JP2000007842A - Polyamide-fiber reinforced polyolefin resin composition and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce the subject composition excellent in rigidity or strength and further frictional performances by including a polyolefin, specific polyamide fibers and a silane coupling agent in respective specified proportions. SOLUTION: This composition comprises (A) 90-40 pts.wt. of a polyolefin, (B) 10-60 pts.wt. of polyamide fibers containing a phyllosilicate and (C) a silane coupling agent. In the component B, the phyllosilicate is preferably contained in an amount of preferably 0.05-30 pts.wt. based on 100 pts.wt. of the polyamide fibers. The amount of the compounded component C is preferably 0.1-5.5 pts.wt. based on 100 pts.wt. of the total amount of the components A and B. The composition is produced by initially melt-kneading the polyamide in a matrix obtained by melt-kneading the components A with C, extruding the resultant kneaded mixture, orienting or rolling the extrudate at a temperature of the melting point of the polyamide or below and dispersing the polyamide so as to provide a fibrous form having <=1 μm average fiber diameter.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyamide fiber in which a polyolefin and a layered silicate are uniformly dispersed,
It can be suitably used as a reinforcing material for rubbery polymers and resins.

[0002]

2. Description of the Related Art Rubbery polymers have been used as various rubber products because of their high recovery elastic modulus and low elastic modulus. However, the demands have become increasingly higher, such as a higher recovery modulus but a slightly higher modulus, and a higher modulus and higher durability. In the resin field, a material having high elastic modulus, light strength, and high impact resistance has been required.

A fiber reinforced composition in which fine polyamide fibers are dispersed in polyolefin and rubber is disclosed in Japanese Patent Laid-Open No. 7-2381.
No. 89 is disclosed. Since it is obtained in the form of pellets dispersed with an average fiber diameter of 1 μm or less, it is easy to handle and is suitably used as a reinforcing agent for resins and rubbery polymers. However, in the fields of tires, rolls, and footwear, friction performance is required.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to solve the above-mentioned problems and to provide a polyamide fiber-reinforced polyolefin resin composition having excellent rigidity and strength and further excellent friction performance.

[0005]

According to the present invention, there are provided (a) 90 to 40 parts by weight of a polyolefin, (b) 10 to 60 parts by weight of a polyamide fiber containing a layered silicate, and (c) a silane coupling agent. And a polyamide fiber reinforced polyolefin resin composition comprising: The silane coupling agent of the component (c) is added in an amount of 0.1 to 5.5 parts by weight based on 100 parts by weight of the total of the components (a) and (b). Polyamide fibers are dispersed within the average fiber diameter of 1 μm or less,
(B) The layered silicate contained in the component is a polyamide fiber 1
It is 0.05 to 30 parts by weight based on 00 parts by weight. Furthermore, (b) a polyamide containing a layered silicate is melt-kneaded in a matrix in which (a) a polyolefin and (c) a silane coupling agent are melted and kneaded, and extruded,
Provided is a method for producing a polyamide fiber-reinforced polyolefin resin composition which is stretched or rolled at a temperature equal to or lower than the melting point of polyamide and dispersed in a fibrous form.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the polyamide fiber reinforced polyolefin resin composition of the present invention and a method for producing the same will be specifically described. The component (a) is a polyolefin,
Those having a melting point in the range of 50 ° C are preferred. Also, 5
Those having a Vicat softening point of 0 ° C or higher, particularly preferably 50 to 200 ° C, are also used. Preferred examples of the component (a) include homopolymers and copolymers of olefins having 2 to 8 carbon atoms, copolymers of olefins having 2 to 8 carbon atoms and vinyl acetate, and olefins having 2 to 8 carbon atoms. A copolymer of olefin with acrylic acid or an ester thereof, a copolymer of an olefin having 2 to 8 carbon atoms with methacrylic acid or an ester thereof,
And a copolymer of an olefin having 2 to 8 carbon atoms and a vinylsilane compound.

