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WO2004026947A1 - Film de polybenzazole et son procede de fabrication - Google Patents

Film de polybenzazole et son procede de fabrication Download PDF

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Publication number
WO2004026947A1
WO2004026947A1 PCT/JP2003/011862 JP0311862W WO2004026947A1 WO 2004026947 A1 WO2004026947 A1 WO 2004026947A1 JP 0311862 W JP0311862 W JP 0311862W WO 2004026947 A1 WO2004026947 A1 WO 2004026947A1
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WO
WIPO (PCT)
Prior art keywords
film
solution
polymer
concentration
solvent
Prior art date
Application number
PCT/JP2003/011862
Other languages
English (en)
Japanese (ja)
Inventor
Hiroki Murase
Yoshihiko Teramoto
Seiji Watanuki
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 AU2003264476A priority Critical patent/AU2003264476A1/en
Publication of WO2004026947A1 publication Critical patent/WO2004026947A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • 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
    • 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
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/30—Extrusion nozzles or dies
    • B29C48/305—Extrusion nozzles or dies having a wide opening, e.g. for forming sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • 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
    • B29K2079/00—Use of polymers having nitrogen, with or without oxygen or carbon only, in the main chain, not provided for in groups B29K2061/00 - B29K2077/00, as moulding material
    • 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
    • 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
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0012—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular thermal properties
    • B29K2995/0016—Non-flammable or resistant to heat
    • 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
    • B29L2007/002—Panels; Plates; Sheets

