WO1999048970A1

WO1999048970A1 - Polyamide fiber-reinforced elastomer composition and process for the production thereof

Info

Publication number: WO1999048970A1
Application number: PCT/JP1998/001280
Authority: WO
Inventors: Shinji Yamamoto; Hideo Kurihara; Kimio Nakayama; Yukihiko Asano
Original assignee: Ube Industries, Ltd.
Priority date: 1998-03-24
Filing date: 1998-03-24
Publication date: 1999-09-30
Also published as: JP3453760B2

Abstract

A polyamide fiber-reinforced elastomer composition excellent in processability, durability, modulus of elasticity, strength and frictional performance, which comprises (a) 100 parts by weight of at least one rubbery polymer having a glass transition temperature of 0 °C or below, (b) 1 to 40 parts by weight of polyolefin, (c) 1 to 70 parts by weight of a thermoplastic polyamide fiber containing a layer silicate, and (d) a silane coupling agent. This composition is favorable for vulcanization.

Description

Description Polyamide fiber reinforced elastic composition and method for producing the same

Technical field

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.

Background art

A composition in which short fibers are dispersed in a vulcanizable rubber-like polymer such as natural rubber, isoprene rubber, butadiene rubber, and ethylene propylene rubber to improve the modulus and strength, that is, 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. As 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. Also, 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. There is known a method of blending a vulcanizable rubber and a vulcanizing agent with a fiber-reinforced elastic composition obtained by a method of stretching or rolling a cord-like material and vulcanizing the blend. In such a conventional method, a production method using an initial condensate of a resol-type alkylphenol-formaldehyde-based resin as a binder is disclosed in Japanese Patent Publication No. 11174494. No. 5,716,164 discloses a production method using a novolak type alkylphenol roof aldehyde resin, and a production method using a silane coupling agent as a binder is disclosed in No. 33300, Japanese Patent Publication No. 5-88860, and Japanese Patent Application Laid-Open No. 278360/1991.

However, 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. For this reason, 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

SUMMARY 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. To provide a method for producing a mid-fiber reinforced elastic composition and a method for producing a sulfide thereof.

The above object is solved by the present invention.

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,

(b) 1 to 40 parts by weight of polyolefin resin,

(c) 1 to 70 parts by weight of fibrous thermoplastic polyamide containing dispersed layered silicate, and

(d) Silane coupling agent

It contains.

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:

(1) (a) 100 parts by weight of at least one kind of rubbery polymer having a glass transition point of 0 ° C or less,

(b) 1 to 40 parts by weight of polyolefin resin, and

(d) Silane cupping agent

Is melt-kneaded to form a molten matrix,

(2) During the melting matrix,

(c) 1 to 70 parts by weight of thermoplastic polyamide containing layered silicate is melt-kneaded,

(3) extruding the kneading composition containing the components (a) to (d) at a temperature equal to or higher than the melting point of the component (c) (thermoplastic polyamide);

(4) The extrudate is stretched or rolled at a temperature lower than the melting point of the thermoplastic polyamide of the component (c), whereby the layered silicate-containing thermoplastic polyamide is converted into a fibrous form. Disperse,

That is to say.

In the above method, 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.

In the polyamide fiber reinforced elastic composition and the method for producing the same according to the present invention, (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.

Further, in the polyamide fiber-reinforced elastic composition and the method for producing the same according to the present invention, 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

Hereinafter, the polyamide fiber-reinforced elastic composition of the present invention, its vulcanized product, and the production method thereof will be specifically described.

In the polyamide fiber reinforced elastic composition of the present invention, 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. (A) 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 in the main chain are exemplified. Epoxy-modified, silane-modified or maleated rubbers of these rubbers may be used as the component (a).

(a) 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. With a softening point of Can be (B) 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.

(b) Specific examples of the polyolefin resin used as the component 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, ethylene one vinyl preparative Rie Tokishishira emissions copolymers, and ethylene one Binirushira down copolymer. As another specific example of the polyolefin resin used as the component (b), there may be mentioned a hydrogenated polyolefin such as chlorinated polyethylene / brominated polyethylene or chlorosulfonated polyethylene. .

