Classifications

• • 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
  • 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
  • B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
  • B60C9/0007—Reinforcements made of metallic elements, e.g. cords, yarns, filaments or fibres made from metal
• • 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
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/02—Elements
  • C08K3/06—Sulfur
• • 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
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
• • 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
• • 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
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
• • 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
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
  • C08K5/31—Guanidine; Derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
  • C08L63/08—Epoxidised polymerised polyenes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L7/00—Compositions 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
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
  • C08K2003/2296—Oxides; Hydroxides of metals of zinc
• • 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
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
  • C08K5/098—Metal salts of carboxylic acids

Definitions

• Reinforced product based on at least one metallic reinforcing element and a rubber composition.
• the present invention relates to the field of reinforced rubber products, in particular intended for pneumatic or non-pneumatic tires, as well as articles comprising such reinforced products.
• the reinforcement plies of pneumatic tires or reinforced rubber articles usually comprise a rubber composition, called a calender, and metallic reinforcing cords.
• the calendering composition must obviously have good properties of adhesion to the metal reinforcing cords, as well as breaking properties and hysteretic properties giving the plies good endurance and low rolling resistance and this, throughout the tire life.
• Coating compositions comprising a diene elastomer, in particular natural rubber, a reinforcing filler, and a very specific vulcanization system for these compositions are known from the state of the art.
• This vulcanization system usually comprises sulfur and zinc oxide at high levels, stearic acid at low levels, a so-called slow vulcanization accelerator and a vulcanization retarder.
• 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.
• a vulcanization retarder and a so-called slow vulcanization accelerator are used.
• Patent WO2016/058943 discloses a reinforced product comprising a rubber composition coating sheathed reinforcing threads, this composition being based on a diene elastomer, a reinforcing filler and a vulcanization system comprising a so-called “rapid” vulcanization accelerator according to the terminology defined below herein, this composition exhibiting good aging resistance properties.
• Document WO2019/122586 presents a composition substantially devoid of molecular sulfur and comprising an adhesion promoter having good adhesion and rigidity performance, this composition being able to be crosslinked by various crosslinking systems other than vulcanization.
• WO2020/058614 teaches a rubber composition based on at least one elastomer having epoxide functions, at least one reinforcing filler, a crosslinking system comprising a polycarboxylic acid, an imidazole and at least one specific polyphenolic compound with excellent adhesion properties and good retention of properties over time.
• compositions implementing alternative crosslinking systems to vulcanization have, by their variety of constituents, a relative industrial intrusiveness.
• a reinforced product based on at least one metallic reinforcing element embedded in a rubber composition based on at least one epoxidized diene elastomer, crosslinked by vulcanization, and therefore easy to put implemented industrially exhibited both good adhesion properties of the composition to the reinforcing element, while improving the durability of the performance in terms, in particular, of breaking properties and rolling resistance.
• the invention relates to at least one reinforced product based on at least one metallic reinforcing element embedded in a rubber composition based on at least one epoxidized diene elastomer, a reinforcing filler and a crosslinking system comprising at least 1 phr of sulphur.
• the invention relates to a reinforced product in which the crosslinking system comprises from 1 to 5 phr of sulfur, preferentially from 1 to 4 phr of sulfur, and more preferably from 1 to 2.5 phr of sulfur.
• the invention relates to a reinforced product in which the vulcanization system further comprises a vulcanization accelerator used at a rate comprised between 0.1 and 6 phr, more preferably between 0.5 and 4 phr and very preferably between 0.5 and 2.5 phr.
• the invention relates to a reinforced product in which the crosslinking system comprises a vulcanization accelerator having a vulcanization onset time called “tO” of less than 3.5 minutes, preferably less than or equal to 3 minutes.
• tO vulcanization onset time
• the invention relates to a reinforced product in which the reinforcing filler mainly comprises silica.
• the invention relates to a reinforced product in which the rubber composition further comprises a compound from the guanidine family, preferably diphenylguanidine.