Definitions

  • the present invention relates to a high-strength, high-modulus or high-heat-resistant polymer film and a technique for producing the same.
  • a rigid polymer solution a so-called liquid crystalline polymer, has molecular chains oriented in the direction of flow, and once oriented, it takes a long time for the molecular chains to change to random orientation. Molded articles can be manufactured. Furthermore, the rigid polymer has a high glass transition temperature, melting point and thermal decomposition temperature, so that a heat-resistant molded article can be obtained.
  • Rigid polymers are soluble only in limited mineral acids such as methanesulfonic acid and polyphosphoric acid.
  • such polymers are generally formed from either a low-concentration solution of mineral acid of 2% or less or a high-concentration solution of mineral acid of 14% or more as described in Examples of Patent Document 1. It was a target. In the case of processing into a fiber / film of polybenzazole alone, it is formed from a high-concentration liquid crystal dope as described in Patent Documents 2 and 3.
  • Patent Document 4 describes a technique for producing a thin film by biaxial stretching by blow molding
  • Patent Document 5 further improves the anisotropy of mechanical properties by orienting the film in different directions on the front and back. Attempts have been made to do so. However, even if the problem of rupture in the lateral direction can be improved by these methods, the peel strength in the thickness direction cannot be improved, but rather tends to be deteriorated, and a practical improvement is strongly desired.
  • Non-Patent Document 1 describes the optical characteristics of a polybenzazole thin film formed on a silicon wafer using a methanesulfonic acid solution of 0.5% polyparaphenylenebenzenezobisthiazole polymer.
  • forming from a low-concentration solution requires a large amount of mineral acid to make the product, which is not suitable for industrial processes.
  • a method of forming a polymer starting from a blend of a rigid high molecule and a flexible polymer such as a polyamide or polyether ketone as a starting material has been studied.
  • a high-performance material utilizing the characteristics of the rigid polymer has not been put into practical use.
  • the present invention is directed to a biaxially stretched film using a solution of 1 to 1.3 times as high as the optically anisotropic lower limit solution concentration C2 of the rigid polymer and having a peel strength of 100 mNZcm or more.
  • the rigid polymer according to the present invention is a polymer in which the entire molecular chain is composed of a rigid unit, a product obtained by copolymerizing a flexible monomer between rigid units, or a product obtained by combining a rigid unit with a crank type.
  • a material in which a spacer is provided on the side chain of the rigid main chain can be used.
  • preferred rigid polymers include polyparaphenylene terephthalamide, polybenzimid, polyparaphenylene and polybenzazole.
  • Polybenzazole refers to polybenzoxazole (PBO) homopolymer, polybenzotic 7zol (PBT) homopolymer and polybenzimidazole (PBI) homopolymer, or their PBO, PBT , PBI means random, sequential or block copolymer.
  • borenzoxazole, polybenzothiazole and their random, sequential or block copolymers are described, for example, in Wolfe et al., Ijuiquid Crystalline Polymer Compositions, Process and Products J U.S. Pat. No. 4,730,103. (October 27, 1987), "Liquid Crystalline Polymer Compositions, Process and Products J U.S. Pat. No.
  • the structural unit contained in the polybenzazole polymer is preferably selected from a lyotropic liquid crystal polymer.
  • the monomer unit is a structural formula It consists of the monomer units described in (a) to (n), and more preferably consists essentially of one monomer unit selected from structural formulas (a) to (c).
  • Suitable solvents for forming the optically anisotropic solution include non-oxidizing acids that can dissolve cresol and its polymers.
  • Suitable acid solvents include mineral acids such as polyphosphoric acid, methanesulfonic acid and highly concentrated sulfuric acid, or mixtures thereof.
  • the phase inversion concentration C * that develops optical anisotropy depends on the temperature. This fact is also described in Picken (Macromolecules Vol. 22, p. 1766.1771, 1989). In the present invention, the concentration that forms an anisotropic phase that does not include an isotropic phase at the highest temperature from preparation of a solution to molding is important.
  • the present invention covers from solution preparation to molding
  • the solution is characterized by forming a solution having a lower concentration of C 2 to 1.3 times the concentration of C 2 at which the isotropic phase does not appear at the highest temperature.
  • a more preferred concentration range is from C2 to 1.2 times C2, more preferably from 1.1 to 1.1 times C2 to C2.
  • the method of determining the concentration C2 by observation with a polarizing microscope is simple.
  • Another advantage of reducing solution concentration is that it reduces intermolecular interactions in the solution. Even in optically anisotropic solutions having different concentrations, the higher the concentration, the higher the intermolecular interaction.
  • the optically anisotropic solution is derived from the polydomain structure of the nematic liquid crystal. When the solution concentration is high, the repulsion between molecules in the domain becomes strong, so the elasticity of the domain itself increases, and the interaction between domains (academically called long-range order) increases.
  • Such a solution is rich in elasticity, and tends to cause unstable flow at the time of molding, and it is easy to form irregularities on the surface of the molded body. Therefore, it is preferable to form a solution having a concentration of C1 or more and a concentration as low as possible.
  • an isotropic phase does not appear at the highest temperature from the preparation of the solution to the molding. is important.
  • a non-rotating die is a type in which the contacting die wall is not driven during extrusion just before the dope is discharged to obtain a free surface.
  • the film-forming conditions By optimizing the film-forming conditions at the lower concentration of C2, which is 1.3 times the concentration of C2, at which the isotropic phase does not appear at the highest temperature from solution preparation to molding, Stable film formation becomes possible, and when a thin film is manufactured, it can be stretched through the stretching process, which expands the processing range.
  • the molecular orientation by stretching makes the film strength, elastic modulus, and thermal dimension. Stability control is also possible.
  • the obtained films show excellent peel strength. The reason why the peel strength is improved by the present invention is not clear, but it is presumed that as a result of being superior in moldability as compared with the case of using a high-concentration solution, the number of defects serving as starting points of peeling is reduced.
  • Non-rotating dies are dies that are not driven during die extrusion.
  • a relatively simple process is a method of extruding from a circumferential slit die and subjecting it to professional stretching.
  • the first method is to extrude from a circumferential slit die.
  • the biaxial stretching is achieved by the drawdown in the discharge direction and the circumferential expansion of the discharged tube.
  • a dope extruded from a slit die and a supporting film are integrated with a flexible polymer as a supporting film, and the supporting film is sandwiched between tenter clips and stretched.
