Classifications

• • 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
• • 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
• • 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
  • C08K2201/00—Specific properties of additives
  • C08K2201/019—Specific properties of additives the composition being defined by the absence of a certain additive

Definitions

• the present invention relates to rubber compositions intended in particular for the manufacture of tires or of semi-finished products for tires.
• a subject of the present invention is also a finished or semi-finished rubber article comprising a rubber composition according to the invention, as well as a pneumatic or non-pneumatic tire comprising at least one composition according to the invention.
• This stiffening can be obtained by increasing the rate of reinforcing filler or by incorporating certain reinforcing resins in the rubber compositions constituting the parts of the tire.
• the reinforcing resins conventionally used to increase the rigidity of compositions are reinforcing resins based on a methylene acceptor / donor system.
• methylene acceptor and “methylene donor” are well known to those skilled in the art and widely used to denote compounds capable of reacting together to generate, by condensation, a three-dimensional reinforcing resin which comes to be superimposed, to interpenetrate with it.
• the methylene acceptor is a phenolic resin. Phenolic novolac resins have already been described in rubber compositions, in particular intended for pneumatic tires or tire treads, for applications as varied as adhesion or reinforcement: reference will be made, for example, to patent EP 0649446. .
• methylene donor a hardening agent capable of crosslinking or hardening it
• the crosslinking of the resin is then caused during the curing of the rubber matrix, by the formation of methylene bridges between the carbons in the ortho and para positions of the phenolic rings of the resin and the methylene donor, thus creating a three-dimensional resin network.
• Conventionally used methylene donors are hexa-methylenetetramine (abbreviated HMT), or hexamethoxymethylmelamine (abbreviated HMMM or H3M), or hexaethoxymethylmelamine.
• compositions comprising the methylene acceptor formophenolic resin pair with a conventional HMT or H3M hardener donor of methylene have been developed.
• application WO 2011/045342 describes compositions comprising an epoxy resin pair with an amine hardener. These compositions, in addition to the advantage of avoiding the formation of formaldehyde, after crosslinking, exhibit stiffness greater than that of conventional compositions while retaining acceptable rolling resistance.
• Application WO 2018/002538 describes compositions comprising an epoxy resin and an amine hardener comprising at least two primary amine functions located on at least one aromatic ring with six atoms which aims to improve the compromise between processability, in particular the toasting time, and rigidity compared to known compositions.
• the Applicant has discovered during its research that the combination of an epoxy resin and a urea compound makes it possible to avoid the formation of formaldehyde while maintaining the reinforcing properties at the different operating temperatures of the tire. pneumatic, while improving the processability of raw compositions.
• the invention relates to at least one of the following embodiments : 1. Rubber composition based on at least one diene elastomer, a reinforcing filler, a crosslinking system, from 1 to 30 parts by weight per hundred parts by weight of elastomer, phr, of epoxy resin, and a urea compound of general formula (R 1, R 2) N-CON (R 3, R 4 ) in which each R 1, R 2, R 3 and R 4 radical is independently selected from the group consisting of a hydrogen atom, an alkyl radical having from 1 to 20 carbon atoms, a cycloalkyl radical having from 5 to 24 carbon atoms, an aryl radical having from 6 to 30 carbon atoms and an aralkyl radical having from 7 to 25 carbon atoms, the radicals R2 and R3 possibly together forming a cycle, each radical R 1, R 2, R 3 and R 4 being optionally interrupted by one or more heteroatoms and / or substituted.
• each R 1, R 2, R 3 and R 4 radical is independently selected from the group consisting of a hydrogen atom and a compound. hydrocarbon.
• each R 1 and R 3 radical is a hydrogen atom.
• Rubber composition according to any one of the preceding embodiments in which at least one R2 or R4 radical is an aryl radical having from 6 to 8 carbon atoms, preferably a phenyl radical.
