JPS5879037A - Reinforced rubber composition and its preparation - Google Patents

Abstract

PURPOSE:A composition for providing a vulcanized material having improved strength and modulus, wherein fine nylon fibers embedded in vulcanizable rubber have graft bond to rubber through a precondensate of a specific formaldehyde resin. CONSTITUTION:A reinforced rubber composition wherein 1-70pts.wt. fine nylon fibers are embedded in 100pts.wt. vulcanizable rubber having an average particle diameter of 0.05-0.8mu, and graft bond occurrs between the interface of nylon and the vulcanizable rubber through a precondensate of a resol type alkylphenol- formaldehyde resin. 100pts. total amount of rubber and nylon (a molecular weight of<200,000) is blended with 0.2-2.5pts.wt. precondensate at a temperature >= the melting point of nylon and <=270 deg.C, and, if necessary, rubber is added to the blend to give a weight ratio of rubber to nylon of 100:1-70, and the blend is extruded at >= the melting point of nylon and <=270 deg.C and the extrudate is oriented at <= the melting point of nylon.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel reinforced rubber composition in which the vulcanizate has excellent strength and modulus, and a method for producing the same.

Conventional 1 reinforced rubber compositions include vulcanizable rubber, nylon,
1 However, it is manufactured by blending short fibers such as polyester and vinylon.

The strength and modulus of the vulcanizate of the thus obtained reinforced rubber composition is not sufficiently high, and it is desired to develop a reinforced rubber composition that provides a vulcanizate with even better strength and modulus.

Therefore, as a method for manufacturing a reinforced rubber composition that improves the drawbacks of conventionally known reinforced rubber compositions, a method has been proposed in which vulcanizable rubber and powdered 1,2-polybutadiene are kneaded, extruded, and rolled with rolls. (Tokuko Sho! 55-41
No. 652).

The above-mentioned publication describes a number of experimental examples of manufacturing reinforced rubber compositions that provide reinforced elastic bodies with excellent strength and modulus.

However, the method for manufacturing the reinforced rubber composition described in the above publication has a fiber-forming polymer with a structural content of 1.2 and 80%.
% or more, and the melting point is 130° C. or more.The resulting reinforced rubber composition is difficult to obtain during rubber processing because the strength of the fibers formed from the 1,2-polybutadiene is low. In particular, the fibers are cut during carbon blank cross-wiring.

It has the disadvantage that the fiber length is short and the modulus of the vulcanizate at low elongation is small.

As a result of intensive research aimed at providing a reinforced rubber composition that does not have the above-mentioned drawbacks and a method for producing the same, the inventors discovered that they used nylon as the fiber polymer, and that vulcanizable rubber and nylon fibers were used. The present invention has been completed based on the discovery that a reinforced rubber composition can be obtained which provides a vulcanizate with an excellent modulus and alkylphenolform as a crosslinking agent.

That is, in this invention, 1 to 70 parts of fine nylon fibers are embedded in 100 parts by weight of vulcanizable rubber, and the nylon and vulcanizable rubber form a resol type at the interface of #fibers. A reinforced rubber composition graft-bonded via an initial condensate of an alkylphenol formaldehyde resin, and a vulcanizable rubber having a molecular weight of 20,000.
Total amount of nylon less than 0, rubber and nylon 100
0.2 to 2.5 parts by weight of an initial condensate of resol-type alkylphenol formaldehyde resin (hereinafter also simply referred to as alkylphenol formaldehyde resin) at a temperature above the melting point of nylon and 270%
When the ratio of rubber and nylon in the mixed material is 1 to 70 parts by weight of Q nylon per 100 parts by weight of rubber, the resulting mixed material is mixed as is at a temperature below ℃.
When the ratio of rubber and nylon is more than 1 part by weight of 9-nylon per 100 parts by weight of rubber, add additional vulcanizable rubber so that the ratio of nylon to 100 parts by weight of rubber is 1 to 70 parts by weight. Add it to the mixer.

Further, strengthening is characterized by kneading at a temperature above the melting point of nylon and below 270°C, extruding at a temperature above the melting point of nylon and below 270°C, and stretching the extrudate at a temperature below the melting point of nylon. The present invention relates to a method for producing a rubber composition.

The reinforced rubber composition of the present invention can provide a vulcanizate with excellent modulus and tensile strength at low and high elongations.

Furthermore, according to the method of the present invention, a reinforced rubber composition that provides a vulcanizate with excellent physical properties can be manufactured with good reproducibility from vulcanizable rubber, nylon, and alkylphenol formaldehyde resin by simple operations. can.

