EP4337718A1

EP4337718A1 - Composite material, based on a rubber composition and a metal reinforcing element treated in a supercritical medium

Info

Publication number: EP4337718A1
Application number: EP22724814.3A
Authority: EP
Inventors: Anne-Lise THUILLIEZ; Marie CROUZET; Franck Daumas; Odile GAVARD-LONCHAY; Thomas SIMONELLI
Original assignee: Compagnie Generale des Etablissements Michelin SCA
Current assignee: Compagnie Generale des Etablissements Michelin SCA
Priority date: 2021-05-10
Filing date: 2022-05-03
Publication date: 2024-03-20
Also published as: WO2022238638A1; FR3122657A1; FR3122657B1

Abstract

The invention relates to a composite material based on a rubber composition based on at least one diene elastomer, a reinforcing filler, a crosslinking system and at least one metallic reinforcing element embedded in said rubber composition, said reinforcing element being brought into contact with supercritical carbon dioxide before being incorporated into the rubber composition.

Description

DESCRIPTION

TITLE: COMPOSITE BASED ON A RUBBER COMPOSITION AND A METALLIC REINFORCING ELEMENT TREATED IN A SUPERCRITICAL ENVIRONMENT Technical field of the invention

The present invention relates to the field of reinforced composites, in particular suitable for the reinforcement of pneumatic tires.

PRIOR ART Tire reinforcement plies usually comprise a rubber mixture in which reinforcement cords, often metallic and surface-coated with brass, are embedded. The adhesion between the rubber mixture and the metal cables is created via the phenomenon of sulfurization of the brass-coated surface of the cable. However, the mixture, just like the bonds created, can evolve under the effect of humidity, temperature or corrosive elements and their combined effects, for example the combined effect of oxidation and heat. (thermo-oxidation) encountered in tires.

The adhesion function generally imposes specific formulations for the rubber composition, in particular the need for a high level of sulfur and zinc oxide, a low amount of stearic acid, the presence of cobalt salt, the use of a long-delayed phase accelerator. However, these vulcanization systems with a high sulfur content constitute a strong constraint during the manufacture of semi-finished products, in particular to avoid premature crosslinking, and lead to a certain sensitivity of the mixtures to thermo-oxidation. Many studies have focused on improving mix formulations in order to reduce, or even eliminate, the use of sulphur, while maintaining or improving the adhesion properties without compromising the other qualities of the mix. Thus, for example, document WO 2020/058614 teaches a rubber composition based on at least one elastomer comprising epoxide functions, at least one reinforcing filler, a crosslinking system comprising a polycarboxylic acid, an imidazole and at least one specific polyphenolic compound exhibiting characteristics of adhesion to a reinforcing element that are particularly advantageous, in particular for the constitution of composites intended for tires. Other research work has focused on the reformulation of the metal support, in particular by proposing reinforcement elements whose surface is coated with an alloy including cobalt. Mention may be made, for example, of US Patent 4,347,290 which teaches a composite comprising an elastomeric composition and a metal reinforcing element whose surface is coated with a Cu-Zn-Co alloy showing an improvement in adhesion, with however a ZnO ratio / relatively high stearic acid. This document does not address the aspect of the behavior of the properties over time.

Other work, also presented in documents EP 3 336 140, EP 2 371 882 and EP 2 716694, has focused on the treatment of the surface of the reinforcements by an atmospheric plasma, said plasma being generated from a carrier gas comprising an additive such as a halogen compound, a polymerizable compound and/or a sulfur compound. This treatment provides good, long-lasting adhesion, but requires control of the additive content in order to obtain the desired effect.

Document EP 3 552 842 proposes the treatment of the surface of the reinforcement by immersing it in two chemical baths making it possible to adjust the ratio of copper to zinc on the surface and to deposit an anti-corrosion agent, this treatment making it possible to overcome the presence of cobalt salts in rubber composition-metal reinforcement composites.

The document JP2010285711 shows that the adhesion of a metal reinforcement treated with carbon dioxide in the supercritical state is only slightly degraded when the reinforcement is brought into contact with a vulcanized rubber composition. This document is silent on the characteristics of the rubber composition or the evolution of the properties over time.

Continuing her research, the Applicant has discovered a composite comprising a rubber composition and a reinforcement, the reinforcement being brought into contact with carbon dioxide in the supercritical state prior to its incorporation into the rubber composition, exhibiting excellent qualities adhesion, this adhesion also having good durability, this treatment not requiring the use of additives or chemical baths, the reprocessing of which can be problematic. The composite according to the invention has particularly advantageous qualities, in particular when the rubber composition does not comprise any, or very few, sulfur compounds.

Detailed description of the invention

The invention relates to at least one of the following embodiments ^: l) Composite based on a rubber composition based on at least one diene elastomer, a reinforcing filler, a crosslinking system and at least one metallic reinforcement embedded in said rubber composition, said reinforcing element being brought into contact with carbon dioxide in the supercritical state prior to its incorporation into the rubber composition.

2) Composite according to the previous embodiment in which the reinforcing element is brought into contact with carbon dioxide in the supercritical state for a period of between 2 and 80 min, preferably between 2 and 60 min, and preferably between 2 and 30 min.

3) Composite according to any one of the preceding embodiments in which the reinforcing element is brought into contact with carbon dioxide in the supercritical state at a temperature between 35 and 60° C., preferably between 35 and 45° vs.

4) Composite according to any one of the preceding embodiments in which the reinforcing element is brought into contact with carbon dioxide in the supercritical state at a pressure of between 70 and 150 bar.

5) Composite according to any one of the preceding embodiments in which the reinforcing filler of the rubber composition comprises carbon black, silica or a mixture of carbon black and silica.

6) Composite according to the previous embodiment, in which the reinforcing filler of the rubber composition comprises from 10 to 100 phr of carbon black, preferably from 10 to 80 phr and more preferably from 10 to 60 phr of carbon black.

7) Composite according to the previous embodiment in which the reinforcing filler of the rubber composition consists of carbon black.

8) Composite according to embodiment 5, in which the reinforcing filler of the rubber composition comprises from 10 to 150 phr, preferably from 10 to 100 phr, of silica.

9) Composite according to the previous embodiment in which the reinforcing filler of the rubber composition consists of silica.

10) Composite according to any one of the preceding embodiments in which the rubber composition comprises a diene elastomer chosen from the group consisting of polybutadienes, natural rubber, synthetic polyisoprenes, butadiene copolymers, isoprene copolymers, and mixtures of these elastomers.

11) Composite according to any one of the preceding embodiments in which the rubber composition comprises at least 50 phr, preferably at least 70 phr, preferably at least 90 phr of at least one isoprene elastomer.

12) Composite according to the previous embodiment in which the isoprene elastomer is chosen from the group consisting of natural rubber, synthetic polyisoprenes, isoprene copolymers and mixtures thereof. 13) Composite according to any one of the preceding embodiments in which the diene elastomer comprises epoxide functions, the crosslinking system comprising a polycarboxylic acid of general formula (I) in which A represents a covalent bond or a hydrocarbon group containing at least 1 carbon atom, optionally substituted and optionally interrupted by one or more heteroatoms, an imidazole of general formula (II) in which,

Ri represents a hydrocarbon group or a hydrogen atom,

R2 represents a hydrocarbon group,

R3 and R4 represent, independently of each other, a hydrogen atom or a hydrocarbon group, or even R3 and R4 form together, with the carbon atoms of the imidazole ring to which they are attached, a ring. 14) Composite according to the previous embodiment in which A represents a covalent bond or a divalent hydrocarbon group comprising from 1 to 1800 carbon atoms, preferably from 2 to 300 carbon atoms.

15) Composite according to any one of embodiments 13 to 14, in which the level of polycarboxylic acid is within a range ranging from 0.2 to 100 phr, preferably from 0.2 to 50 phr.

