JP2002213656A - Fuel hose - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fuel hose permitting proper adhesion between a resin layer and a rubber layer, without using an adhesive and having a superior fuel barrier property to gasoline fuel. SOLUTION: The fuel hose comprises a laminated structure of the rubber layer 2, formed of a rubber composition requiring following (A)-(D) components as essential components and a blended resin layer 1: (A) a rubber, consisting of at least one of ethylene-propylene-diene terpolymer and ethylene-propylene copolymer, (B) a peroxide vulcanizing agent, (C) a resorcinol compound, and (D) a melamine resin. The blended resin layer 1 is formed of a blended resin, with a fuel barrier resin blended into a base material consisting of at least one of a polyamide resin and an ethylene-vinylalcohol copolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fuel hose used for a gasoline fuel hose of an automobile.

[0002]

2. Description of the Related Art Conventionally, as a fuel hose used for a gasoline fuel hose of an automobile, for example, a resin layer (inner layer) made of a polyamide resin or the like in consideration of battery resistance, chipping resistance, and flame resistance. ), An ethylene-propylene-diene terpolymer (hereinafter referred to as “EP
A fuel hose having a rubber layer (outer layer) based on DM (abbreviated as "DM") is used. The fuel hose having such a configuration is usually manufactured by applying an adhesive to an outer peripheral surface of a resin layer (inner layer) and forming a rubber layer (outer layer) thereon. Therefore, there is a problem that the adhesive strength between the resin layer and the rubber layer is insufficient due to uneven application of the adhesive 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.

In order to solve this problem, the applicant of the present invention has proposed a rubber composition as a material for a rubber layer in order to obtain a fuel hose having excellent adhesion between a resin layer and a rubber layer without using an adhesive. As a result of repeated research on the use of a special rubber composition containing EPDM, a peroxide vulcanizing agent, a resorcinol compound and a melamine resin as essential components, the resin layer and the rubber layer can be used without using an adhesive. And found that the above-mentioned special rubber composition was applied for a patent (Japanese Patent Application No. 2000-304079).

[0004]

However, when a fuel hose formed by bonding a resin layer and a rubber layer using the special rubber composition described in Japanese Patent Application No. 2000-304079, the resin layer is Fuel barrier properties (penetration resistance) for gasoline fuel etc., although excellent in adhesion to rubber layer
Was found to be inferior.

[0005] The present invention has been made in view of such circumstances, and it is possible to satisfactorily bond a resin layer and a rubber layer without using an adhesive, and to provide a fuel barrier property against gasoline fuel and the like. Its purpose is to provide excellent fuel hoses.

[0006]

In order to achieve the above-mentioned object, a fuel hose of the present invention comprises a rubber layer comprising a rubber composition comprising the following (A) to (D) as essential components; Having a laminated structure with a layer, and the blended resin layer is formed of a blended resin obtained by blending a fuel barrier resin with a base material composed of at least one of a polyamide resin and an ethylene-vinyl alcohol copolymer. Configuration. (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 developed a fuel hose which can bond a resin layer and a rubber layer satisfactorily without using an adhesive, and which has excellent fuel barrier properties against gasoline fuel and the like. We continued our research. And
A blended resin layer obtained by blending a fuel barrier resin with a base material composed of at least one of a polyamide resin and an ethylene-vinyl alcohol copolymer (hereinafter abbreviated as “EVOH”), and a rubber layer composed of the special rubber composition The present inventors have found that a fuel hose having a laminated structure with the above can achieve the intended purpose, and have reached the present invention. The reason why the rubber layer made of the special rubber composition has excellent adhesive strength with the blend resin layer is presumed as follows. The resorcinol compound mainly acts as an adhesive, and the melamine resin mainly acts as an adhesion aid,
The resorcinol compound is converted from melamine resin to CH ₂
O is provided, and it is considered that the adhesive force is improved by covalently bonding to the polyamide bond (—CONH—) or EVOH of the polyamide resin which is the base material of the blend resin layer. For example, a resorcinol compound represented by the following general formula (C) is converted from melamine resin to CH ₂
O is supplied 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. I think that the. 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.

