JP2002210892A - Bonded laminate and fuel hose - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make a fluororesin layer which has a large content of a vinylidene fluoride(VDF) unit and is excellent in fuel-barrier properties adhere well and directly to a polyamide resin layer, etc., without deteriorating the fuel-barrier properties. SOLUTION: In a bonded laminate, the fluororesin layer of a fluororesin containing at least 60 mole% of the VDF unit is made to adhere well and directly to a thermoplastic resin layer having the content of a terminal amino group of at least 4×10-5 gram equivalent/g. A fuel hose includes the bonded laminate in which the fluororesin layer is arranged as the inner layer of the hose.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive laminate and a fuel hose, and more particularly, to an adhesive laminate in which a fluororesin layer is firmly and directly adhered to a thermoplastic resin layer without impairing its barrier property against fuel and the like. The present invention also relates to a fuel hose that uses this adhesive laminate and can be used not only for a general fuel and an alcohol mixed fuel, but also for a fuel cell fuel such as hydrogen or methanol.

[0002]

2. Description of the Related Art In the United States, Japan, Europe, and elsewhere, regulations on fuel evaporation from automobiles are becoming increasingly strict in relation to environmental issues and the like, and contribution to this point is high. Measures are also required for fuel hoses. Accordingly, in recent years, various fuel hoses using a fluorocarbon resin having a high barrier property against hydrocarbons for the inner layer have been proposed.

The outer layer of fluororesin in these fuel hoses is usually made of a thermoplastic resin such as polyamide having excellent weather resistance, abrasion resistance and oil resistance.
And, generally, the fluororesin and the thermoplastic resin are hard to adhere. Therefore, in consideration of the characteristics as a laminate (hose), good adhesion between the fluororesin layer and the thermoplastic resin layer is an important technical problem.

As a prior art related to such technical problems, for example, in the invention disclosed in US Pat. No. 5,383,087, a PVDF layer and a polyamide layer are bonded via an intermediate adhesive layer. In the multilayer plastic tube disclosed in JP-A-7-266474, PVDF is modified by mixing an acrylate copolymer to impart adhesion to a polyamide layer.

[0005]

However, the above U
As in the invention according to SP 5,383,087, when the intermediate adhesive layer is set only for the purpose of bonding the PVDF layer and the polyamide layer, the production efficiency and the production cost of the fuel hose are significantly deteriorated. Further, as in the invention according to JP-A-7-266474, modification by introducing a reactive functional group into PVDF by mixing an acrylate copolymer or the like is useful for imparting adhesion to a polyamide layer, There is a problem that the advanced fuel barrier property is impaired.

Accordingly, the present invention provides a method of forming a fluororesin layer containing a large amount of VDF, without impairing the excellent barrier property against fuels and the like, and without using an intermediate adhesive layer which deteriorates production efficiency and production cost. It is an object of the present invention to provide an adhesive laminate that is favorably adhered to a plastic resin layer. Another object of the present invention is to provide a fuel hose using the adhesive laminate.

[0007]

Means for Solving the Problems (Structure of the First Invention) The structure of the first invention of the present application (the invention according to claim 1) for solving the above-mentioned problems is that the fluororesin layer and the thermoplastic resin layer are composed of An adhesive laminate directly adhered, wherein the fluororesin layer has a vinylidene fluoride content of 60 mol% or more (VD
An adhesive laminate using a fluororesin containing F) and a thermoplastic resin having a terminal amino group of 4 × 10 ⁻⁵ g equivalent / g or more for the thermoplastic resin layer.

(Structure of the Second Invention) The structure of the second invention of the present application (the invention described in claim 2) for solving the above problems is as follows.
The fluororesin containing 60 mol% or more of VDF according to the first invention is polyvinylidene fluoride (PVDF),
Vinylidene fluoride-chlorotrifluoroethylene copolymer (VDF / CTFE), vinylidene fluoride-tetrafluoroethylene copolymer (VDF / TF
E), vinylidene fluoride-hexafluoropropylene copolymer (VDF / HFP), tetrafluoroethylene-vinylidene fluoride-propylene copolymer (TFE / VDF / P) or tetrafluoroethylene-
The adhesive laminate is a hexafluoropropylene-vinylidene fluoride copolymer (TFE / HFP / VDF).

(Structure of Third Invention) The structure of the third invention (the invention described in claim 3) for solving the above-mentioned problem is as follows.
The fluororesin according to the first invention or the second invention contains CTFE as a copolymerization component with VDF, and the molar ratio of both is V.
DF / CTFE = 98/2 to 85/15,
It is an adhesive laminate.

