WO2010098135A1 - Procédé pour la production de film polytétrafluoroéthylène étiré, et film polytétrafluoroéthylène étiré - Google Patents

Procédé pour la production de film polytétrafluoroéthylène étiré, et film polytétrafluoroéthylène étiré Download PDF

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WO2010098135A1
WO2010098135A1 PCT/JP2010/001341 JP2010001341W WO2010098135A1 WO 2010098135 A1 WO2010098135 A1 WO 2010098135A1 JP 2010001341 W JP2010001341 W JP 2010001341W WO 2010098135 A1 WO2010098135 A1 WO 2010098135A1
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film
ptfe
stretched
stretching
polytetrafluoroethylene
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PCT/JP2010/001341
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English (en)
Japanese (ja)
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上原宏樹
山延健
荒瀬友貴
樋口義明
湯川裕正
深澤寧司
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国立大学法人群馬大学
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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
    • B29C55/005—Shaping by stretching, e.g. drawing through a die; Apparatus therefor characterised by the choice of materials
    • 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
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
    • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
    • B29C55/16—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial simultaneously
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • B29K2027/00—Use of polyvinylhalogenides or derivatives thereof as moulding material
    • B29K2027/12—Use of polyvinylhalogenides or derivatives thereof as moulding material containing fluorine
    • B29K2027/18—PTFE, i.e. polytetrafluorethene, e.g. ePTFE, i.e. expanded polytetrafluorethene
    • 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
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene

Definitions

  • the present invention relates to a method for producing a stretched polytetrafluoroethylene film and a stretched polytetrafluoroethylene film.
  • PTFE Polytetrafluoroethylene
  • a melting point about 330 ° C.
  • a skive method is generally used in which a film is scraped off from a block-shaped casing obtained by sintering PTFE powder in the manner of peeling katsura.
  • the PTFE film produced by the skive method when stretched in the same manner as a general thermoplastic resin, causes the film to break even when stretched at a low magnification. Therefore, the molecules are oriented by stretching and the strength in the stretching direction is increased. It is difficult to improve. Moreover, transparency of a film is also impaired by stretching. Therefore, as a method for improving the strength of the PTFE film, a method of combining PTFE with glass fiber or the like has been used. In this method, the process of impregnating the glass fiber cloth with the PTFE aqueous dispersion and baking it is repeated, so that the production cost is high and the obtained composite film is inferior in recyclability.
  • the following patent document discloses a stretched film obtained by a solid-phase stretching method in which stretching is performed at a temperature equal to or lower than the melting point of PTFE, that is, in a state where PTFE is not substantially melted, as improving the strength of the PTFE film by stretching. ing.
  • a stretched film obtained by stretching a film obtained by compression molding PTFE powder at a temperature lower than the melting point at a temperature at which the film does not substantially melt (Patent Document 1).
  • a porous film obtained by removing a lubricant from a sheet obtained by extruding and rolling a PTFE powder with a lubricant is stretched at a temperature lower than the melting point of PTFE and becomes nonporous.
  • a stretched film (Patent Document 2).
  • Patent Document 3 A stretched film obtained by adding a lubricant to PTFE powder and extruding and biaxially stretching below the melting point of PTFE.
  • These stretched films of Patent Documents 1 to 3 can be improved in strength as compared with a film produced by a skive method.
  • high transparency and excellent transparency are often required, and these stretched films require further improvements in strength and transparency. It was.
  • Non-patent Documents 1 and 2 The present inventors have reported a method for obtaining a stretched film by stretching (melt stretching) a PTFE film in a molten state. This is an attempt to perform melt stretching, which cannot be performed with a normal thermoplastic resin, focusing on the fact that PTFE has a remarkably high viscosity at a temperature equal to or higher than the melting point. According to the melt stretching of PTFE, since the film can be stretched at a higher magnification than solid phase stretching, a film having high strength can be obtained. However, even when the melt stretching is used, the width is narrower than the original film because of the uniaxial stretching, and a film having a large area suitable for a structural film material such as a dome roofing material or an agricultural greenhouse material is manufactured. That was difficult.
  • the object of the present invention is to provide a method for producing a PTFE stretched film having high strength and excellent transparency, and a PTFE stretched film obtained by the production method.
  • a method for producing a stretched film made of PTFE comprising: a film forming step for obtaining a film by compression-molding PTFE in a molten state under a reduced-pressure atmosphere; and a melt-stretching step for melt-stretching the film
  • a method for producing a PTFE stretched film includes a melting step of pressurizing and melting PTFE in a reduced pressure atmosphere, and a compression forming step of compressing and molding the melted PTFE in a molten state in a reduced pressure atmosphere.
  • [3] The method for producing a stretched PTFE film according to [1] or [2], wherein the reduced-pressure atmosphere is an atmosphere having a pressure of 10 Torr or less.
  • [4] The method for producing a stretched PTFE film according to any one of [1] to [3], wherein the temperature at which PTFE is melted in the film forming step is 330 to 420 ° C.
  • [5] The method for producing a stretched PTFE film according to any one of [1] to [4], wherein the PTFE before melting used in the film forming step is powdery PTFE.
  • [6] The method for producing a stretched PTFE film according to any one of [1] to [5], wherein the PTFE is PTFE obtained by emulsion polymerization.
  • the production method of the present invention it is possible to produce a stretched PTFE film that has very high strength and excellent transparency. Moreover, the PTFE stretched film of the present invention has very high strength and very excellent transparency.
  • the production method of the present invention is a method for producing a stretched film made of PTFE, and a film forming step for obtaining a film (hereinafter referred to as “formed film”) by compression-molding PTFE in a molten state under a reduced-pressure atmosphere; A melt stretching step of stretching the molded film in a molten state to obtain a PTFE stretched film.