16) Composite according to any one of embodiments 13 to 15, in which: a) Ri represents a hydrogen atom or an alkyl group having from 1 to 20 carbon atoms, cycloalkyl having from 5 to 24 carbon atoms, aryl having from 6 to 30 carbon atoms or aralkyl having from 7 to 25 carbon atoms, optionally substituted, b) R2 represents an alkyl group having from 1 to 20 carbon atoms, cycloalkyl having from 5 to 24 carbon atoms, aryl having from 6 to 30 carbon atoms or aralkyl having from 7 to 25 carbon atoms, c) R3 and R4 independently represent identical or different groups chosen from hydrogen or alkyl groups having from 1 to 20 carbon atoms, cycloalkyls having from 5 to 24 carbon atoms, aryls having from 6 to 30 carbon atoms or aralkyls having from 7 to 25 carbon atoms, optionally substituted, or even R3 and R4 form together with the carbon atoms of the imidazole ring to which they are attached, a ring chosen from aromatic, heteroaromatic or aliphatic rings, comprising from 5 to 12 carbon atoms, preferably 5 or 6 carbon atoms.

17) Composite according to any one of the preceding embodiments in which the rubber composition comprises a polyphenolic compound comprising at least three aromatic rings comprising 6 carbon atoms, each carrying at least two vicinal hydroxyl groups, preferably chosen from gallotannins, preferably from esters based on gallic acid and a polyol chosen from pentoses and hexoses.

18) Composite according to the previous embodiment in which the polyphenolic compound is chosen from glucose and gallic acid esters, preferably chosen from polygalloyl glucoses comprising from 3 to 10, and preferably from 5 to 10 galloyl units.

19) Composite according to any one of embodiments 17 to 18 in which the level of polyphenolic compound in the rubber composition is between 0.1 and 25 phr.

20) Composite according to any one of embodiments 17 to 19 when embodiment 17 depends on any one of embodiments 13 to 16 in which said composition is devoid of molecular sulfur or contains less than 1 phr thereof.

21) Composite according to any one of embodiments 17 to 20 in which said composition is devoid of cobalt salts or contains less than 1 phr thereof.

22) Composite according to any one of the preceding embodiments in which the metal surface of said reinforcing element comprises a metal chosen from the group consisting of iron, copper, zinc, tin, aluminum, cobalt, nickel and alloys comprising at least one of these metals.

23) Composite according to the previous embodiment in which the metal of the metal surface is chosen from iron, copper, tin, zinc or an alloy comprising at least one of these metals, preferably chosen from the group consisting of brass , steel, zinc and bronze and very preferably brass.

24) Rubber article comprising a composite according to any one of the preceding embodiments. 25) Article according to the previous embodiment chosen from the group comprising pneumatic or non-pneumatic tires, transmission belts, conveyor belts, caterpillars.

26) Process for manufacturing a composite based on at least one reinforcing element and a rubber composition comprising at least the following successive steps: a) A step of bringing each reinforcing element into contact with carbon dioxide carbon in the supercritical state; b) A step in which each reinforcing element is embedded in the rubber composition so as to obtain the composite.

Definitions

The compounds comprising carbon mentioned in the description can be of fossil origin or biobased. In the latter case, they can be, partially or totally, derived from biomass or obtained from renewable raw materials derived from biomass. This concerns in particular polymers, plasticizers, fillers, etc. In the same way, the compounds mentioned can also come from the recycling of materials already used, that is to say they can be, partially or totally, from a recycling process, or obtained from materials raw materials themselves from a recycling process.

Organic compound means, in accordance with Directive 1999/13/EC, any compound containing at least the element carbon and one or more of the following elements ^: hydrogen, halogens, oxygen, sulphur, phosphorus, silicon or nitrogen, except carbon oxides and inorganic carbonates and bicarbonates.

Composite

The composite in accordance with the invention is based on a rubber composition based on at least one elastomer, a reinforcing filler, a crosslinking system and at least one metallic reinforcing element, said reinforcing element being placed in contact with carbon dioxide in the supercritical state prior to its incorporation into the rubber composition.

elastomer

By elastomer or rubber (the two terms being in a known manner synonymous and interchangeable), is meant any type of elastomer in the sense known to those skilled in the art, whether it is a homopolymer or a block copolymer, random or otherwise, having elastomeric properties.

By elastomer of the diene type, it is recalled that an elastomer which is derived at least in part (i.e. a homopolymer or a copolymer) from diene monomers (monomers bearing two carbon-carbon double bonds, conjugated or not) should be understood.

These diene elastomers, by definition non-thermoplastic in the present application, exhibiting a glass transition temperature Tg in the vast majority of cases which is negative (that is to say less than 0° C.), can be classified in such a way known in two categories ^: those called "essentially unsaturated" and those called "essentially saturated". Butyl rubbers, such as, for example, copolymers of dienes and alpha-olefins of the EPDM type, fall into the category of essentially saturated diene elastomers, having a rate of units of diene origin which is low or very low, always less than 15 % (% by moles). Conversely, by essentially unsaturated diene elastomer is meant a diene elastomer resulting at least in part from conjugated diene monomers, having a rate of units or units of diene origin (conjugated dienes) which is greater than 15% (% in moles) . In the category of “essentially unsaturated” diene elastomers, the term “highly unsaturated” diene elastomer in particular means a diene elastomer having a content of units of diene origin (conjugated dienes) which is greater than 50%.

It is preferred to use at least one diene elastomer of the highly unsaturated type, in particular a diene elastomer chosen from the group consisting of natural rubber (NR), synthetic polyisoprenes (IR), polybutadienes (BR), butadiene copolymers, isoprene copolymers and mixtures of these elastomers. Such copolymers are more preferably chosen from the group consisting of butadiene-styrene (SBR) copolymers, isoprene-butadiene (BIR) copolymers, isoprene-styrene (SIR) copolymers, isoprene- butadiene-styrene (SBIR) and mixtures of such copolymers.

Preferably, the diene elastomer is epoxidized, that is to say carrying epoxide functional groups. The expressions “diene elastomer comprising epoxide functions” or “epoxidized diene elastomer” or “epoxide functionalized elastomer” are used without distinction to designate it.

The epoxidized diene elastomers are, in a known manner, solid at ambient temperature (20° C.); by solid is meant any substance that does not have the capacity to set in the long term, later after 24 hours, under the sole effect of gravity and at room temperature (20°C), the shape of the container which contains it.

The glass transition temperature Tg of the elastomers described in this text is measured in a known manner by DSC (Differential Scanning Calorimetry), for example and unless otherwise specified, according to standard ASTM D3418 of 1999.

The rubber composition of the composite according to the invention may contain a single epoxidized diene elastomer or a mixture of several epoxidized diene elastomers (which will then be noted in the singular as being “the epoxidized diene elastomer” to represent the sum of the epoxidized diene elastomers of the composition), the diene elastomer comprising epoxide functions being able to be used in combination with any type of non-epoxidized elastomer, for example diene, or even with elastomers other than diene elastomers.

The epoxidized diene elastomer preferably predominates in the rubber composition of the composite according to the invention, that is to say that it is either the only elastomer, or it is the one that represents the greatest mass, among the elastomers of composition.

According to a preferred embodiment of the invention, the rubber composition comprises from 51 to 100 phr, preferably from 60 to 100 phr, and more preferably from 75 to 95 phr of majority epoxidized diene elastomer in a blend with 0 to 49 phr, preferably from 0 to 40 phr, preferably from 5 to 25 phr of one or more other non-epoxidized minor elastomers.

Preferably in this embodiment, the minority non-epoxidized elastomer is a non-epoxidized diene elastomer chosen from the group consisting of polybutadienes, natural rubber, synthetic polyisoprenes, butadiene copolymers, isoprene copolymers, and mixtures of these elastomers, preferably chosen from natural rubber and synthetic polyisoprenes

According to another preferred embodiment of the invention, the composition comprises, for all of the 100 phr of elastomer, one or more epoxidized diene elastomers.

