Thermoplastic pvc composites for multilayer fuel hoses

Abstract

A hose has an inner tube, a reinforcement layer disposed outwardly from the inner tube, and a cover layer disposed outwardly from the reinforcement layer. The inner tube has a thermoplastic material including polyvinyl chloride (PVC) and a non-leached plasticizer, the non-leached plasticizer having an ethylene copolymer and butyl acrylate. The non-leached plasticizer binds itself to the PVC polymer chain, making it more stable when exposed to chemicals such as fuels. This reduces the deformation effect of the PVC material, making it suitable for use as an inner tube for a fuel hose.

Description

[0001] This application claims priority to U.S. Provisional Application No. 63 / 579,310, filed August 29, 2023, the entire contents of which are incorporated herein by reference. Technical Field

[0002] This disclosure relates substantially to a thermoplastic polyvinyl chloride compound, particularly for use in hoses, and more particularly to multilayer reinforced hoses for high-performance applications such as fuel delivery. Background Technology

[0003] Thermoplastic, rubber-like hoses are used in a variety of applications for conveying fluids such as liquids and gases. For example, a common application of thermoplastic multilayer hoses is as fuel delivery hoses (also known as droop hoses), used to transfer fuel from fuel delivery vehicles to storage tanks located at refueling facilities. Typically, droop hoses should have sufficient flexibility to allow for bending; chemical resistance to hydrocarbons in the fuel; tensile strength to withstand pressure during fuel delivery; abrasion resistance when dragged on rough surfaces; and lightweight for ease of handling. However, unlike conventional roadside pump hoses, droop hoses are used only intermittently and are therefore less exposed to fuel, and are repeatedly cycled to dry between deliveries. Therefore, a typical construction of a droop hose that meets performance requirements may include a thermoplastic polyurethane (TPU) inner tube, a reinforcing layer outside the inner tube, and a thermoplastic outer covering layer, which may be made of polyvinyl chloride (PVC). Summary of the Invention

[0004] One problem with conventional hoses (such as droop hoses with a TPU inner tube) is that they are more expensive than other thermoplastic materials (such as PVC). This is particularly problematic for droop hoses, which may have a relatively short lifespan compared to other fuel hoses. Therefore, there is a need for a low-cost hose design that can meet the requirements of this application.

[0005] While PVC is generally much cheaper than TPU, these PVC materials are typically not used in fuel-related applications because they have limited resistance to certain organic solvents, including gasoline and other hydrocarbons found in fuels. In particular, when conventional PVC comes into contact with these hydrocarbons, the plasticizers in the material leach out, causing the material to deform (e.g., shrink or expand). This deformation leads to a decrease in material properties, such as reduced strength, increased permeability, altered dimensional stability, and hardening or softening. Therefore, there remains a need for an inexpensive, PVC-like material suitable for use as the inner lining of hoses.

[0006] At least one aspect of the present invention addresses one or more problems associated with conventional materials for inner tubing of hoses, such as droop hoses used in fuel delivery applications. More particularly, one aspect of this disclosure provides a unique PVC compound that uses a non-leaching plasticizer to reduce dimensional changes upon exposure to fuel, and / or provides other material properties that make the PVC compound suitable for use as inner tubing of hoses, particularly as inner tubing for fuel droop hoses with intermittent fuel exposure.

[0007] According to one aspect, an exemplary hose includes: an inner tube forming an internal channel; a reinforcing layer disposed outward from the inner tube; and a covering layer disposed outward from the reinforcing layer, wherein the inner tube has a thermoplastic material comprising polyvinyl chloride (PVC) and a non-leaching plasticizer, the non-leaching plasticizer having an ethylene copolymer and butyl acrylate.

[0008] This non-leaching plasticizer binds itself to the PVC polymer chain, making it more stable when exposed to chemicals such as fuels. This reduces the deformation effect of the PVC material, making it suitable for use as the inner tubing of hoses for specific applications.

[0009] According to another aspect, an exemplary thermoplastic material includes polyvinyl chloride in a total content of 80 phr to 100 phr; a non-leaching plasticizer in a total content of 20 phr to 50 phr, said non-leaching plasticizer having an ethylene copolymer and butyl acrylate; at least one additional plasticizer in a total content of 20 phr to 60 phr; and at least one stabilizer in a total content of 2 phr to 25 phr.

[0010] According to another aspect, an exemplary thermoplastic PVC composite includes a non-leaching plasticizer comprising an ethylene copolymer and butyl acrylate, and has material properties suitable for use in hoses, etc.

[0011] The following description and accompanying drawings illustrate some illustrative embodiments according to this disclosure. However, these embodiments only show a few of the many ways in which the principles of the invention can be applied. Other objects, advantages, and novel features of aspects of this disclosure will become apparent from the following detailed description taken in conjunction with the accompanying drawings. Attached Figure Description

[0012] The accompanying drawings (not necessarily drawn to scale) illustrate various aspects of this disclosure.

[0013] Figure 1 An exemplary embodiment of the hose according to this disclosure is shown.

[0014] Figure 2 Another exemplary embodiment of the hose according to this disclosure is shown.

[0015] Figure 3 Another exemplary embodiment of the hose according to this disclosure is shown.

[0016] Figure 4 Another exemplary embodiment of the hose according to this disclosure is shown.

[0017] Figure 5 Another exemplary embodiment of the hose according to this disclosure is shown.

[0018] Figure 6 Another exemplary embodiment of the hose according to this disclosure is shown.

[0019] Figure 7 and Figure 8 Another exemplary embodiment of the hose according to this disclosure is shown. Detailed Implementation

[0020] The principles and aspects of this disclosure have a specific application to hoses (particularly fuel droop hoses) and will therefore be described primarily in this context. However, it should be understood that the principles and aspects of this disclosure, when it is desired to provide one or more advantages of the materials and / or structures described herein, can be applied to other hose types for other applications or to other articles of general manufacture.

[0021] Conventional polyvinyl chloride (PVC) materials typically contain processing aids, plasticizers, stabilizers, and may contain other additives. Because conventional plasticizers can leach from PVC materials when exposed to chemicals such as hydrocarbons in fuels, these conventional PVC materials are generally not used as inner tubing materials for hoses. Instead, more expensive composites, such as thermoplastic polyurethane (TPU), nitrile rubber, or fluoroelastomers, are used to form the inner tubing of hoses.

[0022] One or more aspects of this disclosure provide a unique thermoplastic PVC compound as described herein that reduces the leaching of plasticizers upon exposure to chemicals such as fuels, thereby reducing dimensional changes (e.g., swelling). The unique PVC compound may also possess other material properties that make it particularly suitable for articles such as hoses. As described in further detail below, one or more exemplary embodiments of this disclosure include a hose having at least one inner tube comprising an exemplary thermoplastic PVC compound. One or more embodiments of this disclosure also include a multilayer hose structure having an inner tube, a reinforcing layer disposed outward from the inner tube, and a covering layer disposed outward from the reinforcing layer.

[0023] The inner tube of a hose is the innermost layer that forms the internal fluid passage or cavity of the hose and is in contact with the fluid being transported. This tubular inner layer can simply be referred to as the "tube" or "core." The inner tube contains and transports the working fluid and is therefore chemically resistant to it. The inner tube can also form a permeation barrier, preventing the fluid transported through it from seeping in. The inner tube gives the hose strength to increase burst pressure and can work in conjunction with one or more other layers of the hose to provide a relatively high burst pressure. To maintain the overall flexibility of the hose, the inner tube material can be relatively flexible and have a relatively low initial modulus.

