JPH11315966A - Fuel hose - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain preferable vulcanization adhesive recipe of FKM/NBR.PVC by blending polyvinyl chloride having a specified weight part, including combined acrylonitrile having a specified weight %, and blending 1,8-diazabicyclo-(5,4,0)- undecene-7 salt of carboxylic acid. SOLUTION: A device is composed of a inner layer using fluorine-contained rubber and an outer layer vulcanization-adhering to the inner layer using a blend material of acrylonitrile-butadiene rubber and polyvinyl chloride. A blend rate of polyvinyl chloride in the blend material is set to 15 to 45 weight part in 100 weight part of the blend, combined acrylonitrile contents in acrylonitrile- butadiene rubber is set to 28 to 42 weight %, and 1,8-diazabicyclo-(5,4,0)- undecene-7 salt of carboxylic acid showing a formula is blended. R is saturation or unsaturation hydrocarbon radical having a chain, annular, or both structures, or an induction substrate, and including atom other than carbon atom or hydrogen atom.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a fuel hose,
More specifically, the present invention relates to a fuel hose used for a fuel pipe around a fuel tank of an automobile.

[0002]

2. Description of the Related Art Conventionally, acrylonitrile-butadiene rubber (NBR) has been used as such a fuel hose to improve the gasoline resistance and gasoline permeation resistance of polyvinyl chloride (PV).
C) NBR ・ P with weather resistance such as ozone resistance
Single layer hoses made of VC blend materials are well known.

[0003] However, the recent single-layer hose alone is not sufficient for strict regulations on gasoline permeation in recent years. The use of fluorine rubber (FKM) having high gasoline resistance and high gasoline resistance has also been proposed, but FKM is expensive.

Therefore, it is considered that a fuel hose using FKM only for the inner layer and using NBR / PVC for the outer layer, which is inexpensive and has good gasoline resistance, gasoline permeability and ozone resistance, is most suitable. However, in this case, it is required that the inner and outer layers be bonded by a simple vulcanization process and firmly adhered to the extent that peeling between the inner and outer layers can be sufficiently prevented. It becomes a problem.

Japanese Patent Publication No. 33633/1985 discloses that when the inner layer is FKM and the outer layer is epichlorohydrin rubber (ECO), the carboxylic acid 1,8-diazabicyclo-
A technique for enhancing vulcanization adhesion by blending (5,4,0) -undecene-7 salt is described.

[0006] On the other hand, Japanese Patent Publication No. 60-33632 discloses a method of bonding FKM and NBR with FKM or NB.
R represents a carboxylic acid 1,8-diazabicyclo- (5,4,
It describes that a basic silica-based filler and an epoxy compound are mixed with NBR while mixing 0) -undecene-7 salt.

[0007]

However, JP-B-60-33633 only shows the adhesive prescription of FKM / ECO, and JP-B-60-33632 shows the adhesive prescription of FKM / NBR.・ PV
No desirable vulcanized adhesive formulation of C is suggested. In addition, FKM originally has poor adhesion to other rubber materials, and NB
Since the addition of PVC to R makes it more difficult to secure the adhesive strength to FKM, the vulcanized adhesive formulation of the above prior art is not very useful.

[0008] Accordingly, the present invention provides an FKM / NBR-PVC.
It is an object of the present invention to specifically elucidate a desirable vulcanization adhesive formulation, thereby realizing a fuel hose in which the inner layer FKM and the outer layer NBR / PVC blend material are firmly bonded.

[0009]

Means for Solving the Problems (Structure of the First Invention) The structure of the first invention of the present application (the invention as set forth in claim 1) for solving the above-mentioned problems is that an inner layer using fluororubber, an acrylonitrile A fuel hose comprising: a blended material of butadiene rubber and polyvinyl chloride; and an outer layer vulcanized and bonded to the inner layer, wherein the blending amount of polyvinyl chloride in the blended material is 100 parts by weight of the blended material. 15 to 45 parts by weight, the acrylonitrile-butadiene rubber in the blended material has a bound acrylonitrile content of 28 to 42% by weight, and the blended material and / or fluororubber has the following “ 3. A fuel hose containing a 1,8-diazabicyclo- (5,4,0) -undecene-7 salt of a carboxylic acid shown in 3).

