JP4211599B2 - Oil hose and its manufacturing method - Google Patents

Description

  TECHNICAL FIELD The present invention relates to an oil hose and a method for producing the same, and more particularly to an anti-lubricating oil system for automobiles such as automatic transmission fluid (ATF), power steering fluid (PSF), and engine oil in vehicles such as automobiles. The present invention relates to an oil hose useful as an oil hose and a method for producing the same.

In vehicles such as automobiles, lubricating oil-based oil hoses such as ATF, PSF, and engine oil are usually formed in a multilayer structure in which reinforcing yarn layers are provided in two or more rubber layers. Conventionally, acrylonitrile butadiene rubber or the like has been mainly used as a material for forming the rubber layer. However, in recent years, instead of this, those using acrylic rubber having excellent heat resistance and oil resistance are becoming mainstream. As such an oil hose, what was formed using the acrylic rubber composition containing a diamine type | system | group vulcanizing agent and a guanidine type | system | group vulcanization adjuvant, for example has already been proposed (for example, patent documents 1-1). 4).
Japanese Patent Laid-Open No. 3-101932 JP 11-92614 A JP 2001-192420 A JP 2003-201380 A

  However, the acrylic rubber composition vulcanized with a diamine-based vulcanizing agent as described above has a short scorch time and is prone to rubber scorch. There is a problem that the rubber hose is easily broken. In order to solve this problem, if the extrusion temperature is lowered to cope with it, the load of rubber pressure on the extruder increases, which causes a problem in operation. Therefore, in order to manufacture an oil hose using the rubber composition, there is no choice but to extrude it slowly, taking care not to tear it halfway, and the production efficiency is very poor.

  On the other hand, an oil hose is usually manufactured by inserting the rubber composition extruded into a hose shape as described above into a linear or bent mandrel, performing steam vulcanization in that state, and finally extracting from the mandrel. Is done. However, when steam vulcanization is performed as described above, the moisture of the release agent tends to remain in the gap between the rubber layer made of the rubber composition and the mandrel, and the moisture is increased in temperature during steam vulcanization. Bumping may occur at the time of pressurization and cooling / decompression, and as a result, foaming marks may be formed on the inner peripheral surface of the rubber layer. In order to solve this problem, conventionally, a water-insoluble release agent such as silicone oil is applied to the mandrel surface in advance, and the rubber layer is vulcanized so that moisture does not enter the gap between the mandrel and the rubber layer. It was. However, if vulcanization molding is performed using a water-insoluble release agent in this way, it takes time to clean the hose surface, and the water-insoluble release agent itself is expensive, so the cost of manufacturing the hose is high. Invite up.

  The present invention has been made in view of such circumstances, and has an object to provide an oil hose excellent in heat resistance and oil resistance, having no foaming marks on its inner peripheral surface, and excellent in mass productivity, and a manufacturing method thereof. To do.

In order to achieve the above object, the present invention provides an oil hose having at least one constituent layer, wherein at least the innermost layer of the hose contains the following components (A) to (C) , the component (C), per 100 weight parts component (a), the first gist ing oil hose from a rubber composition comprising in the range of 0.2 to 0.5 parts by weight.
(A) Epoxy group-containing acrylic elastomer.
(B) Imidazole vulcanizing agent.
(C) 4,4'-methylenedianiline, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4 '-(m-phenylenediisopropylidene) dianiline, 4, 4 '-(p-phenylenediisopropylidene) dianiline, 2,2'-bis [4- (4-aminophenoxy) phenyl] propane, 4,4'-diaminobenzanilide, 4,4'-bis (4- (Aminophenoxy) biphenyl, m-xylylenediamine, p-xylylenediamine and at least one diamine-based vulcanization aid selected from the group consisting of N, N'-dicinnamylidene-1,6-hexanediamine .

