JPH06228374A - Rubber article reinforced with organic fiber and its production - Google Patents

Abstract

PURPOSE:To improve the adhesive properties and heat resistance of a rubber for coating an org. fiber by compounding a natural or diene rubber with a specific compd. CONSTITUTION:A rubber compsn. obtd. by compounding 100 pts.wt. raw rubber comprising a natural rubber and/or a diene rubber with 0.5-5 pts.wt. 2,2,4- trimethyl-1,2-dihydroquinoline polymer contg. 1wt.% or lower prim. amine, 3wt.% or lower monomer, and 30wt.% or lower dimer is vulcanized in contact with an org. fiber, giving an org.-fiber-reinforced rubber article. The obtd. article exhibits a strong adhesion between the fiber and the rubber and an excellent heat resistance of the rubber.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic fiber reinforced rubber product used for automobile tires, conveyor belts, hoses and the like, and a method for producing the same.

[0002]

2. Description of the Related Art Automotive tires, conveyor belts, hoses, etc. are usually made of polyester, polyamide, etc. as a reinforcing material in order to improve and maintain the strength and durability of the products.
Organic fibers such as aramid are widely used. Above all, polyester fiber has excellent heat resistance and fatigue resistance,
In addition, it has good dimensional stability, has large lateral rigidity when used for tires, and has excellent steering stability, and is widely used in many rubber products including rubber for automobile tires.

However, a problem with polyester fibers is that they have poor adhesion to the coating rubber composition. Therefore, methods such as pretreatment of polyester fibers with an adhesive such as resorcin or a resorcin-based resin and a method of blending these adhesives during rubber processing have been adopted. However, although the use of these adhesives improves the initial adhesive strength between the rubber and the polyester fiber, the polyester cord itself tends to be significantly deteriorated by heat, and further, the heat resistance and the flex crack resistance of the rubber tend to be significantly deteriorated. It was

On the other hand, as a means for improving the heat resistance and flex crack resistance of rubber, a method of blending various amine-based deterioration inhibitors is known. Examples of amine-based deterioration inhibitors include N-isopropyl-N′-phenyl-p-diaminobenzene and N- (1,3-dimethylbutyl)-
N'-phenyl-p-diaminobenzene, N, N'-ditolyl-p-diaminobenzene, a condensate of acetone and diphenylamine and the like are known.

However, in these conventional deterioration preventive agents,
Not only is the anti-deterioration performance of rubber such as heat resistance not sufficient, but the addition of an anti-deterioration agent causes poor initial adhesion between rubber and organic fibers, and also causes a decrease in adhesion after heat aging. It had a problem that the performance was adversely affected. For this reason, the type and the amount of the deterioration inhibitor are greatly restricted, and it has not been possible to sufficiently satisfy both the adhesive performance between the rubber and the polyester cord and the heat resistance of the rubber.

[0006]

In view of the above circumstances, the present inventors have conducted various studies to solve the drawbacks of known deterioration inhibitors, and as a result, have determined that a given raw material rubber has a specific composition. By blending a specific amount of a 2,2,4-trimethyl-1,2-dihydroquinoline polymer, not only the adhesion between rubber and polyester fibers is improved, but also general organic fibers such as polyamide fibers and aramid fibers. The present invention has been completed by finding the fact that the adhesive property of is improved, and the heat resistance of rubber is remarkably improved.

[0007]

That is, the present invention provides a primary amine content of 1% by weight or less, a monomer content of 3% by weight or less, and 100 parts by weight of a raw rubber selected from natural rubber and diene rubber. 30% by weight of dimer component
A rubber composition comprising 0.5 to 5 parts by weight of the above 2,2,4-trimethyl-1,2-dihydroquinoline polymer, and an organic fiber present in contact with the rubber composition. A rubber product in which the rubber composition is vulcanized in a state where both are in contact with each other.

The present invention also provides a primary amine content of 1% by weight or less, a monomer content of 3% by weight or less, and a dimer content of 30% by weight based on 100 parts by weight of a raw rubber selected from natural rubber and diene rubber. % Or more 2,
The composition was blended with 0.5 to 5 parts by weight of a 2,4-trimethyl-1,2-dihydroquinoline polymer, and the resulting rubber composition was vulcanized under contact with organic fibers to be reinforced with organic fibers. A method for manufacturing a rubber product is provided.

