JPH08157646A - Adhesive rubber composition and heat-resistant hose - Google Patents

Abstract

PURPOSE: To obtain a high-modulus adhesive rubber composition excellent in heat resistance, oil resistance, and the adhesivity to reinforcing layer steel wires, and to obtain a heat-resistant hose using this composition. CONSTITUTION: This adhesive rubber composition excellent in adhesivity to brass is obtained by incorporating 100 pts.wt. of a copolymer rubber made up of 10-45wt.% of unsaturated nitrile-derived unit, 0-20wt.% of conjugated diene-derived unit and 90-35wt.% of other unit formed by hydrogenating the unit derived from ethylenic unsaturated monomer and/or conjugated diene except the unsaturated nitrile, with 0.1-15 pts.wt. of an organic sulfur-contg. compound, 0.1-15 pts.wt. of maleic anhydride-modified polybutadiene, 1-30 pts.wt. of silica, and 1-15 pts.wt. of an organic peroxide curing agent. The heat-resistant hose is obtained by using this rubber composition.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive rubber composition having excellent adhesion to brass in the production of rubber / metal composite products used in fields requiring heat resistance and oil resistance. Further, the present invention relates to a heat resistant hose having an adhesive rubber composition having excellent adhesiveness with brass used at least in an inner tube and having a pressure resistant reinforcing steel wire layer thereon.

[0002]

2. Description of the Related Art In recent years, tires, belts, moldings, rolls,
Many rubber products such as hoses have been used for a long time with oil heated under high temperature and pressure, and the deterioration of rubber products in such a state is always a serious problem. If the deterioration of rubber products is severe, it takes a lot of time and labor for maintenance and replacement, and sometimes it causes a serious accident.
Excellent oil resistance and at such high temperature (120 ℃ ~ 150
(° C) Polymers that can withstand continuous use in an environment include acrylonitrile-butadiene copolymer rubber (NBR), acrylic rubber (ACM), ethylene-acrylic rubber (AEM); ethylene-acrylic-vinyl acetate copolymer rubber ( ER), chlorosulfonated polyethylene rubber (CSM), chlorinated polyethylene rubber (CM), acrylonitrile-butadiene copolymer rubber (NBR), and other rubbers with hydrogenated conjugated diene moieties (so-called hydrogenated NBR). Has been.

On the other hand, in order to increase the heat resistance of a rubber product, an organic peroxide vulcanized rubber composition using an organic peroxide is used as compared with a sulfur vulcanized rubber composition using sulfur during vulcanization. It is known that the heat resistance is better. However, since the organic peroxide vulcanized rubber composition generally does not contain sulfur, it does not adhere well to brass products such as brass-plated wires (hereinafter referred to as brass wires). When a brass wire is used as a reinforcing material for a rubber product, there is a drawback that the product is destroyed due to interfacial peeling between the brass wire and the like.

For example, a composition comprising hydrogenated NBR having a high hydrogenation rate has excellent heat resistance, but must be vulcanized with an organic peroxide. However, when vulcanized with an organic peroxide, the composition does not adhere to a metal such as brass. Therefore, JP-A-62-104864 describes that an organic peroxide and an organic sulfur-containing vulcanizing agent are added to impart adhesiveness between the composition and the metal. However, even in that case, in a high-pressure hose having a pressure-resistant reinforcing steel wire plated with brass as a reinforcing layer, particularly in a single-tube high-pressure hose, the adhesion between the rubber composition and brass is insufficient, and during use of the hose, There is peeling of the rubber composition and brass,
Due to the low modulus, it may not be possible to obtain sufficient strength as a high-pressure hose. Further, a hose in which an organic peroxide vulcanized rubber composition layer and a sulfur vulcanized rubber composition layer are laminated is disclosed, but the organic peroxide vulcanized rubber composition is a normal sulfur vulcanized rubber composition. Because of the interference of sulfur / organic peroxide reaction with each other, the physical properties of the vulcanization may not be fully exhibited, or the adhesion between the organic peroxide vulcanized rubber and the sulfur vulcanized rubber may be insufficient. There is a case.

[0005]

As described above, there is a demand for a rubber composition which uses hydrogenated NBR having a high hydrogenation rate and is excellent in adhesiveness to brass and has a high modulus (high elastic modulus). However, in the prior art no such composition is known.

