Adhesion promoting compositions for textile materials and related reinforced textile materials

Abstract

The present invention relates to an adhesion promoting composition for textile materials, comprising a lignosulfonate salt, an epoxy curing agent for said salt containing at least two epoxide units, and an elastomeric latex. The lignosulfonate salt can be sodium, potassium, magnesium, ammonium, or calcium lignosulfonate. The invention also relates to the use of such a composition in relation to rubber materials to impart adhesive properties to reinforced textile materials, reinforced textile materials, particularly textile structures, yarns, or cords, at least partially coated and / or impregnated with said composition, and rubber or rubber-containing parts, in which the rubber contains at least one reinforcing textile material integrated on and / or within the rubber material.

Description

[Technical Field]

[0001] The present invention relates to adhesive or bonding compositions for textiles, in particular compositions for bonding textiles to rubber. The invention is particularly concerned with applications in the fields of belts, pipes, tires, air springs, and more generally any parts or articles made of rubber or containing rubber parts, in which the rubber contains a reinforcing textile on the surface and / or in the depth (mass). The invention therefore also relates to reinforcing textiles coated with this adhesive, and to parts or articles incorporating this adhesive both on the surface and in the depth. [Background technology]

[0002] Taking the example of a power transmission belt, the textile reinforcement must first and foremost ensure the dimensional stability of the belt. This requires the reinforcement to have specific mechanical properties in different environments. To ensure the required properties and in particular to avoid the risk of delamination, the textile reinforcement must adhere to the rubber of the belt. The reinforcement may be in contact with one rubber or several different rubbers. To allow good compatibility with the rubber, the reinforcement is generally treated with an adhesive. More complex properties may also be required of the reinforcement. For example, the edges of the reinforcement must be easy to cut, but must not fray when cut and exposed at the side of the belt. To ensure these other properties, other types of treatments can be applied to the yarn.

[0003] To obtain all these properties, it is necessary to provide the yarn with a certain structure, particularly in the form of a cord, and to provide it with several chemical and thermal treatments.

[0004] Since textile reinforcements are subjected to several different treatments, it is essential to ensure compatibility of the adhesive with the reinforcement, rubber, and other treatments applied to the reinforcement.

[0005] The primary purpose of chemical treatments is to bond a given reinforcement to the various rubbers it may come into contact with. Treatments vary as much as the number of reinforcement types (glass, aramid, polyamide (PA), polyethylene terephthalate (PET), etc.) and rubbers present.

[0006] At the heart of the process for bonding reinforced textiles to rubber is the so-called resorcinol-formaldehyde latex, or RFL, process. This is a system that involves mixing latex (a colloidal aqueous dispersion of elastomers or polymers) with a thermosetting resin of the phenoplast or aminoplast type. This system has a long history, was widely developed in the 1970s, and remains the process of choice. Despite numerous attempts to replace this process, it has never been possible to offer a comprehensive solution to achieve equivalent performance. It is fully optimized to obtain maximum static adhesion, i.e., adhesion without dynamic stress.

[0007] Heat treatment affects not only the chemical properties (adhesion) but also the mechanical properties of synthetic reinforcements. This affects, among other things, the shrinkage characteristics. Treatment in an oven results in a compromise between maintaining the mechanical properties and cross-linking the adhesive.

[0008] Therefore, for all these reasons, new processes must be able to adapt to current processing conditions in order to guarantee mechanical properties. However, adhesives that allow processing at lower temperatures offer potentially new advantageous properties in certain applications and exhibit favorable energetic profiles.

[0009] However, to improve adhesion performance or provide abrasion resistance, it may be necessary to apply up to four different treatments to the textile in succession, including treatment with RFL. These are the following treatments: 1) A core treatment of the yarn that allows the filaments to be trapped within the matrix and blocked between them, thus providing fray resistance and giving stiffness to the yarn. 2) Pre-activation to improve adhesion. 3) RFL treatment in one or two layers. 4) An overcoat in the form of a commercially available adhesion promoter or elastomer solution (sometimes called cementation).

[0010] It is therefore equally preferable that any modification of the formulation does not compromise the functionality of the various chemical and thermal (or more generally physical) treatments typically used for the various applications.

[0011] Considering all the constraints mentioned above, RFL processing has been recognized as the process of choice for enabling adhesion between textiles and rubber. While the phenomena responsible for adhesion are activated during the vulcanization of the rubber component, the RFL processing itself can be applied to the textile several months in advance. For this reason, the term "bonding" is often used, with "adhesion" reserved for the adhesive state. In RFL, the latex is generally an aqueous colloidal dispersion of an elastomer or polymer with properties similar to those of the rubber to be bonded. However, these latexes do not possess any real mechanical properties in their natural state. To ensure the strength of the system, a thermosetting (thermosetting) resin is added. This is an RF resin made from resorcinol and formaldehyde. Due to its polarity, it provides excellent adhesion to the textile. This forms a mesh in which the latex is trapped, stiffening the system. This mesh remains flexible enough to allow diffusion of the elastomer chains within the matrix and then provide excellent adhesion to the rubber (entanglement during vulcanization, molecular interaction and possibly co-crosslinking).

[0012] RFLs contain formalin and resorcinol, which are currently known suspected carcinogens. It would therefore be advantageous to find alternatives to the formalin and resorcinol, or to the RFL composition as a whole. The complex characteristics of RFLs, as reiterated above, both in terms of their implementation and the use characteristics of the end products that contain them, make it difficult to find alternative solutions. It would be even more advantageous to find such solutions that are not only more than alternatives but also offer enhanced performance. These are the challenges the inventors set out to overcome. Summary of the Invention [Problem to be solved by the invention]

[0013] It is therefore an object of the present invention to provide a novel adhesive solution that replaces RFLs, in particular in their known applications, and that provides a performance level close to or even better than that of RFLs, and that makes it possible to achieve this using components that are acceptable under favorable economic conditions in relation to sustainable development.

[0014] Lignosulfonates have been used as natural adhesives and as short fiber binders in combination with lignosulfonate hardeners to make mats (nonwovens), or as adhesives in multi-layer wood-based products. They have never been proposed as replacement compositions for RFL, and there is no indication that lignosulfonates would be suitable for developing adhesive formulations to ensure a bond with rubber and provide sufficient mechanical performance. They are also used as surfactants in compositions that do not contain hardeners, as described in patent documents JP 2002-226812 A and JP 2001-234143 A. [Means for solving the problem]

[0015] The subject of the present invention is therefore a composition comprising (or based on, consisting essentially of, or consisting of) a lignosulfonate salt, an epoxy curing agent of this salt and a polymeric latex, in particular an elastomeric latex, in particular an adhesive or bonding composition for textiles.

[0016] The term "epoxy curing agent" as used herein is understood to mean a compound containing at least two epoxy units or oxacyclopropane or -CH-CH-O rings. This compound can undergo an addition reaction with components such as alcohols by opening the epoxy rings. The presence of two epoxy units allows for reaction with two alcohol-containing units, thus allowing for a polymerization reaction, also known as crosslinking. Therefore, the epoxy curing agent of the present invention is a crosslinking agent for crosslinking lignosulfonates.

[0017] The subject of the present invention is also a composition for textiles, in particular an adhesive or bonding composition, obtained or obtainable by mixing a lignosulfonate, an epoxy curing agent of this salt, and a polymer latex, in particular an elastomeric latex. In one embodiment, the composition is obtained or obtainable by mixing the lignosulfonate with the epoxy curing agent of this salt in a basic medium and then adding the polymer latex, in particular an elastomeric latex; or by mixing the lignosulfonate with the polymer latex, in particular an elastomeric latex, in a basic medium and then adding the epoxy curing agent of this salt.

[0018] In one embodiment, the composition comprises the product resulting from the reaction between a lignosulfonate salt and an epoxy hardener of the salt in a basic medium.

[0019] The compositions may be bonding compositions used to bond textiles to rubber or similar materials. These compositions are compositions that can be applied to substrates, such as in particular textiles, in particular textiles according to the invention. The invention also relates to a method for their preparation.