[0024] The inner tube comprises an exemplary thermoplastic PVC composite with a non-leaching plasticizer to at least improve the material's chemical resistance and resistance to deformation (e.g., swelling). This material is particularly suitable for applications involving intermittent fuel exposure, such as applications where the material is exposed to fuel for less than half its normal operating life, and / or experiences intermittent drying between two fuel exposures—both typical scenarios for fuel droop hoses. The PVC composite may be particularly chemically resistant to the following exemplary fuel types, including: conventional petroleum-based fuels, such as gasoline or diesel; bio-based fuels, such as biodiesel (e.g., up to grade B20) or biogas (e.g., up to grade CE10 conforming to ASTM B6751). Or blends thereof. As described in further detail below, PVC compounds may also contain various additional additives in suitable amounts, including but not limited to one or more additional plasticizers, stabilizers, processing aids, etc. Additional additives, including reinforcing agents, fillers, etc., may be further included or may be specifically excluded.

[0025] The matrix of the composition comprises a PVC polymer as the base of the composition. The composition may also contain other polymers (one or more) blended with the base elastomer (one or more), which also form part of the composition matrix. The total polymer content forming the base composition (which may include a mixture of base polymers) is set to 100 phr. Additives in the composition are blended relative to the total base polymer content of the composition and can therefore be expressed in parts per hundred (phr), i.e., parts by weight of additives per 100 parts by weight of the base polymer (one or more).

[0026] Thermoplastic PVC composites may include one or more polyvinyl chloride homopolymer resins in a total content of about 80 parts per hundred (phr) to about 100 phr, more particularly about 90 phr to about 100 phr, for example, about 100 phr. The PVC resin, or blends thereof, may have any suitable molecular weight or intrinsic viscosity for a particular application, including the final material properties for the application or the processing properties for preparing the product of the application. For example, the PVC resin, or blends thereof, may have an intrinsic viscosity measured by a Fickentscher K value, which is in the range of about K65 to about K80, more particularly in the range of about K72 to about K78, for example, about K65, K68, K72, K73, K74, K75, K76, K77, K78, or K80. In the case of blends, the K values ​​of the individual component resins may be taken to calculate the total (average) K value. The K-value is a dimensionless empirical measure closely related to intrinsic viscosity. It is typically defined in slightly different ways across industries to represent the statistical molecular weight and average degree of polymerization of polymeric materials (particularly for PVC) based on viscosity estimates. In Europe, the commonly used K-value is the Fikentscher K-value, obtained through dilute solution viscometry and solving the Fikentscher equation (refer to DIN EN ISO 1628-1). The K-value is generally related to the molecular weight of the PVC resin; therefore, a higher K-value indicates a higher molecular weight PVC (and thus higher strength), while a lower K-value indicates a lower molecular weight PVC.

[0027] Non-leaching plasticizers used in PVC composites can affect processing and material properties. Therefore, in exemplary embodiments, the PVC mixture includes a blend of at least one first PVC homopolymer resin having a lower K value (and thus a lower molecular weight) compared to at least one second PVC homopolymer resin. This can improve the mechanical properties of the composite while still providing the effects of a non-leaching plasticizer. For example, the first PVC resin may have a K value in the range of about K65 to about K75 (e.g., K65, K68, K69, K70, K71, K72, K73, K74, K75), and the second PVC resin may have a K value in the range of about K76 to about K85 (e.g., K76, K77, K78, K79, K80, K81, K82, K83, K85). The K values ​​of the blend of the first and second PVC resins may also be within the above ranges.

[0028] In an exemplary embodiment, a first PVC resin with a lower K-value may be present in the PVC composite at a content of about 20 phr to about 60 phr, more particularly about 40 phr to about 55 phr, for example, about 40, 45, 50, or 55 phr. A second PVC resin with a higher K-value may be present in the PVC composite at a content of about 20 phr to about 60 phr, more particularly about 40 phr to about 55 phr, for example, about 40, 45, 50, or 55 phr. As described above, the total PVC resin content may be in the range of about 80 phr to 100 phr, or within its subrange. Therefore, the ratio of the low-K-value PVC resin content (phr) to the total PVC resin content (phr) may be in the range of 20:50 to 60:40 (e.g., 20:80, 20:100, 40:80, 40:100, 60:80, 60:100, etc.); the ratio of the high-K-value PVC resin to the total PVC resin content may be the same as or a balance thereof.

[0029] Non-leaching plasticizers in PVC compounds may be present in any suitable amount and may include one or more types of non-leaching plasticizers, including any suitable amount of ethylene copolymers and butyl acrylate. For example, the total amount of non-leaching plasticizers present in the PVC compound may be in the range of about 20 phr to about 60 phr, more particularly about 20 phr to about 50 phr, further more particularly about 20 phr to about 40 phr, such as about 20, 25, 30, 35, 40, 45, 50, 55 or 60 phr (inclusive of all values ​​and the range between the listed values).

[0030] Non-leaching plasticizers are soluble in PVC blends and exhibit good compatibility with the PVC matrix. Typically, non-leaching plasticizers are configured to bind to the PVC polymer backbone to enhance its stability and non-leaching properties. Non-leaching plasticizers may include additional functional groups to form terpolymers and improve coordination bonding with the PVC backbone.

[0031] The proportion of butyl acrylate in the non-leaching plasticizer can be 5% to 50% by weight (e.g., 10% to 40% by weight, or 30% by weight), and when additional functional groups are present, its content can be 3% to 30% by weight (e.g., 3% to 10% by weight), and the remainder of the plasticizer complex is an ethylene copolymer (e.g., 40% to 80% by weight, or 50% to 65% by weight). For example, the non-leaching plasticizer can be a terpolymer having 40% ethylene copolymer, 40% butyl acrylate, and 20% functional groups (which improve coordination bonding). These values ​​can be used to determine the proportions of these components in the PVC complex. For example, considering that the total content of non-leaching plasticizers present in the PVC compound is from about 20 phr to about 60 phr, the content of butyl acrylate present in the PVC compound can be from about 1 phr to 30 phr, more particularly from about 5 phr to about 15 phr (e.g., 1, 3, 5, 8, 10, 15, 20, 25 or 30 phr); and the content of ethylene copolymers that may be present in the PVC compound can be from about 8 phr to about 55 phr, more particularly from about 10 phr to about 30 phr (e.g., 8, 10, 15, 20, 25, 30, 35, 40, 45, 48, 50 or 55 phr). When additional functional groups are present, their content can be calculated similarly.

[0032] Exemplary PVC compounds may include one or more additional plasticizers. For example, the total content of one or more additional plasticizers that may be present in the PVC compound may be from about 20 phr to about 90 phr, more particularly from about 30 phr to about 50 phr, such as about 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, or 90 phr. Any suitable plasticizer or combination of such plasticizers may be used in the PVC compound, particularly including one or more stable types of plasticizers in the PVC compound to further reduce the leaching of one or more additional plasticizers. In one or more exemplary embodiments, one or more additional plasticizers may include carboxylic acid esters, such as trimellitate plasticizers, such as trioctyl trimellitate (TOTM). This TOTM plasticizer has relatively low volatility, making it less prone to evaporation or leaching at normal operating temperatures. The TOTM plasticizer also provides good resistance at higher temperatures.

