Direct binding textile thermoplasticity technology

Abstract

Improved reinforced thermoplastic hoses are provided that exhibit improved layer adhesion, improved burst pressure response, and better fitting securement. High quality adhesion between the pipe layer, the cover layer and the reinforcement layer is exhibited. Also provided are improved methods of manufacturing reinforced thermoplastic hoses to reduce the use of SVHC chemicals and improve manufacturing efficiency. The thermoplastic hose is suitable for pneumatic and hydraulic applications.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application was filed on June 27, 2023 as a PCT international patent application and claims the benefit of U.S. patent application serial number 63 / 356,411 filed on June 28, 2022, the disclosure of which is incorporated herein by reference in its entirety. Background Art

[0002] Currently available reinforced thermoplastic hoses utilizing textile reinforcements may exhibit uneven layer adhesion, resulting in inconsistent hose performance, for example, due to fitting fixation issues and variable burst pressure response. Current methods of manufacturing reinforced hoses may use substances of very high concern (SVHC) adhesive chemistries such as isocyanate gases and N-methyl-2-pyrrolidone, as well as a subjective "bonding" step that requires 6-10 hours to complete.

[0003] Improved reinforced thermoplastic hoses that exhibit improved layer adhesion, improved burst pressure response, and better fitting fixation are desirable. In particular, thermoplastic hoses that exhibit high quality adhesion between the tube layers, cover layers, and reinforcement layers are desirable. Improved methods of manufacturing reinforced thermoplastic hoses that reduce the use of SVHC chemicals and increase manufacturing efficiency by eliminating subjective and messy processing steps are also desirable. Summary of the invention

[0004] Improved reinforced thermoplastic hoses are provided that exhibit improved layer adhesion, improved burst pressure response, and better fitting fixation. High quality adhesion between the tube layers, cover layers, and reinforcement layers is exhibited by using a pretreated yarn comprising a reactive adhesive coating, optionally together with a thermoplastic elastomer comprising a reactive blend. Improved methods of manufacturing reinforced thermoplastic hoses are also provided to reduce the use of SVHC chemicals and improve manufacturing efficiency. The thermoplastic hoses are suitable for pneumatic and hydraulic applications.

[0005] A thermoplastic hose is provided, comprising a plurality of layers including a first textile braid reinforcement layer covalently bonded to an inner tube layer comprising a first thermoplastic elastomer, and an outer cover layer comprising a second thermoplastic elastomer. In some examples, the bond strength between the inner tube layer and the textile braid reinforcement layer is at least 8 lbf, at least 10 lbf, or at least 15 lbf when tested according to ASTM D413 Type B, 90° peel. The thermoplastic hose comprises an inner tube layer directly bonded to the textile reinforcement layer without an intermediate adhesive layer. The thermoplastic hose comprises an outer cover layer directly bonded to the textile reinforcement layer without an intermediate adhesive layer.

[0006] The first textile braid reinforcement layer can include the pretreated yarn of the group consisting of polyester, aramid, nylon, cotton and rayon pretreated yarn. The pretreated yarn can include a reactive adhesive coating that can form covalent bonding with the first thermoplastic elastomer. The pretreated yarn can include fixed isocyanate, resorcinol formaldehyde (RF) or phenol resorcinol formaldehyde (PRF) reactive adhesive coating. The pretreated yarn can be an isocyanate pretreated polyester yarn. The first pretreated yarn can include polyester, aramid, nylon, cotton or rayon yarn pretreated with a reactive adhesive coating that can form covalent bonding with the first thermoplastic elastomer in the first thermoplastic elastomer composition. In some cases, the first pretreated yarn includes fixed isocyanate, resorcinol formaldehyde (RF) or phenol resorcinol formaldehyde (PRF) reactive adhesive coating.

[0007] The inner tube layer may comprise a first thermoplastic elastomer, for example, selected from the group consisting of polyamides, thermoplastic polyurethanes, thermoplastic polyester elastomers, copolyesters, acrylic copolymers, polyolefin blends, and polyolefin admixtures, optionally wherein the first thermoplastic elastomer is a polyamide or a thermoplastic polyurethane. The first thermoplastic elastomer may be a polyamide, such as PA6, PA 12, PA 6,6, or PA 6,12. The first thermoplastic elastomer may be a thermoplastic polyether polyurethane. The inner tube layer may further comprise a maleic anhydride grafted copolymer. The maleic anhydride grafted copolymer may be selected from the group consisting of maleic anhydride grafted ethylene-butyl acrylate copolymers and maleic anhydride grafted plastomers (ethylene alpha olefin copolymers).

[0008] In some examples, the inner tube layer may contain 10-50 wt%, or 15-40 wt%, or 20-35 wt% of maleic anhydride grafted ethylene-butyl acrylate copolymer or maleic anhydride grafted ethylene alpha olefin copolymer in the thermoplastic polyurethane or polyamide, compared to the total weight of the thermoplastic elastomer in the inner tube layer.

[0009] The outer cover layer may comprise a second thermoplastic elastomer, for example selected from the group consisting of polyamides, thermoplastic polyurethanes, thermoplastic polyester elastomers, copolyesters, acrylic copolymers, polyolefin blends and polyolefin blends, optionally wherein the second thermoplastic elastomer is a polyamide or a thermoplastic polyurethane.

[0010] The outer cover layer may comprise a reactive blend comprising a maleic anhydride grafted thermoplastic copolymer. The maleic anhydride grafted copolymer may be selected from the group consisting of maleic anhydride grafted ethylene-butyl acrylate copolymer and maleic anhydride grafted plastomer (ethylene alpha olefin copolymer). In some examples, the outer cover layer may comprise 10-50 wt%, or 15-40 wt%, or 20-35 wt% of maleic anhydride grafted ethylene-butyl acrylate copolymer or maleic anhydride grafted ethylene alpha olefin copolymer in a thermoplastic polyurethane or polyamide, compared to the total weight of the thermoplastic elastomer in the outer cover layer.

[0011] In some examples, the first thermoplastic elastomer and the second thermoplastic elastomer are different. In some examples, the first thermoplastic elastomer and the second thermoplastic elastomer are the same.

[0012] The inner tube layer may include polyamide. The polyamide may be polyamide 6. The polyamide may be polyamide 12. The outer cover layer may include polyamide. The outer cover layer may include thermoplastic polyurethane.

[0013] In some examples, the thermoplastic hose further includes a second textile braid layer covalently bonded to the outer cover layer.

[0014] A thermoplastic hose is provided, which includes, in a direction from the inside to the outside surface of the hose, an inner tube layer comprising a first thermoplastic elastomer covalently bonded to a first textile braid reinforcement layer; and a second textile braid layer covalently bonded to an outer cover layer comprising a second thermoplastic elastomer. The first and second textile reinforcement layers may be covalently bonded.

