JP2001241573A - Hose - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hose in which a reinforced layer is made up of reinforced steel wire which is brass plated, adhesiveness and heat resistance between an inner pipe or the like and the reinforced layer have superior performance, and a modulus of elasticity and a resistance to permanent set are in sufficient level. SOLUTION: The hose which is composed of the reinforced layer made of the brass plated reinforced steel wire and the inner and outer pipes, wherein the inner pipe and/or the outer pipe comprising (1): specific Copolymerization rubber of 100 pts.wt., (2): organic peroxide of 1 to 10 pts.wt., (3): 2,4-Dimercapto- substitution-1,3,5-Triazine of 0.1 to 15 parts as shown in Formula 1, and (4): a rubber component A containing Polymer of 1 to 100 pts.wt. having an epoxy group which can cross-link the organic peroxide. (In the Formula 1, R indicates a group selected from the group including mercapto group, alkoxyl group, monoalkylamino group, dialkylamino group, monocycloalkylamino group, dicycloalkylamino group, and N-alkyl-N-arylamino group).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hose having excellent adhesion and heat resistance between an inner tube or the like and a reinforcing layer.

[0002]

2. Description of the Related Art A wire used as a reinforcing material for a rubber hose is usually a high-carbon steel wire, and is often plated with brass (brass) in order to improve adhesion to rubber. However, in order to impart heat resistance to the hose, ethylene-acrylic acid such as hydrogenated acrylonitrile-butadiene copolymer rubber (HNBR) or ethylene-methyl acrylate copolymer rubber having excellent heat resistance is used as the inner tube material of the hose. When an ester copolymer rubber (AEM) is used, since these are rubbers having no unsaturated bond in the main chain and the side chain, sulfur cannot be used as a crosslinking agent,
Adhesion with a reinforcing layer using a brass-plated reinforcing steel wire is not exhibited.

Hitherto, hydrogenated acrylonitrile-butadiene copolymer rubber (HNBR) and ethylene-acrylate copolymer rubber (AEM) have been used for the inner tube material of hoses having brass-plated reinforcing steel wire as a reinforcing layer. Although many studies have been made on a formulation that exhibits adhesiveness when using a compound, a suitable formulation has not yet been obtained. For example, JP-A-55-125155 discloses a polymer composition comprising an organic peroxide-crosslinkable polymer, an organic peroxide, an epoxy resin and 2,4-dimercapto-6-R-1,3,5-triazine. The product is described as having good adhesion to brass, but from the results of verification and the description in the examples, chlorine in a chlorine-containing polymer such as chlorinated polyethylene and 2,4-dimercapto-6-R -1, 3,
Reaction of 5-triazine, 2,4-dimercapto-6-R
Reaction of -1,3,5-triazine with epoxy resin,
It utilizes the reaction between 2,4-dimercapto-6-R-1,3,5-triazine and copper in brass, and is a non-chlorine-containing polymer such as hydrogenated acrylonitrile-butadiene copolymer rubber (HNBR) and ethylene. -Acrylic ester copolymer rubber (AEM) does not undergo an adhesive reaction, so the adhesiveness is insufficient, and from the technical level currently required,
Adhesion is not sufficient. Further, other formulations have sufficient adhesiveness, but have problems such as a decrease in modulus, deterioration of set resistance, and a decrease in heat resistance.

[0004]

SUMMARY OF THE INVENTION The present invention relates to a hydrogenated acrylonitrile-butadiene copolymer rubber (HNBR) comprising a reinforcing steel wire in which a reinforcing layer is plated with brass, and an inner tube material or the like.
And ethylene-acrylate copolymer rubber (AEM)
It is an object of the present invention to provide a hose which is excellent in adhesiveness and heat resistance between an inner tube or the like and a reinforcing layer, and has sufficient modulus and set resistance.

[0005]

That is, the present invention relates to a reinforcing layer comprising a brass-plated reinforcing steel wire and a hose comprising an inner tube and an outer tube, wherein the inner tube and / or the outer tube comprises (1) ) 10 to 45% by mass of a unit portion from an unsaturated nitrile (Y portion; VCN) in a polymer chain, 0 to 5% by mass of a unit portion from a conjugated diene (Z portion; C = C) and other than the unsaturated nitrile 90 to 50% by mass of a unit part (X part; CC) obtained by hydrogenating a unit part from an ethylenically unsaturated monomer and / or a unit part from a conjugated diene.
100 parts by mass of a copolymer rubber having an iodine value of 15 or less,
(2) 1 to 10 parts by mass of an organic peroxide, (3) 2,4-dimercapto-6-substituted-1,3,5 represented by the following formula 1
-Polymers 1 to 100 having 0.1 to 15 parts by mass of triazine and (4) an epoxy group capable of crosslinking with an organic peroxide.
A hose characterized by comprising a rubber composition A containing parts by mass.

