JP2003159714A - Method for manufacturing hose for fuel system of vehicle and hose obtained thereby - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a hose for a fuel system of a vehicle excellent in an interlayer adhesion force between a low permeation resin layer and a rubber layer without using an adhesive particularly. <P>SOLUTION: In the method for manufacturing the hose for the fuel system of the vehicle, a laminated body of the low permeation resin layer using polyester resin, and an unvulcanized rubber layer using a rubber composition composed of at least either an amine addition agent or an amine vulcanizing agent as an indispensable component are prepared. The low permeation resin layer and the unvulcanized rubber layer are bonded by vulcanizing the laminated body. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a fuel system hose for an automobile used for a fuel pipe of an automobile and a fuel system hose for an automobile obtained by the method.

[0002]

2. Description of the Related Art In recent years, the regulation of evaporation of fuel gas surrounding an automobile has become strict, and various low-permeability fuel system hoses have been studied to meet this requirement. As such a fuel system hose, for example, a resin hose using a low permeation resin such as polybutylene naphthalate (PBN) or polybutylene terephthalate (PBT) has been proposed. However, since the low permeation resins such as PBN and PBT described above are very rigid, the flexibility of the hose is poor when the hose is formed using only these low permeation resins. Therefore, the low-permeability resin layer is thinned to have a laminated structure with a thermoplastic resin layer made of polyamide or the like. However, since the low-permeability resin does not easily adhere to a different material such as polyamide, It is common to form an adhesive layer at the interface with the thermoplastic resin layer.

[0003]

However, the resin hose provided with the above-mentioned adhesive layer requires complicated steps such as an extrusion process for forming the adhesive layer, which complicates the molding process and results in an expensive adhesive material. However, there is a problem that the cost becomes high because of using. In addition, when the adhesive layer is formed by extrusion processing, it is necessary to set the temperature higher in order to increase the adhesive force, and therefore PBN or PB may be generated due to the high temperature during melting.
There is also a problem that a low-permeability resin such as T is likely to cause molecular deterioration, resulting in poor hose performance such as low-permeability performance. Further, the resin hose has a drawback that it is inferior in flexibility and chipping resistance because the outermost layer of the hose is made of resin. Therefore, a rubber layer called a protector layer is often used as the outermost layer of the hose, which further increases the cost. Further, in the case of the laminated body of the low permeation resin layer and the rubber layer, there is a problem that they are not adhered at all.

The present invention has been made in view of the above circumstances, and a method for producing a fuel system hose for an automobile, which is excellent in interlayer adhesion between a low-permeability resin layer and a rubber layer without using an adhesive, and It is an object of the invention to provide a fuel system hose for an automobile obtained by the above.

[0005]

In order to achieve the above object, the present invention provides a low permeation resin layer using a polyester resin and at least one of an amine-based additive and an amine vulcanizing agent as an essential component. For a vehicle in which a low-permeability resin layer and an unvulcanized rubber layer are bonded to each other by preparing a laminate with an unvulcanized rubber layer using the rubber composition, and vulcanizing the laminate. The manufacturing method of the fuel system hose is referred to as the first gist, and the automotive fuel system hose obtained by the manufacturing method of the fuel system hose for the vehicle is referred to as the second gist.

That is, the inventors of the present invention, in order to obtain a fuel system hose for an automobile, which has excellent interlayer adhesion between the low-permeability resin layer and the rubber layer without using an adhesive (adhesive-less),
We have earnestly studied. As a result, a laminate having a low-permeability resin layer using a polyester resin and an unvulcanized rubber layer using a rubber composition containing at least one of an amine-based additive and an amine vulcanizing agent as essential components is prepared. When this laminate is vulcanized, the amine group in the amine-based additive or amine vulcanizing agent is chemically bonded to the terminal group or ester bond of the polyester-based resin due to heat during vulcanization. Therefore, the interlayer adhesion between the unvulcanized rubber layer and the low-permeability resin layer was improved, and it was found that both layers can be bonded without using an adhesive, and the present invention was reached. When the above-mentioned amine vulcanizing agent is used, the amino group in the amine vulcanizing agent can be chemically bonded to the terminal group or ester bond of the polyester resin, and the unvulcanized rubber layer and the low permeation rate can be reduced. The interface with the resin layer can also be crosslinked.

