WO2019110922A1 - Pneumatique pourvu d'une couche interne - Google Patents
Pneumatique pourvu d'une couche interne Download PDFInfo
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- WO2019110922A1 WO2019110922A1 PCT/FR2018/053110 FR2018053110W WO2019110922A1 WO 2019110922 A1 WO2019110922 A1 WO 2019110922A1 FR 2018053110 W FR2018053110 W FR 2018053110W WO 2019110922 A1 WO2019110922 A1 WO 2019110922A1
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- Prior art keywords
- phr
- tire according
- composition
- oils
- tire
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D30/00—Producing pneumatic or solid tyres or parts thereof
- B29D30/06—Pneumatic tyres or parts thereof (e.g. produced by casting, moulding, compression moulding, injection moulding, centrifugal casting)
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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
- B60C1/0008—Compositions of the inner liner
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
Definitions
- the radially inner zone and in contact with the inflation gas this zone being generally constituted by the inflation-gas-tight layer, sometimes called inner waterproof layer or inner liner.
- the inner area of the tire that is to say the area between the outer and inner zones.
- This zone includes layers or plies which are here called internal layers of the tire. These are, for example, carcass plies, tread sub-layers, tire belt plies or any other layer that is not in contact with the ambient air or the inflation gas of the tire.
- the present invention relates to tires for agricultural vehicles or civil engineering, and more particularly the inner layers of such tires.
- Tires for agricultural vehicles or civil engineering are large tires that are subject to constraints specific to their uses. These tires are in particular driven on various types of soil, such as the more or less compact ground fields, yards or mines, sometimes aggressive, but also on tarmac surfaces of roads. They are also subject to heavy loads.
- the subject of the present invention is a tire of which at least one inner layer comprises a rubber composition based on at least:
- an elastomeric matrix comprising from 10 to 40 phr of polyisoprene, from 10 to 40 phr of polybutadiene and from 40 to 80 phr of styrene butadiene copolymer functionalized with tin,
- 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 matrix and sulfur comprises the matrix elastomeric and sulfur before firing, while after cooking the sulfur is no longer detectable because it has reacted with the elastomeric matrix forming sulfur bridges (polysulfides, disulfides, mono-sulfide).
- a majority compound in the sense of the present invention, it is understood that this compound is predominant among the compounds of the same type in the composition, that is to say that it is the one which represents the largest amount by mass among the compounds of the same type, for example more than 50%, 60%, 70%, 80%, 90% or even 100% by weight relative to the total weight of the type of compound.
- 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, for example less than 50%, 40%, 30%, 20%, 10% or less.
- 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.
- the glass transition temperature (Tg) values of the compounds is the value as measured according to ASTM D3418.
- compositions of the inner layer of the tire according to the invention comprise a specific mixture of several diene elastomers.
- elastomer or "rubber”, the two terms being considered synonymous
- diene monomers monomers bearing two carbon-carbon double bonds, conjugated or otherwise
- 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%.
- the rubber composition of the inner layer of the tire according to the invention is based on an elastomeric matrix comprising from 10 to 40 phr of polyisoprene, from 10 to 40 phr of polybutadiene and from 40 to 80 phr of copolymer. styrene butadiene functionalized with tin.
- each of the polyisoprene, polybutadiene or styrene butadiene copolymers functionalized with tin can be a mixture of several styrene butadiene polyisoprenes, polybutadienes or copolymers functionalized with tin, respectively.
- the level of polyisoprene in the composition of the internal mixture of the tire according to the invention is in a range from 15 to 35 phr, preferably 15 to 30 phr, more preferably from 15 to 25 phr.
- the content of polybutadiene in the composition of the internal mixture of the tire according to the invention is advantageously in a range from 15 to 35 phr, preferably from 20 to 35 phr, more preferably from 25 to 35 phr.
- the level of styrene-butadiene copolymer functionalized with tin in the composition of the internal mixture of the tire according to the invention is advantageously included in a range from 45 to 75 phr, preferably from 45 to 70 phr, more preferably from 45 to 65 pce.
- the total content of polyisoprene elastomers, polybutadiene and styrene butadiene copolymer functionalized with tin is 100 phr, that is to say that the composition does not include any other elastomer than those mentioned above.
- the tin-functionalized styrene butadiene copolymer may be an emulsion SBR or ESBR (that is prepared by emulsion polymerization), an SBR solution or SSBR (ie prepared by solution polymerization) , or a mixture of both.
- the stannene butadiene copolymer functionalized with tin has a styrene content ranging from 5% to less than 30%, preferably from 5% to less than 20%, more preferably from 10% to 19%. by weight relative to the total weight of the styrene butadiene copolymer functionalized with tin.
