream side balances with the clip in the transverse stretching process, and in the longitudinal stretching process of the gel sheet 12. Can be prevented from slipping.
- the ratio of the tenter clip speed in the most upstream direction in the conveying direction to the circumferential speed of the stretching roller 423 is as small as possible.
- two-stage stretching is performed between the first stretching roller 421 and the second stretching roller 422 and between the second stretching roller 422 and the third stretching roller 423 in the longitudinal stretching step 4. Do. Thereby, it becomes easy to disperse stretching tension and prevent slipping.
- the most downstream roller of the stretching roller that is, the third stretching roller 423 is regarded as the stretching roller (B)
- the second stretching roller 422 that is one upstream in the transport direction is defined as the stretching roller (A).
- the stretching roller (B) the stretching roller (B).
- produces between the 2nd extending
- the first stretching roller generated by the first-stage stretching tension as the balance of the main stretching tension on the upstream side described above by stretching also between the first stretching roller 421 and the second stretching roller 422.
- the frictional force between the 421 and the second stretching roller 422 and the gel sheet 12 is increased, and slipping is easily prevented. More preferably, by arranging the nip roller 44 on a roller upstream of the second stretching roller 422 as shown in FIG. 1, the upstream stretching tension can be balanced and slippage can be prevented.
- the cooling roller group 43 may bear a part of the stretching tension, it is preferable that the transverse stretching step 5, the second stretching roller 422, the uniaxially stretched sheet 13, The same speed is good.
- the third stretching roller 423 to the cooling roller group 43 are all the same as the second stretching roller 422 and the most upstream tenter clip in the transport direction. It is good to be fast.
- the cooling roller group 43 cools the stretched sheet before sending it to the transverse stretching step 5 and conveys it to the tenter oven 5, thereby facilitating the process paper passing operation of the uniaxially stretched sheet 13 and the transverse stretching.
- a highly oriented and high strength microporous plastic film can be obtained by the effect of solidifying the crystal structure formed by longitudinal stretching.
- cooling roller group after the second stretching roller 422 cooling is performed simultaneously with the completion of stretching, thereby preventing unnecessary dimensional deformation, change in tension, and the like.
- the cooling roller group 43 from the stretching roller 423 that is, the stretching roller (B)
- the stretching roller (B) is all set at the same speed as the tenter clip that is the most upstream in the transport direction, and preferably these are cooled.
- the stretched portion has three stages and four stages to disperse and reduce the main stretching tension and improve the upstream gripping force.
- the stretching must be performed at the largest magnification between the stretching roller (B) on the most downstream side in the transport direction and the stretching roller (A) on the one upstream side.
- the uniaxially stretched sheet 13 traveling between the stretching roller (B) and the lateral stretching step 5 is substantially the same as the stretching tension generated between the stretching roller (A) and the stretching roller (B). It becomes tension.
- the stretching tension generated between the second stretching roller 422 and the third stretching roller 423 is the third stretching with the same speed. It is maintained from the roller 423 to the tenter clip, and the tenter clip without slipping bears.
- the ratio of the traveling speed of the uppermost clip in the conveying direction to the circumferential speed of the stretching roller (B) is set in the range of ⁇ 3 to + 3%, and the stretching tension is not significantly different within this range.
- the sheet contracts in the transport direction, and preferably the speed ratio between the sheet and the roller is reduced by making the speed ratio negative between 0 and ⁇ 3%.
- the stretching tension and the tension on the downstream side of the longitudinal stretching process are the same, making it easy to balance.
- the ratio of the tenter clip speed on the upstream side in the transport direction with respect to the peripheral speed of the stretching roller 423 is as small as possible.
- the speed ratio can be adjusted with higher accuracy and the tension can be balanced.
- the longitudinal draw ratio is preferably 4 to 12 times the total draw ratio.
- the speed ratio between the stretching roller (A) and the stretching roller (B) having the largest magnification is 2 to 6 times, and the ratio between the stretching roller (A) and the stretching roller (B).
