WO1999048973A1 - Composition de resine renforcee par des fibres de polyamide et procede de fabrication associe - Google Patents

Composition de resine renforcee par des fibres de polyamide et procede de fabrication associe Download PDF

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Publication number
WO1999048973A1
WO1999048973A1 PCT/JP1998/001216 JP9801216W WO9948973A1 WO 1999048973 A1 WO1999048973 A1 WO 1999048973A1 JP 9801216 W JP9801216 W JP 9801216W WO 9948973 A1 WO9948973 A1 WO 9948973A1
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Prior art keywords
weight
parts
polyamide
component
layered silicate
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PCT/JP1998/001216
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English (en)
Japanese (ja)
Inventor
Shinji Yamamoto
Hideo Kurihara
Kimio Nakayama
Yukihiko Asano
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Ube Industries, Ltd.
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Priority to PCT/JP1998/001216 priority Critical patent/WO1999048973A1/fr
Publication of WO1999048973A1 publication Critical patent/WO1999048973A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers

Definitions

  • the present invention relates to a polyamide fiber reinforced resin composition and a method for producing the same. More specifically, the present invention provides a resin matrix containing a polyolefin resin and a rubbery polymer, in which a fibrous polyamide containing a layered silicate is dispersed and captured. The present invention relates to a polyamide fiber reinforced resin composition and a method for producing the same. Background art
  • Rubber-like polymers have been used as various rubber products because of their high recovery elastic modulus and low elastic modulus.
  • the demands have become increasingly higher, such as those with a higher recovery modulus but a slightly higher modulus, and those with a higher modulus and higher durability.
  • Even in the resin field, a material with high elastic modulus, light strength, and high impact resistance has been required.
  • a fiber reinforced composition in which fine polyamide fibers are dispersed in a polyolefin and a rubber-like polymer is disclosed in JP-A-7-238189. Since it is obtained in the form of pellets with an average fiber diameter of 1 / m or less, it is easy to handle and is suitably used as a reinforcing agent for resins and rubber-like polymers. However, in fields such as tires, rolls, and footwear, friction performance is also required. Disclosure of the invention
  • the present invention solves the above-mentioned problems of the prior art, and has excellent rigidity and strength.
  • Another object of the present invention is to provide a polyamide fiber reinforced resin composition having excellent friction performance and a method for producing the same.
  • the polyamide fiber reinforced resin composition of the present invention comprises the following components mixed with each other;
  • the method for producing the polyamide fiber reinforced resin composition of the present invention comprises the steps of (a) 100 parts by weight of a polyolefin resin, and (b) 100 to 400 parts by weight of a rubbery polymer having a glass transition temperature of 0 ° C. or less. And (d) the silane coupling agent is melt-kneaded to form a molten matrix, and the molten matrix is mixed with (c) the layered silicate-containing thermoplastic polyamide. 10 to 400 parts by weight are mixed at a temperature equal to or higher than the melting temperature of the thermoplastic polymer, and the molten mixture is extruded to a temperature lower than the melting point of the thermoplastic polymer (c). In the matrix comprising the mixture of the other components (a) and (b), the layered silicate-containing thermoplastic polyamide is dispersed in a fibrous form. Including this.
  • the silane coupling agent (d) is used based on a total of 100 parts by weight of the components (a), (b) and (c). However, it is preferable that the content is 0.1 to 5.5 parts by weight.
  • the polyamide fiber reinforced resin composition of the present invention and a method for producing the same
  • the layered silicate is blended at a ratio of 0.05 to 30 parts by weight with respect to 100 parts by weight of the thermoplastic polymer.
  • the polyolefin resin preferably has a melting point in the range of 80 to 250 ° C, more preferably 50 ° C or more, and particularly preferably 50 to 50 ° C. Those having a vicat softening point of 200 ° C can also be used.
  • the polyolefin resin (a) include homopolymers and copolymers of olefins having 2 to 8 carbon atoms, for example, olefins having 2 to 8 carbon atoms and styrene, Copolymers with aromatic vinyl compounds such as chlorostyrene and monomethylstyrene; copolymers of C2 to C8 olefins with vinyl acetate; C2 to C8 olefins and acrylates Copolymers of acrylic acid or its esters, copolymers of C2 to C8 olefins and methacrylic acid or its esters, and C2 to C8 olefins and vinyl Copolymers with a lucirane compound are exemplified.