[0006]

On the other hand, in order to solve the above-mentioned problems, the present inventors have developed a high hydrogenation rate N
By adding an appropriate amount of maleic anhydride-modified polybutadiene and silica to BR in addition to an organic peroxide and an organic sulfur-containing vulcanizing agent, heat resistance, which cannot be obtained with a conventional rubber composition containing hydrogenated NBR, is obtained. It was found that a rubber composition having a high degree of adhesiveness with brass and a high elastic modulus while having excellent properties and oil resistance can be obtained, and arrived at the present invention.

That is, according to the present invention, the polymer chain contains 10 to 45% by weight of a unit portion derived from an unsaturated nitrile and 0 to 20% by weight of a unit portion derived from a conjugated diene. Unit part from saturated monomer and /
Alternatively, 0.1 to 15 parts by weight of an organic sulfur-containing compound, and 0.1 to 15 parts by weight of a maleic anhydride-modified polybutadiene, based on 100 parts by weight of a copolymer rubber containing 90 to 35% by weight of a hydrogenated unit part derived from a conjugated diene. 1 to 15 parts by weight of silica, 1 to 30 parts by weight of silica, and 1 to 15 parts by weight of an organic peroxide vulcanizing agent are provided to provide an adhesive rubber composition having excellent adhesion to brass.

The organic sulfur-containing compound is represented by the general formula: 6-R-2,4-dimercapto-1,3,5-triazine (wherein R is a mercapto group, an alkoxy group, a mono- or di-cycloalkylamino group, a mono- Alternatively, it is preferably a compound selected from the group consisting of a di-arylamino group, a mono- or di-cycloalkylamino group and an N-alkyl-N′-arylamino group.).

In a hose having at least an inner tube and a brass-plated pressure-resistant steel wire layer, the inner tube is
10-45 unit parts from unsaturated nitriles in the polymer chain
0% to 20% by weight and the unit portion from the conjugated diene
To 100 parts by weight of a copolymer rubber containing 90 to 35% by weight of a unit part obtained by hydrogenating a unit part from an ethylenically unsaturated monomer other than the unsaturated nitrile and / or a unit part from a conjugated diene. In contrast, 0.1 to 15 parts by weight of an organic sulfur-containing compound, 0.1 to 15 parts by weight of maleic anhydride-modified polybutadiene, 1 to 30 parts by weight of silica, and 1 to 15 parts by weight of an organic peroxide vulcanizing agent are blended. By using an adhesive rubber composition having excellent adhesiveness with brass, a brass-plated pressure-resistant steel wire layer is applied thereon, and vulcanized to integrate the inner pipe and pressure-resistant steel wire layer. Provided is a heat-resistant hose in which and are firmly bonded.

The organic sulfur-containing compound is represented by the general formula: 6-R-2,4-dimercapto-1,3,5-triazine (wherein R is a mercapto group, an alkoxy group, a mono- or di-cycloalkylamino group, a mono- Or a group selected from the group consisting of a di-arylamino group, a mono- or di-cycloalkylamino group, and an N-alkyl-N′-arylamino group.) A heat resistant hose which is a compound represented by the above.

The present invention will be described in detail below. The adhesive rubber composition of the present invention comprises (1) an unsaturated nitrile having a unit portion of 10 to 45% by weight and a conjugated diene having a unit portion of 0 to 20% by weight in the polymer chain. Other than ethylenically unsaturated monomers other than and / or hydrogenated unit parts from conjugated dienes 90-35
(2) 0.1 to 15 parts by weight of an organic sulfur-containing compound, and (3) maleic anhydride-modified polybutadiene 0.1 to 0.1 parts by weight with respect to 100 parts by weight of a copolymer rubber containing 100% by weight.
15 parts by weight, (4) 1 to 30 parts by weight of silica, and (5) 1 to 15 parts by weight of organic peroxide vulcanizing agent are blended.

The copolymer rubber (1) used in the present invention is the following copolymer rubber called hydrogenated NBR. That is, in the polymer chain, (a) 10 to 45% by weight of the unit portion from the unsaturated nitrile, (b) 0 to 20% by weight of the unit portion from the conjugated diene, and (c) ethylene other than the unsaturated nitrile. 90-35 hydrogenated unit part from a polyunsaturated monomer and / or conjugated diene
% By weight. Hydrogenated NBR is a saturated methylene chain (CC) represented by the following formula, a nitrile group moiety (VCN), a carbon-
It is a copolymer rubber composed of carbon double bond moieties (C = C).

