JP3124092B2 - Hose for fuel - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a fuel hose particularly suitable for transporting city gas, liquefied petroleum gas and the like.

[0002]

2. Description of the Related Art A hose for fuel such as city gas or liquefied petroleum gas must have rubber-like elasticity and does not soften thermally. In other words, a resin or a conventional thermoplastic elastomer cannot satisfy both rubber-like elasticity and heat-softening resistance.Therefore, there is no usable material for such a hose other than vulcanized rubber. Was.

[0003] By examining the production cost of such a hose, it has been found that the contribution of the vulcanization step is large. That is, if a hose having performance equivalent to that of a vulcanized rubber hose can be manufactured without going through a vulcanization step, the manufacturing process of the hose is simplified and the manufacturing cost is reduced.

However, up to the present, there is no known hose which has characteristics and functions required for a hose for fuel and which does not require a vulcanization step, that is, has a small production cost.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances, and has been made in response to industrial requirements. The present invention satisfies various characteristics required for a fuel hose, and
An object of the present invention is to provide a hose having a low production cost because a vulcanization step is not required.

[0006]

According to the present invention, at least the innermost layer comprises a thermoplastic resin having a chlorine atom as a continuous phase (matrix phase) and a rubber having a chlorine atom and / or a nitrile group as a discontinuous phase. (Dispersed phase), at least a part of rubber is formed of a composition mainly composed of a thermoplastic elastomer which is vulcanized, and vulcanized after molding.
Instead, the permanent elongation specified in JIS K 6301
15% or less, butane gas 19.6 KPa, 35
Volume change rate 1 in LP gas resistance test at 72 ° C for 72 hours
0% or less, and propane gas 55.99 KPa, 35
℃, in the gas permeation test during 6 hours after 24 hours
An object of the present invention is to provide a fuel hose having a gas permeation amount of 5 ml / h or less .

[0007]

Hereinafter, the present invention will be described in detail. First, the thermoplastic elastomer used in the present invention will be described.

The thermoplastic elastomer used in the present invention comprises:
It has the following physical properties. That is, ASTM
It is a value measured according to the test method described in D638 and D1566, the tension set is 160% or less, preferably 150% or less, the compression set at 120 ° C. × 72 h is 50% or less, and the guideline of flexibility. Has a Young's modulus (initial tensile elastic modulus) of 2500 kgf / cm ² or less, and has rubber elasticity up to about 120 ° C. That is, the thermoplastic elastomer used in the present invention is ASTM.
Standard V. 28, page 756 (D1566). Since the thermoplastic elastomer used in the present invention has the above-mentioned physical properties, it exhibits excellent workability and has the property of not requiring vulcanization at the time of molding, despite exhibiting the same behavior as vulcanized rubber.

The components of the thermoplastic elastomer used in the present invention are as follows.

That is, the thermoplastic elastomer used in the present invention has a sufficient amount of chlorine source to give it thermoplasticity.
A thermoplastic resin having a child, a sufficient amount providing elastomeric, chlorine atoms and at least partially vulcanized /
Or a blend with a rubber having a nitrile group ,
The thermoplastic resin forms at least a continuous phase (matrix phase), and the rubber component forms at least a discontinuous phase (dispersed phase). Note that a so-called salami structure in which a thermoplastic resin is further dispersed in a discontinuous phase (rubber phase) may be used.

The amount ratio of the thermoplastic resin to the rubber in the thermoplastic elastomer used in the present invention is not particularly limited as described above, but when the total amount is 100 parts by weight, the rubber is 25 to 75 parts by weight. Preferably 30
More preferably, the amount is from 70 to 70 parts by weight.

In the dispersion form, the particle size of the discontinuous phase is preferably 50 μm or less, more preferably 20 μm or less, and particularly preferably 5 μm or less.

In the thermoplastic elastomer used in the present invention, the rubber as a constituent component thereof contains chlorine atoms and
And / or having a nitrile group . In the thermoplastic elastomer, the rubber component as a constituent component is chlorine atom and / or nitrile.
Since it has a group , it has excellent properties such as oil resistance, fuel oil resistance, and chemical resistance.

The thermoplastic elastomer used in the present invention has a chlorine atom and / or a nitrile group.
Beam is, click Roropurengomu (CR), acrylonitrile -
Butadiene copolymer rubber (NBR), chlorosulfonated polyethylene rubber (CSM), chlorinated polyethylene rubber (CM), ethylene-vinyl acetate copolymer rubber (EV
A), acrylic rubber (ACM), epichlorohydrin rubber (CHR), ethylene-acrylate copolymer rubber (AEM), ethylene-vinyl acetate-acrylate copolymer terpolymer rubber (ER), acrylonitrile-butadiene copolymer rubber (H-NBR) and the like.