When the above-mentioned specific amine-based additive or amine vulcanizing agent is used, the interlayer adhesion between the rubber layer and the low-permeability resin layer is further improved.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Next, embodiments of the present invention will be described in detail.

The method of manufacturing the fuel system hose for automobiles of the present invention is as follows.
A low-permeability resin layer using a polyester resin and an unvulcanized rubber layer using a rubber composition containing at least one of an amine-based additive and an amine vulcanizing agent as essential components are prepared, and the laminated body is prepared. By vulcanizing the body, the low permeability resin layer and the unvulcanized rubber layer are bonded together.

In the present invention, the order of laminating the low permeation resin layer and the unvulcanized rubber layer is not particularly limited. However, when the rubber layer is positioned and formed on the outermost layer, this rubber layer serves as a protector layer. Is preferred, and flexibility, chipping resistance, flame resistance, low temperature impact resistance, caulking resistance, etc. are improved. Further, it is preferable to form the low permeation resin layer so as to be sandwiched between the unvulcanized rubber layers, because the sealing property with the joint, the insertability of the joint, the flexibility, and the low temperature impact resistance are further improved.

The polyester resin as the material for the low permeation resin layer is not particularly limited, and examples thereof include polybutylene naphthalate (PBN) and polybutylene terephthalate (PBT). In addition, the above PBN and PB
T is a thermoplastic elastomer (T which has flexibility by copolymerizing an ether segment within a range satisfying the permeability).
It is also possible to knead PEE) or an elastomer and use it as a material having flexibility. These may be used alone or in combination of two or more. Among these, PBN is preferably used because it is particularly excellent in low permeability.

The rubber which is the main component of the rubber composition forming the rubber layer is not particularly limited, and examples thereof include epichlorohydrin rubber (ECO) and fluororubber (FK).
M), acrylonitrile-butadiene copolymer rubber (NB
R), a blend polymer (NBR-PVC) composed of NBR and polyvinyl chloride (PVC), chlorosulfonated polyethylene (CSM), and the like. These may be used alone or in combination of two or more. When an amine vulcanizing agent is used, epichlorohydrin rubber (EC
O) or fluororubber (FKM) is used.

The amine-based additive used together with the above rubber does not usually act as a vulcanizing agent, but chemically bonds the amino group in the amine-based additive to the terminal group or ester bond of the polyester-based resin. It is used for the purpose of equalizing. As the amine-based additive,
There is no particular limitation, and for example, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) salt of carboxylic acid,
Examples thereof include DBU salt of phenol resin, tetramethylammonium hydrogensulfate, tetraethylammonium hydrogensulfate, tetrabutylammonium hydrogensulfate, trioctylmethylammonium hydrogensulfate, tridodecylmethylammonium hydrogensulfate and trimethylbenzylammonium hydrogensulfate. These may be used alone or in combination of two or more. Among these, DBU salt of carboxylic acid and DB of phenol resin are used because they do not deteriorate mechanical properties.
U salt is preferably used.

The blending ratio of the amine-based additive is 0.5 with respect to 100 parts by weight of the rubber (hereinafter abbreviated as "part").
The range is preferably from 3 to 3 parts, particularly preferably from 0.5 to 2 parts. That is, the amine-based additive is 0.5
If it is less than 3 parts, the effect of improving the interlayer adhesive force between the low permeation resin layer and the rubber layer will be poor, and if it exceeds 3 parts, the mechanical properties will tend to be poor.