[0013]

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Here noted by the nitrile group moiety (VCN)

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Is a unit part from unsaturated nitrile, and is 10 to 45% by weight, in particular 25 to 40% by weight.
It is preferred that If it is less than 10% by weight, oil resistance is poor, and if it exceeds 45% by weight, cold resistance becomes poor.

Notated by a saturated methylene chain (CC) (--CH
₂ -CH ₂ -) x is a unit part and unit part of the mixture was hydrogenated thereof from the unit portion or a conjugated diene from ethylenically unsaturated monomer other than unsaturated nitrile, 90 wt% ~ 35% by weight. Here, as the ethylenically unsaturated monomer other than unsaturated nitrile, unsaturated carboxylic acids such as vinyl chloride, acrylic acid, methacrylic acid, itaconic acid, maleic acid and salts thereof; methyl acrylate, 2-ethylhexyl acrylate Such an alkyl ester of galbonic acid; an alkoxyalkyl ester of an unsaturated carboxylic acid such as methoxy acrylate, ethoxyethyl acrylate, methoxyethoxyethyl acrylate; acrylamide, methacrylamide; N-methyl (meth) acrylamide, N,
N'-dimethyl (meth) acrylamide, N-methylol (meth) acrylamide, sodium taurine (meth)
Examples thereof include N-substituted (meth) acrylamide such as acrylate.

In particular, the hydrogenation rate is 95% or more, particularly 98-
100% is preferable in terms of heat resistance. When the saturated methylene chain (CC) is more than 90% by weight, the unit portion (VCN) from the unsaturated nitrile is relatively reduced, and the oil resistance is poor and it cannot be used. Also, the saturated methylene chain (CC) has 3
If it is less than 5% by weight and the unit portion (VCN) from unsaturated nitrile is large, cold resistance is poor and saturated methylene chain (C-
If C) is less than 35% by weight, the unit portion (VCN) from unsaturated nitrile is small, and if the C = C portion described later is large, deterioration oil resistance becomes poor.

Marked carbon double bond moiety (C = C) - - [0018] Carbon _{(- CH 2 -CH = CH-} CH 2 -) z is a unit portion of conjugated diene, from 0 weight% It is preferably 20% by weight, especially 0 to 5% by weight. This is because if it is out of this range, the resistance to deteriorated oil is poor.

Specific examples of such a copolymer rubber include:
Hydrogenated butadiene-acrylonitrile copolymer rubber, isoprene-acrylonitrile copolymer rubber, butadiene-isoprene-acrylonitrile copolymer rubber, etc .:
Butadiene-methyl acrylate-acrylonitrile copolymer rubber, butadiene-acrylic acid-acrylonitrile copolymer rubber, etc. and hydrogenated products thereof: butadiene-ethylene-acrylonitrile copolymer rubber, butyl acrylate-ethoxyethyl acrylate-vinyl chloroacetate-acrylonitrile copolymer Examples thereof include polymerized rubber, butyl acrylate-ethoxyethyl acrylate-vinyl norbornene-acrylonitrile copolymerized rubber, and hydrogenated products thereof. These copolymer rubbers are used alone or in some cases in combination with other rubbers within a range not impairing the gist of the present invention.

(2) Organic Sulfur-Containing Compound The organic sulfur-containing compound used in the present invention has the following formula (1):

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It is preferably a 6-R-2,4-dimercapto-1,3,5-triazine compound represented by:
However, R is selected from the group consisting of mercapto group, alkoxy group, mono- or di-cycloalkylamino group, mono- or di-arylamino group, mono- or di-cycloalkylamino group, N-alkyl-N'-arylamino group. It is the group of choice. Particularly, 2,4,6-trimercapto-1,3,5-triazine is preferable.

Commercial products such as ZISNET-F manufactured by Sankyo Kasei Co., Ltd. and TDCA manufactured by Ouchi Shinko Chemical Co., Ltd. can be used. The compounding amount of the organic sulfur-containing compound is 0.1 to 15 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the (1) copolymer rubber. If the compounding amount of the organic sulfur-containing compound is less than 0.1 part by weight, there is no adhesive effect with brass,
If it exceeds 15 parts by weight, the vulcanization reaction of organic peroxide vulcanization is hindered, which is not preferable.

