WO2018104671A1 - Pneumatique comprenant une composition de caoutchouc a base de polyisoprene epoxyde - Google Patents
Pneumatique comprenant une composition de caoutchouc a base de polyisoprene epoxyde Download PDFInfo
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- WO2018104671A1 WO2018104671A1 PCT/FR2017/053437 FR2017053437W WO2018104671A1 WO 2018104671 A1 WO2018104671 A1 WO 2018104671A1 FR 2017053437 W FR2017053437 W FR 2017053437W WO 2018104671 A1 WO2018104671 A1 WO 2018104671A1
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- polyisoprene
- tire
- epoxidized
- phr
- rubber composition
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L15/00—Compositions of rubber derivatives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- 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
- B60C11/005—Tyre tread bands; Tread patterns; Anti-skid inserts comprising different tread rubber layers with cap and base layers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- 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
- B60C11/0008—Tyre tread bands; Tread patterns; Anti-skid inserts characterised by the tread rubber
- B60C2011/0016—Physical properties or dimensions
- B60C2011/0025—Modulus or tan delta
-
- 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
- B60C11/0008—Tyre tread bands; Tread patterns; Anti-skid inserts characterised by the tread rubber
- B60C2011/0016—Physical properties or dimensions
- B60C2011/0033—Thickness of the tread
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- 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
- B60C2200/00—Tyres specially adapted for particular applications
- B60C2200/06—Tyres specially adapted for particular applications for heavy duty vehicles
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- 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
- B60C2200/00—Tyres specially adapted for particular applications
- B60C2200/06—Tyres specially adapted for particular applications for heavy duty vehicles
- B60C2200/065—Tyres specially adapted for particular applications for heavy duty vehicles for construction vehicles
-
- 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
- B60C2200/00—Tyres specially adapted for particular applications
- B60C2200/08—Tyres specially adapted for particular applications for agricultural vehicles
-
- 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
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
Definitions
- the field of the present invention is that of reinforcing filler-reinforced rubber compositions which can be used for the manufacture of vehicle tires.
- a tire tread undergoes mechanical stresses and aggression resulting from the direct contact with the ground.
- the mechanical stresses and the aggressions suffered by the tire are amplified under the effect of the weight carried by the tire.
- a rubber composition comprising in particular (i) more than 50 to 100 phr of polyisoprene containing an epoxidized polyisoprene having a molar epoxidation rate ranging from 5% to less than 50%, (ii) as a carbon black filler, further reduces hysteresis and improves resistance to crack propagation.
- a rubber composition comprising:
- the epoxidized polyisoprene being an epoxidized natural rubber or an epoxidized synthetic polyisoprene having a molar ratio of 1,4-cis bond of at least 90% before epoxidation or their mixture,
- the rubber composition contains more than 50 phr of epoxidized polyisoprene,
- composition being free of silica.
- the invention relates in particular to a tire which comprises the rubber composition according to the invention. Also described herein is a method for making the rubber composition usable in the context of the present invention.
- part by weight per hundred parts by weight of elastomer (or phr) is meant for the purposes of the present invention, the part, by mass per hundred parts by weight of elastomer or rubber. In the present, unless expressly indicated otherwise, all the percentages (%) indicated are percentages (%) by mass.
- any range of values designated by the expression "between a and b" represents the range of values from more than a to less than b (i.e. terminals a and b excluded) while any range of values designated by the term “from a to b” means the range from a to b (i.e., including the strict limits a and b).
- the interval represented by the expression "between a and b" is also designated and preferentially.
- composition based on is understood to mean a composition comprising the mixture and / or the reaction product of the various constituents used, some of these basic constituents being capable of or intended to react between they, at least in part, during the various phases of manufacture of the composition, in particular during its crosslinking or vulcanization.
- a composition based on an elastomeric and sulfur matrix comprises the elastomeric matrix and the sulfur before firing, whereas after firing the sulfur is no longer detectable because the latter has reacted with the elastomeric matrix in forming sulfur bridges (polysulfides, disulfides, mono-sulphide).
- a majority reinforcing filler is the reinforcing filler representing the largest mass relative to the total weight of the reinforcing fillers in the composition.
- a “minor” compound is a compound that does not represent the largest mass fraction among compounds of the same type.
- the carbonaceous products mentioned in the description may be of fossil origin or biobased. In the latter case, they can be, partially or totally, derived from biomass or obtained from renewable raw materials derived from biomass. These include polymers, plasticizers, fillers, etc.
- polyisoprene all the polyisoprenes and epoxidized polyisoprenes present in the rubber composition.
- polyisoprene is meant a polyisoprene which is not epoxidized.
- the polyisoprene may be natural rubber, a synthetic polyisoprene having a molar ratio of 1,4-cis bond of at least 90% or their mixture.
- epoxidized polyisoprene an epoxidized natural rubber or an epoxidized synthetic polyisoprene having a molar ratio of 1,4-cis bond of at least 90% before epoxidation or their mixture.
- the epoxidized polyisoprene which is wholly or partly polyisoprene is an elastomer and is not to be confused with an epoxidized polyisoprene of low molar mass generally used as a plasticizer which is not an elastomer in view of its low molecular weight.
- An epoxidized polyisoprene as an elastomer generally has a high raw Mooney viscosity.
- the Mooney viscosity (ML 1 + 4) at 100 ° C. of the epoxidized polyisoprene used in the context of the present invention is preferably greater than 20, more preferably 30, even more preferably 40.
- the Mooney viscosities (ML 1 + 4) at 100 ° C. of 25% molar natural epoxidized rubbers can be of the order of 40 to 150.