  • polyolefin resin used as the component examples include high-density polyethylene, low-density polyethylene, linear low-density polyethylene, polypropylene, and ethylene-propylene block.
  • Copolymer ethylene-propylene random copolymer, poly (4-methylpentene-11), polybutene-11, polyhexene-11, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer Copolymer, ethylene-acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid propylene copolymer, ethylene-acrylic acid Acid butyl copolymer, ethylene-acrylate 2-ethylhexyl acrylate copolymer, ethylene-hydroxyhexyl acrylate copolymer, ethylene-vinyl trimethoxy silane copolymer, ethylene-vinyl tri
  • polyolefin resin used as the component ( a ) there may be mentioned a polyolefin resin such as chlorinated polyethylene, brominated polyethylene, and chlorosulfonated polyolefin. Is mentioned.
  • polyolefin resins particularly preferred are high-density polyethylene (HDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and polypropylene (LPE).
  • HDPE high-density polyethylene
  • LDPE low-density polyethylene
  • LLDPE linear low-density polyethylene
  • PP polypropylene
  • PP ethylene-propylene block copolymer
  • ethylene-propylene random copolymer ethylene-propylene random copolymer
  • P4MP1 poly4-methylpentene 1
  • EVA ethylene-vinyl acetate copolymer
  • Alcohol-copolymers and among them, those having a Menoletov Mouth Index (MFI) force of 0.2 to 50 g / 10 minutes are the most preferable.
  • MFI Menoletov Mouth Index
  • the component (a) may be composed of one kind of polyolefin resin, or may be used in combination of
  • the glass transition temperature is 0 ° C or less, preferably —2
  • a rubbery polymer of 0 ° C or less is used.
  • Specific examples of the rubbery polymer for components include natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene'butadiene rubber (SBR), and acrylonitrile.
  • NR natural rubber
  • IR isoprene rubber
  • BR butadiene rubber
  • SBR styrene'butadiene rubber
  • NBR Nore butadiene rubber
  • NBR butyl rubber
  • chlorinated butyl rubber brominated butyl rubber, chlorobrene rubber (CR), acrylonitrile monocrop copolymer rubber, acrylonitrile copolymer rubber, acrylyl Tobutage Rubbers such as ethylene copolymer rubber, vinyl pyridine-butadiene copolymer rubber, vinyl pyridine-styrene copolymer rubber, etc.
  • EPR Ethylene propylene copolymer rubber
  • EPDM Ethylene butene copolymer rubber
  • Ethylene butene copolymer rubber Chlorinated polyethylene rubber
  • Polyolefin rubbers such as chlorosulfonated polyethylene rubber (CSM), acryl rubber, ethylene acryl rubber, polychlorinated trifluorinated rubber, and fluorinated rubber Rubbers having oxygen atoms in the main chain, such as rubbers having a polymethylene-type main chain, such as rubber, epichlorohydrin rubber, and ethyleneoxy-epichlorohydrin copolymer rubber.
  • Rubber in the main chain such as silicone rubber such as polyvinylmethylsiloxane rubber and polymethylethylsiloxane rubber, dinitro rubber, polyester urethane rubber, and polyether urethane rubber. Rubbers having nitrogen atoms and oxygen atoms in addition to carbon atoms are included. Epoxy-modified, silane-modified, or maleated rubbers of these rubbers may be used as component (b).
  • thermoplastic elastomer styrene-butadiene-styrene block copolymer, styrene-ethylene block styrene-styrene block copolymer, styrene-isoprene-styrene block copolymer Polymers, styrene-ethylene-propylene-styrene-block copolymers, polyolefin-based thermoplastic elastomers, chlorinated polyolefin-based thermoplastic elastomers, Thermoplastic elastomer, Polyester thermoplastic elastomer 1, 1, 2 —Polybutadiene thermoplastic elastomer, Transform 1,4,1-Polyisoprene thermoplastic Plastic elastomers, polyamide thermoplastic elastomers, polyvinyl chloride thermoplastic elastomers and the like can be mentioned.