[0006]

Embedded image

(Wherein R is selected from the group consisting of mercapto, alkoxy, monoalkylamino, dialkylamino, monocycloalkylamino, dicycloalkylamino and N-alkyl-N-arylamino groups. Represents a group represented by

Further, the present invention provides a reinforcing layer comprising a brass-plated reinforcing steel wire and a hose comprising an inner tube and an outer tube, wherein the inner tube and / or the outer tube comprises (1) an ethylene-acrylate ester 100 parts by mass of copolymer rubber,
(2) 1 to 10 parts by mass of an organic peroxide, (3) 2,4-dimercapto-6-substituted-1,3,5 represented by the following formula 1
-Polymers 1 to 100 having 0.1 to 15 parts by mass of triazine and (4) an epoxy group capable of crosslinking with an organic peroxide.
A hose comprising a rubber composition B containing parts by mass.

[0009]

Embedded image

Wherein R is selected from the group consisting of mercapto, alkoxy, monoalkylamino, dialkylamino, monocycloalkylamino, dicycloalkylamino and N-alkyl-N-arylamino groups. Represents a group represented by

Particularly, in a reinforcing layer made of brass-plated reinforcing steel wire and a hose made of an inner tube and an outer tube, the inner tube is made of the rubber composition A, and the outer tube is made of the rubber composition B. A hose characterized in that it is preferred.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The present invention relates to a hose comprising a reinforcing layer comprising a brass-plated reinforcing steel wire and an inner tube and / or an outer tube, wherein the inner tube and / or the outer tube comprises a specific rubber composition. is there. In the hose,
It is the first aspect of the present invention that the inner tube and / or the outer tube is made of the rubber composition A, and the second embodiment of the present invention is that the inner tube and / or the outer tube is made of the rubber composition B. In a third embodiment of the present invention, the inner tube is made of the rubber composition A, and the outer tube is made of the rubber composition B. Therefore, the third embodiment of the present invention is a preferable example of the first embodiment of the present invention, and is a preferable example of the second embodiment of the present invention.

The reinforcing layer of the hose of the present invention comprises a brass-plated reinforcing steel wire. The reinforcing steel wire is not particularly limited as long as the surface is plated with brass, and a wire generally used as a hose wire can be used. For example, a high carbon hard steel wire or the like containing 0.70 to 1.10 mass% of carbon and having a wire diameter of 0.2 to 0.8 mm can be suitably used.

The surface of the hose wire is plated with brass. Brass plating is also called brass plating or brass plating.

The reinforcing layer of the hose of the present invention is formed by braiding the brass-plated reinforcing steel wire into, for example, a blade shape, a spiral shape, or the like.

In the first embodiment of the present invention, the inner tube and / or the outer tube have (1) 10 to 45% by mass of a unit portion (Y portion; VCN) from unsaturated nitrile in a polymer chain,
0 to 5% by mass of a unit moiety (Z moiety; C = C) from a conjugated diene and a unit obtained by hydrogenating a unit moiety from an ethylenically unsaturated monomer other than an unsaturated nitrile and / or a unit moiety from a conjugated diene. Part (X part; CC) 90 to
Copolymer rubber 10 having an iodine value of 15 or less having 50% by mass
0 parts by mass, (2) 1 to 10 parts by mass of organic peroxide, (3)
2,4-dimercapto-6-substituted represented by the above formula 1
The rubber composition A contains 0.1 to 15 parts by mass of 1,3,5-triazine and (4) 1 to 100 parts by mass of a polymer having an epoxy group capable of crosslinking with an organic peroxide.

In the second embodiment of the present invention, the inner pipe and / or the outer pipe are composed of (1) 100 parts by mass of an ethylene-acrylate copolymer rubber, (2) organic peroxides 1 to 1
0 parts by mass, (3) 2,4-dimercapto-6-substituted-1,3,5-triazine 0.1 to 15 represented by the above formula 1
It is composed of a rubber composition B containing 1 to 100 parts by mass of a polymer having 1 part by mass and (4) a polymer having an epoxy group capable of crosslinking with an organic peroxide.

The copolymer rubber used for the rubber composition A is
In the polymer chain, a unit moiety from an unsaturated nitrile (Y moiety;
VCN), a unit moiety (Z moiety; C =
C) and a unit portion (X portion; CC) having a hydrogenated unit portion from an ethylenically unsaturated monomer other than an unsaturated nitrile and / or a unit portion from a conjugated diene and having an iodine value of 15 or less. Polymerized rubber (hereinafter "hydrogenated acrylonitrile-butadiene copolymer rubber" or "HNB
R ". ). In the composition of HNBR used in the present invention, the Y portion is 10 to 45% by mass, the Z portion is 0 to 5% by mass, and the X portion is 90 to 50% by mass.
When the Z portion exceeds 5% by mass, the heat resistance of the rubber composition A becomes insufficient, and when the composition is within the above range, the heat resistance becomes excellent. The iodine value is a value that represents the mass of iodine that can be added per 100 g of rubber in units of g, and is defined by JIS K
Measured according to 6235 and used as an indicator of rubber unsaturation. The smaller the value of the iodine value, the smaller the degree of unsaturation. HNBR used in the present invention has an iodine value of 15 or less, preferably 10 or less. When it is in the above range, the heat resistance is excellent.