[0015] A thermoplastic hose is provided, which includes an inner tube layer comprising a first thermoplastic elastomer covalently bonded to a textile braid reinforcement layer in a direction from the inner to the outer surface of the hose; and an outer cover layer comprising a second thermoplastic elastomer. In some examples, the textile braid reinforcement layer is covalently bonded to the outer cover layer.

[0016] A method for making a thermoplastic hose is provided, comprising extruding a first thermoplastic elastomer composition on a mandrel to form an inner tube layer; braiding a first pretreated yarn on the inner tube layer to form a first textile braid reinforcement layer; heating the first textile braid reinforcement layer to a temperature of >100°C to form a covalent bond between the pretreated yarn and the first thermoplastic elastomer to form a covalently bonded first textile braid reinforcement layer; and extruding a second thermoplastic elastomer composition on the covalently bonded first textile braid reinforcement layer to form a cover layer, heating to a temperature of >100°C, and cooling to form a thermoplastic hose. In some examples, the method further comprises braiding the second pretreated yarn on the reinforced inner tube layer before the second extrusion step. The method may further comprise driving the hose off the mandrel. The method provides a thermoplastic hose comprising an inner tube layer directly bonded to the textile reinforcement layer without the step of applying an intermediate adhesive layer. The method provides a thermoplastic hose comprising an outer cover layer directly bonded to the textile reinforcement layer without the step of applying an intermediate adhesive layer. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 An exemplary thermoplastic hose 100 according to the present disclosure is shown including a plurality of layers including an inner tube layer 102 , a reinforcement layer 106 , and an outer cover layer 110 .

[0018] Figure 2 An exemplary thermoplastic hose 200 according to the present disclosure is shown including a plurality of layers including an inner tube layer 102 , a first reinforcement layer 106 , a second reinforcement layer 108 , and an outer cover layer 110 .

[0019] Figure 3 Two exemplary direct bonded textile thermoplastic elastomer adhesion reactions are shown. The upper inset shows a sketch of a representative adhesive urea bond formed by a diisocyanate treated textile fabric with a polyamide 6 layer (such as a tube or cover) in a polycondensation reaction. The lower inset shows a sketch of a representative covalent bond formed by a resorcinol formaldehyde treated textile with a polyamide 6 layer (such as a tube or cover) in a polycondensation reaction via the amino terminus and with additional hydrogen bonds. DETAILED DESCRIPTION

[0020] A method of making a reinforced multi-layer thermoplastic hose is provided that utilizes RFL pre-treated or isocyanate pre-treated yarns that are capable of synergistically reacting with reactive chemicals formulated into thermoplastic polyurethane (TPU) and nylon resins to achieve improved quality adhesion between layers of the thermoplastic hose. A thermoplastic hose is provided that exhibits high quality adhesion between tube layers, cover layers, and reinforcement layers. Improved product consistency is exhibited, at least in part, due to the elimination of subjective and messy processing steps in the hose production process. Removal of SVHC chemicals isocyanate gas and methyl pyrrolidone in the hose production process is another advantage.

[0021] Thermoplastic hoses according to the present disclosure are suitable for use in pneumatic or hydraulic applications, for example, for lifts, cranes, material handling, lubrication, and air brake hoses. The hydraulic fluid may be selected from, for example, hydrocarbon oils, polyalkylene glycols (PAGs), or polyol ester (POE) oils.

[0022] The singular forms “a”, “an” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise.

[0023] The term "and / or" refers to and encompasses any and all possible combinations of one or more of the associated listed items.

[0024] The term "about" when referring to a measurable value (eg, an amount of a compound, time, temperature, etc.) is meant to encompass variations of 10%, 5%, 1%, 0.5%, or even 0.1% of the specified amount.

[0025] Unless otherwise indicated, the terms "percent" or "%" refer to percent by weight.

[0026] As used herein, the term "composition" may refer to one or more of a composite, a mixture, a blend, an admixture, a polymer and / or a copolymer.

[0027] The term "room temperature" refers to a temperature in the range of 20°C to 25°C, with an average of 23°C.

[0028] As provided herein, ranges are intended to include at least the numbers defining the limits of the range.

[0029] All patents, patent applications, and publications mentioned herein are incorporated by reference in their entirety.

[0030] Hose layout

[0031] The present disclosure provides a thermoplastic hose comprising a plurality of layers. For example, the hose may include a tube layer, a reinforcement layer, and a cover layer. In some examples, the hose may include a treated textile reinforcement layer covalently bonded to an inner thermoplastic tube layer and a thermoplastic outer cover layer. A thermoplastic hose according to the present disclosure may include three or more layers. A thermoplastic hose according to the present disclosure may include one or more, or two or more textile braid reinforcement layers. The textile braid reinforcement layer may be an intermediate layer.

[0032] Figure 1 An exemplary thermoplastic hose 100 according to the present disclosure is shown, which includes, from the inside to the outside direction, an inner tube layer 102, a textile braid reinforcement layer 106, and a cover layer 110. The inner tube layer 102 can include a thermoplastic elastomer covalently bonded to the textile braid reinforcement layer 106. The textile braid reinforcement layer can be covalently bonded to the inner tube layer 102 and the outer cover layer 110. The outer cover layer 110 can include a thermoplastic elastomer covalently bonded to the textile braid reinforcement layer 106.

[0033] The inner tube layer 102 comprises a thermoplastic elastomer. The thermoplastic elastomer may be prepared from a composition comprising a thermoplastic polymer, a copolymer, a terpolymer, or a blend thereof. The inner tube layer 102 may comprise a thermoplastic elastomer selected from the group consisting of polyamide, thermoplastic polyurethane (TPU), thermoplastic polyester elastomer, thermoplastic copolyester elastomer, maleic anhydride grafted ethylene-butyl acrylate copolymer, and maleic anhydride grafted plastomer (ethylene alpha olefin copolymer).

[0034] For example, the inner tube layer 102 can be prepared from a composition comprising TPU or polyamide and maleic anhydride grafted ethylene-butyl acrylate copolymer or maleic anhydride grafted ethylene alpha olefin copolymer. In some examples, the inner tube layer 102 can be prepared from a composition comprising a reactive blend between 10%-50%, or 15%-40%, or 20%-35%, comprising maleic anhydride grafted ethylene-butyl acrylate copolymer or maleic anhydride grafted ethylene alpha olefin copolymer in polyamide or thermoplastic polyurethane (TPU). The polyamide can be PA 12, PA 6 / 12, PA6, or PA6 / 6. In some examples, the inner tube layer 102 comprises PA12. In some examples, the inner tube layer 102 comprises PA6.