• the content of compound of the guanidine family ranges from 0.5 to 3 phr, preferentially from 0.5 to 2.5 phr and more preferably from 0.5 to 2 phr.
• the invention relates to a reinforced product in which the degree of epoxidation of the epoxidized diene elastomer is within a range of 5 and 40%, preferably 10 to 35%.
• the invention relates to a reinforced product in which the epoxidized diene elastomer is chosen from the group consisting of epoxidized natural rubbers, epoxidized synthetic polyisoprenes, epoxidized polybutadienes preferably having a higher cis'1,4 bond rate at 90%, epoxidized butadiene-styrene copolymers and mixtures of these elastomers, preferably chosen from the group consisting of epoxidized natural rubbers and epoxidized synthetic polyisoprenes.
• the epoxidized diene elastomer is chosen from the group consisting of epoxidized natural rubbers, epoxidized synthetic polyisoprenes, epoxidized polybutadienes preferably having a higher cis'1,4 bond rate at 90%, epoxidized butadiene-styrene copolymers and mixtures of these elastomers, preferably chosen from the group consisting of e
• the invention relates to a reinforced product according to the invention, in which the rubber composition also comprises 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 content of non-epoxidized diene elastomer is preferably between 0 and 49 phr, preferably from 0 to 40 phr, preferably between 5 and 25 phr.
• the invention relates to a reinforced product in which the rubber composition comprises as sole elastomers one or more epoxy diene elastomers.
• the invention relates to a reinforced product in which the rubber composition does not comprise any cobalt salt or comprises less than 2 phr, preferably less than 1 phr, preferably less than 0.5 phr, very preferably less of 0.1 pc.
• the invention relates to a reinforced product in which the rubber composition does not comprise stearic acid or one of its derivatives, or comprises less than 2 phr thereof, preferentially less than 1 phr, more preferably less than 0.5 phr, very preferably less than 0.1 phr.
• the invention relates to a reinforced product in which the rubber composition comprises an agent chosen from coupling agents and silica covering agents as well as their mixture, the content of agent being in a range ranging from 5 to 20% by weight relative to the quantity of silica, preferably from 6 to 18% by weight relative to the quantity of silica.
• the silica coupling agent is chosen from organosilanes, preferably chosen from the group consisting of polysulphide organosilanes, polyorganosiloxanes, mercaptosilanes, blocked mercaptosilanes, and very preferably chosen from the group consisting of by polysulfide organosilanes.
• the silica covering agent is chosen from alkylalkoxysilanes, polyols, polyethers, primary, secondary or tertiary amines, polyorganosiloxanes, very preferably chosen from alkylalkoxysilanes.
• the invention relates to a reinforced product in which the rubber composition comprises at most 4 phr of zinc oxide, preferentially at most 3 phr of zinc oxide, preferentially at most 2.5 phr of zinc oxide .
• the invention relates to a reinforced product in which the content of total reinforcing filler is between 10 and 200 phr, preferably between 10 and 100 phr, more preferably from 25 to 75 phr.
• the invention relates to a reinforced product in which the metallic reinforcement comprises a surface comprising a metal chosen from the group consisting of copper, zinc, tin, aluminium, cobalt, nickel and alloys comprising at least one of these metals, preferably a metal chosen from the group consisting of copper, tin, zinc or an alloy comprising at least one of these metals.
• the metal of the metal surface of the metal reinforcement is brass.
• the invention also relates to a finished or semi-finished article comprising a reinforced product according to the invention.
• the invention also relates to a pneumatic or non-pneumatic tire comprising a reinforced product according to the invention.
• based on it is meant a product or a composition comprising the mixture and/or the in situ reaction product of the various constituents used, some of these constituents being able to react and/or being intended to react with each other , at least partially, during the various phases of manufacture of the composition; the product or composition can thus be in the totally or partially crosslinked state or in the uncrosslinked state.