- the ranges of the Mooney viscosity of the epoxidized polyisoprene are preferably 30.degree. at 150, more preferably from 40 to 150, even more preferably from 50 to 140. These preferred values of Mooney viscosity apply to any of the embodiments of the invention.
- the epoxidized polyisoprene whether it be an epoxidized natural rubber or an epoxidized synthetic polyisoprene, can be obtained in a known manner by epoxidation of the polyisoprene, for example by chlorohydrin or bromohydrin-based processes or processes based on peroxidized peroxides. hydrogen, alkyl hydroperoxides or peracids (such as peracetic acid or performic acid). Epoxidized polyisoprenes are commercially available.
- the molar epoxidation rate which is a supplier data, corresponds to the ratio of the number of moles of epoxidized isoprene unit to the number of moles of isoprene unit in the polyisoprene before epoxidation.
- the term "epoxidized polyisoprene” is to be understood as one or more epoxidized polyisoprenes which can be differentiated either by their microstructure, macrostructure or epoxidation rate.
- the reference to the amount of polyisoprene epoxidized polyisoprene applies to the total mass of the epoxidized polyisoprenes of polyisoprene.
- the characteristic according to which the epoxidized polyisoprene is present in the rubber composition at a level greater than 50 phr means that, in the case of a mixture of epoxidized polyisoprenes, the total mass of epoxidized polyisoprenes is greater than 50 phr.
- the epoxidized polyisoprene is a mixture of epoxidized polyisoprenes which can be differentiated from each other by their molar epoxidation rate
- the reference to a mole ratio of epoxidation applies to each of the epoxidized polyisoprenes of the mixture.
- the rubber composition contains more than 50 phr of epoxidized polyisoprene.
- the rubber composition contains more than 50 phr of this epoxidized polyisoprene or this mixture of epoxidized polyisoprenes.
- the epoxidized polyisoprene comprises mainly, or even preferentially exclusively, an epoxidized natural rubber.
- the polyisoprene contains a polyisoprene having a molar ratio of 1,4-cis bond of at least 90%.
- the polyisoprene is preferably constituted by a mixture of a polyisoprene having a molar ratio of 1,4-cis bond of at least 90% and epoxidized polyisoprene.
- the polyisoprene having a molar ratio of 1,4-cis bond of at least 90% is a natural rubber.
- the epoxidized polyisoprene whether derived from the epoxidation of synthetic polyisoprene or natural rubber, has a molar epoxidation rate ranging from 5% to less than 50%.
- the molar epoxidation rate is preferably 5 to 40%, more preferably 10 to 35%.
- the epoxidized polyisoprene comprises mainly, or even preferentially exclusively, an epoxidized polyisoprene having a molar epoxidation rate of 5 to 40%, more preferably 10 to 35%
- the epoxidized polyisoprene is an epoxidized polyisoprene having a molar epoxidation level of 5 to 35%, more preferably 5 to 30%, even more preferably 5 to 25%.
- the epoxidized polyisoprene comprises mainly, or even preferentially exclusively, an epoxidized polyisoprene having an epoxidation molar ratio of 5 to 35%, more preferably 5 to 30%, even more preferably 5 to 30%. 25%.
- the polyisoprene content in the rubber composition is more than 50 phr to 100 phr.
- the level of polyisoprene in the rubber composition is preferably greater than 80 phr, more preferably equal to 100 phr.
- the epoxidized polyisoprene is an epoxidized polyisoprene having a molar epoxidation level of 5 to 35%, preferably 5 to 30%, of more preferably from 5% to 25%
- the level of epoxidized polyisoprene is preferably greater than 80 phr, more preferably equal to 100 phr.
- the rubber composition according to the invention comprises a complementary elastomer, preferably diene.
- a complementary elastomer preferably diene.
- diene elastomer
- diene elastomers can be classified into two categories: “essentially unsaturated” or "essentially saturated”.
- essentially unsaturated is generally 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% (mol%);
- diene elastomers such as butyl rubbers or copolymers of dienes and alpha-olefins of the EPDM type do not fall within the above definition and may in particular be described as "essentially saturated” diene elastomers ( low or very low diene origin, always less than 15%).
- the term “highly unsaturated” diene elastomer is particularly understood to mean a diene elastomer having a content of units of diene origin (conjugated dienes) which is greater than 50%.
- iene elastomer can be understood more particularly to be used in the compositions according to the invention: a) a ternary copolymer obtained by copolymerization of ethylene, of an ⁇ -olefin having 3 to 6 carbon atoms; carbon with a non-conjugated diene monomer having 6 to 12 carbon atoms, for example elastomers obtained from ethylene, propylene with a non-conjugated diene monomer of the aforementioned type, such as in particular 1,4-hexadiene, ethylidene norbornene, dicyclopentadiene; b) a copolymer of isobutene and isoprene (butyl rubber), as well as the halogenated versions, in particular chlorinated or brominated, of this type of copolymer.
- diene elastomer any type of diene elastomer
- the person skilled in the tire art will understand that the present invention is preferably implemented with essentially unsaturated diene elastomers, in particular of the type (a) or (b). ) above.
- copolymers of type (b) contain from 20 to 99% by weight of diene units and from 1 to 80% by weight of vinylaromatic units.
- 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, 2-methyl-3-isopropyl-1 3-butadiene, aryl-1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene.
- Suitable vinylaromatic compounds are, for example, styrene, ortho-, meta-, para-methylstyrene, the "vinyl-toluene" commercial mixture, para-tert-butylstyrene, methoxystyrenes, chlorostyrenes, vinylmesitylene, divinylbenzene, vinylnaphthalene.