[0035] In some examples, the inner tube layer 102 is prepared from a composition comprising a thermoplastic elastomer such as a polyamide or a thermoplastic polyurethane, optionally further comprising a reactive blend, and optionally comprising additives such as a reinforcing agent, a flame retardant, a stabilizer, a processing aid, metal fibers, carbon black, graphite, metal foil, titanium dioxide, a color pigment, and / or zinc sulfide.

[0036] Layer 106 is a reinforcing layer. Reinforcing layer 106 can include a textile braid processed. The textile braid processed can be prepared by a reactive adhesive pretreated yarn. The example of the pretreated yarn for reinforcing layer 106 includes polyester, aramid, nylon, cotton and rayon pretreated yarn. In certain embodiments, reinforcing layer 106 is a discontinuous layer. In certain embodiments, reinforcing layer 106 is a discontinuous layer, which includes a polyester braid processed, an aramid braid processed, a nylon braid processed, a cotton braid processed or a rayon braid processed. In some instances, reinforcing layer 106 includes an isocyanate processed polyester yarn. In some instances, reinforcing layer 106 includes an RFL processed polyester yarn.

[0037] The cover layer 110 may include a thermoplastic elastomer. The cover layer may include a thermoplastic polymer, a copolymer, a terpolymer, or a blend thereof. The cover layer 110 may include a thermoplastic elastomer selected from the group consisting of polyamide, thermoplastic polyurethane (TPU), thermoplastic polyester elastomer, thermoplastic copolyester elastomer, maleic anhydride grafted ethylene-butyl acrylate copolymer, and maleic anhydride grafted plastomer (ethylene alpha olefin copolymer).

[0038] In some examples, the outer cover layer 110 comprises a thermoplastic elastomer such as a thermoplastic polyurethane (TPU) layer or a polyamide. The outer cover layer may comprise a non-stick polyurethane. The outer cover layer may be a continuous layer. The outer cover layer may be a perforated layer. The outer cover layer 110 may be a non-stick perforated polyurethane. The outer cover layer 110 may comprise a polyamide (nylon).

[0039] The outer cover layer 110 can be made from a composition comprising TPU or polyamide and maleic anhydride grafted ethylene-butyl acrylate copolymer or maleic anhydride grafted ethylene alpha olefin copolymer. In some examples, the outer cover layer 110 can be made from a composition comprising between 10%-50%, or 15%-40%, or 20%-35% of a reactive blend comprising maleic anhydride grafted ethylene-butyl acrylate copolymer or maleic anhydride grafted ethylene alpha olefin copolymer in polyamide or thermoplastic polyurethane. The polyamide can be PA 12, PA 6 / 12, PA 6, or PA 6 / 6. In some examples, the polyamide is PA 12. In some examples, the polyamide is PA 6 / 12. In some examples, the polyamide is PA 6. In some examples, the polyamide is PA 6 / 6.

[0040] In some embodiments, the outer cover 110 is prepared from a composition comprising a thermoplastic elastomer such as a polyamide or a thermoplastic polyurethane, optionally further comprising a reactive blend, and optionally comprising additives such as reinforcing agents, flame retardants, stabilizers, processing aids, metal fibers, carbon black, graphite, metal foil, titanium dioxide, color pigments, and / or zinc sulfide.

[0041] In some examples, the thermoplastic hose 100 of the present disclosure includes an inner tube layer 102 comprising polyamide (nylon), a reinforcement layer 106 comprising an isocyanate treated polyester textile braid, and an outer cover layer 110 comprising thermoplastic polyurethane (TPU). The inner tube layer 102 and / or the cover layer 110 may further comprise a reactive blend.

[0042] Thermoplastic hose 100 may be any suitable diameter, such as -04, -05, -06, -08, -10, -12, or -16, having an inside diameter (ID) and outside diameter (OD) (nominal) as shown in Table 1.

[0043] In some examples, the disclosed thermoplastic hose 100 includes an inner tube layer 102 comprising polyamide (nylon), a reinforcement layer 106 comprising an isocyanate treated polyester textile braid, and an outer cover layer 110 comprising polyamide (nylon). The inner tube layer 102 and / or the cover layer 110 may further comprise a reactive blend.

[0044] Figure 2 An exemplary thermoplastic hose 200 according to the present disclosure is shown including, from inside to outside direction, an inner tube layer 202 , a first textile knit reinforcement layer 206 , a second textile knit reinforcement layer 208 , and an outer cover layer 210 .

[0045] The inner tube layer 202 may include a thermoplastic elastomer. The thermoplastic elastomer may be prepared from a composition comprising a thermoplastic polymer, a copolymer, a terpolymer, or a blend thereof. The inner tube layer 202 may include a thermoplastic elastomer selected from the group consisting of polyamide, thermoplastic polyurethane (TPU), thermoplastic polyester elastomer, thermoplastic copolyester elastomer, maleic anhydride grafted ethylene-butyl acrylate copolymer, and maleic anhydride grafted plastomer (ethylene alpha olefin copolymer). For example, the inner tube layer 202 may be prepared from a composition comprising TPU or polyamide and maleic anhydride grafted ethylene-butyl acrylate copolymer or maleic anhydride grafted ethylene alpha olefin copolymer. The polyamide may be PA 12, PA6 / 12, PA6, or PA 6 / 6. In some examples, the inner tube layer 202 includes PA 12. The inner tube layer 202 may include a maleic anhydride grafted elastomer.

[0046] The first and second reinforcing layers 206 and 208 can each independently include a textile braid processed. The textile braid processed can be prepared by a yarn processed by resorcinol formaldehyde (RFL) or isocyanate. The example of the yarn processed for the first or second reinforcing layer 206 or 208 includes a yarn processed by polyester, aramid, nylon, cotton and rayon independently. In certain embodiments, each reinforcing layer 206 or 208 is independently a discontinuous layer. In certain embodiments, reinforcing layer 206 or 208 is a discontinuous layer, which independently includes a polyester braid processed, an aramid braid processed, a nylon braid processed, a cotton braid processed or a rayon braid processed. In some instances, reinforcing layer 206 or 208 each independently includes a polyester yarn processed by isocyanate. In some instances, reinforcing layer 206 or 208 can each independently include a polyester yarn processed by RFL.

[0047] The cover layer 210 may include a thermoplastic elastomer. The cover layer may include a thermoplastic polymer, a copolymer, a terpolymer, or a blend thereof. The cover layer 210 may include a thermoplastic elastomer selected from the group consisting of polyamide, thermoplastic polyurethane (TPU), thermoplastic polyester elastomer, thermoplastic copolyester elastomer, maleic anhydride grafted ethylene-butyl acrylate copolymer, and maleic anhydride grafted plastomer (ethylene alpha olefin copolymer).

