WO2019122686A1

WO2019122686A1 - Reinforced product comprising a composition comprising a polysulfide compound and tyre comprising said reinforced product

Info

Publication number: WO2019122686A1
Application number: PCT/FR2018/053370
Authority: WO
Inventors: Anne-Frédérique SALIT; Sophie GANDER; Anne-Lise THUILLIEZ
Original assignee: Compagnie Generale Des Etablissements Michelin
Priority date: 2017-12-19
Filing date: 2018-12-18
Publication date: 2019-06-27
Also published as: EP3728432A1

Abstract

The invention relates to a reinforced product, which can be used in particular for reinforcing a rubber finished article, comprising one or more textile or metal reinforcing thread(s), said thread(s) being covered with a sheath comprising a thermoplastic polymer composition, the thread(s) being themselves embedded in a rubber composition referred to as coating rubber, characterized in that this coating rubber is a composition based on at least one diene elastomer, a reinforcing filler and a polysulfide compound of general formula (I) wherein A and B together form a covalent bond, or A is a hydrogen atom and B is a hydrogen atom or an S-R₁-Z-R₂-SH group; n is a number greater than or equal to 1; p is a number greater than or equal to 1; Z represents a covalent bond or a heteroatom selected from -O-, -Si-, -(S)_m- and -N(H)-, wherein m is a number greater than or equal to 1; and R1 and R2 represent, independently of each other, identical or different, linear or branched divalent hydrocarbon-based groups comprising from 1 to 18 carbon atoms.

Description

REINFORCED PRODUCT COMPRISING A COMPOSITION COMPRISING A POLY SULFURED AND PNEUMATIC COMPOUND COMPRISING SAID PRODUCT

STRENGTHENS

The field of the present invention is that of reinforced products (or reinforced semi-finished products) comprising reinforcement elements or "reinforcements", metal or textile, sheathed with a thermoplastic polymeric composition, said sheathed reinforcements being embedded in a composition of rubber. These reinforced products or reinforced semi-finished products can be used in particular for reinforcing finished articles of rubber such as for example tires for motor vehicles.

These reinforced products or reinforced semi-finished products can be used in particular in the carcass reinforcement of the tires, the crown, and in the protection of the reinforcement reinforcement of the crown, also called belts. ("belts") of these tires.

A tire with a radial carcass reinforcement, in known manner, comprises a tread, two inextensible beads, two flanks connecting the beads to the tread and a belt circumferentially disposed between the carcass reinforcement and the tread, this belt and the carcass reinforcement being constituted by various plies (or "layers") of rubber reinforced by reinforcing elements or reinforcements such as cords or monofilaments, of the metal or textile type.

More specifically, a tire belt generally consists of at least two superposed belt plies, sometimes called "working" or "crossed" plies, whose reinforcements, textile or metal are arranged substantially parallel to each other at the same time. interior of a web, but crossed from one web to another, that is to say inclined, symmetrically or otherwise, with respect to the median circumferential plane, of an angle which is generally between 10 ° and 45 ° depending on the type of tire considered. Each of these two crossed plies consists of a rubber matrix or "coating gum" or sometimes "calendering gum" coating the reinforcements. In the belt, the crossed plies may be supplemented by various other plies or layers of auxiliary rubber, of varying widths depending on the case, with or without reinforcements; examples of simple rubber cushions include so-called "protection" plies intended to protect the rest of the belt from external aggression, perforations, or so-called "hooping" plies comprising reinforcements oriented substantially along the circumferential direction (so-called "zero degree" plies), whether radially external or internal with respect to the crossed plies. For reinforcing the above belts, in particular their crossed plies, protective plies or hooping plies, reinforcement is generally used in the form of steel cords or textile cords. ") consisting of thin wires assembled together by wiring or twisting.

To effectively fulfill their function of reinforcing radial tire belts, subject as we know to very important constraints when rolling tires, these steel cables or textiles must meet a very large number of technical criteria, sometimes contradictory, such as high compression endurance, high tensile, wear and corrosion resistance, high adhesion to the surrounding rubber, and be able to maintain such performance at a very high level for as long as possible.

The adhesion between the cables, in particular metal and the surrounding rubber is therefore a key property for the effectiveness of the reinforced semi-finishes. State of the art is known of coating compositions comprising a diene elastomer, in particular natural rubber, a reinforcing filler, and a very specific vulcanization system for these compositions. This vulcanization system usually comprises sulfur and zinc oxide at high levels, low rate stearic acid, a so-called slow vulcanization accelerator and a vulcanization retarder.

The presence of a high level of sulfur has the advantage of allowing the consumption of a portion of this sulfur for the sulphidation of metal cables, especially brass, and the crosslinking of the elastomeric matrix by vulcanization.

This specific vulcanization system, if it makes it possible to obtain a satisfactory adhesion between the cable and the surrounding rubber composition, constitutes a strong constraint during the manufacture of semi-finished products. In particular, the processability, the cooking time or the elongation modulus can be impacted, causing implementation difficulties, an extended preparation time and therefore a greater cost of the reinforced semi-finished products. In addition, this specific vulcanization system causes a certain sensitivity to thermooxidation, resulting in a change of mixtures over time, which can lead to cracking of the mixtures.

In order to meet the disadvantages of conventional coating systems, it has been proposed in WO2016 / 058942 a coating gum based on at least one diene elastomer, a reinforcing filler and a sulfur vulcanization system, in which the ratio of the amounts, in phr (parts by weight per hundred parts by weight elastomer), sulfur and reinforcing filler is less than 0.08. For example in the described compositions, the amount of sulfur is 1.6 phr and the amount of carbon black is 47 phr. It is interesting for the manufacturers to have coating gum compositions that can be crosslinked at high temperature, in order to save time in the manufacturing process, without penalizing the adhesion of the coating gum to the reinforcement, such as a sheathed wire, embedded in this coating gum.

In this context, the applicants have now discovered the present invention, which relates to a reinforced product, used in particular for the reinforcement of a finished article of rubber, comprising one or more wire (s) of reinforcement, textile (s) or metal (S), said one or more yarn (s) being covered with a sheath comprising a thermoplastic polymeric composition, the sheathed yarn (s) being themselves embedded in a so-called rubber compound coating composition, characterized in that said coating gum is a composition based on at least one diene elastomer, a reinforcing filler and a polyisulfide compound of general formula (I)

in which :

A and B together form a covalent bond, or A represents a hydrogen atom and B represents a hydrogen atom or a group -SR _I -ZR ₂ -SH,

n is a number greater than or equal to 1,

p is a number greater than or equal to 1,

Z represents a covalent bond or a heteroatom selected from -O-, -Si-, - (S) _m - and -N (H) -, wherein m is a number greater than or equal to 1,

and R1 and R2 represent, independently of one another, identical or different linear or branched divalent hydrocarbon groups having from 1 to 18 carbon atoms.

By the expression A and B together form a covalent bond, it is meant that the sulfur atoms adjacent to A and B respectively are connected directly by a covalent bond. In this case, the polysulfurized compound of general formula (I) is cyclic.

This invention allows a high temperature crosslinking, and therefore an accelerated production of reinforced products (or semi-finished reinforced), without reducing the adhesion of the coating gum to the reinforcement, such as a sheathed wire, embedded in this coating gum.

Preferably, the invention relates to a reinforced product as defined above in which R1 and R2 represent linear divalent hydrocarbon groups. Preferably, R1 and R2 represent an alkylene radical having from 1 to 18 carbon atoms. carbon, preferably from 2 to 10 carbon atoms. According to a preferred embodiment for the invention, R 1 and R 2 are identical radicals.

Also preferentially, the invention relates to a reinforced product as defined above in which n represents a number in a range from 1 to 8, preferably from 1 to 6, more preferably from 1 to 3.

Preferably, the invention relates to a reinforced product as defined above in which p represents a number in a range from 1 to 30, preferably from 1 to 15, more preferably from 1 to 3.

Also preferably, the invention relates to a reinforced product as defined above wherein A and B together form a covalent bond. Alternatively and preferably also, A represents a hydrogen atom and B represents a hydrogen atom or a -S-R1-Z-R2-SH group, preferably B represents a -S-R1-Z-R2-SH group. .

Preferably, the invention relates to a reinforced product as defined above wherein Z represents a covalent bond or a heteroatom selected from the group consisting of -Si, - (S) m- and -N (H) -.

Also preferentially, the invention relates to a reinforced product as defined above in which m is a number in a range from 1 to 8, preferably from 1 to 6. Preferably, m is a number included in a range ranging from 1 to 3, preferably from 1 to 2.

Preferably, the invention relates to a reinforced product as defined above in which Z represents a covalent bond. Alternatively and preferably also, Z represents a radical - (S) m-.

Preferably, the invention relates to a reinforced product as defined above in which A and B together form a covalent bond, R1 and R2 are C1-C7 alkylenes, Z is a covalent bond or a group -S- or - SS-, n represents 1 or 3 and p represents 1.

Alternatively and preferably also, the invention relates to a reinforced product as defined above in which A is a hydrogen atom, B represents a group -S-R1-Z-R2-SH; Wherein R 1 and R 2 are C 1 -C 7 alkylenes, Z being a bond or a group -S- or -SS-, where n is 1 or 3 and p is a number within a range of 1 to 30. Preferably, the invention relates to a reinforced product as defined above in which the polysulfurized compound of general formula (I) is present in the composition of the coating gum at a rate in a range from 0, From 5 to 10 phr, preferably from 0.5 to 5 phr, and more preferably from 0.5 to 3 phr.