[0033] One or more additional plasticizers may act in combination with non-leaching plasticizers to improve the deformation resistance of the PVC composite. The use of one or more additional plasticizers in combination with non-leaching plasticizers may also contribute to processing performance and / or cost reduction. In an exemplary embodiment, a non-leaching plasticizer (as described above) and an additional plasticizer (e.g., TOTM) may constitute the total plasticizer content in the PVC composite. The total plasticizer content in the PVC composite (total plasticizer content in the PVC composite) may be from about 40 phr to about 110 phr, more particularly from about 50 phr to about 70 phr, for example, about 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, or 110 phr. Therefore, given the aforementioned contents of non-leaching plasticizers and (one or more) additional plasticizers, the ratio of non-leaching plasticizer content (phr) to total plasticizer content (phr) can range from about 20:110 to about 60:100, more particularly from about 20:70 to about 40:80 (inclusive of all ranges and subranges thereof), and the content of (one or more) additional plasticizers (e.g., TOTM) is the remainder. Thus, for example, the ratio of non-leaching plasticizer to total plasticizer content can range from 25% to 50%, more particularly from 25% to 40% (inclusive of all values ​​and ranges between the listed values).

[0034] Because PVC is heat-sensitive, PVC compounds may include one or more stabilizers. The total amount of stabilizers(one or more) that may be present in the PVC compound may be from about 5 phr to about 40 phr, more particularly from about 5 phr to about 15 phr, for example, about 5, 10, 15, 20, or 25 phr. Any suitable stabilizer or combination of such stabilizers may be used in the PVC compound. For example, suitable stabilizers may include carboxylates, such as barium zinc, and / or epoxidized natural oils, such as epoxidized soybean oil. In one or more exemplary embodiments, barium zinc stabilizer may be used in the PVC compound at a total amount of about 1.5 phr to about 15 phr, more particularly from about 1.5 phr to about 5 phr, and more particularly from about 2.5 phr. Additional stabilizers of epoxidized soybean oil may also be used at a total amount of about 3 phr to about 40 phr, more particularly from about 3 phr to about 10 phr, for example, in the range of about 3, 4, 5, 7, 10, 15, or 20 phr.

[0035] The PVC compound may also include additional additives, such as processing aids. For example, stearic acid can be used to improve the processability of the PVC compound by increasing the flowability of the material and aiding the diffusion of other components. In an exemplary embodiment, stearic acid may be provided in the PVC compound in a total amount of about 0.1 phr to about 0.5 phr, for example, about 0.3 phr.

[0036] Other non-limiting examples of thermoplastic PVC compounds used for inner tubes are described in further detail below in conjunction with Tables 1-5.

[0037] Turning now to the reinforcing layer of the hose, which lies between the inner tube and the cover layer. The reinforcing layer typically provides additional strength to the hose by applying reinforcing threads around the inner tube. These threads may include monofilaments, multifilaments, bundles, yarns, etc. The layers (one or more) of these threads may have any suitable structure or combination of structures, and the threads may be made of any suitable material or combination of materials for reinforcing the hose.

[0038] The reinforcing material of the thread can include, but is not limited to, metals, compounds, or natural materials. For example, the reinforcing thread can be steel wire (e.g., stainless steel wire, coated steel wire, plain steel wire, etc.). Alternatively or additionally, the reinforcing thread can be filaments, such as fibers, which can be in the form of yarn (or fabric woven from yarn). Such materials can include nylon, vinylon, aramid, rayon, polyester (e.g., polyethylene terephthalate or polyethylene naphthalate), polyvinyl acetate, polyvinyl alcohol (PVA), poly(p-phenylene-2,6-benzodioxazole) (PBO), polypropylene, polyamide, carbon fiber, ceramic fiber (e.g., silicon carbide), cotton, linen, etc.

[0039] In some embodiments, the reinforcing material threads are arranged in a braided, helical, knitted, or wound reinforcing structure. The hose may include one or more of these reinforcing layers, and each layer may have threads arranged with different orientations. For example, where two or more helical reinforcing layers can be used, the first layer may be helically wound in a first winding direction, and the second layer may be helically wound in a second winding direction opposite to the first winding direction. Typically, braided or woven reinforcing elements may include one to three layers, and helical reinforcing elements may include four to six layers, but each can also be varied depending on the properties desired for a particular application. Between each layer of reinforcing threads, an intermediate layer or friction layer may be provided to create an adhesive effect and reduce frictional wear between the threads.

[0040] The turn-over cover layer, located outside the reinforcement layer, protects the inner tubing and / or reinforcement layer from the environmental conditions the hose will encounter during actual use. The cover layer can have any suitable structure and can be made of any suitable material. Several factors can be used to determine the structure and / or material selection of the cover layer, including but not limited to abrasion resistance, chemical resistance, cost-effectiveness, and aesthetics.

[0041] The capping material may include, but is not limited to, ethylene propylene rubber (EPR), ethylene propylene diene rubber (EPDM), EPDM / EPR, acrylonitrile butadiene rubber (NBR), hydrogenated NBR, carboxylated NBR, polychloroprene rubber, fluoroelastomer rubber, epichlorohydrin (ECO) rubber, nitrile rubber, carboxylated nitrile rubber, chlorinated polyethylene (CPE), chlorosulfonated polyethylene (CSM) rubber, styrene butadiene rubber (SBR), polyvinyl chloride (PVC), nitrile / PVC rubber, styrene / ethylene-butene / styrene-based (SEBS), thermoplastic elastomer (TPE), thermoplastic vulcanizate (TPV), thermoplastic polyurethane (TPU), polyolefin elastomer (POE), or any suitable mixture thereof. The capping compound may further include various additives in conventional or suitable amounts, including but not limited to, pigments and / or dyes providing color, flame retardants, antioxidants, vulcanizing agents, curing accelerators or other processing aids, reinforcing agents, and fillers such as carbon black, silica, and other mineral fillers (e.g., calcium carbonate, talc, etc.). As an example, reinforcing fillers can be supplied in the range of about 20 phr to about 700 phr, and include, for example, carbon black of about 200 phr to about 400 phr; plasticizers (e.g., oils) can be supplied in the range of about 10 phr to about 200 phr.

[0042] Some embodiments of this disclosure will be described below with reference to the accompanying drawings, wherein the same reference numerals denote the same elements. However, it should be understood that while the drawings illustrate various implementations described herein, they are not intended to limit the scope of the various techniques described herein. Furthermore, it should be understood that various aspects and features of these embodiments may be used interchangeably or in combination with each other where applicable.

[0043] Figures 1-8 An exemplary embodiment of a hose according to this disclosure is shown. As shown, the exemplary hose typically includes at least an inner tube 102, a reinforcing layer 104, and an outer covering layer 106. These layers 102, 104, and 106 can be formed using any materials and / or structures described above.

[0044] In various embodiments, the inner diameter, outer diameter, and thickness of the different layers of the hose can be configured as needed to achieve the characteristics of the hose for one or more specific applications. For example, an exemplary hose may have an inner diameter ranging from about 0.5 inches (12.7 mm) to about 4 inches (about 100 mm) and an outer diameter ranging from about 1 inch (25.4 mm) to about 6 inches (about 150 mm). The total wall thickness of the hose, including all layers, may range from about 0.10 inches (2.5 mm) to about 0.4 inches (10 mm) or greater. The wall thickness of the inner tube 102 may range from about 0.02 inches (0.5 mm) to about 0.16 inches (4 mm), more particularly from about 1 mm to about 3 mm. The wall thickness of the outer tube 106 may range from about 0.04 inches (1 mm) to about 0.12 inches (3 mm).

