EP3996915A1 - Composition de caoutchouc - Google Patents

Composition de caoutchouc

Info

Publication number
EP3996915A1
EP3996915A1 EP19749816.5A EP19749816A EP3996915A1 EP 3996915 A1 EP3996915 A1 EP 3996915A1 EP 19749816 A EP19749816 A EP 19749816A EP 3996915 A1 EP3996915 A1 EP 3996915A1
Authority
EP
European Patent Office
Prior art keywords
rubber composition
composition according
phr
epoxy hardener
epoxy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP19749816.5A
Other languages
German (de)
English (en)
Inventor
Tomoya Sakurada
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Compagnie Generale des Etablissements Michelin SCA
Original Assignee
Compagnie Generale des Etablissements Michelin SCA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Compagnie Generale des Etablissements Michelin SCA filed Critical Compagnie Generale des Etablissements Michelin SCA
Publication of EP3996915A1 publication Critical patent/EP3996915A1/fr
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/042—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of natural rubber or synthetic rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/12—Layered products comprising a layer of natural or synthetic rubber comprising natural rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/14—Layered products comprising a layer of natural or synthetic rubber comprising synthetic rubber copolymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/16—Layered products comprising a layer of natural or synthetic rubber comprising polydienes homopolymers or poly-halodienes homopolymers

Definitions

  • the field of the invention is that of rubber compositions intended in particular for laminates, in more particular for articles, for example, tires, shoes, conveyors or caterpillar tracks, in still more particular for tires, in especial for treads of tires.
  • Rubber articles are often required contrary performance with softness and hardness (for instance, in case of a tire tread, softness: to catch the ground and/or to reduce shock from the ground, hardness: to transmit the force obtained from the ground), which implies that a rubber composition comprised in the rubber articles is required to have a soft part and a hard part, that is, have a sufficient gap of the hardness (softness) in the rubber composition.
  • elastomer matrix is understood to mean, in a given composition, all of the elastomers present in said rubber composition.
  • each Tg DSC glass transition temperature
  • DSC Densilic Acid
  • any interval of values denoted by the expression “between a and b” represents the range of values of more than “a” and of less than “b” (i.e. the limits a and b excluded) whereas any interval of values denoted by the expression “from a to b” means the range of values going from “a” to “b” (i.e. including the strict limits a and b).
  • composition comprising the mixture(s) and/or the product of the reaction of the various constituents used, some of the constituents being able or intended to react together, at least partly, during the various manufacturing phases of the composition, in particular during the vulcanization (curing).
  • a first aspect of the invention is a rubber composition based on at least an elastomer matrix, a reinforcing filler, and a condensate of at least one polyamine with at least one carboxylic acid.
  • the specific rubber composition makes it possible to have an unexpectedly sufficient hardness gap.
  • the rubber composition according to the invention is based on an elastomer matrix.
  • Elastomer (or loosely “rubber”, the two terms being regarded as synonyms) of the “diene” type is to be understood in a known manner as an (meaning one or more) elastomer derived at least partly (i.e. a homopolymer or a copolymer) from diene monomers (monomers bearing two carbon-carbon double 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 resulting at least in part from conjugated diene monomers having a content of units of diene origin (conjugated dienes) which is greater than 15% (mol %); thus it is that diene elastomers such as butyl rubbers or diene/ ⁇ -olefin copolymers of the EPDM type do not fall under the preceding definition and may especially be described as “essentially saturated” diene elastomers (low or very low content of units of diene origin, always less than 15%).
  • the expression “highly unsaturated” diene elastomer is understood to mean in particular a diene elastomer having a content of units of diene origin (conjugated dienes) which is greater than 50%.
  • diene elastomer capable of being used in the compositions in accordance with the invention is understood in particular to mean: (a) - any homopolymer obtained by polymerization of a conjugated diene monomer, preferably having from 4 to 12 carbon atoms; (b) - any copolymer obtained by copolymerization of one or more conjugated dienes with one another or with one or more vinyl aromatic compounds preferably having from 8 to 20 carbon atoms.
  • conjugated dienes 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-di(C 1 -C 5 alkyl)-1,3-butadienes, such as, for example, 2,3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-3-ethyl-1 ,3-butadiene or 2-methyl-3-isopropyl-1 ,3-butadiene, an aryl-1,3-butadiene, 1,3-pentadiene or 2,4-hexadiene.
