WO2021019709A1 - Stratifié - Google Patents

Stratifié Download PDF

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Publication number
WO2021019709A1
WO2021019709A1 PCT/JP2019/029947 JP2019029947W WO2021019709A1 WO 2021019709 A1 WO2021019709 A1 WO 2021019709A1 JP 2019029947 W JP2019029947 W JP 2019029947W WO 2021019709 A1 WO2021019709 A1 WO 2021019709A1
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WO
WIPO (PCT)
Prior art keywords
rubber composition
phr
rubber
laminate according
sulfur
Prior art date
Application number
PCT/JP2019/029947
Other languages
English (en)
Inventor
Masahiko Moriyama
Original Assignee
Compagnie Generale Des Etablissements Michelin
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Priority to PCT/JP2019/029947 priority Critical patent/WO2021019709A1/fr
Publication of WO2021019709A1 publication Critical patent/WO2021019709A1/fr

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Classifications

    • 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
    • B32B25/02—Layered products comprising a layer of natural or synthetic rubber with fibres or particles being present as additives in the layer
    • 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
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/027—Thermal properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0016—Compositions of the tread
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C11/00—Tyre tread bands; Tread patterns; Anti-skid inserts
    • B60C11/0041—Tyre tread bands; Tread patterns; Anti-skid inserts comprising different tread rubber layers
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/03—3 layers
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B32B2250/248—All polymers belonging to those covered by group B32B25/00
    • 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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/102—Oxide or hydroxide
    • 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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/107—Ceramic
    • B32B2264/108—Carbon, e.g. graphite particles
    • 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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/12—Mixture of at least two particles made of different materials
    • 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
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/712—Weather resistant
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/744—Non-slip, anti-slip
    • 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
    • B32B2605/00—Vehicles
    • B32B2605/08—Cars