[0008]

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[0009]

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[0010]

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Further, when at least one of polyphenylene sulfide (PPS) and polybutylene naphthalate (PBN) is used as the fuel barrier resin,
Fuel barrier properties against gasoline fuel and the like are further improved.

When the weight mixing ratio of the base material composed of at least one of the above polyamide resin and ethylene-vinyl alcohol copolymer (EVOH) and the fuel barrier resin is controlled to a specific range, the fuel barrier property and the adhesion are improved. The balance with the properties is further improved.

When a fuel barrier layer made of a fuel barrier resin is formed on the inner peripheral surface of the blend resin layer, the fuel barrier property against gasoline fuel and the like is further improved.
In this case, by using the same material for the fuel barrier resin used for the blended resin layer and the fuel barrier resin used for the fuel barrier layer, the adhesive strength between the blended resin layer and the fuel barrier layer is improved. More preferred.

[0014]

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

The fuel hose of the present invention comprises, for example, as shown in FIG. 1, a rubber layer 2 made of a special rubber composition formed on the outer peripheral surface of a blended resin layer 1.

The blend resin as the material for the blend resin layer 1 is obtained by blending a base material composed of at least one of a polyamide resin and an ethylene-vinyl alcohol copolymer (EVOH) with a fuel barrier resin. As described above, by blending the fuel barrier resin with the base material, compared to the case where the base material is used alone,
Good fuel barrier properties against gasoline fuel and the like.

The polyamide resin is not particularly limited as long as it is a polymer compound having a polyamide bond (—CONH—) as a repeating unit, and examples thereof include the following depending on the type of polymerization.

(1) Polycondensation of diamine and dibasic acid, for example, hexamethylene diamine, decamethylene diamine, dodecamethylene diamine, 2,2,4- or 2,4,4-trimethylhexamethylene diamine,
1,3- or 1,4-bis (aminomethyl) cyclohexane, bis (p-aminocyclohexylmethane), m
-Or an aliphatic, alicyclic or aromatic diamine such as p-xylylenediamine and an aliphatic or alicyclic such as adipic acid, suberic acid, sebacic acid, cyclohexanedicarboxylic acid, terephthalic acid or isophthalic acid. Or a polyamide resin produced from an aromatic dicarboxylic acid.

(2) By polycondensation of aminocarboxylic acids, for example, crystalline or non-crystalline prepared from aminocarboxylic acids such as 6-aminocaproic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid Polyamide resin.

(3) Polyamide resins produced by lactam ring-opening polymerization, for example, lactams such as ε-caprolactam and ω-dodecalactam.

The polyamide resin used in the present invention includes:
In addition to the above polyamide resin, a copolymerized polyamide resin, a mixture of polyamide resins, and the like can be used. Specific examples of the polyamide resin include nylon 6, nylon 6-66,
Nylon 610, nylon 612, nylon 11, nylon 12, aromatic nylon, amorphous nylon and the like. Among these, nylon 6 and nylon 6-66 are preferable in terms of particularly good rigidity and heat resistance.

The above EVOH is not particularly limited, but is usually of ASTM D 1238, 190 ° C., 2.1
A melt flow rate [MFR] at 6 kg (Japanese name: melt index) of 1 to 10 g / 10 min, preferably 1 to 6 g / 10 min is used.

The fuel barrier resin blended with the matrix composed of at least one of the above polyamide resin and EVOH has excellent fuel barrier properties (permeation resistance) against hydrocarbon fuels such as gasoline fuel (including gasohol). There is no particular limitation as long as it is a resin. For example, polyphenylene sulfide (PPS), polybutylene naphthalate (PBN), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), PBN, PE
N, PBT thermoplastic elastomer, PBN, PE
N, PBT blend, ethylene-tetrafluoroethylene (ETFE), vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene (TH
V) and the like. These may be used alone or in combination of two or more. Among them, polyphenylene sulfide (PP
S) and polybutylene naphthalate (PBN) are preferably used.