By blending a specific amount of the 2,2,4-trimethyl-1,2-dihydroquinoline polymer having such a specific composition, a high adhesive property between the rubber and the organic fiber is maintained, and an excellent heat resistance is obtained. A rubber product is obtained.

The first feature of the present invention is that the primary amine content in the deterioration preventing agent is 1 from the viewpoint that the deterioration preventing agent does not adversely affect the adhesive performance between the rubber and the organic fiber.
It is in the point that the weight% is less than or equal to. That is, the primary amine component in the deterioration preventive agent reduces the initial adhesive force between the rubber and the organic fiber and, as a major problem, the adhesive force after thermal history is greatly reduced. It has been found that the rubber surface easily blooms in unvulcanized rubber, causing a decrease in the adhesion between the rubber and the organic fibers. Therefore, in the present invention, it is necessary to suppress the primary amine component in the deterioration inhibitor to 1% by weight or less.

The second feature of the present invention is, from the viewpoint of increasing the heat resistance of rubber, 30 weight parts of 2,2,4-trimethyl-1,2-dihydroquinoline dimer, which exhibits excellent deterioration preventing performance over a long period of time. %, And a 2,2,4-trimethyl-1,2-dihydroquinoline polymer containing 3% by weight or less of a low molecular weight and easily volatilized monomer is used as a deterioration inhibitor. That is,
When a rubber is mixed with a deterioration inhibitor, it must have high dispersibility in the rubber, and considering the long-term sustainability of heat resistance during use of rubber products, it deteriorates even under heat aging conditions. It is necessary that the inhibitor is difficult to evaporate from the rubber. Therefore, the deterioration inhibitor having a low molecular weight is not preferable because it easily volatilizes. From such a viewpoint, in the present invention, a predetermined amount of a 2,2,4-trimethyl-1,2-dihydroquinoline polymer having a low monomer content and a high dimer content is blended as a deterioration inhibitor. The lower the monomer content is, the more preferable. For example, it is more preferably 1% by weight or less. The higher the dimer content is, the more preferable.

The 2,2,4-trimethyl-1,2-dihydroquinoline polymer is usually produced by reacting aniline with acetone, diacetone alcohol or mesityl oxide in the presence of an acidic catalyst under heating. Has been done. In general, the structure represented by the following formula (I) is mainly used.

[0013]

[Chemical 1]

In the formula, n represents an integer of 1 or more.

The term "monomer" used in the present invention means the above formula (I).
Is a compound of n = 1, and a dimer is a compound of n = 2 in the above formula (I).
As it increases to 3, 4, ..., It becomes a trimer, a tetramer, .... The primary amine is produced mainly due to aniline as a raw material and can have various structures, and a typical example thereof is one having a structure represented by the following formula.

[0016]

[Chemical 2]

In the formula, m represents an integer of 1 or more.

Commercially available 2,2,4-trimethyl-1,2-
Since the dihydroquinoline polymer has various grades depending on the manufacturer and the brand name, the one used in the present invention must be carefully selected. In the present invention, as described above, 2,2,4-trimethyl-1,2-having a low primary amine content and a high monomer content and a high dimer content.
It is necessary to use a dihydroquinoline polymer, and one satisfying the conditions specified in the present invention may be selected, but such a polymer is preferably produced, for example, as follows.

That is, first, in the presence of an acidic catalyst such as hydrochloric acid, hydrobromic acid, hydrofluoric acid, iodine, organic sulfonic acid, boron trifluoride, etc., or a mixture of two or more thereof, aniline. 2,2,4-trimethyl-1,2-dihydroquinoline monomer is produced by reacting with acetone, diacetone alcohol or mesityl oxide under heating and distilling and purifying the resulting reaction product. . The higher the monomer purity by distillation, the more preferable it is. Generally, it is preferable that the monomer purity is 85% by weight or more, and further it is more preferable that the monomer purity is 90% by weight or more.