- the rubber composition according to the invention may also comprise a substantially unsaturated complementary diene elastomer chosen from the group consisting of polybutadienes, butadiene copolymers, isoprene copolymers and their mixtures.
- the level of this substantially unsaturated complementary diene elastomer in the rubber composition is advantageously less than 20 phr (ie from 0 to less than 20 phr), preferably it is in a range from 0 to 10 preferably from 0 to 5 phr.
- the rubber composition according to the invention is free of substantially unsaturated complementary diene elastomer chosen from the group consisting of polybutadienes, butadiene copolymers, isoprene copolymers and their mixtures.
- the rubber composition according to the invention optionally contains from 0 to less than 20 phr of a butyl rubber.
- Butyl rubber is understood to mean isoprene and isobutylene copolymers, in particular halogenated copolymers.
- the level of butyl rubber in the composition of rubber is preferably 0 to 10 phr, more preferably 0 to 5 phr.
- the rubber composition according to the invention is devoid of butyl rubber. 11.3 Charge
- the rubber composition has the essential feature of comprising a carbon black.
- Suitable carbon blacks are all carbon blacks, especially blacks conventionally used in tires or their treads (so-called pneumatic grade blacks).
- pneumatic grade blacks there will be mentioned more particularly the reinforcing carbon blacks of the series 100, 200, 300, or the series blacks 500, 600 or 700 (ASTM grades), such as, for example, the blacks N115, N134, N234, N326, N330. , N339, N347, N375, N550, N683, N772).
- These carbon blacks can be used in the isolated state, as commercially available, or in any other form, for example as a carrier for some of the rubber additives used.
- the carbon black has a BET specific surface area of at least 90 m 2 / g, preferably at least 100 m 2 / g.
- the BET specific surface area of the carbon blacks is measured according to standard D6556-10 [multipoint method (at least 5 points) - gas: nitrogen - relative pressure range ⁇ / ⁇ 0: 0.01 to 0.5].
- the level of carbon black in the composition described herein is 30 to 90 phr, preferably 30 to 70 phr, more preferably 35 to 60 phr.
- the composition described herein has the essential feature of being silica-free. In other words, the composition described herein comprises 0 phr of silica.
- the silica used may be any silica known to those skilled in the art, capable of reinforcing on its own, without any other means than an intermediate coupling agent, a rubber composition intended for the manufacture of pneumatic tires, in other words capable of replacing, in its reinforcing function, a conventional carbon black of pneumatic grade.
- the silica used may be a precipitated or fumed silica having a BET surface and a CTAB specific surface area both less than 450 m 2 / g, preferably 30 to 400 m 2 / g, especially between 60 and 300 m 2 /
- silica "Ultrasil VN3" marketed by the company Evonik.
- HDS highly dispersible precipitated silicas
- the physical state in which the silica is presented is indifferent, whether in the form of powder, microbeads, granules or beads.
- silica is also understood to mean mixtures of different silicas.
- the composition described herein is free of reinforcing inorganic filler, preferably of inorganic filler, other than silica, or contains less than 10 phr, preferably less than 5 phr.
- the composition described herein is free of reinforcing inorganic filler, preferably inorganic filler
- Inorganic filler means any inorganic or mineral filler, irrespective of its color and origin (natural or synthetic), also called “white” filler, “clear” filler or even “non-black” filler by opposition to carbon black. Such a charge is generally characterized, in a known manner, by the presence of hydroxyl groups (-OH) on its surface.
- An inorganic filler is said to be “reinforcing” when it is capable of reinforcing on its own, with no other means than an intermediate coupling agent, a rubber composition intended for the manufacture of pneumatic tires. In other words, without a coupling agent, the inorganic filler does not make it possible to reinforce or not sufficiently the composition and is therefore not included in the definition of "reinforcing inorganic filler".
- inorganic fillers there may be mentioned mineral fillers of the siliceous type, preferentially silica (SiO 2 ). Mention may also be made, as inorganic fillers, of mineral fillers of the aluminous type, in particular alumina (Al 2 O 3 ) or aluminum (oxide) hydroxides, or reinforcing titanium oxides, for example described in US Pat. No. 6,610,261. and US 6,747,087.
- the rubber composition does not contain a coupling agent, which is to say that the level of the coupling agent is equal to 0 phr.
- alkoxysilane-polysulphide compounds in particular bis (trialkoxylsilylpropyl) polysulfides, especially bis-triethoxysilylpropyl disulfide (abbreviated to "TESPD”) and bis (3-triethoxysilylpropyl) tetrasulfide (abbreviated to "TESPT”).
- TESPD bis-triethoxysilylpropyl disulfide
- TESPT bis (3-triethoxysilylpropyl) tetrasulfide
- TESPT of formula is marketed in particular by the company Degussa under the name Si69 (or X50S when it is supported at 50% by weight on carbon black), in the form of a commercial mixture of polysulfides S x with a mean value for x which is close to 4.
- composition described herein advantageously does not comprise a covering agent or comprises less than 0.5 phr, such as hydrolyzable hydroxysilanes or silanes such as hydroxysilanes (see for example WO 2009/062733), alkylalkoxysilanes, especially alkyltriethoxysilanes such as, for example, 1-octyltriethoxysilane, polyols (for example diols or triols), polyethers (for example polyethylene glycols), primary, secondary or tertiary amines (for example trialkanol-amines), an optionally substituted guanidine, in particular diphenylguanidine, hydroxylated or hydrolysable polyorganosiloxanes (for example ⁇ , ⁇ -dihydroxy-poly-organosilanes (especially ⁇ , ⁇ -dihydroxy-polydimethylsiloxanes) (see for example EP 0 784 072), fatty acids
- the crosslinking system may be based on sulfur, sulfur donors, peroxide, bismaleimides or mixtures thereof.
