JP4691913B2 - Dimethyl ether transport hose - Google Patents

Description

  The present invention relates to a transport hose for dimethyl ether (hereinafter also referred to as “DME”), which is attracting attention as one of the next fuels to replace fossil fuels typified by petroleum, coal, and natural gas.

  Conventionally, various hoses have been used for automobiles, electrical products and the like. The fluid used for these hoses is not particularly limited, and examples thereof include air conditioner and refrigerator refrigerants, fuel such as gasoline, oil, and the like. For example, as an example of a hose used for fuel (transportation), a hose having a multilayer structure including an inner layer composed of a polyamide-based resin composition can be given (see, for example, Patent Document 1 and Patent Document 2).

  By the way, in recent years, as the next fuel to replace fossil fuels, there is little environmental impact such as no generation of sulfur oxides and soot, and the amount of nitrogen oxides generated can be greatly reduced. Fuel for diesel vehicles, fuel for power generation, LP DME that can be used for a wide range of applications such as gas substitute fuel is expected (see Non-Patent Document 1).

JP 2003-154586 A JP 2003-21276 A "Dimethyl ether strategy study group report", Agency for Natural Resources and Energy, Coal Division, New Energy Department, September 2000

However, since the conventional hose is not supposed to use DME as a fluid (fuel), there is a problem that DME easily permeates and abnormal swelling occurs in the portion of the hose that contacts the DME. Further, as a result of intensive studies by the present inventors, it has been found that the polyamide-based resin composition is excellent in stability and permeation resistance against DME, but is inferior in flexibility, without impairing flexibility as a hose. Therefore, it is impossible to form a layer having a sufficient resistance to permeation to DME. Therefore, the multi-layered hose having a polyamide resin composition layer may be permeated by DME depending on the configuration of each layer, and may be limited in use because of its poor flexibility.
Therefore, it is desired to provide a hose that can sufficiently exhibit the performance as a hose even when DME that is expected as the next fuel is used.
Accordingly, an object of the present invention is to provide a hose that can sufficiently suppress permeation leakage of DME, transport and supply DME for a long period of time, and is excellent in flexibility.

As a result of intensive studies to solve the above problems, the present inventor has found that butyl rubber and the like are excellent in DME stability and permeation resistance. Further, it has been found that by using a butyl rubber composition as a material for forming an inner tube of a hose, stability against DME and permeation resistance are further improved, and the performance as a hose is not impaired. The present inventor has completed the present invention based on these findings. Here, the stability with respect to DME means that swelling or cracking does not occur even when contacted with DME. Hereinafter, the stability against DME and the permeation resistance are collectively referred to as DME resistance.
Such an object is achieved by the present inventions (1) to (10) below.

(1) A dimethyl ether transport hose comprising at least an inner tube having at least one layer composed of a butyl rubber composition.
Here, the butyl rubber composition is a composition containing butyl rubber and various additives when necessary.

  (2) The dimethyl ether transport hose according to (1), wherein the inner pipe is an inner pipe having an inner layer made of a butyl rubber composition.

(3) The dimethyl ether transport hose according to (2), wherein the inner pipe is an inner pipe having a layer composed of a polyamide-based resin composition outside the inner layer.
In addition, the layer comprised by the polyamide-type resin composition formed in the outer side of the inner layer comprised by the said butyl-type rubber composition is hereafter called "an intermediate | middle layer" for convenience. The polyamide-based resin composition is a composition containing a polyamide-based resin and various additives when necessary.

(4) The dimethyl ether transport according to (3), wherein the inner tube is an inner tube having a layer formed of a butyl rubber composition on the outside of the layer formed of the polyamide resin composition. For hose.
In addition, the layer comprised by the butyl-type rubber composition formed in the outer side of the layer (intermediate layer) comprised by the said polyamide-type resin composition is hereafter called an "outer layer" for convenience.

(5) The dimethyl ether transport according to (1), wherein the inner pipe is an inner pipe having an inner layer composed of a polyamide resin composition and a layer composed of a butyl rubber composition outside the inner layer. For hose.
In addition, the layer comprised by the butyl-type rubber composition formed in the outer side of the inner layer comprised by the said polyamide-type resin composition is hereafter called an "intermediate layer" for convenience.

(6) The dimethyl ether transport hose according to any one of (3) to (5), wherein the polyamide-based resin composition has a dimethyl ether permeability coefficient of 0.017 mg · mm / (hr · cm ² ) or less.

(7) The dimethyl ether transport hose according to any one of (1) to (6), wherein a dimethyl ether permeability coefficient of the butyl rubber composition is 0.167 mg · mm / (hr · cm ² ) or less.

  (8) The dimethyl ether transport hose according to any one of (1) to (7), further including an outer tube made of a rubber composition outside the inner tube.

  (9) The dimethyl ether transport hose according to any one of (1) to (7), wherein a reinforcing layer is provided outside the inner tube.

