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WO1999048970A1 - Composition d'elastomere renforce de fibres de polyamide et procede de production - Google Patents

Composition d'elastomere renforce de fibres de polyamide et procede de production Download PDF

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Publication number
WO1999048970A1
WO1999048970A1 PCT/JP1998/001280 JP9801280W WO9948970A1 WO 1999048970 A1 WO1999048970 A1 WO 1999048970A1 JP 9801280 W JP9801280 W JP 9801280W WO 9948970 A1 WO9948970 A1 WO 9948970A1
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WIPO (PCT)
Prior art keywords
weight
parts
component
polyamide
polyamide fiber
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP1998/001280
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English (en)
Japanese (ja)
Inventor
Shinji Yamamoto
Hideo Kurihara
Kimio Nakayama
Yukihiko Asano
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Ube Corp
Original Assignee
Ube Industries Ltd
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Filing date
Publication date
Application filed by Ube Industries Ltd filed Critical Ube Industries Ltd
Priority to JP54803999A priority Critical patent/JP3453760B2/ja
Priority to PCT/JP1998/001280 priority patent/WO1999048970A1/fr
Publication of WO1999048970A1 publication Critical patent/WO1999048970A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2321/00—Characterised by the use of unspecified rubbers

Definitions

  • the present invention relates to a polyamide fiber reinforced elastic composition having good workability and excellent modulus, strength and friction performance.
  • the present invention relates to a vulcanized product, a method for producing the elastic composition, and a method for producing a vulcanized product of the elastic composition.
  • the elastic composition and the vulcanizate thereof of the present invention can be used for tire external members such as treads and side walls in tires, and tires such as car power, beads, belts, and chafers. It is preferably used for internal parts, industrial products such as hoses, belts, rubber rolls and rubber crawlers, and footwear.
  • a vulcanizable rubber-like polymer such as natural rubber, isoprene rubber, butadiene rubber, and ethylene propylene rubber to improve the modulus and strength
  • a fiber-reinforced elastic composition has been manufactured by blending short fibers such as nylon, polyester, and vinylon into an elastic resin material, and vulcanizing this as necessary.
  • the fiber-reinforced elastic composition obtained by the above conventional method had insufficient strength and elongation for use as a tire member of an automobile. Therefore, there has been a demand for a fiber-reinforced elastic composition in which these points are improved.
  • a fiber-reinforced elastic composition that meets such demands for example, a fiber-reinforced elastic composition containing fine fibers having an average submicron diameter, such as nylon, has been proposed.
  • vulcanizable Functional rubber, nylon, and a binder are melt-kneaded at a temperature equal to or higher than the melting point of nylon, and the resulting kneaded material is extruded into a string at a temperature equal to or higher than the melting point of nylon.
  • the above-mentioned conventional fiber-reinforced elastic composition is excellent in modulus and strength, and is excellent in workability and durability, but cannot be said to be excellent in friction performance.
  • the use of the conventional fiber-reinforced elastic resin composition for applications such as tires and rolls has been limited to some extent. Disclosure of the invention
  • An object of the present invention is to solve the above-mentioned problems in the prior art, and to provide a polyamide fiber reinforced elastic composition having excellent modulus and strength, and excellent friction performance, a vulcanized product thereof, and a polyamide.
  • the polyamide fiber reinforced elastic composition of the present invention comprises the following components mixed with each other: (a) 100 parts by weight of at least one kind of rubbery polymer having a glass transition temperature of 0 ° C or less,
  • the above-described polyamide fiber-reinforced elastic composition of the present invention can be vulcanized into a vulcanized product.
  • the method for producing a polyamide fiber reinforced elastic composition of the present invention comprises:
  • thermoplastic polyamide containing layered silicate 1 to 70 parts by weight of thermoplastic polyamide containing layered silicate is melt-kneaded
  • the component (a), that is, a part of 100 parts by weight of the rubbery polymer may be used in the step (1), and the remaining amount may be added to the composition obtained in the step (4).
  • a step of performing vulcanization can be added to the above method for producing a polyamide fiber reinforced elastic body.
  • (d) is added to the total of 100 parts by weight of the components (a), (b) and (c). It is preferable that a silane coupling agent is added as a component in a ratio of 0.1 to 5.5 parts by weight.