The copolymer rubber used in the rubber composition B is
Copolymer rubber of ethylene and acrylate (hereinafter "ethylene-acrylate copolymer rubber" or "AE
M ”. ). In the present invention, acrylates also include methacrylates. Acrylic esters, for example, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate,
Butyl acrylate, butyl methacrylate, t-acrylate
-Butyl, t-butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate. As described above, the ethylene-acrylate copolymer rubber used in the rubber composition B is a copolymer of ethylene and the acrylate, and may further include a crosslinkable monomer as the third copolymer component. . For example, ethylene-methyl acrylate copolymer rubber, ethylene-ethyl acrylate copolymer rubber, ethylene-methyl methacrylate copolymer rubber can be used. Among them, ethylene-
Methyl acrylate copolymer rubber is preferred. The composition of the ethylene-acrylate copolymer rubber is not particularly limited, and a rubbery polymer having an ethylene content in a commonly used range can be used. That is, any composition ratio may be used as long as it has an ethylene content sufficient to improve properties such as heat resistance and cold resistance and does not impair the rubbery state.

The organic peroxide used in the rubber composition A or B is not particularly limited as long as it is generally used for rubber crosslinking, but an organic peroxide in which the crosslinking reaction does not extremely proceed at the temperature during processing in the rubber composition. Peroxides are preferred,
Dialkyl peroxide having a decomposition temperature (a temperature at which the half-life becomes 10 hours) of 80 ° C. or more is preferable. For example,
Dicumyl peroxide, di-t-butyl peroxide, 1,3-bis- (t-butylperoxyisopropyl) benzene, n-butyl 4,4′-di- (t-butylperoxy) valerate, 2 , 5-dimethyl-2,
5-di- (t-butylperoxy) hexane. The content of the organic peroxide in the rubber composition A or B is preferably 1 to 10 parts by mass with respect to 100 parts by mass of HNBR or AEM. If the amount is less than 1 part by mass, the crosslinking density of the rubber composition A or B may be low, and the modulus or the like may be impaired. If it exceeds 10 parts by mass, the crosslink density of the rubber composition A or B may increase, and the elongation at break may decrease.

The 2,4-dimercapto-6-substituted-1, represented by the above formula 1, used for the rubber composition A or B,
In the 3,5-triazine, R in the formula is a mercapto group, an alkoxy group, a monoalkylamino group, a dialkylamino group, a monocycloalkylamino group, a dicycloalkylamino group, and an N-alkyl-N-arylamino group. It is a group selected from the group. In view of the bonding speed between the brass-plated reinforcing steel wire forming the reinforcing layer and the polymer having an epoxy group, 2,4,6-trimercapto-1,3,5-triazine where R is a mercapto group is preferred. . Further, two or more kinds of 2,4-dimercapto-6-R-1, represented by the above formula 1 having different Rs,
3,5-Triazine may be used in combination. The content of 2,4-dimercapto-6-R-1,3,5-triazine represented by the above formula 1 in the rubber composition A or B is preferably from 0.1 to 100 parts by mass of HNBR or AEM. 15 parts by mass. If the amount is less than 0.1 parts by mass, the adhesiveness between the inner tube and / or the outer tube using the rubber composition A or B and the reinforcing layer made of brass-plated reinforcing steel wire may be insufficient. . If the amount exceeds 15 parts by mass, a large amount of reaction with the organic peroxide occurs, so that crosslinking may be inhibited and the modulus may be reduced. Also, 15
If the amount is more than 10 parts by mass, a large number of reactions with the polymer having an epoxy group occur. Therefore, among the polymers having an epoxy group in the rubber composition A or B, those which bind to HNBR or AEM are reduced. Alternatively, the adhesion between the inner tube and / or the outer tube in which B is used and the reinforcing layer may be insufficient.

The polymer having an epoxy group used in the rubber composition A or B can be crosslinked with an organic peroxide. Epoxy resins such as bisphenol A type are not included in the polymer having an organic peroxide crosslinkable epoxy group used in the rubber composition A or B, since crosslinking with an organic peroxide hardly occurs.
When an epoxy resin is used in place of the polymer having an organic peroxide crosslinkable epoxy group used in the rubber composition A or B, the bonding with the HNBR or AEM is small, so that the inner tube and / or the rubber composition is used. Alternatively, the adhesion between the outer tube and the reinforcing layer becomes insufficient. The content of the polymer having an epoxy group in the rubber composition A or B is
The amount is generally 1 to 100 parts by mass, and preferably 5 to 50 parts by mass, based on 100 parts by mass of HNBR or AEM, although it depends on the amount of the epoxy group. If the amount is less than 1 part by mass, the adhesion between the inner tube and / or the outer tube in which the rubber composition A or B is used and the reinforcing layer may be insufficient. If it exceeds 100 parts by mass, the adhesiveness and heat resistance between the inner tube and / or the outer tube in which the rubber composition A or B is used and the reinforcing layer may be reduced. When the amount is 5 to 50 parts by mass, the balance between the adhesion, the modulus, the set resistance and the heat resistance between the inner tube and / or the outer tube in which the rubber composition A or B is used and the reinforcing layer is further improved.