[0010]

Embedded image (In the chemical formula 3, R is a saturated or unsaturated hydrocarbon group having a chain structure, a cyclic structure or a combination of both, or a derivative group thereof, and in the structure other than a carbon atom or a hydrogen atom, In the following, the compound represented by Chemical formula 3 is also simply referred to as “DBU salt of carboxylic acid”.)

(Structure of the Second Invention) The structure of the second invention of the present application (the invention according to claim 2) for solving the above problems is as follows.
The compounding amount of the 1,8-diazabicyclo- (5,4,0) -undecene-7 salt of the carboxylic acid in the first invention is as follows:
The fuel hose is 0.1 to 4 parts by weight based on 100 parts by weight of the blend material and / or the fluororubber.

(Structure of Third Invention) The structure of the third invention (the invention according to claim 3) for solving the above-mentioned problem is as follows.
A fuel hose in which the fluororubber of the first invention or the second invention is blended with a polyol vulcanization compounding material, an organic peroxide and a polyfunctional unsaturated compound.

(Structure of Fourth Invention) The structure of the fourth invention (the invention described in claim 4) for solving the above-mentioned problem is as follows.
In the blended material according to any one of the first to third aspects, 30 parts by weight or less of a plasticizer is blended with respect to 100 parts by weight of the blended material, and at least one of the plasticizers is as follows. The fuel hose is an ether ester-based plasticizer represented by Chemical Formula 4.

[0014]

Embedded image (In “Formula 4,” R represents an alkyl group, and R ′ represents an alkylene group.)

(Structure of Fifth Invention) The structure of the fifth invention (the invention described in claim 5) for solving the above problems is as follows.
In the blend material according to any one of the first to fourth inventions, a metal oxide and an epoxy resin are blended,
It is a fuel hose.

[0016]

(Action and effect of the first invention) In the first invention, since the blending amount of PVC in the blend material is 15 parts by weight or more in 100 parts by weight of the blend material, the resistance of the outer layer of the fuel hose is reduced. Since the ozone property is ensured and the content is 45 parts by weight or less, the adhesive strength of the blend material to FKM is also good. In addition, since the bound acrylonitrile content in the NBR in the blend material is adjusted to a proper polarity range of 28 to 42% by weight, the inner layer FKM and the outer layer NBR / PVC blend material are firmly bonded. . or,
Since the DBU salt of a carboxylic acid is blended in the blend material and / or the FKM, the blend material and the FKM are strongly vulcanized and adhered.

The above-mentioned actions and effects are synergistic,
A fuel hose in which the inner layer and the outer layer are not peeled, in which the inner layer FKM and the outer layer NBR / PVC blend material are firmly bonded, is realized.

The fuel hose of the first invention has an FKM only in the inner layer.
Needless to say, it is relatively inexpensive to use, and exhibits high gasoline resistance and gasoline permeation resistance.

(Function / Effect of the Second Invention) With the compounding amount of the DBU salt of the carboxylic acid shown in the second invention, the vulcanization adhesion between the blend material and the FKM is performed most strongly.

(Function / Effect of Third Invention) In the third invention, in addition to an organic peroxide and a polyfunctional unsaturated compound which are peroxide vulcanized compounding materials, a polyol vulcanized compounding material is used.
M, the adhesion between the blend material and FKM is further improved.

(Function / Effect of the Fourth Invention) In the fourth invention, a plasticizer of 30 parts by weight or less is blended with respect to 100 parts by weight of the blended material, and at least one of the above plasticizers is used as the plasticizer. , The adhesion between the blend material and the FKM is further improved.

(Function / Effect of the Fifth Invention) In the fifth invention, since the metal oxide and the epoxy resin are used in combination with the blend material, the blend material and the FKM are further firmly adhered to each other.

