JPH0959435A - Production of fiber-reinforced elastomer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a fiber-reinforced elastomer composition improved in workability, modulus and strengths by melt-kneading a specified fiber-reinforced thermoplastic resin composition and a rubbery polymer. SOLUTION: One hundred (100) pts.wt. rubbery polymer (a) of a glass transition point of 0 deg.C or below, 30-500 pts.wt. polyolefin (b) of a melting point of 80-250 deg.C and 0.1-20 pts.wt., per 100 pts.wt. component (b), silane coupling agent (c) are melt-kneaded, or component (a) and component (b) treated with component (c) are melt-kneaded to obtain a matrix. This matrix and 10-500 pts.wt., per 100 pts.wt. component (d), thermoplastic polymer having amide groups in the main chain at a temperature equal to or higher than the melting point of component (d), the obtained mixture is extruded, and the extrudate is drawn and/or rolled at a temperature below the melting point of component (d) and equal to or higher than the melting point of component (a) to obtain a fiber- reinforced thermoplastic resin composition (A). Component (A) and a rubbery polymer (B) of a glass transition temperature of 0 deg.C or below are melt-kneaded to form a composition containing 1-40 pts.wt. component (b) and 1-70 pts.wt. fibers per 100 pts.wt. total weight of component (a) and component (B).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fiber-reinforced elastic body composition having good workability and excellent in modulus and strength, which is a tire external member such as a tread or a sidewall of a tire, a carcass, a bead, a belt, It is preferably used for tire inner members such as chafers and industrial products such as hoses, belts, rubber rolls and rubber crawlers.

[0002]

2. Description of the Related Art A composition in which short fibers are dispersed in a vulcanizable rubber-like polymer such as natural rubber, polyisoprene, polybutadiene, or ethylene-propylene rubber to improve modulus and strength, that is, a fiber-reinforced elastic composition is It has been manufactured by blending short fibers such as nylon, polyester, and vinylon, and vulcanizing as necessary.

The fiber-reinforced elastic composition obtained by such a method is suitable for use as a tire member for automobiles.
Since strength and elongation were insufficient, a fiber-reinforced elastic body composition in which these points were improved has been demanded. As a fiber-reinforced elastic body composition that meets such requirements, for example, a fiber-reinforced elastic body composition in which short fibers such as nylon are fine fibers having an average diameter of submicron has been proposed.
For example, vulcanizable rubber, nylon and a binder are melt-kneaded at a temperature not lower than the melting point of nylon, the obtained kneaded product is extruded in a string shape at a temperature not lower than the melting point of nylon, and the obtained string-shaped product is stretched. Alternatively, the fiber-reinforced elastic body composition obtained by a method of rolling and a vulcanizable rubber and a vulcanizing agent added thereto are mixed and vulcanized. A method of using an initial condensate of a resol type alkylphenol formaldehyde resin as a binder in such a method is disclosed in JP-A-58-79037, and a method of using a novolak type alkylphenol formaldehyde resin as a binder is The production method using a silane coupling agent as a binder is disclosed in JP-A-59-43041.
It is described in JP-A-3-81137, JP-A-63-179945 and JP-A-6-70810.

[0004]

However, when nylon is blended, there is a problem that it becomes extremely hard. For this reason, when compounding other vulcanizable rubber or vulcanizing agent into the fiber reinforced elastic body composition, it must be cut manually, and the nylon fiber or vulcanized rubber in the fiber reinforced elastic body composition must be cut. The possible rubber was not well dispersed in some cases. To prevent this, extend the kneading time,
It is necessary to heat and soften the fiber reinforced elastic body composition, and then to mix vulcanizable rubber and the like, which causes decrease in productivity and increase in cost of the fiber reinforced elastic body composition. It's coming. Moreover, although the modulus in the orientation direction of the fibers and the fatigue resistance are high, there is a problem that the modulus in the direction orthogonal to the orientation direction of the fibers and the fatigue resistance are extremely low.
Another problem is that the process is complicated and the reproducibility is low.

[Means for Solving the Problems]

The present invention solves these problems, is excellent in productivity and can be manufactured at low cost, and has a small difference in the orientation direction of the fiber with respect to modulus and fatigue resistance and the direction perpendicular thereto. It is an object to provide a method for producing a reinforced elastic body composition.

That is, according to the present invention, (A) a fiber-reinforced thermoplastic resin composition, that is, (1) a rubber-like polymer (first elastomer) having a glass transition temperature of 0 ° C. or less and a component (a) Melt-kneading the polyolefin of (b) with the silane coupling agent of component (d), or
The first step of melt-kneading the first elastomer of (a) and the polyolefin of component (b) treated with component (d) to prepare a matrix, and (2) adding an amide group to the main chain of component (c). The second step of melt-kneading the thermoplastic polymer having the above-mentioned matrix and the component (c) at a temperature higher than either melting point, and then extruding, (3) lowering the melting point of the component (c) to the component (b). ) The fiber-reinforced thermoplastic resin composition comprising a third step of stretching and / or rolling at a temperature higher than the melting point of the polyolefin, and (B) a rubber-like polymer having a glass transition temperature of 0 ° C. or lower (second elastomer). A fiber-reinforced elastic body composition comprising a fourth step of melt-kneading, wherein the ratio of the component (b) is 1 to 40 parts by weight based on 100 parts by weight of the total amount of the first elastomer and the second elastomer. , There is provided a method for producing a fiber-reinforced elastic body composition, characterized in that the proportion of fine fibers of the component (c) is 1 to 70 parts by weight.

