Patent Description:
This section provides background information to facilitate a better understanding of the various aspects of the disclosure. It should be understood that the statements in this section of this document are to be read in this light, and not as admissions of prior art.

A wide array of performance demands are put on the hoses used on fuel pumps, such as those used at gasoline filling stations, truck stops and airports. For instance, such hoses must be strong, durable, flexible, resistant to organic solvents, resistant to volumetric expansion, offer a long service life, and have low permeability to gasoline, gasohol, diesel, biodiesel, avgas and/or jet fuel. Such fuel hoses must also be capable of being coupled to fittings in a manner that prevents fuel from escaping.

There is currently a demand to further improve such hoses to make them even less permeable to fuels, such as gasoline, gasohol (gasoline which contains a significant amount of ethyl alcohol such as <NUM> percent or more), diesel, biodiesel, avgas and/or jet fuel. This is because the fuel which migrates through the hose ultimately evaporates and escapes into the atmosphere, which is an environmental concerns. Accordingly, such hoses must comply with various standards imposed by the Environmental Protection Agency, the California Air Resources Board, and a host of other governmental authorities. However, improving the resistance of such hoses to permeation by fuel and particularly gasohol without compromising the needed physical and chemical characteristics of the hose has proven to be an extremely difficult task.

Today there is also a strong demand for hoses that do not include sulfur or organic compounds which can be extracted by fuel thereby increasing the fuel's level of sulfur and other extractable organic compounds. This is particularly true in China where hoses which do not appreciably increase the levels of sulfur and undesirable organic compounds in fuels conveyed there through is mandated. For example, certain areas of China now require that DB11/<NUM> be met for gasoline and DB11/<NUM> be met for diesel fuel, which calls for a sulfur content that is less than <NUM> ppm (or <NUM>/kg), unwashed gum content of less than <NUM>/<NUM>, and solvent washed gum content that is less than <NUM>/<NUM>. Throughout the world, more stringent standards which have proven to be extremely elusive to meet have continually lowered the maximum level of sulfur which is allowed to migrate into the fuel. Additionally, stricter standards are in place for hoses to meet with regard to unwashed and washed gum content testing. Fuel having a low sulfur content and a low extractable gum content is an important aspect of meeting stricter standards throughout the world and lowering total vehicle emissions.

The development of fuel hoses, which do not increase the level of sulfur and/or gum in fuels conveyed there through, has proven to be elusive. For example, dispensing fuels through most existing commercial hoses results in levels of sulfur in fuel that are unacceptably high, such as in the range of <NUM> to <NUM> ppm of sulfur, and <NUM> to over <NUM>/<NUM> unwashed gum extractables after being used subsequent to a period of inactivity, such as not being used overnight.

It is difficult to meet today's standards because fuel hoses must possess an array of physical and chemical characteristics that cannot be compromised. For instance, such fuel hoses should be capable of performing over a long service life without deterioration by the elements and without having extractables dissolved by the fuel. Such hoses must also be capable of providing adequate flexibility to perform in a desired manner, and must be resistant to expansion during service. As previously explained, such fuel hoses must also exhibit a low degree of permeability to fuels and must also be capable of being coupled to fittings in a permanent and reliable manner.

Thus, there is an ongoing need in the industry for a hose having this critical combination of physical and chemical characteristics, such need met, at least in part, with embodiments according to the following disclosure. <CIT> discloses a low permeation curb pump hose comprising: (a) a tube layer, wherein the tube layer is comprised of a first nitrile rubber; (b) a barrier layer which is situated over the tube layer, wherein the barrier layer is comprised of a fluorothermoplastic; (c) a friction layer which is situated over the barrier layer, wherein the friction layer is comprised of a second nitrile rubber; (d) a reinforcement layer which is situated over the friction layer, wherein the reinforcement layer is comprised of braided steel wire, wherein the braided steel wire has a wire pack coverage of about <NUM> percent to about <NUM> percent; and (e) a cover layer which is situated over the reinforcing layer, wherein the cover layer is comprised of a chlorinated polyethylene. <CIT> discloses a hose including a fluorothermoplastic tube layer, a nitrile rubber friction layer disposed over the tube layer, a reinforcement layer disposed over the friction layer, the reinforcement layer comprising braided steel wire, and a cover layer disposed over the reinforcing layer, where the cover layer may comprise chlorinated polyethylene. The tube layer defines a lumen in the hose, and a vapor return line may further be disposed within the lumen of the hose.

