JP2002181254A - Hose - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hose excellent in adhesion between a polyamide resin layer and a rubber layer without applying an adhesive to the interface between the polyamide resin layer and the rubber layer. SOLUTION: This hose has a laminated structure of the rubber layer 2 formed of a rubber composition containing the following (A)-(D) as essential components and the layer 1 formed of polyamide resin. (A) Rubber formed of at least one of ethylene-propylene-diene ternary copolymer and ethylene-propylene copolymer (B) Peroxide vulcanizer, (C) Resorcinol-based compound, and (D) Melamine resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to hoses, and more particularly, to gasoline fuel hoses, hoses for fuel cell vehicles (methanol fuel hoses, hydrogen fuel hoses), engine cooling system hoses (radiator hoses, heater hoses, etc.), The present invention relates to an automotive hose such as a refrigerant transfer hose for a cooler.

[0002]

2. Description of the Related Art Conventionally, as hoses for automobiles such as gasoline fuel hoses, for example, ethylene-propylene is used on the outer peripheral surface of a polyamide resin layer (inner layer) because of battery resistance, chipping resistance and flame resistance. -A hose having a rubber layer (outer layer) based on a diene terpolymer (EPDM) is used.

[0003]

However, in the conventional hose described above, the polyamide resin layer (inner layer) is directly inserted into the rubber layer (outer layer), or an adhesive is applied to the outer peripheral surface of the polyamide resin layer (inner layer). And, because a rubber layer (outer layer) is formed on it,
There is a problem that the adhesive force between the polyamide resin layer and the rubber layer is insufficient, and the sealing property is poor. In addition, since an adhesive coating process is required, the manufacturing process is complicated and the cost is increased. In addition, there is a problem that the pot life of the adhesive is required, the concentration must be controlled, and the stable productivity is poor. Furthermore, since an organic solvent such as toluene is used as a solvent for diluting the adhesive, there is a problem of environmental pollution and the like.

The present invention has been made in view of such circumstances, and a hose having excellent adhesion between a polyamide resin layer and a rubber layer without applying an adhesive to the interface between the polyamide resin layer and the rubber layer. The purpose is to provide.

[0005]

Means for Solving the Problems In order to achieve the above object, the hose of the present invention comprises a rubber layer comprising a rubber composition containing the following (A) to (D) as essential components, and a polyamide resin. It has a structure of having a laminated structure with the formed layer. (A) A rubber comprising at least one of an ethylene-propylene-diene terpolymer and an ethylene-propylene copolymer. (B) a peroxide vulcanizing agent. (C) a resorcinol compound. (D) Melamine resin.

That is, the present inventors have conducted intensive studies to obtain a hose having excellent adhesion between the polyamide resin layer and the rubber layer without applying an adhesive to the interface between the polyamide resin layer and the rubber layer. Was. Recalling that the adhesive component was kneaded into the rubber composition, which is a material for the rubber layer, we continued research and development on a combination of rubber and adhesive components with excellent adhesive properties. Focusing on EPDM and ethylene-propylene copolymer (hereinafter abbreviated as “EPM”), which are cheap in terms of cost, knead a specific adhesive component (resorcinol compound and melamine resin) into this, and vulcanize it with peroxide. It has been found that vulcanization using an agent gives excellent adhesion to the polyamide resin layer, and the present invention has been achieved. The reason why the rubber layer made of the special rubber composition has excellent adhesive strength with the polyamide resin layer is presumed as follows. The resorcinol-based compound mainly acts as an adhesive, the melamine resin mainly acts as an adhesion aid, and the resorcinol-based compound is provided with CH ₂ O from the melamine resin, which is a polyamide bond (−) of the polyamide resin. CON
It is thought that the cohesive bond with H-) improves the adhesive strength. For example, a resorcinol compound represented by the following general formula (C) is converted from melamine resin to CH ₂ O.
To form a structure represented by the following general formula (C ′), which is covalently bonded to a polyamide bond (—CONH—) of a polyamide resin and strongly adheres as shown in the following reaction formula. Seem. In addition, a part of the hydroxyl group of the resorcinol-based compound is hydrogen-bonded with a polyamide bond of the polyamide resin, and it is considered that this hydrogen bond is also involved in improving the adhesive effect.