The present invention also includes a step of extruding the rubber layer material into a hose shape, a step of inserting the extruded unvulcanized rubber hose into a linear or bent mandrel, and steaming the unvulcanized rubber hose. A method for producing an oil hose comprising a step of vulcanizing and a step of extracting a vulcanized rubber hose from a mandrel, and the rubber layer material includes the following components (A) to (C) : the proportion of the component (C), per 100 weight parts component (a), a second aspect of the preparation of oil hose using range der Ru rubber composition of 0.2 to 0.5 parts by weight To do.
(A) Epoxy group-containing acrylic elastomer.
(B) Imidazole vulcanizing agent.
(C) 4,4'-methylenedianiline, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4 '-(m-phenylenediisopropylidene) dianiline, 4, 4 '-(p-phenylenediisopropylidene) dianiline, 2,2'-bis [4- (4-aminophenoxy) phenyl] propane, 4,4'-diaminobenzanilide, 4,4'-bis (4- (Aminophenoxy) biphenyl, m-xylylenediamine, p-xylylenediamine and at least one diamine-based vulcanization aid selected from the group consisting of N, N'-dicinnamylidene-1,6-hexanediamine .

That is, the present inventors have intensively studied to solve the above problems. As a result, the epoxy group-containing acrylic elastomer, added imidazole curing agent, a specific diamine-based vulcanizing agent with a specific amount of added rubber composition prepared further, when the production of oil hose of interest It has been found that since excellent heat resistance and oil resistance are obtained and rubber burns are less likely to occur, the work during extrusion molding becomes easy and smooth and excellent in mass productivity. Moreover, since the rubber composition has a high unvulcanized viscosity, it is strong against moisture bumping during steam vulcanization, and it is difficult to form foam marks on the inner peripheral surface of the rubber layer made of the rubber composition. And the present invention has been reached.

As described above, the oil hose of the present invention has an epoxy group-containing acrylic elastomer, an imidazole-based vulcanizing agent, and a specific diamine-based vulcanizing aid as a material for forming the innermost layer at a specific ratio. Used and formed. Therefore, the scorch time of the rubber composition, which is the innermost layer forming material, is increased, and an oil hose having high quality and excellent mass productivity can be obtained without rubber burning.

  In particular, when an oil hose is obtained by adding a fatty acid metal salt to the rubber composition, the oil hose has a much longer scorch time, excellent storage stability, and higher quality and mass productivity. be able to.

A step of extruding the rubber layer material into a hose, a step of inserting the extruded unvulcanized rubber hose into a linear or bent mandrel, and a step of steam vulcanizing the unvulcanized rubber hose. , A method of producing an oil hose comprising a step of extracting a vulcanized rubber hose from a mandrel, wherein the rubber layer material includes an epoxy group-containing acrylic elastomer, an imidazole vulcanizing agent, and a specific diamine. When a rubber composition containing a specific amount of the system vulcanization aid is used, it is possible to eliminate the burnt rubber due to the effect of scorch time delay, so that the production efficiency can be improved. Further, it is difficult to form foam marks on the inner peripheral surface of the rubber layer during steam vulcanization, so that it is not necessary to apply a water-insoluble release agent to the mandrel surface, and the manufacturing cost can be reduced.

  Furthermore, when a fatty acid metal salt is added to the rubber layer material, the scorch time is significantly increased and the storage stability is excellent, so that a higher quality hose can be produced.

  Next, embodiments of the present invention will be described in detail.

For example, as shown in FIG. 1, the oil hose of the present invention is configured by forming a reinforcing yarn layer 2 on the outer peripheral surface of the innermost layer 1 and further forming an outer layer 3 on the outer peripheral surface thereof. In the present invention, at least the innermost layer 1 comprises an epoxy group-containing acrylic elastomer (A component), an imidazole vulcanizing agent (B component), and a specific diamine vulcanizing aid (C component). , Which are formed using a specific ratio, and this is the greatest feature.

As the material for the innermost layer 1, an epoxy group-containing acrylic elastomer (component A), an imidazole vulcanizing agent (component B), and a specific diamine vulcanizing auxiliary (component C) are used as essential components. It is done.

  Examples of the epoxy group-containing acrylic elastomer (component A) include, as a main component, an acrylic acid alkyl ester, an acrylic acid alkoxy-substituted alkyl ester, and an epoxy group-containing ethylenically unsaturated compound that serves as a cross-linking site. It can be obtained by copolymerizing other ethylenically unsaturated compounds copolymerizable with these.

