WO2015189308A1

WO2015189308A1 - Cable rubberized in situ comprising a rubberizing composition comprising an adhesion promoter

Info

Publication number: WO2015189308A1
Application number: PCT/EP2015/063012
Authority: WO
Inventors: Lionel BELIN; Nathalie Salgues; Sébastien Noel
Original assignee: Compagnie Generale Des Etablissements Michelin; Michelin Recherche Et Technique S.A.
Priority date: 2014-06-12
Filing date: 2015-06-11
Publication date: 2015-12-17
Also published as: FR3022260A1

Abstract

The invention relates to a single-strand cable (C) rubberized in situ and comprising: a layer (CT1) inside the cable comprising N1 inner wires; a layer (CT3) outside the cable comprising N3 outer wires wound helically about the layer inside the cable; and a rubber composition (20) disposed between the inner and outer layers of the cable. The rubber composition (20) comprises a metal oxide and an epoxy resin comprising at least one unit having an aromatic nucleus and/or an unsaturated aliphatic chain.

Description

In situ gummed cable comprising a scrub composition comprising an adhesion promoter

[001] The invention relates to a monotoron cable gummed in situ, a multi-strand cable gummed in situ and the use of such cables for the reinforcement of a semi-finished rubber product and a tire comprising such cables.

[002] A radial tire comprises in a known manner a tread, two inextensible beads, two flanks connecting the beads to the tread and a belt, or crown reinforcement, disposed circumferentially between the carcass reinforcement and the tread band. rolling. The carcass and / or crown reinforcement is constituted in known manner by at least one ply (or "layer") of rubber reinforced by reinforcement elements such as cables, generally of the metal type in the case of tires for industrial vehicles carrying heavy loads.

[003] For reinforcement carcass reinforcement and or vertex, generally used monotoron metal cables consist of a core layer or core and one or more layers of concentric son disposed around this core. The most used three-layer cables are essentially M + N + P construction cables, formed of a core of M wire (s), M varying from 1 to 4, surrounded by an intermediate layer of N wires, N typically ranging from 3 to 12, itself surrounded by an outer layer of P son, P typically ranging from 8 to 20, the assembly may be optionally shrunk by an outer hoop thread wound helically around the outer layer. Multistrand metal cables comprising several strands as described above are also used.

[004] In a well-known manner, these metal cables are subjected, particularly in the case of the carcass reinforcement, to significant stresses during the rolling of the tires, in particular to repeated bending or variations of curvature inducing at the level of the wires of the tires. friction, particularly as a result of contact between adjacent layers, and therefore wear, as well as fatigue; they must therefore have a high resistance to phenomena known as "fatigue-fretting".

[005] Regarding the crown reinforcement, a heavy industrial vehicle tire, including civil engineering, is subjected to many attacks. Indeed, the rolling of this type of tire is usually done on a rough surface sometimes leading to perforations of the tread. These perforations allow the entry of corrosive agents, for example air and water, which oxidize the metal reinforcing elements of the crown reinforcement, in particular crown plies, and considerably reduce the service life of the tire. .

SUBSTITUTE SHEET (RULE 26) It is particularly important further that the reinforcing elements are impregnated as much as possible by the rubber, that this material penetrates into all the spaces between the son and / or the strands constituting the cables. Indeed, if this penetration is insufficient, then empty channels or capillaries are formed, along and inside the cables, and corrosive agents such as water or even oxygen in the air, likely to to enter the tires for example as a result of cuts in their tread, walk along these empty channels. The presence of this moisture plays an important role in causing corrosion and accelerating the degradation processes above (so-called phenomena of "fatigue-corrosion" and aggression of the summit), compared to use in a dry atmosphere, in particular, the degradation of the adhesive interface between the wires of the metal cables and the rubber composition adjacent to these metal cables, called the calendering composition.

[007] All these phenomena of fatigue and aggression are at the origin of a gradual degeneration of the mechanical properties of the cables and can affect, for the most severe driving conditions, the service life of the latter.

[008] To overcome the above drawbacks, the application WO 2005/071157 proposed cables with three building layers 1 + M + N, in particular of construction 1 + 6 + 12, one of the essential characteristics is that a sheath made of a rubber composition, called scrubbing, covers at least the intermediate layer consisting of M son, the core (or unit wire) of the cable may itself be covered or not rubber. With this specific architecture, the cable has excellent fatigue-fretting endurance and resistance to aggression properties that are significantly improved over the cables of the prior art. The longevity of the tires and that of their carcass reinforcement and / or crown are thus very significantly improved.

However, despite the presence of the scrubbing composition between the son, during the use of the tire, corrosive agents, for example water, can penetrate, in the armatures, in contact with the metal reinforcing elements. and corroding them through external strands and / or strands, thereby rapidly degrading their mechanical and adhesion properties to the adjacent rubber calendering composition.

[010] A tire composition comprising natural rubber as a diene elastomer, silica as a reinforcing filler, a vulcanization system comprising sulfur and various other materials is known from the state of the art. additives comprising in particular an adhesion promoter, for example a cobalt salt.

[011] The composition is used for the manufacture of semi-finished products intended to be in contact with one or more metal reinforcing elements, for example metal cables. The cobalt salt allows a good adhesion of the composition to the metal cables, in particular to their coating comprising for example brass.

[012] However, such cobalt salts are relatively expensive. In addition, it is desired as much as possible to limit the amount to be used of these salts to reduce their environmental impact.

The object of the invention is to propose a cable gummed in situ with a scrubbing composition in which the cobalt salts are replaced, at least partially, as adhesion promoter.

[014] For this purpose, the subject of the invention is a monotoron cable gummed in situ, comprising:

an inner layer of the cable comprising N1 internal wire (s),

an outer layer of the cable comprising N3 external wires wound helically around the inner layer of the cable,

a rubber composition disposed between the inner layer of the cable and the outer layer of the cable,

characterized in that the rubber composition comprises a metal oxide and an epoxy resin comprising at least one unit comprising an aromatic ring and / or an unsaturated aliphatic chain.

[015] The combination of the resin and the metal oxide makes it possible to replace the cobalt salts while preserving or even improving the adhesion performance with the son of the cable according to the invention. The resin and the metal oxide are relatively inexpensive and are relatively neutral to the environment.

[016] The aromatic ring and / or the unsaturated aliphatic chain confer excellent adhesion between the composition and the cable son, in particular because of their respective unsaturations.

