JP4959391B2 - Fuel hose - Google Patents

Description

  The present invention is suitable for transportation of fuels such as automobiles [gasoline, alcohol mixed gasoline, diesel fuel, FAME (fatty acid methyl ester) mixed diesel fuel, synthetic fuel mixed diesel fuel such as GTL (Gas to Liquid), CNG, LPG]. The fuel hose is used.

  Due to the growing global environmental awareness, regulations on the amount of fuel permeated from fuel hoses used in automobiles and the like have been strengthened. In particular, in North America, fairly strict regulations are becoming legislated. Under such circumstances, for example, an inner layer made of acrylonitrile-butadiene rubber (NBR), an intermediate layer made of tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer (THV), and an NBR-PVC product A four-layer fuel hose with an outer layer made of NBR, or an outer layer made of NBR and an outermost layer made of chlorosulfonated polyethylene rubber (CSM) has been proposed.

Since the NBR layer and the THV layer have poor adhesion, NBR is added by adding 1,8-diazabicyclo (5.4.0) undecene-7 salt (DBU salt) to the NBR layer. A fuel hose has been proposed for the purpose of improving interlayer adhesion between the layer-forming layer and the THV-layering layer (see, for example, Patent Document 1).
Japanese Patent Laid-Open No. 8-169085

  However, NBR used for the fuel hose material described in Patent Document 1 is more resistant to fuel permeation, ozone and sour than a blend of acrylonitrile-butadiene rubber and polyvinyl chloride (NBR-PVC). Etc. are inferior, and the reliability as a hose product is low. Therefore, in place of the above NBR, NBR-PVC excellent in fuel permeation resistance, ozone resistance, sour resistance, etc. is used as a hose material, and DBU salt is added to the NBR-PVC layer in the same manner as described above. Thus, it is conceivable to improve the interlayer adhesion between the NBR-PVC layer and the THV layer. However, the adhesion between the NBR-PVC layer and the THV layer does not improve the interlayer adhesion even when the DBU salt is added to the NBR-PVC layer as in the case where the DBU salt is added to the NBR layer. There is a disadvantage that it is inferior to the interlayer adhesion between the NBR layer and the THV layer.

  The present invention has been made in view of such circumstances, and an object of the present invention is to provide a fuel hose that has excellent fuel permeation resistance and excellent interlayer adhesion.

In order to achieve the above object, a fuel hose of the present invention is a fuel hose having a layer structure composed of a tubular resin layer and a rubber layer adjacent to the tubular resin layer, and the rubber layer has the following (A ) to together are formed of a rubber composition as essential components (F), the resin layer Gath tetrafluoroethylene - hexafluoropropylene - vinylidene fluoride - mainly perfluoroalkyl vinyl ether quaternary polymer It is configured to be formed using a material as a component.
(A) A blend of acrylonitrile-butadiene rubber and polyvinyl chloride.
(B) 1,8-diazabicyclo (5.4.0) undecene-7 salt, 1,5-diazabicyclo (4.3.0) -nonene-5 salt, 1,8-diazabicyclo (5.4.0) At least one selected from the group consisting of undecene-7 and 1,5-diazabicyclo (4.3.0) -nonene-5.
(C) Zeolite.
(D) Magnesium oxide.
(E) Layered mineral.
(F) Basic silica.

The inventors of the present invention have made extensive studies in order to obtain a fuel hose that has excellent fuel permeation resistance and excellent interlayer adhesion. As a result, a blend of acrylonitrile-butadiene rubber and polyvinyl chloride (NBR-PVC) was added to DBU salt or DBU, 1,5-diazabicyclo (4.3.0) -nonene-5 salt (DBN salt) or DBN. In addition, the inventors have found that the intended purpose can be achieved by using a rubber composition containing zeolite, magnesium oxide, layered mineral and basic silica, and the present invention has been achieved. This is thought to be based on the following reasons. That, DBU salt is a strong dehydrohalogenating agent, Te tetrafluoroethylene - Become a perfluoroalkyl vinyl ether quaternary polymer of a material composed mainly specific resin layer - hexafluoropropylene - vinylidene fluoride Since dehydrochlorination of PVC in the NBR-PVC layer occurs preferentially over deHF, the interlaminar adhesion between the specific resin layer and the NBR-PVC layer is deteriorated, resulting in interfacial peeling. In the present invention, the chlorine catcher agent such as zeolite, magnesium oxide, layered mineral and basic silica catches the chlorine of PVC, prevents the dehydrochlorination of PVC in the NBR-PVC layer, and the DBU salt is adjacent. As a result of the de-HF from the 2F of the specific resin layer and the de-HF part reacting with the NBR double bond of the NBR-PVC layer with a vulcanizing agent, the interlayer adhesion is improved and the release mode is improved. This is considered to be rubber destruction rather than interfacial peeling.