Preferably, the invention relates to a reinforced product as defined above wherein the composition of the coating gum comprises a vulcanization accelerator selected from the group consisting of thiazoles, sulfenamides, guanidines, amines, aldehyde amines, dithiophosphates, xanthates, thiurams, dithiocarbamates and mixtures thereof.

Also preferably, the invention relates to a reinforced product as defined above in which the composition of the coating gum comprises a complementary vulcanization accelerator, different from the preceding accelerator, described above, chosen from the group consisting of diphenyl guanidine (DPG), triphenyl guanidine (TPG), diorthotolyl guanidine (DOTG), o-tolylbiguanide (OTBG), benzothiazole disulfide (MBTS), tetramethylthiuram disulfide (TMTD), disulfide tetrabenzylthiuram (TBzTD), zinc dibenzyldithiocarbamate (ZBEC), zinc N, N'-dimethylcarbamodithioates (ZDMC), zinc N, N'-diethylcarbamodithioates (ZDEC), zinc N, N'-dibutylcarbamodithioates (ZDBC), zinc N, N'-dibenzylcarbamodithioates (ZDBC), zinc isopropylxanthate (ZIX), and mixtures thereof. Very preferably, the complementary vulcanization accelerator is zinc dibenzyldithiocarbamate (ZBEC).

Preferably, the invention relates to a reinforced product as defined above in which the composition of the coating gum does not comprise a vulcanization retarder.

Also preferably, the invention relates to a reinforced product as defined above in which the composition of the coating gum does not comprise elemental sulfur or comprises less than 1 phr, preferably less than 0.5 phr. .

Also preferentially, the invention relates to a reinforced product as defined above in which the composition of the coating gum does not comprise a cobalt salt. Preferably, the composition of the coating gum does not comprise an adhesion promoter.

Preferably, the invention relates to a reinforced product as defined above in which the diene elastomer of the composition of the coating gum predominantly comprises an elastomer chosen from the group consisting of natural rubber, synthetic polyisoprene or mixture of these. Preferably, the composition of the The coating gum comprises from 60 to 100 phr, preferably from 70 to 100 phr of an elastomer selected from the group consisting of natural rubber, synthetic polyisoprene or a mixture thereof. More preferably, the composition of the coating gum comprises from 80 to 100 phr, preferably from 90 to 100 phr, of an elastomer chosen from the group consisting of natural rubber, synthetic polyisoprene or a mixture of these.

Preferably, the invention relates to a reinforced product as defined above in which the composition of the coating gum comprises from 20 to 80 phr, preferably from 30 to 70 phr, of reinforcing filler. Preferably, the composition of the coating gum comprises from 35 to 60 phr, preferably from 40 to 55 phr, of reinforcing filler.

Also preferably, the invention relates to a reinforced product as defined above wherein the composition of the coating gum comprises carbon black as the majority filler.

Preferably, the invention relates to a reinforced product as defined above in which the reinforcement son or son are metal son.

Also preferentially, the invention relates to a reinforced product as defined above in which the sheathed yarn (s) is coated with an adhesive, preferably a Resorcinol-F oraldehyde-based adhesive. Latex.

The invention also relates to a tire comprising a reinforced product as defined above, preferably at least in a web chosen from the reinforcement plies of the crown and the carcass plies.

Among these tires, the invention relates in particular to tires intended to equip tourism-type motor vehicles, SUVs ("Sport Utility Vehicles"), two wheels (in particular bicycles, motorcycles), planes, such as industrial vehicles chosen from light trucks, "Heavy goods vehicles" means metros, buses, road transport vehicles (trucks, tractors, trailers), off-the-road vehicles such as agricultural or civil engineering machinery, other transport vehicles or handling. Also, the reinforced product of the invention can be used for the manufacture of rubber belts or for conveyor belts such as conveyor belts.

The invention as well as its advantages will be readily understood in the light of the description and the following exemplary embodiments, as well as figures relating to these examples which diagrammatically show: in radial section, a pneumatic tire with a radial carcass reinforcement according to the invention, incorporating in its belt or in its carcass a reinforced product according to the invention (FIG.

in cross section, an example of a reinforced product according to the invention, in the form of 3 cables individually covered with a sheath, and embedded together in the coating composition (Figure 2);

in cross section, another example of a reinforced product according to the invention, in the form of 3 groups of cables, each group of cables being covered with a sheath, the three groups of cables, sheathed, being embedded in the composition coating (Fig. 3); in cross section, another example of a reinforced product according to the invention, in the form of a strip of 3 cables covered with the same sheath and embedded in the coating composition (Figure 4);

in cross section, another example of a reinforced product according to the invention, in the form of a strip of 3 groups of cables covered with the same sheath and embedded in the coating composition (Figure 5).

DETAILED DESCRIPTION OF THE INVENTION

In the present description, unless expressly indicated otherwise, all the percentages (%) indicated are% by weight.

The abbreviation "pce" (usually "phr" in English) means parts by weight per hundred parts of elastomer or rubber (of the total elastomers if several elastomers are present).

On the other hand, any range of values designated by the expression "between a and b" represents the range of values from more than a to less than b (i.e. terminals a and b excluded) while any range of values designated by the term "from a to b" means the range from a to b (i.e., including the strict limits a and b).

The reinforced product of the invention also known as "reinforced semi-finished", "composite reinforcement" is thus a sheathed reinforcement, that is to say covered with a sheath, then embedded in a so-called coating composition, in rubber, raw or cooked (crosslinked). It has the essential characteristic of comprising at least one (that is to say one or more) reinforcing wire (s), textile (s) or metal (s), and a specific composition called cladding layer or sheath, which covers, individually wraps said wire or collectively several wires, forming a sheathed reinforcement. This sheathed reinforcement is then itself embedded in a rubber composition, called coating composition or coating gum. The structure of this reinforced product of the invention is described in detail below. By the term "composition based on" is meant a composition comprising the mixture and / or the reaction product in situ of the various basic constituents used, some of these constituents being able to react and / or being intended to react with one another, at least partially, during the various phases of manufacture of the composition, or during subsequent firing, modifying the composition as it was initially prepared. Thus, the compositions as implemented for the invention may be different in the uncrosslinked state and in the crosslinked state.

When reference is made to a "majority" compound, in the sense of the present invention, it is understood that this compound is predominant among the compounds of the same type in the composition, that is to say that it is the one which represents the largest amount by mass among the compounds of the same type. Thus, for example, a majority polymer is the polymer representing the largest mass relative to the total mass of the polymers in the composition. In the same way, a so-called majority charge is that representing the largest mass among the charges of the composition. For example, in a system comprising a single polymer, it is the majority within the meaning of the present invention; and in a system comprising two polymers, the majority polymer accounts for more than half of the mass of the polymers. In contrast, a "minor" compound is a compound that does not represent the largest mass fraction among compounds of the same type.

1 - Sheathed reinforcement

Reinforcement thread

In the present application, the term "reinforcing thread" is generally understood to mean any elongate element of great length relative to its cross section, whatever the shape of the latter, for example circular, oblong, rectangular or square. , or even flat, this wire may be rectilinear as non-rectilinear, for example twisted or corrugated. When it is circular in shape, its diameter is preferably less than 5 mm, more preferably in a range of 0.1 to 2 mm.

This reinforcement yarn may take any known form, it may be for example an elementary monofilament of large diameter (for example and preferably equal to or greater than 50 mh), an elementary ribbon, a film, a multifilament fiber (consisting of a plurality of elementary filaments of small diameter, typically less than 30 mhi), a textile twist formed of several fibers twisted together, a textile or metal cable formed of several fibers or monofilaments Wired or twisted together, or an assembly, a row of threads comprising several of these monofilaments, fibers, twisted or ropes grouped together. In the present application, generally means by wire reinforcement or sheathed reinforcement, one or more reinforcing wire (s) covered (s) of a sheath.

According to a preferred embodiment, the filament reinforcement useful for the needs of the invention may therefore be in the form of a single reinforcing thread, covered in its sheath, to form a sheathed unitary composite yarn embedded in the composition of the invention. specific coating of the invention.

According to another preferred embodiment, the filament reinforcement useful for the purposes of the invention may also be in the form of several reinforcing threads (monofilaments, ribbons, films, fibers, twists or cables) grouped together, for example aligned according to a main direction, rectilinear or not. These reinforcing threads are then collectively covered in their sheath and then embedded in the specific coating composition of the invention, to constitute a reinforced product according to the invention, for example a band, strip, a composite rubber fabric of various shapes. such as those usually encountered in the tire structure. As preferred examples of reinforced products in accordance with the invention, mention will be made in particular of the fabrics constituting the carcass reinforcement plies, the crown protection plies, the hooping crest plies or the working crown plies present in the belts. tires.

According to a preferred embodiment, the reinforcing wire is a metal reinforcing wire.

By metal, is meant by definition a wire (or monofilament) consisting predominantly (that is to say, for more than 50% of its mass) or integrally (for 100% of its mass) of a metallic material. Each monofilament is preferably made of steel, more preferably of pearlitic (or ferrito-pearlitic) carbon steel hereinafter referred to as "carbon steel", or else of stainless steel (by definition, steel comprising at least 11% chromium and at least minus 50% iron). When carbon steel is used, its carbon content (% by weight of steel) is preferably between 0.2% and 0.9%. It is preferable to use a Steel Cord type steel with normal resistance (called "NT" for "Normal Tensile") or high resistance (called "HT" for "High Tensile") whose tensile strength (Rm) is preferably greater than 2000 MPa, more preferably greater than 2500 MPa and less than 3000 MPa (measurement carried out in traction according to ISO 6892 of 1984). The steel may be coated with an adhesive layer such as brass or zinc.

