WO2003024695A1 - Film polymere et procede pour sa preparation - Google Patents

Film polymere et procede pour sa preparation Download PDF

Info

Publication number
WO2003024695A1
WO2003024695A1 PCT/JP2002/009510 JP0209510W WO03024695A1 WO 2003024695 A1 WO2003024695 A1 WO 2003024695A1 JP 0209510 W JP0209510 W JP 0209510W WO 03024695 A1 WO03024695 A1 WO 03024695A1
Authority
WO
WIPO (PCT)
Prior art keywords
film
solution
polymer
liquid crystalline
polymer film
Prior art date
Application number
PCT/JP2002/009510
Other languages
English (en)
Japanese (ja)
Inventor
Hiroki Murase
Seiji Watanuki
Yoshihiko Teramoto
Original Assignee
Toyo Boseki Kabushiki Kaisha
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toyo Boseki Kabushiki Kaisha filed Critical Toyo Boseki Kabushiki Kaisha
Priority to JP2003528378A priority Critical patent/JP4048436B2/ja
Publication of WO2003024695A1 publication Critical patent/WO2003024695A1/fr

Links

Classifications

    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—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
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0079—Liquid crystals
    • 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
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/12—Polymers characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material

Definitions

  • the present invention relates to a polymer film having high heat resistance, high strength, and high elastic modulus, and a method for producing the same.
  • the present invention relates to a homogenous polybenzazole film having the above-mentioned performance, having a small mechanical property anisotropy, excellent in vertical and horizontal strength balance, and having high peel strength, and a method for producing the same.
  • any of the above films formed from liquid crystalline polymer anisotropic solutions tend to be heterogeneous due to uneven alignment due to the liquid crystal polydomain structure. It is difficult to process thinly and uniformly.
  • 0 has been attempted to obtain a thin transparent film by film of low density solvent by spin coating for example, L .. A. Cintavey et al. In Journal of Applied Polymer Science, Vol. 76, ppl448-1456 (2000), using a 0.5% solution of polyparaphenylenebenzenezobisthiazole polymer in methanesulfonic acid on a silicon wafer using polybenzazo.
  • An optical thin film is formed and its optical characteristics are described.
  • films obtained by such a method are less likely to cause defects (such as tilting) in a solution state than films obtained by a conventional film forming method from an optically anisotropic solution. There are good aspects too.
  • Polybenzazole has good heat resistance, high strength, high elastic modulus, and low dielectric constant, so processing of films is desired.However, it has the above-mentioned problems, and it is difficult to obtain industrial solutions from high-concentration polymer solutions. It was difficult to produce a thin and uniform film. In particular, it was very difficult to adjust the composition of the dope that was capable of isotropic phase inversion.
  • FIG. 4 is a diagram showing how to determine a peeling force.
  • An object of the present invention is to provide a high-heat-resistant, high-strength, high-modulus polymer film made of a rigid heat-resistant polymer, and to provide a homogeneous film having little anisotropy of mechanical properties, and production thereof
  • the aim is to provide a method.
  • the present inventors have conducted intensive studies in order to achieve the above object, and as a result, obtained an isotropic solution using a rigid and highly heat-resistant liquid crystalline polymer such as polyphosphoric acid such as polybenzazole as a solvent from a die slit.
  • the above object was achieved by extruding into a film, subsequently stretching in at least one axis direction, coagulating and washing. That is, the present invention
  • An isotropic solution composed of a liquid crystalline polymer is extruded from a die slit into a film, and then the film-like isotropic solution is stretched in at least one axis direction, and then coagulated in a coagulating solution.
  • An isotropic solution composed of a liquid crystalline polymer is extruded from a die slit into a film, and the film-like isotropic solution is stretched in at least one direction, and then coagulated in a coagulating solution.
  • a method for producing a polymer film comprising removing a washing solution after washing.
  • the liquid crystalline polymer according to the present invention means that the main skeleton is mainly formed by bonding of fused rings. It is a rigid polymer in which many of the condensed ring bonds are nearly linear, and the solution has optical anisotropy at a critical concentration or higher. Specific examples include polybenzazole.
  • polybenzazole in the present invention examples include polybenzoxazole (PBO) homopolymer, polybenzothiazole (PBT) homopolymer and polybenzimidazole (PBI) homopolymer, or PBO, PBT And PBI random copolymers, sequential copolymers and block copolymers.
  • PBO, PBT and their random copolymers, sequential copolymers or block copolymers are described in, for example, Wolfe et al., “Liquid Crystalline Polymer Compositions, Process and Products J US Pat. No. 4,703,103 (1). October 27, 987), ⁇ Liquid Crystalline Polymer Compositions, Process and Products J U.S. Patent No.