  As described above, the fuel hose of the present invention has an NBR-PVC layer formed by adding zeolite, magnesium oxide, layered mineral and basic silica together with DBU salt and the like to NBR-PVC and a specific resin layer. Adjacent layer structure. Therefore, for the reasons described above, both layers have excellent interlaminar adhesion, and the peeling mode is not interface peeling, but rubber destruction, and NBR-PVC is used instead of NBR. 、 Excellent sour resistance and reliability as a hose product.

In the fuel hose of the present invention, an intermediate layer is formed on the outer peripheral surface of the tubular inner layer, an outer layer is further formed on the outer peripheral surface, and the inner layer and the outer layer are formed using the rubber composition. together, the intermediate layer is above Kite tetrafluoroethylene - hexafluoropropylene - vinylidene fluoride - When formed using a material mainly composed of perfluoroalkyl vinyl ether quaternary copolymer, and the inner layer and the intermediate layer Both the interlayer adhesion and the interlayer adhesion between the intermediate layer and the outer layer are improved, and the interlayer adhesion of the entire hose is improved.

Furthermore, the rubber composition containing the above (A) to (F) as essential components further contains the following (G), and the content thereof is 10 parts by weight or less with respect to 100 parts by weight of the component (A). This improves the heat resistance of the fuel hose.
(G) Zinc oxide.

  Next, an embodiment of the present invention will be described.

  The fuel hose of the present invention has a layer structure including a tubular resin layer and a rubber layer adjacent thereto.

In the present invention, the rubber layer are in the form of a rubber composition to below the (A) ~ (F) as essential components, the resin layer Gath tetrafluoroethylene - hexafluoropropylene - vinylidene It is formed using a material mainly composed of a fluoride-perfluoroalkyl vinyl ether quaternary copolymer, and these are the greatest features.
(A) A blend of acrylonitrile-butadiene rubber and polyvinyl chloride.
(B) 1,8-diazabicyclo (5.4.0) undecene-7 salt, 1,5-diazabicyclo (4.3.0) -nonene-5 salt, 1,8-diazabicyclo (5.4.0) At least one selected from the group consisting of undecene-7 and 1,5-diazabicyclo (4.3.0) -nonene-5.
(C) Zeolite.
(D) Magnesium oxide.
(E) Layered mineral.
(F) Basic silica.

As the fuel hose of the present invention, for example, as shown in FIG. 1, an intermediate layer 2 is formed on the outer peripheral surface of a tubular inner layer 1, and an outer layer 3 is formed on the outer peripheral surface of the intermediate layer 2. together with the inner layer 1 and the outer layer 3 is formed from the rubber composition, the intermediate layer 2 Gath tetrafluoroethylene - and mainly of perfluoroalkyl vinyl ether quaternary polymer - hexafluoropropylene - vinylidene fluoride And those formed using the material to be used.

  In the present invention, the main component usually means a component occupying the majority of the whole, and includes the case where the whole consists only of the main component.

  As the material for forming the inner layer 1 (inner layer material) and the material for forming the outer layer 3 (outer layer material) of the fuel hose of the present invention, rubber compositions containing the above (A) to (F) as essential components are used.