According to another preferred embodiment, the reinforcing yarn is a textile yarn, consisting of a synthetic or natural polymeric material, or even a mineral material. By way of examples, mention may be made in particular of reinforcing yarns made of polyvinyl alcohol (PVA), aliphatic polyamide (eg polyamides 4-6, 6, 6-6, 11 or 12), aromatic polyamide (or "aramid"), polyamide-imide, polyimide, polyester (eg PET, PEN), aromatic polyester, polyethylene, polypropylene, polyketone, cellulose, rayon, viscose, polyphenylene benzobisoxazole (PBO), glass, carbon or ceramic.

Sheath

The wire reinforcement described below includes a sheath, also called sheathing layer. This type of sheath is well known to those skilled in the art. For the purposes of the invention, the sheath comprises a thermoplastic polymeric composition. In one embodiment, the sheath comprises a single layer of the thermoplastic polymeric composition. In a variant, the sheath comprises several layers, at least one of which comprises a thermoplastic polymeric composition.

By thermoplastic polymeric composition is meant a composition comprising at least one polymer having the properties of a thermoplastic polymer. The composition may optionally further include other thermoplastic polymers, elastomers and other non-polymeric components.

Among the thermoplastic polymers that are useful in the preparation of the sheath, a thermoplastic polymer preferably selected from the group consisting of polyamides, polyesters and polyimides, more particularly from the group consisting of aliphatic polyamides, and preferably a thermoplastic polymer, will be selected for example and the polyesters. Among the polyesters that may be mentioned for example are PET (polyethylene terephthalate), PEN (polyethylene naphthalate), PBT (polybutylene terephthalate), PBN (polybutylene naphthalate), PPT (polypropylene terephthalate), PPN (polypropylene naphthalate). Among the aliphatic polyamides that may be mentioned in particular are polyamides 4-6, 6, 6-6, 11 or 12. This thermoplastic polymer is preferably an aliphatic polyamide, more preferably a polyamide 6, 6-6 or a polyamide 11.

The elastomers that can be used in the thermoplastic composition of the sheath may preferably be of two types: styrenic thermoplastic elastomers and functionalized diene elastomers. These two types of elastomers are described below.

Styrenic thermoplastic elastomers (abbreviated to "TPS") are thermoplastic elastomers in the form of styrene-based block copolymers. Of intermediate structure between thermoplastic polymers and elastomers, they consist in a known manner of rigid polystyrene blocks connected by flexible elastomer blocks, for example polybutadiene, polyisoprene or poly (ethylene / butylene). This is the reason why, in known manner, TPS copolymers are generally characterized by the presence of two glass transition peaks, the first peak (the lowest temperature, negative) being relative to the elastomer block of the TPS copolymer, the second peak (highest temperature, positive, typically around 80 ° C or more) being relative to the thermoplastic portion (styrene blocks) of the TPS copolymer. These TPS elastomers are often triblock elastomers with two rigid segments connected by a flexible segment. The rigid and flexible segments can be arranged linearly, star or connected. These TPS elastomers may also be diblock elastomers with a single rigid segment connected to a flexible segment. Typically, each of these segments or blocks contains at least more than 5, usually more than 10 base units (e.g., styrene units and isoprene units for a styrene / isoprene / styrene block copolymer). In this, of course, they should not be confused with random diene copolymer elastomers such as for example SIR (styrene-isoprene copolymers) or SBR (styrene-butadiene copolymers) which, in a well-known manner, have no thermoplastic character .

The TPS useful for preparing the sheath is preferably unsaturated. By unsaturated TPS elastomer is defined by definition and well known a TPS elastomer which is provided with ethylenic unsaturations, that is to say which has carbon-carbon double bonds (conjugated or not); conversely, a TPS elastomer said saturated is of course a TPS elastomer which is free of such double bonds.

Also preferably, the TPS useful for the preparation of the cladding, is functionalized carrying functional groups chosen from epoxide, carboxyl, anhydride or acid ester groups or functional groups. According to a particularly preferred embodiment, this TPS elastomer is an epoxidized elastomer, that is to say one carrying one or more epoxide groups.

Preferably, the TPS used in the preparation of the sheath is chosen from the group consisting of styrene / butadiene (SB), styrene / isoprene (SI), styrene / butadiene / butylene (SBB), styrene / butadiene / block copolymers. isoprene (SBI), styrene / butadiene / styrene (SBS), styrene / butadiene / butylene / styrene (SBBS), styrene / isoprene / styrene (SIS), styrene / butadiene / isoprene / styrene (SBIS) and mixtures of these copolymers . Many TPS elastomers are commercially available. As an example of unsaturated and epoxidized SBS, mention may be made of the "Epoffiend" known and commercially available from Daicel.

Among the elastomers useful in the preparation of the sheath, there will be chosen for example and preferably a functionalized diene elastomer, said elastomer carrying functional groups selected from groups or functions epoxide, carboxyl, anhydride or acid ester. Preferably, the functional groups are epoxide groups, that is to say that the diene elastomer is an epoxide diene elastomer. Among the poly (p phenylene ether) (or PPE) used for the preparation of the sheath, one will choose, for example and preferably a PPE selected from the group consisting of poly (2,6-dimethyl-1,4-phenylene -ether), poly (2,6-dimethyl-2,3,6-trimethyl-1,4-phenylene ether), poly (2,3,6-trimethyl-1,4-phenylene ether) , poly (2,6-diethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), poly (2-methyl-6-propyl) -1,4 phenylene ether), poly (2,6-dipropyl-1,4-phenylene ether), poly (2-ethyl-6-propyl-1,4-phenylene ether), poly (2,6-dilauryl) 1,4-phenylene ether), poly (2,6-diphenyl-1,4-phenylene ether), poly (2,6-dimethoxy-1,4-phenylene ether), poly (1,6- 1,4-diethoxy-phenylene ether), poly (2-methoxy-6-ethoxy-1,4-phenylene ether), poly (2-ethyl-6-stearyloxy-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether), poly (2-methyl-6-phenyl-1,4-phenylene ether), poly (2 ethoxy-1,4-phenylene ether), poly (2-chloro-1,4-phenylene ether), poly (2,6-dibromo-1,4-phenylene ether), poly (3-bromo- 2,6-dimethyl-1,4-phenylene ether), their respective copolymers, and mixtures of these homopolymers or copolymers. According to a particular and preferred embodiment, the EPP used is poly (2,6-dimethyl-1,4-phenylene ether) also sometimes referred to as polyphenylene oxide (or abbreviated as "PPO"). Examples of such commercially available EPPs or PPOs are, for example, the PEP under the name "Xyron S202" from Asahi Kasei or the "Noryl SA120" EPP from Sabic.

Preferably, according to its precise composition, the sheath comprising a thermoplastic polymeric composition as described above may be self-adhering, that is to say that its composition may be such that it has a very good adhesion to the composition surrounding rubber without requiring the use of glue. This type of thermoplastic polymer composition as self-adhering sheath is described in the applications WO2010 / 136389, WO2010 / 105975, WO2011 / 012521, WO2011 / 051204, WO2012 / 016757, WO2012 / 038340, WO2012 / 038341, WO2012 / 069346, WO2012 / 104279. , WO2012 / 104280, WO2012 / 104281, WO2013 / 117474 and WO2013 / 117475.

Alternatively and advantageously also, the sheath is coated with an adhesion layer (glue) between the sheath and the elastomer matrix. The adhesive used is for example of the RFL type (Resorcinol-Formaldehyde-Latex) or for example, as described in publications WO2013017421, WO2013017422, WO2013017423.

2 - Diene Elastomer Coating Composition

The coating composition of the reinforced product of the invention may contain a single diene elastomer or a mixture of several diene elastomers.

By elastomer (or "rubber", the two terms being considered synonymous) of the "diene" type, it will be recalled here that it is to be understood in known manner that one (or several) elastomer derived at least in part (ie, a homopolymer or a copolymer) of monomers dienes (monomers bearing two carbon-carbon double bonds, conjugated or not).

The diene elastomers can be classified into two categories: "essentially unsaturated" or "essentially saturated". The term "essentially unsaturated" is generally understood to mean a diene elastomer derived at least in part from conjugated diene monomers, having a level of units or units of diene origin (conjugated dienes) which is greater than 15% (mol%); Thus, diene elastomers such as butyl rubbers or copolymers of dienes and alpha-olefins of the EPDM type do not fall within the above definition and may in particular be described as "essentially saturated" diene elastomers ( low or very low diene origin, always less than 15%). In the category of "essentially unsaturated" diene elastomers, the term "highly unsaturated" diene elastomer is particularly understood to mean a diene elastomer having a content of units of diene origin (conjugated dienes) which is greater than 50%.