Among the above polyolefin resins, particularly preferred are high-density polyethylene (HDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), polypropylene (PP), and ethylene-propylene. Pyrene block copolymer, ethylene-propylene random copolymer Body, poly 4-methylidene 1 (P4MP 1), ethylene vinyl acetate copolymer (EVA), and ethylene vinyl alcohol copolymer, among which Melt flow index (MFI) A range of 0.2 to 50 g of ZIO is the most preferred. 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.

(c) 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).

(c) Specific examples of the thermoplastic polyamide for the component 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, decame Polycondensate of rangedamine and terephthalic acid, polycondensate of pendecamethylenediamin and terephthalic acid, polycondensate of dodecamethylenediamine and terephthalic acid, polycondensation of tetramethylenediamin and isophthalic acid Body, Hexamethylenediamine and Isophthalic acid Condensates, polycondensates of octamethylenediamine and isophthalic acid, polycondensates of trimethylethylhexamethylenediamine and isophthalic acid, decamethylenediamine and isofalic acid Examples include a polycondensate of tallic acid, a polycondensate of indecamethylenediamine and isophthalic acid, and a polycondensate of dodecamethylenediamin and isophthalic acid.

Among the above 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. As used herein, "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. A state in which parallel and / or random are mixed and dispersed in parallel and / or at random. Therefore, layered silicate is a fine layer with a length of 1 to 1, OO Onm and a thickness of 0.6 to 2 nm. As such 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. There is no limitation on the method of uniformly dispersing such a layered silicate in a polyamide resin, but when the raw material of the layered silicate of the present invention is a multilayered clay mineral, this is used as a swelling agent. A method may be used in which the layers are preliminarily brought into contact with each other so that the monomers can be easily taken in between the layers, and then mixed with a monomer for forming a polyamide to polymerize the monomer (Japanese Patent Publication No. 22946/1996). . In addition, 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.

Examples of the swelling agent include amino acid and nylon salt. Specific examples thereof include ω-amino decanoic acid, ω-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. Lan, vinyl triethoxyquin silane, vinyl tris (^ -methoxhetoxy) silane, vinyl triacetyl silane, alpha-methacryloxyprovir trimethoxy lan, β — (3 , 4—Epoxycyclohexyl) ethyl trimethoxysilane, α-glycidoxypropyl trimethoxysilane, α-glycidoxypropyl dimethyldimethyxylane, α-glycidoxypropyl methylethyl ethoxysilane, α Glycidoxypropyl pyrethyldimethoxysilane, y—Glycidoxypropyl pyrethyljetoxirane, N—3— (Aminoethyl) Aminop mouth Bilitrimethoxysilane, N_S— (Aminoethyl) Amino propyl triethoxysilane, N— / 3 — (Aminoethyl) amino Propinolemethyldimethoxysilane, N— / 3— (Aminoethyl) amino Propyreethyldimethoxysilane, N—yS— (Aminoethyl) aminobutamate Pyruethyljetoxirane, A_ami N-propyl triethoxysilane, N—vinylamine trimethoxysilane, r- [N- (S—methacryloxyshethyl) N, N—dimethylanmonium (Chloride)] propyl methoxy silane, and styrene diamino silane. Among these, a group which easily desorbs a hydrogen atom from an alkoxy group or the like and a group having Z or a polar group and a vinyl group are particularly preferably used.

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.

(d) An organic peroxide can be used in combination with the silane coupling agent used as the component. When the organic peroxide is used in combination, 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. As the organic peroxide, 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. Those in the range are preferably used. More specifically, 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).

Specific examples of the organic peroxide used in the present invention include 1,1-di_t_butylperoxy-1,3,5—trimethylcyclohexane and 1,1-di-t-butylperoxy. Oxycyclohexane, 2,2-di-t-butyl-butoxybutane, 4,4-di-t-butyl-vinyl-lenoic acid n-butyl ester, 2,2-bis (4, 4 —Di-t-butylbutyloxycyclohexane) propane, peroxyneodecanoic acid, 2,2,4-trimethylpentyl, α-cumyl peroxyneodecanoate, t-butyl peroxyneodecanoate, peroxybivari And t-butyl peroxyacetate, t-butyl peroxyperinate, t-butyl peroxybenzoate, t-butyl peroxyisophthalate and the like.