Examples of aromatic rings are acridine, anthracene, benzene, benzofuran, benzol, borazine, diazine, furan, imidazole, indole, isobenzofuran and isoquinoline. , naphthalene, naphthene, purine, pyrazine, pyridazine, pyridine, pyrimidine, pyrrole, quinoline, thiazole and thiophene. [018] An unsaturated aliphatic chain is a non-aromatic organic compound comprising at least one ethylenically unsaturated function, that is to say comprising at least one double bond or even a carbon-carbon triple bond. Examples of unsaturated functions are the alkene (C = C) and alkyne (-C C-) functions.

In the case of a homopolymer resin, a pattern is understood to mean the chemical structure repeating along the resin and, in the case of a copolymer resin, the chemical structure originating from each of the monomers and repeating itself. , randomly or sequentially, the loin of the resin.

[020] Each unit may comprise one or more aromatic nuclei and / or unsaturated aliphatic chains.

[021] Epoxy resin means that the resin comprises at least one epoxide function and preferably at least one epoxy function per unit. The epoxy function makes it possible to improve the adhesion between the composition and the metallic reinforcement element. In particular, when the composition comprises sulfur, the epoxy function reacts easily with sulfur and allows excellent adhesion between the composition and the metal reinforcing element.

[022] The epoxy resin can come from the polymerization of a single type of monomer or the copolymerization of at least two different types of monomers. In the case of a homopolymer comprising a single type of monomer, all the units are identical and each unit comprises an epoxide function. In the case of a copolymer comprising at least two different types of monomers, at least one unit derived from one of the monomers comprises an epoxide function.

[023] The metal oxide consists of oxygen (one or more atoms) and at least one metal in the sense of the periodic table. Metals include alkali metals, alkaline earth metals, transition metals and poor metals.

[024] A metal oxide is such that the presence of the oxygen element or elements makes it possible to complete the valence of the metal. In particular, a metal oxide should not be confused with a metal hydroxide.

[025] In addition, the resin allows, unexpectedly, to remove a part of the vulcanization system of the composition. Indeed, unexpectedly, the resin makes it possible to delay the vulcanization of the composition according to the invention.

[026] Advantageously, the aromatic nucleus is benzene.

[027] Preferably, the epoxy resin is poly [(o-cresylglycidylether-) co-formaldehyde]. [028] Such a resin has the following formula whose unit unit is represented in square brackets:

[029] Advantageously, the metal oxide is chosen from alkaline earth metal oxides, alkali metal oxides and transition metal oxides, preferably from alkaline earth metal oxides and metal oxides. alkalis and more preferably from alkaline earth metal oxides.

[030] Advantageously, the metal oxide is a calcium oxide.

[031] Advantageously, the rubber composition comprises at most 8 pce inclusive terminal, preferably at most 6 pce included terminal and more preferably at most 4 pce included terminal of the epoxy resin.

[032] Advantageously, the rubber composition comprises at most 3 pce inclusive, preferably at most 1 pce inclusive and more preferably at most 0.5 pce included terminal of the metal oxide.

[033] The rubber composition can be in raw or vulcanized form.

[034] In one embodiment, the rubber composition is present in each of the capillaries located between the one or more internal threads N 1 of the inner layer and the outer threads N 3 of the outer layer.

[035] In another embodiment, the cable further comprises an intermediate layer of the cable comprising N2 intermediate son helically wrapped around the inner layer of the cable, the N3 external son of the outer layer of the cable being helically wound around the middle layer of the cable.

[036] Preferably, the rubber composition is present in each of the capillaries located between the N1 or inner thread (s) of the inner layer and the N2 intermediate son of the intermediate layer.

[037] Still more preferably, the rubber composition is present in each of the capillaries located between the N2 intermediate son of the intermediate layer and the N3 external son of the outer layer. [038] The invention also relates to a multi-strand cable gummed in situ, comprising at least strand being a monotoron cable gummed in situ according to the invention.

[039] In a preferred embodiment, the multi-strand cable gummed in situ comprises:

an inner layer of the cable comprising T1 internal strand (s),

an outer layer of the cable comprising T2 outer strands wound helically around the inner layer of the cable,

at least one of the inner and / or outer strands being a monotoron cable gummed in situ according to the invention.

[040] The multi-strand cable gummed in situ may also include one or more of the following characteristics, considered individually or in any technically possible combination:

each outer strand is a monotoron cable gummed in situ according to the invention; and or

each inner strand is a monotoron cable gummed in situ according to the invention; and or

the multi-strand cable comprises a rubber composition disposed between the inner layer of the inner strand (s) of the cable and the outer layer of the outer two strands of the cable, the rubber composition comprising a metal oxide and an epoxy resin comprising at least one unit comprising an aromatic ring and / or an unsaturated aliphatic chain.

[041] The invention also relates to a multi-strand cable gummed in situ, comprising:

an inner layer of the cable comprising T1 internal strand (s),

a rubber composition disposed between the inner layer of the cable and the outer layer of the cable, the rubber composition comprising a metal oxide and an epoxy resin comprising at least one unit comprising an aromatic ring and / or an unsaturated aliphatic chain.

[042] The advantages mentioned above for the monotoron cable gummed in situ apply mutatis mutandis to multitoron cables described above.

[043] The invention also relates to the use of a monotoron cable gummed in situ according to the invention or a multi-strand cable gummed in situ according to the invention for the reinforcement of an article or semi-finished product rubber, for example a tire. [044] The invention furthermore relates to a tire comprising a monotoron cable gummed in situ according to the invention or to a multi-strand cable gummed in situ according to the invention.

[045] The invention will be better understood on reading the following description given by way of non-limiting example of implementation thereof, and on examining the appended figures in which:

FIG. 1 is a diagrammatic representation of a cross-section of a monotoron cable of construction 1 + 6, gummed in situ, according to the invention, FIGS. 2 to 4 are diagrammatic representations of cross-sections of monotoron cables of construction 1 + 6 + 12, gummed in situ, according to various embodiments of the invention, and

FIGS. 5 to 10 are diagrammatic representations of cross-sections of multi-strand cables of construction 1 + 6, gummed in situ, and according to various embodiments of the invention and comprising several strands of structure 1 + 6 + 12.

[046] In the present description, unless expressly indicated otherwise, all the percentages (%) indicated are% by weight. The term "phr" means parts by weight per hundred parts of solid elastomer.

[047] On the other hand, the term gummed cable in situ in the sense of the invention, a cable gummed from the inside, during its manufacture itself, so in the raw state of manufacture, by a so-called rubber composition scrub. In other words, at least one of the capillaries or interstices (the two interchangeable terms denoting voids, free spaces in the absence of filling rubber) formed by the adjacent strands or strands is filled, at least in part (so continuous or not along the axis of the cable), by the scrub composition such that for any cable length of 2 cm, each capillary comprises at least one rubber stopper.