The 2,2,4-trimethyl-1,2-dihydroquinoline monomer thus purified is further reacted in the presence of hydrochloric acid and the above-mentioned acidic catalyst in a heated state to obtain a polymer mixture. , Unreacted monomer is removed from the polymer mixture. In reaction,
For example, when a hydrochloric acid catalyst is used, the hydrochloric acid concentration is 15 to 25
It is preferable that the content of the hydrochloric acid is in the range of about wt%, and hydrochloric acid is added to the total amount of the starting 2,2,4-trimethyl-1,2-dihydroquinoline monomer and other amines contained as impurities. It is preferably used in the range of 0.2 to 0.5 mol times. The reaction temperature is preferably about 80 to 100 ° C. By adopting such mild conditions, a polymer having a high dimer content can be obtained. The unreacted monomer is usually removed by removing the low boiling point fraction by distillation.

In the present invention, a 2,2,4-trimethyl-1,2-dihydroquinoline polymer having a specific composition as described above is used, and particularly dimers, trimers and tetramers, that is, the above-mentioned formula (I). Where n is 2, 3
Polymers containing 4 and 4 are preferably contained in a total amount of 75% by weight or more, and further preferably contained in a total of 80% by weight or more of such dimers, trimers and tetramers.

According to the present invention, the 2,2,4-trimethyl-1,2-dihydroquinoline polymer having a small amount of primary amine and monomer and a large amount of dimer is used per 100 parts by weight of the raw rubber. It is compounded in the range of 0.5 to 5 parts by weight. If the amount is less than 0.5 parts by weight, the heat resistance of the rubber is insufficient, and if it is more than 5 parts by weight, the adhesive performance is deteriorated, which is not preferable.

The raw rubber used in the present invention is a natural rubber or a diene rubber, and each can be used alone or as a blend of two or more kinds. Examples of the diene rubber include styrene-butadiene copolymer rubber, butadiene rubber, isoprene rubber, chloroprene rubber, ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber and the like.

2,2,4-trimethyl-1, having a specific composition,
In order to reinforce the rubber composition containing the 2-dihydroquinoline polymer, an organic fiber is used as a reinforcing material. The organic fibers can be those usually used for automobile tires, conveyor belts, hoses, and the like, and preferable examples include polyester, polyamide, aramid, and the like. It is valid. The organic fibers used are preferably pretreated with a resorcin-based adhesive. In addition to resorcin itself, resorcin-based adhesives include resorcin-formaldehyde resin, resorcin-alkylphenol-formaldehyde resin, resorcin-p-chlorophenol-formaldehyde resin, resorcin-resin.
It may be a resin mainly composed of resorcin, such as a mixture of formaldehyde resin and alkylphenol / formaldehyde resin, or a mixture of resorcin / formaldehyde resin and resorcin sulfide resin.

Further, in the present invention, various fillers usually used in the rubber industry, such as carbon black,
Inorganic fillers such as silica, clay, calcium carbonate, glass fibers and the like can be added to the rubber as required. Of these, carbon black is preferably used. The carbon black to be blended is of the type normally used in the rubber industry, such as SAF, ISA.
It can be F, HAF, FEF, SRF, GPF, MT and the like. The compounding amount is not particularly limited, but from the viewpoint of the reinforcing property and the strength of rubber, the range of 20 to 150 parts by weight is preferable per 100 parts by weight of rubber. Further, in addition to carbon black or in addition to carbon black, it is preferable to mix hydrous silica for the purpose of improving adhesiveness, and the compounding amount thereof is 5 to 80 per 100 parts by weight of rubber.
A range of parts by weight is preferred.

Since the rubber composition used in the present invention is vulcanized under contact with organic fibers, a vulcanizing agent, preferably sulfur, is usually added. Sulfur as a vulcanizing agent may be insoluble sulfur or various soluble sulfur usually used in the rubber industry, and its compounding amount is usually 0.5 to 8 parts by weight per 100 parts by weight of the raw rubber. It is a range of degrees.

