Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
  • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
  • C08J5/041—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with metal fibres
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
  • B29D30/00—Producing pneumatic or solid tyres or parts thereof
  • B29D30/06—Pneumatic tyres or parts thereof (e.g. produced by casting, moulding, compression moulding, injection moulding, centrifugal casting)
  • B29D30/38—Textile inserts, e.g. cord or canvas layers, for tyres; Treatment of inserts prior to building the tyre
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B60—VEHICLES IN GENERAL
  • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
  • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B60—VEHICLES IN GENERAL
  • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
  • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
  • B60C1/0016—Compositions of the tread
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B60—VEHICLES IN GENERAL
  • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
  • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
  • B60C1/0041—Compositions of the carcass layers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
  • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/02—Elements
  • C08K3/04—Carbon
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L15/00—Compositions of rubber derivatives
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
  • B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
  • B29B15/08—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of reinforcements or fillers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
  • B29D30/00—Producing pneumatic or solid tyres or parts thereof
  • B29D30/0005—Pretreatment of tyres or parts thereof, e.g. preheating, irradiation, precuring
  • B29D2030/0011—Surface activation of tyres or parts thereof, e.g. by plasma treatment
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
  • B29D30/00—Producing pneumatic or solid tyres or parts thereof
  • B29D30/06—Pneumatic tyres or parts thereof (e.g. produced by casting, moulding, compression moulding, injection moulding, centrifugal casting)
  • B29D30/38—Textile inserts, e.g. cord or canvas layers, for tyres; Treatment of inserts prior to building the tyre
  • B29D2030/383—Chemical treatment of the reinforcing elements, e.g. cords, wires and filamentary materials, to increase the adhesion to the rubber
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2307/00—Characterised by the use of natural rubber
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/36—Silica