The degree (mol %) of epoxidation of the epoxidized diene elastomers can vary to a large extent according to the particular embodiments of the invention, preferably within a range of 0.1% to 80%, preferentially within a range of 0 1% to 50%, more preferably in a range of 0.3% to 50%. When the epoxidation rate is lower at 0.1%, the targeted technical effect risks being insufficient, whereas beyond 80%, the intrinsic properties of the polymer are degraded. For all these reasons, the degree of functionalization, in particular of epoxidation, is more preferably comprised in a range of 5% to 40%, advantageously comprised in a range of 10% to 35%.

The epoxide functions present in the epoxidized diene elastomer are obtained by copolymerization or by post-polymerization modification, and are either carried directly by the backbone of the chain, or carried by a side group depending on the mode of production, for example by epoxidation. or any other modification of the diene functions present in the elastomeric chain after copolymerization.

The epoxidized diene elastomers can for example be obtained in a known manner by epoxidation of the equivalent non-epoxidized diene elastomer, for example by processes based on chlorohydrin or bromohydrin or processes based on hydrogen peroxides, alkyl hydroperoxides or peracids (such as peracetic acid or performic acid), see in particular Kautsch. Gummi Kunstst. 2004, 57(3), 82. The epoxy functions are then in the polymer chain. Mention may in particular be made of epoxidized natural rubbers (abbreviated to “ENR”); such ENRs are, for example, sold under the names "ENR-25" and "ENR-50" (respective epoxidation rates of 25% and 50%) by the company Guthrie Polymer. Epoxidized BRs are themselves also well known, sold for example by the company Sartomer under the name "Poly Bd" (for example "Poly Bd 605E"). Epoxidized SBRs can be prepared by epoxidation techniques well known to those skilled in the art.

Diene elastomers bearing epoxide groups have been described for example in US 2003/120007 or EP 0763564, US 6903165 or EP 1403287.

Preferably, the epoxidized diene elastomer is chosen from the group consisting of epoxidized natural rubbers (NR) (abbreviated "ENR"), epoxidized synthetic polyisoprenes (IR), epoxidized polybutadienes (BR) preferably having a rate of bonds cis-1,4 greater than 90%, epoxidized butadiene-styrene (SBR) copolymers and mixtures of these elastomers.

The epoxidized diene elastomers can also have pendant epoxide functions. In this case, they can be obtained either by post-polymerization modification (see for example J. Appl. Polym. Sci. 1999, 73, 1733), or by radical copolymerization of the diene monomers with monomers bearing epoxide functions, in particular the methacrylic acid esters comprising epoxide functions, such as for example glycidyl methacrylate (this radical polymerization, in particular in bulk, in solution or in a dispersed medium - in particular dispersion, emulsion or suspension - is well known to those skilled in the art of polymer synthesis, let us quote for example the following reference ^: Macromolecules 1998 , 31, 2822) or by the use of nitrile oxides carrying epoxide functions. For example, document US20110098404 describes the emulsion copolymerization of 1,3 butadiene, styrene and glycidyl methacrylate.

Reinforcing charge

The rubber composition of the composite according to the invention is based on at least one reinforcing filler.

It is possible to use any type of so-called reinforcing filler, known for its ability to reinforce a rubber composition that can be used in particular for the manufacture of tires, for example an organic filler such as carbon black, an inorganic filler such as silica or else a mixture of these two types of fillers.

Suitable carbon blacks are all carbon blacks, in particular the blacks conventionally used in tires or their treads. Among the latter, mention will be made more particularly of the reinforcing carbon blacks of the 100, 200, 300 series, or the blacks of the 500, 600 or 700 series (ASTM D-1765-2017 grades), such as for example the blacks N115, N134, N234, N326, N330, N339, N347, N375, N550, N683, N772). These carbon blacks can be used in the isolated state, as commercially available, or in any other form, for example as a carrier for some of the rubber additives used. The carbon blacks could for example already be incorporated into the diene elastomer, in particular isoprene in the form of a masterbatch (see for example applications W097/36724-A2 or W099/16600-A1). Also suitable are carbon blacks obtained from the recycling of tires such as blacks obtained from the pyrolysis of pneumatic tires, such as for example the black EnviroCB P550 of the 500 series produced by the company Scandinavian Enviro Systems.

As an example of organic fillers other than carbon blacks, mention may be made of functionalized polyvinyl organic fillers as described in applications W02006/069792-A1, W02006/069793-A1, W02008/003434-A1 and W02008/003435-A1 .

By “reinforcing inorganic filler”, should be understood here any inorganic or mineral filler, whatever its color and its origin (natural or synthetic), also called “white” filler, “clear” filler or even “non-black” filler. » as opposed to carbon black, capable of reinforcing on its own, without any means other than an intermediate coupling agent, a rubber composition intended for the manufacture of tires. In a known manner, certain reinforcing inorganic fillers can be characterized in particular by the presence of hydroxyl (OH) groups at their surface.

Suitable reinforcing inorganic fillers are in particular mineral fillers of the siliceous type, preferably silica (S1O2) or of the aluminous type, in particular alumina (Al2O3). The silica used can be any reinforcing silica known to those skilled in the art, in particular any precipitated or fumed silica having a BET specific surface area as well as a CTAB specific surface area, both of which are less than 450 m ² /g, preferably comprised in a range ranging from 30 to 400 m ² /g, in particular from 60 to 300 m ² /g. It is possible to use any type of precipitated silica, in particular highly dispersible precipitated silicas (called “HDS” for “highly dispersible” or “highly dispersible silica”). These precipitated silicas, highly dispersible or not, are well known to those skilled in the art. Mention may be made, for example, of the silicas described in applications W003/016215-A1 and W003/016387-Al. company Evonik, the “Zeosil® 1085GR”, “Zeosil® 1115 MP”, “Zeosil® 1165MP”, “Zeosil® Premium 200MP”, “Zeosil® HRS 1200 MP” silicas from Solvay. As non-HDS silica, the following commercial silicas can be used: "Ultrasil ® VN2GR" and "Ultrasil ® VN3GR" silicas from Evonik, "Zeosil® 175GR" silica from Solvay, "Hi -Sil EZ120GCD), “Hi-Sil EZ160G(- D)”, “Hi-Sil EZ200G(-D)”, “Hi-Sil 243LD”, “Hi-Sil 210”, “Hi-Sil HDP 320G” from PPG and “K-160” from Wilmar.

In this disclosure, BET surface area is determined by gas adsorption using the Brunauer-Emmett-Teller method described in "The Journal of the American Chemical Society" (Vol. 60, page 309, February 1938) , and more specifically according to a method adapted from standard NF ISO 5794-1, appendix E of June 2010 [multipoint volumetric method (5 points) - gas: nitrogen - vacuum degassing ^: one hour at 160°C - relative pressure range p/in: 0.05 to 0.17]

For inorganic fillers such as silica for example, the CTAB specific surface values were determined according to standard NF ISO 5794-1, appendix G of June 2010. The process is based on the adsorption of CTAB (N-bromide hexadecyl-N,N,N-trimethylammonium) on the "external" surface of the reinforcing filler. For carbon blacks, the STSA specific surface area is determined according to the ASTM D6556-2016 standard.

The physical state in which the reinforcing inorganic filler is present is irrelevant, whether it be in the form of powder, microbeads, granules, or else beads or any other appropriate densified form. Of course, the term “reinforcing inorganic filler” also means mixtures of different reinforcing inorganic fillers, in particular of silicas as described above.