When the organic fibers are treated with a resorcin-based adhesive, the rubber composition can have a proper adhesiveness even if the rubber composition is not blended with the adhesive, but the organic fibers are a resorcin-based adhesive. When it is not treated or when it is desired to secure a more sufficient adhesiveness, it is preferable to add an adhesive to the rubber composition. The adhesive used here is also a resorcin-based one, and in addition to resorcin itself, a resorcin-based resin such as resorcin-formaldehyde resin,
It may be a resorcin / alkylphenol / formaldehyde resin, a mixture of a resorcin / formaldehyde resin and an alkylphenol / formaldehyde resin, and the like. When a resorcin-based adhesive is used, it is usually added in an amount of 8 parts by weight or less, preferably 0.5 to 5 parts by weight, per 100 parts by weight of the raw rubber.

In order to further secure the adhesive strength, it is also effective to mix a formaldehyde generator, that is, a compound which generates formaldehyde by heating, together with the resorcin-based adhesive. The formaldehyde generator here may be one that has been conventionally used with resorcin or resorcin-based resin which is a formaldehyde acceptor, and for example, a condensate of melamine and formaldehyde, that is, dimethylolmelamine, trimethylolmelamine. , Tetramethylol melamine, hexamethylol melamine, condensates of melamine with formaldehyde and methanol, such as hexakis (methoxymethyl) melamine, pentakis (methoxymethyl) methylolmelamine, and hexamethylenetetramine. To be When a formaldehyde generator is used, it is usually added in an amount of 8 parts by weight or less, preferably 0.5 to 5 parts by weight, per 100 parts by weight of the raw material rubber.

Further, in the present invention, various other rubber chemicals usually used in the rubber industry, for example, other deterioration inhibitors, crosslinking agents, vulcanization accelerators, retarders, peptizers, softening agents, petroleum resins. It goes without saying that a lubricant, a plasticizer, a tackifier and the like may be used in combination as necessary.

The rubber composition thus blended is vulcanized in contact with the organic fibers as described above. There is no particular limitation on the vulcanization conditions, and it may be carried out under the conditions generally adopted conventionally. Appropriate vulcanization conditions vary considerably depending on the rubber composition used and the intended product. Normally, the temperature is about 100 to 200 ° C. and the time is about 1 minute to 2 hours. The condition is selected. That is, the rubber composition is formed into a rubber product such as a tire through a molding and vulcanization step in a state of being in contact with the organic fiber by a commonly used method. The rubber product thus reinforced with the organic fiber exhibits excellent adhesiveness and heat resistance when applied to various members of automobile tires and other rubber products.

[0031]

EXAMPLES Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. In the following examples,% and parts representing addition amounts or contents are respectively% by weight and parts by weight, unless otherwise specified.

Reference Example 1

In a 500 ml four-necked flask equipped with an acetone introduction device, a thermometer, a stirrer and a condenser, 121 g (1.3 mol) of aniline, 12.4 g of p-toluenesulfonic acid monohydrate (as p-toluenesulfonic acid) 0.065
Mol) was charged and heated. While maintaining the internal temperature at 95 to 100 ° C, 755 g of acetone was introduced in 8 hours. The reaction product was diluted with 100 ml of toluene, neutralized with 2.6 g of caustic soda and 50 ml of water while maintaining the temperature at 85 to 95 ° C., allowed to stand and then separated to remove an aqueous layer. The oil layer is washed several times with 100 ml of water, and when the solution becomes neutral, the toluene layer is separated, toluene is removed by distillation, and further rectification is carried out under reduced pressure, so that unreacted at a boiling point of 100 ° C / 10 mmHg. 20 g of the aniline fraction was obtained, and 142.4 g of the monomer fraction was obtained between 100 ° C./10 mmHg and 90 ° C./2 mmHg.

When this monomer fraction was analyzed by gas chromatography, its composition ratio was as follows.

2,2,4-Trimethyl-1,2-dihydroquinoline 97.0% Aniline 0.2% Low-boiling impurities 2.8%

Subsequently, in a 500 ml four-necked flask equipped with a thermometer, a stirrer and a condenser, 100 g of the monomer fraction obtained above, 20.9 g of concentrated hydrochloric acid and 20 parts of water were added.
ml was charged and the temperature was raised to 90 ° C. Further 90-100
The mixture was kept warm at 6 ° C for 6 hours. Then, the reaction product was diluted with 100 ml of toluene, and while maintaining the temperature at 85 to 90 ° C., 19.8 g of a 45% aqueous sodium hydroxide solution was added to neutralize the mixture, and the mixture was allowed to stand to perform liquid separation to remove the aqueous layer. The toluene layer was washed several times with 100 ml of water.

