Fluid transport hose

Abstract

To provide a hose for fluid transportation which is flexible and furthermore is excellent in kink resistance.SOLUTION: A hose for fluid transportation including an inner layer, a reinforcement layer and an outer layer is provided, wherein the inner layer includes a layer (A) composed of a thermoplastic resin composition ax composed of: a matrix am including a thermoplastic resin ar; and a domain ad including rubber ae, a layer (B) composed of a thermoplastic resin composition bx composed of: a matrix bm including a thermoplastic resin b or a thermoplastic resin br; and a domain bd including rubber be, and a layer (C) composed of a rubber composition cx, the layer (A) is an innermost layer, the layer (B) is arranged outside the layer (A), the layer (C) is arranged outside the layer (B), a ratio of 10% modulus M10 (AB) to 100% modulus M100 (AB) of a laminate including the layer (A) and the layer (B) is more than 0.5 and less than 1.2, and an inequation 100% modulus of layer (C)<100% modulus of layer (A)<100% modulus of layer (B) is satisfied.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a hose for transporting fluids, and more particularly to a hose used to transport fluids such as gasoline and fuel. [Background technology]

[0002] A laminated tube including a layer of an aliphatic polyamide composition and a layer of a saponified ethylene / vinyl acetate copolymer composition is known as a hose for transporting fluids (JP 2019-73025 A). The laminated tube has excellent chemical resistance, interlayer adhesiveness, and durability while maintaining various properties such as chemical barrier properties, low-temperature impact resistance, and resistance to elution of monomers and oligomers. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2019-73025 Summary of the Invention [Problem to be solved by the invention]

[0004] Hoses for transporting fluids are required to be flexible for ease of handling, but are also desired to be less likely to collapse and become blocked when bent at a small curvature, i.e., less likely to kink. An object of the present invention is to provide a hose for transporting fluids that is flexible yet has excellent kink resistance. [Means for solving the problem]

[0005] The present inventors discovered that by sandwiching a layer of a thermoplastic resin with excellent barrier properties between a layer of a thermoplastic resin composition consisting of a thermoplastic resin matrix and a rubber domain and a layer of a rubber composition, it is possible to obtain a hose with excellent kink resistance while maintaining the barrier properties of the thermoplastic resin, and completed the present invention. The present invention relates to a hose for fluid transportation, comprising an inner layer, a reinforcing layer, and an outer layer, where the inner layer comprises a layer (A) made of a thermoplastic resin composition ax composed of a matrix am containing a thermoplastic resin ar and a domain ad containing a rubber ae, a layer (B) made of a thermoplastic resin composition bx composed of a matrix bm containing a thermoplastic resin b or a thermoplastic resin br and a domain bd containing a rubber be, and a layer (C) made of a rubber composition cx, the layer (A) is the innermost layer, the layer (B) is disposed outside the layer (A), and the layer (C) is disposed outside the layer (B), the ratio M10(AB) / M100(AB) of the 10% modulus M10(AB) to the 100% modulus M100(AB) of the laminate including the layer (A) and the layer (B) is more than 0.5 and less than 1.2, and the 100% modulus M100(A) of the layer (A), the 100% modulus M100(B) of the layer (B), and the 100% modulus M100(C) of the layer (C) satisfy the relational expression M100(C) < M100(A) < M100(B).