The polymer having an epoxy group used in the rubber composition A or B is not particularly limited as long as it is crosslinked with HNBR or AEM by organic peroxide crosslinking and further has an epoxy group. ,
Considering the adhesion between the inner tube and / or the outer tube in which the rubber composition A or B is used and the reinforcing layer, a graft copolymer whose main chain is an organic peroxide crosslinkable polymer, Preferably, at least one has an epoxy group. Glycidyl methacrylate or the like is preferably used as a monomer of the graft chain. The main chain of the graft copolymer is not particularly limited, but is preferably an ethylene-based polymer. Examples of the ethylene-based polymer include low-density polyethylene (LDPE), ethylene-vinyl acetate copolymer resin (EVA), ethylene-acrylate copolymer (eg, ethylene-methyl acrylate copolymer (EMA), ethylene -Ethyl acrylate copolymer (E
EA), ethylene-methyl methacrylate copolymer (EM
MA)), ethylene-propylene copolymer (EPM),
Polypropylene (PP). Each of the graft chain and the main chain may be obtained from one kind of monomer, or may be obtained from two or more kinds of monomers. The graft copolymer has a structure in which a graft chain is branched and bonded to a main chain, and the main chain is crosslinked with HNBR or AEM, and an epoxy group, which is a graft chain, is represented by the formula (2) or (4). -Dimercapto-6-substitution-
It is believed that it reacts with 1,3,5-triazine and adheres via a graft copolymer to HNBR or AEM to a brass-plated reinforcing steel wire forming a reinforcing layer.

As described above, Japanese Patent Application Laid-Open No. 55-12515
In JP-A-5, there is a description about a polymer composition comprising an organic peroxide-crosslinkable polymer, an organic peroxide, an epoxy resin, and 2,4-dimercapto-6-substituted-1,3,5-triazine. The composition comprises chlorine in a chlorine-containing polymer such as chlorinated polyethylene and 2,2.
Reaction of 4-dimercapto-6-substituted-1,3,5-triazine, 2,4-dimercapto-6-substituted-1,3,5
It utilizes the reaction between triazine and epoxy resin and the reaction between 2,4-dimercapto-6-substituted-1,3,5-triazine and copper in brass. The adhesion was insufficient. Also,
In the above publication, no mention is made of the adhesiveness of the non-chlorine-containing polymer, and chlorinated polyethylene rubber and chlorosulfonated polyethylene rubber are used in Examples. Furthermore, no mention is made of the crosslinkability of the epoxy resin by organic peroxide crosslinking, and an epoxy resin having no organic peroxide crosslinking property is used in the examples. That is, the effect of adhesion to the metal by the epoxy resin entering and cross-linking between 2,4-dimercapto-6-substituted-1,3,5-triazine reacted with chlorine in the polymer and copper in the brass. It is presumed that it was added in the expectation that the adhesion reaction by the same reaction mechanism in the non-chlorine-containing polymer could not be expected, and even in the case where the epoxy group-containing polymer such as the present invention co-crosslinked with the non-chlorine-containing polymer. Rather, due to a different mechanism of action.

On the other hand, the hose according to the first embodiment of the present invention is not an epoxy resin which is generally considered to greatly contribute to the adhesion to metal, but is capable of crosslinking other organic peroxides. It has been found that the use of a polymer having a suitable epoxy group improves the adhesiveness, and has been completed. Although the reason for this has not been elucidated, general epoxy resins have poor radical reactivity and are unlikely to undergo hydrogen abstraction, and since there is no double bond other than the aromatic ring in the main chain, a cross-linking reaction other than epoxy groups occurs. On the other hand, a polymer having an epoxy group used in the rubber composition A or B has high radical reactivity of a methylene chain such as ethylene, and further has a main chain such as a double bond other than an aromatic ring. Since it may also have a portion that contributes to the cross-linking reaction, the bond with HNBR or AEM effectively occurs,
At the same time, 2,4-dimercapto-6-substituted-1,3,5
-Triazine binds to a brass-plated reinforcing steel wire forming a reinforcing layer via a mercapto group, and binds to a polymer having an epoxy group by a ring-opening reaction of an epoxy group via another mercapto group in the same molecule. Is generated. That is, the bond between HNBR or AEM and the polymer having an epoxy group, the bond between the polymer having an epoxy group and the 2,4-dimercapto-6-substituted-1,3,5-triazine represented by the above formula 1 and the formula 1 The indicated 2,4-dimercapto-6-substituted-1,3,5-
Since the bonding of the triazine and the brass-plated reinforcing steel wire occurs simultaneously, the rubber composition A or B and the brass-plated reinforcing steel wire forming the reinforcing layer are bonded and integrated.
Further, some of the polymers having an epoxy group react with and bond to a brass-plated reinforcing steel wire. When a polymer having such an epoxy group is selected, the rubber composition A or B is reinforced. The connection with the brass-plated reinforcing steel wire forming the layer is stronger.