  • the layered silicate is added in an amount of 0.05 to 30 parts by weight based on 100 parts by weight of the thermoplastic polyamide. It is preferred that they be blended in a proportion of BEST MODE FOR CARRYING OUT THE INVENTION
  • polyamide fiber-reinforced elastic composition of the present invention its vulcanized product, and the production method thereof will be specifically described.
  • the component (a) has a glass transition temperature of 0 ° C or less, preferably at least 20 ° C or less, and at least one kind of rubbery material.
  • Polymer is used.
  • This rubbery polymer is a solid that is elastic at room temperature and in its natural state.
  • Specific examples of the rubbery polymer for the component include natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene'butadiene rubber (SBR), and acrylic rubber.
  • Trinole butadiene rubber NBR
  • butyl rubber 11R
  • chlorinated butyl rubber brominated butyl rubber
  • chloroprene rubber CR
  • acrylonitrile-chloroprene copolymer rubber ATA Lilonitreyl souprene copolymer rubber, acrylate-butadiene copolymer rubber, vinylpyridine-butadiene copolymer rubber, vinylpyridine-styrene-butadiene copolymer rubber, etc.
  • Ethylene rubber ethylene-propylene copolymer rubber (EPR), ethylene-propylene-gene copolymer rubber (EPDM), ethylene-butene copolymer rubber, ethylene Polyolefin rubbers such as butene-gene copolymer rubbers, chlorinated polyethylene rubbers, chlorosulfonated polyethylene rubbers (CSM), acryl rubber, ethylene acryl rubber, Main chain, such as rubber having a polymethylene-type main chain such as trichlorinated trifluorinated rubber and fluororubber, epichlorohydrin rubber, and ethyleneoxydopechlorohydrin copolymer rubber Rubbers containing oxygen atoms, such as silicone rubber such as poly (methylmethylsiloxane) rubber and poly (methylethylsiloxane) rubber, nitroso rubber, polyester urethane rubber, polyether urethane rubber, etc. Rubbers having a carbon atom and an oxygen atom in addition to the carbon atom
  • thermoplastic elastomer Another specific example of the rubbery polymer constituting the component is a thermoplastic elastomer.
  • examples are styrene-butadiene-styrene block copolymer, styrene-ethylene-butylene-styrene block copolymer, styrene-isoprene-styrene block copolymer, Styrene-ethylene-propylene-styrene block copolymer, polyolefin-based thermoplastic elastomer, chlorinated polyolefin-based thermoplastic elastomer, urethane Thermoplastic elastomer, polyester thermoplastic elastomer, 1, 2 — polybutadiene thermoplastic elastomer, trans 1, 4 — polyisoprene thermoplastic elastomer And polyamide-based thermoplastic elastomers, and polyvinyl chloride-based thermoplastic elastomers.
  • the polyolefin resin used as the component (b) preferably has a melting point in the range of 80 to 250 ° C, more preferably 50 ° C or more, and particularly preferably 50 to 200 ° C.
  • a softening point of Can be Preferable examples of the polyolefin resin for the component include homopolymers and copolymers of olefins having 2 to 8 carbon atoms, for example, olefins having 2 to 8 carbon atoms.
  • Copolymer of olefin with vinyl acetate Copolymer of olefin having 2 to 8 carbon atoms with acrylic acid or ester thereof, and copolymer of olefin with 2 to 8 carbon atoms with metaacrylic acid or ester thereof
  • Copolymers and copolymers of a C2-8 carbon olefin and a vinylsilane compound are exemplified.
  • polyolefin resin used as the component examples include high-density polyethylene, low-density polyethylene, linear low-density polyethylene, polypropylene, ethylene-propylene block copolymer, Ethylene-propylene random copolymer, poly (4-methylpentene-1), polybutene-11, polyhexene-1, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-acrylic acid copolymer Polymer, Ethylene monomethyl acrylate copolymer, Ethylene monoacrylate copolymer, Ethylene acrylate copolymer, Ethylene monobutyl acrylate copolymer, Ethylene monoacrylate 2-Ethylhexyl acrylate copolymer, Ethylene-hydroxy acetyl acrylate copolymer, Ethylene-vinyl Li main Tokishishira down copolymer,
  • polyolefin resins particularly preferred are high-density polyethylene (HDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), polypropylene (PP), and ethylene-propylene.
  • HDPE high-density polyethylene
  • LDPE low-density polyethylene
  • LLDPE linear low-density polyethylene
  • PP polypropylene
  • ethylene-propylene ethylene-propylene.