  • modified PTFE polytetrafluoroethylene
  • TFE homopolymer of tetrafluoroethylene
  • Modified PTFE is a copolymer obtained by copolymerizing a fluorine-containing comonomer with TFE within a range that does not impart melt-formability such as ordinary extrusion molding or injection molding to PTFE.
  • fluorine-containing comonomer examples include vinylidene fluoride (VdF), hexafluoropropylene (HFP), perfluoro (alkyl vinyl ether) (PFAVE), chlorotrifluoroethylene (CTFE), polyfluoroalkylethylene, perfluoro-2, From 2-dimethyl-1,3-dioxole, perfluoro-4-alkyl-1,3-dioxole and CF 2 ⁇ CFO (CF 2 ) n CF ⁇ CF 2 (wherein n is 1 or 2).
  • PTFE is characterized by a high melting point and low melt moldability.
  • the content of the structural unit based on the fluorine-containing comonomer in the modified PTFE is preferably 0.5% by mass or less, and 0.4% by mass or less in order to maintain the heat resistance, weather resistance, and water repellency inherent to PTFE. More preferably.
  • the number average molecular weight (hereinafter referred to as “Mn”) of PTFE is preferably 1 ⁇ 10 6 to 5 ⁇ 10 7 g / mol, and preferably 2 ⁇ 10 6 to 1 ⁇ 10 7 g / mol. More preferred.
  • Mn of PTFE is 1 ⁇ 10 6 g / mol or more, the strength of the obtained PTFE stretched film is improved. Further, if the Mn of PTFE is 5 ⁇ 10 7 g / mol or less, the melt viscosity does not become too high, so that melt stretching becomes easy.
  • the PTFE in the present invention is particularly preferably obtained by emulsion polymerization of TFE.
  • Emulsion polymerization gives higher molecular weight PTFE than suspension polymerization.
  • a higher-strength PTFE stretched film can be obtained as the PTFE molecular weight of the molded film to be melt stretched is higher. Therefore, a PTFE stretched film having particularly high strength can be obtained by using PTFE obtained by emulsion polymerization.
  • PTFE obtained by emulsion polymerization it is superior in transparency even in an unstretched state as compared with the case where PTFE obtained by suspension polymerization is used, so that a PTFE stretched film superior in transparency can be obtained.
  • Cheap is preferably obtained by emulsion polymerization of TFE.
  • Examples of the emulsifier used for the emulsion polymerization of TFE include fluorine-containing surfactants.
  • a fluorine-containing surfactant is generally used in emulsion polymerization of TFE because it does not interfere with the polymerization reaction of TFE by chain transfer in an aqueous medium.
  • the fluorine-containing surfactant is preferably at least one selected from the group consisting of the following surfactant ( ⁇ 1) to surfactant ( ⁇ 4).
  • Surfactant ( ⁇ 1) a fluorine-containing carboxylic acid and a salt thereof containing 1 to 4 etheric oxygen atoms in the molecule.
  • Surfactant ( ⁇ 2) perfluoroalkylcarboxylic acid and its salt.
  • Surfactant ( ⁇ 3) ⁇ -hydroperfluoroalkylcarboxylic acid and salt thereof.
  • the number of carbon atoms constituting the fluorine-containing surfactant is preferably 4 to 10, more preferably 4 to 8, and most preferably 4 to 7. When the number of carbon atoms of the fluorine-containing surfactant is in the above range, the polymerization stability is excellent and the bioaccumulation property is low.
  • Examples of the surfactant ( ⁇ 1) include C 3 F 7 OCF 2 CF 2 OCF 2 COOH, C 4 F 9 OCF 2 CF 2 OCF 2 COOH, C 5 F 11 OCF 2 CF 2 OCF 2 COOH, and C 6 F. 13 OCF 2 CF 2 OCF 2 COOH , CF 3 O (CF 2 CF 2 O) 2 CF 2 COOH, C 3 F 7 O (CF 2 CF 2 O) 2 CF 2 COOH, C 4 F 9 O (CF 2 CF 2 O) 2 CF 2 COOH, C 5 F 11 O (CF 2 CF 2 O) 2 CF 2 COOH, C 6 F 13 O (CF 2 CF 2 O) 2 CF 2 COOH, C 3 F 7 O (CF 2 CF 2 O) 3 CF 2 COOH , C 4 F 9 O (CF 2 CF 2 O) 3 CF 2 COOH, C 5 F 11 O (CF 2 CF 2 O) 3 CF 2 COOH, C 6 13 O (CF 2 CF 2 O ) 3 CF 2
  • Examples of the surfactant ( ⁇ 2) include perfluorohexanoic acid, perfluoroheptanoic acid, perfluorooctanoic acid, and perfluorononanoic acid.
  • the salt in the surfactant ([alpha] 2) Li of the compound, Na, K, include salts, such as NH 4.
  • Examples of the surfactant ( ⁇ 3) include ⁇ -hydroperfluorohexanoic acid, ⁇ -hydroperfluoroheptanoic acid, ⁇ -hydroperfluorooctanoic acid, and ⁇ -hydroperfluorononanoic acid.
  • the salt in the surfactant (.alpha.3) Li of the compound, Na, K, include salts, such as NH 4.
  • Examples of the surfactant ( ⁇ 4) include perfluorooctane sulfonic acid and C 6 F 13 CH 2 CH 2 SO 3 H.
  • Examples of the salt in the surfactant ( ⁇ 4) include salts of Li, Na, K, NH 4 and the like of the above compound.
  • Preferred fluorine-containing surface active agent perfluorohexane acid, perfluoroheptanoic acid, C 4 F 9 OCF (CF 3) COOH, C 4 F 9 OCF 2 CF 2 COOH, CF 3 OCF 2 CF 2 CF 2 OCF 2 COOH , C 2 F 5 OCF 2 CF 2 OCF 2 COOH, CF 3 OCF 2 OCF 2 OCF 2 COOH, C 4 F 9 OCF 2 COOH, C 3 F 7 OCF 2 CF 2 COOH, CF 3 OCF 2 CF 2 OCF 2 COOH , C 2 F 5 OCF 2 CF 2 COOH, and salts thereof.