  • the structural unit contained in the polybenzazole is preferably selected from a lyotropic liquid crystal polymer.
  • the monomer unit consists of one monomer unit described in structural formulas (a) to (n), and more preferably essentially consists of a monomer unit selected from structural formulas (a) to (f).
  • the polybenzazole is specifically subjected to condensation polymerization in a polyphosphoric acid solvent or the like. That is, a polymer can be obtained according to the method of Wolfe et al.
  • the polyben The molecular weight of Zazol is not less than 20,000, preferably not less than 50,000 by weight average molecular weight, 9 ⁇ r. -The resulting film tends to be brittle. Also, if ir less than 20,000
  • the molecular weight is 300,000 or less, preferably 100,000 or less. ⁇ If it exceeds 300,000, the viscosity of the solution is too high to make processing difficult.
  • a polymer solution of the same solvent as the polymerization solvent as a solvent for the polymer solution when forming the film.
  • the same solvent as the polymerization solvent is used, so that the polymer is not once separated as a solid from the polymerized polymer solution, but the polymerized polymer solution remains as it is or is further polymerized on the polymer solution.
  • a solvent whose concentration has been adjusted by adding and diluting the solvent used sometimes or another solvent can be subjected to film formation.
  • Preferred solvents include, for example, mineral acids such as polyphosphoric acid, sulfuric acid, and methanesulfonic acid. Among them, polyphosphoric acid is particularly preferred.
  • an isotropic solution composed of a liquid crystalline polymer is used as a film forming raw material. By using an isotropic solution, it is possible to obtain a polymer film which has excellent thickness uniformity and is difficult to peel.
  • An isotropic solution composed of a liquid crystalline polymer refers to a solution that does not show optical anisotropy under crossed Nicols using a polarizing microscope and does not show a domain structure derived from a liquid crystal structure.
  • an isotropic solution composed of a liquid crystalline polymer is obtained by performing polymerization at a low concentration. Further, it can be obtained by diluting a liquid crystalline solution obtained by performing polymerization at a high concentration with a solvent.
  • the concentration range in which an isotropic solution composed of a liquid crystalline polymer is obtained tends to be lower as the main chain skeleton of the polymer is linear. Also, as the solution temperature increases, an isotropic solution tends to be obtained in a higher concentration range.
  • an isotropic solution composed of a liquid crystalline polymer in a high concentration range
  • it is effective to reduce the linearity of the molecular chain of the liquid crystalline polymer.
  • an isotropic solution can be obtained up to a high concentration.
  • the concentration range of the isotropic solution composed of a liquid crystalline polymer is preferably 3% by weight or more. If the amount is less than 3% by weight, the extruded polymer solution has a low viscosity, and the stretching of the film-shaped polymer solution tends to be unstable. Therefore, in the present invention, it is preferable to use a polymer solution having a high concentration within a range that does not exhibit optical anisotropy. However, if the solution concentration is too high, the solution composed of the liquid crystal polymer tends to exhibit liquid crystallinity, and the resulting film tends to have reduced isotropy and homogeneity. In addition, there is a tendency that the viscosity of the polymer solution becomes too high and the film formation becomes difficult.
  • the concentration range of the isotropic solution composed of a liquid crystalline polymer is preferably 10% by weight or less.
  • a polymer solution is extruded from a die slit into a film under conditions such as composition and temperature at which a liquid crystalline polymer solution of a film forming raw material shows an isotropic solution. At least one axis After stretching, the polymer is coagulated in a coagulating solution, the solvent is washed with a washing solution, and a polymer film from which the washing solution is removed is obtained.
  • an isotropic solution as a raw material for forming a film, a polymer film having excellent isotropy and thickness uniformity and being difficult to peel off can be obtained.
  • a T die having a linear or annular slit portion, a circuit die, or the like is used as the die of the present invention.
  • the present invention when a polymer solution having an appropriate concentration exhibiting isotropic properties is used as a raw material for film formation, it is possible to smoothly carry out subsequent stretching of the polymer solution and obtain a uniform film with little thickness unevenness. can get. Further, by stretching the polymer solution, a thinner film can be produced. Further, the molecular orientation by stretching can improve the strength and elastic modulus of the film, and furthermore, the stability of mature dimensions.
  • a relatively simple film forming method there is a method in which the film is extruded from a slit of a die and blow-stretched.
  • a method as described in U.S. Pat. No. 4,889,924 is suitable.