Preferably, the content of total reinforcing filler (carbon black and/or reinforcing inorganic filler such as silica) ranges from 10 to 100 phr, more preferably from 10 to 80 phr, and very preferably from 10 to 60 phr, the optimum being in known manner different according to the particular applications targeted.

In a preferred arrangement, the reinforcing filler of the rubber composition mainly comprises carbon black. By predominantly, it is meant that the carbon black represents more than 50% of the total mass of reinforcing filler. Preferably in this arrangement, the reinforcing filler of the composition consists of carbon black.

In another preferred arrangement, the reinforcing filler of the rubber composition mainly comprises silica. By predominantly, it is meant that the silica represents more than 50% of the total mass of reinforcing filler. Preferably in this arrangement, the reinforcing filler of the composition consists of silica.

When the reinforcing filler comprises silica, preferably mostly silica, the rubber composition of the reinforced product according to the invention preferably comprises an agent chosen from coupling agents and silica covering agents as well as their mixture, the agent content being in a range ranging from 5 to 20% by weight relative to the amount of silica, preferably from 6 to 18% by weight relative to the amount of silica.

Coupling agent means an at least bifunctional coupling agent (or binding agent) intended to ensure a sufficient connection, of a chemical and/or physical nature, between the inorganic filler (surface of its particles) and the diene elastomer epoxidized. In particular, at least bifunctional organosilanes or polyorganosiloxanes are used. By “bifunctional”, we mean a compound having a first functional group capable of to interact with the inorganic filler and a second functional group capable of interacting with the epoxidized diene elastomer. For example, such a bifunctional compound may comprise a first functional group comprising a silicon atom, said first functional group being capable of interacting with the hydroxyl groups of an inorganic filler and a second functional group comprising a sulfur atom, said second functional group being capable of interacting with the diene elastomer.

Preferably, the organosilanes are chosen from the group consisting of polysulphide organosilanes (symmetrical or asymmetrical) such as bis(3-triethoxysilylpropyl) tetrasulphide, abbreviated as TESPT marketed under the name “Si69” by the company Evonik or bis disulphide -(triethoxysilylpropyl), abbreviated as TESPD marketed under the name "Si75" by the company Evonik, polyorganosiloxanes, mercaptosilanes, blocked mercaptosilanes, such as S-(3-(triethoxysilyl)propyl) octanethioate marketed by the company Momentive under the name “NXT Silane”. More preferably, the organosilane is a polysulphide organosilane.

Covering agent means, in a manner known to those skilled in the art, an agent which does not provide a bond between the filler and the elastomeric matrix. By bonding by covalent bond to the surface functional sites of the inorganic filler, for example, in a known manner, to the surface hydroxyl sites of the silica when the reinforcing inorganic filler is a silica, the covering agents improve the processability of the composition and reduce the green viscosity thereof.

As covering agent, consideration will generally be given to processing aid agents capable in a known manner, thanks to an improvement in the dispersion of the inorganic filler in the rubber matrix and to a lowering of the viscosity of the compositions, to improve their processability in the raw state, these agents being for example hydrolyzable silanes such as alkylalkoxysilanes (in particular alkyltriethoxysilanes), polyols, polyethers (for example polyethyleneglycols), primary amines , secondary or tertiary (for example trialcanohamines), hydroxylated or hydrolyzable POS, for example a, or dihydroxy polyorganosiloxanes (in particular cqordihydroxy-polydimethylsiloxanes).

Cross-linking system

The rubber composition of the composite according to the invention is based on at least one crosslinking system. Vulcanization

In the particular case where the composition according to the invention comprises a non-functionalized diene elastomer, the crosslinking system can preferably be sulfur-based. We then speak of a vulcanization system. The sulfur can be provided in any form, in particular in the form of molecular sulfur, or of a sulfur-donating agent. At least one vulcanization accelerator is also preferentially present, and, optionally, also preferentially, various known vulcanization activators such as zinc oxide, stearic acid or equivalent compound such as stearic acid salts and salts can be used. of transition metals, guanidine derivatives (in particular diphenylguanidine), or alternatively known vulcanization retarders.

The sulfur is used at a preferential rate of between 0.5 and 12 phr, in particular between 1 and 10 phr. The vulcanization accelerator is used at a preferential rate comprised between 0.5 and 10 phr, more preferentially comprised between 0.5 and 5 phr.

Any compound capable of acting as a vulcanization accelerator for diene elastomers in the presence of sulfur can be used as an accelerator, in particular accelerators of the thiazole type as well as their derivatives, accelerators of the sulfenamide, thiuram, dithiocarbamate, dithiophosphate, thiourea and xanthate type. As examples of such accelerators, mention may be made in particular of the following compounds ^: 2-mercaptobenzothiazyl disulphide (abbreviated as "MBTS"), N-cyclohexylb2-benzothiazyl sulfenamide ("CBS"), N,N-dicyclohexylb2-benzothiazyl sulfenamide ("DCBS"), N-ter-butyl-2-benzothiazyl sulfenamide ("TBBS"), N-ter-butyl-2-benzothiazyl sulfenimide ("TBSI"), tetrabenzylthiuram disulfide ("TBZTD"), zinc dibenzyldithiocarbamate ("ZBEC") and mixtures of these compounds.

Peroxide crosslinking

In a preferred arrangement, the rubber composition of the composite according to the invention comprises a crosslinking system based on at least one peroxide compound.

In this arrangement, the said peroxide compound or compounds represent from 0.01 to 10 phr of the rubber composition, preferably from 1 to 5 phr.

As peroxide that can be used according to the invention, any peroxide known to those skilled in the art can be used.

Preferably, the peroxide is chosen from organic peroxides. By “organic peroxide”, is meant an organic compound, that is to say one containing carbon, comprising an —OΌ— group (two oxygen atoms linked by a single covalent bond).

During the crosslinking process, the organic peroxide breaks down at its unstable OO bond into free radicals. These free radicals allow the creation of cross-linking bonds. According to one embodiment, the organic peroxide is chosen from the group consisting of dialkyl peroxides, monoperoxycarbonates, diacyl peroxides, peroxyketals, peroxyesters, and mixtures thereof.

Preferably, the dialkyl peroxides are chosen from the group consisting of dicumyl peroxide, di-t-butyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy )hexane, 2,5-dimethyl-2,5-di(t-amylperoxy)-hexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, 2,5-dimethyl -2,5-di(t-amylperoxy)hexyne-3, a,a'-dr[(t-butyl peroxyXsopropyl] benzene, a,a'-di-[(t-amyl-peroxy)isopropyl] benzene , di-t-amyl peroxide, l,3,5-tri-[(t-butylperoxy)isopropyl]benzene, l,3-dimethyl-3-(t-butylperoxy)butanol, l,3- dimethyl-3-(t-amylperoxy)butanol, and mixtures thereof.

Certain monoperoxycarbonates such as 00-tert-butyhO-(2-ethylhexyl) monoperoxycarbonate, 00-tert-butyhCHsopropyl monoperoxycarbonate, 00-tert-amyhO-2-ethyl hexyl monoperoxycarbonate, and mixtures thereof, can also be used.

Among the diacyl peroxides, the preferred peroxide is benzoyl peroxide.

Among the peroxyketals, the preferred peroxides are chosen from the group consisting of 1,1-di-(t-butylperoxy)-3,3,5-trimethylcyclohexane, 4,4-di-(t-butylperoxy)valerate of mbutyl , ethyl 3,3-di-(t-butylperoxy)butyrate, 2,2-di-(t-amylperoxy)-propane, 3,6,9-triethyl

3,6,9-trimethylhl,4,7-triperoxynonane (or cyclic trimer methyl ethyl ketone peroxide), 3,3,5,7,7-pentamethyhl,2,4-trioxepane, 4,4-bis( mbutyl t-amylperoxy)valerate, ethyl 3,3-di(t-amylperoxy)butyrate, 1,1-di(t-butylperoxy)cyclohexane, 1,1-di(t-amylperoxy)cyclohexane, and their mixtures. Preferably, the peroxyesters are chosen from the group consisting of tert-butylperoxybenzoate, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxy-3,5,5-trimethylhexanoate and mixtures thereof.