  • an ammonium salt (NH 4 ) of the above compound is particularly preferable.
  • the ammonium salt is excellent in solubility in an aqueous medium, and there is no possibility that the metal ion component remains as an impurity in the PTFE powder.
  • the emulsion polymerization can be started by adding a polymerization initiator.
  • a polymerization initiator the radical initiator normally used for emulsion polymerization can be used, and a water-soluble initiator is preferable.
  • water-soluble initiators include inorganic initiators and organic initiators.
  • inorganic initiators include, for example, persulfates such as ammonium persulfate, hydrogen peroxide, or redox initiators composed of a combination of these with a reducing agent such as sodium bisulfite and sodium thiosulfate, and a small amount thereof.
  • examples include initiators in which iron, ferrous salt, silver sulfate and the like coexist.
  • organic initiator examples include dibasic acid peroxides such as disuccinic acid peroxide and diglutaric acid peroxide, azobisisobutylamidine hydrochloride, and azobisisobutyronitrile. These polymerization initiators may be added all at once or in divided portions.
  • the amount of the polymerization initiator used can be appropriately changed according to the kind of the polymerization initiator, emulsion polymerization conditions and the like, and is preferably 0.005 to 0.5 parts by mass with respect to 100 parts by mass of the monomer to be emulsion polymerized.
  • the starting temperature of the emulsion polymerization can be appropriately selected according to the type of the polymerization initiator, and is preferably 0 to 100 ° C, more preferably 10 to 90 ° C.
  • the reaction pressure for emulsion polymerization can also be selected as appropriate, preferably 0.2 to 10 MPa, more preferably 0.2 to 5 MPa.
  • Examples of commercially available PTFE produced by emulsion polymerization include fluon CD123 (trade name, polytetrafluoroethylene powder, number average molecular weight 1 ⁇ 10 7 , manufactured by Asahi Glass Co., Ltd.).
  • PTFE is compression-molded in a molten state under a reduced pressure atmosphere to obtain a formed film.
  • the molding process includes the following three steps. First, in a reduced pressure atmosphere, PTFE is heated and melted in a state where pressure is applied to PTFE (melting step). Next, compression molding is performed by further applying pressure while maintaining PTFE in a molten state in a reduced-pressure atmosphere (compression molding step). Subsequently, it cools with the state which applied the pressure, and obtains a shaping
  • PTFE powder is preferable as PTFE used in the film forming step.
  • a first pressure V 1 unit: MPa
  • a second pressure V 2 unit: MPa
  • the entire film forming process is performed under a reduced pressure atmosphere.
  • PTFE can be degassed and air can be prevented from being mixed into the molded film. Therefore, the adhesiveness between the PTFE in the molded film is improved, the molded film is hardly damaged in the melt stretching process, and the transparency of the obtained PTFE stretched film is also improved.
  • the decompressed atmosphere in the present invention is preferably 10 Torr (about 1.33 kPa) or less, preferably 1 Torr (about 1.33 ⁇ 10 2 Pa) or less in terms of excellent degassing efficiency from PTFE. Is more preferable.
  • the pressure reduction condition is preferably 1 ⁇ 10 ⁇ 3 Torr (about 0.13 Pa) or more, and 1 ⁇ 10 ⁇ 2 Torr (about 1.33 Pa) or more is more preferable.
  • PTFE is heated to a molten state under pressure (first pressure V 1 ).
  • first pressure V 1 first pressure
  • PTFE is melted in a pressurized state
  • the adhesiveness between the PTFE raw material powders is improved and a molded film having high strength is obtained as compared with the case where PTFE is melted in a non-pressurized state. Therefore, a molded film obtained by compressing and molding in a pressurized state can be melt-stretched at a high magnification because the molded film is hardly damaged in the melt-stretching process, and thus a PTFE stretched film having particularly high strength is obtained. It is done.
  • the first pressure V 1 in the melting step is preferably 0.01 to 100 MPa, more preferably 0.01 to 50 MPa, and further preferably 0.1 to 10 MPa. If the first pressure V 1 is 0.01MPa or more, molding the film is hardly damaged at high molding film obtained melt drawing process strength, PTFE oriented film strength and excellent high transparency is obtained Cheap. Further, if the first pressure V 1 is 0.1MPa or more, obtained by PTFE oriented film stably having a high strength easily.
  • the first pressure V 1 is equal to or less than 100 MPa, it is possible to mold in conventional press molding machine.
  • the first pressure V 1 in the melting step the pressure within the above range increases, may be varied down or performing both. However, it is preferable that the first pressure V 1 is maintained at a constant pressure within the above range from the viewpoint that a molded film having a constant quality is easily obtained stably.
  • the ambient temperature of PTFE (hereinafter, the ambient temperature of PTFE in the melting step is referred to as “temperature T 1 ”) is maintained at a temperature at which PTFE melts, that is, a temperature equal to or higher than the melting point of PTFE for a certain period of time.
  • the melting point of PTFE usually indicates a melting peak temperature measured by differential scanning calorimetry (based on JIS standard K7121).
  • the temperature T 1 is preferably 330 to 420 ° C., more preferably 350 to 400 ° C. If the temperature T 1 is 330 ° C. or higher, high molding film is easily obtained with good strength adhesion because PTFE is melted. Also, if the temperature T 1 is 420 ° C. or less, it is easy to prevent the PTFE is degraded by thermal decomposition.
  • the time for maintaining the first pressure V 1 and the temperature T 1 within the pressure range and the temperature range in the melting step is preferably 1 to 100 minutes, and more preferably 5 to 60 minutes.
