WO2004003272A1 - ポリベンザゾール繊維及びその利用 - Google Patents
ポリベンザゾール繊維及びその利用 Download PDFInfo
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- WO2004003272A1 WO2004003272A1 PCT/JP2003/008066 JP0308066W WO2004003272A1 WO 2004003272 A1 WO2004003272 A1 WO 2004003272A1 JP 0308066 W JP0308066 W JP 0308066W WO 2004003272 A1 WO2004003272 A1 WO 2004003272A1
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- polybenzazole
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- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04C—STRUCTURAL ELEMENTS; BUILDING MATERIALS
- E04C5/00—Reinforcing elements, e.g. for concrete; Auxiliary elements therefor
- E04C5/07—Reinforcing elements of material other than metal, e.g. of glass, of plastics, or not exclusively made of metal
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/04—Pigments
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/74—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polycondensates of cyclic compounds, e.g. polyimides, polybenzimidazoles
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- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/44—Yarns or threads characterised by the purpose for which they are designed
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- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/44—Yarns or threads characterised by the purpose for which they are designed
- D02G3/48—Tyre cords
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- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
- D03D15/20—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads
- D03D15/283—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads synthetic polymer-based, e.g. polyamide or polyester fibres
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- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
- D03D15/50—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the properties of the yarns or threads
- D03D15/513—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the properties of the yarns or threads heat-resistant or fireproof
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- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
- D03D15/50—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the properties of the yarns or threads
- D03D15/587—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the properties of the yarns or threads adhesive; fusible
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- D—TEXTILES; PAPER
- D07—ROPES; CABLES OTHER THAN ELECTRIC
- D07B—ROPES OR CABLES IN GENERAL
- D07B1/00—Constructional features of ropes or cables
- D07B1/02—Ropes built-up from fibrous or filamentary material, e.g. of vegetable origin, of animal origin, regenerated cellulose, plastics
- D07B1/025—Ropes built-up from fibrous or filamentary material, e.g. of vegetable origin, of animal origin, regenerated cellulose, plastics comprising high modulus, or high tenacity, polymer filaments or fibres, e.g. liquid-crystal polymers
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- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04C—STRUCTURAL ELEMENTS; BUILDING MATERIALS
- E04C5/00—Reinforcing elements, e.g. for concrete; Auxiliary elements therefor
- E04C5/07—Reinforcing elements of material other than metal, e.g. of glass, of plastics, or not exclusively made of metal
- E04C5/073—Discrete reinforcing elements, e.g. fibres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B63—SHIPS OR OTHER WATERBORNE VESSELS; RELATED EQUIPMENT
- B63H—MARINE PROPULSION OR STEERING
- B63H9/00—Marine propulsion provided directly by wind power
- B63H9/04—Marine propulsion provided directly by wind power using sails or like wind-catching surfaces
- B63H9/06—Types of sail; Constructional features of sails; Arrangements thereof on vessels
- B63H9/067—Sails characterised by their construction or manufacturing process
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B63—SHIPS OR OTHER WATERBORNE VESSELS; RELATED EQUIPMENT
- B63H—MARINE PROPULSION OR STEERING
- B63H9/00—Marine propulsion provided directly by wind power
- B63H9/04—Marine propulsion provided directly by wind power using sails or like wind-catching surfaces
- B63H9/06—Types of sail; Constructional features of sails; Arrangements thereof on vessels
- B63H9/067—Sails characterised by their construction or manufacturing process
- B63H9/0678—Laminated sails
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- D—TEXTILES; PAPER
- D07—ROPES; CABLES OTHER THAN ELECTRIC
- D07B—ROPES OR CABLES IN GENERAL
- D07B2205/00—Rope or cable materials
- D07B2205/20—Organic high polymers
- D07B2205/2096—Poly-p-phenylenebenzo-bisoxazole [PBO]
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/04—Heat-responsive characteristics
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/06—Load-responsive characteristics
- D10B2401/063—Load-responsive characteristics high strength
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2501/00—Wearing apparel
- D10B2501/04—Outerwear; Protective garments
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2505/00—Industrial
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
- Y10T428/2964—Artificial fiber or filament
- Y10T428/2967—Synthetic resin or polymer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
- Y10T428/2964—Artificial fiber or filament
- Y10T428/2967—Synthetic resin or polymer
- Y10T428/2969—Polyamide, polyimide or polyester
Definitions
- the present invention relates to a polibenzazole fiber having excellent durability when exposed to high temperature and high humidity, and an application using such a fiber.
- porbenzoxazole or porbenzothiazole or a polymer composed of these copolymers is used as a fiber having high strength and high heat resistance.
- Libenzasol fiber is known as a fiber having high strength and high heat resistance.
- the polibenzazole fiber is extruded from a spinneret through a dope containing the above-mentioned polymer / copolymer and an acid solvent, and then is subjected to a coagulating fluid (water or water and inorganic material).
- a coagulating fluid water or water and inorganic material.
- a mixed solution of acid to coagulate, then thoroughly wash in a washing bath to remove most of the solvent, and then an aqueous solution tank of an inorganic base such as sodium hydroxide. After neutralizing the acid remaining without being extracted in the yarn through the fiber, and then drying.
- Polybenzazole fibers produced in this manner have excellent mechanical properties such as strength and high heat resistance, as described above, and are therefore used in various applications. However, in recent years, further improvement in performance has been desired, and in particular, sufficient strength can be maintained even when exposed to high temperature and high humidity for a long time. Polybenzazole fibers that can be used are strongly desired.
- Polybenzazole fibers produced in this way have excellent mechanical properties such as strength and high heat resistance. It is used as a heat-resistant cushioning material for supporting high-temperature products without damaging them in manufacturing processes such as the non-ferrous metal field.
- the temperature of hot products immediately after forming is 350 or more, and in many cases it is used. In some cases, it is necessary to maintain sufficient strength in recent years, especially when exposed to high temperatures and high humidity for a long period of time, since the root material may be used while being cooled with water. There is a strong demand for a felt material made of polybenzazole fiber that can be used.
- Polybenzazole fibers produced in this way are excellent in mechanical properties such as strength and elastic modulus, so that the fiber structure constituting protective materials, protective clothing and industrial materials can be used. Although it is still used as described above, further improvement in performance is expected, especially in high temperature / humidity and light irradiation for a long time. There has been a strong demand for a woven or knitted fabric made of polybenzazole fibers that can maintain sufficient strength when exposed.
- a fiber having high strength and high heat resistance it is composed of polibenzoxazole or polibenzothiazole, or a copolymer thereof.
- Polybenzazole fibers are known. Conventionally, fibers used as rubber reinforcing materials for tires, hoses and belts are mainly nylon fibers, polyester fibers, glass fibers and steel fibers. However, in recent years, aromatic polyamide fibers typified by Kevlar, which have high strength and high elastic modulus, have been used as various rubber reinforcing materials. Polybenzazole fiber, which has a much higher strength and elastic modulus than this aromatic polyamide fiber, and is also excellent in heat resistance and dimensional stability, is rubber-reinforced. It is noted as a material.
- a fiber having high strength and high heat resistance it is composed of polibenzoxazole or polibenzothiazole or these copolymers.
- Polybenzazole fiber is known. Conventionally, steel has been used as a cement / concrete reinforcement material, but recently, glass fiber, carbon fiber or aramide fiber has been used. It has been developed and put into practical use. However, although carbon fiber is very excellent in mechanical performance, there is a problem that it cannot be used near transmission lines because of its conductivity. On the other hand, aramid fiber has relatively good performance, but its elasticity is lower than that of carbon fiber, so the reinforcing effect is small.
- the cement-concrete reinforced sheet made of polybenzazole fiber shows a reinforcing effect that surpasses that of aramid fiber and carbon fiber, and is expected to be a next-generation product. I'm waiting for you.
- Polybenzazole fiber produced in this way has excellent mechanical properties such as strength and elastic modulus, so it is also used as a cement-concrete reinforcing sheet. As described above, it is expected that the performance including light resistance will be improved, especially when exposed to high temperature and high humidity for a long time.
- polibenzazole fiber for reinforcing cement and concrete, which can maintain sufficient strength.
- reinforcing rods have been used as reinforcing materials for rod-shaped cement concrete, but recently reinforcing fibers have been used. Everything has been developed and put into practical use.
- the characteristic feature of the rod made of aramid fiber is that it is non-magnetic and non-conductive. It is used as reinforcement for cement-concrete structures where steel bars cannot be used.
- rods made of non-magnetic and non-conductive polybenzazole fiber show a reinforcing effect that surpasses that of aramid fiber, and are expected to be next-generation products. Yes.