[0045] First refer to Figure 1 The diagram illustrates an exemplary structure of a hose 100, comprising an inner tube 102, a reinforcing layer 104, and a cover layer 106. Typically, to provide the advantages of the exemplary thermoplastic PVC composite, the inner tube 102 can be integrally formed from the PVC composite. As an example, the hose 100 can be manufactured by forming the inner tube 102 according to a known extrusion process, optionally having an adhesive layer on its outer surface, and then applying the reinforcing layer 104 in the arrangement described above. The outer cover layer 106 then covers the reinforcing layer 104, for example by extrusion, winding, etc., to integrally bond the hose layers. The applicable hose material can then be cured.

[0046] Figure 2Another exemplary embodiment of the hose 200 is shown, which includes an inner tube 102, a reinforcing layer 104, and an outer cover layer 106, similar to the hose 100 described above, and also includes an intermediate layer 208, which may be a curtain-like reinforcing layer, an adhesive layer, a backing layer, or a barrier layer, etc. As shown, the intermediate layer 208 is disposed between the inner tube 102 and the reinforcing layer 104. For example, when used as a curtain-like reinforcing layer, layer 208 is not particularly limited, but can be made into a curtain structure from any suitable natural or synthetic material, such as vinylon fiber, rayon fiber, polyester fiber, nylon fiber, natural fiber, or aramid fiber, etc. When used as an adhesive layer (also called an adhesive layer), the intermediate layer 208 can be formed from any suitable material(s), such as those materials that are compatible with its adjacent layers (e.g., reinforcing layer 104 and inner tube 102). When used as a barrier layer, layer 208 is not particularly limited, but can be made of polyamide, thermoplastic fluoropolymers, such as polyvinylidene fluoride (PVDF), tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride (THV), etc. As a barrier layer, layer 208 can be a permeation-inhibiting layer, which can be a relatively thin finish or layer, with a thickness, for example, ranging from about 0.002 inches (0.05 mm) to about 0.01 inches (0.254 mm). A thin barrier layer can contribute to permeation resistance while still allowing the hose sufficient flexibility. In an exemplary embodiment, the inner tube 104 provides sufficient permeation resistance so that the hose does not require this barrier layer 208.

[0047] Go to Figure 3Another exemplary hose 300 is shown, comprising an inner tube 102, a reinforcing layer 104, a filler layer or friction layer 310, a second reinforcing layer 312, and an outer cover layer 106. The second reinforcing layer 312 is not particularly limited, but may be made of any suitable material(s) or structure as described above in conjunction with reinforcing layer 104. The friction layer 310 is also not particularly limited and is configured to reduce frictional wear between the lines of reinforcing layers 104 and 312. The friction layer 312 may be formed of any suitable material, such as one or more curable rubber-based composites containing, for example, rubbers such as EPR, EPDM, acrylonitrile butadiene rubber (NBR), hydrogenated NBR, carboxylated NBR, polychloroprene, fluoroelastomers, epichlorohydrin, nitrile butadiene rubber, carboxylated nitrile butadiene rubber, CPE, CSM, styrene butadiene rubber (SBR), NBR / PVC blends, or any blend of the above materials. The rubber-based compound of friction layer 312 may also contain various additives in conventional or suitable amounts, including but not limited to, adhesion promoters, flame retardants, antioxidants, vulcanizing agents, curing accelerators or other processing aids, reinforcing agents, and fillers such as carbon black, silica, and other mineral fillers (e.g., calcium carbonate, talc, etc.). As an example, reinforcing fillers may be provided in the range of about 20 phr to about 700 phr and include, for example, carbon black of about 200 phr to about 400 phr; plasticizers (e.g., oils) may be provided in the range of about 10 phr to about 200 phr. The thickness of friction layer 312 may be from about 0.020 inches (0.5 mm) to about 0.120 inches (3 mm).

[0048] Figure 4 Another exemplary hose 400 is shown, which includes an inner tube 102, a reinforcing layer 104, a friction layer 310, a second reinforcing layer 312, and an outer cover layer 106. The hose 400 may also optionally include an intermediate layer 208 disposed between the inner tube 102 and the reinforcing layer 104. The intermediate layer 208 may be combined as described above. Figure 2 As described above, for example, it includes a curtain-like reinforcing layer that can be made of any suitable material and in any suitable structure.

[0049] See Figure 5 The diagram illustrates another exemplary hose 500, which includes an inner tube 102, a reinforcing layer 104, an outer covering layer 106, and an intermediate layer 208. This intermediate layer may be a curtain-like reinforcing layer, an adhesive layer, a backing layer, or a barrier layer, as described above in connection with hose 200. Hose 500 also includes a filler layer or friction layer 502 disposed between the inner tube 102 and the intermediate layer 208. Similarly, a filler layer or friction layer 504 is disposed between the intermediate layer 208 and the reinforcing layer 104. The filler or friction layers 502 and 504 may be made of the materials described above for use with hoses 200. Figure 3The friction layer 310 is formed of a material, and / or has the above-mentioned material for... Figure 3 The structure of friction layer 310. Friction layers 502 and 504 may have the same or different (one or more) materials and may have the same or different structures. In an exemplary embodiment without intermediate layer 208, only one filler or friction layer 502 may be provided between inner tube 102 and reinforcing layer 104. In this way, friction layer 502 can be in direct contact with inner tube 102 and / or reinforcing layer 104.

[0050] Figure 6 Another exemplary hose 600 is shown, similar to hose 500, and further includes a friction layer 310 and a second reinforcement layer 312 disposed between the reinforcement layer 104 and the outer cover layer 106. The friction layer 312 and the second reinforcement layer 312 can be combined with the above description. Figure 3 As described above.

[0051] Go to Figure 7 and Figure 8 The diagram illustrates an exemplary dangling hose 700, comprising an inner tube 102, a reinforcing layer 104, an intermediate layer 208, and an outer cover layer 106. The inner tube 102 is formed from an exemplary PVC composite having a non-leaching plasticizer as described herein. In the dangling hose configuration, the reinforcing layer may comprise yarns of polyethylene fibers or other suitable materials (one or more), which may be biaxially helically wound around the inner tube 102. In this configuration, the intermediate layer 208 may be formed as an adhesive layer of suitable materials, such as thermoplastic polyurethane (TPU), and may bond adjacent reinforcing layers 104 and the outer cover layer 106 together. The outer cover layer 106 may be formed of thermoplastic PVC or other suitable materials or combinations thereof, and may include, for example, a spiral layer made using rigid PVC.