• part by weight per hundred parts by weight of elastomer (or phr) is meant within the meaning of the present invention, the part, by mass per hundred parts by mass of elastomer.
• any interval of values denoted by the expression “between a and b” represents the domain of values going from more than a to less than b (i.e. limits a and b excluded) while any interval of values denoted by the expression “from a to b” signifies the range of values going from a to b (that is to say including the strict limits a and b).
• the compounds comprising carbon mentioned in the description can be of fossil origin or biobased. In the latter case, they may be, partially or totally, from biomass or obtained from renewable raw materials derived from biomass. This concerns in particular polymers, plasticizers, fillers, etc.
• the reinforced product according to the invention is based on at least one metallic reinforcing element embedded in a rubber composition based on at least one epoxidized diene elastomer, a reinforcing filler and a crosslinking system comprising at least 1 phr of sulfur.
• epoxidized elastomer or rubber is meant any type of elastomer within the meaning known to those skilled in the art, whether it is a homopolymer or a block copolymer, random or otherwise, having elastomeric properties, epoxide functionalized (or epoxidized), that is to say carrying epoxide functional groups.
• epoxidized elastomer or rubber the two terms being in a known way synonymous and interchangeable
• elastomer any type of elastomer within the meaning known to those skilled in the art, whether it is a homopolymer or a block copolymer, random or otherwise, having elastomeric properties, epoxide functionalized (or epoxidized), that is to say carrying epoxide functional groups.
• epoxidized elastomer or rubber are used without distinction.
• 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 reinforced product 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 diene elastomers epoxides 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 is predominant in the rubber composition according to the invention, that is to say that it is either the only elastomer, or it is the one which represents the greatest mass, among the elastomers of the 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%.
• elastomer of the epoxidized diene type it should be remembered that an elastomer which is derived at least in part (i.e. a homopolymer or a copolymer) from diene monomers (monomers carrying two carbon-carbon double bonds, conjugated or not), should be understood, this polymer being functionalized, that is to say that it bears epoxide functional groups.
• a first characteristic of epoxidized diene elastomers is therefore that they are diene elastomers.
• These diene elastomers by definition non-thermoplastic in the present application, having a Tg in the vast majority of cases which is negative (that is to say less than 0° C.), can be classified in a known manner into two categories : those called “essentially unsaturated” and those called “essentially saturated”.
• essentially unsaturated diene elastomer a diene elastomer resulting at least in part from conjugated diene monomers, having a content of units or units of diene origin (conjugated dienes) which is greater than 15% (% in moles).
• conjugated diene monomers having a content of units or units of diene origin (conjugated dienes) which is greater than 15% (% in moles).
• 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% (% in moles).
• 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
• a second essential characteristic of the epoxidized diene elastomer useful for the purposes of the invention is that it is functionalized, carrying epoxide functional groups.
• the epoxy functions present in the 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 method 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
• 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”).
• 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 g
• the rubber composition of the reinforced product according to the invention comprises one or more reinforcing fillers.
• 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 WO97/36724-A2 or WO99/1660Q-A1). Also suitable are carbon blacks resulting from the recycling of tires such as blacks resulting 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 (SiCh) 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.
• 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 EZ160GC D)”, “Hi-Sil EZ200G(-D)”, “Hi-Sil 243LD”, “Hi-Sil 210”, “Hi-Sil HDP 320G” from the company 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 is between 10 and 200 phr, more preferably between 10 and 100 phr, and very preferably from 25 to 75 phr , the optimum being in a known manner different according to the particular applications targeted.
• the reinforcing filler of the rubber composition mainly comprises silica.
• silica represents more than 50% of the total mass of reinforcing filler.
• 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 epoxy.
• at least bifunctional organosilanes or polyorganosiloxanes are used.
• bifunctional is meant a compound possessing a first functional group capable of interacting with the inorganic filler and a second functional group capable of interacting with the epoxidized diene elastomer.
• 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”. 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.
• 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.