- Polybenzazole fibers produced in this way have excellent mechanical properties such as strength and elastic modulus, so they can also be used as cement-concrete reinforcing materials.
- Polybenzazole fibers produced in this way are excellent in mechanical properties such as strength and elastic modulus, so that they can be used as fibrous structures constituting protective materials, protective clothing, and industrial materials. Although it is still used as described above, further improvements in performance are expected, especially for prolonged exposure to high temperatures and humidity and light irradiation. There has been a strong demand for a spun yarn made of polibenzazole fiber, which can maintain sufficient strength when it is used.
- glass fibers have been used as a fiber-reinforced composite material.
- carbon fibers or aramide fibers have been used for the purpose of increasing strength and reducing weight. Everything has been developed and put into practical use.
- carbon fiber is very excellent in mechanical performance, it has a problem that it has poor impact resistance and is brittle.
- the amide fiber shows relatively good impact resistance, but its elasticity is lower than that of carbon fiber, so the reinforcing effect is small.
- Composite materials composed of polybenzazole fibers are excellent in both impact resistance and elastic modulus, exhibit a reinforcing effect exceeding that of carbon fibers, and are expected as next-generation products.
- Polybenzazole fiber produced in this way has excellent mechanical properties such as strength and elastic modulus as described above, and As mentioned above, it is also used as a reinforced composite material, but it is expected that its performance, including light resistance, will be improved. There is a strong need for a durable polybenzazole fiber composite material that can maintain sufficient strength after prolonged exposure to humidity. Was.
- a fiber having high strength and high elastic modulus polybenzoxazole or polybenzothiazole, or a polymer composed of these copolymers
- Ribenzazole fiber is known, and the sale cloth containing the fiber is also widely used.
- the sailboats used in the racing are required to have a high tensile resistance and a high tensile strength so that the designed shape does not change even when exposed to wind. Is received.
- a woven fabric made of high-strength and high-modulus fibers has been sandwiched between two films, which can be represented by two polyesters. Auto-molded sell cloth is the mainstream, and is disclosed in, for example, US Pat. No.
- polybenzazole fiber has excellent mechanical properties such as strength and high heat resistance, so that the strength, such as the yacht rope, is high. It has been widely used in rope applications that require high performance.
- polybenzazole fibers are very susceptible to mechanical damage in the rope manufacturing process due to the highly oriented molecular chain structure. For this reason, the resulting rope had a problem that its long-term durability, especially at high temperatures and high humidity, was inferior to the performance of the polybenzazole fiber itself. .
- polybenzoxazole or polibenzothiazole or a copolymer thereof is used as a fiber having high strength and high heat resistance.
- Polybenzazole fiber is known.
- alamido fibers have been used in blade-proofed chocks, but recently, high-strength polyethylene fibers have been developed and put into practical use.
- blade-type chocks using aramide fiber require a large number of fibers to achieve the required protection performance, and are therefore heavy and thick. Because of the thickness, it was not always worn because it was not comfortable to wear.
- the weight of the blade-proof horseshoe made of high-strength polyethylene fiber was reduced, the specific gravity was too small to reduce the thickness.
- the blade-proof chocks made of polybenzazole fiber show protection performance superior to that of aramide fiber and high-strength polyethylene fiber, and are next-generation lightweight and thin. It is expected to be a blade-proof chuck.
- polibenzazole fiber has excellent mechanical properties such as strength and elastic modulus, and is therefore used as a blade-proof jumper. As expected, further improvements in performance, including light resistance, are expected.
- the blade is made of polybenzazole fiber that can maintain sufficient strength when exposed to high temperature and high humidity for a long time. Was strongly desired.
- polybenzazole fiber has excellent mechanical properties such as strength and elastic modulus, as described above, so it has not been used as a bulletproof jockey before.
- improvements in performance, including light resistance, are expected, and sufficient strength is maintained, especially when exposed to high temperatures and high humidity for a long time.
- the present invention has been made with the above in mind, and its purpose is to reduce the strength even when exposed to high temperature and high humidity for a long time.
- An object of the present invention is to provide various uses using nzazole fiber and other fibers. Ming's
- the present invention has the following configurations. 1. Polybenzazole fiber characterized by having a tensile strength retention of 85% or more after exposure for 700 hours in a temperature of 80 ° C and a relative humidity of 80%.
- the polibenzazole according to the above item 1 characterized in that the fiber has an organic pigment which has a thermal decomposition temperature of 200 or higher and has high heat resistance and is soluble in a mineral acid. fiber.
- Polybenzazole staple fiber characterized by having a tensile strength retention of 85% or more after exposure for 700 hours at an atmosphere of 80 ° C and a relative humidity of 80%.
- a cement core characterized by having a tensile strength retention of 75% or more after exposure for 70 hours in an atmosphere of 80% relative humidity at a temperature of 80%.
- Polybenzazole fiber rod for concrete reinforcement 14 Tensile strength retention after exposure for 700 hours in a temperature of 80 ° C and a relative humidity of 80% is 75% or more
- High temperature characterized by a polybenzazole fiber having a tensile strength retention of 85% or more after exposure for 700 hours in an atmosphere of 80% relative humidity and 80% relative humidity.
- Strength fiber rope
- the organic pigment having a thermal decomposition temperature of 200 or higher and having the above-mentioned high heat resistance and soluble in mineral acids is an insoluble azo pigment, a condensed azo pigment, a dye lake, and an isoindolino.
- Isoindolins, dioxazines, perinone and Z or perylenes, phthalocyanines, quinacridones, etc. Is received.
- phthalocyanines and quinacridones are preferred, and more preferably dioxazines, perlinones and / or perylenes.
- One or a combination of two or more of these perrinons may be used.
- the amount of addition is from 0.01% to 20%, preferably from 0.1% to: 10%, based on the amount of polybenzazole.
- the presence or absence of the metal coordinating in the center and the atomic type are not limited.
- Specific examples of these compounds include 29 H, 31 H—phthalocyaninate (2 —)-N 29, N 30, N 31, N 32 copper, 9H, 31H—phthalocyanine (2—) N29, N30, N31, N32 Iron, 29H, 31H—phthalocyanine G 1 N 29, N 30, N 31, N 32 Cobalt, 29 H, 31 H—phthalocyanine (2—) 1 N 29, N 30, N 3 1, N32 copper, oxo (29H, 31H-phthalocyanine (2-) one N29, N30, N31, N32), (SP- 5 — 1 2) Titans, etc. are removed.
- these phthalocyanine skeletons may have one or more substituents such as a halogen atom, a methyl group and a methoxy group.
- One or more of these phthalocyanines may be used in combination.
- the amount of addition is 0.11% to 20%, preferably 0.1% to 10%, based on polibenzazole.
- quinacridones examples include 5,12-dihydro-1,2,9-dimethylquino [2,3—b] acridin-17,14-dione, 5 , 1 2 — dihydroquino [2,3-b] acridin 17, 14-dione, 5, 12 — dihydroquinone 2, 9-dichloro mouth Quino [2,31-b] acrysine 1-7,14-dion, 5,12-dihydro-12,9-dibromoquino [2,3-b] ac Rins 17 and 14 are given.
- the amount of addition is 0.11% to 20%, preferably 0.1% to 10%, based on polibenzazole.
- dioxazines examples include 9,19-dichloro-1,5-diethyl-5,15—dihydroindolo [2,3—c: 2 ', 3,1n ] Tripheno dioxazine, 8, 18-Dichloro 5, 15-Jethyl-5, 15-Dihydroindro [3, 2-b: 3 ', 2, 1 m] trifenodioxazine and the like.
- One or a combination of two or more of these dioxazines may also be used.
- the amount of addition is from 0.01% to 20%, preferably from 0.1% to: 10%, based on the amount of polybenzazole.
- polybenzazole fiber refers to a fiber consisting of a polybenzazole polymer
- PBZ polybenzazole fiber
- PBO polybenzothiazole
- PBI polybenzimidazole
- PBO refers to a polymer containing an oxazole ring bonded to an aromatic group, and the aromatic group does not necessarily need to be a benzene ring.
- PBO is a polymer composed of units of poly (p-phenylbenzobisoxazole) and a plurality of oxazole rings bonded to an aromatic group. Widely included. Similar considerations apply to PBT and PBI. Also, two or more ports, such as a PBO, PBT and a mixture of PBI, a block of PBO, PBT and PBI, or a random copolymer, etc.
- Libenzazo Includes mixtures of copolymers, copolymers, and block polymers.
- polybenzazole is present in mineral acids at specific concentrations. It is a light-exit pick-up liquid crystal polymer that forms liquid crystals.
- the structural unit contained in the PBZ polymer is preferably selected from a radiotropic liquid crystal polymer.