- the crosslinking system is preferably a vulcanization system, that is to say a system based on sulfur (or a sulfur-donor agent) and a primary vulcanization accelerator.
- a vulcanization system that is to say a system based on sulfur (or a sulfur-donor agent) and a primary vulcanization accelerator.
- various known secondary accelerators or vulcanization activators such as zinc oxide.
- stearic acid or equivalent compounds such as zinc oxide.
- guanidine derivatives in particular diphenylguanidine
- known vulcanization retarders such as zinc oxide.
- sulfur When sulfur is used, it is used at a preferential rate of between 0.5 and 12 phr, in particular between 1 and 10 phr.
- the primary vulcanization accelerator is used at a preferred level of between 0.5 and 10 phr, more preferably between 0.5 and 5.0 phr.
- accelerator primary or secondary
- any compound capable of acting as an accelerator for vulcanization of diene elastomers in the presence of sulfur in particular thiazole accelerators and their derivatives, accelerators of the sulfenamide, thiuram, dithiocarbamate or dithiophosphate type. , thioureas and xanthates.
- MBTS 2-mercaptobenzothiazyl disulfide
- CBS N-cyclohexyl-2-benzothiazyl sulfenamide
- DCBS N-dicyclohexyl- 2-benzothiazyl sulfenamide
- TBBS N-tert-butyl-2-benzothiazyl sulfenamide
- TZTD tetrabenzylthiuram disulfide
- ZBEC Zinc dibenzyldithiocarbamate
- the rubber composition in accordance with the invention may also comprise all or part of the usual additives normally used in rubber compositions intended to constitute mixtures of finished articles of rubber such as tires, for example plasticizers (hydrocarbon resins or extension oils), pigments, protective agents such as anti-ozone waxes, anti-ozonants chemicals, anti-oxidants, anti-fatigue agents.
- plasticizers hydrocarbon resins or extension oils
- protective agents such as anti-ozone waxes, anti-ozonants chemicals, anti-oxidants, anti-fatigue agents.
- the amount of plasticizer, in particular extension oil or other liquid plasticizer at 23 ° C. is preferably less than 10 phr (that is to say from 0 to less than 10 phr), more preferably less than 5 phr (that is to say from 0 to less than 5 phr).
- This plasticizer may be a solid hydrocarbon resin (or plasticizing resin), an extender oil (or plasticizing oil), or a mixture of both.
- the extender oil or other liquid plasticizer at 23 ° C. (the composition of which is described herein lacks or contains less than 10 phr, preferably less than 2 phr) is chosen from the group consisting of naphthenic oils (low or high viscosity, especially hydrogenated), paraffinic oils, MES (Medium Extracted Solvates) oils, Treated Distillate Aromatic Extracts (TDAE) oils, mineral oils, vegetable oils, ether plasticisers , ester plasticizers, phosphate plasticizers, sulphonate plasticizers and mixtures of these compounds.
- naphthenic oils low or high viscosity, especially hydrogenated
- paraffinic oils MES (Medium Extracted Solvates) oils
- Treated Distillate Aromatic Extracts (TDAE) oils Treated Distillate Aromatic Extracts
- mineral oils mineral oils
- vegetable oils ether plasticisers
- ester plasticizers ester plasticizers
- phosphate plasticizers phosphate plasticizers
- thermoplastic hydrocarbon resin (the composition of which is described herein lacks or contains less than 10 phr, preferably less than 5 phr) is chosen from the group consisting of naphthenic oils (at low or high viscosity, in particular whether or not hydrogenated) is chosen from the group consisting of aliphatic or aromatic resins or else of the aliphatic / aromatic type, that is to say based on aliphatic and / or aromatic monomers.
- these resins are natural or synthetic, whether or not based on petroleum (if so, also known as petroleum resins).
- composition described herein is particularly well suited to tire treads.
- a tread comprising a composition described herein.
- composition described herein may be present throughout the tread described herein.
- the composition described herein is present in a radially inner portion of the tread described herein.
- a radially outer portion of the tread is not a composition different from that of the present invention.
- the tread may also comprise two different compositions between it but both of them in accordance with the present invention, one being present in a portion radially outer of the tread, the other in a radially inner portion.
- a tire comprising a composition described herein or a tread described herein is described herein.
- a tire having a geometry of revolution with respect to an axis of rotation its geometry is usually described in a meridian plane containing the axis of rotation of the tire.
- the radial, axial and circumferential directions respectively designate the directions perpendicular to the axis of rotation of the tire, parallel to the axis of rotation of the tire and perpendicular to the meridian plane.
- the terms “radially inner or radially outer” mean "closer or farther from the axis of rotation of the tire” respectively.
- axially inner, respectively axially outer is meant “closer or more distant from the equatorial plane of the tire", the equatorial plane of the tire being the plane passing through the middle of the running surface of the tire and perpendicular to the tire. rotation axis of the tire.
- the tire is preferably made before vulcanization (or cooking). The vulcanization is then carried out conventionally.