This section provides a general summary of the disclosure, and is not a necessarily a comprehensive disclosure of its full scope or all of its features.

In a first aspect of the disclosure, a hose, such as a hose or fuel hose, is provided which offers the advantage of not attributing significantly to the level of sulfur or extractable organic compounds to fuels conveyed there through. Additionally, such hoses can accomplish this important objective without compromising other important chemical and physical characteristics of the hose. More specifically, the hoses of the disclosure achieve these objectives without compromising resistance to permeation by fuels, strength, durability, flexibility, and resistance to volumetric expansion. In some aspects, the hoses of according to the disclosure offer resistance to permeation by gasoline and gasohol of equal to or less than about <NUM> grams/m<NUM>/day, or even from about <NUM> to about <NUM> grams/m<NUM>/day. These hoses also offer a long service life and are capable of being coupled to fittings in a manner that prevents fuel from escaping.

In some cases, the hoses of the disclosure do not significantly attribute to the gum or sulfur content of fuel conveyed there through which helps with the dispensing of "clean" fuel. Furthermore, this hose offers high compatibility with fuels having varying amounts of ethanol (diesel fuels, flexfuels, biofuels, etc.) and gasoline. The invention relates to a hose (<NUM>) comprising (a) a tube layer (<NUM>); (b) a reinforcement layer (<NUM>) disposed outwardly from the tube layer (<NUM>); and, (c) a cover layer (<NUM>) disposed over the reinforcing layer, characterized in that the tube layer comprises a bisphenol A curable rubber, wherein the tube layer (<NUM>) defines an inner volume (<NUM>) for containing and/or transferring fuel through the hose and wherein the tube layer (<NUM>) is the innermost layer of the tube, and wherein the bisphenol A curable rubber is selected from the group consisting of hydrogenated nitrile rubber, epichlorohydrin rubber, fluoroelastomer rubber and perfluoroelastomer rubber.

Certain embodiments of the disclosure will hereafter be described with reference to the accompanying drawings, wherein like reference numerals denote like elements. It should be understood, however, that the accompanying figures illustrate the various implementations described herein and are not meant to limit the scope of various technologies described herein, and:.

The following description of the variations is merely illustrative in nature and is in no way intended to limit the scope of the disclosure, its application, or uses. The description and examples are presented herein solely for the purpose of illustrating the various embodiments of the disclosure and should not be construed as a limitation to the scope and applicability of the disclosure. While the compositions of the present disclosure are described herein as comprising certain materials, it should be understood that the composition could optionally comprise two or more chemically different materials. In addition, the composition can also comprise some components other than the ones already cited. In the summary of the disclosure and this detailed description, each numerical value should be read once as modified by the term "about" (unless already expressly so modified), and then read again as not so modified unless otherwise indicated in context. Also, in the summary of the disclosure and this detailed description, it should be understood that a concentration or amount range or dimension listed or described as being useful, suitable, or the like, is intended that any and every concentration or amount or dimension within the range, including the end points, is to be considered as having been stated. For example, "a range of from <NUM> to <NUM>" is to be read as indicating each and every possible number along the continuum between about <NUM> and about <NUM>. Thus, even if specific data points within the range, or even no data points within the range, are explicitly identified or refer to only a few specific, it is to be understood that inventors appreciate and understand that any and all data points within the range are to be considered to have been specified, and that inventors had possession of the entire range and all points within the range.