  Specific examples of the acrylic acid alkyl ester include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, isoamyl acrylate, n-hexyl acrylate, and 2-methylpentyl acrylate. N-octyl acrylate, 2-ethylhexyl acrylate, n-decyl acrylate, n-dodecyl acrylate, n-octadecyl acrylate and the like. Of these, methyl acrylate, ethyl acrylate, n-propyl acrylate, and n-butyl acrylate are preferable, and ethyl acrylate and n-butyl acrylate are more preferable.

  Specific examples of the alkoxy-substituted alkyl ester of acrylic acid include 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2- (n-propoxy) ethyl acrylate, 2- (n-butoxy) ethyl acrylate, 3 -Methoxypropyl acrylate, 3-ethoxypropyl acrylate, 2- (n-propoxy) propyl acrylate, 2- (n-butoxy) propyl acrylate and the like. Of these, 2-methoxyethyl acrylate and 2-ethoxyethyl acrylate are preferable, and 2-methoxyethyl acrylate is more preferable.

  Furthermore, specific examples of the epoxy group-containing ethylenically unsaturated compound include allyl glycidyl ether, glycidyl methacrylate, glycidyl acrylate, and the like.

  In addition, as other ethylenically unsaturated compounds added as required, specifically, carboxyl group containing acrylic acid, methacrylic acid, crotonic acid, 2-pentenoic acid, maleic acid, fumaric acid, itaconic acid, etc. Compound, methacrylate such as methyl methacrylate and octyl methacrylate, alkyl vinyl ketone such as methyl vinyl ketone, vinyl and allyl ether such as vinyl ethyl ether and acrylic methyl ether, vinyl such as styrene, α-methyl styrene, chlorostyrene and vinyl toluene Aromatic compounds, vinyl nitriles such as acrylonitrile and methacrylonitrile, vinyl amides such as acrylamide, methacrylamide, N-methylol acrylamide, ethylene, propylene, vinyl chloride, vinylidene chloride, Kka vinyl, vinylidene fluoride, vinyl acetate, alkyl fumarate and the like. Of these, acrylonitrile, ethylene, and vinyl acetate are preferable.

  And the ratio of an epoxy-group-containing ethylenically unsaturated compound is normally set to 0.1 to 5 weight% among the composition ratios of the said epoxy-group-containing acrylic elastomer (A component). Moreover, the ratio of another ethylenically unsaturated compound is set to 30 weight% at most.

Used with an epoxy group-containing acrylic elastomer is the component A, as the imidazole curing agent (B component), if example embodiment, imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole 2-undecylimidazole, 2-heptadecylimidazole, 1-methyl-2-ethylimidazole, 1,2-dimethylimidazole, 1-benzyl-2-ethylimidazole, 1-dodecyl-2-methyl-3-benzylimidazo Lilium-chloride, 1,3-dibenzyl-2-methylimidazolium-chloride, 2-methylimidazoline, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-Cyanoe Ru-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole-trimellitate, 1-cyanoethyl-2-phenylimidazole-trimellitate, 1-cyanoethyl-2-ethyl -4-methylimidazole-trimellitate, 2,4-diamino-6- {2'-methylimidazolyl (1 ')} ethyl-S-triazine, 2,4-diamino-6- {2'-undecylimidazolyl (1 ′)} Ethyl-S-triazine, 1-cyanoethyl-2-phenyl-4,5-di- (cyanoethoxymethyl) imidazole, 2-methylimidazole / isocyanuric acid adduct, 2-phenylimidazole / isocyanuric acid addition Product, 2-phenyl-4,5-dihydromethylimida Lumpur, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 4,4'-methylene - bis - (2-ethyl-5-methylimidazole) and the like. These may be used alone or in combination of two or more.

  In the present invention, the blending ratio of the imidazole vulcanizing agent (component B) is 0.2 to 5 parts with respect to 100 parts by weight (hereinafter abbreviated as “part”) of the epoxy group-containing acrylic elastomer that is the component A. Is preferably set within the range of 0.5 to 3 parts. That is, when the proportion of the component B is less than 0.2 parts, vulcanization is insufficient and compression set characteristics are deteriorated, and conversely when it exceeds 5 parts, scorching is likely to occur. This is because the product quality of the hose becomes inferior.