As the vulcanizable rubber in this invention, all rubbers that can be vulcanized to give a rubber elastic body can be used, and for example, natural rubber.

Cis-1,4-polybutadiene, polyisoprene.

Polychloroprene 5 styrene-butadiene copolymer rubber, isoprene-isobutylene copolymer, ethylene-propylene-nonconjugated diene copolymer.

Mention may be made of mixtures of these. Among these rubbers, natural rubber is preferred because it hardly causes gluing when vulcanizable rubber, nylon, and alkylphenol formaldehyde-based resin are kneaded, and then the mixed material is extruded.

In the composition of the present invention, 1 to 70 parts by weight, preferably 10 to 60 parts by weight, of fine nylon fibers are embedded in 100 parts by weight of the above-mentioned vulcanizable rubber, and the nylon fibers are embedded at the interface of the fibers. and vulcanizable rubber are graft-bonded via an alkylphenol formaldehyde resin as a crosslinking agent.

The above-mentioned nylon fiber is nylon having a melting point of 190 to 225°C, preferably 200 to 220°C, such as nylon 6, nylon 610. Nylon 12° Nylon 611.
It is made of nylon 612, etc., and has an average diameter of 0.
05~0.8μ, 0-circle circular surface, shortest fiber length is 1μ
As mentioned above, the fibers are embedded in the vulcanizable rubber in the form of fine fibers with molecules arranged in the direction of the fiber axis, preferably having a diameter of 8μ or more.

Moreover, at the interface of the nylon fibers mentioned above, the nylon and the vulcanizable rubber are graft-bonded via an alkylphenol formaldehyde resin as a crosslinking agent.

The above alkylphenol formaldehyde resin has the general formula (R is an alkyl group or a combination of a hydrogen atom and an alkyl group, x is a hydroxyl group or a halogen atom such as chlorine or bromine, and L - is 1 or 2, and n is a number from 2 to 15.) A resol obtained by reacting an alkylphenol such as cresol with formaldehyde or acetaldehyde in the presence of an alkali catalyst. Examples include initial type condensates and modified products thereof. In particular, those having 2' or more methylol groups in one molecule can be suitably used as alkyl phenylene aldehyde resins. As an alkylphenol formaldehyde resin 1
for example. Sumilight Resin PR-22193, Sumilight Resin:y PR-50'994゜Sumilight Resin P'R-175. Sumilightre, Jin PR-50530
@, Sumilight Resin PR-51466, Sumilight Resin PR-22193゜Sumilight Resin PR-286
33 (manufactured by Juman Durres Co., Ltd.), Tanokirol 201
．． Takki Roll 2'50-1. Takki Roll 250-
n, Takki Roll 250-1 (manufactured by Sumima Kagaku Kogyo (closed)), PP-45 ()? (manufactured by Gunei Chemical Industry Co., Ltd.), Tamanol 521 (manufactured by Arayo Chemical Industry Co., Ltd.), Chenectady (8chenectady) 8 P IJO59
, 8chenectady S
P 1055 (8chenectady Chemi
cals), ORR-0803 (Union
Carbide (USA)), Synp
horm ) C1000, -CI OO1 (Ancho
r Ohem (UK)), Vulkarezart (Vu
lk, aresat) 510 E.

-532, Vulkarese
n) 105E, -130g, Purcaresol (Vul
karesol) 315 E (Hoechst
Commercially available resin crosslinking agents such as (manufactured by West Germany) can be mentioned. Incidentally, the alkylphenol formaldehyde resin to which various auxiliary agents such as thickeners, solvents, and plasticizers are added and blended in the production of the alkylphenol formaldehyde resin naturally also falls under the alkylphenol formaldehyde resin referred to herein.

In the reinforced rubber composition of the present invention, the strength of the fine nylon fibers embedded in the vulcanizable rubber is high, and the nylon and vulcanizable rubber on the surface of the nylon fibers are bonded to alkylphenol formaldehyde. Craft bonding via resin provides a vulcanizate with excellent modulus and tensile strength at low and high elongations, as well as excellent adhesion to materials such as natural rubber vulcanizates and steel. Thus, a reinforced rubber composition can be obtained.

Further, the above-mentioned graft bond is 1, for example, methylo/' (
0HtOH) In the case of an alkylphenol formaldehyde resin having a, the hydrogen atom of the methylene group in the vulcanizable rubber polymer molecule and the hydrogen atom of the alkylphenol formaldehyde resin molecule are bonded to the vulcanizable rubber polymer molecule. It is thought that it is produced by a dehydration reaction with the hydroxyl group of the remaining methylol in the alkylphenol-formaldehyde resin molecule.

