Plywood-type barrel or hose with diffusion barrier

Abstract

The invention relates to a multi-layer hose (1, 10) having a plurality of coaxially arranged sheaths (2, 3, 4, 5, 6, 7, 8, 12, 13). The multi-layer hose (1, 10) comprises at least: a load-bearing sheath (2, 6), a diffusion-reducing sheath (4) and an adhesion-promoting layer (3, 5) arranged between the load-bearing sheath (2, 6) and the diffusion-reducing sheath (4) and increasing the bonding force between the load-bearing sheath (2, 6) and the diffusion-reducing sheath (4). The adhesion promoting layer (3, 5) comprises a mixture of 65 to 85 parts of acrylonitrile butadiene rubber, 15 to 35 parts of styrene butadiene rubber, 75 to 125 parts of carbon black N990, 30 to 100 parts of calcium magnesium carbonate, 5 to 15 parts of zinc oxide, 5 to 20 parts of hydroxy aluminum magnesium carbonate, 25 to 125 parts of a resin-in-blend, 2 to 10 parts of N-(1.3-dimethylbutyl)-N '-phenyl-p-phenylenediamine, and 5 to 20 parts of an adhesive. 5 to 15 parts of triallyl cyanurate; and 0.5 to 5 parts of a vulcanizing agent.

Description

Technical Field

[0001] The invention relates to a multilayer tube or hose, which comprises a plurality of coaxially arranged sheaths, wherein the coaxially arranged sheaths are joined together. The multilayer tube or hose comprises at least a load-bearing sheath, a diffusion-reducing sheath and an adhesion-promoting layer arranged between the load-bearing sheath and the diffusion-reducing sheath. Background Art

[0002] Materials, in particular fluids, frequently have to be transported between different locations. In the present context, the term "fluid" may relate to gases, liquids, mixtures of gases and liquids, and also to supercritical fluids, in which a distinction can no longer be made between liquid and gas phases. It is also possible that the fluid may contain solid particles, including situations in which the solid particles are conveyed using the fluid as a transport agent, or even situations in which the solid particles are transported as such, in particular by means of gravity.

[0003] The transfer of materials such as fluids may be required between different devices that are distinct from one another and are only temporarily connected to one another and / or between sub-units within a more complex machine.

[0004] These devices and machines can come from a wide variety of different technological applications. To name just a few: they can involve chemical processes, food processing, internal combustion engines, air supply, etc.

[0005] In some technical fields, there are increased requirements for the permeability of delivery tubes or hoses to certain substances. This may be related to the material or fluid (or certain components of the fluid) being transported in the tube or hose. However, it may also be related to certain substances in the surrounding environment that have to be prevented from entering the tube or hose.

[0006] An example of requiring low permeability for certain substances (or parts thereof) transported inside a tube or hose is chemistry. Here, toxic, flammable, explosive or other dangerous substances should not penetrate through the wall of the tube or shell. Another example of this requirement is the field of internal combustion engines, because they are widely used in fixed arrangements (power plants, emergency generators, etc.) or mobile applications (such as cars, trucks, buses, boats, ships or airplanes). Here, the fuel transported should not penetrate through the tube or hose, which is not only for safety reasons (no air-fuel mixture that may explode will be formed in the closed area where the tube / hose passes), but also to minimize the waste caused by the fuel penetrating through the wall of the tube or hose without doing useful work. Especially for mobile applications, relatively long downtimes often occur, during which a non-negligible amount of fuel may penetrate through the tube and hose.

[0007] An example of a situation in which environmental substances should be prevented from entering a tube or hose is food processing or the transport of highly sensitive substances. Here, the permeability of the tube or hose to (for example) oxygen may be problematic, since oxygen may cause the food to be processed to deteriorate or spoil prematurely. Obviously, this should be avoided.

[0008] Based on the importance of this problem, and also in view of the huge number of technical fields in which this problem is a problem, it is not surprising that a large number of solutions have been proposed in the past.

[0009] A first approach is to use a material for the outer shell of the tube or hose which exhibits a low permeability to the substance whose penetration into the tube / hose wall has to be avoided. An example for this is a standard metal tube. However, it is easy to understand that metal tubes do have a certain weight and a certain cost factor, which can be problematic. Furthermore, the flexibility of metal tubes is very limited, thus reducing the field of applicability of this approach.

[0010] When it comes to flexible hoses, the availability of suitable materials with regard to low permeability to certain substances is often limited, especially if cost aspects are also taken into account. In order to solve this problem, it has been proposed to use hoses with additional special layers, which exhibit particularly low permeability to the substance in question. This is often referred to in the prior art as a diffusion barrier.

[0011] US2018 / 371213A1 discloses a multilayer hose having a metal reinforcement layer, a rubber layer and a nylon cloth layer. The rubber layer provides adhesion to other layers. The rubber composition may include acrylonitrile butadiene rubber, styrene butadiene rubber, ethylene propylene diene rubber, 0.5-4.0 wt % of a vulcanizing agent, zinc oxide, carbon black, calcium carbonate, magnesium carbonate, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine and a melamine resin blend.

[0012] US2006 / 127619A1 discloses a multilayer hose comprising a rubber composition layer inserted between an inner layer and an outer layer and providing adhesion to the layers. The rubber composition may contain 20-65 wt% acrylonitrile butadiene rubber, 0.1-8 phr of a vulcanizing agent, 0.1-15 phr of triallyl cyanurate, amidine carbonate as a co-agent, 3-20 phr of zinc oxide or hydrotalcite as an acid acceptor, 5-250 phr of carbon black N990, 1-50 phr of a processing aid such as polyethylene glycol, and 0.5-10 phr of a tackifier resin.

[0013] US 6,037,025 A discloses a multilayer rubber hose comprising an inner tube inner layer, an inner tube outer layer and a reinforcing layer. The inner tube outer layer is formed by a rubber composition that provides adhesion to the other layers. The rubber composition may include acrylonitrile butadiene rubber, 0.1-3 phr of a vulcanizing agent, p-phenylenediamine, carbon black and zinc oxide.

