JPH0433300B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel reinforced rubber composition that has excellent productivity and processability, as well as excellent modulus, strength, and crack growth resistance of the vulcanizate, and a method for producing the same. [Industrial Application Fields] The reinforced rubber composition of the present invention can be used in tire internal parts such as belts, carcass, and beads, tire external parts such as treads and sidewalls, belts, hoses, etc. by utilizing its excellent properties. industrial supplies,
It can be used for purposes such as footwear materials. [Prior Art] Conventionally, reinforced rubber compositions used for various parts of tires have been manufactured by blending short fibers such as nylon, polyester, vinylon, etc. with vulcanizable rubber. However, the reinforced rubber composition obtained in this way has a large fiber diameter and does not have a bond between the fibers and the rubber, and therefore the modulus and strength of the vulcanizate, especially at high elongation, are insufficient. There is a desire to develop a reinforced rubber composition that provides a vulcanizate with even greater modulus and strength. Therefore, an elastomer strengthening method and a reinforced elastomer composition have been proposed in which a polymer having fiber-forming ability and rubber are kneaded and then the kneaded product is extruded (Japanese Patent Application Laid-Open No. 8682/1982). However, even with this method, thick polymer fibers or films are generated, and the rubber and polymer (fibers) at the fiber interface
To obtain a reinforced rubber composition that can be used as a tire component and has low tensile strength of a vulcanizate, modulus at high elongation, and peel strength indicating adhesive strength with other types of base materials because of no bonding with It is not possible. Japanese Patent Publication No. 55-41652 describes a method for producing a reinforced rubber composition by kneading vulcanizable rubber and powdered 1,2-polybutadiene, extruding the kneaded product, and then rolling it with rolls. There is. In the reinforced rubber composition obtained by this method, the vulcanizate exhibits high elasticity, high elongation, high strength, and high peel strength, but the strength of the fibers formed from 1,2-polybutadiene is low. Fibers are cut during rubber processing, especially during carbon black kneading, resulting in short fiber lengths and have the disadvantage that the stress at low elongation of the vulcanizate is small. Therefore, in order to improve the drawbacks of conventionally known reinforced rubber compositions, the present inventors developed a composition in which a block copolymer of liquid diene rubber and nylon was blended into vulcanizable rubber by melt extrusion. proposed a method for producing a reinforced rubber composition in which nylon is made into fibers and vulcanizable rubber and liquid diene rubber are grafted together (Japanese Patent Application Laid-open No. 19342/1983). However, this production method has problems in practice because the reproducibility of block polymerization is not very good and the cost is high. Furthermore, in order to improve this drawback, the present inventor embedded fine polyamide fibers in vulcanizable rubber, and at the fiber interface, the vulcanizable rubber and the fibers formed an initial condensate of phenol formaldehyde. (Japanese Patent Application Laid-Open No. 186550/1986) proposed a reinforced rubber composition in which the rubber composition was graft-bonded through the bonding method. However, although this reinforced rubber composition has excellent productivity and processability, and provides a vulcanizate with excellent modulus, tensile strength, and adhesion at low and high elongations, it has poor crack growth resistance. The drawbacks have severely limited its use. [Problems to be Solved by the Invention] The present invention solves the drawbacks of low productivity and crack growth resistance of the prior art, has excellent productivity and processability, and also has low elongation and It is an object of the present invention to provide a reinforced rubber composition having excellent modulus at high elongation, tensile strength, and especially crack growth resistance, and a method for producing the same. [Means for Solving the Problems] The present invention is characterized in that 1 to 100 parts by weight of fine short fibers of fiber-formable polyamide are embedded in 100 parts by weight of vulcanizable rubber, and the polyamide and the rubber are This problem is solved by using a reinforced rubber composition characterized in that these are bonded together via a silane coupling agent. The reinforced rubber composition of the present invention has excellent productivity and processability, and also has excellent modulus, tensile strength, and adhesion at low elongation and high elongation in vulcanized products, and has excellent crack growth resistance. ing. As the vulcanizable rubber in this invention, all rubbers that give a rubber elastic body by vulcanization can be used, such as natural rubber,
Mention may be made of cis-1,4-polybutadiene, polyisoprene, polychloroprene, styrene-butadiene copolymer rubber, isoprene-isobutylene copolymer, ethylene-propylene-nonconjugated diene terpolymer and mixtures thereof. . Among these rubbers, natural rubber, polyisoprene, and isoprene hardly gel when a mixture of vulcanizable rubber, polyamide, and silane coupling agent is melted and kneaded, and then the kneaded product is extruded. - Isobutylene copolymers are particularly preferred. In the present invention, the fiber-formable polyamides include nylon 6, nylon 6/66, nylon 6/66, and nylon 6/66.