In the reinforced rubber composition of the present invention, the vulcanizable rubber graft-bonded to the nylon via the alkylphenol formaldehyde resin at the interface of the nylon fibers is based on the weight of the nylon fibers embedded in the vulcanizable rubber. Grafting ratio indicated by the ratio of major prize (vulcanizable rubber/nylon fiber) is 3 to 25 weight ratio, 5 to l#
It is preferable that the nylon and the vulcanizable rubber are graft-bonded via an alkylphenol formaldehyde resin so that the weight is 202%.

Furthermore, if the proportion of nylon fibers embedded in the reinforced rubber composition is outside the above range, the strength and modulus of the vulcanizate obtained by vulcanizing the composition will decrease, which is not preferable.

The reinforced rubber composition of the present invention having the above-mentioned characteristics includes, for example, vulcanizable rubber, nylon having a molecular weight of less than 20'0000, and 1) o, z to 100 parts by weight of the total amount of rubber and nylon. 2.5 parts by weight of alkylphenol formaldehyde resin at a temperature above the melting point of nylon and 2.5 parts by weight of alkylphenol formaldehyde resin.
When the ratio of rubber and nylon in the mixed material is 100 parts by weight of rubber and 1 to 70 parts by weight of nylon, the obtained mixed material is kneaded at a temperature of 70° C. or lower. When the ratio of nylon to 100 parts by weight of rubber exceeds 11 parts by weight of nylon, add 1 part of nylon to 100 parts by weight of total rubber.
~70 parts by weight is added to the mixed material, and the mixture is further kneaded at a temperature above the melting point of nylon and below 270°C, and then extruded at a temperature above the melting point of nylon and below 270°C to obtain an extrudate. It can be produced by stretching at a temperature of 1 degree lower than the melting point of nylon.

In the method of this invention, the above-mentioned vulcanizable rubber and the molecular weight (number average molecular weight) less than zoooo, o.

Preferably 1OO00 to 10oOOOO of the aforementioned nylon and a total amount of the vulcanizable rubber and nylon of 100
90.2 to 2.5 parts by weight, preferably 0.7 to 2.5 parts by weight
2.0 weight of the aforementioned alkylphenol formaldehyde resin is kneaded at a temperature above the melting point of nylon and below 270°C.

What is the ratio of the vulcanizable rubber and nylon?

100 parts by weight of vulcanizable rubber, 1 to 200 parts of nylon
0 parts by weight, especially 10 to 500 parts by weight are preferred.

The mixture of vulcanizable rubber, nylon, and alkylphenol formaldehyde resin is carried out at a temperature above the melting point of nylon and below 270°C, preferably 5°C below the melting point of nylon.
The mixture of vulcanizable rubber, nylon, and alkylphenol formaldehyde resin is molten at a temperature higher than 0.degree. C. and lower than 260.degree. The mixing of the vulcanizable rubber, nylon, and alkylphenol formaldehyde resin is preferably carried out using a Brabensie plastograph, a Banbury mixer, a roll, an extruder, etc.
It is held for 15 minutes.

In the method of the present invention, the alkylphenol formaldehyde resin described above is used, and the vulcanizable Nacomb, nylon, and alkylphenol formaldehyde resin are kneaded as described above, and the vulcanizable rubber and nylon are bonded together using a crosslinking agent. In addition to graft bonding via the alkylphenol formaldehyde resin, nylon can be finely and uniformly dispersed in the vulcanizable rubber.

If the amount of the alkylphenol formaldehyde resin is less than the lower limit, it will be difficult to obtain a reinforced rubber composition that provides a vulcanizate with excellent bonding properties with other members. If it is more than the above upper limit.

Gelation occurs due to reactions between vulcanizable rubbers or nylons, making it difficult to obtain a reinforced rubber composition that provides a vulcanizate with excellent modulus and strength.

In the method of the present invention, there is no particular restriction on the order of addition of each component when kneading the vulcanizable rubber and the nylontoalkylphenol formaldehyde resin. Also,
Vulcanizable rubber KN-(3-methacryloyloxy-2-hydroxypropyl)-N/-7enyl-p-phenylenediamine, phenyl- for the purpose of preventing cross-contamination and gelation of vulcanizable rubber during extrusion. α-Naphthylamine.