  • 1,3-butadiene 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-di(C 1 -C 5 alkyl)-1,3-butadienes, such as, for example, 2,3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-3-ethyl-1 ,
  • vinylaromatic compounds styrene, ortho-, meta- or para-methylstyrene, the“vinyltoluene” commercial mixture, para-(tert-butyl) styrene, methoxystyrenes, chlorostyrenes, vinylmesitylene, divinylbenzene or vinylnaphthalene.
  • a second aspect of the invention is the rubber composition according to the first aspect, wherein the elastomer matrix comprises at least one diene elastomer selected from the group consisting of polybutadienes, natural rubber, synthetic polyisoprenes, butadiene copolymers, isoprene copolymers, and the combinations thereof.
  • the copolymers are preferably selected from the group consisting of butadiene copolymers the combinations thereof, more preferably selected from the group consisting of styrene-butadiene copolymers (SBR), butadiene-isoprene copolymers (BIR), styrene-isoprene copolymers (SIR), styrene-butadiene-isoprene copolymers (SBIR) and the combinations thereof, still more preferably selected from the group consisting of styrene-butadiene copolymers (SBR) and the combinations thereof.
  • SBR styrene-butadiene copolymers
  • BIR butadiene-isoprene copolymers
  • SIR styrene-isoprene copolymers
  • SBIR styrene-butadiene-isoprene copolymers
  • the diene elastomer may have any microstructure which depends on the polymerization conditions used, in particular on the presence or absence of a modifying and/or randomizing agent and on the amounts of modifying and/or randomizing agent employed.
  • This elastomer may, for example, be a block, statistical, sequential or micro sequential elastomer and may be prepared in dispersion or in solution.
  • This elastomer may be coupled and/or star-branched or else functionalized with a coupling and/or star-branching or functionalizing agent.
  • the elastomer matrix comprises more than 50 phr and up to 100 phr, preferably 55 to 95 phr, more preferably 60 to 90 phr, still more preferably 65 to 85 phr, particularly 70 to 80 phr, of a first diene elastomer which is a styrene butadiene copolymer(s), preferably a solution styrene butadiene copolymer(s), and the elastomer matrix comprises no second diene elastomer or comprises less than 50 phr, preferably 5 to 45 phr, more preferably 10 to 40 phr, still more preferably 15 to 35 phr, particularly 20 to 30 phr, of a second diene elastomer which is different from the first diene elastomer.
  • a first diene elastomer which is a styrene butadiene copolymer(s),
  • the first diene elastomer exhibits a glass transition temperature (TgDSC) of less than -40°C (for example, between -40°C and -110°C), preferably less than -45°C (for example, between -45°C and -105°C), more preferably less than -50°C (for example, between -50°C and -100°C), still more preferably less than -55°C (for example, between -55°C and -95°C), particularly at most -60°C (for example, -60°C to -90°C).
  • TgDSC glass transition temperature
  • the second diene elastomer is a polybutadiene(s) (BR) more preferably having a content (molar %) of 1,2-units of between 4% and 80% or those having a content (molar %) of cis-1,4-units of greater than 80%, more preferably greater than 90% (molar %), still more preferably greater than or equal to 96% (molar %).
  • BR polybutadiene(s)
  • the styrene-butadiene copolymer exhibits a styrene unit of less than 30% by weight (for example, between 3 and 30% by weight) per 100% by weight of the styrene-butadiene copolymer, preferably less than 27% by weight (for example, between 5 and 27% by weight), more preferably less than 23% by weight (for example, between 7 and 23% by weight), still more preferably less than 20% by weight (for example, between 10 and 20% by weight), particularly at most 18% by weight (for example, from 12 to 18%).
  • the styrene unit can be determined by 1H NMR method in accordance with ISO 21561.
  • the rubber composition according to the invention is based on a reinforcing filler.
  • a third aspect of the invention is the rubber composition according to the first aspect or the second aspect, wherein the amount of reinforcing filler is more than 10 phr, preferably more than 20 phr, more preferably more than 30 phr, still more preferably more than 40 phr, particularly more than 50 phr, more particularly more than 60 phr, still more particularly more than 70 phr, advantageously more than 80 phr, more advantageously more than 90 phr, still more advantageously more than 100 phr, especially more than 110 phr.