  (10) The hose for transporting dimethyl ether according to (9), further including an outer tube made of a rubber composition outside the reinforcing layer.

  The DME transport hose of the present invention can sufficiently suppress the permeation leakage of DME, and can transport and supply DME for a long period of time. Furthermore, since it is excellent in flexibility, it can be used for various purposes.

In the DME transport hose of the present invention (hereinafter referred to as “the hose of the present invention”), at least one layer of the inner tube is composed of a butyl rubber composition.
A first aspect of the hose of the present invention (hereinafter referred to as “first hose”) is a DME transport hose provided with an inner tube having an inner layer composed of a butyl rubber composition.
The inner tube of the first hose may be formed of one inner layer or an inner layer formed by laminating a plurality of layers as long as it has an inner layer composed of a butyl rubber composition. When the inner layer is formed by laminating a plurality of layers, the butyl rubber contained in the butyl rubber composition constituting each layer may be the same or different.

The butyl rubber contained in the butyl rubber composition is not particularly limited as long as it is a butyl rubber that does not depart from the purpose of the present invention, its molecular weight, substituent, and introduction rate thereof. For example, butyl rubber (IIR), chlorinated butyl rubber (CIIR), brominated butyl rubber (BIIR), brominated isobutylene-p-methylstyrene copolymer rubber (BIMS) and the like are preferably exemplified.
These butyl rubbers may be used alone or in combination of two or more, and may be used in combination with other rubbers or resins.

The butyl rubber composition preferably has a DME permeability coefficient of 0.167 mg · mm / (hr · cm ² ) or less determined by a test method for a DME permeability test described later. When the DME permeability coefficient is 0.167 mg · mm / (hr · cm ² ) or less, the permeability to DME is excellent and the stability to DME is high, so that it can be used for a long time as a hose. From the viewpoint of excellent this effect, DME permeability coefficient is more preferably 0.125mg · mm / (hr · cm 2) or less, 0.104mg · mm / (hr · cm 2) further be less is preferable.

Hereinafter, a test method for the DME permeability test will be described.
FIG. 4 is a cross-sectional view of a laboratory cup used to measure DME permeation resistance.
In a stainless steel cup 10 as shown in FIG. Next, the upper opening of the cup 10 is covered with a sheet-like test body 14 made of a rubber composition or resin, and the sintered metal plate 16 is placed on the test body 14. Next, the fixing member 18 is disposed on the sintered metal plate 16, and the test body 14 and the sintered metal plate 16 are brought into close contact with the cup 10 and fixed by the bolt 20 and the nut 22 via the fixing member 18. . Thereafter, the total mass (initial mass) of the cup is measured.
Next, after leaving the cup to stand at 40 ° C. for 14 days (336 hours), the total mass of the cup (the mass after being left) is measured. The mass after the standing is subtracted from the initial mass to obtain the mass reduction amount, and the DME permeability coefficient is calculated according to the following formula (I).

DME transmission coefficient [mg · mm / (hr · cm ² )] = M · t / (T · A) (I)

In the formula, M is the mass loss (mg), t is the thickness (mm) of the specimen, T is the test time (hr), and A is the permeation area (cm ² ). The transmission area of A is the area of the opening of the cup.

  As described above, the butyl rubber composition, particularly the butyl rubber composition satisfying the DME permeability coefficient, is excellent in DME resistance, and also has high heat resistance and electrical insulation, so that it is in direct contact with DME. It is suitable as a material for the inner layer of a DME transport hose.

  In the present invention, specific examples of the additive contained in the butyl rubber composition include a vulcanizing agent, a vulcanization accelerator, a filler, a reinforcing agent, a plasticizer, an antiaging agent, and a softening agent. , Tackifiers, lubricants, dispersants, processing aids, and the like. These additives can be appropriately selected from those generally used for various hoses according to the type of butyl rubber, the use of the hose, the production conditions, and the like. The content of the additive may be a generally used amount.

A dimethyl ether transport hose (including a reinforcing layer and an outer tube) including an inner tube having an inner layer composed of a butyl rubber composition will be described with reference to FIG. 1, but the hose of the present invention is not limited thereto.
FIG. 1 is a perspective conceptual view showing each layer (each pipe) of a hose which is an embodiment of a DME transport hose according to the present invention. The DME transport hose 1 is a hose including an inner tube 2, a reinforcing layer 6, and an outer tube 7.

