Hydrogen filling hose

Abstract

To provide a hydrogen charging hose improved in handleability and durability.SOLUTION: A hydrogen charging hose of the present invention has an inner layer, a reinforcement layer, and an outer layer which are laminated in this order. The inner layer is a layer of a thermoplastic resin composition having a sea-island structure having a matrix containing a thermoplastic resin and a domain containing elastomer, and the reinforcement layer contains at least one organic fiber layer. The hydrogen charging hose of the present invention preferably includes a layer made of an adhesive agent containing polyurethane between the inner layer and the reinforcement layer.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a hose for filling hydrogen gas, and more particularly to a hose for filling a fuel cell vehicle or the like with hydrogen gas from a dispenser installed at a hydrogen station. [Background technology]

[0002] In recent years, the development of fuel cell vehicles and the like has been active. Accordingly, the development of hoses for filling fuel cell vehicles and the like with hydrogen gas from dispensers installed at hydrogen stations is also progressing. These hydrogen filling hoses are required to have hydrogen gas barrier properties, flexibility in low-temperature environments, durability, etc.

[0003] Patent Document 1 discloses a hydrogen transport hose that has an inner layer made of a resin composition containing polyamide 11 and a modified olefin-based elastomer, a reinforcing layer, and an outer layer containing a polyamide resin, and that has excellent hydrogen gas barrier properties and can improve flexibility in low-temperature environments, and therefore can improve durability in low-temperature environments. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2018 / 155491 Summary of the Invention [Problem to be solved by the invention]

[0005] Hydrogen filling hoses are expected to be used, for example, in situations where hydrogen gas is filled into fuel cell vehicles and the like from a dispenser installed at a hydrogen station. In such situations, if the hydrogen filling hose has low flexibility, for example, it is not easy to handle. In addition, hydrogen filling hoses are also required to have high durability.

[0006] It is desirable to further improve the ease of handling and durability of hydrogen filling hoses.

[0007] The present inventors have an object to provide a hose for filling hydrogen with improved ease of handling and durability. [Means for solving the problem]

[0008] The present inventors have found that the above object can be achieved by the following means: Aspect 1 A hydrogen filling hose having an inner layer, a reinforcing layer, and an outer layer laminated in this order, the inner layer is a layer of a thermoplastic resin composition having a sea-island structure composed of a matrix containing a thermoplastic resin and domains containing an elastomer, The reinforcing layer includes at least one organic fiber layer. Hose for hydrogen filling. Aspect 2 The hydrogen filling hose according to aspect 1, wherein the thermoplastic resin comprises at least one selected from the group consisting of polyoxymethylene resin, polyester resin, polyketone resin, polycarbonate resin, polyphenylene sulfide resin, polyphenylene ether resin, and modified polyphenylene ether resin. Aspect 3 3. The hydrogen filling hose according to claim 1 or 2, wherein the elastomer comprises at least one selected from the group consisting of a polyurethane elastomer, a polyester elastomer, a polyolefin elastomer, a polystyrene elastomer, a polyamide elastomer, and a polyvinyl chloride elastomer. Aspect 4 A hydrogen filling hose according to any one of aspects 1 to 3, further comprising a layer made of an adhesive containing polyurethane between the inner layer and the reinforcing layer. Aspect 5 A hydrogen filling hose according to any one of Aspects 1 to 4, wherein the organic fiber layer contains fibers including at least one selected from the group consisting of polyparaphenylene benzbisoxazole, polyester, polyamide, and polyketone. Aspect 6 A hydrogen filling hose according to any one of aspects 1 to 5, wherein the outer layer contains at least one type of thermoplastic elastomer. Aspect 7 7. The hydrogen filling hose according to claim 6, wherein the thermoplastic elastomer comprises at least one selected from the group consisting of polyester elastomers, polyurethane elastomers, polyamide elastomers, polyolefin elastomers, polystyrene elastomers, and polyvinyl chloride elastomers. Aspect 8 A hydrogen filling hose according to any one of Aspects 1 to 7, wherein a rate of change in outer diameter when pressurized at 70 MPa is 0.2 to 10.0%. Aspect 9: A hydrogen filling hose according to any one of Aspects 1 to 8, wherein a rate of change in inner diameter when pressurized at 70 MPa is 4.0 to 18.0%. Aspect 10 A hydrogen filling hose according to any one of Aspects 1 to 9, wherein the flexural rigidity at a bending radius of 180 mm is 5.0 to 23.0 N. Aspect 11 The thermoplastic resin composition was exposed to a hydrogen atmosphere at 30°C and a pressure of 90 MPa for 24 hours, and the volume (V) after the pressure was reduced to atmospheric pressure was compared with the volume before exposure (V 0 ) ratio, V / V 0 11. The hydrogen filling hose according to any one of aspects 1 to 10, wherein is less than 1.20. Aspect 12 The thermoplastic resin composition has an impact energy of 5.0 kJ / m in a notched Izod impact test at a temperature of -40°C. 2 12. The hydrogen filling hose according to any one of aspects 1 to 11, wherein the hose is equal to or greater than the above or does not break. Aspect 13 The hydrogen permeability coefficient of the thermoplastic resin composition is 12.0×10 -10cc cm / (cm 2 13. The hydrogen filling hose according to any one of aspects 1 to 12, wherein the hydrogen filling pressure is 0.001 MPa (0.001 MPa) or less. Effect of the Invention