Definitions

  • the field of the invention is that of laminates intended in particular for rubber articles, in more particular for tires, in still more particular for treads of tires, in especial for treads of tires capable of rolling over ground surface covered with snow.
  • the snow tires classified in a category of use “snow”, identified by an inscription the alpine symbol (“3-peak-mountain with snowflake”), marked on their sidewalls, mean tires whose tread patterns, tread compounds and/or structures are primarily designed to achieve, in snow conditions, a performance better than that of normal tires intended for normal on-road use with regard to their abilities to initiate, maintain or stop vehicle motion.
  • Snowy ground has a feature of having a low friction coefficient and a constant objective of manufacturers of rubber articles is improvement of a grip performance of rubber articles on snow-covered (snowy) ground during the service life of the rubber articles.
  • 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
  • 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, the product of the reaction of the various constituents used, or both; some of the constituents being able, intended, or both, 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 laminate comprising at least three superposed portions comprising a first portion being made of a first rubber composition (FC), a second portion being made of a second rubber composition (SC) and a third portion being made of a third rubber composition (TC), the second portion being arranged between the first portion and the third portion, wherein each of the rubber compositions is based on at least an elastomer matrix, and more than 65 phr of a reinforcing filler, wherein the average glass transition temperature of elastomer matrix in the first rubber composition (FC) is lower than that in the second rubber composition (SC), and wherein the average glass transition temperature of elastomer matrix in the second rubber composition (SC) is higher than that in the third rubber composition (TC).
  • FC first rubber composition
  • SC second rubber composition
  • TC third rubber composition
  • the specific laminate with the rubber compositions allows an unexpectedly improved grip performance on snowy ground in the new state and in the worn state.
  • Each of the rubber compositions (FC, SC and TC) of the laminate according to the invention is based on each 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 a person skilled in the art of rubber products (for example, tires) will understand that the invention is preferably employed with essentially unsaturated diene elastomers.
  • 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 laminate according to the first aspect, wherein each of the rubber compositions is such that the elastomer matrix comprises at least one diene elastomer selected from the group consisting of polybutadienes (BR), natural rubber (NR), synthetic polyisoprenes (IR), butadiene copolymers, and isoprene copolymers, and combinations thereof.
  • BR polybutadienes
  • NR natural rubber
  • IR synthetic polyisoprenes
  • butadiene copolymers butadiene copolymers
  • isoprene copolymers and combinations thereof.
  • At least one of the rubber compositions, especially each of the rubber compositions, is such that the copolymers are preferably selected from the group consisting of butadiene copolymers, and 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 combinations thereof, still more preferably selected from the group consisting of styrene-butadiene copolymers (SBR), and combinations thereof.
  • SBR styrene-butadiene copolymers
  • BIR butadiene-isoprene copolymers
  • SIR styrene-isoprene copolymers
  • SBIR styrene-butadiene-iso
  • the diene elastomer may have any microstructure which depends on the polymerization conditions used, in particular on the presence or absence of a modifying agent, randomizing agent, or both and on the amounts of modifying agent, randomizing agent, or both 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, star-branched, or both; or else functionalized with a coupling, star-branching, or both; or functionalizing agent.
  • At least one of the first rubber composition (FC) or the third rubber composition (TC), especially each of the first rubber composition (FC) and the third rubber composition (TC), is such that 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 rubber, especially a solution styrene butadiene rubber, as a styrene butadiene copolymer, 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
  • At least one of the first rubber composition (FC) or the third rubber composition (TC), especially each of the first rubber composition (FC) and the third rubber composition (TC), is such that the first diene elastomer exhibits a glass transition temperature (Tg DSC ) 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).
  • Tg DSC glass transition temperature
  • At least one of the first rubber composition (FC) or the third rubber composition (TC), especially each of the first rubber composition (FC) and the third rubber composition (TC), is such that 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)
  • At least one of the first rubber composition (FC) or the third rubber composition (TC), especially each of the first rubber composition (FC) and the third rubber composition (TC), is such that 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.
  • a third aspect of the invention is the laminate according to the first aspect or the second aspect, wherein the second rubber composition (SC) is such that the elastomer matrix comprises more than 50 phr and up to 100 phr, preferably 60 to 100 phr, more preferably 70 to 100 phr, still more preferably 80 to 100 phr, particularly 90 to 100 phr, more particularly 100 phr, of a first diene elastomer which is a styrene butadiene rubber, especially a solution styrene butadiene rubber, as a styrene butadiene copolymer, and the elastomer matrix comprises no second diene elastomer or comprises less than 50 phr, preferably less than 40 phr, more preferably less than 30 phr, still more preferably less than 20 phr, particularly less than 10 phr, of a second diene elastomer which is different from