10, nylon 12, nylon 6/11, nylon 6/
12, nylon 66, etc., and its melting point is 150-260
℃, preferably 180-235℃. The polyamide is not particularly limited as long as it has fiber-forming ability, but it has a number average molecular weight of 5,000 or more, preferably 8,000 or more. If the molecular weight is too low, the fiber forming ability will be poor and the strength will also be low. In the reinforced rubber composition of the present invention, the proportion of fine short polyamide fibers embedded in the vulcanizable rubber is 1 to 100 parts by weight, preferably 1 to 100 parts by weight of the fibers per 100 parts by weight of the vulcanizable rubber. 1 to 70 parts by weight,
Particularly preferably 30 to 70 parts by weight. If the proportion of fibers embedded in vulcanizable rubber is less than the above-mentioned lower limit, the strength and modulus of the vulcanizate will not be improved, and the proportion of fibers embedded in vulcanizable rubber will be lower than the above-mentioned upper limit. When the amount is higher, crack growth resistance decreases. In addition, the average diameter of the fine short polyamide fibers is
The fiber length is 0.05 to 0.8μ, and the shortest fiber length in a circular cross section is preferably 1μ or more, and is embedded in the vulcanizable rubber in the form of fine short fibers with molecules arranged in the fiber axis direction. Furthermore, at the interface of the fibers, the polyamide and the vulcanizable rubber are bonded via a silane coupling agent. As the silane coupling agent in the present invention, a compound represented by the structural formula Y-R ₁ SiX ₃ or Y-R ₁ SiR ₂ X ₂ is used. Here, Y, R ₁ , R ₂ and X each represent the following groups. Y: _H2N- , _CH2 =CH-,

【formula】

[Formula] Cl-, HS- C ₆ H ₅ - R ₁ : A _P CnH ₂ nB _Q CmH ₂ mB _Q ClH ₂ l A: C ₆ H ₄ P=0~2 n=0~5 B: O, NH Q=0-2 m=0-5 l=0-5 R ₂ :CnH _2o+1 n=1-4 X: DrCnH ₂ nEsCmH _2n+1 D: O, Cl r=0-2 n=0-5 E: Os=1-2 m=1-5 Specifically, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane,
N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-(diethylenetriamino)propyltrimethoxysilane, γ-ureito-propyltriethoxysilane, Vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris(βmethoxyethoxy)silane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-(3,4epoxycyclohexyl)ethyltri Methoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, N-phenyl-γ
-aminopropyltriethoxysilane, N-β
(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride and the like can be suitably used. The amount of the silane coupling agent used in the present invention is 0.1 to 5.5 parts by weight, preferably 0.2 to 5 parts by weight, per 100 parts by weight of the fiber-formable polyamide. If the amount of the silane coupling agent is less than the lower limit, the reaction between the vulcanizable rubber and the polyamide through the silane coupling agent is difficult to occur, and therefore thick polyamide fibers or films are not formed. Furthermore, since the bond between the polyamide and the rubber at the fiber interface is weak, the strength, crack growth resistance, etc. of the vulcanizate obtained by vulcanizing this reinforced rubber composition are reduced. Furthermore, if the amount of the silane coupling agent is greater than the above upper limit, the silane coupling agent will cause gelation of the vulcanizable rubber, which will prevent polyamide fiber formation. The resulting vulcanizate is strengthened and its modulus is reduced. The method for producing the composition of the present invention includes vulcanizable rubber,
Fiber-formable polyamides and said polyamides