[048] The invention relates to a monotoron cable gummed in situ C comprising at least one inner layer of the cable CT1 and an outer layer of the cable CT3. The inner layer of the cable CT1 comprises N1 internal wire (s) with N1 greater than or equal to 1. The outer layer of the cable CT3 comprises N3 external wires wound helically around the inner layer of the cable CT1.

[049] In particular the inner layer CT1 may comprise one or more son (ie N 1 varies from 1 to 3). The outer layer CT3 can comprise from ten to fourteen threads (ie N3 varies from 5 to 7). [050] The cable of the invention is erased in situ and therefore comprises a so-called scrub rubber composition 20 disposed between the inner layer of the cable CT1 and the outer layer of the cable CT3.

[051] The rubber (or indistinctly "elastomer", both of which are considered synonymous) of the scrub composition 20 is preferably a diene elastomer, that is to say by definition an elastomer derived at least in part ( that is to say a homopolymer or a copolymer) of monomer (s) diene (s) (ie, monomer (s) carrier (s) of two carbon-carbon double bonds, conjugated or not).

[052] In a particularly preferred manner, the diene elastomer of the composition is chosen from the group of diene elastomers consisting of polybutadienes (BR), synthetic polyisoprenes (IR), natural rubber (NR) and butadiene copolymers. , isoprene copolymers and mixtures of these elastomers. Such copolymers are more preferably selected from the group consisting of butadiene-styrene copolymers (SBR), isoprene-butadiene copolymers (BIR), isoprene-styrene copolymers (SIR), isoprene-copolymers of butadiene-styrene (SBIR) and mixtures of such copolymers.

[053] The compositions may contain a single diene elastomer or a mixture of several diene elastomers, the diene elastomer (s) may be used in combination with any type of synthetic elastomer other than diene, or even with polymers other than elastomers, by example of thermoplastic polymers.

[054] Preferably, the scrub rubber composition comprises a reinforcing filler.

[055] When a reinforcing filler is used, it is possible to use any type of reinforcing filler known for its ability to reinforce a rubber composition that can be used for the manufacture of tires, for example an organic filler such as carbon black, a filler reinforcing inorganic such as silica, or a blend of these two types of filler, including a blend of carbon black and silica.

[056] As carbon blacks are suitable all the carbon blacks conventionally used in tires (so-called pneumatic grade blacks). For example, mention will be made more particularly of reinforcing carbon blacks of the 100, 200 or 300 series (ASTM grades). [057] By "reinforcing inorganic filler" is meant in this application, by definition, any inorganic or mineral filler (regardless of its color and origin (natural or synthetic), also called "white" filler, "clear" or "non-black filler" as opposed to carbon black, capable of reinforcing on its own, with no other means than an intermediate coupling agent, a rubber composition for manufacturing In other words, it is capable of replacing, in its reinforcing function, a conventional carbon black of pneumatic grade, which load is generally characterized, in a known manner, by the presence of hydroxyl groups (-OH) at its stage. area.

[058] The physical state in which the reinforcing inorganic filler is present is indifferent, whether in the form of powder, micro-beads, granules, beads or any other suitable densified form. Of course, the term "reinforcing inorganic filler" also refers to mixtures of different reinforcing inorganic fillers, in particular highly dispersible siliceous fillers as described below.

[059] Suitable reinforcing inorganic fillers include mineral fillers of the siliceous type, in particular silica (SiO 2). The silica used may be any reinforcing silica known to those skilled in the art, especially any precipitated or pyrogenated silica having a BET surface and a CTAB specific surface both less than 450 m 2 / g, preferably from 30 to 400 m 2 / boy Wut. As highly dispersible precipitated silicas (called "HDS"), mention may be made, for example, of the "Ultrasil" 7000 and "Ultrasil" silicas 7005 from Evonik, the "Zeosil" 1165MP, 1,135MP and 1115MP silicas from Rhodia, the "Hi-Sil" silica EZ150G from the company PPG, the "Zeopol" silicas 8715, 8745 and 8755 from the Huber Company, the high surface area silicas as described in the application WO 03/16837.

Those skilled in the art will understand that, as the equivalent filler of the reinforcing inorganic filler described in this paragraph, it would be possible to use a reinforcing filler of another nature, in particular organic, as long as this reinforcing filler is covered. an inorganic layer such as silica, or would comprise on its surface functional sites, especially hydroxyl, requiring the use of a coupling agent to establish the bond between the filler and the elastomer.

[061] The total reinforcing filler content (carbon black and / or reinforcing inorganic filler such as silica) is within a range from 0 to 120 phr inclusive, more preferably 0 to 70 phr included terminals, more particularly from 5 to 70 pce included terminals and more preferably also from 0 to 60 pce included terminals and very preferably from 5 to 60 pce inclusive terminals, the optimum being of course differ depending on the particular applications targeted.

[062] Of course we can use a single carbon black or a blend of several carbon blacks of different ASTM grades. The carbon black may also be used in blending with other reinforcing fillers and in particular reinforcing inorganic fillers as described above, and in particular silica.

[063] When an inorganic filler (for example silica) is used in the composition, alone or in a blend with carbon black, its content is within a range from 0 to 70 phr inclusive limits (preferably from 0 to 60 pce terminals included), in particular also from 5 to 70 pce inclusive terminals, and even more preferably this proportion varies from 5 to 60 pce inclusive terminals.

[064] Advantageously, the scrub rubber composition comprises at least 30 pce inclusive and preferably at least 40 pce inclusive silica.

[065] The use of the resin and the oxide makes it possible to obtain an excellent adhesion, preferably in the case where the composition comprises a reinforcing filler comprising predominantly by weight of the silica. For the most part, it is understood that the proportion by weight of silica is greater than the proportion by weight of the rest of the other reinforcing fillers of the composition, whether these fillers are organic, for example carbon black, or inorganic.

[066] Preferably, the scrub rubber composition comprises various additives.

[067] The compositions may also comprise all or part of the usual additives usually used in elastomer compositions intended for the manufacture of tires, for example plasticizers or extension oils, whether these are aromatic in nature or not -aromatic, pigments, protective agents such as anti-oxidants, anti-fatigue agents, reinforcing resins such as bismaleimides, acceptors (for example phenolic novolac resin) or methylene donors (for example HMT or H3M).