In a particularly preferred manner, the organic peroxide is chosen from the group consisting of dicumyl peroxide, aryl or diaryl peroxides, diacetyl peroxide, benzoyl peroxide, dibenzoyl peroxide, ditertbutyl peroxide, tertbutylcumyl peroxide, 2,5 bis (tertbutylperoxy)-2,5 dimethylhexane, n-butyl-4,4'-di(tert-butylperoxy) valerate, 00-(t-butyl)-(2-ethylhexyl) monoperoxycarbonate, tert-butyl peroxyisopropylcarbonate, tert-butyl peroxybenzoate, tert-butyl peroxy-3,5,5-trimethylhexanoate, l,3(4)-bis(tert-butylperoxyisopropyl)benzene, l,l-di- (t-butylperoxy)-3,3,5-trimethylcyclohexane and mixtures thereof, more preferably from the group consisting of dicumyl peroxide, n-butyl-4,4'-di(tert-butylperoxy)-valerate , OO-(t-butyl) 0-(2-ethylhexyl) monoperoxycarbonate, tert-butyl peroxyisopropylcarbonate, tert-butyl peroxybenzoate, tert-butyl peroxy-3,5,5-trimethyl hexanoate, 1,3(4)-bis(tert-butylperoxyisopropylbenzene, 1,1-di-(t-butylperoxy)-3,3,5-trimethylcyclohexane and mixtures thereof.

In this arrangement, the rubber composition of the composite according to the invention comprises at least one compound from the guanidine family. These compounds are often used in combination with a sulfur-based crosslinking system, called vulcanization, as vulcanization accelerators. However, it has been observed that in combination with a reinforcing filler mainly comprising silica, a polyphenolic compound and a crosslinking system based on at least one peroxide compound, the presence of at least one compound from the guanidine family made it possible to significantly improve the properties of the composite according to the invention.

Preferably, the content of compound of the guanidine family in the rubber composition ranges from 0.5 to 3 phr, preferentially from 0.5 to 2.5 phr and more preferably from 0.5 to 2 phr.

Preferably, the compound of the guanidine family is diphenylguanidine.

Polyacid - Imidazole

In a preferred arrangement, the diene elastomer of the rubber composition comprises epoxy functions, the crosslinking system comprising a polycarboxylic acid of general formula (I) and an imidazole of general formula (II). The polyacid useful for the purposes of the invention is a polycarboxylic acid of general formula (I) in which A represents a covalent bond or a hydrocarbon group containing at least 1 carbon atom, optionally substituted and optionally interrupted by one or more heteroatoms.

Preferably, in the polyacid of general formula (I), A represents a covalent bond or a divalent hydrocarbon group comprising from 1 to 1800 carbon atoms, preferentially from 2 to 300 carbon atoms, more preferentially from 2 to 100 carbon atoms, and very preferably from 2 to 50 carbon atoms. Above 1800 carbon atoms, the polyacid is a less effective crosslinking agent. Thus, A preferably represents a divalent hydrocarbon group comprising from 3 to 50 carbon atoms, preferentially from 5 to 50 carbon atoms, more preferentially from 8 to 50 carbon atoms, and even more preferentially from 10 to 40 carbon atoms. In a particular arrangement, the rubber composition according to the invention comprises between 0.9 and 30 phr of at least one polyacid whose group A contains between 10 and 40 carbon atoms and between 5 and 30 phr of at least one polyacid whose A group contains between 100 and 300 carbon atoms.

Preferably, in the polyacid of general formula (I), A can be a divalent group of the aliphatic or aromatic type or a group comprising at least one aliphatic part and one aromatic part. Preferably, A can be a divalent group of the aliphatic type, or a group comprising at least one aliphatic part and one aromatic part. Alternatively, and also preferably, A can be a divalent group of saturated or unsaturated aliphatic type, for example an alkylene group.

The group A of the polyacid of general formula (I) can be interrupted by at least one heteroatom chosen from oxygen, nitrogen and sulphur, preferably oxygen.

Also, the group A of the polyacid of general formula (I) can be substituted by at least one radical chosen from alkyl, cycloalkylalkyl, aryl, aralkyl, hydroxyl, alkoxy, amino and carbonyl radicals. The polyacid of general formula (I) can comprise more than two carboxylic acid functions, in this case, the group A is substituted by one or more carboxylic acid functions and/or by one or more hydrocarbon radicals chosen from alkyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, themselves substituted by one or more carboxylic acid functions.

According to a preferential mode, the radical A does not comprise any other carboxylic acid function, the polyacid is therefore a diacid.

The polyacid content is preferably within a range ranging from 0.2 to 100 phr, preferably from 0.2 to 50 phr, more preferably from 0.4 to 30 phr, and even more preferably from 0.9 to 25 phr . Below 0.2 phr of polyacid, the crosslinking effect is not significant, whereas above 100 phr of polyacid, the polyacid, crosslinking agent, becomes the majority by weight relative to the elastomeric matrix. .

The polyacids useful for the purposes of the invention are either commercially available or easily prepared by those skilled in the art according to well-known techniques such as the chemical routes described for example in document US 7534917 as well as in the references cited therein, or biological pathways, such as the fermentation described in US 3843466.

For example, as polyacids commercially available and useful for the purposes of the invention, mention may be made of: oxalic acid, succinic acid, adipic acid, sebacic acid, dodecanedioic acid, terephthalic acid or else polyacids such as trimesic acid or 3,4-bis(carboxymethyl)cyclopentanecarboxylic acid.

The imidazole useful for the crosslinking system according to the invention is an imidazole of general formula (II) in which,

- Ri represents a hydrogen atom or a hydrocarbon group, optionally interrupted by one or more heteroatoms and/or substituted, - R2 represents a hydrocarbon group,

- R3 and R4 represent, independently of each other, a hydrogen atom or a hydrocarbon group, optionally interrupted by one or more heteroatoms and/or substituted,

- Or else R3 and R4 form together with the carbon atoms of the imidazole cycle to which they are attached, a cycle optionally interrupted by one or more heteroatoms and/or substituted.

By the expression "optionally interrupted by one or more heteroatoms and/or substituted", it is meant that the groups R1, R3 and R4 can, independently and when they represent a hydrocarbon group, be interrupted by a heteroatom (i.e. that is to say in other words that a heteroatom is intercalated in the hydrocarbon chain), preferably chosen from nitrogen, oxygen and sulfur, and/or substituted by a functional group. By functional group is meant a group comprising a heteroatom, preferentially chosen from among the amino, alkylamine, alkoxyl and hydroxyl groups, preferentially chosen from the hydroxyl and amino groups.

Preferably, the imidazole of general formula (II) has groups such as ^:

- Ri represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, cycloalkyl having 5 to 24 carbon atoms, aryl having 6 to 30 carbon atoms or aralkyl having 7 to 25 carbon atoms , optionally substituted,

- R2 represents an alkyl group having from 1 to 20 carbon atoms, cycloalkyl having from 5 to 24 carbon atoms, aryl having from 6 to 30 carbon atoms or aralkyl having from 7 to 25 carbon atoms,

- R3 and R4 independently represent identical or different groups chosen from hydrogen or alkyl groups having from 1 to 20 carbon atoms, cycloalkyls having from 5 to 24 carbon atoms, aryls having from 6 to 30 carbon atoms or aralkyls having from 7 to 25 carbon atoms, optionally substituted, or even R3 and R4 form together with the carbon atoms of the imidazole ring to which they are attached, a ring chosen from aromatic, heteroaromatic or aliphatic rings, comprising from 5 to 12 carbon atoms carbon, preferably 5 or 6 carbon atoms.