[0048] In some examples, the outer cover 210 may include a thermoplastic polyurethane (TPU) layer or a polyamide. The outer cover may include a non-stick polyurethane. The outer cover may be a continuous layer. The outer cover may be a perforated layer. The outer cover 210 may be a non-stick perforated polyurethane. The outer cover 210 may include a polyamide (nylon). The outer cover 210 may be prepared from a composition comprising TPU or polyamide and maleic anhydride grafted ethylene-butyl acrylate copolymer or maleic anhydride grafted ethylene alpha olefin copolymer. The outer cover may be prepared from a composition comprising 10%-50%, or 15%-40%, or 20%-35% maleic anhydride grafted ethylene-butyl acrylate copolymer or maleic anhydride grafted ethylene alpha olefin copolymer in a thermoplastic polyurethane. The polyamide may be PA 12, PA 6 / 12, PA 6, or PA 6 / 6. In some examples, the polyamide is PA 12.

[0049] In some examples, the thermoplastic hose 200 of the present disclosure includes an inner tube layer 202 comprising polyamide (nylon), a first reinforcement layer 206 comprising an isocyanate-treated polyester textile braid, a second reinforcement layer 208 comprising an isocyanate-treated polyester textile braid, and an outer cover layer 210 comprising thermoplastic polyurethane (TPU). The inner tube layer 202 can be prepared from a composition comprising 10%-50%, or 15%-40%, or 20%-35% of maleic anhydride-grafted ethylene-butyl acrylate copolymer or maleic anhydride-grafted ethylene alpha olefin copolymer in polyamide. The outer cover layer 210 can be prepared from a composition comprising 10%-50%, or 15%-40%, or 20%-35% of maleic anhydride-grafted ethylene-butyl acrylate copolymer or maleic anhydride-grafted ethylene alpha olefin copolymer in thermoplastic polyurethane (TPU).

[0050] In some examples, the thermoplastic hose 200 of the present disclosure includes an inner tube layer 202 comprising polyamide (nylon), a first reinforcement layer 206 comprising an isocyanate treated polyester textile braid, a second reinforcement layer 208 comprising an isocyanate treated polyester textile braid, and an outer cover layer 210 comprising polyamide (nylon). The inner tube layer 202 can be prepared from a composition comprising between 10%-50%, or 15%-40%, or 20%-35% of maleic anhydride grafted ethylene-butyl acrylate copolymer or maleic anhydride grafted ethylene alpha olefin copolymer in polyamide.

[0051] The outer cover layer 210 can be made of a composition comprising between 10%-50%, or 15%-40%, or 20%-35% of maleic anhydride grafted ethylene-butyl acrylate copolymer or maleic anhydride grafted ethylene alpha olefin copolymer in polyamide. The polyamide can be PA 12, PA 6 / 12, PA 6, or PA 6 / 6. In some examples, the polyamide is PA12.

[0052] The outer cover layer 210 may include thermoplastic polyurethane (TPU). The outer cover layer may include non-stick polyurethane. The outer cover layer may be a continuous layer. The outer cover layer may be a perforated layer. The outer cover layer 210 may be a non-stick perforated polyurethane. The outer cover layer 210 may be a polyamide (nylon) layer.

[0053] Thermoplastic hose 200 may be of any suitable diameter, such as -06 (ID 9.7 mm; OD 17.0 mm), -08 (ID 13.0 mm; OD 21.6 mm), or -10 (ID 16.2 mm; OD 27.0 mm), etc.

[0054] Thermoplastic elastomer

[0055] The thermoplastic hose may contain one or more thermoplastic layers. The inner tube layer may comprise a thermoplastic elastomer. The outer cover layer may comprise a thermoplastic elastomer. The thermoplastic elastomer may be selected from the group consisting of polyamide (nylon), thermoplastic polyurethane (TPU), thermoplastic polyester elastomer and thermoplastic copolyester elastomer. The thermoplastic layer may be prepared from a composition comprising a thermoplastic polymer, copolymer, terpolymer or blend. For example, the thermoplastic elastomer may be selected from the group consisting of polyamide, thermoplastic polyurethane (TPU), thermoplastic polyester elastomer, thermoplastic copolyester elastomer, maleic anhydride grafted ethylene-butyl acrylate copolymer and maleic anhydride grafted plastomer (ethylene alpha olefin copolymer).

[0056] Thermoplastic polyurethane (TPU) can be obtained, for example, from BASF as 1598A is a commercially available thermoplastic polyether-based polyurethane. TPU can be obtained from BASF as 1195A Available thermoplastic polyether-based polyurethane.

[0057] Examples of suitable polyamides (nylons) may include PA 6 (polyamide 6; nylon 6), PA 6 / 6 (polyamide 6,6; nylon 6,6), PA 11 (polyamide 11; nylon 11), PA 12 (polyamide 12; nylon 12), PA 6 / 12 (polyamide 612; nylon 6,12), and PA 610 (polyamide 610; nylon 6,10). In some embodiments, suitable nylon polyamides may include PA 6, PA 6,6, PA 12, and PA 11. In still other embodiments, suitable nylon polyamides include PA 12, PA 6, and PA 6,6. In some examples, the polyamide may be PA 12. Polyamides are commercially available from, for example, Arkema.

[0058] Elastomeric compositions comprising maleic anhydride grafted elastomers are referred to as reactive blends.

[0059] Thermoplastic elastomers can include maleic anhydride grafted elastomers. Maleic anhydride grafted elastomers can be commercially available. Maleic anhydride grafted elastomers can be selected from the group consisting of maleic anhydride grafted ethylene-butyl acrylate copolymers and maleic anhydride grafted plastomers (ethylene alpha olefin copolymers). Ethylene butyl acrylate (EBA) is a copolymer comprising ethylene and butyl acrylate that can be prepared by high pressure free radical polymerization. The butyl acrylate can be n-butyl acrylate. Maleic anhydride grafted EBA is commercially available from, for example, Industrie Polieco-MPB Srl., Italy. Due to the butyl acrylate content, it can be used in applications where softness, flexibility and polarity are required. For example, 40 is a maleic anhydride grafted ethylene-butyl acrylate copolymer containing about 17% butyl acrylate content.

[0060] Maleic anhydride grafted plastomers (ethylene alpha olefin copolymers) can be obtained from Industrie PoliecoM.PBSrl, Italy as C50 is commercially available. Maleic anhydride grafted ethylene-butyl acrylate copolymer was purchased from Industrie Polieco MPBSrl, Italy as EB40 is commercially available. In some examples, the reactive blend comprises a composition comprising between 10%-50%, or 15%-40%, or 20%-35% of maleic anhydride grafted ethylene-butyl acrylate copolymer or maleic anhydride grafted ethylene alpha olefin copolymer in polyamide or TPU.