[068] As presented in the preamble, an adhesion promoter is commonly used for compositions intended to be in contact with a metallic reinforcing element. In the state of the art, the promoter comprises a cobalt salt while the scrub rubber composition uses, in partial replacement or total of the cobalt salt, the combination of the epoxy resin and the metal oxide, the epoxy resin comprising at least one unit comprising an aromatic ring and / or an unsaturated aliphatic chain.

[069] Preferably, the scrub rubber composition comprises a crosslinking system, more preferably a vulcanization system.

[070] The crosslinking system, here vulcanization comprises sulfur or a sulfur donor agent, a vulcanization activator and a vulcanization accelerator. The system may optionally comprise one of the compounds selected from a peroxide, a bismaleimide and a vulcanization retarder.

[071] The vulcanization system preferably comprises sulfur and an accelerator, in particular of the sulfenamide type, such as chosen from the group consisting of 2-mercaptobenzothiazyl disulfide (abbreviated "MBTS"), N-cyclohexyl-2-benzothiazyl sulfenamide. (abbreviated "CBS"), N, N-dicyclohexyl-2-benzothiazyl sulfenamide (abbreviated "DCBS"), N-tert-butyl-2-benzothiazyl sulfenamide (abbreviated as "TBBS"), N-tert-butyl- 2-benzothiazyl sulfenimide (abbreviated as "TBSI") and mixtures of these compounds.

[072] The vulcanization system optionally comprises other accelerators and vulcanization activators such as zinc oxide and stearic acid. The vulcanization system also optionally includes a vulcanization retarder, for example N- (cyclohexylthio) phthalimide (abbreviated "CTP").

[073] The sulfur or sulfur donor agent is used at a preferential rate of between 0.5 and 10 pce inclusive limits, more preferably between 0.5 and 8.0 pce inclusive limits. All accelerators, retarders and vulcanization activators are used at a preferential rate of between 0.5 and 15 pce inclusive. The vulcanization activator (s) is or are used at a preferential rate of between 0.5 and 10 pb inclusive.

[074] In a variant, it may be envisaged to eliminate the crosslinking system, that is to say to have a scrubbing composition 20 free of sulfur-donor agents, for example sulfur and sulfur-activating agents. vulcanization such as zinc oxide and stearic acid. By composition free of a compound, it is understood that the composition does not include this compound voluntarily introduced into the composition and that this compound, if present, is in the form of traces related for example to its manufacturing process. For example, the composition lacking a compound comprises the latter in an amount less than or equal to 0.1 phr and preferably less than or equal to 0.05 phr. [075] According to optional features of the scrub rubber composition:

The scrub rubber composition comprises at least 0.1 pce inclusive, preferably at least 1 pce inclusive and more preferably at least 1.5 pce inclusive terminal of the epoxy resin.

The scrub rubber composition comprises at most 8 pce inclusive, preferably at most 6 pce inclusive and more preferably at most 4 pce included terminal of the epoxy resin.

The scrub rubber composition comprises at least 0.05 pce inclusive and preferably at least 0.1 pce inclusive terminal of the metal oxide. The scrub rubber composition comprises at most 3 phr included, preferably at most 1 pce inclusive and more preferably at most 0.5 pce inclusive metal oxide.

[076] The metal oxide may be chosen from alkaline earth metal oxides, alkali metal oxides and transition metal oxides, preferably from alkaline earth metal oxides and alkali metal oxides and more. preferentially among the alkaline earth metal oxides.

[077] According to one embodiment, the metal oxide is a calcium oxide.

[078] Advantageously, the scrub rubber composition comprises at most 2 pce inclusive, preferably at most 1 pce inclusive of an adhesion promoter other than the combination of the epoxy resin and the metal oxide. Thus, the amount of the other promoter is reduced as much as possible.

[079] Advantageously, the other promoter or promoters are chosen from metal salts, preferably from cobalt salts, nickel salts, lead salts, iron salts, manganese salts, chromium, cadmium salts and copper salts and more preferably from cobalt salts.

[080] Advantageously, the scrub rubber composition comprises at most 0.20 pce inclusive of a vulcanization retarder other than the epoxy resin. Thus, the amount of the other vulcanization retarder is reduced as much as possible. Preferably, the other vulcanization retarder is N- (cyclohexylthio) phthalimide.

[081] By rubber composition free of compound X, it is understood that the composition does not include compound X voluntarily introduced into the composition and that compound X, if present, is in the form of bound traces for example to its manufacturing process. For example, the composition without Compound X comprises compound X in an amount of less than or equal to 0.1 phr and preferably less than or equal to 0.05 phr.

[082] Advantageously, the scrub rubber composition is free of amine hardener. The aminated hardener is chosen from (poly) amine compounds including polyphenol compounds, polyimines and cationic photoinitiators, in particular dicyandiamides, hydrazides, imidazole compounds, sulphonium salts, onium salts, ketimines, acid anhydrides, for example polyanhydride 4,4 '- (4,4'-isopropylidenediphenoxy) bis (phthalic anhydride), and pyromellitic dianhydride.

[083] Preferably, the scrub rubber composition is free of cobalt salt. In particular, the cobalt salts absent from the composition are chosen from cobalt acetylacetonate, cobalt naphthenate, cobalt resinate, cobalt stearate, cobalt tallate, cobalt benzoylacetonate and boron rosinate. Cobalt Toluate.

[084] Still more preferably, the rubber scrub composition is free of metal salt. The term "metal salt" includes salts selected from cobalt salts, nickel salts, lead salts, iron salts, manganese salts, chromium salts, cadmium salts and copper salts.

[085] Preferably, the scrub rubber composition is free of an adhesion promoter other than the combination of the epoxy resin and the metal oxide.

[086] Preferably, the scrub rubber composition is free of N- (cyclohexylthio) phthalimide.

[087] In addition to its adhesion promoter function, the resin has revealed an unexpected function of a vulcanization retarder which makes it possible to overcome a specific vulcanization retarder, here N- (cyclohexylthio) phthalimide.

[088] Preferably, the scrub rubber composition is devoid of a curing retarder other than the epoxy resin.

[089] According to a first embodiment shown in FIG. 1 of a monolithic cable gummed in situ C with two layers, the inner layer CT1 of the monotoron cable gummed in situ C comprises an inner wire 10 and the outer layer of the cable CT3 comprising six outer wires 13 wound helically around the inner wire.

[090] Preferably, the scrub rubber composition 20 is present in each of the capillaries or interstices located between the internal thread of the inner layer CT1 and the six outer threads of the outer layer CT3. [091] Although not shown, it is possible to provide two-layer cables with for example three internal son and nine external son.