[0014] Although this approach is successful, it also brings with it the problem that the base material of the tube (load-bearing sheath) and the material of the diffusion barrier (diffusion-reducing sheath), which are primarily used to handle the forces that occur, must adhere to each other well enough so that the corresponding layers do not delaminate from each other. This is a particular problem for hoses that are frequently subjected to bending, vibrations, pressure changes or other types of movements. Although solutions to this problem exist in the prior art, these solutions still show certain drawbacks, such as requiring expensive materials, requiring very complex connection technology, or, despite all efforts, the corresponding layers delaminate prematurely, resulting in the need to replace the hose after relatively short time intervals.

[0015] In order to increase the joint strength and the life of the connection between the diffusion barrier and the load-bearing sheath, it has been proposed to use a special intermediate layer (such as glue) for joining the two layers together.

[0016] Although this approach has led to undeniable improvements, there is still room for improvement, particularly in terms of cost efficiency, life span and connection strength. In particular, it is still desirable to use cost-effective and / or very functional materials for the load-bearing sheath and / or diffusion barrier. As another result, the choice of material for these sheaths has an impact on the remaining possible materials for the adhesion-promoting layer. Functionality in this context may be related to low permeability and high stability. Summary of the invention

[0017] Therefore, the purpose of the present disclosure is to propose a multi-layer tube or hose, which includes a plurality of coaxially arranged sheaths, wherein the coaxially arranged sheaths are joined together, wherein the multi-layer tube or hose includes at least: a load-bearing sheath, a diffusion reducing sheath and an adhesion promoting layer, wherein the adhesion promoting layer is arranged between the load-bearing sheath and the diffusion reducing sheath and increases the bonding force between the load-bearing sheath and the diffusion reducing sheath, and is improved relative to the multi-layer tubes or hoses known in the prior art.

[0018] This object is achieved according to a multilayer tube or hose according to claim 1 .

[0019] A multilayer tube or hose is proposed, which includes a plurality of coaxially arranged sheaths, wherein the coaxially arranged sheaths are joined together. The multilayer tube or hose includes at least a load-bearing sheath; a diffusion-reducing sheath; and an adhesion-promoting layer, which is arranged between the load-bearing sheath and the diffusion-reducing sheath and increases the joining force between the load-bearing sheath and the diffusion-reducing sheath.

[0020] The adhesion promoting layer comprises a mixture of:

[0021] 65 to 85 parts of acrylonitrile butadiene rubber,

[0022] 15 to 35 parts of styrene butadiene rubber,

[0023] 75 to 125 parts of carbon black N990,

[0024] 30 to 100 parts of calcium magnesium carbonate,

[0025] 5 to 15 parts of zinc oxide,

[0026] 5 to 20 parts of magnesium aluminum hydroxycarbonate,

[0027] 25 to 125 parts of resin package blend,

[0028] 2 to 10 parts of N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine,

[0029] 5 to 15 parts of triallyl cyanurate, and

[0030] 0.5 to 5 parts of vulcanizing agent.

[0031] In this context, when discussing "parts", in particular, parts by weight, parts by number or parts by volume can be considered. "Parts by weight" can be understood in the sense that one part is equal to one mass unit (wherein the mass unit can be selected according to current needs and can be, for example, 1 g, 1 kg, 1 ton, etc.). Similarly, "parts by volume" can be understood in the sense that one part is equal to one volume unit (wherein the volume unit can be selected according to current needs and can be, for example, 1 L, 1 m 3The term "parts by quantity" is used in a manner that is understood in a manner that is not limited to a certain number of molecules (e.g., one part can be equivalent to 1 mol, etc.). "Parts by quantity" can relate to a certain number of molecules (e.g., one part can be equivalent to 1 mol, etc.). It should be understood that when the parts are added together, 100 parts are not usually obtained in the end, especially when (some of) the currently disclosed formulations are used. Therefore, "parts" in this context are generally different from percentages. However, percentages can be easily calculated. To do this, all parts of the individual ingredients must be added together to obtain the "total parts" number. The parts of the corresponding ingredients can then be divided by the "total parts" to obtain the percentage number. Depending on the selected "part type", the percentage number will be the corresponding percentage number. Just to give an example: if parts by weight are selected, after performing the calculations mentioned, the weight percentage (wt%) will be obtained in the end.

[0032] The material mixture of the adhesion promoting layer can be understood as comprising the mentioned materials. However, it can also be understood as being composed (substantially / only) of the mentioned materials. Including can be understood in a way that additional materials can be added. Those additional materials can be basically materials that have basically no significant effect on the resulting adhesion promoting layer (especially with respect to the adhesion promoting effect). For example, these can be fillers. Including, and in particular "substantially composed of...", can also be understood in a way that can contain several (very small) amounts of additional materials. Those (very small) amounts can be residual substances, and the removal of these residual substances may be too time-consuming or costly. In this regard, an extreme case will be impurities (wherein in the case of impurities, even the wording "consisting only of..." can be used, even from the perspective of a technician in the field).

[0033] For some or each of the aforementioned substances, the aforementioned numerals may also be selected from narrower intervals. In particular, 65 to 85 parts of acrylonitrile butadiene rubber may preferably be narrowed to 70 to 80 parts of acrylonitrile butadiene rubber, and even more preferably narrowed to 72 to 78 parts of acrylonitrile butadiene rubber, most preferably narrowed to 75 parts of acrylonitrile butadiene rubber. It should be noted that the upper and lower limits of different wide intervals may be combined, for example, meaning that the interval of 65 to 80 parts or 75 to 80 parts of acrylonitrile butadiene rubber also should be considered as clearly disclosed. This statement may be applicable to intervals of different sizes of all series mentioned in the present disclosure. For completeness, it should be mentioned that acrylonitrile butadiene rubber is often mentioned with its abbreviation NBR.