[0052] like Figure 8As shown, the outer cover layer 106 may have at least one helically wound reinforcing strip 730, which is at least partially embedded within the outer cover layer 106; or formed together with the cover layer 106 in an alternating pattern. Each reinforcing strip 730 may comprise a plurality of consecutive loops or turns wound in a helical or spiral pattern with a pitch, such that adjacent turns are spaced apart from each other in the longitudinal direction. The strip(s) 730 may be formed of a material with a higher modulus than the material of the cover layer 106 to impart greater rigidity and torsional resistance to the hose 700. For example, the strip(s) 730 may be formed of a PVC material (or other suitable material) having a higher molecular weight and modulus than the PVC material of the cover layer 106. The strip(s) 730 may be manufactured and applied to the cover layer 106 using known extrusion processes or other(s) processes; or the strip 730 may be co-extruded together with the material of the cover layer 106 in an alternating pattern to form a monolithic cover layer. In this way, the outer cover layer 106 of the hose 700 may comprise a spirally or helically wound strip 730 or segment 730 made of a high-modulus material, the strips or segments being spaced apart axially, wherein at least between the strips or segments is a region of low-modulus material. In some embodiments, another layer (not shown) may be applied over the strip 730 and layer 106 to form the entire cover layer.

[0053] like Figure 7 As shown, hose 700 includes opposing ends 720, 722, which can be terminated by fluid connectors 724, 726, respectively, to connect hose 700 to a fluid source (e.g., a fuel vehicle) and a fluid destination (e.g., a storage tank). In applications with dangling hoses, fluid connectors 724, 726 can be connectors of the type conforming to the American Petroleum Institute (API). Other suitable connectors available include, but are not limited to, cam-lock connectors, flange connectors, quick-break connectors, etc.

[0054] Typically, this type of droop hose 700 offers sufficient flexibility to allow for bending, chemical resistance to hydrocarbons in the fuel, tensile strength to withstand pressure during fuel delivery, abrasion resistance when dragged on rough surfaces, and lightweight for ease of handling. During the service life of this type of droop hose 700, exposure to fuel in the inner cavity is typically intermittent, for example, a few hours per day. Between fuel supply intervals, the PVC composite of the inner tube dries and is then re-exposed to fuel, repeating this process. This contrasts with conventional roadside pump hoses, which are typically exposed to fuel for more than 50% of the time.

[0055] The purpose of preparing and testing the examples is to further illustrate the nature of some embodiments and aspects of this disclosure, and not to limit its scope. These examples are shown in Tables 1-5.

[0056] First, turn to Table 1, which provides formulations for different test samples, including an exemplary PVC compound (“Ex.1”) with a total content of non-leaching plasticizer of 20 phr according to the present invention, and a similar PVC compound (“CE1”) without non-leaching plasticizer as a control example. All values ​​in Table 1 are in parts per hundred (phr).

[0057] Table 1:

[0058]

[0059] Table 2 shows test data comparing the samples in Table 1, along with test samples from commercially available hoses, listed as CE2. CE2 hose material is understood to be based on conventional thermoplastic polyurethane (TPU) for the inner tube. The tests in Table 2 involved: 1) immersing each test sample in its respective container with a specific fresh fuel for one week; 2) removing each sample and drying it in ambient air for 24 hours; 3) recording the volume change; 4) refilling each container with the same type of fresh fuel and immersing the same sample again for one week; and 5) repeating this process for four consecutive weeks. The data in Table 2 show tests using two different types of fuel, including B20 (80% diesel and 20% biodiesel) and CE10 (90% fuel C and 10% ethanol, where fuel C consists of 50% isooctane and 50% toluene). In the test data, negative volume change indicates contraction, and positive volume change indicates expansion.

[0060] Table 2

[0061]

[0062] As shown in Table 2, the exemplary compound of Ex.1 performs similarly to the commercially available TPU compound of CE2 in B-20 and CE-10 fuels. However, as described above, PVC compounds are generally less expensive than TPU materials, so the exemplary compound Ex.1 provides at least the aforementioned benefits over the TPU compound. Furthermore, compared to other PVC samples CE1 without non-leaching plasticizers, the exemplary compound Ex.1, with non-leaching plasticizers, exhibits a significant improvement in dimensional change when immersed in CE-10 fuel. The specification of this test method indicates that a volume change of -10% to +25% is acceptable when immersed in CE-10 fuel; and the specification indicates that a volume change of -10% to +40% is acceptable when immersed in B-20 fuel. Therefore, the exemplary compound Ex.1 meets these requirements.

[0063] Tables 3-5 show additional test data with variations in the exemplary formulations. Table 3 shows cases where the content of the non-leaching plasticizer was varied in the exemplary formulations to determine its effect, and these test samples are listed below as Ex.A to Ex.D. Table 4 shows cases where different contents of nitrile rubber were included in addition to the non-leaching plasticizer, and these samples are listed as Ex.E to Ex.H. Again, in Tables 3 and 4, all values ​​are listed in parts per hundred (phr). Table 5 lists the test data for compounds Ex.A to Ex.H, including standard tensile tests according to ASTM D412 and Shore A hardness tests according to ASTM D2240. Table 5 also lists the volume change data after immersing the samples in CE10 fuel for one week.

[0064] Table 3

[0065]

[0066] Table 4

[0067]

[0068] Table 5

[0069]

[0070] The test data in Table 5 indicate that increasing the content of non-leached plasticizer reduces volume change upon exposure to fuel; however, increasing the content of non-leached plasticizer also appears to reduce mechanical properties. While the entire range of non-leached plasticizers from 20 phr to 50 phr is suitable for many fuel applications, in some embodiments, particularly for industrial hoses and more particularly for extruded hose products, including lower amounts of non-leached plasticizers, such as 20 phr to 40 phr, or more specifically 20 phr to 30 phr, may be beneficial in improving non-leached functionality while maintaining strength. It may also be considered that in some applications, lower amounts of non-leached plasticizers, such as 10 phr or 15 phr (inclusive of sub-values ​​of the above range), may also be suitable and fall within the scope of this disclosure; however, it has been found that using 20 phr as a lower limit provides a good trade-off between dimensional stability and mechanical strength in fuel.

[0071] As mentioned above, it may also be beneficial to include blends of low and high molecular weight PVC in the compound, as shown in Ex.1, which can further improve mechanical properties when used in combination with non-leaching plasticizers.

[0072] An exemplary thermoplastic PVC compound has a non-leaching plasticizer and material properties suitable for hoses, particularly as an extrusion material for hoses, the exemplary thermoplastic PVC compound having one or more of the following properties: (i) tensile strength according to ASTM D412 in the range of about 5 MPa to about 25 MPa, more particularly in the range of about 10 MPa to about 20 MPa, to provide burst resistance, durability and connection retention; (ii) elongation according to ASTM D412 less than 400%; (iii) hardness according to ASTM D2240 in the range of about 50 Shore A to about 90 Shore A, more specifically in the range of about 60 Shore A to about 80 Shore A, to provide flexibility, resistance to flexural fatigue and connection retention. Furthermore, as described above, an exemplary thermoplastic PVC composite suitable for fuel hoses, particularly as a dangling hose, may have a total volume change in the range of -10% to +25% when continuously immersed in CE-10 fuel for a total of four weeks and dried at ambient temperature (approximately 25°C) for 24 hours after each week of immersion; and / or, when continuously immersed in B-20 fuel for a total of four weeks and dried at ambient temperature (approximately 25°C) for 24 hours after each week of immersion, may have a total volume change in the range of -10% to +40%.

[0073] As also shown in the test data, it has been found that the addition of nitrile to PVC composites in fuel immersion tests results in additional dimensional changes and reduced mechanical properties; therefore, exemplary PVC composites may be nitrile-free; however, it should be understood that some composites within the scope of this disclosure may include the nitrile content described above.