[0007]

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[0008]

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[0009]

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The resorcinol compound (C)
When the compounding ratio between the rubber layer and the melamine resin (D) is set in a predetermined range, the adhesion between the rubber layer and the polyamide resin layer is improved.

Further, when the compounding ratio of the resorcinol compound (C) to the specific rubber (A) is set within a predetermined range, the adhesion between the rubber layer and the polyamide resin layer is improved.

[0012]

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

As the hose of the present invention, for example, a hose in which a rubber layer 2 made of a special rubber composition is formed on the outer peripheral surface of a polyamide resin layer 1 as shown in FIG. The hose having such a configuration is suitably used as an engine cooling system hose such as a radiator hose or a heater hose in a vehicle such as an automobile.

The polyamide resin used as the material for the polyamide resin layer 1 is not particularly limited, such as an aliphatic resin or an aromatic resin. Examples thereof include a lactam polymer, a condensate of a diamine and a dicarboxylic acid, and a polymer of an amino acid. And their copolymers and blends. Specifically, nylon 6, nylon 11, nylon 12, nylon 610, nylon 612, polyphthalamide, a copolymer of nylon 6 and nylon 66 or a blend of two or more of these, a viscous mineral (nanocomposite) ) Are preferably used.

The special rubber composition as the material for the rubber layer 2 includes a specific rubber (A component), a peroxide vulcanizing agent (B component), a resorcinol compound (C component), and a melamine resin. (D component).

As the specific rubber (component A), at least one of an ethylene-propylene-diene terpolymer (EPDM) and an ethylene-propylene copolymer (EPM) is used. The EPDM is not particularly limited as long as it is used as a base material of the rubber composition, but preferably has an iodine value in a range of 6 to 30, and an ethylene ratio in a range of 48 to 70% by weight, Preferably, the iodine value is in the range of 10 to 24, and the ethylene ratio is 50.
-60% by weight.

The diene monomer (third component) contained in the EPDM is not particularly limited, but has 5 to 5 carbon atoms.
20 diene monomers are preferred.
4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 2,5-dimethyl-1,5-hexadiene, 1,4-octadiene, 1,4-cyclohexadiene, cyclooctadiene, dicyclopentadiene (DC
P), 5-ethylidene-2-norbornene (ENB),
5-butylidene-2-norbornene, 2-methallyl-5
-Norbornene, 2-isopropenyl-5-norbornene and the like. Among these diene monomers (third component), dicyclopentadiene (DCP), 5
-Ethylidene-2-norbornene (ENB) is preferred.

The peroxide vulcanizing agent (component B) used together with the specific rubber (component A) includes, for example, 2,2.
4-dichlorobenzoyl peroxide, benzoyl peroxide, 1,1-di-t-butylperoxy-3,
3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-dibenzoylperoxyhexane, n-butyl-4,4'-di-t-butylperoxyvalerate,
Dicumyl peroxide, t-butylperoxybenzoate, di-t-butylperoxy-diisopropylbenzene, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di-t-butylperoxyhexane,
Di-t-butyl peroxide, 2,5-dimethyl-
2,5-di-t-butylperoxyhexine-3 and the like. These may be used alone or in combination of two or more. Among them, odor is not a problem,
t-Butylperoxy-diisopropylbenzene is preferably used.

The mixing ratio of the peroxide vulcanizing agent (component B) is in the range of 1.5 to 20 parts with respect to 100 parts by weight (hereinafter abbreviated as "parts") of the specific rubber (component A). Is preferred. That is, when the B component is less than 1.5 parts, the crosslinking is insufficient and the strength of the hose is inferior. On the contrary, when the B component exceeds 20 parts, the hardness tends to be too hard and the hose is inferior in flexibility. Because it can be done.