[0009] According to the present disclosure, it is possible to provide a hydrogen filling hose with improved ease of handling and durability. [Brief description of the drawings]

[0010] [Figure 1] FIG. 1 is a partially cutaway perspective view of a hydrogen filling hose 1 according to one embodiment of the present disclosure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] Hereinafter, embodiments of the present disclosure will be described in detail. Note that the present disclosure is not limited to the following embodiments, and various modifications can be made within the scope of the present disclosure.

[0012] The hydrogen filling hose of the present disclosure is a hydrogen filling hose having an inner layer, a reinforcing layer, and an outer layer laminated in this order. The inner layer is a layer of a thermoplastic resin composition having a sea-island structure consisting of a matrix containing a thermoplastic resin and domains containing an elastomer. The reinforcing layer includes at least one organic fiber layer.

[0013] A hydrogen filling hose is a hose used to fill hydrogen from a tank, cylinder, etc. into another tank, cylinder, etc., and is preferably a hose used to fill hydrogen gas into a fuel cell vehicle, etc. from a dispenser installed at a hydrogen station.

[0014] When hydrogen gas is filled from a dispenser into a fuel cell vehicle or the like, the hydrogen is cooled in advance by a pre-cooling facility to prevent the gas temperature inside the on-board container from rising too high. Hydrogen is generally supplied in a cooled state of about -40°C, so the hose is cooled by the hydrogen during filling, but once filling is complete, it is warmed by the outside air and returns to room temperature. In other words, if the hose is repeatedly filled, the temperature of the hose will repeatedly change between low and room temperatures. In particular, the inner layer is in direct contact with hydrogen, so the temperature changes are large and it expands and contracts repeatedly, making it easy for delamination to occur between the inner layer and the reinforcing layer placed on the outside.

[0015] One possible solution to this problem is to use a material that is less likely to expand and contract for the inner layer, but using such a material for the inner layer increases the bending rigidity of the hydrogen filling hose, which tends to reduce its ease of handling.

[0016] In the hydrogen filling hose of the present disclosure, the thermoplastic resin composition constituting the inner layer is composed of a matrix and a domain. That is, the thermoplastic resin composition has a sea-island structure. Such a thermoplastic resin composition has high conformity to deformation. Therefore, failure due to peeling between the inner layer and the reinforcing layer caused by temperature changes due to hydrogen is suppressed. In addition, organic fibers have high elasticity and good adhesion to the thermoplastic resin composition as described above. Therefore, by adopting such a configuration of the inner layer and employing at least one organic fiber layer in the reinforcing layer, peeling between the inner layer and the reinforcing layer is suppressed, high durability is obtained, and the handleability is also excellent.

[0017] As a result, the hydrogen filling hose of the present disclosure has a bending rigidity that is not too high and is less likely to experience delamination between the inner layer and the reinforcing layer due to repeated use, thereby achieving both ease of handling and durability.

[0018] FIG. 1 is a partially cutaway perspective view of a hydrogen filling hose 1 according to one embodiment of the present disclosure.