  • the supporting film may be integrated on both sides of the dope, or may be bonded on only one side. If both sides are laminated, it is necessary to peel off the flexible fillem on one side before solidification.
  • Suitable flexible polymers for this method include polyesters such as polyethylene terephthalate, polyethylene isophthalate, and polyethylene naphthalate; polyolefins such as polyethylene and polypropylene; and fluorine-based resins such as polytetrafluoroethylene. , And these multilayer molded films can be used.
  • the stretched dope solidifies upon contact with the non-solvent.
  • the non-solvent may be in a liquid phase or a gas phase.
  • the solvent may be coagulated by evaporation or extraction.
  • the medium used for coagulation and extraction is An inorganic aqueous solution or an organic solvent such as alcohol or dalicol can be used.
  • a preferred coagulant is water or a mixture of water and a mineral acid.
  • the third component is introduced at least from the coagulated product of a high-concentration solution as disclosed in Japanese Patent No. 2522828. It is also possible. That is, it is suitable as a method for producing an open-cell network structure for an impregnated polymer film.
  • the film obtained by the film forming method of the present invention is very suitable as a substrate of the patent and can be used for producing a homogeneous composite.
  • washing with water, washing with water, neutralization, and drying the non-solvent from the resin-impregnated complex involves more volume change than solvent extraction. Therefore, it is preferable to use a fixing method as disclosed in US Pat. No. 5,445,779. Drying may be performed with dry air at room temperature, but in an industrial process, a hot air method is preferable. In addition, if the material is rapidly dried with a high-temperature gas, fine crack defects may occur inside, so it is preferable to dry the material over time.
  • a film having a thickness of 0.05 to 20 and preferably 1 to 10 / im was obtained.
  • the homogeneity was ⁇ 0.3 m with respect to the film thickness of 5 / m, and a homogeneous film was obtained.
  • the film obtained by drying as described above becomes a strong film with a high elastic modulus, it can be heat-treated at a temperature of 350 ° C or more to further arrange the internal molecules. is there.
  • packing between polymer molecules improves, increasing density, increasing elastic modulus, and increasing equilibrium moisture content. Changes in film physical properties such as a decrease occur.
  • dyeing As means for modifying the polybenzazole film obtained by the present invention, dyeing, addition of inorganic particles, stabilizers, antioxidants, and ultraviolet absorbers can be used in addition to the impregnation method. Furthermore, it is possible to modify the surface properties of the film by corona treatment, plasma treatment, and application of an anchoring agent.
  • the polybenzazole film produced by the present invention is excellent in mechanical properties, heat resistance, thermal dimensional stability, gas barrier properties, electrical insulation properties, and the like. Utilizing these properties, magnetic recording films, electronic circuit boards, substrates for mounting electronic components, composite material reinforcing materials, structural surface protective 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 desirably at least 10 OmNZcm or more, and below this, peeling occurs during secondary processing such as formation of an adhesive layer and a magnetic layer. Not only that, but also products that have low durability in actual use environments can be obtained. More preferably, a peel strength of 500 OmNZcm or more, more preferably 200 OmN / cm or more is desirable from the viewpoint of durability in an actual use environment.
  • FIG. 1 is a method for testing a peeling force according to the present invention. (Schematic diagram of test method) Adhesive tape
  • the dried film is cut into strips with a length of 100 mm and a width of 10 mm in the machine direction (MD direction) and the transverse direction (TD direction), respectively, to obtain test pieces.
  • Tensile a tensile test was performed at a tensile speed of 50 mm Z and a distance between chucks of 40 mm, and tensile strength and elastic modulus were measured.
  • a micrometer was used to measure the homogeneity.
  • homogeneity was measured at every four corners and the center point where the diagonal line of the obtained square film intersects with a micrometer, and the average was calculated.
  • E-31B tape manufactured by Nitto Denko Corporation was attached to the dried film with a rubber roller, and the film was reciprocated once from above with a 20 N rubber roller to make close contact. The sample was allowed to stand for 30 minutes under the conditions of a temperature of 23 ° C and a humidity of 55 ⁇ 5% RH, and then cut into a strip having a width of 25 mm. Tapes shall be applied in the machine direction (MD direction) and the transverse direction (TD direction) in parallel, and five test pieces shall be prepared. However, if only one direction of the test piece can be obtained due to the shape of the film to be tested, measure only the direction that can be manufactured.
  • MD direction machine direction
  • TD direction transverse direction
  • the film under test and the adhesive tape are each checked as shown in Fig. 1 and pulled at a tensile speed of 30 O mrnZ in the manner of T-type peeling, and the peeling force is used. (Unit: mNZ cm) was measured.
  • the peel force is defined as the average stress during peel propagation after the yield stress, as shown in Figure 2. Obtained from each test piece The value obtained by averaging the obtained peeling forces is defined as the peeling strength of the film under test.
  • a 6-, 8-, and 14-percent poly-paraffinylene-cis-benzbisoxazolyl polymer solution with a concentration of 116% polyphosphoric acid as a solvent was polymerized in a 2 L flask.
  • the concentration of phosphoric anhydride at the time of charging was adjusted to equalize the concentration of the solvent.
  • the resulting dope was sandwiched between slide glasses, the temperature was adjusted with a linker hot stage, and observed using a polarizing microscope (Nikon ECLIPSE E600 POL) in a crossed Nicol field of view.
  • the present invention provides a high-strength, high-modulus, and high-heat-resistant polymer film that satisfies both moldability and economic efficiency and has excellent peel strength. ⁇ It is possible to industrially produce a film having a good balance of mechanical properties in the lateral direction and excellent heat resistance and a high elastic modulus, and the industrial applicability of the present invention is great.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (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 a trait à la production d'un film polymérique à résistance thermique présentant une résistance élevée à l'arrachement et un excellent équilibre de résistances longitudinale et transversale. En particulier, le procédé de production d'un film de polybenzazole comprend l'extrusion d'une solution de polymères rigides de 1 à 1,3 fois la concentration en solution d'anisotropie optique de limite inférieure (C2) à travers une filière irrotationnelle, la réalisation ultérieure d'un étirage biaxe de la solution de polymères rigides sous forme de film, la solidification de ladite solution dans un bain de coagulation, l'élimination du solvant avec un liquide de lavage, et l'élimination du liquide de lavage.
PCT/JP2003/011862 2002-09-19 2003-09-17 Film de polybenzazole et son procede de fabrication WO2004026947A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003264476A AU2003264476A1 (en) 2002-09-19 2003-09-17 Polybenzazole film and process for producing the same