[0023]

Next, embodiments of the first to fifth inventions will be described. In the following, simply "the present invention"
When it says, it refers to 1st invention-5th invention collectively.

[Fuel Hose] The fuel hose of the present invention mainly refers to a fuel hose used for a fuel pipe around a fuel tank of an automobile, but also includes a fuel hose used for other than an automobile. Further, in addition to a fuel hose of a type including an inner layer using FKM and an outer layer using a blended material of NBR / PVC, the above-mentioned inner layer and outer layer constitute an inner tube, and an outer tube made of a further appropriate material is provided outside the inner tube. Also included are fuel hoses of the type in which the tubes are constructed.

[FKM] As the FKM, those used for this kind of application can be arbitrarily selected without limitation. For example, a vinylidene fluoride-6-propylene copolymer,
Preference is given to a terpolymer of vinylidene fluoride-6-fluoride-propylene / 4-fluoroethylene, and the latter is particularly excellent in gasoline resistance.

In the FKM, a polyol vulcanization compounding agent or, in addition to the polyol vulcanization compounding agent, an organic peroxide and a polyfunctional unsaturated compound which are peroxide vulcanization compounding materials are compounded. Can be. In the case where only the peroxide vulcanization compounding material is not contained without the polyol vulcanization compounding agent, the adhesion is relatively poor.

The polyol vulcanization compounding agent comprises (a) a polyhydroxy aromatic compound as a crosslinking agent and (b) at least one selected from ammonium salts, phosphonium salts or iminium salts as a vulcanization accelerator. Seeds and (c)
And at least one selected from divalent metal oxides and divalent metal hydroxides as the acid acceptor.

Examples of the polyhydroxy aromatic compound include hydroquinone, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 2,2-
One or more kinds of bis (4-hydroxyphenyl) perfluoropropane (bisphenol AF), 4,4'-dihydroxydiphenylmethane, 2,2-bis (4-hydroxyphenyl) butane, etc. are added to 100 parts by weight of FKM. 0.1 to 10 parts by weight, more preferably 0.6
Up to 5 parts by weight can be used.

The ammonium salt, phosphonium salt or iminium salt includes, for example, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, tetrabutylammonium bromide,
One or more of bis (benzylphenylphosphine) iminium chloride, tetrabutylphosphonium chloride, benzyltriphenylphosphonium chloride, benzyltrioctylphosphonium chloride, etc.
0.05 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, can be used per 100 parts by weight.

As the divalent metal oxide or divalent metal hydroxide, for example, one or more of oxides and hydroxides such as Mg, Ca, Zn, and Pb are added to 100 parts by weight of FKM. It can be used in an amount of 1 to 30 parts by weight, more preferably 2 to 10 parts by weight. Further, in order to enhance the effect of the vulcanization accelerator, if necessary, various vulcanization acceleration activators represented by sulfone compounds such as dimethyl sulfone and dichlorodiphenyl sulfone can be added.

The organic peroxide is not particularly limited. For example, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3,2,5-dimethyl-
2,5-di (t-butylperoxy) hexane and the like are preferable, and one or more of these are added in an amount of 0.1 to 100 parts by weight of FKM in consideration of the amount of active oxygen, decomposition temperature, and the like.
It can be used in an amount of from 0.5 to 5 parts by weight, more preferably from 0.1 to 2 parts by weight.

The above-mentioned polyfunctional unsaturated compound is used to promote the crosslinking reaction more effectively, and the kind thereof is not limited. For example, triallyl isocyanurate,
Tris (diallylamine) -S-triazine and especially triallyl cyanurate are preferred, and one or more of these may be used in an amount of 0.01 to 100 parts by weight of FKM.
10 to 10 parts by weight, more preferably 0.1 to 3 parts by weight.

As the vulcanizing compounding agent to be compounded in the FKM of the present invention, from the viewpoint of good vulcanization adhesiveness with NBR / PVC, a vulcanizing system using a combination of polyol vulcanization and peroxide vulcanization includes:
More preferred.