A DME transport hose 1 shown in FIG. 1 includes an inner tube 2 having an inner layer 3 made of the butyl rubber composition, a reinforcing layer 6 on the outer side, and an outer tube 7 on the outer side. I have. The inner tube 2 is composed of a single inner layer 3 composed of the butyl rubber composition, and forms the innermost layer of the hose. The thickness of the inner layer 3 (inner tube 2) may be arbitrarily designed as necessary. However, from the viewpoint of improvement in permeation resistance to DME and problems in manufacturing and handling, for example, 0.5-5 About 0.0 mm is preferable, and about 0.8 to 3.0 mm is more preferable.
Even if the hose of the present invention has a thickness in the above range, the inner layer is formed of a butyl rubber composition having flexibility, and thus has excellent flexibility. In addition, the hose of the present invention satisfies the flexibility required for each application by appropriately changing the type and amount of the additive or appropriately changing the thickness of each layer such as an intermediate layer described later or the outer tube. can do.

Further, the DME transport hose 1 of the present invention does not necessarily have the reinforcing layer 6, but if the reinforcing layer 6 is provided, the breaking strength, usable pressure range, and fitting of the DME transport hose 1 are attached. This is preferable because of improved properties. The reinforcing layer 6 will be described later.
The outer tube 7 is the outermost layer of the DME transport hose 1 and is a layer that retains the weather resistance, heat resistance, water permeability resistance, etc. of the DME transport hose 1. In the present invention, the outer tube 7 is not necessarily provided. The outer tube 7 will be described later.

  The first hose is excellent in DME resistance and includes an inner layer composed of a flexible butyl rubber composition, so that permeation leakage of DME can be suppressed and DME can be transported and supplied for a long period of time. Furthermore, it is excellent in flexibility.

In the hose of the present invention, the inner pipe has a layer (intermediate layer) composed of a polyamide resin composition on the outer side so as to cover the outer peripheral surface of the inner layer composed of the butyl rubber composition. It is preferable that the inner tube has a layer structure.
It is easy to reduce the thickness of the layer, and a DME transport hose (hereinafter referred to as “second hose”) having an inner pipe having the above two-layer structure using a polyamide-based resin that is a material excellent in DME resistance. Say) has better DME resistance.

  The polyamide resin contained in the polyamide resin composition constituting the intermediate layer is not particularly limited as long as it is a polyamide resin that does not depart from the object of the present invention. A polyamide-based resin that can be bonded to the rubber layer and the resin layer and is particularly excellent in permeation resistance, heat resistance, and flexibility is preferably exemplified.

  Specific examples of the polyamide-based resin having such characteristics include nylon 46, nylon 6, nylon 66, nylon 610, nylon 611, nylon 612, nylon 11, nylon 12, nylon 666, nylon MXD6, and nylon. 6T, nylon 6/66 copolymer, nylon 6/66/610 copolymer, nylon 6 / 6T copolymer, nylon 66 / PP copolymer, nylon 66 / PPS copolymer, meta-xylene in the main chain Examples thereof include polyamide resins having an aromatic ring such as diamine, polyamide / modified polyolefin blend resins, and the like. Among these, nylon 6, nylon 66, nylon 11 and nylon 12 are preferable because they are more excellent in the above characteristics. These polyamide resins may be used alone or in combination of two or more, and may be used in combination with other resins.

The polyamide resin preferably has a DME permeability coefficient determined by the test method of 0.017 mg · mm / (hr · cm ² ) or less. When the DME permeability coefficient is 0.017 mg · mm / (hr · cm ² ) or less, the DME has excellent permeation resistance to DME, has high stability to DME, and can be used for a long time as a hose. From the viewpoint of excellent this effect, DME permeability coefficient is more preferably 0.015mg · mm / (hr · cm 2) or less, 0.014mg · mm / (hr · cm 2) further be less is preferable.

  The second hose includes an inner tube having an inner layer of a butyl rubber composition and an intermediate layer of a polyamide resin composition, and the butyl rubber and the polyamide resin composition contained in the butyl rubber composition. The combination of polyamide-based resins contained in is not particularly limited, and is a group consisting of butyl rubber selected from the group consisting of IIR, CIIR, BIIR and BIMS, and nylon 6, nylon 66, nylon 11 and nylon 12 It is preferably a polyamide resin selected more.

In the second hose, the intermediate layer may be formed of the polyamide-based resin alone, but the intermediate layer is constituted by the polyamide-based resin composition containing various additives in that the performance as a hose can be secured. Is preferred.
If necessary, specific examples of additives contained in the polyamide-based resin composition include fillers, reinforcing agents, plasticizers, anti-aging agents, softeners, tackifiers, lubricants, dispersants, and processing. An auxiliary agent etc. can be mentioned. These additives can be appropriately selected from those generally used for various hoses depending on the type, application, production conditions, and the like of the polyamide resin. The content of the additive may be a generally used amount.

A dimethyl ether transport hose comprising a two-layer inner tube having a layer (intermediate layer) composed of a polyamide-based resin composition on the outside so as to cover the outer peripheral surface of the inner layer composed of a butyl-based rubber composition (A reinforcing layer and an outer tube are also provided) will be described with reference to FIG. 2, but the hose of the present invention is not limited thereto.
FIG. 2 is a perspective conceptual view showing notches each layer (each tube) of a hose which is an embodiment of a DME transport hose having an inner tube having a two-layer structure of the present invention. The DME transport hose 1 is a hose provided with an inner tube 2 having an inner layer 3 and an intermediate layer 4, a reinforcing layer 6, and an outer tube 7.