The resorcinol compound (component C) used together with the above components A and B is not particularly limited as long as it mainly acts as an adhesive. For example, modified resorcin / formaldehyde resin, resorcin, Formaldehyde (RF) resin and the like. These may be used alone or in combination of two or more. Among these, modified resorcinol-formaldehyde resin is preferably used in terms of transpiration, hygroscopicity, and compatibility with rubber.

Examples of the modified resorcinol-formaldehyde resin include those represented by the following general formulas (1) to (3). Among them, those represented by the following general formula (1) are particularly preferable.

[0022]

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[0023]

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[0024]

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The compounding ratio of the resorcinol compound (component C) is preferably in the range of 0.1 to 10 parts, more preferably 0.5 to 5 parts, per 100 parts of the specific rubber (component A). It is. That is, if the C component is less than 0.1 part, the adhesion to the polyamide resin layer is poor, and
If the amount of the component exceeds 10 parts, the cost is increased.

The melamine resin (component D) used together with the above components A to C is not particularly limited as long as it mainly acts as an adhesion aid. For example, a methylated formaldehyde / melamine polymer, hexamethylene Tetramine and the like. These may be used alone or in combination of two or more. Among these, a methylated formaldehyde / melamine polymer is preferably used in view of its transpiration, hygroscopicity, and compatibility with rubber.

As the methylated formaldehyde / melamine polymer, for example, those represented by the following general formula (4) are preferably used.

[0028]

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Among the melamine resins (component D), a mixture of the compounds represented by the above general formula (4) is preferable. The compound of n = 1 is 43 to 44% by weight, and n = 2.
27 to 30% by weight of the compound of the formula
A mixture of 30% by weight is particularly preferred.

The compounding ratio of the resorcinol compound (component C) to the melamine resin (component D) is preferably in the range of C / D = 1 / 0.5 to 1/2 by weight. And particularly preferably C component / D component = 1 / 0.77-
1 / 1.5. That is, the weight ratio of the D component is 0.5
If it is less than the tensile strength (TB) and elongation (E) of the rubber layer,
B) and the like tend to be slightly deteriorated. Conversely, when the weight ratio of the D component exceeds 2, the adhesiveness is saturated and the adhesive force is stabilized, so that even if the weight ratio of the D component is further increased, This is because it only leads to an increase in cost, and no further effect can be expected.

The above-mentioned special rubber composition includes the above-mentioned A
It is preferable to mix carbon black, process oil and the like in addition to the components D to D.

Further, in addition to the above components, the special rubber composition may optionally contain an antioxidant, a processing aid, a crosslinking accelerator, a white filler, a reactive monomer, a foaming agent, and the like, if necessary. It can be mixed.

The above-mentioned special rubber composition is prepared by blending the above-mentioned components A to D and other components as necessary, and kneading them using a kneading machine such as a roll, kneader, or Banbury mixer. Can be.

The hose shown in FIG. 1 can be manufactured, for example, as follows. That is, first, the polyamide resin is extruded to form the polyamide resin layer 1. Next, after extruding the special rubber composition, vulcanization is performed to form the rubber layer 2, whereby a target hose can be manufactured.

The hose shown in FIG. 1 is not limited to the above manufacturing method, but is formed by co-extrusion of a polyamide resin layer 1 made of a polyamide resin and a rubber layer 2 made of a special rubber composition. It is also possible.

The thickness of each layer of the hose thus obtained varies depending on the use of the hose, but the thickness of the polyamide resin layer 1 is usually 0.1 to 1.5 mm, preferably 0.3 to 1.5 mm. 1.2 mm, the thickness of the rubber layer 2 is usually 0.5 to 4.0 mm, preferably 1.0 to
3.0 mm. The inner diameter of the hose varies depending on the application, but is usually 2 to 60 mm, preferably 4 to 60 mm.
５０50 mm.