  • the time is 1 minute or longer, PTFE is sufficiently melted and the deaeration efficiency from PTFE is improved, so that a molded film having high strength and good adhesion between PTFE powders can be easily obtained.
  • productivity will improve.
  • the molten PTFE is compressed at the second pressure V 2 to be formed into a film shape.
  • the second pressure V 2 is preferably 0.1 to 100 MPa, more preferably 1 to 50 MPa. If the second pressure V 2 is 0.1MPa or more, the adhesion between PTFE is improved, easy high strength molded film can be obtained.
  • the second pressure V 2 is equal to or less than 100 MPa, it is possible to mold in conventional press molding machine.
  • the second pressure V 2 in the compression molding step the pressure within the above range increases, may be varied down or performing both. However, easily obtained by molding a film stable quality is constant, from the point it is relatively easy to manufacture, it is preferred that the second pressure V 2 is to maintain a constant pressure within said range.
  • the first pressure V 1 may be a relatively low pressure in order to completely melt the raw material powder that is initially in a crystalline state.
  • the second pressure V 2 so is the process for obtaining a uniform film to improve the adhesion between the raw material powder is preferably at a higher pressure than the first pressure V 1.
  • a difference (V 2 ⁇ V 1 ) between the second pressure V 2 and the first pressure V 1 is preferably 0.1 to 99 MPa, and more preferably 1 to 50 MPa.
  • the difference (V 2 ⁇ V 1 ) is 0.1 MPa or more, the raw material powder in the molten state obtained in the melting step can be easily formed into a film. Further, if the difference (V 2 ⁇ V 1 ) is 99 MPa or less, molding with a normal press molding machine is possible.
  • the ambient temperature of PTFE (hereinafter, the ambient temperature in the compression molding step is referred to as “temperature T 2 ”) is maintained above the melting point of PTFE, so that the compression molding is performed in a molten state.
  • the temperature T 2 is preferably 330 to 420 ° C., more preferably 350 to 400 ° C. If temperature T 2 is 330 ° C. or higher, already raw material powder is easily obtained molded film can be melt drawn in close contact by pressure of the PTFE in a molten state in a melt step. Further, if the temperature T 2 is 420 ° C. or less, it is easy to prevent the PTFE is degraded by thermal decomposition. Also, temperature T 2 may be a temperature different from the temperature T 1. However, from the viewpoint of excellent productivity, it is preferable that the temperature T 2 are the same as the temperature T 1 of the melting step.
  • the compression time in the compression molding step is preferably 1 to 100 minutes.
  • the compression time is 1 minute or longer, a molded film having good strength and high strength between PTFE can be easily obtained. Moreover, if the said compression time is 100 minutes or less, productivity will improve.
  • the cooling step by cooling while applying a pressure in a reduced pressure atmosphere and the second pressure V 2, less than the melting point of PTFE, which is compressed into a film shape, preferably solidified by cooling to room temperature. Thereby, a molded film made of PTFE is obtained.
  • a vacuum press machine in which a press machine is installed in a vacuum chamber can be used.
  • a release polyimide film 12 is placed on a stainless steel plate 11, and a stainless steel plate 13 in which an opening 13 a having a desired shape is formed.
  • a release polyimide film 14 is placed on the stainless steel plate 13, and a stainless steel plate 15 is placed on the release polyimide film 14 (hereinafter referred to as "laminate"). 1 ”).
  • Examples of the state of PTFE charged into the opening 13a include a powder form and a lump form.
  • PTFE is preferably powdery because it is easy to handle and has high degassing efficiency.
  • the average particle size of the powdered PTFE is preferably 0.001 to 1 mm.
  • the average particle diameter means a value obtained by averaging the maximum diameter of a plurality of PTFE particles by the number of the particles. When the average particle diameter is 0.001 mm or more, it is easy to obtain PTFE powder. Further, if the average particle diameter is 1 mm or less, it is easy to uniformly put the PTFE powder into the openings 13a.
  • the amount of PTFE introduced into the opening 13a is preferably such that the ratio (V A / V B ) of the volume V A of PTFE to be introduced and the volume V B of the opening 13a is 1 to 10.
  • the ratio (V A / V B ) is 1 or more, a high-strength molded film suitable for melt stretching at a high magnification is obtained with good adhesion between PTFE.
  • the ratio (V A / V B ) is 10 or less, it becomes easy to produce a molded film by compression molding.
  • the laminated body 1 is installed between the upper and lower plates of the press machine installed in the vacuum chamber at room temperature, the inside of the vacuum chamber is depressurized so as to have the above-described reduced pressure atmosphere, and PTFE is added by the press machine. pressurized with 1 pressure V 1.
  • the order of the depressurization operation and the pressurization operation is not particularly limited, and it may be pressurized after depressurization, may be depressurized after pressurization, or may be pressurized while depressurizing.
  • the temperature T 1 of the periphery of the PTFE in the above the melting point of PTFE to maintain a certain time, heating and melting PTFE (melting step).
  • the heating can be performed by contact with a hot plate, laser irradiation with infrared rays, or blowing hot air.
  • the PTFE is sufficiently cooled in a reduced pressure atmosphere while maintaining the press machine pressure at the second pressure V 2 (cooling step).
  • the laminated body 1 taken out from the inside of a vacuum chamber is decomposed
  • the shape of the molded film is not particularly limited as long as it is a shape according to the use of the stretched PTFE film produced by the production method of the present invention.
  • the shape of the molded film can be changed to a desired shape by adjusting the shape of the opening 13 a of the stainless steel plate 13.
  • the thickness of the formed film is preferably from 0.01 to 100 mm, more preferably from 0.1 to 10 mm.
  • the thickness of the molded film is 0.01 mm or more, a film with good adhesion of the raw material powder is easily obtained. Moreover, if the thickness of a molded film is 100 mm or less, melt stretch of a molded film will become easy.