Among these, 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.

In the polyamide fiber reinforced elastic composition of the present invention, 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. If the content of the component (b) exceeds 40 parts by weight, only a composition having low rubber elasticity can be obtained, which is not preferable. 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. Specifically, preferably 70% by weight, more preferably 80% by weight, and even more preferably 90% by weight of 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).

(1) At least one part (one part or all) of at least one kind of rubbery polymer whose component (a) has a glass transition temperature of 0 ° C or less, and the polyolefin of component (b) d) a step of melting and kneading the component silane coupling agent to prepare a molten matrix containing the (a) component and the (b) component;

(2) The above molten matrix and the 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. A step of producing a modified melt-kneaded composition,

(3) A step of extruding the chemically modified melt-kneaded composition from a die at a temperature equal to or higher than the melting point of the thermoplastic polyimide (c) (preferably at a temperature higher by 10 ° C or more than the melting point). ,

(4) A step of stretching or rolling the above extrudate while drafting at a temperature lower than the melting point of the thermoplastic polyamide of the component (c), and the stretching or rolling temperature at this time is the component (b). The melting point may be lower than the melting point.

(5) In the 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.

Each step in the method for producing a polyamide fiber reinforced resin composition of the present invention will be described in more detail.

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). In this step (1), 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. When 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. For the melt-kneading operation, an apparatus usually used for kneading resin and rubber can be used. As such a device, 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. In this case, 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. I do. In the extrusion process, 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). Specifically, 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). By drawing or rolling, a tough polyamide fiber that reinforces the elastic body composition is formed. For stretching or rolling, for example, 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. Here, applying the draft means that the winding speed is faster than the spinneret speed. The ratio of the take-up speed / the die speed (draft ratio) 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. .

As described above, 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. When performing step (5), 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. In this case, 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. It is preferable to use a device used for the compounding of ordinary rubber, for example, a device such as a Plavender plaster, a roll, and a Banbury mixer. After this kneading, 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. Thus, a vulcanized product of the polyamide fiber-reinforced elastic composition of the present invention is obtained.

In the polyamide fiber reinforced elastic composition of the present invention, 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.

(b) 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). .

Further, the fiber-reinforced resin composition to be subjected to the step (5) preferably has a pellet shape. By using the pellet-shaped fiber reinforced resin composition, 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.

During this kneading in the step (5), carbon black, process oil, zinc white, stearic acid, and an antioxidant may be added and kneaded. At this time, 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. At this time, 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. At this time, 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). New 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.

In the method of the present invention, 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.

Examples of vulcanization aids include aldehyde 'ammonia, aldehyde amines, guanidines, thioureas, thiazols, thiurams, dithiolbamates and xanthates. Can be used ο

In the vulcanization performed by adding a vulcanizing agent or the like to the polyimide fiber reinforced elastic composition of the present invention, the vulcanization temperature is preferably about 100 to 180 ° C. . However, 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. Example

The present invention will be further described by the following examples, which do not limit the scope of the present invention.

In the following Examples and Comparative Examples, the physical properties of the polyamide fiber reinforced elastic composition and other fiber reinforced resin compositions were measured by the following methods.

(1) Physical properties of unvulcanized product;

(A) Organic composite layered silicate content:; Ignition of layered silicate composite polyamide (montmorillonite composite nylon) at 650 ° C by thermogravimetric analysis, and the residual weight of ignition From the following equation.

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) )

(B) Fiber shape:; Form · dispersibility and average fiber diameter: Dissolve in hot xylene, take out the fiber, wash, observe with a scanning electron microscope, and disperse if fine fibers are dispersed. 200 fine fibers dispersed as good were observed with the above-mentioned scanning electron microscope, the fiber diameter was measured from the electron microscope image, and the average was determined to be the average fiber diameter.

(C) Mooney viscosity: Measure the viscosity of ML1 + 4 at a temperature of 100 ° C.

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(2) physical properties of the vulcanized product;

(A) Tensile properties:; Measured at 23 ° C according to JIS K6251, at a tensile speed of 500 mm / min., Tensile strength, 100% elastic modulus, 300% elastic modulus and elongation, and expressed in M Pa and%, respectively. .