The FKM of the present invention may optionally contain various additives, for example, reinforcing agents such as carbon black, silica, clay, and talc, and processing aids such as waxes and silicone rubber powder. .

[NBR / PVC] Blend material NBR / P
As the NBR and PVC constituting the VC, those used for this kind of application can be arbitrarily selected and blended.

The blending amount of PVC in the NBR / PVC blend material is preferably 15 to 45 parts by weight based on 100 parts by weight of the blend material. If the amount is less than 15 parts by weight, the ozone resistance of the NBR / PVC constituting the outer layer becomes insufficient, and if the amount exceeds 45 parts by weight, the adhesive strength of the NBR / PVC becomes low, so that the adhesion to the FKM constituting the inner layer is reduced. Power drops.

It is preferable that the bound acrylonitrile content in NBR in the NBR / PVC blend material is 28 to 42% by weight. If this is less than 28% by weight, the gasoline resistance of NBR / PVC becomes insufficient,
If the amount is more than 10% by weight, the adhesive strength of NBR / PVC to FKM is insufficient.

Outer layer NBR for FKM forming inner layer
・ To further strengthen the adhesion of PVC, NBR ・ PV
C may contain at least one of metal oxides, silica-based fillers, and epoxy resins. In particular, a combination of a metal oxide and an epoxy resin is preferable for improving the adhesiveness.

Examples of the metal oxide include MgO, PbO, and aluminum oxide. MgO is particularly preferable, and the compounding amount is preferably 1 to 20 parts by weight based on 100 parts by weight of NBR / PVC.

Examples of the silica-based filler include acidic silica (eg, Nipsil VN3 (trade name, manufactured by Nippon Silica Co., Ltd., pH: about 6)) and basic silica (eg, manufactured by Shionogi & Co., Ltd.) Product name "Carplex 112
0 "and a pH of about 11), and the compounding amount is preferably 5 to 50 parts by weight based on 100 parts by weight of NBR / PVC.

The above-mentioned epoxy resin includes a thermoplastic resin having two or more epoxy groups in one molecule, and a type obtained by a reaction between bisphenol A and epichlorohydrin, for example, a trade name of Shell Chemical Co., Ltd. "Epicoat 828" or the like is preferably used, and its blending amount is 15 parts by weight or more based on 100 parts by weight of NBR / PVC.
It is preferably at most about part by weight.

A plasticizer can be compounded in the NBR / PVC blend material.
The effective amount is preferably at least 30 parts by weight based on 0 part by weight, and particularly preferably at most 20 parts by weight for adhesion. Particularly suitable plasticizers are those described in the above “Chemical Formula 4”, for example, the trade name “ADEKASIZER R” manufactured by Asahi Denka Co., Ltd.
S-107 "and the like.
In addition, phthalate plasticizers such as DOP can be preferably used.

The FKM of the present invention includes various known vulcanizing agents,
Vulcanization accelerators, antioxidants, fillers such as carbon black and the like can be arbitrarily added.

[DBU salt of carboxylic acid]
The BU salt is blended in a blend material of NBR / PVC and / or fluororubber. In particular, it is preferable to mix it with an NBR / PVC blend material. Representative examples of the carboxylic acid in the DBU salt of the carboxylic acid shown in the above “Chemical Formula 2” include naphthoic acid, 2-hydroxynaphthoic acid, sorbic acid, 2-ethylhexylnaphthoic acid, gallic acid and p-acid.
Hydroxybenzoic acid, cinnamic acid and the like, and particularly preferred are DBU salts of naphthoic acid and sorbic acid.

The amount of the DBU salt of carboxylic acid is determined by the amount of NBR / PVC and / or fluororubber 100
0.1 to 4 parts by weight, more preferably 0.1 to 4 parts by weight, per part by weight.
5 to 3 parts by weight. If this amount is too small, FKM
Between VBR and NBR / PVC cannot be sufficiently strengthened,
If the amount is too large, the adhesive strength is sufficient, but on the other hand, ozone resistance and cold resistance decrease.

[0046]

Next, embodiments of the present invention will be described.