The amine vulcanizing agent used together with the above-mentioned rubber chemically bonds the amino group in the amine vulcanizing agent to the terminal group or the ester bond of the polyester resin, and at the same time, forms an unvulcanized rubber layer. It is used for the purpose of cross-linking the interface with the low-permeable resin layer. The amine vulcanizing agent is not particularly limited, and examples thereof include N, N ′.
-Dicinnamylidene-1,6-hexanediamine, 1,
6-hexanediamine, triethylenetetramine, tetraethylenepentamine, triethylenediamine, hexamethylenediamine carbamate [N ⁺ H ₃ (CH ₂ ) ₆
NHCOO ⁻ ], ethylenediamine carbamate, alicyclic amine salts and the like. These alone or 2
Used in combination with more than one species. Among these, N, N'-dicinnamylidene-1,6-hexanediamine is preferably used from the viewpoint of processing safety and physical property balance.

The mixing ratio of the amine vulcanizing agent is preferably in the range of 1 to 3 parts, particularly preferably 1.5 to 3 parts, relative to 100 parts of the rubber. That is, when the amount of the amine-based additive is less than 1 part, the effect of improving the interlayer adhesive force between the low permeation resin layer and the rubber layer is poor, and when it exceeds 3 parts, mechanical properties tend to be poor. Because.

In the present invention, when only the amine-based additive is used as an essential component of the rubber composition, the vulcanizing agent for the rubber is not limited to the amine vulcanizing agent, and is suitable for the type of rubber. A vulcanizing agent can be selected and used. Further, when an amine vulcanizing agent is used as an essential component of the rubber composition, the amine-based additive does not have to be blended in particular, but from the viewpoint of adhesiveness, the amine vulcanizing agent and the amine-based additive are included. It is more preferable to use and together.

In the rubber composition forming the rubber layer, a processing aid, an antioxidant, a reinforcing agent, a plasticizer, a vulcanizing agent, a rubber, and at least one of an amine-based additive and an amine vulcanizing agent are included. Vulcanization accelerator, vulcanization acceleration aid, vulcanization retarder,
A filler or the like may be appropriately blended if necessary.

Examples of the processing aids include stearic acid, fatty acid esters, fatty acid amides, hydrocarbon resins and the like.

Examples of the above antiaging agents include carbamate antiaging agents, phenylenediamine antiaging agents, phenol antiaging agents, diphenylamine antiaging agents, quinoline antiaging agents, waxes and the like.

Examples of the reinforcing agent include carbon black and white carbon.

Examples of the plasticizer include dioctyl phthalate (DOP) and di-n-butyl phthalate (DB
P) and other phthalic acid plasticizers, dibutyl carbitol adipate, dioctyl adipate (DOA) and other adipic acid plasticizers, dioctyl sebacate (DOS), sebacate dibutyl sebacate (DBS) and other sebacic acid plasticizers, etc. can give.

Examples of the vulcanizing agent include sulfur, morpholine, sulfur compounds such as disulfide, organic peroxides,
Examples include ethylene thiourea.

Examples of the vulcanization accelerators include thiazole accelerators, thiuram accelerators, sulfenamide accelerators such as N-cyclohexyl-2-benzothiazyl sulfenamide (CBS), and the like. .

Examples of the vulcanization accelerating aid include zinc oxide, activated zinc white, magnesium oxide, and red lead (komeitan).
Etc.

Examples of the vulcanization retarder include N-
Examples thereof include (cyclohexylthio) phthalimide.

Examples of the filler include calcium carbonate, magnesium carbonate, clay, talc and the like.