[0019] As shown in Fig. 1, a hydrogen filling hose 1 according to one embodiment of the present disclosure has an inner layer 2, a reinforcing layer 3, and an outer layer 4 laminated in this order. Although not essential in the present disclosure, the inner layer 2, the reinforcing layer 3, and the outer layer 4 are arranged coaxially. The inner layer 2 is a layer of a thermoplastic resin composition having an island-in-sea structure composed of a matrix containing a thermoplastic resin and domains containing an elastomer. The reinforcing layer 3 includes three organic fiber layers 5a-c and a steel wire layer 6, in this order from the inner layer side to the outer layer side.

[0020] In a hydrogen filling hose 1 according to one embodiment of the present disclosure, the inner layer 2 undergoes large expansion and contraction between when exposed to high pressure in a hydrogen atmosphere and when reduced pressure is applied. However, the reinforcing layer 3 having the organic fiber layers 5a-c is easily deformed following the expansion and contraction of the inner layer 2, so that delamination between the inner layer 2 and the reinforcing layer 3 is unlikely to occur.

[0021] As a result, the hydrogen filling hose 1 according to one embodiment of the present disclosure is both easy to handle and durable.

[0022] It should be noted that Fig. 1 does not intend to limit the hydrogen filling hose of the present disclosure. In particular, in Fig. 1, the reinforcing layer 3 has three organic fiber layers 5a-c, but at least one layer is sufficient. Also, the steel wire layer 6 is preferable but not essential.

[0023] The hydrogen filling hose of the present disclosure preferably has an outer diameter change rate of 0.2 to 10.0% when pressurized at 70 MPa.

[0024] When the rate of change in outer diameter is within this range, the hydrogen filling hose has particularly high flexibility and excellent handleability.

[0025] This rate of change in outer diameter is preferably 0.2% or more and 10.0% or less, more preferably 0.4% or more and 9.0% or less, and further preferably 0.6% or more and 8.0% or less.

[0026] The hydrogen filling hose of the present disclosure preferably has an inner diameter change rate of 5.0 to 18.0% when pressurized at 70 MPa.

[0027] When the rate of change in the inner diameter is within this range, the hydrogen filling hose has particularly high flexibility and excellent handleability.

[0028] This rate of change in inner diameter is preferably 4.0% or more and 18.0% or less, more preferably 4.5% or more and 16.0% or less, and further preferably 5.0% or more and 14.0% or less.

[0029] The hydrogen filling hose of the present disclosure preferably has a bending stiffness of 5.0 to 23.0 N at a bending radius of 180 mm.

[0030] When the bending stiffness is within this range, the hydrogen filling hose bends appropriately and is easy to handle, for example, when filling a fuel cell vehicle or the like with hydrogen gas from a dispenser installed at a hydrogen station.

[0031] This bending rigidity is preferably 5.0N or more and 23.0N or less, more preferably 7.0N or more and 21.0N or less, and further preferably 9.0N or more and 19.0N or less.

[0032] The hydrogen filling hose of the present disclosure is a thermoplastic resin composition that is exposed to a hydrogen atmosphere at 30°C and a pressure of 90 MPa for 24 hours, and the volume (V) after the pressure is reduced to atmospheric pressure is compared with the volume before exposure (V 0 ) ratio, V / V 0 It is preferable that the ratio is less than 1.20.

[0033] V / V 0 If it is less than 1.20, the dimensional change of the inner layer is not too large when the pressure is reduced during hydrogen filling, and the occurrence of fracture origins due to the inner layer biting into the reinforcing layer can be suppressed.

[0034] V / V 0is preferably less than 1.20, more preferably 0.95 or more and 1.18 or less, and further preferably 0.98 or more and 1.15 or less.

[0035] The hydrogen filling hose of the present disclosure has an impact energy of 5.0 kJ / m in a notched Izod impact test at a temperature of -40°C of a thermoplastic resin composition. 2 It is preferable that the crack does not occur or break.

[0036] Impact energy in notched Izod impact test is 5.0kJ / m 2 The fact that the impact energy is 5.0 kJ / m or more or does not break indicates that the hydrogen filling hose has high durability against external impacts. 2 If the resistance is equal to or greater than this, it can be said that the durability against external shocks expected during use is sufficiently high.