  • the amount of reinforcing filler is more than 10 phr, preferably more than 20 phr, more preferably more than 30 phr, still more preferably more than 40 phr, particularly more than 50 phr, more particularly more than 60 phr, still more particularly more than 70 phr, advantageously more than 80 phr, more advantageously more than 90 phr, still more advantageously more
  • the amount of reinforcing filler is less than 300 phr.
  • the reinforcing filler may comprise a reinforcing organic filler (for example, carbon black), a reinforcing inorganic filler (for instance, silica) or the combinations thereof.
  • a reinforcing organic filler for example, carbon black
  • a reinforcing inorganic filler for instance, silica
  • Use may be made of any type of reinforcing filler known for its capabilities of reinforcing a rubber composition which can be used for the manufacture of the article, for example a reinforcing organic filler, such as carbon black, or a reinforcing inorganic filler, such as silica, with which a coupling agent is combined in a known way.
  • a reinforcing organic filler such as carbon black
  • a reinforcing inorganic filler such as silica
  • a fourth aspect of the invention is the rubber composition according to any one of the first to the third aspects, wherein the reinforcing filler predominately comprises a reinforcing filler, that is, the reinforcing filler comprises more than 50% by weight of the reinforcing inorganic filler per 100% of the reinforcing filler, preferably the reinforcing filler comprises more than 60%, more preferably more than 70%, still more preferably more than 80%, particularly more than 90%, by weight of the reinforcing inorganic filler per 100% of the reinforcing filler.
  • the reinforcing filler predominately comprises a reinforcing filler, that is, the reinforcing filler comprises more than 50% by weight of the reinforcing inorganic filler per 100% of the reinforcing filler, preferably the reinforcing filler comprises more than 60%, more preferably more than 70%, still more preferably more than 80%, particularly more than 90%, by weight of the reinforcing inorganic filler per 100% of
  • the reinforcing filler predominately comprises a reinforcing inorganic filler (preferably silica), and carbon black of which the amount is less than 50%, preferably less than 40%, more preferably less than 30%, still more preferably less than 20%, particularly less than 10%, by weight per 100% of the reinforcing filler.
  • a reinforcing inorganic filler preferably silica
  • carbon black of which the amount is less than 50%, preferably less than 40%, more preferably less than 30%, still more preferably less than 20%, particularly less than 10%, by weight per 100% of the reinforcing filler.
  • filler should be understood here to mean any inorganic or mineral filler, whatever its color and its origin (natural or synthetic), also referred to as “white filler”, “clear filler” or even “non-black filler”, in contrast to carbon black, capable of reinforcing by itself alone, without means other than an intermediate coupling agent, a rubber composition intended for the manufacture of tires, in other words capable of replacing, in its reinforcing role, a conventional tire-grade carbon black; such a filler is generally characterized, in a known manner, by the presence of hydroxyl (-OH) groups at its surface.
  • -OH hydroxyl
  • this filler is unimportant, whether it is in the form of powder, microbeads, granules, beads or any other suitable densified form.
  • the reinforcing inorganic filler of the mixtures of various reinforcing inorganic fillers, preferably of highly dispersible siliceous, aluminous fillers or the combinations thereof is described hereafter.
  • Mineral fillers of the siliceous type preferably silica (SiO 2 )
  • the aluminous type preferably alumina (Al 2 O 3 )
  • the combinations thereof are suitable in particular as the reinforcing inorganic fillers.
  • a fifth aspect of the invention is the rubber composition according to the fourth aspect, wherein the reinforcing inorganic filler predominately comprises silica, that is, the reinforcing inorganic filler comprises more than 50% by weight of silica per 100% of the reinforcing inorganic filler, preferably the reinforcing filler comprises more than 60%, more preferably more than 70%, still more preferably more than 80%, particularly more than 90%, by weight of silica per 100% of the reinforcing inorganic filler.
  • the silica may be a type of silica or a blend of several silicas.
  • the silica used may be any reinforcing silica known to a person skilled in the art, in particular any precipitated or pyrogenic silica having a BET surface area and a CTAB specific surface area that are both less than 450 m 2 /g, preferably from 20 to 400 m 2 /g, more preferably 50 to 350 m 2 /g, still more preferably 100 to 300 m 2 /g, particularly between 150 and 250 m 2 /g, wherein the BET surface area is measured according to a known method, that is, by gas adsorption using the Brunauer-Emmett-Teller method described in “The Journal of the American Chemical Society”, Vol.