[0020] The present invention also relates to these compositions that have been subjected to a suitable treatment process, such as heat treatment, followed by drying and curing. The term "drying" is understood to mean the evaporation of water or volatile substances. The term "curing" is understood to mean any polymerization or crosslinking reaction, either total or partial, of compounds present in the composition that are capable of reacting under the applied treatment conditions, including those without the need for heat treatment. These dried and cured compositions are then generally associated with a substrate, such as a textile, particularly a textile according to the present invention, or a rubber part incorporating such a textile. The term "associated" is used to indicate that the composition impregnates, coats, or impregnates and coats the textile. The coating may be continuous or discontinuous. The impregnation may be complete, extending to the core, or partial.

[0021] The subject of the present invention is also a kit or set comprising a first composition comprising a lignosulfonate and a polymer latex, in particular an elastomeric latex; and a second composition comprising an epoxy hardener for the lignosulfonate. The first and second compositions are suitable and intended to be mixed to form a bonding composition, which is then applied onto a textile within the meaning of the present invention.

[0022] The present invention also relates to a method of application for applying the bonding composition according to the present invention to impart adhesive properties to reinforced textiles, such as in relation to rubber, which method includes the steps of drying and curing the composition using a suitable treatment process, such as heat treatment.

[0023] The invention also relates to the use of the composition according to the invention or the dried and cured bonding composition to impart adhesive properties to reinforced textiles, such as in relation to rubber.

[0024] The present invention also relates to reinforcing textiles, in particular yarns, cords or textile structures, which are at least partially coated and / or impregnated with the bonding composition according to the invention, in particular dried and cured.

[0025] The present invention also relates to articles or parts made of rubber (or similar materials) or including portions made of rubber (or similar materials), wherein the rubber comprises at least one reinforcing textile according to the present invention incorporated on the surface of and / or within the rubber or rubber matrix.

[0026] Other objects of the present invention will become apparent upon reading the following detailed description. DETAILED DESCRIPTION OF THE INVENTION

[0027] A first subject of the present invention is therefore an adhesive or bonding composition for textiles comprising (or based on, consisting essentially of or consisting of) at least one lignosulfonate salt, at least one epoxy curing agent of this salt, and an elastomeric latex.

[0028] Without intending to be bound by theory, it is believed that the lignosulfonate salt and the epoxy curing agent salt react together to form a reaction product when mixed, regardless of whether the mixture is subjected to heat, such as a heat treatment applied to a textile after coating and / or impregnation with a bonding composition. The lignosulfonate salt is expected to initiate a crosslinking reaction with the epoxy curing agent by adding the reactive unit of the lignosulfonate salt to an epoxy ring and opening the ring when the compound is subjected to heat. This heat can be applied during a heat treatment process, such as a heat treatment applied to a textile after coating and / or impregnation with a bonding composition. Because the epoxy curing agent contains at least two epoxy units, a crosslinking reaction and, therefore, the formation of a polymer or resin are expected to occur. In one advantageous embodiment, the presence of a basic medium is expected to favor this reaction. This reaction condition is discussed and explained in more detail in the first part of the Examples. However, it cannot be excluded that one or more reaction mechanisms between the lignosulfonate salt and the epoxy may occur during preparation or storage. The term "reaction product" is understood to mean the product of the reaction between the lignosulfonate and the epoxy hardener, naturally excluding any additives that may find their way into the final composition.

[0029] This composition can be obtained in particular by a process which is also an object of the present invention, in which the three components are mixed with stirring.

[0030] As illustrated in the examples, according to a first embodiment, lignosulfonate can be dissolved in water and then the resulting solution can be mixed with latex and epoxy. This solubilization can be accelerated by adding soda and / or ammonia-type agents to act in a basic medium. According to one method, the lignosulfonate solution and latex are mixed first, and only then is the epoxy added. According to another method, the lignosulfonate solution and epoxy hardener are mixed first, and only then is the latex added. Thus, the foregoing constitute two modes. Note that, unless otherwise indicated, the term "addition" may be understood to mean the addition of a first product to a second product, or vice versa.

[0031] In one embodiment of the preparation method, the lignosulfonate can be dissolved in water with stirring, and the mixture is stirred, preferably until complete solubilization, in the presence of a pH-basifying agent. The mixture is then added to the latex with stirring, followed by the incorporation of the hardener (preferably, the hardener has been previously dissolved or dispersed in water, e.g., with vigorous stirring), while still stirring. In one practical mode, the lignosulfonate and latex mixture is added to a solution or dispersion of the epoxy hardener. Mixing with the epoxy hardener can be carried out following the preparation of the lignosulfonate and latex mixture, or later, as in the case of the kit or set that is the subject of the present invention. The composition can be used as a ready-to-use bonding composition or as a bonding composition that can be diluted as needed.

[0032] According to another embodiment of the method, an aqueous solution of lignosulfonate and epoxy hardener can be mixed and then added to the aqueous latex dispersion while stirring. According to one practical mode, the mixture of lignosulfonate and epoxy hardener is added to the latex. Advantageously, the pH of the lignosulfonate solution or the lignosulfonate and hardener solution is adjusted to be basic, for example, by adding sodium hydroxide and / or ammonia, before the incorporation of the latex. The composition can be used as a ready-to-use adhesive composition or as an adhesive composition that can be diluted as required.

[0033] The following features are applicable to various aspects of the present invention.

[0034] The latex is preferably a basic aqueous dispersion of a polymer and / or elastomer. It is also possible to carry out the invention at a neutral pH. The pH values used may in particular be those mentioned below with respect to the pH of the composition.

[0035] The term "elastomer" is understood to mean in particular a polymer or copolymer having a glass transition temperature (Tv) below approximately 25°C. The elastomer is present in the rubber to be bonded and in the latex of the bonding composition. An "elastomeric latex" is a colloidal aqueous dispersion of an elastomer.

[0036] The term "rubber" or "elastomeric material" in this specification is understood to mean the vulcanized or crosslinked product prepared from elastomers or elastomeric rubbers, either synthetic or natural, of one or more types of fillers, reinforcing agents (carbon black, silica, kaolin, etc.), plasticizers, vulcanizing agents (sulfur, peroxides, metal oxides and necessary accelerators), any other usual additives for the application in question (e.g., to facilitate application, for protection against oxygen, ozone, heat, flame, UV). The present invention likewise relates to both synthetic and natural rubbers. Rubbers formulated on the basis of elastomers are the product of the resulting Tv is below the service, operating, or application / utilization temperature of a mechanical part or assembly formed from one or more rubbers.

[0037] Lignosulfonates are by-products resulting from wood processing, in particular wood treatment for paper pulp production according to the process known as "acid bisulfite calcination." This process, using bisulfite salts, makes it possible to obtain the corresponding lignosulfonates, depending on the nature of the counterion used. These lignosulfonates can also be derived from processes intended to produce them from wood.

[0038] Preferably, in the bonding composition, the lignosulfonate may be a sodium, potassium, magnesium, ammonium or calcium salt.

[0039] In one exemplary embodiment, lignosulfonates prepared by the bisulfite method, for example from French maritime pine from the Landes (France), are used.

[0040] Preferably, the bonding composition does not contain formaldehyde or formalin. Preferably, the bonding composition does not contain resorcinol. Preferably, the bonding composition does not contain formaldehyde or formalin and resorcinol. Preferably, the bonding composition does not contain organic solvents. The bonding composition uses water as a solvent, and the pH can be adjusted as needed.