The weight mixing ratio between the base material and the fuel barrier resin is as follows: base material / fuel barrier resin = 60/40 to 20/8.
0 is preferable, and particularly preferably, base material / fuel barrier resin = 50/50 to 30/70. That is, when the weight mixing ratio of the fuel barrier resin is less than 40, the fuel barrier property against gasoline fuel and the like tends to be inferior. On the contrary, when the weight mixing ratio of the fuel barrier resin exceeds 80, the blend resin layer This is because there is a tendency that adhesion between the rubber layer 1 and the rubber layer 2 is inferior.

The special rubber composition which is a material for the rubber layer 2 includes a specific rubber (component A), a peroxide vulcanizing agent (component B), a resorcinol compound (component C), 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 (hereinafter abbreviated as “EPM”) is used. EPDM above
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, and particularly preferably. An iodine value in the range of 10 to 24,
The ethylene ratio is in the range of 50 to 60% by weight.

The diene monomer (third component) contained in the above 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.

As the peroxide vulcanizing agent (component B) used together with the specific rubber (component A), for example,
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, if the B component is less than 1.5 parts, the crosslinking is insufficient and the strength of the fuel hose is inferior.
If the amount exceeds 0 parts, the fuel hose becomes too hard and the fuel hose tends to be inferior in flexibility.

The resorcinol compound (component C) used together with the components A and B is not particularly limited as long as it mainly acts as an adhesive. For example, modified resorcinol-formaldehyde resin, resorcinol, 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.

[0032]

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[0033]

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[0034]

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The mixing 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 amount of the C component is less than 0.1 part, the adhesiveness to the blend resin layer is poor, and if the amount of the C component exceeds 10 parts, the cost increases.

The melamine resin (component D) used together with the 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.

[0038]

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

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

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

The fuel hose shown in FIG.
For example, it can be manufactured as follows. That is, first, a blend resin obtained by blending a fuel barrier resin with a base material composed of at least one of a polyamide resin and an ethylene-vinyl alcohol copolymer is extruded to form a blend resin layer 1. Then, after extruding the special rubber composition on the surface of the blended resin layer 1 and then vulcanizing to form the rubber layer 2, a target fuel hose can be manufactured.

It should be noted that the fuel hose shown in FIG. 1 is not limited to the above-mentioned manufacturing method, but is formed by co-extrusion of a blended resin layer 1 made of a blended resin and a rubber layer 2 made of a special rubber composition. It is also possible.

In the fuel hose thus obtained, the thickness of the blended resin layer 1 is usually 0.1 to 1.5.
mm, preferably 0.3 to 1.2 mm, and 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 fuel hose is usually 2 to 60 mm, preferably 4 to 60 mm.
50 mm.

The fuel hose of the present invention is not limited to the two-layer structure of the blended resin layer 1 and the rubber layer 2 as shown in FIG. Any configuration may be used as long as it has a structure. For example, as shown in FIG. 2, a fuel barrier layer (innermost layer) 3 may be formed on the inner peripheral surface of the blend resin layer 1. In this case, the fuel barrier property against gasoline fuel or the like is further improved, which is preferable.

The fuel barrier resin used as the material for the fuel barrier layer 3 is not particularly limited. For example, the same fuel barrier resin as that blended in the blend resin layer 1 can be used. In this case, by making the fuel barrier resin used for the blend resin layer 1 and the fuel barrier resin used for the fuel barrier layer 3 the same material, the adhesive strength between the blend resin layer 1 and the fuel barrier layer 3 is increased. Is more preferred because of the improvement in

The fuel hose shown in FIG.
For example, it can be manufactured as follows. That is, first, the material for the fuel barrier layer 3 and the blend resin layer 1
A hose having the blend resin layer 1 formed on the outer peripheral surface of the fuel barrier layer 3 is produced by co-extrusion molding with a material for use. Next, the special rubber composition is extruded on the outer peripheral surface of the blended resin layer 1 and vulcanized, whereby the blended resin layer 1 is formed on the outer peripheral surface of the fuel barrier layer 3, and the outer peripheral surface is further formed. The fuel hose in which the rubber layer 2 is formed can be manufactured.