A DME transport hose 1 shown in FIG. 2 has a layer (intermediate layer) formed of a polyamide resin composition on the outer side thereof so as to cover the outer peripheral surface of the inner layer 3 formed of the butyl rubber composition. 4 is provided with an inner tube 2 having a two-layer structure, a reinforcing layer 6 on the outer side, and an outer tube 7 on the outer side.
Except for the inner tube 2 having a two-layer structure having an intermediate layer 4 on the outer side of the inner layer 3, it is the same as the DME transport hose shown in FIG.

  The thickness of the layer (intermediate layer) 4 composed of the polyamide-based resin composition may be arbitrarily designed as necessary, but it is 0.05 to 0.5 mm from the viewpoint of DME permeation resistance and hose flexibility. And preferably 0.1 to 0.3 mm.

In the hose of the present invention, the inner tube is preferably a three-layered inner tube having an outer layer made of a butyl rubber composition on the outer side so as to cover the outer peripheral surface of the intermediate layer. .
The inner layer (innermost layer) and the intermediate layer are the same as described above, and the butyl rubber composition constituting the outer layer is basically the same as the butyl rubber composition constituting the inner layer. The butyl rubber contained in the butyl rubber composition constituting the inner layer and the outer layer may be the same or different.
The DME transport hose (hereinafter referred to as “third hose”) having such a structure has further excellent DME resistance.

  A third hose having an inner tube having a three-layer structure has at least one selected from the group consisting of IIR, CIIR, BIIR, and BIMS, wherein the butyl rubber contained in the butyl rubber composition constituting the inner layer and the outer layer It is preferable to combine the seed and at least one selected from the group consisting of nylon 6, nylon 66, nylon 11 and nylon 12 as the polyamide resin contained in the polyamide resin composition constituting the intermediate layer.

A dimethyl ether transport hose comprising a three-layer inner pipe having an outer layer composed of a butyl rubber composition on the outer side so as to cover the outer peripheral surface of the intermediate layer (also provided with a reinforcing layer and an outer pipe) However, the hose of the present invention is not limited to this.
FIG. 3 is a perspective conceptual view showing notches each layer (each tube) of a hose which is an embodiment of a DME transport hose having an inner tube having a three-layer structure of the present invention. The DME transport hose 1 is a hose including an inner tube 2 having an inner layer 3, an intermediate layer 4, and an outer layer 5, a reinforcing layer 6, and an outer tube 7.

The DME transport hose 1 shown in FIG. 3 has an outer layer 5 made of a butyl rubber composition on the outer side so as to cover the outer peripheral surface of the intermediate layer 4 made of the polyamide resin composition. An inner tube 2 having a layer structure is provided, a reinforcing layer 6 is provided on the outer side, and an outer tube 7 is provided on the outer side.
The DME transport hose shown in FIGS. 1 and 2 is the same as that described above except that the inner pipe 2 has a three-layer structure having an outer layer 5 outside the intermediate layer 4.

  The thickness of the outer layer 5 composed of the butyl rubber composition may be arbitrarily designed as necessary, but is preferably 0.5 to 5.0 mm, and preferably 0.8 to 3.0 mm. It is more preferable.

Another aspect of the hose of the present invention is for DME transportation comprising an inner pipe composed of a polyamide-based resin composition and an inner pipe having a layer (intermediate layer) composed of a butyl-based rubber composition outside the inner layer. Hose (hereinafter referred to as “fourth hose”).
The polyamide resin composition constituting the inner layer of the fourth hose is basically the same as the polyamide resin composition described in the second hose. The butyl rubber composition constituting the intermediate layer of the fourth hose is basically the same as the butyl rubber composition described in the first hose.

  A fourth hose comprising a two-layer inner tube having a layer (intermediate layer) composed of a butyl rubber composition on its outer side so as to cover the outer peripheral surface of the inner layer composed of the polyamide resin composition The structure is basically the same as that of the second hose including the two-layer inner pipe. Further, a reinforcing layer and an outer tube may be provided outside the intermediate layer.

  The thickness of the inner layer of the fourth hose is the same as the thickness of the intermediate layer made of the polyamide resin composition described for the second hose. The thickness of the intermediate layer of the fourth hose is the same as the thickness of the inner layer formed of the butyl rubber composition described for the first hose.

  The fourth hose includes an inner tube having an inner layer of a polyamide-based resin composition and an intermediate layer of a butyl-based rubber composition, and the polyamide-based resin and the butyl-based rubber composition contained in the polyamide-based resin composition. The combination of butyl rubbers contained in is not particularly limited, but is a polyamide resin selected from the group consisting of nylon 6, nylon 66, nylon 11 and nylon 12, and a group consisting of IIR, CIIR, BIIR and BIMS. A butyl rubber selected more is preferable.