  • the first method is to extrude from the slit of a circuit die.
  • biaxial stretching is achieved by a drawdown in the discharge direction and a circumferential expansion of the discharged tube.
  • it is more preferable to form a film by adding a coagulating liquid also inside the tube. It is more preferable to add a coagulating liquid inside as it can coagulate from both sides.
  • a film forming method using a double-rotating die is known, but the die used in the present invention does not need to be a rotary die. According to the present invention, even when a non-rotating die is used, a film with molecular orientation can be obtained by stretching the extruded film-like polymer solution.
  • Non-rotary die equipment is advantageous in that it is relatively inexpensive and easier to maintain than dual rotary dies.
  • Another stretching method is to use a flexible polymer
  • a film-like polymer solution extruded from a slit and a support film are laminated and integrated, and the laminate is sandwiched and stretched by a tenter clip.
  • the support film may be integrated on both sides of the film-like polymer solution, or may be bonded on only one side. When both surfaces are laminated, it is necessary to peel off at least one flexible film before solidification.
  • Suitable support film materials for this method include polyesters such as polyethylene terephthalate, polyethylene phthalophthalate, and polyethylene naphthalate; polyolefins such as polyethylene and polypropylene; and fluorine-based resins such as polytetrafluoroethylene. And multilayer molded films thereof can be used.
  • the stretched polymer solution is solidified by contact with a non-solvent.
  • the non-solvent may be in a liquid phase or a gas phase.
  • the solvent may be coagulated by evaporation or extraction.
  • an inorganic aqueous solution such as a mineral acid aqueous solution, or an organic solvent such as alcohol / glycol can be used.
  • Preferred coagulants are water or mixtures of water and mineral acids.
  • the solvent in the coagulated film is a mineral acid
  • a basic compound for example, caustic soda
  • the extraction washing solution is preferably water from the viewpoint of economy and safety, but is not limited thereto.
  • the polymer film obtained in the above-mentioned process is at least as disclosed in Japanese Patent No. 2522828 as a polybenzazole molded article. It is also possible to introduce a third component from the coagulated product of a highly concentrated solution.
  • the stretching ratio in the TD direction is strengthened to compensate for relaxation during drying, and the size is restricted only in the MD direction. It is preferable to use a drying method. Drying may be performed with dry air at room temperature, but industrially, a hot air method is preferred. In addition, if drying is rapidly performed with a high-temperature gas, fine crack defects may occur inside, and thus drying is preferably performed over a long period of time.
  • a polymer film having a thickness of 0.05 to 20 ⁇ m is obtained.
  • the obtained film is excellent in homogeneity, and a film having a thickness unevenness of 10% or less in terms of thickness uniformity can be obtained.
  • the thickness unevenness of the film must be 10% or less.c
  • the film obtained by drying as described above is a strong film with a high elastic modulus.
  • impregnation dyeing color, inorganic particles, a stabilizer, an antioxidant, an ultraviolet absorber and the like can be added.
  • the surface of the film can be modified by corona treatment, plasma treatment, or application of an anchoring agent.
  • the polymer film produced by the present invention has excellent mechanical properties, heat resistance, thermal dimensional stability, gas barrier properties, electrical insulation properties, and the like. Taking advantage of these properties, magnetic recording films, electronic circuit boards, substrates for mounting electronic components, composite material reinforcing materials, structural surface protection films, flame-resistant heat-resistant electric wire coating materials for aircraft, window materials for vacuum vessels, optical control It can be used as an application material.
  • the peel strength of the film is preferably at least 10 OmNZ cm or more. If the peel strength of the film is less than 10 OmNZcm, peeling occurs when an adhesive layer or a magnetic layer is formed on the film surface or during secondary processing, which is not preferable. In addition, the durability of the resulting product may be low. More preferably, the peel strength of the film is at least 50 OmNZ cm, more preferably at least 200 OmNZ cm.
  • the measurement was performed at 30 ° C using methanesulfonic acid as a solvent.
  • a tensile tester (Tensilon manufactured by Orientec) it was calculated from the stress-strain curve measured by a tensile test using a sample width of 10 mm, a sample length of 5 Omm, and a tensile speed of 25 mm.
  • the distortion origin is defined as zero distortion when the weight rises to 0.5N.
  • the tensile direction was measured for the discharge direction (machine direction: MD) and the transverse direction perpendicular to it: TD.
  • the thickness was measured by using a micrometer (Miritron 1245D, manufactured by Fine Lieuf).