  The acrylonitrile-butadiene rubber (NBR) and polyvinyl chloride (PVC) blend (NBR-PVC) (component A) is not particularly limited, but the blend ratio (weight ratio) of NBR and PVC is: NBR / PVC = 99/1 to 50/50 is preferable, and NBR / PVC = 90/10 to 60/40 is particularly preferable. Further, the acrylonitrile amount (AN amount) of the NBR is preferably 25 to 60, particularly preferably 31 to 55.

  As the B component used together with the NBR-PVC (component A), 1,8-diazabicyclo (5.4.0) undecene-7 salt (DBU salt), 1,5-diazabicyclo (4.3.0)- Nonene-5 salt (DBN salt), DBU, and DBN are used alone or in combination.

  Examples of the 1,8-diazabicyclo (5.4.0) undecene-7 salt (DBU salt) (component B) include, for example, naphthoate, sorbate, formate, octylate, and oleate of DBU. , O-phthalate, p-toluenesulfonate, DBU phenol resin salt, phenol salt and the like. These may be used alone or in combination of two or more.

  Examples of 1,5-diazabicyclo (4.3.0) -nonene-5 salt (DBN salt) (component B) include, for example, naphthoate, sorbate, formate, octylate and olein of DBN. Acid salts, o-phthalates, p-toluenesulfonates, DBN phenol resin salts, phenol salts, and the like. These may be used alone or in combination of two or more.

  The amount of the DBU salt or the like (component B) is preferably 1 to 4 parts with respect to 100 parts by weight (hereinafter abbreviated as “part”) of NBR-PVC (component A) from the viewpoints of interlayer adhesion and rubber properties. Particularly preferred is 2 to 3 parts.

  As said zeolite (C component), what is represented by following General formula (1) is used, As such a thing, for example, A type zeolite K type, A type zeolite Na type, A type zeolite Ca Type, A type zeolite Mg type, X type zeolite Na type, X type zeolite Ca type and the like. These may be used alone or in combination of two or more. Among these, A-type zeolite Na type is preferably used in terms of adhesiveness.

  As for the compounding quantity of the said zeolite (C component), 5-20 parts is preferable with respect to 100 parts of NBR-PVC (A component). That is, when the blending amount of zeolite (C component) is less than 5 parts, the interlaminar adhesion tends to be lowered, and conversely, when it exceeds 20 parts, the mechanical properties of rubber tend to be lowered. It is.

  The blending amount of magnesium oxide (MgO) (D component) used together with the A to C components is preferably 3 to 20 parts with respect to 100 parts of NBR-PVC (A component) from the viewpoint of adhesiveness and mechanical properties. Particularly preferred is 5 to 15 parts.

  Examples of the layered mineral (component E) include talc, clay, mica, montmorillonite, and the like. These may be used alone or in combination of two or more. Among these, talc is preferably used in terms of excellent adhesiveness.

  The blending amount of the layered mineral (component E) is preferably 10 to 30 parts with respect to 100 parts of NBR-PVC (component A) from the viewpoints of adhesiveness and mechanical properties.

  Examples of the basic silica (F component) include those having a pH of 9 to 12. These may be used alone or in combination of two or more. Among these, those having a high pH are preferable in terms of adhesiveness.

  The blending amount of the basic silica (F component) is preferably 10 to 30 parts with respect to 100 parts of NBR-PVC (A component) from the viewpoint of adhesiveness.

  From the viewpoint of heat resistance of the fuel hose, the rubber composition may contain zinc oxide (G component) as an optional component at a ratio of 10 parts or less with respect to 100 parts of the NBR-PVC (A component). That is, if the content of zinc oxide (G component) exceeds 10 parts, the interlayer adhesion deteriorates.

  In addition to the A to F components, the inner layer material and the outer layer material include zinc oxide (G component), carbon black, lubricant (such as stearic acid), flame retardant, plasticizer, and vulcanizing agent (sulfur). Etc.), vulcanization accelerators, vulcanization aids, anti-aging agents, calcium carbonate, etc. may be blended as necessary.

