WO2008026561A1 - Corps élastique renforcé par des fibres - Google Patents

Corps élastique renforcé par des fibres Download PDF

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Publication number
WO2008026561A1
WO2008026561A1 PCT/JP2007/066602 JP2007066602W WO2008026561A1 WO 2008026561 A1 WO2008026561 A1 WO 2008026561A1 JP 2007066602 W JP2007066602 W JP 2007066602W WO 2008026561 A1 WO2008026561 A1 WO 2008026561A1
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WIPO (PCT)
Prior art keywords
fiber
component
weight
parts
elastomer
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PCT/JP2007/066602
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English (en)
Japanese (ja)
Inventor
Hideo Kurihara
Masashi Yamaguchi
Yuichi Ito
Noriaki Tsukuda
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Daimaru Sangyo Kaisha., Ltd.
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Publication of WO2008026561A1 publication Critical patent/WO2008026561A1/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
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/046—Reinforcing macromolecular compounds with loose or coherent fibrous material with synthetic macromolecular fibrous material
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; 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
    • 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

Definitions

  • the present invention relates to a fiber-reinforced elastic body excellent in wear resistance, and is used for various members such as tires, conveyance rollers, industrial hoses, industrial belts, daily goods, and automobile hoses.
  • the present invention relates to a reinforced elastic body.
  • Patent Document 1 discloses a fiber-reinforced elastic body in which (A) a fiber-reinforced thermoplastic composition and (C) a second elastomer are kneaded! It is disclosed that this fiber-reinforced elastic body is excellent in strength properties such as modular tensile strength.
  • Patent Document 1 Japanese Patent No. 3379208
  • Patent Document 1 since the technique disclosed in the above-mentioned Patent Document 1 is not disclosed in terms of wear resistance, it has not been improved!
  • polyurethane elastomers are known as an elastic body with excellent wear resistance. Because polyurethane elastomers are complex and expensive to manufacture, they can be replaced with polyurethane elastomers. A fiber-reinforced elastic body having the above is desired.
  • the present invention provides a fiber-reinforced elastic body having excellent strength properties such as modulus and tensile strength, and excellent wear resistance, and in particular wear resistance that can be replaced with a polyurethane elastomer. It is aimed.
  • the present invention includes (a) 100 parts by weight of a first polyolefin, (b) 10 to 400 parts by weight of a first elastomer, and (c) 10 to 400 parts by weight of a thermoplastic polyamide.
  • the component (a) and the component (b) constitute a matrix, and the component (c) is dispersed as fine fibers having an average fiber diameter of ⁇ ⁇ or less in the matrix.
  • the second polyolefin is 50 to 200 parts by weight
  • (A) the fiber-reinforced thermoplastic composition is !! to 70 parts by weight
  • (C) the second elastomer is 10 to 450 parts by weight. It is preferable to include parts by weight
  • the reactive compatibilizer (D) it is preferable to use an ethylene-based copolymer as the reactive compatibilizer (D) as necessary, and (D) a reactive compatibilizer as required.
  • the reactive compatibilizer is an ethylene copolymer, it is preferably contained in an amount of 1 to 50 parts by weight.
  • the second elastomer is preferably a styrene-based thermoplastic elastomer.
  • Fiber reinforced thermoplastic composition comprises ⁇ polyolefin, (b) first elastomer, and (c) thermoplastic polyamide as the main constituents, and (a) component and (b) component are It has a structure in which most of the component (c) is dispersed in the matrix as fine fibers having an average fiber diameter of 1 m or less. The fine fibers of component (c) are chemically bonded to the Matritus.
  • the first polyolefin has a melting point of 80 to 250 ° C. Further, those having a Vicat softening point of 50 ° C or higher, particularly a Vicat softening point of 50 to 200 ° C are also preferably used. Examples of such polyolefins include homopolymers and copolymers of C2 to C8 olefins, and copolymers of C2 to C8 olefins with aromatic bur compounds such as styrene, chlorostyrene, and ⁇ -methylstyrene.