In addition, use of the "a" or "an" are employed to describe elements and components of the embodiments herein. This is done merely for convenience and to give a general sense of concepts according to the disclosure. This description should be read to include one or at least one and the singular also includes the plural unless otherwise stated.

The terminology and phraseology used herein is for descriptive purposes and should not be construed as limiting in scope. Language such as "including," "comprising," "having," "containing," or "involving," and variations thereof, is intended to be broad and encompass the subject matter listed thereafter, equivalents, and additional subject matter not recited.

Also, as used herein any references to "one embodiment" or "an embodiment" means that a particular element, feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily referring to the same embodiment.

<FIG> illustrates some hose embodiments of the disclosure in a cut-away perspective view. Hose <NUM> typically has an inside diameter which is within the range of about <NUM> inch (<NUM>) to about <NUM> inches (about <NUM>) and has an outside diameter of about <NUM> inch (<NUM>) to about <NUM> inches (about <NUM>). For instance, the hose <NUM> may have an inside diameter of <NUM>/<NUM> inch (<NUM>), <NUM>/<NUM> inch (<NUM>), <NUM>/<NUM> inch (<NUM>), <NUM> inch (<NUM>), <NUM> inches (<NUM>), or even up to about <NUM> inches (about <NUM>), or any value between these inner diameters. In an embodiment, the hose can have in inside diameter of about <NUM> inch to about <NUM> inch (<NUM> to <NUM>) and an outside diameter of about <NUM> inch to about <NUM> inch (<NUM> to <NUM>), while in another embodiment, the hose has in inside diameter of about <NUM> inch to about <NUM> inch (<NUM> to <NUM>) and an outside diameter of about <NUM> inch to about <NUM> inch (<NUM> to <NUM>). The hose <NUM> has a tube layer (core layer) <NUM>, relative to the radial direction of the hose and the longitudinal hose axis. The tube layer <NUM> is the innermost layer of the hose and in accordance with embodiments of the disclosure, is formed from a non-sulfur cured rubber. This tubular inner core layer <NUM> may be referred to in the art as simply the "tube," or as the "core".

Tube layer <NUM> is comprised of a non-sulfur cured rubber and is typically about <NUM> inches (<NUM>) to about <NUM> inches (<NUM>) in wall thickness. The tube layer wall thickness is more typically from about <NUM> inches (<NUM>) to about <NUM> inches (<NUM>). For instance, the tube layer can have a wall thickness which is in the range from about <NUM> inches (<NUM>) to about <NUM> inches (<NUM>), or within the range of about <NUM> inches (<NUM>) to about <NUM> inches (<NUM>). The non-sulfur cured rubber is a bisphenol A curable rubber is selected from the group consisting of nitrile rubber, hydrogenated nitrile rubber, epichlorohydrin rubber, fluoroelastomer rubber, perfluoroelastomer rubber, thermoplastic elastomer. In contrast with a typical veneer designs for the hoses, such as those disclosed in <CIT>, tube layer <NUM> is not a thermoplastic veneer or barrier type structure, but rather tube layer <NUM> is very flexible, even at cold temperatures, thus overcoming the possibility of fatigue failures in the field during cold weather and fuel contact. Embodiments according to the disclosure are also unique in that the performance for other required properties are at least equivalent to thermoplastic veneer or barrier type hose constructions.

In some embodiments of the disclosure, fuel is contained within an inner volume <NUM> defined by the tube layer <NUM>. The inner volume <NUM> is open space, lumen, or a conduit therein, for containing and/or transferring fuel through the hose. Fuels, such as gasoline, gasohol, diesel, biodiesel, avgas, jet fuel, and like, are typically the types of fuel contained and/or transferred by inner volume <NUM>.

Tube layer <NUM> formed from the non-sulfur cured rubber minimizes sulfur contamination, as well as avoids the use high amounts of plasticizers, thereby minimizing gum extractions. Generally, the non-sulfur cured rubber has low glass transition temperature to prevent cracking at low temperature, as well. The non-sulfur curable rubber is capable of easy extrusion despite being rich in rubber content and having no/low plasticizer concentration. Also, the mixing of the rubber is done in such a way to prevent oil or sulfur contamination during production.