Then, as the intermediate layer 2 of the forming material of the fuel hose of the present invention (intermediate layer material), Te tetrafluoroethylene - and mainly of perfluoroalkyl vinyl ether quaternary polymer - hexafluoropropylene - vinylidene fluoride The material to be used is used . Upper Symbol tetrafluoroethylene - hexafluoropropylene - vinylidene fluoride - perfluoroalkyl vinyl ether quaternary copolymer, the perfluoroalkyl vinyl ether is not copolymerized, tetrafluoroethylene - hexafluoropropylene - vinylidene fluoride terpolymer Compared to a polymer, it has excellent crazing properties and fuel permeation resistance.

Note that the intermediate layer material, Te tetrafluoroethylene - hexafluoropropylene - vinylidene fluoride - to other perfluoroalkyl vinyl ether quaternary polymer, carbon black, lubricants (such as wax), coloring agents and the like, If necessary, it may be blended appropriately.

As another example of the fuel hose of the present invention, the inner layer 1, an acrylonitrile - it is formed using a rubber composition which is butadiene rubber (NBR) as an essential component, the intermediate layer 2 on Kite tetrafluoroethylene A rubber composition which is formed using a material mainly composed of hexafluoropropylene-vinylidene fluoride-perfluoroalkyl vinyl ether quaternary copolymer, and the outer layer 3 contains the A component to the F component as essential components. The one formed using is used. That is, the fuel hose shown in FIG. 1 has the same configuration as that shown in FIG. 1 except that an acrylonitrile-butadiene rubber (NBR) is used as the inner layer material instead of the rubber composition. It is also possible to use.

  Thus, when using a rubber composition containing NBR as an essential component as the inner layer material, in addition to NBR, carbon black, lubricant (such as stearic acid), zinc oxide, plasticizer, vulcanizing agent (such as sulfur) Further, vulcanization accelerators, vulcanization aids, anti-aging agents, fillers such as calcium carbonate, and the like may be appropriately blended as necessary. In addition, the B component to the F component may be blended.

  The fuel hose of the present invention can be manufactured, for example, as follows. That is, the inner layer material, the intermediate layer material, and the outer layer material are respectively prepared, and these materials are continuously extruded using an extruder to form the intermediate layer 2 on the outer peripheral surface of the inner layer 1. In addition, a fuel hose having an outer layer 3 formed on the outer peripheral surface thereof can be obtained (see FIG. 1). In the fuel hose of the present invention, at the time of hose vulcanization, the interface of each layer is firmly bonded without an adhesive and is laminated and integrated.

  The fuel hose of the present invention is not limited to the above-described manufacturing method. For example, after the inner layer material is extruded with an extruder to form a hose having a single layer structure, the intermediate layer material and the outer layer are formed on the outer peripheral surface. A three-layer fuel hose may be produced by sequentially extruding materials for use. In addition, although the interface of each said layer is normally adhere | attached without an adhesive agent, you may use an adhesive agent supplementarily depending on the case. Further, if necessary, reinforcing yarn (polyester, vinylon, aramid, nylon, etc.) may be put between the layers.

  As for the thickness of each layer of the fuel hose of the present invention, the thickness of the inner layer 1 is usually 0.2 to 4 mm, preferably 0.5 to 2 mm, and the thickness of the intermediate layer 2 is usually 0.02 to 1 mm, preferably Is 0.05 to 0.5 mm, and the thickness of the outer layer 3 is usually 0.2 to 4 mm, preferably 0.5 to 2 mm. Moreover, the internal diameter of the fuel hose of this invention is 2-50 mm normally, Preferably it is 5-35 mm.

  The fuel hose of the present invention is not limited to the three-layer structure as shown in FIG. 1. For example, a rubber layer (innermost layer) is provided on the inner peripheral surface of the inner layer 1 or the outer periphery of the outer layer 3. A rubber layer (outermost layer) made of chlorosulfonated polyethylene rubber (CSM) or the like may be formed on the surface, and a coating layer of rubber glue or the like may be formed over the end or the entire length of the fuel hose. .

  Next, examples will be described together with comparative examples. However, the present invention is not limited to these examples.

  Prior to the examples and comparative examples, the following NBR-PVC materials and NBR materials were prepared.