Phenyl-β-7thylamine, aldol-α-naphthylamine, reaction product of phenyl-I-7thylamine and acetone, p-impropoxy diphenylamine,
p-(p-)luene sulfonylamide)-diphenylamine, a reaction product of diphenylamine and acetone,
reaction product of diphenylamine and diisobutylene,
N,N'-C712-p-7enylenediamine,N
-isopropyl-N'-phenyl-p-phenylenediamine.

N-'yprohexyl-N'-phenyl-p-phenylenediamine, N,N'-bis(1,4-dimethylpentyl)-p-7 2,2,4-
) dimethyl-1,2-dihydroquinoline polymer, 6
-Nitoxy2.2.4-trimethyl-1,2-dihydroquinoline, 6-dozosil-2.2.4-trimethyl-
1,2-dihydroquinoline, 2,6-di-tert-butyl-4
-Methylphenol, 6-tert-butyl-3-methylphenol derivative, 2,6-di-tert-butyl-4-n-butylphenol, 4-hydroxymethyl-α-dimethylamino-p-cresol, 2,2- Methylene-bis (4
-methyl-6-cyclohexyl phenol), 4.4
'-/tyrenebis(2β-ditert-butylphenol)
, 2.2'-methylene-bis(6-alphamethyl-benzyl-p-cresol), 4.4'-butylidenebis(3-methyl-6-tert-butylphenol), 2.2
A low-volatility antiaging agent such as '-dihydroxy-3,3'-di(α-methylcyclohexyl)-5°5'-dimethyl diphenylmethane may be blended.

In the method of the present invention, a kneaded product obtained by kneading a rubber that can be molded, nylon, and an alkylphenol formaldehyde resin is prepared such that the ratio of rubber and nylon in the kneaded product is 1 nylon per 100 parts by weight of rubber. ~70 parts by weight, preferably 10 to 60 parts by weight, it is extruded as is, and the ratio of rubber and nylon in the mixed material is 100 parts by weight.
When the amount of nylon used in the double neck is larger than the single neck, it is added to the kneaded material so as to form the above-mentioned part, and then heated at a temperature higher than the melting point of nylon and 270°C or lower, preferably 95°C or higher than the melting point of nylon. It is extruded after mixing at a temperature of high and below 260°C.

If the proportion of nylon in the mixed material when extruding the mixed material is less than the above-mentioned lower limit, it will not be possible to obtain a reinforced rubber composition that provides a vulcanizate with excellent strength and modulus; If the proportion of nylon in the mixed material exceeds the above upper limit, it becomes difficult to obtain a reinforced rubber composition that provides a vulcanizate with excellent adhesiveness.

The contaminant is made into a goo whose discharge port has a circular or rectangular shape, such as a circular goo, by an extrusion method known per se.
It can be extruded into a string (or sheet) through a rectangular die. When using a circular die, it is preferable that the inner diameter of the outlet is 0.1 to 5+w and the ratio of the length of the outlet to the inner diameter of the outlet (L/D) is 1 to 2 convex. It is preferable to use

Among the various dies described above, it is preferable to use circular dies. As the circular goo, one having one discharge port or one having multiple discharge ports (multi-hold type) can be used.

When extruding the mixed material, use a known extruder, for example, a one-screw extruder, and set the temperature of the one-screw extrusion to above the melting point of nylon and below 270°C, and the temperature of one circular die to above the melting point of nylon. and below 270℃,
Especially the melting point of nylon! l15℃ or more high and 260℃
It is preferable to extrude the mixed wire by setting the temperature below.

In the method of this invention, by extruding the kneaded material as described above, the nylon in the vulcanizable rubber of the resulting extrudate becomes fibrous.

Moreover, at the interface of the fibrous nylon, the nylon and the above-mentioned vulcanizable rubber are crosslinking agents.

Preferably air-cooled or water-cooled while continuously applying tension.

Cooling with an inert organic solvent such as chilled methanol, or a machine for taking it off from the guipure (also called a winding machine)
Cool to a temperature lower than the melting point of nylon by a method such as increasing the distance to the nylon, and then by a method known per se.
The film can be obtained by taking it to a take-up machine such as a bobbin or take-up roll, rolling it using a pair of rolling rolls, and uniaxially stretching it using a stretching roll. The temperature of the take-off machine when taking off the extrudate is preferably 0 to 100°C, and the draft ratio is 1.5 to 5.
0. Particularly preferred is 3.20. If the extrudate is taken without cooling, some of the fibrous nylon may become flat (in extreme cases, film-like) and good results may not be obtained. It is preferable that the diameter or thickness of the rolled product obtained by rolling with the above-mentioned rolling rolls is equal to or less than the diameter or thickness of the extrudate obtained by compression and rolling. Moreover, it is preferable to carry out the stretching using a stretching roll so that the stretching ratio is 1.1 to 1.0, and the temperature of the stretching roll is preferably 0 to 100°C.