- the value obtained by dividing by the total draw ratio is 0.3 or more. If the total draw ratio is 4 times or more, the thickness unevenness of the gel-like sheet 12 can be sufficiently dispersed, and sufficient physical properties can be obtained as mechanical properties such as strength and elastic modulus of the sheet obtained by stretching. On the other hand, if it is 12 times or less, tearing in the stretching process is unlikely to occur, and the stretching tension is not excessively increased and slipping is unlikely to occur.
- the magnification between the stretching roller (A) and the stretching roller (B) is 10 ⁇ 0.3 or more, so it is 3 times or more.
- the first stage stretching is 2.85 times and the second stage stretching (that is, stretching) What is necessary is just to make 3.5 times a roller (A) and an extending
- the ratio of the first stage and the second stage may be adjusted as long as the above condition is satisfied. For example, when the first stage is to be increased by 2.5 times, the second stage may be increased by 4 times.
- the magnification between the stretching roller (A) and the stretching roller (B) is in the range of 2 to 6 times. If this magnification is 6 times or more, it becomes difficult to prevent slipping in one extending section, and the downstream side can be gripped by the clip, but slipping occurs on the upstream side. On the contrary, between the stretching roller (A) and the stretching roller (B), 0.3 or more of the lower limit 4 times of the total stretching ratio is 1.2 or more, but let's obtain the largest stretching ratio in the same section. Then, more than twice is essential.
- the longitudinal draw ratio in the third stage is the section between the stretch roller (A) and the stretch roller (B), and the magnification is preferably 2 to 6 times, and is 10 ⁇ 0.3 or more, so it is 3 times or more.
- the nip roller 44 from the temperature raising roller group to the stretching roller (A), and the nip pressure may be adjusted / changed for each driving roller originally.
- the nip pressure is preferably about 300 to 2000 [N / m] per unit width so as not to meander by excessive pressing with a pair of rollers.
- a nip roller may be used for the cooling roller group 43 as shown in FIG.
- the surface of the nip roller is made of a rubber-like elastic body that is flexible so that the gel-like sheet 12 can be uniformly pressed against uneven thickness of the gel-like sheet 12, deflection of the roller, and slight irregularities on the surface. Since the longitudinal stretching process involves conveyance at a temperature equal to or higher than the thermal diffusion temperature, rubbers with high heat resistance such as EPDM and hyperon rubber are preferable, and silicone rubber and fluororubber are more preferable. In this case as well, it is preferable to select a rubber that is less swelled by the diluent because it can prevent the roller shape from becoming distorted with time.
- the gel-like sheet 12 when introduced into the temperature raising roller or the drawing roller by the nip roller as shown in FIG. 1, it is more longitudinally stretched by niping substantially tangentially to prevent the air bank. Thickness spot appearance and appearance quality can be improved, and slipping and meandering can be prevented.
- the roughness of the roller surface is preferably about 0.2 to 40 ⁇ m at the maximum height, about 0.2 to 0.8 ⁇ m for a mirror surface, and 20 to 40 ⁇ m for a sufficiently rough surface. . Since this roller is wet with a diluent, in the case of a mirror surface, the friction coefficient is reduced by lubrication. The rough surface has an effect of reducing or preventing the amount of lubrication by discharging the diluent from the unevenness, and increases the coefficient of friction.
- Mirror surface and rough surface may be combined if necessary, but basically the mirror surface improves maintenance and speed control accuracy such as cleaning, and there is a certain amount of lubricant lubrication on the mirror surface. This is preferable in order to prevent appearance irregularity of the sheet.
- the surface of the driving roller has a good mirror surface and the maximum height is 1 S or less, that is, 1 ⁇ m or less. More preferably, the thickness is 0.2 to 0.8 ⁇ m.
- metal or ceramic is used as described above.
- a polyethylene (PE) composition comprising 40% by mass of ultrahigh molecular weight polyethylene having a weight average molecular weight (Mw) of 2.5 ⁇ 10 6 and 60% by mass of high density polyethylene (HDPE) having an Mw of 2.8 ⁇ 10 5
- Mw weight average molecular weight
- HDPE high density polyethylene
- the obtained mixture is fed into a twin screw extruder 21 at a flow rate of 97 kg / hr using a film forming method as shown in FIG. 1, and liquid paraffin is further used as a diluent at a flow rate of 291 kg / hr.