  • the thickness unevenness was obtained by measuring the thickness of the obtained film of 20 mm 10 Omm at 10 points at intervals of about 1 Omm, dividing the difference between the maximum thickness and the minimum thickness by the average thickness, and displaying the result in%.
  • the measurement was performed in the air under the conditions of 20 ° CZ using TGA manufactured by Mac Science.
  • the temperature at which the weight decreased by 5% was defined as the pyrolysis temperature.
  • peel force was the average value of the stress during peel propagation after the yield stress.
  • the value obtained by averaging the peeling force obtained from each test piece is defined as the peeling strength of the film under test.
  • Poly (2,5-benzazole) (AB P BO) having a polymer solution concentration of 4% by weight and an intrinsic viscosity of 7.5 was polymerized by the method described in Macromolecules, Vol. 22, page 3514 by Chow et al. It was confirmed by a polarizing microscope on a heating stage that this solution did not exhibit optical anisotropy.
  • the solution was discharged from a circuit die having an inner diameter of 49 mm and a die gap of 0.5 mm, and was drawn in water at a rate of 5 mZ while being stretched through a 230 mm air gap.
  • the die temperature was 70 ° C
  • the professional pressure was 15 kPa in gauge pressure
  • the stretching ratio in the circumferential direction was 2.5 times
  • the stretching ratio in the drawdown direction was 3 times.
  • the obtained undried film is unfolded into a single-layer film having a width of about 350 mm, and a group of mouths is run in a drying oven having a built-in oven at 180 ° C for 5 minutes under tension. It was dried.
  • the resulting film was a very homogeneous transparent film which was colored yellow-brown but had no light and shade pattern, and had good quality.
  • Table 1 shows the mechanical properties.
  • the thermal decomposition temperature of Example 1 was 597 ° C.
  • Example 1 The dried film produced in Example 1 was fixed in a frame of 15 Omm square and heat-treated at 380 ° C for 2 minutes in a nitrogen stream. As shown in Table 1, the heat treatment Lum's Young's Modulus was increased. The thermal decomposition temperature of Example 2 was 597 ° C. (Comparative Example 1)
  • a 14% by weight polyphosphoric acid solution of poly'paraphenylene-cis-benzbisoxazole polymer having an intrinsic viscosity of 27 was obtained by solution polymerization.
  • This solution showed optical anisotropy by observation with a polarizing microscope on a heating stage.
  • This solution is discharged vertically downward at 170 ° C from a T die slit with a width of 120 mm and a gap of 0.5 mm, sandwiched by a 140 mm thick polypropylene unstretched film at a position of 36 Omm from the die, and stretched.
  • the roll was stretched 2.5 times in the MD direction and then 4 times in the TD direction using a heating tenter at 133 ° C, and the tenter grip was cut off with a slitter and wound up. While peeling the one-sided stretched polypropylene film in cold water at 5 ° C, a DuPont Tyvek sheet was sandwiched and wound up in water. Peel the polypropylene film and Tyvek sheet from both sides of the sheet immersed in water for 6 hours, run the washing tank for 2 minutes, and then run it in a drying oven with built-in rollers for 5 minutes at 180 ° C. And dried under tension. An FB ⁇ film having a thickness of 2 ⁇ m was obtained. The film was a yellow-brown colored transparent film, but had a mottled film with a light and shade pattern.
  • a 14% by weight polyphosphoric acid solution of poly'barapurenylene 'cispens bisoxazole polymer having an intrinsic viscosity of 27 used in Comparative Example 1 was diluted to a concentration of 3% by weight with a polyphosphoric acid having a phosphoric acid concentration of 11.6% by weight. And kept at 160 ° C. Observation of this solution by a polarizing microscope on a heating stage confirmed that it did not exhibit optical anisotropy.
  • This solution was discharged vertically downward at 160 ° C from a slit die with a width of 120 mm and a gap of 0.5 mm at a temperature of 160 ° C, and sandwiched with a 140 m thick unstretched polypropylene film at a position of 360 mm from the die.
  • the stretching roll was stretched 2.5 times in the MD direction, and then stretched 2 times in the TD direction with a heating tenter at 133 ° C, and the tenter grip was cut and wound with a slitter ( one side in cold water at 5 ° C).
  • DuPont while peeling the polypropylene stretched film of It was wound up in water with a Tyvek sheet made by the company.
  • the polymer film of the present invention is a polymer film having high heat resistance, high strength, and high elastic modulus, and has low anisotropy in mechanical properties, excellent in vertical and horizontal strength balance, and uniform in high peel strength. Since it is a film, its properties are utilized to make magnetic recording films, electronic circuit boards, substrates for mounting electronic components, composite material reinforcing materials, structural surface protective films, flame-resistant heat-resistant wire coating materials for aircraft, and vacuum containers. It can be used as window material, optical control material, etc. Further, the polymer film can be industrially obtained by the method for producing a polymer film of the present invention.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)