The thickness of the fuel barrier layer 3 is usually 0.05 to 1.0 mm, preferably 0.1 to 1.0 mm.
0.5 mm.

In the present invention, a reinforcing layer may be formed on the outer peripheral surface of the rubber layer 2, and a general-purpose rubber layer may be formed on the outer peripheral surface.

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

Examples of the general-purpose rubber layer material include:
EPDM, butyl rubber (IIR), halogenated butyl rubber (Cl-IIR, Br-IIR), isoprene rubber (IR), urethane rubber, chloroprene rubber (CR),
General-purpose rubbers such as epichlorohydrin rubber (ECO) and fluorine rubber can be used. Among them, EPDM is preferably used because it is relatively inexpensive.

Next, examples will be described together with comparative examples.

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

[Rubber (component A)] EPDM (Esprene 501A, manufactured by Sumitomo Chemical Co., Ltd.) [Iodine value: 12, ethylene ratio: 50% by weight, Mooney viscosity (ML1 + 4)
100 ° C): 43]

[Rubber (A component)] EPM (Esprene 201, manufactured by Sumitomo Chemical Co., Ltd.)

[Peroxide vulcanizing agent (component B)] di-t-butylperoxy-diisopropylbenzene (Peroximon F-40, manufactured by NOF Corporation)

[Resorcinol-based compound (component C)] Modified resorcinol-formaldehyde resin represented by the general formula (1) (Sumikanol 620, manufactured by Sumitomo Chemical Co., Ltd.)

[Melamine resin (D component)] Methylated formaldehyde / melamine polymer (Sumitomo Chemical Co., Ltd., Sumikanol 507A)

[Carbon black] manufactured by Tokai Carbon Co., Ltd.
Seast SO

[Process oil] Diana Process PW-380 manufactured by Idemitsu Kosan Co., Ltd.

[Polyamide resin] Nylon 6

[EVOH] EVAL EP- manufactured by Kuraray Co., Ltd.
F101, MFR = 1.3 g / 10 min

[Fuel Barrier Resin] Polyphenylene Sulfide (PPS)

[Fuel Barrier Resin] Polybutylene naphthalate (PBN)

[Vulcanization Accelerator] Tetramethylthiuram disulfide (Sunshiner TT manufactured by Sanshin Chemical Co., Ltd.)

[Vulcanization accelerator] Zinc dimethyldithiocarbamate (Sanshin Chemical Co., Suncellar PZ)

[Vulcanizing agent] Sulfur

[0070]

Example 1 [Preparation of rubber composition] 100 parts of EPDM, 4.2 parts of a peroxide vulcanizing agent, 3 parts of a resorcinol compound, 3 parts of a melamine resin, and carbon black 10
0 parts and 60 parts of process oil were blended and kneaded using a roll to prepare a rubber composition.

[Preparation of Fuel Hose] A blend resin composed of 60 parts of nylon 6 and 40 parts of PPS was extruded to form a blend resin layer (inner diameter 6.0 mm, thickness 1.0 m).
m) was formed. Next, after extruding the rubber composition on the surface of the blended resin layer, the rubber composition was heated at 160 ° C. for 45 minutes.
The fuel hose is formed by forming a rubber layer (2 mm in thickness) on the outer peripheral surface of the blended resin layer by vulcanization for one minute (see FIG. 1).
) Was manufactured.