Definitions

• the present invention relates to the field of reinforced composites, in particular suitable for the reinforcement of pneumatic tires.
• 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.
• 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.
• 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.
• document WO2020/058614 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 compound specific polyphenolic exhibiting characteristics of adhesion to a reinforcing element that are particularly advantageous, in particular for the constitution of composites intended for tires.
• a crosslinking system comprising a polycarboxylic acid, an imidazole and at least one compound specific polyphenolic 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.
• EP 3 336 140, EP 2 371 882 and EP 2 716694 also related to the treatment of the surface of the reinforcements by an atmospheric plasma, said plasma being generated from a carrier gas comprising a additive such as a halogen compound, a polymerizable compound and/or a sulfur compound.
• a carrier gas comprising a additive such as a halogen compound, a polymerizable compound and/or a sulfur compound.
• the applicant discovered a composite comprising a rubber composition and a reinforcement, the reinforcement having been treated with an atmospheric plasma having excellent adhesion qualities, this adhesion also having good durability, this treatment not requiring reuse of additives.
• 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.
• step b) Composite according to any one of the preceding embodiments in which, during step b), the metal reinforcing element moves continuously during its exposure to the plasma, preferably at a speed of between 3 and 100 m/min, from preferably at a speed of between 5 and 80 m/min.
• 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.
• Composite according to embodiment 7 in which the reinforcing filler of the rubber composition comprises from 10 to 150 phr, preferably from 10 to 100 phr, of silica.
• 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.
• the rubber composition comprises at least 50 phr, preferably at least 70 phr, preferably at least 90 phr of at least one isoprene elastomer.
• 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.
• A represents a covalent bond or a divalent hydrocarbon group comprising from 1 to 1800 carbon atoms, preferably from 2 to 300 carbon atoms.
• 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
• 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
• 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.
• 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.
• 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.
• 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.
• Rubber article comprising a composite according to any one of the preceding embodiments.
• Article according to the previous embodiment selected from the group comprising pneumatic or non-pneumatic tires, transmission belts, conveyor belts, caterpillars.
• a method of manufacturing a composite according to any one of claims 1 to 25 comprising at least the following successive steps: a) A step of generating an atmospheric plasma from compressed air; b) A step of bringing the surface of the metallic reinforcing element into contact with the atmospheric plasma generated during step a); c) A step in which the reinforcing element is embedded in the rubber composition so as to obtain the composite.
• 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.
• 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.
• 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 embedded in said rubber composition, said composite being obtained by a process comprising at least the following successive steps: a. A step of generating an atmospheric plasma from a compressed gas chosen from air and an inert gas chosen from argon, helium and nitrogen; b. A step of bringing the surface of the metallic reinforcing element into contact with the atmospheric plasma generated during step a); vs. A step in which the metallic reinforcing element is embedded in the rubber composition so as to obtain the composite.
• the method according to the invention making it possible to obtain the composite according to the invention, comprises a step a) of generating an atmospheric plasma from a compressed gas chosen from air and an inert gas chosen from argon, helium and nitrogen.
• Plasma is a well-known physical state.
• the plasma can be generated by any device known to those skilled in the art for generating an atmospheric plasma, atmospheric plasma being understood as a plasma at atmospheric pressure, such as a plasma torch.
• the plasma is generated by means of an electric discharge generated through the gas, the control of the electric discharge making it possible to control the ionization of the gas and its temperature at the torch outlet.
• Plasma is generated from a compressed gas.
• compressed it is meant that the gas is at a pressure greater than atmospheric pressure prior to the generation of the plasma, the pressure to which the gas is compressed being a simple means of managing the flow rate of atmospheric plasma.
• the gas is air.
• air we mean this term in its common meaning, that is to say a majority mixture of nitrogen, of the order of 78% molar, of the order of 21% of oxygen, the complement being a mixture of gases such as for example argon and carbon dioxide.
• the compressed gas is a compressed and filtered gas. Filtration of the gas makes it possible to capture any undesirable bodies, such as fine oil droplets.
• a conventional practice is to use a one micrometer filter.
• the gas, preferably air, used for generating the atmospheric plasma is free of organic compounds, or contains less than 1% by volume, preferably less than 0.5% by volume, very preferably less than 0, 1% by volume.
• the gas, preferably air, used for generating the atmospheric plasma is free of halogenated compounds, or contains less than 1% by volume, preferably less than 0.5% by volume, very preferably less than 0, 1% by volume.
• Step b) of bringing the surface of the metal reinforcement element into contact with the atmospheric plasma generated during step a) The plasma generated during step a) is brought into contact with the surface of the element metal reinforcement.
• the metal reinforcement element moves continuously during its exposure to the plasma, preferably at a speed of between 3 and 100 m/min, preferably at a speed of between 5 and 80 m/min.
• the plasma is brought into contact with the surface of the metallic reinforcement element using at least one plasma-generating torch.
• at least two plasma-generating torches are used, placed on either side of the metallic reinforcing element.
• the torches are placed so as not to face each other.
• the placement of the torches around the metallic reinforcement element is intended to ensure that the entire surface of the reinforcement is brought into contact with the plasma.
• the total number of torches can therefore be adjusted according to geometric constraints or the individual powers of each torch.
• the flow rate of plasma brought into contact with the metal reinforcement element is preferably between 1000 and 3000 l/h.