  • the layered silicate-containing thermoplastic polyamide constituting the component contains the layered silicate uniformly dispersed therein, and the thermoplastic polyamide is tough by extrusion and stretching or rolling. It is formed in a fibrous form.
  • the melting point of the thermoplastic polyamide is preferably in the range of 135 to 350 ° C, particularly preferably in the range of 160 to 265 ° C.
  • thermoplastic polyamide for the component examples include Nylon 6, Nylon 66, Nylon 6-Nylon 66 copolymer, and Nylon 610. , Nylon 61 2, Nylon 46, Nylon 11, Nylon 12, Nylon MXD 6, Polycondensate of xylylenediamine and adipic acid, xylylenediamine Polycondensate of xylylenediamine and sperinic acid, polycondensate of xylylenediamine and azearic acid, xylylenediamine Polycondensate of terephthalene diamine and terephthalic acid, polycondensate of hexamethylene diamine and terephthalic acid, polycondensate of octamethylenediamine and terephthalic acid, trimethyl Hexamethylenediamine and terephthalic acid polycondensate Polycondensate of decamethylenediamine and terephthalic acid, polycondensate
  • thermoplastic polyamides particularly preferred ones have a melting point higher than that of the constituent polyolefin resin by 30 ° C or more.
  • Nylon 6 (PA 6) 66 (PA66) Nylon 6—Nylon 66 copolymer
  • Nylon 61, Nylon 61, Nylon 46, Nylon 11 and Nylon 1 and 2 are particularly preferred.
  • These thermoplastic polyamides may be used alone or in combination of two or more. It is also preferable that these thermoplastic polyamides have a molecular weight in the range of 100,000 to 200,000.
  • the layered silicate uniformly dispersed and contained in the component is effective in imparting excellent mechanical properties and frictional properties to the polyamide resin composition.
  • the phyllosilicate particles preferably have a thickness of usually 0.6 to 2 nm and a length of 2 to 1,000 nm.
  • the component (c) of the present invention is characterized in that the layered silicate is uniformly dispersed in the thermoplastic polyamide while maintaining an average interlayer distance of 2 nm or more.
  • inter-brows distance refers to the distance between the plate-shaped centers of gravity of the silicate layer, and “uniformly dispersed” refers to 50% or more, preferably 70% or more of the layered silicate.
  • the layered silicate is a fine layer having a length of 2 to 100 nm and a thickness of 0.6 to 2 nm.
  • a layered silicate include a layered phyllosilicate mineral composed of layered particles of magnesium silicate or aluminum silicate.
  • Layered silicates include, specifically, smectite clay minerals such as montmorillonite, savonite, nontronite, hectrite, and stevensite, as well as bamiyucurite and harasite. Is included. These layered silicates may be natural products or synthetic ones.
  • the method of uniformly dispersing such layered silicate particles in a polyamide resin is not limited, but the method of the present invention is not limited.
  • the raw material of the silicate particles is a multi-layered clay mineral
  • it is brought into contact with a swelling agent to expand the layers in advance to make it easy to take in the monomers between the layers, and then to form the monomer for forming the polyamide.
  • a method of polymerizing this monomer Japanese Patent Publication No. 08-222946.
  • the interlayer is spread to 10 nm or more in advance, and this is melt-kneaded with a polyamide resin or a resin containing the same to be uniformly dispersed.
  • a method may be used.
  • the mixing ratio 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. Department. If 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 will be small, and if it exceeds 30 parts by weight, the flow of the resin composition will increase. It is not preferable because sex is extremely reduced.
  • the silane coupling agent used as the component (d) is a binder that binds the components (a), (b) and (c) to each other.
  • this silane coupling agent include vinyl trimethoxysilane, vinyl triethoxy silane, vinyl tris ( ⁇ -methoxetoxy) silane, vinyl tri Acetylsilane, amethacryloxyprovir trimethoxysilane, / 5— (3,4-epoxycyclohexyl) ethyl trimethoxysilane, aglycidoxypropyltrimethoxy Silane, ⁇ -glycidoxypropylmethyldimethoxysilane, aglycidoxypropylmethylethylethoxysilane, ⁇ -glycidoxypropylpyrethyldimethoxysilan, ⁇ -glycidoxypropylpropylethylethoxysilane, ⁇ —; 5_ ( Aminoethyl) Am
  • the amount of the silane coupling agent is preferably 0.1 to 5.5 parts by weight based on 100 parts by weight of the total of the components (a), (b) and (c). Particularly preferred is 0.2 to 3.0 parts by weight.