- the tire preferably a tire for civil engineering vehicles or heavy vehicles, may comprise a tread:
- the first portion being constituted by a radial superposition of N layers Ci ,, i ranging from 1 to N,
- each layer Ci having a radial thickness ⁇ ,, measured in an equatorial plane of the tire, substantially constant over at least 80% of the axial width L of the tread, and consisting of a polymeric material Mi, having a modulus of dynamic shear Gi ,, measured for a frequency equal to 10 Hz, a deformation equal to 50% of the peak-peak deformation amplitude and a temperature equal to 60 ° C,
- the second portion being constituted by a single layer C 2 ,
- the layer C 2 having a radial thickness E 2 , measured in the equatorial plane of the tire, substantially constant over at least 80% of the axial width L of the tread, and consisting of a polymeric material M 2 having a dynamic shear modulus G 2 , measured for a frequency equal to 10 Hz, a deformation equal to 50% of the peak-peak deformation amplitude and a temperature equal to 60 ° C,
- the dynamic shear modulus is measured on a Metravib VA4000 viscoanalyzer, according to ASTM D 5992-96.
- the response of a sample of vulcanized polymeric material, in the form of a cylindrical specimen 4 mm in thickness and 400 mm 2 in section, subjected to a sinusoidal stress in alternating simple shear at the frequency of 10 Hz is recorded. with a strain amplitude range of 0.1% to 45% (forward cycle), then 45% to 0.1% (return cycle), and at a temperature of 60 ° C.
- the dynamic shear modulus is thus measured for a frequency equal to 10 Hz, a deformation equal to 50% of the peak-peak deformation amplitude and a temperature equal to 60 ° C.
- i 1.
- the first portion being constituted by a single layer Ci
- the layer Ci having a radial thickness Ei, measured in an equatorial plane (XZ) of the tire, substantially constant over at least 80% of the axial width L of the tread, and consisting of a polymeric material Mi having a modulus of dynamic shear Gi, measured for a frequency equal to 10 Hz, a deformation equal to 50% of the peak-peak deformation amplitude and a temperature equal to 60 ° C.,
- the second portion being constituted by a single layer C 2 ,
- the layer C 2 having a radial thickness E 2 , measured in the equatorial plane (XZ) of the tire, substantially constant over at least 80% of the axial width L of the tread, and consisting of a polymeric material M 2 having a dynamic shear modulus G 2 , measured for a frequency equal to 10 Hz, a deformation equal to 50% of the peak-peak deformation amplitude and a temperature equal to 60 ° C,
- the material M 1 being constituted by a composition described herein.
- Figure 1 there is shown a meridian section of the top of a tire 1 for a heavy vehicle type of civil engineering according to the invention, comprising a tread 2, intended to come into contact with a floor.
- the directions XX ', YY' and ZZ ' are respectively the circumferential, axial and radial directions of the tire.
- the plane XZ is the equatorial plane of the tire.
- the tread having an axial width L, is constituted by a radial superposition of a first portion 21 and a second portion 22 radially external to the first portion 21.
- the first portion 21 consists of a radial superposition of N layers Ci ,, i ranging from 1 to N, each layer Ci having a radial thickness ⁇ ,, measured in an equatorial plane XZ of the tire, substantially constant over at least 80% of the axial width L of the tread 2, and consisting of a polymeric material Mi, having a dynamic shear modulus Gi ,, measured for a frequency equal to 10 Hz, a deformation equal to 50% of the amplitude of peak-peak deformation and a temperature equal to 60 ° C.
- the first multilayer portion 21 can be likened to a monolayer portion whose equivalent radial thickness Ei is equal to the sum of the respective radial thicknesses Ei, of the layers Ci, and whose equivalent flexibility Ei / Gi of the first portion is equal to the sum of respective flexibility E ⁇ / GI, CH layers.
- the second portion 22 is constituted by a single layer C 2 , the layer C 2 having a radial thickness E 2 , measured in the equatorial plane XZ of the tire, substantially constant over at least 80% of the axial width L of the tread 2, and consisting of a polymeric material M 2 having a dynamic shear modulus G 2 , measured for a frequency equal to 10 Hz, a deformation equal to 50% of the peak-peak deformation amplitude and a temperature equal to 60 ° C.
- Radially inside the first radially inner portion 21 is shown the crown reinforcement 3, comprising two crown layers comprising metal reinforcements.
- Radially inside the crown reinforcement 3 is shown the carcass reinforcement 4 comprising a carcass layer comprising metal reinforcements.
- a meridian section of the top of a tire 1 for a heavy vehicle type of civil engineering comprising a tread 2, intended to come into contact with a ground.
- the first portion 21 is constituted by a single layer Ci.
- the tread is constituted by the radial superposition of two layers, the first and second portions being monolayer: the tread is called bilayer.
- a radial layer thickness is a measured distance, in the radial direction, between the respectively radially inner and radially outer faces of the layer. This thickness is measured in the equatorial plane of the tire, passing through the middle of the tread and perpendicular to the axis of rotation of the tire.
- substantially constant radial thickness means a thickness in a range of + or -5% relative to an average thickness and at least 80% of the axial width L of the tread.
- a dynamic shear modulus is measured on a Metravib VA4000 viscoanalyzer, according to ASTM D 5992-96.
- the response of a sample of vulcanized polymeric material, in the form of a cylindrical specimen 4 mm in thickness and 400 mm 2 in section, subjected to a sinusoidal stress in alternating simple shear at the frequency of 10 Hz is recorded. , with a strain amplitude sweep from 0.1% to 45% (forward cycle), then from 45% to 0.1% (return cycle), and at a temperature of 60 ° C.