(3) Maleic anhydride-modified polybutadiene The maleic anhydride-modified polybutadiene used in the present invention is
If polybutadiene is modified with maleic anhydride, any polybutadiene of cis-1,4 body, trans-1,4 body, vinyl body (1,2-isotactic, 1,2-syndiotactic and atactic) can be obtained. It may be one or a mixture thereof. The modification rate of maleic anhydride in polybutadiene is 1 to 40% by weight, specifically 10% by weight, 17% by weight, and 23% by weight.
Although there are some modified ones, 10% by weight or more is particularly preferable from the viewpoint of the effect of imparting adhesion. Further, a commercially available product such as RICOBOND manufactured by Advanced Resins can also be used.

The amount of the maleic anhydride-modified polybutadiene compounded is (1) 0.1 to 1 per 100 parts by weight of the copolymer rubber.
It is 5 parts by weight, preferably 0.5 to 5 parts by weight. If the maleic anhydride-modified polybutadiene is less than 0.1 parts by weight, the adhesion to brass will not be improved, and if it is more than 15 parts by weight, the modulus will be extremely lowered and it cannot be used for a high pressure hose tube.

(4) Silica The silica (SiO ₂ ) used in the present invention is crystalline silica or amorphous silica such as precipitated silica or high temperature treated silica, as long as it is of a grade generally used in rubber compositions. Alternatively, a commercially available product such as Nipseal AQ manufactured by Nippon Silica Industry Co., Ltd. may be used. The amount of silica blended is 1 to 3 with respect to 100 parts by weight of (1) copolymer rubber.
It is preferably 0 parts by weight, particularly preferably 1 to 10 parts by weight.
If the amount of silica is less than 1 part by weight, the adhesion to brass will not be improved, and if it exceeds 30 parts by weight, the heat resistance will deteriorate, which is not preferable.

(5) Organic Peroxide Vulcanizing Agent The organic peroxide as a vulcanizing agent used in the present invention is an organic peroxide which does not undergo a crosslinking reaction extremely at a temperature during processing in a rubber composition. Any of these may be used, and dialkyl peroxide having a half-life of 10 hours and a decomposition temperature of 80 ° C. or higher is preferable. Examples thereof include dicumyl peroxide, 1,3-bis- (t-butyl-peroxy-isopropyl) benzene, and n-butyl 4,4-di-tert-butyl-peroxyvalerate. Also,
A commercial product such as Kayaku Nouri Co.'s Perkadox 14/40 may be used.

The organic peroxide vulcanizing agent is a copolymer rubber (1) 1
It is preferable to add 1 to 15 parts by weight, especially 2 to 10 parts by weight, relative to 00 parts by weight. If the amount is less than 1 part by weight, the number of cross-linking points is small and the physical properties are difficult to develop, and if it exceeds 15 parts by weight, the organic peroxide residue affects the heat aging, which is not preferable.

The adhesive rubber composition of the present invention further comprises, if necessary, a filler, a reinforcing agent, a plasticizer, which are usually used.
You may mix | blend an antiaging agent and other compounding agents with an appropriate amount. One example of the method for producing the adhesive rubber composition of the present invention is a copolymer rubber (1) containing an organic sulfur-containing compound (2), a maleic anhydride-modified polybutadiene (3), silica (4), and an organic peroxide. (5) Further, if necessary, other compounding agents are compounded in appropriate amounts and kneaded to obtain a rubber compounding composition.

Furthermore, by vulcanizing the obtained adhesive rubber composition of the present invention in close contact with brass, it has excellent heat resistance and oil resistance, and has sufficient reaction force (elasticity) even under pressure. A brass / rubber composite can be obtained. Therefore, the adhesive rubber composition of the present invention can be applied to many rubber products such as tires, belts, molds, rolls and hoses, which require oil resistance due to long-term use under high temperature and high pressure environment. You can In particular, it is most suitable for a heat-resistant high-pressure hose that requires heat resistance and oil resistance for long-term use under a high-temperature and high-pressure environment.

As shown in one embodiment in FIG. 1, the heat-resistant hose 1 of the present invention has at least an inner tube 2 and a pressure-proof reinforcing layer 3 made of the adhesive rubber composition of the present invention, and further requires With outer tube 4 and other layers accordingly. Further, the inner tube and the outer tube may have two or more layers, if necessary. Further, the reinforcing layer may also have two or more layers, and two or more layers are interposed between each reinforcing layer via the adhesive rubber composition of the present invention or a rubber composition such as chloroprene generally used for hoses. May have.