By kneading 0.1 to 5.5 parts by weight of a silane coupling agent per 100 parts by weight at a temperature higher than the melting point of the polyamide, and extruding the resulting kneaded product at a temperature higher than the melting point of the polyamide, or by appropriately extruding the extrudate It is provided by stretching at a temperature higher than the melting point of the polyamide, stretching at a temperature lower than the melting point, or a combination of these stretching. The method for producing the reinforced rubber composition in the present invention includes dry blending predetermined amounts of vulcanizable rubber, polyamide, and silane coupling agent, and melt-kneading the mixture at a temperature higher than the melting point of the polyamide to form a vulcanizable rubber composition. A kneaded product can be obtained comprising 100 parts by weight of polyamide, 1 to 100 parts by weight of polyamide, and 0.1 to 5.5 parts by weight of a silane coupling agent per 100 parts by weight of polyamide. Alternatively, vulcanizable rubber or polyamide and a silane coupling agent are melt-kneaded, and polyamide or vulcanizable rubber is added or melt-kneaded to this kneaded product, and 100 parts by weight of vulcanizable rubber and 1 part by weight of polyamide are added. A kneaded product can be obtained consisting of 0.1 to 5.5 parts by weight of a silane coupling agent per 100 parts by weight and 100 parts by weight of polyamide. In addition, polyamide or vulcanizable rubber may be added to the kneaded material using the above kneaded material as a master to obtain 100 parts by weight of vulcanizable rubber, 1 to 100 parts by weight of polyamide, and 0.1 to 5.5 parts by weight per 100 parts by weight of polyamide. A kneaded product consisting of a silane coupling agent can be obtained. The above-mentioned components are preferably kneaded for 1 to 15 minutes using a Brapender blastograph, a Bumperley mixer, a roll, an extruder, or the like. In the method of this invention, an anti-aging agent, for example N-
(3-methacryloyloxy-2-hydroxypropyl)-N'-phenyl-p-phenyldiamine, phenyl-α-naphthylamine, phenyl-β-naphthylamine, N,N'-diphenyl-
p-phenylenediamine, N-isopropyl-
N'-phenyl-p-phenylenediamine, N-
Cyclohexyl-N'-phenyl-p-phenylenediamine, 2,6-di-tert-butyl-4-methylphenol-2,6-di-tert-butyl-α-dimethylamino-p-cresol, 2,2'- Dihydroxy-3,3'-bis(α-methylcyclohexyl)
It is preferable to incorporate a low volatility anti-aging agent such as -5,5'-dimethyl diphenylmethane. Next, the obtained kneaded product is melt-extruded at a temperature higher than the melting point of the polyamide, preferably 5°C higher than the melting point, and lower than 300°C, or appropriately stretched or stretched at a temperature higher than the melting point of the polyamide. A reinforced rubber composition can be obtained by stretching at a lower temperature or by using these stretching in combination. At this time, production of the kneaded material, melt extrusion, and stretching can also be performed in one step. Specifically, the material can be extruded into a string (or sheet) through a die having a circular or rectangular discharge opening, such as a circular die or a rectangular die. When using a circular die, the inner diameter of its discharge port should be 0.1
~5mm, the ratio of the length of the outlet to the inner diameter of the outlet (L/
D) is preferably 1 to 20, and when using a rectangular die, the slit gap is 0.1 to 5 mm,
It is preferable that the width is 0.2 to 200 mm and the length of the die land is 10 to 20 mm. Among the various dies described above, it is preferable to use circular dies. As the circular die, one having one discharge port or one having multiple discharge ports (multi-hold type) can be used. For extrusion of the kneaded product, a known extruder, such as a screw type extruder, is used, and the temperature at the screw tip is kept at a temperature higher than the melting point of the polyamide and at a temperature of 300 °C.