  As a result of intensive studies by the present inventors, it has been found that the polyamide-based resin composition is excellent in DME resistance. However, since the polyamide resin composition is inferior in flexibility, the structure of a hose having an inner layer of a conventional polyamide resin composition has sufficient DME permeability resistance without impairing flexibility as a hose. There wasn't. On the other hand, in the fourth hose of the present invention, the inner layer constituted by the polyamide-based resin composition has a thickness that does not impair the flexibility of the hose, and is further improved in DME resistance and flexibility outside the inner layer. Since the inner tube having a layer composed of an excellent butyl rubber composition is provided, it is possible to achieve both DME resistance and flexibility.

In the hose of the present invention, the inner tube has a three-layer structure in which an outer layer made of a polyamide resin composition is further provided on the outer side so as to cover the outer peripheral surface of the intermediate layer of the fourth hose. It can also be a tube.
The inner layer and the intermediate layer are the same as the fourth hose described above, and the polyamide resin composition constituting the outer layer is basically the same as the polyamide resin composition constituting the inner layer. The polyamide resin contained in the polyamide resin composition constituting the inner layer and the outer layer may be the same or different.
The DME transport hose having such a structure has further excellent DME resistance.

As described above, the hose of the present invention is characterized by the inner tube. However, the outer tube is further provided on the outer side so as to cover the outer peripheral surface of the inner tube. It is preferable for reasons such as water permeability and hose protection.
Although it does not specifically limit as a material which comprises an outer tube | pipe, Ethylene-propylene-diene rubber (EPDM), chloroprene rubber (CR), chlorosulfonated polyethylene rubber (CSM) and IIR, BIIR, CIIR, which have good weather resistance, Rubber composition containing rubber such as butyl rubber such as BIMS; Thermoplastic elastomer composition containing thermoplastic elastomer such as polyamide elastomer, polyester elastomer, polyolefin elastomer, EPDM / PP thermoplastic elastomer composition, etc. be able to.
The outer tube may be formed of one layer or a plurality of layers.
The thickness of the outer tube may be arbitrarily designed as necessary, but is preferably about 0.5 to 3.0 mm, and more preferably about 0.8 to 2.0 mm.

Although the hose of the present invention is characterized by the inner pipe as described above, it is preferable to provide a reinforcing layer on the outer side of the inner pipe so as to cover the outer peripheral surface of the hose from the viewpoint of excellent breaking strength and durability of the hose.
The reinforcing layer is not particularly limited as long as it is generally used. However, the reinforcing layer may be formed in a blade shape or a spiral shape, and specifically, for example, a wire or an aramid. Examples of the yarn include reinforcing yarns such as fibers and polyester fibers wound with a blade or two layers of spirals in the opposite direction, and an intermediate rubber layer interposed between two layers of spirals in the opposite direction. Among these, a reinforcing layer in which reinforcing yarns such as aramid fibers and polyester fibers are braided is preferable because of the excellent flexibility of the resulting DME transport hose.

In addition, it is preferable that the hose of the present invention further includes an outer tube on the outer side so as to cover the outer peripheral surface of the reinforcing layer in terms of excellent weather resistance, heat resistance, and water permeability of the hose. The material constituting the outer tube is the same as the material constituting the outer tube provided to cover the outer peripheral surface of the inner tube.
The outer tube may be formed of one layer or a plurality of layers.

  In the present invention, an adhesive layer for adhering the inner tube (inner layer, intermediate layer, outer layer), reinforcing layer, and outer tube may be provided. The adhesive composition used for the adhesive layer is not particularly limited as long as both adherends can be bonded to each other. For example, phenol resin-based, epoxy resin-based and urethane-based adhesive compositions can be used. is there. Further, instead of using an adhesive layer, melt adhesion by heating or adhesion by crosslinking may be performed.

  As a method for producing the hose of the present invention, a conventionally known method for producing a hose can be used. For example, a plurality of reinforcing yarns or reinforcing wires are gathered on the outer periphery of the unvulcanized butyl rubber composition formed in a cylindrical shape on the outer periphery of a mandrel or the like and braided into a spiral shape or a blade shape. A reinforcing layer is formed, and an outer tube is formed on the outer periphery thereof by extrusion molding. Subsequently, the entire hose is heated. The heating temperature may be a temperature at which the rubber is vulcanized, and is preferably 120 ° C. or higher, more preferably 140 to 170 ° C. After sufficiently cooling, the hose of the present invention can be obtained by extracting the mandrel.