Specific examples of component (a) include high-density polyethylene, low-density polyethylene, linear low-density polyethylene, polypropylene, ethylene-propylene block copolymer, ethylene-propylene random copolymer, and 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,
Examples include ethylene / 2-ethylhexyl acrylate copolymer, ethylene / hydroxyethyl acrylate copolymer, ethylene / vinyltrimethoxysilane copolymer, ethylene / vinyltriethoxysilane copolymer, and ethylene / vinylsilane copolymer. Can be Another specific example of the component (a) includes halogenated polyolefins such as chlorinated polyethylene, brominated polyethylene, and chlorosulfonated polyethylene.

Among these, particularly preferred are high-density polyethylene (HDPE), low-density polyethylene (LDPE), and linear low-density polyethylene (LLDP).
E), polypropylene (PP), ethylene / propylene block copolymer, ethylene / propylene random copolymer, poly-4-methylpentene-1 (P4MP1), ethylene / vinyl acetate copolymer (EVA), and ethylene / vinyl Alcohol copolymers, among which the melt flow index (MFI) is 0.2 to 50 g / 10
The range of min is the most preferable. (A) Only one type of component may be used, or two or more types may be used in combination.

The component (b) is a polyamide in which the layered silicate is uniformly dispersed and contained, and which gives a tough fiber by extrusion and drawing.
Particularly, those having a melting point in the range of 160 to 265 ° C are preferable.

Specific examples of polyamides include nylon 6, nylon 66, nylon 6-nylon 66 copolymer, nylon 610, nylon 612, nylon 46,
Nylon 11, Nylon 12, Nylon MXD6, polycondensate of xylylenediamine and adipic acid, polycondensate of xylylenediamine and pimelic acid, polycondensate of xylylenediamine and speric acid, xylylenediamine and azelaine Polycondensates with acids, polycondensates of xylylenediamine and sebacic acid, polycondensates of tetramethylenediamine and terephthalic acid, polycondensates of hexamethylenediamine and terephthalic acid, polycondensation of octamethylenediamine and terephthalic acid Isomer, polycondensate of trimethylhexamethylenediamine and terephthalic acid, polycondensate of decamethylenediamine and terephthalic acid, polycondensate of undecamethylenediamine and terephthalic acid, polycondensate of dodecamethylenediamine and terephthalic acid, tetramethylene Polycondensate of diamine and isophthalic acid, hex Polycondensates of methylenediamine and isophthalic acid, polycondensates of octamethylenediamine and isophthalic acid, polycondensates of trimethylhexamethylenediamine and isophthalic acid, polycondensates of decamethylenediamine and isophthalic acid, undecamethylenediamine and isophthalic acid Examples include a polycondensate of an acid and a polycondensate of dodecamethylenediamine and isophthalic acid.

Among these polyamides, particularly preferred are those having a melting point higher than the polyolefin of the component (a) by 30 ° C. or more. Specifically, nylon 6
(PA6), nylon 66 (PA66), nylon 6
Nylon 66 copolymer, Nylon 610, Nylon 61
2, nylon 46, nylon 11, and nylon 12. These may be used alone or in combination of two or more. These polyamides are available at 10,000
It preferably has a molecular weight in the range of 0 to 200,000.