After separating the toluene layer and removing toluene by distillation, the inner temperature was 200 ° C. and the degree of vacuum was 2 mm.
Distillation was carried out under the conditions up to Hg to distill off 21.8 g of a low-boiling component, thereby obtaining 73.2 g of a 2,2,4-trimethyl-1,2-dihydroquinoline polymer as a residue. This polymer is designated as deterioration inhibitor A. When the components of the deterioration inhibitor A were quantified, it was as shown in Table 1.

The amount of the monomer, dimer, trimer and tetramer was determined by gas chromatography using dibutyl phthalate as an internal standard under the following conditions.

Column: Chromosolve WAW as a carrier was coated with 3% silicon OV-1 in a liquid layer and packed with 3
mmφ × 0.5m separation tube (manufactured by GL Sciences Inc.) Injection temperature: 350 ° C Column temperature: Temperature rising rate from 100 ° C to 350 ° C 10 ° C
Temperature rises per minute Carrier gas: Nitrogen (50 ml / min) Detector: Flame ionization detector

For the primary amine content, the polymer is dissolved in chloroform, hydrochloric acid and p-dimethylaminobenzaldehyde are further added to prepare a sample solution, and the absorbance of this sample solution is measured by a spectrophotometer (measurement wavelength: 440 nm). The blank test value was subtracted from the obtained absorbance, and the value was obtained from the calibration curve.

Reference Example 2

500 equipped with an acetone introducer, a thermometer, a stirrer and a water separator connected to the reflux condenser at the top
An aniline 93.1 g (1 mol), concentrated hydrochloric acid 27 g (0.27 mol) and n-hexane 3 g were charged into a ml four-necked flask and heated. N-Hexane was previously put in the water separator. When the internal temperature reached 85 ° C, the introduction of acetone was started, and 174 g was maintained while maintaining the internal temperature at 70 to 90 ° C.
(3 mol) of acetone was introduced over 8 hours. The water generated by the condensation reaction is azeotropically distilled with n-hexane to be removed from the flask, and n-hexane and water are vertically separated in the water separator, so the liquid is separated and continuously removed from the system. . After the completion of the introduction of acetone, while maintaining the temperature at 60 to 80 ° C., it was neutralized with 15 g of 28% aqueous sodium hydroxide solution and 100 ml of water, diluted with 100 ml of toluene, and then filtered using a G3 glass filter precoated with radiolite to obtain a catalyst residue. Was removed. The filtrate was allowed to stand and then separated to remove the aqueous layer.

The oil layer was washed several times with 100 ml of water, and when the solution became neutral, the oil layer was separated, low boiling components such as n-hexane, toluene and unreacted acetone were removed by distillation, and further under reduced pressure. By rectifying, boiling point 100 ℃ / 10
23 g of unreacted aniline fraction was obtained up to mmHg, and it was 2, 2, 100 ° C / 10 mmHg to 90 ° C / 2 mmHg.
4-Trimethyl-1,2-dihydroquinoline monomer fraction 57.5 g (purity 96.8 by gas chromatography)
%) Was removed and 82.6 g of 2,2,4-trimethyl-
A 1,2-dihydroquinoline polymer was obtained. This polymer is referred to as deterioration inhibitor X. When the deterioration inhibitor X was quantified in the same manner as in Reference Example 1, the components were as shown in Table 1.

Reference Example 3

After obtaining a monomer fraction in the same manner as in Reference Example 1, 100 g of the monomer fraction was added to 60.8 g of concentrated hydrochloric acid.
(0.6 mol) and 30 ml water, except
Polymerization reaction and post-treatment were performed in the same manner as in Reference Example 1, 1
By distilling off 4.5 g of the low boiling point, 8
0.5 g of 2,2,4-trimethyl-1,2-dihydroquinoline polymer was obtained. This polymer is referred to as a deterioration inhibitor Y. When the deterioration inhibitor Y was quantified in the same manner as in Reference Example 1, the components were as shown in Table 1.