(Structure of the Fourth Invention) The structure of the fourth invention of the present application (the invention according to claim 4) for solving the above problems is as follows.
An adhesive laminate, wherein an effective amount of a conductive compound is added to the fluororesin layer according to the first to third inventions.

(Structure of Fifth Invention) The structure of the fifth invention of the present application (the invention according to claim 5) for solving the above problems is as follows.
An adhesive laminate wherein the thermoplastic resin according to the first to fourth inventions is a polyamide or a polyolefin.

(Structure of the Sixth Invention) The structure of the sixth invention of the present application (the invention according to claim 6) for solving the above problems is as follows.
The polyamide according to the first to fifth inventions is polyamide 6, polyamide 66, polyamide 46, polyamide 6
10, polyamide 116, polyamide 612, polyamide 11, polyamide 12, polyamide TMHT, polyamide 6I, polyamide 6T / 6I, polyamide PACM
12, an adhesive laminate, which is any of polyamide MXD6, polyamide 11T, and polyamide 11T (H), or a copolymer or a mixture thereof.

(Structure of the Seventh Invention) The structure of the seventh invention (the invention according to claim 7) for solving the above problems is as follows.
A fuel hose including the adhesive laminate according to any one of the first to sixth inventions in a state where the fluororesin layer is an inner layer.

(Structure of the Eighth Invention) The structure of the eighth invention (the invention according to claim 8) for solving the above problems is as follows.
The fuel hose according to the seventh aspect of the present invention is a fuel hose including a protector layer made of an arbitrary resin material or rubber material outside the adhesive laminate.

(Structure of the ninth invention) The structure of the ninth invention of the present application (the invention according to claim 9) for solving the above problems is as follows.
The fuel hose according to the seventh or eighth aspect of the present invention is a fuel hose in which at least a part thereof has a corrugated pipe shape.

[0016]

Operation and Effect of the Invention (Operation and Effect of the First Invention) The adhesive laminate of the first invention is obtained by directly bonding a fluororesin layer and a thermoplastic resin layer, for example, as described in US Pat. No. 5,383,08.
Since the intermediate adhesive layer is not set as in the invention according to No. 7, the production efficiency and production cost are good, including when the adhesive laminate is produced as a hose. Furthermore,
Since the fluororesin layer has not been modified to introduce a reactive functional group or the like, high fuel barrier properties are not impaired.

In general, it is said that a fluororesin which has not been modified by introduction of a reactive functional group or the like is difficult to directly adhere to a thermoplastic resin. However, according to the study of the present inventor, VDF containing fluorine resin at 60 mol% or more was
And the thermoplastic resin contains 4 × 10 ⁻⁵ g equivalent / g
It was found that when the above terminal amino groups were contained, both adhered well. The reason is not clear yet,
It is presumed that VDF in the fluororesin is bonded to the terminal amino group of the thermoplastic resin by hydrofluoric acid removal. The terminal amino group content of the thermoplastic resin is 4 × 10 ⁻⁵ g equivalent / g
If it is less than 30, the adhesion to the fluororesin layer is not good.

(Function / Effect of the Second Invention) The type of the above-mentioned "fluororesin containing 60 mol% or more of VDF" is not limited, and various kinds of materials listed in the second invention including PVDF having 100 mol% of VDF are included. VDF copolymerized fluororesin is representatively exemplified.

(Function / Effect of Third Invention) As in the third invention, a high fuel barrier property and adhesion to a thermoplastic resin can be maintained by copolymerizing CTFE with VDF at a predetermined molar ratio. Moreover, a higher degree of flexibility can be secured.

(Function / Effect of the Fourth Invention) As in the fourth invention, by adding an effective amount of a conductive compounding agent to the fluororesin layer, the adhesive laminate is formed on the fuel hose using the fluororesin layer as an inner layer. When incorporated, charging in the inner layer is effectively prevented. Therefore, for example, there is less fear of spark generation at the time of refueling when the fuel hose is a filler neck hose and spark generation at the time of fuel transport accompanying engine operation when the fuel hose is a feed hose or a return hose.

(Function / Effect of the Fifth Invention) The constituent material of the thermoplastic resin layer to be bonded to the fluororesin layer in the adhesive laminate is not limited. However, considering the weather resistance, abrasion resistance, oil resistance, etc. The polyamides and polyolefins listed in the five inventions are particularly preferred.