The hose of the present invention is not limited to the two-layer structure of the polyamide resin layer 1 and the rubber layer 2 as shown in FIG. 1, but has a laminated structure of the polyamide resin layer and the rubber layer. Any configuration is acceptable. For example, as shown in FIG. 2, an adhesive layer 22 is formed on the outer peripheral surface of the polyolefin-based resin layer 21, and the polyamide resin layer 1 is formed on the outer peripheral surface of the adhesive layer 22.
Further, a hose in which a rubber layer 2 is formed on the outer peripheral surface of the polyamide resin layer 1 can be used.

The material for the polyolefin resin layer 21 is not particularly limited, and examples thereof include polypropylene, polyethylene, polybutylene, and polybutene. Among them, polypropylene is preferably used in terms of heat resistance.

The material for the adhesive layer 22 is not particularly limited, and examples thereof include modified materials such as acid-modified polypropylene, acid-modified polyethylene, amine-modified polypropylene, amine-modified polyethylene, silane-modified polypropylene, and silane-modified polyethylene. And the like.

The hose shown in FIG. 2 is, for example, formed by extruding three layers of a material for the polyolefin resin layer 21, a material for the adhesive layer 22, and a polyamide resin to form an outer peripheral surface of the polyolefin resin layer 21. A hose having the adhesive layer 22 formed thereon and the polyamide resin layer 1 formed on the outer peripheral surface of the adhesive layer 22 is manufactured. Subsequently, after extruding the above special rubber composition, it is vulcanized to obtain a rubber layer 2.
By forming the above, the desired hose can be manufactured.

Further, as still another example of the hose of the present invention, for example, as shown in FIG. 3, a reinforcing layer 31 is formed on the outer peripheral surface of the rubber layer 2 of the hose shown in FIG. A hose in which a general-purpose rubber layer 32 is formed on the outer peripheral surface is exemplified.

As the material for the reinforcing layer 31, for example,
Examples include vinylon yarn, polyamide yarn (nylon) yarn, aramid yarn, polyethylene terephthalate (PET) yarn, and wire.

Examples of the material for the general-purpose rubber layer 32 include EPDM, butyl rubber (IIR), halogenated butyl rubber (Cl-IIR, Br-IIR), isoprene rubber (IR), urethane rubber, chloroprene rubber (C
R), epichlorohydrin rubber (ECO), general-purpose rubber such as fluororubber. Among them, EPDM is preferably used because it is relatively inexpensive.

The hose shown in FIG. 3 can be manufactured, for example, as follows. That is, first, in the same manner as in FIG. 2, the adhesive layer 22 is formed on the outer peripheral surface of the polyolefin-based resin layer 21, the polyamide resin layer 1 is formed on the outer peripheral surface of the adhesive layer 22, and the polyamide resin layer 1 is further formed. A hose having the rubber layer 2 formed on the outer peripheral surface of the above is manufactured. Next, a reinforcing layer 31 is formed by braiding vinylon yarn or the like on the outer peripheral surface of the rubber layer 2. Subsequently, after extruding a general-purpose rubber such as EPDM on the outer peripheral surface of the reinforcing layer 31, vulcanization is performed to perform general-purpose rubber layer 3.
By forming 2, a desired hose can be manufactured.

The hose of the present invention can be used to connect gasoline fuel hoses, fuel cell vehicle hoses (methanol fuel hoses, hydrogen fuel hoses), and the connection between the engine and radiator in vehicles such as automobiles by appropriately selecting the configuration of each layer. It can be suitably used as a radiator hose to be used, an engine cooling system hose such as a heater hose used for connecting an engine to a heater core, and an automobile hose such as a refrigerant transfer hose for a cooler. Since EPDM is inferior in gasoline resistance, when used as a gasoline fuel hose, it is desirable to use a rubber layer made of a special rubber composition as a layer other than the inner layer (for example, an outer layer).

Next, examples will be described together with comparative examples.

First, prior to Examples and Comparative Examples, the following rubber compositions were prepared.