[0041] The epoxy curing agent according to the present invention is a polyepoxy compound containing at least two epoxide or epoxy groups or units. In particular, it may refer to one containing an average of two or more glycidyl or methyl-glycidyl radicals carried by heteroatoms, preferably oxygen or nitrogen atoms, more particularly oxygen atoms; or one containing an average of two or more epoxy-cyclohexyl groups. Several different compounds from the following list can be used:

[0042] Hardeners that may be mentioned in particular are: - diglycidyl or polyglycidyl ethers of aliphatic polyols; - diglycidyl or polyglycidyl ethers of polyfunctional phenols; - polyglycidyl ethers of condensation products of formaldehyde and phenols obtained under acidic conditions; - di- or polyglycidyl esters of aliphatic or aromatic polycarboxylic acids; - compounds containing epoxycyclohexyl groups; - Polyepoxy compounds obtained as a result of the epoxidation of olefinically unsaturated compounds.

[0043] Specifically, the following can be mentioned: - diglycidyl or polyglycidyl ethers of aliphatic polyols, such as butanediol-1,4; hexanediol-1,6; 1,2,6-hexanetriol; glycerol; neopentyl glycol; ethylene glycol; triethylene glycol; 1,2-propylene glycol or polyalkylene glycols, such as polypropylene glycol; or derivatives of polyalkylene glycols, such as polypropylene glycol; - diglycidyl or polyglycidyl ethers of polyfunctional phenols, such as 2,2-bis(4-hydroxyphenyl)propane (or BPA); 2,2-bis(4-hydroxyphenyl)hexafluoropropane (or BPA-F); 1,1-bis(4-hydroxyphenyl)-1-phenyl-ethane (or BPA-P); 2,2-bis(4-hydroxyphenyl)butane (BPB); bis(4-hydroxyphenyl)diphenylmethane (or BPBP); 2,2-bis(3-methyl-4-hydroxyphenyl)propane propane (or BPC); bis(4-hydroxyphenyl)-2,2-dichloroethylene (or BPCII); bis(4-hydroxyphenyl)methane (or BPF); 4,4'-(9H-fluoren-9-ylidene)bisphenol (or BPFL); 2,2-bis(4-hydroxy-3-isopropylphenyl)propane (or BPG); 1,3-bis(2-(4-hydroxyphenyl)-2-propyl)benzene (or BPM); 1,1-bis(4-hydroxyphenyl)cyclohexane (BPZ), etc. - polyglycidyl ethers of condensation products of phenols with formaldehyde obtained under acidic conditions, i.e. phenol novolacs and cresol novolacs; ethers of compounds containing epoxycyclohexyl groups, such as 3,4-epoxycyclohexylmethyl 3,4 epoxycyclohexanecarboxylate; epoxy-8,9(epoxy-3,4cyclohexyl)-3di-oxa-2,4spiro5.5undecane; and bis(3,4-epoxycyclohexylmethyl)adipate; - Di- or polyglycidyl esters of polycarboxylic acids such as phthalic acid, terephthalic acid, A-tetrahydrophthalic acid, hexahydrophthalic acid, trimellitic acid, oxalic acid, succinic acid, glutaric acid, dimerized linoleic acid, etc.

[0044] The epoxy hardener may in particular be selected from among the compounds listed below, it being understood that the composition may include one or more of them, in particular two of them: - 1,4 butanediol diglycidyl ether (diglycidyl ether of aliphatic polyol) - 2,2-bis(4-hydroxyphenyl)propane diglycidyl ether (diglycidyl ether of polyfunctional phenol) - Diglycidyl 1,2-cyclohexanedicarboxylate (di- or poly-glycidyl esters of polycarboxylic acids) - 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (a compound containing an epoxycyclohexyl group) - 1,6 Hexanediol Diglycidyl Ether (Diglycidyl Ether of Aliphatic Polyol) - Glycerol diglycidyl ether (diglycidyl ether of aliphatic polyol) - Glycerol triglycidyl ether (polyglycidyl ether of aliphatic polyol) mixtures of glycerol diglycidyl ether and glycerol triglycidyl ether, commercially available, for example, from Raschig under product number GE100 (diglycidyl ethers of aliphatic polyols); Novolac epoxy resins, such as those sold by the company HUNTSMAN under the product number Araldite PZ323 (polyglycidyl ether of a condensation product of formaldehyde and phenol).

[0045] Epoxy curing agents may also be selected from among N-glycidyl derivatives of heterocyclic amines, amides and nitrogen-containing bases, such as N,N-diglycidyl-aniline; N,N-diglycidyl-toluidine; N,N,N',N'-tetrakis-glycidylbis(4-aminophenyl)-methane; triglycidyl derivatives of 4-hydroxyaniline; triglycidyl isocyanurate; N,N'-diglycidyl-ethylene-urea; N,N'-diglycidyl-5,5-dimethylhydantoin; N,N'-diglycidylisopropyl-5hydantoin; and N,N'-diglycidyl-5,5-dimethyl-6-isopropyl-5,6-dihydro-uracil.

[0046] The latex may advantageously be an acrylonitrile / carboxylated butadiene copolymer latex (XNBR), an acrylonitrile / hydrogenated butadiene latex (HNBR), a chlorosulfonated polyethylene latex (CSM), a styrene-butadiene-vinylpyridine copolymer latex (VPSBR), a styrene-butadiene copolymer latex (SBR), an acrylonitrile / butadiene copolymer latex (NBR), a polybutadiene latex (BR), a chlorobutadiene latex (CR), a natural rubber latex (NR), a polyurethane latex or a mixture of at least two thereof.

[0047] The weight content of dry matter of the composition may in particular be from about 2 to about 38%, in particular from about 4 to about 30%, more particularly from about 7 to about 25%.

[0048] The composition according to the invention may in particular comprise from about 40 to about 95% by weight, preferably from about 55 to about 90% by weight or from about 40 to about 60, 70, 80 or 90% by weight of elastomer relative to the composition.

[0049] Unless otherwise indicated, the compositions are provided as a dry substance.

[0050] In the composition, the hardener / lignosulfonate mass ratio may be particularly from about 0.01 to about 5, more particularly from about 0.03 to about 1, and typically from about 0.05 to about 0.5. Depending on the hardener and lignosulfonate pair selected, lower or higher values may prove possible, and this parameter can be determined by the skilled artisan based on this specification.

[0051] In the composition, the [curing agent + lignosulfonate] / latex mass ratio may be in particular from about 0.05 to about 0.6, more particularly from about 0.15 to about 0.5. Depending on the compounds selected in combination, lower or higher values may prove possible, and this parameter can be determined by the skilled artisan based on this specification.

[0052] According to an advantageous feature, the composition has a neutral or basic pH, in particular a pH of approximately 7 to approximately 13, in particular a pH of approximately 9 to approximately 13. To this end, the composition can contain additives that make it possible to adjust the pH, such as, for example, soda.

[0053] The composition comprises an elastomeric latex of water. Further water can be added, for example by impregnation, to make the applicable composition sufficiently fluid for conventional applications.

[0054] The composition may also contain additives, particularly in a content of approximately 0.01 or 0.1% to approximately 50% by dry weight. The composition may contain, in particular, bonding or adhesion promoters soluble in aqueous media (e.g., silanes, blocked isocyanates), surfactants, dispersants, defoamers, waxes (e.g., microcrystalline hydrocarbon waxes in emulsion), fillers (e.g., carbon black, silica), colorants, metal oxides (e.g., zinc oxide ZnO), elastomer crosslinkers, UV and ozone inhibitors, and thermal protectants. These agents are additives conventionally used in RFL formulations. They are compatible with the adhesives targeted by the present invention.

[0055] In one embodiment, the textile bonding composition consists essentially of a lignosulfonate salt, an epoxy curing agent for this salt, and an elastomeric latex, and may include one or more additives, in particular one or more of the adhesives mentioned in the previous paragraph. Advantageously, the composition according to the invention does not contain any conventional catalysts or curing agents for compounds containing epoxy groups or units, such as triethylenetriamine (TETA) and triethylamine (TEA).

[0056] The viscosity of the bonding composition is measured at 23°C using, for example, a Brookfield viscometer equipped with a ULA module, which is suitable for low viscosities. As detailed in the examples, the viscosity can be adjusted, in particular, by adjusting the water content. The viscosity can be adjusted to the desired level to allow good application to textiles in the coating or impregnation process used. In the case of impregnation by immersion, this viscosity can be, in particular, from about 1 to about 10, typically from about 1 to about 5 Cp or mPa.s.