The layered silicate uniformly dispersed and contained in the component (b) is a component that imparts excellent mechanical properties and friction performance to the polyamide fiber reinforced polyolefin resin composition. As the properties, those having a thickness of 0.6 to 2 nm and a length of one piece in a range of 2 to 1,000 nm are generally preferable in order to exhibit the above characteristics. When the layered silicate is dispersed in the polyamide component, each of the layered silicates maintains an interlayer distance of 2 nm or more on average and is uniformly dispersed. The term “interlayer distance” as used herein refers to the distance between the plate-shaped centers of gravity of the layered silicate, and the term “uniformly dispersed” means that each layered silicate is randomly distributed in parallel or in a state where both parallel and random are mixed. A state in which 50% or more, preferably 70% or more, disperses without forming a lump. Therefore, the layered silicate has a piece of 2 to 1,000 nm and a thickness of 0.6 to 2 nm.
1 shows one fine unit of the substance. As a raw material of such a layered silicate, a layered phyllosilicate mineral composed of a layer of magnesium silicate or aluminum silicate can be exemplified. Specifically, montmorillonite,
Examples thereof include smectite-based clay minerals such as saponite, nontronite, hectorite, and stevensite, bamucurite, and halashiite. These may be natural products or synthetic ones. Of these, montmorillonite is preferred. There is no limitation on the method of uniformly dispersing the layered silicate in the polyamide resin. However, in order to synthesize a polyamide between the layers of the layered silicate, an organic substance satisfying the following three points is first inserted between the layers (intercalation). Need to be polymerized. First, (1) one end is an ammonium ion to form an ionic bond with a layered silicate, and (2) the other end is a carboxyl group (-COOH) for ring-opening polymerization of a nylon monomer (ε-caprolactam). Having,
(3) It is necessary to use a compound satisfying, for example, that ε-caprolactam has a polarity such that the silicate layer swells.
As a typical compound, for example, an ω-amino acid (H ₂ N (C
H ₂ ) _n-1 COOH) (n is 2 to 18). When the raw material of the layered silicate of the present invention is a multilayered clay mineral, a method of contacting with a swelling agent to expand the layers in advance to make it easier to take in monomers between the layers, and then mixing and polymerizing with a polyamide monomer (particularly). (No. 8-22946). Alternatively, a method may be used in which a polymer compound is used as a swelling agent, the interlayer is expanded to 10 nm or more in advance, and this is melted and kneaded with a polyamide resin or a resin containing the same to uniformly disperse them. The ratio of the layered silicate is polyamide component 1
0.05 to 30 parts by weight per 100 parts by weight is preferable,
More preferably, it is 0.1 to 10 parts by weight. If the compounding ratio of the layered silicate component is less than 0.05 part by weight, the rigidity and heat resistance of the molded article will not be improved, and if it exceeds 30 parts by weight, the fluidity of the resin composition will be extremely reduced, which is not preferable. .

The silane coupling agent of the component (c) is a binder that binds the components (a) and (b) to each other. Specific examples thereof include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, vinyltriacetylsilane,
γ-methacryloxypropyltrimethoxysilane, β-
(3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyl Ethyldimethoxysilane, 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-phenyl-γ-aminopropyltrimethoxysilane, γ-
[N- (β-methacryloxyethyl) -N, N-dimethylammonium (chloride)] propylmethoxysilane and styryldiaminosilane. Among them, a group having a group and / or a polar group and a vinyl group which easily desorb a hydrogen atom from an alkoxy group or the like is particularly preferably used.

[0014] The amount of the silane coupling agent is 0.1 to 5.0 parts by weight based on 100 parts by weight of the total of the components (a) and (b).
The content is preferably in the range of 5 parts by weight, particularly preferably 0.2 to
3.0 parts by weight. If the amount is less than 0.1 part by weight, the component (a) and the component (b) do not bond to each other via a coupling agent, so that a composition having high strength cannot be obtained.
If the amount exceeds 5 parts by weight, a fine fiber structure of the polyamide of the component (b) is not exhibited, so that a composition having an excellent elastic modulus cannot be obtained.

An organic peroxide can be used in combination with the silane coupling agent of the component (c). When used in combination, radicals are formed on the molecular chains of the component (a) and the component (b) and react with the silane coupling agent to promote the mutual bonding of the component (a) and the component (b). Then, the component (a) and the component (b) are mutually bonded at the interface. Organic peroxide has a half-life temperature of 1 minute,
Those having the same temperature as the higher of the melting point of the component (a) and the melting point of the component (b) or a temperature range higher by about 30 ° C. than this temperature are preferably used. Specifically, those having a half-life temperature of about 110 to 250 ° C. for one minute are preferably used. The amount of organic peroxide used at this time is
The range is preferably 0.01 to 1.0 part by weight based on 100 parts by weight of the component (a).