Moreover, the manufacturing method of a hose provided with the inner pipe | tube of a 3 layer structure is demonstrated concretely using FIG.
First, by using an extruder, a butyl rubber composition is extruded on a mandrel to which a release agent has been added in advance to form the inner layer 3. Next, the mandrel formed with the inner layer 3 is passed through a suitable extruder, and the polyamide resin composition is extruded onto the inner layer 3 to form the intermediate layer 4.
If necessary, the intermediate layer 4 can be formed after applying an adhesive such as phenol resin, epoxy resin, or urethane to the surface of the inner layer 3 by coating, spraying, or the like.

An adhesive is applied onto the formed intermediate layer 4 as necessary, and a butyl rubber composition is extruded onto the intermediate layer 4 in the same manner as described above to form the outer layer 5. This is tube 2.
If necessary, an adhesive is applied to the formed outer layer 5 for adhesion to the reinforcing yarn, and then the reinforcing yarn is braided using a braiding machine to form the reinforcing layer 6. If necessary, after braiding, an adhesive is applied for adhesion to the outer tube 7, and the rubber composition is extruded thereon using an extruder to form the outer tube 7.
When the inner layer 3, the intermediate layer 4, the outer layer 5, the reinforcing layer 6 and the outer tube 7 are formed in this way, vulcanization is performed, and finally the mandrel is pulled out to form the inner tube 2 having the three-layer structure of the present invention. The DME transport hose 1 provided is obtained.

  As described above, the hose of the present invention has a layer composed of a butyl rubber composition having excellent stability, permeation resistance and flexibility with respect to DME, thereby suppressing permeation leakage of DME and making DME safe. It enables long-term transportation and supply, and is excellent in flexibility.

  The hose of the present invention is capable of transporting and supplying DME safely and for a long time, has excellent flexibility, and further has characteristics such as heat resistance, weather resistance, and electrical insulation, and therefore transports DME. Although it can be used for various applications, it can be suitably used particularly for oil supply hoses, automobile inner pipes and the like.

  Hereinafter, the DME transport hose of the present invention will be specifically described according to examples. However, the present invention is not limited to this.

(Reference example)
<DME resistance test>
As a material constituting the innermost layer of the DME transport hose, high stability and permeation resistance against DME are required. Therefore, first, a rubber composition in which the components shown in Table 1 below are mixed in the composition (parts by mass) shown in Table 1 is vulcanized at 160 ° C. for 45 minutes to obtain a sheet-like specimen (thickness of 0. 5 mm). About each obtained test body, the DME permeation resistance and the stability with respect to DME were evaluated by the following method.
The results are shown in Table 1.

(DME permeability test)
In a stainless steel cup 10 (opening area: 5.72 cm ² ) as shown in FIG. 4, half of the cup capacity of DME 12 was placed. Next, the upper opening of the cup 10 was covered with each sheet-like test body 14, and the sintered metal plate 16 was placed on the test body 14. Next, the fixing member 18 is disposed on the sintered metal plate 16 and is tightened with the bolt 20 and the nut 22 via the fixing member 18 so that the test body 14 and the sintered metal plate 16 are brought into close contact with the cup and fixed. did. Thereafter, the total mass (initial mass) of the cup was measured.
Next, after leaving at 40 ° C. for 14 days (336 hours), the mass of the entire cup (mass after standing) was measured. The mass loss was calculated by subtracting the mass after standing from the initial mass, and the DME permeability coefficient was calculated according to the above formula (I).

(Stability test against DME)
The stability of the rubber or resin after the measurement of the DME permeability coefficient was confirmed visually by checking the degree of swelling, the presence or absence of cracks on the surface, or deformation (hereinafter also referred to as “abnormal appearance”). In Table 1, “O” indicates that no swelling was observed and no cracks or deformations were observed on the rubber or resin surface, and “X” indicates that swelling or cracks were observed. It was.

Each component in Table 1 is as follows.
・ IIR: EXXON BUTYL 268, manufactured by ExxonMobil ・ CIIR: EXXON CHLOROBUTYL 1066, manufactured by ExxonMobil ・ BIIR: EXXON BROMOBUTYL 2255, manufactured by ExxonMobil ・ NR: RSS # 1
SBR: Nipol 1502, manufactured by Nippon Zeon Co., Ltd. CR: electrified chloroprene, manufactured by Denki Kagaku Kogyo Co., Ltd. NBR (AN = 18%): Nipol DN401 (acrylonitrile content 18%), manufactured by Nippon Zeon Co., Ltd. NBR (AN = 29 %): Nipol 1043 (acrylonitrile content 29%), manufactured by Nippon Zeon Co., Ltd. • NBR (AN = 33%): Nipol 1042 (acrylonitrile content 33%), manufactured by Nippon Zeon Co., Ltd. • NBR (AN = 41%): Nipol 1041 (acrylonitrile content 41%), manufactured by Nippon Zeon Co., Ltd. • HNBR (AN = 36%): Zetpol 2000L (acrylonitrile content 36%), manufactured by Nippon Zeon Co., Ltd. • EPDM: MITSUI EPT 4070, manufactured by Mitsui Chemicals, Inc.