Used together with the components A and B, the specific diamine-based vulcanization agent as component (C) is 4, 4'-methylenedianiline, m- phenylenediamine, 4,4'-diaminodiphenyl ether, 3, 4'-diaminodiphenyl ether, 4,4 '-(m-phenylenediisopropylidene) dianiline, 4,4'-(p-phenylenediisopropylidene) dianiline, 2,2'-bis [4- (4-aminophenoxy) ) Phenyl] propane, 4,4'-diaminobenzanilide, 4,4'-bis (4-aminophenoxy) biphenyl, m-xylylenediamine, p-xylylenediamine, N, N'-dicinnamylidene-1,6 - Hekisanjiami down, and the like. These may be used alone or in combination of two or more.

In the present invention, the blending ratio of the specific diamine-based vulcanization aid (component C) is 0 . Within the range of 2 to 0.5 parts. That is, the ratio of the C component is 0. If it is less than 2 parts, there is a possibility that the foaming countermeasure at the time of steam vulcanization may be incomplete. Conversely, if it exceeds 0.5 parts, the scorch time will be accelerated, and there is a concern of rubber burning during extrusion. .

  As described above, the A to C components are used as essential components for the innermost layer 1 material. In addition, when a fatty acid metal salt (D component) is used, the scorch time is significantly increased. Therefore, since it is excellent in storage stability, an oil hose with higher quality and excellent mass productivity can be obtained, which is preferable.

Then, the above A~C components used as needed, as the fatty acid metal salt (D component), if example embodiment, oleic acid, lauric acid, myristic acid, palmitic acid, stearic acid, naphthenic acid, such as caprylic acid A metal salt of a fatty acid, and examples of the metal include lithium, sodium, potassium, calcium, manganese, zinc, and cobalt. These fatty acid metal salts are used alone or in combination of two or more.

  The rubber layer material for forming the specific rubber layer (innermost layer 1) is preferably compounded with carbon black, plasticizer, etc. in addition to the above components, and may be reinforced as necessary. Materials, fillers, anti-aging agents, etc. may be appropriately blended.

Then, as the reinforcing yarn to form a reinforcing fiber layer 2 formed on the outer peripheral surface of the innermost layer 1, if example embodiment, an aramid (aromatic polyamide) yarn, nylon 6, nylon such as nylon 66 (polyamide) yarn, Examples include rayon yarn and polyester yarn. These may be used alone or in combination of two or more. Among these, an aramid yarn is preferably used in terms of excellent heat resistance.

Braid method of the reinforcing yarn, if example embodiment, braided spiral braiding, knitting knitting and the like.

As the outer layer 3 material formed on an outer peripheral surface of the reinforcing fiber layer 2, eg if, acrylic rubber, ethylene acrylic rubber, acrylonitrile-butadiene rubber, hydrin, ethylene-propylene rubber, ethylene-propylene-diene rubber, Fluorine-modified acrylic rubber, chlorinated polyethylene rubber, chloroprene rubber and the like are used alone or in combination of two or more. Especially, the special acrylic rubber composition similar to the material for innermost layer 1 mentioned above is used suitably.

  The oil hose of the present invention can be manufactured, for example, as follows. That is, first, the above-mentioned specific rubber is prepared by blending the above-mentioned components A to C and, if necessary, other components (such as component D) and kneading them using a kneader such as a roll, kneader, or Banbury mixer. A rubber layer material for forming a layer is prepared. Then, after the rubber layer material is extruded, an adhesive is applied to the outer peripheral surface as necessary, and the reinforcing yarn is wound in a spiral shape to form the reinforcing yarn layer 2. Next, an adhesive is applied to the outer peripheral surface of the reinforcing yarn layer 2 as necessary, and the material for the outer layer 3 is extruded. The hose-like laminate (unvulcanized) thus obtained was inserted into a linear or bent mandrel, steam vulcanized, and then extracted from the mandrel, whereby the innermost layer 1 / the reinforcing yarn layer 2 / A hose having a three-layer structure (oil hose according to the present invention) integrally formed in the order of the outer layer 3 can be obtained (see FIG. 1).

The oil hose of the present invention is not limited to the three-layer structure as shown in FIG. 1, and may have a single-layer structure, a two-layer structure, or a multilayer structure having four or more layers. However, at least the innermost layer (in the case of a single-layer structure hose, the layer) of the oil hose is composed of an epoxy group-containing acrylic elastomer (component A), an imidazole vulcanizing agent (component B), and a specific diamine-based additive. It must be formed using sulfur auxiliary (C component) as an essential component and using these in a specific ratio .