[0034] Thus, 15 to 35 parts of styrene butadiene rubber may preferably be narrowed to 20 to 33 parts of styrene butadiene rubber, more preferably 23 to 32 parts of styrene butadiene rubber, most preferably 25 to 30 parts of styrene butadiene rubber. For the sake of completeness, it should be mentioned that styrene butadiene rubber is often referred to by its abbreviation SBR.

[0035] It should be noted that acrylonitrile butadiene rubber and / or styrene butadiene rubber can be considered as the elastomeric component (elastomer) constituting the above-mentioned mixture. However, it may or may not be possible to add additional elastomeric components and / or consider other materials from the above-mentioned mixture as elastomeric components.

[0036] 75 to 125 parts of carbon black N990 can preferably be narrowed to 80 to 120 parts of carbon black N990, more preferably to 85 to 115 parts of carbon black N990, even more preferably to 90 to 110 parts of carbon black N990, still more preferably to 95 to 105 parts of carbon black N990, most preferably to 100 parts of carbon black N990. It should be noted that carbon black should be considered to conform to the ASTM definition (ASTM = American Society for Testing and Materials) on the date of filing of this application. For subsequent applications, claiming an earlier priority, of course the priority date of the corresponding application should be considered as the effective date.

[0037] 30 to 100 parts of calcium magnesium carbonate may preferably be narrowed to 35 to 80 parts of calcium magnesium carbonate, more preferably to 40 to 60 parts of calcium magnesium carbonate, even more preferably to 42 to 50 parts of calcium magnesium carbonate, most preferably to 45 parts of calcium magnesium carbonate.

[0038] 5 to 15 parts of zinc oxide may preferably be narrowed to 7 to 13 parts of zinc oxide, more preferably to 9 to 11 parts of zinc oxide, and most preferably to 10 parts of zinc oxide.

[0039] 5 to 20 parts of magnesium aluminum hydroxycarbonate can preferably be narrowed to 7 to 15 parts of magnesium aluminum hydroxycarbonate, even more preferably to 9 to 12 parts of magnesium aluminum hydroxycarbonate, most preferably to 10 parts of magnesium aluminum hydroxycarbonate. For the sake of completeness, it should be mentioned that magnesium aluminum hydroxycarbonate is often referred to by its abbreviation hydrotalcite.

[0040] The 25 to 125 parts of resin pack blend may preferably be narrowed to 30 to 110 parts of resin pack blend, more preferably to 35 to 90 parts of resin pack blend, even more preferably to 40 to 70 parts of resin pack blend, still more preferably to 42 to 50 parts of resin pack blend, and most preferably to 46 parts of resin pack blend.

[0041] 2 to 10 parts of N-(1.3-dimethylbutyl)-N'-phenyl-p-phenylenediamine can be preferably narrowed to 2.5 to 5 parts of N-(1.3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, most preferably narrowed to 3 parts of N-(1.3-dimethylbutyl)-N'-phenyl-p-phenylenediamine.

[0042] 5 to 15 parts of triallyl cyanurate can preferably be narrowed to 2 to 13 parts of triallyl cyanurate, more preferably 3 to 10 parts of triallyl cyanurate, most preferably 4 parts of triallyl cyanurate. For the sake of completeness, it should be mentioned that triallyl cyanurate is often referred to by its abbreviation TAC-50.

[0043] Furthermore, 0.5 to 5 parts of the vulcanizing agent may be preferably narrowed to 1 to 3 parts of the vulcanizing agent, more preferably to 1.5 to 2 parts of the vulcanizing agent.

[0044] The inventors have found that the described mixture will lead to a particularly strong and durable bond between the diffusion reducing sheath and the adhesion promoting layer of a multilayer tube or hose and between the adhesion promoting layer and the load-bearing sheath. This in turn will lead to a particularly strong and durable bond between the diffusion reducing sheath and the load-bearing sheath.

[0045] In general, a tube or hose is considered to be an elongated device with a hollow interior (inner channel) for conducting fluids (gas, liquid, mixtures of gas and liquid, supercritical fluids (wherein a distinction can no longer be made between gas and liquid)) and / or for conveying materials, in particular granular materials (such as grain, gravel, granules, cement, fertilizers, fly ash, glass, carbon residues from steel mills, rock salt, etc.). In the case of mainly conveying fluids, it is possible that the fluid can contain a certain amount of solid particles (essentially conveying fumes and / or suspensions). If mainly solid particles are conveyed, or in the case of only ambient fluid in the tube or hose (so that a vacuum does not have to be achieved; or in the case of a fluid in the form of a protective atmosphere), they can be conveyed together with the fluid flow (wherein, for example, the movement of the solid particles is caused or supported by the fluid). In general, the tube or hose comprises at least one inner channel (hollow interior), possibly even a plurality of inner channels. Often, the tube or hose has a substantially circular cross section, in particular with regard to pressure and mechanical stability. However, different cross sections are also possible, such as oval or polygonal shapes (possibly with rounded corners). Typically, if the flexibility of the device is relatively low, then we talk about a tube, and if the flexibility of the device is relatively high, then we talk about a hose. The different layers of a multilayer tube or hose are usually arranged in a coaxial manner around the longitudinal axis of the multilayer tube or hose, i.e. radially following each other. Typically, these layers are essentially rotationally symmetrical (or may show n-fold symmetry). This does not exclude the possibility that there may be variations in thickness even in the circumferential direction or even gaps in one or more sheaths. A particular example of such a gap is a reinforcing fabric, in which there is no rotational symmetry in a mathematical sense, because the fabric is constructed in the form of an arrangement of individual filaments of finite size (which show a certain spacing between each other). However, even so, typically there is usually "what can be said to be" rotational symmetry.