[Rubber Composition A] As a specific rubber (component A), EPDM (Esplen 501 manufactured by Sumitomo Chemical Co., Ltd.) is used.
A) 100 parts of [iodine value: 12, ethylene ratio: 50% by weight, Mooney viscosity (ML1 + 4 100 ° C): 43] and carbon black (Tokai Carbon Co., Ltd., Seast S
O) 100 parts, process oil (manufactured by Idemitsu Kosan Co., Diana Process PW-380) 60 parts, and di-t-butylperoxy-diisopropylbenzene (manufactured by NOF Corporation) as a peroxide vulcanizing agent (component B) Peroximon F-4
0) 4.2 parts and a modified resorcinol-formaldehyde resin represented by the general formula (1) as a resorcinol-based compound (component C) (Sumikanol 6 manufactured by Sumitomo Chemical Co., Ltd.)
20) 1 part and 0.77 part of a methylated formaldehyde / melamine polymer (Sumitomo Chemical Co., Ltd., Sumikanol 507A) as a melamine resin (D component),
The rubber composition was prepared by kneading using a roll.

[Rubber Composition B] The mixing ratio of Sumikanol 620 was changed to 5 parts and the mixing ratio of Sumikanol 507A was changed to 3.85 parts. Except for this, the rubber composition was prepared in the same manner as the rubber composition A.

[Rubber Composition C] The mixing ratio of Sumikanol 620 was changed to 10 parts, and the mixing ratio of Sumikanol 507A was changed to 3.85 parts. Except for this, the rubber composition was prepared in the same manner as the rubber composition A.

[Rubber Composition D] A rubber composition was prepared in the same manner as the rubber composition A, except that the mixing ratio of Sumikanol 507A was changed to 0.5 part.

[Rubber Composition E] A rubber composition was prepared in the same manner as the rubber composition A, except that the mixing ratio of Sumikanol 507A was changed to 2 parts.

[Rubber Composition F] The mixing ratio of Sumikanol 620 was changed to 0.1 part and the mixing ratio of Sumikanol 507A was changed to 0.05 part. Except for this, the rubber composition was prepared in the same manner as the rubber composition A.

[Rubber Composition G] A rubber composition was prepared in the same manner as the rubber composition A except that EPM (Esprene 201, manufactured by Sumitomo Chemical Co., Ltd.) was used instead of EPDM (Esprene 501A, manufactured by Sumitomo Chemical Co., Ltd.). A composition was prepared.

[Rubber Composition a] Both Sumikanol 620 and Sumikanol 507A were not blended. Except for this, the rubber composition was prepared in the same manner as the rubber composition A.

[Rubber Composition b] A rubber composition was prepared in the same manner as in Rubber Composition A except that Sumikanol 507A was not blended.

[Rubber Composition c] Sumikanol 620 was not added, and the mixing ratio of Sumikanol 507A was changed to 1 part. Except for this, the rubber composition was prepared in the same manner as the rubber composition A.

[Rubber Composition d] Instead of 4.2 parts of a peroxide vulcanizing agent (component B), tetramethylthiuram disulfide as a vulcanization accelerator (Suncellar T, manufactured by Sanshin Chemical Co., Ltd.)
T) 0.75 part, zinc dimethyldithiocarbamate (Sanshin Chemical Co., Suncellar PZ) 0.75 part, mercaptobenzothiazole (Sanshin Chemical Co., Suncellar M) 0.5 part, sulfur ( 1.5 parts of a sulfurizing agent). Except for this, the rubber composition was prepared in the same manner as the rubber composition A.

Next, a hose was manufactured using the above rubber composition as follows.

[0060]

Example 1 First, polyamide 6 was extruded to form a polyamide resin layer (inner diameter 6 mm, thickness 1 mm). Next, the rubber composition A is extruded on the surface and vulcanized at 160 ° C. for 45 minutes to form a rubber layer (2 mm thick).
By forming a hose, the target hose (see FIG. 1)
Was manufactured.

[0061]

Examples 2 to 7 and Comparative Examples 1 to 5 Hoses were prepared in the same manner as in Example 1 except that the rubber composition as the material for the outer layer was changed to the rubber compositions shown in Tables 1 and 2 below. Was manufactured. In Comparative Example 2, a rubber layer was formed after applying an adhesive (rubber-based adhesive) to the surface of the polyamide resin layer.