[0037] The impact energy in the notched Izod impact test is preferably 5.0 kJ / m 2 More than 100.0kJ / m 2 More preferably, it is 8.0 kJ / m or less. 2 More than 80.0kJ / m 2 or less, more preferably 10.0 kJ / m 2 More than 60.0kJ / m 2 or less or no breakage.

[0038] The hydrogen filling hose of the present disclosure has a hydrogen permeability coefficient of 12.0×10 at 30° C. and 0% RH of the thermoplastic resin composition. -10 cc cm / (cm 2 It is preferable that the blood pressure is less than 1.5 s cmHg.

[0039] The hydrogen permeability coefficient of the thermoplastic resin composition is 12.0×10 -10 cc cm / (cm 2 When the pressure drop is less than or equal to 1.0 MPa (s·cmHg), leakage of hydrogen to the outside of the hose during use of the hydrogen filling hose can be particularly suppressed.

[0040] The hydrogen permeability coefficient of the thermoplastic resin composition is preferably 12.0×10 -10 cc cm / (cm 2 s cmHg), and more preferably 6.0×10 -10 cc cm / (cm 2 s cmHg) or less, and more preferably 3.0×10 -10 cc cm / (cm 2 The lower the hydrogen permeability coefficient of the thermoplastic resin composition, the better. However, the hydrogen permeability coefficient of polymeric materials is practically 1.0×10 -14 cc cm / (cm 2 ·s·cmHg or higher.

[0041] Inner Layer The inner layer is a layer of a thermoplastic resin composition having an island-in-sea structure consisting of a matrix containing a thermoplastic resin and domains containing an elastomer.

[0042] The thermoplastic resin may include at least one selected from the group consisting of polyoxymethylene resin, polyester resin, polyketone resin, polycarbonate resin, polyphenylene sulfide resin, polyphenylene ether resin, and modified polyphenylene ether resin. From the viewpoint of processability, particularly from the viewpoint of processing temperature, the thermoplastic resin is particularly preferably a polyoxymethylene resin.

[0043] The elastomer may include, for example, at least one selected from the group consisting of polyurethane elastomers, polyester elastomers, polyolefin elastomers, polystyrene elastomers, polyamide elastomers, and polyvinyl chloride elastomers.

[0044] From the viewpoint of suppressing hydrogen permeability, the ratio of the thermoplastic resin in the thermoplastic resin composition is preferably, for example, 50 to 95%.

[0045] The proportion of the thermoplastic resin in the thermoplastic resin composition is preferably 50.0 mass % or more and 95.0 mass % or less, more preferably 55.0 mass % or more and 92.5 mass % or less, and even more preferably 60.0 mass % or more and 90.0 mass % or less.

[0046] The thickness of the inner layer is preferably 0.2 to 2.0 mm.

[0047] If the thickness of the inner layer is too thin, melt extrusion may be difficult or the extrusion technique may be limited, whereas if the thickness of the inner layer is too thick, the flexibility of the hose may be insufficient, resulting in poor handling.

[0048] The thickness of the inner layer is preferably 0.20 mm or more and 2.00 mm or less, more preferably 0.35 mm or more and 1.80 mm or less, and further preferably 0.50 mm or more and 1.60 mm or less.

[0049] Reinforcement Layer The reinforcing layer is a layer provided between the inner layer and the outer layer, and includes at least one organic fiber layer.

[0050] <Organic fiber layer> The organic fiber layer is a layer containing organic fibers. The organic fiber layer may be, for example, a layer formed by braiding organic fibers. Organic fibers have higher elasticity than steel wires, etc., and therefore the hydrogen filling hose is flexible and easy to handle when in use.

[0051] The organic fiber layer may contain fibers including at least one selected from the group consisting of polyparaphenylene benzbisoxazole, polyester, polyamide, and polyketone.

[0052] Furthermore, the organic fiber layer may be a layer in which yarns made of organic fibers are braided. The organic fiber layer has a braided structure or a spiral structure, preferably a braided structure. The braided structure has higher stretchability than the spiral structure. Therefore, when the organic fiber layer has a braided structure, it is more flexible and easier to handle.