  • a reinforcing filler of another nature, in particular organic nature, such as carbon black might be used as filler equivalent to the reinforcing inorganic filler described in the present section, provided that this reinforcing filler is covered with an inorganic layer, such as silica, or else comprises, at its surface, functional sites, in particular hydroxyls, requiring the use of a coupling agent in order to form the connection between the filler and the elastomer.
  • an inorganic layer such as silica
  • silane polysulphides referred to as “symmetrical” or “asymmetrical” depending on their particular structure, as described, for example, in applications WO 03/002648, WO 03/002649 and WO 2004/033548.
  • silane polysulphides correspond to the following general formula (I): (I) Z - A - Sx - A - Z , in which: - x is an integer from 2 to 8 (preferably from 2 to 5); - A is a divalent hydrocarbon radical (preferably, C 1 -C 18 alkylene groups or C 6 -C 12 arylene groups, more particularly C 1 -C 10 , in particular C 1 -C 4 , alkylenes, especially propylene); - Z corresponds to one of the formulae below: in which: - the R 1 radicals which are unsubstituted or substituted and identical to or different from one another, represent a C 1 -C 18 alkyl, C 5 -C 18 cycloalkyl or C 6 -C 18 aryl group (preferably, C 1 -C 6 alkyl, cyclohexyl or phenyl groups, in particular C 1 -C 4 alkyl groups, more particularly methyl and/or ethy
  • the mean value of the "x" indices is a fractional number preferably of between 2 and 5, more preferably of approximately 4.
  • silane polysulphides of bis((C 1 -C 4 )alkoxyl(C 1 -C 4 )alkylsilyl(C 1 -C 4 )alkyl)polysulphides (in particular disulphides, trisulphides or tetrasulphides), such as, for example, bis(3-trimethoxysilylpropyl) or bis(3-triethoxysilylpropyl)polysulphides.
  • TESPT bis(3-triethoxysilylpropyl)tetrasulphide
  • TESPD bis(3-triethoxysilylpropyl)disulphide
  • silanes bearing at least one thiol (-SH) function referred to as mercaptosilanes
  • at least one blocked thiol function such as described, for example, in patents or patent applications US 6 849 754, WO 99/09036, WO 2006/023815, WO 2007/098080, WO 2008/055986 and WO 2010/072685.
  • the rubber composition according to the invention comprises a reinforcing inorganic filler (preferably silica), and a coupling agent of which the amount is from 0.5 to 15% by weight per 100% by weight of the reinforcing inorganic filler (preferably silica).
  • the rubber composition according to the invention comprises a reinforcing inorganic filler (preferably silica), and a coupling agent of which the amount is less than 30 phr (for example, between 0.1 and 30 phr), preferably less than 25 phr (for example, between 0.5 and 25 phr), more preferably less than 20 phr (for example, between 1 and 20 phr), still more preferably less than 15 phr (for example, between 1.5 and 15 phr).
  • a reinforcing inorganic filler preferably silica
  • a coupling agent of which the amount is less than 30 phr for example, between 0.1 and 30 phr
  • 25 phr for example, between 0.5 and 25 phr
  • 20 phr for example, between 1 and 20 phr
  • 15 phr for example, between 1.5 and 15 phr
  • the rubber composition according to the invention is based on a condensate of at least one polyamide with at least one carboxylic acid.
  • the condensate is a compound obtained by condensation reaction of at least one polyamide with at least one carboxylic acid.
  • the polyamine is a compound that comprises more than one amine groups in a molecule.
  • the carboxylic acid is a compound that comprises at least one carboxylic group in a molecule.
  • a sixth aspect of the invention is the rubber composition according to any one of the first to the fifth aspects, wherein the polyamine has at least two, preferably more than two, amine groups in a molecule.
  • a seventh aspect of the invention is the rubber composition according to any one of the first to the sixth aspects, wherein the carboxylic acid comprises at least one fatty acid, preferably wherein the fatty acid comprises at least one unsaturated fatty acid, more preferably wherein the unsaturated fatty acid comprises at least one C18 unsaturated fatty acid (for example, alpha-linolenic acid, linoleic acid, oleic acid), still more preferably wherein the C18 unsaturated fatty acid comprises at least one linoleic acid.