It is preferable to extrude the kneaded product by setting the temperature of the die to a temperature not lower than the melting point of the polyamide and not higher than 300°C, particularly at least 5°C higher than the melting point of the polyamide and not higher than 280°C. In the method of the present invention, by extruding the kneaded product as described above, the polyamide in the vulcanizable rubber of the extrudate obtained is in a fibrous form, and moreover, at the interface of the fibrous polyamide, polyamide and a vulcanizable rubber are bonded together via a silane coupling agent. The reinforced rubber composition of the present invention is produced by heating the above extrudate at a temperature above the melting point of the polyamide, preferably under continuous tension, by a method known per se.
Rubber and polyamide, such as methanol, are stretched on a winding machine (stretching machine) such as a bobbin or a winding roll at a winding speed of 1 to 100 m/min, preferably 20 to 40 m/min, and are air-cooled, water-cooled, or cooled. After cooling to a temperature lower than the melting point of the polyamide by cooling with an inert organic solvent or by increasing the distance from the die to the winding machine (also called a drawing machine), a pair of It can also be obtained by stretching using a rolling roll or by uniaxially stretching using a stretching roll. The temperature of the winder (stretching machine) when winding up the extrudate is preferably 0 to 100°C. If the extrudate touches the surface of the winding machine (stretching machine) at a temperature above the melting point of the polyamide, a portion of the fibrous polyamide will become flat (in extreme cases, film-like), making it impossible to obtain a good reinforced rubber composition. There are cases. The temperature of the stretching using the rolling rolls is preferably 0 to 100°C. Further, it is preferable that the stretching using the stretching rolls be performed at a stretching ratio of 1.1 to 10. In the method of the present invention, the extrudate is stretched above the melting point of the polyamide, below the melting point, or in combination with stretching of the extrudate as described above. The fibers of polyamide undergo molecular orientation and transform into a fibrous structure, resulting in fine short fibers with great strength. The reinforced rubber composition obtained by the method of the present invention contains 1 to 100 parts by weight of fiber-formable polyamide per 100 parts by weight of vulcanizable rubber, and the polyamide is in the form of fine short fibers, and At the interface of the fibers, polyamide and vulcanizable rubber are bonded via a silane coupling agent, and it can be used alone or in a blend with vulcanizable rubber to achieve low elongation and high elongation. It is possible to provide a vulcanizate with excellent modulus during elongation, tensile strength, and crack growth resistance. In addition, in the reinforced rubber composition of the present invention, the vulcanizate bonded to the polyamide via the silane coupling agent at the interface of the polyamide fine short fibers embedded in the vulcanizable rubber is Polyamide forming fibers in such a way that the amount of bonded rubber expressed as a weight ratio of vulcanizable rubber (vulcanizable rubber/fine short polyamide fibers) is 10 to 30% by weight, especially 15 to 30% by weight. Preferably, the vulcanizable rubber and the vulcanizable rubber are bonded together via a silane coupling agent. By utilizing its excellent properties, the reinforced rubber composition of the present invention can be applied to tire internal parts such as belts, carcass, and beads, tire external parts such as treads and sidewalls, industrial products such as belts and holes, and footwear materials. It can be used for the following purposes. [Effects of the present invention] The composition of the present invention has fine short polyamide fibers embedded in vulcanizable rubber, and the vulcanizable rubber and polyamide are bonded via a silane coupling agent. Thus, a novel rubber reinforced composition with excellent strength, modulus and crack growth resistance of the vulcanizate can be obtained. This composition also has excellent productivity and processability. [Examples of the present invention] Next, Examples, Comparative Examples, and Reference Examples are shown. Physical property tests of vulcanizates conducted to evaluate the (reinforced) rubber compositions obtained in Examples, Comparative Examples, and Reference Examples were measured in accordance with JISK6301. Example 1 100 parts of natural rubber (NR) having a melt viscosity of 1×10 ⁶ poise and N-(3-methacryloyloxy-2- Hydroxypropyl)-N'-phenyl-p-phenylenediamine [Nokrac G-1, Ouchi Shinko Chemical Industry Co., Ltd.