[0006] The present invention includes the following embodiments. [1] A hose for fluid transportation, comprising an inner layer, a reinforcing layer, and an outer layer, where the inner layer comprises a layer (A) made of a thermoplastic resin composition ax composed of a matrix am containing a thermoplastic resin ar and a domain ad containing a rubber ae, a layer (B) made of a thermoplastic resin composition bx composed of a matrix bm containing a thermoplastic resin b or a thermoplastic resin br and a domain bd containing a rubber be, and a layer (C) made of a rubber composition cx, the layer (A) is the innermost layer, the layer (B) is disposed outside the layer (A), and the layer (C) is disposed outside the layer (B), the ratio M10(AB) / M100(AB) of the 10% modulus M10(AB) to the 100% modulus M100(AB) of the laminate including the layer (A) and the layer (B) is more than 0.5 and less than 1.2, The 100% modulus M100(A) of layer (A), the 100% modulus M100(B) of layer (B), and the 100% modulus M100(C) of layer (C) satisfy the relational expression M100(C) < M100(A) < M100(B). A hose for fluid transportation is characterized by this. [2] The hose for fluid transportation according to [1], characterized in that layer (A) and layer (B) are directly adhered or adhered via an adhesive layer. [3] The ratio T(AB) / T(C) of the total thickness T(AB) of layer (A) and layer (B) to the thickness T(C) of layer (C) is 0.01 to 2.0. The hose for fluid transportation according to [1] or [2] is characterized by this. [4] The ratio T(A) / T(B) of the thickness T(A) of layer (A) to the thickness T(B) of layer (B) is greater than 0.1 and less than 20, and the thickness T(B) of layer (B) is 0.01 to 0.5 mm. The hose for fluid transportation according to any one of [1] to [3] is characterized by this. [5] The hose for fluid transportation according to any one of [1] to [4], characterized in that the thermoplastic resin composition ax contains 5 to 70% by mass of the domain ad. [6] The hose for fluid transportation according to any one of [1] to [5], characterized in that the thermoplastic resin composition ax contains 0.1% by mass or more of a compound having a plasticizing effect. [7] The hose for fluid transportation according to any one of [1] to [6], characterized in that the thermoplastic resin b or the thermoplastic resin br contains at least one selected from the group consisting of ethylene-vinyl alcohol copolymer, polyamide 6, polyamide 6 / 66 copolymer, polyamide 66, polyamide 610, polyamide 6 / 12 copolymer, polyamide 1010, polyamide 11, and polyamide 12. [8] The hose for fluid transportation according to any one of [1] to [7], characterized in that 50% by mass or more of the rubber in the rubber composition cx is at least one selected from the group consisting of acrylonitrile-butadiene rubber, acrylic rubber, and fluorine rubber. [9] The fuel permeability at 23°C of layer (B) is 2.0 mm·mg / 24h·cm 2 The hose for fluid transportation according to any one of [1] to [8], characterized by the following.

[10] The hose for transporting a fluid according to any one of [1] to [9], wherein the fluid is gasoline, alcohol-mixed gasoline, kerosene, light oil, heavy oil, vegetable oil, an organic solvent, or a mixture thereof. [Effects of the Invention]

[0007] The hose for transporting fluid of the present invention is flexible yet has excellent kink resistance. [Brief explanation of the drawings]

[0008] [Figure 1] FIG. 1 is a cross-sectional view of a hose for transporting fluid according to the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0009] The present invention relates to a hose for transporting fluids. The fluid to be transported is preferably, but not limited to, a liquid fuel. The liquid fuel may include gasoline, alcohol-blended gasoline, kerosene, diesel, heavy oil, vegetable oil, organic solvents, or mixtures thereof.

[0010] 1 shows a cross-sectional view of one embodiment of a hose for transporting fluid of the present invention, however, the hose for transporting fluid of the present invention is not limited to that shown in FIG. The fluid transportation hose 1 of the present invention comprises an inner layer 2, a reinforcing layer 3, and an outer layer 4, and the inner layer comprises an (A) layer 2a, a (B) layer 2b, and a (C) layer 2c.

[0011] Layer (A) is made of a thermoplastic resin composition ax, which is composed of a matrix am containing a thermoplastic resin ar and domains ad containing rubber ae. Layer (B) is made of a thermoplastic resin b or a thermoplastic resin composition bx. The thermoplastic resin composition bx is made of a matrix bm containing a thermoplastic resin br and a domain bd containing a rubber be. The layer (C) is made of a rubber composition cx.

[0012] The ratio M10(AB) / M100(AB) of the 10% modulus M10(AB) to the 100% modulus M100(AB) of the laminate including Layer (A) and Layer (B) is more than 0.5 and less than 1.2, preferably more than 0.7 and less than 1.1, and more preferably more than 0.9 and less than 1.1. When M10(AB) / M100(AB) is within the above range, a hose having kink resistance can be obtained. To make M10(AB) / M100(AB) fall within the above numerical range, it is preferable to use a material for layer A that is more ductile than layer B, and to bond layer A and layer B together. The 10% modulus and 100% modulus of the laminate are measured in accordance with JIS K 6301 "Physical testing method for vulcanized rubber."

[0013] The 100% modulus M100(A) of the (A) layer, the 100% modulus M100(B) of the (B) layer, and the 100% modulus M100(C) of the (C) layer are expressed by the following formula: M100(C) <M100(A)<M100(B) That is, the 100% modulus M100(A) of the layer (A) must be smaller than the 100% modulus M100(B) of the layer (B) and larger than the 100% modulus M100(C) of the layer (C). By satisfying the above relational expression, it is easy to achieve both kink resistance and flexibility. The 100% modulus of layers (A) and (B) is measured in accordance with JIS K 6301 "Physical test methods for vulcanized rubber," and the 100% modulus of layer (C) is measured in accordance with JIS K 6301 "Physical test methods for vulcanized rubber."