[0053] The yarn diameter of the organic fiber layer may be, for example, 0.25 to 0.50 mm.

[0054] The reinforcing layer may have one or more organic fiber layers, and may have, for example, 1 to 6 organic fiber layers.

[0055] When the reinforcing layer includes a plurality of organic fiber layers, it is preferable that the basis weight of the organic fiber layers increases from the innermost organic fiber layer toward the outermost organic fiber layer.

[0056] More specifically, for example, in FIG. 1, it is preferable that the basis weight increases in the order of the organic fiber layer 5a, the organic fiber layer 5b, and the organic fiber layer 5c.

[0057] In this configuration, the elasticity of the reinforcing layer decreases from the inside to the outside of the hydrogen filling hose, so that it is possible to suppress delamination between the inner layer and the reinforcing layer while suppressing expansion and contraction of the hydrogen filling hose as a whole on the outer layer side.

[0058] <Metal wire layer> The reinforcing layer may further include a metal wire layer in addition to the organic fiber layer.

[0059] The metal wire layer may be a layer in which metal wires, such as steel wires, copper and copper alloy wires, aluminum and aluminum alloy wires, magnesium alloy wires, titanium and titanium alloy wires, etc., are braided. The metal wire layer is particularly preferably a layer in which steel wires are braided. Examples of the steel wires include stainless steel wires and galvanized steel wires.

[0060] The metal wire layer may be a layer having a braided structure or a spiral structure, preferably a braided structure. The braided structure is a braided form that has higher elasticity than the spiral structure. Therefore, when the metal wire layer has a braided structure, it has a certain degree of elasticity and therefore has high durability while maintaining handleability.

[0061] Although the positional relationship between the organic fiber layer and the metal wire layer in the reinforcing layer is not particularly limited, it is preferable that the organic fiber layer is disposed on the inner layer side and the metal wire layer is disposed on the outer layer side, and in particular, that the metal wire layer is disposed on the outermost layer side of the reinforcing layer, whereby the expansion and contraction of the inner layer during use of the hydrogen filling hose can be cushioned by the organic fiber layer on the inner layer side of the reinforcing layer, while the metal wire layer on the outer layer side of the reinforcing layer can ensure high durability.

[0062] Furthermore, in a configuration in which the organic fiber layer is arranged on the inner layer side and the metal wire layer is arranged on the outermost layer side of the reinforcing layer, if the metal wire layer has a braid structure, the metal wire layer has significant elasticity, and the elasticity decreases in the order of the organic fiber layer and the metal wire layer, so that the expansion and contraction of the entire hydrogen filling hose due to the expansion and contraction of the inner layer, particularly in the radial direction, can be particularly mitigated.

[0063] 《Outer layer》 The outer layer may contain at least one thermoplastic elastomer.

[0064] When the reinforcing layer has a metal wire layer, the outer layer contains a thermoplastic elastomer, which allows the small amount of hydrogen that permeates from the inside when hydrogen is filled to immediately permeate to the outside of the hose, making it easier to suppress hydrogen embrittlement of the metal wire layer.

[0065] The thermoplastic elastomer preferably has a glass transition temperature of 0° C. or lower. By having a glass transition temperature of 0° C. or lower, the hose becomes more flexible because the hose is flexible in the operating temperature environment.

[0066] The thermoplastic elastomer preferably includes at least one selected from the group consisting of, for example, polyester elastomers, polyurethane elastomers, polyamide elastomers, polyolefin elastomers, polystyrene elastomers, and polyvinyl chloride elastomers.

[0067] The outer layer may contain components other than the thermoplastic elastomer as long as the effects of the present invention are not impaired.

[0068] The thickness of the outer layer may be 0.20 to 1.20 mm.

[0069] If the outer layer is too thin, it will be easily damaged by friction, deformation, impact, etc. when handling the hose, and there is a risk that the reinforcing layer will not be adequately protected. If it is too thick, the hose will be heavy and difficult to handle.

[0070] The thickness of the outer layer is preferably 0.20 mm or more and 1.20 mm or less, more preferably 0.30 mm or more and 1.10 mm or less, and further preferably 0.40 mm or more and 1.00 mm or less.