[0072]

Examples 2 to 12 and Comparative Examples 1 to 3 The same procedures as in Example 1 were carried out except that the materials for the rubber layer and the materials for the blended resin layer were changed to the materials and ratios shown in Tables 1 to 3 below. I got a fuel hose.

[0073]

Example 13 [Preparation of rubber composition] A rubber composition was prepared in the same manner as in Example 1.

[Production of Fuel Hose] First, polyphenylene sulfide (PPS), which is a material for the fuel barrier layer (innermost layer), and a blend resin composed of 660 parts of nylon and 40 parts of PPS are co-extruded and formed. A blend resin layer (thickness 0.5 mm) was formed on the outer peripheral surface of the inner layer (inner diameter 6.0 mm, thickness 0.5 mm). Next, the rubber composition is extruded on the surface of the blended resin layer and vulcanized at 160 ° C. for 45 minutes to form a rubber layer (2 mm thick).
Thus, a target fuel hose (see FIG. 2) was manufactured.

[0075]

Example 14 A fuel hose was obtained in the same manner as in Example 13, except that the materials for the blend resin layer and the material for the innermost layer were changed to the materials and ratios shown in Table 3 below.

[0076]

Example 15 A fuel hose was obtained in the same manner as in Example 13, except that the materials for the blend resin layer and the material for the innermost layer were changed to the materials and ratios shown in Table 3 below.

Using the fuel hoses of Examples and Comparative Examples thus obtained, each characteristic was evaluated according to the following criteria. These results are shown in Tables 1 to 3 below.
Are also shown.

[Tensile Strength (TB), Elongation (EB)] The above rubber composition was press-vulcanized at 160 ° C. for 45 minutes to prepare 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.

[Peel strength (blend resin layer / rubber layer)]
The peel strength between the blend resin layer (or resin layer) and the rubber layer was measured as follows. That is, the fuel hose was cut in half, cut out to a length of 100 mm, attached to a tensile tester (JIS B 7721), the rubber layer side was fixed, and the blended resin layer side was pulled at a speed of 50 mm per minute. The peel strength (N / cm) was measured.

[Peeling Strength (Fuel Barrier Layer / Blend Resin Layer)] The peel strength between the blended resin layer (or resin layer) and the fuel barrier layer (innermost layer) was measured as follows. That is, the fuel hose is halved and the length is 100 m
m, and this is cut into a tensile tester (JIS B 772).
1), the blend resin layer side was fixed, and the fuel barrier layer side was pulled at a speed of 50 mm / min, and the peel strength (N / cm) was measured.

[Fuel barrier property (permeation resistance)] Fuel C (toluene: isooctane = 50 vol%: 50 vol%) / E10 (Fuel C / ethanol = 90 vol% / 10 vol%) is sealed in the above fuel hose. Then, it was left at a temperature of 60 ° C. for 7 days to evaluate the fuel barrier property. And
The one with the best fuel barrier property was indicated by ◎, the one with excellent fuel barrier property was indicated by ○, and the one with poor fuel barrier property was indicated by x.

[0082]

[Table 1]

[0083]

[Table 2]

[0084]

[Table 3]

From the above results, it can be seen that the fuel hoses of Examples 1 to 12 have excellent adhesiveness between the blended resin layer and the rubber layer, and also have excellent fuel barrier properties. Example 1
The fuel hoses of 3 to 15 articles have a fuel barrier layer (innermost layer), so that the fuel hose has better fuel barrier properties and excellent adhesion between the blended resin layer and the rubber layer. It can be seen that the adhesiveness with the barrier layer (the innermost layer) is also excellent.

On the other hand, the fuel hoses of Comparative Examples 1 and 2 are excellent in the adhesion between the resin layer and the rubber layer, but are inferior in the fuel barrier property. The fuel hose of Comparative Example 3 was
It can be seen that the adhesion between the resin layer and the rubber layer is poor, and the fuel barrier property is also poor.