- the dynamic shear modulus is thus measured for a frequency equal to 10 Hz, a deformation equal to 50% of the peak-peak deformation amplitude and a temperature equal to 60 ° C.
- the first inequality l / (Ei / Gi + E 2 / G 2 )> G 0 / (Ei + E 2 ), with Ei Eu / Gu) with E 1 , E 1 , E 2 in mm, G 1 , G 1 , G 2 in MPa and with MPa ⁇ G 0 ⁇ 1.8 MPa, means that the rigidity of a tread according to the invention, constituted by a first portion, itself constituted by the radial superposition of N layers Ci ,, having respective radial thicknesses Ei, and consisting of polymeric materials Mi, having respective shear moduli Gi , and a second outer radial portion, constituted by a layer single C 2 , having a radial thickness E 2 and consisting of a polymeric material M 2 having a respective shear modulus G 2 , must be greater than the rigidity of a tread of the state of the art, consisting of a single equivalent layer, having a radial thickness equal to the sum of the radial thicknesses of all the
- the equivalent radial thickness Ei and the equivalent dynamic shear modulus Gi of the first portion assimilated to a single equivalent layer Ci are introduced.
- the equivalent radial thickness Ei of the first portion is equal to the sum of the respective radial thicknesses Ei, layers Ci ,.
- the equivalent flexibility Ei / Gi of the first portion which is the inverse of the equivalent stiffness Gi / Ei, is equal to the sum of the respective flexibilities Eii / Gii of the layers Ci, hence the expression equivalent dynamic shear modulus Gi of the first portion.
- This first inequality expresses that, on the new tire, that is to say at the beginning of its life, when it is mounted on the front axle of the vehicle, the multilayer tread of a tire according to the invention must be more rigid than the single-layer tread of a tire of the state of the art.
- the tread of a new tire at the beginning of life on the front axle, uses predominantly under imposed force.
- the force applied on the tread is the product of the rigidity of the tread by the local slip rate which is proportional wear. Therefore, imposed force, when the rigidity of the tread increases, the local slip rate, and therefore the wear, decrease.
- the multilayer tread of the invention more rigid, will wear less quickly than the single-layer tread of the state of the art.
- the second inequality Gi ⁇ G 0 means that the equivalent dynamic shear modulus Gi of the first portion must be smaller than the dynamic shear modulus G 0 of the single polymeric material constituting the tread of a tire of the the technique, measured under the same conditions.
- E r the residual radial thickness of the tread, at the end of the life of the tire on the rear axle, measured from the crown reinforcement
- the second inequality can also be written Gi / E r ⁇ G 0 / E r .
- E r corresponds to the residual radial thickness of the first radially inner portion of the partially worn tread, with some of the radially outermost layers Ci having been completely worn out.
- the first two inequalities express that the wear of a tread of a tire according to the invention is slower than that of a tire of the state of the art, at the beginning of life as at the end of life , that is to say throughout the life of the tire.
- the first radially inner portion must be thick enough to be able to have sufficient flexibility to ensure a cushion effect to envelop the indenter.
- the fourth inequality G 2 > G 0 > G 1 means that the dynamic shear modulus G 2 of the second portion must be both greater than the dynamic shear modulus G 0 of reference and the equivalent dynamic shear modulus Gi of the first portion that is, there must be a decreasing gradient of the dynamic shear modules as we move from the second portion to the first portion.
- the second radially outer portion should not be too thick to allow the cushioning effect of the first radially inner portion and to guarantee a sufficient rigidity of this second radially outer portion intended to come into contact with the indenters.
- the radially most radially inner layers the least rigid and therefore the most flexible, provide a cushioning role vis-à-vis the most radially outer layers.
- the present invention can be applied to any type of tire.
- the tire according to the invention may be intended to equip motor vehicles of the tourism type, SUV ("Sport Utility Vehicles"), or two wheels (including motorcycles), or planes, or industrial vehicles chosen among vans, "Weight "heavy” - that is, metros, buses, road transport vehicles (trucks, tractors, trailers), off-the-road vehicles such as agricultural or civil engineering equipment, and others.
- a tire includes a tread whose tread surface is provided with a tread formed by a plurality of grooves delimiting relief elements (blocks, ribs) so as to generate material edges and troughs.
- grooves represent a void volume which, in relation to the total volume of the tread (including both the volume of relief elements and that of all grooves) is expressed as a percentage referred to herein as " hollow volume ratio ".
- a trough volume equal to zero indicates a tread without grooves or recesses.
- the present invention is particularly well suited to tires intended for civil engineering vehicles, agricultural vehicles and heavy goods vehicles, more particularly to civil engineering or agricultural vehicles whose tires are subject to very specific constraints, in particular the stony soils on which they roll.
- the tire according to the invention is a tire for civil engineering vehicles, agricultural or heavy vehicles, preferably civil engineering.
- the tread described herein may have one or more grooves with an average depth of 15 to 120 mm, preferably 65 to 120 mm.
- the tires according to the invention may have a diameter of from 20 to 63 inches, preferably from 35 to 63 inches.
- the average trough volume rate over the entire tread described herein can range from 5 to 40%, preferably from 5 to 25%.
- the rubber composition can be manufactured in suitable mixers, using two successive preparation phases well known to those skilled in the art: a first phase of work or thermomechanical mixing (so-called “non-productive” phase) at high temperature, up to at a maximum temperature of between 110 ° C. and 200 ° C., followed by a second mechanical working phase (so-called “productive” phase) to a lower temperature, typically less than 110 ° C., for example between 40 ° C. ° C and 100 ° C, finishing phase during which is incorporated the crosslinking system.