[0071] 《Adhesive layer》 The hydrogen filling hose of the present disclosure may include a layer made of an adhesive containing polyurethane between the inner layer and the reinforcing layer. The adhesive preferably contains 5 mass % or more of polyurethane.

[0072] Example of manufacturing method The method for producing the hydrogen filling hose is not particularly limited, but it can be produced as follows: First, the inner layer (inner tube) is extruded into a tube shape by extrusion molding, an adhesive layer is applied to the outer surface of the inner layer and then dried, fibers that will become a reinforcing layer are braided on the tube, and the outer layer (outer tube) is further extrusion molded to cover the fibers. EXAMPLES

[0073] Examples 1 to 22 and Comparative Examples 1 to 3 <Preparation of hydrogen filling hose for each example> (Preparation of Thermoplastic Resin Composition) For each example, the thermoplastic resin (A) and elastomer (B) shown in Table 1 below were introduced in a twin-screw kneading extruder (manufactured by The Japan Steel Works, Ltd.) with the cylinder temperature set to the melting point of the thermoplastic resin (flow initiation temperature for amorphous resin) + 20°C, melt-kneaded for a residence time of about 5 minutes, and the molten kneaded product was extruded in a strand shape from a die attached to the discharge port. The obtained strand-shaped extrudate was pelletized with a resin pelletizer to prepare a pellet-shaped thermoplastic resin composition.

[0074] The structure of each of the obtained thermoplastic resin compositions, ie, the presence or absence of an island structure, for example, is as shown in Table 1.

[0075] In Table 1, "POM" is an abbreviation for polyoxymethylene, "PBT" is an abbreviation for polybutylene terephthalate, "PBN" is an abbreviation for polybutylene naphthalate, "POK" is an abbreviation for polyketone, "PC" is an abbreviation for polycarbonate, "PPS" is an abbreviation for polyphenylene sulfide, "m-PPE" is an abbreviation for modified polyphenylene ether, "TPU" is an abbreviation for thermoplastic polyurethane elastomer, "TPEE" is an abbreviation for thermoplastic polyester elastomer, "PO" is an abbreviation for polyolefin, "TPA" is an abbreviation for polyamide-based thermoplastic elastomer, and "PS" is an abbreviation for polystyrene. In addition, Examples 12 to 16 show that commercially available alloys were adopted.

[0076] (Manufacture of hydrogen filling hose) The prepared thermoplastic resin composition was extruded into a tube with an inner diameter of 9.00 mm and a thickness of 1 mm. This tube was used as the inner layer, and the outer surface of the inner layer was coated with a moisture-curing urethane adhesive (manufactured by Lord Far East, product name Tyrite 7411) and dried. The outer side of the inner layer was braided with an organic fiber layer having a braided structure of yarn (fiber diameter 0.28 mm) of organic fiber (polyparaphenylenebenzoxazole (PBO)) and a steel wire layer having a braided structure of steel wire (wire diameter 0.35 mm) as a reinforcing layer, in the configuration shown in Table 1 below.

[0077] In the description of "reinforcing layer configuration" in Table 1, "W" stands for steel wire, "Y" stands for organic fiber, "B" stands for braided structure, and "S" stands for spiral structure. The numbers indicate the number of layers. The layers are from the inside to the outside of the hose from left to right.

[0078] For example, "4W / S" means that the reinforcing layer is made up of four steel wire layers, and the steel wire layers are layers of spiral steel wires. Also, for example, "3Y / B+1W / B" means that the reinforcing layer is made up of three organic fiber layers on the inside of the hose and one steel wire layer on the outside, and both the organic fiber layers and the steel wire layers are braided layers.

[0079] Finally, the resin shown in Table 1 was extruded to a thickness of 0.7 mm on the outside of the reinforcing layer to form an outer layer, thereby completing a hydrogen filling hose.

[0080] In Table 1, "Ny12" is an abbreviation for nylon 12, and "TPEE" is an abbreviation for thermoplastic polyester elastomer. Specifically, Hytrel 4057N (manufactured by DuPont-Toray Co., Ltd.) was used.