  • the carboxylic acid comprises at least one fatty acid, preferably wherein the fatty acid comprises at least one unsaturated fatty acid, more preferably wherein the unsaturated fatty acid comprises at least one C18 unsaturated fatty acid (for example, alpha-linolenic acid, linoleic acid, oleic acid), still more preferably wherein the C18 unsaturated fatty acid comprises at least one linoleic acid.
  • An eighth aspect of the invention is the rubber composition according to any one of the first to the seventh aspects, wherein the carboxylic acid comprises at least one polybasic carboxylic acid, preferably wherein the polybasic carboxylic acid comprises at least one dicarboxylic acid, more preferably wherein the dicarboxylic acid comprises at least one dimer acid.
  • a ninth aspect of the invention is the rubber composition according to any one of the first to the eighth aspects, wherein the rubber composition is based on an epoxy hardener, and wherein the condensate is comprised in the epoxy hardener.
  • An epoxy comprises at least one compound whose molecule comprises at least one epoxide functional group which is a three-membered ring comprising an oxygen atom and two carbon atoms.
  • the epoxy may harden by reacting with at least one co-reactant which is the epoxy hardener.
  • the epoxy hardener is available commercially, for example known as Vegechem green V115, Vegechem green V125, Vegechem green V140 (Tsuno Food Industrial Co., Ltd.), Aradur 115, Aradur 125, Aradur 140 (Huntsman corporation), Versamid 115, Versamid 125, Versamid 140 (BASF SE).
  • a tenth aspect of the invention is the rubber composition according to the ninth aspect, wherein the amount of epoxy hardener is at least 1 phr, preferably at least 5 phr, more preferably at least 10 phr, still more preferably at least 15 phr, particularly at least 20 phr, more particularly at least 25 phr.
  • the amount of epoxy hardener is at most 50 phr.
  • An eleventh aspect of the invention is the rubber composition according to the ninth aspect or the tenth aspect, wherein the epoxy hardener has a viscosity of at least 1000 mPa ⁇ s, preferably at least 2000 mPa ⁇ s, more preferably at least 3000 mPa ⁇ s, still more preferably at least 4000 mPa ⁇ s, particularly at least 5000 mPa ⁇ s, more particularly at least 6000 mPa ⁇ s, still more particularly at least 7000 mPa ⁇ s, advantageously at least 8000 mPa ⁇ s, more advantageously at least 9000 mPa ⁇ s, still more advantageously at least 10000 mPa ⁇ s, at 25°C.
  • the epoxy hardener has a viscosity of at least 1000 mPa ⁇ s, preferably at least 2000 mPa ⁇ s, more preferably at least 3000 mPa ⁇ s, still more preferably at least 4000 mPa ⁇ s, particularly at least 5000 mPa ⁇ s, more
  • the epoxy hardener has a viscosity of at most 1000000 mPa ⁇ s, preferably at most 500000 mPa ⁇ s, at 25°C.
  • the above viscosity at 25°C can measured in accordance with ASTM D4287.
  • a twelfth aspect of the invention is the rubber composition according to any one of the ninth to the eleventh aspects, wherein the epoxy hardener has a viscosity of at least 100 mPa ⁇ s, preferably at least 200 mPa ⁇ s, more preferably at least 300 mPa ⁇ s, still more preferably at least 400 mPa ⁇ s, particularly at least 500 mPa ⁇ s, more particularly at least 600 mPa ⁇ s, still more particularly at least 700 mPa ⁇ s, at 75°C.
  • the epoxy hardener has a viscosity of at most 10000 mPa ⁇ s, preferably at most 5000 mPa ⁇ s, at 75°C.
  • the above viscosity at 75°C can measured in accordance with ASTM D4287.
  • a thirteenth aspect of the invention is the rubber composition according to any one of the ninth to the twelfth aspects, wherein the rubber composition is free of or is further based on an epoxy of which the amount in phr is lower than that of the epoxy hardener, preferably wherein the amount of epoxy is less than 20 phr, preferably less than 15 phr, more preferably less than 10 phr, still preferably less than 5 phr, particularly less than 1 phr.
  • the epoxy may comprise at least one epoxy resin comprising at least two, preferably more than two, more preferably at least three, epoxide functional groups in a molecule.