- the stanned butadiene copolymer functionalized with tin has a vinyl content ranging from 15 to 50%, preferably from 20 to 30%, by weight relative to the total weight of butadiene unit of the styrene copolymer. butadiene functionalized with tin.
- the level of carbon black having a BET specific surface area greater than 99 m 2 / g is in a range from 15 to 75 phr, preferably from 25 to 70 phr, more preferably from 35 to 65 phr, more preferably from 40 to 60 phr, more preferably from 45 to 55 phr.
- the carbon black having a BET surface area greater than 99 m 2 / g has a BET specific surface area in a range from 100 to 150 m 2 / g, preferably from 100 to 120 m 2 / g. more preferably from 105 to 115 m 2 / g.
- the blacks that can be used in the context of the present invention may be all black 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 and 200 (ASTM grades), such as, for example, the blacks N115, N134, N234, N326).
- ASTM grades the blacks N115, N134, N234, N326
- These carbon blacks can be used in the isolated state, as commercially available, or in any other form, for example as a carrier for some of the rubber additives used.
- the carbon blacks could for example already be incorporated into the diene elastomer, in particular isoprene in the form of a masterbatch (see for example applications WO 97/36724 or WO 99/16600).
- the rubber composition according to the invention may contain, in a minority manner, one or more reinforcing fillers different from the carbon black specifically required for the invention (this is that is to say a reinforcing filler other than carbon black having a BET specific surface area greater than 99 m 2 / g).
- This or these different reinforcing fillers are hereinafter called "other reinforcing filler” for the sake of simplification of drafting.
- the other reinforcing filler may for example comprise a carbon black different from the carbon black used in the context of the present invention, an organic filler other than carbon black, an inorganic filler or the mixture of at least two of these. loads.
- the carbon blacks can be used in the isolated state, as commercially available, or in any other form, for example as a carrier for some of the rubber additives used.
- the carbon blacks could for example already be incorporated into the diene elastomer, in particular isoprene in the form of a masterbatch (see for example applications WO 97/36724 or WO 99/16600).
- Reinforcing 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. as opposed to carbon black, capable of reinforcing on its own, with no other means than an intermediate coupling agent, a rubber composition intended for the manufacture of pneumatic tires, in other words able to replace, in its reinforcing function, a conventional carbon black of pneumatic grade; such a filler is generally characterized, in known manner, by the presence of hydroxyl groups (-OH) on its surface.
- 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".
- Suitable reinforcing inorganic fillers are in particular mineral fillers of the siliceous type, preferentially silica (SiO 2 ).
- the silica used may be any reinforcing silica known to those skilled in the art, in particular any precipitated or fumed silica having a BET surface and a CTAB specific surface both less than 450 m 2 / g, preferably from 30 to 400 m 2 / g, especially between 60 and 300 m 2 / g.
- HDS highly dispersible precipitated silicas
- an at least bifunctional coupling agent (or bonding agent) is used in a well known manner intended to ensure a sufficient chemical and / or physical connection between the silica (surface of its particles) and the diene elastomer.
- organosilanes or at least bifunctional polyorganosiloxanes are used.
- TESPT of formula [(C 2 H 5 O) 3 Si (CH 2 ) 3 S] 2 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 Sx with a mean value for x which is close to 4.
- an inorganic filler for example silica
- the content of coupling agent is advantageously less than 10 phr, it being understood that it is generally desirable to use as little as possible.
- the level of coupling agent is from 0.5% to 15% by weight based on the amount of inorganic filler. The level is easily adjusted by those skilled in the art according to the level of inorganic filler used in the composition.
- the composition of the inner layer of the tire according to the invention does not contain silica, preferably no reinforcing inorganic filler, or comprises less than 20 phr, preferably less than 10 phr, more preferably less than 5 phr. . More preferably, the composition of the inner layer of the tire according to the invention does not contain any other reinforcing filler (that is to say, reinforcing filler other than carbon black having a BBET specific surface greater than 99 m 2 / g) or contains less than 20 phr, preferably less than 10 phr, more preferably less than 5 phr.
- any other reinforcing filler that is to say, reinforcing filler other than carbon black having a BBET specific surface greater than 99 m 2 / g
- the crosslinking system is preferably a sulfur-based vulcanization system (molecular sulfur and / or sulfur donor agent).
- composition of the tread of the tire according to the invention advantageously comprises a vulcanization accelerator, which is preferably selected from the group consisting of thiazole accelerators and their derivatives, sulfenamide, thiourea accelerators and their mixtures.