  • a fourth aspect of the invention is the laminate according to any one of the first to the third aspects, wherein the second rubber composition (SC) is such that the average glass transition temperature of elastomer matrix is more than -65°C, preferably more than -60°C, more preferably more than -55°C, still more preferably more than -50°C, particularly more than -45°C, more particularly more than -40°C, still more particularly more than -35°C, advantageously more than -30°C.
  • SC second rubber composition
  • the second rubber composition (SC) is such that the average glass transition temperature of elastomer matrix is less than 0°C, preferably less than -5°C, more preferably less than -10°C, still more preferably less than -15°C, particularly less than -20°C.
  • a fifth aspect of the invention is the laminate according to any one of the first to the fourth aspects, wherein each of the first rubber composition (FC) and the third rubber composition (TC) is such that the average glass transition temperature of elastomer matrix is at most -40°C, preferably at most -45°C, more preferably at most -50°C, still more preferably at most -55°C, particularly more than -60°C, more particularly at most -65°C, still more particularly at most -70°C, advantageously at most -75°C.
  • each of the first rubber composition (FC) and the third rubber composition (TC) is such that the average glass transition temperature of elastomer matrix is at least -120°C, preferably at least -115°C, more preferably at least -110°C, still more preferably at least -105°C, particularly at least -100°C, more particularly at least -95°C, still more particularly at least -90°C, advantageously at least -85°C.
  • Each of the rubber compositions (FC, SC and TC) of the laminate according to the invention is based on more than 65 phr of a reinforcing filler.
  • 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 rubber 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
  • each of the rubber compositions is such that the reinforcing filler may comprise at least one of carbon black or a reinforcing inorganic filler (preferably, silica).
  • a sixth aspect of the invention is the laminate according to any one of the first to the fifth aspects, wherein each of the rubber compositions is such that the reinforcing filler predominately comprises a reinforcing inorganic filler, that is, the reinforcing filler comprises more than 50% by weight of the reinforcing inorganic filler per 100% by weight 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% by weight 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 filler(s), aluminous filler(s), or both is described hereafter.
  • Mineral fillers of the siliceous type preferably silica (SiO 2 )
  • the aluminous type preferably alumina (Al 2 O 3 )
  • the reinforcing inorganic fillers are suitable in particular as the reinforcing inorganic fillers.
  • the reinforcing inorganic filler predominately comprises silica, that is, the reinforcing inorganic filler comprises more than 50% by weight of silica per 100% by weight of the reinforcing inorganic filler, preferably the reinforcing inorganic filler comprises more than 60%, more preferably more than 70%, still more preferably more than 80%, particularly more than 90%, more particularly 100%, by weight of silica per 100% by weight 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
  • 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.
  • carbon blacks for rubber articles for example, tires
  • silane polysulfides 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 polysulfides 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, ethyl
  • the mean value of the "x" indices is a fractional number preferably of between 2 and 5, more preferably of approximately 4.
  • silane polysulfides of bis((C 1 -C 4 )alkoxyl(C 1 -C 4 )alkylsilyl(C 1 -C 4 )alkyl)polysulfides (in particular disulfides, trisulfides or tetrasulfides), such as, for example, bis(3-trimethoxysilylpropyl) or bis(3-triethoxysilylpropyl)polysulfides.
  • TESPT bis(3-triethoxysilylpropyl)tetrasulfide
  • TESPD bis(3-triethoxysilylpropyl)disulfide
  • silanes bearing at least one thiol (-SH) function referred to as mercaptosilanes
  • at least one blocked thiol function or both, 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.
  • each of the rubber compositions 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).
  • each of the rubber compositions 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), 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 seventh aspect of the invention is the laminate according to any one of the first to the sixth aspects, wherein each of the rubber compositions is such that the reinforcing filler comprises less than 65 phr, preferably less than 60 phr, more preferably less than 55 phr, still more preferably less than 50 phr, particularly less than 45 phr, more particularly less than 40 phr, still more particularly less than 35 phr, advantageously less than 30 phr, more advantageously less than 25 phr, still more advantageously less than 20 phr, especially less than 15 phr, more especially less than 10 phr, still more especially less than 5 phr, of carbon black.
  • each of the rubber compositions is such that the reinforcing filler comprises more than 0 phr of carbon black.
  • An eighth aspect of the invention is the laminate according to any one of the first to the seventh aspects, wherein each of the rubber compositions is such that the amount of reinforcing filler is more than 70 phr, preferably more than 75 phr, more preferably more than 80 phr, still more preferably more than 85 phr, particularly more than 90 phr, more particularly more than 95 phr, still more particularly more than 100 phr.
  • each of the rubber compositions is such that the amount of reinforcing filler is less than 300 phr, preferably less than 250 phr, more preferably less than 200 phr.
  • a ninth aspect of the invention is the laminate according to any one of the first to the eighth aspects, wherein the amount in phr of the reinforcing filler in the first rubber composition (FC) is higher than that in the second rubber composition (SC), and wherein the amount in phr of the reinforcing filler in the second rubber composition (SC) is lower than that in the third rubber composition (TC).