Reference Example 4

The procedure of Reference Example 1 was repeated, but in the rectification after the condensation of the monomer, the boiling point of 100 ° C./20 mmHg was taken as the unreacted aniline fraction, and 14 g was obtained.
Monomer fraction 14 between 20mmHg and 90 ℃ / 2mmHg
8.6 g was obtained (monomer purity 84.2%, aniline content 4.8%). Then, a polymerization reaction and a post-treatment were carried out in the same manner as in Reference Example 1 to obtain 71.6 g of a 2,2,4-trimethyl-1,2-dihydroquinoline polymer as a residue. This polymer is referred to as a deterioration inhibitor Z. The deterioration preventive agent Z was used in Reference Example 1
When quantified in the same manner as above, the components were as shown in Table 1.

[0048]

[Table 1]

In addition to these deterioration inhibitors A, X, Y and Z, in the following examples, N- (1,
3-Dimethylbutyl) -N'-phenyl-p-diaminobenzene (designated V) was also used.

Example 1

[0051]

<Table 2> <Composition> Natural rubber (RSS # 1) 70 parts Butadiene rubber (BR-01 made by Japan Synthetic Rubber) 15 parts Styrene-butadiene copolymer rubber (# 1500) 15 parts HAF carbon black (N330) 45 Parts Stearic acid 2 parts Aroma oil 12 parts Platinum flower 3 parts Deterioration inhibitor Table 3 Resorcin-formaldehyde resin 1.5 parts Vulcanization accelerator 1.1 parts (N-cyclohexyl-2-benzothiazole sulfenamide) a Oh 3 parts Methoxylated methylol melamine resin 4 parts (Sumitomo Chemical Co., Sumikanol 507)

6 made by Toyo Seiki as a Banbury mixer
Oil bath temperature 150 using 00 ml Labo Plastomill
Based on the above-mentioned compounding recipe, at 3 ° C, three kinds of blend rubbers were prepared.
Carbon black, stearic acid, aroma oil, zinc white,
The resorcin-formaldehyde resin and the deterioration inhibitor were added and the mixture was kneaded at a mixer rotation speed of 50 rpm for 15 minutes. The rubber temperature at this time was 160-170 degreeC.
Next, this compound was transferred to an open mill, and at a temperature of 50 to 70 ° C., the vulcanization accelerator, sulfur and methoxylated methylol melamine resin shown in the above compounding formulation were added and kneaded.

A part of the sample after kneading was immediately vulcanized at 145 ° C. for 40 minutes for a heat aging test to prepare a test piece. Furthermore, for adhesion test, immediately after the preparation of the unvulcanized rubber compound, the polyester fiber was embedded, and immediately after vulcanization press, 1
A test piece was prepared by vulcanizing at 45 ° C for 40 minutes. The remaining samples were left at room temperature for 3 days, embedded with polyester fibers, and then vulcanized under the same conditions as above to prepare test pieces for adhesion test. The polyester fiber used in this example is 1100d
/ 3, which was subjected to latex treatment with resorcin / p-chlorophenol / formaldehyde resin.

Each test piece was tested for rubber physical properties by the following method, and the results are shown in Table 3 together with the variable values of the compounding recipe.

Initial Adhesion Property As described above, 3 pieces of the test piece for adhesion test and the unvulcanized rubber compound which were vulcanized and bonded immediately after preparation of the unvulcanized rubber compound were prepared.
Using a test piece for adhesion test that was vulcanized and adhered after being left for a day,
Adhesion was evaluated by the H test method described in TM D 2138. The test result was displayed as an average value of 12 test pieces.

Adhesiveness after heat aging A test piece for adhesion test, which was vulcanized and bonded immediately after preparation of an unvulcanized rubber compound, was heat aged at 100 ° C. for 72 hours, and then ASTM
The adhesive strength was measured by the H test method described in D 2138. The test result was displayed as an average value of 12 test pieces.

Adhesiveness after aging under moist heat A test piece for adhesion test, which was vulcanized and adhered immediately after the preparation of the unvulcanized rubber compound, was conducted at a temperature of 50 ° C. and a relative humidity of 80%.
After aging by heat and humidity for a day, the adhesive strength was measured by the H test method described in ASTM D 2138. The test result was displayed as an average value of 12 test pieces.