  • Pyrene block copolymer ethylene-propylene random copolymer Body
  • P4MP 1 poly 4-methylidene 1
  • EVA ethylene vinyl acetate copolymer
  • MFI Melt flow index
  • the component (b) may be composed of one kind of polyolefin resin, or may be used in combination of two or more kinds of polyolefin resins.
  • the layered silicate-containing thermoplastic polyamide constituting the component contains the layered silicate dispersed uniformly, and the thermoplastic polyamide is tough by extrusion and stretching or rolling. It is formed in a fibrous form.
  • This thermoplastic polyamide has a temperature in the range of 135-350 ° C, especially 160-265. It preferably has a melting point within the same range as above, and the melting point is higher than the melting point of the polyolefin resin used as the component (b).
  • thermoplastic polyamide for the component examples include Nylon 6, Nylon 66, Nylon 6-Nylon 66 copolymer, Nylon 610, and Nylon 612. , Nylon 46, Nylon 11, Nylon 12, Nylon MX D6, polycondensate of xylylenediamine and adipic acid, xylylenediamine and pimelic acid Polycondensates, polycondensates of xylylenediamine and speric acid, polycondensates of xylylenediamine and azelayic acid, polycondensates of xylylenediamine and sebacic acid, tetramethylenedia Polycondensate of mine and terephthalic acid, polycondensate of hexamethylene diamine and terephthalic acid, polycondensate of octamethylenediamine and terephthalic acid, trimethylhexamethylenediamine and terephthalic acid Polycondensate, decam
  • thermoplastic polyamides particularly preferred are those having a melting point higher by at least 30 ° C. than the polyolefin resin constituting the component (b). More specifically, Nylon 6 (PA6), Nylon 66 (PA66), Nylon 6—Nylon 66 copolymer, Nylon 610, Nylon 612, Nylon 66 Particularly preferred are lon 46, nylon 11 and nylon 12. These thermoplastic polyamides may be used alone or in combination of two or more. It is also preferred that these thermoplastic polyamides have a molecular weight in the range of 10,000 to 200,000.
  • the layered silicate uniformly dispersed and contained in the component (c) is effective for imparting excellent mechanical properties and friction performance to the polyamide resin composition.
  • This layered silicate preferably has a thickness of typically 0.6 to 2 nm and a length of 0.002 to 1 nm.
  • the component (c) of the present invention is characterized in that the lamellar silicate is uniformly dispersed in the thermoplastic polyimide resin while maintaining an average interlayer distance of 2 nm or more.
  • interlayer distance refers to the distance between the centers of gravity of the silicate layers, and "uniformly dispersed” means that at least 50%, preferably at least 70%, of the layered silicate forms aggregates.
  • layered silicate is a fine layer with a length of 1 to 1, OO Onm and a thickness of 0.6 to 2 nm.
  • a layered silicate a layered phyllosilicate mineral composed of layered particles of magnesium silicate or aluminum silicate can be exemplified.
  • the layered silicate is, specifically, Includes smectite-based clay minerals such as limestone, savonite, nontronite, hectorite, and stevensite, as well as bamyculite and harasite. These layered silicates may be natural products or synthetic ones. Of these, it is preferable to use monomoronilonite.
  • a polymer compound is used as a swelling agent, and the interlayer is preliminarily expanded to 10 nm or more, and this is melt-kneaded with a polyamide resin or a resin containing the same to uniformly disperse them. Is also good.
  • the proportion of the layered silicate is preferably 0.05 to 30 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the polyamide component. When the compounding ratio of the layered silicate is less than 0.05 parts by weight, the rigidity and heat resistance of the obtained molded article are reduced, and when it exceeds 30 parts by weight, the fluidity of the resin composition is reduced. It is not preferable because it drops extremely.
  • the swelling agent examples include amino acid and nylon salt. Specific examples thereof include ⁇ -amino decanoic acid, ⁇ -amino dodecanoic acid, and salts composed of equimolar amounts of diamine and dicarboxylic acid, for example, tetramethylenediammonium. There are mupaipite, hexamethylene diammonium salt, and nylon salt composed of hexamethylene diammonium sebacate.
  • the silane coupling agent used as the component (d) is a binder that binds the components (a), (b) and (c) to each other.
  • a specific example of this silane coupling agent is vinyl trimethoxy siloxane.