• urea compound is chosen from the compounds urea, N, N'-dimethylurea, ethylèneurea, N-phenylurea, 1,3-diphenylurea, preferably chosen from the compounds urea, N , N'-dimethylurea, N-phenylurea, 1,3-diphenylurea and very preferably chosen from the compounds urea and N, N'-dimethylurea.
• the diene elastomer is chosen from the group consisting of polybutadienes, natural rubber, synthetic polyisoprenes, butadiene copolymers, copolymers of isoprene, and mixtures of these elastomers and is preferably an isoprene elastomer.
• Rubber composition according to any one of the preceding embodiments not comprising a nitrile compound, or comprising less than 10 phr, preferably less than 5 phr, and preferably less than 2 phr.
• a finished or semi-finished rubber article comprising a rubber composition according to any one of the preceding embodiments.
• Pneumatic or non-pneumatic tire comprising a rubber composition according to any one of embodiments 1 to 14.
• Bandage according to the previous embodiment comprising an inner layer comprising a rubber composition according to any one of embodiments 1 to 14.
• part by weight per hundred parts by weight of elastomer (or phr) is meant within the meaning of the present invention, the part, by weight per hundred parts by weight of elastomer or rubber.
• any interval of values designated by the expression "between a and b" represents the range of values going from more than a to less than b (that is to say limits a and b excluded) while any range of values designated 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).
• composition based on is meant 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, less partially, during the various phases of manufacture of the composition; the composition may thus be in the totally or partially crosslinked state or in the non-crosslinked state.
• a “majority” compound it is understood, within the meaning of the present invention, that this compound is the majority among the compounds of the same type in the composition, that is to say that it is the one which represents the greatest amount by mass among compounds of the same type.
• a major elastomer is the elastomer representing the greatest mass relative to the total mass of the elastomers in the composition.
• a so-called majority filler is that representing the greatest mass among the fillers of the composition.
• a “minority” compound is a compound which does not represent the largest mass fraction among compounds of the same type.
• the term “majority” is understood to mean present at more than 50%, preferably more than 60%, 70%, 80%, 90%, and more preferably the “majority” compound represents 100%.
• 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, derived from biomass or obtained from renewable raw materials derived from biomass. This concerns in particular polymers, plasticizers, fillers, etc.
• composition according to the invention comprises at least one diene elastomer. It can therefore contain a single diene elastomer or a mixture of several diene elastomers.
• elastomer or indistinctly rubber
• diene monomer units monomers carrying two double carbon-carbon bonds, conjugated or not.
• diene elastomers can be classified into two categories: "essentially unsaturated” or “essentially saturated”.
• essentially unsaturated is understood to mean a diene elastomer derived at least in part from conjugated diene monomers, having a level of units or units of diene origin (conjugated dienes) which is greater than 15% (% by moles); thus diene elastomers such as butyl rubbers or copolymers of dienes and alpha-olefins of the EPDM type do not fall within the definition above and can in particular be qualified as “essentially saturated” diene elastomers (level of units of low or very low diene origin, always less than 15%).
• the diene elastomers included in the composition according to the invention are preferably essentially unsaturated.
• die elastomer capable of being used in the compositions in accordance with the invention is particularly understood to mean: a) any homopolymer of a diene monomer, conjugated or not, having from 4 to 18 carbon atoms; b) any copolymer of a diene, conjugated or not, having 4 to 18 carbon atoms and at least one other monomer.
• the other monomer can be ethylene, an olefin or a diene, conjugated or not.
• Suitable conjugated dienes are conjugated dienes having from 4 to 12 carbon atoms, in particular 1,3 dienes, such as in particular 1,3 butadiene and isoprene.
• Suitable olefins are vinyl aromatic compounds having from 8 to 20 carbon atoms and aliphatic monoolefins having from 3 to 12 carbon atoms.
• Suitable vinyl aromatic compounds are, for example, styrene, ortho-, meta-, para-methylstyrene, the commercial mixture “vinyl-toluene” and para-tert-butylstyrene.
• Suitable aliphatic monoolefins are in particular acyclic aliphatic monoolefins having from 3 to 18 carbon atoms.