[0014] The (A) layer 2a is the innermost layer, the (B) layer 2b is disposed outside the (A) layer 2a, and the (C) layer 2c is disposed outside the (B) layer 2b. By sandwiching the (B) layer 2b between the (A) layer 2a and the (C) layer 2c, kinking can be suppressed while maintaining the barrier properties of the (B) layer.

[0015] The ratio T(AB) / T(C) of the total thickness T(AB) of layers (A) and (B) to the thickness T(C) of layer (C) is preferably 0.01 to 2.0, more preferably 0.05 to 1.5, and even more preferably 0.05 to 1.0. When T(AB) / T(C) is within the above range, desired kink resistance is easily obtained.

[0016] The ratio T(A) / T(B), of the thickness T(A) of layer (A) to the thickness T(B) of layer (B), is preferably more than 0.1 and less than 20, more preferably more than 0.5 and less than 10, and even more preferably more than 1.0 and less than 5.0. When T(A) / T(B) is within the above range, it is easy to achieve both the barrier properties that suppress leakage of the transported fluid and the ductility of the laminate including the A layer and the B layer.

[0017] The thickness T(B) of the layer (B) is preferably 0.01 to 0.5 mm, more preferably 0.05 to 0.3 mm, and even more preferably 0.05 to 0.2 mm. By setting the thickness T(B) of the (B) layer within the above range, the yield point due to the B layer is reduced.

[0018] The thickness T(A) of layer (A) is not limited as long as T(AB) / T(C), T(A) / T(B), and T(B) are within the above numerical ranges, but is preferably 0.5 to 0.01 mm, more preferably 0.4 to 0.05 mm, and even more preferably 0.3 to 0.1 mm.

[0019] The thickness T(C) of layer (C) is not limited as long as T(AB) / T(C), T(A) / T(B), and T(B) are within the above numerical ranges, but is preferably 0.1 to 5.0 mm, more preferably 0.5 to 4.0 mm, and even more preferably 1.0 to 3.0 mm.

[0020] The thermoplastic resin composition ax constituting the layer (A) is composed of a matrix am containing a thermoplastic resin ar and domains ad containing rubber ae, that is, the thermoplastic resin composition ax has a so-called sea-island structure. The thermoplastic resin ar is not limited as long as M10(AB) / M100(AB) is within the above numerical range and the relational expression M100(C) < M100(A) < M100(B) is satisfied. Preferably, it is an ethylene-vinyl alcohol copolymer, polyamide 6, polyamide 6 / 66 copolymer, polyamide 66, polyamide 610, polyamide 6 / 12 copolymer, polyamide 1010, polyamide 11, polyamide 12, and particularly preferably polyamide 6, polyamide 6 / 12 copolymer, polyamide 11, polyamide 12, ethylene-vinyl alcohol copolymer (hereinafter also referred to as "EVOH"). The matrix am may contain various additives as long as the effects of the present invention are not inhibited. The rubber ae is not limited as long as M10(AB) / M100(AB) is within the above numerical range and the relational expression M100(C) < M100(A) < M100(B) is satisfied. Preferably, it is an olefinic thermoplastic elastomer, styrenic thermoplastic elastomer, polyester thermoplastic elastomer, polyamide thermoplastic elastomer, polyurethane thermoplastic elastomer, and acid-modified products of these thermoplastic elastomers, natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), 1,2-butadiene rubber, styrene-butadiene rubber (SBR), chloroprene rubber (CR), butyl rubber (IIR), acrylonitrile-butadiene rubber (NBR), halogenated butyl rubber, brominated isobutylene-p-methylstyrene copolymer, styrene-isobutylene-styrene block copolymer, acrylic rubber (ACM), fluorine rubber, diene rubber such as ethylene-propylene-diene rubber (EPDM), and particularly preferably maleic anhydride-modified ethylene-1-butene copolymer, brominated isobutylene-p-methylstyrene copolymer (hereinafter also referred to as "Br-IPMS"). The domain ad may contain various additives as long as the effects of the present invention are not inhibited.

[0021] The thermoplastic resin composition ax preferably contains 30 to 95 mass % of the matrix am, more preferably 30 to 90 mass % of the matrix am, and even more preferably 30 to 85 mass % of the matrix am. The thermoplastic resin composition ax preferably contains 5 to 70% by mass of the domains ad, more preferably 10 to 70% by mass of the domains ad, and even more preferably 15 to 70% by mass of the domains ad. When the proportion of the domains ad in the thermoplastic resin composition ax is within the above range, it is easy to achieve a good balance between barrier properties, flexibility, reduction in volume expansion due to transport fluids, and the like.