  • vinyl trimethoxy siloxane Lan, vinyl triethoxyquin silane, vinyl tris ( ⁇ -methoxhetoxy) silane, vinyl triacetyl silane, alpha-methacryloxyprovir trimethoxy lan, ⁇ — (3 , 4—Epoxycyclohexyl) ethyl trimethoxysilane, ⁇ -glycidoxypropyl trimethoxysilane, ⁇ -glycidoxypropyl dimethyldimethyxylane, ⁇ -glycidoxypropyl methylethyl ethoxysilane, ⁇ Glycidoxypropyl pyrethyldimethoxysilane, y—Glycidoxypropyl
  • the amount of the silane coupling agent is preferably from 0.1 to 5.5 parts by weight, particularly preferably 100 parts by weight of the total of the components (a), (b) and (c). Is from 0.2 to 3.0 parts by weight. If the content of the silane coupling agent is less than 0.1 part by weight, the mutual bonding of the components (a), (b) and (c) becomes insufficient, so that the composition having a high strength is obtained. May not be obtained. If the content exceeds 5.5 parts by weight, it becomes difficult for the polyamide in the component (c) to form a fine fiber structure, so that a composition having excellent modulus (elastic modulus) can be obtained. Difficult It may be.
  • An organic peroxide can be used in combination with the silane coupling agent used as the component.
  • radicals are formed on the molecular chains of the component (a), component (b) and component (c) resins, which react with the silane coupling agent to form the component (a),
  • the mutual bonding of the component (b) and the component (c) resin is promoted, and in this case, the component (a), the component (b) and the component (c) are mutually bonded at the interface.
  • the half-life temperature for one minute is from the same temperature as the melting point of component (a) or the higher of the melting point of component (c), whichever is higher, to a temperature about 30 ° C higher than this temperature.
  • an organic peroxide having a half-life temperature of about 110 to 250 ° C. for one minute is preferably used.
  • the amount of the organic peroxide used at this time is preferably in the range of 0.01 to 1.0 part by weight based on 100 parts by weight of the component (b).
  • organic peroxide used in the present invention include 1,1-di_t_butylperoxy-1,3,5—trimethylcyclohexane and 1,1-di-t-butylperoxy.
  • the one-minute half-life temperature is the melting kneading temperature or Those having a temperature range of about 30 ° C higher than the above temperature, specifically, those having a one-minute half-life temperature of about 80 to 250 ° C are preferably used.
  • the mixing ratios of the components (a), (b) and (c) are as follows.
  • the polyolefin resin of the component (b) is contained in an amount of 1 to 40 parts by weight, preferably 2 to 30 parts by weight, based on 100 parts by weight of the component (a). If the content of the component (b) is less than 1 part by weight, it is difficult to form the obtained fiber-reinforced elastic composition, for example, into a pellet, and it is difficult to form the composition in the arrangement direction of the polyamide fibers. It is not preferable because the physical properties in the direction at right angles decrease.
  • the component (c) is contained in a proportion of 1 to 70 parts by weight, preferably 1 to 60 parts by weight, per 100 parts by weight of the component (a). If the proportion of the component (c) is less than 1 part by weight, the resulting composition will have insufficient modulus and braking performance. On the other hand, when the content of the component (c) exceeds 70 parts by weight, the resulting fiber-reinforced elastic body has insufficient elongation. Most of the component (c) is finely dispersed in the matrix composed of the components (a), (b) and (d) as fine fibers.
  • the component (c) is dispersed in the matrix as fine fibers.
  • the average fiber diameter of the dispersed fibers is preferably 1 m or less, and the aspect ratio (the ratio of the fiber length Z average fiber diameter) is preferably 20 or more and 1,000 or less. In this case, the dispersibility of the c-component fiber is improved.
  • the component (a), the component (b), and the component (c) are mutually bonded at each interface.
  • the method for producing the polyamide fiber reinforced elastic composition of the present invention is described below.
  • the method of the present invention comprises the following steps (1) to (4) and optionally (5).
  • thermoplastic polyamide in which the layered silicate of the component (c) is dispersed are kneaded at a temperature not lower than the melting point of the thermoplastic polyamide.
  • thermoplastic polyimide (c) preferably at a temperature higher by 10 ° C or more than the melting point
  • the melting point may be lower than the melting point.
  • step (1) when only a part of the component (a) is used, the remainder of the component (a) is used as the composition obtained in the step (4). To obtain a polyamide fiber reinforced elastic composition. When all of the component (a) is used in the step (1), the step (5) is unnecessary.