The rubber composition A or B may be used in addition to the above components, as long as the adhesiveness to the brass-plated reinforcing steel wire forming the reinforcing layer, the modulus, the set resistance and the heat resistance are not impaired. Accordingly, additives such as a crosslinking aid, a reinforcing agent, a filler, an antioxidant, a processing aid, a plasticizer, and a softener can be compounded.

It is preferable that triallyl isocyanurate and / or triallyl cyanurate be blended as a crosslinking aid because modulus and adhesion to metal are improved. Triallyl isocyanurate and triallyl cyanurate are trifunctional polymerizable monomers, and are used as a crosslinking aid of an organic peroxide-crosslinked rubber composition,
When used for the rubber composition A or B, the crosslinking density can be increased to improve the modulus. Only one of triallyl isocyanurate and triallyl cyanurate may be used, or both may be used in combination. Rubber composition A
Or triallyl isocyanurate in B and / or
Alternatively, the content of triallyl cyanurate depends on the content of the epoxy group in the polymer having an epoxy group, but is generally preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of HNBR or AEM.

Examples of the filler include silica (white carbon), calcium carbonate, barium sulfate, talc, clay, titanium oxide, carbon black and the like. Among them, silica is preferred. Silica is an acidic compounding agent and effectively contributes to the control of the reaction rate of 2,4-dimercapto-6-substituted-1,3,5-triazine represented by the above formula 1, and the physical properties of the rubber composition A or B And stabilizes adhesion. The silica (white carbon) is not particularly limited, and examples thereof include dry white carbon, wet white carbon, colloidal silica used as a filler for rubber, and precipitated silica described in JP-A-62-62838. No. Among them, wet-process white carbon mainly containing hydrous silicate is preferable. Wet process precipitated silica which is the main component of white carbon, nitrogen adsorption specific surface area (BET method) is 50 to 400 m ² / g, preferably may be mentioned suitably hydrated silicic acid 100 to 250 m ² / g. Further, the hydrous silicic acid preferably has a pH (hydrogen ion concentration) of less than 7.0.
It is more preferably 6.7 or less. When the pH is within the above range, 2,4-dimercapto-6-substituted-1,3,3 is used.
This is because an early reaction of 5-triazine can be suppressed.
The specific surface area of nitrogen adsorption was determined according to ASTM D3037 81
The pH is a value measured by a BET method according to the above, and the pH is a value obtained by stirring silica in water, filtering the solution, and then measuring the pH of the filtrate using a pH meter. The content of silica in the rubber composition A or B depends on the amount of the epoxy group in the polymer having an epoxy group, but is generally preferably 1 to 50 parts by mass with respect to 100 parts by mass of HNBR or AEM.

Although triallyl isocyanurate and / or triallyl cyanurate and silica are effective even if they are separately blended, a mixture containing triallyl isocyanurate and / or triallyl cyanurate and silica is heat-treated. It is particularly preferable to mix the resulting mixture into a solidified product. The solidified product is preferably triallyl isocyanurate or the like, preferably 30 to 80% by mass,
More preferably, it is a solidified substance present on the silica surface of 50 to 70% by mass. Details of this solidification are unknown,
Triallyl isocyanurate and / or triallyl cyanurate, which are polymerizable monomers, are formed by performing a heat treatment on the surface of silica particles, with a portion of the surface of the silica particles being subjected to a polymerization reaction using a hydroxyl group or the like present on the silica particle surface as a catalyst. It is thought that it was done. The conditions for the heat treatment are as follows:
Any conditions may be used as long as the triallyl isocyanurate and / or the triallyl cyanurate and the silica are solidified, but preferably at least 150 ° C, more preferably at a temperature of 160 to 200 ° C, preferably at least 10 minutes, More preferably, heating is performed in air for about 30 minutes to 24 hours. When the heat treatment conditions are in this range, a solid can be obtained efficiently.

The anti-aging agent is not particularly limited as long as it is a heat-resistant anti-aging agent, a weather-resistant anti-aging agent and the like which are usually used in rubber compositions. Examples thereof include naphthylamines (phenyl-α-naphthylamine and the like). , Diphenylamines (such as octylated diphenylamine), p-phenylenediamines (N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl)-
N'-phenyl-p-phenylenediamine, N, N'-
Amine-based antioxidants such as di-2-naphthyl-p-phenylenediamine and the like; 2,2,4-trimethyl-1,2-
A quinoline antioxidant such as a polymer of dihydroquinoline;
Monophenols (2,6-di-t-butyl-4-methylphenol, styrenated phenol, etc.), bis, tris, polyphenols (tetrakis- [methylene-3-)
(3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane and the like.