- the mixture was put in and mixed in a twin-screw extruder 21 at 210 ° C.
- the obtained polyethylene solution was supplied to the base 23 while being measured with a gear pump, and the polyethylene solution having a temperature of 210 ° C. was discharged onto a cooling drum 31 whose temperature was controlled to 35 ° C. to form a gel-like sheet 12.
- the cooling drum 31 was rotationally driven at a speed of 10 m / min.
- the thickness of the obtained gel-like sheet 12 was 100 mm square before being introduced into the longitudinal stretching step 4 and measured with a contact-type thickness meter. As a result, the average of 10 times was 1.5 mm. A bleed-out diluent adheres to the surface, and the thickness measurement has a variation of ⁇ 0.1 mm at the maximum.
- the obtained gel-like sheet 12 was heated with the temperature rising roller group 41 and the metal flow roller of the first stretching roller 421 so that the temperature of the sheet surface was 110 ° C.
- the number of rotations of the motor directly connected to the roller was controlled so as to increase in the downstream with a speed difference of 1% according to the thermal expansion of the sheet.
- the stretching roller group 42 is composed of three rollers as shown in FIG. 1, and a nip roller 44 whose surface is covered with rubber is disposed on each roller, and longitudinal stretching is performed by a speed difference between the rollers.
- the speed of the first cooling drum 31 is 10 m / min
- the speed ratio between the temperature raising roller group 41 and the first stretching roller 421 is 1% each
- the speed of the first stretching roller 421 is 10.4 m / min
- the second stretching The speed of the roller 422 was set to 12.8 m / min which is 10.4 ⁇ 1.23 times.
- the maximum stretching ratio is performed between the second stretching roller 422 as the stretching roller (A) and the third stretching roller 423 as the stretching roller (B), and the speed of the third stretching roller 423 is 12.8.
- X7 times 90 m / min, and the speed was controlled so that the total draw ratio of the uniaxially stretched sheet 13 was 9 times by passing through the longitudinal stretching step 4.
- the stretched film 13 was cooled by the four rollers of the cooling roller group 43 including the third stretching roller 423 which is the last roller of the stretching roller group 42, and the water feeding roller temperature was adjusted so that the sheet temperature became 50 ° C. .
- the third stretching roller 423 (stretching roller (B)), which is the last stretching roller, and the cooling roller group 43 have the same speed as that of the uniaxially stretched sheet 13 that contracts, and the most upstream in the transport direction of the lateral stretching step 5.
- the clip speed was set to -8.2% to 88.2 m / min.
- the number of the upstream nip rollers 44 is six as the number of the temperature rising roller group 41 facing the second stretching roller 422, and the number of the downstream nip rollers 44 includes the third stretching roller 423.
- the number of rollers was 4 so as to be opposed to 4 rollers.
- the speed of the first cooling drum 31 is 10 m / min
- the speed ratio between the heating roller group 41 and the first stretching roller 421 is 1%
- the speed of the first stretching roller 421 is 10
- the speed of the second stretching roller 422 was 10.4 ⁇ 2.163 times 22.5 m / min.
- the maximum stretching ratio is performed between the second stretching roller 422 as the stretching roller (A) and the third stretching roller 423 as the stretching roller (B), and the speed of the third stretching roller 423 is 22.5 ⁇ .
- the ratio of magnification between A) and the stretching roller (B) was 0.44, which was 0.3 or more.
- Other conditions were the same as in Example 1. [Example 3]
- the speed of the first cooling drum 31 is 10 m / min
- the speed ratio between the heating roller group 41 and the first stretching roller 421 is 1%
- the speed of the first stretching roller 421 is 10 .4 m / min
- longitudinal stretching was controlled so that the total draw ratio of the sheet 13 was 9 times by passing through the step 4.