(B):; Measured with JIS-A type according to JIS K6253.

(C) Abrasion resistance: A Lambourn abrasion test was performed in accordance with JIS K6254, and Comparative Example 1 was indicated as an index, with 100 as 100. (D) Dynamic friction coefficient:; A rectangular glass plate with a sample thickness of 0.2 or less and a width of 80 mm and a length of 200 mm according to JIS K7125, using a transparent glass plate as the mating material, a load of 200 g, and a pulling speed The larger the value, the better the measure of slip resistance, as measured by SOOmmZmin.

Reference Example 1 (Preparation of layered silicate-containing polyamide)

At atmospheric pressure, in a 20 liter Hastelloy reactor equipped with a stirrer and temperature controller, as a layered silicate, 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. By this operation, 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%. Next, 10 kg of ε-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.

Reference Examples 2 to 4 (Preparation of Layered Silicate-Containing Polyamide)

In each of Reference Examples 2 to 4, a layered silicate-containing polyamide was prepared in the same manner as in Reference Example 1. However, the amount of the same montmorillonite complex used in Reference Example 1 was assumed to be 270 g, 360 g or 720 g, and this was reduced to 10 kg of £ -force prolactam and 1 liter of water. In the same manner as in Reference Example 1, monmorillonite composite nylon 6 was produced. The content of the montmorillonite complex in the montmorillonite complex Nylon 6 was 3.0%, 4.1%, and 7.9%, respectively. Table 1 shows the results.

table 1

Reference Example 5 (Preparation of Polyamide Fiber Reinforced Resin Composition of the Present Invention Containing One Part of Component (a))

(a) 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). As a result, 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 components (a) and (b) were extracted and removed from the pellets with hot xylene, and the fine fibers consisting of the montmorillon-mouth-night composite complex 6 of component (c) were observed with a scanning electron microscope. However, the average fiber diameter was 0.2 ^ m. The results are shown in Table 2.

Reference Examples 6 to 7 (Preparation of Polyamide Fiber Reinforced Resin Composition of the Present Invention Containing One Part of Component (a))

In each of Reference Examples 6 to 7, the same procedure as in Reference Example 5 was carried out, except that 100 parts by weight and 200 parts by weight of the compound (c) of the component-monitor-night-mixed nylon 6 were used. A fiber reinforced resin composition was obtained. Table 2 shows the evaluation results.

Reference Examples 8 to 10 (Preparation of polyamide fiber reinforced resin composition of the present invention containing one part of component (a))

In each of Reference Examples 8 to 10, a fiber-reinforced resin composition was prepared in the same manner as in Reference Example 5, except that 650 parts by weight of montmorillonite-combined nylon was used as the component (c). Obtained. The evaluation results are shown in Table 2. Reference Example 11 (Preparation of comparative polyimide fiber reinforced resin composition)

(c) 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

(a): Rubbery polymer (b): Polyolefin

(c): Montmorillonite composite PA 6 (d): Silane coupling agent

Example 1

5 parts by weight of the fiber reinforced resin composition of Reference Example 5 and 98 parts by weight of natural rubber (SRM-L) as an additional component (a) were added to carbon black (HAF), process oil, and zinc white. , Stearic acid, an antioxidant, a vulcanization accelerator and sulfur were compounded according to the compounding table in Table 4. The compounding procedure is as follows: a natural rubber and a fiber reinforced resin composition are charged into a Brabender plastic graph heated to 160 ° C, masticated for 30 seconds, and then a force black, a process oil, a zinc oxide, Stearic acid and an antioxidant are added in the stated order and kneaded for 4 minutes, and the mixture is placed on an open roll heated to 80 ° C. In, the sulfur and the vulcanization accelerator were oriented. The obtained composition was vulcanized at 145 ° C for 30 minutes to obtain a polyamide fiber reinforced elastic composition. The Mooney viscosity of the blend when the carbon black was blended and the physical properties of the vulcanizate were measured. The results are shown in Table 3.

Examples 2 to 5

In each of Examples 2 to 5, 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.

Comparative Example 1

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 2-3

In 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.