• the diene elastomer is chosen from the group consisting of polybutadienes (BR), natural rubber (NR), synthetic polyisoprenes (IR), butadiene copolymers, isoprene copolymers, and mixtures of these. elastomers.
• the butadiene copolymers are particularly chosen from the group consisting of butadiene-styrene (SBR) copolymers.
• the diene elastomer is an isoprene elastomer.
• isoprene elastomer is understood to mean, in a known manner, an isoprene homopolymer or copolymer, in other words a diene elastomer chosen from the group consisting of natural rubber (NR), synthetic polyisoprenes (IR), different isoprene copolymers and mixtures of these elastomers.
• NR natural rubber
• IR synthetic polyisoprenes
• isoprene copolymers there may be mentioned in particular the copolymers of isobutenedsoprene (butyl rubber - IIR), of isoprene-styrene (SIR), of isoprene-butadiene (BIR) or of isoprene-butadiene-styrene (SBIR ).
• This isoprene elastomer is preferably chosen from the group consisting of natural rubber, synthetic cis-1,4 polyisoprenes and mixtures thereof; among these synthetic polyisoprenes, use is preferably made of polyisoprenes having a content (mol%) of cis-1,4 bonds greater than 90%, more preferably still greater than 98%.
• the diene elastomer is natural rubber.
• the rate of diene elastomer is from 50 to 100 phr, more preferably from 60 to 100 phr, more preferably from 70 to 100 phr, more preferably still from 80 to 100 phr and very preferably from 90 to 100 phr.
• the content of diene elastomer, preferably isoprene elastomer, more preferably natural rubber, is very preferably 100 phr.
• the rubber composition according to the invention may also contain in a minority manner any type of synthetic elastomer other than diene, or even polymers other than elastomers, for example. thermoplastic polymers.
• the rubber composition according to the invention does not contain any synthetic elastomer other than diene or any polymer other than elastomers or contains less than 10 phr thereof, preferably less than 5 phr.
• Epoxy resins usable in the present invention include all polyepoxy compounds. These may be, for example, aromatic epoxy resins, alicyclic epoxides, and aliphatic epoxides.
• the aromatic epoxy resin can be an amine-aromatic epoxy resin.
• the epoxy resins are preferably epoxy novolac resins, that is to say epoxy resins obtained by acid catalysis, as opposed to resol resins, obtained by basic catalysis.
• epoxy resins chosen from the group consisting of 2,2 bis [4- (glycidyloxy) phenyl] propane, poly [(o-cresylglycidyl ether) -co-formaldehyde], poly [(phenylglycidyl ether) -co-formaldehyde], poly [(phenylglycidyl ether) -co (hydroxybenzaldehyde glycidyl ether)], epoxy resins aromatic amines and mixtures of these compounds, and preferably epoxy resins selected from the group consisting of poly [(o-cresylglycidyl ether) -co-formaldehyde, and poly [(phenylglycidyl ether) -coOiydroxybenzaldehyde glycidyl ether)] .
• the epoxy resin is selected from the group consisting of polytocresylglycidyl ether) -co-formaldehyde], polytphenylglycidyl ether) -co-formaldehyde], aromatic amine epoxy resins and mixtures of these compounds.
• epoxy resins available commercially and which can be used in the context of the present invention, mention may be made, for example, of the epoxy resin “DEN 439” from the company Uniqema, the epoxy resin “Tris (4-hydroxyphenyl) methane. triglycidyl ether “from the company Sigma-Aldrich, the cresol novolac araldite epoxy resin” ECN 1299 “from the company Hunstman, the phenol novolac araldite epoxy resin” EPN 1138 "from the company Huntsman.
• the composition according to the invention comprises between 1 and 30 phr of epoxy resin.
• the level of epoxy resin is preferably between 10 and 25 phr. More preferably, the level of epoxy resin in the composition according to the invention is between 10 and 20 phr.