The non-sulfur cured rubber mixtures used to form tube layer <NUM> may also contain various additives in conventional or suitable amounts known to persons having ordinary skill in the art. Such additives may include, but are not limited to, retardants to prevent an unduly quick cure, antioxidants, adhesion promoters, processing aids, reinforcing agents and fillers, such as carbon black, silica, other mineral fillers, lignin, and the like.

In some aspects of the disclosure, an optional friction layer <NUM> is disposed over and outwardly from tube layer <NUM> in the hose <NUM> of this disclosure. The optional friction layer may typically be from about <NUM> inches (<NUM>) to about <NUM> inches (<NUM>) thick, is more typically from about <NUM> inches (<NUM>) to about <NUM> inches (<NUM>) thick, and in some aspects, will be from about <NUM> inches (<NUM>) to about <NUM> inches (<NUM>) in thickness. When used, friction layer <NUM> will typically be in direct contact with layer <NUM>. The friction layer <NUM> may be comprised of a peroxide or bisphenol A cured rubber. In some embodiments of the disclosure, a nitrile rubber having a bound acrylonitrile monomer content which is within the range of about <NUM> percent to about <NUM> percent, or within the range of about <NUM> weight percent to about <NUM> weight percent, can be used. In another embodiment, the optional friction layer can be comprised of a fluoroelastomer, epichlorohydrin, nitrile, hydrogenated nitrile rubber, carboxylated nitrile rubber, or blends thereof.

The nitrile rubber employed in the optional friction layer <NUM> of hoses, or other layers as well, in accordance with the disclosure, may also contain various additives in conventional or suitable amounts known to persons having ordinary skill in the art. Such additives may include, and are not limited to, retardants to prevent an unduly quick cure, antioxidants, adhesion promoters, processing aids, reinforcing agents and fillers, such as carbon black, silica, other mineral fillers, lignin, and the like. Reinforcing fillers are typically utilized at a level which is within the range of about <NUM> parts per hundred parts of resin (phr) to about <NUM> phr.

Hoses according to the disclosure further include a reinforcing layer <NUM>, which is situated over and outwardly from layer <NUM>, or optional layer <NUM> when incorporated, which is depicted in <FIG> in further detail. In some embodiments, reinforcing layer <NUM> is formed of a reinforcing material in a braided, spiral, knitted reinforcement or wrapped construction. A braided reinforcing layer <NUM> is depicted in <FIG>. The reinforcing material may be any suitable material for reinforcing the hose, such as, but not limited to, steel wire (such as stainless steel wire, plated steel wire, plain steel wire, and the like), or yarns (or fabrics woven from yarns) such as those based upon woven nylon fabric composite, rayon, polyester, aramid, polyamide, cotton, and the like.

In preparing a braided reinforcing layer, in some aspects, the inner tube is extruded onto a suitable mandrel and then passed through the braiding head. Here, a number of single-end packages are arranged and rotate around the tube, to give the braiding pattern of winding and interlacing as required. Where preparing a spiral reinforcing layer, yarns or wires are wound on helically, with individual yarns or wires being laid together in the neutral angle of wrap, providing cover of the yarns. In order to prevent twisting or curving, an even number of layers, with alternate direction of lay, is applied, with a layer of rubber between each layer of reinforcement. Wrapped reinforcement layer hoses are built on a large lathe or building table, usually with a mandrel. The inner rubber lining is firstly wrapped onto the mandrel, and then the fabric reinforcement layers wound on. The fabric may be cut into relatively narrow widths, so that it can be spiraled on, or can be bias cut into wider sections, so that it can be wrapped directly onto the inner tube. Both of these methods allow the warp to lie at approximately the neutral angle. Hoses with knitted reinforcement layers are frequently used for hoses requiring changes in bore size, and/or with many bends and curves. When preparing such hoses, the inner tube is extruded and the reinforcement fabric is then knitted directly onto it, in a similar manner to the braiding system.