Further, according to the present invention, the fiber-reinforced elastic body composition is (A) a fiber-reinforced thermoplastic resin composition, that is, the first elastomer of the component (a), the component (b) and the component (C) is the main constituent component, and component (a) and component
Most of the component (c) is dispersed as fine fibers in the matrix composed of (b). The fine fiber of the component (c) is the component (a)
A fiber reinforced elastic body composition obtained by kneading the component (b) and the thermoplastic resin composition bound at its interface with an additional (B) second elastomer, and further vulcanizing sulfur or the like to this composition. Provided is a method for producing a vulcanized product to which a vulcanization agent and, if necessary, a vulcanization aid are added.

Further, according to the present invention, the kneading ratio which can be produced by kneading (A) the fiber-reinforced thermoplastic resin composition and (B) the second elastomer is (B) the second elastomer. A) The weight ratio of the fiber reinforced thermoplastic resin composition is in the range of 20/1 to 0.1 / 1, and the kneading temperature is a component (c) constituting the fine short fibers in the fiber reinforced thermoplastic resin composition. ) And a temperature higher than the melting point of component (b), a method for producing a fiber-reinforced elastic composition is provided.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Each step and main constituent components in the method for producing the fiber-reinforced elastic composition of the present invention will be specifically described below. First Step The first step is to prepare the first elastomer and component of component (a)
(b) A step of preparing a matrix made of polyolefin. As a matrix preparation method,
Examples include a method of melt-kneading the silane coupling agent of (a), the component (b) and the component (d), and a method of melt-kneading the component (b) with the component (d) and then with the component (a). . The melt-kneading temperature is higher than the melting point of the component (b), and the melt-kneading can be carried out by an apparatus usually used for kneading resins and rubbers. As such a device, a Banbury type mixer, a kneader, a kneader extruder, an open roll, a single-screw kneader, a twin-screw kneader, or the like is used. Among these devices, the twin-screw kneader is most preferable in that melt kneading can be performed continuously in a short time.

The component (a) is preferably a first elastomer, which is a rubber-like elastomer at room temperature and a rubber-like polymer having a glass transition temperature of 0 ° C. or lower. Particularly preferably, the glass transition temperature is −20 ° C. or lower. As such a specific example, natural rubber (NR),
Isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), butyl rubber (IIR),
Chlorinated butyl rubber, brominated butyl rubber, chloroprene rubber (CR), nitrile-chloroprene rubber, nitrile
Diene rubbers such as isoprene rubber, acrylate / butadiene rubber, vinylpyridine / butadiene rubber, vinylpyridine / styrene / butadiene rubber, ethylene / propylene rubber (EPR), ethylene / propylene / diene rubber (EPDM), ethylene / butene rubber, ethylene / Polyolefin rubber such as butene / diene rubber, chlorinated polyethylene rubber, chlorosulfonated polyethylene rubber (CSM), acrylic rubber, ethylene acrylic rubber, polychlorinated trifluorinated rubber, rubber having a polymethylene type main chain such as fluorinated rubber , Epichlorohydrin rubber, ethylene oxide / epichlorohydrin rubber, etc. having oxygen atom in the main chain, polyphenylmethylsiloxane rubber, polymethylethylsiloxane rubber, etc. silicone rubber, nit Sogomu, polyester urethane rubber, the main chain such as polyether urethane rubber such as rubber having other nitrogen atom and an oxygen atom of the carbon atom. Further, those obtained by subjecting these rubbers to epoxy modification, silane modification, or maleation may also be mentioned. As another specific example of the component (a), a thermoplastic butadiene
Examples thereof include styrene block copolymer, olefin rubber, urethane rubber, polyester rubber, 1,2-polybutadiene rubber, polyamide rubber, vinyl chloride rubber and the like.

Component (b) is a polyolefin,
It preferably has a melting point in the range of 80 to 250 ° C. Again 5
Those having a Vicat softening point of 0 ° C. or higher, particularly preferably 50 to 200 ° C. are also used. Such preferable examples include homopolymers and copolymers of olefins having 2 to 8 carbon atoms, and olefins having 2 to 8 carbon atoms and aromatic vinyl compounds such as styrene, chlorostyrene and α-methylstyrene. A copolymer of C2-8 olefin and vinyl acetate, a copolymer of C2-8 olefin and acrylic acid or its ester, and C2
Preferable examples include a copolymer of 8 olefin and methacrylic acid or its ester, and a copolymer of 2 to 8 carbon olefin and vinylsilane compound.

Specific examples of the component (b) include high density polyethylene, low density polyethylene, polypropylene, ethylene / propylene block copolymer, ethylene / propylene random copolymer, linear low density polyethylene, poly-4-methylpentene. -1, polybutene-1, polyhexene-1, ethylene / vinyl acetate copolymer, ethylene / vinyl alcohol 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 / vinyltrimethoxysilane copolymer, ethylene / vinyltriethoxysilane copolymer, ethylene / vinylsilane copolymer, ethylene / Examples include styrene copolymers and propylene / styrene copolymers. Further, halogenated polyolefins such as chlorinated polyethylene, brominated polyethylene, and chlorosulfonated polyethylene are also preferably used.

Among the polyolefins as the component (b), particularly preferable are high density polyethylene (HDPE), low density polyethylene (LDPE), polypropylene (PP), ethylene / propylene block copolymer, ethylene / propylene. Random copolymers, linear low density polyethylene (LLDPE), poly-4-methylpentene-1 (P4MP1), ethylene / vinyl acetate copolymer (EVA), and ethylene / vinyl alcohol copolymer are mentioned, among which, The most preferable one has a melt flow index in the range of 0.2 to 50 g / 10 min. These may be used alone,
You may combine 2 or more types.