As these definitions are given, the term "diene elastomer" can be understood more particularly to be used in the compositions according to the invention:

(a) any homopolymer obtainable by polymerization of a conjugated diene monomer having from 4 to 12 carbon atoms;

(b) any copolymer obtained by copolymerization of one or more conjugated dienes with each other or with one or more vinyl aromatic compounds having from 8 to 20 carbon atoms;

(c) a ternary copolymer obtained by copolymerization of ethylene, an α-olefin having 3 to 6 carbon atoms with a non-conjugated diene monomer having from 6 to 12 carbon atoms, for example elastomers obtained from ethylene, propylene with a non-conjugated diene monomer of the aforementioned type, such as in particular hexadiene-1,4, ethylidene norbornene, dicyclopentadiene;

(d) a copolymer of isobutene and isoprene (butyl rubber), as well as the halogenated versions, in particular chlorinated or brominated, of this type of copolymer.

Although it applies to any type of diene elastomer, the person skilled in the tire art will understand that the present invention is preferably implemented with essentially unsaturated diene elastomers, in particular of the type (a) or (b). ) above.

As conjugated dienes 1,3-butadiene, 2-methyl-1,3-butadiene (or isoprene), 2,3-di (C 1 -C 5) alkyl-1,3-butadienes, such as for example 2,3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-butadiene, 2-methyl-3- isopropyl-1,3-butadiene, aryl-1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene. Suitable vinylaromatic compounds are, for example, styrene, ortho-, meta-, para-methylstyrene, the commercial mixture "vinyl-toluene", para-tert-butylstyrene, methoxystyrenes, chlorostyrenes, vinylmesitylene, divinylbenzene, vinylnaphthalene.

The copolymers may contain between 99% and 20% by weight of diene units and between 1% and 80% by weight of vinylaromatic units. The elastomers may have any microstructure which is a function of the polymerization conditions used, in particular the presence or absence of a modifying and / or randomizing agent and the amounts of modifying and / or randomizing agent used. The elastomers can be for example block, statistical, sequenced, microsequenced, and be prepared in dispersion or in solution; they may be coupled and / or starred or functionalized with a coupling agent and / or starring or functionalization. For coupling with carbon black, there may be mentioned, for example, functional groups comprising a C-Sn bond or amine functional groups such as aminobenzophenone for example; for coupling to a reinforcing inorganic filler such as silica, mention may be made, for example, of silanol or polysiloxane functional groups having a silanol end (as described, for example, in FR 2,740,778, US 6,013,718 and WO 2008/141702), alkoxysilane groups (as described for example in FR 2,765,882 or US 5,977,238), carboxylic groups (as described for example in WO 01/92402 or US 6,815,473, WO 2004/096865 or US 2006/0089445). ) or polyether groups (as described for example in EP 1 127 909, US 6,503,973, WO 2009/000750 and WO 2009/000752). As other examples of functionalized elastomers, mention may also be made of elastomers (such as SBR, BR, NR or IR) of the epoxidized type. These functionalized elastomers may be used in a blend with each other or with unfunctionalized elastomers. For example, a functionalized silanol or polysiloxane elastomer having a silanol end, in admixture with a coupled and / or stanned tin elastomer (described in WO 11/042507), may be used, the latter representing a rate of from 5 to 50 %, for example from 25 to 50%.

Suitable polybutadienes and in particular those having a content (mol%) in units-1,2 of between 4% and 80% or those having a content (mol%) in cis-1,4, greater than 80%, polyisoprenes, copolymers of butadiene-styrene and in particular those having a Tg (glass transition temperature Tg, measured according to ASTM D3418) of between 0 ° C. and -70 ° C. and more particularly between -10 ° C. and -60 ° C., styrene content between 5% and 60% by weight and more particularly between 20% and 50%, a content (% molar) in -1,2 bonds of the butadiene part of between 4% and 75%, a content (% molar) in trans-1,4 bonds between 10% and 80%, butadiene-isoprene copolymers and in particular those having an isoprene content of between 5% and 90% by weight and a Tg of -40 ° C to At 80 ° C., the isoprene-styrene copolymers and especially those having a styrene content of between 5% and 50% by weight and a Tg between -5 ° C and -60 ° C. In the case of butadiene-styrene-isoprene copolymers, those having a styrene content of between 5% and 50% by weight and more particularly between 10% and 40%, an isoprene content of between 15% and 60% by weight and more particularly between 20% and 50%, a butadiene content of between 5% and 50% by weight and more particularly between 20% and 40%, a content (mol%) in units - 1,2 of the butadiene part of between 4% and 85%, a content (mol%) in trans units -1,4 of the butadiene part of between 6% and 80% %, a content (mol%) in -1,2 units plus -3,4 of the isoprene part of between 5% and 70% and a content (mol%) in trans units -1,4 of the isoprene part between 10% and 50%, and more generally any butadiene-styrene-isoprene copolymer having a Tg of between -20 ° C and -70 ° C.

In summary, the diene elastomer of the composition is preferably chosen from the group of highly unsaturated diene elastomers consisting of polybutadienes (abbreviated "BR"), synthetic polyisoprenes (IR), natural rubber (NR), copolymers butadiene, 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), butadiene-acrylonitrile copolymers (NBR), butadiene-styrene-acrylonitrile copolymers (NSBR) or a mixture of two or more of these compounds. In the case of an SBR elastomer (ESBR or SSBR), an SBR having an average styrene content, for example between 20% and 35% by weight, or a high styrene content, for example 35 to 35% by weight, is used in particular. 45%, a vinyl ring content of the butadiene part of between 15% and 70%, a content (mol%) of trans 1,4 bonds of between 15% and 75% and a Tg of between -10 ° C. and 55 ° C; such an SBR can be advantageously used in admixture with a BR preferably having more than 90% (mol%) of 1,4 cis bonds.

According to a particular preferential embodiment, the diene elastomer is a predominantly isoprene elastomer (that is to say whose mass fraction of isoprene elastomer is the largest, compared to the mass fraction of other elastomers). By "isoprene elastomer" is meant in known manner a homopolymer or copolymer of isoprene, in other words a diene elastomer selected from the group consisting of natural rubber (NR) which can be plasticized or peptized, the polyisoprenes of synthesis (IR), the various isoprene copolymers and the mixtures of these elastomers. Among the isoprene copolymers, mention will in particular be made of copolymers of isobutene-isoprene (butyl rubber IIR), isoprene-styrene (SIR), isoprene-butadiene (BIR) or isoprene-butadiene-styrene ( SBIR). This isoprene elastomer is preferably natural rubber or a synthetic cis-1,4 polyisoprene; of these synthetic polyisoprenes, polyisoprenes having a level (mol%) of cis-1,4 bonds greater than 90%, more preferably still greater than 98%, are preferably used. Preferably according to this embodiment, the level of isoprene diene elastomer is more than 50 phr (that is to say 50 to 100 phr), more preferably at least 60 phr (i.e. 60 to 100 phr), more preferably at least 70 phr (i.e. 70 to 100 phr). pce), more preferably still at least 80 phr (that is to say 80 to 100 phr) and very preferably at least 90 phr (that is to say 90 to 100 phr). ). In particular according to this embodiment, the level of isoprene diene elastomer is very preferably 100 phr.

Reinforcing charge

The composition according to the invention comprises a reinforcing filler. 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 reinforcing inorganic filler such as silica, silica, can be used. alumina, or a blend of these two types of filler.

Carbon blacks are suitable for all carbon blacks, especially so-called pneumatic grade blacks. Among these, the reinforcing carbon blacks of the 100, 200 or 300 series (ASTM grades), for example the N115, N134, N234, N326, N330, N339, N347 or N375 blacks, or even targeted applications, blacks of higher series (eg N660, N683, N772). The carbon blacks could for example already be incorporated into an isoprene elastomer in the form of a masterbatch (see for example WO 97/36724 or WO 99/16600).

As examples of organic fillers other than carbon blacks, mention may be made of functionalized polyvinyl organic fillers as described in applications WO-A-2006/069792 and WO-A-2006/069793, WO-A-2008/003434. and WO-A-2008/003435.

The composition may contain a type of silica or a blend of several silicas. The silica used may be any reinforcing silica known to those skilled in the art, in particular any precipitated or fumed silica having a BET surface and a CTAB specific surface both less than 450 m 2 / g, preferably from 30 to 400 m 2 / g. As highly dispersible precipitated silicas (referred to as "HDS"), mention may be made, for example, of the "Ultrasil 7000" and "Ultrasil 7005" silicas of the company Evonik, the "Zeosil" silicas 1165MP, 1135MP and 1115MP of the company Rhodia, the "Hi-Sil EZ150G" silica from PPG, the "Zeopol" silicas 8715, 8745 and 8755 from Huber, processed precipitated silicas such as, for example, the "aluminum doped" silicas described in the EP-A application; A-0735088 or silicas with a high specific surface area as described in application WO 03/16837.

Those skilled in the art will understand that, as an equivalent load of the silica described above, could be used a reinforcing filler of another nature, in particular organic, since this reinforcing filler would be covered with a layer of silica, or well would comprise on its surface functional sites, including hydroxyl, requiring the use of a coupling agent to establish the connection between the filler and the elastomer.

These compositions may optionally also contain, in addition to the coupling agents, coupling activators, inorganic charge-covering agents or, more generally, processing aid agents that can be used in a known manner, thanks to an improvement in the dispersion of the filler in the rubber matrix and a lowering of the viscosity of the compositions, to improve their ability to use in the green state, these agents, well known to those skilled in the art, being examples of hydrolysable silanes such as alkylalkoxysilanes, polyols, fatty acids, polyethers, primary, secondary or tertiary amines, hydroxylated or hydrolysable polyorganosiloxanes. In particular, polysulfide silanes, called "symmetrical" or "asymmetrical" silanes according to their particular structure, are used, as described, for example, in claims WO 03/002648 (or US 2005/016651) and WO 00/002649 (or US 2005/016650).