• 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 hydrolysable silanes such as alkylalkoxysilanes (in particular alkyl triethoxysilanes), polyols, polyethers (for example polyethyleneglycols), amines primary, secondary or tertiary (e.g. trialcanobamines), POS hydroxylated or hydrolyzable, for example ⁇ , o-dihydroxy-polyorganosiloxanes (in particular ⁇ -dihydroxy-polydimethylsiloxanes).
• the rubber composition of the reinforced product according to the invention comprises a sulfur-based crosslinking system, comprising at least 1 phr of sulphur, called the vulcanization system.
• the sulfur can be provided in any form, in particular in the form of molecular sulfur, or of a sulfur-donating agent.
• the composition of the reinforced product according to the invention has a low sulfur content.
• the sulfur is used at a preferential rate ranging from 1 to 5 phr, preferentially ranging from 1 to 4 phr, very preferentially ranging from 1 to 2.5 phr.
• the crosslinking system comprises a so-called “rapid” vulcanization accelerator, that is to say having a so-called “tO" vulcanization initiation time of less than 3.5 minutes, preferably less than or equal to 3 minutes .
• tO for a given accelerator must be measured in a given rubber composition, at a given vulcanization temperature.
• the reference composition is given here as a composition comprising 100 phr of NR, 47 phr of carbon black N326, 0.9 phr of stearic acid, 7, 5 phr of ZnO, 4.5 phr of sulfur, and the accelerator whose tO is to be determined, at a molar rate of 2.3 mmol per 100 parts by weight of elastomer (the commercial references of the ingredients indicated here are identical to those of the ingredients used in Example 1).
• the tO measurement method complies with DIN-53529, at 150°C. Within the meaning of the present application, the “tO” means the tO as defined and measured above.
• DCBS denotes N-dicyclohexyl-2-benzothiazol-sulfenamide
• TBBS denotes N-tert-butyl-2-benzothiazol-sulfenamide
• CBS denotes N-cyclohexyl-2-benzothiazol-sulfenamide.
• the vulcanization accelerator is chosen from the group consisting of compounds of the thiuram family, derivatives of thiocarbamates, sulfenamides, thiophosphates and mixtures of the latter, and whose tO is less than or equal to 3, 5 minutes, preferably less than 3 minutes.
• the rubber composition of the reinforced product according to the invention comprises N-cyclohexyl-2-benzothiazol-sulfenamide as vulcanization accelerator.
• the vulcanization accelerator is used at a preferential rate comprised between 0.1 and 6 phr, more preferentially comprised between 0.5 and 4 phr and very preferentially comprised between 0.5 and 2.5 phr.
• the rubber composition of the reinforced product according to the invention comprises at least 0.5 phr of zinc oxide, and preferentially at least 1 phr of zinc oxide.
• the rubber composition of the reinforced product according to the invention comprises at most 5 phr of zinc oxide, and preferably at most 3 phr of zinc oxide.
• the rubber compositions of the reinforced product in accordance with the invention may also comprise all or part of the usual additives and processing agents, known to those skilled in the art and usually used in rubber compositions for pneumatic tires, such as for example plasticizers (such as plasticizing oils and/or plasticizing resins), fillers (reinforcing or non-reinforcing/other than those mentioned above such as for example regenerated or devulcanized crumbs from the recycling of pneumatic tires), pigments, protective agents such as anti-ozone waxes, chemical anti-ozonants, antioxidants, anti-fatigue agents, reinforcing resins (as described for example in application WO 02/10269).
• plasticizers such as plasticizing oils and/or plasticizing resins
• fillers reinforcing or non-reinforcing/other than those mentioned above such as for example regenerated or devulcanized crumbs from the recycling of pneumatic tires
• pigments such as for example plasticizers (such as plasticizing oils and/or plasticizing resins), fillers
• the formulation of the rubber composition of the reinforced product according to the invention makes it possible to minimize or even eliminate the use of cobalt salts while maintaining excellent adhesion properties.