Acrylonitrile-butadiene copolymer rubber (NBR) is also known to have a third component (divinylbenzene, vinylpyridine, acrylic acid, etc.) introduced in addition to a binary copolymer of acrylonitrile and butadiene. And these are also included in the NBR used in the present invention.

[0017] Thermoplastic elastomers with chlorine atoms for use in the present invention, resistance to oil, fuel oil, excellent properties such as chemical resistance. Thermoplastic resin having a chlorine atom that make up the thermoplastic elastomer used in the present invention, chlorinated olefin resins, vinyl chloride resins, vinylidene chloride resins and the like.

Examples of the olefin monomer constituting the chlorinated olefin resin include, for example, ethylene,
Propylene, 1-butene, 1-pentene, 4-methyl-
1-pentene, 5-methyl-1-hexene and mixtures thereof.

The constituent components of the thermoplastic elastomer used in the present invention are the above-mentioned thermoplastic resin having a chlorine atom and the above-mentioned rubber having a chlorine atom and / or a nitrile group . Such a thermoplastic elastomer constitutes the thermoplastic elastomer. Although at least a part of the rubber component is vulcanized, such a thermoplastic elastomer is generally used by using a Banbury mixer, a Brabender mixer or a kind of kneading extruder (a twin-screw kneading extruder). While maintaining the melt of the resin and the rubber in these devices, finely kneading and dispersing the rubber phase, further adding a crosslinking agent until the vulcanization of the rubber phase is completed to a desired degree. It is manufactured by masticating at a temperature that promotes vulcanization.

That is, the thermoplastic elastomer used in the present invention advances vulcanization of the rubber phase while masticating.
In other words, dynamic vulcanization (Dynami
c Cure or Dynamic Vulcanization). In addition, such a thermoplastic elastomer is also called a dynamically vulcanized rubber or a dynamically vulcanized thermoplastic rubber because it is obtained by its manufacturing characteristics, that is, by being dynamically heat-treated. For such a manufacturing method,
Since the obtained thermoplastic elastomer shows the same behavior as the vulcanized rubber, and at least the continuous phase is a resin phase, it can be processed according to the thermoplastic resin at the time of molding.

In producing such a dynamically vulcanized rubber, the vulcanization system of the rubber may be any vulcanizable system. If the rubber is CR, the vulcanization system may be sulfur or metal. Oxide or thiourea type vulcanizing agent, NBR for sulfur type, metal oxide or alkylphenol type vulcanizing agent, CSM for sulfur type or metal oxide type vulcanizing agent, CM for thiourea type or Triazine thiol vulcanizing agent, E
VA is an organic peroxide vulcanizing agent, ACM is a polyfunctional amine vulcanizing agent, CHR is a metal oxide vulcanizing agent, AEM is a polyfunctional amine vulcanizing agent, ER In the case of (1), an imidazole vulcanizing agent is preferable, and in the case of H-NBR, a sulfur-based or organic peroxide-based vulcanizing agent is preferable.

[0022] Commercially available products equivalent to the thermoplastic elastomer used in the present invention is a thermoplastic resin as a vinyl chloride resin, Novacor's Sarlink using NBR as the rubber component 1000 series and the like.

The fuel hose of the present invention (hereinafter simply referred to as
Ming's hose. " At least the innermost layer is formed of the composition containing the above-mentioned dynamic vulcanized rubber as a main component. In the present invention, the term “main component” generally means a substance called a main component. Of the rubber composition in the rubber composition.

The composition containing a dynamically vulcanized rubber as a main component is a composition containing a dynamically vulcanized rubber as a main component and, if necessary, a softening agent within a range not to impair the purpose of the present invention. The composition also contains an agent, an inorganic filler, a pigment, a small amount of a plasticizer and an antioxidant.

In the hose of the present invention, at least the innermost layer has
Formed with a composition containing the above-mentioned dynamic vulcanized rubber as a main component,
Not vulcanized after molding , stipulated in JIS K6301
Is less than 15%, butane gas 1
LP gas resistance test at 9.6 KPa, 35 ° C, 72 hours
Volume change rate is 10% or less, and propane gas 5
5.99 KPa, 35 ° C, gas for 24 hours after 6 hours
A fuel hose having a gas permeation amount of 5 ml / h or less in a water permeation test .