The physical state under which the reinforcing filler is present is indifferent, whether in the form of powder, microbeads, granules, beads or any other suitable densified form.

Preferably, the content of total reinforcing filler (carbon black and / or reinforcing inorganic filler such as silica) is 20 to 80 phr, more preferably 30 to 70 phr, very preferably 35 to 60 phr, better from 40 to 55 pce. Below 20 phr of the load, the composition could be less effective in rigidity depending on the desired application while above 80 phr of the load, the composition could be less effective in rolling resistance.

By majority reinforcing filler is meant that which has the highest rate among the reinforcing fillers present in the composition. In particular, the term "majority reinforcing filler" means any reinforcing filler which represents at least 50% by weight of the reinforcing fillers present, preferably more than 50% and more preferably more than 60%.

According to one embodiment, the composition comprises carbon black as a majority filler, in optional cutting with silica, as a minority filler. In this case, the level of black is preferably in a range from 20 to 80 phr, preferably from 30 to 70 phr, more preferably from 35 to 60 phr, more preferably from 40 to 55 phr. In this embodiment, the silica content is preferably less than 10 phr, and more preferably 0 phr. According to another embodiment, the composition comprises silica as a majority filler, optionally in the form of carbon black, as a minority filler. In this case, the silica content is preferably within a range from 20 to 80 phr, preferably from 30 to 70 phr, more preferably from 35 to 60 phr, more preferably from 40 to 55 phr. In this embodiment, the black content is preferably less than 10 phr, and more preferably less than 5 phr.

Crosslinking system

As seen above, the composition of the invention comprises at least one polysulfurized compound of general formula (I)

in which :

n is a number greater than or equal to 1,

p is a number greater than or equal to 1,

The polysulfurized compound of general formula (I) may be a crosslinking agent. It can advantageously replace the elemental sulfur usually used in crosslinking. It can also be used in addition to a crosslinking system, as an anti reversion agent.

For the purposes of the present invention, the term "divalent hydrocarbon group" means a group comprising carbon and hydrogen atoms. The hydrocarbon group may optionally be branched, in particular substituted with C 1 -C 6 alkyl groups, with phenyl and / or with benzyl. The hydrocarbon group may also and preferably be linear, that is to say, it is not branched. It can be cyclical too. It can optionally include one or more carbon-carbon double bonds. Preferably, in the general formula (I), the radicals R 1 and R 2, which are identical or different, represent an alkylene radical containing from 1 to 18 carbon atoms, preferably from 2 to 10 carbon atoms, more preferably still from 2 to 8 atoms. of carbon. According to a preferred embodiment, the groups R 1 and R 2 are identical.

Preferably, n represents a number in a range from 1 to 8, preferably from 1 to 6, more preferably from 1 to 3.

Preferably, p represents a number comprised in a range from 1 to 30, preferably from 1 to 15, more preferably from 1 to 3.

According to a preferred embodiment, A and B together form a covalent bond. In this embodiment, the polysulfide compound is a cyclic compound.

According to another preferred embodiment, A represents a hydrogen atom and B represents a hydrogen atom or a group -SR _I -ZR ₂ -SH, and preferably, B represents a group -SR _I -ZR ₂ - SH. In this embodiment, the polysulfide compound is a non-cyclic compound.

Preferentially, Z represents a covalent bond or a heteroatom selected from the group consisting of -Si, - (S) _m - and -N (H) -. Preferably, Z represents a covalent bond. Also preferably, Z represents a radical - (S) _m - in which m is a number in a range from 1 to 8, preferably from 1 to 6, more preferably from 1 to 3. More preferably, m is in a range from 1 to 2.

The polysulfide compounds of general formula (I), including their preferred variants, can be mixtures of compounds of general formula (I) in which case the indices n, p and m are average values. These indices can therefore be integers like fractional numbers. Also, the polysulfide compound may be in the form of a mixture of cyclic and non-cyclic form.

Very preferred embodiments are those in which the compound of general formula (I) is such that A and B together form a covalent bond, R1 and R2 are C1-C7 alkylenes, Z being a bond or a group -S or -SS-, n representing 1 or 3 and p representing 1.

Other very preferred embodiments are those in which the compound of general formula (I) is such that A is a hydrogen atom, B represents a group -SR _I -ZR ₂ -SH, R 1 and R 2 being alkylene in C1-C7, Z being a bond or a group -S- or -SS-, n representing 1 or 3 and p representing a number in a range from 1 to 30.

Preferably, the composition has a content of polysulfurized compound of general formula (I) in a range from 0.5 to 10 phr, preferably from 0.5 to 5 phr, and more preferably from 0.5 to 3 phr. .

In the crosslinking system comprising the polysulfide compound described above, basic crosslinking system of the invention may be added, incorporated during the first non-productive phase and / or during the productive phase such as described later, various co-crosslinking agents known to those skilled in the art.

These co-agents, optional, may be vulcanization activators, vulcanization accelerators, well known to those skilled in the art.

As vulcanization activators, mention may be made of zinc oxide and stearic acid derivatives. The term "stearic acid derivative", stearic acid or a salt of stearic acid, both of which are well known to those skilled in the art. As an example of a stearic acid salt that may be used in the context of the present invention, there may be mentioned in particular zinc or magnesium stearate.

As vulcanization accelerators well known to those skilled in the art, preference will be given to the group consisting of thiazoles, sulfenamides, guanidines, amines, aldehyde-amines, dithiophosphates, xanthates, thiuramides , dithiocarbamates and mixtures thereof. In particular, benzothiazyl-2-cyclohexyl sulfenamide (CBS), benzothiazepicyclohexyl sulfenamide (DCBS), benzothiazoyl-2-tert.-butyl sulphenamide (TBBS), 2-mercaptobenzothiazole (MBT) are preferred for the present invention. ), benzothiazole disulfide (MBTS), 2-mercaptobenzothiazole zinc salt or sodium salt (ZMBT), benzothiazyl-2-sulfene morpholide (MBS), guanidine diphenyl (DPG), guanidine triphenyl (TPG) , diorthotolyl guanidine (DOTG), o-tolylbiguanide (OTBG), benzothiazole disulfide (MBTS), tetramethylthiuram disulfide (TMTD), tetrabenzylthiuram disulfide (TBzTD), zinc dibenzyldithiocarbamate (ZBEC), zinc N, N'-dimethylcarbamodithioates (ZDMC), zinc N, N'-diethylcarbamodithioates (ZDEC), zinc N, N'-dibutylcarbamodithioates (ZDBC), zinc N, N'-dibenzylcarbamodithioates (ZDBC), zinc isopropylxanthate ( ZIX) and mixtures thereof.

According to a preferred embodiment, the coating composition comprises a complementary vulcanization accelerator, different from the preceding accelerator, described above, selected from the group consisting of diphenyl guanidine (DPG), triphenyl guanidine (GPT) , the Diolotolyl guanidine (DOTG), o-tolylbiguanide (OTBG), benzothiazole disulfide (MBTS), tetramethylthiuram disulfide (TMTD), tetrabenzylthiuram disulfide (TBzTD), zinc dibenzyldithiocarbamate (ZBEC), zinc N, N'-dimethylcarbamodithioates (ZDMC), zinc N, N'-diethylcarbamodithioates (ZDEC), zinc N, N'-dibutylcarbamodithioates (ZDBC), zinc N, N'-dibenzylcarbamodithioates (ZDBC), zinc isopropylxanthate (ZIX) , and their mixtures. Very preferably, the complementary vulcanization accelerator is zinc dibenzyldithiocarbamate (ZBEC).

The person skilled in the art knows how to adjust the level of these co-agents, activators and accelerators in particular of crosslinking in the composition of the invention as a function of the various constituents of this composition and as a function of the use of the composition.

Also as a crosslinking co-agent, in the usual manner in the coating compositions, a vulcanization retarder is used, in order to allow the sulfurization of the reinforcement before the sulfur is consumed by the vulcanization. This retarder is well known to those skilled in the art, for example N-cyclohexylthiophthalimide (abbreviated as "CTP") sold under the name "Vulkalent G" by the company Lanxess, and N- (trichloromethylthio) benzene-sulfonamide marketed under the name "Vulkalent E / C" by Lanxess, or the phthalic anhydride sold under the name "Vulkalent B / C" by Lanxess. In the coating composition of the reinforced product of the invention, no vulcanization retarder is preferably used, thereby simplifying the mixing and decreasing the cost.

The coating compositions for the purposes of the invention may contain elemental sulfur, in a manner complementary to the polysulfurized compound. However, preferably to obtain the full benefit of the invention, the coating compositions do not comprise elemental sulfur or comprise less than 1 phr, preferably less than 0.5 phr and more preferably less than 0.2 phr. .

Other additives

The coating composition of the reinforced product according to the invention optionally also includes all or part of the usual additives usually used in elastomer compositions intended in particular for the manufacture of tires, for example pigments, protective agents such as waxes. anti-ozone agents, chemical anti-ozonants, antioxidants, plasticizing agents such as plasticizing oils or hydrocarbon resins well known to those skilled in the art, reinforcing resins, acceptors (for example phenolic novolac resin) or methylene donors (eg HMT or H3M). Usually, the coating compositions also comprise an adhesion promoter, for example a cobalt salt. Indeed, 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 durable adhesion of the composition to the metal cables, in particular to their coating comprising for example brass. 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. In the coating composition of the reinforced product of the invention, preferably no cobalt salt is used and preferably no adhesion promoter.