Heat resistance According to JIS K 6301, 10 dumbbell-shaped No. 3 test pieces were used.
It was heat-aged at 0 ° C. for 72 hours, the tensile strength before and after the aging was measured, and the tensile strength retention rate was calculated.

[0059]

[Table 3]

Example 2

[0061]

<Table 4> <Composition> Natural rubber (RSS # 1) 100 parts HAF carbon black (N330) 45 parts Stearic acid 3 parts Hydrous silica (Nipsil VN3 manufactured by Nippon Silica Industry Co., Ltd.) 10 parts Lead zinc 2 parts Anti-deterioration agent table 5. Resorcin / alkylphenol / formaldehyde resin 2 parts (Sumitomo Chemical Co., Sumikanol 620) Vulcanization accelerator 1 part (Nt-butyl-2-benzothiazolesulfenamide) io 4 parts Methoxylated methylol melamine resin 4 copies (Sumitomo Chemical Co., Sumikanol 507)

6 made by Toyo Seiki as a Banbury mixer
Oil bath temperature 150 using 00 ml Labo Plastomill
At ℃, add carbon black, stearic acid, hydrous silica, zinc white, resorcin / alkylphenol / formaldehyde resin and deterioration inhibitor to natural rubber based on the above compounding recipe, and mix at 1 rpm at a mixer rotation speed of 50 rpm.
Kneading for 5 minutes. The rubber temperature at this time is 160 to 170.
It was ℃. The formulation is then transferred to an open mill and 5
At a temperature of 0 to 70 ° C., the vulcanization accelerator, sulfur and methoxylated methylol melamine resin shown in the above formulation were added and kneaded.

A part of the sample after kneading was immediately vulcanized at 145 ° C. for 40 minutes for a heat aging test to prepare a test piece. Furthermore, for adhesion testing, polyamide fibers were embedded immediately after preparation of the unvulcanized rubber compound, and immediately after vulcanization press 14
A test piece was prepared by vulcanizing at 5 ° C for 40 minutes. The remaining samples were left at room temperature for 3 days, embedded with polyamide fibers, and then vulcanized under the same conditions as above to prepare test pieces for adhesion test. The polyamide fiber used in this example is 1260d / 3
Which was subjected to latex treatment with resorcin-formaldehyde resin.

Each of the test pieces thus obtained was tested for rubber physical properties in the same manner as in Example 1, and the test results are shown in Table 5 together with the variable values of the compounding recipe.

[0065]

[Table 5]

[0066]

INDUSTRIAL APPLICABILITY The rubber product reinforced with the organic fiber according to the present invention has an improved adhesive property between the rubber and the organic fiber, and particularly shows a high adhesive force even after heat aging or wet heat aging, and unvulcanized rubber. Even when it is vulcanized and adhered to the organic fiber after being left as it is for a long period of time, good adhesiveness is maintained, and various properties such as heat resistance of rubber are excellent.

Claims (5)

[Claims] 1. A primary amine content of 1% by weight or less, a monomer content of 3% by weight or less, and a dimer content of 30% by weight or more based on 100 parts by weight of a raw rubber selected from natural rubber and diene rubber. 2,2,4-trimethyl-
A rubber composition comprising 0.5 to 5 parts by weight of a 1,2-dihydroquinoline polymer, and an organic fiber present in contact with the rubber composition, the rubber composition being in contact with both. A rubber product reinforced with organic fibers characterized by being vulcanized. 2. The rubber product according to claim 1, wherein the 2,2,4-trimethyl-1,2-dihydroquinoline polymer contains a total of 75% by weight or more of dimer, trimer and tetramer. 3. The rubber product according to claim 1, wherein the organic fiber is treated with a resorcin-based adhesive. 4. The rubber product according to claim 1, wherein the organic fiber is selected from polyester, polyamide and aramid. 5. A primary amine content of 1% by weight or less, a monomer content of 3% by weight or less, and a dimer content of 30% by weight or more based on 100 parts by weight of a raw rubber selected from natural rubber and diene rubber. An organic compound characterized by including 0.5 to 5 parts by weight of a certain 2,2,4-trimethyl-1,2-dihydroquinoline polymer and vulcanizing the resulting rubber composition in contact with organic fibers. A method of manufacturing a fiber reinforced rubber product.