[0061] In some examples, the outer cover layer is prepared from a composition comprising between 10%-50% of maleic anhydride grafted ethylene-butyl acrylate copolymer (EB40) or maleic anhydride grafted ethylene alpha olefin copolymer (C50) in polyamide or TPU.

[0062] In some examples, the reactive blend comprises between 10%-50% maleic anhydride grafted ethylene-butyl acrylate copolymer in the polyamide. In some examples, the reactive blend comprises between 10%-50% maleic anhydride grafted ethylene alpha olefin copolymer in the polyamide.

[0063] In some examples, the inner tube layer is made of a composition comprising between 10%-50% maleic anhydride grafted ethylene-butyl acrylate copolymer (EB40) or maleic anhydride grafted ethylene alpha olefin copolymer (C50) in polyamide or TPU. The inner tube layer may include one or more layers. In some examples, the inner tube layer comprises polyamide. In some examples, the inner tube layer may be polyester lined. In some examples, the inner tube layer 102 comprises TPU.

[0064] Isocyanate

[0065] Isocyanates are a family of low molecular weight, highly reactive compounds containing an isocyanate moiety (-N=C=O). Isocyanates are used to make a variety of materials, such as adhesives, rigid foams, fibers, coatings (such as paints and varnishes), and elastomers. Isocyanates are irritants to mucous membranes, eyes, gastrointestinal tract, and respiratory tract. Isocyanates can cause skin inflammation. Respiratory and skin exposure may lead to sensitization. Preventing exposure to isocyanates can help eliminate potential health hazards. Commonly used isocyanates can include methylene bis (phenyl isocyanate) (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), naphthalene diisocyanate (NDI), methylene bis-cyclohexyl isocyanate (HMDI) (hydrogenated MDI), and isophorone diisocyanate (IPDI). Polyisocyanates can include HDI biuret and HDI isocyanate.

[0066] Directly bonded to textile TPE adhesion reaction such as Figure 3 shown.

[0067] The isocyanate moiety -N=C=O chemically reacts with the amide moiety -C(=O)NH- to form an adhesive urea linkage -C(=O)-NC(=O)-NH-.

[0068] RFL

[0069] Resorcinol-formaldehyde (RF) resin is a synthetic thermosetting resin system obtained from the polycondensation of formaldehyde and resorcinol (1,3-dihydroxybenzene). Resorcinol-formaldehyde latex (RFL) adhesives can be used to treat textiles so that they can be chemically bonded to rubber. RFL is chemically combined to make a strong, heat-resistant, flexible adhesive suitable for rubber and fabric textile bonding. Rubber latex can be, for example, natural rubber latex, styrene butadiene vinyl pyridine (terpolymer) (SBVPL), or chloroprene rubber latex.

[0070] Resorcinol can also be copolymerized with phenol and formaldehyde resins (PRF resins). Resorcinol resins form very durable and strong bonds with good humidity, water and corrosion tolerance. RF and PRF resins can be used as binders in vulcanized rubber products to enhance adhesion between rubber and plastic layers. RF resins can be used to achieve good adhesion to organic fiber substrates (such as polyester, rayon, or nylon).

[0071] Manufacturing method

[0072] Thermoplastic hoses can be made in an "in-line" process, for example, the inner plastic tube can be extruded and then passed through a braiding machine loaded with spindles of treated polyester yarn. The braiding process wraps the yarn around the hose, applying the necessary intimate contact between the textile and the thermoplastic. The process can be carried out under heating (>100°C), where the reaction between the RFL or isocyanate treated yarn and the thermoplastic will occur, creating a covalent interaction.

[0073] Adhesion of the cover to the braid will occur in a similar manner where the outer jacket is extruded on top of the fibers at high temperature. In some examples, suitable thermoplastics include thermoplastic polyurethane (TPU), polyamide 6, polyamide 12, and reactive blends incorporating maleic anhydride chemistry into the polymer matrix.

[0074] In some examples, the reactive blend comprises a composition comprising between 10%-50%, or 15%-40%, or 20%-35% of maleic anhydride grafted ethylene-butyl acrylate copolymer or maleic anhydride grafted ethylene alpha olefin copolymer in polyamide. In some examples, the reactive blend comprises a composition comprising between 10%-50%, or 15%-40%, or 20%-35% of maleic anhydride grafted ethylene-butyl acrylate copolymer or maleic anhydride grafted ethylene alpha olefin copolymer in thermoplastic polyurethane (TPU).

[0075] test

[0076] The strip adhesion test between layers can be carried out according to ASTM D 413-81. This test measures the adhesion strength between different layers, for example, between a thermoplastic layer and a reinforcement layer, or between two thermoplastic layers with an intermediate reinforcement layer. Sample type B-90° peeling was used. Samples were prepared using 4" long, 1" wide and 0.075" thick thermoplastic elastomer (e.g., polyamide 12) injection molded samples. PA12 samples can be placed on 4" long, 1" wide and 0.09" thick reinforcement samples on standard pressed cured products. Samples were vulcanized at 320°F for 45 minutes. Twenty-four hours after vulcanization, samples were tested at a rate of 2" / min using a 5KN load cell on a calibrated Instron5965 (according to ASTM D413 type B (90° peeling)). Tensile strength and percentage elongation can be tested according to ASTM D412 standard test methods. Standard ASTM samples can be tested at a rate of 20" / min using a 5KN load cell on a calibrated Instron 5965.

[0077] The hardness of the elastomeric material can be tested in the Shore A hardness test according to ASTM D 2240-95. The hardness can be tested using a calibrated Instron automatic durometer tester.

[0078] Compression set of elastomeric materials can be tested according to ASTM D 395-89. Samples can be prepared as follows. After curing, the material can be formed into a 0.49" thick by 1.14" diameter button. The button is then compressed 25% into a C Set fixture. After curing, the sample is exposed to -40°C for 24 hours, and the sample is removed and measured at the specified time increments. Overall compression set can be evaluated on samples that are allowed to run for 24 hours and then rebounded outside the C Set fixture at room temperature before the final measurement.

[0079] Permeation of the test hose and control hose may be tested in accordance with SAE J2064. The samples are stabilized at 23°C ± 2°C for 24 hours prior to testing and inspected to ensure the specified charge and to identify charge loss.

[0080] Pressure testing (including impulse testing and burst testing) can be performed in accordance with SAE J343 testing and SAE 100R Series Hydraulic Hose Test Procedures. The maximum allowable "working pressure" assigned to a hose product can be based on test conditions, straight length and at 20°C.

[0081] Hose size

[0082] In some embodiments, thermoplastic hoses according to the present disclosure may exhibit the following dimensions and properties as shown in Table 1.