In the method of the present invention, by stretching the extrudate as described above, the nylon in the vulcanizable rubber of the resulting reinforced rubber composition has fibers that are molecularly oriented and converted into a fibrous structure that has high strength. Made of fine nylon fibers. .

The reinforced rubber composition obtained by the method of the present invention contains 1 to 70 parts by weight of nylon per 1,000 parts by weight of vulcanizable rubber, and the nylon is in the form of fine fibers, and at the interface of the fibers. Nylon and vulcanizable rubber are graft-bonded via an alkylphenol formaldehyde resin as a crosslinking agent.It can be used alone or blended with other vulcanizable rubbers to achieve low elongation. By utilizing its excellent properties, the reinforced rubber composition of the present invention can be applied to various parts such as modulus and tensile strength at high elongation and at high elongation.
Tire external parts such as treads and sidewalls, industrial supplies such as belts and hoses.

It can be used for purposes such as footwear materials.

Next, Examples and Comparative Examples will be shown.

The physical properties of vulcanizates obtained using the (reinforced) rubber compositions obtained in Examples and Comparative Examples were measured in accordance with JI8 and 63'O1, except for fatigue tests and abrasion tests.

In the following description, all parts are by weight.

Example 1 35 parts of natural rubber (NR) with a viscosity of 1X10'bois was placed in a Grapenda-Plastograph, and after stripping for 30 seconds at 245°C and a rotor rotation speed of 50 r, p, m, alkylphenol formaldehyde resin ( damanol 52l
0.126 part of 6-Nylon (manufactured by Arakawa Chemical Industry Co., Ltd.) was added thereto, and after further mixing for 30 seconds, the mixture was kneaded with 6-nylon (4 minutes at 245°C). The obtained mixed wire was extruded into a string shape (diameter: 2 wm) at a temperature of 245°C using an extrusion model (HOake company lit) having a circular die with a nozzle inner diameter of 2 m and a length-to-inner diameter ratio (L/D) of 2. ), and the extrudate is placed in a funnel located vertically below the nozzle (cooling water at 0°C is supplied into the funnel by a pump and pipes, and the supplied cooling water flows through the funnel, The cooling water flows down into a cooling water storage vessel located vertically below the funnel, from where it is returned into the funnel by means of pumps and pipes).

Then, it passed through a guide roll and was wound onto a bobbin at a draft ratio of 7. After vacuum drying this rolled product at room temperature overnight to remove adhering water, the pJ between the rolls was 0.1 m.

Roll rolled with a pair of rolling rolls at a temperature of 60°C.

A reinforced rubber composition (sample 1) was obtained.

Fractionation and Graft Ratio Measurement 2 tons of the reinforced rubber composition obtained in Example 1 was mixed with 20% of benzene.
The above-mentioned procedure was repeated seven times on the precipitate portion of the zero-strengthened rubber composition, which was added at room temperature, and then the precipitate portion was dried to obtain nylon fibers.

This nylon fiber was dissolved in a mixed solvent of 7 enol and orthodichlorobenzene (l:3 (weight ratio)) and analyzed by IH nuclear magnetic resonance spectroscopy (NMR) (internal standard: tetramethylsilane). Natural rubber was determined from the NMR chart. The peaks of the methyl group and methylene group resulting from 6-nylon, the methylene group adjacent to the CO group resulting from 6-nylon, the methylene group adjacent to the NR group, and the other three methylene groups were calculated using the cut area method. The graft ratio was calculated by determining the molar ratio of Yojiro nylon and natural rubber.

Further, the shape of the nylon fibers was measured using a scanning microscope (manufactured by Hitachi Seisakusho, Ltd.) at a magnification of 10,000 times for about 200 fibers. The fibers were extremely thin fibers with a circular cross section. The results are shown in Table 1.

Evaluation Test The reinforced rubber composition obtained in Example 1 was vulcanized at 7.150°C for 40 minutes according to the formulation shown in Table 2.

The object was measured. The results are shown in Table 2.