[092] According to embodiments illustrated in Figures 2 to 4 monotoron cable gummed in situ three layers, monotoron cable gummed in situ according to the invention C may comprise an intermediate layer of the cable CT2 comprising N2 intermediate son. The N2 intermediate son are helically wound around the inner layer CT1 of the cable and the N3 external son of the outer layer CT3 of the cable are helically wound around the intermediate layer CT2 of the cable.

[093] In the embodiments illustrated in Figures 2 to 4, the inner layer CT1 comprises an inner wire 10, the intermediate layer CT2 comprises six intermediate son 12 and the outer layer CT3 comprises twelve outer son 13. The cables of Figures 2 at 4 have a structure 1 + 6 + 12.

[094] The invention is not limited to the configuration illustrated in FIGS. 2 to 4.

[095] In particular the inner layer CT1 may comprise more son, for example two or three son assembled together (i.e. N 1 varies from 1 to 3).

[096] In addition, the intermediate layer CT2 may comprise five to seven wires (i.e. N2 ranges from 5 to 7).

[097] Finally, the outer layer CT3 may comprise from ten to fourteen threads (i.e., N3 ranges from 10 to 14).

[098] According to the embodiment shown in Figure 2, the rubber gum composition 20 is present in each of the capillaries between the inner wire 10 of the inner layer CT1 and the six intermediate son 12 of the intermediate layer CT2.

[099] Advantageously, such a configuration ensures good adhesion of the inner (s) and intermediate son with the scrub composition for effective protection of the inner (s) and intermediate son.

According to the embodiment shown in Figure 3, the rubber composition is present in each of the capillaries located between the six intermediate son 12 of the intermediate layer CT2 and the twelve outer son 13 of the outer layer CT3.

Advantageously, such a configuration ensures good adhesion of intermediate and external son with the scrub composition. The scrub composition thus adheres effectively to the son and / or strands of the cables according to the invention and effectively protects the son of the cable according to the invention. As shown in Figure 4, it is also possible to provide that the rubber scrub composition 20 is present in each of the capillaries located between the inner wire 10 of the inner layer CT1 and the six intermediate wires 12 of the layer intermediate CT2 and in each of the capillaries located between the six intermediate wires 12 of the intermediate layer CT2 and the twelve outer wires 13 of the outer layer CT3.

Advantageously, such a configuration ensures maximum adhesion of the various layers of the cable with the scrub composition, thus providing maximum protection of the various layers of the cable.

The invention also relates to a multi-strand cable gummed in situ C comprising at least one inner layer of the cable CCI and an outer layer of the cable CCE cable.

The inner layer of the CCI cable comprises T1 internal strand (s).

The outer layer of the CCE cable comprises T2 outer strands wound helically around the inner layer CCI of the C cable.

Each internal strand T1 and external TE is a single-strand cable comprising at least one inner layer of the cable CT1 and an outer layer of the cable CT3. The inner layer comprises N1 internal thread (s) and the outer layer comprises N3 outer threads helically wrapped around the inner layer of the cable.

In the embodiments of multi-strand cables gummed in situ C shown in Figures 5 to 10, each inner strand Tl and outer TE is a monotoron cable comprises an intermediate layer CT2. The intermediate layer of the cable CT2 comprises N2 intermediate wires wound helically around the inner layer CT1 of the cable, the outer N3 son of the outer layer CT3 of the cable being helically wound around the intermediate layer CT2 of the cable.

The multi-strand cables C according to the invention are not limited to cables comprising strands of structures shown in FIGS. 5 to 10.

According to embodiments of the invention, examples of embodiments of which are shown in FIGS. 5 to 9, at least one of the inner and / or outer strands is a monotoron cable according to the invention, namely a monotoron cable gummed in situ with a rubber composition comprising a metal oxide and an epoxy resin comprising at least one unit comprising an aromatic ring and / or an unsaturated aliphatic chain.

According to the embodiment shown in FIG. 5, each outer strand TE is a monotoron cable gummed in situ according to the invention as described with reference to FIG. 4. According to the embodiment shown in FIG. 6, each internal strand T1 is a monotoron cable gummed in situ according to the invention as described with reference to FIG. 4.

According to the embodiment shown in FIG. 7, each outer strand TE and each inner strand T1 is a monotoron cable gummed in situ according to the invention as described with reference to FIG. 4.

According to embodiments shown in Figures 8 and 9, the multi-strand cables according to the invention may comprise a scrub rubber composition 20 disposed between the inner layer CCI of the inner strand T1 of the cable and the outer layer CCE outer strands TE of the cable, the scrub rubber composition comprising a metal oxide and an epoxy resin comprising at least one unit comprising an aromatic ring and / or an unsaturated aliphatic chain.

In these examples, the rubber scrub composition 20 is the same as that described above for single-strand cables.

According to the embodiment shown in FIG. 8, each outer strand TE is a monotoron cable gummed in situ according to the invention as described with reference to FIG. 4, the inner strand is a non-gummed strand in situ and a gum rubber composition comprising a metal oxide and an epoxy resin comprising at least one unit comprising an aromatic ring and / or an unsaturated aliphatic chain is disposed between the inner layer of the CCI cable and the outer layer of the CCE cable. In this example, the scrub rubber composition 20 disposed between the inner layer of the CCI cable and the outer layer of the CCE cable is the same as previously described for the single-rod cables.

According to the embodiment shown in FIG. 9, each outer strand TE and each inner strand T1 is a monotoron cable gummed in situ according to the invention and a scrub rubber composition 20 comprising a metal oxide and an epoxy resin. comprising at least one unit comprising an aromatic ring and / or an unsaturated aliphatic chain is arranged between the inner layer of the CCI cable and the outer layer of the CCE cable. In this example, the scrub rubber composition 20 disposed between the inner layer of the CCI cable and the outer layer of the CCE cable is the same as previously described for the single-rod cables.

The invention also relates to a multi-strand cable gummed in situ comprising at least:

an inner layer CCI of the cable comprising T1 internal strand (s) T1, an outer layer CCE of the cable comprising T2 outer strands TE wound helically around the inner layer CCI of the cable,

a rubber composition disposed between the inner layer CCI of the cable and the outer layer CCE of the cable, the rubber composition comprising a metal oxide and an epoxy resin comprising at least one unit comprising an aromatic ring and / or an unsaturated aliphatic chain.