( Peeling test using test piece ) FKM and NBR
A peel test of a test piece obtained by vulcanization bonding with PVC was performed.

First, FKM is represented by A, B, C in Table 1 at the end.
And kneaded with an open roll according to the formulation. In Table 1, “FKM-1” means vinylidene fluoride-6
It is a fluorinated propylene-tetrafluoroethylene terpolymer, which has a fluorine content of 69% by weight and contains a polyol vulcanizing agent and can be vulcanized together with a peroxide.
"FKM-2" is a terpolymer of vinylidene fluoride-6-propylene-tetrafluoroethylene having a fluorine content of 69% by weight and a peroxide vulcanization type.
"TAIC" refers to triallyl isocyanurate, and "Perhexa 25B" refers to an organic peroxide [2,5-dimethyl-2,6 (tert-butylperoxy) hexane] manufactured by NOF Corporation. .

Further, NBR / PVC was kneaded with a Banbury mixer and an open roll according to the blending formulas with circled numbers 1 to 12 in Table 2 and with circled numbers 13 to 20 in Table 3 at the end. In Tables 2 and 3, "NBR / PVC
"-1" means that the weight blend ratio of NBR / PVC (hereinafter, simply referred to as "blend ratio") is 70/30 and the bound acrylonitrile content in NBR (hereinafter, simply referred to as "content") is 35% by weight. Points to something.

Further, "NBR PVC-2" to "NBR
・ PVC-7 has a blend ratio of 70/3
0 and the content is 29 wt%, the blend ratio is 85/15
With a content of 29 wt%, a blend ratio of 85/15 and a content of 41 wt%, a blend ratio of 60/40 and a content of 41 wt%, a blend ratio of 50/50 and a content of 35 wt% % And a blend ratio of 70/30 and a content of 45 wt%.

"Nipseal VN3", "Carplex 1120", "Epicoat 828" and "Adekasizer RS-107" are as described above.

The unvulcanized Kneaded FKM 2 mm thick sheets and the NBR / PVC 2 mm thick No. 1 to 20 NBR / PVC sheets kneaded as described above are Combinations such as Example-1 to Example-30 and Comparative example-1 to Comparative example-11 in Table 4 at the end are superimposed on each other, and first preliminarily pressed at 100 ° C. and a surface pressure of 20 kgf / cm ² for 5 minutes. After molding, 160 ° in a steam vulcanizer
C / 45 minute steam vulcanization was performed. Then this is 25
It was cut into a mm width and subjected to a T-type peeling test according to JIS K6256.

The test results are shown in Table 4 at the end. In Table 4, "adhesion state" means FKM sheet and NBR / PV.
Visual observation of the adhesion state with the C sheet means "rubber destruction" when the entire surface of the peeled surfaces of both sheets is in a state of rubber destruction, and "interfacial delamination" when the entire surface is in a state of interfacial separation. A part in which a fractured part and an interfacial peeling part coexist was described as "partial rubber fracture". From the results in Table 4, the following items 1) to 5) are understood.

1) All the examples corresponding to the vulcanized adhesive prescription of the first invention described in claim 1 exhibit an adhesive state of "partial rubber destruction" or "rubber destruction". there were.

However, as seen in Comparative Example-6 and Comparative Example-10, if the blending amount of PVC in 100 parts by weight of NBR / PVC exceeds 45 parts by weight, the adhesiveness becomes insufficient. Although not shown as data, NBR / PVC
If the amount of PVC in 100 parts by weight is less than 15 parts by weight, the ozone resistance of NBR / PVC as an outer layer material of the fuel hose becomes insufficient.

Further, as seen in Comparative Example-7 and Comparative Example-11, when the bound acrylonitrile content in the acrylonitrile-butadiene rubber in the blend material NBR / PVC exceeds 42% by weight, the adhesiveness becomes insufficient. Become. Although not shown as data, if the bound acrylonitrile content is less than 29% by weight, the fuel oil resistance of NBR / PVC as an outer layer material of the fuel hose becomes insufficient.