  • the rubber composition according to the invention may be based on all or a portion(s) of the usual additives generally used in the elastomer composition(s) intended in particular for laminates, in more particular for articles (for example, tires, shoes, conveyors or caterpillar tracks), in more particular for tires, such as, for example, protection agents, such as antiozone waxes, chemical antiozonants, antioxidants, plasticizing agent (for example, liquid plasticizer(s), hydrocarbon resin(s)), tackifying resins, a crosslinking system based on sulphur, vulcanization accelerator(s), vulcanization activator(s) or the combinations thereof.
  • protection agents such as antiozone waxes, chemical antiozonants, antioxidants
  • plasticizing agent for example, liquid plasticizer(s), hydrocarbon resin(s)
  • tackifying resins for example, a crosslinking system based on sulphur, vulcanization accelerator(s), vulcanization activator(s) or the combinations thereof.
  • the rubber composition is free of the epoxy.
  • the composition can be also based on coupling activators when a coupling agent is used, agents for covering the reinforcing inorganic filler or more generally processing aids capable, in a known way, by virtue of an improvement in the dispersion of the filler in the rubber matrix and of a lowering of the viscosity of the compositions, of improving their property of processing in the raw state; these agents are, for example, hydrolysable silanes, such as alkylalkoxysilanes, polyols, polyethers, or hydroxylated or hydrolysable polyorganosiloxanes.
  • hydrolysable silanes such as alkylalkoxysilanes, polyols, polyethers, or hydroxylated or hydrolysable polyorganosiloxanes.
  • the rubber compositions according to the invention may be manufactured in appropriate mixers using two successive preparation phases well known to a person skilled in the art: a first phase of thermomechanical working or kneading (referred to as “non-productive” phase) at high temperature, up to a maximum temperature of between 110°C and 190°C, preferably between 130°C and 180°C, followed by a second phase of mechanical working (referred to as “productive” phase) at a lower temperature, typically of less than 110°C, for example between 40°C and 100°C, finishing phase during which sulphur and the vulcanization accelerator in the crosslinking system are incorporated.
  • a first phase of thermomechanical working or kneading referred to as “non-productive” phase
  • productive phase a second phase of mechanical working
  • a process which can be used for the manufacture of such composition comprises, for example and preferably, the following steps: - incorporating in the elastomer matrix(es), for instance, the diene elastomer(s), in a mixer, the reinforcing filler, the condensate of at least one polyamine with at least one carboxylic acid, during a first stage (referred to as a “non productive” stage) everything being kneaded thermomechanically (for example in one or more steps) until a maximum temperature of between 110°C and 190°C is reached; - cooling the combined mixture to a temperature of less than 100°C; - subsequently incorporating, during a second stage (referred to as a "productive" stage), sulphur and the vulcanization accelerator in the crosslinking system; and - kneading everything up to a maximum temperature of less than 110°C.
  • the first (non-productive) phase is carried out in a single thermomechanical stage during which all the necessary constituents are introduced into an appropriate mixer, such as a standard internal mixer, followed, in a second step, for example after kneading for 1 to 2 minutes, by the other additives, optional additional filler-covering agents or processing aids, with the exception of sulphur and the vulcanization accelerator in the crosslinking system.
  • the total kneading time, in this non-productive phase is preferably between 1 and 15 min.
  • sulphur and the vulcanization accelerator in the crosslinking system are then incorporated at low temperature (for example, between 40°C and 100°C), generally in an external mixer, such as an open mill; the combined mixture is then mixed (the second (productive) phase) for a few minutes, for example between 2 and 15 min.
  • the rubber composition according to the invention is further based on a crosslinking system.
  • the crosslinking system is based on sulphur, vulcanization activator(s) or the combinations thereof.
  • the amount of sulphur is preferably between 0 and 10 phr.
  • the sulphur in the crosslinking (or vulcanization) system is to say vulcanization sulphur which may be sulphur, sulphur derived from a sulphur-donating agent or the combinations thereof.
  • the vulcanization activator(s) may be based on zinc (pure zinc and/or zinc derivatives (for example, zinc fatty acid salt)), fatty acid (in particular, stearic acid) or the combinations thereof.
  • the crosslinking system is based on at least one vulcanization accelerator, preferably the amount of vulcanization accelerator is between 0 and 10 phr.
  • the vulcanization accelerator can promote the sulphur vulcanization reaction in each of the rubber compositions.