- a first phase of work or thermomechanical mixing at high temperature, up to at a maximum temperature of between 110 ° C. and 200 ° C.
- a second mechanical working phase typically less than 110 ° C., for example between 40 ° C. ° C and 100 ° C, finishing phase during which is incorporated the crosslinking system.
- the first (non-productive) phase is carried out in a single thermomechanical step during which all the necessary constituents, the possible coating agents, are introduced into a suitable mixer such as a conventional internal mixer. or other complementary additives and other additives, with the exception of the vulcanization system.
- the total mixing time, in this non-productive phase is preferably between 2 and 10 min.
- the vulcanization system is then incorporated at low temperature, generally in an external mixer such as a roller mixer; the whole is then mixed (productive phase) for a few minutes, for example between 5 and 15 min.
- the first kneading step is generally carried out by incorporating the reinforcing filler to the elastomer in one or more times by thermomechanically kneading.
- the reinforcing filler in particular carbon black
- the masterbatch is directly kneaded and if necessary is incorporated other elastomers or reinforcing fillers present in the composition that are not in the form of masterbatch, as well as additives other than the crosslinking system.
- the process for preparing the rubber composition according to the invention may comprise the following steps:
- the method may also include the following step:
- the final composition thus obtained is then calendered, for example in the form of a sheet or a plate, in particular for a characterization in the laboratory, or else extruded, for for example forming a rubber profile used as a rubber component for the manufacture of the tire.
- the rubber composition according to the invention can be used in the form of calendering in a tire.
- the rubber composition according to the invention can be either in the green state (before crosslinking or vulcanization), or in the fired state (after crosslinking or vulcanization), is in a tire, for example in a tire tread.
- the tire, another object of the invention, which contains the rubber composition according to the invention, can be either in the green state (before crosslinking or vulcanization), or in the fired state (after crosslinking or vulcanization), which composition may be in the form of a calendering or an extrudate to form a rubber component of the tire.
- Dynamic properties are measured on a viscoanalyzer (Metravib VA4000) according to ASTM D 5992-96.
- the response of a sample of vulcanized composition (cylindrical specimen 4 mm in height and 400 mm 2 in section), subjected to a sinusoidal stress in alternating simple shear, at the frequency of 10 Hz, at 80 ° C. and at 100 ° C.
- a strain amplitude sweep of 0.1% to 100% is carried out (go cycle), then from 100% to 0.1% (return cycle).
- the results exploited are the complex dynamic shear modulus G * and the loss factor tan ( ⁇ ). On the return cycle, the value of the G * at 50% deformation is recorded as well as the loss factor, denoted tan ( ⁇ ) max .
- composition of the example under consideration has a lower rigidity, which is particularly for compositions used in a radially inner portion of a tire tread, in particular of a tire intended for heavy wear. loads, in particular rolling on stony soils such as a tire of a civil engineering vehicle
- the dynamic cracking test makes it possible to evaluate the resistance of the mixtures to the propagation of a crack on a specimen.
- the measurement of the propagated lengths is carried out after stopping the solicitation.
- the crack propagation velocity Vp represents the crack length propagated per cycle of solicitation. Because of the dimensions of the specimen, it is expressed in nanometers per cycle.
- the composition T1 is a control composition which is conventionally used in a tread of a tire for a vehicle intended to carry heavy loads, in particular rolling on stony soils such as a vehicle tire. civil engineering.
- the composition C1 is in accordance with the invention.
- the control compositions T2 to T7 differ from the compositions according to the present invention in that they comprise silica, either in addition to carbon black, or in replacement of an equivalent amount of carbon black, and in the presence or absence of in the absence of a collection agent.
- compositions based on natural epoxy rubber have a tan ( ⁇ ) max value at 100 ° C significantly lower than the composition T1, demonstrating a particularly advantageous decrease in hysteresis.
- the composition C1 according to the invention has a value of tan ( ⁇ ) ma x at 100 ° C among the lowest of those of the control compositions based on epoxidized natural rubber, which shows a decrease in the hysteresis and therefore a better rolling resistance.
- the values of G * 50% and the MAS10 and MAS100 modules of the composition C1 are at an acceptable level for use in a tire.
- the composition C1 is, compared with the control compositions, less rigid, which is particularly advantageous when the composition is used in a radially inner portion of a tire tread, in particular a tire intended to carry heavy loads, in particular rolling. on stony soils such as a tire of a civil engineering vehicle.
- composition C1 according to the present invention has a particularly remarkable crack propagation resistance compared to compositions conventionally used in a tread of a tire for a vehicle intended to carry heavy loads.