  • Polyethylene poly-4-methylpentene 1, polybutene 1, polyhexene 1, ethylene, butyl acetate copolymer, ethylene 'acrylic acid copolymer, ethylene, methyl acrylate copolymer, ethylene' ethyl acrylate copolymer, Ethylene 'propyl acrylate copolymer, ethylene' butyl acrylate copolymer, ethylene 2-ethylhexyl acrylate copolymer, ethylene hydroxyethyl acrylate copolymer, ethylene butyltrimethoxysilane copolymer , Ethylene 'butyltriethoxysilane copolymer, ethylene' butyl silane copolymer, ethylene 'styrene copolymer, and propylene' styrene copolymer.
  • chlorinated polyethylene, brominated polyethylene, or chlorosulfonated polyethylene may be used,
  • the first elastomer is a force that can be used with any polymer called a so-called elastomer that is rubber-like at room temperature.
  • a so-called elastomer that is rubber-like at room temperature.
  • Preferred is an elastomer having a glass transition temperature of 0 ° C. or less.
  • One example is an elastomer having a glass transition temperature of 20 ° C or lower.
  • Genylene rubber such as isoprene block copolymer, force lene block copolymer, chlorinated polyethylene, chlorosulfonated polyethylene, ethylene 'vinyl acetate copolymer, ethylene' propylene rubber, ethylene 'propylene.
  • Three Polymethylene type such as copolymer, ethylene butene rubber, ethylene butene gen terpolymer, polyolefin rubber, polychlorotrifluorinated styrene, acrylic rubber, ethylene acrylic rubber, fluoro rubber, hydrogenated NBR, etc. Rubber with main chain, polyester-based thermoplastic elastomer, epichlorohydrin polymer, ethylene oxide. Epoxychlorohydrin. Allylic glycidyl ether copolymer, propylene oxide.
  • Allylic allysidyl ether copolymer, etc. rubber having oxygen atom in the main chain, polyphenylmethyl siloxane, polydimethylol siloxane, polymethylol ethinore Silicone rubbers such as siloxane and polymethylenobutinorexane, polyamide thermoplastic elastomers, nitroso rubbers, polyester urethanes, polyether urethanes, rubbers having nitrogen atoms and oxygen atoms in the main chain, etc. Is mentioned. In addition, those obtained by epoxy-modifying these rubbers, silan-modified, or rubber-modified ones are also preferably used.
  • thermoplastic polyamide can be used after being modified with a silane coupling agent.
  • Preferable examples include those having a melting point of 135 ° C to 350 ° C, and particularly preferable examples include thermoplastic polyamides having a melting point of 150 ° C to 300 ° C.
  • thermoplastic polyamide used is nylon 6, nylon 66, nylon 6-nylon 66 copolymer, nylon 610, nylon 612, nylon 46, nylon 11, nylon 12, nylon MXD6, xylylene ranger Polycondensates of amine and adipic acid, polycondensates of xylylenediamine and pimelic acid, polycondensates of xylylenediamine and speric acid, polycondensates of xylylenediamine and azelaic acid, xylylenediamine Polycondensates of amines and sebacic acid, polycondensates of tetramethylene diamine and terephthalic acid, polycondensates of hexamethylene diamine and terephthalic acid, polycondensation of otatamethylene diamine and terephthalic acid , Polycondensate of trimethylhexamethylenediamine and terephthalic acid, polycondensate of decamethylenediamine
  • thermoplastic polyamides the most preferable one is a thermoplastic polyamide having a melting point of 160 to 265 ° C. Specifically, nylon 6, nylon 66, nylon 6-nylon 66 copolymer , Nylon 610, nylon 612, nylon 46, nylon 11, and nylon 12 etc. are mentioned.
  • (a) fiber-reinforced thermoplastic composition used in the present invention (a) polyolefin and (b) the first elastomer form a matrix.
  • This matrix may have a structure in which the component (b) is dispersed in the form of islands in the component (a).
  • the structure in which the component (a) is dispersed in the form of islands in the component (b). May be adopted.