Specific examples of the silane coupling agent as the component (d) include vinyltrimethoxysilane, vinyltriethoxysilane and vinyltris (β-methoxyethoxy).
Silane, vinyltriacetylsilane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane , Γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, N-β- (aminoethyl) aminopropyltrimethoxysilane, N-β -(Aminoethyl) aminopropyltriethoxysilane, N-
β- (aminoethyl) aminopropylmethyldimethoxysilane, N-β- (aminoethyl) aminopropylethyldimethoxysilane, N-β- (aminoethyl) aminopropylethyldiethoxysilane, γ-aminopropyltriethoxysilane, N Examples include -phenyl-γ-aminopropyltrimethoxysilane, γ- [N- (β-methacryloxyethyl) -N, N-dimethylammonium (chloride)] propylmethoxysilane, and styryldiaminosilane. Among them, those having a group that easily desorbs a hydrogen atom from an alkoxy group and / or a polar group and a vinyl group are particularly preferably used.

The silane coupling agent as the component (d) is preferably in the range of 0.1 to 2.0 parts by weight, particularly preferably 0.2 to 1.0 parts by weight, based on 100 parts by weight of the component (b). Is the range. If the amount of the silane coupling agent is less than 0.1 part by weight, a composition having high strength cannot be obtained, and if the amount of the silane coupling agent is more than 2.0 parts by weight, a composition excellent in modulus is obtained. I can't get it. When the amount of the silane coupling agent is less than 0.1% by weight, a strong bond is not formed between the component (a) and the component (b), and only a composition having low strength can be obtained. On the other hand, when the amount of the silane coupling agent is more than 5.5% by weight, the component (c) does not form good fine fibers, so that only a composition having a poor modulus can be obtained.

When the silane coupling agent as the component (d) is used, an organic peroxide can be used together. The organic peroxide has a half-life temperature of 1 minute as the component (a).
Or the melting point of the component (c), whichever is higher, or a temperature range higher by about 30 ° C. than this temperature is preferably used. Specifically, one having a half-life temperature of about 110 to 200 ° C. for 1 minute is preferably used.

Specific examples of the organic peroxide include 1,1-
Di-t-butylperoxy-3,3,5-trimethylcyclohexane, 1,1-di-t-butylperoxycyclohexane, 2,2-di-t-butylperoxybutane, 4,4-di-t -Butylperoxyvaleric acid n-
Butyl ester, 2,2-bis (4,4-di-t-butylperoxycyclohexane) propane, peroxyneodecanoic acid 2,2,4-trimethylpentyl peroxyneodecanoate α-cumyl, peroxyneohexanoic acid Examples thereof include t-butyl, t-butyl peroxypivalate, t-butyl peroxyacetate, t-butyl peroxylaurylate, t-butyl peroxybenzoate, and t-butyl peroxyisophthalate. Above all, the half-life temperature of 1 minute is the melt-kneading temperature or 30 ° C from this temperature.
Those having a moderately high temperature range, specifically, those having a one-minute half-life temperature of about 80 to 260 ° C. are preferably used.

When the organic peroxide is used in combination, a radical is formed on the molecular chain of the component (b) polyolefin, and this radical reacts with the silane coupling agent to form the component (b) and the silane cup. It is believed to promote the reaction with the ring agent. The amount of the organic peroxide used at this time is preferably in the range of 0.01 to 1.0 parts by weight with respect to 100 parts by weight of the component (b).

However, when natural rubber, polyisoprene, or a styrene / isoprene / styrene block copolymer is used as the component (a), it is not necessary to use an organic peroxide. Rubber having an isoprene structure, such as natural rubber, polyisoprene, and styrene / isoprene / styrene block copolymers, is a type that has a -COO / group at the end of the main chain due to the main chain breaking due to a mechanochemical reaction during kneading. This is because it is considered that the above-mentioned peroxide is generated, and this has the same action as the above-mentioned peroxide.

Second Step In the second step, the matrix comprising the components (a) and (b) obtained in the first step and the thermoplastic polymer having an amide group in the main chain of the component (c), Melt-kneading is performed at a temperature higher than the melting point of any of the components (a), (b) and (c), and then extruded. Second
The melt-kneading in the step is limited to a device capable of kneading at a high shear rate such as a Banbury type mixer and a twin-screw kneader because the silane coupling agent as the component (d) does not exist.

The kneaded material obtained in the extrusion step is extruded from a spinneret, an inflation die or a T die. Both spinning and extrusion must be carried out at a temperature higher than the melting point of component (c). Specifically, the component (c)
It is preferable to carry out the reaction at a temperature higher than the melting point of, and a temperature higher than this melting point by 30 ° C. Even if melting and kneading are performed at a temperature lower than the melting point of the component (c) in this step, the kneaded product has a structure in which fine particles of the component (c) are dispersed in a matrix composed of the component (a) and the component (b). It doesn't. Therefore, even if such a kneaded product is spun and drawn, the component (c) cannot become fine fibers.

The component (c) is a thermoplastic polymer having an amide group in the main chain, and has a melting point in the range of 135 to 350 ° C., and is higher than the melting point of the component (b) polyolefin, Above all, melting point 160-265 ° C
The range of is preferable. As the component (c),
Included are thermoplastic polyamides and urea resins. Of these, thermoplastic polyamides are preferred because they give tough fibers by extrusion and drawing.