- the polymer is composed of the monomer units described in structural formulas (a) to (i).
- Polybenzazole fiber is manufactured from a solution of polybenzazole polymer (PBZ polymer dope), but a suitable solvent for preparing the dope is as follows.
- PBZ polymer dope polybenzazole polymer
- suitable non-oxidizing mineral acids include polyphosphoric acid, methansulphonic acid and concentrated sulfuric acid or mixtures thereof.
- polyphosphoric acid and methansulfonic acid are most preferably polyphosphoric acid.
- the polymer concentration in the dope is 1 to 30%, preferably; ⁇ 20%.
- the maximum concentration is limited by practical handling properties, such as, for example, polymer solubility and dope viscosity. Because of these limiting factors, the polymer concentration does not usually exceed 20% by weight.
- a suitable polymer or copolymer and dope are synthesized by a known method.
- Wolfe et al. U.S. Patent No. 4,533,693 (1985.8.6), Sybert et al., U.S. Patent No. 4,772,678, (1988.9.22), Harris It is described in US Patent No. 4,847,350 (July 11, 1989) or US Patent No. 5,089,591 to Gregory et al. (1992.2.18).
- the preferred monomers are in a non-oxidizing, dehydrating acid solution, under high-speed stirring and high-shear conditions in a non-oxidizing atmosphere, from about 60 to 230. The reaction is carried out by increasing the temperature stepwise or at a constant heating rate.
- the dope obtained in this way is extruded from the spinneret and stretched in space to form a filament. Suitable preparation methods are described in the references mentioned above and in US Pat. No. 5,034,250.
- the spinneret that has exited the spinneret is the spinneret
- This space is commonly called an air gap, but it does not need to be air.
- This space must be filled with a solvent that does not remove the solvent and does not react with the dopant, e.g., air, nitrogen, argon, helium , Carbon dioxide and the like.
- a solvent that does not remove the solvent and does not react with the dopant, e.g., air, nitrogen, argon, helium , Carbon dioxide and the like.
- the filaments are washed and some of the solvent is removed to avoid overdrawing. Then, it is further washed, and is appropriately neutralized with an inorganic base such as sodium hydroxide, calcium hydroxide, or potassium hydroxide, and most of the solvent is removed. Washing here refers to a liquid that is compatible with the mineral acid in which the polibenzazole polymer is dissolved and is not a solvent for the polibenzazole polymer.
- Suitable cleaning liquids include water or a mixture of water and an acid solvent.
- the filaments are preferably washed to a residual mineral acid concentration of less than 800 ppm, more preferably less than 500 ppm. After that, the filaments are dried, heat-treated, rolled up, etc. as necessary.
- crimping is performed by a press-type crimper or the like as necessary. Then, for example, by using a mouthpiece with radially installed cutting blades between slits formed in a pair of facing rotors.
- Short fibers can be obtained by cutting into fixed lengths.
- the fiber length is not particularly limited, but is preferably from 100 mm to 0.05 mm, and more preferably from 70 mm to 0.5 mm.
- the polybenzazole staple fiber obtained in this way can be used for 700 hours even in a high-temperature, high-humidity environment, such as an atmosphere with a temperature of 8 Ot and a relative humidity of 80%. It has excellent durability, with a tensile strength retention of 85% or more, preferably 90% after exposure.
- the fiber obtained has a breaking strength of 1 GPa or more, preferably 2.75 GPa or more, and more preferably 4.10 GPa or more. Becomes
- the resulting polibenzazole staple fiber is used in a wide variety of applications, and depending on the application, is subjected to various processes such as spinning and felting. Later, tension materials such as cables and mouthpieces, Heat resistant materials such as gloves and other cut-resistant materials, fire-fighting suits, heat-resistant felts, gaskets for plants, heat-resistant fabrics, various sealings, heat-resistant cushions, filters, etc.
- tension materials such as cables and mouthpieces, Heat resistant materials such as gloves and other cut-resistant materials, fire-fighting suits, heat-resistant felts, gaskets for plants, heat-resistant fabrics, various sealings, heat-resistant cushions, filters, etc.
- a wide range of applications including flame-resistant materials, abrasion belts, anti-friction such as clutch facing, reinforcing agents for various building materials and other riders-soots, speaker cones, etc. But are not limited to these.
- the spun yarn made of polibenzazole fiber obtained in this way retains its tensile strength after being exposed for 70 hours at an atmosphere of 80% relative humidity and a temperature of 80%. It has excellent durability with a rate of 70% or more, preferably 75% or more. Furthermore, by using a spun yarn made of the obtained polybenzazole fiber, a durable protective material, protective clothing, and a fiber structure constituting an industrial material are provided. Can be obtained.
- the spun yarn subject to the present invention is also a composite spun yarn blended with other fibers in the scope of the present invention.
- Other fibers include natural fibers, organic fibers, metal fibers, inorganic fibers, and mineral fibers.
- the blending method is not particularly limited, and may be a general blended cotton blend or a core-sheath structure.
- the polybenzazole fiber obtained in this way is subjected to a usual crimping step and cutting step to be processed into a short fiber of the polybenzazole fiber. Furthermore, it is processed into a felt material through a normal felt manufacturing method.
- a known nonwoven fabric manufacturing method can be applied.
- a web is formed from short fibers, and a needle punch method, a stitch bond method, or the like is used.
- a molding method such as a water punch method and a method using a binder can be employed. It is also possible to adopt a spanbond method using long fibers.
- the felt material of the present invention can mix different types of fibers, and the higher the heat resistance requirement, the higher the mixture of polybenzazole fibers. It is effective to increase the rate.
- the weight fraction of the polybenzazole fiber is preferably at least 50%, and more preferably at least 80%. If it is less than 50%, the excellent heat resistance and abrasion resistance of the polybenzazole fiber may not be sufficiently exhibited.
- the mixing method the one mixed uniformly was filtered, or the fiber mixed with the polybenzazole fiber was filtered separately. Thereafter, these may be laminated in two or more layers or any method may be used as long as it can be molded as a felt.
- the fertilized material thus obtained is composed of a polibenzazole fiber whose strength decreases little even after prolonged exposure to high temperature and high humidity. Therefore, the strength can be maintained sufficiently even when exposed to high temperature and high humidity, and as a result, the wear resistance under high humidity is improved, and the life of the heat-resistant cushioning material is improved. It is possible to make it.
- the woven or knitted fabric made of the polenzazol fiber obtained in this way retains its tensile strength after being exposed for 70 hours at an atmosphere of 80 t and a relative humidity of 80%.
- the durability is 70% or more, preferably 75% or more.
- a woven or knitted fabric made of the obtained polybenzazole fiber it is possible to produce a protective material having excellent durability, protective clothing, and a fiber material constituting an industrial material. It is possible to obtain.
- the woven or knitted fabric which is the object of the present invention is also a composite woven or knitted fabric combined with other fibers.
- Other fibers are natural fibers, organic fibers, metal fibers, inorganic fibers, mineral fibers, and the like.
- Further knitting is possible, such as circular knitting, weft knitting, warp knitting, and rassel knitting.
- the fiber bundles constituting the woven or knitted fabric are not particularly limited, but may be monofilaments, multifilaments, or twisted fibers. Yarns, ply-twisted yarns, power-balancing yarns, spun yarns, drawn-off spun yarns, core-sheath structured yarns, braids, and the like can be used.
- the polybenzazole fiber according to the present invention is given a single twist or a twin twist using a ring twisting machine or the like from the viewpoint of improving fatigue resistance.
- the twist coefficient may be in the range of 350 to 2000.
- T w twist Ri Number [T / l 0 cm]
- D en Preparative chromatography
- Tal denier p fiber density [g Z cm 3]
- the surface of the above-mentioned polybenzazole fiber may be subjected to corona treatment or plasma treatment. Further, a compound capable of reacting with the fiber surface or the fiber surface subjected to corona treatment or the like may be provided to the polibenzazole fiber. Dip treatment may be applied to improve the adhesion to rubber.
- the treatment liquid examples include (A) an aqueous dispersion of an epoxy resin, (B) an aqueous dispersion of a block-isolated resin, (C) an aqueous dispersion of a rubber latex, D) Resorcin-formaldehyde resin-rubber latex (RFL) mixed solution, or a single step or two or more steps, usually applied in multiple steps
- RTL Resorcin-formaldehyde resin-rubber latex
- the weight is 1 0 0 g Z m 2 or al 1 5 0 0 g / m 2 , and at least one of the sheets is made of polybenzazole fiber. If the weight is less than 100 g Zm 2 , the required strength cannot be obtained, and the number of laminated sheets must be increased, which is not efficient.