  • Components (a) and (b) are bonded together at the interface!
  • thermoplastic polyamide component Most of the thermoplastic polyamide component is dispersed in the matrix as fine fibers having an average fiber diameter of 1 ⁇ m or less. Specifically, 70% by weight, preferably 80% by weight, and particularly preferably 90% by weight or more is dispersed as fine fibers.
  • the fiber of component (c) has an average fiber diameter of 1 m or less, and a particularly preferred range is from 0.05 to 0.8111.
  • the aspect ratio (fiber length / fiber diameter) is 1.0 or more, and the thermoplastic polyamide component includes particles (aspect ratio is 1 ⁇ 0).
  • the component (c) is chemically bonded to the matrix composed of the components (a) and (b) at the interface. This can be confirmed, for example, as follows.
  • the fiber-reinforced thermoplastic composition is refluxed in a solvent that dissolves only the components (a) and (b), such as xylene, and the components (a) and (b) are removed.
  • a solvent that dissolves only the components (a) and (b), such as xylene
  • the remaining fiber of component (c) is dissolved in a solvent and NMR is measured, peaks derived from component (a) and component (b) can be observed. This is considered to indicate that the components (a) and (b) are bound in some form to the surface of the fiber! /.
  • the proportions of (a) the first polyolefin, (b) the first elastomer, and (c) the thermoplastic polyamide are preferably as follows! /.
  • Component 100 parts by weight Component (b) is preferably in the range of 10 to 400 parts by weight, particularly preferably in the range of 20 to 250 parts by weight, and most preferably in the range of 50 to 200 parts by weight. ,. Only 100% by weight of the component (a) component (b) is more than 300 parts by weight, and only a fiber-reinforced thermoplastic composition that is difficult to be pelletized can be obtained!
  • the proportion of component (c) is preferably in the range of 10 to 400 parts by weight with respect to 100 parts by weight of component (a), more preferably in the range of 5 to 300 parts by weight, in the range of 10 to 300 parts by weight. Is most preferred. If the proportion of component (c) exceeds 400 parts by weight relative to 100 parts by weight of component (a), fine fibers of component (c) will not be formed in the fiber-reinforced thermoplastic composition! /. Even when a fiber-reinforced elastic body is produced using such a fiber-reinforced thermoplastic composition, the strength is high! This is because a modified elastic body cannot be obtained!
  • the (A) fiber-reinforced thermoplastic composition of the present invention can be produced by the following steps. (1) In step 1, prepare a matrix consisting of component (a) and component (b). (2) In the second step, (c) the component is reacted with a silane coupling agent. (3) In the third step, the matrix and the component (c) reacted with the silane coupling agent are melted and kneaded. (4) In the fourth step, the obtained kneaded product is extruded at a temperature equal to or higher than the melting point of component (c), and then stretched and / or rolled at a temperature lower than the melting point of component (c).
  • the component (a) is first melt-kneaded with the binder and reacted.
  • the component (b) may be melt-kneaded.
  • the ⁇ component and the component (b) may be melted and kneaded together with the binder.
  • Melting and kneading can be performed by an apparatus usually used for kneading resin and rubber. Examples of such apparatuses include Banbury type 1 mixers, kneaders, kneader extruders, open rolls, uniaxial kneaders, and biaxial kneaders.
  • the amount of the binder is preferably from 0 .;! To 2.0 parts by weight, particularly preferably from 0.2 to 1.0 parts by weight, per 100 parts by weight of component (a).
  • amount of the binder is less than 0.1 parts by weight, a composition having high strength cannot be obtained, and when it is more than 2.0 parts by weight, a composition having excellent modulus may not be obtained.
  • binder examples include silane coupling agents, titanate coupling agents, nopolac-type alkylphenol formaldehyde initial condensates, resol-type alkylphenol formaldehyde initial condensates, nopolac-type phenol formaldehyde initial condensates, ⁇ Nolformaldehyde precondensates, unsaturated carboxylic acids and derivatives thereof, organic peroxides, and the like that are usually used as polymer coupling agents can be used.