  • the thickness of the molded film can be adjusted by the thickness of the stainless steel plate 13 and the amount of PTFE introduced into the opening 13a.
  • the film forming method in this invention is not limited to the method using the above-mentioned laminated body 1.
  • FIG. for example, in the present embodiment, the stainless steel plate 11, the release polyimide film 12, the stainless steel plate 13, the release polyimide film 14 and the stainless steel plate 15 are all in a disk shape, but these shapes are other than the disk shape. May be.
  • the opening 13a is also rectangular in the present embodiment, but may have a shape other than a rectangle.
  • a laminated body in which PTFE is sandwiched between two release polyimide films without using the disk-shaped stainless steel plate 13 in which the openings 13a are formed may be used.
  • a mold having a film-shaped opening may be used.
  • the release polyimide film may not be used.
  • the release material is not a polyimide film, but a polymer, metal, or the like that does not decompose up to 400 ° C. can be suitably used.
  • a method in which PTFE subjected to the melting step is taken out and roll-rolled in a molten state as the compression forming step can be suitably used in that pressure is applied to the film.
  • melt stretching step the molded film obtained in the film forming step is stretched and stretched in a molten state.
  • the melt stretching is performed at a temperature equal to or higher than the melting point of the PTFE film. Since PTFE has an extremely high melt viscosity, it can be stretched while maintaining a film state even in a molten state.
  • the stretching may be uniaxial stretching or biaxial stretching.
  • biaxial stretching a method of sequentially stretching one axis at a time (sequential biaxial stretching) or a method of simultaneously stretching biaxials (simultaneous biaxial stretching) may be used.
  • it is preferable to perform simultaneous biaxial stretching because a PTFE stretched film having high strength and excellent transparency can be obtained stably.
  • the temperature around the molded film (hereinafter referred to as “temperature T 3 ”) is maintained for a certain period of time at a temperature at which the molded film melts, that is, a temperature equal to or higher than the melting point. Stretching is performed in a molten state.
  • the temperature T 3 is preferably 330 to 420 ° C., more preferably 350 to 400 ° C. If the temperature T 3 is 330 ° C. or higher, since the formed film can be stretched in the molten state, PTFE oriented film is easily obtained strength and excellent high transparency. Also, if the temperature T 3 is 420 ° C. or less, easily suppress the obtained PTFE oriented film is deteriorated by thermal decomposition.
  • the time for maintaining the temperature T 3 in the temperature range is preferably 0.1 to 100 minutes, and more preferably 1 to 10 minutes. If the time is 1 minute or longer, it becomes easier to sufficiently melt the molded film. Moreover, if the said time is 100 minutes or less, productivity will improve.
  • the stretching speed for stretching the formed film is preferably 1 to 1000 mm / min, and more preferably 10 to 100 mm / min. If the stretching speed is 1 mm / min or more, productivity is improved. Further, when the stretching speed is 1000 mm / min or less, it becomes easy to produce a PTFE stretched film without causing breakage.
  • Stretch ratio in the melt drawing process i.e. the ratio of the length b of the stretching axis direction of the PTFE stretched film after stretching to the length a of the stretching axis direction of the formed film before stretching (b / a) is, by the temperature T 3 However, it is preferably 1.1 to 10, more preferably 2 to 5.
  • the stretch ratio (b / a) is 1.1 or more, a PTFE stretched film having high strength and excellent transparency is easily obtained. Further, when the stretch ratio (b / a) is 10 or less, it becomes easy to stably produce a PTFE stretched film without causing damage to the film.
  • the stretching ratios in the longitudinal and lateral biaxial are both within the above range.
  • the biaxial stretch ratio is the same and within the above range. preferable.
  • Stretching in the melt stretching process can be performed by a chuck type stretching machine.
  • the stretching machine may be a uniaxial stretching machine or a biaxial stretching machine.
  • the melt stretching step of the present invention when the molded film is stretched by a stretching machine, the molded film is heated so that the portion of the molded film held by the stretching machine and the vicinity thereof do not exceed the melting point of PTFE. Thereby, it is possible to prevent the molded film from being damaged in the vicinity of the portion gripped by the stretching machine during the stretching operation.
  • the stretching method in the melt stretching step in the present invention is preferably a method in which a molded film is melted and stretched by partial hot air blowing.
  • partial hot air blowing the molded film is partially melted except for the gripped portion and its vicinity, and it becomes easy to melt and stretch without causing damage to the film, and it has high strength and excellent transparency. It is easy to obtain a stretched PTFE film.
  • 2A and 2B are conceptual diagrams showing an example of an embodiment of a stretching machine that melts and stretches a molded film by blowing hot air. As illustrated in FIG.
  • the stretching machine 101 of the present embodiment includes an upper hot air blowing unit 110 (hereinafter referred to as “blowing unit 110”), a chuck unit 120 that holds the molded film 20, and a lower hot air blowing unit 130. (Hereinafter referred to as “blowing part 130”).
  • the chuck part 120 is a part that holds the molded film 20 and pulls and stretches the molten molded film 20.
  • the chuck unit 120 grips four corners of the molded film 20 with four chucks on the same horizontal plane (a plane orthogonal to FIG. 2A), and separates the chucks in the diagonal direction of the molded film 20.
  • the molded film 20 can be biaxially stretched in the vertical direction and the horizontal direction.
  • the blowing part 110 is a part that blows hot air on the molded film 20 from above.
  • the blowing unit 110 is provided with a hot air introduction port 111 for introducing hot air into the interior 110a and a blowout port 112 for blowing the hot air, and a transparent upper lid 113 is provided on the upper part.
  • the shape of the inside 110a of the spraying portion 110 is a shape that becomes narrower toward the molded film 20 side.