Specific examples of the thermoplastic polyamide include nylon 6, nylon 66, nylon 6-nylon 66 copolymer, nylon 610, nylon 612, nylon 4
6, nylon 11, nylon 12, nylon MXD6,
Polycondensate of xylylenediamine and adipic acid, Polycondensate of xylylenediamine and pimelic acid, Polycondensate of xylylenediamine and speric acid, Polycondensate of xylylenediamine and azelaic acid, Xylylenediene Polycondensate of amine and sebacic acid, Polycondensate of tetramethylenediamine and terephthalic acid, Polycondensate of hexamethylenediamine and terephthalic acid, Polycondensate of octamethylenediamine and terephthalic acid, Trimethylhexamethylenediamine and terephthalic acid Polycondensate of decamethylenediamine and terephthalic acid, polycondensate of undecamethylenediamine and terephthalic acid, polycondensate of dodecamethylenediamine and terephthalic acid, polycondensate of tetramethylenediamine and isophthalic acid, Polycondensate of hexamethylenediamine and isophthalic acid, Polycondensate of Tamethylenediamine and isophthalic acid, Polycondensate of trimethylhexamethylenediamine and isophthalic acid, Polycondensate of decamethylenediamine and isophthalic acid, Polycondensate of undecamethylenediamine and isophthalic acid, and Dodecamethylenediamine And a polycondensation product of isophthalic acid.

Of these thermoplastic polyamides, particularly preferred specific examples include nylon 6 (PA6), nylon 66 (PA66), nylon 6-nylon 66 copolymer, nylon 610, nylon 612, nylon 46,
Examples thereof include nylon 11 and nylon 12. One or more of these may be used. It is preferable that these thermoplastic polyamides have a molecular weight in the range of 10,000 to 200,000.

The proportions of component (a), component (b) and component (c) are as follows. The amount of the component (b) is 30 to 500 parts by weight based on 100 parts by weight of the component (a). Preferably 3
It is in the range of 0 to 300 parts by weight, particularly preferably 40 to
The range is 200 parts by weight. If the ratio of the component (b) is less than 30 parts by weight, pellets cannot be obtained. If the ratio of the component (b) exceeds 500 parts by weight, the workability will deteriorate. The component (c) is 1 per 100 parts by weight of the component (a).
0 to 500 parts by weight. It is preferably 20 to 400 parts by weight, and particularly preferably 30 to 300 parts by weight. When the ratio of the component (c) is less than 10 parts by weight, the productivity is low and the cost is increased. On the other hand, when the ratio of the component (c) exceeds 500 parts by weight, the ratio of the component (c) existing as fine fibers in the composition becomes too small, and therefore, even when such a composition is molded, a smooth surface is obtained. It becomes difficult to obtain a molded product having the above-mentioned properties and the strength is significantly reduced.

Most of the component (c) is uniformly dispersed in the above matrix as fine fibers. Specifically, 70% by weight, preferably 80% by weight, and particularly preferably 90% by weight or more are dispersed as fine fibers. The fibers of the component (c) preferably have an average fiber diameter of 1 μm or less, and a particularly preferable range is 0.05 to 0.5.
It is in the range of 8 μm. Aspect ratio (fiber length / fiber diameter)
Is preferably 10 or more. And component (c)
Is bound to both component (a) and component (b) at the interface. It is preferable that the sum of the components (a) and (b) bonded to the component (c) is 1 to 20% by weight, particularly 5 to 15% by weight.

Third Step In the third step, the cord-like or thread-like extrudate obtained in the second step is stretched and / or rolled to obtain the component (c).
Is converted into a fiber shape to obtain a fiber-reinforced fiber thermoplastic resin composition. In the step of extruding from a spinneret, an inflation die or a T die, and then stretching and / or rolling this, the fine particles of the component (c) during kneading are transformed into fibers by spinning or extrusion. This fiber is subjected to a drawing treatment by subsequent drawing or rolling to become a stronger fiber. Therefore, spinning and extrusion must be carried out at a temperature above the melting point of component (c), and stretching and rolling must be carried out at a temperature lower than the melting point of component (c).

The spinning or extrusion and the subsequent stretching or rolling can be carried out, for example, by extruding the kneaded product from the spinneret to spin it into a string or thread, and winding it on a hobbin while drafting it. . Here, "drafting" means that the winding speed is higher than the spinneret speed. The ratio of the winding speed / the spinneret speed (draft ratio) is preferably in the range of 1.5 to 100,
More preferably, it is in the range of 2-70, particularly preferably 3-5.
0.

The extruded cord-shaped or thread-shaped yarn is continuously cooled, drawn or rolled. The cooling / stretching or rolling treatment is performed at a temperature lower than the melting point of the component (c) by 10 ° C. or less. By stretching and rolling, a stronger fiber is formed, so that the characteristics of the fiber-reinforced thermoplastic resin composition can be more exerted, which is more preferable.

In addition to this, the third step can be carried out by continuously rolling the spun kneaded material with a rolling roll or the like. Further, the kneaded product can be extruded from an inflation die or a T die and wound on a roll or the like while being drafted. Further, instead of winding a draft while winding it on a roll, it may be rolled by a rolling roll or the like. The fiber-reinforced thermoplastic resin composition after rolling or drawing is preferably pelletized. The reason for this is that pelletization allows uniform kneading with the additional elastomer, that is, the second elastomer.

In the fiber-reinforced thermoplastic resin composition of the present invention, the component (a) and the component (b) form a matrix. The component (a) has an island-like structure dispersed in the component (b). The component (a) and the component (b) are bonded to each other at the interface. Further component (a),
Consists of component (b) and component (c), and component (a) and component
(b) forms a matrix, and most of the component (c) has a structure in which fine fibers are uniformly dispersed in the matrix, and the fine fibers of the component (c) are bonded to the matrix. .

Component (c) binds to both component (a) and component (b) at the interface. The existence of this interfacial bond is
When the fiber-reinforced thermoplastic resin composition is thermally extracted in a solvent that dissolves in both the component (a) and the component (b), such as xylene, the component (a) and the component (b) are extracted and removed. The remaining fiber of component (c) was dissolved in o-dichlorobenzene-phenol mixed solvent (85:15) and measured by NMR, which proved that peaks derived from component (a) and component (b) were observed. To be done.