- the vulcanization accelerator is selected from the group consisting of 2-mercaptobenzothiazyl disulfide (MBTS), N-cyclohexyl-2-benzothiazyl sulfenamide (CBS), N, N-dicyclohexyl-2-benzothiazyl sulfenamide (DCBS).
- MBTS 2-mercaptobenzothiazyl disulfide
- CBS N-cyclohexyl-2-benzothiazyl sulfenamide
- DCBS N-dicyclohexyl-2-benzothiazyl sulfenamide
- the weight ratio sulfur or sulfur donor / vulcanization accelerator ranges from 0.8 to 1.2.
- the rubber composition of the inner layer of the tire according to the invention may comprise a hydrocarbon plasticizing resin having a glass transition temperature greater than 20 ° C. (named hereinafter "plasticizing resin").
- the composition does not comprise a plasticizing resin, or comprises at most 20 phr, preferably at most 10 phr.
- the composition comprises a plasticizing resin, it may comprise from 2 to 20 phr, preferably from 2 to 10 phr.
- resin is hereby reserved, by definition known to those skilled in the art, to a compound that is solid at room temperature (23 ° C), as opposed to a liquid plasticizer such as an oil.
- hydrocarbon plasticizing resins are polymers well known to those skilled in the art, essentially based on carbon and hydrogen but may include other types of atoms, used in particular as plasticizers or tackifiers in polymeric matrices. They are inherently miscible (i.e., compatible) with the levels used with the polymer compositions for which they are intended, so as to act as true diluents. They have been described, for example, in the book "Hydrocarbon Resins” by R. Mildenberg, M. Zander and G. Collin (New York, VCH, 1997, ISBN 3-527-28617-9), chapter 5 of which is devoted their applications, in particular pneumatic rubber (5.5 “Rubber Tires and Mechanical Goods”).
- They can be aliphatic, cycloaliphatic, aromatic, hydrogenated aromatic, aliphatic / aromatic type that is to say based on aliphatic and / or aromatic monomers. They may be natural or synthetic, whether or not based on petroleum (if so, also known as petroleum resins). Their Tg is preferably greater than 20 ° C (most often between 30 ° C and 95 ° C).
- these hydrocarbon plasticizing resins can also be qualified as thermoplastic resins in that they soften by heating and can thus be molded. They can also be defined by a point or softening point (in English, "softening point”).
- the softening temperature of a plasticizing hydrocarbon resin is generally greater from about 50 to 60 ° C at its Tg value.
- the softening point is measured according to ISO 4625 ("Ring and Bail” method).
- the macrostructure (Mw, Mn and Ip) is determined by size exclusion chromatography (SEC) as indicated below.
- the SEC analysis for example, consists in separating the macromolecules in solution according to their size through columns filled with a porous gel; the molecules are separated according to their hydrodynamic volume, the larger ones being eluted first.
- the sample to be analyzed is simply solubilized beforehand in a suitable solvent, tetrahydrofuran at a concentration of 1 g / liter.
- the solution is then filtered through a 0.45 ⁇ m porosity filter before injection into the apparatus.
- the apparatus used is for example a "Waters alliance" chromatographic chain according to the following conditions:
- differential refractometer for example “WATERS 2410”
- operating software for example “Waters Millenium”
- a Moore calibration is conducted with a series of low Ip (less than 1.2) polystyrene commercial standards of known molar masses covering the field of masses to be analyzed.
- Tg greater than 25 ° C (in particular between 30 ° C and 100 ° C), more preferably greater than 30 ° C (in particular between 30 ° C and 95 ° C); a softening point greater than 50 ° C (in particular between 50 ° C and 150 ° C);
- Ip Mw / Mn with Mw weight average molar mass
- the plasticizing resin may be chosen from the group consisting of or consisting of homopolymer or copolymer resins of cyclopentadiene (abbreviated to CPD), homopolymer or copolymer resins of dicyclopentadiene (abbreviated to DCPD), resins of terpene homopolymer or copolymer, C5 homopolymer or copolymer resins, C9 homopolymer or copolymer resins, alpha-methylstyrene homopolymer or copolymer resins and mixtures of these plasticizing resins .
- CPD cyclopentadiene
- DCPD dicyclopentadiene
- the plasticizing resin is selected from the group consisting of or consisting of CPD / vinylaromatic (D) copolymer resins, (D) CPD / terpene copolymer resins, terpene phenol copolymer resins, copolymer resins (D) ) CPD / C5 cut, (D) CPD / C9 cut copolymer resins, terpene / vinylaromatic copolymer resins, terpene / phenol copolymer resins, C5 / vinylaromatic cut copolymer resins, and blends of these plasticizing resins .