- a fiber sheet is a woven fabric, knitted fabric, nonwoven fabric, net, There are net-like sheets where the fiber intersections are fixed with adhesive, and film-laminated fibers.
- the strength of the fiber sheet is at least 50 kg / cm, preferably at least 100 kg Z cm. At 50 kg / cm, the cement / concrete reinforcement effect cannot be obtained.
- a common method of reinforcing cement concrete with a fiber sheet is to simply wrap or affix it to the mating material to be reinforced. For example, there are a method in which the fiber sheet is wound around a pier under tension, and a method in which the fiber sheet is bonded to a lower surface of a bridge.
- the fiber sheet of the present invention can be applied to any of the methods.
- the composite material comprising the durable polybenzazole fiber according to the present invention may be in any form of unidirectional reinforcement, quasi-isotropic lamination, and woven lamination.
- the matrix resin may be a thermosetting resin such as epoxy resin, phenolic resin, or a super-engineering resin such as PPS, PEEK, or PE, PP, or the like. It does not matter which resin is used, such as general-purpose thermoplastic resin such as polyamide.
- the sale loss in the present invention includes a part of a polbenzazole fiber containing an organic pigment, for example, a polyethylene fiber, Other high-strength fibers such as laramid fibers, wholly aromatic polyester fibers or carbon fibers can be used in combination.
- Cell cross is reinforced with fibers in complex directions.
- a woven fabric made of polibenzazole fiber used in the blade-proof jumper is constituted by laminating a woven fabric made of polibenzazole fiber used in the blade-proof jumper according to the present invention.
- the texture of the woven fabric may be any of a plain texture, a twill texture, and other textures commonly used for woven fabrics.
- the blade performance can be exhibited.
- the fineness of the polibenzazole fiber used in the present invention is 600 dtex or less, preferably 300 dtex or less, so that a high blade-proof performance is easily obtained.
- the weaving density of the woven fabric of the present invention is 30 yarns / 25 mm or more, preferably 50 yarns / 25 mm or more. If the density is low, the yarn will move easily, and it will not be possible to obtain sufficient blade performance.
- the basis weight of the woven fabric is 100 g / m 2 or more, preferably 150 g / ni 2 or more, excellent blade-proof performance can be exhibited.
- the woven fabric used in the present invention may be coated or impregnated with a resin on a part or the whole of the woven fabric.
- the blade-proof jumper according to the present invention is obtained by laminating the woven fabrics, the woven fabrics can be used in a state where the woven fabrics are sewn together with a high-strength sewing thread.
- the bulletproof chest according to the present invention is formed by laminating a woven fabric made of porbenzazole fiber.
- the texture of the woven fabric may be any of a plain weave, a twill texture, or any other texture normally used for woven fabrics, but it is preferable to use a flat texture, a twill texture, etc. In other words, high bulletproof performance can be achieved.
- the polybenzazole fiber used in the present invention has a fineness of 1110 dtex or less, preferably 600 dtex or less. Further, the woven density of the woven fabric of the present invention needs to be 40 yarns / 25 mm or less.
- the eyes of the fabric With the 2 0 0 g Z m 2 Ri der below, rather than the favored Ru can exhibit excellent ballistic performance and Ru Oh in 1 5 0 g / m 2.
- the bulletproof jumper of the present invention is obtained by laminating the woven fabrics, it is also possible to use the woven fabrics in a state where the woven fabrics are integrally sewn with a high-strength sewing thread.
- the first feature of the polybenzazole fiber according to the present invention is that it contains an organic pigment, whereby the polybenzazole fiber can be used for 700 hours at a temperature of 80 and a relative humidity of 80%. A tensile strength retention of 85% or more after exposure can be achieved.
- the organic pigment used here has a thermal decomposition temperature of 200 ° C or higher, as described above, and is soluble in a mineral acid. And / or NH—. More preferably, they are perrinone and quinone or perylenes, phthalocyanines, quinacridones, or dioxazines.
- the mineral acid is methansulfonic acid or polyphosphoric acid.
- the method for incorporating these organic pigments into the yarn is not particularly limited, and may be contained at any stage of the polymerization of polibenzazole or at the polymer dope at the end of the polymerization. It can be done.
- the method of adding the organic pigment at the same time as the raw material of the polybenzazole is added the method of adding the organic pigment at any time during which the temperature is raised stepwise or at a constant heating rate, and It is preferable to add to the reaction system at the end of the polymerization reaction and stir and mix.
- the organic pigment After washing with water, the organic pigment is fixed by drying the filament at 5 or more, usually at 300 or less.
- the tensile strength retention rate after the drying treatment is 80% or more with respect to the olibenzazole fiber containing no organic pigment. There is little adverse effect on the environment.
- the second feature of the polybenzazole fiber according to the present invention is that the fiber is maintained satisfactorily without the organic pigment in the yarn becoming a defect and the initial strength of the fiber being reduced. . Also, the spinnability during spinning is Good and good operability without yarn breakage is maintained. This is presumed to be due to the fact that the added pigment was dissolved in the mineral acid and thus dissolved even in the polymer. If the organic pigment content exceeds 20%, the filament yarn fineness is increased and the initial yarn strength is lowered, which is not preferable.
- a third feature of the polybenzazole fiber according to the present invention is an improvement in light resistance. It is known that the polbenzazole fiber usually loses its strength when exposed to sunlight for a long time. For example, in the case of poly (p-phenylene benzobisoxazole) fiber, the intensity is about 15 to 3 compared to the initial intensity by irradiating xenon light for 100 hours. Drops to 0%. On the other hand, in the fiber of the present invention containing the high heat-resistant organic pigment, the intensity after irradiation with xenon light for 100 hours is preferably 50% or more of the initial intensity. Or more than 75%.
- the function of the highly heat-resistant organic pigment is that light irradiation is alleviated by the light-shielding effect, or the polibenzazole molecules excited by the light irradiation are immediately converted to the ground state. It is presumed that the process returns to the initial state, or that the system captures radicals generated by the interaction with oxygen molecules and stabilizes the system. Is not bound by this consideration.
- the measuring method in the examples is as follows.
- the sample was stored at high temperature and high humidity in a thermo-hygrostat with the fiber wound around a 10 cm diameter paper tube, and then the sample was removed. The specimens were taken out, subjected to a tensile test at room temperature, and evaluated based on the strength retention before and after treatment.
- Humidic Chamber 1G43M manufactured by Yamato Scientific Co., Ltd. was used, and the treatment was performed for 70 hours at 80 and relative humidity of 80%. Carried out.
- the strength retention was determined by measuring the tensile strength before and after storage at high temperature and high humidity, and dividing the tensile strength after storage test at high temperature and high humidity by the tensile strength before storage test at high temperature and high humidity.
- the tensile strength was measured using a tensile tester (model AGA-50KNG, manufactured by Shimadzu Corporation) in accordance with JIS-L101.
- the residual phosphorus concentration in the filament is measured using a fluorescent X-ray measuring device (Phillips PW144 / DY6865) after solidifying the sample into a pellet. And the sodium concentration was determined by neutron activation analysis. It was measured.
- Abrasion treatment using a high-temperature abrasion tester and rotating the sample at 300 rpm while the friction element heated at 500 and in contact with the sample under a load of 300 g / cm2 was implemented.
- the sample was immersed in pure water for 10 seconds and then the abrasion treatment was started.
- the abrasion treatment was started again by immersion in the inside for 10 seconds, and the abrasion treatment was started again for a total of 20 hours.
- the abrasion resistance was evaluated based on the amount of weight loss after abrasion treatment for 20 hours. (Woven and knitted fabric strength measurement)
- the strength retention was determined by measuring the tensile strength before and after storage at high temperature and high humidity, and dividing the tensile strength after storage test at high temperature and high humidity by the tensile strength before storage test at high temperature and high humidity.
- the tensile strength of the fabric is measured in accordance with JIS-L1096, and the tensile strength of the knitted fabric is measured in accordance with JIS-L118, using a tensile tester (Shimadzu Corporation, Model AG — 50 KNG).
- the strength of the sail cross was measured with a sample width of 2.5 cm according to JIS L106.
- Filament diameter should be 11.5 ⁇ m and 1.5 denier. Spinning was performed under such conditions.
- the filament is converged at an appropriate position from a nozzle with a hole diameter of 180 / xm and a hole number of 1666 at a spinning temperature of 17.5 to form a multi-filament. It was extruded during the first washing bath arranged as follows. The airgap between the spinning nozzle and the first cleaning bath was equipped with a quench chamber to allow the filament to be stretched at a more uniform temperature. The air gap length was 30 cm. The filament was spun into the air at 60 ° C. The take-up speed was 200 m / min, and the spinning draw ratio was 30.