  The use of the oil hose of the present invention thus obtained is suitably used for piping of oil such as ATF, PSF, and engine oil in vehicles such as automobiles (including tractors and cultivators). However, if it is an oil hose use, it will not be limited to this.

  Next, examples will be described together with comparative examples.

  First, prior to the examples and comparative examples, the following materials were prepared.

[Acrylic elastomer (I) (component A)]
A quaternary copolymer obtained by polymerizing 84.5% by weight of n-butyl acrylate, 0.5% by weight of ethylene, 13.5% by weight of vinyl acetate, and 1.1% by weight of glycidyl ether.

[Vulcanizing agent (I) (component B)]
1-cyanoethyl-2-methylimidazole (CN-25, manufactured by Shikoku Chemicals)

(Vulcanizing agent (II))
Hexamethylenediamine carbamate (Diac # 1, DuPont)

[Vulcanization aid (I) (C component)]
N, N'-dicinnamylidene-1,6-hexanediamine (Diac # 3, manufactured by DuPont)

[Vulcanization aid (II) (component D)]
Sodium lauryl sulfate (Emar 2F needle, manufactured by Kao Corporation)

[Vulcanization aid (III)]
1-Orthotolyl biguanide (Noxeller DT, Ouchi Shinsei Chemical Co., Ltd.)

〔stearic acid〕
LUNAC S-30, manufactured by Kao

[Anti-aging agent]
Nowguard 445, made by Uniroyal

〔Carbon black〕
Seast 116, manufactured by Tokai Carbon

[Plasticizer]
Adeka Sizer RS735, manufactured by Asahi Denka Kogyo Co., Ltd.

[Processing aid]
Diana Process PW32, manufactured by Idemitsu Kosan Co., Ltd.

[Examples 1-6, Comparative Examples 1-3]
Each material shown above was blended in the proportions shown in Tables 1 and 2 below, and then kneaded using a Banbury mixer to prepare a rubber layer material. The unvulcanized viscosity is also shown in the same table (measurement criteria are described later). And after extruding this rubber layer material at a pace of 20 m / min, a reinforcing yarn layer was formed by spirally winding a reinforcing yarn (aramid yarn) on the surface using a braiding machine. Subsequently, the rubber layer material was extruded at a pace of 20 m / min on the outer peripheral surface of the reinforcing yarn layer. The hose-like laminate (unvulcanized) thus obtained was inserted into a bent mandrel, steam vulcanized at 160 ° C. for 60 minutes, and then taken out from the mandrel, whereby the innermost layer (thickness 2 mm) was obtained. An oil hose (bent pipe, inner diameter: 10 mm) in which a reinforcing yarn layer was integrally formed on the outer peripheral surface and an outer layer (thickness 2 mm) was integrally formed on the outer peripheral surface of this reinforcing yarn layer was produced.

  With respect to the hose of the example product and the comparative product thus obtained, each characteristic was evaluated according to the following criteria. These results are shown in Tables 1 and 2 below.

[Unvulcanized viscosity]
The Mooney viscosity ML _{1 + 4} at a measurement temperature of 125 ° C. was measured according to the Mooney viscosity test of the unvulcanized rubber physical property test method of JIS K6300.

[Tensile strength / elongation]
The rubber layer material composition was heated at 160 ° C. for 60 minutes by press molding to produce a sheet having a thickness of 2 mm, and further left to stand at 150 ° C. for 8 hours for secondary crosslinking, and then a JIS No. 5 dumbbell test piece was attached. Using this, the tensile strength (TB) and the elongation (EB) of the vulcanizate were evaluated under the conditions of a tensile speed of 500 mm / min according to JIS K6251.

[Foam marks]
The state of the innermost layer surface (inner peripheral surface) of the hose was visually observed, and the presence or absence of foaming marks was evaluated. That is, the case where no foaming marks were observed was evaluated as ◯, and the case where foaming marks were observed was evaluated as x.

[Rubber burn]
The rubber burnt state of the innermost layer and the outer layer of the hose was visually evaluated. That is, the case where no rubber burn was observed was evaluated as “good”, and the case where rubber burn was observed was evaluated as “poor”.