  • silane coupling agents are preferred because they are less likely to gel components (a) and (b) and can form strong bonds at the interfaces of these components.
  • silane coupling agent examples include butulalkoxysilanes such as butritrimethoxysilane, butritriethoxysilane, butrithris (/ 3-methoxyethoxy) silane, butyrriacetylsilane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ - [ ⁇ - ( ⁇ -methacryloquichetil) - ⁇ , ⁇ -dimethylammonium (chloride)] propylmethoxysilane, and
  • a silane coupling agent having a group and / or a polar group that easily desorbs a hydrogen atom from other groups such as styryldiaminosilane, a bur group, and an alkyloxy group is preferably used.
  • an organic peroxide can be used in combination.
  • the 1 minute half-life temperature is the same as the higher of the melting point of component (a) or the melting point of component (b), or a temperature range of about 30 ° C higher than this temperature. Those are preferably used. Specifically, a one-minute half-life temperature of about 110 to 200 ° C is preferably used.
  • Such organic peroxides include 1,1-di-t-butylperoxy 3,3,5-trimethylolcyclohexane, 1,1-di-t-butylperoxycyclohexane, 2,2-di-t-butinoleper.
  • the amount of the organic peroxide used is preferably in the range of 0.01 to 1.0 part by weight per 100 parts by weight of component (a).
  • component (a) component and (b) component are melted and kneaded with silane coupling agent and modified with silane! /
  • component (B) component is natural rubber, polyisoprene, or styrene 'isoprene' styrene
  • a block copolymer it is not necessary to use an organic peroxide.
  • Rubbers with an isoprene structure such as natural rubber, polyisoprene, and styrene 'isoprene' styrene block copolymers, have a main chain scission caused by a mechanochemical reaction during kneading and have a COO 'group at the end of the main chain. This is because it is considered that this peroxide produces almost the same action as the above organic peroxide.
  • the component (c) may be melt kneaded and reacted with the silane coupling agent in advance and then melt kneaded with the matrix! /, Or melt kneaded with the matrix in the presence of the silane coupling agent.
  • Yo! / Melt kneading is an apparatus usually used for kneading resins and rubbers, such as Banbury type mixers, kneaders, kneader extract noraders, open rolls, uniaxial kneaders, and What can be performed with a biaxial kneader or the like is the same as in the case of the matrix preparation.
  • the ratio of the silane coupling agent to the component (c) is preferably in the range of 0.;! To 5.5% by weight when the total amount of the component (c) and the silane coupling agent is 100% by weight.
  • the range of 0.2 to 5.5% by weight is particularly preferred.
  • the range of 0.2 to 3% by weight is most preferred.
  • the silane coupling agent is most preferable in that the component (c) is less gelled and can form a strong bond at the interface with the matrix.
  • the silane coupling agent include an alkyloxy group or the like having a group capable of forming a bond with the nitrogen atom of the NHCO-bond of component (c) by dehydration reaction or dealcoholization reaction.
  • Specific examples of such silane coupling agents include butylalkoxysilanes such as butyltrimethoxysilane, butyltriethoxysilane , and vinyltris (/ 3-methoxyethoxy) silane, butyltriacetylsilane, and ⁇ ⁇ -methacryloxypropyl trimethoxy.
  • Examples include silane, ⁇ - [ ⁇ - ( ⁇ -methacryloxyaminoethyl) ⁇ -aminopropyltrimethoxysilane, styryldiaminosilane, ⁇ -ureidopropyltriethoxysilane, and the like.
  • the temperature at which the matrix and the component (c) are melted and kneaded needs to be equal to or higher than the melting point of the component (c). Even if melting and kneading are performed at a temperature lower than the melting point of the component (c), the kneaded product does not have a structure in which the fine particles of the component (c) are dispersed in the matrix. This is because the component (c) cannot be a fine fiber even if the fiber is spun and drawn.
  • the kneading temperature is preferably a temperature equal to or higher than the melting point or Vicat softening point of the polyolefin as component (a).