• the epoxy resin of the composition of the invention is combined with a specific hardener, in this case a urea compound, which allows the resin to crosslink.
• the hardener is a urea compound of general formula (Ri, R2) N-CO N (R3,
• each radical R 1, R 2, R 3 and R 4 is independently selected from the group consisting of:
• urea compound in which the R2 and R3 radicals together form a ring is 2-imidazolidinone, or ethylenerea.
• the radicals do not, together, form a cycle.
• the urea compound is a mono-urea
• each R 1, R 2, R 3 and R 4 radical is independently selected from the group consisting of a hydrogen atom and a hydrocarbon compound.
• each R 1 and R 3 radical is a hydrogen atom.
• Urea is then a compound of formula R2-HN-CONH-R 4 .
• At least one R2 or R4 radical is an aryl radical having from 6 to 8 carbon atoms, preferably a phenyl radical.
• the urea compound can be an N-phenylurea or 1,3-diphenylurea.
• the urea compound does not include an aromatic nucleus.
• each R 1, R 2, R 3 and R 4 radical is a hydrogen atom.
• the urea compound is then a compound of formula H2N-CO-NH2 commonly designated under the term “urea” or “carbamide”.
• the urea compound is chosen from the compounds urea, N, N'-dimethylurea, ethylèneurea, N-phenylurea, 1,3-diphenylurea, preferably chosen from the compounds urea, N, N'-.
• the urea compound is urea of formula H2N-CO-NH2.
• the amount of urea compound in the rubber composition is within a range from 1 to 15 phr. Below the minimum indicated, the targeted technical effect has been shown to be insufficient, while beyond the maximum indicated, there is a risk of penalizing the use of the compositions in the raw state.
• the urea content is within a range ranging from 0.5 to 10 phr, preferably from 0.5 to 8 phr and preferably from 0.5 to 5 phr.
• composition according to the invention preferably comprises a reinforcing filler.
• the reinforcing filler can comprise any type of reinforcing filler known for its capacity to reinforce a rubber composition which can be used for the manufacture of pneumatic tires, for example an organic filler such as carbon black, a reinforcing inorganic filler such as silica, or a mixture of carbon black and reinforcing inorganic filler. More preferably, the reinforcing filler comprises mainly, or even exclusively, carbon black, in particular in the case where the composition is used in an internal layer.
• the reinforcing filler can also mainly comprise a reinforcing inorganic filler, in particular in the case where the composition is used in a tread.
• Such a reinforcing filler typically consists of particles whose average size (by mass) is less than one micrometer, generally less than 500 nm, most often between 20 and 200 nm, in particular and more preferably between 20 and 150 nm.
• Suitable carbon blacks are all carbon blacks, in particular blacks of the HAF, ISAF, SAF type conventionally used in pneumatic tires (so-called tire grade blacks).
• tire grade blacks there will be mentioned more particularly the carbon blacks reinforcing the 100, 200 or 300 series (ASTM grades), such as for example the blacks NI 15, N134, N234, N326, N330, N339, N347, N375, or else, depending on the targeted applications, blacks of higher series (for example N660, N683, N772).
• the carbon blacks could, for example, already be incorporated into an isoprene elastomer in the form of a masterbatch (see for example applications WO 97/36724 or WO 99/16600).
• the BET specific surface area of carbon blacks is measured according to standard D6556-10 [multipoint method (at least 5 points) - gas: nitrogen - relative pressure range R / R0: 0.1 to 0.3]
• any inorganic or mineral filler (whatever its color and its natural or synthetic origin), also called “white” filler, “clear” filler or even “load no black “(” non-black f ⁇ ller ”) as opposed to carbon black, capable of reinforcing on its own, without other means than an intermediate coupling agent, a rubber composition intended for the manufacture of pneumatic tires, in other terms capable of replacing, in its reinforcing function, a conventional carbon black of pneumatic grade; such a filler is generally characterized, in a known manner, by the presence of hydroxyl groups (—OH) at its surface.