[0022] The thermoplastic resin composition ax preferably contains 0.1 mass % or more of a compound having a plasticizing effect, more preferably 0.1 to 5.0 mass % of a compound having a plasticizing effect, and even more preferably 0.3 to 5.0 mass % of a compound having a plasticizing effect. When the thermoplastic resin composition ax contains a compound with a plasticizing effect, Layer A becomes a ductile material, and when it is laminated with Layer B, the brittle behavior (e.g., yield point) of Layer B can be reduced, making it easier to achieve both flexibility and kink resistance. The compound having a plasticizing effect may be any compound capable of plasticizing the thermoplastic resin ar, and may be, for example, a residue of a monomer used in polymerizing the thermoplastic resin ar, or a low molecular weight compound that dissolves in the resin and increases molecular mobility. Specific examples of compounds with plasticizing properties include dioctyl phthalate (DOP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), dibutyl phthalate (DBP), dioctyl adipate (DOA), diisononyl adipate (DIDA), tricresyl phosphate, isodecyl succinate, diethylene glycol dibenzoate, pentaerythritol ester, butyl oleate, acetylricinoleic acid ester, propylene glycol adipate polyester, butylene glycol adipate polyester, naphthenic oil, glyceryl triacetate, and N-butylbenzenesulfonamide. In Tables 4 to 6, "compounds having a plasticizing effect" are abbreviated to "plasticizers."

[0023] The thermoplastic resin composition ax may contain components other than the thermoplastic resin ar, rubber ae, and compound having a plasticizing effect, as long as the effects of the present invention are not impaired.

[0024] Layer (B) is made of a thermoplastic resin b or a thermoplastic resin composition bx. The thermoplastic resin b is preferably a resin with high barrier properties, and preferably contains at least one selected from the group consisting of ethylene-vinyl alcohol copolymer, polyamide 6, polyamide 6 / 66 copolymer, polyamide 66, polyamide 610, polyamide 6 / 12 copolymer, polyamide 1010, polyamide 11, and polyamide 12. When the (B) layer is made of the thermoplastic resin b, the (B) layer may contain components other than the thermoplastic resin b, such as various additives, to the extent that the effects of the present invention are not impaired.

[0025] The thermoplastic resin composition bx constituting the layer (B) is composed of a matrix bm containing a thermoplastic resin br and domains bd containing rubber be, that is, the thermoplastic resin composition bx has a so-called sea-island structure. The thermoplastic resin br is preferably a resin with high barrier properties, and preferably includes at least one selected from the group consisting of ethylene-vinyl alcohol copolymer, polyamide 6, polyamide 6 / 66 copolymer, polyamide 66, polyamide 610, polyamide 6 / 12 copolymer, polyamide 1010, polyamide 11, and polyamide 12. The matrix bm may contain various additives to the extent that the effects of the present invention are not impaired. The rubber be is not limited as long as M10(AB) / M100(AB) is within the above numerical range and the relational expression M100(C) < M100(A) < M100(B) is satisfied. Preferably, it is an olefin thermoplastic elastomer, a styrene thermoplastic elastomer, a polyester thermoplastic elastomer, a polyamide thermoplastic elastomer, a polyurethane thermoplastic elastomer, an acid-modified product of these thermoplastic elastomers, natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), 1,2-butadiene rubber, styrene-butadiene rubber (SBR), chloroprene rubber (CR), butyl rubber (IIR), acrylonitrile-butadiene rubber (NBR), halogenated butyl rubber, brominated isobutylene-p-methylstyrene copolymer, styrene-isobutylene-styrene block copolymer, acrylic rubber (ACM), fluorine rubber, ethylene-propylene-diene rubber (EPDM), etc. A diene rubber, and particularly preferably a maleic anhydride-modified ethylene-1-butene copolymer. The domain bd may contain various additives as long as the effects of the present invention are not inhibited. The thermoplastic resin composition bx may contain components other than the thermoplastic resin br and the rubber be as long as the effects of the present invention are not inhibited.

[0026] The thermoplastic resin composition bx preferably contains 30 to 95% by mass of the matrix bm, more preferably 30 to 90% by mass of the matrix bm, and even more preferably 30 to 85% by mass of the matrix bm. The thermoplastic resin composition bx preferably contains 5 to 70% by mass of the domain bd, more preferably 10 to 70% by mass of the domain bd, and even more preferably 15 to 70% by mass of the domain bd. When the ratio of the domain bd in the thermoplastic resin composition bx is within the above numerical range, it is easy to achieve both the barrier property and flexibility for suppressing the leakage of the transported fluid.