Specific examples of the organic peroxide include 1,1-
Di-tert-butylperoxy-3,3,5-trimethylcyclohexane, 1,1-di-tert-butylperoxycyclohexane, 2,2-di-tert-butylperoxybutane, n-butyl-4,4 -Di-t-butylperoxyvalerinate, 2,2-bis (4,4-di-t-butylperoxycyclohexane) propane, 2,2,4-trimethylpentyl-peroxyneodecanate, α-cumyl -Peroxy neodecanoate, t-butyl-peroxy neohexanate, t-butyl peroxy pivalate, t-butyl peroxy acetate, t-butyl peroxy laurate, t-butyl peroxy benzoate, t- Butyl peroxyisophthalate and the like can be mentioned.

Most of the polyamide in the component (b) is uniformly dispersed as fine fibers in the matrix of the component (a). Specifically, 70% by weight, preferably 80% by weight,
Particularly preferably, 90% by weight or more is dispersed as fine fibers. The average fiber diameter of the polyamide fibers is preferably 1 μm or less, and the average fiber length is preferably 1,000 μm or less. The aspect ratio represented by the ratio between the average fiber length and the average fiber diameter is 20 or more, and desirably 1,000 or less. The component (a) and the component (b) are mutually bonded at the interface.

The ratio of the components (a) and (b) is (a)
Component (b) is 10 to 60 with respect to 90 to 40 parts by weight of component.
Parts by weight. When the amount of the component (b) is less than 10 parts by weight, the effect of improving the elastic modulus and strength is small, and when the amount exceeds 60 parts by weight, the appearance of the molded product becomes poor.

A filler may be added to the polyamide fiber reinforced polyolefin resin composition of the present invention as long as physical properties are not impaired. As the filler, carbon fiber, glass fiber, metal fiber, glass bead, talc, kaolin, clay, mica, montmorillonite, basic magnesium carbonate, walasonite and the like may be added. In addition, antioxidants, ultraviolet absorbers, softeners, flame retardants, softeners, lubricants, tackifiers and the like can be added as appropriate.

Next, a method for producing the polyamide fiber reinforced polyolefin resin composition of the present invention will be described. Before that, a method for producing a polyamide in which the layered silicate of the component (b) is uniformly dispersed will be described in advance. There is no particular limitation as long as the layered silicate is uniformly dispersed. For example, when the raw material of the silicate is a multi-layered clay mineral, the layered silicate is ionized with hydrochloric acid to form a salt with a swelling agent, for example, 12-aminododecanoic acid. The above method of mixing and polymerizing with the monomer forming the component (b) polyamide (Japanese Patent Publication No.
No. 22946), a polyamide in which the layer silicate of the component (b) is uniformly dispersed is produced by a method of mixing the layer silicate and the polyamide.

The method for producing the polyamide fiber reinforced polyolefin resin composition is produced from the following steps (1) to (4). (1) a step of preparing a reactive matrix of the component (a) by melt-kneading the polyolefin of the component (a) and the silane coupling agent of the component (c); A step of producing a chemically modified composition by melt-kneading a composite of a silicate and a polyamide at a temperature equal to or higher than the melting point of the polyamide; (3) a temperature higher than the melting point of the polyamide of the component (b) ( (10 ° C. or higher) from a die, and (4) a step of drawing or rolling the above extrudate while drafting at a temperature higher than the melting point of the component (a) and lower than the melting point of the polyamide of the component (b). Manufactured.

Each step of the production method of the present invention will be described more specifically. It is as follows. Step (1): a step of preparing a reactive matrix of the component (a) by melt-kneading with the polyolefin of the component (a) and the silane coupling agent of the component (c): melting is at least the melting point of the polyolefin of the component (a). Which is higher than the melting point by 10 ° C. or more. When kneaded at a temperature higher than the melting point by 10 ° C. or more, the silane coupling agent of the component (a) and the component (c) react to form a reactive matrix. Melt kneading can be performed with an apparatus usually used for resin or rubber. As such an apparatus, a Banbury mixer, a kneader, a kneader extruder, an open roll, a single-screw kneader, a twin-screw kneader, or the like is used. Among these apparatuses, a twin-screw kneader is most preferable because melt kneading can be performed in a short time and continuously.