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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CN201780075017.5A CN110072707A (zh) | 2016-12-08 | 2017-12-07 | 包含基于环氧化聚异戊二烯的橡胶组合物的轮胎 |
BR112019011307-0A BR112019011307B1 (pt) | 2016-12-08 | 2017-12-07 | Pneumático que compreende uma composição de borracha à base de poliisopreno epoxidado |
AU2017371532A AU2017371532B2 (en) | 2016-12-08 | 2017-12-07 | Tyre comprising a rubber composition based on epoxidized polyisoprene |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR1662120A FR3060013A1 (fr) | 2016-12-08 | 2016-12-08 | Composition de caoutchouc a base de polyisoprene epoxyde |
FR1662120 | 2016-12-08 |
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WO2018104671A1 true WO2018104671A1 (fr) | 2018-06-14 |
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PCT/FR2017/053437 WO2018104671A1 (fr) | 2016-12-08 | 2017-12-07 | Pneumatique comprenant une composition de caoutchouc a base de polyisoprene epoxyde |
Country Status (5)
Country | Link |
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CN (1) | CN110072707A (fr) |
AU (1) | AU2017371532B2 (fr) |
BR (1) | BR112019011307B1 (fr) |
FR (1) | FR3060013A1 (fr) |
WO (1) | WO2018104671A1 (fr) |
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WO2020074815A1 (fr) * | 2018-10-11 | 2020-04-16 | Compagnie Generale Des Etablissements Michelin | Pneumatique comprenant une composition de caoutchouc a base de polyisoprene epoxyde et d'un polyamide a basse temperature de fusion |
WO2020128224A1 (fr) * | 2018-12-21 | 2020-06-25 | Compagnie Generale Des Etablissements Michelin | Bande de roulement pour pneumatique |
WO2020246087A1 (fr) * | 2019-06-05 | 2020-12-10 | 住友ゴム工業株式会社 | Pneumatique |
FR3101353A1 (fr) * | 2019-09-30 | 2021-04-02 | Compagnie Generale Des Etablissements Michelin | Composition de caoutchouc pour pneumatique de grande dimension |
WO2021105591A1 (fr) | 2019-11-28 | 2021-06-03 | Compagnie Generale Des Etablissements Michelin | Bandage hors la route comprenant des fibres d'alcool polyvinylique |
FR3117122A1 (fr) | 2020-12-09 | 2022-06-10 | Compagnie Generale Des Etablissements Michelin | Bandage pour vehicule hors la route |
FR3135223A1 (fr) * | 2022-05-09 | 2023-11-10 | Compagnie Generale Des Etablissements Michelin | Architecture optimisée de pneumatique de génie civil |
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FR3087204B1 (fr) | 2018-10-15 | 2020-09-18 | Michelin & Cie | Pneumatique comprenant une composition de caoutchouc comprenant un polyurethane thermoplastique |
FR3087200B1 (fr) * | 2018-10-15 | 2020-09-25 | Michelin & Cie | Pneumatique comprenant une composition de caoutchouc a base de polyisoprene epoxyde et d'un polyurethane thermoplastique |
CN113185760B (zh) * | 2021-05-17 | 2022-06-07 | 中国科学院长春应用化学研究所 | 一种功能化纳米环氧异戊橡胶及其在航空轮胎中的应用 |
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DATABASE WPI Week 200917, Derwent World Patents Index; AN 2009-E48216, XP002772119 * |
Cited By (14)
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CN112888578A (zh) * | 2018-10-11 | 2021-06-01 | 米其林集团总公司 | 包含基于环氧化聚异戊二烯和低熔点聚酰胺的橡胶组合物的充气轮胎 |
FR3087199A1 (fr) * | 2018-10-11 | 2020-04-17 | Compagnie Generale Des Etablissements Michelin | Pneumatique comprenant une composition de caoutchouc a base de polyisoprene epoxyde et d'un polyamide a basse temperature de fusion |
WO2020074815A1 (fr) * | 2018-10-11 | 2020-04-16 | Compagnie Generale Des Etablissements Michelin | Pneumatique comprenant une composition de caoutchouc a base de polyisoprene epoxyde et d'un polyamide a basse temperature de fusion |
WO2020128224A1 (fr) * | 2018-12-21 | 2020-06-25 | Compagnie Generale Des Etablissements Michelin | Bande de roulement pour pneumatique |
FR3090657A1 (fr) * | 2018-12-21 | 2020-06-26 | Compagnie Generale Des Etablissements Michelin | Bande de roulement pour pneumatique |
WO2020246087A1 (fr) * | 2019-06-05 | 2020-12-10 | 住友ゴム工業株式会社 | Pneumatique |
JP7435603B2 (ja) | 2019-06-05 | 2024-02-21 | 住友ゴム工業株式会社 | 空気入りタイヤ |
WO2021064317A1 (fr) * | 2019-09-30 | 2021-04-08 | Compagnie Generale Des Etablissements Michelin | Composition de caoutchouc pour pneumatique de grande dimension |
FR3101353A1 (fr) * | 2019-09-30 | 2021-04-02 | Compagnie Generale Des Etablissements Michelin | Composition de caoutchouc pour pneumatique de grande dimension |
WO2021105591A1 (fr) | 2019-11-28 | 2021-06-03 | Compagnie Generale Des Etablissements Michelin | Bandage hors la route comprenant des fibres d'alcool polyvinylique |
FR3103819A1 (fr) | 2019-11-28 | 2021-06-04 | Compagnie Generale Des Etablissements Michelin | Bandage hors la route comprenant des fibres d’alcool polyvinylique |
FR3117122A1 (fr) | 2020-12-09 | 2022-06-10 | Compagnie Generale Des Etablissements Michelin | Bandage pour vehicule hors la route |
FR3135223A1 (fr) * | 2022-05-09 | 2023-11-10 | Compagnie Generale Des Etablissements Michelin | Architecture optimisée de pneumatique de génie civil |
WO2023217622A1 (fr) * | 2022-05-09 | 2023-11-16 | Compagnie Generale Des Etablissements Michelin | Architecture optimisée de pneumatique de génie civil |
Also Published As
Publication number | Publication date |
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BR112019011307B1 (pt) | 2023-03-21 |
AU2017371532A1 (en) | 2019-07-04 |
CN110072707A (zh) | 2019-07-30 |
FR3060013A1 (fr) | 2018-06-15 |
AU2017371532B2 (en) | 2023-11-09 |
BR112019011307A2 (pt) | 2019-10-15 |
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