Although the first, second and third steps are described separately for each step, the components (a), (b) and (c) are described.
And a first supply port capable of supplying the component (d), a second supply port and a third supply port, and a first kneading zone, a second kneading zone and a third kneading zone corresponding to the respective supply ports. It is also possible to carry out a batch process using a shaft kneader in a continuous process. Doing so will result in an economical, stable and safe manufacturing method.

Fourth Step In this step, the pellets of the fiber-reinforced thermoplastic resin composition obtained in the third step are melt-kneaded with a rubber-like polymer having a glass transition temperature of 0 ° C. or lower, that is, a second elastomer. The method of melt kneading is such that the second elastomer and the fiber reinforced thermoplastic resin composition are in the following weight ratios, and the components (a), (b) and (c) are in the following composition ranges. And melt kneading at a temperature higher than the melting point of the component (b) and lower than the melting point of the component (c). The melt-kneading can be performed by an apparatus usually used for kneading resins and rubbers. As such a device, a Banbury type mixer, a kneader, a kneader extruder, an open roll, a single-screw kneader, a twin-screw kneader, or the like is used.
The kneading time is 1 to 5 minutes, and a fiber-reinforced elastic body composition is obtained.

The second elastomer will be described. That is, as the elastomer to be added to the fiber-reinforced thermoplastic resin composition, the same elastomer as that used as the first elastomer of the component (a) of the fiber-reinforced thermoplastic resin composition is used. Thus, mention may be made of rubber-like elastomers at room temperature, preferably those having a glass transition temperature of 0 ° C. or lower, particularly preferably a glass transition temperature of −20 ° C. or lower, which are selected from the above-mentioned component (a). .
The second elastomer may be the same as or different from the first elastomer, or may be a combination of two or more kinds.

In the fiber-reinforced elastic composition of the present invention, the ratio of the polyolefin of the component (b) is 1 to 40 parts by weight, preferably 2 to 100 parts by weight of the total amount of the first and second elastomers. 30 parts by weight, the proportion of fine fibers of the thermoplastic polymer having an amide group in the main chain of component (c) is 1 to 7
It is 0 part by weight, preferably 2-55 parts by weight. When the ratio of the component (b) is more than 40 parts by weight, only a fiber-reinforced elastic body composition having no rubber elasticity can be obtained. On the other hand, when the ratio of the component (b) is less than 1 part by weight, the physical properties of the fiber-reinforced elastic body composition have a direction in which the fatigue resistance is particularly remarkable, and the physical properties in the direction perpendicular to the fiber orientation are It is not preferable because it becomes low. The ratio of fine fibers of component (c) is 1
When the amount is less than the amount by weight, only a fiber-reinforced elastic body composition having a low modulus can be obtained. On the other hand, when the proportion of the fine fibers of the component (c) is more than 70 parts by weight, only a fiber-reinforced elastic body composition having a small elongation can be obtained.

The fiber-reinforced elastic composition of the present invention can be produced by kneading the fiber-reinforced thermoplastic resin composition and the second elastomer as described above. When the ratio of the polyolefin and the fine fibers to the total amount of the first and second elastomers in the obtained fiber reinforced elastic body composition is within the above range, the second elastomer and the fiber reinforced thermoplastic resin composition The kneading ratio is not particularly limited, but the weight ratio of the second elastomer to the fiber reinforced thermoplastic resin composition is 20/1 to 0.1 / 1, and particularly 10/1 to 0.5 / 1. It is preferable because the kneading operation is easy.

The kneading temperature of the fiber-reinforced thermoplastic resin composition and the second elastomer is lower than the melting point of the thermoplastic polyamide of the component (c) constituting the fine short fibers in the fiber-reinforced thermoplastic resin composition, The temperature must be higher than the melting point of the polyolefin (b). Kneading at a temperature higher than the melting point of this thermoplastic polyamide is not preferable because the fine short fibers in the fiber-reinforced thermoplastic resin composition are dissolved and transformed into spherical particles or the like. Further, when kneading at a temperature lower than the melting point of the component (b) polyolefin, the short fibers are poorly dispersed and the desired strength and elongation cannot be obtained. Specifically, the temperature 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, as the fiber reinforced thermoplastic resin composition, it is preferable to use a pellet form. By using the pellet-shaped fiber-reinforced thermoplastic resin composition, the fiber-reinforced thermoplastic resin composition can be uniformly kneaded with the second elastomer, and a fiber-reinforced elastic body composition in which fine fibers are uniformly dispersed can be easily obtained. Because it will be done.

At the time of this kneading, carbon black, process oil, zinc white, stearic acid and an antioxidant are added and kneaded. At this time, the temperature of the kneaded product rises, but the temperature is controlled as necessary so as not to rise above the melting point of the thermoplastic polyamide of the component (c). Preferably 160-18
At 0 ° C, the kneading time is 1 to 5 minutes. At this time, various vulcanizing agents and vulcanizing aids may be kneaded together at room temperature to 100 ° C in necessary amounts. Disperse well and pull out into a sheet. When the obtained sheet is molded and vulcanized, a vulcanized product of a fiber-reinforced elastic body is obtained. At this time, the amount of the vulcanizing agent was 0.10 with respect to 100 parts by weight of the total amount of the first and second elastomers.
A range of 1 to 5.0 parts by weight, particularly 0.5 to 3.0 parts by weight is preferable. The amount of the vulcanization aid is preferably 0.01 to 2.0 parts by weight, and particularly preferably 0.1 to 1.0 part by weight, based on 100 parts by weight of the total amount of the first and second elastomers.