[Rupture pressure]
Immediately after its manufacture, each hose was assembled into a bulge-shaped aluminum casting product pipe having a straight diameter of 11 mm and conforming to JASO M101. And it tightened with the tightening torque of 3 N * m with the worm gear clamp based on JASO F207. Next, the hose was filled with water and pressurized, and this pressurization was continued until the hose burst. The maximum pressure (MPa) until the hose was ruptured was measured.

  From the above results, it can be seen that the oil hose of the example product is high quality and excellent in mass productivity without rubber burning or foaming marks. On the other hand, since no foaming marks were observed without applying silicone oil or the like to the mandrel surface, it can also be seen that the manufacturing cost can be reduced according to the examples.

  On the other hand, although the product of Comparative Example 1 does not show rubber burn, since foaming marks are seen, it is necessary to apply silicone oil or the like to the mandrel surface, which is inferior in terms of manufacturing cost. It can be seen that the comparative example 2 product is inferior in the productivity of the extrusion process because no foaming marks are observed but rubber burn is observed. In Comparative Example 3 products, neither rubber burn nor foaming marks were confirmed.

It is a block diagram which shows an example of the oil hose of this invention.

Explanation of symbols

1 innermost layer 2 reinforcing yarn layer 3 outer layer

Claims (6)

An oil hose provided with at least one constituent layer, wherein at least the innermost layer of the hose contains the following components (A) to (C), and the component (C) is added to 100 parts by weight of the component (A). respect, oil hose, characterized in Rukoto such a rubber composition containing a range of 0.2 to 0.5 parts by weight.
(A) Epoxy group-containing acrylic elastomer.
(B) Imidazole vulcanizing agent.
(C) 4,4'-methylenedianiline, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4 '-(m-phenylenediisopropylidene) dianiline, 4, 4 '-(p-phenylenediisopropylidene) dianiline, 2,2'-bis [4- (4-aminophenoxy) phenyl] propane, 4,4'-diaminobenzanilide, 4,4'-bis (4- (Aminophenoxy) biphenyl, m-xylylenediamine, p-xylylenediamine and at least one diamine-based vulcanization aid selected from the group consisting of N, N'-dicinnamylidene-1,6-hexanediamine . The oil hose according to claim 1, wherein the innermost layer is formed by using the following component (D) together with the components (A) to (C).
(D) Fatty acid metal salt. In the rubber composition forming the innermost layer, the blending ratio of the imidazole vulcanizing agent of the component (B) is in the range of 0.2 to 5 parts by weight with respect to 100 parts by weight of the component (A). The oil hose according to claim 1 or 2. Extruding the rubber layer material into a hose, inserting the extruded unvulcanized rubber hose into a straight or bent mandrel, steam vulcanizing the unvulcanized rubber hose, A method for producing an oil hose comprising a step of extracting a rubber-formed rubber hose from a mandrel, wherein the rubber layer material contains the following components (A) to (C): A method for producing an oil hose characterized by using a rubber composition having a ratio in the range of 0.2 to 0.5 parts by weight per 100 parts by weight of component (A) .
(A) Epoxy group-containing acrylic elastomer.
(B) Imidazole vulcanizing agent.
(C) 4,4'-methylenedianiline, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4 '-(m-phenylenediisopropylidene) dianiline, 4, 4 '-(p-phenylenediisopropylidene) dianiline, 2,2'-bis [4- (4-aminophenoxy) phenyl] propane, 4,4'-diaminobenzanilide, 4,4'-bis (4- (Aminophenoxy) biphenyl, m-xylylenediamine, p-xylylenediamine and at least one diamine-based vulcanization aid selected from the group consisting of N, N'-dicinnamylidene-1,6-hexanediamine. The manufacturing method of the oil hose of Claim 4 using the rubber composition containing the following (D) component with the said (A)-(C) component for the said rubber layer material.
( D ) Fatty acid metal salt. Of the rubber composition, the mixing ratio of the imidazole-based vulcanizing agent of the component (B), 100 weight parts component (A), according to claim 4 or in the range of 0.2 to 5 parts by weight 5. A method for producing an oil hose according to 5 .