• —OH hydroxyl groups
• suitable in particular mineral fillers of the siliceous type in particular 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 pyrogenic silica having a BET surface as well as a CTAB specific surface area both less than 450 m 2 / g, preferably from 30 to 400 m 2 / g.
• HDS highly dispersible precipitated silicas
• the BET specific surface area of silica is determined in a known manner by gas adsorption using the Brunauer-Emmett-Teller method described in "The Journal of the American Chemical Society” Vol. 60, page 309, February 1938, more precisely according to the French standard NF ISO 9277 of December 1996 (multipoint volumetric method (5 points) - gas: nitrogen - degassing: time at 160 ° C - relative pressure range p / in: 0.05 to 0.17).
• the CTAB specific surface of the silica is determined according to the French standard NF T 45 ⁇ 07 of November 1987 (method B).
• mineral fillers of the aluminous type in particular alumina (Al2O3) or aluminum (oxide) hydroxides, or else reinforcing titanium oxides, for example described in US Pat. No. 6,610,261 and US 6,747,087.
• reinforcing inorganic filler is understood to mean mixtures of various reinforcing inorganic fillers, in particular of highly dispersible siliceous and / or aluminous fillers.
• an at least bifunctional coupling agent intended to ensure a sufficient connection, of a chemical and / or physical nature, between the filler. inorganic (surface of its particles) and the diene elastomer.
• 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 diene elastomer.
• such a bifunctional compound can comprise a first functional group comprising a silicon atom, the said first functional group being able to interact with the hydroxyl groups of an inorganic filler and a second functional group comprising a sulfur atom, the said second functional group being able to interact with the diene elastomer.
• the organosilanes are chosen from the group consisting of polysulfurized organosilanes (symmetrical or asymmetrical) such as bis (3-triethoxysilylpropyl) tetrasulfide, in short TESPT marketed under the name “Si69” by the company Evonik or bis disulfide.
• polysulfurized organosilanes symmetrical or asymmetrical
• bis (3-triethoxysilylpropyl) tetrasulfide in short TESPT marketed under the name “Si69” by the company Evonik or bis disulfide.
• the organosilane is a polysulfurized organosilane.
• the content of coupling agent is preferably less than 12 phr, it being understood that it is generally desirable to use as little as possible.
• the level of coupling agent represents from 0.5% to 15% by weight relative to the amount of inorganic filler. Its rate is preferably within a range ranging from 0.5 to 15 phr. This rate is easily adjusted by a person skilled in the art according to the rate of inorganic filler used in the composition.
• the level of reinforcing filler preferably the reinforcing filler comprising mainly, or even exclusively carbon black
• the level of reinforcing filler can be within a range ranging from 20 to 200 phr, preferably from 30 to 150 phr, preferably 40 to 100 phr, preferably 50 to 80 phr.
• the crosslinking system can be any type of system known to those skilled in the art in the field of rubber compositions for pneumatic tires. It can in particular be based on sulfur, and / or peroxide and / or bismaleimides.
• the crosslinking system is sulfur-based, this is called a vulcanization system.
• the sulfur can be provided in any form, in particular in the form of molecular sulfur, or of a sulfur donor agent.
• At least one vulcanization accelerator is also preferably present, and, optionally, also preferentially, one can use various known vulcanization activators such as zinc oxide, stearic acid or equivalent compound such as salts of stearic acid and salts. transition metals, guanide derivatives (in particular diphenylguanidine), or else known vulcanization retarders.
• 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 of between 0.5 and 10 phr, more preferably between 0.5 and 8.0 phr.
• MBTS 2-mercaptobenzothiazyl disulfide
• CBS N-cyclohexyl-2-benzothiazyl sulfenamide
• DCBS N-dicyclohexyl- 2-Benzothiazyl sulfenamide
• TBBS N-ter-butyl-2-benzothiazyl sulfenamide
• TZTD tetrabenzylthiuram disulfide
• ZBEC zinc dibenzyldithiocarbamate
• the rubber compositions in accordance with the invention may also contain 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), pigments, protective agents such as anti-ozone waxes, chemical anti-ozonants, anti-oxidants , anti-fatigue agents.