  • Step (1) All or part of the rubbery polymer having a glass transition temperature of component (a) of 0 ° C or less and the polyolefin of component (b), and the silane coupling of component (d) Melt-knead with the ingredients to prepare a matrix of component (a) and component (b).
  • the kneading temperature is equal to or higher than the melting point of the component (b), and is preferably 10 ° C or higher than this melting point.
  • this kneading is performed at a temperature higher than the melting point of the component (b) by 10 ° C. or more, the components (a) and (b) react with the silane coupling agent (d) to form a reactive matrix. Form a box.
  • an apparatus usually used for kneading resin and rubber can be used.
  • a Banbury type mixer, a kneader, a nickle extruder, an open mouth, a single-screw kneader, a twin-screw kneader, and the like are used. These devices are also used in the steps after step (1).
  • Step (2) The above reaction matrix is kneaded at a temperature higher than the melting point of the thermoplastic polyamide by kneading a composite of the thermoplastic polyamide in which the layered silicate of the component (c) is dispersed.
  • a modified kneading composition is produced.
  • the temperature at which the component (c) is melt-kneaded is at least the melting point of the polyamide of the component (c), preferably at least 10 ° C higher than the melting point.
  • the component (c) is dispersed in the molten matrix composed of the components (a), (b) and (d) by forming fine spherical particles.
  • Step (3) extruding the above chemically modified kneaded product from a die at a temperature equal to or higher than the melting point of component (c) (preferably, a temperature higher than the melting point by at least 10 ° C) to form a shape that can be subjected to stretching or rolling.
  • the chemically modified melt-kneaded product is extruded from a spinneret, an inflation die or a T-die.
  • This extrusion step (3) is performed at a temperature higher than the melting point of the thermoplastic polyamide of the component (c).
  • the heat treatment is carried out at a temperature higher than the melting point of the thermoplastic polyamide (c), preferably at a temperature higher than 10 ° C. Even if extruded below the melting point of the thermoplastic polyamide of the component (c), the fused particles of the polyamide of the component (c) cannot be made into fine fibers.
  • Step (4) Extrudate at a temperature lower than the melting point of component (c) And stretch or roll while drafting.
  • the extruded filaments are continuously cooled or cooled to a temperature lower than the melting point of the component (C) and stretched or rolled.
  • the stretching or rolling treatment is performed at a temperature lower than the melting point of the component (C).
  • a tough polyamide fiber that reinforces the elastic body composition is formed.
  • the kneaded material is extruded from a spinneret and spun into a string or thread, cooled, wound around a bobbin or the like while drafting, or cut into a beret. It is carried out by such a method.
  • the ratio of the take-up speed / the die speed is preferably in the range of 1.5 to 100, more preferably in the range of 2 to 50, and particularly preferably in the range of 3 to 30. .
  • each of the processes (1), (2), (3) and (4) has been described for each process, but the components (a), (b), (c) and (d) And a first supply port, a second supply port, a third supply port, a fourth supply port, etc., capable of supplying an organic peroxide or the like as necessary, and a first kneading for kneading the parentheses. It is also possible to perform continuous treatment using a twin-screw extruder having a band, a second kneading band, a third kneading band, a fourth kneading band, and the like. By doing so, the production method of the present invention can be implemented more economically and more stably.
  • Step (5) In the step (1), when only a part of the component (a) is used in an amount of 100 parts by weight, the residual component of the component (a) is contained in the composition obtained in the step (4). It is added and kneaded.
  • the residual amount of the component (a) used in the step (5) may be the same as the part of the component (a) used in the step (1), or may be a glass of 0 ° C or lower. A different kind of rubbery polymer having a transition temperature may be used.
  • 0.05 to 70 parts by weight of 100 parts by weight of the component (a) is used in step (1), and the remaining 30 to 99.5 parts by weight is used in step (5). Is preferred.
  • the residual amount of the component (a) used in step (5) shall be no more than 120 weight of the polyamide fiber reinforced elastic composition (product of step (4)) to which it is added. And more preferably 110 to 1 Z0.5. This facilitates the kneading operation.
  • the polyamide fiber reinforced elastic composition of the present invention can be made into a vulcanizate by vulcanization.
  • This vulcanization can be performed by the following method.
  • a predetermined amount of carbon black, process oil, antioxidant, zinc white, stearic acid, and other primary additives are added to the above-mentioned polyamide fiber reinforced elastic composition while kneading it. Knead.