[0083] Table 1. Thermoplastic Hose Dimensions and Properties Examples Example 1. Adhesion strength of thermoplastic elastomer to textile braid reinforcement

[0084] The adhesion strength of the standard and test samples of the textile reinforcement containing isocyanate polyester yarn to various elastomers was tested by ASTM D413 type B 90 degree peel test to the maximum load. Various unpretreated and pretreated isocyanate polyester yarns were used to prepare the textile braid reinforcement layer bonded to the thermoplastic elastomer layer. The elastomer samples included thermoplastic elastomer polyamide (PA12), polyurethane (1195A), maleic anhydride grafted plastomer (ethylene alpha olefin copolymer) (C50) and maleic anhydride grafted ethylene-butyl acrylate copolymer (EB40).

[0085] Pretreated isocyanate adhesive treated polyester yarn was commercially obtained from Beaver Manufacturing Company, Mansfield, Georgia. Test yarns included those designed to adhere to EPDM, CPE, and CSM. 102 Isocyanate treated fiber; designed to adhere to a variety of rubbers, including EPDM, CPE and CSM 108 Isocyanate treated adhesive activated polyester; designed for butyl rubber adhesion 304 isocyanate treated fibers; and designed to adhere to various rubber types such as NBR, CR, ACM / AEM 140 treated fibers.

[0086] The standard and test samples of the isocyanate polyester yarn reinforcement layer were tested for maximum load of adhesion to various elastomers by ASTM D413 Type B 90°C peel test. The results are shown in Table 2. The final results are in lbf units.

[0087] Table 2. Polyester Yarn-Elastomer Adhesion Strength Maximum Load (lbf)

[0088] Results: Samples containing thermoplastic elastomeric polyamide (PA12), maleic anhydride grafted plastomers (ethylene alpha olefin copolymers) (C50), and maleic anhydride grafted ethylene-butyl acrylate copolymers (EB40) each exhibited improved adhesion strength to a braid reinforcement layer containing isocyanate pretreated polyester yarns when compared to standard isocyanate treatments, as shown in Table 2. Thermoplastic polyurethane (1195A) exhibited improved adhesion to pretreated test fibers 108 polyester T-161ST2 and 140 polyester T-174S compared to standard isocyanate treatments. The EB40 reactive blend exhibited the best adhesion to all fibers. PA12 polyamide exhibited significantly improved adhesion to a textile braid reinforcement layer containing isocyanate pretreated polyester yarns when compared to standard isocyanate treatments using untreated polyester yarns. Terms

[0089] Clause 1. A thermoplastic hose comprising a plurality of layers, the layers comprising: A first textile knit reinforcement layer covalently bonded to an inner tube layer comprising a first thermoplastic elastomer, and An outer cover layer comprises a second thermoplastic elastomer.

[0090] Clause 2. The thermoplastic hose of Clause 1, wherein the first textile braid reinforcement layer comprises pretreated yarns selected from the group consisting of polyester, aramid, nylon, cotton, and rayon pretreated yarns.

[0091] Clause 3. The thermoplastic hose of Clause 2, wherein the pretreated yarn comprises a reactive adhesive coating capable of forming a covalent bond with the first thermoplastic elastomer.

[0092] Clause 4. A thermoplastic hose according to clause 3, wherein the pretreated yarn comprises a fixed isocyanate, resorcinol formaldehyde (RF), or phenol resorcinol formaldehyde (PRF) reactive adhesive coating, optionally wherein the pretreated yarn is an isocyanate pretreated polyester yarn.

[0093] Clause 5. The thermoplastic hose according to any one of clauses 1 to 4, wherein the inner tube layer comprises a first thermoplastic elastomer selected from the group consisting of polyamides, thermoplastic polyurethanes, thermoplastic polyester elastomers, copolyesters, acrylic copolymers, polyolefin blends and polyolefin blends, optionally wherein the first thermoplastic elastomer is polyamide or thermoplastic polyurethane.

[0094] Clause 6. The thermoplastic hose of Clause 5, wherein the inner tube layer further comprises a maleic anhydride grafted copolymer.

[0095] Clause 7. The thermoplastic hose according to Clause 6, wherein the maleic anhydride grafted copolymer is selected from the group consisting of maleic anhydride grafted ethylene-butyl acrylate copolymers and maleic anhydride grafted plastomers (ethylene alpha olefin copolymers).

[0096] Clause 8. A thermoplastic hose according to any one of clauses 1 to 7, wherein the inner tube layer comprises 10-50 wt%, or 15-40 wt%, or 20-35 wt% of maleic anhydride grafted ethylene-butyl acrylate copolymer or maleic anhydride grafted ethylene alpha olefin copolymer in thermoplastic polyurethane or polyamide, compared to the total weight of thermoplastic elastomer in the inner tube layer.

[0097] Clause 9. The thermoplastic hose of any one of clauses 1 to 8, wherein the outer cover comprises a second thermoplastic elastomer selected from the group consisting of polyamides, thermoplastic polyurethanes, thermoplastic polyester elastomers, copolyesters, acrylic copolymers, polyolefin blends and polyolefin blends, optionally wherein the second thermoplastic elastomer is a polyamide or a thermoplastic polyurethane.

[0098] Clause 10. The thermoplastic hose of Clause 9, wherein the outer cover comprises a maleic anhydride grafted thermoplastic copolymer.

[0099] Clause 11. The thermoplastic hose according to Clause 10, wherein the maleic anhydride grafted copolymer is selected from the group consisting of maleic anhydride grafted ethylene-butyl acrylate copolymers and maleic anhydride grafted plastomers (ethylene alpha olefin copolymers).

[0100] Clause 12. The thermoplastic hose according to any one of clauses 1 to 11, wherein the outer cover layer comprises 10-50 wt%, or 15-40 wt%, or 20-35 wt% of maleic anhydride grafted ethylene-butyl acrylate copolymer or maleic anhydride grafted ethylene alpha olefin copolymer in the thermoplastic polyurethane or polyamide, compared to the total weight of the thermoplastic elastomer in the outer cover layer.

[0101] Clause 13. The thermoplastic hose of any of Clauses 1 to 12, wherein the first thermoplastic elastomer and the second thermoplastic elastomer are different.

[0102] Clause 14. The thermoplastic hose of any one of Clauses 1 to 13, wherein the first textile knit reinforcement layer is covalently bonded to the outer cover layer.

[0103] Clause 15. The thermoplastic hose of any of Clauses 1 to 14, further comprising a second textile braid layer covalently bonded to the outer cover layer.

[0104] Clause 16. The thermoplastic hose according to any one of clauses 1 to 15, comprising, from the inner surface to the outer surface of the hose: an inner tube layer comprising a first thermoplastic elastomer covalently bonded to a first textile braid reinforcement layer; and A second textile knit layer covalently bonded to An outer cover layer comprises a second thermoplastic elastomer.