[0057] The composition according to the invention can be applied to any textile. The term "textile" in the context of the present invention is understood to mean any assembly of continuous monofilament yarns, continuous multifilament yarns, staple fibers, monofilament and / or multifilament continuous yarns or chopped yarns, in particular wicks, cords formed from such yarns by conventional twisting techniques, and "textile structures" formed from assemblies of twisted or cabled yarns, in particular in the form of fabrics, grids, etc. The textiles according to the invention treated with the composition according to the invention are designated by the expression "reinforced textiles".

[0058] Textiles can be organic or inorganic in nature. Examples of textile types include glass (especially E-glass or high modulus glass), basalt, carbon, aramid (meta or para), polyvinyl alcohol, cellulose, high-density polyethylene (HDPE), polyester (especially polyethylene terephthalate, PET), polyamide (PA, especially PA4.6, PA6.6, PA6), acrylic, hybrids (aramid yarns + nylon yarns cabled together; acrylic + glass + copper cabled together), etc. If the textile is a cord or textile structure of multiple yarns, all of the yarns can be organic or inorganic in nature, or the cord or textile structure can include both organic and inorganic types of yarns.

[0059] The subject of the present invention is also the application or use of the bonding composition according to the invention, in particular in relation to elastomeric materials, for imparting bonding properties to such textiles. This use can be extended to the term textile bonding method according to the invention. This use or method comprises the step of applying said composition to textiles (yarns, cords, textile structures) and then drying it. This application can be carried out by methods currently used in the industry for coating, in particular by impregnation, as explained below. The selection of the latex and therefore the constituent elastomers advantageously tends towards a formulation similar in properties to the elastomers that make up the rubber to be treated.

[0060] In one embodiment, the textile is impregnated by "dipping" it into a tank containing the adhesive formulation.

[0061] Yarns, cords, and cables can be subjected to either direct immersion in a tank or kiss-roll impregnation to apply the bonding composition. After immersion or impregnation, excess wet preparation is preferably removed by physical compression between porous supports, such as a press (pad), a spinneret die, suction, or a foam. After immersion or impregnation, and optionally final removal of excess preparation, drying and heat curing of the bonding composition are then carried out. The thus-coated, impregnated textile can be passed through an oven to allow drying and crosslinking of the bonding composition. After removal from the oven, the textile can be subjected to another impregnation step (by kiss-roll impregnation or immersion) and then passed through an oven; these steps can be repeated, in particular up to a total of four impregnations (2, 3, or 4 times).

[0062] In another impregnation method, particularly suitable for mineral fibers (glass, basalt, carbon, etc.), a debundling system consisting of combs and / or "pigtails" can be used before the impregnation of the multifilament yarn. This allows for maximum opening of the multifilament yarn to promote thorough impregnation. After the kiss-roll impregnation or dipping as described above, the excess wet preparation is preferably removed by physical compression between porous supports, such as a press (padding), suction, or foam. After dipping or impregnation and, optionally, final removal of the excess preparation, drying and heat curing of the bonding composition are then carried out. The thus-coated impregnated yarn can be passed through an oven to allow drying and crosslinking of the bonding composition. After removal from the oven, the yarn can again undergo an impregnation step (by kiss-roll impregnation or dipping) and then pass through the oven; these steps can be repeated, in particular up to a total of four impregnations (2, 3, or 4 times).

[0063] After the yarns are impregnated, dried, and heat-set, they are then twisted in-line. Cable formation is preferably performed on already treated yarns, although it is equally possible to perform cable formation first, followed by the impregnation, drying, and heat-setting steps. In various different methods, the speed can range from 1 m / min to 150 m / min, and the oven temperature ranges from 30°C to 350°C, more specifically from 100 to 300°C, and even more specifically from 140 to 220°C. Mechanical tension can also be applied to the textile throughout the process.

[0064] One embodiment relates to the production of textile reinforcements for incorporation into assemblies such as power transmission or conveyor belts. For this purpose, polyamide cords, such as PA4-6, are constructed by twisting and then cabling. The resulting cords may optionally and advantageously be treated with a first core impregnation process designed to block the filaments together, making the yarn fray-resistant and thus stiffening it as well. This can be done with a methylene diphenyl diisocyanate solution in toluene, and the impregnated cords are then dried and heat-cured in an oven. The cords are then impregnated in a tank containing the adhesive composition of the present invention, followed by drying and heat-curing in an oven.

[0065] Another embodiment relates to the production of textile reinforcements for incorporation into profiles and seals, such as window or door seals. Such reinforcements may be made, in particular, of glass yarns containing a glass fiber size with which the adhesive composition should be compatible. It is possible to start with glass yarns (especially E-glass), which are subjected to the debundling process (supra) and an impregnation process in a tank containing the bonding composition of the present invention. The impregnated yarns are subjected to drying and heat curing in an oven. After removal from the oven, the yarns are subjected to a twisting operation. Several, for example, three, impregnated twisted yarns can then be cabled together.

[0066] Another embodiment relates to the production of textile reinforcements designed to serve as braided, coiled, wrapped, or knitted reinforcements in brake pipes. It is possible to start with yarns made of organic materials, such as polyethylene terephthalate (PET), high-density polyethylene (HDPE), or polyamide. Preferably, twisting is applied to them. The twisted yarns are preferably treated by impregnation with the bonding composition of the present invention, followed by drying and heat curing in an oven.

[0067] As a variant of this embodiment, it is possible to start with similar yarns and then construct a cord using successive twisting and subsequent cable-making steps. The resulting cord is treated with a first core impregnation process, intended to block the filaments with one another and make the yarn fray-resistant, thus also stiffening it, for example by using a methylene diphenyl diisocyanate solution in toluene; the cord is then dried and heat-cured in an oven. The resulting cord is then treated by impregnation in the bonding composition of the present invention, followed by drying and heat-curing in an oven.

[0068] Other features related to the use or method will become apparent upon reading the remaining description.

[0069] The subject of the present invention is also a reinforced textile coated and / or impregnated with the bonding composition according to the invention. The object of the present invention is in particular a reinforced textile coated and / or impregnated with the bonding composition and obtainable by implementing the method described herein. It also relates to a textile treatment method for treating a textile with the aim of producing a reinforced textile by applying an adhesive composition to said textile.

[0070] The present invention is particularly directed to yarns coated and / or impregnated with the bonding composition according to the invention. The yarns may be twisted yarns, and twisting may be carried out before or after application of the composition and its drying and / or curing. If the yarn is multifilament, it may be completely impregnated to the core, which could be achieved, if necessary, by splitting the yarn (separation of the filaments by means known to those skilled in the art) before impregnation with the composition. The yarns may in particular comprise or be coated with the cured bonding composition (dried and / or crosslinked).

[0071] The subject of the present invention is also a cord coated and / or impregnated with the bonding composition according to the invention, which cord may in particular comprise or be coated with the cured bonding composition (dried and / or crosslinked).

[0072] The cord may be formed from at least two yarns that are not coated or impregnated with an adhesive composition. Generally, the yarns are first twisted together, then the yarns are cabled (gathered together and twisted in a direction opposite to that of the twist of the base yarns), and then the cord is impregnated with an adhesive composition that is cured after application.

[0073] The cord may be formed by assembling at least two yarns coated or impregnated with an adhesive composition. Typically, the yarns are twisted together after solidification of the composition, after which the yarns are cabled (gathered together and twisted in a direction opposite to that of the twist of the base yarns); it is possible to provide a coating process for the cord together with other treatment processes ("overcoat" or "topcoat") and its drying.

[0074] The subject of the present invention is also textile structures formed by assembling yarns by known techniques such as weaving, or in the case of grids, by sizing or bonding, which are coated or impregnated with the compositions of the present invention, and the present invention covers such textile structures coated with the cured bonding composition.