  • a device used for the compounding of ordinary rubber for example, a device such as a Plavender plaster, a roll, and a Banbury mixer.
  • a vulcanizing agent such as sulfur and a vulcanization accelerator are added to the kneaded material on an open roll, and the mixture is further kneaded.
  • the kneaded material is compressed using a compression molding machine, an extruder, an injection molding machine, or the like. Molding, heating and vulcanizing.
  • a vulcanized product of the polyamide fiber-reinforced elastic composition of the present invention is obtained.
  • the component (a) and the component (b) mainly form a matrix, and the component (c) is contained in the matrix.
  • the fine fibers of the composite of the layered silicate and the polyamide are uniformly dispersed, and the components (a) and (b) and the fine fibers of the layered silicate-dispersed polyamide are (d) ) They are firmly bound to each other at their interface via the component silane coupling agent. And, by this structure, a fiber reinforcing effect is exhibited.
  • the fiber reinforced resin composition in the step (5) and the residue added thereto The kneading temperature of the amount of the component (a) is lower than the melting point of the thermoplastic polyamide of the component (c) constituting the fine short fibers in the fiber-reinforced resin composition.
  • the temperature may be higher than the melting point of the component polyolefin. If kneading is performed at a temperature higher than the melting point of the thermoplastic polyamide in step (5), fine short fibers in the fiber-reinforced resin composition are dissolved and deformed into spherical particles. It is not desirable because there is. Also, if kneading at a temperature lower than the melting point of the polyolefin resin of component (b), the uniformity of the dispersion of the polyamide fibers becomes insufficient, so that the target strength and elongation may not be obtained. is there. Specifically, it is preferable to use a temperature that is 20 ° C lower than the melting point of the thermoplastic polyamide of the component (c) and 10 ° C higher than the melting point of the polyolefin of the component (b). .
  • the fiber-reinforced resin composition to be subjected to the step (5) preferably has a pellet shape.
  • the fiber reinforced resin composition is kneaded uniformly with the addition of the component (a), and is a polyamide fiber in which fine fibers are uniformly dispersed. A reinforced elastic composition is easily obtained.
  • carbon black, process oil, zinc white, stearic acid, and an antioxidant may be added and kneaded.
  • the temperature of the kneaded material rises, but the temperature is controlled as necessary so that it does not become higher than the melting point of the thermoplastic polyimide of the component (c).
  • the kneading temperature is preferably from 160 to 180 ° C, and the kneading time is preferably from 1 to 5 minutes.
  • the required amounts of various vulcanizing agents and vulcanizing aids may be kneaded together or sequentially at room temperature to 100 ° C.
  • the sufficiently kneaded and dispersed composition is drawn out in a sheet form.
  • the obtained sheet is molded and vulcanized to obtain a vulcanized fiber-reinforced elastic body.
  • the amount of the vulcanizing agent is preferably 0.1 to 5.0 parts by weight, more preferably 0.5 to 3.0 parts by weight, based on 100 parts by weight of the total amount of the component (a).
  • the amount of the vulcanization aid is preferably 0.01 to 2.0 parts by weight, particularly 0.1 to 1.0 part by weight, based on 100 parts by weight of the total amount of the component (a). Is more preferable.
  • known vulcanizing agents such as sulfur, organic peroxides, resin vulcanizing agents, and metal oxides such as magnesium oxide can be used as the vulcanizing agent.
  • vulcanization aids include aldehyde 'ammonia, aldehyde amines, guanidines, thioureas, thiazols, thiurams, dithiolbamates and xanthates. Can be used ⁇
  • the vulcanization temperature is preferably about 100 to 180 ° C. .
  • the vulcanization temperature must be lower than the melting point of the thermoplastic resin constituting the fine fibers in the polyamide fiber reinforced elastic composition. If vulcanization is performed at a temperature equal to or higher than the melting point of the thermoplastic resin, the fibers formed during the preparation of the fiber reinforced resin composition will be dissolved, and the polyamide fiber reinforced elastic material having a high modulus will be dissolved. You will not be able to get things.
  • the polyamide fiber reinforced elastic composition of the present invention further comprises, in addition to the above components, carbon black, white carbon, activated calcium carbonate, ultrafine magnesium silicate, high styrene resin, and phenol.