[0105] Clause 17. The thermoplastic hose of any of Clauses 1 to 16, wherein the bond strength between the inner tube layer and the first textile braid reinforcement layer is at least 8 lbf, at least 10 lbf, or at least 15 lbf when tested according to ASTM D413 Type B, 90° peel.

[0106] Clause 18. A method of making a thermoplastic hose according to any one of clauses 1 to 16, comprising: extruding a first thermoplastic elastomer composition onto a mandrel to form the inner tube layer; braiding a first pretreated yarn on the inner tube layer to form a first textile braid reinforcement layer; heating the first textile knit reinforcement layer to a temperature >100C to form covalent bonds between the pretreated yarn and the first thermoplastic elastomer to form a covalently bonded first textile knit reinforcement layer; and A second thermoplastic elastomer composition is extruded over the covalently bonded first textile braid reinforcement layer to form the cover layer, heated to a temperature >100°C, and cooled to form the thermoplastic hose.

[0107] Clause 19. The method according to clause 18, further comprising: The hose is driven off the mandrel.

[0108] Clause 20. The method according to clause 18 or 19, further comprising: A second pre-treated yarn is braided onto the reinforced inner tube layer prior to the second extrusion step.

[0109] Clause 21. A method according to any one of clauses 18 to 20, wherein the first pretreated yarn comprises a polyester, aramid, nylon, cotton or rayon yarn pretreated with a reactive adhesive coating capable of forming a covalent bond with the first thermoplastic elastomer in the first thermoplastic elastomer composition.

[0110] Clause 22. The method of Clause 21, wherein the first pretreated yarn comprises an immobilized isocyanate, resorcinol formaldehyde (RF), or phenol resorcinol formaldehyde (PRF) reactive binder coating.

[0111] Clause 23. The method of any one of Clauses 18 to 22, wherein the first thermoplastic elastomer composition comprises a first thermoplastic elastomer selected from the group consisting of polyamides, thermoplastic polyurethanes, thermoplastic polyester elastomers, copolyesters, acrylic copolymers, polyolefin blends, and polyolefin blends.

[0112] Clause 24. The method of Clause 23, wherein the first thermoplastic elastomer composition comprises a maleic anhydride grafted thermoplastic copolymer.

[0113] Clause 25. The method according to Clause 24, wherein the maleic anhydride grafted copolymer is selected from the group consisting of maleic anhydride grafted ethylene-butyl acrylate copolymer and maleic anhydride grafted plastomers (ethylene alpha olefin copolymers).

[0114] Clause 26. A method according to any one of clauses 18 to 25, wherein the first thermoplastic elastomer composition comprises 10-50 wt%, or 15-40 wt%, or 20-35 wt% of maleic anhydride grafted ethylene-butyl acrylate copolymer or maleic anhydride grafted ethylene alpha olefin copolymer in the thermoplastic polyurethane or polyamide, compared to the total weight of the thermoplastic elastomer in the composition.

[0115] Clause 27. The method according to any one of Clauses 18 to 26, wherein the second thermoplastic elastomer composition comprises a second thermoplastic elastomer selected from the group consisting of polyamides, thermoplastic polyurethanes, thermoplastic polyester elastomers, copolyesters, acrylic copolymers, polyolefin blends, and polyolefin blends.

[0116] Clause 28. The method of Clause 27, wherein the second thermoplastic elastomer composition comprises a maleic anhydride grafted copolymer.

[0117] Clause 29. The method according to Clause 28, wherein the maleic anhydride grafted copolymer is selected from the group consisting of maleic anhydride grafted ethylene-butyl acrylate copolymer and maleic anhydride grafted plastomers (ethylene alpha olefin copolymers).

[0118] Clause 30. A method according to any one of clauses 18 to 29, wherein the second thermoplastic elastomer composition comprises 10-50 wt%, or 15-40 wt%, or 20-35 wt% of maleic anhydride grafted ethylene-butyl acrylate copolymer or maleic anhydride grafted ethylene alpha olefin copolymer in the thermoplastic polyurethane or polyamide, compared to the total weight of the thermoplastic elastomer in the composition.

[0119] Clause 31. The method of any one of Clauses 18 to 30, wherein the first thermoplastic elastomer and the second thermoplastic elastomer are different.

[0120] Clause 32. The method of any one of Clauses 18 to 31, wherein the first textile knit reinforcement layer is covalently bonded to the outer cover layer.

[0121] Clause 33. The method of Clause 20, wherein the second textile knit reinforcement layer is covalently bonded to the outer cover layer. Clause 34. The method of any one of clauses 18 to 33, wherein the thermoplastic hose comprises, in a direction from the inside to the outside surface of the hose: an inner tube layer comprising a first thermoplastic elastomer covalently bonded to a first textile braid reinforcement layer; and A second textile braid reinforcement layer covalently bonded to The outer cover layer comprises a second thermoplastic elastomer.

[0122] Clause 35. The method of any one of clauses 18 to 34, wherein the bond strength between the inner tube layer and the first textile woven fabric layer of the thermoplastic hose is at least 8 lbf, at least 10 lbf, or at least 15 lbf when tested according to ASTM D413 Type B, 90° peel.

Claims

1. A thermoplastic hose comprising a plurality of layers, the layers comprising: A first textile knit reinforcement layer covalently bonded to an inner tube layer comprising a first thermoplastic elastomer, and An outer cover layer comprises a second thermoplastic elastomer.

2. The thermoplastic hose according to claim 1, wherein: The first textile knit reinforcement layer comprises pretreated yarns selected from the group consisting of polyester, aramid, nylon, cotton and rayon pretreated yarns.

3. The thermoplastic hose according to claim 2, wherein: The pretreated yarn includes a reactive adhesive coating capable of forming a covalent bond with the first thermoplastic elastomer.

4. The thermoplastic hose according to claim 3, wherein: The pretreated yarn comprises an immobilized isocyanate, resorcinol formaldehyde (RF), or phenol resorcinol formaldehyde (PRF) reactive adhesive coating, optionally wherein the pretreated yarn is an isocyanate pretreated polyester yarn.

5. The thermoplastic hose according to claim 1, wherein The inner tube layer comprises a first thermoplastic elastomer selected from the group consisting of polyamides, thermoplastic polyurethanes, thermoplastic polyester elastomers, copolyesters, acrylic copolymers, polyolefin blends and polyolefin blends, optionally wherein the first thermoplastic elastomer is polyamide or thermoplastic polyurethane.

6. The thermoplastic hose according to claim 5, wherein: The inner tube layer further comprises a maleic anhydride grafted copolymer.

7. The thermoplastic hose according to claim 6, wherein: The maleic anhydride grafted copolymer is selected from the group consisting of maleic anhydride grafted ethylene-butyl acrylate copolymer and maleic anhydride grafted plastomers (ethylene alpha olefin copolymers).