[0075] The bonding composition can be applied to textiles in the sense of the present invention by the method used for RFL: by impregnation, direct dipping or kiss roll, which must first be chosen.

[0076] The subject of the present invention is also an article or part made of rubber (or containing a rubber part) comprising at least one reinforcing textile according to the invention, in particular a yarn, cord and / or textile structure, which reinforcing textile may in particular be applied to the surface of the article or part and / or integrated into the interior of the article or part.

[0077] As mentioned above, rubber is a vulcanizable formulation based on natural or synthetic elastomers, such as vulcanized (crosslinked) natural rubber (NR or polyisoprene), or synthetic, vulcanized (crosslinked) rubber. Examples of synthetic rubbers are polybutadiene (BR), polyurethane (AU or EU), polychloroprene (CR), silicones (VMQ, PVMQ) and fluorosilicones (FVMQ), ethylene-propylene-diene monomer (EPDM), butadiene-acrylonitrile copolymer (NBR or nitrile butadiene rubber), hydrogenated butadiene-acrylonitrile copolymer (HNBR), styrene-butadiene copolymer (SBR), epichlorohydrin (ECO or or CO), butyl (IIR), bromobutyl (BIIR), chlorobutyl (CIIR), chlorinated polyethylene (CM), chlorosulfonated polyethylene (CSM), carboxylated nitrile butadiene acrylonitrile (XNBR), ethylene methyl acrylate copolymer (AEM), ethylene vinyl acetate copolymer (EVM and EVA), polyacrylate (ACM), fluorinated rubber (FKM), and perfluorinated rubber (FFKM).

[0078] The rubber may likewise be a vulcanizable formulation based on a mix or cut of such elastomeric gums.

[0079] The rubber can also be a formulation based on a thermoplastic elastomer (a so-called "physically crosslinked" elastomer, such as SBS, styrene-butadiene-styrene block).

[0080] The subject of the present invention is in particular an elastomeric or rubber article or part comprising a reinforcing textile bonded according to the invention (either embedded within the elastomer or rubber mass or flush with the surface), for example one or more yarns that may be individual or cabled or otherwise assembled in the form of a textile structure, or that belong to two or more of these categories.

[0081] The term "bonded" is understood to indicate, inter alia, that the reinforcing textile comprises or is coated with a cured (dried and / or crosslinked) bonding composition.

[0082] The subject of the present invention is also an article or part made of elastomer or rubber, which comprises one or more yarns, which may be individual or cabled or assembled in the form of a textile structure, or which belong to two or more of these categories, embedded within its mass made of elastomer or rubber, and which additionally comprises a textile structure according to the invention, bonded or adhered to at least one surface of this elastomer or rubber material, wherein these reinforcing textiles are adhered according to the present invention.

[0083] As articles, mention may be made, without being exhaustive, of the following list of articles which may incorporate at least one reinforcing textile adhered or bonded according to the invention, in particular a yarn, cord or textile structure treated with the bonding composition of the invention, applied onto the surface of the article to be adhered and / or integrated inside the elastomeric material of the article: - Belts, in particular power transmission belts, synchronous belts, conveyor belts, elevator belts, V-belts. Belts may contain yarns or cords embedded in an elastomer or rubber mass. These belts may also contain, instead of or in addition to the yarns and cords, textile structures, in particular fabrics, adhered to the surface, for example the back surface for power transmission belts and the back surface and notches for distribution belts. - Flexible or rigid hoses, in particular brake hoses (including braided textile structures, either single or double braided), hoses, industrial hoses including oil and gas hoses (including wrapped or spiral textile structures, i.e. textile structures produced by wrapping or spiraling), hoses (knitted textile structures). Braiding, spiraling and knitting are generally performed during the packaging of the pipe by extrusion. - Specialty items: air springs ("air springs"), dynamic coupling discs, pipe plugs, compensation / offset seals. - Tyres: especially for heavy goods vehicles and racing.

[0084] Examples of rubber compositions for these articles include: power transmission belts: EPDM or CR based; synchronous belts: HNBR and CR based; hoses: SBR or EPDM, or NBR / PVC blends or epichlorohydrin or butyl based; air springs: CR based; dynamic discs: CR or NR based; tires: thick parts containing multiple mixtures of NR, BR or SBR based.

[0085] The present invention has the advantage of being integrated into the recovery of renewable non-food raw materials. It allows the recovery of lignin, currently a waste product from the wood and paper industries. This compound is completely non-toxic, low in cost, and high in performance. Its use in this context does not compete with the food market and is not subject to regulations for chemical products. It is an agricultural resource.

[0086] The invention will now be explained in more detail using embodiments that are considered as non-limiting examples. [Example]

[0087] Part I. Preparation of formulations containing lignosulfonates and epoxy hardeners (two-component examples) The crosslinking or "sintering" of thermosetting materials, i.e., the formation of a three-dimensional covalent network that results in a reaction product, is accompanied by the release of heat. Therefore, differential scanning calorimetry (DSC) is traditionally used to characterize the crosslinking of thermosetting materials. This is accomplished by subjecting the unsintered thermosetting material to a controlled temperature gradient and then analyzing the location, size, and shape of the resulting exothermic peak.

[0088] A few grams of sodium lignosulfonate (Arbo N18; Tembec N18) and an epoxy hardener (1,4 butanediol diglycidyl ether) are homogenized in an aluminum cup under a hood at ambient temperature for 2 minutes. The mass ratio of lignosulfonate to epoxy hardener is exactly 1. A few milligrams of this composition are then sealed in an aluminum crucible with a diameter of 43 mm and a depth of 12 mm. The mixture is then measured using a METTER TOLEDO DSC3+STAR. e The sample was placed in a DSC system and subjected to a temperature gradient from 25 to 300 °C at 10 °C per minute under a nitrogen flow of 80 ml per minute. The total enthalpy change experienced by the sample was recorded by integrating the surface area under the exothermic peak using STAR SW14.00 software, and then expressed as J g -1 The baking temperature in °C at which the crosslinking reaction rate is maximum is measured at the peakmax of the exothermic peak with an accuracy of ±1 °C.

[0089] The same method is applied to produce other compositions containing 2,2-bis(4-hydroxyphenyl)propane diglycidyl ether; diglycidyl 1,2-cyclohexanedicarboxylate; 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate; 1,6-hexanediol diglycidyl ether; glycerol diglycidyl ether; glycerol triglycidyl ether; a mixture of glycerol diglycidyl ether and glycerol triglycidyl ether available from Raschig under the product number GE100; and a novolac epoxy resin available from HUNTSMAN under the product number Araldite® PZ323.

[0090] The same method is applied to generate other samples containing only sodium lignosulfonate.

[0091] The same method is applied to generate other samples containing only epoxy hardener.

[0092] Table 1 [Table 1]

[0093] The change in exothermic energy measured for the control sample containing only lignosulfonate is normalized to 100%.

[0094] Compositions containing only epoxy hardener (lignosulfonate / hardener mass ratio 0) show zero or low exotherm variation, such as 0-33%, relative to the lignosulfonate control.

[0095] Compositions containing sodium lignosulfonate and an epoxy hardener (lignosulfonate / hardener mass ratio of 1) exhibit exothermic energy variations of 595-1199% relative to the lignosulfonate control. This high exothermic energy variation relative to the control is characteristic of the phenomenon of crosslinking or "baking" of thermosetting materials. The role of the epoxy hardener relative to the lignosulfonate is clearly evident here.

[0096] example Part II: Preparation examples of adhesive formulations The definitions and measurement or control methods described in this section are generally applicable as desired unless otherwise specified.

[0097] The dry extract (or mass concentration) of a preparation is defined as the percentage of residual dry matter after evaporation of volatile materials (water, solvents) according to a defined drying method. Mass m ech Analysis is performed using a dry balance on wet samples taken at 2-5 grams. Surface density 52 g m -2 The sample is placed in a pre-tared aluminum cup containing a binder-free glass fiber filter with a threshold of 1.6 μm. The whole is then subjected to a temperature of 120° C. until the mass has completely stabilized. The results are expressed in %.