[0046] As mentioned above (and hereinafter), different sheaths and layers are generally different in material composition and / or thickness. This generally results in different mechanical properties, such as different strengths, etc. It should be noted that the load-bearing sheath will inevitably provide a fluid flow barrier at least to a certain extent. Therefore, in a sense, the load-bearing sheath will generally also serve as a certain diffusion reduction sheath. Nevertheless, the main purpose of the load-bearing sheath is generally to support the mechanical integrity of the tube or hose. Therefore, materials, thickness and other design considerations are selected in a manner to achieve the main purpose of the load-bearing sheath. Similarly, the diffusion reduction sheath will typically contribute to the mechanical strength of the corresponding tube or hose to a certain extent. Nevertheless, the main purpose of the diffusion reduction sheath (diffusion barrier) is to reduce the diffusion of the corresponding substance in question through the diffusion reduction sheath, and therefore the diffusion through the wall of the multilayer tube or hose.

[0047] The adhesion promoting layer can show various thicknesses, so that the adhesion promoting layer can also be regarded as an adhesion promoting sheath. The main purpose of the adhesion promoting layer is to ensure a firm and lasting connection between the adjacent diffusion reducing sheath and the load-bearing sheath. In particular, the risk of delamination of the diffusion reducing sheath and the load-bearing sheath should be reduced and especially postponed (i.e., resulting in a long life of the resulting multilayer tube or hose). As previously described, the adhesion promoting layer can also show certain load-bearing performance and / or diffusion reducing performance. Nevertheless, its main purpose is to increase the bonding force and / or increase the life of the corresponding bonding. It should be noted that the material of the adhesion promoting layer can even invade the adjacent surface of the adjacent sheath to a certain extent, in particular the adjacent surface of the adjacent diffusion reducing sheath and / or the adjacent load-bearing sheath. This can be in the form of nails or dendrites of the material of the adhesion promoting layer, which extend into the cavity of the adjacent sheath, in particular the adjacent anti-wear sheath and / or the adjacent load-bearing sheath (or vice versa). Such an invasion typically leads to an increased bonding force. In addition, additionally or alternatively, a certain material mixing can occur between the material of the adhesion promoting layer and the material of the adjacent layer / sheath. It is even possible that the adhesion promoting layer leads to partial intrusion / mixing of adjacent sheaths, in particular the load-bearing sheath and the diffusion reducing sheath.

[0048] Regarding the aforementioned acrylonitrile butadiene rubber, it preferably contains 18 to 28% by weight of acrylonitrile, and / or, the styrene butadiene rubber contains 10 to 25% by weight of styrene, wherein the butadiene part is preferably composed of 60 to 70% by weight of trans-1,4 configuration, 15 to 20% by weight of cis-1,4 configuration, and the balance of 1,2 configuration, especially according to 100 parts of the elastomer containing acrylonitrile butadiene rubber and styrene butadiene rubber.

[0049] Similar to the "basic" mixture of aforementioned adhesion promoting layer, can select narrower corresponding interval range.Especially, the acrylonitrile of 18 to 28 weight % in acrylonitrile-butadiene rubber can preferably be narrowed to the acrylonitrile of 20 to 27 weight %, more preferably narrowed to the acrylonitrile of 22 to 26 weight %, even more preferably narrowed to the acrylonitrile of 24 to 25 weight %.In addition or alternatively, the styrene of 10 to 25 weight % in styrene-butadiene rubber can preferably be narrowed to the styrene of 15 to 20 weight %, more preferably narrowed to the styrene of 17 to 18 weight %.Even further, the butadiene part can more preferably be by the trans-1 of 62 to 68 weight %, 4 configuration and / or the cis-1 of 17 to 18 weight %, 1,2 configuration of surplus forms, particularly according to 100 parts of the elastomers that comprise acrylonitrile-butadiene rubber and styrene-butadiene rubber.

[0050] According to a preferred embodiment, the resin package blend comprises 5 to 25 parts of hexa(methoxymethyl)melamine liquid resin; 5 to 15 parts of self-curing modified phenolic resin component; 5 to 25 parts of aliphatic-aromatic soft resin; 5 to 25 parts of benzene-1,3-diphenol binder; 5 to 25 parts of aromatic hydrocarbon resin component, especially elastomers containing acrylonitrile butadiene rubber and styrene butadiene rubber according to 100 parts. More preferably, the resin package blend comprises 10 to 20 parts of hexa(methoxymethyl)melamine liquid resin and / or 7 to 13 parts of self-curing modified phenolic resin component and / or 10 to 20 parts of aliphatic-aromatic soft resin and / or 10 to 20 parts of benzene-1,3-diphenol binder and / or 10 to 20 parts of aromatic hydrocarbon resin component, especially elastomers containing acrylonitrile butadiene rubber and styrene butadiene rubber according to 100 parts. The "and / or" relationship in the preceding list is to be understood as a combination with the earlier list as much as possible, so that, for example, 5 to 25 parts of hexa(methoxymethyl)melamine liquid resin (from the scope of the "broader list") can be combined with 7 to 13 parts of self-curing modified phenolic resin components (from the scope of the "narrower list"), etc., wherein such combinations are to be regarded as explicitly disclosed. For the sake of completeness only, it is to be pointed out that benzene-1,3-diol is also known by the name resorcinol.

[0051] Although a wide range of vulcanizing agents (possibly even mixtures of various vulcanizing agents) can be envisaged as vulcanizing agents are known in the prior art, it is suggested that the vulcanizing agent comprises dicumyl peroxide (wherein dicumyl peroxide may be substantially the only vulcanizing agent, but where other vulcanizing agents may also be used). Preliminary experiments have shown that particularly good curing of the remaining ingredients can be achieved when dicumyl peroxide is used at least in part.

[0052] According to another embodiment, it is suggested that the diffusion reducing sheath comprises a polyamide plastic material, preferably a poly[azanediyl(1-oxohexane-1,6-diyl)] or a poly(azanediyladipoylazanediylhexane-1,6-diyl) material. Again, in the first experiments, when using the above-mentioned adhesion promoting layer, these materials showed good diffusion reducing properties and resulted in good bonding with the load-bearing sheath. For the sake of completeness, it should be pointed out that poly[azanediyl(1-oxohexane-1,6-diyl)] is sometimes referred to by the name polyamide 6, while poly(azanediyladipoylazanediylhexane-1,6-diyl) is sometimes referred to by the name polyamide 66.