In the embodiment shown in Figure 10, the strands are monotoron cables not gummed in situ. A scrub rubber composition comprising a metal oxide and an epoxy resin comprising at least one unit comprising an aromatic ring and / or an unsaturated aliphatic chain is disposed between the inner layer of the CCI cable and the outer layer of the CCE cable. Preferably, the scrub rubber composition 20 disposed between the inner layer of the CCI cable and the outer layer of the CCE cable is the same as previously described for single-rod cables.

The invention also relates to the use of a cable according to the invention for reinforcing articles or semi-finished products made of plastic and / or rubber, for example plies, pipes, belts, conveyor belts, tires, more particularly tires for industrial vehicles.

In order to manufacture the cables described above, the rubber scrub composition 20 is available in accordance with the general knowledge of those skilled in the art during the assembly of the different layers of the cable. Reference is especially made to publications EP1699973, WO2006 / 013077, WO2007 / 090603, WO09 / 083212, WO09 / 083213, WO10 / 012411, WO10 / 054790, WO10 / 054791, WO10 / 112444, WO10 / 112445, WO10 / 139583, WO11 / 000963, WO11 / 000964, WO11 / 000950 and WO11 / 000951.

The cable of the invention is particularly intended to be used as a reinforcing element for industrial vehicles selected from vans, "heavy goods vehicles" - ie, metro, bus, road transport vehicles (trucks, tractors, trailers), off-the-road vehicles, agricultural or civil engineering machinery, aircraft, other transport or handling vehicles.

The cable according to the invention can be used to reinforce different parts of the tires, in particular carcass reinforcement, crown reinforcement of such tires, in particular of industrial tires such as heavy goods vehicles or civil engineering. The invention also relates to these articles or semi-finished products made of plastic and / or rubber themselves when reinforced by a cable according to the invention, in particular the tires intended for the industrial vehicles mentioned. above, more particularly heavy-duty tires or civil engineering, as well as composite fabrics comprising a matrix of rubber composition of rubber reinforced with a gummed cable in situ according to the invention, usable as carcass reinforcement ply or top of such tires. [0124] COMPARATIVE TESTS

We compared several scrub compositions whose components and proportions are summarized in Table 1 below. The amounts of the components of the various compositions are expressed in parts per 100 parts by weight of elastomer (phr).

Table 1

[0126] Compositions tested

The composition T is in accordance with the state of the art known to those skilled in the art. Only the composition 4 is a scrubbing composition of a cable according to the invention. The compositions 1 to 3 and 5 allow to show the effects of certain components of the composition 4. The compositions T and 1 to 5 are uniform, that is to say identical at every point of the composition.

The compositions of Table 1 all comprise an elastomer, here a natural rubber and a reinforcing filler comprising predominantly by weight of the silica, here at least 30 pce inclusive, and preferably at least 40 pce inclusive silica. The silica is of the "HD" type - "Zeosil 1 165MP" from the company RHODIA in the form of microbeads (BET and CTAB: approximately 150-160 m2 / g). The antioxidant is N-1,3-dimethylbutyl-N-phenyl-para-phenylenediamine ("Santoflex 6- PPD" from FLEXSYS). The organosilane is TESPT ("Si69" from EVONIK). The vulcanization accelerator is N-cyclohexyl-2-benzothiazylsulfenamide ("Santocure CBS" from FLEXSYS).

The cobalt salt used in the composition T as adhesion promoter is cobalt naphthenate. Each composition 1 to 5 comprises at most 2 pce inclusive, preferably at most 1 pce inclusive of an adhesion promoter other than the combination of the epoxy resin and the metal oxide. In this case, each composition 1 to 5 is free of an adhesion promoter other than the combination of the epoxy resin and the metal oxide, more specifically free of metal salt, even more specifically free of cobalt salt.

Each composition 1 to 5 is free of amine hardener.

The vulcanization retarder of the composition T is N- (cyclohexylthio) phthalimide (CAS No. 17796-82-6). Each composition 1 to 5 comprises at most 0.20 phr included terminal of a vulcanization retarder other than the epoxy resin. In this case, each composition 1 to 5 is devoid of a vulcanization retarder other than the epoxy resin, more specifically free of N- (cyclohexylthio) phthalimide.

The epoxy resin of compositions 2 and 4 comprises at least one aromatic ring per unit, in this case a benzene ring per unit. The epoxy resin comprises, on average, between 3 and 10 epoxide functions per molecule, preferably between 4 and 7 epoxide functions per molecule. In this case, the epoxy resin is poly [(o-cresylglycidylether-) co-formaldehyde] (CAS No. 29690-82-2) also known as epoxy-cresol. The epoxy resin of composition 5 is polyglycerol polyglycidyl ether sold under the name Denacol EX512 (CAS No. 1 18549-88-5). The compositions 2, 4 and 5 comprise at most 8 pce inclusive, preferably at most 6 pce inclusive and more preferably at most 4 pce included terminal of the epoxy resin. Compositions 2, 4 and 5 comprise at least 0.1 pc. included, preferably at least 1 pce inclusive terminal and more preferably at least 1, 5 pce included terminal of the epoxy resin.

The metal oxide of the compositions 3, 4 and 5 is chosen from alkaline earth metal oxides, alkali metal oxides and transition metal oxides, preferably from alkaline earth metal oxides and alkali metal oxides. alkali metal oxides and more preferably among the alkaline earth metal oxides. In this case, the metal oxide of compositions 3, 4 and 5 is calcium oxide CaO (CAS No. 1305-78-8). The compositions 3, 4 and 5 comprise at most 3 phr included, preferably at most 1 pce inclusive and more preferably at most 0.5 phr of the metal oxide. Compositions 3, 4 and 5 comprise at least 0.05 pce inclusive and preferably at least 0.1 pce included terminal of the metal oxide.

[0134] Preparation of the compositions tested

The compositions are manufactured in appropriate mixers, using two successive preparation phases well known to those skilled in the art: a first phase of work or thermomechanical mixing (sometimes called "non-productive" phase) to high temperature, up to a maximum temperature (denoted Tmax) between 1 10 ° C and 190 ° C, preferably between 130 ° C and 180 ° C, followed by a second phase of mechanical work (sometimes called phase " productive ") at a lower temperature, typically below 110 ° C, for example between 60 ° C and 100 ° C, finishing phase during which is incorporated the crosslinking system or vulcanization; such phases have been described for example in the aforementioned documents EP 501227, EP 735088, WO00 / 05300, WO00 / 05301 or W002 / 083782.