  • the blowing unit 110 hot air is guided from the hot air inlet 111 to the inside 110 a and blown out from the outlet 112 toward the molded film 20.
  • the shape of the inside 110a of the spraying part 110 is made narrow so that hot air from the air outlet 112 is blown to the part of the molded film 20 held by the chuck part 120 and the vicinity thereof. Instead, hot air is sprayed only on the central portion of the molded film 20. Therefore, the central portion of the molded film 20 can be melted without melting the portion gripped by the chuck portion 120 of the molded film 20 and the vicinity thereof.
  • the transparent upper cover 113 is provided in the upper part of the spraying part 110, it can transfer to extending
  • the blowing part 130 is a part that blows hot air from below on the molded film 20.
  • the blowing unit 130 includes a hot air introduction port 131 for introducing hot air into the inside 130a, a hot air blowing plate 135 in which a blowing port 135a for blowing out hot air is formed, and air guide plates 132 and 133 for guiding the hot air to the blowing port 135a in the inside 130a. , 134 are provided. Openings 132a, 133a, and 134a are formed in the air guide plates 132, 133, and 134, respectively.
  • outlets 135 a are formed in the hot air blowing plate 135.
  • Each of the outlets 135a is formed at a position where hot air is blown only to a portion of the molded film 20 that is gripped by the chuck portion 120 and a portion other than the vicinity thereof. That is, all the outlets 135a are formed at positions corresponding to the central portion of the unstretched molded film 20.
  • the number, size, position, and the like of the openings 132a, 133a, and 134a formed in the air guide plates 132, 133, and 134 are such that hot air can be efficiently blown out vertically from the outlet 135a by computer simulation. Has been calculated.
  • hot air is introduced from the hot air inlet 131, and sequentially passes through the openings 132 a, 133 a, and 134 a formed in the air guide plates 132, 133, and 134 in the interior 130 a, and is blown out on the hot air blowing plate 135. It blows out from the mouth 135a. As a result, hot air is blown only on the central portion of the molded film 20.
  • the hot air from the blowing unit 110 and the hot air from the blowing unit 130 are not blown to the portion of the molded film 20 gripped by the chuck portion 120 and the vicinity thereof. Only the central portion of the molded film 20 can be melted in a state where these portions are maintained at a temperature lower than the melting point of PTFE. Then, in the state where the molded film 20 is melted, the stretched film 20 can be melt stretched by being stretched by the chuck portion 120.
  • the manufacturing method of this invention is not limited to the above-mentioned method.
  • the stretching machine used in the melt stretching process is not limited to the above-described stretching machine 101.
  • the stretching machine has chucks that respectively grip four corners of the molded film, and the molded film is in either the vertical or horizontal direction. It may be a stretching machine that can be uniaxially stretched, or may be a stretching machine that can be uniaxially stretched by gripping two opposite sides of the formed film.
  • stretching machine which has a heating mechanism which heats the whole molded film, and a cooling mechanism which cools the part hold
  • the stretched PTFE film of the present invention is a film manufactured by the above-described manufacturing method, and has high strength and excellent transparency.
  • the thickness of the stretched PTFE film may be appropriately determined according to the use, and is preferably 0.001 to 10 mm, and more preferably 0.01 to 1 mm. If thickness is 0.001 mm or more, it will be easy to obtain the uniform PTFE stretched film which does not have damage, such as a pinhole and a crack, in a film. Moreover, if thickness is 10 mm or less, the intensity
  • the thickness of the stretched PTFE film can be controlled by adjusting the thickness of the molded film and the stretch ratio of melt stretching.
  • the stretched PTFE film of the present invention preferably has a tensile strength at break of 30 MPa or more, more preferably 50 MPa or more.
  • the tensile breaking strength means that a sample piece is cut out from a PTFE stretched film into a JIS dumbbell shape No. 5 (straight portion 12.5 mm, width 4 mm), and the sample piece is pulled at a pulling rate of 20 mm / min. It means a value obtained by conducting a tensile test at room temperature.
  • the tensile tester include a tensile tester RTC-1325A (manufactured by Baldwin).
  • the tensile strength can be adjusted by the Mn of PTFE to be used, the press pressure (V 1 , V 2 ) in the film forming step, the press temperature (T 1 , T 2 ), the melting temperature in the melt drawing step, the draw ratio, and the like.
  • the stretched PTFE film preferably has a tear breaking strength of 3 N / mm or more, and more preferably 5 N / mm or more.
  • the tear rupture strength means that a strip-shaped sample piece having a width of 10 mm ⁇ a length of 40 mm is cut out from a stretched PTFE film, and a 20 mm notch is formed along the longitudinal direction at the center of the width direction of the sample piece. It means a value calculated from the stress detected by the stress detection cell mounted on the tester by connecting the handles on both sides to a tensile tester and tearing at a tearing speed of 200 mm / min.
  • An example of a tensile tester used for the tear rupture strength test is the RTC-1325A.
  • the tear rupture strength can be adjusted by the Mn of PTFE to be used, the pressing pressure (V 1 , V 2 ) in the film forming process, the pressing temperature (T 1 , T 2 ), the melting temperature in the melt stretching process, the stretching ratio, and the like.
  • the stretched PTFE film preferably has a haze (cloudiness) of 30% or less, and more preferably 15% or less.
  • the haze means a value measured according to JIS K7105 “Testing methods for optical properties of plastics”. The haze can be adjusted by the Mn of PTFE to be used, the pressing pressure (V 1 , V 2 ) in the film forming process, the pressing temperature (T 1 , T 2 ), the melting temperature in the melt stretching process, the stretching ratio, and the like.
  • the stretched PTFE film of the present invention can be suitably used for applications such as dome roofing materials and agricultural vinyl sheets, which are particularly required to have both high strength and excellent transparency.