[0053] Preferably, at least one of the load-bearing sheaths comprises acrylonitrile butadiene rubber, styrene butadiene rubber and / or ethylene propylene diene rubber.

[0054] Even further, it is suggested that the multilayer tube or hose comprises at least a second load-bearing sheath, wherein the diffusion-reducing sheath is preferably embedded between at least two load-bearing sheaths. In this way, the mechanical strength of the resulting multilayer tube or hose can be even further improved. In addition, using this design, the diffusion-reducing sheath can be prevented from directly contacting the fluid to be transported in the tube or hose. It should be noted that the main function of the diffusion-reducing sheath is to reduce diffusion, and therefore the diffusion-reducing sheath is relatively easy to wear or be damaged when it is in mechanical contact with the fluid (material) to be transmitted through the tube or hose or when it is exposed to external influences. Therefore, the life of the multilayer tube or hose can be increased, typically even significantly increased.

[0055] If multilayer tube or hose at least comprise low combustible layer, particularly low combustible jacket or coating, then another preferred embodiment of multilayer tube or hose can be realized, and described low combustible layer preferably comprises acrylonitrile-butadiene rubber and / or polyvinyl chloride (or (basically) be made up of acrylonitrile-butadiene rubber and / or polyvinyl chloride).Like this, safety problem can be solved, particularly when tube or hose are associated with flammable fluid or environment and are used.The example in this respect can be motor vehicle (for example automobile, bus, truck, ship, railway, tram or airplane) or fixed internal combustion engine device (it can be found in power plant or about emergency generator).Here (and not only here), there is the risk of fire that increases.Therefore, the low combustibility of corresponding multilayer tube or hose can prove to improve safety, or may even be necessary in some jurisdictions.Only as a side note, the material that is different from acrylonitrile-butadiene rubber and / or polyvinyl chloride can be used alternatively or additionally.

[0056] A preferred embodiment of the multilayer tube or hose can be achieved if the multilayer tube or hose comprises at least strength-reinforcing means, in particular a strength-reinforcing fabric, more preferably a crimped or non-crimped fabric. In this way, the mechanical strength of the resulting multilayer tube or hose can typically be significantly increased without unduly increasing the size, cost and / or weight of the resulting multilayer tube or hose. As threads for the fabric, in particular polyester textile yarns, carbon fibers, aramid fibers, nylon filaments, etc. can advantageously be used.

[0057] An even further preferred embodiment can be achieved if the multilayer tube or hose comprises at least an anti-wear sheath, in particular on the inner side of the multilayer tube or hose. In this way, the life of the multilayer tube or hose can be advantageously increased, typically even significantly increased. This is particularly advantageous if solid materials are to be conveyed (together with the fluid, or even possibly "as is"). This will typically cause severe wear of the inner surface of the tube or hose, which can advantageously be reduced by the anti-wear material. Preferably, the anti-wear sheath comprises (or (essentially consists of) a thermoplastic polyurethane material. Preliminary experiments have shown that this results in a particularly wear-resistant multilayer tube or hose, but which is cost-effective, flexible and lightweight.

[0058] Preferably, the multilayer tube or hose comprises at least a second type of adhesion promoting sheath between the anti-wear sheath and at least one adjacent sheath, preferably at least one adjacent load-bearing sheath. Similar to the aforementioned adhesion promoting sheath (of the first type) between at least one load-bearing sheath and the diffusion reducing sheath, the bond between the anti-wear sheath and the adjacent (load-bearing) sheath may become more secure and / or may exhibit an increased lifetime, in particular an increased time before delineation occurs.

[0059] Preferably, the second type of adhesion promoting sheath comprises a mixture of:

[0060] 55 to 85 parts of acrylonitrile butadiene rubber,

[0061] 5 to 25 parts of styrene butadiene rubber,

[0062] 5 to 25 parts of EPDM,

[0063] 75 to 125 parts of carbon black N990,

[0064] 30 to 90 parts of calcium magnesium carbonate,

[0065] 5 to 15 parts of zinc oxide,

[0066] 5 to 25 parts of aluminum magnesium hydroxycarbonate,

[0067] 20 to 95 parts of the resin package blend,

[0068] 2 to 10 parts of N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine,

[0069] 5 to 15 parts of triallyl cyanurate, and

[0070] 0.5 to 5 parts of vulcanizing agent.

[0071] This mixture has proven to be particularly well suited for the present purpose of joining together the wear-resistant sheath and the load-bearing sheath.

[0072] The material contents defined by the indicated ranges may also be narrowed according to previous suggestions.

[0073] However, for the acrylonitrile butadiene rubber, the range of 55 to 85 parts of the acrylonitrile butadiene rubber mentioned may preferably be narrowed to 60 to 80 parts of the acrylonitrile butadiene rubber.

[0074] Thus, 5 to 25 parts of styrene butadiene rubber may preferably be narrowed to 10 to 20 parts of styrene butadiene rubber.

[0075] The (emerging) EPDM rubber may preferably contain a (narrower) range of 10 to 20 parts of EPDM rubber, more preferably 12 to 15 parts of EPDM rubber.

[0076] Even further, in the present context, 30 to 90 parts of calcium magnesium carbonate may preferably be narrowed to 35 to 80 parts of calcium magnesium carbonate, more preferably to 40 to 60 parts of calcium magnesium carbonate, even more preferably to 42 to 50 parts of calcium magnesium carbonate, most preferably to 45 parts of calcium magnesium carbonate.