[0027] The fuel permeability at 23°C of the (B) layer is preferably 2.0 mm·mg / 24h·cm 2 or less, and more preferably 1.5 mm·mg / 24h·cm2 It is preferably 1.0 mm·mg / 24h·cm or less. 2 The following is the result. When the fuel permeability of Layer (B) at 23°C is within the above range, a hose with low fuel permeability can be obtained. The fuel permeability is measured by the method described below.

[0028] The layer (C) is made of a rubber composition cx. The rubber composition cx includes a rubber ce. Examples of rubber ce include natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), 1,2-butadiene rubber, styrene-butadiene rubber (SBR), chloroprene rubber (CR), butyl rubber (IIR), acrylonitrile-butadiene rubber (NBR), acrylic rubber (ACM), fluororubber, and diene rubber such as ethylene-propylene-diene rubber (EPDM). Of these, acrylonitrile-butadiene rubber (NBR), acrylic rubber (ACM), and fluororubber are preferred. Preferably, 50% by mass or more of the rubber in the rubber composition cx is at least one selected from the group consisting of acrylonitrile-butadiene rubber, acrylic rubber, and fluororubber. The rubber composition cx contains various additives in addition to rubber, such as a crosslinking agent, an antioxidant, a plasticizer, a processing aid, a crosslinking accelerator, a crosslinking accelerator, a reinforcing agent (filler), a scorch inhibitor, a mastication accelerator, an organic modifier, a softener, and a tackifier.

[0029] The layer (A) and the layer (B) may be bonded directly or via an adhesive layer. When the adhesive is formed via an adhesive layer, the material constituting the adhesive layer may be a phenolic resin adhesive, a melamine resin adhesive, a urethane resin adhesive, or an epoxy resin adhesive, with urethane resin adhesives and phenolic resin adhesives being preferred. The thickness of the adhesive layer is not limited as long as sufficient adhesive strength is obtained, but is preferably 0.5 to 10 μm, more preferably 0.5 to 5.0 μm, and even more preferably 0.5 to 3.0 μm. The method for forming the adhesive layer is not particularly limited, but the adhesive layer can be provided by applying, coating, spraying, or the like an adhesive solution to the outside of Layer A. By bonding via an adhesive layer, layers A and B are less likely to peel off when the hose is repeatedly deformed, which is advantageous for durability.

[0030] The reinforcing layer is usually a braided or spiral layer formed by braiding metal wires or organic fibers. Examples of metal wires include steel wires, copper and copper alloy wires, aluminum and aluminum alloy wires, magnesium alloy wires, and titanium and titanium alloy wires, with steel wires being preferred. The diameter of the metal wires is preferably 0.25 to 0.40 mm. Examples of organic fibers include polyparaphenylenebenzbisoxazole (PBO) fibers, aramid fibers, and carbon fibers, with PBO fibers being preferred. The diameter of the organic fibers is preferably 0.25 to 0.30 mm. Two or more braided or spiral layers may be laminated, or a braided layer and a spiral layer may be combined.

[0031] The outer layer is usually made of a rubber composition, a thermoplastic elastomer, or a thermoplastic elastomer composition. Examples of rubber compositions include, but are not limited to, rubbers such as acrylonitrile-butadiene rubber (NBR), acrylonitrile-butadiene rubber (NBR) / polyvinyl chloride (PVC) blends, chlorosulfonated polyethylene (CSM), and butyl rubber (IIR), to which additives such as crosslinking agents, antioxidants, plasticizers, processing aids, crosslinking accelerators, crosslinking accelerators, reinforcing agents (fillers), scorch inhibitors, peptizers, organic modifiers, softeners, and tackifiers have been added. Examples of the thermoplastic elastomer include olefin-based thermoplastic elastomers, styrene-based thermoplastic elastomers, polyamide elastomers, polyester elastomers, and polyurethane elastomers. Examples of thermoplastic elastomer compositions include those comprising a matrix containing a thermoplastic resin such as a polyamide resin, a polyester resin, an ethylene-vinyl alcohol resin, a polyolefin resin, a polyketone resin, a polyacetal resin, a polyphenylene sulfide resin, a polyphenylene ether resin, or a fluorine-based resin, and a domain containing a rubber such as butyl rubber, modified butyl rubber, an olefin-based thermoplastic elastomer, a styrene-based thermoplastic elastomer, an ethylene-unsaturated carboxylic acid ester copolymer, a polyamide elastomer, a polyester elastomer, or a polyurethane elastomer.