- the polymer group of a polyparaphenylene benzobenzoxazole having an intrinsic viscosity of 26 dL / g measured with a methansulfonate solution of 30 was prepared by the method described above. Spinning. Table 1 shows the results of a high-temperature, high-humidity storage test (80, 80 RH%) and a light exposure test of the yarn thus obtained.
- the polymer dope of porino and rafene benzobenzoxazole having an intrinsic viscosity of 28 dL / g measured in methanesulfonate solution at 30 ° C was prepared as described above. It was spun by the method. Table 1 shows the results of a high-temperature, high-humidity storage test (80%, 80% R%) and a light exposure test of the yarn obtained in this way.
- the polymer dope of a polyparaphenylenebenzobisoxazol with an intrinsic viscosity of 28 dL / g measured with a 30X methanesulfonate solution was prepared according to the method described above. More spun.
- Table 1 shows the results of a high-temperature, high-humidity storage test (80, 80 RH%) and a light exposure test of the yarn thus obtained.
- polyphosphoric acid 2,165.5 g, 4,6-diaminoresorcinol dihydrochloride 34.5.5 g, terephthalic acid Add 252.7 g, stir at 60 ° for 30 minutes, raise the temperature to ⁇ , and heat up with 12 O for 3.5 hours, 13.5 for 20 hours, 150 ° For 5 hours.
- the oligodope dope has terephthalic acid 5.6 and 2911, 31H-phthalocyanine (2-)-N29, N30, N 3 1, N 3 2 Copper 22.Og was added to 71.6 g of polyphosphoric acid, 74.4 g of polydispersion, and then added at 170 ° C for 5 hours at 200 ° C. And reacted for 5 hours.
- a polyparaphenylenebenzene benzobisthiazole having an intrinsic viscosity of 26 dL / g measured in a methanesulfonate solution at 30 ° C was used as a primer. Spinning was performed by the method described above. Table 1 shows the results of a high-temperature, high-humidity storage test (80 ° C, 80 RH%) and a light exposure test of the yarn thus obtained.
- a polybenzoxazol polymer having an intrinsic viscosity of 10 dLZg measured in a methansulfonate solution at 30 ° C. was spun by the method described above.
- Table 1 shows the results of a high-temperature, high-humidity storage test (80 ° C, 80 RH%) and a light exposure test of the yarn thus obtained.
- the high-temperature, high-humidity storage test of the yarn obtained in this manner was performed. (At 80, 80 RH%) and the results of the light exposure test are shown in Table 1.
- a polymer dope of a poly (vinylaphenylenebenzenezobisoxazole) having an intrinsic viscosity of 26 dLZg measured in a methanesulfonic acid solution at 30 ° was spun by the method described above.
- Table 1 shows the results of a high-temperature, high-humidity storage test (80, 80 RH%) and a light exposure test of the thus obtained yarn.
- Table 1 summarizes the above results. As is evident from Table 1, the borobenzazole fiber of the example has a very high strength retention rate after exposure to high temperature and high humidity and after exposure to xenon light, as compared with the comparative example. I understand.
- the polydope with a specific viscosity of 24 dLZg and a polymer dope of laphenylenebenzozoxazole was spun by the above-described method, followed by a 300-denier tow.
- the yarn is joined, the crimp is applied by a press-type crimper having a mouth width of 2 O mm, and the crimped tow is applied to the towel with a single-unit cutter.
- Short fibers were obtained by cutting to a fixed length of 4 mm. (In 8 0, 8 0 R H%) High temperature and high humidity storage test of the yarn obtained in Remind as in Table 2 and results of light exposure test.
- a step fiber with a cut length of 51 mm was manufactured from the obtained poly-benzorsole fiber, and the twist factor was set to 3.5.
- Spun yarn The obtained spinning The tensile strength of the yarn was 9.3 c NZ dte X.
- a high-temperature, high-humidity storage test 80 ° C, 80 RH% of the obtained spun yarn was performed, and as a result, the strength retention was 63%. Furthermore, as a result of a light exposure test, the strength retention was 19%.
- the obtained yarn was combined with a 30000 denier tow and crimped by a push-in type crimper having a roll width of 20 mm. Subsequently, the crimped tow was cut to a fixed length of 44 mm with a rotary cutter to obtain short fibers (staples).
- the obtained table is opened with an opener and then opened.
- a web with a basis weight of 200 g / m2 is prepared with a mouth card and the obtained web is obtained. Then, a needle having a thickness of 10.0 mm and a basis weight of 260,000 g / m 2 was obtained by needle punching.
- the height of the obtained fault The weight loss due to abrasion evaluated for thermal abrasion resistance was 3 mg / cm 2.
- the obtained yarn was processed in the same manner as in Example 26 to obtain a felt having a thickness of 10.0 mm and a basis weight of 2500 g Zm 2.
- the high-temperature abrasion resistance of the obtained ferrite was evaluated.
- the weight loss due to abrasion was 33 mg Z cm 2.
- the obtained yarn was processed in the same manner as in Example 26 to obtain a felt having a thickness of 9.9 mm and a basis weight of 2500 g Zm 2. Evaluation of the obtained felt at high temperature and abrasion resistance revealed that the weight loss due to abrasion was 3.4 mg / cm 2.
- the obtained yarn was processed in the same manner as in Example 26 to obtain a felt having a thickness of 10.3 mm and a basis weight of 2700 g / m 2.
- the high-temperature abrasion resistance of the obtained ferrite was evaluated.
- the weight loss due to abrasion was 3 ArngZcms.
- the obtained yarn was processed in the same manner as in Example 26 to obtain a felt having a thickness of 10 .1 mm and a basis weight of 2600 g / m 2.
- the high-temperature abrasion resistance of the obtained ferrite was evaluated.
- the weight loss due to wear was 3.2 mg / cm 2.
- the obtained yarn was processed in the same manner as in Example 26 to obtain a felt having a thickness of 9.8 mm and a basis weight of 2500 g / m.
- the weight loss due to abrasion was 4.0 mg / cm 2.
- Table 3 summarizes the above results. As is clear from Table 1, the ratio Compared with the comparative example, it can be seen that the felt material made of the polibenzazole fiber of the example has very good abrasion resistance under high temperature and high humidity.
- the ferrule which consists of a polibenzazole fiber which can maintain sufficient intensity
- Example 31 Using the spun yarn 20 / l Ne obtained in Example 31, a circular knitted fabric having a warp direction of 68 stitches / inch and a transverse direction of 29th stitches was used. The obtained circular knitted fabric had a tensile strength in the vertical direction of 1650 N / 5 cm. Subsequently, the obtained woven fabric was subjected to a high temperature and high humidity storage test (80, 80 RH%), and as a result, the strength retention was 75%. In addition, a light exposure test revealed that the strength retention was 44%.
- a spun yarn was produced, and the two yarns were twisted to obtain a 20/2 Ne twin yarn.
- 21 twill fabrics were manufactured with a driving number of 68 / inch in the warp direction and 60 / inch in the horizontal direction.
- the tensile strength in the vertical direction of the obtained woven fabric was 4320 N / 3 cm.
- the obtained woven fabric was subjected to a high-temperature and high-humidity storage test (801:, 80 RH%), and as a result, the strength retention was 62%.
- a light exposure test revealed a strength retention of 21%.
- Comparative Example 10 Using the spun yarn 20/1 Ne obtained in Comparative Example 9, a circular knitted fabric having a warp direction of 68 stitches / inch and a horizontal direction of 29th stitches / inch was manufactured. The tensile strength in the vertical direction was 1580 N / 5 cm. Subsequently, the obtained woven fabric was subjected to a storage test under high temperature and high humidity conditions (80 t, 80 RH%), and as a result, the strength retention was 59%. In addition, a light exposure test revealed that the strength retention was 18%. From the above results, compared with Comparative Examples 9 and 10, the woven and knitted fabrics composed of the polybenzazole fibers of Examples 31 and 32 exhibited a higher strength retention after exposure to high temperature and humidity. It can be seen that the strength retention after light exposure is very high.
- the filament diameter was 11.5 m and 1.5 denier.
- the filaments are arranged so that the filaments converge at an appropriate position from a nozzle with a pore diameter of 180 jum and a hole number of 1666 to form a multifilament.
- a quench chamber was installed in the airgap between the spinning nozzle and the first cleaning bath so that the filament could be stretched at a more uniform temperature.
- the airgap length was 30 cm.
- Filament was spun into air at 60 ° C. Spinning at a take-up speed of 200 m / min The magnification was 30.
- the obtained polybenzasol fibers were twisted together with a twist of 32 T in the Z direction while adding 10 cm in the Z direction, and then the two fibers were combined to form 32 T / 1 in the S direction.