Of course, the compositions according to the invention can be used alone or in a blend (i.e., in a mixture) with any other rubber composition that can be used for the manufacture of tires.

It goes without saying that the invention relates to reinforced products whose coating composition is in the "raw" or non-crosslinked state (ie, before cooking) or in the so-called "cooked" or cross-linked state, or vulcanized (ie, after crosslinking or vulcanization).

Preparation of polysulfide compounds of the coating composition

The polysulfide compounds useful for the invention, if they are not commercially available, may be prepared by any means known to those skilled in the art.

For example, a process generally comprising a step of reacting a sulfur compound with a compound of formula (II) according to the following reaction scheme can be used.

The definition of the groups R 1 and R 2 of the general formula (I) also applies to the groups of the general formula (II).

For example, the polysulphide compounds of general formula (I) may in particular be obtained by an oxidative coupling reaction of the alkylthiol precursors, corresponding arylthiols. In particular, all the reactions described in the following references make it possible to obtain polysulphide compounds by oxidative coupling. R. Hunter, M. Caira, N. Stellenboom, J. Org. Chem., 2006, 71, 8268-8271. R. Hunter, M. Caira, N. Stellenboom, J. Org. Chem., 2006, 71, 8268-8271. S. Antoniow, D. Witt, Synthesis, 2007, 363-366. Mr. Szymelfejnik, S. Demkowicz, J. Rachon, D. Witt, Synthesis, 2007, 3528-3534. M. Bao, M. Shimizu, Tetrahedron, 2003, 59, 9655-9659. CK Maurya, A. Mazumder, A. Kumar, Gupta PK, Synlett, 2016, 27, 409-411. . Kirihara, Y. Asai, S. Ogawa, T. Noguchi, A. Hatano, Y. Hirai, Synthesis, 2007, 3286-3289. A. Khazaei, MA Zolfigol, A. Rostami, Synthesis, 2004, 2959-2961.

Manufacture of the coating composition

The rubber compositions forming the coating gum are manufactured in suitable mixers, for example using two successive preparation phases according to a general procedure well known to those skilled in the art: a first thermomechanical working or mixing phase (sometimes qualified of "non-productive" phase) at a high temperature, up to a maximum temperature of between l30 ° C and 200 ° C, preferably between l45 ° C and l85 ° C, followed by a second phase of mechanical work (sometimes described as "productive" phase) at a lower temperature, typically below 120 ° C., for example between 60 ° C. and 100 ° C., a finishing phase during which the crosslinking system is incorporated.

A process which can be used for the manufacture of such rubber compositions comprises, for example, and preferably the following steps: in a mixer, incorporate into the diene elastomer and the reinforcing filler and any other ingredients of the composition except for the crosslinking, by thermomechanically kneading the whole, one or more times, until a maximum temperature of between 130 ° C and 200 ° C is reached;

cool the assembly to a temperature below 100 ° C;

then incorporate the crosslinking system;

mix everything to a maximum temperature below 120 ° C; extruding or calendering the resulting rubber composition.

By way of example, the first (non-productive) phase is carried out in a single thermomechanical step during which all the necessary constituents, the possible coating agents, are introduced into a suitable mixer such as a conventional internal mixer. or other complementary additives and other additives, with the exception of the crosslinking system. After cooling the mixture thus obtained during the first non-productive phase, the low temperature crosslinking system is then incorporated, 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 min. The final composition thus obtained is then calendered, for example in the form of a sheet or a plate, in particular for a characterization in the laboratory, or else calendered or extruded in the form of a sheet or a usable rubber profile. directly as gum coating a sheathed reinforcement, that is to say, one (or more) thread (s) reinforcement, textile (s) or metal (s) said son or son being covered in a sheath, as previously described.

The crosslinking (or cooking) is conducted in a known manner at a temperature generally between 130 ° C. and 200 ° C., for a sufficient time which may vary, for example, between 5 and 90 min, depending in particular on the cooking temperature, the system adopted crosslinking and crosslinking kinetics of the composition under consideration.

3 - EXAMPLES OF REALIZATION OF THE INVENTION

3.1 - Examples of reinforced products according to the invention

Figure 1 attached represents a tire according to a first embodiment of the invention and designated by the general reference 10. The tire 10 is substantially of revolution about an axis substantially parallel to the axial direction. The tire 10 is here intended for a passenger vehicle or a heavy vehicle such as a truck.

The tire 10 has an apex 12 comprising a crown reinforcement 14 comprising a working reinforcement 15 comprising two working plies 16, 18 of reinforcing elements and a frettage reinforcement 17 comprising a hooping ply 19. The crown reinforcement 14 is surmounted by a tread 20. The hooping reinforcement 17, here the hooping web 19, is radially interposed between the working reinforcement 15 and the tread 20.

Two flanks 22 extend the vertex 12 radially inwards. The tire 10 further comprises two beads 24 radially inner to the flanks 22 and each having an annular reinforcement structure 26, in this case a bead wire 28, surmounted by a mass of tamping rubber 30, and a carcass reinforcement. radial 32. The crown reinforcement 14 is radially interposed between the carcass reinforcement 32 and the tread 20. Each flank 22 connects each bead 24 to the top 14.

The carcass reinforcement 32 preferably comprises a single carcass ply 34 of radial textile reinforcement elements. The carcass reinforcement 32 is anchored to each of the beads 24 by a turn around the rod 28 so as to form in each bead 24 a forward strand 38 extending from the beads 24 through the flanks 22 to the vertex 12 , and a return strand 40, the radially outer end 42 of the return strand 40 being radially outside the annular reinforcing structure 26. The carcass reinforcement 32 thus extends from the beads 24 through the flanks 22 to the crown 12. In this embodiment, the carcass reinforcement 32 also extends axially through the top 12.

Each working ply 16, 18 forms a reinforced product 21 according to the invention comprising reinforcing elements 44 forming an angle ranging from 15 ° and 40 °, preferably from 20 ° to 30 ° and here equal to 26 ° with the circumferential direction of the tire 10. The reinforcing elements 44 are crossed with one working ply with respect to the other.

The hooping web 19 comprises reinforcing textile reinforcing elements forming an angle at most equal to 10 °, preferably ranging from 5 ° to 10 ° with the circumferential direction of the tire 10. In this case, the textile reinforcing elements shrink sleeves are twists made of a heat-shrinkable material, here polyamide 66, each twist consisting of two yarns of 140 tex which have been twisted together (on direct wirer) at 250 revolutions / meter, whose diameter is equal to about 0, 66 mm. The thermal contraction CT of each shrinkable textile reinforcing element is about 7%.

The working plies 16, 18, frettage 19 and carcass 34 comprise an elastomer matrix 23 in which are embedded the reinforcing elements of the corresponding ply. The rubber compositions of the elastomeric matrices 23 of the working plies 16, 18, shrinkwrap 19 and carcass plies 34 may be conventional compositions for the coating of reinforcement elements conventionally comprising a diene elastomer, for example natural rubber, a reinforcing filler, for example carbon black and / or silica, a crosslinking system, for example a vulcanization system, preferably comprising sulfur, stearic acid and zinc oxide and optionally an accelerator and / or a vulcanization retarder and / or various additives. At least one of the plies comprising a reinforced product comprises a reinforced product according to the invention. As such, this web comprises a specific coating composition 23 of the invention, that is to say a composition as defined above and hereinafter for the purposes of the invention.

Figures 2 to 5 show various embodiments of the invention, that is to say various arrangements of reinforced products 21 according to the invention. The reinforcing elements (one or more threads) 44 of the reinforced product 21 are arranged side by side in a main direction. The reinforcing elements 44 extend parallel to each other. Each reinforcing element 44 comprises at least one wire element 46. Each reinforcing element 44 also comprises at least one sheath 48 coating the wire element 46 and comprising at least one layer 50 of a thermoplastic polymeric composition. The sheathed reinforcement 44 is embedded in a coating composition 23. The sheath 48 comprises a single layer 50 of the thermoplastic polymeric composition which may comprise a thermoplastic polymer, a functionalized diene elastomer, a poly (p-phenylene ether) or a mixture of these materials. Here the thermoplastic polymeric composition comprises a thermoplastic polymer, for example polyamide 66. Optionally, the thermoplastic polymeric composition may comprise a functionalized diene elastomer, for example a styrenic thermoplastic comprising an epoxide, carbonyl, anhydride or ester function and / or a poly- p-phenylene ether. The sheath 48 is coated with a layer of adhesion adhesive (not shown) between the sheath 48 and the elastomer matrix 23.

The difference between the embodiments shown in Figures 2 to 5 lies in the arrangement and / or the number of cables in the sheath to form the sheathed reinforcement 44 useful for the reinforced product 21 of the invention. Thus, the sheathed reinforcement 44 is in the form of 3 cables individually covered with a sheath, and embedded together in the coating composition in Figure 2; in the form of 3 groups of cables, each group of cables being covered with a sheath, the three groups of cables, sheathed, being embedded in the coating composition in FIG. 3; in the form of a strip of 3 cables, here each consisting of a monofilament, covered with the same sheath and embedded in the coating composition in Figure 4; in the form of a strip of 3 groups of cables covered with the same sheath and embedded in the coating composition in FIG.