Preferably, R represents a group chosen from alkyl groups having from 2 to 12 carbon atoms, or aralkyl groups having from 7 to 13 carbon atoms, optionally substituted. More preferentially, Ri represents an aralkyl group having from 7 to 13 optionally substituted carbon atoms and R2 represents an alkyl group having from 1 to 12 carbon atoms. Even more preferably, R1 represents an optionally substituted aralkyl group having 7 to 9 carbon atoms and R2 represents an alkyl group having 1 to 4 carbon atoms.

Preferably, R3 and R4 independently represent identical or different groups chosen from hydrogen or alkyl groups having from 1 to 12 carbon atoms, cycloalkyls having from 5 to 8 carbon atoms, aryls having from 6 to 24 carbon atoms or aralkyls having from 7 to 13 carbon atoms, optionally substituted. Alternatively and also preferentially, R3 and R4 represent form with the carbon atoms of the imidazole ring to which they are attached, a phenyl, cyclohexene or cyclopentene ring.

For proper operation of the invention, the level of imidazole is preferably within a range ranging from 0.01 to 4 molar equivalents, and preferably from 0.01 to 3 molar equivalents, relative to the carboxylic acid functions present on the polycarboxylic acid of general formula (I). Below 0.01 molar equivalents, no effect of the imidazole coagent is observed compared to the situation where the polyacid is used alone, whereas above a value of 4 molar equivalents, no effect is observed. no additional benefit over lower rates. Thus, the level of imidazole is more preferably within a range ranging from 0.01 to 2.5 molar equivalents, and preferably from 0.01 to 2 molar equivalents, and even more preferably from 0.01 to 1 .5 molar equivalents and preferably from 0.5 to 1.5 molar equivalents with respect to the carboxylic acid functions present on the polycarboxylic acid of general formula (I).

The imidazoles useful for the purposes of the invention are either commercially available or easily prepared by those skilled in the art according to well-known techniques such as described for example in the documents JP2012211122, JP2007269658 or in Science of Synthesis 2002, 12, 325-528.

For example, as commercially available imidazoles useful for the purposes of the invention, mention may be made of 1,2-dimethylimidazole, 1-decyl-2-methylimidazole, or 1-benzyl-2-methylimidazole.

Obviously, and in accordance with the definition of the expression "based on" for the present invention, a composition based on the polyacid of general formula (I) and the imidazole of general formula (II) presented below above could be a composition in which said polyacid and said imidazole would have previously reacted together to form a salt between one or more acid functions of the polyacid and respectively one or more imidazole rings. Polyphenol compound

The rubber composition of the composite according to the invention preferably comprises at least one polyphenolic compound comprising at least three aromatic rings comprising 6 carbon atoms, each carrying at least two vicinal hydroxyl groups. By vicinal, it is meant that the two hydroxyl groups carried by the aromatic ring are in the ortho position with respect to each other.

The molar mass of the polyphenolic compound is preferentially greater than 600 g/mol, preferentially greater than 800 g/mol, more preferably greater than 1000 g/mol and very preferably greater than 1200 g/mol. The molar mass of the polyphenolic compound is preferably less than 3000 g/mol, preferably less than 2000 g/mol.

Preferably, the polyphenolic compound is chosen from gallotannins, that is to say esters of gallic acid and polyol, the polyol preferably being chosen from pentoses and hexoses. Preferably, the polyphenolic compound is chosen from glucose and gallic acid esters, preferably chosen from polygalloyl glucoses comprising from 3 to 10 galloyl units, preferably comprising from 5 to 10 galloyl units. Preferably, the polyphenolic compound is chosen from trigalloyl glucoses, pentagalloyl glucoses and decagalloyl glucoses, and preferably from 1,2,6-Trigalloyl glucose, 1,3,6-Trigalloyl glucose, 1,2 ,3,4,6-Pentagalloyl-glucose and tannic acid (or beta-D-Glucose pentakis(3,4-dihydroxy-5-((3,4,5-trihydroxybenzoyl)oxy)benzoate)). Very preferably, the polyphenolic compound is tannic acid. These compounds can be obtained commercially, for example from a supplier such as Sigma Aldrich. The rubber composition according to the invention advantageously comprises from 0.1 to 25 phr of polyphenolic compound.

Miscellaneous additives

The rubber compositions of the composite in accordance with the invention may also comprise all or part of the usual additives, known to those skilled in the art and usually used in rubber compositions for tires, in particular of internal layers as defined later. in the present application, such as for example plasticizers (plasticizing oils and/or plasticizing resins), reinforcing or non-reinforcing fillers other than those mentioned above, pigments, protective agents such as anti-ozone waxes, chemical antrozonants, antioxidants, anti-fatigue agents, reinforcing resins (as described for example in application WO 02/10269).

Preferably, the rubber composition according to the invention does not contain a vulcanization system, or contains less than 1 phr thereof, preferably less than 0.5 phr and more preferably less than 0.2 phr. Thus, the rubber composition according to the invention is preferably devoid of molecular sulfur or contains less than 1 phr thereof, preferably less than 0.5 phr and more preferably less than 0.2 phr. Likewise, the composition is preferably devoid of any vulcanization accelerator or activator, as they are known to those skilled in the art, or contains less than 1 phr thereof, preferably less than 0.5 phr and more preferably less than 0 ,2 pc. In particular, the rubber composition according to the invention is preferably devoid of zinc or zinc oxide, or contains less than 1 phr thereof, preferably less than 0.5 phr and very preferably less than 0.2 phr. .

Similarly, the rubber composition according to the invention is preferably free of cobalt salts, as they are known to those skilled in the art, and the effect of which, known to those skilled in the art, is an improvement in adhesion. , or contains less than 1 phr, preferably less than 0.5 phr, more preferably less than 0.2 phr and very preferably less than 0.1 phr.

Reinforcement element

The composite according to the invention is based on at least one metallic reinforcing element embedded in a rubber composition.

The expression "based on at least one metallic reinforcing element embedded in a rubber composition" means a composite comprising the reinforcing element and said composition, the composition having been able to react with the surface of the reinforcing element during the various phases of manufacture of the composite, in particular during the crosslinking of the composition or during the manufacture of the composite before crosslinking of the rubber composition. By embedded, it is meant that the metal reinforcing element is directly in contact with the rubber composition over its entire surface.

Said metal reinforcement element is a wire element. It can be all or part metal. The metallic surface of the reinforcing element is intended to come into direct contact with the rubber composition. According to a first variant of the invention, the surface of the metallic reinforcing element is made of a metallic material different from the rest of the reinforcing element. In other words, the reinforcing element is made of a material which is at least partly, preferably totally, covered by a metallic layer which constitutes the metallic surface. The material at least partly, preferably completely, covered by the metallic surface is metallic in nature.

According to a second variant of the invention, the reinforcing element is made of the same material, in which case the reinforcing element is made of a metal which is identical to the metal of the metal surface.

A specific metallic surface can make it possible to improve, for example, the implementation properties of the reinforcing element, or the usage properties of the composite and/or the tire themselves, such as the adhesion properties, corrosion resistance or aging resistance.

According to one embodiment of the invention, the metal surface of the metal reinforcement element comprises a metal chosen from the group consisting of iron, copper, zinc, tin, aluminum, cobalt, nickel and alloys comprising at least one of these metals. The alloys can be, for example, binary or ternary alloys, such as bronze and brass. Preferably, the metal of the metallic surface is iron, copper, tin, zinc or an alloy comprising at least one of these metals. More preferably, the metal of the metallic surface is brass (Cu-Zn alloy), steel, zinc or bronze (Cu-Sn alloy), even more preferably brass. Some metals being subject to oxidation in contact with ambient air, the metal can be partly oxidized.