- Other conditions were the same as in Example 1. [Sliding on stretching roller]
- the sheet and roller speeds were measured with a non-contact Doppler speedometer (Model 1522, manufactured by Act Electronics Co., Ltd.) with an accuracy of 1% including the installation accuracy.
- X impossible
- ⁇ possible
- the speed difference between the roller and the sheet is 5% or more and less than 10% with respect to the roller rotation speed.
- ) The speed difference between the roller and the sheet is less than 5% with respect to the roller rotation speed.
- X The amount of meandering is 10 mm or more.
- ⁇ The meandering amount is 5 mm or more and less than 10 mm.
- ⁇ Good
- the Gurley air resistance was measured according to JIS P8117 using an Oken type air resistance meter (EGO-1T, manufactured by Asahi Seiko Co., Ltd.).
- the maximum load was measured when a microporous film having a film thickness T1 ( ⁇ m) was pierced at a speed of 2 mm / sec with a needle having a spherical surface (curvature radius R: 0.5 mm) and a diameter of 1 mm.
- the largest draw ratio was given between the second draw roller 422 and the third draw roller 423.
- main stretching tension was generated in the same section, and the speeds of the second stretching roller 422 and the third stretching roller 423 were controlled to be substantially the same as the speed of the tenter clip.
- the tenter clip bears the downstream stretching tension, and the microporous plastic film 11 can be produced continuously and stably without slipping and meandering.
- the speed ratio in the stretching section was adjusted to 2 to 6 times, slippage due to the upstream stretching tension could be stably prevented.
- a microporous plastic film excellent in strength and physical properties while maintaining running stability under the necessary stretching conditions when performing stretching necessary to obtain various properties of the microporous film. Can be obtained.
- the present invention is not particularly limited, but can be used for microporous plastic films used for separators of electrochemical reactors such as secondary batteries, fuel cells, capacitors, etc., and functions such as filtration membranes, printed membranes and various clothing materials It can be applied to sex web.
- Microporous plastic film 12 Gel-like sheet (film) 13 Uniaxially stretched sheet (film) 14 Biaxially stretched sheet (film) 15 Microporous Plastic Film Roll 21 Extruder 22 Gear Pump 23 Base 31 First Cooling Drum 32 Second Cooling Drum 4 Longitudinal Stretching Step 41 Heating Roller Group 42 Stretching Roller Group 421 First Stretching Roller 422 Second Stretching Roller (stretching Roller A) ) 423 Third Stretching Roller (Stretching Roller B) 43 Cooling roller group 44 Nip roller 5 Transverse stretching process 6 Cleaning / drying process 61 Cleaning solvent 7 Re-stretching heat treatment process 8 Winding process
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Abstract