  • the kneaded product obtained in the above step is extruded from a spinneret, an inflation die or a T die, and then stretched or rolled.
  • the fine particles of the component (c) in the kneaded product are transformed into fibers by spinning or extrusion.
  • This fiber is drawn by subsequent drawing or rolling to become a stronger fiber. Therefore, spinning and extrusion must be performed at a temperature equal to or higher than the melting point of component (c), and stretching and rolling must be performed at a temperature lower than the melting point of component (c).
  • Spinning or extrusion, and subsequent stretching or rolling can be performed by, for example, mixing a kneaded product with a spinneret. It can be carried out by a method of extruding from gold and spinning it into a string or thread and winding it around a bobbin or the like while drafting.
  • drafting means that the winding speed is higher than the spinning speed.
  • the ratio of the winding speed / spinning speed is in the range of 1.5 to 100; The most preferred draft ratio range is 3-30.
  • this step can also be carried out by continuously rolling the spun kneaded product with a rolling roll or the like.
  • the kneaded product can be also carried out by extruding it from an inflation die or a T die and winding it on a roll or the like while drafting it. You can also roll with a rolling roll instead of winding it on a roll while drafting!
  • the stretched or! / is preferably a pellet of the fiber-reinforced thermoplastic composition after rolling! This is because the fiber-reinforced thermoplastic composition can be uniformly kneaded with the additional elastomer, that is, the second elastomer, by forming pellets.
  • the second polyolefin as component (B) will be described.
  • the same one as previously used as the first polyolefin (A) component (a) of the fiber-reinforced thermoplastic composition is used.
  • the second elastomer As the second elastomer, The same material as that used as the first elastomer of the component (b) of the fiber-reinforced thermoplastic composition is used. Therefore, any polymer that is rubber-like so-called elastomer at room temperature can be used as the second elastomer.
  • Preferred is an elastomer having a glass transition temperature of 0 ° C or less, and particularly preferred is One example is an elastomer having a glass transition temperature of 20 ° C or less.
  • Isoprene block copolymer styrene butadiene styrene copolymer, styrene isoprene styrene copolymer, styrene ethylene / butylene styrene copolymer, styrene ethylene / propylene styrene copolymer, styrene 'Echile / Propylene copolymer, styrene 'ethylene / butylene copolymer, styrene 1,4 butadiene / butylene' styrene copolymer, styrene '(ethylene.ethylene / propylene)' styrene copolymer, carboxylated styrene 'pig Gen-block copolymer, carboxylated styrene, isoprene block copolymer, etc.
  • Gen-based rubber chlorinated polyethylene, chlorosulfonated polyethylene, ethylene, vinyl acetate copolymer, ethylene 'propylene rubber, ethylene' propylene ' Polyethylene type rubbers such as base copolymer, ethylene butene rubber, ethylene 'butene' gen terpolymer, polyolefin rubber, polychlorotrifluorinated styrene, acrylic rubber, ethylene acrylic rubber, fluoro rubber, hydrogenated NBR, etc.
  • Rubber with polyester main chain polyester thermoplastic Rubbers, oxygen polymers in the main chain, such as lastomer, epichlorohydrin polymer, ethylene oxide ep chlorohydrin, allylic glycidyl ether copolymer, propylene oxide, allylic glycidyl ether copolymer, etc.
  • Silicone rubbers such as enylmethylsiloxane, polydimethylsiloxane, polymethylenoethylenosiloxane, polymethylenobutynolesiloxane, polyamide thermoplastic elastomer, nitroso rubber, polyester urethane, polyether Examples thereof include rubbers having nitrogen atoms and oxygen atoms in addition to carbon atoms in the main chain, such as Nourethane.
  • the second elastomer only one type of these rubbers may be used, or two or more types may be used in combination.
  • the second elastomer may be the same as or different from (b) the first elastomer.
  • the fiber-reinforced elastic body of the present invention (A) the fiber-reinforced thermoplastic composition, (B) the second polyolefin, and (C) the second elastomer are kneaded.