  • Example 1 Film forming process
  • a release-use polyimide film 12 having a thickness of 125 ⁇ m is placed on a disk-shaped stainless steel plate 11 having a diameter of 100 mm ⁇ a thickness of 2 mm, and a rectangular opening 13 a having a length of 70 mm ⁇ width of 70 mm is formed.
  • a PTFE powder (trade name: Fullon CD123, number average molecular weight 1 ⁇ 10 7 , number average particle) synthesized by an emulsion polymerization method is placed in the opening 13a.
  • PTFE powder 4.5 g of 0.55 mm diameter manufactured by Asahi Glass Co., Ltd.
  • PTFE powder 4.5 g of 0.55 mm diameter manufactured by Asahi Glass Co., Ltd.
  • a 125 ⁇ m-thickness release polyimide film 14 is placed on the disk-shaped stainless steel plate 13, and a disk-shaped stainless steel plate 15 having a diameter of 100 mm ⁇ thickness 2 mm is further placed thereon to form a laminate for film formation (lamination Body 1) was obtained.
  • a vacuum press machine made by Baldwin having a top plate and a bottom plate and a cylinder for generating pressure between the top plate and the bottom plate was installed in a vacuum chamber at room temperature.
  • the laminate 1 was placed between the upper plate and the lower plate of the press machine, and the inside of the vacuum chamber was depressurized to 1 ⁇ 10 ⁇ 1 Torr with a roller pump. Then, pressure is applied to the PTFE powder at 2.2314 MPa (first pressure V 1 , cylinder pressure 30 MPa) with a vacuum press machine, and the temperature in the vacuum chamber (temperature T 1 around the PTFE powder) is applied for 50 minutes in that state. The temperature was raised to 370 ° C. and kept at 370 ° C. for 10 minutes.
  • the pressure in the vacuum press is 2.9752 MPa (second pressure V 2 , cylinder pressure 40 MPa) while maintaining the temperature in the vacuum chamber (temperature T 2 around the PTFE powder) at 370 ° C. In that state, it was held for 5 minutes to perform vacuum compression molding.
  • the temperature in the vacuum chamber is cooled to room temperature by allowing to cool while maintaining the pressurized state at the second pressure V 2 in the reduced pressure atmosphere, and the laminate 1 taken out from the vacuum chamber is cooled. A molded film was obtained.
  • the effective pressure was converted from the cylinder pressure by the following method. Table 1 shows the relationship between cylinder pressure and effective pressure.
  • Example 2 Simultaneous biaxial stretching was performed in the molten state in the same manner as in Example 1 except that the temperature of hot air in the stretching step (temperature T 3 around the molded film) and the stretching ratio were changed as shown in Table 2.
  • Example 4 In the film forming process, the first pressure V 1 is changed to 0.7438 MPa (cylinder pressure 10 MPa) and the second pressure V 2 is changed to 2.2314 MPa (cylinder pressure 30 MPa). Biaxial stretching was performed.
  • Example 5 Except that the first pressure V 1 in the film forming step was changed as shown in Table 2 were subjected to simultaneous biaxial stretching in the same molten state as in Example 4. Incidentally, the cylinder pressure at which the first pressure V 1 in Example 5 was 1.4876MPa is 20 MPa.
  • Example 6 Simultaneous biaxial stretching was performed in the molten state in the same manner as in Example 1 except that the temperature of the hot air in the stretching step and the stretching ratio were changed as shown in Table 2.
  • Example 6 instead of the molded film of Example 1, a commercially available PTFE film (Nichias Naflon: thickness 0.2 mm) was used, and the melt ratio was changed as shown in Table 2 except that the stretch ratio was changed as shown in Table 2. Simultaneous biaxial stretching was performed.
  • the commercially available PTFE film is a film manufactured by a skive method using PTFE obtained by suspension polymerization.
  • Example 7 The commercially available PTFE film was used in place of the molded film of Example 1, and the stretching temperature and the stretching ratio in the stretching process were changed as shown in Table 2. Axial stretching was performed.
  • the tensile strength at break was measured by cutting out a sample piece A from the obtained PTFE stretched film in the shape of JIS dumbbell No. 5 (straight portion 12.5 mm, width 4 mm) and using a tensile tester RTC-1325A (Baldwin). At room temperature. The pulling speed was 20 mm / min.
  • tearing rupture strength For the measurement of the tearing rupture strength, a strip-shaped sample piece B having a width of 10 mm ⁇ a length of 40 mm was cut out from the obtained PTFE stretched film, and a notch of 20 mm was put along the longitudinal direction in the center of the width direction of the sample piece B. A tear test was conducted by connecting the handles on both sides of the notch to the tensile tester RTC-1325A, and the notch was obtained from the stress detected by a stress detection cell mounted on the tester. The tearing speed was 200 mm / min.
  • Tear energy The tear energy was calculated from the product of the stress detected in the tear test and the distance to which the sample piece B was torn.
  • the PTFE stretched films of Examples 1, 6 and 7 obtained by melt-stretching molded films obtained by melting and compressing PTFE powder under pressure in a reduced-pressure atmosphere were tensile.
  • the breaking strength was high, which was remarkably improved as compared with the tensile breaking strength of the molded film of Reference Example 2 before stretching, and the strength was very high. From these comparisons, it was found that the higher the stretch ratio, the higher the tensile strength at break and the easier to obtain a high-strength PTFE stretched film.
  • the stretched PTFE films of Examples 2 and 3 in which the stretching temperature was changed to 370 ° C. and 360 ° C. also had high tensile strength at break.
  • the PTFE stretched film of Example 4 also has a high tensile strength as compared with the unstretched film of Reference Example 1 before stretching by melt stretching, as with the PTFE stretched film of Example 1. It was. Furthermore, from a comparison of Examples 1, 4 and 5, the higher the first pressure V 1 in the film forming process, tensile break strength is high, high-strength PTFE oriented film is found to result.