2) As shown in Comparative Examples 1 to 3, when the DBU salt of the carboxylic acid is not blended in any of the NBR / PVC sheet and the FKM sheet, the adhesiveness is remarkably poor. As in Comparative Example-9, good adhesion is obtained even when the amount of the DBU salt of carboxylic acid exceeds 4 parts by weight with respect to 100 parts by weight of NBR / PVC and / or FKM. As can be seen from Comparative Example-12 in Table 5 below, NBR / PV is used as the outer layer material of the fuel hose.
The ozone resistance of C becomes insufficient.

3) As shown in Comparative Example-4, FKM
Is not blended with a polyol vulcanizing compound (FK
M in the case of “C” in Table 1), the adhesiveness was insufficient. On the other hand, as shown in Examples 16 to 30, the polyol vulcanizing compounding agent and the organic peroxide were added to FKM. When the oxide and the polyfunctional unsaturated compound are compounded, a stronger adhesive force is obtained than when only the polyol vulcanizing compounding agent is compounded.

4) Example-6, 8, 9, 21, 23, 2
As seen in Comparative Example 4, the amount of the plasticizer to be added to 100 parts by weight of NBR / PVC is preferably 30 parts by weight or less, particularly preferably 25 parts by weight or less from the viewpoint of adhesiveness. As can be seen, if the amount exceeds 30 parts by weight, the adhesion becomes insufficient. Also, as can be seen from the comparison between Example-6 and Example-10, and Example-21 and Example-25, the case where ether ester-based Adecizer RS-107 was used as the plasticizer was more phthalate. Stronger adhesive strength is obtained than when an acid DOP is used.

5) As shown in Examples-4 and -19, when NBR / PVC is mixed with a metal oxide and an epoxy resin, and in Examples-5, 6, 20, and 21, When silica, in particular, basic silica is blended with NBR / PVC, stronger adhesive strength can be obtained.

( Physical property test using test pieces ) NBR / PVC
The vulcanized test specimen was subjected to a normal physical property test and an ozone deterioration test.

First, NBR / PVC was kneaded with a Banbury mixer and an open roll according to the compounding formulas of circled numbers 2 to 12 in Table 2 and circled numbers 13 to 18 in Table 3 above. Example 45 and Comparative Example 12 were used.

Then, the kneaded, unvulcanized 2 mm-thick sheet was subjected to a pressure of 100 ° C. and a surface pressure of 20 kgf / cm.
After pre-press molding at ² for 5 minutes, steam vulcanization was performed at 160 ° C./45 minutes in a steam vulcanizer. The vulcanized product was subjected to a normal physical property test (TB, EB, HS) according to JIS K6251. Also, JISK 6
An ozone deterioration test was performed in accordance with 259. The conditions of the ozone deterioration test were a temperature of 40 ° C., an ozone concentration of 50 pphm, and an elongation of 20%. Table 5 shows the test results.

According to the results shown in Table 5, Examples 31 to 45 have no abnormality and have good resistance to ozone deterioration, whereas Comparative Example 12 has an ozone deterioration resistance of "B-3". Is inadequate and unsuitable as an outer layer material of a fuel hose.

( Preparation of Hose and Test Thereof) A hose having an inner layer made of a compound of FKM and an outer layer made of a compound of NBR / PVC was prepared, and its performance was evaluated.

First, FKM was kneaded with an open roll according to the blending formulas A to C in Table 1 above, while NBR was blended according to various blending formulas in Tables 2 and 3 above.
・ PVC is kneaded by a Banbury mixer and an open roll, and these are extruded into an inner layer of FKM by an extruder.
Two layers were simultaneously extruded using BR / PVC as the outer layer,
The hoses shown in each Example No. and Comparative Example No. were used. In addition, these Example numbers and Comparative example numbers are numbers corresponding to Table 4 above by the combination of the FKM layer and the NBR / PVC layer.

The hose extruded in this manner has an inner diameter of 30.
mm, inner layer thickness 0.5mm, outer layer thickness 3.5m
m. These extruded hoses were subjected to steam vulcanization in a steam vulcanizer at 160 ° C./45 minutes to obtain vulcanized hoses.