Carbon black (HAF): Show black N330T, manufactured by Showa Cabot Corporation Carbon black (FEF): Show black N550, manufactured by Showa Cabot Corporation MgO: Kyowa Mag 150, manufactured by Kyowa Chemical Industry Co., Ltd.
・ ZnO: 3 types of zinc oxide, manufactured by Shodo Chemical Co., Ltd. ・ Stearic acid: Lunac YA, manufactured by Kao Corporation ・ Aroma oil: Desolex No. 3, manufactured by Showa Shell Sekiyu KK ・ Paraffin oil: Machine oil 22, manufactured by Showa Shell Sekiyu KK -Naphthenic oil: Fukkor 1150N, manufactured by Fuji Kosan Co., Ltd.-Dioctyl phthalate: Sansosizer DOP, manufactured by Shin Nippon Chemical Co., Ltd.-Triallyl isocyanate: Thaik, manufactured by Nippon Kasei Co., Ltd.・ Sulfur: Powdered sulfur, manufactured by Karuizawa Smelter ・ Vulcanization accelerator NS: Noxeller NS-F, manufactured by Ouchi Shinsei Chemical Co., Ltd. ・ Vulcanization accelerator TT: Noxeller TT, manufactured by Ouchi New Chemical Co., Ltd.・ Peroxide: Parkadox 14/40, manufactured by Kayaku Akzo

Test specimens (thickness 0.5 mm) made of various resins shown in Table 2 below were evaluated for DME permeation resistance and stability against DME in the same manner as described above.
The results are shown in Table 2.

Each component in Table 2 is as follows.
・ Nylon 6: CM1017, manufactured by Toray Industries, Inc. ・ Nylon 11: BESN O TL, manufactured by Atofina ・ PE (HD): Hi-Zex, manufactured by Mitsui Chemicals, Inc. ・ PET: Toyobo Ester E5100, manufactured by Toyobo
PTFE: Fluon (registered trademark) PTFE, manufactured by Asahi Glass
-PVC: Kane Vinyl, Kaneka Chemical Industry Co., Ltd.

  When cured DME is used as the cured product of the rubber composition shown in Table 1 and the resin shown in Table 2, butyl rubber of IIR, CIIR and BIIR, or polyamide of nylon 6 and nylon 11 The resin had a low DME permeability coefficient and good stability against DME.

Therefore, a DME transport hose was produced using these rubbers or resins, and the DME resistance as a hose was evaluated.
( Example 1 )
A rubber composition containing the IIR of Reference Example 1 obtained above was extruded from a rubber extruder onto a mandrel previously coated with a release agent, and vulcanized at 160 ° C. for 60 minutes. Thereafter, the mandrel was pulled out to obtain the hose of Example 1 having an inner layer thickness of 1.6 mm and a length of 500 mm.

After sealing one end of the hose of Example 1 and pouring DME into the hose from the opening of the hose until it is full, the opening of the hose is similarly sealed. Thereafter, the hose was left in an oven at 40 ° C. for 14 days (336 hours), and the mass loss was measured.
The hose of Example 1 was a hose suitable for DME transportation with less permeation leakage of DME and no abnormal appearance compared to the hoses of Comparative Examples 1 to 9 described later.

( Example 2 )
In the same manner as Example 1 using a rubber composition containing CIIR of Reference Example 2, the inner layer having a thickness of 1.6 mm, an example 2 of the hose length 500mm was prepared.
This hose, in a similar manner to Example 1, was measured weight loss due to transmission of DME, small transmission leakage DME compared to hoses of Comparative Examples 1-9 which will be described later, no abnormal appearance, Example 2 The DME transport hose was a hose suitable for DME transport.

( Example 3 )
A DME transport hose having an inner layer thickness of 1.6 mm and a length of 500 mm was produced in the same manner as in Example 1 using the rubber composition containing BIIR of Reference Example 3.
With respect to this hose, the amount of mass decrease due to DME permeation was measured in the same manner as in Example 1. As a result, the permeation leakage of DME was small compared to the hoses of Comparative Examples 1 to 9 described later, there was no appearance abnormality, and Example 3 The DME transport hose was a hose suitable for DME transport.

(Comparative Examples 1-9)
About each rubber composition of the reference examples 4-12, it carried out similarly to Example 1 , respectively, and manufactured the hose whose thickness of an inner layer is 1.6 mm, and length 500mm.
For these hoses, the amount of mass loss due to DME permeation was measured in the same manner as in Example 1. As a result, either hose had permeation leakage of DME or abnormal appearance, and was suitable for a DME transport hose. I found that there was no.