Next, with respect to the method of manufacturing the automobile fuel system hose of the present invention using each of the above materials, as shown in FIG.
A specific description will be given using an automobile fuel system hose in which a rubber layer 2 is laminated on the outer peripheral surface of a low-permeability resin layer 1. That is, first, a low-permeability resin material such as PBN is prepared, and this is extruded into a sizing water tank in a reduced pressure state using an extrusion molding machine to form the low-permeability resin layer 1 having a predetermined size. Next, a rubber composition is extruded onto the outer peripheral surface of the low permeation resin layer 1 by using an extrusion molding machine to prepare a laminate in which an unvulcanized rubber layer is formed on the outer peripheral surface of the low permeation resin layer 1. Then, the laminated body is vulcanized under predetermined conditions to bond the low-permeability resin layer 1 and the rubber layer 2 to each other to produce a target automobile fuel system hose (see FIG. 1). be able to. In addition, as described above, the low-permeability resin layer 1
A hose in which the stacking order of the rubber layer 2 and the hose in which the low permeation resin layer 1 is sandwiched between the rubber layers 2 can be manufactured in the same manner as in FIG. 1.

By the way, in the above manufacturing method, the method of forming the low-permeability resin layer by using the sizing water tank without using the mandrel has been described. However, the low-permeability resin layer is formed on the mandrel without using the sizing water tank. The permeable resin layer may be extrusion-molded. The low-permeability resin layer (inner layer) 1 is carbon black or the like for the purpose of discharging static electricity generated by the fuel pump to the outside of the hose and letting it escape, thereby preventing accidents such as ignition of fuel (gasoline etc.) due to static electricity. It is preferable that the conductive layer is prepared by blending the conductive agent. The low permeable resin layer 1 and the rubber layer 2 are
Usually, the bonding is performed without an adhesive, but an adhesive may be used as an auxiliary in some cases.

In the fuel system hose of the present invention thus obtained, the inner diameter of the hose is preferably in the range of 4 to 40 mm, particularly preferably in the range of 6 to 33 mm, and the outer diameter of the hose is in the range of 6 to 50 mm. Is preferable, and particularly preferably in the range of 8 to 40 mm. The thickness of the low permeation resin layer 1 is preferably in the range of 0.05 to 1 mm, particularly preferably in the range of 0.1 to 0.6 mm, and the thickness of the rubber layer 2 is preferably in the range of 0.5 to 5 mm. , Particularly preferably in the range of 1 to 4 mm.

In the present invention, the low permeation resin layer 1 is not limited to the single layer structure as shown in FIG. 1 and may have a multilayer structure of two or more layers. For example, the low-permeable resin layer 1 may have a two-layer structure, the inner layer may be a conductive layer, and the outer layer may be a non-conductive layer. The low-permeability resin layer (inner layer) 1 having such a two-layer structure is
It can be produced by simultaneously extruding a conductive resin and a non-conductive resin with each extruder and joining them into two layers with a die.

It is also possible to form a rubber layer on the inner peripheral surface of the low-permeability resin layer 1 and form a sandwich structure (three-layer structure) in which the low-permeability resin layer 1 is sandwiched between the rubber layers. As the rubber material of the innermost layer (rubber layer), fluororubber or NBR-PVC rubber is preferably used because of its excellent fuel oil resistance.

Next, examples will be described together with comparative examples.

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

[PBN] Condensation product of tetramethylene glycol and 2,6-naphthalenedicarboxylic acid

[Conductive PBN] 5% by weight of conductive carbon black (Ketjen Black EC manufactured by Ketjen Black International) is mixed with PBN.

[TPEE] PBN thermoplastic elastomer (flexural modulus: 480 MPa)

[TPEE] PBN thermoplastic elastomer (flexural modulus: 1000 MPa)

[Conductive TPEE] 15% by weight of TPEE is mixed with conductive carbon black (Ketjen Black EC manufactured by Ketjen Black International).

[Rubber Compositions A1 to A9, B1 to B3] The rubber compositions were prepared by mixing the components shown in Tables 1 to 3 below in the proportions shown in the same table.

[0041]

[Table 1]

[0042]

[Table 2]

[0043]

[Table 3]

[0044]

Example 1 PBN, which is the material for the inner layer, was extruded into a sizing water tank under reduced pressure using an extruder to form an inner layer, and then the rubber composition A1 was applied to the outer peripheral surface of the inner layer using an extruder. I pushed it out. Then, vulcanize it (160
(° C. × 45 minutes) to prepare a fuel hose (inner diameter 6 mm) in which an outer layer is laminated on the outer peripheral surface of the inner layer.