Add 35 parts of natural rubber (NR) of the same type as that used in the test, and remove the bare rubber for 20 seconds at 245°C and 50 r, p, m, to give N-(3-methacryloyloxy-2-hydroxypropyl)-N. '-Phenyl-p-7 22-diamine [
Knock Luck G-1. Manufactured by Ouchi Shinko Chemical Industry Co., Ltd.) 0,
After further kneading for 10 seconds, 17.5 parts of 6-nylon of the same type as used in Example 1 was added.
After an additional 4.5 minutes of crosstalk, 0.78 g of the same type of alkylphenol formaldehyde resin used in Example 1 was used.
8 parts were added and kneaded for an additional 2 minutes at 245° C. and 100 r, p, m. A reinforced rubber composition (t-mixture 2) was obtained in the same manner as in Example 1 using the obtained mixed material. The results are summarized in Tables 1 and 2.

Comparative Example: 35 parts of natural rubber of the same type used in Example 1 was added to a Gravender Plastograph.

The mixture was added and kneaded for an additional 4 minutes. A reinforced rubber composition (sample 3) was obtained in the same manner as in Example 1 using the obtained kneaded product. This reinforced rubber composition contained a large number of nylon film-like materials. The results are summarized in Tables 1 and 2.

Example 3 40 parts of 6-nylon of the same type used in Example 1 was placed in a Gravender Plastograph.

Knead for 9 minutes at 245°C and 50 r, p, m to give 6-
After the nylon was completely melted, 15 parts of the same type of natural rubber as used in Example 1 was added, and after mixing for an additional 1.5 minutes, the same type of alkylphenol formaldehyde resin as used in Example 1 was added. 0275 parts were added and kneaded for an additional 3.5 minutes. The obtained mixed material (first-stage kneaded material) was taken out from the Brabender Plastograph and granulated. Next, 30.7 parts of the above natural rubber was placed in a Gravender Plastograph, and heated at 245°C for 50 r.
p, m for 30 seconds) was extruded into a string in the same manner as in Example 1, and the extrudate was passed through the same funnel as used in Example 1.

It was cooled only by tension under water flow without winding it onto a bobbin. The obtained string-like extrudate was rolled in the same manner as in Example 1 to obtain a zero-reinforced rubber composition (Sample 4). The results are summarized in Tables 1 and 2. Example 4 Alkylphenol formaldehyde resin was 0.275
2 parts to 0.825 parts, and the draft ratio when winding the extrudate onto a bobbin was changed from 7 to 7.7. Obtained.

The results are summarized in Tables 1 and 2.

Example 5 The amount of granulated contaminants was changed from 14.4 parts to 20.7 parts, and the amount of natural rubber (i-30.7 parts to 24.4 parts) was changed in the same manner as in Example 3. Reinforced rubber composition Example 6 N-(3-methacryloyloxy-2-hydroxypropyl) N/
-Phenyl-p-phenylenediamine was added to natural rubber by IPHR in the same manner as in Example 5 to obtain a reinforced rubber assembly (Sample 7). The results are summarized in Tables 1 and 2.

Example 7 40 parts of 6-nylon of the same type used in Example 1 was placed in a Gravender Plastograph.

Knead for 9 minutes at 245°C and 50 r, p, m to give 6-
After completely melting the nylon, 100 parts of natural rubber of the same kind used in Example 1, 5.5 parts of alkylphenol formaldehyde resin and N-(3-methacryloyloxy-2-hydroxypropyl)-N'- 1.0 parts of phenyl-p-phenylenediamine were mixed at 60 DEG C. using a 3-inch roll, taken out from a Brabender plastograph, and granulated. Then, the above natural rubber 30. 'i'21f4 and 307 parts of N-(3-methacryloyloxy-2-hydroxypropyl) N/-phenyl-p-phenylenediamine were added, and the mixture was heated at 245°C, 50 r, p,
m, for 1 minute, the granulated cross-wire material 14
．． 533 parts were added and kneaded for an additional 4.5 minutes. A reinforced rubber composition (sample 8) was obtained in the same manner as in Example 1 using the obtained mixed material (second stage mixed material). The results are summarized in Tables 1 and 2.