(Function / Effect of the Sixth Invention) When the constituent material of the thermoplastic resin layer in the adhesive laminate is a polyamide, the kind of polyamide is not limited, but various polyamides listed in the sixth invention are representative examples. Is done.

(Function and Effect of Seventh Invention) First to Sixth Inventions
In a fuel hose including the adhesive laminate according to the present invention in a state where the fluororesin layer is an inner layer, high fuel barrier properties can be expected due to the inner fluororesin layer, and the inner fluororesin layer and the outer thermoplastic resin layer can be combined with each other. Insufficiency in insertion of the fastening part due to insufficient adhesive force can be avoided, and deterioration in efficiency and cost of hose production due to provision of an intermediate adhesive layer between the fluororesin layer and the thermoplastic resin layer can be prevented.

(Function / Effect of the Eighth Invention) As in the eighth invention, by providing a protector layer on the outside of the adhesive laminate in the fuel hose, the adhesive laminate has physical impact, ultraviolet rays, chemicals derived from the outside world. And other various causes of deterioration.

(Function / Effect of Ninth Invention) As in the ninth invention, when the fuel hose is a so-called corrugated pipe, the flexibility of the fuel hose can be further secured.

[0026]

Next, embodiments of the first to ninth inventions will be described. In the following, simply "the present invention"
This means that the first to ninth inventions are collectively referred to.

[Fuel Hose and Adhesive Laminated Body] The fuel hose of the present invention has an adhesive (agent) layer interposed between an inner layer using a predetermined fluororesin and an outer layer using a predetermined thermoplastic resin. And an adhesive laminate directly adhered thereto. The fluororesin layer forms the innermost layer of the fuel hose. The thickness of the fluororesin layer and the thermoplastic resin layer can be set arbitrarily,
For example, the thickness of the former is about 0.05 to 1.0 mm, the thickness of the latter is about 0.3 to 2.0 mm, and the inner diameter of the hose (the inner diameter of the fluorine resin layer as the inner layer) is about 4 to 50 mm. can do.

Further, any hose component, for example, any resin material suitable as an outer layer material, for example, a soft vinyl chloride, an olefin-based thermoplastic elastomer, or a rubber material, for example, EPDM (ethylene -Propylene-diene terpolymer rubber), NBR / PVC
(Blend material of acrylonitrile-butadiene rubber and polyvinyl chloride), NBR / EPDM (blend material of acrylonitrile-butadiene rubber and ethylene-propylene-diene terpolymer rubber), CPE (chlorinated polyethylene rubber), CSM (Chlorosulfonated polyethylene rubber) or the like. Further, one or more layers of a resin material or a rubber material may be provided on the outer periphery of the outer layer having such a configuration, and a protector layer made of a resin material or a rubber material may be provided on the outermost layer. Further, any resin material or rubber material other than the protector may be laminated on the outer periphery of the adhesive laminate.

The shape of the fuel hose tube is not limited. For example, it may be a straight tube or a curved tube, that is, a so-called smooth tube, or a corrugated tube in which at least a part of the tube has a corrugated (bellows) shape.

The fuel hose of the present invention can be used as a fuel transport pipe without any limitation, and is particularly suitable for various fuel hoses for automobiles. For automotive fuel hoses that require particular flexibility on piping or when used,
For example, a fuel hose including the adhesive laminate according to the third invention,
Alternatively, the fuel hose according to the ninth aspect of the present invention can be particularly preferably used. For example, when the fuel hose is a filler neck hose, it is necessary to pay attention to spark generation at the time of refueling, or when the fuel hose is a feed hose or a return hose. A fuel hose provided with the adhesive laminate according to the fourth aspect of the present invention can be particularly preferably used for an application in which spark generation at the time of fuel transport accompanying engine operation is to be noted, as in a certain case.

The fuel hose can be manufactured by arbitrarily adopting various known hose manufacturing methods. However, in general, the fluororesin layer and the thermoplastic resin layer constituting the adhesive laminate, or including the protector layer, can be co-extruded, and it is also possible to cover only the protector layer. It is. Co-extrusion molding refers to a molding method in which the constituent materials of each of the above-mentioned layers constituting the hose are concentrically and simultaneously contacted in a molten state and extruded. In order to perform the co-extrusion molding, various known devices such as a co-extrusion head can be used arbitrarily.

[Fluororesin Layer] The type of the copolymer monomer is not limited as long as the fluororesin layer uses a fluororesin containing 60 mol% or more, more preferably 65 mol% or more of VDF. Any one or more copolymer monomers other than VDF can be used in any mole% within the above-mentioned limits.