As the vulcanizing agent, known vulcanizing agents such as sulfur, organic peroxides, resin vulcanizing agents, and metal oxides such as magnesium oxide are used. Vulcanization aids include aldehydes / ammonias, aldehydes / amines, guanidines, thioureas, thiazoles, thiurams,
Dithiocarbamates, xanthate, etc. are used.

The vulcanization temperature when a vulcanizing agent or the like is added to the fiber-reinforced elastic material composition of the present invention is preferably about 100 to 180 ° C. However, the vulcanization temperature needs to be lower than the melting point of the thermoplastic resin forming the fine fibers in the fiber-reinforced elastic body composition. When vulcanization is performed at a temperature equal to or higher than the melting point of this thermoplastic resin, the fibers formed in the stage of preparing the fiber-reinforced thermoplastic resin composition are dissolved, and a fiber-reinforced elastic body composition having a high modulus is obtained. Because there is no.

In addition to the fiber-reinforced elastic composition of the present invention, carbon black, white carbon, activated calcium carbonate, ultrafine magnesium silicate, high styrene resin, phenol resin, lignin, modified melamine resin, coumarone indene resin, Auxiliaries such as petroleum resin, calcium carbonate, basic magnesium carbonate, clay, zinc white, diatomaceous earth, reclaimed rubber, powdered rubber, various fillers such as ebonite powder, amines / aldehydes, amines / ketones, amines , Phenols, imidazoles, sulfur-containing antioxidants, stabilizers such as phosphorus-containing antioxidants, and various pigments may be contained.

[0044]

EXAMPLES The present invention will be described in more detail below by showing Examples and Comparative Examples, but the present invention is not limited to the scope of these Examples. In Examples and Comparative Examples, the physical properties of the fiber reinforced thermoplastic resin composition and the fiber reinforced elastic body composition were measured as follows. Unvulcanized physical properties Pelletization possible: Yes; ○, impossible; ×. Fiber shape: morphology / dispersibility and average fiber diameter: 10 in a mixed solvent of o-dichlorobenzene and xylene (a mixed solvent of o-dichlorobenzene and xylene; volume ratio 50:50)
Reflux at 0 ° C. to extract and remove the components (a) and (b) in the fiber reinforced thermoplastic resin composition, and observe the remaining fibers with an electron microscope. Good dispersibility was evaluated as ◯, and dispersibility was evaluated as poor when fine fibers were not dispersed. When the dispersibility was good, the fiber diameter of 200 dispersed fine fibers was measured from the above-mentioned electron microscope image, and the average thereof was calculated to obtain the average fiber diameter. Bonding ratio: The fiber-reinforced elastic body composition is refluxed in a solvent, xylene, which dissolves only the components (a) and (b) to remove the components (a) and (b). The remaining fiber of the component (c) is dried and then weighed, and this weight is designated as W _C. And
Ratio of component (c) in composition to weight W _C0 W _C / W
_C0 × 100 is obtained and this is taken as the binding rate.

Vulcanization physical properties 100%, 200%, 300% modulus, tensile strength and elongation: JIS K625 punched out with No. 3 dumbbell
It measured according to 1. Fatigue under constant load: punched into No. 3 dumbbell, repeatedly loaded with a load of 70 kg / cm ² and pulled, and the number of times until the dumbbell was cut was displayed. Tear strength: Measured according to JIS-B type according to JIS K6252. Hardness: Measured with JIS-A type according to JIS K6253. Pyrogenicity: ΔT measured according to ASTM D623A
It was shown in (° C).

Preparation of Fiber Reinforced Thermoplastic Resin Composition

Sample 1 Natural rubber (NR, SMR-L) was used as the component (a), and polypropylene was used as the component (b) [Ube Polysan JI09, Ube Polypro JI09, melting point 165-170 ° C., melt flow index 9 g / 10. Min) and nylon 6 as a component (c) (Ube nylon 102 manufactured by Ube Industries, Ltd.)
2B, melting point 215 to 220 ° C., molecular weight 30,000) were used. First, 0.5 part by weight of γ-methacryloxypropyltrimethoxysilane, and 0.1 part by weight of 4,4-di-t-butylperoxyvaleric acid n-butyl ester, relative to 100 parts by weight of component (b). And melt kneading (temperature:
(210 ° C.) denatured. Component (b) modified as described above
Was melt-kneaded with the component (a) in a Banbury type mixer to prepare a matrix. This was dumped at 170 ° C. and pelletized. This matrix and component (c) at 240 ° C
The kneaded product was pelletized by kneading with a twin-screw kneader heated to above. This was extruded into a string shape with a twin-screw kneader set at 245 ° C., and it was pelletized with a pelletizer while being drawn at a draft ratio of 10 at room temperature. The pellets were formed into a sheet by pressing at 180 ° C. This sheet had a smooth surface. Samples were taken from this sheet and the physical properties were measured. The component (c) is dispersed in fine fibrous form and the average fiber diameter is in the range of 0.2 to 0.3 μm. In addition to the peak of the component (c) in NMR measurement, the component (a) and the component (b) are A derived peak was observed. The blending ratio of each component and the properties of nylon 6 fiber are shown in Table 1.

Sample 2 The component (c) was pelletized in the same manner as in Sample 1 except that 200 parts by weight of nylon 6 was used. The physical properties of the pellets were measured. The results are shown in Table 1.

Sample 3 The same procedure as in Sample 1 was carried out without using polypropylene as the component (b) except that 50 parts by weight of nylon 6 was used as the component (c). However, it could not be pelletized. In the electron microscope observation of the extraction residual, fine fibers were observed. The results are shown in Table 1.

Sample 4 Pelletization was performed in the same manner as in Sample 1 except that 75 parts by weight of component (b) polypropylene and 88 parts by weight of nylon 6 were used as component (c). The physical properties of the pellets were measured. The results are shown in Table 1.