The heat-resistant hose of the present invention uses the adhesive rubber composition of the present invention having excellent adhesiveness with the brass as an inner tube, and a brass-plated pressure-resistant steel wire layer is applied thereon and vulcanized. The inner tube and the pressure-proof reinforcing steel wire layer are firmly bonded to each other by being integrated with each other. The vulcanization conditions can be freely selected depending on the type of rubber product, but the vulcanization temperature is 130 ° C.
The temperature is preferably ˜200 ° C., and the vulcanization method can be a commonly used method such as ordinary press vulcanization, steam vulcanization, or hot water vulcanization. By this vulcanization step, the rubber composition of each layer becomes to have rubber-like elasticity and the brass-plated pressure-resistant steel wire layer is formed at the interface with the rubber composition, particularly the adhesive rubber composition of the present invention. , It is firmly bonded by a chemical reaction.
The resulting heat resistant hose forms a brass / rubber composite.

The heat-resistant hose of the present invention has, at least in the inner tube thereof, an adhesive rubber composition having excellent adhesion to the brass of the present invention. By using the adhesive rubber composition of the present invention for the inner pipe of the heat-resistant hose of the present invention, the adhesive rubber composition of the present invention can be strongly adhered directly to the brass-plated reinforcing steel wire layer. Also, peeling between the rubber composition of the present invention and brass during use under high temperature and high pressure can be prevented, and there is no need to take a double tube structure of an inner tube using other general-purpose adhesive rubber or the like. The inner tube has a thickness of about 1.0 to 4.0 mm.

The outer tube may be a rubber composition generally used for heat resistant hoses, and may be the adhesive rubber composition of the present invention. Specifically, styrene-butadiene copolymer rubber (SBR), chloroprene rubber (CR), acrylonitrile-butadiene copolymer rubber (NBR), chlorosulfonated polyethylene rubber (CSM), chlorinated polyethylene rubber (CM), etc. Alternatively, a compounded rubber having good adhesion to the pressure-proof reinforcing steel wire may be used.

The pressure-proof reinforcing layer (pressure-proof reinforcing steel wire layer) used in the present invention is a brass-plated steel material and is mainly used as a reinforcing material for rubber products such as hoses and tires, and can be used for any wire material, pipe material, plate material, steel material or the like. Although it may be a wire, it is preferably a steel wire, and a wire diameter is appropriately selected depending on the pressure applied to the high pressure hose, and a braided structure or a so-called spiral reinforcing structure wound in a spiral left-right alternating direction is adopted. Is mentioned.

One example of the method for producing a heat-resistant hose of the present invention is one in which the adhesive rubber composition of the present invention is extrusion-molded on a mandrel, a brass body is placed thereon, and the adhesive of the present invention is further applied thereon. Rubber composition or rubber composition such as CR that is generally used for hoses is extruded, wrapped with lead pipe by a machine to be lead, put in a vulcanization can, and
By holding in steam at 30 to 200 ° C. for a certain period of time, the rubber composition of each layer such as the inner pipe and the outer pipe is vulcanized to integrate rubber and brass.

[0036]

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples. (Examples 1 to 3 and Comparative Examples 1 to 10) Each rubber composition having the composition shown in Table 1 (Examples 1 to 3 and Comparative Examples 1 to 10)
Are mixed for 15 minutes on a mixing roll at 60 ° C., then on a small lab roll, 2.0 mm and 2.5 m
The sheet was taken out to a thickness of m and subjected to the test shown below.

(1) Measurement of elastic modulus Each rubber composition shown in Table 1 (Examples 1 to 3 and Comparative Examples 1 to 1)
0) 2.0mm sheet with a lab press molding machine
Pressure vulcanization was performed at 60 ° C. for 60 minutes at a surface pressure of 30 kgf / cm ² . A 100% modulus was measured using a tensile tester specified in JIS K6301 and a tensile speed of 500 mm / mi.
It was measured by n and used as a standard of elastic modulus. The measurement methods and calculations are all performed according to JIS K6301.3. It was conducted according to the method described in the tensile test. The results are shown in Table 1.