[0032] The thickness of the outer layer is preferably 0.2 to 5.0 mm, more preferably 0.2 to 4.0 mm, and even more preferably 0.2 to 3.0 mm.

[0033] The method for producing a hose for transporting fluid is not limited to the following method. A thermoplastic resin composition for layer (A) and a thermoplastic resin or thermoplastic resin composition for layer (B) are extruded into a tubular shape using an extruder onto a mandrel that has been pre-coated with a release agent, with the thermoplastic resin composition for layer (A) being the innermost layer, to form layers (A) and (B). Next, a rubber composition for layer (C) is extruded into a tubular shape using an extruder onto layer (B), to form layer (C). Next, an adhesive is applied onto layer (C), and steel wire or organic fiber is braided using a braiding machine to form a reinforcing layer. Next, a rubber composition for an outer layer is extruded into a tubular shape onto the reinforcing layer using an extruder to form the outer layer. Steam vulcanization is then performed, and the mandrel is then removed to produce a hose. [Example]

[0034] [raw materials] The raw materials used in the following examples and comparative examples are as follows:

[0035] (thermoplastic resin) PA6: Polyamide 6, Ube Industries, Ltd. "UBE Nylon" (registered trademark) 1011FB PA610: Polyamide 610, Daicel-Evonik "Daiamide" (registered trademark) HS16 PA6 / 12: Polyamide 6 / 12 copolymer, Ube Industries, Ltd. "UBE Nylon" (registered trademark) 7024B PA6 / 66: Polyamide 6 / 66 copolymer, Ube Industries, Ltd. "UBE Nylon" 5033B PA66: Polyamide 66, Toray Industries, Inc. "Amilan" (registered trademark) CM3001-N PA1010: Polyamide 1010, Daicel-Evonik "Daiamide" (registered trademark) DS16 PA11-1: Polyamide 11, Arkema's "RILSAN" (registered trademark) BESN P40TL, with plasticizer (type of plasticizer: N-butylbenzenesulfonamide, plasticizer content: 12% by mass) PA11-2: Polyamide 11, Arkema "RILSAN" (registered trademark) BESN OTL, no plasticizer PA12: Polyamide 12, UBE STA (registered trademark) 3012U manufactured by Ube Industries, Ltd. MXD6: Polyamide MXD6, "Reny" (registered trademark) S6001 manufactured by Mitsubishi Gas Chemical Company, Inc. EVOH: Ethylene-vinyl alcohol copolymer, Kuraray Co., Ltd. "EVAL" (registered trademark) FP201B

[0036] (rubber) Acid-modified PO: Maleic anhydride-modified ethylene-1-butene copolymer, "Tafmer" (registered trademark) MH7010 manufactured by Mitsui Chemicals, Inc. Br-IPMS: Brominated isobutylene-p-methylstyrene copolymer, ExxonMobil Chemical Company "EXXPRO"® 3745 NBR: Acrylonitrile-butadiene rubber, "NIPOL" (registered trademark) 1043 manufactured by Zeon Corporation NBR-PVC: Nitrile rubber / polyvinyl chloride blend, Zeon Corporation "NIPOL" (registered trademark) DN517 CSM: Chlorosulfonated polyethylene rubber, DuPont "Hypalon" (registered trademark) 40S

[0037] (others) ε-Caprolactam: Fujifilm Wako Pure Chemical Industries, Ltd. Carbon black: "Seast" (registered trademark) V manufactured by Tokai Carbon Co., Ltd. Sulfur: Oil-treated sulfur manufactured by Hosoi Chemical Industry Co., Ltd. Vulcanization accelerator: Di-2-benzothiazolyl disulfide, "Noccela" (registered trademark) DM manufactured by Ouchi Shinko Chemical Industry Co., Ltd. Antioxidant: 2,2,4-trimethyl-1,2-dihydroquinoline polymer, "Nocrac" (registered trademark) 224 manufactured by Ouchi Shinko Chemical Industry Co., Ltd. Zinc oxide: Three types of zinc oxide manufactured by Seido Chemical Industry Co., Ltd. Stearic acid: Kanto Chemical Co., Ltd., stearic acid, grade 1 Plasticizer: Diisononyl phthalate, manufactured by Taoka Chemical Co., Ltd.