[0045]

Example 2 Conductive PBN and PBN which are materials for the inner layer
Was extruded into a sizing water tank under reduced pressure using each extruder to form an inner layer having a two-layer structure. Then, the rubber composition A1 was extruded on the outer peripheral surface of the inner layer by using an extrusion molding machine, and then vulcanized (160 ° C. × 45 minutes) to obtain 2
A fuel hose (inner diameter: 6 mm) was produced in which an outer layer was laminated on the outer peripheral surface of the inner layer of the layer structure.

[0046]

Example 3 A fuel hose was produced in the same manner as in Example 1 except that the material for the inner layer was changed to conductive PBN.

[0047]

Example 4 A fuel hose was produced in the same manner as in Example 2 except that the material for the inner layer (inner layer) was changed to TPEE.

[0048]

Example 5 A fuel hose was produced in the same manner as in Example 2 except that the material for the inner layer (inner layer) was changed to conductive TPEE.

[0049]

Example 6 The rubber composition B1 was extrusion-molded on a mandrel to form an inner layer, and then the surface was coated with PBN to form an intermediate layer. Then, the surface of this intermediate layer is coated with the rubber composition A1 and vulcanized (160 ° C. × 45 ° C.).
Minutes) After that, the mandrel was taken out, and a fuel hose (inner diameter: 6 mm) having a three-layer structure in which the intermediate layer was formed on the outer peripheral surface of the inner layer and the outer layer was further formed on the surface was produced.

[0050]

Examples 7 to 15 In the same manner as in Example 1 or Example 6 except that the materials for the inner layer, the material for the intermediate layer or the material for the outer layer were changed as shown in Tables 5 and 6 below.
A fuel hose was made.

[0051]

Comparative Example A fuel hose was produced in the same manner as in Example 1 except that the rubber composition A9 (containing neither an amine-based additive nor an amine vulcanizing agent) was used as the outer layer material.

Using the fuel hoses of Examples and Comparative Examples thus obtained, the interlayer adhesion was evaluated according to the following criteria. These results are shown in Table 4 below.
The results are also shown in Table 6.

[Interlayer adhesion] Fuel hose (inner diameter 6 mm)
Is divided into two in the longitudinal direction, and one of them is used to peel off the interface between the low-permeability resin layer and the rubber layer to obtain the interlayer adhesive force (N /
cm) was calculated. In addition, the fuel (Fue
A mixed solution obtained by mixing 10% by volume of ethanol with lC) was sealed, and allowed to stand at 40 ° C. for 1 week, and then, in the same manner as described above, the interlayer adhesive force (N / cm) between the low permeation resin layer and the rubber layer.
Was calculated.

[0054]

[Table 4]

[0055]

[Table 5]

[0056]

[Table 6]

From the above results, the fuel hose of the example product is
It can be seen that all have excellent interlaminar adhesive strength between the low-permeability resin layer and the rubber layer.

On the other hand, in the comparative example, since the rubber layer is formed by using the rubber composition containing neither the amine-based additive nor the amine vulcanizing agent, the low permeation resin layer and the rubber are not formed. It can be seen that the interlayer adhesive strength with the layer is significantly poor.