Description
図1は、本発明の一実施形態である微多孔プラスチックフィルムの製造工程の概略側面図である。
ゲル状シート12の厚みは、吐出量に応じた口金スリット部からの流速に対し、冷却ドラムの速度を調整することで調整するのが好ましい。
好ましくは、延伸ローラー群42~横延伸工程5に張力計を設置して実測することで、より高い精度で速度比を調整し、張力の釣りあいをとることができる。
[実施例1]
[実施例2]
[実施例3]
[実施例4]
[比較例1]
[比較例2]
[延伸ローラー上での滑り]
×(不可):ローラーとシートの速度差が、ローラー回転速度に対して10%以上
△(可):ローラーとシートの速度差が、ローラー回転速度に対して5%以上10%未満
○(良好):ローラーとシートの速度差が、ローラー回転速度に対して5%未満。
[縦延伸工程の蛇行量]
縦延伸工程4における蛇行量を以下の基準で評価した。
×(不可):蛇行量が10mm以上。
△(可):蛇行量が5mm以上10mm未満。
○(良好):蛇行量が5mm未満。
[微多孔プラスチックフィルム物性および機械的性質]
ガーレ透気抵抗度は、王研式透気抵抗度計(旭精工株式会社製、EGO-1T)を使用して、JIS P8117に準拠して測定した。
○(良好):ガーレ透気抵抗度が250sec±20sec及び突刺強度6N以上
×(不可):上記範囲外
12 ゲル状シート(フィルム)
13 一軸延伸シート(フィルム)
14 二軸延伸シート(フィルム)
15 微多孔プラスチックフィルムロール
21 押出機
22 ギアポンプ
23 口金
31 第1冷却ドラム
32 第2冷却ドラム
4 縦延伸工程
41 昇温ローラー群
42 延伸ローラー群
421 第1延伸ローラー
422 第2延伸ローラー(延伸ローラーA)
423 第3延伸ローラー(延伸ローラーB)
43 冷却ローラー群
44 ニップローラー
5 横延伸工程
6 洗浄・乾燥工程
61 洗浄溶剤
7 再延伸熱処理工程
8 巻取工程
Claims (5)
- 希釈剤とポリオレフィンポリマーとを押出機にて混練し、前記希釈剤が混練されたポリマーを口金からシート状に吐出し、前記口金から吐出されたシートをドラム上で冷却固化した後、前記固化したシートを再び加熱して、複数のローラーによりシートの搬送方向に延伸し、前記シートの搬送方向に延伸した前記シートを冷却した後に前記シート両端をクリップにて把持してテンターに導入し、その後希釈剤を洗浄する1軸または2軸延伸微多孔プラスチックフィルムの製造方法において、
前記複数のローラーのうちの搬送方向最下流のローラー(B)と、前記ローラー(B)の一つ搬送方向上流側でモーターにより駆動されるローラー(A)との間で、前記シートの搬送方向の延伸のうちの最も大きな倍率で延伸を行い、前記ローラー(B)の周速度に対する、前記テンターの搬送方向最上流側の前記クリップの走行速度の比を-3%~+3%の範囲内とする、微多孔プラスチックフィルムの製造方法。 - 前記シートの搬送方向の総延伸倍率が4~12倍であり、
前記ローラー(A)の周速度に対する前記ローラー(B)の周速度の比が2~6倍であり、
このローラー(A)の周速度に対する前記ローラー(B)の周速度の比を、前記シートの搬送方向の総延伸倍率で除した値が0.3以上である、請求項1に記載の微多孔プラスチックフィルムの製造方法。 - 請求項1または2に記載の微多孔プラスチックフィルムの製造方法で製造した微多孔プラスチックフィルム。
- 請求項3に記載の微多孔プラスチックフィルムを用いた電池用セパレーター。
- 請求項4に記載の電池用セパレーターを用いた電池。
Priority Applications (5)
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US15/551,615 US20180036930A1 (en) | 2015-02-20 | 2016-01-22 | Method of producing microporous plastic film |
JP2017500562A JP6773023B2 (ja) | 2015-02-20 | 2016-01-22 | 微多孔プラスチックフィルムの製造方法 |
CN201680011153.3A CN107249852A (zh) | 2015-02-20 | 2016-01-22 | 微多孔塑料膜的制造方法 |
KR1020177023228A KR102357542B1 (ko) | 2015-02-20 | 2016-01-22 | 미다공 플라스틱 필름의 제조 방법 |
EP16752197.0A EP3260267A4 (en) | 2015-02-20 | 2016-01-22 | Method for producing microporous plastic film |
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JP2015031390 | 2015-02-20 | ||
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EP (1) | EP3260267A4 (ja) |
JP (1) | JP6773023B2 (ja) |
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WO2018043331A1 (ja) * | 2016-08-29 | 2018-03-08 | 東レ株式会社 | 微多孔膜、リチウムイオン二次電池及び微多孔膜製造方法 |
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JP2018065895A (ja) * | 2016-10-17 | 2018-04-26 | 西工業株式会社 | 可塑剤抽出装置 |
Also Published As
Publication number | Publication date |
---|---|
KR20170118748A (ko) | 2017-10-25 |
JPWO2016132808A1 (ja) | 2018-01-18 |
JP6773023B2 (ja) | 2020-10-21 |
EP3260267A1 (en) | 2017-12-27 |
CN107249852A (zh) | 2017-10-13 |
US20180036930A1 (en) | 2018-02-08 |
KR102357542B1 (ko) | 2022-02-03 |
EP3260267A4 (en) | 2018-11-07 |
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