Examples of the softener include process oils such as paraffin, naphthene and aroma; plant oils such as castor oil, cottonseed oil, linseed oil, rapeseed oil, soybean oil, and palm oil, and rosin.

The plasticizer is, for example, diethyl phthalate,
Phthalates such as dibutyl phthalate, di- (2-ethylhexyl) phthalate and di-n-octyl phthalate; di- (2-ethylhexyl) adipate, di-
Synthetic plasticizers such as adipate esters such as (butoxyethoxyethyl) adipate; and trimellitate esters such as tri- (2-ethylhexyl) trimellitate.

Of the above-described first and second embodiments of the present invention, it is particularly preferable that the inner tube is made of the rubber composition A and the outer tube is made of the rubber composition B. This is the third embodiment. HNB used for rubber composition A
R is excellent in heat resistance and oil resistance and has a high modulus.
The acrylate copolymer rubber has a feature of being excellent in heat resistance and weather resistance. Therefore, the hose according to the third aspect of the present invention has an inner tube having excellent heat resistance and oil resistance, an outer tube having excellent heat resistance and weather resistance, and an adhesion between the inner tube and the outer tube and the reinforcing layer. It is particularly useful because it is excellent.

The case where the hose of the present invention is a reinforcing layer composed of one layer of brass-plated reinforcing steel wire and a hose composed of one inner tube and one outer tube has been described above. However, the present invention is not limited thereto, and the reinforcing layer and the inner tube and the outer tube may each be a multilayer.
In this case, in the first embodiment and the second embodiment of the present invention, at least one of the layers forming the inner tube and / or the outer tube, which is in close contact with the reinforcing layer, is the rubber composition A.
Or B may be sufficient. Further, in the third aspect of the present invention, it is preferable that, in the above configuration, the innermost layer of the inner tube is the rubber composition A, and the outermost layer of the outer tube is the rubber composition B.

The inner and outer diameters of the hose of the present invention are not particularly limited.

The thickness of the inner tube of the hose of the present invention is not particularly limited, but may preferably be 0.8 to 3.0 mm. Also, a layer of the inner tube of the hose of the present invention,
The thickness of the layer composed of the rubber composition A is preferably 0.8 to 2.5 mm, more preferably 0.8 to 2.0 m
m. Although the thickness of the outer tube of the hose of the present invention is not particularly limited, it can be preferably 0.5 to 3.0 mm. Further, the thickness of the layer which is one layer of the outer tube of the hose of the present invention and is composed of the rubber composition B is preferably 0.5 to 2.5 mm, more preferably 0.5 to 2.0 m.
m.

The method for producing the hose of the present invention is not particularly limited, and a conventional method for producing a hose can be used.
For example, an unvulcanized rubber composition A or B is extruded from an extruder onto a mandrel to which a release agent has been previously applied to form an inner tube. Next, a brass-plated reinforcing steel wire is braided on the inner tube using a braiding machine. Rubber composition A by extruder
Or extrude B to form an outer tube. Pressure is applied directly or by wrapping the hose using a tape or the like, and then vulcanization is performed by applying pressure. Finally pull out the mandrel,
The hose of the present invention can be obtained.

The hose of the present invention comprises a reinforcing steel wire having a reinforcing layer plated with brass, and is made of HNBR or AEM as an inner tube material or the like.
Hose that has excellent adhesion and heat resistance between the inner tube and the reinforcing layer and the heat resistance, and has sufficient modulus and set resistance, so it is used in a wide range of applications, especially hydraulic hoses, hot water hoses, steam hoses, etc. Can be suitably used.

[0039]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. 1. Preparation of Rubber Composition Using the raw materials shown below in the amounts shown in Table 1, each rubber composition shown in Table 1 was obtained. (1) Raw material rubber HNBR (hydrogenated acrylonitrile-butadiene copolymer rubber): a unit portion (Y portion; V) from unsaturated nitrile
CN, AN) 33.0% by mass, unit portion from conjugated diene (Z portion; C = C) 1.3% by mass, unit portion from ethylenically unsaturated monomer other than unsaturated nitrile and conjugated diene A unit portion obtained by hydrogenating the unit portion of (X portion;
C-C) 65.7% by mass, iodine value 6 AEM (ethylene-acrylate copolymer rubber): Esprene EMA-2152, manufactured by Sumitomo Chemical Co., Ltd. (2) Epoxy-containing polymer EMA-g-GMA (ethylene -Methyl acrylate-G
(MA copolymer rubber): Bond First 7L, manufactured by Sumitomo Chemical Co., Ltd. (3) Compounding agent SRF grade carbon black: Asahi # 50, zinc oxide (ZnO) stearic acid manufactured by Asahi Carbon Co. Antiaging agent: Nocrack MBZ, Ouchi Shinko Wax (WAX) manufactured by Chemical Co., Ltd .: Sunwax 171P, 2,4,6-trimercapto-1,3,5-triazine manufactured by Sanyo Kasei: ZISNET-F, triallyl isocyanurate (TAIC) diallyl manufactured by Sankyo Kasei Phthalate (DAP) (4) Crosslinking agent 1,3-bis (t-butylperoxyisopropyl) benzene: Percadox 14/40 (40% by mass),
Chemicals manufactured by Akzo