  • Auxiliaries such as resin, lignin, denatured melamine resin, coumalonindene resin, petroleum resin, calcium carbonate, basic magnesium carbonate, clay, zinc oxide, diatomaceous earth, recycled rubber, powdered rubber,
  • Various fillers such as ebonite powder, amine aldehydes, amines' ketones, amines, phenols, imidazoles, sulfur-containing antioxidants, including It may contain a stabilizer such as a phosphorus-based antioxidant, and various pigments.
  • Organic composite montmorillonite content (%) w / (aXb) w; Burning residual weight% a; Inorganic content ratio converted to organic content (0.791) b; Inorganic content ratio converted to crystal water (0.9462) )
  • each unit has an average width of 0.95 nm and a length of about 100 rnn.
  • 100 g of montmorillonite and 10 liters of distilled water were added, and montmorillonite was dispersed in water. While maintaining the dispersion at 35 ° C., 51.2 g of 12-aminododecanoic acid and 24 milliliters of concentrated hydrochloric acid were added thereto, and the mixture was stirred for 5 minutes. Was. Further, the particles were washed with water until the filtrate became neutral, and then collected by filtration, followed by vacuum drying at 80 ° C for 48 hours.
  • montmorillonite complex a complex of 12-aminododecanoate ion and montmorillonite (hereinafter referred to as montmorillonite complex) was prepared.
  • the layered silicate content in the composite was about 80%.
  • 10 kg of ⁇ -force prolactam, 1 kg of distilled water and 180 g of the montmorillonite complex were placed in the reactor and stirred at 100 ° C. so that the reaction system became uniform.
  • the temperature was further increased to 260 ° C, and the mixture was stirred for 1 hour under a pressure of 15 kgZcm 2 (pressurized with nitrogen). Thereafter, the reaction mixture was returned to normal pressure and reacted at 260 ° C. for 3 hours.
  • the reaction mixture was taken out from the lower nozzle of the reaction vessel in a strand form, cooled with water, and subjected to polyamide (average).
  • a pellet consisting of a molecular weight of 15,000) and montmorillonite particles was obtained.
  • the pellet was immersed in hot water at 90 ° C to extract and remove unreacted monomers and oligosaccharides, and vacuum dried at 90 ° C for 48 hours.
  • the obtained layered silicate-containing polyamide (monmorinite nitride composite nylon 6) was ignited to 650 ° C, and the content of the montmorillonite composite was determined from the burning residual weight. When measured, it was 2.0% I got it. Table 1 shows the results.
  • component as natural rubber (SRM-100 parts by weight, (b) Component as low density polyethylene (Ube Industries, F522, melting point 110 ° C, melt flow index 5g / 10min) 100 parts by weight, 1.5 parts by weight of 7- methacryloxypropyl trimethoxysilane as component (d) is melt-kneaded with Banbury type mixer at 110 ° C which is higher than the melting point of component (b).
  • a silane-modified matrix was prepared, dumped at a temperature of 170 ° C., and pelletized.200 parts by weight of the pellet and those used in Reference Example 1 And 50 parts by weight of the component (c), which is composed of the same compound as the montmornite-nitrite composite nylon 6, is mixed with a twin-screw extruder heated to 250 ° C. The mixture was kneaded, extruded in the form of a strand from a nozzle, taken up at a draft ratio of 20 at room temperature, and pelletized using these pelletizers.
  • the fiber-reinforced resin was the same as in Reference Example 5, except that the component Montmorillonite Composite Nylon 6 was not used, and instead, Nylon 650 was used in an amount of 50 parts by weight. A composition was obtained. Table 2 shows the evaluation results. Table 2
  • Example 2 the fiber reinforced resin composition of Reference Example 5, 10, 15, 25 or 50 parts by weight, and (a) 96, 94, 90 or 80 parts by weight of the additional component Except for using it, the others were blended and vulcanized in the same manner as in Example 1 to obtain a vulcanized polyamide fiber reinforced elastic composition.
  • the blend viscosity and the physical properties of the vulcanizate were measured. The results are shown in Table 3.
  • the compound was compounded and vulcanized in the same manner as in Example 1 except that the fiber-reinforced resin composition of Reference Example 5 was not used and only natural rubber was used. Table 3 shows the results. The dynamic friction coefficient of this vulcanizate was low and inferior.