- CPD / vinylaromatic (D) copolymer resins (D) CPD / terpene copolymer resins, terpene / phenol copolymer resins, C5 / vinylaromatic cut copolymer resins, and blends of these plasticizing resins .
- pene includes, in a known manner, the alpha-pinene, beta- pinene and limonene monomers; preferably, a limonene monomer is used which is present in a known manner in the form of three possible isomers: L-limonene (laevorotatory enantiomer), D-limonene (dextrorotatory enantiomer), or the dipentene, racemic of the dextrorotatory and levorotatory enantiomers. .
- 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 in the form of a semifinished (or profiled) of rubber usable by example as an inner tire layer for agricultural vehicles.
- the composition can be either in the green state (before crosslinking or vulcanization), or in the fired state (after crosslinking or vulcanization), can be a semi-finished product that can be used in a tire.
- the cooking can be carried out, in a manner known to those skilled in the art, at a temperature generally between 130 ° C. and 200 ° C., under pressure, for a sufficient time which may vary, for example, between 5 and 90 min, depending in particular the firing temperature, the crosslinking system adopted, the kinetics of crosslinking of the composition in question or the size of the tire.
- 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.
- SUV Sport Utility Vehicles
- two wheels including motorcycles
- 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.
- the composition of the inner layer of the tire according to the invention is particularly well suited to large tires.
- the tire according to the invention is a pneumatic agricultural vehicle or civil engineering vehicle, preferably agricultural vehicle.
- the tires of agricultural vehicles or civil engineering vehicles, in particular of agricultural vehicles are characterized in particular by their large diameter, generally ranging from 20 to 63 inches, preferably from 28 to 54 inches, more preferably from 36 to 42 inches.
- their tread may have one or more grooves with an average depth of 15 to 120 mm, preferably 65 to 120 mm.
- the average trough volume rate over their entire tread can be in a range from 5 to 40%, preferably from 5 to 25%.
- the dynamic properties G * (10%) and tan ( ⁇ ) max at 60 ° C are measured on a viscoanalyzer (Metravib VA4000) according to ASTM D 5992-96.
- the response of a reticulated composition sample (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 under the defined conditions of temperature for example at 60 ° C according to ASTM D 1349-99, or as the case may be at a different temperature.
- a strain amplitude sweep of 0.1 to 50% (forward cycle) and then 50% to 0.1% (return cycle) are performed.
- tan ( ⁇ ) max at 60 ° C are expressed in base 100, the value 100 being attributed to the control.
- a result less than 100 indicates that the composition of the example under consideration is less hysteretic at 60 ° C, reflecting a reduction in heat dissipation and a lower rolling resistance of the inner layer comprising such a composition.
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Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA3081408A CA3081408A1 (fr) | 2017-12-08 | 2018-12-05 | Pneumatique pourvu d'une couche interne |
BR112020010159-1A BR112020010159B1 (pt) | 2017-12-08 | 2018-12-05 | Pneu dotado de uma camada interna |
RU2020115502A RU2747313C1 (ru) | 2017-12-08 | 2018-12-05 | Пневматическая шина, снабженная внутренним слоем |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1761822 | 2017-12-08 | ||
FR1761822 | 2017-12-08 |
Publications (1)
Publication Number | Publication Date |
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WO2019110922A1 true WO2019110922A1 (fr) | 2019-06-13 |
Family
ID=61187501
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/FR2018/053110 WO2019110922A1 (fr) | 2017-12-08 | 2018-12-05 | Pneumatique pourvu d'une couche interne |
Country Status (4)
Country | Link |
---|---|
BR (1) | BR112020010159B1 (fr) |
CA (1) | CA3081408A1 (fr) |
RU (1) | RU2747313C1 (fr) |
WO (1) | WO2019110922A1 (fr) |
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2018
- 2018-12-05 WO PCT/FR2018/053110 patent/WO2019110922A1/fr active Application Filing
- 2018-12-05 CA CA3081408A patent/CA3081408A1/fr active Pending
- 2018-12-05 BR BR112020010159-1A patent/BR112020010159B1/pt active IP Right Grant
- 2018-12-05 RU RU2020115502A patent/RU2747313C1/ru active
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RU2747313C1 (ru) | 2021-05-04 |
BR112020010159A2 (pt) | 2020-11-03 |
BR112020010159B1 (pt) | 2023-11-28 |
CA3081408A1 (fr) | 2019-06-13 |
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