  • the vulcanization accelerator comprises sulphenamide type vulcanization accelerator(s) (for example, N-cyclohexyl-2-benzothiazole sulfenamide (CBS), N-tert-butyl-2-benzothiazole sulfenamide (TBBS), 2-(4-morpholinothio)-benzothiazole (MBS), N,N’-dicyclohexyl-2-benzothiazole sulfenamide (DCBS)), thiazole type vulcanization accelerator(s) (for example, 2-2’-dithiobis(benzothiazole) (MBTS), zinc-2-mercaptobenzothiazole (ZMBT)), thiourea type vulcanization accelerator(s), thiuram type vulcanization acclerator(s) (for example, Tetrabenzylthiuram dis
  • the final composition thus obtained is subsequently extruded or calendered, for example in the form of a sheet or of a plaque, in particular for laboratory characterization, or else extruded in the form of a rubber profiled element which can be used directly as a laminate or an article, for example, a tire tread, a shoe sole, a conveyor belt and a caterpillar track tread.
  • a fourteenth aspect of the invention is a laminate comprising at least two superposed portions comprising a first portion being made of a first rubber composition (FC) being a rubber composition according to any one of the ninth to the thirteenth aspects, and a second rubber composition (SC) different from the first rubber composition (FC), and the second rubber composition (SC) based on an elastomer matrix, a reinforcing filler and at least one of an epoxy or epoxy hardener, preferably wherein the amount in phr of the epoxy hardener in the first rubber composition (FC) is higher than that in the second rubber composition (SC).
  • FC first rubber composition
  • SC second rubber composition
  • the laminate according to the fourteenth aspect it is possible to build a first layer of a homogeneous rubber composition, as the first rubber composition (FC), and a second layer of a homogeneous rubber composition, as the second rubber composition (SC), then to superpose the first layer onto the second layer or then to superpose the second layer onto the first layer, or to sandwich the other layer(s) or portion(s) between the first layer and the second layer, to get the laminate of the article.
  • FC first rubber composition
  • SC second layer of a homogeneous rubber composition
  • the first portion is adjacent to the second portion.
  • a preferred embodiment of the invention is an article comprising a rubber composition according to any one of the first to the thirteenth aspects, preferably the article comprises a laminate according to the fourteenth aspect.
  • the article is intended to contact with the ground, preferably the article comprises a laminate according to the fourteenth aspect, and at least one of the first portion or the second portion, more preferably each of the portions, is intended to contact with the ground during the service life of the article.
  • the service life means the duration to use the article (for example, the term from the new state to the final state of the article, in case of that the article is a tire, the final state means a state on reaching the wear indicator bar(s) in the tread of tire).
  • the article comprises a laminate according to the fourteenth aspect, and the first portion is arranged nearer to the ground than the second portion.
  • the superposed portions which are the first portion and the second portion are radially superposed portions, that is, the first portion is radially exterior to the second portion.
  • the article comprises a laminate according to the fourteenth aspect, and the second portion is arranged nearer to the ground than the first portion.
  • the superposed portions which are the second portion and the first portion are radially superposed portions, that is, the second portion is radially exterior to the first portion.
  • the “radially” means “in the radial direction” which is a direction perpendicular to the axis of the rotation of a tire.
  • the article is a tire (for example, a tire tread), a shoe (for example, a shoe sole), a conveyor (for example, a conveyor belt) or a caterpillar track (for example, a caterpillar track tread), preferably a tire, a shoe or a caterpillar track, more preferably a tire tread, a shoe sole or a caterpillar track tread, still more preferably a tire tread.
  • a tire for example, a tire tread
  • a shoe for example, a shoe sole
  • a conveyor for example, a conveyor belt
  • a caterpillar track for example, a caterpillar track tread
  • the article is a tire comprising several tire parts which are a tread intended to at least partially contact with the ground, two sidewalls intended to contact with the outside air, but not to contact with the ground, two beads, a crown prolonged by two sidewalls ended by two beads, a carcass reinforcement formed at least one ply reinforced by radial textile cards, the carcass reinforcement passing into the crown and the sidewalls and the carcass reinforcement anchored in the two beads, preferably further comprising crown reinforcement placed between carcass reinforcement and the tread, more preferably further comprising an inner liner intended to protect the carcass reinforcement from diffusion of air coming from a space inside the tire, and the inner liner placed radially inner than carcass reinforcement.