Step (2): a step of producing a composition obtained by chemically modifying the above-mentioned reactive matrix by melt-kneading a composite of the layered silicate of the component (b) and the polyamide at a temperature equal to or higher than the melting point of the polyamide; The temperature is equal to or higher than the melting point of the polyamide (b). The components are chemically modified with each other at a temperature higher than the melting point. If the melting temperature is lower than the melting point of the polyamide, it cannot be kneaded and does not disperse. Therefore, the component (b) is melt-kneaded at a temperature higher than the melting point of the polyamide as the component (b), particularly preferably at a temperature higher by 10 ° C. or more. Disperse in the component matrix to form a chemically modified composition.

Step (3): The above chemically modified composition is treated with (b)
Extruding from a die at a temperature higher than the melting point of the component polyamide (10 ° C. or more): In the extrusion process, the chemically modified composition is extruded from a spinneret or a T-die. In both spinning and extrusion, the temperature is higher than the melting point of the polyamide (b).
Preferably, it is performed at a temperature higher than 10 ° C. Even when the temperature is lower than the melting point of the polyamide, the polyamide does not have a fine particle structure in which the polyamide is melt-dispersed in the matrix. Therefore, even when the polyamide is spun and drawn, fine fibers are not formed.

Step (4): a step of stretching or rolling the extrudate while drafting at a temperature higher than the melting point of the component (a) and lower than the melting point of the polyamide of the component (b): Extruded string or thread The material or tape is continuously cooled, stretched or rolled. The cooling, stretching or rolling is performed at a temperature lower than the melting point of the polyamide. Stretching or rolling is preferable because stronger fibers are formed and the physical properties of the fiber-reinforced composition can be further exhibited. The stretching or rolling treatment is carried out, for example, by extruding the kneaded composition from a spinneret, spinning it into a string or a thread, and winding or cutting it while drafting it, and collecting it as pellets. The draft ratio when stretching the extrudate is preferably 1.5 to 100, more preferably 2 to 5
0, most preferably 3 to 30. The draft ratio means the ratio of the winding speed to the speed of the extrudate passing through the extrusion die. Thus, a polyamide fiber reinforced polyolefin resin composition is obtained.

As described above, the steps (1), (2),
Although described separately in (3) and (4), the component (a)
A supply port capable of supplying the component (b), the component (c), the organic peroxide, and the like; a first supply port, a second supply port, a third supply port, a fourth supply port, and the like. It is also possible to carry out the treatment in a batch continuous process using a twin-screw extruder having a first kneading zone, a second kneading zone, a third kneading zone, a fourth kneading zone and the like. This results in an economical and stable manufacturing method.

[0027]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but these do not limit the present invention. In the examples and comparative examples, the physical properties of the polyamide fiber reinforced polyolefin resin composition were measured as follows. Average fiber diameter and fiber shape : The polyamide fiber-reinforced polyolefin resin composition was dissolved in hot xylene, and the fiber portion was collected and observed with a scanning electron microscope to confirm whether the fiber was fine and to evaluate the dispersibility. For fibers having good dispersibility, the fiber diameter was measured from 200 fibers, and the average was determined to be the average fiber diameter. Interlayer distance of layered silicate : Polyamide fiber reinforced polyolefin resin composition is dissolved in hot xylene, fiber portion is collected and observed with a transmission electron microscope, and each layer of montmorillonite is molecularly dispersed, and the interlayer distance is 10 nm or more. The formation of a spreading layer was not maintained at all, and a new morphology was formed. That is, a nano-order montmorillonite layer was dispersed in a micron-order polyamide fiber. Surface appearance : Sheet is prepared by hot pressing at 180 ° C,
The smoothness of the sheet surface was visually observed and evaluated as follows. ◎: Excellent at all, ○: Almost smooth,
×: Unable to mold due to roughness or stickiness. Tensile properties : at a temperature of 25 ° C. and a tensile speed of 200 mm / min according to ASTM D638. The tensile strength, the tensile modulus and the tensile elongation were measured and indicated in MPa, MPa and%. Dynamic friction coefficient : 0.2 m thick according to JIS K7125
Using a transparent glass plate with a sample of mx 80 mm wide x 200 mm long as a mating material, load 200 g, pulling speed 100
mm / min. Was measured. The larger this value is, the better the scale showing the difficulty of slipping is.