However, polyvinylidene fluoride (PVD) is used as a fluororesin containing 60 mol% or more of VDF.
F), vinylidene fluoride-chlorotrifluoroethylene copolymer (VDF / CTFE), vinylidene fluoride-tetrafluoroethylene copolymer (VDF /
TFE), vinylidene fluoride-hexafluoropropylene copolymer (VDF / HFP), tetrafluoroethylene-vinylidene fluoride-propylene copolymer (TFE / VDF / P) or tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride Copolymers (TFE / HFP / VDF) can be particularly preferably exemplified.

From the viewpoint of the flexibility of the fluororesin layer,
The fluororesin contains CTFE as a copolymerization component with VDF, and the molar ratio of both is VDF / CTFE = 98/2 to 85
/ 15, especially VDF / CTFE
= 95/5 to 85/15 are also preferable.

Further, when the fuel hose is a filler neck hose, a feed hose, a return hose, or the like,
It is also preferable that an effective amount of a conductive compounding agent is added to the fluororesin layer. As the conductive compounding agent, carbon black, carbon nanotube, metal powder and the like can be optionally used. By adding the conductive compounding agent, the volume resistivity of the fluororesin layer is preferably set to 10 ⁹ Ω ·
cm or less.

[Thermoplastic Resin Layer] The type of the thermoplastic resin constituting the thermoplastic resin layer is not limited as long as it contains a terminal amino group of 4 × 10 ⁻⁵ g equivalent / g or more. If necessary, a plasticizer, a pigment, a heat stabilizer, an antioxidant, an anti-deterioration agent, a weathering agent, a flame retardant, a reinforcing agent, and the like are appropriately added to the thermoplastic resin.

Particularly preferred thermoplastic resins include:
Polyamide or polyolefin. As the polyamide, polyamide 6, polyamide 66, polyamide 4
6, polyamide 610, polyamide 116, polyamide 612, polyamide 11, polyamide 12, polyamide TMHT, polyamide 6I, polyamide 6T / 6I, polyamide PACM12, polyamide MXD6, polyamide 11T, polyamide 11T (H), or a combination thereof. Polymers or mixtures are more preferred. As the polyolefin, for example, polyethylene, polypropylene, ethylene-propylene copolymer or olefin-based thermoplastic elastomer is more preferable.

In order to increase the amino group content of the thermoplastic resin to 4 × 10 ⁻⁵ g equivalent / g or more, which is higher than the normal state, a carboxyl group is modified with an amino group after polymerization of the polyamide (for example, by adding a terminal group). A diamine compound is bonded to the carboxyl group of the above). Examples of the amino group compound used for this purpose include aliphatic diamine, aliphatic polyamine, γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ
-Aminopropylmethyldiethoxysilane, N-cyclohexyl-γ-aminopropyltrimethoxysilane and the like can be preferably exemplified.

[0039]

EXAMPLES ( Preparation of Fuel Hose ) Fuel hoses according to Examples 1 to 8 and Comparative Examples 1 to 3 listed in Tables 1 and 2 at the end were prepared.

Each of the fuel hoses according to Examples 1 to 6 and Comparative Examples 1 to 3 has a single inner layer and a single outer layer using predetermined constituent materials shown in Tables 1 and 2. This is a straight tubular hose that is extruded and has a corrugated shape formed in part by a corrugating mold. The fuel hose according to the seventh embodiment has a single inner layer and “○” in Table 1.
This is a straight tubular hose formed by co-extrusion of a total of three layers including two outer layers described as “inner” and “outer”, and partly having a corrugated shape formed by a corrugating mold.

The fuel hose according to Example 8 was obtained by co-extruding an inner layer and an inner layer of an outer layer described in Table 1 as “inner”, and then forming a rubber layer described in Table 1 as “outer”. This is a straight tubular hose in which a coating extrusion is performed, vulcanization is performed, and a part of the hose is provided with a corrugated shape formed by a corrugating mold.

The straight tubular fuel hose according to each of the above-described examples, in which a corrugated shape is partially provided, has an inner diameter of 1 in the smooth portion.
4mm, total thickness 1.5mm, inner layer thickness 0.4m
m, and the thickness of the outer layer is 1.1 mm.