  • 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 a composition having high strength can be obtained. May not be possible.
  • it exceeds 5.5 parts by weight it becomes difficult for the polyamide in the component (c) to form a fine fiber structure, so that it is difficult to obtain a composition having excellent elastic modulus. There is power.
  • an organic peroxide can be used in combination with the silane coupling agent used as the component.
  • a radical is formed on the molecular chain of the component (a), component (b), and component (c), and this reacts with the silane coupling agent to form the component (a).
  • (B) component and (c) component resin are promoted to bond with each other. In this way, (a) component, (b) component and (c) component are mutually bonded at the interface.
  • the half-life temperature for 1 minute is from the same temperature as the melting point of component (a) or the melting point of component (c), whichever is higher, to a temperature 30 ° C higher than this temperature. Those within the range are preferably used. More specifically, as an organic peroxide, the half-life temperature of one minute is about 110 to 250 ° C. Things are preferably used. The amount of organic peroxide used at this time is
  • organic peroxide used in the present invention examples include 1,1-di-t-butylperoxy-1,3,5, -trimethylcyclohexane, 1,1-di-t-butylperoxy.
  • thermoplastic polyamide are dispersed in the form of fine fibers.
  • the average fiber diameter of the polyamide fiber is preferably 1 zm or less, and the average fiber length is preferably 1,000 m or less.
  • the aspect ratio expressed by the ratio of the average fiber length to the average fiber diameter is preferably 20 or more, more preferably 20 or more and 1,000 or less.
  • Component (a), component (b) and component (c) are bonded to each other at their respective interfaces, and this bond is strengthened by the silane coupling agent forming component (d). Have been.
  • the proportions of component (a), component (b) and component (c) are 100 to 400 parts by weight of component (a), 100 to 400 parts by weight of component (b), and 100% by weight of component (c). ⁇ 400 parts by weight.
  • the component (b) is 20 to 250 parts by weight, and the component (c) is 20 to 300 parts by weight. More preferably, the component (b) is 50 to 200 parts by weight, and the component (c) is 50 to 300 parts by weight. If the amount of the component (b) is less than 100 parts by weight based on 100 parts by weight of the component (a), the resulting composition will have insufficient impact resistance, and will exceed 400 parts by weight. The resulting composition has insufficient creep resistance.
  • the resulting composition has insufficient creep resistance. If the amount exceeds 400 parts by weight, the proportion of polyamide fibers present as fine fibers in the composition becomes too large, and the dispersion of the fibers becomes poor. The appearance of the molded product obtained by this is poor.
  • a filler may be added to the resin composition of the present invention as long as the physical properties are not impaired.
  • the filler carbon fibers, glass fibers, metal fibers, glass beads, talc, kaolin, cres, mica, montmorillonite, basic magnesium carbonate, walazite, etc. can be used.
  • antioxidants, ultraviolet absorbers, softeners, flame retardants, softeners, lubricants, tackifiers, and the like can be appropriately added to the resin composition of the present invention.
  • thermoplastic polyamide for component (c) in which layered silicate particles are uniformly dispersed will be described.
  • This dispersion method is not particularly limited as long as the layered silicate can be uniformly dispersed.
  • the layered silicate is ionized with hydrochloric acid. Reacts with a swelling agent, for example, 12-aminododecanic acid, to expand the layers in advance, to facilitate the incorporation of monomers between the layers, and to form a polyamide for the component (c).
  • a swelling agent for example, 12-aminododecanic acid
  • the swelling agent examples include aminoic acid and nitric acid salt, and specific examples thereof are ⁇ -amino-decanoic acid, ⁇ -amino-dodecanoic acid, and diamin.
  • equimolar salts of dicarboxylic acids such as tetramethylammonium adipate, hexamethylene diammonium diagedate, and hexamethylene diammonium sebague toka and so on.