[0077] 5 to 25 parts of magnesium aluminum hydroxycarbonate can preferably be narrowed to 7 to 20 parts of magnesium aluminum hydroxycarbonate, more preferably to 9 to 15 parts of magnesium aluminum hydroxycarbonate, most preferably to 10 parts of magnesium aluminum hydroxycarbonate. For the sake of completeness, it should be mentioned that magnesium aluminum hydroxycarbonate is often referred to by its abbreviation hydrotalcite.

[0078] Furthermore, in the present context, 20 to 95 parts of the resin pack blend may preferably be narrowed to 30 to 85 parts of the resin pack blend, more preferably to 35 to 90 parts of the resin pack blend, even more preferably to 40 to 70 parts of the resin pack blend, still more preferably to 42 to 50 parts of the resin pack blend, and most preferably to 46 parts of the resin pack blend.

[0079] With regard to possible compositions of the acrylonitrile butadiene rubber, the styrene butadiene rubber, the resin package blend and / or the vulcanizing agent, reference is made to the previous description.

[0080] Furthermore, the EPDM rubber may contain 44 to 85% by weight of ethylene and 2.8 to 11% by weight of ethylidene norbornene, in particular per 100 parts of the elastomer containing acrylonitrile butadiene rubber and styrene butadiene rubber. This can be narrowed to 60 to 70% by weight of ethylene and / or 5 to 8% by weight of ethylidene norbornene.

[0081] Just for the sake of completeness, it should be mentioned that - although it is preferred to arrange at least one load-bearing sheath between the diffusion-reducing sheath and the anti-wear sheath, it is also possible that a direct / adjacent placement and joining of the diffusion-reducing sheath and the anti-wear sheath is possible. An intermediate adhesion-promoting layer between the diffusion-reducing sheath and the anti-wear sheath may or may not be present. BRIEF DESCRIPTION OF THE DRAWINGS

[0082] Further advantages, features and objects of the present invention will become apparent from the following detailed description of the invention in conjunction with the associated drawings, in which:

[0083] Figure 1 : A schematic perspective view of a cutaway portion of a first possible embodiment of a multilayer hose including a diffusion reducing sheath, a plurality of load-bearing sheaths, and an adhesion promoting layer according to the present disclosure;

[0084] Figure 2 : Schematic cross-sectional view of a second possible embodiment of a multilayer hose, in particular including an anti-wear sheath and a diffusion reducing sheath. DETAILED DESCRIPTION

[0085] Figure 1 A first possible embodiment of a multilayer hose 1 according to the invention is shown. The multilayer hose 1 is currently designed as a first fire-resistant fuel hose (gasoline, oil, diesel, etc.) for vehicles. Therefore, the multilayer hose 1 according to the first embodiment shows additional layers and / or jackets compared to the so-called "minimal design".

[0086] As in Figure 1 As can be seen in the figure, the multilayer hose 1 comprises a first and a second load-bearing sheath 2, 6. The load-bearing sheaths 2, 6 are made of standard hose rubber materials, which are known in the prior art. Currently, the two sheaths 2, 6 are made of NBR rubber, SBR rubber or a mixture thereof (NBR = acrylonitrile butadiene rubber; SBR = styrene butadiene rubber). However, at least in principle, different material compositions are also conceivable.

[0087] Furthermore, a diffusion reduction sheath 4 (diffusion barrier) is arranged between the two load-bearing sheaths 2, 6. For the diffusion reduction sheath 4, the material polyamide 6 has currently been selected. This material exhibits a favorable diffusion resistance to the passage of common fuels.

[0088] In order to provide sufficient stability of the resulting multilayer hose 1, and depending on the different materials / material compositions of the load-bearing sheaths 2, 6 and the diffusion-reducing sheath 4, adhesion-promoting layers 3, 5 have to be provided respectively between the first inner load-bearing sheath 2 and the diffusion-reducing sheath 4 and between the diffusion-reducing sheath 4 and the second outer load-bearing sheath 6. The materials that can be chosen for these adhesion-promoting layers 3, 5 have to be a compromise between secure bonding, long life (especially with respect to delamination of the sheaths 2, 4, 6 bonded together), manufacturing practicality, material costs, etc.

[0089] Currently, a material composition for the first adhesion promoting layer 3 and the second adhesion promoting layer 5 is proposed, wherein the corresponding layers include a material mixture comprising: 65 to 85 parts of acrylonitrile butadiene rubber, 15 to 35 parts of styrene butadiene rubber, 75 to 125 parts of carbon black N990, 30 to 100 parts of calcium magnesium carbonate, 5 to 15 parts of zinc oxide, 5 to 20 parts of hydroxy magnesium aluminum carbonate, 25 to 125 parts of resin package blend, 2 to 10 parts of N-(1.3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, 5 to 15 parts of triallyl cyanurate and 0.5 to 5 parts of vulcanizing agent.

[0090] It is to be noted that it is possible that the first adhesion promoting layer 3 and the second adhesion promoting layer 5 exhibit the same material mixture. Nevertheless, it is also possible that the first and second adhesion promoting layers 3, 5 do exhibit different material compositions.

[0091] Experimental results using two specific examples of material mixtures according to the present disclosure, as well as measured parameters of certain physical properties, are shown in Table 1. From Table 1 it is evident that the use of the currently proposed adhesion promoting layers 3, 5 shows improved properties of the resulting multilayer hose 1.

[0092] In particular, in the experimental setup, the daily permeation rate of the fuel through the wall of a hose with a diameter of 12.7 mm and a length of 350 mm was measured as

[0093] Table 1

[0094]

[0095]

[0096] In order to further increase the mechanical resistance of the multilayer hose 1, an additional strength-reinforcing sheath 7 is provided. Currently, the strength-reinforcing sheath 7 comprises a fabric 9 of textile yarns, wherein the yarns are currently made of polyester textile yarns. The reinforcing fabric 9 is embedded in an elastomeric matrix, wherein the material composition can be selected to be the same and / or different from that in the first load-bearing sheath 2 and in particular in the second load-bearing sheath 6. In particular, the elastomeric matrix can include acrylonitrile butadiene rubber, styrene butadiene rubber and / or ethylene propylene diene rubber.