[0038] (1) Preparation of thermoplastic resin composition The raw materials having the blending ratios shown in Table 1 were fed into a twin-screw kneader (manufactured by The Japan Steel Works, Ltd.) and kneaded at 200 to 240°C for 3 minutes. The resulting kneaded material was extruded into a strand shape, washed with cold water, and then cut with a strand cutter to prepare a pellet-shaped thermoplastic resin composition.

[0039] (2) Preparation of rubber composition The raw materials having the compounding ratios shown in Table 2 were kneaded in a Banbury mixer to prepare rubber compositions.

[0040] (3) Preparation of rubber composition for outer layer The raw materials having the compounding ratios shown in Table 3 were kneaded in a Banbury mixer to prepare rubber compositions for the outer layer.

[0041] (4) Making the hose The (A) layer materials and (B) layer materials shown in Tables 4 to 6 were extruded onto a mandrel pre-coated with a release agent into a tubular shape with the thickness shown in Tables 4 to 6, with the (A) layer being the innermost layer, using an extruder to form the (A) layer and (B) layer. The (C) layer material shown in Tables 4 to 6 was extruded onto the (B) layer to the thickness shown in Tables 4 to 6 to form the (C) layer. A phenolic adhesive was applied onto the (C) layer, and steel wire was braided using a braiding machine to form a reinforcing layer. The outer layer rubber composition shown in Table 3 was extruded onto the reinforcing layer to a thickness of 2.0 mm to form an outer layer. The hose was then steam vulcanized at 143°C for 60 minutes, and the mandrel was removed to produce a hose.

[0042] For each example and comparative example, the 10% modulus M10(AB) and 100% modulus M100(AB) of the laminate including Layer A and Layer B, the 100% modulus M100(A) of Layer A, the 100% modulus M100(B) of Layer B, the 100% modulus M100(C) of Layer C, and the fuel permeability, kink suppression, hose bending force, and room temperature handleability of Layer B were evaluated. The evaluation results are shown in Tables 4 to 6. The measurement and evaluation methods for each evaluation item are as follows:

[0043] [Modulus measurement] The modulus of the thermoplastic resin, thermoplastic resin composition, or laminate was determined by punching out a sheet of the thermoplastic resin, a sheet of the thermoplastic resin composition, or a laminate into a JIS No. 3 dumbbell shape, conducting a tensile test at 25°C and a tensile speed of 100 mm / min, and from the resulting stress-strain curve, defining the stress at 10% elongation as the 10% modulus M10 [MPa] and the stress at 100% elongation as the 100% modulus M100 [MPa]. The rubber modulus was determined in accordance with JIS K 6251 by punching a vulcanized rubber sheet into a JIS No. 3 dumbbell shape and conducting a tensile test at 25°C and a tensile speed of 500 mm / min. From the obtained stress-strain curve, the stress at 10% elongation was defined as the 10% modulus M10 [MPa], and the stress at 100% elongation was defined as the 100% modulus M100 [MPa]. However, the thermoplastic resin sheet or thermoplastic resin composition sheet was produced by extruding the thermoplastic resin or thermoplastic resin composition into a sheet with an average thickness of 0.15 mm using a Φ40 mm single-screw extruder equipped with a 550 mm wide T-type die (manufactured by Plagiken Co., Ltd.) with the cylinder and die temperatures set to 220 to 245°C and the take-up speed set to 0.5 to 3.0 mm / min. The vulcanized rubber sheets were produced by cutting the rubber composition prepared in a Banbury mixer to a specified size, sandwiching it between iron plates using a mold 2 mm thick and 150 mm x 150 mm long, and vulcanizing it for 60 minutes using a press at a temperature of 143°C and a pressure of 3.0 MPa. A laminate including layers (A) and (B) was prepared by cutting a sheet of the material for layer (A) and a sheet of the material for layer (B) into 150 mm x 150 mm squares, and then hot pressing them at 3.0 MPa for 5 minutes using a press set at a temperature 10°C above the melting point of either the material for layer (A) or the material for layer (B), whichever is higher. In Comparative Example 3, an adhesive layer was provided between Layer (A) and Layer (B), and the resulting product was vulcanized using a press at a temperature of 143°C and a pressure of 3.0 MPa for 60 minutes.

[0044] [Fuel permeability measurement] 20 mL of test fuel CE10 (isooctane / toluene / ethanol = 45 / 45 / 10% by volume) was placed in an aluminum cup used in JIS Z 0208 "Test method for moisture permeation of moisture-proof packaging materials," and a sheet of the material for layer (B) prepared in the above "Modulus measurement" was cut out so that the permeable surface was a circle with a diameter of 60 mm and attached. The sheet was left in an atmosphere at 23°C with the sheet surface facing downwards so that the sheet and test fuel were always in contact, and the weight of the cup was measured every day. The fuel permeability was calculated from the weight loss up to 7 days.