In some aspects of the disclosure, the reinforcing layer <NUM> is formed by braiding steel wires, which in some cases are brass plated wires. For instance, the reinforcing layer <NUM> can be manufactured utilizing a braiding machine having <NUM> to <NUM> carriers (bobbins of wire), with <NUM> to <NUM> wire ends of about <NUM> to about <NUM> inch (<NUM> to <NUM>) gage. In one embodiment, the reinforcing layer <NUM> is manufactured utilizing a braiding machine having <NUM> carriers (bobbins of wire) with wire ends of <NUM> inch (<NUM>) gage wire. In some aspects, the braided steel wire used in the reinforcing layer <NUM> has a wire pack coverage, which is within the range of about <NUM> percent to about <NUM> percent. In other words, the wires of the reinforcement layer cover from about <NUM> percent to about <NUM> percent of the surface area of tube layer <NUM>, or optional friction layer <NUM>, with the remaining <NUM> percent to <NUM> percent of the underlying layer being exposed through windows <NUM> in the braid pattern. While the braided steel wire will typically have a wire pack coverage, which is within the range of about <NUM> percent to about <NUM> percent and, in some aspects, the wire pack coverage is within the range of about <NUM> percent to about <NUM> percent. The braided steel wire, may in some embodiments, have a wire pack coverage which is within the range of about <NUM> percent to about <NUM> percent. In one specific embodiment of the disclosure, to attain improved kink resistance, the reinforcement layer is comprised of multiple spiral laid wires of different sizes in conjunction with a textile braided construction.

Referring again to <FIG>, a cover layer <NUM> is positional outwardly from the reinforcement layer <NUM>. The cover layer <NUM> in some embodiments, is from about <NUM> inches (<NUM>) to about <NUM> inches (<NUM>), from about <NUM> inches (<NUM>) to about <NUM> inches (<NUM>) in thickness, and in some instances, about <NUM> inches (<NUM>) to about <NUM> inches (<NUM>) in thickness. In some aspects, the cover layer <NUM> can be comprised of a chlorinated polyethylene, which typically has a chlorine content within the range of about <NUM> percent to about <NUM> percent. The cover layer <NUM> can also optionally be comprised of polychloroprene rubber, nitrile/PVC rubber, nitrile rubber, epicholorhydrin rubber, chlorosulfonated polyethylene, hydrogenated nitrile rubber, fluoroelastomer, styrene-butadiene rubber, or blends thereof. In some aspects, the chlorinated polyethylene has a chlorine content which is within the range of about <NUM> percent to about <NUM> percent.

In some embodiments of the disclosure, the hose is a vapor assist hose (otherwise known as a 'vapor recovery hose') as illustrated in <FIG>. Hose <NUM> includes a vapor return line <NUM> situated in the lumen <NUM> of the hose, where the lumen <NUM> is defined within tube layer <NUM>, as depicted in <FIG>. The vapor assist hose may be terminated by any suitable fitting, such as, for example, an internally expanded fitting coupled on the hose surrounding vapor return line <NUM>, while the vapor return line <NUM> is coupled to a push on fitting. Lumen <NUM> may also serve as an inner volume, open space, or conduit, for containing and/or transferring fuel through the hose.