- a raw cord was obtained by applying a twist of 0 cm, and then the raw cord was subjected to two-step dip treatment to prepare a dip code.
- the first-stage dip treatment liquid is an aqueous dispersion of epoxy resin
- the treatment temperature is 240
- the second-stage dip treatment liquid is an RFL solution
- the treatment temperature is 235.
- the strength of the obtained dip code was 655 N.
- the strength retention of this dip code at high temperature and high humidity was excellent at 76%.
- the obtained six polybenzasol fibers were twisted together with a twist of 32 T / 10 cm in the Z direction, and then the two fibers were combined to form 32 T / 10 in the S direction.
- the raw cord was obtained by applying a twist of cm, and then the raw code was subjected to a two-step dipping process to prepare a dip code.
- the first dipping treatment liquid is an aqueous dispersion of an epoxy resin, and the treatment temperature is 240, and the second dipping treatment is performed.
- the solution was an RFL solution, the treatment temperature was 235, and the strength of the obtained iPad code was 662N.
- the strength retention of this dip code under high temperature and high humidity was 59%, which was inferior to Example 33.
- the filament diameter was 11.5 / im and 1.5 denier.
- the first nozzle is arranged so that the filaments are converged at an appropriate position from a nozzle with a pore diameter of 180 m and a number of mosquitoes of 1666 at an appropriate position to form a multifilament.
- a quench chamber was installed in the air gap between the spinning nozzle and the first cleaning bath so that the filament could be stretched at a more uniform temperature.
- the airgap length was 30 cm. Filament was spun into the air at 60 ° C.
- the take-up speed was 200 m / min, and the spinning draw ratio was 30.
- washing was carried out until the residual phosphorus concentration in the polybenzazole fiber became 600 ppm or less. Further, the yarn was neutralized with a 1% Na0H aqueous solution for 10 seconds, washed with water for 30 seconds, dried at 200 for 3 minutes, and wound around a yarn tube.
- Example 35 Twenty-two obtained polybenzasol fibers were twisted 20 times per 1 m while twisting to obtain a 300-denier ply-twisted yarn. Using the obtained ply-twisted yarn, a plain weave was manufactured using a rapier loom with a number of 17-inch punches in each direction. The weight of the obtained woven fabric was 490 g / m 2. The tensile strength in the warp direction was 637 kg / cm. The strength reduction of the obtained woven fabric under high temperature and high humidity and the strength reduction after the light resistance test were measured, and the strength retention rates were 65% and 48%, respectively, as compared with Example 34. Was inferior. (Example 35)
- the filament diameter was 11.5 m and 1.5 denier.
- the filament is converged at an appropriate position from a nozzle with a hole diameter of 180 am and a number of holes of 1666 to form a multi-filament.
- Extruded into the first washing bath arranged in the following manner.
- the air gap between the spinning nozzle and the first cleaning bath was equipped with a quench chamber to allow the filament to be stretched at a more uniform temperature.
- the air gap length was 30 cm.
- the filament was spun into the air at 60 ° C.
- Washing was carried out until the residual phosphorus concentration in the polibenzazole fiber with the take-up speed of 200 m / min and the spinning draw ratio of 30 was 600 ppm or less. . Furthermore, after neutralizing with a 1% NaOH aqueous solution for 10 seconds, washing with water for 30 seconds, drying at 200 ° C. for 3 minutes, the yarn was wound around a yarn tube.
- the filament diameter was 11.5 m and 1.5 denier.
- the filament should be converged at an appropriate position from a nozzle with a hole diameter of 180 am and a hole number of 1666 at a spinning temperature of 17.5 ° C to form a multifilament.
- Extruded into the first cleaning bath located at The air gap between the spinning nozzle and the first cleaning bath stretches the filament at a more uniform temperature
- the quench chamber was set up.
- the air gap length was 30 cm.
- the filament was spun into the air at 60 ° C. When the take-up speed is set to 20 OmZ and the spinning draw ratio is set to 30, the residual phosphorus concentration in the polybenzazole fiber becomes 600 ppm or less. Washed with water. Further, the resultant was neutralized with a 1% NaOH aqueous solution for 10 seconds, washed with water for 30 seconds, dried at 200 for 3 minutes, and wound around a yarn tube.
- Example 37 The yarn thus obtained was evaluated for durability using the method described above. The results were as follows: 75% in the light exposure test and 37% in the storage test under high temperature and high humidity. The result was inferior to Example 36. (Example 37)
- the resulting pigment-containing polybenzazole fiber is plied into a yarn having a total denier of 150, and the yarn is laid in both the warp direction and the weft direction. A slim with 5 inserts per inch was manufactured.
- the resulting squeeze is sandwiched between 12 micron-thick biaxially stretched polyester films to which a polyurethane adhesive has been applied, and cured and dried.
- the weight of the obtained sale cloth was 320 g / m 2.
- the obtained sale cloth was cut into a size of 2.5 cm in width and 5 Ocm in length to contain five reinforcing fibers, and subjected to high-temperature, high-humidity exposure and light exposure tests.
- Table 4 shows the results.
- Example 2 A 29 dL / g poly (polyphenylene benzobisoxazole) dope obtained in the same manner as in Example 37. Dope was added to 2.0 kg of bisbenzi imidazo. [2, 1—b: 2 ', 1'-i] benzo [lmn] [3, 8] phenanthone-line, 18, 17—dione 15.2 g And mixed by stirring. Thereafter, spinning was performed by the method described above.
- the resulting pigment-containing polybenzazole fiber is plied into a yarn having a total denier of 150, and the yarn is warped and crossed by one inch. A slim with five inserts each was manufactured.
- the resulting squeeze is sandwiched between a 12-micron-thick biaxially stretched polystyrene film coated with a polyurethane adhesive, cured and dried, and then sold. Manufactured.
- the weight of the obtained sale cloth was 32 OgZms.
- the resulting sale cloth is 2.5 cm wide and 5 Ocm long so that it contains five reinforcing fibers. They were cut out and subjected to high-temperature, high-humidity exposure and light exposure tests. Table 4 shows the results.
- the resulting pigment-containing polybenzazole fiber is plied into a yarn having a total denier of 150, and the yarn is warped and crossed by one inch.
- a slim was manufactured with 5 pieces per unit.
- the resulting squeeze is sandwiched between 12-micron-thick biaxially stretched polyester films to which a polyurethane adhesive has been applied, and cured and dried.
- the weight of the obtained sale cloth was 32 0 g Zm 2.
- the obtained sale cloth was cut into a size of 2.5 cm in width and 50 cm in length to contain five reinforcing fibers, and subjected to high-temperature, high-humidity exposure and light exposure tests. . Table 4 shows the results.
- the resulting pigment-containing polybenzazole fiber is plied into a yarn having a total denier of 150, and the yarn is set to 1 inch in both the warp direction and the weft direction.
- a slim with five inserts per unit was manufactured.
- the resulting squeeze is sandwiched between 12 micron-thick biaxially stretched polystyrene films coated with a polyurethane adhesive, cured and dried. —Lucros was manufactured.
- the weight of the obtained sales cross is
- the obtained sale cloth was cut into a size of 2.5 cm in width and 50 cm in length so as to include five reinforcing fibers, and subjected to high-temperature, high-humidity exposure and light exposure tests. . Table 4 shows the results.
- the resulting polybenzazole fiber containing the pigment is plied into a yarn having a total denier of 1500, and the yarn is turned 1 inch in the warp direction and the weft direction. 5 screws were manufactured.
- the resulting squeeze is sandwiched between a 12-micron-thick biaxially stretched polyester film coated with a polyurethane-based adhesive, cured, dried, and sold. Loss was manufactured. The weight of the obtained sales cross is
- the obtained sale cloth was cut into a size of 2.5 cm in width and 50 cm in length so as to include five reinforcing fibers, and subjected to high-temperature, high-humidity exposure and light exposure tests. .
- Table 4 shows the results. As is clear from Table 4, compared to Comparative Example 15, the sailcloths containing the polibenzazole fibers of Examples 37 to 40 were exposed or exposed to high temperature and high humidity. It can be seen that the strength retention after exposure is very high.
- the strength retention of the obtained product after storage at high temperature and humidity is 81%, which is 9% lower than the strength retention of polibenzazole fiber used as a raw material. It was just. A light exposure test was performed on the obtained rope. As a result, the strength retention after irradiation for 100 hours was as good as 80%.
- Example 21 A poly (p-phenylene benzobisoxazole) with a specific year of 29 dL / g obtained in the same manner as in Example 1 and a 2.0 kg bis-benzsui dope Midazo [2, 1—b: 2, 1, 1'-i] Benzo [1 mn] [3, 8] was added and mixed by stirring. Thereafter, spinning was performed by the method described above. The strength retention of the obtained yarn after the high-temperature high-humidity storage test was 86%.