3.2 - Use of the reinforced tire product

The reinforced product of the invention described above can especially be used for the manufacture of any finished article or semi-finished rubber product, in particular for the reinforcement of pneumatic tires of all types of vehicles, in particular passenger vehicles or industrial vehicles such as Heavy weights.

As already indicated above, this reinforced product of the invention can be in various forms, in a unitary form (with a single reinforcing thread) or in the form of a sheet, strip, band or block of rubber in which are incorporated, for example by calendering, several textile reinforcement son (s) and / or metal (s). The definitive adhesion between the sheathed wire reinforcement and the coating rubber can be obtained after the firing, preferably under pressure, of the finished article for which the wire reinforcement of the invention is intended.

3.3 - Example of polysulfide compounds

The preparation of the polysulfide compounds 1 to 4 as used in the composition examples is described below. Synthesis of Polysulfide Compound 1: 1.8 dithiacvclotctradcancan-1,8-disulfurc

The 1,8-dithiacyclotetradecane 1,8-disulfide is synthesized according to the scheme below and according to the following synthesis protocol:

To a solution of sodium hydrosulphide (111.3 g, 1.35 mol, monohydrate, 90% of technical purity) in methanol (440 mL) at 39 ° C is added, for 1 hour, a solution of 6-dichlorohexane (70.0 g, 0.452 mol) in methanol (200 mL). The reaction is exothermic: the temperature of the reaction medium reaches 60 ° C. The mixture obtained is refluxed for 4 hours.

After returning to ambient temperature, the precipitate is filtered and washed with MTBE (250 mL) (MTBE = methyl tert-butyl ether). The solvents are evaporated under reduced pressure (70 mbar, 36 ° C.). The expected product is treated with MTBE (350 mL) and washed 3 times with water (50 mL). The organic phase is dried with sodium sulphate and then concentrated under reduced pressure (35 mbar, 36 ° C.).

After distillation under reduced pressure (84-87 ° C fraction at 5-6 mbar) an oil is obtained (13.94 g, 21% yield). 1.6-hexanedithiol is obtained, the molar purity of which is greater than 97 mol%. ⁽¹ H NMR).

To a solution of 1,6-hexanedithiol (24.0 g, 0.160 mol) synthesized above in MTBE methyl-tert-butyl ether (390 mL) is added, portionwise, an iodine solution ( 42.55 g, 0.167 mol) and potassium iodide (59.64 g, 0.359 mol) in water (400 mL) for 20-25 minutes. After stirring for 7 hours at room temperature, bicarbonate of sodium hydroxide (for neutralization) and sodium hydrogen sulfite (NaHSO ₃ , for a decolorization of about 1.5 g) are added. The precipitate formed (expected product) is filtered and washed with water (200 mL). The solid is treated twice with acetone (twice for 250 ml): after stirring for 3 hours at room temperature, the precipitate is filtered and washed on the filter with acetone (twice per 25 ml). After drying, the product is treated with MB TE (200 ml) with stirring for 3 hours at room temperature, then the residual solid is filtered and washed with MTBE (twice in 15 ml) and finally dried for 10 - 15 hours at room temperature. room. A white solid (20.09 g, 85% yield) with a melting point of 62 ° C. is obtained. The molar purity is greater than 94% (1 H NMR).

Synthesis of the polysulfide compound 2: 1, 2,3,4-tetrathiecane

1,2,3,4-Tetrathiecane is synthesized according to the reaction scheme below and according to the following synthesis protocol:

To a solution of 1,6-hexanedithiol (8.0 g, 0.053 mol) in ethyl ether (150 ml) at -3 ° C. (bath temperature) is added dropwise a solution of S ₂ Cl ₂ (7.19 g, 0.053 mmol) in ethyl ether (80 ml). The temperature of the reaction medium is brought to room temperature (at 23 ° C.) over 1.5 hours. Then, the medium is heated for 1.5 hours at 30 ° C. (bath temperature). The precipitate formed is filtered and then solubilized in dichloromethane (200 ml) at 40 ° C. The dichloromethane is evaporated under reduced pressure (1-2 mbar, 35-40 ° C.). After drying the product for 6 hours under vacuum (1-2 mbar, 40 ° C), a very viscous oil is obtained (8.61 g, 77% yield).

The molar purity is greater than 98 mol%. (1H NMR).

The distribution of x is as follows: 0.3% for x = 2; 1.2% for x = 3; 98.5% for x> 4

Synthesis of the polysulfide compound 3: 4; 7 pentathiocane mixed

The mixed polysulfide compound 3 is synthesized according to the reaction scheme below and the following synthesis protocol:

A solution of 2,2'-thiodiethanethiol (10 g, 0.0648 mol, 1e, Aldrich, commercial purity) in diethyl ether (400 mL) is cooled to 0-2 ° C (bath temperature). The solution of S ₂ Cl ₂ (8.93 g, 0.0661 mol, 1.02 eq.) In anhydrous diethyl ether (200 mL) is added dropwise over 1 hour. Gradually the reaction mixture becomes cloudy and then a white solid is formed. After the addition of all the reagents, the reaction mixture is stirred at room temperature for 1 hour and finally the mixture is refluxed for 2 hours. Then, after returning to ~ 25 ° C, the white solid obtained is filtered, washed with petroleum ether (twice for 25 mL) and dried at room temperature under atmospheric pressure. The product is then taken up in chloroform (6 ml of the solvent to 1 g of product) and is heated at 50 ° C. (bath temperature) for 3 hours. An insoluble fraction and a soluble fraction are obtained.

The compound is thus obtained in the form of a mixture of the cyclic form (insoluble fraction) and of the open form (soluble fraction). The proportion of the reactants is such that the value of the index n is centered on 3.

The insoluble fraction (cyclic form) is filtered and washed on the filter with chloroform (50 ml) and dried at room temperature under atmospheric pressure. At the end of this treatment, a white polymer product (9.8 g) is obtained. This product being insoluble in the usual solvents, it has not been characterized. The soluble fraction (open form) is in turn concentrated and analyzed by NMR (see NMR characterization below). The product obtained contains oligomers in which the index p has a value in the range from 12 to 23.

The NMR data are as follows:

The chemical shifts in ¹ H and ¹³ C for patterns 1, 2, 3 and 4 are approximate since they change according to the number of sulfur (S) _n.

Synthesis of the Polysulfide Compound 4: 1, 2,5-trithiepane

The 1, 2,5-trithiepane is synthesized according to the reaction scheme below and the following synthesis protocol:

In a 2 L three-neck equipped with a mechanical stirrer is added triethylamine (20.2g, 0.20 mol, 2 eq.) And chloroform (500 mL). To this reaction medium is added a solution of 2,2'-thiodiethanethiol (15.4 g, 0.10 mol, 1 eq., Aldrich, commercial purity) in chloroform (250 ml) by a first dropping funnel. By a second ampoule is added in parallel a solution of iodine (25.1 g, 0.10 mol, 1 eq.) In chloroform (800 mL). These two solutions are added to the reaction medium dropwise separately and simultaneously for 4 hours to maintain the yellow color of the reaction mixture. After 4 hours, an excess of iodine solution can be added to ensure total conversion and maintain a yellow or orange color of the reaction medium. This mixture is then stirred for 10 minutes. The reaction mixture is then extracted with 50 ml of water with a few crystals of Na ₂ S ₂ O ₃ to reduce the excess iodine. The organic phase is then washed with an aqueous solution of hydrochloric acid (10 ml of concentrated acid in 500 ml of water) and finally with water (2 times 500 ml). Finally, the organic solution is separated and dried with anhydrous Na ₂ SO ₄ . After filtration, the chloroform is evaporated under reduced pressure (bath temperature = 40 ° C., up to 4 mbar). The final product (yellow oil) (15.2 g, 99.8% yield) is then obtained with a molar purity greater than 95 mol%. (1H NMR).

3.4 - Example of coating compositions

For the purposes of these tests, rubber compositions have been prepared in accordance with the invention, the formulations of which are given in Table 1; the rate of the different products is expressed in phr (parts by weight per hundred parts by weight of elastomer).

For the production of these compositions, the following procedure was carried out: the reinforcing filler (carbon black), the elastomer, were successively introduced into an internal mixer, the initial batch temperature of which was approximately 50 ° C. diene, as well as the various other ingredients with the exception of the crosslinking system; the mixer was thus filled to about 70% (% by volume). Theromechanical work (non-productive phase) was then carried out in one step of about 3 to 5 minutes, until a maximum temperature of "falling" of 160 ° C. was reached. The mixture thus obtained was recovered, cooled, and sulfur and a sulfenamide accelerator were incorporated on an external mixer (homo-finisher) at 40 ° C, mixing the whole (productive phase) for a few minutes. . The composition thus obtained was then calendered in the form of plates that can be used as coating gum for the sheathed wire reinforcements according to the invention.

The compositions according to the invention C1 to C5 were compared with two control compositions (T1 and T2) of similar formulation-prepared identically, of which only the crosslinking system differs. Table 1

(1) Natural rubber

(2) ASTM N335 Grade Carbon Black (Cabot Company); (3) Polysulfide compounds 1 to 4 as presented in Chapter 3.3 above;

(4) Industrial grade zinc oxide - Umicore company;

(5) Stearin "Pristerene 4931" from Uniqema;

(6) N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine (Santoflex 6-PPD) from Flexsys;

(7) N-tert-butyl-2-benzothiazyl sulfenamide ("Santocure TBBS" from Flexsys);

(8) Zinc dibenzyldithiocarbamate (CAS No.14726-36-4) ("ZBEC" from Anvis France Decize).