Co., Ltd.] 1.0 part, and after masticating for 30 seconds, nylon 6
(Product name 1030B, manufactured by Ube Industries, Ltd., melting point 221°C, molecular weight 30000) 2 parts by weight per 100 parts by weight of N-β (aminoethyl)γ-aminopropyltrimethoxysilane (Product name KMB603, manufactured by Shin-Etsu Chemical Co., Ltd. 51 parts of pellets into which Silane A (manufactured by Co., Ltd., hereinafter referred to as Silane A) had been kneaded in advance were added and kneaded for 13 minutes (during which time the temperature inside the Brabender rose to 230°C) to obtain a kneaded product. The obtained kneaded material was passed through a circular die having a nozzle with an inner diameter of 2 mm and a length to inner diameter ratio (L/D) of 2.
mm = Die setting temperature using an extruder (manufactured by Haake)
It was extruded into a string at 235°C, and then passed through a guide roll placed 3 m directly below the nozzle and wound onto a bobbin at a draft ratio of 10 (at a speed of 38.8 m/min). Approximately 500 of these rolls are bundled into a sheet (approximately 2 mm thick, approximately 150 mm wide), and this sheet is rolled using a pair of rolling rolls with a roll gap of 0.2 mm and a temperature of 60°C.
Roll stretching was carried out approximately 10 times to obtain a masterbatch of a reinforced rubber composition. Separation and measurement of bonded rubber amount 2 g of the reinforced rubber composition obtained in Example 1 was added to 200 ml of toluene at 80°C to dissolve the rubber content in the reinforced rubber composition, and the resulting slurry was centrifuged at room temperature. It was divided into a solution part and a precipitate part. After repeating the above operation seven times for the precipitated portion, the precipitated portion was dried to obtain nylon fibers. This nylon fiber was dissolved in a mixed solvent of phenol and orthodichlorobenzene, analyzed by ¹ H nuclear magnetic resonance spectroscopy (tetramethylsilane as internal standard), and methyl groups and methylene groups originating from the rubber were determined from the NMR chart. For each peak of the methylene group adjacent to the CO group, the methylene group adjacent to the NH group, and the other three methylene groups due to nylon, the molar ratio of nylon and rubber was determined by the cut area method, and the bond was determined. The amount of rubber was calculated. In addition, the shape of the nylon fiber is
Approximately 200 fibers were measured using a scanning microscope at a magnification of 10,000 times. The fibers were extremely thin short fibers with a circular cross section. The results are summarized in Table 1. Evaluation Test The reinforced rubber composition obtained in Example 1 was vulcanized at 145° C. for 30 minutes according to the formulation shown in Table 2, and its physical properties were measured. The results are shown in Table 2. Example 2 30mm single screw extruder set at 240℃ (L/D=
Natural rubber (NR) with a melt viscosity of 5 × 10 ⁵ poise and N-(3
Natural rubber and N-(3-methacryloyloxy -2-hydroxypropyl)
-N'-Phenyl-p-phenylenediamine and nylon pellets were charged at a ratio of 100/1/51 and extruded at a rate of 2 kg/hr to obtain a kneaded product. The subsequent operations were carried out in the same manner as in Example 1. The results are summarized in Tables 1 and 2. Example 3 100 parts of natural rubber (NR) having a viscosity of 1×10 ⁶ poise and N-(3
-methacryloyloxy-2-hydroxypropyl)-N'-phenyl-p-phenylenediamine 1.0
After masticating for 30 seconds, 50 parts by weight of 6-nylon (trade name 1030B, manufactured by Ube Industries, Ltd.) and silane were added.