[0059]

As described above, according to the present invention, a low permeation resin layer using a polyester resin and a rubber composition containing at least one of an amine additive and an amine vulcanizing agent as essential components are not used. A laminate with a vulcanized rubber layer is prepared, and the laminate is vulcanized. As a result, the amino group in the amine-based additive or amine vulcanizing agent chemically bonds with the terminal group or ester bond of the polyester-based resin due to the heat during vulcanization, resulting in low permeability with the unvulcanized rubber layer. The interlayer adhesion with the resin layer is improved, and both layers can be bonded without using an adhesive. When the above-mentioned amine vulcanizing agent is used, the amino group in the amine vulcanizing agent can be chemically bonded to the terminal group or ester bond of the polyester resin, and the unvulcanized rubber layer and the low permeation rate can be reduced. The interface with the resin layer can also be crosslinked. As described above, in the production method of the present invention, since adhesive is not required, the molding can be simplified, and at the same time, the cost is low and the adhesive is not required to be managed. Etc. are reduced and the adhesion reliability is improved. Further, unlike the conventional case, it is not necessary to extrude the adhesive layer, so that the polyester-based resin does not undergo molecular deterioration due to high temperature during melting, and hose performance such as low permeability can be stabilized. When the outermost layer of the hose is composed of a rubber layer, this rubber layer acts as a protector layer and is excellent in flexibility, chipping resistance, flame resistance, low temperature impact resistance, caulking resistance, etc. You can get a hose.
Furthermore, when the inner layer of the hose is made of a low-permeability resin layer, the inner layer does not shrink due to heat during vulcanization, so that the dimensional stability is excellent. Further, when the low permeation resin layer is sandwiched between the rubber layers, the hose can be obtained with further improved sealability with the joint, insertability of the joint, flexibility, and low temperature impact resistance.

When the above-mentioned specific amine-based additive or amine vulcanizing agent is used, the interlayer adhesion between the rubber layer and the low-permeability resin layer is further improved.

[Brief description of drawings]

FIG. 1 is a configuration diagram showing an example of an automobile fuel system hose obtained by a method for producing an automobile fuel system hose of the present invention.

[Explanation of symbols]

1 Low permeability resin layer 2 rubber layers

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) F16L 11/04 B29K 21:00 // B29K 21:00 67:00 67:00 105: 24 105: 24 B29L 9:00 B29L 9:00 23:00 23:00 B60K 15/02 CF Term (reference) 3D038 CA22 CB01 CC17 3H111 AA02 BA13 BA15 BA31 CB03 CB14 DA26 DB08 EA12 EA14 4F100 AH03B AH03H AK41A AN00B BA02 BA07 CA00B CA00H CA06B03 CA03B03 GB32 JD05A 4F203 AA24 AA45 AB03 AG03 AG08 AH17 DA11 DC01 DD04 DJ01 4F211 AA24 AA45 AB03 AD12 AG03 AG08 AH17 TA09 TC07 TD11 TH02 TH06 TN84

Claims (4)

[Claims] 1. A laminate comprising a low-permeability resin layer using a polyester resin and an unvulcanized rubber layer using a rubber composition containing at least one of an amine-based additive and an amine vulcanizing agent as an essential component. A method for producing an automobile fuel system hose, characterized in that the low permeability resin layer and the unvulcanized rubber layer are bonded to each other by preparing and vulcanizing the laminate. 2. The above-mentioned amine-based additive is 1,8-diazabicyclo [5.4.0] undecene-7 of carboxylic acid.
Salt, phenol resin 1,8-diazabicyclo [5.
4.0] undecene-7 salt, tetramethylammonium hydrogensulfate, tetraethylammonium hydrogensulfate, tetrabutylammonium hydrogensulfate, trioctylmethylammonium hydrogensulfate, tridodecylmethylammonium hydrogensulfate and trimethylbenzylammonium hydrogensulfate. At least one selected
A method for producing the fuel system hose for automobiles described. 3. The amine vulcanizing agent is N, N′-dicinnamylidene-1,6-hexanediamine, 1,6-hexanediamine, triethylenetetramine, tetraethylenepentamine, triethylenediamine, hexamethylenediaminecarbamate, The method for producing a fuel hose for an automobile according to claim 1 or 2, wherein the hose is at least one selected from the group consisting of ethylenediamine carbamate and an alicyclic amine salt. 4. An automobile fuel system hose obtained by the method for producing an automobile fuel system hose according to claim 1.