More specifically, a single-pipe hose extruded from the composition containing the above-mentioned dynamic vulcanized rubber as a main component, and a double-pipe hose in which the pipe made of the composition is doubled A hose having a three-layer structure including a hose, an inner tube made of the composition, a reinforcing layer, and an outer tube made of the composition is exemplified.

The reinforcing layer of the three-layer hose is
It is not particularly limited, and like the reinforcing layer of a normal hose, a yarn made of vinylon fiber, rayon fiber, polyester fiber, nylon fiber, aromatic polyamide fiber, or the like, or a hard steel wire, is braided or spiral braided. A layer consisting of

An example of the method for producing the hose of the present invention is as follows.

That is, in the case of a single tube hose, on a mandrel or without using a mandrel,
In the case where a composition mainly composed of the dynamically vulcanized rubber used in the present invention described above is extruded and a mandrel is used, the mandrel may be pulled out.

In the case of a double-pipe hose, the composition mainly composed of the dynamically vulcanized rubber used in the present invention is extruded onto a mandrel or without using a mandrel. Is formed, the composition mainly composed of the dynamically vulcanized rubber used in the present invention is pressed thereon to form an outer tube. When a mandrel is used, the mandrel may be pulled out.

Further, in the case of a hose having a three-layer structure, the above-mentioned composition mainly composed of the dynamically vulcanized rubber used in the present invention is extruded onto a mandrel or without using a mandrel, and the inner tube is extruded. After forming the above, a fiber or a steel wire is braided to form a reinforcing layer, and further thereon, a composition mainly composed of the dynamic vulcanized rubber used in the present invention described above is extruded, When an outer tube is formed and a mandrel is used, the mandrel may be pulled out.

In the double-pipe or three-layer hose, the composition for the inner pipe and the composition for the outer pipe may be the same or different. Thus, the hose of the present invention can be manufactured without going through the vulcanization step.

[0033]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below based on embodiments.

(Examples and Comparative Examples ) Using alkrine (comparative example) and surlink ( example) (both shown in Tables 1 and 2 ) as thermoplastic elastomers, a low-pressure rubber in a layer for liquefied petroleum gas was used. A tube was made. Its structure is a single tube (thermoplastic elastomer), its dimensions are 9.4 mm in inside diameter and 3.0 mm in wall thickness. About the above material and rubber tube using this material,
Various tests were conducted based on the voluntary inspection standards of the Chemical Inspection Association. The results are shown in Tables 1 and 2, respectively . The hose of the present invention met all specifications for both material and rubber tubing .

[0035]

[Table 1]

[0036]

[Table 2]

[0037]

According to the present invention, there is provided a hose which satisfies various characteristics required for a hose for transporting fuel such as city gas or liquefied petroleum gas, and which is manufactured without a vulcanization step. . The hose of the present invention exhibits rubber-like elasticity and does not soften even though it is manufactured without a vulcanization step. In addition, the hose of the present invention has a small extraction of hose components by the transport medium, and is excellent in properties such as oil resistance, weather resistance, and coloring resistance. Therefore, according to the present invention, it is possible to provide a hose which is manufactured in a simplified manufacturing process and satisfies various characteristics required for a fuel transport hose, despite the low manufacturing cost.

Continuation of front page (56) References JP-A-59-45339 (JP, A) JP-A-61-98754 (JP, A) JP-A-2-124958 (JP, A) JP-A-51-117742 (JP) JP-A-61-195144 (JP, A) JP-A-58-8736 (JP, A) JP-A-2-22351 (JP, A) JP-A-62-20545 (JP, A) 61-59342 (JP, B2) (58) Fields investigated (Int. Cl. ⁷ , DB name) B32B 1/00-35/00 F16L 9/00-9/22 F16L 11/00-11/24 WPI / L (QUESTEL)

Claims (1)

(57) [Claims] At least the innermost layer comprises a thermoplastic resin having chlorine atoms constituting a continuous phase (matrix phase), and a rubber having chlorine atoms and / or nitrile groups constituting a discontinuous phase (dispersed phase), The rubber is formed of a composition mainly composed of a vulcanized thermoplastic elastomer, at least a part of which is not vulcanized after molding, and has a permanent elongation of 15% specified in JIS K 6301.
And L resistance at 72 ° C. for 72 hours at 19.6 KPa of butane gas.
Volume change rate in P gas test is 10% or less, propane gas 55.99 KPa, 35 ° C., 24 hours elapse
Gas permeation amount 5ml / h in gas permeation test during the next 6 hours
Fuel hose, wherein a is, it follows.