  • the method for producing a polyamide fiber reinforced resin composition includes the following steps (1) to (4).
  • a reactive matrix is prepared by melt-kneading the (a) component polyolefin resin and the (b) component rubbery polymer together with the (d) component silane coupling agent.
  • thermoplastic polyamide in the component (c) A step of stretching or rolling the extrudate while drafting at a temperature lower than the melting point of the thermoplastic polyamide in the component (c) and at which the thermoplasticity is exhibited.
  • the stretching or rolling temperature at this time may be equal to or higher than the melting point of the components (a) and (b).
  • Step (1) Melt and knead the polyolefin of component (a) and the rubbery polymer of component (b) with the silane coupling agent of component (d), and mix the components (a) and (b) with each other.
  • A) a step of preparing a reactive matrix between the component (d) and the component (d).
  • This melting is performed at a temperature higher than the melting point of the polyolefin of component (a), and preferably at a temperature higher by at least 10 ° C than this melting point. If kneaded at a temperature higher than the melting point by 10 ° C. or more, the (a) component and the (d) component silane coupling agent react to form a reactive matrix.
  • Melt kneading can be carried out by a device usually used for resin and rubber.
  • a kneading mixer, a kneader, a kneader extruder, an open roll, a single-screw kneader, a twin-screw kneader, and the like are used.
  • a twin-screw kneader it is most preferable to use a twin-screw kneader in that melt kneading can be performed in a short time and continuously.
  • Step (2) The above-mentioned reactive matrix is treated with a composite of the layered silicate of the component (c) and the thermoplastic polyamide at a temperature not lower than the melting point of the thermoplastic polyamide.
  • the component (c) is melt-kneaded at a temperature higher than the melting point of the polyamide of the component (c), particularly preferably at a temperature higher than the melting point by 10 ° C or more, and the component (c) is added to the matrix. Disperse to prepare a chemically modified composition.
  • the chemically modified composition is extruded from a spinneret or T-die. Both spinning and extrusion are preferably performed at a temperature higher than the melting point of the component (c), preferably at a temperature higher than the melting point by 10 ° C or more. If the extrusion is performed at a temperature lower than the melting point of the polyamide, the polyamide cannot be further finely divided in the matrix. For this reason, the polyamide fibers formed by drawing or rolling the composition may become coarse.
  • Step (4) a step of drawing or rolling the above extrudate while drafting at a temperature lower than the melting point of the polyamide in the component (c) but exhibiting thermoplasticity.
  • the stretching or rolling temperature at this time may be lower than the melting point of the components (a) and (b).
  • the melt-extruded string, thread, or tape obtained in step (3) is continuously cooled and stretched or rolled.
  • the stretching or rolling treatment is performed at a temperature lower than the melting point of the polyamide. This temperature is such that the mixture of components (a), (b) and (d) and component (c) exhibit thermoplasticity.
  • the stretching or rolling treatment is, for example, a method in which the kneaded composition is extruded from a spinneret and spun into a string or a thread, and this is stretched and wound while being drafted, or cut and collected as a pellet. It will be implemented in.
  • the draft ratio when the extrudate is stretched is preferably 1.5 to 100, more preferably 2 to 50, and most preferably 3 to 30.
  • the draft ratio means the ratio of the winding speed to the speed of the extrudate passing through the extrusion die.
  • Average fiber diameter and fiber shape The sample polymer fiber reinforced resin composition was dissolved in hot xylene to separate and collect the fiber, which was observed with a scanning electron microscope. The dispersibility was evaluated by checking whether the fibers were fine. For fibers with good dispersibility, the fiber diameters of 200 fibers were measured, and the average was determined as the average fiber diameter.
  • Sheets were prepared from the test resin composition at 180 ° C using a hot press, and the smoothness of the sheet surface was visually observed, evaluated and indicated as follows.
  • Tensile properties Tensile strength, tensile elongation at break and tensile modulus were measured at a temperature of 23 ° C and a tensile speed of 5 O mm Z according to ASTMD 638.