(Preparation of NBR-PVC material and NBR material)
The components shown in Table 1 and Table 2 below were blended in the proportions shown in the same table, and these were kneaded using Banbury and rolls to prepare NBR-PVC materials and NBR materials.

The materials shown in Table 1 and Table 2 are as follows.
[NBR-PVC * 1]
Nipol 1203JNS [NBR / PVC = 70/30 (weight ratio), AN amount: 33.5]
[NBR * 2]
Nipol DN101 (AN quantity: 42.5) manufactured by Nippon Zeon
[Stearic acid * 3]
Made by Kao, Lunac S30
[ZnO * 4]
Mitsui Metal Mining Co., Ltd., zinc oxide 2 types [MgO * 5]
Kyowa Chemical Co., Ltd., Kyowa Mug # 150
[DBU salt * 6]
DBU naphthoate (carbon black * 7)
SRF grade carbon black (Tokai Carbon, Seast S)
[Zeolite * 8]
Mizusawa Chemical Industry Co., Ltd.
[Talc * 9]
Mistrone Vapor Talc [Basic Silica * 10], manufactured by Nippon Mytron
Carplex 1120, manufactured by DSL Japan
[Ether ester plasticizer * 11]
Asahi Denka Co., Ltd., Adeka Sizer RS107
[Sulfur * 12]
Tsurumi Chemical Co., Ltd., Jinhua stamped sulfur (thiazole vulcanization accelerator (OBS) * 13)
N-oxydiethylene-2-benzothiazolylsulfenamide (OBS) (Ouchi Shinsei Chemical Co., Ltd., Noxeller MSA-G)

[Examples 1 to 10 , 12 to 15 , Reference Example, Comparative Examples 1 to 4]
The outer layer of the inner layer (thickness 2 mm) was prepared by preparing the forming materials for each layer prepared as described above, and continuously extruding them with the combinations shown in Tables 3 to 5 below using an extruder. A fuel hose (inner diameter: 24 mm) having a three-layer structure in which an intermediate layer (thickness: 0.1 mm) was formed on the surface and an outer layer (thickness: 2 mm) was formed on the outer peripheral surface was prepared.

Example 11
(Preparation of outermost layer material)
100 parts of chlorosulfonated polyethylene rubber (CSM) (manufactured by DuPont Elastomer, Hypalon 40), 10 parts of titanium oxide, 90 parts of calcium carbonate, 5 parts of SRF grade carbon black (Seast S, manufactured by Tokai Carbon Co., Ltd.) 5 parts of magnesium oxide (Kyowa Chemical Co., Ltd., Kyowa Mag # 150), 3 parts of pentaerythritol, 25 parts of dioctyl sebacate, 1 part of Nocrack NBC (Ouchi Shinsei Chemical Co., Ltd.), Noxeller TRA (Ouchi) 2 parts) (manufactured by Shinsei Chemical Co., Ltd.) were blended, and these were kneaded with a banbury and a roll to prepare an outermost layer material (CSM material).

(Production of fuel hose)
Preparation materials for each layer prepared as described above were prepared, and these were continuously extruded using an extrusion molding machine in the combinations shown in Table 4 below, so that an intermediate layer was formed on the outer peripheral surface of the inner layer (thickness 2 mm). A fuel having a four-layer structure in which a layer (thickness 0.1 mm) is formed, an outer layer (thickness 0.5 mm) is formed on the outer peripheral surface, and an outermost layer (thickness 1.5 mm) is formed on the outer peripheral surface. A hose (inner diameter 24 mm) was prepared.

  Using the fuel hoses of Examples and Comparative Examples thus obtained, the peeling mode and the rate of change in elongation after heat aging were evaluated according to the following criteria. These results are shown in Tables 3 to 5 above.

[Peeling mode (interlayer adhesion)]
A test piece having a width of 25.4 mm was cut out from each fuel hose, and the outer layer of the test piece was peeled off at a rate of 50 mm per minute using a tensile tester (JIS B 7721). Was observed. In the evaluation, “◯” indicates that the outer layer was destroyed by rubber, and “X” indicates that the outer layer was peeled off at the interface between the intermediate layer and the intermediate layer.