- Example 29 A specific year of 29 dL / g of poly (—phenylene benzobisoxazole) obtained in the same manner as in Example 1 Low 5, 15_Jetyl-5, 15—Dihydroindro [2, 3—c: 2 ′, 3′—n] Trifenodioxazine 15.2 g The mixture was added and mixed with stirring. Thereafter, spinning was performed according to the method described above. The strength retention of the obtained yarn after storage at high temperature and high humidity was 85%.
- Table 5 summarizes the above results. As is clear from Table 5, the high-strength fiber ropes composed of the polibenzazole fibers of Examples 4 and! -44 were exposed to high temperature and high humidity compared to Comparative Example 16. It can be seen that the strength retention after the treatment was very high.
- the filament diameter was 11.5 ⁇ m and 1.5 denier.
- a filament is converged at an appropriate position from a nozzle with a pore diameter of 180 m and a number of holes of 16.6 to form a multifilament.
- Extruded into the first cleaning bath which was positioned as follows. The air gap between the spinning nozzle and the first cleaning bath was equipped with a quench chamber to allow the filament to be stretched at a more uniform temperature. The air gap length was 30 cm. Filament was spun into the air at 6 Ot :. The take-up speed was 20 OmZ min and the spinning draw ratio was 30.
- washing was carried out until the residual phosphorus concentration in the polybenzazole fiber became 600 ppm or less. Further, the yarn was neutralized with a 1% NaOH aqueous solution for 10 seconds, washed with water for 30 seconds, dried at 200 for 3 minutes, and wound around a yarn tube.
- a plain weave is manufactured using a weaving loom with 30/25 mm punches in each direction. did.
- the weight of the obtained woven fabric was 136 g / m 2.
- the tensile strength in the warp direction is 267 ON /
- a plain fabric is manufactured using a repia loom with 60/25 mm punches in each direction. did.
- the weight of the obtained woven fabric was 138 g Zm 2.
- the tensile strength in the warp direction was 281 ON / 3 cm.
- the strength reduction of the obtained woven fabric under high temperature and high humidity and the decrease in strength after the light fastness test were measured, and the strength retention was 63% and 47%, respectively. And inferior to Examples 45.
- the filament diameter was 11.5 _tm and 1.5 denier.
- a filament is converged at an appropriate position from a nozzle with a pore diameter of 180, m and a number of holes of 1.66 to form a multi-filament.
- Extruded into the first washing bath arranged in the following manner.
- the air chamber between the spinning nozzle and the first washing bath was equipped with a quench chamber to allow the filament to be stretched at a more uniform temperature.
- the air gap length was 30 cm.
- the filament was spun into 60 * C air.
- the take-up speed is set to 20 OmZ minutes and the spinning draw ratio is set to 30, the residual phosphorus concentration in the polybenzazole fiber becomes 600 ppm or less. Washed with water. Further, the fiber was neutralized with a 1% NaOH aqueous solution for 10 seconds, washed with water for 30 seconds, dried at 200 ° C. for 3 minutes, and wound around a yarn tube.
- the two polybenzazole fibers thus obtained were combined so as not to be twisted, and a yarn with a thickness of 5.55 dtex was obtained.
- a plain woven fabric was manufactured by using a weaving loom with 30 Z-inches in each direction.
- the weight of the obtained woven fabric was 135 g / m 2.
- the tensile strength in the warp direction was 570 N / 3 cm.
- the obtained fabric was measured for the strength loss under high temperature and high humidity and the strength loss after the light fastness test. As a result, the strength retention was excellent at 81% and 64%, respectively.
- the obtained two polybenzazole fibers were combined so as not to be twisted to obtain a yarn with a thickness of 5.55 dtex.
- a plain woven fabric was manufactured by using a looms with 30 Z-inches in each direction.
- the weight of the obtained woven fabric was ISS g Zms.
- the tensile strength in the warp direction was 574 NZ 3 cm.
- the strength retention rates were 63% and 47%, respectively, and were obtained as in Example 46. It was inferior to.
- Example 27 3603 2942 1.10 5.8 5.0 86 4.8 82 3.3
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- Ocean & Marine Engineering (AREA)
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Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2003244068A AU2003244068A1 (en) | 2002-06-26 | 2003-06-26 | Polybenzazole fiber and use thereof |
CA002490025A CA2490025A1 (en) | 2002-06-26 | 2003-06-26 | Polybenzazole fiber and use thereof |
US10/517,832 US7357982B2 (en) | 2002-06-26 | 2003-06-26 | Polybenzazole fiber and use thereof |
DE60323849T DE60323849D1 (de) | 2002-06-26 | 2003-06-26 | Polybenzazolfaser und deren verwendung |
KR10-2004-7021071A KR20050013241A (ko) | 2002-06-26 | 2003-06-26 | 폴리벤즈아졸 섬유 및 그의 용도 |
EP03761809A EP1541726B1 (en) | 2002-06-26 | 2003-06-26 | Polybenzazole fiber and use thereof |
Applications Claiming Priority (26)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2002186418A JP4062496B2 (ja) | 2002-06-26 | 2002-06-26 | 耐久性に優れるポリベンザゾール繊維 |
JP2002-186418 | 2002-06-26 | ||
JP2002-238458 | 2002-08-19 | ||
JP2002238458A JP2004076205A (ja) | 2002-08-19 | 2002-08-19 | 耐久性に優れるセールクロス |
JP2002239698A JP2004076213A (ja) | 2002-08-20 | 2002-08-20 | 耐久性に優れる高強度繊維ロープ |
JP2002-239698 | 2002-08-20 | ||
JP2002-264464 | 2002-09-10 | ||
JP2002264465A JP2004100100A (ja) | 2002-09-10 | 2002-09-10 | フェルト材料 |
JP2002-264465 | 2002-09-10 | ||
JP2002264464A JP2004100099A (ja) | 2002-09-10 | 2002-09-10 | 耐久性に優れるゴム補強用ポリベンザゾール繊維コード |
JP2002264463A JP2004100098A (ja) | 2002-09-10 | 2002-09-10 | セメント・コンクリート補強用ポリベンザゾール繊維製シート |
JP2002-264463 | 2002-09-10 | ||
JP2002-307544 | 2002-10-22 | ||
JP2002307544A JP2004143731A (ja) | 2002-10-22 | 2002-10-22 | セメント・コンクリート補強用ポリベンザゾール繊維製ロッド |
JP2002314708A JP4066248B2 (ja) | 2002-10-29 | 2002-10-29 | ポリベンザゾール繊維からなる防弾チョッキ |
JP2002-314709 | 2002-10-29 | ||
JP2002-314710 | 2002-10-29 | ||
JP2002-314706 | 2002-10-29 | ||
JP2002-314708 | 2002-10-29 | ||
JP2002-314707 | 2002-10-29 | ||
JP2002314710A JP2004149628A (ja) | 2002-10-29 | 2002-10-29 | ポリベンザゾール繊維からなる複合材料 |
JP2002314706A JP4032300B2 (ja) | 2002-10-29 | 2002-10-29 | ポリベンザゾール繊維からなる紡績糸 |
JP2002314707A JP2004149944A (ja) | 2002-10-29 | 2002-10-29 | ポリベンザゾール繊維からなる織編物 |
JP2002314709A JP2004150666A (ja) | 2002-10-29 | 2002-10-29 | ポリベンザゾール繊維からなる防刃チョッキ |
JP2002-319829 | 2002-11-01 | ||
JP2002319829A JP4032302B2 (ja) | 2002-11-01 | 2002-11-01 | ポリベンザゾール短繊維 |
Publications (1)
Publication Number | Publication Date |
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WO2004003272A1 true WO2004003272A1 (ja) | 2004-01-08 |
Family
ID=30004162
Family Applications (1)