For example, the first phase (non-productive) is conducted in a single thermomechanical step during which is introduced, in a suitable mixer such as a conventional internal mixer, initially all the constituents base materials (diene elastomer, reinforcing inorganic filler, antioxidant, resin, metal oxide and coupling agent), then in a second step, for example after one to two minutes of mixing, the possible agents of recovery or setting other additives and other additives, with the exception of the vulcanisation system; when the bulk density of the reinforcing inorganic filler is low (general case of silicas), it may be advantageous to split its introduction into two or more parts. A second thermomechanical work step can be added in this mixer internal, after falling of the mixture and intermediate cooling (cooling temperature preferably below 100 ° C), in order to subject the compositions a complementary thermomechanical treatment, in particular to further improve the dispersion in the elastomeric matrix, the load reinforcing inorganic agent and its coupling agent. The total mixing time, in this non-productive phase, is preferably between 2 and 10 minutes.

After cooling the mixture thus obtained, then incorporates, if necessary, the vulcanization system at low temperature, generally in an external mixer such as a roll mill; the whole is then mixed (productive phase) for a few minutes, for example between 5 and 15 minutes.

The final composition thus obtained is then calendered, for example in the form of a sheet, a plate or extruded, for example to form a rubber profile.

The vulcanization (or cooking) is conducted in a known manner at a temperature generally between 130 ° C and 200 ° C, preferably under pressure, for a sufficient time which may vary for example between 5 and 90 min in particular the baking temperature, the vulcanization system adopted, the vulcanization kinetics of the composition in question or the size of the tire.

[0140] Membership test

The peel test is carried out according to ASTM D-4393-98 on test pieces comprising metal cables of 2.30NF structure, a portion of which is interposed between two strips made in the prepared rubber composition and another portion is left free.

The force required to take off or peel the cable / rubber interface between the cables and one of the two strips is measured. The appearance of the peeled interface is evaluated by a representative score of the peel facies.

The facies of the control test piece comprising two rubber bands made with the composition is noted 100.

If, for a given composition, the number of stripped cables is less than the number of stripped cables of the test specimen, the adhesion of the cables to the rubber band is better than that of the test specimen and therefore the facies score is higher (greater than 100), proportionally to the number of non-bare cables. Conversely, if, for a given composition, the number of bare wires is greater than the number of bare cables of the test piece, the adhesion of the cables to the rubber band is less good than that of the test specimen and therefore the grade of facies is smaller (less than 100), proportionally to the number of non-denuded cables.

The adhesion test described above is carried out with vulcanized test specimens and / or aged under different conditions A, B, C and D.

Condition A (normal cooking) corresponds to a test carried out on a specimen cooked for a period of less than 1 hour at a temperature above 100 ° C.

Condition B (wet wet aging) corresponds to a test carried out on a specimen comprising the raw composition and aged for several days at a temperature above 30 ° C and at more than 50% relative humidity.

Condition C (aging in a corrosive atmosphere) corresponds to a test carried out on a specimen comprising the raw composition and aged for several days in an NaCl solution.

Condition D (wet wet aging) corresponds to a test carried out on a specimen fired for a period of less than 1 hour at a temperature above 100 ° C. and aged for several days at a temperature greater than 100.degree.

30 ° C and more than 50% relative humidity.

It will be understood that the higher the adhesion measured, the better the adhesive performance of the scrubbing composition and therefore the better are the endurance properties in fatigue-fretting and tire resistance, including a cable comprising such scrub composition.

The results of the adhesion test were collected under the different conditions in Table 2 below.

Table 2

The composition 4 has adhesion performance at least equivalent to the composition T of the state of the art regardless of the test conditions except condition A, conditions for which the difference is not significant, however. . The composition 4 has superior performance to the composition T of the state of the art under conditions B and C. The comparison of compositions 1 and 4 shows that the mere absence of vulcanization retarder is not responsible for the adhesion performance of the composition of the cables according to the invention.

The use of the epoxy resin without the oxide (composition 2) or the use of the oxide without the epoxy resin (composition 3) does not make it possible to obtain adhesion performance at least as high as the composition of the cables according to the invention, especially in the condition A. Thus, the comparison of the compositions 2, 3 and 4 shows that the epoxy resin and the oxide are, in combination, responsible for the adhesion performance of the composition 4 .

The epoxy resin of composition 4 comprising at least one aromatic ring per unit makes it possible to improve, in combination with the metal oxide, the adhesion performance with the metallic reinforcement element, unlike other epoxy resins. with saturated aliphatic chains, for example that of the composition 5.

[0156] Properties before cooking

[0157] Mooney plasticity

Mooney plasticity is achieved using a consistometer according to ASTM D 1646-99. Mooney plasticity measurement is carried out according to the following principle: the generally raw mixture is molded in a cylindrical chamber heated to a given temperature, usually 100 ° C and here 60 ° C. After a minute of preheating, a type L rotor rotates within the test tube at 2 revolutions per minute and the useful torque is measured to maintain this movement after 4 minutes of rotation. Mooney plasticity (ML 1 +4) is expressed in "Mooney unit" (UM, with 1 UM = 0.83 Newton meter).

[0159] Rheometry

The measurements are carried out at 150 ° C. with an oscillating chamber rheometer according to DIN 53529 - part 3 (June 1983). The evolution of the rheometric torque, ACouple, as a function of time describes the evolution of the stiffening of the composition as a result of the vulcanization reaction. The measurements are processed according to DIN 53529 - Part 2 (March 1983): T0 is the induction time, that is to say the time required for the beginning of the vulcanization reaction; Ta (for example T95) is the time necessary to reach a conversion of a%, that is to say a% (for example 95%) of the difference between the minimum and maximum couples. [0161] Properties after cooking

[0162] Traction tests

These tensile tests make it possible to determine the elastic stresses and the properties at break of the gum compositions. Unless otherwise indicated, they are carried out in accordance with the French standard NF T 46-002 of September 1988. A second elongation (Le., After a cycle of accommodation at the extension rate provided for the measurement itself) is measured. nominal secant modulus (or apparent stress, in MPa) at 10% elongation (denoted MA10), at 100% elongation (denoted MA100) and at 300% elongation (denoted MA300).

The results of the properties measurements before and after baking of the various compositions are summarized in Table 3 below. The values of the different properties are indicated in relative units (UR) relative to the values of the corresponding properties of the composition T. When the value of the property is greater than 100, the value of the property is greater than that of the composition T. Conversely, when the value of the property is less than 100, the value of the property is lower than that of the composition T.

Table 3

The Mooney plasticity of the compositions 1 to 4 is little modified compared to that of the composition T. Thus, the fluidity of composition 4 is not or little modified which allows to quickly adapt the industrial processes using the composition 4.