As a performance test of the vulcanized hose, first, the peel strength between the inner layer and the outer layer in a normal state was measured according to JIS K6256. A commercially available regular gasoline was sealed in a hose having a length of 300 mm, and both ends were sealed. After aging in an explosion-proof gear oven at 40 ° C. for 168 hours, the peel strength was measured. .

Further, the ozone deterioration test of the hose was performed according to JIS.
K 6330 was carried out according to the method B in 4.2.5. The conditions of the ozone deterioration test are as follows: temperature 40 ° C, ozone concentration 50p
phm and the elongation ratio were 20%.

Table 6 shows the results of the above tests. “*” In Table 6 indicates “out of rubber”. According to the results in Table 6, the obtained results were similar to those in Table 4 above.

[0071]

[Table 1]

[0072]

[Table 2]

[0073]

[Table 3]

[0074]

[Table 4]

[0075]

[Table 5]

[0076]

[Table 6]

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[Procedure amendment]

[Submission date] June 24, 1999

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

Embedded image (In the chemical formula 1, R is a saturated or unsaturated hydrocarbon group having a chain structure, a cyclic structure or a combination of both, or a derivative group thereof, and in the structure other than a carbon atom or a hydrogen atom, May be included.)

Embedded image (In “Formula 2,” R represents an alkyl group, and R ′ represents an alkylene group.)

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0005

[Correction method] Change

[Correction contents]

[0005] When the JP-B 60-336 6 3 JP, inner layer FKM, the outer layer is epichlorohydrin rubber (ECO), carboxylic acid 1,8-diazabicyclo -
A technique for enhancing vulcanization adhesion by blending (5,4,0) -undecene-7 salt is described.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0006

[Correction method] Change

[Correction contents]

[0006] On the other hand, in JP-B-60-336 6 2 JP, per the adhesion of the FKM and NBR, FKM or NB
R represents a carboxylic acid 1,8-diazabicyclo- (5,4,
It describes that a basic silica-based filler and an epoxy compound are mixed with NBR while mixing 0) -undecene-7 salt.

Claims (5)

[Claims] 1. A fuel hose comprising: an inner layer using a fluororubber; and an outer layer vulcanized and bonded to the inner layer using a blend material of acrylonitrile-butadiene rubber and polyvinyl chloride. The blending amount of polyvinyl chloride is 15 to 45 parts by weight in 100 parts by weight of the blended material, and the acrylonitrile-butadiene rubber in the blended material has a bound acrylonitrile content of 28 to 42% by weight, and The blend material and / or the fluororubber include 1,8-diazabicyclo-carboxylic acid represented by the following Chemical Formula 1.
A fuel hose containing (5,4,0) -undecene-7 salt. Embedded image (In the chemical formula 1, R is a saturated or unsaturated hydrocarbon group having a chain structure, a cyclic structure or a combination of both, or a derivative group thereof, and in the structure other than a carbon atom or a hydrogen atom, May be included.) 2. The compounding amount of the 1,8-diazabicyclo- (5,4,0) -undecene-7 salt of the carboxylic acid is from 0.1 to 100 parts by weight based on 100 parts by weight of the blend material and / or the fluoroelastomer. The fuel hose according to claim 1, wherein the amount is 4 parts by weight. 3. The fluorine rubber according to claim 1, wherein a polyol vulcanizing compounding agent, an organic peroxide and a polyfunctional unsaturated compound are compounded. Fuel hose. 4. The blend material according to claim 1, wherein
30 parts by weight or less of a plasticizer is blended with respect to 0 parts by weight,
The fuel hose according to any one of claims 1 to 3, wherein at least one of the plasticizers is an ether ester plasticizer represented by the following Chemical Formula 2. Embedded image (In “Formula 2,” R represents an alkyl group, and R ′ represents an alkylene group.) 5. The method according to claim 1, wherein the blend material contains a metal oxide and an epoxy resin.
The fuel hose according to claim 4.