[0045] [Kink suppression] In accordance with JIS K 6330-9, a bending test was conducted on the hose at 23°C. When one end of the hose was fixed and the other end was bent, those that did not kink at a bending radius of R = 100 mm were marked with a ◯, and those that did kink were marked with an ×.

[0046] [Handling at room temperature] A hose bending test was conducted at 23°C in accordance with JIS K 6330-9, and the bending force was measured at a bending radius R of 130 mm when one end of the hose was fixed and the other end was bent. The hose bending force of each example and comparative example was expressed as an index with the hose bending force of Comparative Example 1 being set at 100. The handleability at room temperature was rated as "poor" when the hose bending force index was 100 or more, "good" when it was 90 or more but less than 100, and "excellent" when it was less than 90.

[0047] [Table 1]

[0048] [Table 2]

[0049] [Table 3]

[0050] [Table 4]

[0051] [Table 5]

[0052] [Table 6] [Industrial Applicability]

[0053] The fluid transport hose of the present invention can be suitably used as a hose for transporting fluids such as gasoline and fuel. [Explanation of symbols]

[0054] 1. Fluid transport hose 2. Inner layer 2a (A) layer 2b (B) layer 2c (C) layer 3 Reinforcement layer 4 Outer layer

Claims

1. A hose for transporting fluid, comprising an inner layer, a reinforcing layer, and an outer layer, the inner layer includes: an (A) layer made of a thermoplastic resin composition ax including a matrix am containing a thermoplastic resin ar and a domain ad containing a rubber ae; a (B) layer made of a thermoplastic resin composition bx including a matrix bm containing a thermoplastic resin b or a thermoplastic resin br and a domain bd containing a rubber be; and a (C) layer made of a rubber composition cx; The layer (A) is the innermost layer, the layer (B) is disposed outside the layer (A), and the layer (C) is disposed outside the layer (B); a ratio M10(AB) / M100(AB) of the 10% modulus M10(AB) to the 100% modulus M100(AB) of a laminate including the layer (A) and the layer (B), being greater than 0.5 and less than 1.2; A hose for transporting fluids, characterized in that the 100% modulus M100(A) of layer (A), the 100% modulus M100(B) of layer (B), and the 100% modulus M100(C) of layer (C) satisfy the relation M100(C) < M100(A) < M100(B).

2. 2. The hose for transporting fluid according to claim 1, wherein the layer (A) and the layer (B) are bonded directly or via an adhesive layer.

3. 3. The hose for transporting fluid according to claim 1, wherein the ratio T(AB) / T(C) of the total thickness T(AB) of layers (A) and (B) to the thickness T(C) of layer (C) is 0.01 to 2.

0.

4. 4. The hose for transporting fluid according to any one of claims 1 to 3, characterized in that the ratio T(A) / T(B) of the thickness T(A) of layer (A) to the thickness T(B) of layer (B) is more than 0.1 and less than 20, and the thickness T(B) of layer (B) is 0.01 to 0.5 mm.

5. 5. The hose for transporting fluid according to claim 1, wherein the thermoplastic resin composition ax contains 5 to 70 mass % of the domains ad.

6. 6. The hose for transporting fluid according to claim 1, wherein the thermoplastic resin composition ax contains 0.1% by mass or more of a compound having a plasticizing effect.

7. 7. The hose for transporting a fluid according to claim 1, wherein the thermoplastic resin b or the thermoplastic resin br comprises at least one selected from the group consisting of an ethylene-vinyl alcohol copolymer, polyamide 6, a polyamide 6 / 66 copolymer, polyamide 66, polyamide 610, a polyamide 6 / 12 copolymer, polyamide 1010, polyamide 11, and polyamide 12.

8. The hose for transporting fluid according to any one of claims 1 to 7, characterized in that 50% by mass or more of the rubber in the rubber composition cx is at least one selected from the group consisting of acrylonitrile-butadiene rubber, acrylic rubber, and fluororubber.

9. (B) The fuel permeability of the layer at 23°C is 2.0 mm mg / 24 h cm ２ The hose for transporting fluid according to any one of claims 1 to 8, characterized in that:

10. 10. The hose for transporting fluid according to claim 1, wherein the fluid is gasoline, alcohol-mixed gasoline, kerosene, light oil, heavy oil, vegetable oil, an organic solvent, or a mixture thereof.

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