[0074] In view of the foregoing, one aspect of this disclosure provides an exemplary thermoplastic PVC composite having a non-leaching plasticizer comprising ethylene copolymer and butyl acrylate, and having material properties suitable for hoses, etc.

[0075] Another aspect of this disclosure provides a thermoplastic material comprising: polyvinyl chloride in a total content of 80 phr to 100 phr; a non-leaching plasticizer in a total content of 20 phr to 50 phr, said non-leaching plasticizer having an ethylene copolymer and butyl acrylate; at least one additional plasticizer in a total content of 20 phr to 60 phr; and at least one stabilizer in a total content of 2 phr to 25 phr.

[0076] According to another aspect, the hose includes an inner tube (102), a reinforcing layer (104) disposed outward from the inner tube (102), and a covering layer (106) disposed outward from the reinforcing layer (104), wherein the inner tube (102) has a thermoplastic material, the thermoplastic material including polyvinyl chloride (PVC) and a non-leaching plasticizer, the non-leaching plasticizer having an ethylene copolymer and butyl acrylate.

[0077] One or more exemplary embodiments may be combined with any of the foregoing aspects to include one or more of the following additional features, wherein one or more of these additional features may be combined individually or in any suitable manner with each other.

[0078] In one or more exemplary embodiments, a non-leaching plasticizer is present in the thermoplastic material at a total content of 20 phr to 60 phr.

[0079] In one or more exemplary embodiments, a non-leaching plasticizer is present in the thermoplastic material at a total content of 20 phr to 40 phr.

[0080] In one or more exemplary embodiments, the non-leaching plasticizer is present in the thermoplastic material at a total content of 20 phr to 30 phr.

[0081] In one or more exemplary embodiments, the ethylene copolymer is present in the thermoplastic material in a total content of 8 phr to 40 phr, for example 10 phr to 30 phr.

[0082] In one or more exemplary embodiments, butyl acrylate is present in the thermoplastic material in a total content of 4 phr to 30 phr, for example 5 phr to 15 phr.

[0083] In one or more exemplary embodiments, the non-leaching plasticizer is a terpolymer having an ethylene copolymer, butyl acrylate, and functional groups, and the non-leaching plasticizer is coordinated and bonded to the polymer chain of PVC.

[0084] In one or more exemplary embodiments, the non-leaching plasticizer comprises one or more such polymers having an ethylene copolymer and butyl acrylate, and more specifically, such non-leaching plasticizer, as a non-leaching agent, improves the volume expansion of the composite in at least CE-10 fuels compared to the same material without the non-leaching plasticizer.

[0085] In one or more exemplary embodiments, the PVC has a K value in the range of K73 to K80, and more particularly, the PVC is present in the thermoplastic material at a total content of 80 phr to 100 phr.

[0086] In one or more exemplary embodiments, the PVC comprises a blend of a first PVC resin and a second PVC resin, wherein the first PVC resin has a lower molecular weight than the second PVC resin.

[0087] In one or more exemplary embodiments, a first PVC resin is present in the thermoplastic material at a total content of 20 phr to 60 phr.

[0088] In one or more exemplary embodiments, the second PVC resin is present in the thermoplastic material at a total content of 20 phr to 60 phr.

[0089] In one or more exemplary embodiments, the first PVC resin has a K value in the range of K65 to K75.

[0090] In one or more exemplary embodiments, the second PVC resin has a K value in the range of K76 to K85.

[0091] In one or more exemplary embodiments, the total plasticizer content of the thermoplastic material includes a non-leaching plasticizer and a second plasticizer, and the total plasticizer content is in the range of 40 phr to 95 phr, more particularly in the range of 50 phr to 70 phr.

[0092] In one or more exemplary embodiments, the proportion of non-leaching plasticizer in the total plasticizer content is in the range of 25% to 50%, more particularly in the range of 25% to 40%.

[0093] In one or more exemplary embodiments, the second plasticizer is a carboxylic acid ester, more particularly a trimellitate plasticizer, and more particularly trioctyl trimellitate.

[0094] In one or more exemplary embodiments, the thermoplastic material further includes one or more stabilizers in a total amount of 5 phr to 25 phr, more particularly 5 phr to 15 phr.

[0095] In one or more exemplary embodiments, the one or more stabilizers include: carboxylates, more particularly barium zinc, especially in a total content of 1.5 phr to 3 phr.

[0096] In one or more exemplary embodiments, the one or more stabilizers include: epoxidized natural oil, more particularly epoxidized soybean oil.

[0097] In one or more exemplary embodiments, the epoxidized natural oil is present in a total content of 3 phr to 20 phr, more particularly in a total content of 3 phr to 10 phr.

[0098] In one or more exemplary embodiments, the thermoplastic material has one or more of the following properties: (i) a tensile strength of about 5 MPa to about 25 MPa, more particularly about 10 MPa to about 20 MPa, according to ASTM D412; (ii) an elongation of less than 400% according to ASTM D412; (iii) a hardness of about 50 Shore A to about 90 Shore A, more specifically about 60 Shore A to about 80 Shore A, according to ASTM D2240; (iv) a total volume change of -10% to +25% when continuously immersed in CE-10 fuel for a total of four weeks, and dried for 24 hours at ambient temperature (about 25°C) after each week of immersion; and / or, (v) a total volume change of -10% to +40% when continuously immersed in B-20 fuel for a total of four weeks, and dried for 24 hours at ambient temperature (about 25°C) after each week of immersion.

[0099] In one or more exemplary embodiments, the material may be suitable for articles of hoses or other non-fuel hoses, for example, for other fluid hoses requiring leaching resistance, such as oil, solvent, or water hoses; or for articles exposed to these chemicals.

[0100] In one or more exemplary embodiments, the hose is configured as a fuel droop hose, wherein: the inner tube is formed of a thermoplastic material; the reinforcing layer comprises threads of polyethylene fibers; and the outer cover layer is formed of a second thermoplastic PVC material different from the thermoplastic material of the inner tube.

[0101] According to another aspect, a fuel system includes: a vehicle storage tank, a second storage tank, and a hose according to any one of the foregoing embodiments, having a first connector for connecting the hose to the vehicle storage tank and a second connector for connecting the hose to the second storage tank.

[0102] According to another aspect, a method of using a fuel droop hose includes: providing a hose as a fuel droop hose according to any one of the foregoing embodiments; and allowing fuel to pass through an internal passage of the fuel droop hose.

[0103] For illustrative and descriptive purposes, the above description of the embodiments has been provided. Examples of embodiments are provided so that this disclosure conveys its scope thoroughly and completely to those skilled in the art. Numerous specific details, such as examples of specific components, apparatus, and methods, are set forth to provide a thorough understanding of the embodiments of this disclosure, but are not intended to be exhaustive or limiting. It should be understood that within the scope of this disclosure, individual elements or features of a particular embodiment are generally not limited to that particular embodiment, but are interchangeable and can be used in selected embodiments as long as applicable, even if not specifically shown or described. Thus, while specific features may be described only with respect to one or more of several embodiments, these features may be used individually or in arbitrary combinations with one or more other features of other embodiments. Similarly, variations are possible. Such variations should not be considered as departing from this disclosure, and all such modifications should be included within the scope of this disclosure, as this may be desired and advantageous for any given or particular application.