8. The thermoplastic hose according to claim 7, wherein: The inner tube layer comprises 10-50 wt%, or 15-40 wt%, or 20-35 wt% of maleic anhydride grafted ethylene-butyl acrylate copolymer or maleic anhydride grafted ethylene alpha olefin copolymer in thermoplastic polyurethane or polyamide, compared to the total weight of thermoplastic elastomer in the inner tube layer.

9. The thermoplastic hose according to claim 1, wherein: The outer cover layer comprises a second thermoplastic elastomer selected from the group consisting of polyamides, thermoplastic polyurethanes, thermoplastic polyester elastomers, copolyesters, acrylic copolymers, polyolefin blends and polyolefin blends, optionally wherein the second thermoplastic elastomer is a polyamide or a thermoplastic polyurethane.

10. The thermoplastic hose according to claim 9, wherein The outer cover layer comprises a maleic anhydride grafted thermoplastic copolymer.

11. The thermoplastic hose according to claim 10, wherein: The maleic anhydride grafted copolymer is selected from the group consisting of maleic anhydride grafted ethylene-butyl acrylate copolymer and maleic anhydride grafted plastomers (ethylene alpha olefin copolymers).

12. The thermoplastic hose according to claim 11, wherein The outer cover layer comprises 10-50 wt%, or 15-40 wt%, or 20-35 wt% of maleic anhydride grafted ethylene-butyl acrylate copolymer or maleic anhydride grafted ethylene alpha olefin copolymer in thermoplastic polyurethane or polyamide, compared to the total weight of thermoplastic elastomer in the outer cover layer.

13. The thermoplastic hose according to claim 1, wherein: The first thermoplastic elastomer and the second thermoplastic elastomer are different.

14. The thermoplastic hose according to claim 1, wherein: The first textile knit reinforcement layer is covalently bonded to the outer cover layer.

15. The thermoplastic hose of claim 1 further comprising a second textile braid layer covalently bonded to the outer cover layer.

16. The thermoplastic hose of claim 15, comprising, in a direction from the inner surface to the outer surface of the hose: an inner tube layer comprising a first thermoplastic elastomer covalently bonded to a first textile braid reinforcement layer; and A second textile knit layer covalently bonded to An outer cover layer comprises a second thermoplastic elastomer.

17. The thermoplastic hose of claim 1, wherein: The bond strength between the inner tube layer and the first textile braid reinforcement layer is at least 8 lbf, at least 10 lbf, or at least 15 lbf when tested according to ASTM D413 Type B, 90° peel.

18. A method of making a thermoplastic hose according to claim 1, comprising: extruding a first thermoplastic elastomer composition onto a mandrel to form the inner tube layer; braiding a first pretreated yarn on the inner tube layer to form a first textile braid reinforcement layer; heating the first textile knit reinforcement layer to a temperature >100C to form covalent bonds between the pretreated yarn and the first thermoplastic elastomer to form a covalently bonded first textile knit reinforcement layer; as well as A second thermoplastic elastomer composition is extruded over the covalently bonded first textile braid reinforcement layer to form the cover layer, heated to a temperature >100C, and cooled to form the thermoplastic hose.

19. The method according to claim 18, further comprising: The hose is driven off the mandrel.

20. The method of claim 18, further comprising: A second pre-treated yarn is braided onto the reinforced inner tube layer prior to the second extrusion step.

21. The method according to claim 18, wherein: The first pretreated yarn comprises polyester, aramid, nylon, cotton or rayon yarn pretreated with a reactive adhesive coating capable of forming covalent bonds with the first thermoplastic elastomer in the first thermoplastic elastomer composition.

22. The method according to claim 21, wherein: The first pretreated yarn comprises an immobilized isocyanate, resorcinol formaldehyde (RF), or phenol resorcinol formaldehyde (PRF) reactive binder coating.

23. The method according to claim 18, wherein: The first thermoplastic elastomer composition comprises a first thermoplastic elastomer selected from the group consisting of polyamides, thermoplastic polyurethanes, thermoplastic polyester elastomers, copolyesters, acrylic copolymers, polyolefin blends, and polyolefin blends.

24. The method according to claim 23, wherein: The first thermoplastic elastomer composition comprises a maleic anhydride grafted thermoplastic copolymer.

25. The method according to claim 24, wherein: The maleic anhydride grafted copolymer is selected from the group consisting of maleic anhydride grafted ethylene-butyl acrylate copolymer and maleic anhydride grafted plastomers (ethylene alpha olefin copolymers).

26. The method according to claim 25, wherein: The first thermoplastic elastomer composition comprises 10-50 wt%, or 15-40 wt%, or 20-35 wt% of maleic anhydride grafted ethylene-butyl acrylate copolymer or maleic anhydride grafted ethylene alpha olefin copolymer in thermoplastic polyurethane or polyamide, compared to the total weight of the thermoplastic elastomer in the composition.

27. The method according to claim 18, wherein: The second thermoplastic elastomer composition comprises a second thermoplastic elastomer selected from the group consisting of polyamides, thermoplastic polyurethanes, thermoplastic polyester elastomers, copolyesters, acrylic copolymers, polyolefin blends, and polyolefin blends.

28. The method according to claim 27, wherein: The second thermoplastic elastomer composition comprises a maleic anhydride grafted copolymer.

29. The method according to claim 28, wherein: The maleic anhydride grafted copolymer is selected from the group consisting of maleic anhydride grafted ethylene-butyl acrylate copolymer and maleic anhydride grafted plastomers (ethylene alpha olefin copolymers).

30. The method of claim 18, wherein: The second thermoplastic elastomer composition comprises 10-50 wt%, or 15-40 wt%, or 20-35 wt% of maleic anhydride grafted ethylene-butyl acrylate copolymer or maleic anhydride grafted ethylene alpha olefin copolymer in thermoplastic polyurethane or polyamide, compared to the total weight of the thermoplastic elastomer in the composition.

31. The method of claim 18, wherein: The first thermoplastic elastomer and the second thermoplastic elastomer are different.

32. The method of claim 18, wherein: The first textile knit reinforcement layer is covalently bonded to the outer cover layer.

33. The method of claim 20, wherein: The second textile knit reinforcement layer is covalently bonded to the outer cover layer.

34. The method of claim 33, wherein: The thermoplastic hose comprises, in a direction from the inside to the outside surface of the hose: an inner tube layer comprising a first thermoplastic elastomer covalently bonded to a first textile braid reinforcement layer; and A second textile braid reinforcement layer covalently bonded to The outer cover layer comprises a second thermoplastic elastomer.

35. The method of claim 18, wherein: The bond strength between the inner tube layer and the first textile braid layer of the thermoplastic hose is at least 8 lbf, at least 10 lbf, or at least 15 lbf when tested according to ASTM D413 Type B, 90° peel.

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