Sample 5 High-density polyethylene (HDPE) [Maruzen Polymer Co., Ltd., Chemillets-HD3070, melting point 1 as component (b)]
30 ° C., MFI = 8.0 g / 10 min. ], 130 parts by weight of component (c) nylon 6 was used. Component (a)
100 parts by weight and component (b) 75 parts by weight, γ-methacryloxypropyltrimethoxysilane 0.56 parts and 0.1
1 part by weight of 4,4-di-t-butylperoxyvaleric acid n-butyl ester in a Banbury mixer at the same time.
A matrix was prepared by melt-kneading at 60 ° C. This one
It was dumped at 70 ° C. and pelletized. Next, 88 parts by weight of this matrix and component (c) were set at 245 ° C. 2
It was kneaded with a shaft kneader and pelletized. The obtained pellets were kneaded with a uniaxial extruder set at 245 ° C., extruded into a string shape, and taken in at a draft ratio of 10, while being pelletized by a pelletizer. The resulting pellets were subjected to reflux extraction in a mixed solvent of o-dichlorobenzene and xylene to obtain the component (a).
The component (b) polyethylene and natural rubber were removed, and the remaining fine fibers were observed with an electron microscope. The results are shown in Table 1.

Sample 6 Pelletization was carried out in the same manner as in Sample 5, except that 130 parts by weight of component (c) nylon 6 was used, a Banbury mixer was used instead of the twin-screw kneader, and dumping was performed at 260 ° C. In the electron microscope observation of the extraction residual, fine fibers were observed. The results are shown in Table 1.

Vulcanization Physical Properties of Fiber Reinforced Elastic Body Composition

[0054]

【Example】

Examples 1 to 6 According to the formulations shown in Table 2, a fiber reinforced thermoplastic resin composition (Sample 1, Sample 2), a second elastomer (natural rubber: NR), carbon black (HAF), process oil, zinc white, Stearic acid, an antioxidant (N-phenyl-N'-isopropyl-p-phenylenediamine), a vulcanization accelerator (N-oxydiethylene-2-benzothiazolylsulfenamide) and sulfur were blended. The compounding procedure was as follows: put NR and the fiber reinforced thermoplastic resin composition into a Brabender plastograph set at 160 ° C., masticate for 30 seconds, then add carbon black, process oil, zinc white, stearic acid, and an antioxidant. Throw in 4
After kneading for a minute, sulfur and a vulcanization accelerator were mixed on an open roll set at 80 ° C. 145 of the resulting formulation
It was vulcanized at 30 ° C. for 30 minutes to obtain a vulcanized product of the fiber-reinforced elastic body composition.

The ratio of nylon 6 fibers to the total of NR in the fiber reinforced thermoplastic resin composition and NR added as the second elastomer was in the range of 5 to 50% by weight (Examples 1 to 6). . In all of the vulcanized products of Examples 1 to 6, fine fibers of nylon 6 were uniformly dispersed in NR.
The tensile properties are 100% modulus of 7.5 to 20.
The value was 0 MPa, which was extremely higher than that of the comparative example having no nylon 6 fiber. The same was true for a 300% modulus. The results are shown in Table 4.

Comparative Example 1 According to the formulation shown in Table 2, a fiber reinforced thermoplastic resin composition (Sample 3) and a second elastomer (natural rubber: N
R), carbon black (HAF), process oil,
Zinc white, stearic acid, antioxidant (N-phenyl-
N'-isopropyl-p-phenylenediamine), a vulcanization accelerator (N-oxydiethylene-2-benzothiazolylsulfenamide) and sulfur were added. Compounding and vulcanization were performed in the same procedure as in Examples 1-6. The ratio of nylon 6 fibers to the total of NR in the fiber-reinforced thermoplastic resin composition and NR added as the second elastomer was 30.
Although it was wt%, the fine fiber dispersion of nylon 6 was poor. Although the 100% modulus was as high as 17.4 MPa, the elongation was only 110%. The results are shown in Table 4.

Comparative Example 2 NR was used instead of blending the fiber reinforced thermoplastic resin composition.
The same as Example 1 except that the ratio was increased to 100 parts by weight. Very few fine fibers of nylon 6 were seen. The 100% modulus is 2.1 MPa and the 300% modulus is 10.9 PAa.
It was an extremely low value as compared with 6. The results are shown in Table 4.

Example 7 75% by weight of NR as the second elastomer, polybutadiene rubber (BR: UBEPOL BR 15)
Example 1 was repeated except that 20 parts by weight of 0) was used. Nylon 6 with respect to the total of NR in the fiber reinforced thermoplastic resin composition and BR added as the second elastomer
The ratio of the fibers was 5% by weight. The fine fiber dispersion of nylon 6 was good. The 100% modulus was as high as 7.2 MPa, the 300% modulus was as high as 18.6 MPa, and the elongation was also as high as 450%. The results are shown in Table 4.

Comparative Example 3 NR was used instead of blending the fiber reinforced thermoplastic resin composition.
Example 1 was repeated except that the proportion of was increased to 80 parts by weight. Very few fine fibers of nylon 6 were seen.
The 100% modulus was 2.7 MPa and the 300% modulus was 13.1 MPa, which were extremely low values as compared with Examples 1 to 6 of the present invention. The results are shown in Table 4.

Examples 8 to 9 The same procedures as in Example 1 were carried out except that Samples 5 and 6 were used as the fiber reinforced thermoplastic resin composition. The results are shown in Table 4. The result was similar to that of Example 7.