Abstract

La présente invention concerne un film polymère se caractérisant en ce qu'il peut être produit par un procédé comprenant les étapes suivantes: extrusion d'une solution isotrope d'un polymère cristallin liquide qui est rigide et a une résistance élevée à la chaleur, tel que du polybenzazole, dans un solvant tel que l'acide polyphosphorique, sous une forme de film, à partir d'une fente matricielle; puis étirage de la solution sous la forme d'un film, au moins selon un axe; puis coagulation et lavage. L'invention a également pour objet un procédé permettant la préparation du film polymère. Le film polymère est uniforme, a une résistance élevée à la chaleur, une résistance mécanique élevée et un coefficient d'élasticité élevé, une anisotropie réduite des propriétés mécaniques, et une résistance au décollement élevée. Il peut ainsi être largement utilisé pour des applications électriques et électroniques, par exemple en tant que film d'enregistrement magnétique, carte de circuits imprimés électronique, substrat pour le montage de composants électroniques, renfort dans un matériau composite, pour des applications dans le domaine de l'espace et de l'aviation, par exemple en tant que film de protection pour la surface d'une structure, et analogue.
PCT/JP2002/009510 2001-09-18 2002-09-17 Film polymere et procede pour sa preparation WO2003024695A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2003528378A JP4048436B2 (ja) 2001-09-18 2002-09-17 高分子フィルムおよびその製造方法

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2001283877 2001-09-18
JP2001-283877 2001-09-18
JP2002-268905 2002-09-13
JP2002268905 2002-09-13

Publications (1)

Publication Number Publication Date
WO2003024695A1 true WO2003024695A1 (fr) 2003-03-27

Family

ID=26622443

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2002/009510 WO2003024695A1 (fr) 2001-09-18 2002-09-17 Film polymere et procede pour sa preparation

Country Status (2)

Country Link
JP (1) JP4048436B2 (fr)
WO (1) WO2003024695A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005023217A (ja) * 2003-07-03 2005-01-27 Toyobo Co Ltd ポリベンザゾール系フィルムおよびその製造法
JP2006035628A (ja) * 2004-07-27 2006-02-09 Toyobo Co Ltd ポリベンザゾール系フィルムおよびその製造法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6374612A (ja) * 1986-09-19 1988-04-05 Asahi Chem Ind Co Ltd フイルムの製法
JPH01287141A (ja) * 1988-05-16 1989-11-17 Agency Of Ind Science & Technol ポリアゾール二軸配向フイルムの製造法
EP0377963A2 (fr) * 1989-01-11 1990-07-18 Hoechst Celanese Corporation Procédé de fabrication de films biaxialement orientés à partir de polymères, cristaux liquides hétérocycliques rigides
WO1992010527A1 (fr) * 1990-12-07 1992-06-25 The Dow Chemical Company Procede d'etirage de polymeres de cristaux liquides lyotropes
JP2000273214A (ja) * 1999-03-29 2000-10-03 Toray Ind Inc ポリベンザゾールフィルム及びそれを用いた磁気記録媒体