A1 part by weight was added and kneaded for 13 minutes to obtain a kneaded product. The subsequent operations were carried out in the same manner as in Example 1. The results are summarized in Tables 1 and 2. Example 4 N-β (aminoethyl)γ- in place of silane A
Aminopropylmethyldimethoxysilane (trade name)
The same procedure as in Example 1 was conducted except that KBM502 (manufactured by Shin-Etsu Chemical Co., Ltd., hereinafter referred to as Silane B) was used. The results are summarized in Tables 1 and 2. Example 5 The same procedure as in Example 1 was carried out, except that vinyltris(β-methoxyethoxy)silane (trade name KBM1003, manufactured by Shin-Etsu Chemical Co., Ltd., hereinafter referred to as Silane C) was used in place of Silane A. The results are summarized in Tables 1 and 2. Example 6 The same procedure as in Example 1 was carried out except that γ-methacryloxypropyltrimethoxysilane (trade name KBM503, manufactured by Shin-Etsu Chemical Co., Ltd., hereinafter referred to as silane D) was used in place of silane A. The results are summarized in Tables 1 and 2. Example 7 The same procedure as in Example 1 was carried out except that γ-mercaptopropyltrimethoxysilane (trade name KBM803, manufactured by Shin-Etsu Chemical Co., Ltd., hereinafter referred to as silane E) was used in place of silane A. The results are summarized in Tables 1 and 2. Example 8 β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (trade name
The same procedure as in Example 1 was conducted except that KBM303 (manufactured by Shin-Etsu Chemical Co., Ltd., hereinafter referred to as Silane F) was used. The results are summarized in Tables 1 and 2. Example 9 γ-chloropropyltrimethoxysilane (trade name KBM703, Shin-Etsu Chemical Co., Ltd.) in place of Silane A
Example 1 was carried out in the same manner as in Example 1, except that Silane G (manufactured by Silane G) was used. The results are summarized in Tables 1 and 2. Example 10 N-β (N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride (trade name SZ-6032, manufactured by Toray Silicone Co., Ltd., hereinafter referred to as Silane H) was used in place of Silane A. Other than that,
It was carried out in the same manner as in Example 1. The results are summarized in Tables 1 and 2. Comparative Example 1 100 parts of natural rubber (NR) having a viscosity of 1 x 10 ⁶ poise and N-(3-methacryloyloxy-2-hydroxypropyl-p) were placed in a Brabender plastograph set at 220°C and 50 rpm. - Add phenylene diamine and masticate for 30 seconds, then add 50 parts of 6-nylon (1030B) and mix for 4.5 minutes.
Next, a novolac type phenol formaldehyde initial condensate [trade name 550PL, manufactured by Meiwa Kasei Co., Ltd.] 2.25
After 3 minutes of kneading, 0.225 parts of hexamethylene latramine was added and kneaded for 3.5 minutes to obtain a kneaded product. The subsequent operations were carried out in the same manner as in Example 1. The results are summarized in Tables 1 and 2. Example 11 The same procedure as in Example 1 was carried out except that polyisoprene (Kuraprene IR-10) was used instead of natural rubber (NR). The results are summarized in Tables 1 and 2. Example 12 The same procedure as Example 1 was carried out except that an isoprene-isobutylene copolymer (ethobutyl 365) was used instead of natural rubber (NR). The results are summarized in Tables 1 and 2. Example 13 In a Brabender Plastograph set at 200°C and 50 rpm, 100 parts of cis-1,4-polybutadiene (UBEPOLBR-150, manufactured by Ube Industries, Ltd.) and N-(3-methacryloyl) were added as an anti-aging agent. Oxy-2-hydroxypropyl)-N'-phenyl-p-phenylenediamine [Nokrac G-