On the day of the example, the amount of granulated contaminants was reduced from 14.533 parts to 17°99.
1 part, natural rubber storage from 30.721 parts to 2'7
．． 322 parts, N-(3-methacryloyloxy-
The amount of 2-hydroxypropyl)-N'-phenyl-p-7 2-diamine was changed from 3 parts to 0.273 parts.The pond was the same as in Example 7. *Stream side 9 Granulated. 20°99 from 14.533 copies of the mixed child
The amount of N-(3-methacryloyloxy-2-hydroxypropyl), I-phenyl-p-7 2-diamine was changed from 0.307 parts to 0.244 parts, and the amount of natural rubber was changed to 0.244 parts. 3'0. ! 24.3'7 from 721 copies
The procedure was the same as on the day of the example except that the number was changed to 5 parts.

A reinforced rubber composition (sample 10) was obtained. The results are summarized in Tables 1 and 2.

Example 1O The amount of granulated contaminants was reduced from 14.533 parts to 23°61
4 parts, and the amount of natural rubber from 30.721 parts to 21 parts,
'i' was changed to 97 parts, and the amount of N-(3-methacryloyloxy-2-hydroxypropyl)-N'-phenyl-p-phenylenediamine was changed from 0.307 parts to 0.218 parts. Same as day.

A reinforced rubber composition (Sample 11) was obtained. The results are summarized in Tables 1 and 2.

Comparative Example 2 The amount of N-(3-methacryloyloxy-2-hydroxypropyl)ul-phenyl-p-phenylenediamine was changed from 0.307 parts to 0.218 parts. A reinforced rubber composition (Sample 12) was obtained in the same manner as in Example 8. This reinforced rubber composition contains nylon fibers.

Many nylon film-like substances were torn. The results are summarized in Tables 1 and 2.

Example 11 40 parts of 6-nylon of the same type used in Example 1 was placed in a Gravender Plastograph.

Knead for 9 minutes at 245°C and 50 r, p, m to give 6-
After completely melting the nylon, 100 parts of natural rubber of the same type used in Example 1, N-(3-methacryloyloxy-2-hydroxypropyl)-N'-7enyl p-7 Amine 1. Part O and alkylphenol formaldehyde resin were taken out from Gouplastograph and made into one granule.

Then, 24.375 parts of the above natural rubber and N-(3-methacryloyloxy-2-hydroxypropyl)-N/-7enylp were added to a gravender plastograph.
-7 Add 0.244 parts of enylene diamine, and add 24.5 parts of
After stripping for 30 seconds at 50°C and 50r, p, m, 20.784 parts of the granulated cross-contact material was added.

The mixture was kneaded for an additional 4.5 minutes. Using the obtained kneaded product, a 2-reinforced rubber composition i (sample 13) was obtained in the same manner as in Example 1. The results are summarized in Tables 1 and 2.

Example 12.13 Alkylphenol formaldehyde resin (Tamanol 5
21) was changed from 1.833 parts to 3.66'7 parts, and from 720.784 parts of 20B to 88 parts of 20B (Example 12), or the amount of alkylphenol formaldehyde resin was changed to 1. .833 Example 13) The pond was prepared in the same manner as in Example 11. 1 Reinforced rubber compound <-Sample 14. Sample 15) was obtained. The results are summarized in Tables 1 and 2.

Comparative Example 3 Natural comb of the same type as used in Example 1 (Sample 1)
The results of the evaluation test regarding 6) are shown in Table 2.

Tamanol 5311): Alkylphenol formaldehyde resin (Tamanol 521) o-12): N-(3-methacryloyloxy-2-hydroxypropyl)-N'-phenyl-p-phenylenediamine Fiber length 3): For example, ≧8 is the shortest The fiber length is 8μ'. Note that, except for the fiber of Example 3, the average fiber length could not be measured.

1-104): Average fiber length was 5μ.

(35) Note 1): Carbon Plaque (Product Name: Diamond Black■
(manufactured by Mitsubishi Chemical Industries, Ltd.) Note 2): N-phenyl-N'-infropyru-p-7 2-2-diamine Note 3): 2.2.4-) dimethyl-1,2-dihydro.

Quinoline polymer (product name: Tsurank 224, manufactured by Ohmukai Shinko Kagaku Kogyo Co., Ltd.) Note 4): Dipenzothiazyl disulfide Note 5): Mercaptobenzothiazole Note 6): Adhesion to natural rubber vulcanizates Note 7):
Total Comparative Example 4 of Nylon Fiber and Nylon Film-like Material 100 parts of natural rubber (NR) of the same type as used in Example 1 was placed in a Gravender Plastograph and heated at 80°C.
, 50 r, p, m, for 30 seconds! rear.