  • the kneading is carried out by means of melt kneading, equipment usually used for kneading resins and rubbers, such as Banbury type mixers, kneaders, kneader extruders, open rolls, uniaxial kneaders, and biaxial kneaders. be able to.
  • the blend of (A) the fiber reinforced thermoplastic composition, (B) the second polyolefin, and (C) the second elastomer is preferably (B) the second polyolefin is 50 to 50%.
  • (A) the fiber-reinforced thermoplastic composition is 1 to 70 parts by weight
  • (C) the second elastomer is 10 to 450 parts by weight.
  • the amount of the second polyolefin is less than 50 parts by weight! /, which is inferior to the physical properties of the fiber-reinforced elastic body, particularly the wear properties with low stress, which are not preferable in terms of physical properties.
  • the amount exceeds 200 parts by weight, there is a problem of rubber elasticity! /, Only fiber-reinforced elastic bodies can be obtained! /, And! /.
  • the kneading temperature of (A) the fiber reinforced thermoplastic composition, (B) the second polyolefin, and (C) the second elastomer is such that (A) the fine fiber in the fiber reinforced thermoplastic composition It must be lower than the melting point of the thermoplastic polyamide (c) constituting the short fiber. Higher than the melting point of this thermoplastic polyamide! / When kneaded at a temperature, the fine short fibers in the fiber-reinforced thermoplastic composition melt and become spherical. It is not preferable because it is deformed into particles.
  • a pellet-like (A) fiber-reinforced thermoplastic composition it is preferable to use a pellet-like (A) fiber-reinforced thermoplastic composition. If a pellet-like fiber reinforced thermoplastic composition is used, (A) the fiber reinforced thermoplastic composition can be uniformly kneaded with (B) the second polyolefin and (C) the second elastomer, (c) This is because a fiber-reinforced elastic body in which fine components are uniformly dispersed can be easily obtained.
  • a reactive compatibilizer and a vulcanizing agent may be kneaded together.
  • the reactive compatibilizer for example, when an ethylene copolymer or an organic peroxide is used, (B) the second polyolefin is preferably 1 part by weight based on 100 parts by weight. To 50 parts by weight.
  • Examples of the ethylene copolymer include ethylene / glycidyl methacrylate copolymer, ethylene / glycidyl methacrylate / butyl acetate copolymer, ethylene / glycidyl methacrylate / methyl acrylate copolymer, maleic anhydride-modified polyolefin. , Ionomer resins, and ethylene / methacrylic acid copolymers.
  • organic peroxide examples include 1,1-di-t-butylperoxy 3,3,5 trimethylenocyclohexane, 1,1-di-t-butinoleperoxycyclohexane, 2,2-di-t-butyl Peroxybutane, 4,4-di-t-butyl peroxyvalerate n-butyl estenole, 2,2 bis (4,4-di-t-butinoleperoxycyclohexane) propane, peroxyneodecane 2, 2 , 4 Trimethylpentyl, ⁇ -Tamil peroxyneodecanoate, t-butyl peroxyneohexane, t-butyl peroxybivalate, t-butyl peroxyacetate, t-butyl peroxylaurate, t-butyl peroxybenzoate, There is t-butyl peroxyisophthalate.
  • vulcanizing agent known vulcanizing agents such as sulfur, organic peroxides, resin vulcanizing agents, metal oxides such as magnesium oxide, and the like are used.
  • vulcanization aids include aldehyde 'ammoures, aldehydes amines, guanidines, thioreas, thiazoles, thiurams, dithiorubamate, xanthate and the like.
  • the vulcanization temperature when a vulcanizing agent or the like is added to the fiber-reinforced elastic body of the present invention is preferably about 100 to 180 ° C.
  • the vulcanization temperature needs to be lower / lower than the melting point of (c) the thermoplastic polyamide constituting the fine fibers in the fiber-reinforced elastic body. Vulcanize at a temperature above the melting point of this thermoplastic resin. In other words, there is a possibility that the fibers formed at the stage of preparation of the bent fiber reinforced thermoplastic composition will melt.