[0081] <test> (Measurement of the rate of change in outer diameter of a hydrogen filling hose) The hydrogen filling hose of each example was cut to a specified length, and the rate of change in outer diameter was measured when pressurized to 70 MPa at room temperature in accordance with JIS K6330-2 "Test methods for rubber and plastic hoses - Part 2: Pressure resistance of hoses and hose assemblies".

[0082] (Measurement of the rate of change in inner diameter of a hydrogen filling hose) The hydrogen filling hose of each example was cut to a specified length, and the internal volume V and length L were measured at room temperature without load and when pressurized to 70 MPa, and the formula V = (D / 2) was obtained. 2 The inner diameter D was calculated by π×L, and the rate of change in the inner diameter was measured.

[0083] (Measurement of bending stiffness of hydrogen filling hose) The hydrogen filling hose of each example was cut to a specified length, and the bending stiffness was measured at room temperature (25°C) at a bending radius of 180 mm in accordance with JIS K6330-9 "Test methods for rubber and plastic hoses - Part 9 Bending properties of hoses and pipes."

[0084] (Measurement of volume change of thermoplastic resin composition due to exposure to hydrogen) The pellet-shaped thermoplastic resin composition used in each example was molded into a sheet with an average thickness of 1.0 mm using a 40 mmφ single-screw extruder with a 200 mm wide T-shaped die (manufactured by Plagiken Co., Ltd.), with the cylinder and die temperatures set to the melting point of the material with the highest melting point in the composition + 20 ° C, and the cooling roll temperature was 50 ° C, and the take-up speed was 1 m / min. This sheet was cut into a disk shape with a diameter of 13 mm, placed in a pressure-resistant container, and exposed to hydrogen at 30 ° C and 90 MPa for 24 hours. Immediately after decompression to atmospheric pressure, the area of ​​the disk-shaped sample was measured with a Keyence 2D multipoint dimension measuring instrument TM-3000, and the volume change was calculated. The volume becomes smaller as hydrogen is desorbed, and the largest volume (maximum value) in the process was divided by the volume before exposure measured in the same manner to obtain the rate of change.

[0085] (Low temperature Izod impact test of thermoplastic resin composition) The thermoplastic resin composition was extruded into a sheet having a thickness of 3.00 mm in the same manner as in "(Measurement of volume change due to exposure of thermoplastic resin composition to hydrogen)" above. This sheet was cut into strips having a length of 63.50 mm and a width of 12.70 mm, which were notched and subjected to an Izod impact test at -40°C in accordance with ASTM D256. The impact energy of the broken pieces was calculated.

[0086] (Measurement of hydrogen permeability coefficient of thermoplastic resin composition) The pellet-shaped thermoplastic resin composition used in each example was molded into a film with an average thickness of 0.20 mm using a 40 mmφ single-screw extruder with a 550 mm wide T-shaped die (manufactured by Plagiken Co., Ltd.), with the cylinder and die temperatures set to the melting point of the material with the highest melting point in the composition + 20 ° C., a cooling roll temperature of 50 ° C., and a take-up speed of 3 m / min. This sheet was cut to a predetermined size, and hydrogen gas was passed through it using a gas permeation tester manufactured by GTR Tech under conditions of 30 ° C., 0% RH, and 0.5 MPa, and the hydrogen gas that permeated the film was detected by gas chromatography to determine the hydrogen permeation coefficient.

[0087] (Shock pressure cycle test) For each hydrogen filling hose, in accordance with JIS K6330-8 "Rubber and resin hose test methods - Part 8 Impact pressure test", a fluid was circulated inside the hydrogen filling hose fixed in a U-shape, and a shock wave pressure of 90 MPa was applied 200,000 times at a pressure rise rate of 50 MPa / s or until the hydrogen filling hose was broken, and measurements were made to see if damage occurred to the inner layer or between the inner layer and the reinforcing layer. The fluid was nitrogen gas at room temperature, and the ambient temperature of the hydrogen filling hose was repeatedly switched between room temperature and -30°C every hour to apply temperature changes.

[0088] <result> The configuration and test results of each example of the hydrogen filling hose are shown in Table 1 below.