The vulcanization kinetics of the compositions 1, 2 and 4 is slower than that of the composition T, in particular that of the compositions 2 and 4. The comparison of the compositions T and 1 shows a retarding effect of the simultaneous disappearance of the salt of cobalt and the vulcanization retarder. The comparison of compositions 1, 2 and 4 shows that the mere presence of the resin makes it possible to slow down the kinetics of vulcanization and that it is not the absence of cobalt salt that induces the retarding effect. Thus, the resin can therefore supplement, or even replace, partially or totally, N- (cyclohexylthio) phthalimide.

The nominal secant moduli at 10%, 100% and 300% of the compositions 1 to 4 are little modified compared to those of the composition T.

Of course, the invention is not limited to the previously described embodiments.

It may be expected to mix several adhesion promoters.

For example, some son could be of non-circular section, for example plastically deformed, in particular with a substantially oval or polygonal section, for example triangular, square or rectangular.

The son of circular section or not, for example a corrugated wire, may be twisted, twisted helical or zig-zag. In such cases, it must of course be understood that the diameter of the wire represents the diameter of the cylinder of imaginary revolution which surrounds the wire (space diameter), and no longer the diameter (or any other transverse size, if its section is not circular) of the core wire itself.

For reasons of industrial feasibility, cost and overall performance, it is preferred to implement the invention with linear son, that is to say right, and conventional circular cross section.

It is also possible to envisage a multi-toned cable gummed in situ in accordance with the invention and of structure 1 × N in which N represents the number of strands wound together in a helix.

The characteristics of the various embodiments described or envisaged above may also be combined provided that they are compatible with one another.

Claims

1. In situ gummed monotoron cable (C) comprising:

an inner layer of the cable (CT1) comprising N1 internal wire (s),

an outer layer of the cable (CT3) comprising N3 external wires wound helically around the inner layer of the cable,

a rubber composition (20) disposed between the inner layer of the cable and the outer layer of the cable,

characterized in that the rubber composition (20) comprises a metal oxide and an epoxy resin comprising at least one unit comprising an aromatic ring and / or an unsaturated aliphatic chain.

2. monoforte cable gummed in situ (C) according to the preceding claim, wherein the aromatic ring is benzene.

3. In situ gummed monofilament (C) cable according to claim 1 or 2, wherein the epoxy resin is poly [(o-cresylglycidylether-) co-formaldehyde].

An in situ gummed monotoron cable (C) according to any one of the preceding claims, wherein the metal oxide is selected from alkaline earth metal oxides, alkali metal oxides and transition metal oxides, preferably from alkaline earth metal oxides and alkali metal oxides and more preferably from alkaline earth metal oxides.

5. In situ gummed monofilament (C) cable according to any one of the preceding claims, wherein the metal oxide is a calcium oxide.

6. In-situ gummed monotoron cable (C) according to any one of the preceding claims, wherein the rubber composition (20) comprises at most 8 pce inclusive, preferably at most 6 pce included and more preferably at most 4 pce included terminal of the epoxy resin.

7. In situ gummed monofilament cable (C) according to any one of the preceding claims, wherein the rubber composition (20) comprises at most 3 pce inclusive, preferably at most 1 pce included and more preferably at most 0 , 5 pce inclusive terminal of the metal oxide.

An in situ gummed single-ended cable (C) according to any one of claims 1 to 7, wherein the rubber composition (20) is present in each of the capillaries between the at least one internal wire (s). of the inner layer (CT1) and the N3 external wires of the outer layer (CT3).

9. In-situ gummed monotoron cable (C) according to any one of claims 1 to 7, comprising an intermediate layer of the cable (CT2) comprising N2 intermediate son helically wound around the inner layer (CT1) of the cable, the N3 external wires of the outer layer (CT3) of the cable being wound helically around the intermediate layer (CT2) of the cable.

In-situ gummed monofilament cable (C) according to claim 9, wherein the rubber composition (20) is present in each of the capillaries located between the internal thread (s) N1 (s) of the inner layer (CT1 ) and N2 intermediate son of the intermediate layer (CT2).

1. A monotoron gummed in situ cable (C) according to claim 9 or 10, wherein the rubber composition (20) is present in each of the capillaries between the N2 intermediate son of the intermediate layer (CT2) and the N3 son external layers (CT3).

12. Multi-strand cable gummed in situ (C), characterized in that it comprises at least one strand being a monotoron cable gummed in situ (C) according to any one of the preceding claims.

13. Multi-strand cable gummed in situ (C) according to the preceding claim, comprising:

an inner cable layer (CCI) comprising T1 internal strand (s) (Tl); an outer cable layer (CCE) comprising T2 outer strands (TE) wound helically around the inner layer (CCI); cable,

at least one of the inner and / or outer strands being a monotoron cable gummed in situ (C) according to any one of claims 1 to 11.

The in-situ gummed multi-strand cable (C) according to claim 13, wherein each outer strand (TE) is an in-situ gummed single-wired cable according to any one of claims 1 to 11.

The in-situ gummed multi-strand cable (C) according to claim 13 or 14, wherein each inner strand (Tl) is an in-situ gummed single-wired cable according to any one of claims 1 to 11.

16. Multi-strand cable gummed in situ (C) according to one of claims 13 to 15, comprising a rubber composition (20) disposed between the inner layer (CCI) T1 inner strand (s) (Tl ) of the cable and the outer layer (CCE) of the T2 outer strands (TE) of the cable (C), the rubber composition (20) comprising a metal oxide and an epoxy resin comprising at least one unit comprising an aromatic ring and / or an unsaturated aliphatic chain.

17. Multi-strand cable gummed in situ (C), characterized in that it comprises:

an inner layer (CCI) of the cable comprising T1 internal strand (s) (Tl),

an outer layer (CCE) of the cable comprising T2 outer strands (TE) wound helically around the inner layer (CCI) of the cable,

a rubber composition (20) disposed between the inner layer (CCI) of the cable (C) and the outer layer (CCE) of the cable, the rubber composition (20) comprising a metal oxide and an epoxy resin comprising at least one pattern comprising an aromatic ring and / or an unsaturated aliphatic chain.

18. Use of a monotoron cable gummed in situ (C) according to any one of claims 1 to 11 or a multi-strand cable gummed in situ (C) according to any one of claims 12 to 17 for the reinforcement of an article or semi-finished rubber product.

19. Use according to the preceding claim, wherein the rubber article is a tire.

20. A tire comprising an in-situ gummed monofilament cable (C) according to any one of claims 1 to 11 or an in-situ gummed multi-strand cable (C) according to any one of claims 12 to 17.