Vapor return line <NUM> is comprised of a polymeric material which does not contain appreciable levels of sulfur, or gum, which can migrate into fuel which flows through the hose. Furthermore, the vapor return line <NUM> is comprised of a material, which provides it with all of the physical and chemical attributes that are required for the vapor return line in such a hose. For instance, the material should have an ultimate tensile strength of at least <NUM> psi about (<NUM> MPa), at least about <NUM> psi (<NUM> MPa), and in some cases, at least about <NUM> psi (<NUM> MPa). The polymeric material used in making the vapor return line <NUM> will also typically have a tensile strength at <NUM>% elongation which is within the range of about <NUM> psi (<NUM> MPa) to about <NUM> psi (<NUM> MPa), within the range of about <NUM> psi (<NUM> MPa) to about <NUM> psi (<NUM> MPa), and in some instances, within the range of about <NUM> psi (<NUM> MPa) to about <NUM> psi (<NUM> MPa). The polymeric material used in making the vapor return line <NUM> will also typically have a tensile strength at <NUM>% elongation which is within the range of about <NUM> psi (<NUM> MPa) to about <NUM> psi (<NUM> MPa), within the range of about <NUM> psi (<NUM> MPa) to about <NUM> psi <NUM> MPa), and in some cases, within the range of about <NUM> psi (<NUM> MPa) to about <NUM> psi (<NUM> MPa). The polymeric material used in making vapor return line <NUM> will also typically have a tensile strength at <NUM>% elongation which is within the range of about <NUM> psi (<NUM> MPa) to about <NUM> psi (<NUM> MPa), within the range of about <NUM> psi (<NUM> MPa) to about <NUM> psi (<NUM> MPa), or even within the range of about <NUM> psi (<NUM> MPa) to about <NUM> psi (<NUM> MPa). In some aspects, the vapor return line <NUM> is comprised of a material, which allows hose <NUM> to pass the EN <NUM> flex test, after <NUM>,<NUM> cycles using Fuel C.

Vapor return line <NUM> may be made of any suitable material, such as, but not limited to, polyamides (i.e. nylon, and the like) which is plasticized with a non-migrating plasticizer, or fluoropolymers, and the materials are those which are void of sulfur and gums that can migrate into fuel which flows through the hose. In some embodiments, the nylon can be impact modified nylon, such as impact modified Nylon <NUM>, having a melting point which is within the range of about <NUM> to about <NUM>, an ultimate tensile strength within the range of about <NUM> MPa to about <NUM> MPa and will typically have a flexural modulus within the range of about <NUM> MPa to about <NUM> MPa. Such impact modified nylon will also have characteristics that allow it to have high impact strength at low temperatures, high flexibility, and low density. Some representative examples of fluoropolymers that can be used in making the vapor return line <NUM> include polymers of tetrafluoroethylene, hexafluoropropylene, vinylidene difluoride, fluorinated ethylene propylene, ethylene tetrafluoroethylene, perfluorovinyl ether tetrafluoroethylene, ethylene-tetrafluoroethylene, polyvinylidene fluoride and terpolymers of tetrafluoroethylene, hexafluoropropylene, and vinylidene fluoride. Such fluoropolymers typically have a melting point within the range of about <NUM> to about <NUM>, an ultimate tensile strength within the range of about <NUM> MPa to about <NUM> MPa, and will typically have a flexural modulus within the range of about <NUM> MPa to about <NUM> MPa. The fluoropolymers will more typically have a melting point in the range of about <NUM> to about <NUM>. In some embodiments of the disclosure, a non-migrating plasticizer or impact modifier can be included in the polymeric composition used in making the vapor return line to provide a higher level of flexibility and toughness. The vapor return line can be comprised of a single layer or can be comprised of one or more coextruded layers of various combinations of polyamides and/or fluoropolymers.

Claim 1:
A hose (<NUM>) comprising:
(a) a tube layer (<NUM>),;
(b) a reinforcement layer (<NUM>) disposed outwardly from the tube layer (<NUM>); and,
(c) a cover layer (<NUM>) disposed over the reinforcing layer,
characterized in that the tube layer comprises a bisphenol A curable rubber, wherein the tube layer (<NUM>) defines an inner volume (<NUM>) for containing and/or transferring fuel through the hose and wherein the tube layer (<NUM>) is the innermost layer of the tube, and wherein the bisphenol A curable rubber is selected from the group consisting of hydrogenated nitrile rubber, epichlorohydrin rubber, fluoroelastomer rubber and perfluoroelastomer rubber.