[0097] In addition, for the additional fire resistance of the multilayer hose 1, a low-flammability sheath 8 is provided as an outer layer, coating or sheath. Currently, the low-flammability sheath 8 comprises a mixture of nitrile rubber and polyvinyl chloride. This material mixture is known in the prior art to be relatively flame-resistant.

[0098] Due to the low diffusion of fuel through the multilayer hose 1 and the reduced flammability due to the low flammability jacket 8, the currently proposed multilayer hose 1 specifically meets the new marine fuel hose standards SAE J1 527 category A1-15 and ISO7840, respectively, which will come into effect on January 1, 2023. Obviously, this is an advantage.

[0099] Just for the sake of completeness, it is mentioned that the multilayer hose 1 shows an elongated design with an axial, longitudinally arranged central axis. The different jackets and layers of the wall of the multilayer hose 1 are arranged in a coaxial manner and are placed adjacent to each other (and joined together) in the following order (from inside to outside, as seen in radial direction): first load-bearing jacket 2, first adhesion promoting layer 3, diffusion reducing jacket 4, second adhesion promoting layer 5, second load-bearing jacket 6, strength-reinforcing jacket 7 and low-flammability jacket 8.

[0100] Figure 2 A second possible embodiment of a multilayer hose 10 is shown in schematic cross-section. Note that the thickness of the individual jackets and layers are exaggerated relative to the diameter of the inner fluid conduit 11. Furthermore, the thickness of the individual jackets and layers will typically also vary between individual jackets and layers.

[0101] The second embodiment of the multilayer hose 10 shown here is similar to the Figure 1 The first embodiment of the multilayer hose 1 shown is somewhat similar. That is, the outer portion of the hose sheath according to the second embodiment of the multilayer hose 10 is similar to the outer portion of the hose sheath according to Figure 1The design of the first embodiment of the multilayer hose 1 is equivalent. That is, from the outside towards the fluid channel 11, the following sheaths and layers are arranged adjacent to each other and joined together: the low-flammability sheath 8 is followed by the strength-enhancing sheath 7, the second load-bearing sheath 6, the second adhesion-promoting layer 5, the diffusion-reducing sheath 4, the first adhesion-promoting layer 3 and the first load-bearing sheath 2. For the sake of brevity, reference is made to the previous description. For the sake of brevity, reference is made to the previous description. For the sake of completeness only, it is mentioned that in Figure 2 In the cross-sectional view of FIG. 7 , the various threads of the polyester spun yarn 9 inside the strength reinforcing sheath 7 can be seen.

[0102] In addition to the first embodiment of the multilayer hose 1, the second embodiment of the multilayer hose 10 shown here additionally includes an inner anti-wear jacket 12 adjacent to the inner fluid channel 11. Currently, the anti-wear jacket 12 is essentially composed of a thermoplastic polyurethane material. Such materials are known in the prior art to have very good wear resistance, while also combining various other advantages, such as flexibility, low cost, etc.

[0103] In order to provide a good bond between the wear resistant sheath 12 and the first load bearing sheath 2, a further adhesion promoting layer 13 of a different composition is provided. It is to be noted that generally the composition of the second type adhesion promoting layer 13 has to be different from the composition of the first and second adhesion promoting layers 3, 5, since different materials have to be bonded together depending on the different material compositions of the sheath 13 and the sheaths 3, 5.

[0104] Currently, a material composition is used for the second type of adhesion promoting layer 13, which includes: 55 to 85 parts of acrylonitrile butadiene rubber; 5 to 25 parts of styrene butadiene rubber; 5 to 25 parts of ethylene propylene rubber; 75 to 125 parts of carbon black N990; 30 to 90 parts of calcium magnesium carbonate; 5 to 15 parts of zinc oxide; 5 to 25 parts of hydroxy magnesium aluminum carbonate; 20 to 95 parts of resin package blend; 2 to 10 parts of N-(1.3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, 5 to 15 parts of triallyl cyanurate; and 0.5 to 5 parts of vulcanizing agent.

[0105] In detail, in Table 2, three different material compositions are explicitly shown for which experiments have been carried out. Table 2 also indicates certain measured parameters.

[0106] Table 2

[0107]

[0108]

[0109] Just for the sake of completeness, it is mentioned that the multilayer hose 10 according to the second embodiment shows an elongated design with an axial, longitudinally arranged central axis. The different jackets and layers of the wall of the multilayer hose 10 are arranged in a coaxial manner and are placed adjacent to each other (and joined together) in the following order (from inside to outside, as seen in radial direction): anti-wear jacket 12, additional adhesion promoting layer 13 of different composition, first load-bearing jacket 2, first adhesion promoting layer 3, diffusion reducing jacket 4, second adhesion promoting layer 5, second load-bearing jacket 6, strength-reinforcing jacket 7 and low-flammability jacket 8.

[0110] Additional information may be obtained from a parallely filed patent application filed by the same applicant on the same date under applicant's reference number DAN 2204EP. The disclosure of that application is to be deemed to be fully incorporated in the present application.

[0111] It is noted that single or multiple features of the presently disclosed detailed embodiments may be used in combination with the general description of the present disclosure.