[0089] In the "Results" section of Table 1, for "handleability," in the above "(Measurement of bending stiffness of hydrogen filling hose)," a bending stiffness of 25 N or more at a bending radius of 180 mm is rated as "poor," 20 N or more but less than 25 N is rated as "passable," 17 N or more but less than 20 N is rated as "good," and less than 17 N is rated as "excellent."

[0090] In addition, in the "Results" of Table 1, for "durability," in the above "(impact pressure cycle test)," those that showed damage to the inner layer or between the inner layer and the reinforcing layer in less than 50,000 times were rated "poor," those that showed damage to the inner layer or between the inner layer and the reinforcing layer in between 50,000 and 100,000 times were rated "fair," those that showed damage to the inner layer or between the inner layer and the reinforcing layer in between 100,000 and 200,000 times were rated "good," and those that showed no damage to the inner layer or between the inner layer and the reinforcing layer even after 200,000 times were rated "excellent." Examples rated "fair," "good," and "excellent" have improved durability compared to examples rated "poor."

[0091] [Table 1] [Industrial Applicability]

[0092] The hydrogen filling hose of the present invention can be suitably used as a hose for filling hydrogen gas into fuel cell vehicles and the like from a dispenser installed at a hydrogen station. [Explanation of symbols]

[0093] 1 Hydrogen filling hose 2. Inner layer 3 Reinforcement layer 4 Outer layer 5a~c Organic fiber layer 6 steel wire layers

Claims

1. A hydrogen filling hose having an inner layer, a reinforcing layer, and an outer layer laminated in this order, the inner layer is a layer of a thermoplastic resin composition having a sea-island structure composed of a matrix containing a thermoplastic resin and domains containing an elastomer, The reinforcing layer includes at least one organic fiber layer, the thermoplastic resin includes at least one selected from the group consisting of polyoxymethylene resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polyketone resin, polycarbonate resin, polyphenylene sulfide resin, and modified polyphenylene ether resin; The elastomer includes at least one selected from the group consisting of a thermoplastic polyurethane elastomer, a thermoplastic polyester elastomer, and a polyamide-based thermoplastic elastomer. Hose for hydrogen filling.

2. 2. The hydrogen filling hose according to claim 1, further comprising a layer of an adhesive containing polyurethane between the inner layer and the reinforcing layer.

3. 3. The hydrogen filling hose according to claim 1, wherein the organic fiber layer contains fibers including at least one selected from the group consisting of polyparaphenylene benzbisoxazole, polyester, polyamide, and polyketone.

4. 4. The hose for filling hydrogen gas according to claim 1, wherein the outer layer contains at least one type of thermoplastic elastomer.

5. 5. The hydrogen filling hose according to claim 4, wherein the thermoplastic elastomer comprises at least one selected from the group consisting of polyester elastomers, polyurethane elastomers, polyamide elastomers, polyolefin elastomers, polystyrene elastomers, and polyvinyl chloride elastomers.

6. 6. The hydrogen filling hose according to claim 1, wherein the rate of change in outer diameter when pressurized at 70 MPa is 0.2 to 10.0%.

7. 7. The hydrogen filling hose according to claim 1, wherein the rate of change in inner diameter when pressurized at 70 MPa is 4.0 to 18.0%.

8. 8. The hydrogen filling hose according to claim 1, wherein the flexural rigidity at a bending radius of 180 mm is 5.0 to 23.0 N.

9. The thermoplastic resin composition was exposed to a hydrogen atmosphere at 30° C. and a pressure of 90 MPa for 24 hours, and the volume (V) when the pressure was reduced to atmospheric pressure was compared with the volume (V) before exposure. ０ ) ratio, V / V ０ The hydrogen filling hose according to any one of claims 1 to 8, wherein is less than 1.

20.

10. The thermoplastic resin composition has an impact energy of 5.0 kJ / m in a notched Izod impact test at a temperature of -40°C. ２ The hydrogen filling hose according to any one of claims 1 to 9, wherein the hose is at least ruptured or does not rupture.

11. The hydrogen permeability coefficient of the thermoplastic resin composition is 12.0×10 －１０ cc cm / (cm ２ The hydrogen filling hose according to any one of claims 1 to 10, wherein the hydrogen pressure is 0.05 - 0.5MPa (s - cmHg) or less.

Images