  • a portion made of the rubber composition according to any one of the first to the thirteenth aspects, preferably the laminate according to the fourteenth aspect, is placed in at least one of the above tire parts, between two of the above tire parts, radially outer than one of the above tire parts, radially inner than one of the above tire parts or the combinations thereof.
  • a fifteenth aspect of the invention is a tire comprising a rubber composition according to any one of the first to the thirteenth aspects, preferably wherein the tire comprises a laminate according to the fourteenth aspect, more preferably wherein the tire comprising a tread comprising a laminate according to the fourteenth aspect.
  • the tires are particularly intended to equip passenger motor vehicles, including 4 ⁇ 4 (four-wheel drive) vehicles and SUV (Sport Utility Vehicles) vehicles, and industrial vehicles particularly selected from vans and heavy duty vehicles (i.e., bus or heavy road transport vehicles (lorries, tractors, trailers)).
  • passenger motor vehicles including 4 ⁇ 4 (four-wheel drive) vehicles and SUV (Sport Utility Vehicles) vehicles
  • industrial vehicles particularly selected from vans and heavy duty vehicles (i.e., bus or heavy road transport vehicles (lorries, tractors, trailers)).
  • the vulcanization (or curing) is carried out in a known way at a temperature generally of between 110°C and 190°C for a sufficient time which can vary, for example, between 5 and 90 min depending in particular on the curing temperature, the vulcanization system adopted and the vulcanization kinetics of the composition(s) under consideration.
  • the invention relates to the rubber composition(s), to the laminate(s), to the article(s), to the tire (s) and the tire tread(s) described above, both in the raw state (i.e., before curing) and in the cured state (i.e., after crosslinking or vulcanization).
  • the rubber compositions are based on a diene elastomer (a blend of SBR and BR) reinforced with carbon black or a blend of silica (as a reinforcing inorganic filler) and carbon black, an epoxy comprising an epoxy resin or an epoxy hardener comprising a condensate of at one polyamine (“ethane-1,2-diamine” or “N’-(2-aminoethyl)ethane-1,2-diamine”) and one dimer acid comprising two linoleic acids (as carboxylic acids), and a crosslinking system based on sulphur and 2-mercaptobenzothiazyl disulfide (as a vulcanization accelerator).
  • the formulations of the rubber compositions are given at Table 1 with the content of the various products expressed in phr.
  • Each rubber composition was produced as follows: The reinforcing filler, the epoxy or the epoxy hardener comprising the condensate of the polyamine and the carboxylic acids, the elastomer matrix and the various other ingredients, with the exception of sulphur and the vulcanization accelerator in the crosslinking system, were successively introduced into an internal mixer having an initial vessel temperature of approximately 60°C; the mixer was thus approximately 70% full (% by volume). Thermomechanical working (non-productive phase) was then carried out in one stage, which lasts in total approximately 3 to 4 minutes, until a maximum “dropping” temperature of 165°C was reached.
  • the rubber compositions thus obtained were subsequently calendered, either in the form of sheets (thickness of 2 to 3 mm) or of fine sheets of rubber, for the measurement of their physical or mechanical properties, or in the form of profiled elements which could be used directly, after cutting and/or assembling to the desired dimensions, for example as tire semi-finished products, in particular as tire treads.
  • T-1, T-2 examples according to the invention
  • T-3 a comparative example
  • Each of the laminates comprises two radially superposed portions which are a first portion (FC) and a second portion (SC) adjacent to the first portion (FC), each of the laminates being produced by superposition of sheets of the rubber compositions (C-1 to C-3) respectively.
  • the first portions are made of C-1 to C-3 respectively
  • each of the second portion is made of C-3.
  • the rubber composition according to the invention makes it possible to have an unexpectedly sufficient hardness gap.
  • Epoxy hardener 2 Epoxy hardener based on ethane-1,2-diamine,(9Z,12Z)-octadeca-9,12-dienoic acid (((C 18 H 32 O 2 ) 2.

Abstract

L'invention concerne une composition de caoutchouc qui comprend au moins une matrice élastomère, une charge de renforcement et un condensat d'au moins une polyamine avec au moins un acide carboxylique.
EP19749816.5A 2019-07-09 2019-07-09 Composition de caoutchouc Pending EP3996915A1 (fr)

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PCT/JP2019/027177 WO2021005720A1 (fr) 2019-07-09 2019-07-09 Composition de caoutchouc

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