• 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 composite according to the invention is obtained by a step c) in which the metal reinforcing element treated during step b) is embedded in the rubber composition.
• composite based on at least one metallic reinforcing element embedded in a rubber composition it is meant 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.
• embedded it is meant that the metal reinforcing element is directly in contact with the rubber composition over its entire surface.
• Step c) can be carried out by any method known to those skilled in the art allowing the metal reinforcing element to be embedded in the rubber composition, for example by a method comprising the following steps: • Make two layers of the rubber composition,
• step c) can be carried out 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 its entire length or part of its length.
• the production of the layers can be done by calendering.
• the rubber composition is crosslinked.
• the curing of the composite according to the invention generally takes place during the curing of the tire.
• 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.
• 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.
• 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).
• essentially unsaturated diene elastomer 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) .
• conjugated diene monomers having a rate of units or units of diene origin (conjugated dienes) which is greater than 15% (% in moles) .
• conjugated diene monomers having a rate of units or units of diene origin (conjugated dienes) which is greater than 15% (% in moles) .
• conjugated diene monomers having a rate of units or units of diene origin (conjugated dienes) which is greater than 15% (% in moles) .
• highly unsaturated diene elastomer a diene elastomer having a content of units of diene origin (conjugated dienes) which is greater than 50%.
• 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.
• 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.
• SBR butadiene-styrene
• BIR isoprene-butadiene
• SIR isoprene-styrene copolymers
• SBIR isoprene-butadiene-styrene
• 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 take in the long term, at the latest 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.
• 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.
• 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
• 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%.
• 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. Kunststoff Kunststoffst. 2004, 57(3), 82.
• the epoxy functions are then in the polymer chain.
• ENR epoxidized natural rubbers
• ENR-25 epoxidized natural rubbers
• ENR-50 epoxidized natural rubbers
• Epoxidized BRs are themselves also well known, sold for example by the company Sartomer under the name "Poly Bd” (for example “Poly Bd 605E”).
• the 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.
• 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.
• NR epoxidized natural rubbers
• EMR epoxidized synthetic polyisoprenes
• BR epoxidized polybutadienes
• SBR epoxidized butadiene-styrene 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 the synthesis of polymers, let us quote for example the following reference : Macromolecules 1998, 31, 2822) or by the use of nitrile oxides bearing epoxide functions.
• document US20110098404 describes the emulsion copolymerization of 1,3 butadiene, styrene and gly
• the rubber composition of the composite according to the invention is based on at least one reinforcing filler.
• 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 these 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.
• 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 .
• 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, with no other means than an intermediate coupling agent, a rubber composition intended for the manufacture of tires.
• 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.
• any type of precipitated silica in particular highly dispersible precipitated silicas (called “HDS” for “highly dispersible” or “highly dispersible silica”).
• HDS highly dispersible precipitated silicas
• 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 the Solvay company.
• Non-HD S silica the following commercial silicas can be used: "Ultrasil ® VN2GR” and “Ultrasil ® VN3GR” silicas from Evonik, "Zeosil® 175GR” silica from Solvay, "Ultrasil® 175GR” silica from Solvay, Hi-Sil EZ120G(-D)", “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.
• 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]
• CTAB N-bromide hexadecyl-N,N,N-trimethylammonium
• the STSA specific surface area is determined according to the ASTM D6556-2016 standard.
• reinforcing inorganic filler also means mixtures of different reinforcing inorganic fillers, in particular of silicas as described above.
• the content of total reinforcing filler 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.
• the reinforcing filler of the rubber composition mainly comprises carbon black.
• the carbon black represents more than 50% of the total mass of reinforcing filler.
• the reinforcing filler of the composition consists of carbon black.
• the reinforcing filler of the rubber composition mainly comprises silica.
• the silica represents more than 50% of the total mass of reinforcing filler.
• the reinforcing filler of the composition consists of 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.
• at least bifunctional organosilanes or polyorganosiloxanes are used.
• bifunctional is meant a compound having a first functional group capable of interacting with the inorganic filler and a second functional group capable of interacting with the epoxidized diene elastomer.
• 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.
• 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”.
• polysulphide organosilanes such as bis(3-triethoxysilylpropyl) tetrasulphide
• TESPT bis(3-triethoxysilylprop
• 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.
• the covering agents improve the processability of the composition and reduce the viscosity in the green state of the latter.
• 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).
• hydrolyzable silanes such as alkylalkoxysilanes (in particular alkyltriethoxysilanes), polyols, polyethers (for example polyethyleneglycols), primary amines , secondary or tertiary
• the rubber composition of the composite according to the invention is based on at least one crosslinking system.
• the crosslinking system can preferably be sulfur-based.
• 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.
• MBTS 2-mercaptobenzothiazyl disulphide
• CBS N-cyclohexyl-2-benzothiazyl sulfenamide
• DCBS N,N-dicyclohexyl-2-benzothiazyl sulfenamide
• TBBS N-ter-butyl-2-benzothiazyl sulfenamide
• TZTD tetrabenzylthiuram disulfide
• ZBEC zinc dibenzyldithiocarbamate
• 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 comprising at least 1 carbon atom, optionally substituted and optionally interrupted by one or more heteroatoms.
• 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.
• 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.
• 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.
• A in the polyacid of general formula (I), can be a divalent group of the aliphatic or aromatic type or a group comprising at least one aliphatic part and one aromatic part.