( Example 4 )
A resin composition containing nylon 6 (CM1021FS, manufactured by Toray Industries, Inc.) was extruded to a thickness of 0.2 mm so as to cover the outer peripheral surface of the DME transport hose (inner pipe) obtained in Example 3. An intermediate layer was formed and vulcanized at 160 ° C. for 60 minutes to prepare a hose having a two-layer inner tube. At this time, the interface of each layer was adhered by a phenol-based adhesive.
With respect to this hose, the amount of mass loss due to DME permeation was measured in the same manner as in Example 1. As a result, there was less permeation leakage of DME than the hose of Example 3 , there was no appearance abnormality, and the DME transport hose of Example 4 The hose was suitable for DME transportation.

( Example 1 )
To cover the outer peripheral surface of the hose (intermediate layer) obtained in Example 4 , a rubber composition containing BIIR is further extruded to a thickness of 1.5 mm and a length of 500 mm to form an outer layer. And vulcanized at 160 ° C. for 60 minutes to produce a hose having a three-layer inner tube structure. At this time, the outer peripheral surface of the hose of Example 4 and the inner surface of the layer composed of BIIR provided so as to cover the hose were bonded with a phenol-based adhesive.
Next, the amount of mass loss due to DME permeation was measured in the same manner as in Example 1. As a result, there was less permeation leakage of DME than the hose of Example 4 , there was no appearance abnormality, and the hose of Example 1 was transported by DME. Hose suitable for.

( Example 5 )
A rubber composition containing BIIR is formed by extruding a resin composition containing nylon 6 (CM1021FS, manufactured by Toray Industries, Inc.) to a thickness of 0.2 mm to form an inner layer, and covering the outer peripheral surface of the inner layer. The product was further extruded to have a thickness of 1.5 mm and a length of 500 mm to form an intermediate layer, and vulcanized at 160 ° C. for 60 minutes to produce a hose having a two-layer inner tube. .
Then, in the same manner as in Example 1, was measured weight loss due to transmission of DME, small transmission leakage DME compared to hoses of Comparative Examples 1-9 which will be described later, no abnormal appearance, Example 5 The hose was a hose suitable for DME transportation.

In addition, the rubber | gum containing EPDM of the reference example 12 in the outer side of the reinforcement layer which braided the appropriate kind of reinforcement thread | yarn so that the outer peripheral surface of the inner tube | pipe of the hose of Example 1 and Examples 1-5 may be covered. The composition is extruded to a thickness of 2 mm and a length of 500 mm to form an outer tube, vulcanized at 160 ° C. for 60 minutes, and a hose (for example, a hose having the structure shown in FIG. 1). The hose produced and measured for mass loss due to DME permeation in the same manner as in Example 1 was a hose suitable for DME transport.

FIG. 1 is a perspective conceptual view showing notches each layer (each inner pipe) of a hose which is an embodiment of a DME transport hose of the present invention. FIG. 2 is a perspective conceptual view showing notches each layer (each tube) of a hose which is an embodiment of a DME transport hose having an inner tube having a two-layer structure of the present invention. FIG. 3 is a perspective conceptual view showing notches each layer (each tube) of a hose which is an embodiment of a DME transport hose having an inner tube having a three-layer structure of the present invention. FIG. 4 is a cross-sectional view of a laboratory cup used to measure DME permeation resistance.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 DME transport hose 2 Inner tube 3 Inner layer 4 Middle layer 5 Outer layer 6 Reinforcement layer 7 Outer tube 10 Cup 12 DME
14 Specimen 16 Sintered metal plate 18 Fixing member 20 Bolt 22 Nut

Claims (3)

An inner tube, a reinforcing layer outside the inner tube, and an outer tube made of a rubber composition outside the reinforcing layer,
The inner tube is made of a butyl rubber composition and has an inner layer having a thickness of 0.5 to 5.0 mm, and a polyamide resin composition so as to cover the outer peripheral surface of the inner layer outside the inner layer. And an intermediate layer having a thickness of 0.05 to 0.5 mm and a butyl rubber composition so as to cover the outer peripheral surface of the intermediate layer outside the intermediate layer and having a thickness of 0.5 to 5 An outer layer that is 0.0 mm;
The polyamide resin composition has a dimethyl ether permeability coefficient of 0.017 mg · mm / (hr · cm ² ) or less,
Dimethyl transmission coefficient of the butyl-based rubber composition, 0.167mg · mm / (hr · cm 2) Ri Der below,
The butyl rubber contained in the butyl rubber composition is from butyl rubber (IIR), chlorinated butyl rubber (CIIR), brominated butyl rubber (BIIR), brominated isobutylene-p-methylstyrene copolymer rubber (BIMS). A dimethyl ether transport hose that is at least one selected .   The hose for transporting dimethyl ether according to claim 1, wherein the inner layer and the intermediate layer are bonded with an adhesive.   The dimethyl ether transport hose according to claim 1 or 2, wherein the intermediate layer and the outer layer are adhered to each other with an adhesive.

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