  • Dynamic friction According to JISK 7125, the gravitational friction coefficient between a 0.2 mm thick x 80 mm wide x 200 mm long sample and a transparent glass plate as the mating material The measurement was performed at 200 g and a pulling speed of 100 mm / min. The coefficient of gravitational friction is a measure of the difficulty of slipping on the surface of an article.
  • a 20 liter Hastelloy reactor equipped with a stirrer and temperature controller was used as a layered silicate, with an average width of 0.95 nm and a length of phyllosilicate.
  • About 10 O nm of montmorillonite 10 Og and 10 liters of distilled water were added to disperse montmorillonite particles in water.
  • 51.2 g of 12-aminododecanic acid and 24 milliliters of concentrated hydrochloric acid were added thereto, followed by stirring for 5 minutes. The particles were collected by filtration.
  • montmorillonite complex 12-amino dodecanoate ion and montmorillonite (hereinafter, montmorillonite complex) was prepared.
  • the content of layered silicate in the composite was about 80%.
  • 10 kg of ⁇ -caprolactam, 1 kg of distilled water and 180 g of the above monomorillonite complex were placed in the reactor, and nitrogen gas was introduced to replace the air. The mixture was 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 kg Z cm 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 the form of a strand, cooled with water, cut, and mixed with a polyamid. (Average molecular weight: 15,000), montmorillonite and strength were obtained. This pellet was immersed in hot water at 90 ° C to remove unreacted monomers and oligomers. Was extracted and removed, followed by vacuum drying at 90 ° C for 48 hours.
  • the obtained layered silicate-containing polyamide (monmorillonite composite nylon 6) was ignited at 65 ° C, and the content of organic composite monmorillonite was determined from the residual weight of the burning. The measured value was 2.0%. Table 1 shows the results.
  • a layered silicate-containing polyamide was prepared in the same manner as in Reference Example 1.
  • the amount of the same monomorillonite complex used in Reference Example 1 was set to 270 g, 36008 or 720, and this was set to 1
  • Monomorillonite composite Nylon 6 was produced in the same manner as in Reference Example 1 using 0 kg of one-strength prolactam and 1 liter of water.
  • the content of monmorillonite in the mixed montrinite composite mouth 6 was 3.0%, 4.1% and 7.9%, respectively. Table 1 shows the results.
  • component (a) low-density polyethylene (available from Ube Industries, trade name: F522, melting point: 110 ° C, MFI 5 g / 10 minutes) as a component: 100 parts by weight, b) 100 parts by weight of natural rubber (SMR-L) as a component, and 1.0 parts by weight of 7-methacryloxyprovir trimethoxysilane as a silane coupling agent of component (d).
  • SMR-L natural rubber
  • 7-methacryloxyprovir trimethoxysilane 7-methacryloxyprovir trimethoxysilane
  • This matrix was mixed with 50 parts by weight of the monomoronilonite composite nylon 6 of Reference Example 1 as the component (c) in a twin-screw extruder heated to 250 ° C.
  • the mixture was kneaded, extruded in a strand shape through a nozzle attached to the tip of a twin-screw extruder, and stretched at a draft ratio of 20 in the air and at room temperature, and pelletized.
  • This pellet was pressed at 180 ° C. to form a sheet.
  • a dumbbell-shaped test piece was punched out of the sheet to measure desired physical properties. The results are shown in Table 2 .
  • the low-density polyethylene of component (a) and the natural rubber of component (b) are extracted and removed from the obtained sheet with hot xylen, and the ammonium nitrate composite nylon of component (c) is extracted.
  • the fine fiber composed of No. 6 was collected and observed with a scanning electron microscope. The average fiber diameter was 0.2 ⁇ m.
  • Example 2 a polyimide fiber reinforced resin composition sheet was produced in the same manner as in Example 1. However, the type of the monmorillonite composite nylon 6 of the component (c) and the draft ratio were as shown in Table 2. Table 2 shows the measurement results of the physical properties of the obtained sheet.
  • any one of (a) component LDPE, (b) component NR, and (c) component montmorillonite composite nylon 6 was used.
  • a sheet was prepared in the same manner as in Example 1 except that one component was not added. Table 4 shows the measurement results.