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6374612A (ja) * 1986-09-19 1988-04-05 Asahi Chem Ind Co Ltd フイルムの製法
JPH01287141A (ja) * 1988-05-16 1989-11-17 Agency Of Ind Science & Technol ポリアゾール二軸配向フイルムの製造法
EP0377963A2 (fr) * 1989-01-11 1990-07-18 Hoechst Celanese Corporation Procédé de fabrication de films biaxialement orientés à partir de polymères, cristaux liquides hétérocycliques rigides
WO1992010527A1 (fr) * 1990-12-07 1992-06-25 The Dow Chemical Company Procede d'etirage de polymeres de cristaux liquides lyotropes
JP2000273214A (ja) * 1999-03-29 2000-10-03 Toray Ind Inc ポリベンザゾールフィルム及びそれを用いた磁気記録媒体

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005023217A (ja) * 2003-07-03 2005-01-27 Toyobo Co Ltd ポリベンザゾール系フィルムおよびその製造法
JP2006035628A (ja) * 2004-07-27 2006-02-09 Toyobo Co Ltd ポリベンザゾール系フィルムおよびその製造法
JP4622366B2 (ja) * 2004-07-27 2011-02-02 東洋紡績株式会社 ポリベンザゾール系フィルムおよびその製造法

Also Published As

Publication number Publication date
JP4048436B2 (ja) 2008-02-20
JPWO2003024695A1 (ja) 2004-12-24

Similar Documents

Publication Publication Date Title
Cakmak et al. Processing characteristics, structure development, and properties of uni and biaxially stretched poly (ethylene 2, 6 naphthalate)(PEN) films
US5367042A (en) Process for fabricating oriented polybenzazole films
EP2025496A2 (fr) Procédé de fabrication de films polymériques ultra fins
JP6344506B2 (ja) ポリエステルフィルム
JP2004231875A (ja) ポリベンゾオキサゾールフィルムおよびその製造方法
KR20170068443A (ko) 폴리비닐 알코올계 필름 및 이의 제조방법, 및 편광 필름, 편광판
JP6642748B2 (ja) 積層フィルム
US4857255A (en) Poly-p-phenylene-terephthalamide film and process for producing the same
US4752643A (en) Transparent poly-p-phenylene-terephthalamide film
JP7192973B2 (ja) ポリプロピレンフィルム、金属層一体型ポリプロピレンフィルム、及び、フィルムコンデンサ
KR20120001539A (ko) 수축필름 및 이의 제조방법
JPS6386731A (ja) ポリパラフエニレンテレフタルアミドフイルムの製造法
WO2010058657A1 (fr) Film de résine de polyphénylène sulfide et son procédé de fabrication
WO2003024695A1 (fr) Film polymere et procede pour sa preparation
JPH06503521A (ja) 配向ポリベンゾアゾールフィルムの加工方法
WO2004026947A1 (fr) Film de polybenzazole et son procede de fabrication
JP2008266538A (ja) ポリベンザゾールフィルムおよびその製造方法。
EP0612610B1 (fr) Film polymère à cristaux liquides et procédé pour sa production
KR20180036378A (ko) 폴리에스테르 필름 및 이의 제조방법
JPH0352775B2 (fr)
WO2019172390A1 (fr) Film en polypropylène à étirage biaxial, film métallisé, condensateur à film et rouleau de film
TW202110934A (zh) 相位差薄膜及其製造方法
JP2004231874A (ja) ポリベンゾオキサゾールフィルムおよびその製造方法
US5445779A (en) Process for the drying and heat-treatment of polybenzazole films
JPS62174129A (ja) ポリパラフエニレンテレフタルアミド系フイルム

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BY BZ CA CH CN CO CR CU CZ DE DM DZ EC EE ES FI GB GD GE GH HR HU ID IL IN IS JP KE KG KP KR LC LK LR LS LT LU LV MA MD MG MN MW MX MZ NO NZ OM PH PL PT RU SD SE SG SI SK SL TJ TM TN TR TZ UA UG US UZ VC VN YU ZA ZM

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ UG ZM ZW AM AZ BY KG KZ RU TJ TM AT BE BG CH CY CZ DK EE ES FI FR GB GR IE IT LU MC PT SE SK TR BF BJ CF CG CI GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 2003528378

Country of ref document: JP

122 Ep: pct application non-entry in european phase