• A can be a group divalent aliphatic type, or a group comprising at least one aliphatic part and one aromatic part.
• 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.
• 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.
• 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 .
• 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. .
• 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.
• 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,
• 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,
• 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.
• 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.
• a heteroatom i.e. that is to say in other words that a heteroatom is intercalated in the hydrocarbon chain
• 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.
• 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.
• 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 preferably, R1 represents an optionally substituted aralkyl group having 7 to 13 carbon atoms and R2 represents an alkyl group having 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.
• 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.
• R3 and R4 represent form with the carbon atoms of the imidazole ring to which they are attached, a phenyl, cyclohexene or cyclopentene ring.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• the polyphenolic compound is chosen from gallotannins, that is to say esters of gallic acid and of polyol, the polyol preferably being chosen from pentoses and hexoses.
• 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.
• 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)).
• 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.
• 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.
• 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.
• plasticizers plasticizing oils and/or plasticizing resins
• pigments 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, anti -oxidants, anti-fatigue agents, reinforcing resins (as described for example in application WO 02/10269).
• 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.
• 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.
• 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.
• 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. .
• 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.
• the composite according to the invention is based on at least one metallic reinforcing element embedded in a rubber composition.
• 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.
• the surface of the metallic reinforcing element is made of a metallic material differing from the remainder of the reinforcing element.
• the reinforcing element is made of a material which is at least partly, preferably completely, 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.
• 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.
• 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.
• 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.
• the metal may be partly oxidized.
• 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.
• the reinforcing elements are arranged generally side by side along a main direction.
• 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. 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 a 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).
• 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.
• 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 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.
• composition defined in the present description is particularly well suited to the inner layers of bandages.
• the invention also relates to a pneumatic or non-pneumatic tire comprising an inner layer comprising a composite according to the present 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.
• 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.
• 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.
• composites are prepared in the form of test specimens comprising metal reinforcing elements of the "2.30" type commonly used in the reinforcement plies for the crowns of pneumatic tires and consisting of two brass-coated steel monofilaments of 30 hundredths of a millimeter twisted together caught in a rubber composition.
• 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 (homo-finisher) to 30° C., while mixing the whole.
• 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 C 1 is a typical sulfur composition for calendering metal reinforcements.
• N-(cyclohexylthio)phthalimide marketed under the name “Vulkalent G” by Lanxess or also “Duslin P” by Duslo
• the rubber compositions thus prepared are used to make test specimens according to the following protocol:
• a block of rubber is made up of two raw plates cut with a punch of dimensions 70x12 mm and thickness
• 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 uncured state, the length of the trapped reinforcement is 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 two single wires 0.30 mm in diameter (“2.30” cables) very commonly used for producing the working plies of passenger car type tires; the thickness of the brass coating ranges from 50 nm to 300 nm.
• the reinforcing elements are treated in accordance with the process according to the invention according to the conditions indicated in table 3.
• the plasma treatment is carried out on a "PT5001N” machine developed by the Plasmatreat company, this is the model with two "FG5001” model generators (1 KV, 19-23 KHz), two "PFW10” model torches, and having a power of 1 kW.
• the ionized plasma gas used is filtered compressed air at a flow rate of 1800 litres/hour.
• the plasma is applied continuously to the surface of the brass-coated metal cable using two torches placed in opposition to the cable (above / below) and offset by 10mm so that the plasma flows are not opposite each other. notice.
• the cable passes under the torches thanks to an unwinding-winding system.
• the specimens thus prepared with conforming compositions correspond to composites conforming to the invention.
• 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).
• Gent et al. Genetic Engineering, 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.
• 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.
• thermo-oxidative type of aging representative of the aging encountered over the life of a tire.
• composition in accordance with the invention maintains, or even improves, its adhesion properties over time thanks to the treatment applied to the reinforcement.

Landscapes

• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Medicinal Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Mechanical Engineering (AREA)
• Materials Engineering (AREA)
• Manufacturing & Machinery (AREA)
• Textile Engineering (AREA)
• Inorganic Chemistry (AREA)
• Compositions Of Macromolecular Compounds (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=76159668

Family Applications (1)

Country Status (3)

Family Cites Families (25)

• 2021
  • 2021-05-10 FR FR2104899A patent/FR3122658B1/fr active Active
• 2022
  • 2022-05-03 EP EP22724813.5A patent/EP4337717A1/de active Pending
  • 2022-05-03 WO PCT/FR2022/050854 patent/WO2022238637A1/fr not_active Ceased

Also Published As

Similar Documents

Legal Events