The following tests were conducted on the rubber composition obtained as described above. <Adhesion Test> The adhesion test was carried out in accordance with the provisions of JIS K6256 “90 ° Peeling Test of Metal Piece and Vulcanized Rubber”. Each of the obtained rubber compositions is formed into a sheet having a thickness of 2.5 mm by a laboratory roll, and combined with a brass plate,
Crimped. However, a cellophane paper was disposed in a portion to be gripped by the chuck during peeling, so that the upper and lower layers did not adhere. Then, it was vulcanized under pressure at a surface pressure of 3.0 MPa at 160 ° C. for 60 minutes using a laboratory press molding machine and integrated to obtain a test piece that was a composite of brass and rubber. After the test piece was left at room temperature for 24 hours, the test piece was cut into a width of 2.54 cm, and a peeling test for peeling the rubber composition from the brass plate was performed. The peel strength is measured according to JIS K6256.
The peel strength was measured using a tensile tester specified in JIS K6256 under the condition of a tensile speed of 50 mm / min in accordance with the rule of “90-degree peel test of metal piece and vulcanized rubber”. When the value of the peel strength was 150 N / 25 mm or more, it was determined that the adhesiveness was good.

<Tensile Stress (Modulus) Test> Each of the obtained rubber compositions was vulcanized under pressure at 160 ° C. for 60 minutes to form a sheet having a thickness of 2 mm. In accordance with the provisions of JIS K6251, a dumbbell-shaped No. 3 test piece was punched out of this sheet, and the test piece was cut out in accordance with the provisions of JIS K6251.
The% modulus (M ₁₀₀ ) was measured. When the value of the 100% modulus (M ₁₀₀ ) was 9.0 MPa or more, it was regarded as good.

<Set Resistance Test> Each of the obtained rubber compositions was vulcanized under pressure at 160 ° C. for 60 minutes, and was subjected to JIS K626.
2 “Permanent strain test method for vulcanized rubber and thermoplastic rubber”
In accordance with the provisions of Section 5, "Test method for compression set",
A large test piece specified in 5.3.1 of JIS K6262 was molded. JIS K6
262, a compression of 25% and a compression test of 150% in accordance with the provisions of "Test Method for Permanent Strain of Vulcanized Rubber and Thermoplastic Rubber".
The compression set was measured under aging conditions at 72 ° C. for 72 hours. When the value of the compression set was 60% or less, it was determined that the set resistance was good.

<Heat resistance test> Each of the obtained rubber compositions was
Pressure vulcanization was performed at 60 ° C. for 60 minutes to form a sheet having a thickness of 2 mm. In accordance with JIS K6257 “Aging test method for vulcanized rubber”, paragraph 4 “Aging test by air heating (normal oven method)”, dumbbell-shaped 3
No. 1 specimen was punched out and subjected to an air heating aging treatment at 150 ° C. for 168 hours in accordance with the provisions of JIS K6257, and the elongation at break before and after the treatment was measured. _B ) was calculated. When the value of the rate of change in elongation at break (ΔE _B ) was -50% or more, it was determined that the heat resistance was good.

The results are shown in Table 1. It can be seen that the rubber compositions A and B exhibit high adhesion to metal, have excellent heat resistance, and have sufficient modulus and set resistance. On the other hand, when the polymer having the 2,4-dimercapto-6-substituted-1,3,5-triazine and the epoxy group-containing polymer represented by the above formula 1 is lacking (rubber compositions 1 and 3)
Does not adhere to metal at all, and lacks only the latter (rubber compositions 2 and 4), but adheres very weakly,
Poor physical properties such as modulus.

[0045]

[Table 1]

2. Manufacture of hose A hose was manufactured using the materials shown below. (1) Inner tube Each rubber composition obtained above (2) Reinforcement layer Brass-plated braided steel wire braided layer One layer (1 W /
B) (3) Outer tube Each rubber composition obtained above

Using a rubber extruder, the rubber composition for the inner tube was extruded onto a mandrel having an outer diameter of 12.4 mm to which a release agent was previously applied to form an inner tube. Next, a brass-plated reinforcing steel wire was braided on the inner tube to form a reinforcing layer. Furthermore,
The outer tube rubber composition was extruded on the reinforcing layer using a rubber extruder to form an outer tube. Finally, the mandrel was pulled out to obtain each hose shown in Table 2. Each hose had an inner diameter of 12.7 mm and an outer diameter of 20.0 mm.