6- Add 5 parts of nylon thread (length 2.m) and
After bare removal for 0 seconds, 15 parts of silica, 3 parts of zinc white, 2.5 parts of resorcinol, and 2 parts of stearic acid were added according to the formulation of the H, R, H system, and mixed for 4 minutes. The resulting mixture was placed in a 3-inch roll.

Next, 2 parts of sulfur, 1.6 parts of hexamethylenetetramine and 1 part of dipenzothiacru disulfide were added, and 8 parts of sulfur were added.
Kneaded at 0°C, sheeted the kneaded product (sample 17), supplied to a mold, and vulcanized at 150°C for 40 minutes.
I focused on physical properties. The results are shown in Table 3.

Comparative Example 5 A mixed wire material (sample 18) was obtained in the same manner as in Comparative Example 4, in which no 6-nylon thread was blended, and the physical properties were measured.

The results are shown in Table 3.

Table 3 Note 1): Dibenzothiazyl dithylphide sample 1~
2. Samples 4-11. The stress-strain curves of the vulcanizates obtained from Samples 13 to 15 were smooth "inverted S-shaped". Against this.

In the stress-strain curves of the vulcanizates obtained from Sample 3 and Sample 17, wavy disturbances occurred from around 50% strain.

The reinforced rubber composition of Example 90 and the natural rubber (NR) of Comparative Example 3 were vulcanized at 150° C. for the vulcanization times shown in Table 4, and their physical properties were measured. Pico abrasion test of vulcanizate is A8TM
In accordance with D2228, the fatigue test was performed in air at 100°C using a constant load tensile fatigue testing device (manufactured by Toyo Seiki Co., Ltd., Model SaT).
50% modulus retention rate and tensile breaking strength retention rate after pulling 1X10' times at a constant load of 30Kf/- [(value after wave force test/value before fatigue test)X10
The number of times of tension (working life) until tensile breakage was determined at a constant load of 5° Kf/all. All results are shown in Table 4.

Table 4 A)2 Vulcanization time of the composition: 40 minutes Vulcanization time of the composition: 30 minutes The results shown in Table 4 show that the reinforced rubber composition of the present invention is extremely effective at high temperatures and under high stress. This shows that a vulcanizate with the following properties can be obtained.

Patent Applicant Ube Industries Co., Ltd. Procedural Amendments 1920/2015 Commissioner of the Japan Patent Office 1. Indication of Case Patent Application No. 176428/1982 2. Name of Invention Reinforced Rubber Composition and Process for Producing the Same 3. Amendments Relationship with the case of the person who filed the patent application Postal code of the patent applicant: 755 1-12-32 Nishihonmachi, Ube City, Yamaguchi Prefecture (020)
Ube Industries, Ltd. 4 Date of amendment order There is no amendment order.

5 Column 6 of the detailed description of the invention in the specification subject to amendment, Column 6 of the detailed description of the invention in the description of contents of the amendment (1) After the statement on page 2, line 11, "In the description of this specification""Graft bonding refers to some kind of bonding between nylon and vulcanizable rubber, although the bonding mode is unknown." has been added.

(2) The description of "Example 8" in the 4th line and 13th line of page 29 and the 2nd line of page 30 is corrected to "Example 7."

that's all

Claims (2)

[Claims] (1) Average diameter of 0.0 per 100 parts by weight of vulcanizable rubber
1 to 70 parts by weight of fine nylon fibers of 5 to 0.8μ are embedded, and at the interface of the fibers, the nylon and vulcanizable rubber form an initial condensate of resol type alkylphenol formaldehyde resin. A reinforced rubber composition that is grafted through. (2) Vulcanizable rubber, nylon with a molecular weight of less than 200,000, and 0 per 100 parts by weight of the total amount of rubber and nylon.
．． 2 to 2.5 parts by weight of an initial condensate of a resol-type alkylphenol formaldehyde resin are kneaded at a temperature above the melting point of nylon and below 270°C, and the resulting mixed material is mixed with the rubber in the mixed material and the nylon. The ratio of rubber is 10
If the 0 weight part of Shinylon is 1 to 70 weight parts, leave it as it is. When the ratio of rubber and nylon in the mixed material is more than 1 part by weight of nylon per 100 parts by weight of rubber, add additional vulcanizable rubber from 1 to 70 parts by weight of nylon per 100 parts by weight of total rubber. It is added to the mixed wire material so that it becomes, and then kneaded at a temperature above the melting point of nylon and below 270'C, and then extruded at a temperature above the melting point of nylon and below 270'C. A method for producing a reinforced rubber composition, which comprises stretching an extrudate at a temperature lower than the melting point of nylon.