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PCT/JP2003/008066 WO2004003272A1 (ja) | 2002-06-26 | 2003-06-26 | ポリベンザゾール繊維及びその利用 |
Country Status (8)
Country | Link |
---|---|
US (1) | US7357982B2 (ja) |
EP (1) | EP1541726B1 (ja) |
KR (1) | KR20050013241A (ja) |
CN (1) | CN1301352C (ja) |
AT (1) | ATE409761T1 (ja) |
AU (1) | AU2003244068A1 (ja) |
CA (1) | CA2490025A1 (ja) |
WO (1) | WO2004003272A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7189346B2 (en) | 2004-07-22 | 2007-03-13 | E. I. Du Pont De Nemours And Company | Polybenzazole fibers and processes for their preparation |
Families Citing this family (16)
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EP1693489A1 (en) * | 2003-12-11 | 2006-08-23 | Toyo Boseki Kabushiki Kaisha | Polybenzazole fiber and article comprising the same |
CN101213329B (zh) * | 2005-03-28 | 2011-01-19 | 纳幕尔杜邦公司 | 具有羟基侧基和阳离子的聚芳烃唑聚合物纤维 |
ITMI20052156A1 (it) * | 2005-11-11 | 2007-05-12 | Ruredil Spa | Manufatto edile e metodo di rinforzo di una struttura edile |
US8580380B2 (en) * | 2006-08-23 | 2013-11-12 | Toyo Boseki Kabushiki Kaisha | Polybenzazole fiber and pyridobisimidazole fiber |
CA2716359C (en) * | 2008-02-28 | 2014-01-21 | Bell Helicopter Textron Inc. | Uncured composite rope including a plurality of different fiber materials |
DE08730982T1 (de) * | 2008-02-28 | 2011-03-17 | Bell Helicopter Textron, Inc., Fort Worth | Harzimprägniertes baufaserseil |
US8001999B2 (en) * | 2008-09-05 | 2011-08-23 | Olive Tree Financial Group, L.L.C. | Energy weapon protection fabric |
US20100108225A1 (en) * | 2008-10-30 | 2010-05-06 | E. I. Du Pont De Nemours And Company | Non-Load Bearing Cut Resistant Tire Side-wall Component Comprising Knitted Textile Fabric, Tire Containing Said Component, and Processes for Making Same |
US20100108231A1 (en) * | 2008-10-30 | 2010-05-06 | E. I. Du Pont De Nemours And Company | Non-load bearing cut resistant tire side- wall component and tire containing said component, and processes for making same |
US20110126335A1 (en) * | 2009-12-01 | 2011-06-02 | Gregory Russell Schultz | Staple Fiber Conductive Fabric |
TW201209238A (en) * | 2010-08-31 | 2012-03-01 | Gold Joint Ind Co Ltd | Industrial textile |
JP6310549B2 (ja) * | 2014-05-08 | 2018-04-11 | 国立研究開発法人産業技術総合研究所 | ポリベンズイミダゾール炭素繊維及びその製造方法 |
TWI608740B (zh) * | 2016-02-26 | 2017-12-11 | yuan sen Chen | Trumpet vibrating sheet material and manufacturing method thereof |
US10307795B2 (en) * | 2016-05-04 | 2019-06-04 | Fabscrap, Inc. | Scalable systems and methods for classifying textile samples |
CN109778342A (zh) * | 2017-11-14 | 2019-05-21 | 中蓝晨光化工有限公司 | 一种聚对苯撑苯并二恶唑纤维的原位染色方法 |
CN108793900B (zh) * | 2018-05-15 | 2022-02-22 | 中国石油天然气集团有限公司 | 一种改性聚苯并咪唑纤维增韧水泥浆体系 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0827623A (ja) * | 1994-07-13 | 1996-01-30 | Toyobo Co Ltd | ポリベンザゾール繊維及び繊維布帛 |
WO1996010661A1 (en) * | 1994-09-30 | 1996-04-11 | The Dow Chemical Company | Process for the preparation of polybenzazole filaments and fibres |
JPH11228820A (ja) * | 1998-02-19 | 1999-08-24 | Toyobo Co Ltd | ポリベンザゾール組成物、繊維およびフィルム |
JP2001011311A (ja) * | 1999-06-30 | 2001-01-16 | Toyobo Co Ltd | 耐光性ポリベンザゾール組成物、その繊維およびフィルム |
JP2001172845A (ja) * | 1999-12-17 | 2001-06-26 | Toyobo Co Ltd | 耐光性に優れた耐熱・難燃織編物 |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5001003A (en) * | 1988-08-17 | 1991-03-19 | North Sails Group, Inc. | Laminated sailcloth with scrim |
DE4010086C2 (de) * | 1989-05-16 | 2003-07-24 | Dimension Polyant Sailcloth In | Kontinuierliches Verfahren und Vorrichtung zur kontinuierlichen Herstellung eines verstärkten laminierten Tuches für Segel |
US5097784A (en) * | 1990-08-21 | 1992-03-24 | North Sails Group, Inc. | Sail of one piece three dimensional laminated fabric having uninterrupted load bearing yarns |
DE4405331C2 (de) * | 1994-02-21 | 1999-04-01 | Deutsch Zentr Luft & Raumfahrt | Verfahren zur Herstellung eines Keramikbauteils |
US5527609A (en) * | 1994-04-20 | 1996-06-18 | Toyo Boseki Kabushiki Kaisha | Crimped polybenzazole staple fiber and manufacture thereof |
US5552221A (en) * | 1994-12-29 | 1996-09-03 | The Dow Chemical Company | Polybenzazole fibers having improved tensile strength retention |
JPH09228171A (ja) * | 1996-02-19 | 1997-09-02 | Toyobo Co Ltd | 高耐熱混紡糸 |
JPH10110329A (ja) * | 1996-10-01 | 1998-04-28 | Toyobo Co Ltd | ポリベンザゾール繊維およびその製造方法 |
US6335419B2 (en) * | 1999-12-06 | 2002-01-01 | Toyo Boseki Kabushiki Kaisha | Polybenzazole and fiber thereof |
AU2001252627B2 (en) * | 2000-04-28 | 2004-10-21 | Toyo Boseki Kabushiki Kaisha | Polybenzasol fiber and use of the same |
JP2005016839A (ja) * | 2003-06-26 | 2005-01-20 | Ishikawajima Harima Heavy Ind Co Ltd | 火炎検出装置 |
JP4332780B2 (ja) * | 2003-06-30 | 2009-09-16 | ソニー株式会社 | 表示装置 |
JP2005179852A (ja) * | 2003-12-22 | 2005-07-07 | Toyobo Co Ltd | 高強度繊維ロープ |
JP2005179850A (ja) * | 2003-12-22 | 2005-07-07 | Toyobo Co Ltd | セールクロス |
US7189346B2 (en) * | 2004-07-22 | 2007-03-13 | E. I. Du Pont De Nemours And Company | Polybenzazole fibers and processes for their preparation |
-
2003
- 2003-06-26 KR KR10-2004-7021071A patent/KR20050013241A/ko not_active Application Discontinuation
- 2003-06-26 US US10/517,832 patent/US7357982B2/en not_active Expired - Fee Related
- 2003-06-26 EP EP03761809A patent/EP1541726B1/en not_active Expired - Lifetime
- 2003-06-26 CA CA002490025A patent/CA2490025A1/en not_active Abandoned
- 2003-06-26 AT AT03761809T patent/ATE409761T1/de not_active IP Right Cessation
- 2003-06-26 AU AU2003244068A patent/AU2003244068A1/en not_active Abandoned
- 2003-06-26 CN CNB03815112XA patent/CN1301352C/zh not_active Expired - Fee Related
- 2003-06-26 WO PCT/JP2003/008066 patent/WO2004003272A1/ja active IP Right Grant
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0827623A (ja) * | 1994-07-13 | 1996-01-30 | Toyobo Co Ltd | ポリベンザゾール繊維及び繊維布帛 |
WO1996010661A1 (en) * | 1994-09-30 | 1996-04-11 | The Dow Chemical Company | Process for the preparation of polybenzazole filaments and fibres |
JPH11228820A (ja) * | 1998-02-19 | 1999-08-24 | Toyobo Co Ltd | ポリベンザゾール組成物、繊維およびフィルム |
JP2001011311A (ja) * | 1999-06-30 | 2001-01-16 | Toyobo Co Ltd | 耐光性ポリベンザゾール組成物、その繊維およびフィルム |
JP2001172845A (ja) * | 1999-12-17 | 2001-06-26 | Toyobo Co Ltd | 耐光性に優れた耐熱・難燃織編物 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7189346B2 (en) | 2004-07-22 | 2007-03-13 | E. I. Du Pont De Nemours And Company | Polybenzazole fibers and processes for their preparation |
Also Published As
Publication number | Publication date |
---|---|
CN1301352C (zh) | 2007-02-21 |
EP1541726A1 (en) | 2005-06-15 |
EP1541726B1 (en) | 2008-10-01 |
CN1665973A (zh) | 2005-09-07 |
AU2003244068A1 (en) | 2004-01-19 |
ATE409761T1 (de) | 2008-10-15 |
EP1541726A4 (en) | 2006-08-16 |
CA2490025A1 (en) | 2004-01-08 |
US7357982B2 (en) | 2008-04-15 |
KR20050013241A (ko) | 2005-02-03 |
US20060083923A1 (en) | 2006-04-20 |
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