• the rubber composition of the reinforced product according to the invention does not comprise any cobalt salt or comprises less than 2 phr, preferably less than 1 phr, more preferably less than 0.5 phr, very preferably less than 0.1 pce.
• the formulation of the rubber composition of the reinforced product according to the invention makes it possible to minimize, or even to dispense with, the use of stearic acid or one of its derivatives.
• the rubber composition of the reinforced product according to the invention does not comprise stearic acid or one of its derivatives, or comprises less than 2 phr thereof, preferably less than 1 phr, preferably less than 0.5 phr, very preferably less than 0.1 phr.
• the rubber composition of the reinforced product according to the invention may also comprise a compound from the guanidine family, preferably diphenylguanidine. It was observed that the presence of a compound from the guanidine family, preferably diphenylguanidine, made it possible to further improve the adhesion properties of the rubber composition to the metal reinforcement.
• the content of compound of the guanidine family ranges from 0.5 to 3 phr, preferentially from 0.5 to 2.5 phr and more preferably from 0.5 to 2 phr.
• the reinforced product 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 reinforced product 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 reinforced product, in particular during the crosslinking of the composition or during the manufacture of the reinforced product before crosslinking of the composition.
• Said metal reinforcement element is a wire element. It can be all or part metal.
• said reinforcing element comprises a metallic surface.
• the metallic surface of the reinforcing element constitutes at least a part, and preferably the whole of the surface of said element and is intended to come into direct contact with the rubber composition.
• the reinforcing element is metallic, that is to say made of a metallic material.
• the rubber composition coats at least part of the reinforcing element, preferably all of said element.
• the metallic surface of the reinforcing element is made of a different material from the rest 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 or non-metallic, preferably 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.
• the metal surface can make it possible to improve, for example, the properties of implementation of the reinforcing element, or the properties of use of the reinforced product and/or of the tire themselves, such as the properties of adhesion, corrosion resistance or aging resistance.
• the metallic surface comprises a metal chosen from the group consisting of copper, zinc, tin, aluminium, 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 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), zinc or bronze (Cu-Sn alloy), even more preferably brass.
• the metal may be partly oxidized.
• the reinforced product 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 reinforced product 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 metal reinforcing element is directly in contact with the rubber composition over its entire surface.
• the reinforced product 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 reinforced product according to the invention is cured after bringing the reinforcing element(s) into contact with the rubber composition.
• the reinforced product according to the invention can be manufactured by a process which comprises the following steps ⁇
• the reinforced product 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 on its whole 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 reinforced product according to the invention generally takes place during the curing of the tire.
• the invention also relates to a finished or semi-finished article comprising a reinforced product according to the invention.
• the finished or semi-finished article can be any article comprising a reinforced product. Mention may be made, for example and in a non-limiting manner, of balloons, conveyor belts, shoe soles, pneumatic or non-pneumatic tires.
• the pneumatic or non-pneumatic tire another object of the invention, has the essential characteristic of comprising the reinforced product 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 reinforced product is deposited in the raw 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 tire according to the invention comprises a reinforced layer consisting of a reinforced product according to the invention preferably chosen from carcass plies, crown plies, bead fillers and combinations of these reinforced layers.
• the rubber composition of the reinforced product according to the invention could be used as an inner layer in a pneumatic or non-pneumatic tire, an inner layer being a layer of the tire which is neither in contact with the ambient air nor in contact with the inflation gas.
• Such internal layers are for example the foot-top layers, the decoupling layers, the edge rubbers and the combinations of these internal layers.
• edge rubber means a layer positioned in the tire directly in contact with the end of a reinforced layer, the end of a reinforcing element or another edge rubber .
• 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.
• SUV Sport Utility Vehicles
• two wheels in particular motorcycles
• 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.