[0098] The viscosity of the formulations is measured using a Brookfield viscometer at 23° C. Unless otherwise specified, measurements are carried out at a speed of 60 rpm (revolutions per minute) using a ULA (Ultra Low Viscosity Adapter) module and a No. 1 mobile (low viscosity system).

[0099] The pH of the aqueous preparations is measured using a METLER 340 pH meter calibrated for measurements in basic media using buffer solutions, using a glass electrode and 3M KCl electrolyte.

[0100] Unless otherwise stated, the water used to make the formulations is reverse osmosis quality water with a residual conductivity of less than 70 μS / cm.

[0101] Example C.II-1: Preparation of adhesive based on sodium lignosulfonate and epoxy hardener In a first embodiment of the present invention, 64.2 g of sodium lignosulfonate (Arbo N18; Tembec) is dissolved in 1184 g of water with stirring. 2.5 g of a 10% by weight sodium hydroxide solution is then added to the solution, which is kept under stirring for 10 minutes to ensure complete solubilization. This solution is added to 983 g of styrene-butadiene-vinylpyridine copolymer latex (VPSBR) with stirring. The whole is kept under stirring (150 rpm) during the hardener preparation stage.

[0102] Take 35g of GE100 and stir vigorously (300 rpm) with 230g of water. Add this solution to the lignosulfonate and latex preparation. Maintain stirring for a few minutes until complete homogenization.

[0103] The preparation has a pH of 10.8, a dry extract (solids content) of 19.43% and a viscosity of 2.45 mPa.s.

[0104] The same method was applied to generate two other compositions by varying the following parameters: Hardener / lignosulfonate mass ratio: 56% to 116% [Lignosulfonate + hardener] / latex mass ratio: 18%-21% Mass % of dry latex in the composition: 80-84%.

[0105] A total of three compositions were produced.

[0106] Example C.II-2: Second Preparation Method for Preparing Sodium Lignosulfonate Adhesive and Epoxy Hardener In a second embodiment of the present invention, 34.8 g of sodium lignosulfonate is introduced into a vessel and 782 g of water is gradually added. The solution is stirred at 200 rpm. 20 g of 10% by weight sodium hydroxide solution and 100.7 g of 20% by weight ammonia are then added successively to the preparation while stirring. The mixture is stirred at 200 rpm for 10 minutes.

[0107] To a latex preparation of styrene-butadiene copolymer (SBR wet latex; 946 g) and 157 g of previously homogenized water, the basic solution of sodium lignosulfonate is added with stirring.

[0108] 75.5 g of GE100 is vigorously stirred (300 rpm) and 383.75 grams of water is added to it. This emulsion is immediately added to the lignosulfonate and latex preparation while stirring. Stirring is maintained for several minutes until complete homogenization is achieved.

[0109] The preparation has a pH of 12.2, 19.9% dry extract and a viscosity of 2.7 mPa·s.

[0110] Applying the same method, different compositions were generated by varying the following parameters: Hardener / lignosulfonate mass ratio: 217%~218% [Lignosulfonate + hardener] / latex mass ratio: 21% to 29% The mass percentage of dry latex in the composition: 78% to 82%.

[0111] A total of two compositions were produced.

[0112] Example C.II-3: A third preparation method for preparing an adhesive based on sodium lignosulfonate and an epoxy hardener In a third preparation method of the present invention, a basic solution of sodium lignosulfonate is prepared by dissolving 19 g of sodium lignosulfonate in 955 g of water with stirring and adding 19 g of 10% by weight sodium hydroxide solution. The preparation is left under stirring at 200 rpm for 10 minutes to ensure complete solubilization.

[0113] A basic latex dispersion is prepared by introducing 167 g of water into a vessel, which is then stirred at 200 rpm. 1049 g of styrene-butadiene copolymer latex (SBR) is then introduced in succession, followed by 25 g of a 20% by weight ammonia solution. The basic lignosulfonate solution is then added to the latex dispersion while stirring.

[0114] 49 g of GE100 is vigorously stirred (300 rpm) and 216 grams of water is added to it. This solution is immediately added to the lignosulfonate and latex preparation while stirring. Stirring is maintained for several minutes until complete homogenization is achieved.

[0115] The preparation has a pH of 12.25, a dry extract of 18.33% and a viscosity of 2.25 mPa·s.

[0116] The same method was applied to generate two other compositions by varying the following parameters: Hardener / lignosulfonate mass ratio: 255%~516% [Lignosulfonate + hardener] / latex mass ratio: 16% to 46% The mass percentage of dry latex in the composition: 68% to 86%.

[0117] A total of three compositions were produced.

[0118] Example C.II-4: Fourth Preparation Method for Preparing Adhesives Based on Potassium Lignosulfonate and Epoxy Hardener In this preparation, 94.5 g of aqueous potassium lignosulfonate solution and 63.7 g of GE100 are mixed. Then, 1794.8 g of water is poured into the mixture with vigorous stirring. Then, 33 g of 10% by weight sodium hydroxide solution and 166.6 g of 20% by weight ammonia solution are added successively to the preparation with stirring. The mixture is left under stirring for 10 minutes, and then added to chloroprene latex (wet latex CR; 1004 g) in water (176 g) with stirring.

[0119] The preparation has a pH of 12.69, a dry extract of 19.58% and a viscosity of 2.45 mPa·s.

[0120] The same method was applied to generate two other compositions by varying the following parameters: Hardener / lignosulfonate mass ratio: 33% to 134% Mass ratio of [lignosulfonate + hardener / latex]: 20% to 47% The mass percentage of dry latex in the composition: 65% to 79%.

[0121] A total of three compositions were produced.

[0122] Example C.II-5: Fifth Preparation Method for Preparing Adhesives Based on Potassium Lignosulfonate and Epoxy Hardener In this preparation, 94.5 g of aqueous potassium lignosulfonate solution and 63.7 g of GE100 are mixed. Then, 1794.8 g of water is poured into the mixture with vigorous stirring. Then, 33 g of 10% by weight sodium hydroxide solution and 166.6 g of 20% by weight ammonia solution are added successively to the preparation with stirring. The mixture is left under stirring for 10 minutes, and then added to a dispersion of chloroprene latex (wet latex CR; 1004 g) in water (176 g) with stirring.

[0123] 1306 g of this preparation is taken and diluted in 996 g of water with stirring. Then, 36 g of a 55% by weight zinc oxide aqueous dispersion, 78 g of a 35% by weight carbon black aqueous dispersion, and 83 g of an adhesion promoter (blocked isocyanate) are added successively with gentle stirring.

[0124] The preparation has a pH of 12.32, a dry extract of 14.1% and a viscosity of 1.95 mPa·s.

[0125] The same method was applied to generate two other compositions by varying the following parameters: Hardener / lignosulfonate mass ratio: 33% to 135% [Lignosulfonate + hardener] / latex mass ratio: 20% to 47% The mass percentage of dry latex in the composition: 48% to 59%.

[0126] A total of three compositions were produced.

[0127] These example compositions are used in the section on treating reinforcing textiles.

[0128] Part III - Treatment of reinforced textiles The definitions and measurement or control methods described in this section are generally applicable as desired, unless otherwise specified. The mechanical properties of the treated textiles, such as tensile strength at break, tensile elongation at break, shrinkage, temperature shrinkage, contraction (steam shrinkage), temperature shrinkage force, linear weight, loading rate (dip pick-up; DPU), stiffness, etc., are measured according to standards valid in the textile industry. In the context of the present invention, it has been confirmed that the novel treatment does not result in any modification of these properties compared to standard RFL.

[0129] The adhesive formulation of the present invention is evaluated for its adhesive performance. After coating the textile, the textile is placed in an unvulcanized rubber matrix, ensuring that the surface of the textile in contact with the rubber remains free of any contamination. The matrix containing the textile is then vulcanized by compression according to the temperature, time, and pressure specific to each rubber. The assembly of the textile and the vulcanized matrix forms an adhesive test specimen.