[0062]

Example 8 First, polypropylene (Noblene, manufactured by Sumitomo Chemical Co., Ltd.) which is a material for a polyolefin resin layer
And three layers of acid-modified polypropylene (Admer QF500, manufactured by Mitsui Chemicals, Inc.), which is a material for the adhesive layer, and polyamide 6, which are co-extruded to form a polyolefin resin layer (inner diameter 25 mm, thickness 0.5 mm). A hose having an adhesive layer (thickness 0.1 mm) formed thereon and a polyamide resin layer (thickness 1.0 mm) formed on the outer peripheral surface of the adhesive layer was produced. Next, the rubber composition A was extruded on the surface and vulcanized at 150 ° C. for 60 minutes to form a rubber layer (thickness 4).
mm) to form the desired hose (Fig. 2).
) Was manufactured.

[0063]

Embodiment 9 An adhesive layer (thickness 0.1 mm) was formed on the outer peripheral surface of a polyolefin resin layer (inner diameter 25 mm, thickness 0.5 mm) in the same manner as in Example 8, and a polyamide was formed on the outer peripheral surface of the adhesive layer. A resin layer (1.0 mm thick) is formed,
Further, a rubber layer (thickness 4) is formed on the outer peripheral surface of the polyamide resin layer.
mm) (see FIG. 2). Next, a thickness of 1670 dte was applied to the outer peripheral surface of the rubber layer.
The reinforcing layer was formed by braiding x vinylon yarn (manufactured by Kuraray Co., Ltd., vinylon # 7903). Then, E on the surface
A target hose (see FIG. 3) was produced by extruding PDM (Esplen 501A, manufactured by Sumitomo Chemical Co., Ltd.) and vulcanizing at 150 ° C. for 60 minutes to form a general-purpose rubber layer (2 mm thick). .

Using the hoses of the example product and the comparative example product thus obtained, each characteristic was evaluated according to the following criteria. These results are shown in Tables 1 and 2 below.
Are also shown. In addition, the tensile strength (T
B) and elongation (EB) are also shown.

[Tensile Strength (TB), Elongation (EB)] The above rubber composition was press-vulcanized at 160 ° C. for 45 minutes to produce a vulcanized rubber sheet having a thickness of 2 mm. Then, JIS
No. 5 dumbbell was punched out, and the tensile strength (TB) and elongation (EB) were evaluated according to JIS K6301.
As for the tensile strength (TB) and elongation (EB), the larger the value, the better.

[Adhesiveness] A sample (20 mm in width and 100 mm in length) was cut out from the above hose for adhesion evaluation, attached to a tensile tester (JIS B 7721), the rubber layer side was fixed, and the polyamide resin layer side was fixed. Was pulled at a speed of 50 mm / min, and the adhesive strength (kg / 25 mm) was evaluated. Further, at that time, the peeling state of the rubber layer and the polyamide resin layer was also visually observed.

[Comprehensive evaluation] A sample which does not require the application of an adhesive to the interface between the rubber layer and the polyamide resin layer and has an excellent adhesive force between the rubber layer and the polyamide resin layer is evaluated as "O". Despite the adhesive applied to the interface between the rubber layer and the polyamide resin layer, the adhesive strength is poor, or the adhesive between the rubber layer and the polyamide resin layer does not need to be coated with an adhesive, Those having poor adhesion between the layer and the polyamide resin layer were evaluated as x and comprehensively evaluated.

[0068]

[Table 1]

[0069]

[Table 2]

From the above results, since the hoses of all Examples use a special rubber composition comprising a resorcinol compound and a melamine resin in combination, the adhesion between the rubber layer and the polyamide resin layer is extremely low. It turns out that it is high. In addition,
The hoses of Examples 8 and 9 had the same results as those of Example 1.