The properties of these different compositions have been evaluated and are presented in Table 2 below.

Traction tests

The measured properties are the modules of the compositions, as determined by tensile tests. These tests make it possible to determine the elastic stress and the properties at break. They are carried out in accordance with the French standard NF T 46-002 of September 1988. The elongations at break (in%) are measured in second elongation (i.e. after an accommodation cycle). The measurements of elongation at break (denoted AR) are carried out under the normal conditions of temperature (23 ± 2 ° C.) and hygrometry (50 ± 5% relative humidity), according to the French standard NF T 40- 101 (December 1979), and also at 100 ° C. The nominal secant moduli (or apparent stresses, in MPa, related to deformation, without unit) at 10%, 100% or 300% elongation (denoted MA10, MA100 and MA300) and the true stresses at break (in MPa) can also be measured.

Adhesion tests of the coating composition with the filament reinforcement

To test the adhesion of the coating composition on a filament reinforcement, measurement was made according to ASTM D2229.

The compositions T1 and T2 (controls) and C1 to C5 (in accordance with the invention) presented in Table 2 below were combined with a brass-coated metal reinforcement consisting of 3 steel wires with 0.7% carbon, 18/100 ^e millimeters in diameter with an assembly pitch of 5 mm, the brass comprising 63% copper. The reinforcement is sheathed, the sheath is 6-6 polyamide about 0.1 mm thick on average for a cable diameter sheathed about 0.53 mm, and covered with an RFL glue.

These associations were tested as to the adhesion of the coating composition to the reinforcement, after firing the assembly at 150 ° C. and baking at 190 ° C. The adhesion is evaluated by measuring the force of tearing of the reinforcement out of the coating gum, baked at 150 ° C in a first test and baked at 190 ° C in a second test. It is thus possible to calculate the variation in adhesion between the coating gum and the reinforcement after firing at 190 ° C. with respect to firing at 150 ° C. Results

Table 2

nm: not measured

The results given in Table 2 indicate in particular that compositions C1 to C5, in accordance with the invention, have a lower decrease in adhesion after firing at 190 ° C. compared to adhesion after firing at 150 ° C. , thus saving time in the manufacturing process, without penalizing the adhesion of the coating gum to the reinforcement.

It may further be noted that the compositions in accordance with the invention have the additional advantage of having higher elongation at break properties than those of controls T1 and T2.

Claims

1. Reinforced product, usable in particular for the reinforcement of a finished rubber article, comprising one or more reinforcing thread (s), textile (s) or metal (s), said thread (s) being covered with a sheath comprising a thermoplastic polymeric composition, the sheathed yarn (s) being themselves embedded in a rubber compound called a coating gum, characterized in that this coating gum is a composition based on at least one diene elastomer, a reinforcing filler and a polysulfide compound of general formula (I)

in which :

A and B together form a covalent bond, or A represents a hydrogen atom and B represents a hydrogen atom or a group -SR _I -ZR ₂ -SH, n is a number greater than or equal to 1,

p is a number greater than or equal to 1,

Z represents a covalent bond or a heteroatom selected from the group consisting of -O-, -Si-, - (S) _m - and -N (H) -, wherein m is a number greater than or equal to 1, and R1 and R2 represent, independently of one another, identical or different linear or branched divalent hydrocarbon groups having from 1 to 18 carbon atoms.

2. Reinforced product according to claim 1 wherein R1 and R2 represent linear divalent hydrocarbon groups.

3. Reinforced product according to one of the preceding claims wherein R1 and R2 represent an alkylene radical having 1 to 18 carbon atoms, preferably 2 to 10 carbon atoms.

4. Reinforced product according to one of the preceding claims wherein R1 and R2 are identical radicals.

5. Reinforced product according to one of the preceding claims wherein n represents a number in a range from 1 to 8, preferably from 1 to 6, more preferably from 1 to 3.

6. Reinforced product according to one of the preceding claims wherein p represents a number in a range from 1 to 30, preferably from 1 to 15, more preferably from 1 to 3.

7. Reinforced product according to one of the preceding claims wherein A and B together form a covalent bond.

8. Reinforced product according to one of claims 1 to 6 wherein A represents a hydrogen atom and B represents a hydrogen atom or a group -SR _I -ZR ₂ -SH.

9. Reinforced product according to claim 8 wherein A represents a hydrogen atom and B represents a group -SR _I -ZR ₂ -SH.

10. Reinforced product according to one of the preceding claims wherein Z represents a covalent bond or a heteroatom selected from the group consisting of -Si-, - (S) _m - and N (H) -.

11. Reinforced product according to one of the preceding claims wherein m is a number in a range from 1 to 8, preferably from 1 to 6.

12. Reinforced product according to one of the preceding claims wherein m is a number in a range from 1 to 3, preferably from 1 to 2.

13. Reinforced product according to one of the preceding claims wherein Z represents a covalent bond.

14. Reinforced product according to one of claims 1 to 12 wherein Z represents a radical - (S) _m -

15. Reinforced product according to one of claims 1 to 7 or 10 to 12, wherein A and B together form a covalent bond, R1 and R2 are C1-C7 alkylenes, Z is a covalent bond or a group -S or -SS-, n represents 1 or 3 and p represents 1.

16. Reinforced product according to one of claims 1 to 6 or 8 to 12, wherein A is a hydrogen atom, B represents a group -SR _I -ZR ₂ -SH, R1 and R2 being C1-C4 alkylenes. C7, Z being a bond or a group -S- or -SS-, where n is 1 or 3 and p is a number in a range of 1 to 30.

17. Reinforced product according to one of the preceding claims wherein the polysulfide compound of general formula (I) is present in the composition of the gum coating at a rate in a range from 0.5 to 10 phr, preferably from 0.5 to 5 phr, and more preferably from 0.5 to 3 phr.

18. Reinforced product according to one of the preceding claims wherein the composition of the coating gum comprises a vulcanization accelerator selected from the group consisting of thiazoles, sulfenamides, guanidines, amines, aldehyde-amines, dithiophosphates, xanthates, thiurams, dithiocarbamates and mixtures thereof.

19. Reinforced product according to the preceding claim wherein the composition of the coating gum comprises a complementary vulcanization accelerator, different from the accelerator of the preceding claim, selected from the group consisting of diphenyl guanidine (DPG), triphenyl guanidine (TPG), diorthotolyl guanidine (DOTG), o-tolylbiguanide (OTBG), benzothiazole disulfide (MBTS), tetramethylthiuram disulfide (TMTD), tetrabenzylthiuram disulfide (TBzTD), zinc dibenzyldithiocarbamate (ZBEC) ), zinc N, N'-dimethylcarbamodithioates (ZDMC), zinc N, N'-diethylcarbamodithioates (ZDEC), zinc N, N'-dibutylcarbamodithioates (ZDBC), zinc N, N'-dibenzylcarbamodithioates (ZDBC), zinc isopropylxanthate (ZIX), and mixtures thereof.

20. Reinforced product according to any one of the preceding claims wherein the composition of the coating gum does not comprise a vulcanization retarder.

21. Reinforced product according to any one of the preceding claims wherein the composition of the coating gum does not comprise elemental sulfur or comprises less than 1 phr, preferably less than 0.5 phr.

22. Reinforced product according to any one of the preceding claims wherein the composition of the coating gum does not comprise a cobalt salt.

23. Reinforced product according to the preceding claim wherein the composition of the coating gum does not comprise an adhesion promoter.

24. A reinforced product according to any preceding claim wherein the diene elastomer of the composition of the coating gum comprises predominantly an elastomer selected from the group consisting of natural rubber, synthetic polyisoprene or a mixture thereof. last.

25. Reinforced product according to any one of the preceding claims, in which the composition of the coating gum comprises from 60 to 100 phr, preferably from 70 to 100 phr. 100 phr of an elastomer selected from the group consisting of natural rubber, synthetic polyisoprene or a mixture thereof.

26. Reinforced product according to the preceding claim wherein the composition of the coating gum comprises from 80 to 100 phr, preferably from 90 to 100 phr of an elastomer chosen from the group consisting of natural rubber and synthetic polyisoprene. or a mixture of these.

27. Reinforced product according to any one of the preceding claims wherein the composition of the coating gum comprises from 20 to 80 phr, preferably from 30 to 70 phr, of reinforcing filler.

28. Reinforced product according to the preceding claim wherein the composition of the coating gum comprises from 35 to 60 phr, preferably from 40 to 55 phr, of reinforcing filler.

Reinforced product according to any one of the preceding claims wherein the composition of the coating gum comprises carbon black as the majority filler.

30. Reinforced product according to any one of the preceding claims wherein the composition of the coating gum comprises silica as the majority filler.

31. Reinforced product according to any one of the preceding claims wherein the reinforcement son or son are metal son.

32. Reinforced product according to any one of the preceding claims wherein the sheathed wire (s) is coated with an adhesive, preferably a Resorcinol-formaldehyde-latex glue.

33. A tire comprising a reinforced product according to any one of the preceding claims, preferably at least in a web selected from the top reinforcing plies and the carcass plies.