The following test was performed on the hose obtained as described above. <Fitting Attachment Test> The outer tube rubber of the fitting attaching portion of each hose was removed by puff, and a predetermined fitting was attached. At this time, the hose that could be fitted with the fitting was marked with a circle, and the reinforcing layer spread in the circumferential direction due to insufficient adhesion between the inner tube rubber and the reinforcing layer, making it difficult to attach the fitting. × hose
And was evaluated. In addition, the hose for which fittings were difficult to attach could not be subjected to the following evaluation.

<Durability Test> An impact pressure test was performed in accordance with the provisions of JIS K6330-8. Using test auto multi oil (made by Idemitsu Kosan Co., Ltd.), 150 ℃, 16M
The impact pressure was repeatedly applied under the condition of Pa, and the number of impacts until an abnormality occurred in the hose was determined. After 1 million shocks, no abnormality was evaluated as ○.

The results are shown in Table 2. Hose of the third aspect of the present invention using rubber composition A for the inner tube and rubber composition B for the outer tube (Example 1), and the present invention using rubber composition B for the inner and outer tubes It can be seen that the hose of the second aspect (Example 2) is excellent in fitting attachment and durability. On the other hand, when a rubber composition lacking the 2,4-dimercapto-6-substituted-1,3,5-triazine represented by the above formula 1 and a polymer having an epoxy group is used for the inner tube and the outer tube ( In Comparative Examples 1 and 3), since the inner tube and the outer tube and the reinforcing layer are not bonded, the outer diameter of the reinforcing layer becomes larger (the reinforcing layer expands in the circumferential direction) after the outer tube is removed, and the fitting is mounted. I couldn't do that. When only the polymer having an epoxy group is missing (Comparative Examples 2 and 4),
Since the adhesive strength between the inner tube and the outer tube and the reinforcing layer is weak, the fitting can be attached, but the durability is poor.

[0051]

[Table 2]

[0052]

The hose of the present invention has a reinforcing layer made of brass-plated reinforcing steel wire, has excellent adhesion and heat resistance between the inner tube and the reinforcing layer, and has sufficient modulus and set resistance. , A hydraulic hose, a hot water hose, a steam hose and the like.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/378 C08K 5/378 C08L 9/02 C08L 9/02 63/00 63/00 A (72) Invention Person Takeshi Inoue 2-1 Oiwake, Hiratsuka-shi, Kanagawa Prefecture F-term in the Hiratsuka Works of Yokohama Rubber Co., Ltd. AK28B AK28J AK53B AK53C AK53J AK71C AL01B AL01C AL01J AL05B AN02B AN02C AN02J BA03 BA07 BA10B BA10C CA30B CA30C DA11 DC16A DH00A EH71A GB31 GB51 JB20B JJ03 JK07 JE11 BG01 EB01 EB01 EB01 EB01 EB01 EB01

Claims (3)

[Claims] 1. A reinforcing layer comprising a brass-plated reinforcing steel wire and a hose comprising an inner tube and an outer tube, wherein the inner tube and / or the outer tube comprises: (1) an unsaturated nitrile in a polymer chain; Unit part (Y part; VCN) of 10 to 45
Mass%, unit part from conjugated diene (Z part; C = C)
0 to 5% by mass and a unit portion obtained by hydrogenating a unit portion from an ethylenically unsaturated monomer other than an unsaturated nitrile and / or a unit portion from a conjugated diene (X portion; C-
C) 100 parts by mass of a copolymer rubber having an iodine value of 15 or less having 90 to 50% by mass, (2) 1 to 10 parts by mass of an organic peroxide, (3) 2,4-dimercapto represented by the following formula 1
The rubber composition A comprises 0.1 to 15 parts by mass of 6-substituted-1,3,5-triazine and (4) 1 to 100 parts by mass of a polymer having an organic peroxide crosslinkable epoxy group. Features hose. Embedded image Wherein R is a group selected from the group consisting of a mercapto group, an alkoxy group, a monoalkylamino group, a dialkylamino group, a monocycloalkylamino group, a dicycloalkylamino group, and an N-alkyl-N-arylamino group. Represents.) 2. A reinforcing layer comprising a brass-plated reinforcing steel wire and a hose comprising an inner tube and an outer tube, wherein the inner tube and / or the outer tube are made of (1) ethylene-acrylate copolymer rubber 100. Parts by mass, (2) 1 to 10 parts by mass of an organic peroxide, (3) 2,4-
Dimercapto-6-substituted-1,3,5-triazine
A hose comprising a rubber composition B containing 1 to 15 parts by mass and (4) 1 to 100 parts by mass of a polymer having an epoxy group capable of crosslinking with an organic peroxide. Embedded image Wherein R is a group selected from the group consisting of a mercapto group, an alkoxy group, a monoalkylamino group, a dialkylamino group, a monocycloalkylamino group, a dicycloalkylamino group, and an N-alkyl-N-arylamino group. Represents.) 3. A hose comprising a reinforcing layer made of brass-plated reinforcing steel wire and an inner tube and an outer tube, wherein the inner tube is made of the rubber composition A according to claim 1, and the outer tube is made of a hose. 3. A hose comprising the rubber composition B according to 2.