On the other hand, since the hose of Comparative Example 1 used the rubber composition a containing no adhesive component,
It can be seen that the adhesive strength is extremely low. The hose of Comparative Example 2 has an adhesive applied to the interface between the polyamide resin layer and the rubber layer, but has a lower adhesive strength than the hose of Example.
It can be seen that interfacial peeling occurs. Since the hose of Comparative Example 3 contains the rubber composition b containing only the resorcinol compound and not containing the melamine resin, the hose has low adhesive strength and peels off at the interface. Comparative Example 4
Since the hose of the product is made of the rubber composition c containing only the melamine resin and not containing the resorcinol compound, the adhesive strength is low, and it can be seen that interfacial peeling occurs. The hose of Comparative Example 5 contains an adhesive component, but has a low adhesive strength and an interfacial peel because it uses a rubber composition containing a sulfur-based vulcanizing agent instead of a peroxide vulcanizing agent. It can be seen that this occurs. This is presumed to be because the sulfur-based vulcanizing agent has a higher vulcanization rate than the peroxide vulcanizing agent, and the rubber layer itself vulcanizes before adhering to the polyamide resin layer. You.

[0072]

As described above, the hose of the present invention has a laminated structure of a rubber layer made of a special rubber composition and a polyamide resin layer, and the rubber layer itself has adhesiveness. Even if no adhesive is applied to the interface between the rubber layer and the polyamide resin layer, the adhesiveness between the rubber layer and the polyamide resin layer is excellent. In addition, since there is no need for an adhesive application step (so-called adhesive-less), there is no need to worry about pot life of the adhesive or concentration control, etc., and it is excellent in stable productivity and an organic solvent which is a solvent for diluting the adhesive. Because there is no need to use, there is no problem such as environmental pollution. Furthermore, since the vulcanization is performed using a peroxide vulcanizing agent instead of the conventional sulfur vulcanization system, the blending of zinc oxide can be made unnecessary (zinc-free). Even when used as an inner layer of a hose, it is possible to eliminate hose problems such as clogging of the hose and leakage of liquid at the seal portion.

When the compounding ratio of the resorcinol compound (C) and the melamine resin (D) is set within a predetermined range, the adhesive strength between the rubber layer and the polyamide resin layer is improved.

Further, when the compounding ratio of the resorcinol compound (C) to the specific rubber (A) is set within a predetermined range, the adhesive strength between the rubber layer and the polyamide resin layer is improved.

[Brief description of the drawings]

FIG. 1 is a sectional perspective view showing an example of a hose of the present invention.

FIG. 2 is a perspective view showing another example of the hose of the present invention.

FIG. 3 is a perspective view showing still another example of the hose of the present invention.

[Explanation of symbols]

 1 polyamide resin layer 2 rubber layer

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08K 5/14 C08K 5/14 C08L 23/16 C08L 23/16 61/12 61/12 61/28 61 / 28 (72) Inventor Kazutaka Katayama 3-1, Higashi 3-chome, Komaki City, Aichi Prefecture F-term (reference) 3H111 AA02 BA12 BA13 BA15 BA34 CA52 CB03 CB05 CB07 CC01 CC19 CC20 DA26 DB03 DB08 EA04 4F100 AK34A AK36A AK46BAK64A AK75A AL05A AN00A BA02 CA02A DA11 EH17 GB32 JL11 4J002 BB151 CC042 CC072 CC183 EJ017 EK006 EK036 EK046 EK056 EK066 GN00

Claims (3)

[Claims] 1. A hose having a laminated structure of a rubber layer comprising a rubber composition comprising the following (A) to (D) as essential components and a layer formed of a polyamide resin. (A) A rubber comprising at least one of an ethylene-propylene-diene terpolymer and an ethylene-propylene copolymer. (B) a peroxide vulcanizing agent. (C) a resorcinol compound. (D) Melamine resin. 2. The weight mixing ratio of (C) and (D) is as follows:
2. The hose according to claim 1, wherein (C) / (D) = 1 / 0.5 to 1/2. 3. The compounding ratio of (C) is (A) 1
The hose according to claim 1 or 2, wherein the amount is set in the range of 0.1 to 10 parts by weight with respect to 00 parts by weight.