(2) Adhesion Test Method with Brass Each rubber composition shown in Table 1 (Examples 1 to 3 and Comparative Examples 1 to 1)
0) Sheet 6 (thickness 2.5 mm) and brass plate 8 (adherend)
2, as shown in FIG. 2, and vulcanized under pressure at a surface pressure of 30 kgf / cm ² at 160 ° C. for 60 minutes in a lab press molding machine, molded, and integrated into a brass / rubber composite. 5
(Test piece) was obtained. After being left at room temperature for 24 hours, the test piece was cut into a width of 2.54 cm, and a peeling test between the rubber composition and the brass plate was performed. The peel strength is measured according to JIS K 6301 8.
In accordance with the method described in the test for peeling the rubber adhered to the metal piece in the direction of 3 in 90 degrees, the tensile tester specified in JIS K6301 was used and the tensile speed was 50 mm / min.

Then, the peeled state was observed and evaluated according to the following evaluation criteria. (Evaluation Criteria for Peeling State) O: Destruction of adherend rubber material X: Peeling of adherend / rubber interface Table 1 shows the results.

(3) Preparation of hose test pieces Each rubber composition shown in Table 1 (Examples 1 to 3 and Comparative Examples 1 to 1)
A hose having 0) as an inner tube was produced by the following method and subjected to an oil aging test of the hose. (Hose manufacturing method) (i) Inner tube extrusion With a crosshead extruder, an inner tube made of a rubber composition of each compound was placed on a nylon 11 mandrel to give an inner diameter of 9.5 m.
m and the meat pressure was 1.8 mm. (Ii) Reinforcing Layer Braid A brass-plated diameter of 0.
A 31 mm pressure resistant reinforcing steel wire was braided.

(Iii) Outer tube extrusion Further, an outer tube of the rubber composition shown in Table 2 below was extruded with an outer diameter of 18.0 mm by a crosshead extruder. (Iv) Vulcanization step The unvulcanized hose was ribbon-wrapped and vulcanized by a vulcanizer at 160 ° C for 90 minutes, and then the ribbon was removed. (V) Mandrel extraction step The mandrel was extracted from the hose after vulcanization to obtain a hose test piece for an oil aging test.

(4) Oil aging test of hose Fitting fittings are attached to both ends of the hose test piece manufactured by the process described in (3), and hydraulic oil (manufactured by Showa Shell Sekiyu KK: White Parrot S) is installed inside the hose. -3),
It heat-aged at 150 degreeC for 72 hours. With respect to the heat-aged hose test piece, bulge generation and leakage were evaluated by the following methods. The results are shown in Table 1.

(I) Evaluation of Occurrence of Bulge The presence or absence of occurrence of so-called bulge, such as swelling and breakage of the inner tube rubber at the metal fitting tightening portion, was observed. (Evaluation criteria) x: Bulge occurred. ◯: No bulge was generated.

(Ii) Evaluation of Leakage With respect to the above-described evaluation of bulge generation, a pressure resistance test was conducted on the hose in which bulge generation did not occur. 240kg on the hose
A pressure of f / cm ² was applied and maintained for 5 minutes, during which the presence or absence of abnormalities such as leakage, leakage, and rupture was observed. (Evaluation criteria) x: Leakage occurred. ◯: No leakage occurred. Note that none of the evaluated hoses caused disconnection or rupture.

(Composition of rubber composition used in outer tube) Hypalon 40 ^{* 1} 100 parts by weight Carbon black SRF 70 parts by weight MgO (Kyowamag 150) 4 parts by weight Pentaerythritol 3 parts by weight DOP ^{* 2} 15 parts by weight Sunceller TRA ^{* 3} 2 parts by weight Suncellar DM ^{* 4} 1 part by weight Note) ^{* 1} : DuPont chlorosulfonated polyethylene ^{* 2} : Octyl phthalate ^{* 3} : Sanshin Chemical Co., Ltd. vulcanization accelerator (dipentamethylene thiuram tetrasulfide) ^{* 4} : Vulcanization accelerator (dibenzothiazyl disulfide) manufactured by Sanshin Chemical Co., Ltd.