  • the polyamide fiber reinforced resin composition obtained by the present invention is preferably used in a matrix comprising a polyolefin and a rubber-like polymer, preferably having an average fiber diameter of 1 m or less.
  • natural polyamide fibers are dispersed, and layered silicate particles are uniformly dispersed in the polyamide fibers.
  • the structure is such that polyolefin, rubbery polymer and polyamide fiber are bonded to each other at their respective interfaces.
  • the polyamide fiber reinforced resin composition of the present invention can be easily dispersed in various resins and rubbers, and is excellent in strength, elastic modulus, and friction performance. It is useful as a suitable reinforcing material for floor materials and footwear.

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Abstract

On malaxe à l'état fondu 100 parties en poids d'une résine polyoléfinique (a) avec un mélange qui comprend 10 à 400 parties en poids d'un polymère caoutchouteux (b), ayant une température de transition vitreuse inférieure ou égale à 0 °C, 10 à 400 parties en poids d'un polyamide thermoplastique (c), contenant un phyllosilicate, et un agent de couplage à base de silane (d). On extrude le produit, puis on l'étire ou on le lamine à une température inférieure au point de fusion de l'ingrédient (c), de façon à disperser celui-ci sous forme de fibres. La composition de résine renforcée par des fibres de polyamide ainsi obtenue présente d'excellentes caractéristiques de résistance, de rigidité et de friction.
PCT/JP1998/001216 1998-03-20 1998-03-20 Composition de resine renforcee par des fibres de polyamide et procede de fabrication associe WO1999048973A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1416013A1 (fr) * 2002-10-29 2004-05-06 Yazaki Corporation Elément isolant utilisant une composition de polymères résistante à l'abrasion
EP1557443A1 (fr) * 2002-10-29 2005-07-27 Yazaki Corporation Composition de resine utilisee dans le revetement d'un fil electrique et fil electrique comprenant celle-ci
JP2008523199A (ja) * 2004-12-07 2008-07-03 エルジー・ケム・リミテッド 遮断性パイプ
JP2012102298A (ja) * 2010-11-12 2012-05-31 Tosoh Corp エチレン−酢酸ビニル共重合体樹脂組成物、それからなる合わせガラス用中間膜及びそれを用いた合わせガラス
WO2016125873A1 (fr) * 2015-02-04 2016-08-11 株式会社ブリヂストン Pneumatique

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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
JPH0812881A (ja) * 1993-09-30 1996-01-16 Mitsubishi Chem Corp ポリアミド樹脂組成物及びその製造方法

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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
JPH0812881A (ja) * 1993-09-30 1996-01-16 Mitsubishi Chem Corp ポリアミド樹脂組成物及びその製造方法
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 (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1416013A1 (fr) * 2002-10-29 2004-05-06 Yazaki Corporation Elément isolant utilisant une composition de polymères résistante à l'abrasion
EP1557443A1 (fr) * 2002-10-29 2005-07-27 Yazaki Corporation Composition de resine utilisee dans le revetement d'un fil electrique et fil electrique comprenant celle-ci
US7041726B2 (en) 2002-10-29 2006-05-09 Yazaki Corporation Insulating member using abrasion-resistant resin composition
EP1557443A4 (fr) * 2002-10-29 2010-09-22 Yazaki Corp Composition de resine utilisee dans le revetement d'un fil electrique et fil electrique comprenant celle-ci
JP2008523199A (ja) * 2004-12-07 2008-07-03 エルジー・ケム・リミテッド 遮断性パイプ
JP2012102298A (ja) * 2010-11-12 2012-05-31 Tosoh Corp エチレン−酢酸ビニル共重合体樹脂組成物、それからなる合わせガラス用中間膜及びそれを用いた合わせガラス
WO2016125873A1 (fr) * 2015-02-04 2016-08-11 株式会社ブリヂストン Pneumatique
JP6049946B1 (ja) * 2015-02-04 2016-12-21 株式会社ブリヂストン タイヤ
CN107207803A (zh) * 2015-02-04 2017-09-26 株式会社普利司通 轮胎
US10442922B2 (en) 2015-02-04 2019-10-15 Bridgestone Corporation Tire
CN107207803B (zh) * 2015-02-04 2020-07-17 株式会社普利司通 轮胎

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