[0130] Adhesion test specimens can take several forms, as described in various international standards, such as ISO 36:2017. The test specimens, and therefore the tests performed to determine adhesion, are commonly known to those skilled in the art by names such as the T test ("pull-out test," ASTM D2229-04), the H test (according to NF ISO 4647 standard or ASTM D4776-04), and the peel (peel test). The test is then performed by applying stress to the specimen until failure occurs at the interfacial contact zone, either at the tear of the textile or at the tear of the rubber matrix. The adhesion is then evaluated according to criteria such as the appearance of the textile at break, the maximum adhesion, and the average tear force, which can sometimes be attributed to the thickness of the test specimen.

[0131] General information about impregnation methods Typically, textile impregnation is carried out by dipping in a tank containing an adhesive formulation. A scheme for such a method is illustrated in Gomes A., Nabih N., Kramer T., Adhesion activation of tire textiles by resorcinol formaldehyde-free coatings, Rubber World, March 2016.

[0132] Coils of untreated yarns, cords, and cables are positioned on a creel at the line entrance. Optionally, an accumulator system may be used. For application of the bonding composition, the yarns, cords, and cables can be immersed directly into the tank or impregnated with a kiss roll. After immersion or impregnation, excess wetting preparation is preferably removed, for example, by pressing (padding), suction, or foaming.

[0133] The bonding composition is then dried and / or crosslinked. The coated, impregnated textile can then be passed through an oven, allowing the bonding composition to dry and crosslink. After removal from the oven, the textile can be subjected to another impregnation step and then another pass through the oven, and these steps can be repeated, in particular up to a total of four impregnations (2, 3, or 4 times). After leaving the line, the yarn, cord, or cable can be stored on a winder.

[0134] Another impregnation method, particularly suitable for mineral fibers (glass, basalt, carbon, etc.), allows the use of a de-bundling system consisting of combs and / or "pigtails" at the creel outlet. This allows maximum opening of the multifilament yarns and promotes thorough impregnation. After the impregnation and drying and / or cross-linking steps, the yarns are then twisted in-line. The twisting is preferably carried out on yarns that have already been treated. The cords thus formed can then undergo additional treatment processes.

[0135] In various different methods, the speed can be in the range of 1 m / min to 150 m / min, and the oven temperature is in the range of 30°C to 350°C, more particularly 100 to 300°C, and even more particularly 140 to 220°C. It is also possible to apply mechanical tension to the textile. Unless otherwise indicated, in the following examples, the textiles were treated with the bonding composition that is the subject of the present invention under the same conditions as those applied during treatment with an RFL.

[0136] Example III-1: Treated Polyamide 4-6 Reinforcement for Belts In one preparation of the present invention, the inventors aim to present a solution that may be used as a reinforcement in assemblies such as power transmission or conveyor belts.

[0137] For this purpose, cords made of PA4-6 with a 470 / 5 x 3 dtex (100 / 125) construction were constructed using the successive steps of twisting and then cable formation. The resulting cords were treated by first impregnation in a solution of methylene diphenyl diisocyanate in toluene, followed by drying and heat curing in an oven. Instead of the typically applied RFL treatment, the cords were then impregnated in a tank containing the bonding composition (adhesive) of the present invention at a dry matter concentration of 20% by weight. Various yarns impregnated with the resulting adhesives were evaluated for adhesion to peroxide-accelerated EPDM (ethylene-propylene diene monomer)-based mixtures. Test specimens were prepared by compression molding. RFL-impregnated yarns prepared under the same conditions allowed for the determination of control adhesion values. The obtained adhesion values are presented in Table 2 and are expressed as % adhesion relative to the adhesion obtained with the control RFL yarn.

[0138] Example III-2: Treated glass reinforcement for profiles In one preparation example of the present invention, the inventors aim to present an invention that may be used as a reinforcement in seals and profiles, such as window or door seals, etc. Such reinforcement is made of glass yarns containing a glass fiber size that must be compatible with the bonding composition.

[0139] To do this, several E-glass yarns with a strength of 136 tex were subjected to a debundling process and impregnation in a tank containing the bonding composition (adhesive) of the present invention instead of RFL. In this example, an adhesive with a mass concentration of 20% was evaluated. The impregnated yarns were subjected to drying and heat curing in an oven. After removal from the oven, the yarns were subjected to a twisting operation to impart a twist of 135 turns per meter to the yarns in the Z direction. Three impregnated twisted yarns were then cabled together in one direction at a 135S level.

[0140] The resulting yarns impregnated with the various adhesives were evaluated for adhesion to EPDM rubber mixtures, as conventionally performed in extrusion operations. Test specimens were prepared by compression molding. RFL-impregnated yarns produced under the same conditions allowed control adhesion values to be obtained. The adhesion values obtained are presented in Table 2 and are expressed as % adhesion relative to the adhesion obtained with the control RFL yarn.

[0141] Example III-3: Treated polyethylene terephthalate reinforcement for pipes In another preparation of the invention, the inventors aim to present a solution that can be used as a braided, coiled, wrapped or knitted reinforcement in brake pipes.

[0142] Example III-3(a): For this purpose, a 90Z twisted yarn was applied to a polyethylene terephthalate (PET) yarn having a tenacity of 1100 dtex. The yarn obtained was subjected to a process of impregnation in the bonding composition (adhesive) that is the subject of the present invention, followed by heat curing in an oven. The adhesive used in this example has a dry matter or solids concentration of 20%. Various different yarns impregnated with the adhesive were evaluated for adhesion to peroxide-accelerated EPDM rubber blends conventionally used in brake pipes. Test specimens were prepared by compression molding. Yarns impregnated with RFL prepared under the same conditions made it possible to obtain control adhesion values. The values obtained are presented in Table 2 and are expressed as % adhesion relative to the adhesion obtained with the control RFL yarn.

[0143] Example III-3(b): In another example, a cord of 830 / 2 x 3 dtex construction was constructed using the successive steps of twisting and then cabling. The resulting cord was treated by first impregnation in a solution of methylene diphenyl diisocyanate in toluene, followed by drying and heat curing in an oven. The bonding composition (adhesive) used in this example had a dry matter or solids concentration of 20%. Various different yarns impregnated with the adhesive were evaluated for adhesion to CR-based rubber mixtures. Test specimens were prepared by compression molding. Yarns impregnated with RFL prepared under the same conditions made it possible to obtain control adhesion values. The obtained values are presented in Table 2 and are expressed as % adhesion relative to the adhesion obtained with the control RFL yarn.

[0144] Table 2 [Table 2]

[0145] The polyamide 4-6 cord of Example II1-1 treated with various different adhesives of Example C.11-1 showed satisfactory levels of adhesion to EPDM compared to the control yarn impregnated with RFL. The adhesion levels obtained as well as observation of the break patterns indicate that the adhesives evaluated were compatible with the first impregnation applied to the textile.

[0146] The E-glass cord of Example III-2 treated with various different adhesives of Example C.II-2 exhibited satisfactory levels of adhesion to EPDM compared to the control yarn impregnated with RFL. While these levels were lower than those obtained with RFL, they were still high enough to ensure effective performance in the application. The adhesion levels obtained, as well as observation of the fracture patterns, indicate that the adhesives evaluated are compatible with glass sizing. Furthermore, the glass yarns treated in this manner showed no visual damage and did not cause excessive contamination on the processing line. This indicates that the adhesives evaluated have the ability to impart the same properties as RFL, including mechanical protection.

[0147] The PET yarns of Example III-3(a) treated with each of the various different adhesives of Example C.II-3 exhibited higher adhesion levels to EPDM compared to the control yarn impregnated with RFL. The PET yarns of Example III-3(b) treated with each of the various different adhesives of Example C.II-4 exhibited satisfactory adhesion levels to the CR blend compared to the control yarn impregnated with RFL.