• the invention relates in particular to a pneumatic or non-pneumatic tire
• a crown comprising a crown reinforcement formed of two crown plies of reinforcing elements and surmounted by a tread, two beads intended to come into contact with a rim each comprising a circumferential reinforcing element and two sidewalls each extending radially inwards an axial end of the crown as far as the beads, said tire further comprising a carcass reinforcement anchored to each of the beads and extending from the beads through the sidewalls towards the top, at least one of the two top layers of reinforcing elements being constituted by a reinforced product according to the invention.
• the invention in another particular arrangement, relates to a pneumatic or non-pneumatic tire comprising a crown comprising a crown reinforcement formed of two crown plies of reinforcing elements and surmounted by a tread, two beads intended to come into contact with a rim each comprising a circumferential reinforcing element and two sidewalls each extending radially inwards an axial end of the crown as far as the beads, said tire further comprising a carcass reinforcement anchored to each of the beads and extending from the beads through the sidewalls towards the top, at least the carcass reinforcement being constituted by a reinforced product according to the invention.
• Thermomechanical work is then carried out (non-productive phase) in one step, which lasts a total of around 3 to 4 min, until a maximum "drop" temperature of 165°C is reached.
• compositions thus obtained are then calendered in the form of plates (thickness of 2 to 3 mm) or thin sheets of rubber then are subjected to a curing step at 150° C. for 15 min before measuring their physical or mechanical properties. .
• the prepared rubber compositions are used to make a composite in the form of a test specimen according to the following protocol.
• the metal/rubber composite used in this test is a block of rubber composition, consisting of two plates measuring 200 mm by 4.5 mm (millimeters) and 3.5 mm thick, applied one on the other. before cooking; the thickness of the resulting block is then 7mm. It is during the making of this block that the reinforcements, for example fifteen in number, are trapped between the two raw plates; only a determined length of reinforcement, for example 4.5 mm, is left free to come into contact with the rubber composition to which this length of reinforcement will bond during curing; the rest of the length of the reinforcements is isolated from the rubber composition (for example using a plastic or metal film) to prevent any adhesion outside the determined contact zone. Each reinforcement passes right through the block of rubber, at least one of its free ends being kept of sufficient length (at least 5 cm, for example between 5 and 10 cm) to allow the subsequent traction of the reinforcement.
• Each metal reinforcement consists of 2 steel wires at 0.7% carbon, 30/100th millimeters in diameter twisted together, the brass coating includes 63% copper.
• the block comprising the fifteen reinforcements is then placed in a suitable mold and then baked for 15 minutes at 150° C., under a pressure of approximately 15 bar.
• each reinforcement is split out of the rubber block, using a traction machine according to the method described in standard ASTM D 2229-02; the pulling speed is 100 mm/min; adhesion is thus characterized by the force necessary to pull the reinforcement out of the specimen, at ambient temperature; the tearing force represents the average of the 15 measurements corresponding to the 15 reinforcements of the composite.
• the air humidity is not controlled and corresponds to that of the ambient air, i.e. between 30 and 50%.
• results are expressed in base 100, the value 100 corresponding to a test specimen made with the composition considered and the metal reinforcements described previously.
• the air humidity is not controlled and corresponds to that of the ambient air, i.e. between 30 and 50%.
• the air humidity is not controlled and corresponds to that of the ambient air, i.e. between 30 and 50%.
• Composition T1 is a calendering composition of the prior art as presented, for example, in documents WO2016/058943 and FR2981298.
• ENR 1 Epoxy Natural Rubber at 25% molar, “ENR-25”, from Guthrie
• ENR 2 15% epoxidized natural rubber, produced by epoxidation of a natural rubber from Muang Mai Guthrie;

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• 2020
  • 2020-10-23 FR FR2010880A patent/FR3115541B1/fr active Active
• 2021
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  • 2021-10-08 CN CN202180070245.XA patent/CN116323247A/zh active Pending
  • 2021-10-08 CA CA3194084A patent/CA3194084A1/fr active Pending
  • 2021-10-08 EP EP21802394.3A patent/EP4232509A1/fr active Pending
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