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2002273725A JP2004106407A (ja) 2002-09-19 2002-09-19 ポリベンザゾールフィルムおよびその製造方法
JPP2002-273725 2002-09-19

Publications (1)

Publication Number Publication Date
WO2004026947A1 true WO2004026947A1 (fr) 2004-04-01

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Application Number Title Priority Date Filing Date
PCT/JP2003/011862 WO2004026947A1 (fr) 2002-09-19 2003-09-17 Film de polybenzazole et son procede de fabrication

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JP (1) JP2004106407A (fr)
AU (1) AU2003264476A1 (fr)
WO (1) WO2004026947A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1984001160A1 (fr) * 1982-09-17 1984-03-29 Stanford Res Inst Int Compositions polymeres cristallines liquides, procede et produits
JP2003012851A (ja) * 2001-03-29 2003-01-15 Toyobo Co Ltd 剛直ポリマー溶液から複合体を製造する方法及び複合膜

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1984001160A1 (fr) * 1982-09-17 1984-03-29 Stanford Res Inst Int Compositions polymeres cristallines liquides, procede et produits
JP2003012851A (ja) * 2001-03-29 2003-01-15 Toyobo Co Ltd 剛直ポリマー溶液から複合体を製造する方法及び複合膜

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SONG H H, HONG S-K: "PREPARATION OF RIGID-ROD POLY(P-PHENYLENE BENZOBISTHIAZOLE) FILMS OF SINGLE CRYSTALLINE TEXTURE", POLYMER, vol. 38, no. 16, August 1997 (1997-08-01), pages 4241 - 4245, XP004081567 *

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JP2004106407A (ja) 2004-04-08

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