  • the second rubber composition (SC) is such that the amount of reinforcing filler is less than 120 phr, preferably less than 110 phr.
  • each of the first rubber composition (FC) and the third rubber composition (TC) is such that the amount of reinforcing filler is at least 110 phr, preferably at least 120 phr.
  • Each of the rubber compositions (FC, SC and TC) of the laminate in according to the invention may be based on all or a portion(s) of the usual additives generally used in the elastomer compositions intended for manufacture of rubber articles (for example, 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, methylene acceptors (for example, phenolic novolak resin) or methylene donors (for example, hexamethylenetetramine (HMT) or hexamethoxymethylmelamine (H3M)), a crosslinking system, or combinations thereof.
  • protection agents such as antiozone waxes, chemical antiozonants, antioxidants, plasticizing agent (for example, liquid plasticizer(s), hydrocarbon resin(s)), tackifying resins, methylene acceptors (for example, phenolic novolak resin) or
  • Each of the rubber compositions (FC, SC and TC) of the laminate in according to the invention 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, amines, or hydroxylated or hydrolysable polyorganosiloxanes.
  • a tenth aspect of the invention is the laminate according to any one of the first to the ninth aspects, wherein each of the rubber compositions is further based on a plasticizing agent, preferably wherein the amount of plasticizing agent is more than 50 phr, more preferably more than 60 phr, still more preferably more than 70 phr, particularly more than 80 phr, in order to soften each of the rubber compositions by diluting the elastomer matrix and the reinforcing filler.
  • the plasticizing agent may comprise at least one of a liquid plasticizer or a hydrocarbon resin. At ambient temperature (20°C) under atmosphere pressure, the liquid plasticizer is liquid, and the hydrocarbon resin is solid.
  • Each of the rubber compositions (FC, SC and TC) of the laminate 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 sulfur 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 each of such compositions comprises, for example and preferably, the following steps: - incorporating in the elastomer matrix, in a mixer, the reinforcing filler 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), sulfur 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 sulfur and the vulcanization accelerator in the crosslinking system.
  • the total kneading time, in this non-productive phase is preferably between 1 and 15 min.
  • sulfur 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.
  • An eleventh aspect of the invention is the laminate according to any one of the first to the tenth aspects, wherein each of the rubber compositions is further based on a crosslinking system.
  • the crosslinking system is based on at least one peroxide.
  • the crosslinking system is based on at least one bismaleimide.
  • the crosslinking system is based on at least one vulcanization accelerator other than sulfur-based vulcanization accelerator.
  • the vulcanization accelerator other than sulfur-based vulcanization accelerator may promote a vulcanization reaction in the rubber composition.
  • the vulcanization accelerator other than sulfur-based vulcanization accelerator may be based on guanidine derivatives (in particular diphenylguanidine), or combinations thereof.
  • the crosslinking system is based on at least one vulcanization activator.
  • the vulcanization activator can increase the efficiency of the vulcanization accelerators, and may be based on zinc (pure zinc, zinc derivatives (for example, zinc fatty acid salt), or combinations thereof), fatty acid (in particular, stearic acid), or combinations thereof.
  • a twelfth aspect of the invention is the laminate according to the eleventh aspect, wherein the crosslinking system is based on sulfur, wherein the amount in phr of sulfur in the first rubber composition (FC) is lower than that in the second rubber composition (SC), and wherein the amount in phr of sulfur in the second rubber composition (SC) is higher than that in the third rubber composition (TC).
  • the sulfur in the crosslinking (or vulcanization) system is to say vulcanization sulfur which may be sulfur, sulfur derived from a sulfur-donating agent, or combinations thereof.
  • the amount of sulfur in the first rubber composition (FC) is less than 1.8 phr, preferably less than 1.6 phr
  • the amount of sulfur in the second rubber composition (SC) is more than 1.4 phr, preferably at least 1.6 phr
  • the amount of sulfur in the third rubber composition (TC) is less than 1.8 phr, preferably less than 1.6 phr.
  • each of the rubber compositions is such that the amount of sulfur is less than 10 phr.
  • a thirteenth aspect of the invention is the laminate according to the eleventh aspect, wherein the crosslinking system is based on at least one sulfur-based vulcanization accelerator, wherein the amount in phr of sulfur-based vulcanization accelerator in the first rubber composition (FC) is lower than that in the second rubber composition (SC), and wherein the amount in phr of sulfur-based vulcanization accelerator in the second rubber composition (SC) is higher than that in the third rubber composition (TC).
  • the sulfur-based vulcanization accelerator is a vulcanization accelerator comprising at least one sulfur atom in a molecule.
  • the sulfur-based vulcanization accelerator may promote the sulfur vulcanization reaction in the rubber compositions.
  • sulfur-based vulcanization accelerator is based on sulfenamide type vulcanization accelerator(s) (for example, N-Cyclohexyl-2-benzothiazolesulfenamide (CBS), N-tert-Butyl-2-benzothiazolesulfenamide (TBBS), 2-(Morpholinothio)benzothiazole (MBS), N,N-Dicyclohexyl-2-benzothiazolesulfenamide (DCBS), N-Tert-Butyl-2-benzothiazolesulfenamide (TBSI)), thiazole type vulcanization accelerator(s) (for example, 2,2’-Dithiobisbenzothiazole (MBTS), Zinc 2-mercaptobenzothiazole (ZMBT)), thiourea type vulcanization accelerator(s), thiuram type vulcanization acclerator(s) (for example, Tetrabenzylthionitrile, N-Cyclohex