  • the PTFE stretched films of Examples 1, 6 and 7 had a sufficiently high tear strength and a large tear energy. This is because a molded film having good adhesion between PTFE is obtained by being melted and compression-molded under a reduced-pressure atmosphere, and stretched at a high magnification by melt-stretching so that the PTFE is stretched in the stretching direction. This is considered to be because the film was sufficiently oriented.
  • the PTFE stretched films of Examples 1 and 6 and Example 8 in which the stretching temperature was 390 ° C. had a low haze value and particularly excellent transparency. Moreover, although the haze value was not measured also about the other Example, it has confirmed that it had sufficient transparency by visual observation. This is considered to be because the adhesiveness between the raw material powders was improved by melting PTFE in a state of being pressurized in a reduced pressure atmosphere in the film forming step and performing compression molding.
  • Comparative Example 1 in which the PTFE powder was melted in an unpressurized state in the film forming process and then compression-molded, the film was cracked immediately after stretching, but could not be stretched. It was.
  • the film forming process was performed under the same conditions as in Example 1, the tensile fracture strength of the PTFE stretched films of Comparative Examples 2 to 5 that were stretched in a non-molten state in the stretching process was the same as that of Reference Example 2 before stretching.
  • the tensile strength at break of the molded film was the same or decreased, and the strength was low.
  • the PTFE stretched film of Comparative Example 6 obtained by melt-stretching a commercially available PTFE film at a stretching temperature of 380 ° C. has a tensile rupture strength lower than the tensile rupture strength of the commercially available PTFE film (Reference Example 3) before stretching. was low.
  • the PTFE stretched film of Comparative Example 7 obtained by melt stretching the commercially available PTFE film at a stretching temperature of 360 ° C. has improved tensile strength at break as compared with before stretching, the haze value was high and the transparency was poor.
  • the PTFE stretched films of Comparative Examples 8 to 10 obtained by stretching a commercially available PTFE film in a non-molten state had lower tensile strength and lower strength than before stretching. Moreover, in the PTFE stretched film of Comparative Example 10, the tear rupture strength and tear energy were both lower than those of the Examples, the haze value was very high, and the transparency was particularly inferior.
  • Example 9 A PTFE stretched film was produced three times each in the same manner as in Example 1 and Example 4, and the above-described tensile rupture strength test was performed on each of the obtained PTFE stretched films.
  • the pressure-strain curve obtained in the tensile breaking strength test is shown in FIGS. 3A and 3B.
  • Example 10 to 13 and Comparative Examples 10 to 13 After obtaining a molded film in the film molding process under the same conditions as in Example 1, the temperature of the hot air was set as shown in Table 3, and the film was stretched until a hole was opened, as in Example 1. In a molten or non-molten state, the molded film was simultaneously biaxially stretched at the same magnification in the longitudinal direction and the transverse direction, and the maximum stretching ratio at each hot air temperature was determined.
  • FIG. 5 shows a scanning electron microscope image of the stretched film (stretch ratio: 2.4 times ⁇ 2.4 times).
  • FIG. 4 it can be seen that no voids are generated by stretching from a molten state even when stretched at a high magnification. For this reason, in Example 1, high transparency (low haze value) was obtained. Furthermore, in FIG.
  • lamellar crystals having a thickness of several tens of nm are filled so as to fill in the space between extended chain crystals having a thickness of 200 to 400 nm, which is highly enhanced by the complementary reinforcing effect of such a skeletal structure.
  • Tensile rupture strength, tear rupture strength, and tear energy were obtained.
  • the present invention can be applied to a method for producing a stretched polytetrafluoroethylene film and a stretched polytetrafluoroethylene film.

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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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Abstract

La présente invention concerne un procédé de production d'un film polytétrafluoroéthylène étiré présentant à la fois un résistance élevée et une excellente transparence. L'invention concerne également un film polytétrafluoroéthylène étiré qui est produit selon le procédé de production. Le procédé de production d'un film polytétrafluoroéthylène étiré comprend : une étape de formation de film lors de laquelle un film est obtenu par moulage par compression d'un polytétrafluoroéthylène en fusion dans une atmosphère de pression réduite ; et une étape de fusion-étirage lors de laquelle le film est étiré par fusion. Le film polytétrafluoroéthylène étiré peut être obtenu par le procédé de production.
PCT/JP2010/001341 2009-02-27 2010-02-26 Procédé pour la production de film polytétrafluoroéthylène étiré, et film polytétrafluoroéthylène étiré WO2010098135A1 (fr)

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US20130158220A1 (en) * 2010-08-26 2013-06-20 National University Corporation Gunma University Method Of Manufacture Of Polytetrafluoroethylene Stretched Film, And Polytetrafluoroethylene Stretched Film
US10644339B2 (en) 2013-11-29 2020-05-05 Asahi Kasei Kabushiki Kaisha Polymer electrolyte membrane
US10688448B2 (en) 2013-11-29 2020-06-23 Daikin Industries, Ltd. Porous body, polymer electrolyte membrane, filter material for filter, and filter unit
TWI713443B (zh) * 2013-11-29 2020-12-21 日商大金工業股份有限公司 雙軸拉伸多孔質膜
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EP4353772A1 (fr) 2021-05-31 2024-04-17 National University Corporation Gunma University Film mince submicronique fait de polyéthylène de masse moléculaire ultra-élevée et son procédé de fabrication

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TWI713443B (zh) * 2013-11-29 2020-12-21 日商大金工業股份有限公司 雙軸拉伸多孔質膜
US10944121B2 (en) 2013-11-29 2021-03-09 Asahi Kasei Kabushiki Kaisha Polymer electrolyte film
US11084895B2 (en) 2013-11-29 2021-08-10 Daikin Industries, Ltd. Modified polytetrafluoroethylene fine powder and uniaxially stretched porous body

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