Reference Example 1 In a 20-liter Hastelloy reactor equipped with a stirrer and a temperature controller at atmospheric pressure, the width of one unit of the layered silicate was 0.9 on average.
100 g of montmorillonite having a side length of about 100 nm and 5 nm and 10 liters of distilled water were added and dispersed in water. While maintaining the temperature at 35 ° C., 51.2 g of 12-aminododecanoic acid and 24 ml of concentrated hydrochloric acid were added thereto to give 5
After stirring for minutes, the mixture was filtered. Further, the filtrate was washed with water until neutral, filtered, and vacuum dried at 80 ° C. for 48 hours. By this operation, a complex of ammonium 12-aminododecanoate ion and montmorillonite (hereinafter, montmorillonite complex) was prepared. The layered silicate content in the composite is about 80%
It became. Next, 10 kg of ε-caprolactam, 1 kg
Of distilled water and 180 g of the above montmorillonite complex were added and stirred at 100 ° C. so that the reaction system became uniform.
The temperature was further raised to 260 ° C., and the mixture was stirred under a pressure of 15 kg / cm ² (pressurized with nitrogen) for 1 hour. Thereafter, the mixture was returned to normal pressure and reacted at 260 ° C. for 3 hours. The reaction product was taken out from the lower nozzle of the reaction vessel in the form of a strand, cooled with water and cut to obtain a pellet comprising polyamide (average molecular weight: 15,000) and montmorillonite. . 90 pellets
The unreacted monomers and oligomers were extracted and removed by immersion in hot water at 90 ° C., followed by vacuum drying at 90 ° C. for 48 hours. Montmorillonite composite nylon 6, in which the montmorillonite layer was uniformly dispersed in the obtained polyamide / nylon 6, was ignited at 650 ° C by a thermogravimetric analysis method and contained 2.0% of the composite montmorillonite from the weight of the burning residue. Table 1 shows the results
It was shown to.

Reference Examples 2 to 4 The montmorillonite composites used in Reference Example 1 were 270 g, 360 g, and 720 g, respectively, as shown in Table 1.
montmorillonite composite nylon 6 in the same manner as in Reference Example 1 using kg of ε-caprolactam and 1 liter of water.
Was manufactured. The contents of the composite montmorillonite were 3.0%, 4.1% and 7.9%, respectively. Table 1 shows the results
It was shown to.

[0030]

[Table 1]

Example 1 As a component (a), low density polyethylene LDPE (Ube Industries, F522, melting point 110 ° C., MFI = 5.0 g /
10 min. ) 70 parts by weight and 1.0 part by weight of γ-methacryloxypropyltrimethoxysilane as a silane coupling agent of the component (c) are melt-kneaded in a Banbury mixer at a temperature (150 ° C.) higher than the melting point of the component (a). The mixture was modified with silane to prepare a matrix, which was dumped at 170 ° C. and pelletized. To this matrix, 3 parts of the montmorillonite composite nylon 6 of the component (b) of Reference Example 1 were added.
0 parts by weight were kneaded by a twin-screw extruder heated to 250 ° C., extruded into a strand through a nozzle attached to the tip of the twin-screw extruder, and pelletized at room temperature at a draft ratio of 10 while pelletizing. The pellets were formed into a sheet by pressing at 180 ° C. A dumbbell-shaped test piece was punched out of this sheet, and the desired physical properties were measured. The results are shown in Table 2. Further, a fine fiber composed of the montmorillonite composite nylon 6 of the component (b) obtained by extracting and removing the low-density polyethylene of the component (a) with hot xylene from the obtained pellets was observed with a scanning electron microscope. The average fiber diameter is 0.2 μm
Met. The results are shown in Table 2.

Examples 2 to 4 In the same manner as in Example 1 except that the montmorillonite composite nylon 6 of Reference Examples 2 to 4 was used as the component (b) in place of Reference Example 1, with the formulation shown in Table 2. The results are shown in Table 2.