  • the fiber-reinforced elastic body of the present invention includes carbon black, white carbon, activated calcium carbonate, ultrafine magnesium silicate, high styrene resin, phenol resin, lignin, modified melamine resin, coumarone indene resin, Reinforcing agents such as petroleum resins, various fillers such as calcium carbonate, basic magnesium carbonate, clay, zinc white, diatomaceous earth, recycled rubber, powder rubber, ebonite powder, ammine aldehydes, ammine ketones, Stabilizers such as amines, phenols, imidazoles, sulfur-containing antioxidants and phosphorus-containing antioxidants, and various contents may be included.
  • the fiber-reinforced elastic body of the present invention is excellent in strength properties such as tensile properties and has excellent wear resistance, and in particular, has wear resistance that can be replaced with a polyurethane elastomer.
  • the fiber-reinforced elastic body of the present invention can be produced by kneading (A) a fiber-reinforced thermoplastic composition, (B) polyolefin and (C) a second elastomer, and (A) fiber-reinforced thermoplastic. Since the composition can be pelletized very easily, (B) polyolefin and (C) the second elastomer can be kneaded very easily and uniformly, and the fiber-reinforced elastic body of the present invention can be easily obtained.
  • this kneading can be performed using a screw kneader such as a uniaxial kneader or a biaxial kneader, (A) pellets of a fiber reinforced thermoplastic composition, (B) polyolefin and (C) a second elastomer. Is added to the screw kneader to facilitate unattended production of the fiber-reinforced elastic body of the present invention.
  • a screw kneader such as a uniaxial kneader or a biaxial kneader
  • this matrix and component (c) were kneaded in a twin-screw kneader heated to 240 ° C.
  • the kneaded product was pelletized, and the resulting kneaded product was extruded into a string shape with a single screw extruder set at 245 ° C. and pelletized with a pelletizer while being drawn at a draft ratio of 10.
  • the mixture was refluxed in a mixed solvent of benzene and xylene to remove polyolefin and NR, and the shape and diameter of the remaining fiber were observed with an electron microscope. As a result, it was confirmed that the fiber had an average fiber diameter of 0.2.
  • (B) as the second polyolefin high density polyethylene (HDPE: E8081 (manufactured by Keiyo Polyethylene)), ethylene acetate burcopolymer (EVA: V210 (manufactured by Ube Maruzen Polyethylene)), homopolypropylene (PP: E200GP (prime polymer) Manufactured))) and amorphous / poly ⁇ -olefin ( ⁇ ⁇ ⁇ : manufactured by Degussa) were each adjusted to 100 parts by weight.
  • HDPE high density polyethylene
  • EVA ethylene acetate burcopolymer
  • PP homopolypropylene
  • PP E200GP (prime polymer) Manufactured)
  • amorphous / poly ⁇ -olefin ⁇ ⁇ ⁇ : manufactured by Degussa
  • Examples 1 to 6 5 or 10 parts by weight of the above-mentioned (A) fiber reinforced thermoplastic composition (SHP) was mixed, and 10 to 20 parts by weight of the reactive compatibilizer was adjusted.
  • Reactive compatibilizers include ethylene / glycidyl methacrylate copolymers (ethylene terpolymers). Ma (Sumitomo Chemical Co., Ltd.)).
  • each composition was put into a Brabender plastograph set at 180 ° C. and kneaded for 3 minutes, and the resulting material was subjected to density, taber wear, tear strength, tensile strength. Characteristics and hardness were measured.
  • thermoplastic polyurethane elastomer (adipate type).
  • the Taber abrasion is 1 to 18 mg, compared with 22 to 31 mg of the Taber abrasion of Comparative Examples 1 to 5, compared to the abrasion resistance. It is clear that it is excellent in wear.
  • the Taber wear is 2 mg or less, which is comparable to any of the comparative examples;! To 5 and the reference examples. The difference was excellent wear resistance.