Examples 10 to 12 According to the formulations shown in Table 3, the fiber-reinforced thermoplastic resin composition (Sample 4, Sample 2), the second elastomer (natural rubber: NR), carbon black (HAF), process oil, Zinc white, stearic acid, an antioxidant (N-phenyl-N'-isopropyl-p-phenylenediamine), a vulcanization accelerator (N-oxydiethylene-2-benzothiazolyl sulfenamide) and sulfur were compounded. A compounding procedure was performed in the same manner as in Example 1 to obtain a vulcanized product of the fiber-reinforced elastic body composition. NR and second in fiber-reinforced elastic composition
The ratio of the nylon 6 fibers to the total amount of BR added as the elastomer was 3 to 7% by weight. The fine fiber dispersion of nylon 6 was good. It was found that not only the modulus (100, 200, 300%), the tensile strength, the elongation and the constant load fatigue are remarkably excellent as compared with the comparative example, but also there is little directionality regarding the modulus and the constant load fatigue. . High tear strength. The exothermicity was low and excellent in hardness. Table 5 shows the results.

Comparative Example 4 NR was used instead of blending the fiber reinforced thermoplastic resin composition.
The same as Example 1 except that the ratio was increased to 100 parts by weight. Very few fine fibers of nylon 6 were seen. The modulus, the tensile strength, the elongation and the constant load fatigue are not only significantly superior to those of the comparative example, but there is almost no direction for the modulus and the constant load fatigue. It was a very low value. The exothermicity is large despite the low hardness. Table 5 shows the results.

Comparative Example 5 Polypropylene (PP) was added to the fiber reinforced thermoplastic resin composition.
The second elastomer (N
Same as Example 1 except that the ratio of R) was 90 parts by weight. The fine fiber of nylon 6 was 5% by weight, but the dispersion was poor. Regarding the modulus and the tensile strength, the same values as those in the examples were shown in the direction parallel to the fiber orientation direction, but the modulus and fatigue resistance were extremely poor in the direction perpendicular to the fiber orientation direction. Table 5 shows the results.

[0064]

[Table 1]

[0065]

[Table 2]

[0066]

[Table 3]

[0067]

[Table 4]

[0068]

[Table 5]

[0069]

The fiber-reinforced elastic composition of the present invention comprises various elastomers and a fiber-reinforced thermoplastic resin composition, that is, a fine fiber made of a thermoplastic polyamide in a matrix made of a first elastomer and a polyolefin. It can be manufactured by kneading the dispersed composition. Since this fiber-reinforced thermoplastic resin composition can be extremely easily pelletized, it can be kneaded with the second elastomer extremely easily and uniformly, and the fiber-reinforced elastic body composition of the present invention can be easily obtained. When observed by an electron microscope, the fiber-reinforced elastic composition of the present invention has 0.2 μm of fine thermoplastic polyamide fibers uniformly dispersed therein, and the polyolefin bonded to the polyamide forms a crystalline lamella from the fiber surface. This crystalline lamella plays the role of an anchor effect, and strengthens the interfacial bond between the fiber and the matrix elastomer. On the other hand, the polyolefin bonded to the elastomer is uniformly dispersed in the elastomer as fine particles of 0.1 μm or less, and exhibits the effect of a reinforcing filler. Therefore, the fiber-reinforced elastic body composition of the present invention is excellent in high hardness, high modulus, fatigue resistance, and low heat build-up (compared with the same hardness) as compared with the known fiber-reinforced elastic body composition. It has excellent modulus and fatigue resistance in the direction perpendicular to the grain.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Tatsuro Wada 8-1 Goi Minamikaigan, Ichihara-shi, Chiba Ube Industries Ltd.

Claims (3)

[Claims] 1. A fiber-reinforced thermoplastic resin composition (A), that is, (1) a rubber-like polymer (first elastomer) having a glass transition temperature of 0 ° C. or lower of component (a) and a polyolefin of component (b). A melt-kneading treatment is carried out with the silane coupling agent of the component (d), or the first elastomer of the component (a) and the polyolefin of the component (b) treated with the component (d) are melt-kneaded to prepare a matrix. The first step,
(2) The second step of melt-kneading the thermoplastic polymer having an amide group in the main chain of the component (c) at a temperature higher than the melting point of any of the matrix and the component (c), and then extruding, (3) the above A fiber-reinforced thermoplastic resin composition comprising a third step of stretching and / or rolling the extrudate at a temperature lower than the melting point of the component (c) and higher than the melting point of the polyolefin of the component (b), and (B) a glass transition temperature A fiber-reinforced elastic composition comprising a fourth step of melt-kneading a rubber-like polymer (second elastomer) at 0 ° C. or lower, wherein the total amount of the first elastomer and the second elastomer is 100 parts by weight. hand,
A method for producing a fiber-reinforced elastic body composition, wherein the ratio of the component (b) is 1 to 40 parts by weight, and the ratio of the fine fibers of the component (c) is 1 to 70 parts by weight. 2. A fiber-reinforced thermoplastic resin composition (A) is a component.
A composition comprising a first elastomer (a), a component (b) and a component (c), wherein the component (a) and the component
(b) constitutes a matrix, the component (c) is dispersed as fine fibers in the matrix, and the component (c) is combined with the component (a) and the component (b). Claim 1 which is a plastic resin composition
Item 6. A method for producing the fiber-reinforced elastic composition according to the item. 3. A kneading ratio of the (A) fiber-reinforced thermoplastic resin composition and the (B) second elastomer is in a weight ratio of the (B) second elastomer and the (A) fiber-reinforced thermoplastic resin composition. In the range of 20/1 to 0.1 / 1, the kneading temperature is
The fiber-reinforced elastic body according to claim 1, wherein the temperature is lower than the melting point of the component (c) constituting the fine short fibers in the fiber-reinforced thermoplastic resin composition and higher than the melting point of the component (b). Method of making the composition.