[0104] Any background information contained herein is provided to better understand the various aspects described herein. It should be understood that any such background statements should be read in this sense and not as an endorsement of the prior art. Similarly, the descriptions and examples presented herein are for illustrative purposes only and should not be construed as limiting the scope and applicability of this disclosure.

[0105] The phrase “and / or” as used in this disclosure should be understood to mean “any one or both” of the combined elements, that is, in some cases these elements are present simultaneously, while in others they are present separately. In addition to the elements specifically defined by the “and / or” clause, other elements may optionally exist, whether related to or unrelated to those specifically defined elements, unless explicitly excluded. Thus, as a non-limiting example, when used in conjunction with open-ended language such as “having,” “A and / or B” can mean that in one embodiment there may be A but no B (optionally including elements other than B); in another embodiment there may be B but no A (optionally including elements other than A); in yet another embodiment there may be A and B (optionally including other elements); and so on.

[0106] The word “or” as used in this disclosure should be understood as inclusive rather than exclusive. For example, when listing items in a list, “or” or “and / or” should be interpreted as inclusive, that is, including at least one, but possibly more, of the element package or list, and may selectively include other unlisted items. For example, any of the following conditions A or B are satisfied: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); and both A and B are true (or exist). Only terms that explicitly indicate exclusivity should be interpreted as indicating an exclusive option (i.e., “one or the other, but not both”), such terms include, for example, “any one,” “only one of them,” or “exactly one of them.” In other words, such an exclusive term means including exactly one element from the element package or list.

[0107] As used herein, "one implementation" means that a particular element, feature, structure, or characteristic associated with that implementation is included in at least one implementation. The phrase "in one implementation" appearing throughout the specification does not necessarily refer to the same implementation.

[0108] Furthermore, the term "a" is used herein to describe elements and components of the embodiments. This is done merely for convenience and to give a general understanding of the concepts according to this disclosure. This description should be understood to include one or at least one, and the singular form also includes the plural case, unless otherwise stated.

[0109] The word “exemplary” is used herein to mean “serving as an example or illustration.” Any aspect or design described herein as “exemplary” is not necessarily considered preferred or advantageous over other aspects or designs. Similarly, phrases such as “particularly,” “preferred,” etc., as used in this disclosure may refer to elements or values ​​that provide a preferred advantage in some embodiments, but are not intended to limit the scope of this disclosure to those “particular” or “preferred” features.

[0110] Transitional language such as “including,” “having,” “containing,” “involving,” “involving,” or variations thereof is intended to have a broad meaning that covers the topics listed thereafter, equivalents, and other topics not mentioned; that is, these languages ​​are open-ended and mean including but not limited to.

[0111] It should be understood that terms such as “top,” “bottom,” “up,” “down,” “left,” “right,” “front,” “back,” “forward,” and “backward” can refer to any frame of reference, rather than the usual gravitational frame of reference.

[0112] It should be understood that all values, ranges, ratios, etc., described in this disclosure can be combined in any way. Furthermore, it should be understood that the ranges of concentrations or contents or values ​​listed in this disclosure are intended to include any and every concentration or content or value within that range, including endpoints, as if every value within that range had been explicitly listed. For example, "a range of 1 to 10" should be interpreted as each and every possible number within a continuous interval of about 1 to about 10. Therefore, even if a specific data point within that range is explicitly indicated, or if no data point within that range is explicitly indicated or only a few specific data points are mentioned, it should be understood that the inventor acknowledges and understands that any and all data points within that range have been specified, and that the inventor owns the entire range and all points within that range.

[0113] Furthermore, each numerical value used in this disclosure should be interpreted as being modified once with the term "about" (unless otherwise expressed), and then again without such modification, unless the context otherwise requires. As used herein, the term "about" means any value within a range of at most ±10% of the stated value, for example, ±10%, ±9%, ±8%, ±7%, ±6%, ±5%, ±4%, ±3%, ±2%, ±1%, ±0.01%, or ±0.0% of the stated value, and values ​​between these values. When the term "about" is used to describe an endpoint of a value or range, this disclosure should be understood to include that particular value or endpoint.

[0114] The term "substantially composed" in relation to a complex means that the components present in the complex are substantially (e.g., greater than 95% by weight, or greater than 99% by weight) the listed components. Therefore, this term does not exclude the presence of trace amounts of additives or impurities, as would be understood by one of ordinary skill in the art.

[0115] Although the invention has been shown and described in conjunction with one or more specific embodiments, equivalent modifications and variations will readily conceive of by those skilled in the art upon reading and understanding this disclosure, and all such modifications and variations should be included within the scope of this disclosure as defined by the claims. In particular, with respect to the various functions performed by the foregoing elements (components, parts, devices, combinations, etc.), the terms used to describe these elements (including those referring to "method") are intended to correspond to any element that performs a particular function of said element (i.e., a functionally equivalent element), even if structurally not equivalent to the disclosed structure (which performs that function in one or more exemplary embodiments of this disclosure shown herein), unless otherwise stated.

[0116] Explanation of reference numerals in the attached figures

[0117] 100 hose

[0118] 102 inner tube

[0119] 104 reinforcement layers

[0120] 106 cover layers

[0121] 200 hose

[0122] 208 Intermediate layer, curtain reinforcement, adhesive layer, backing layer or barrier layer

[0123] 300 hose

[0124] 310 friction layer or filler layer

[0125] 312 Second Reinforcement Layer

[0126] 400 hose

[0127] 500 hose

[0128] 502 friction layer or filler layer

[0129] 504 friction layer or filler layer

[0130] 600 hose

[0131] 700 hose

[0132] 720 hose end

[0133] 722 hose end

[0134] 724 fluid connector

[0135] 726 fluid connector

[0136] 730 Enhanced Line.

Claims

1. A flexible hose (100, 200, 300, 400, 500, 600, 700) having: Inner tube (102), which forms an internal channel, The reinforcing layer (104) is arranged from the inner tube outwards, and A cover layer (106) is set outward from the reinforcement layer. in, The inner tube (102) has a thermoplastic material comprising polyvinyl chloride (PVC) and a non-leaching plasticizer, wherein the non-leaching plasticizer comprises an ethylene copolymer and butyl acrylate.

2. The hose according to claim 1, in, The non-leaching plasticizer is present in the thermoplastic material at a total content of 20 phr to 60 phr.

3. The hose according to claim 2 or any other preceding claim, wherein, The non-leaching plasticizer is present in the thermoplastic material in a total content of 20 phr to 40 phr, more particularly 20 phr to 30 phr.

4. The hose according to claim 2 or any other preceding claim, in, The ethylene copolymer is present in the thermoplastic material in a total content of 8 phr to 40 phr, more particularly in a total content of 10 phr to 30 phr; and The butyl acrylate is present in the thermoplastic material in a total content of 4 phr to 30 phr, and more particularly in a total content of 5 phr to 15 phr.

5. The hose according to claim 1 or any other preceding claim, in, Non-leaching plasticizers are terpolymers containing ethylene copolymers, butyl acrylate, and functional groups, and are coordinated and bonded to the polymer chains of PVC.

6. The hose according to claim 1 or any other preceding claim, in, The PVC has a K value in the range of K73 to K80. Specifically, the PVC is present in the thermoplastic material at a total content of 80 phr to 100 phr.