  • the amount of sulfur-based vulcanization accelerator in the first rubber composition (FC) is less than 2.0 phr, preferably less than 1.8 phr
  • the amount of sulfur in the second rubber composition (SC) is more than 1.6 phr, preferably at least 1.8 phr
  • the amount of sulfur-based vulcanization accelerator in the third rubber composition (TC) is less than 2.0 phr, preferably less than 1.8 phr.
  • each of the rubber compositions is such that the amount of sulfur-based vulcanization accelerator is less than 10 phr.
  • Each of the final compositions 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 a rubber article, for example, a tire tread.
  • the laminate according to the invention it is possible to build a first layer of a homogeneous rubber composition, as the first rubber composition (FC), a second layer of a homogeneous rubber composition, as the second rubber composition (SC), and a third layer of a homogeneous rubber composition, as the third rubber composition (TC), then to superpose the second layer onto the third layer and next to superpose the first layer onto the second layer, or sandwich the other layer(s) or portion(s) between these layers (between the first layer and the second layer or between the second layer and the third layer), to get the laminate.
  • FC first rubber composition
  • SC second layer of a homogeneous rubber composition
  • TC third layer of a homogeneous rubber composition
  • the second portion is adjacent to at least one of the first portion or the third portion, preferably the second portion is adjacent to the first portion and the third portion.
  • a preferred embodiment of the invention is an article comprising a laminate according to the invention.
  • the article is intended to contact with the ground.
  • the first portion (or the third portion) is arranged nearer to the ground than the second portion which is arranged near to the ground than the third portion (or the first portion).
  • the superposed portions which are the first portion, the second portion and the third portion are radially superposed portions, that is, the first portion (or the third portion) is radially exterior to the second portion which is radially exterior to the third portion (or the first portion).
  • the “radially” means “in the radial direction” which is a direction perpendicular to the axis of the rotation of a tire.
  • At least one of the first portion, the second portion or the third portion, preferably each of the portions, is intended to come into contact with the ground during the service life of 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 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 (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.
  • 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.
  • the laminate according to any one of the first to the thirteenth 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 combinations thereof.
  • a fourteenth aspect of the invention is a tire comprising a laminate according to any one of the first to the thirteenth aspects.
  • a fifteenth aspect of the invention is the tire according to the fourteenth aspect, wherein the tire comprises a tread comprising a laminate according to any one of the first to the thirteenth aspects.
  • the tire is a snow tire.
  • 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 or SBR only) reinforced with a blend of silica and carbon black (as a reinforcing filler).
  • the formulations of the rubber compositions are shown in Table 1 with the amount of the various products expressed in phr.
  • Each average glass transition temperature of elastomer is also shown in Table 1.
  • Each rubber composition was produced as follows: The reinforcing filler, the elastomer matrix and the various other ingredients, with the exception of sulfur and a 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, assembling, or both to the desired dimensions, for example as tire semi-finished products, in particular as tire treads.
  • three tires (T-1: a reference, T-2 and T-3: examples according to the invention) having treads comprising laminates comprising a radially external portion being made of a first rubber composition, a radially intermediate portion being made of a second rubber composition and a radially internal portion being made of a second rubber composition, the radially intermediate portion being adjacent to the radially externally and internally portions, the laminate being produced by superposition of the sheets of the rubber compositions (C-1, C-2, C-3 or combinations thereof) respectively which are the first rubber composition, the second rubber composition or the third rubber composition, as shown in Table 2, are compared.
  • These tires as snow tires having treads comprising grooves circumferentially, axially, or both extending, were conventionally manufactured and in all respects identical apart from the rubber compositions and the laminates of the tire treads. These tires are radial carcass passenger vehicle tires and the size of them is 245/40R18.
  • the laminate according to the invention allows an unexpectedly improved grip performance on snowy ground in the new state and in the worn state.

Abstract

L'invention concerne un stratifié comprenant au moins trois parties superposées comprenant une première partie constituée d'une première composition de caoutchouc (FC), une deuxième partie constituée d'une deuxième composition de caoutchouc (SC) et une troisième partie constituée d'une troisième composition de caoutchouc (TC), la deuxième partie étant disposée entre la première partie et la troisième partie ; chacune des compositions de caoutchouc étant basée sur au moins une matrice élastomère et plus de 65 phr d'une charge de renforcement ; la température de transition vitreuse moyenne de la matrice élastomère dans la première composition de caoutchouc (FC) étant inférieure à celle régnant dans la deuxième composition de caoutchouc (SC) ; et la température de transition vitreuse moyenne de la matrice élastomère dans la deuxième composition de caoutchouc (SC) étant supérieure à celle régnant dans la troisième composition de caoutchouc (TC).
PCT/JP2019/029947 2019-07-31 2019-07-31 Stratifié WO2021019709A1 (fr)

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