[0112] Reference Mark List

[0113] 1. Multilayer hose (first embodiment)

[0114] 2. The first load-bearing sheath

[0115] 3. First adhesion promoting layer

[0116] 4. Diffusion reduction sheath

[0117] 5. Second adhesion promoting layer

[0118] 6. Second load-bearing sheath

[0119] 7.Strength enhanced sheath

[0120] 8. Low flammability sheath

[0121] 9. Polyester yarn

[0122] 10. Multilayer hose (second embodiment)

[0123] 11. Fluid Channel

[0124] 12. Anti-wear sheath

[0125] 13. Adhesion promoting layers of different compositions

Claims

1. A multi-layer tube or hose (1, 10), comprising a plurality of coaxially arranged sheaths (2, 3, 4, 5, 6, 7, 8, 12, 13), wherein the coaxially arranged sheaths (2, 3, 4, 5, 6, 7, 8, 12, 13) are joined together, and the multi-layer tube or hose (1, 10) comprises at least: Load-bearing sheath (2, 6), a diffusion reducing sheath (4), and an adhesion promoting layer (3, 5) which is arranged between the load-bearing sheath (2, 6) and the diffusion-reducing sheath (4) and which increases the joining force between the load-bearing sheath (2, 6) and the diffusion-reducing sheath (4), Characterized in that the adhesion promoting layer (3, 5) comprises a mixture of: 65 to 85 parts by weight of acrylonitrile butadiene rubber, 15 to 35 parts by weight of styrene butadiene rubber, 75 to 125 parts by weight of carbon black N990, 5 to 15 parts by weight of zinc oxide, 2 to 10 parts by weight of N-(1.3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, 0.5 to 5 parts by weight of a vulcanizing agent, and 25 to 125 parts by weight of a resin package blend, wherein the resin package blend comprises 5 to 25 parts by weight of a hexa(methoxymethyl)melamine liquid resin; 5 to 15 parts by weight of a self-curing modified phenolic resin component; 5 to 25 parts by weight of an aliphatic-aromatic soft resin; 5 to 25 parts by weight of a benzene-1,3-diphenol binder; 5 to 25 parts by weight of an aromatic hydrocarbon resin component, particularly an elastomer comprising acrylonitrile butadiene rubber and styrene butadiene rubber, based on 100 parts by weight, It is characterized in that 5 to 15 parts by weight of triallyl cyanurate, 30 to 100 parts by weight of calcium magnesium carbonate, and 5 to 20 parts by weight of magnesium aluminum hydroxycarbonate.

2. The multilayer tube or hose (1, 10) according to claim 1, characterized in that The acrylonitrile butadiene rubber contains 18 to 28% by weight of acrylonitrile and / or the styrene butadiene rubber contains 10 to 25% by weight of styrene, wherein the butadiene part is preferably composed of 60 to 70% by weight of trans-1,4 configuration, 15 to 20% by weight of cis-1,4 configuration, and the remainder of 1,2 configuration, especially based on 100 parts of the elastomer containing acrylonitrile butadiene rubber and styrene butadiene rubber.

3. The multilayer tube or hose (1, 10) according to any one of the preceding claims, characterized in that The vulcanizing agent includes dicumyl peroxide.

4. The multilayer tube or hose (1, 10) according to any one of the preceding claims, characterized in that The diffusion reducing sheath (4) comprises a polyamide plastic material, preferably a poly[azanediyl(1-oxohexane-1,6-diyl)] or poly(azanediyladipylazanediylhexane-1,6-diyl) material.

5. The multilayer tube or hose (1, 10) according to any one of the preceding claims, characterized in that The at least one load-bearing sheath (2, 6) comprises acrylonitrile butadiene rubber, styrene butadiene rubber and / or ethylene propylene diene rubber.

6. A multilayer tube or hose (1, 10) according to any one of the preceding claims, characterized in that at least A second load-bearing sheath (2, 6), wherein the diffusion-reducing sheath (4) is preferably embedded between at least two load-bearing sheaths (2, 6).

7. A multilayer tube or hose (1, 10) according to any one of the preceding claims, characterized in that at least A low flammability layer (8), in particular a low flammability jacket or coating (8), the low flammability layer (8) preferably comprises nitrile rubber and / or polyvinyl chloride.

8. A multilayer tube or hose (1, 10) according to any of the preceding claims, characterised by at least a strength-reinforcing means (7), in particular a strength-reinforcing fabric (9), more preferably a crimped or non-crimped fabric.

9. A multilayer tube or hose (1, 10) according to any one of the preceding claims, characterized in that at least An anti-wear sheath (12), in particular on the inner side of the multi-layer sleeve or hose (10), wherein the anti-wear sheath (12) preferably comprises a thermoplastic polyurethane material.

10. Multilayer tube or hose (1, 10) according to claim 9, characterized by at least a second type of adhesion promoting sheath (13) between the wear resistant sheath (12) and the at least one adjacent sheath (2), preferably the at least one adjacent load-bearing sheath (2).

11. The multilayer tube or hose (1, 10) according to claim 10, characterized in that The second type of adhesion promoting sheath (13) comprises a mixture of: 55 to 85 parts by weight of acrylonitrile butadiene rubber, 5 to 25 parts by weight of styrene butadiene rubber, 5 to 25 parts by weight of EPDM rubber, 75 to 125 parts by weight of carbon black N990, 30 to 90 parts by weight of calcium magnesium carbonate, 5 to 15 parts by weight of zinc oxide, 5 to 25 parts by weight of aluminum magnesium hydroxycarbonate, 2 to 10 parts by weight of N-(1.3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, 5 to 15 parts by weight of triallyl cyanurate, 0.5 to 5 parts by weight of a vulcanizing agent, and 20 to 95 parts by weight of a resin package blend, wherein the resin package blend comprises 5 to 25 parts by weight of a hexa(methoxymethyl)melamine liquid resin; 5 to 15 parts by weight of a self-curing modified phenolic resin component; 5 to 25 parts by weight of an aliphatic-aromatic soft resin; 5 to 25 parts by weight of a benzene-1,3-diphenol binder; and 5 to 25 parts by weight of an aromatic hydrocarbon resin component, particularly an elastomer comprising acrylonitrile butadiene rubber and styrene butadiene rubber, based on 100 parts by weight.

12. The multilayer tube or hose (1, 10) according to claim 11, characterized in that The EPDM rubber contains 44 to 85% by weight of ethylene and 2.8 to 11% by weight of ethylidene norbornene, particularly based on 100 parts of an elastomer containing acrylonitrile butadiene rubber and styrene butadiene rubber.

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