[0046]

[Table 1]

Note) In the table, the amounts of the composition components represent parts by weight. Polymer: Hydrogenated NBR (VCN: 33%, C = C:
1.3%, C-C: 65.7%) SRF: Asahi Carbon Asahi # 50 (SRF grade carbon black) Vulkanox DDA: Bayer diphenylamine derivative Vulkanox ZMB-2: Bayer 4,5 -Zinc salt of methyl mercaptobenzimidazole Wax: PE 520 ZISNET-F manufactured by Hoechst: manufactured by Sankyo Kasei (2,4,6-trimercapto-1,3,5-triazine)

RICOBOND: Maleic anhydride-modified polybutadiene manufactured by Advanced Resins (maleic anhydride modification rate: 17% by weight) TAIC: Nihon Kasei Co., Ltd. (triallyl isocyanurate) Silica: Nipseal AQ DAP manufactured by Nippon Silica Industry Co., Ltd. : Daiso tap monomer (diallyl phthalate) manufactured by Osaka Tanka Perkadox 14/40: manufactured by Kayaku Noury (1,3
-Containing 40% by weight of bis- (t-butylperoxyisopropyl) benzene)

[0049]

The adhesive rubber composition of the present invention is obtained by adding an appropriate amount of maleic anhydride-modified polybutadiene and silica to highly hydrogenated NBR containing an organic peroxide vulcanizing agent.
Adhesion between highly hydrogenated NBR containing an organic peroxide vulcanizing agent, which has been difficult to achieve in the past, and brass is sufficiently improved, heat resistance and oil resistance are excellent, and a high elastic modulus is provided. The heat-resistant hose of the present invention in which this adhesive rubber composition is used for at least the inner tube has excellent adhesiveness to brass, heat resistance, and oil resistance, and has a high elastic modulus. The present invention achieves at least one of the above effects.

[Brief description of drawings]

FIG. 1 is a perspective view of a heat resistant hose of the present invention.

FIG. 2 is a view showing a cross section of a vulcanization-molded test piece of a rubber composition sheet and a brass-plated plate.

[Explanation of symbols]

 1 Heat Resistant Hose 2 Inner Tube 3 Pressure Resistant Reinforcing Layer 4 Outer Tube 5 Brass / Rubber Complex 6 Rubber Composition Sheet 7 Cellophane 8 Brass Plate

Claims (4)

[Claims] 1. A polymer chain containing 10 to 45% by weight of a unit portion derived from an unsaturated nitrile and 0 to a unit portion derived from a conjugated diene.
To 20% by weight and 90 to 35% by weight of a unit portion derived from an ethylenically unsaturated monomer other than the unsaturated nitrile and / or a unit portion derived from a conjugated diene. Organic sulfur-containing compound 0.1 to 15 parts by weight, maleic anhydride-modified polybutadiene 0.1 to 15 parts by weight, silica 1 to 30 parts by weight, organic peroxide vulcanizing agent 1 to 15 parts by weight, relative to 100 parts by weight. An adhesive rubber composition having excellent adhesiveness to brass, which is characterized by being compounded with. 2. The organic sulfur-containing compound is represented by the general formula: 6-R-2,4-dimercapto-1,3,5-triazine (wherein R is a mercapto group, an alkoxy group, mono- or di-cycloalkylamino). Group, a mono- or di-arylamino group, a mono- or di-cycloalkylamino group, a group selected from the group consisting of N-alkyl-N'-arylamino groups)). An adhesive rubber composition having excellent adhesion to the described brass. 3. A hose having at least an inner tube and a brass-plated pressure-proof reinforcing steel wire layer, wherein the inner tube has a unit portion of unsaturated nitrile in the polymer chain.
0 to 45% by weight and 0 to 2 unit parts from conjugated dienes
Copolymer rubber 100 containing 0% by weight and 90 to 35% by weight of a unit portion derived from an ethylenically unsaturated monomer other than the unsaturated nitrile and / or a unit portion derived from a conjugated diene. 0.1 to 15 parts by weight of an organic sulfur-containing compound, 0.1 to 15 parts by weight of maleic anhydride-modified polybutadiene, 1 to 30 parts by weight of silica, and 1 to 15 parts by weight of an organic peroxide vulcanizing agent, based on parts by weight. By using an adhesive rubber composition having excellent adhesiveness with the compounded brass and applying a brass-plated pressure-resistant steel wire layer thereon, and vulcanizing and integrating the composition, the inner pipe and the pressure-resistant A heat resistant hose characterized by being firmly bonded to a reinforcing steel wire layer. 4. The organic sulfur-containing compound has the general formula: 6-R-2,4-dimercapto-1,3,5-triazine (wherein R is a mercapto group, an alkoxy group, mono- or di-cycloalkylamino). Group, a mono- or di-arylamino group, a mono- or di-cycloalkylamino group, and a group selected from the group consisting of N-alkyl-N'-arylamino groups). Heat resistant hose described.