In Tables 1 and 2, for the constituent materials of the inner layer, the corresponding material type is indicated by a circle in the column of “Inner layer material” in each table, and for the constituent materials of the outer layer, the “Outer layer material” in each table is shown. The corresponding material type is indicated by a circle in the column of "". In the table, for example, “VDF / CTFE
= 95/5 "indicates that the constituent material is a copolymer of 95 mol% of VDF and 5 mol% of CTFE.
For PA12 (polyamide 12) or PO (polyolefin), for example, the notation “4 × 10 ⁻⁵ ”
The amino group concentration of these materials is 4 × 10 ⁻⁵ g equivalent / g
Is shown.

(Fuel hose evaluation)Adhesion evaluation  For the fuel hoses according to the above examples,
Cut into four equally divided shapes along the inside of one divided piece
Peeling force per 1cm by peeling the interface between layer and outer layer
Is calculated to determine the adhesive force between the inner and outer layers.
(N / cm) was evaluated. The results of these evaluations are
It is shown in the column of "Adhesive strength".

[0045]Fuel impermeability evaluation  The fuel hose according to each of the above examples
Certain "Fuel C" (such as toluene and isooctane)
vol.% mixture) and left at 40 ° C for 168 hours.
And then discharge it to reseal a new Fuel C.
After entering, leave it at 40 ° C for 72 hours
From the weight change before and after the inclusion body was left for 72 hours,
The amount of fuel permeated per day (g) (g) was calculated.
The results are shown in the “Fuel impermeability” column of each table.
uel C ".

In addition, "Fuel," which is an evaluation test gasoline
The same fuel permeation amount evaluation as described above using "C / E10" (a mixture of Fuel C with 10 vol.% Of ethanol) was also performed. The results of these evaluations are shown in the section "E10" in the column "Fuel impermeability" in each table.

[0047]

[Table 1]

[0048]

[Table 2]

Continued on the front page F-term (reference) 3H111 AA02 BA15 BA34 CA47 CA53 CB03 DA26 DB08 EA04 4F100 AK01B AK03B AK14A AK14J AK17A AK17J AK18A AK18J AK19A J JAKBJB12 AK19B AK48B AK48B AK48JK13 JL09 4J002 BD131 BD141 BD151 BD161 DA036 DA066 FD116 GF00

Claims (9)

[Claims] 1. An adhesive laminate comprising a fluororesin layer and a thermoplastic resin layer directly adhered to each other, wherein the fluororesin layer comprises a fluororesin containing at least 60 mol% of vinylidene fluoride (VDF). An adhesive laminate, wherein a thermoplastic resin having a terminal amino group of 4 × 10 ⁻⁵ g equivalent / g or more is used for the thermoplastic resin layer. 2. The fluororesin containing at least 60 mol% of VDF is polyvinylidene fluoride (PVDF),
Vinylidene fluoride-chlorotrifluoroethylene copolymer (VDF / CTFE), vinylidene fluoride-tetrafluoroethylene copolymer (VDF / TF
E), vinylidene fluoride-hexafluoropropylene copolymer (VDF / HFP), tetrafluoroethylene-vinylidene fluoride-propylene copolymer (TFE / VDF / P) or tetrafluoroethylene-
The adhesive laminate according to claim 1, which is a hexafluoropropylene-vinylidene fluoride copolymer (TFE / HFP / VDF). 3. The fluororesin contains chlorotrifluoroethylene (CTFE) as a copolymerization component with VDF, and the molar ratio of both is VDF / CTFE = 98/2 to 85.
The adhesive laminate according to claim 1 or 2, wherein the ratio is in the range of / 15. 4. The adhesive laminate according to claim 1, wherein an effective amount of a conductive compound is added to the fluororesin layer. 5. The thermoplastic resin according to claim 1, wherein the thermoplastic resin is a polyamide or a polyolefin.
The adhesive laminate according to any one of the above. 6. The polyamide is made of polyamide 6, polyamide 66, polyamide 46, polyamide 610, polyamide 116, polyamide 612, polyamide 11, polyamide 12, polyamide TMHT, polyamide 6I,
Polyamide 6T / 6I, Polyamide PACM12, Polyamide MXD6, Polyamide 11T, Polyamide 11T
The adhesive laminate according to any one of claims 1 to 5, wherein the adhesive laminate is any one of (H), a copolymer or a mixture thereof. 7. A fuel hose comprising the adhesive laminate according to claim 1 in a state where the fluororesin layer is an inner layer. 8. The fuel hose according to claim 7, wherein the fuel hose includes a protector layer made of an arbitrary resin material or a rubber material outside the adhesive laminate. 9. The fuel hose according to claim 7, wherein at least a part of the fuel hose has a corrugated tube shape.