Examples 5 to 6 The same procedures as in Example 1 were carried out except that Reference Example 1 was used as the component (b) and the composition shown in Table 2 was used. The results are shown in Table 2.

Comparative Example 1 Example 1 was repeated except that the LDPE of Example 1 was not used as the component (a) and the silane coupling agent was not used as the component (c).
In the same manner as in the above, the mixture was kneaded with montmorillonite composite nylon 6 and extruded. The strand was fluctuated in discharge to prepare a draft and was barely wound into pellets. The hot xylene insolubles in the pellets were in the form of a film. The physical properties of the pellets were measured in the same manner as in Example 1, and the results are shown in Table 2.

Comparative Example 2 Nylon 6, PA6 (manufactured by Ube Industries, 1022B, melting point 215 to 115) instead of LDPE of Example 1 as component (a) and montmorillonite composite nylon 6 as component (b)
220 ° C.), except that it was the same as in Example 1. The results are shown in Table 2.

[0036]

[Table 2]

Examples 7-9 Polypropylene PP (manufactured by Grand Polymer, J105W, melting point 215-220 ° C, MFI =
5.0 g / 10 min. ), High density polyethylene HDP
E (manufactured by Keiyo Polymer Co., Ltd., M3800, melting point 130 ° C, M
FI = 5.0 g / 10 min. ) And ethylene-vinyl acetate copolymer EVA (V220, melting point 1 manufactured by Ube Industries, Ltd.)
07 ° C., MFI = 5.0 g / 10 min. ) Was used in the same manner as in Example 1 except that 70 parts by weight of Reference Example 2 was used as each of the components (b) and 30 parts by weight. The results are shown in Table 3.

[0038]

[Table 3]

[0039]

According to the polyamide fiber reinforced polyolefin resin composition obtained by the present invention, fine polyamide fibers having an average fiber diameter of 0.2 to 0.8 .mu.m are dispersed in a polyolefin matrix. Are uniformly dispersed and polyolefin and polyamide fibers are bonded at the interface. Polyamide fiber reinforced polyolefin resin compositions can be easily dispersed in resins and rubbers, and have excellent strength and elasticity, especially friction performance, and can be used as suitable reinforcing materials for automobile tires, rolls, floor materials, footwear, etc. .

 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Yukihiko Asano 8-1, Goi-minamikaigan, Ichihara-shi, Chiba F-term in Ube Industries, Ltd. Polymer Research Laboratory 4J002 BB031 BB061 BB061 BB071 BB081 BB121 BB151 BB171 BB221 BB241 BP021 CL012 CL032 EX036 EX066 EX076 FA042 FD206

Claims (5)

[Claims] A polyamide fiber reinforced polyolefin resin composition comprising the following components (a) to (c): (a) 90 to 40 parts by weight of a polyolefin, and (b) 10 to 60 parts by weight of a polyamide fiber containing a layered silicate. Department and
(C) It comprises a silane coupling agent. 2. The silane coupling agent of the component (c) is added in an amount of 0.1 to 100 parts by weight of the total of the components (a) and (b).
The polyamide fiber reinforced polyolefin resin composition according to claim 1, which is blended in an amount of 1 to 5.5 parts by weight. 3. The polyamide fiber reinforced polyolefin resin composition according to claim 1, wherein the polyamide fibers are dispersed in the polyamide fiber reinforced polyolefin resin composition to an average fiber diameter of 1 μm or less. 4. The polyamide fiber reinforced polyolefin resin composition according to claim 1, wherein the layer silicate contained in the component (b) is 0.05 to 30 parts by weight based on 100 parts by weight of the polyamide fiber. 5. A matrix obtained by melting and kneading (a) a polyolefin and (c) a silane coupling agent,
(B) The polyamide fiber-reinforced polyolefin resin composition according to claim 1, wherein the polyamide containing the layered silicate is melt-kneaded, extruded, and stretched or rolled at a temperature lower than the melting point of the polyamide to be dispersed in a fibrous form. Law.