7. The hose according to claim 1 or any other preceding claim, in, The PVC includes a blend of a first PVC resin and a second PVC resin, wherein the first PVC resin has a lower molecular weight than the second PVC resin. More specifically, The first PVC resin is present in the thermoplastic material at a total content of 20 phr to 60 phr, and The second PVC resin is present in the thermoplastic material at a total content of 20 phr to 60 phr.

8. The hose according to claim 7, in, The first PVC resin has a K value in the range of K65 to K75, and The second PVC resin has a K value in the range of K76 to K85.

9. The hose according to claim 1 or any other preceding claim, in, The thermoplastic material includes a second plasticizer in a total content of 20 phr to 60 phr, more particularly 30 phr to 50 phr.

10. The hose according to claim 9, in, The total plasticizer content of the thermoplastic material includes non-leaching plasticizers and a second plasticizer, and the total plasticizer content is in the range of 40 phr to 95 phr, more particularly in the range of 50 phr to 70 phr. The proportion of non-leaching plasticizers in the total plasticizer content is 25% to 50%, and more specifically 25% to 40%.

11. The hose according to claim 9 or 10, in, The second plasticizer is a carboxylic acid ester, more particularly a trimellitate plasticizer, and more particularly trioctyl trimellitate.

12. The hose according to claim 1 or any other preceding claim, in, The thermoplastic material also has one or more stabilizers in a total content of 5 phr to 25 phr, more particularly 5 phr to 15 phr.

13. The hose according to claim 12, wherein, The one or more stabilizers include: Carboxylates, more particularly barium zinc, are present, especially in total contents ranging from 1.5 phr to 3 phr. Epoxidized natural oils, and more particularly epoxidized soybean oils, especially with a total content of 3 phr to 20 phr, and even more particularly with a total content of 3 phr to 10 phr.

14. The hose according to claim 1 or any other preceding claim, in, The thermoplastic material of the inner tube has one or more of the following properties: (i) Tensile strength according to ASTM D412 is about 5 MPa to about 25 MPa, more particularly about 10 MPa to about 20 MPa; (ii) The elongation is less than 400% according to ASTM D412; (iii) The hardness according to ASTM D2240 is in the range of about 50 Shore A to about 90 Shore A, and more particularly in the range of about 60 Shore A to about 80 Shore A; (iv) When continuously soaked in CE-10 fuel for a total of four weeks, and dried for 24 hours at ambient temperature (approximately 25°C) after each week of soaking, the total volume change is within the range of -10% to +25%; and / or (v) When continuously soaked in B-20 fuel for a total of four weeks, and dried for 24 hours at ambient temperature (about 25°C) after each week of soaking, the total volume change is in the range of -10% to +40%.

15. The hose according to claim 1 or any other preceding claim, in, The hose is configured as a fuel droop hose, wherein: The inner tube is formed of the aforementioned thermoplastic material; The reinforcing layer comprises strands of polyethylene fibers; and The outer covering is formed of a second thermoplastic PVC, which is different from the thermoplastic material of the inner tube.

16. A fuel system having, A vehicle storage tank, a second storage tank, and a hose according to claim 1 or any other preceding claim, having a first connector for connecting the hose to the vehicle storage tank and a second connector for connecting the hose to the second storage tank.

17. A method of using a fuel droop hose, comprising: Provide the hose according to claim 1 or any other preceding claim as a fuel droop hose; and This allows fuel to pass through the internal channels of the fuel droop hose.

18. A thermoplastic material having: Polyvinyl chloride, with a total content of 80 phr to 100 phr; A non-leaching plasticizer having a total content of 20 phr to 50 phr, and the non-leaching plasticizer comprising ethylene copolymer and butyl acrylate; At least one additional plasticizer, in a total content of 20 phr to 60 phr; and At least one stabilizer, in a total content of 2 phr to 25 phr.

19. The thermoplastic material according to claim 18, in, The non-leaching plasticizer is present in the thermoplastic material at a total content of 20 phr to 40 phr, more particularly 20 phr to 30 phr. Specifically, the ethylene copolymer is present in the thermoplastic material in a total content of 8 phr to 40 phr, more particularly in a total content of 10 phr to 30 phr; and Specifically, butyl acrylate is present in the thermoplastic material in a total content of 4 phr to 30 phr, and more particularly in a total content of 5 phr to 15 phr.

20. The thermoplastic material according to claim 18 or claim 19, in, The PVC includes a blend of a first PVC resin and a second PVC resin, wherein the first PVC resin has a lower molecular weight than the second PVC resin. The first PVC resin is present in the thermoplastic material at a total content of 20 phr to 60 phr, and the second PVC resin is present in the thermoplastic material at a total content of 20 phr to 60 phr. Specifically, the first PVC resin has a K value in the range of K65 to K75, and the second PVC resin has a K value in the range of K76 to K85.

21. The thermoplastic material according to any one of claims 18 to 20, in, The total plasticizer content of the thermoplastic material includes a non-leaching plasticizer and a second plasticizer, and the total plasticizer content is in the range of 40 phr to 95 phr, more particularly in the range of 50 phr to 70 phr. Among them, the proportion of non-leaching plasticizers in the total plasticizer content is between 25% and 50%, and more specifically between 25% and 40%. In particular, the second plasticizer is a carboxylic acid ester, more particularly a trimellitate plasticizer, and even more particularly a trioctyl trimellitate.

22. The thermoplastic material according to any one of claims 18 to 21, wherein, One or more stabilizers include: Carboxylates, and more particularly barium zinc, especially in total contents of 1.5 phr to 3 phr, and Epoxidized natural oils, and more particularly epoxidized soybean oils, especially with a total content of 3 phr to 20 phr, and even more particularly with a total content of 3 phr to 10 phr.

23. The thermoplastic material according to any one of claims 18 to 22, having one or more of the following properties: (i) Tensile strength according to ASTM D412 is about 5 MPa to about 25 MPa, more particularly about 10 MPa to about 20 MPa; (ii) The elongation is less than 400% according to ASTM D412; (iii) The hardness according to ASTM D2240 is in the range of about 50 Shore A to about 90 Shore A, and more particularly in the range of about 60 Shore A to about 80 Shore A; (iv) When continuously soaked in CE-10 fuel for a total of four weeks, and dried for 24 hours at ambient temperature (approximately 25°C) after each week of soaking, the total volume change is within the range of -10% to +25%; and / or (v) When continuously soaked in B-20 fuel for a total of four weeks, and then dried for 24 hours at ambient temperature (approximately 25°C) after each week of soaking, the total volume change is in the range of -10% to +40%.

24. A thermoplastic PVC composite having a non-leaching plasticizer comprising an ethylene copolymer and butyl acrylate, and having one or more of the following properties: (i) Tensile strength according to ASTM D412 is about 5 MPa to about 25 MPa, more particularly about 10 MPa to about 20 MPa; (ii) The elongation is less than 400% according to ASTM D412; (iii) The hardness according to ASTM D2240 is in the range of about 50 Shore A to about 90 Shore A, and more particularly in the range of about 60 Shore A to about 80 Shore A; (iv) When continuously soaked in CE-10 fuel for a total of four weeks, and dried for 24 hours at ambient temperature (approximately 25°C) after each week of soaking, the total volume change is within the range of -10% to +25%; and / or (v) When continuously soaked in B-20 fuel for a total of four weeks, and dried for 24 hours at ambient temperature (about 25°C) after each week of soaking, the total volume change is in the range of -10% to +40%.

Images