[0148] In conclusion, the results of these various tests clearly demonstrate that the adhesive composition according to the invention constitutes a highly advantageous alternative to the use of conventional RFL adhesive solutions containing formaldehyde and resorcinol. The following embodiments can be given as examples of the present invention. (Appendix 1) A textile bonding composition comprising a lignosulfonate salt, an epoxy curing agent of said salt containing at least two epoxy units, and an elastomeric latex. (Appendix 2) 2. The composition of claim 1, wherein the lignosulfonate is sodium lignosulfonate, potassium lignosulfonate, magnesium lignosulfonate, ammonium lignosulfonate, or calcium lignosulfonate. (Appendix 3) 3. The composition of claim 1 or 2, wherein the curing agent is selected from diglycidyl or polyglycidyl ethers of aliphatic polyols; diglycidyl or polyglycidyl ethers of polyfunctional phenols; polyglycidyl ethers of condensation products of formaldehyde and phenols obtained under acidic conditions; di- or polyglycidyl esters of aliphatic or aromatic polycarboxylic acids; compounds containing epoxycyclohexyl groups; polyepoxy compounds obtained as a result of epoxidation of olefinically unsaturated compounds; and mixtures thereof. (Appendix 4) 4. The composition of claim 3, wherein the curing agent is selected from the group consisting of 1,4 butanediol diglycidyl ether; 2,2-bis(4-hydroxyphenyl)propane diglycidyl ether; diglycidyl 1,2-cyclohexanedicarboxylate; 3,4-epoxycyclohexylmethyl 3,4 epoxycyclohexanecarboxylate; 1,6 hexanediol diglycidyl ether; glycerol diglycidyl ether; glycerol triglycidyl ether; a mixture of glycerol diglycidyl ether and glycerol triglycidyl ether; novolac epoxy resins and mixtures thereof. (Appendix 5) 5. The composition of any one of claims 1 to 4, comprising an acrylonitrile / carboxylated butadiene copolymer latex (XNBR), an acrylonitrile / hydrogenated butadiene latex (HNBR), a chlorosulfonated polyethylene latex (CSM), a styrene-butadiene-vinylpyridine copolymer latex (VPSBR), a styrene / butadiene copolymer latex (SBR), an acrylonitrile / butadiene copolymer latex (NBR), a polybutadiene (BR) latex, a chlorobutadiene (CR) latex, a natural rubber latex (NR), a polyurethane latex, or a mixture of at least two thereof. (Appendix 6) 6. The composition of any one of claims 1 to 5, wherein the mass content of dry matter of the composition may be in particular from about 2 to about 38%, in particular from about 4 to about 30%, and more particularly from about 7 to about 25%. (Appendix 7) 7. The composition according to any one of claims 1 to 6, comprising about 40 to about 95% by weight, preferably about 55 to about 90% by weight, of an elastomer relative to the composition. (Appendix 8) 8. The composition of any one of claims 1 to 7, wherein the mass ratio of the hardener to the lignosulfonate is from about 0.01 to about 5, more particularly from about 0.03 to about 1, typically from about 0.05 to about 0.5. (Appendix 9) 9. The composition according to any one of claims 1 to 8, wherein the [curing agent+lignosulfonate] / latex mass ratio is from about 0.05 to about 0.6, more particularly from about 0.15 to about 0.5. (Appendix 10) 10. The composition of any one of claims 1 to 9, having a neutral or basic pH, particularly a pH of about 7 to about 13, particularly about 9 to about 13. (Appendix 11) A kit for producing the bonding composition described in any one of appendices 1 to 10, comprising a first composition comprising a lignosulfonate and an elastomeric latex, and a second composition comprising an epoxy curing agent for the lignosulfonate comprising at least two epoxy units. (Appendix 12) 12. Use of a composition or kit according to any one of claims 1 to 11 for imparting adhesive properties to reinforced textiles in relation to rubber. (Appendix 13) A reinforced textile, in particular a yarn, cord or textile structure, at least partially coated and / or impregnated with the bonding composition according to any one of claims 1 to 10. (Appendix 14) 14. A part made of or comprising rubber, wherein the rubber comprises at least one reinforcing textile according to any one of claims 1 to 13, incorporated on a surface of and / or within the rubber.

Claims

1. 1. A textile bonding composition configured to form a cured resin comprising an elastomeric latex, the textile bonding composition comprising a lignosulfonate salt, an epoxy curing agent of the salt comprising at least two epoxy units, and an elastomeric latex, wherein the cured resin is formed by a crosslinking reaction between the lignosulfonate salt and the epoxy curing agent, and wherein the curing agent / lignosulfonate mass ratio is 0.01 to 1.

2. 2. The composition of claim 1, wherein the lignosulfonate is sodium lignosulfonate, potassium lignosulfonate, magnesium lignosulfonate, ammonium lignosulfonate, or calcium lignosulfonate.

3. 3. The composition according to claim 1, wherein the curing agent is selected from the group consisting of diglycidyl or polyglycidyl ethers of aliphatic polyols, diglycidyl or polyglycidyl ethers of polyfunctional phenols, polyglycidyl ethers of condensation products of formaldehyde and phenols obtained under acidic conditions, di- or polyglycidyl esters of aliphatic or aromatic polycarboxylic acids, compounds containing epoxycyclohexyl groups, polyepoxy compounds obtained as a result of epoxidation of olefinically unsaturated compounds, and mixtures thereof.

4. 4. The composition of claim 3, wherein the curing agent is selected from the group consisting of 1,4 butanediol diglycidyl ether, 2,2-bis(4-hydroxyphenyl)propane diglycidyl ether, diglycidyl 1,2-cyclohexanedicarboxylate, 3,4-epoxycyclohexylmethyl 3,4 epoxycyclohexanecarboxylate, 1,6 hexanediol diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, a mixture of glycerol diglycidyl ether and glycerol triglycidyl ether, novolac type epoxy resins, and mixtures thereof.

5. 5. The composition according to any one of claims 1 to 4, comprising an acrylonitrile / carboxylated butadiene copolymer latex (XNBR), an acrylonitrile / hydrogenated butadiene latex (HNBR), a chlorosulfonated polyethylene latex (CSM), a styrene-butadiene-vinylpyridine copolymer latex (VPSBR), a styrene / butadiene copolymer latex (SBR), an acrylonitrile / butadiene copolymer latex (NBR), a polybutadiene (BR) latex, a chlorobutadiene (CR) latex, a natural rubber latex (NR), a polyurethane latex, or a mixture of at least two thereof.

6. The composition according to any one of claims 1 to 5, wherein the mass content of dry matter of the composition is between 2 and 38%, particularly between 4 and 30%, more particularly between 7 and 25%.

7. Composition according to any one of claims 1 to 6, comprising from 40 to 95% by weight, preferably from 55 to 90% by weight, of elastomer relative to said composition.

8. A composition according to any one of claims 1 to 7, wherein the hardener / lignosulfonate mass ratio is from 0.03 to 1, typically from 0.05 to 0.

5.

9. 9. The composition according to claim 1, wherein the [curing agent+lignosulfonate] / latex weight ratio is between 0.05 and 0.6, more particularly between 0.15 and 0.

5.

10. The composition according to any one of claims 1 to 9, having a neutral or basic pH, in particular a pH of 7 to 13, in particular a pH of 9 to 13.

11. A kit for producing the bonding composition of any one of claims 1 to 10, comprising a first composition comprising a lignosulfonate and an elastomeric latex, and a second composition comprising an epoxy hardener for the lignosulfonate comprising at least two epoxy units.

12. Use of a composition or kit according to any one of claims 1 to 11 for imparting adhesive properties to reinforced textiles in relation to rubber.

13. A reinforcing textile, in particular a yarn, cord or textile structure, at least partially coated and / or impregnated with a bonding composition according to any one of claims 1 to 10.

14. A part made of or comprising rubber, wherein the rubber comprises at least one reinforcing textile according to any one of claims 1 to 13, on the surface of said rubber and / or incorporated therein.

Images