According to a preferred embodiment, the composite according to the invention comprises several reinforcing elements as defined above and a calendering rubber in which the reinforcing elements are embedded, the calendering rubber consisting of the rubber composition of the product reinforced according to the invention. According to this embodiment, the reinforcing elements are arranged generally side by side along a main direction. For application envisaged in the tire, the reinforced product according to the invention can therefore constitute a reinforcement reinforcement for a tire.

The composite according to the invention can be in the raw state (before crosslinking of the rubber composition) or in the cured state (after crosslinking of the rubber composition). The composite according to the invention is cured after bringing the reinforcing element(s) into contact with the rubber composition.

The composite according to the invention can be manufactured by a process which comprises the following steps:

• Make two layers of the rubber composition,

• Sandwich the reinforcement element(s) in the two layers by placing it (them) between the two layers,

• If necessary, bake the composite according to the invention.

Alternatively, the composite according to the invention can be manufactured by depositing the reinforcing element on a portion of a layer, the layer is then folded back on itself to cover the reinforcing element which is thus sandwiched over the entire its length or part of its length.

The production of the layers can be done by calendering. During the curing of the composite according to the invention, the rubber composition is crosslinked.

When the composite according to the invention is intended to be used as reinforcement in a tire, the curing of the composite according to the invention generally takes place during the curing of the tire.

The metal reinforcing element is brought into contact with carbon dioxide in the supercritical state prior to its incorporation into the rubber composition. Carbon dioxide in the supercritical state is pure carbon dioxide, i.e. it does not contain any additives.

Such treatment of the metallic reinforcing element prior to its incorporation into the rubber composition has the surprising effect not only of improving the initial adhesion of the metallic reinforcing element to the rubber composition, but also of improving the sustainability of this membership. The supercritical state is a well-known physical state of carbon dioxide and widely implemented industrially, in particular for the extraction of aromas.

Preferably, the reinforcing element is brought into contact with carbon dioxide in the supercritical state for a period of between 2 and 80 min, preferably between 2 and 60 min, and more preferably between 2 and 30 min.

Preferably, the reinforcing element is brought into contact with carbon dioxide in the supercritical state at a temperature of between 35 and 60°C, preferably between 35 and 45°C.

Preferably, the reinforcing element is brought into contact with carbon dioxide in the supercritical state at a pressure of between 70 and 150 bar.

Bringing the metallic reinforcing element into contact with carbon dioxide in the supercritical state can be carried out by any means known to those skilled in the art, continuously or in sequence. For example, a coil on which the reinforcing element is wound can be placed in an enclosure capable of being brought to the desired temperature and pressure, into which carbon dioxide is injected.

Manufacturing process

The invention also relates to a process for manufacturing a composite based on at least one reinforcing element and a rubber composition comprising at least the following successive steps: c) A step of bringing each reinforcing element with supercritical carbon dioxide;

A step in which each reinforcing element is embedded in the rubber composition so as to obtain the composite.

Preferably, the composite is a composite as described herein, based on at least one reinforcing element as described above and a rubber composition as described above.

Finished or semi-finished and pneumatic article

The invention also relates to a finished or semi-finished article comprising a composite according to the invention. The finished or semi-finished article can be any article comprising a composite according to the invention. Mention may be made, for example and in a non-limiting manner, of conveyor belts, pneumatic or non-pneumatic tires, the latter being tires whose shape is maintained, for example by means of rigid stays, without the use of pressurized gas.

The pneumatic or non-pneumatic tire, another object of the invention, has the essential characteristic of comprising the composite in accordance with the invention. The tire may be in the raw state (before crosslinking of the rubber composition) or in the cured state (after crosslinking of the rubber composition). Generally, during the manufacture of the tire, the composite is deposited in the green state (that is to say before crosslinking of the rubber composition) in the structure of the tire before the step of curing the tire.

The invention particularly relates to tires intended to be fitted to motor vehicles of the passenger car type, SUV ("Sport Utility Vehicles"), or two wheels (in particular motorcycles), or airplanes, or even industrial vehicles chosen from vans, "Weight- heavy”, i.e. metro, bus, road transport vehicles (trucks, tractors, trailers), off-road vehicles such as agricultural or civil engineering machinery, and others.

It is possible to define three types of zones within the bandage ^:

^• The radially outer zone and in contact with the ambient air, this zone essentially consisting of the tread and the outer side of the tire. An outer sidewall is an elastomeric layer arranged outside the carcass reinforcement with respect to the internal cavity of the tire, between the crown and the bead so as to totally or partially cover the zone of the carcass reinforcement. extending from apex to bead.

^• The radially inner zone and in contact with the inflation gas, this zone generally consisting of the layer impermeable to the inflation gases, sometimes called the inner impermeable layer or inner rubber (“inner liner” in English).

^• The inner zone of the bandage, ie the one between the outer and inner zones. This area includes layers or webs which are referred to herein as inner layers of the tire. These are, for example, carcass plies, tread underlayers, tire belt plies or any other layer which is not in contact with the ambient air or the inflation gas of the tire.

The composition defined in the present description is particularly well suited to the inner layers of bandages. Also, the invention also relates to a pneumatic or non-pneumatic tire comprising an inner layer comprising a composite according to the present invention. According to the invention, the inner layer can be chosen from the group consisting of carcass plies, crown plies, bead wire fillers, crown feet, decoupling layers, tread underlayer and combinations of these inner layers. Preferably, the inner layer is chosen from the group consisting of carcass plies, crown plies, bead wire fillers, crown feet, decoupling layers and combinations of these inner layers.

Examples

The quality of the bond between the rubber composition and the reinforcing element is determined by a test in which the force necessary to extract sections of individual threads or assemblies of individual threads having a metallic surface is measured from the composition cross-linked rubber. To this end, composites are prepared in the form of test specimens comprising metal reinforcing elements of the "19.18" type commonly used in tire carcass reinforcing plies and consisting of nineteen monofilaments of 18 hundredth brass-coated steel of mm in diameter twisted together taken in a rubber composition.

Preparation of rubber compositions

The procedure for preparing rubber composition C2, which corresponds to composition C1 of document WO 2020/058614, is as follows ^: introduction into an internal mixer (final filling rate ^: approximately 70% by volume), the temperature of which initial tank temperature is approximately 60° C., successively the elastomer, comprising for composition C2 epoxy functions, then all the other constituents of the mixture. Thermomechanical work is then carried out in one step until a maximum "drop" temperature of 150°C is reached. The mixture thus obtained is recovered and cooled on an external mixer (homofinisher) to 30° C., while mixing the whole. Composition C3, which represents another sulfur-free crosslinked composition, is prepared in the same way as composition C2.

Composition C1, which corresponds to composition T1 of document WO 2020/058614, is prepared in the same way, with the exception of the sulfur and the accelerator which are added in the external mixer. This composition represents a conventional calendering mixture known to those skilled in the art.