1. Add 1.0 part of Ouchi Shinko Chemical Industry Co., Ltd. and masticate for 30 seconds.
51 parts of pellets in which 2 parts by weight of Silane A per 100 parts by weight (melting point: 176°C) were added and kneaded for 10 minutes (during which time the temperature inside the Brabender rose to 205°C). I got something. The obtained kneaded material was formed into a string at a die temperature of 220°C using a 20mm extruder (manufactured by Haake) having a circular die with a nozzle inner diameter of 2mm and a length to inner diameter ratio (L/D) of 2. Extrusion and the following operations were carried out in the same manner as in Example 1. The results are summarized in Tables 1 and 2. Example 14 Example 14 except that 52 parts of pellets into which 4 parts by weight of Silane A were pre-mixed per 100 parts by weight of nylon 6 (trade name 1013B, manufactured by Ube Industries, Ltd., melting point 221°C, molecular weight 13000) were used. It was carried out in the same manner as in 1. The results are summarized in Tables 1 and 2. Example 15 The same procedure as in Example 1 was carried out except that 30.6 parts of nylon kneaded with Silane A used in Example 1 was used. The results are summarized in Tables 1 and 2. Example 16 The same procedure as in Example 1 was carried out except that 71.4 parts of nylon mixed with Silane A used in Example 1 was used. The results are summarized in Tables 1 and 2. Example 17 Example 1 was carried out in the same manner as in Example 1, except that 102 parts of nylon into which Silane A had been mixed in was used. The results are summarized in Tables 1 and 2. Comparative Example 2 The same procedure as in Example 1 was carried out, except that 122.4 parts of nylon into which Silane A had been mixed in was used. The results are summarized in Tables 1 and 2. Example 18 Pellets in which 0.5 parts by weight of Silane A are mixed in advance per 100 parts by weight of nylon 6 (1030B)
The same procedure as in Example 1 was carried out except that 50.25 parts were used. The results are summarized in Tables 1 and 2. Example 19 Pellets in which 1.0 part by weight of Silane A was mixed in advance per 100 parts by weight of nylon 6 (1030B)
The same procedure as in Example 1 was carried out except that 50.5 parts were used. The results are summarized in Tables 1 and 2. Comparative Example 3 Pellets 53 in which 6.0 parts by weight of Silane A were mixed in advance per 100 parts by weight of nylon 6 (1030B)
Example 1 was carried out in the same manner as in Example 1, except that part was used. The results are summarized in Tables 1 and 2. Comparative Example 4 The same procedure as Example 1 was carried out except that Silane A was not used. The results are summarized in Tables 1 and 2. Comparative Example 5 The same procedure as Example 11 was carried out except that Silane A was not used. The results are summarized in Tables 1 and 2. Comparative Example 6 The same procedure as Example 12 was carried out except that Silane A was not used. The results are summarized in Tables 1 and 2. Comparative Example 7 The same procedure as Example 13 was carried out except that Silane A was not used. The results are summarized in Tables 1 and 2.

【table】

【table】

【table】

【table】

【table】

【table】

Claims (1)

[Claims] 1. 100 parts by weight of vulcanizable rubber with a diameter of 0.05~
Fine short polyamide fibers capable of forming 0.8μ fibers 1
A reinforced rubber composition characterized in that the polyamide and the rubber are bonded via a silane coupling agent. 2 Vulcanizable rubber, fiber-formable polyamide and 0.1 to 5.5 parts per 100 parts by weight of the polyamide
A method for producing a reinforced rubber composition, which comprises kneading parts by weight of a silane coupling agent at a temperature higher than the melting point of the polyamide, and extruding the resulting kneaded product at a temperature higher than the melting point of the polyamide.