[Change in elongation after heat aging]
Using each fuel hose, the elongation change rate of the outer layer material after heat aging at 100 ° C. × 72 hours, 100 ° C. × 168 hours, 120 ° C. × 72 hours was measured.

From the results of Tables 3 to 5 above, all of the examples were good in the peeling mode of rubber breakage. In addition, Examples 9 and 13 to 15 using NBR-PVC materials I, K, L, and M containing ZnO were elongated after heat aging compared to fuel hoses using materials not containing ZnO. Change rate was small and heat resistance was improved.

  On the other hand, since the product of Comparative Example 1 uses a material not containing zeolite, talc, and basic silica, interfacial peeling occurred. Since the comparative example 2 product uses a material not containing zeolite, interfacial peeling occurred. Since the comparative example 3 product uses the material which does not contain basic silica, interfacial peeling occurred. Since the comparative example 4 product used the material which does not contain talc, interface peeling occurred.

  The fuel hose of the present invention is mainly suitably used for automobile fuel hoses, but can also be used for tractors, cultivators, ships and the like.

It is a block diagram which shows an example of the fuel hose of this invention.

Explanation of symbols

1 Inner layer 2 Middle layer 3 Outer layer

Claims (5)

A fuel hose having a layer structure composed of a tubular resin layer and a rubber layer adjacent to the tubular resin layer, wherein the rubber layer uses a rubber composition having the following (A) to (F) as essential components together they are formed Te, the resin layer Gath tetrafluoroethylene - and characterized by being formed using a material mainly composed of perfluoroalkyl vinyl ether quaternary polymer - hexafluoropropylene - vinylidene fluoride Fuel hose.
(A) A blend of acrylonitrile-butadiene rubber and polyvinyl chloride.
(B) 1,8-diazabicyclo (5.4.0) undecene-7 salt, 1,5-diazabicyclo (4.3.0) -nonene-5 salt, 1,8-diazabicyclo (5.4.0) At least one selected from the group consisting of undecene-7 and 1,5-diazabicyclo (4.3.0) -nonene-5.
(C) Zeolite.
(D) Magnesium oxide.
(E) Layered mineral.
(F) Basic silica.   The blending amount of the component (B) is 1 to 4 parts by weight with respect to 100 parts by weight of the component (A), the blending amount of the component (C) is 5 to 20 parts by weight with respect to 100 parts by weight of the component (A), The blending amount of the component (D) is 3 to 20 parts by weight with respect to 100 parts by weight of the component (A), the blending amount of the component (E) is 10 to 30 parts by weight with respect to 100 parts by weight of the component (A), And the compounding quantity of the said (F) component is 10-30 weight part with respect to 100 weight part of (A) component, The fuel hose of Claim 1 characterized by the above-mentioned. An intermediate layer is formed on the outer peripheral surface of the tubular inner layer, an outer layer is further formed on the outer peripheral surface, and the inner layer and the outer layer are made of a rubber composition containing (A) to (F) as essential components. together are formed Te, the upper the intermediate layer Kite tetrafluoroethylene - hexafluoropropylene - vinylidene fluoride - claim is formed using a material mainly composed of perfluoroalkyl vinyl ether quaternary polymer The fuel hose according to 1 or 2. An intermediate layer is formed on the outer peripheral surface of the tubular inner layer, an outer layer is further formed on the outer peripheral surface, and the inner layer is formed using a rubber composition containing acrylonitrile-butadiene rubber as an essential component. There upper Kite tetrafluoroethylene - hexafluoropropylene - vinylidene fluoride - perfluoroalkyl vinyl ether quaternary polymer with is formed using a material mainly composed of, the outer layer is the (a) ~ (F The fuel hose according to claim 1 or 2, which is formed by using a rubber composition having an essential component as a component. The rubber composition containing (A) to (F) as essential components further contains the following (G), and the content thereof is 10 parts by weight or less with respect to 100 parts by weight of the component (A). The fuel hose as described in any one of 1-4.
(G) Zinc oxide.

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