Table 3

(a): rubbery polymer (b): polyolefin

(c): Montmorillonite composite PA6

Examples 6 to 7

In each of Examples 6 and 7, 10 or 25 parts by weight of the fiber-reinforced resin composition of Reference Example 5 and 66 or 50 parts by weight of natural rubber as an additional component (a) , And butadiene rubber (UBE0-150, manufactured by Ube Industries, Ltd.) were compounded and vulcanized in the same manner as in Example 1 except that 30 parts or 40 parts by weight of the compounding ingredients shown in Table 4 were used. . Table 5 shows the results.

Table 4 Combination agent weight parts

(For 100 parts by weight of rubber)

Carbon black 40

Process oil 10

Lead Hana 3

Stearic acid 2

Anti-aging agent 1

Vulcanization accelerator 0.5

Sulfur 2.5

Comparative Examples 4 to 5

In each of Comparative Examples 4 and 5, 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.

Examples 8 to 12

In Examples 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.

Table 5

(a): Polymer (b): Polyolefin

(c): Montmorillonite double PA 6 Industrial applicability

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.

Claims

The scope of the claims

1. The following components mixed with each other:

(a) 100 parts by weight of at least one rubbery polymer having a glass transition temperature of 0 ° C or less,

(b) 1 to 40 parts by weight of polyolefin resin,

(d) Silane coupling agent

A polyamide fiber-reinforced elastic composition comprising:

2. For a total of 100 parts by weight of the components (a), (b) and (c), a silane coupling agent as the component (d) is used.

2. The polyamide fiber reinforced elastic composition according to claim 1, which is blended in a ratio of 0.1 to 5.5 parts by weight.

3. The polyamide fiber-reinforced elastic composition according to claim 1, wherein the layered silicate-containing thermoplastic polyamide fiber has an average fiber diameter of 1 m or less.

4. In the layered silicate-containing thermoplastic polyamide fiber, the layered silicate is blended in a ratio of 0.05 to 30 parts by weight with respect to 100 parts by weight of the thermoplastic polyamide. 2. The polyamide fiber reinforced elastic composition according to item 1 above.

5. A vulcanized product of the polyamide fiber-reinforced elastic composition according to any one of claims 1 to 4.

6. (1) (a) 100 parts by weight of at least one rubbery polymer having a glass transition temperature of 0 ° C or less,

(b) 1 to 40 parts by weight of polyolefin resin, and

(d) Silane cupping agent Is melt-kneaded to form a molten matrix,

(2) During the melting matrix,

(3) The kneading composition containing the components (a) to (d) is extruded at a temperature equal to or higher than the melting point of the thermoplastic polyamide of the component (c).

(4) The extrudate is stretched or rolled at a temperature lower than the melting point of the thermoplastic polyamide of component (c), whereby the layered silicate-containing thermoplastic polyamide is dispersed in a fibrous form. Let

A method for producing a polyamide fiber reinforced elastic composition, comprising:

7. In the formation of the molten matrix in the step (1), only one part of 100 parts by weight of the component (a) is used, and the composition obtained in the step (4) is added to the composition obtained in the step (4). a) The method for producing a polyamide fiber reinforced elastic composition according to claim 6, wherein the remaining part of 100 parts by weight of the components is added and mixed.

8. For a total of 100 parts by weight of the components (a), (b) and (c), the silane coupling agent as the component (d) is:

9. The method for producing a polyamide fiber reinforced elastic composition according to claim 7, wherein the composition is blended in a ratio of 0.1 to 5.5 parts by weight.

9. The method according to claim 7, wherein, in the stretching or rolling step (4), the layered silicate-containing thermoplastic polyamide is dispersed in a fiber having an average fiber diameter of 1 m or less. A method for producing a polyimide fiber reinforced elastic composition according to the above.

10. The component (c), wherein the layered silicate is blended in an amount of 0.05 to 30 parts by weight with respect to 100 parts by weight of the thermoplastic polymer. Polyamide fiber reinforced elastic body described in A method for producing the composition.

1 1. Claims? 11. A polyamide fiber comprising mixing a vulcanizing agent with the polyamide fiber reinforced elastic composition obtained by the method according to any one of items 1 to 10, and vulcanizing the mixture. Method for producing vulcanizate of reinforced elastic composition