  • (B) the second polyolefin and (C) the second elastomer are in the same ratio, the comparison between Example 1 and Comparative Example 1, the comparison between Example 2 and Comparative Example 2, and the implementation In comparison between Example 3 and Comparative Example 3, Example 4 and Comparative Example 4 in comparison, tear strength, modulus (M50 (50% tensile stress), M100 (100% tensile stress), M300 (300% tensile stress) )) And tensile strength (breaking strength) Tb! /, The numerical values of the examples were superior to the comparative examples in terms of strength properties! /.
  • each of the examples is superior to each comparative example and the reference example in terms of wear resistance even in consideration of the variation that is generally known to vary. It was. Also, the Taber abrasion of the thermoplastic polyurethane elastomer shown in the reference example is 20 mg, and even if there is some variation, the examples are superior to or equal to or better than the thermoplastic polyurethane elastomer. A change to one is possible.

Abstract

L'invention concerne un corps élastique renforcé par des fibres, présentant d'excellentes caractéristiques de résistance, telles que le module et la résistance à la traction, ainsi qu'une excellente résistance à l'usure. L'invention concerne notamment un corps élastique renforcé par des fibres présentant une résistance à l'usure comparable à celle des élastomères de polyuréthanne. L'invention concerne notamment un corps élastique renforcé par des fibres qui est obtenu par malaxage d'une composition thermoplastique renforcée par des fibres (A), d'une seconde polyoléfine (B) et d'un second élastomère (C). La composition thermoplastique renforcée par des fibres (A) est une composition composée de 100 parties par poids d'une première polyoléfine (a), de 10 à 400 parties par poids d'un premier élastomère (b) et de 10 à 400 parties par poids d'un polyamide thermoplastique (c). Le composant (a) et le composant (b) forment la matrice, et le composant (c) est dispersé dans la matrice sous forme de fibres fines ayant un diamètre moyen inférieur ou égal à 1 µm. Le composant (c) est lié chimiquement avec le composant (a) et le composant (b).
PCT/JP2007/066602 2006-08-30 2007-08-28 Corps élastique renforcé par des fibres WO2008026561A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012014676A1 (fr) * 2010-07-26 2012-02-02 大丸産業株式会社 Composition de résine thermoplastique renforcée de fibres et procédé pour produire une composition de résine thermoplastique renforcée de fibres
CN108797122A (zh) * 2018-06-06 2018-11-13 广西民族大学 一种热牵引聚酰胺纳米纤维膜/聚烯烃弹性体复合材料及其制备方法

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012077223A (ja) * 2010-10-04 2012-04-19 Daimaru Sangyo Kk 繊維強化弾性体及びその製造方法
JP5674863B2 (ja) * 2013-05-31 2015-02-25 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
ES2700405T3 (es) * 2014-07-04 2019-02-15 Dsm Ip Assets Bv Lámina posterior monocapa para módulos de células solares

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
JPH0987434A (ja) * 1995-09-27 1997-03-31 Ube Ind Ltd 伝動ベルト用ゴム組成物
JP2000143875A (ja) * 1998-11-13 2000-05-26 Bridgestone Corp 短繊維補強ゴム組成物
JP2001214001A (ja) * 2000-02-03 2001-08-07 Ube Ind Ltd 繊維強化弾性体

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
JPH0987434A (ja) * 1995-09-27 1997-03-31 Ube Ind Ltd 伝動ベルト用ゴム組成物
JP2000143875A (ja) * 1998-11-13 2000-05-26 Bridgestone Corp 短繊維補強ゴム組成物
JP2001214001A (ja) * 2000-02-03 2001-08-07 Ube Ind Ltd 繊維強化弾性体

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012014676A1 (fr) * 2010-07-26 2012-02-02 大丸産業株式会社 Composition de résine thermoplastique renforcée de fibres et procédé pour produire une composition de résine thermoplastique renforcée de fibres
CN108797122A (zh) * 2018-06-06 2018-11-13 广西民族大学 一种热牵引聚酰胺纳米纤维膜/聚烯烃弹性体复合材料及其制备方法

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