Composition “C1” is a typical sulfur composition for calendering metal reinforcements. The various rubber compositions prepared are presented in Tables 1 to 3. [Table 1]

[Table 2]

[Table 3]

For Tables 1 to 3, all the compositions are given in phr. The following captions apply to all three tables. (1) Natural Rubber

(2) Carbon Black N326 (per ASTM D-1765)

(3) Cobalt Naphthenate - Fluka Company Product No. 60830

(4) Stearin (“Pristerene 4931” from Uniqema)

(5) Zinc oxide, industrial grade, Umicore company

(6) N-(cyclohexylthio)phthalimide, marketed under the name “Vulkalent G” by Lanxess or also “Duslin P” by Duslo

(7) N-ter-butyl-2-benzothiazyl sulfenamide “Santocure TBBS” from the company Flexsys

(8) Epoxy Natural Rubber, “ENR-25”, from Guthrie Polymer;

(9) Silica 160 MP, “Zeosil 1165MP” from Rhodia;

(10) “Dynasylan Octeo”, from Degussa;

(11) N-1,3-dimethylbutyl-N-phenylparaphenylenediamine (Santoflex 6-PPD from the company Flexsys);

(12) Poly(acrylonitrile-co-butadiene), dicarboxy terminated, Sigma-Aldrich ref.418870, Mn=3800 g/mol;

(13) 1-benzyl-2-methylimidazole, CAS=13750-62-4 from Sigma-Aldrich;

(14) CAS 1401-55-4 provided by Sigma-Aldrich

(15) Luperox 231XL40 from Arkema

(16) Diphenylguanidine Preparation of test specimens

The rubber compositions thus prepared are used to make test specimens according to the following protocol:

To manufacture adhesion specimens, a block of rubber is made up of two raw plates cut with a punch of dimensions 70x12 mm and thickness

64/10 ^th mm, applied one on the other before firing. Both plates of the block consist of the same rubber composition. It is during the manufacture of the block that the reinforcing elements are trapped between the two plates in the raw state, the length of the imprisoned reinforcement being 20mm, at equal distance and leaving protrude on either side of these plates one end of the reinforcing element of sufficient length (approximately 20 cm) for subsequent traction (with slip jaws). The block comprising the reinforcing elements is then baked at 170° C. for a time varying from 5 min to 90 min depending on the composition under pressure of 6 tonnes. The reinforcing elements are an assembly of nineteen individual wires 0.18 mm in diameter (“19.18” cables) used very commonly for producing the carcass plies of tires of the heavy-vehicle type; the thickness of the brass coating ranges from 50 nm to 300 nm. The reinforcing elements are treated prior to their incorporation into the block of rubber in accordance with the method according to the invention according to the conditions indicated in Table 3. Thus, the reinforcing elements are placed in a receptacle. This receptacle is closed in a sealed manner, then brought to temperature and pressure in accordance with the parameters indicated in table 3. The carbon dioxide is injected into the receptacle so as to come into contact with all the reinforcements contained in the receptacle. After the curing time has elapsed, the carbon dioxide is vented and the cured reinforcements are incorporated into the rubber block.

Treated and untreated reinforcements differ only in whether or not the treatment is applied.

The specimens thus prepared with conforming compositions and reinforcements correspond to composites conforming to the invention.

Measures carried out

Membership

Adherence is assessed using the method described by Gent et al. (Gent, A. N., Fielding-Russell, G. S., Livingston, D.I., Nicholson, D.W., 1981. Failure of cord-rubber composites by pulhout or transverse fracture. Journal of Materials Science 16(4), 949 956). After curing the adhesion test pieces described above, the test piece thus made up of the reticulated block and the two assembly sections is placed in the jaws of a tensile machine suitable for testing the adhesion between the sections and the rubber, at a given speed and temperature (for example, in the present case, at 100 mm/min and ambient temperature).

Adhesion levels are characterized by measuring the so-called tearing force, in N, to tear off the sections of the specimen.

The properties of the rubber and adhesion test specimens produced from the various compositions were evaluated and are presented in Table 4 below. These properties were evaluated initially, that is to say after the firing of the test pieces, then after aging of the fired test pieces, aging having taken place at 55° C. and under a relative humidity of 95% for a period of 21 days. These conditions make it possible to subject the various test specimens to aging of the thermo-oxidative type representative of the aging encountered over the life of a tire. The results of the various measurements are expressed in base 100, the value of 100 corresponding to the value of the property measured when the sample is in its initial state, i.e. it has just been produced ( that is to say cooked) and has not undergone any aging (T=0j). They are reported in Table 3. [Table 3]

It is observed that the composition in accordance with the invention maintains, or even improves, its adhesion properties over time thanks to the treatment applied to the reinforcement. The initial adhesion and its durability over time is improved with composition Cl.

The adhesion in the case of composition C2 showed excellent stability. The composite according to the invention, however, has an even improved initial and after aging adhesion. The sulfur-free compositions exhibit excellent adhesion, superior to composition C1.

Tests carried out on metal reinforcements of architecture 1.32, i.e. a monofilament 0.32 mm in diameter, 2.30, i.e. an assembly of two monofilaments 0.30 mm in diameter, and 9.35, ie an assembly of nine 0.35 mm diameter filaments, lead to similar results.

Claims

[Claim l] Composite based on a rubber composition based on at least one diene elastomer, a reinforcing filler, a crosslinking system and at least one metallic reinforcing element embedded in said rubber composition, said element reinforcement being brought into contact with carbon dioxide in the supercritical state prior to its incorporation into the rubber composition.

[Claim 2] Composite according to the preceding claim, in which the reinforcing element is brought into contact with carbon dioxide in the supercritical state for a period of between 2 and 80 min, preferably between 2 and 60 min, and preferably between 2 and 30 min.

[Claim 3] Composite according to any one of the preceding claims, in which the reinforcing element is brought into contact with carbon dioxide in the supercritical state at a temperature of between 35 and 60°C, preferably between 35 and 45°C.

[Claim 4] Composite according to any one of the preceding claims, in which the reinforcing element is brought into contact with carbon dioxide in the supercritical state at a pressure of between 70 and 150 bar.

[Claim 5] A composite according to any preceding claim wherein the reinforcing filler of the rubber composition comprises carbon black, silica or a mixture of carbon black and silica.

[Claim 6] A composite according to any preceding claim wherein the rubber composition comprises a diene elastomer selected from the group consisting of polybutadienes, natural rubber, synthetic polyisoprenes, butadiene copolymers, isoprene, and mixtures of these elastomers.

[Claim 7] Composite according to any one of the preceding claims, in which the rubber composition comprises at least 50 phr, preferably at least 70 phr, preferably at least 90 phr of at least one isoprene elastomer.

[Claim 8] Composite according to any one of the preceding claims, in which the said composition is devoid of molecular sulfur or contains less than 1 phr thereof.

[Claim 9] Composite according to any one of the preceding claims, in which the diene elastomer comprises epoxide functions, the crosslinking system comprising a polycarboxylic acid of general formula (I) in which A represents a covalent bond or a hydrocarbon group containing at least 1 carbon atom, optionally substituted and optionally interrupted by one or more heteroatoms, an imidazole of general formula (II) in which,

Ri represents a hydrocarbon group or a hydrogen atom, R2 represents a hydrocarbon group,

R3 and R4 represent, independently of each other, a hydrogen atom or a hydrocarbon group, or even R3 and R4 form together, with the carbon atoms of the imidazole ring to which they are attached, a cycle.

[Claim 10] Composite according to the preceding claim, in which A represents a covalent bond or a divalent hydrocarbon group comprising from 1 to 1800 carbon atoms, preferably from 2 to 300 carbon atoms.

[Claim 11] Composite according to any one of Claims 9 to 10, in which the content of polycarboxylic acid is within a range extending from 0.2 to 100 phr, preferably from 0.2 to 50 phr.

[Claim 12] Composite according to any one of Claims 1 to 8, in which the crosslinking system of the rubber composition is based on at least one peroxide compound, the rubber composition further comprising at least one compound of the guanidine family.

[Claim 13] Composite according to any one of the preceding claims, in which the rubber composition comprises a polyphenolic compound comprising at least three aromatic rings comprising 6 carbon atoms, each carrying at least two vicinal hydroxyl groups, preferably chosen from gallotannins, preferably from esters based on gallic acid and a polyol chosen from pentoses and hexoses.

[Claim 14] A rubber article comprising a composite according to any preceding claim. [Claim 15] A method of manufacturing a composite based on at least one reinforcing element and a rubber composition according to any one of claims 1 to 13 comprising at least the following successive steps: a. A step of bringing each reinforcement element into contact with carbon dioxide in the supercritical state; b. A step in which each reinforcing element is embedded in the rubber composition so as to obtain the composite.