• plasticizers such as plasticizing oils and / or plasticizing resins
• protective agents such as anti-ozone waxes, chemical anti-ozonants, anti-oxidants , anti-fatigue agents.
• the composition according to the invention does not comprise nitrile compounds or comprises less than 10 phr, preferably less than 5 phr, preferably less than 2 phr, very preferably less than 1 phr and even more. preferably less than 0.5 phr.
• the composition can be either in the uncured state (before crosslinking or vulcanization) or in the cooked state (after crosslinking or vulcanization).
• a subject of the present invention is also a finished or semi-finished rubber article comprising a composition according to the invention.
• a subject of the present invention is also a pneumatic tire which comprises a composition according to the invention.
• An outer sidewall is an elastomeric layer placed outside the carcass reinforcement with respect to the internal cavity of the tire, between the crown and the bead so as to completely or partially cover the area of the carcass reinforcement. 'extending from the top to the bead.
• the internal zone of the pneumatic tire ie the zone between the external and internal zones.
• This area includes layers or plies which are referred to herein as the inner layers of the tire. These are, for example, carcass plies, tread sub-layers, pneumatic tire belt plies or any other layer which is not in contact with the ambient air or the inflation gas of the tire.
• the composition defined in the present description is particularly well suited to the internal and external layers of pneumatic tires, and in particular, for the external layers, to tread compositions.
• the internal layer can be chosen from the group consisting of the carcass plies, the crown plies, the bead fillings, the top feet, the decoupling layers, the edging gums, the stuffing gums, the under -tread layer and combinations of these internal layers.
• the inner layer is chosen from the group consisting of carcass plies, crown plies, bead fillings, top feet, decoupling layers and combinations of these internal layers.
• composition according to the invention may also be suitable for the internal and external layers of non-pneumatic tires, in particular for the treads of non-pneumatic tires. It is recalled that a non-pneumatic tire is a tire which supports the load of a vehicle by a means other than a pressurized inflation gas.
• the invention particularly relates to pneumatic tires intended to be fitted to motor vehicles of the passenger car type, SUV (“Sport Utility Vehicles”), or two-wheeled vehicles (in particular motorcycles), or airplanes, or even industrial vehicles chosen from vans, “Weight "heavy”, that is to say metro, bus, road transport equipment (trucks, tractors, trailers), off-road vehicles such as agricultural or civil engineering machinery, and others.
• SUV Sport Utility Vehicles
• two-wheeled vehicles in particular motorcycles
• airplanes or even industrial vehicles chosen from vans, “Weight "heavy”, that is to say metro, bus, road transport equipment (trucks, tractors, trailers), off-road vehicles such as agricultural or civil engineering machinery, and others.
• the invention relates to articles comprising a rubber composition according to the invention, both in the uncured state (that is to say, before curing) and in the cured state (that is to say, after crosslinking or vulcanization. ).
• the rubber composition in accordance with the invention can be manufactured in suitable mixers, using two successive preparation phases well known to those skilled in the art: a first thermomechanical working or mixing phase (so-called “non-productive” phase) , which can be carried out in a single thermomechanical step during which all the necessary constituents, in particular the elastomeric matrix, the fillers, are introduced into a suitable mixer such as a usual internal mixer (for example of the 'Banbury' type). , any other various additives, with the exception of the crosslinking system.
• a suitable mixer such as a usual internal mixer (for example of the 'Banbury' type).
• any other various additives with the exception of the crosslinking system.
• the incorporation of the filler into the elastomer can be carried out in one or more times by thermomechanically kneading.
• the filler is already incorporated in whole or in part in the elastomer in the form of a masterbatch as described for example in applications WO 97/36724 or WO 99 / 16600, it is the masterbatch which is directly mixed and, where appropriate, the other elastomers or fillers present in the composition which are not in the form of a masterbatch are incorporated, as well as any other various additives other than the crosslinking system.