[0087]

As described above, the fuel hose of the present invention
Rubber layer made of special rubber composition, polyamide resin and ethylene-vinyl alcohol copolymer (EVOH)
Has a laminated structure with a blended resin layer composed of a blended resin obtained by blending a fuel-barrier resin with a matrix composed of at least one of the above. Excellent in permeability (permeation resistance). Further, since the rubber layer itself has adhesiveness, the adhesiveness between the rubber layer and the blended resin layer is excellent without applying an adhesive to the interface between the rubber layer and the blended resin layer. Furthermore, since an adhesive application step is unnecessary (so-called adhesive-less), there is no need to worry about the pot life of the adhesive, control the concentration, etc., and it is excellent in stable productivity, and an organic solvent which is a solvent for diluting the adhesive. Because we do not use
There is no problem such as environmental pollution. Moreover, since the vulcanization is carried out using a peroxide vulcanizing agent instead of the conventional sulfur vulcanization system, the blending of zinc oxide can be made unnecessary (free of zinc). 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 at least one of polyphenylene sulfide (PPS) and polybutylene naphthalate (PBN) is used as the fuel barrier resin,
Fuel barrier properties against gasoline fuel and the like are further improved.

When the weight mixing ratio of the base material composed of at least one of the above polyamide resin and ethylene-vinyl alcohol copolymer (EVOH) and the fuel barrier resin is controlled to a specific range, the fuel barrier property and the adhesion are improved. The balance with the properties is further improved.

When a fuel barrier layer made of a fuel barrier resin is formed on the inner peripheral surface of the blend resin layer, the fuel barrier property against gasoline fuel and the like is further improved.
In this case, by using the same material as the fuel barrier resin used for the blend resin layer and the fuel barrier resin used for the fuel barrier layer, the adhesive strength between the blend resin layer and the fuel barrier layer is improved. More preferred.

[Brief description of the drawings]

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

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

[Explanation of symbols]

 1 Blend resin layer 2 Rubber layer

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 67/02 C08L 67/02 77/00 77/00 81/02 81/02 (72) Inventor Ayumu Ikemoto 3-1, Higashi 3-chome, Komaki-shi, Aichi Prefecture Tokai Rubber Industries Co., Ltd. (72) Inventor Hidehito Ikeda 3-1-1, Higashi 3-chome, Komaki City, Aichi Prefecture F-term (reference) 3H111 AA02 BA34 CA53 CB03 CB04 DA14 DB08 4F100 AA37 AA37H AK34A AK36A AK42B AK42C AK46B AK57B AK57C AK68B AK75A AL05A AL05B BA02 BA03 BA07 BA10A BA10C CA03A DA11 JB07B JL11 4J002 BD14Y BD15Y BD16Y BE03X CF07WCFW CLW01 CN03

Claims (6)

[Claims] 1. A laminated structure of a rubber layer composed of a rubber composition containing the following (A) to (D) as essential components and a blended resin layer, wherein the blended resin layer comprises a polyamide resin and A fuel hose formed of a blended resin obtained by blending a fuel barrier resin with a base material made of at least one of an ethylene-vinyl alcohol copolymer. (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 fuel hose according to claim 1, wherein the fuel barrier resin is at least one of polyphenylene sulfide and polybutylene naphthalate. 3. The weight mixing ratio of the base material composed of at least one of the polyamide resin and the ethylene-vinyl alcohol copolymer to the fuel barrier resin is such that base material / fuel barrier resin = 60/40 to 20 / The fuel hose according to claim 1 or 2, wherein the fuel hose is set in a range of 80. 4. The fuel hose according to claim 1, wherein the blended resin layer is an inner layer, and the rubber layer is formed on an outer peripheral surface of the inner layer. 5. The fuel hose according to claim 4, wherein a fuel barrier layer made of a fuel barrier resin is formed on an inner peripheral surface of the blend resin layer. 6. The fuel hose according to claim 5, wherein the fuel barrier resin used for the blend resin layer and the fuel barrier resin used for the fuel barrier layer are the same material.