  • Comparative Examples 2 and 3 240 parts by weight of Reference Example 6 or 120 parts by weight of Reference Example 7 were used as the fiber reinforced resin composition, and the amount of natural rubber added was 20 or 80 parts by weight. Other parts were blended and vulcanized in the same manner as in Example 1 except that they were used as parts. Table 3 shows the results. The obtained vulcanizate was small in elongation with low elongation and low abrasion resistance.
  • the fiber reinforced resin composition was not blended, and in the same manner as in Example 6 or 7, as an additional component (a), 70 or 60 parts by weight of natural rubber, and 30 parts by weight of butadiene rubber were used.
  • a vulcanizate of an elastic composition was prepared in the same manner as in Example 4 except that 40 parts by weight or 40 parts by weight was used. Table 5 shows the results. The tensile modulus of the obtained vulcanizate was small and inferior.
  • Example 8 to 12 9, 10, 10, 10 or 10 parts by weight of the fiber-reinforced resin composition of Reference Example 6, 7, 8, 9, 10, or 11 and (a) an additional component.
  • a vulcanizate of an elastic composition was prepared in the same manner as in Example 6, except that 97, 97.5, 97, 97 or 97 parts by weight of natural rubber was used. Table 5 shows the results. Comparative Example 6
  • Elastic body composition was the same as in Example 6, except that 25 parts by weight of the fiber-reinforced resin composition of Reference Example 11 and 90 parts by weight of natural rubber were used as an additional component (a).
  • a vulcanizate was prepared. Table 5 shows the results. The dynamic coefficient of friction of the obtained vulcanizate was small and inferior.
  • the polyamide fiber reinforced elastic composition of the present invention is a fiber reinforced elastic body in which fine fibers of thermoplastic polyamide are dispersed in a matrix containing a rubbery polymer and polyolefin. Since the layered silicate is micro-dispersed in the fine fibers of this polyamide, the composition of the present invention has good workability and excellent tensile strength and elastic modulus. Furthermore, it is particularly excellent in the balance between wear resistance and friction performance.
  • the polyamide fiber reinforced elastic composition of the present invention is suitable for applications such as tires, mouthpieces, flooring materials and footwear.

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Abstract

La présente invention concerne une composition d'élastomère renforcé de fibres de polyamide se distinguant par son aptitude au traitement, par sa durabilité, ainsi que par son module élastique. Cette composition comprend (a) 100 parties en poids d'au moins un polymère caoutchouteux dont la température de transition vitreuse n'excède pas 0 °C, (b) de 1 à 40 parties en poids de polyoléfine, (c) de 1 à 70 parties en poids d'une fibre polyamide thermoplastique contenant un silicate en couche, et (d) d'un agent de pontage à base de silane. Cette composition se prête particulièrement bien à la vulcanisation.
PCT/JP1998/001280 1998-03-24 1998-03-24 Composition d'elastomere renforce de fibres de polyamide et procede de production Ceased WO1999048970A1 (fr)

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JP54803999A JP3453760B2 (ja) 1998-03-24 1998-03-24 ポリアミド繊維強化弾性体組成物及びその製造方法
PCT/JP1998/001280 WO1999048970A1 (fr) 1998-03-24 1998-03-24 Composition d'elastomere renforce de fibres de polyamide et procede de production

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8523823B2 (en) 2002-02-14 2013-09-03 Ishay Ostfeld Indwelling device
WO2014192855A1 (fr) * 2013-05-31 2014-12-04 住友理工株式会社 Composition de résine pour durites pour automobiles et durites pour automobiles l'utilisant

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6274957A (ja) * 1985-09-30 1987-04-06 Toyota Central Res & Dev Lab Inc 複合材料およびその製造方法
JPH07278360A (ja) * 1994-04-08 1995-10-24 Ube Ind Ltd 繊維強化弾性体及びその製造方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6274957A (ja) * 1985-09-30 1987-04-06 Toyota Central Res & Dev Lab Inc 複合材料およびその製造方法
JPH07278360A (ja) * 1994-04-08 1995-10-24 Ube Ind Ltd 繊維強化弾性体及びその製造方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8523823B2 (en) 2002-02-14 2013-09-03 Ishay Ostfeld Indwelling device
WO2014192855A1 (fr) * 2013-05-31 2014-12-04 住友理工株式会社 Composition de résine pour durites pour automobiles et durites pour automobiles l'utilisant
JP2014234405A (ja) * 2013-05-31 2014-12-15 住友理工株式会社 自動車用チューブ樹脂組成物およびそれを用いた自動車用チューブ

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