• the non-productive phase is carried out at high temperature, up to a maximum temperature of between 110 ° C and 190 ° C, preferably between 130 ° C and 180 ° C, for a period generally of between 2 and 10 minutes.
• a second phase of mechanical work (so-called "productive" phase), which is carried out in an external mixer such as a roller mixer, after cooling the mixture obtained during the first non-productive phase to a lower temperature , typically below 110 ° C, for example between 40 ° C and 100 ° C.
• the crosslinking system is then incorporated, and the whole is then mixed for a few minutes, for example between 2 and 15 min.
• the process for preparing such compositions comprises for example the following steps: a) incorporating into a diene elastomer, during a first step (called “non-productive"), a reinforcing filler, by thermomechanically kneading the whole (for example in one or more batches), until a maximum temperature of between 110 ° C and 190 ° C is reached; b) cooling the assembly to a temperature below 100 ° C; c) then incorporating, during a second step (called "productive"), a crosslinking system; d) mix everything up to a maximum temperature below 110 ° C.
• the epoxy resin and between 1 and 15 phr of urea compound can be introduced, independently of each other, either during the non-productive phase (a) or during the productive phase (c).
• the epoxy resin is introduced during the non-productive phase (a) while the high latency hardener is introduced during the productive phase (c).
• the final composition thus obtained can then be calendered, for example in the form of a sheet, of a plate in particular for a characterization in the laboratory, or else extruded in the form of a semi-finished (or profiled) rubber used for the manufacture of a pneumatic tire.
• crosslinking of the composition can be carried out in a manner known to those skilled in the art, for example at a temperature of between 130 ° C and 200 ° C, under pressure.
• the measurements are carried out at 130 ° C, in accordance with the French standard NF T 43 ⁇ 05.
• the change in the consistometric index as a function of time makes it possible to determine the roasting time of the rubber compositions, assessed in accordance with the aforementioned standard by the parameter T5 (case of a large rotor), expressed in minutes, and defined as being the time required to obtain an increase in the consistometric index (expressed in MU) of 5 units above the minimum value measured for this index.
• the Mooney plasticity measurement is carried out according to the following principle: the composition in the raw state (i.e., before firing) is molded in a cylindrical chamber heated to 100 ° C. After one minute of preheating, the rotor rotates within the specimen at 2 revolutions / minute and the torque useful to maintain this movement is measured after 4 minutes of rotation.
• the tables show the MA300 / MA100 ratio representative of the reinforcement.
• the elastomer is introduced into an internal mixer (final filling rate : approximately 70% by volume), the initial tank temperature of which is approximately 60 ° C. diene, the reinforcing filler, between 1 and 30 phr of the epoxy resin, as well as the various other ingredients with the exception of the crosslinking system.
• a thermomechanical work (non-productive phase) is then carried out in one step, which lasts in total about 3 to 4 min, until a maximum “fall” temperature of 165 ° C. is reached.
• the mixture thus obtained is recovered, it is cooled and then sulfur, a sulfenamide type accelerator and the high latency hardener are incorporated on a mixer (homofinisher) at 30 ° C, while mixing the whole (productive phase) for a period of time. appropriate time (for example between 5 and 12 min).
• compositions thus obtained are then calendered either in the form of plates (thickness of 2 to 3 mm) or of thin sheets of rubber for the measurement of their physical or mechanical properties, or extruded in the form of a profile.
• the crosslinking of the composition is carried out at a temperature of 150 ° C., for 60 min, under pressure.
• Compositions 02 to 05 contain an epoxy resin and a urea compound replacing the formo-phenolic resin / HMT hardener (s) pair contained in the conventional control composition Ol.
• the compliant compositions make it possible, with a smaller amount of hardener, to obtain a reinforcing effect similar to the control composition, while exhibiting an extended scorching time and a lower Mooney viscosity, therefore improved processability.

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